CA1076200A - Hermetically sealed alkali metal battery - Google Patents
Hermetically sealed alkali metal batteryInfo
- Publication number
- CA1076200A CA1076200A CA281,047A CA281047A CA1076200A CA 1076200 A CA1076200 A CA 1076200A CA 281047 A CA281047 A CA 281047A CA 1076200 A CA1076200 A CA 1076200A
- Authority
- CA
- Canada
- Prior art keywords
- ring
- metal
- casing
- open end
- ceramic ring
- 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
- 229910052751 metal Inorganic materials 0.000 claims abstract description 69
- 239000002184 metal Substances 0.000 claims abstract description 69
- 239000000919 ceramic Substances 0.000 claims abstract description 51
- 239000004020 conductor Substances 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 5
- 239000011521 glass Substances 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims 2
- 239000000376 reactant Substances 0.000 description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 14
- 229910052717 sulfur Inorganic materials 0.000 description 12
- 239000011593 sulfur Substances 0.000 description 12
- 229920001021 polysulfide Polymers 0.000 description 8
- 239000005077 polysulfide Substances 0.000 description 8
- 150000008117 polysulfides Polymers 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000007784 solid electrolyte Substances 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
- 230000000712 assembly Effects 0.000 description 4
- 238000000429 assembly Methods 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 238000010349 cathodic reaction Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 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
- 239000007788 liquid Substances 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 101100285518 Drosophila melanogaster how gene Proteins 0.000 description 1
- 101100536354 Drosophila melanogaster tant gene Proteins 0.000 description 1
- 241001663154 Electron Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 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
-
- 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
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Sealing Battery Cases Or Jackets (AREA)
Abstract
HERMETICALLY SEALED ALKALI METAL BATTERY
ABSTRACT OF THE DISCLOSURE
The invention is embodied in a hermetically sealed alkali metal battery container. Two opposed outer metallic casings are hermetically sealed to a ceramic ring which supports an inner casing of a solid alkali ion-conductive material. The hermetic seal is accomplished by means of annular ridges on metal rings associated with the two outer casings and a pair of washers interposed between the annular ridges and respective top and bottom surfaces of the ceramic ring.
ABSTRACT OF THE DISCLOSURE
The invention is embodied in a hermetically sealed alkali metal battery container. Two opposed outer metallic casings are hermetically sealed to a ceramic ring which supports an inner casing of a solid alkali ion-conductive material. The hermetic seal is accomplished by means of annular ridges on metal rings associated with the two outer casings and a pair of washers interposed between the annular ridges and respective top and bottom surfaces of the ceramic ring.
Description
1~7~2f~
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 a battery's anodic and cathodic zones and a seal against loss of reactants from such zones.
A recently developed type of secondary or recharge-able electrical conversion device comprises: ~1] an anodic r~action zone containing a molten alkali metal anode-reactant, e.g., sodium, in electrical contact with anexternal circuit; ~2~_ a cathodic reaction zone containing ~a] a cathodic reactant comprising sulfur or a mixture of sulfur and molten polysulfide, which is electrochemically reversible react ve with the anodic reactant; [b] a solid electrolyte comprising a cation-permeable ~arrier to mass liquid transfer interposed between and in contact with the anodic and the cathodic reaction zones; and [c] electrode de~ices within the cathodic reaction zone or transporting electrons to and from the ~icinity of the cation-permeable barrier~ As used herein the term "reactant" is intended to mean both reactants and reaction products.
During the discharge cycle of such a device, molten alkali metal atoms such as sodium surrender an elec-tron to an external circuit and t~e resulting cation passes through the solid electrolyte barrier an~ into the liquid electrolyte to unite with polysulfide ions. The polysulfide ions are formed by charge transfer on the electrode by reac tion of the cathodic reactant with the electrons conducted through the electrode from the external circuit. Because the ionic conductivity of the liquid electro~yte is less than the electronic conducti~ity o~ the electrode material~ it is
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 a battery's anodic and cathodic zones and a seal against loss of reactants from such zones.
A recently developed type of secondary or recharge-able electrical conversion device comprises: ~1] an anodic r~action zone containing a molten alkali metal anode-reactant, e.g., sodium, in electrical contact with anexternal circuit; ~2~_ a cathodic reaction zone containing ~a] a cathodic reactant comprising sulfur or a mixture of sulfur and molten polysulfide, which is electrochemically reversible react ve with the anodic reactant; [b] a solid electrolyte comprising a cation-permeable ~arrier to mass liquid transfer interposed between and in contact with the anodic and the cathodic reaction zones; and [c] electrode de~ices within the cathodic reaction zone or transporting electrons to and from the ~icinity of the cation-permeable barrier~ As used herein the term "reactant" is intended to mean both reactants and reaction products.
During the discharge cycle of such a device, molten alkali metal atoms such as sodium surrender an elec-tron to an external circuit and t~e resulting cation passes through the solid electrolyte barrier an~ into the liquid electrolyte to unite with polysulfide ions. The polysulfide ions are formed by charge transfer on the electrode by reac tion of the cathodic reactant with the electrons conducted through the electrode from the external circuit. Because the ionic conductivity of the liquid electro~yte is less than the electronic conducti~ity o~ the electrode material~ it is
2 - ~
~71620g~
desirable during discharge that both electrons and sulfur be applied to and distributed along the surface of the electrode in the vicinity of the cation-permeable solid electrolyte.
During the charge cycle of such a device when a negative potential larger than the open circuit cell voltage is applîed to the anode the opposite process occurs. Thus, electrons are removed from the al~ali metal polysulfide by charge transfer at the surface of the electrode and are con-ducted through the electrode material to the external circuit, and the alkali metal cation is conductéd through the liquid electrolyte and solid electrolyte to the anode where it accepts an electron from the external circuit. Because of the aforementionea 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 ceramic ring having top and bottom surfaces. An inner casing of solid alka~li ion-conductive material having one open end is sealed adjacent its open end to the ceramic ring by a glass seal so that the inner casing extends downwardly from the bottom surface of the ceramic ring. A first outer metal casing with an open end and a closed end surrounds the inner casing and is spaced therefrom. A first ring encircles and is bonded to the open end of the first outer casing. This ring (a) has a raised annular ridge encircling the open end of the first outer casing, (b) has at least a pair of openings for receiving bolts therethrough, and (c) is adjacent the bottom surface of the ceramic ring. A first pair of thin washers are positioned between the raised annular ridge of the first .:
: .
~;; ,, . -.
~ . , . , ~ ..
6ZCI(:~
ring and ~e bottom surface of the ceramic ring~ Thewasher adjacent the first ring has a coefficient of thermal expansion closely matching that of the first ring. The washer adjacent the ceramic ring has a coefficient of thermal expansion closely matching that of the ceramic ring.
A second outer casing having an open end and a closed end has associated therewith a ~econd ring which encircles and is bonded to the open end of the second outer metal casing. The second ring ~a) has a raised annular ridye encircling the open end of the second outex casing, and (b) is located adjacent the top surface of the ceramic ring whereby the second outer casing is spaced ~rom and extends in an opposite direction from the ceramic ring than does the first outer casing. A second pair of thin washers are positioned between the raised annular ridge of the second ring and the top surface of the ceramic ring. The washer adjacént the second ring has a coefficient of thermal expansion closely matching that of the second ring and the washer adjacent the ceramic ring has a coefficient of thermal expansion closely matching that of the ceramic ring.
A Belleville spring encircles the second outer casing and engages an upper surface of the second ring. A
third ring encircles the second outer casing. This third ring both ~a) engages an upper surface of the Belleville spring and (~) has at least a pair of spaced openings aligned with the openings of the fixst ring for receiving bolts therethrough. At least a pair of nut and bolt assemblies ;
extend through the openings in the first and third rings and are securely tightened together to draw the annular ridges on the first and the second rings tightly into engagement with the first and the second pair of washers to provide a hermeti-_ ~ . . . .
. , . ; : . : : : ~
~C~76Z~7~
cally sealed alkali metal battery container.
By using a pair of thin washers as described above, a provision is made for the mismatch in coefficient of thermal expansion between ceramic and material which produces a dimensional change in the materials as they are heated from room temperature to operational temperatures.
The t~pe 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;
~71620g~
desirable during discharge that both electrons and sulfur be applied to and distributed along the surface of the electrode in the vicinity of the cation-permeable solid electrolyte.
During the charge cycle of such a device when a negative potential larger than the open circuit cell voltage is applîed to the anode the opposite process occurs. Thus, electrons are removed from the al~ali metal polysulfide by charge transfer at the surface of the electrode and are con-ducted through the electrode material to the external circuit, and the alkali metal cation is conductéd through the liquid electrolyte and solid electrolyte to the anode where it accepts an electron from the external circuit. Because of the aforementionea 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 ceramic ring having top and bottom surfaces. An inner casing of solid alka~li ion-conductive material having one open end is sealed adjacent its open end to the ceramic ring by a glass seal so that the inner casing extends downwardly from the bottom surface of the ceramic ring. A first outer metal casing with an open end and a closed end surrounds the inner casing and is spaced therefrom. A first ring encircles and is bonded to the open end of the first outer casing. This ring (a) has a raised annular ridge encircling the open end of the first outer casing, (b) has at least a pair of openings for receiving bolts therethrough, and (c) is adjacent the bottom surface of the ceramic ring. A first pair of thin washers are positioned between the raised annular ridge of the first .:
: .
~;; ,, . -.
~ . , . , ~ ..
6ZCI(:~
ring and ~e bottom surface of the ceramic ring~ Thewasher adjacent the first ring has a coefficient of thermal expansion closely matching that of the first ring. The washer adjacent the ceramic ring has a coefficient of thermal expansion closely matching that of the ceramic ring.
A second outer casing having an open end and a closed end has associated therewith a ~econd ring which encircles and is bonded to the open end of the second outer metal casing. The second ring ~a) has a raised annular ridye encircling the open end of the second outex casing, and (b) is located adjacent the top surface of the ceramic ring whereby the second outer casing is spaced ~rom and extends in an opposite direction from the ceramic ring than does the first outer casing. A second pair of thin washers are positioned between the raised annular ridge of the second ring and the top surface of the ceramic ring. The washer adjacént the second ring has a coefficient of thermal expansion closely matching that of the second ring and the washer adjacent the ceramic ring has a coefficient of thermal expansion closely matching that of the ceramic ring.
A Belleville spring encircles the second outer casing and engages an upper surface of the second ring. A
third ring encircles the second outer casing. This third ring both ~a) engages an upper surface of the Belleville spring and (~) has at least a pair of spaced openings aligned with the openings of the fixst ring for receiving bolts therethrough. At least a pair of nut and bolt assemblies ;
extend through the openings in the first and third rings and are securely tightened together to draw the annular ridges on the first and the second rings tightly into engagement with the first and the second pair of washers to provide a hermeti-_ ~ . . . .
. , . ; : . : : : ~
~C~76Z~7~
cally sealed alkali metal battery container.
By using a pair of thin washers as described above, a provision is made for the mismatch in coefficient of thermal expansion between ceramic and material which produces a dimensional change in the materials as they are heated from room temperature to operational temperatures.
The t~pe 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,~75,220; 3,475~223;
3,475,225; 3,535,163; 3,719,531; and 3,811,493~ :
A novelty search conducted on the stru~ture of this invention resulted in the location of the following prior art, all U.S. patents: 2,646,997; 3,188J116; 3,398,978;
3,419,432, 3,46~,709; 3,63~,143; 3,650,550; 3,74~,347;
3,918,919; and 3,9.467751.
This invention i~ described further, by way of illus-tration, with reference ~o the accompanying drawings, in which:
Figure 1 is an elevational view, in cross-section, of the alkali metal battery structure of this invention in a disassembled condition; and Figure 2 is an elevational view, in cross-section, of the hexmetically sealed alkali metal battery of this invention in an assembled condition.
In FIGURES 1 and 2 there is seen a hermetically sealed alkali metal battery designated generally by the numeral 10. Th~s ~attery includes a ceramic ring 12 which has a top surface 14 and a bottom surface 16. The ceramic material may be formed from a material such as alpha alumina of high purity, such as 99~8~.
An inner casing 18 of a solid alkali ion-conductive material is in the form of a closed end tu~e. This casing ~ is used as a reaction zone separator and i5 made from a : 5 .. - . -........ . - , :, ..
6~
1 material which will permit the transfer of ions of an 2 anodic reactant therethrough to a cathodic reactant. The 3 barrier may have a thickness in the range of about 20 to
3,475,225; 3,535,163; 3,719,531; and 3,811,493~ :
A novelty search conducted on the stru~ture of this invention resulted in the location of the following prior art, all U.S. patents: 2,646,997; 3,188J116; 3,398,978;
3,419,432, 3,46~,709; 3,63~,143; 3,650,550; 3,74~,347;
3,918,919; and 3,9.467751.
This invention i~ described further, by way of illus-tration, with reference ~o the accompanying drawings, in which:
Figure 1 is an elevational view, in cross-section, of the alkali metal battery structure of this invention in a disassembled condition; and Figure 2 is an elevational view, in cross-section, of the hexmetically sealed alkali metal battery of this invention in an assembled condition.
In FIGURES 1 and 2 there is seen a hermetically sealed alkali metal battery designated generally by the numeral 10. Th~s ~attery includes a ceramic ring 12 which has a top surface 14 and a bottom surface 16. The ceramic material may be formed from a material such as alpha alumina of high purity, such as 99~8~.
An inner casing 18 of a solid alkali ion-conductive material is in the form of a closed end tu~e. This casing ~ is used as a reaction zone separator and i5 made from a : 5 .. - . -........ . - , :, ..
6~
1 material which will permit the transfer of ions of an 2 anodic reactant therethrough to a cathodic reactant. The 3 barrier may have a thickness in the range of about 20 to
4 2,000 microns and may be made of a material such as glasses and polycrystalline ceramic materials as is well known in 6 the art. One material which is extremely useful is beta-7 type alumina or sodium beta-type alumina. The inner casing is bonded near its open end within and to an interior g surface 20 of the ceramic xing 12 by means of a glass seal 22 so that the inner casing extends downwardly from the 11 bottom surace 16 of the ceramic ring.
12 A first outer metal casing 24 with an open end 26 13 and a closed end 28 surrounds the inner casing 18 and is 14 spaced therefrom.
A first metal ring 30 encircles and is welded b~
16 weldment 32 to the first outer ~etal casing 24. This first 17 metal ring 30 is formed of a metal such as and has a 18 raised annular ridge 34 encircling the open end 26 of the 19 ~ first outer metal casing 24 for a purpose described in detail herein below. The first metal ring also has at 21 least a pair of openings 36 ~only one sIlown) or receiving 22 bolts therethrough. In its assembled condition the firs~
23 metal ring is located adjacent the bottom surface 16 of the 24 ceramic ring 12.
A irst pair of thin metal washers 38 and 40 are 26 positioned ~etween the raised annular ridge 34 of the first 27 metal ring 30 and the bottom surace 16 of the ceramic ring 2a ~ 12. The washers have a thickn ss in the range of 0.003 to 29 0.005 inches. The washer 38 adjacent the first metal ring 30 may be formed of hardened polished steel and has a coeffi 31 cient of thermal expansion closely matching that o the ~7620~
l first metal ring. The metal washer 40 adjacent the ceramic e~9 ~
2 ring 12 may be formed from "Radar", a product name for a 3 cobalt, nickel, iron alloy which has a coefficient of ther-4 mal expansion closely matching that of the ceramic ring.
A second outer metal casing 42 has an open end 44 6 (shown only in FIGU~E ll. A second metal 48 encircles the 7 open end 44 of the second outer metal casing 42 and is 8 secured thereto by weldment 50 (shown in FIGURE 1 only).
9 This second metal ring is formed from the same material as the first metal ring and it also has a raised annular ridge ll 52 encircling the open end 44 of the second outer metal 12 casing 42. In its assem~led condition, the second metal 13 ring 48 is adjacent the top surface 14 of the ceramic 14 ring 12 whereby the second outer casing 42 is spaced from and extends in an opposite direction from the ceramic ring 16 than does the fixst outer casing 24.
17 A second pair of thin metal washers 38 and 40 are 18 positioned between the raised annular ridge 52 of the 19 second metal ring 48 and the top sur~ace 14 of the ceramic ring 12 for the same purposes as the washers were placed 21 between the raised annular ridge 34 o the first metal 22 ring 30 and the bottom surace 16 of the ceramic ring 12.
23 A Belleville spring 54 encircles the second outer 24 metal casing 42. This spring also engages an upper surface of the second metal ring 48.
26 A third metal ring 56 also encircles the second 27 outer metal casing 42. This third metal rîng engages an 28 upper surface of the Belleville spring 54. The third metal 29 ring also has at least a pair of spaced openings 58 (only one shown in the drawing) aligned with the openings 36 in 31 the first metal ring 30 for receiving bolts therethrough.
~ 7~ ~d~ ~nQ~ k 7 -.
~L~76201D
1 At least a pair of nut and bolt assemblies 60 2 (only one shown in each figure) are shown in their un-3 assembled condition in FIGURE 1 and in a securely tightened 4 position in FIGURE 2. In the securely tightened position, the nut and bolt assemblies draw toyether the annular ridges 6 34 and 52 to compress the irst and second pair of thin 7 metal washers 38 and 40 tightly into engagement with one 8 another and with the bottom surface 16 and the top surface 9 14 of the ceramic xing 12 to provide a hermetic seal for the alkali metal battery 10. Pressure is placed on this assembly 11 through the action of the selleville spring 5~ when the nut 12 and bolt assemblies are tightened down.
13 ~y uti.lizing the two pairs of metal washers 38 14 and 40, the mismatch in coefficient of thermal expansion between the ceramic ring 12 and the first metal ring 30 16 and second metal ring 48 are compensated for. The first 17 and second washers 38 and 40 may at their interface slide 18 back and forth su~ficiently to adjust for the differences g in coeicient of thermal expansion. Thus, the hermetic 2b seal of the battery remains even though the battery is 21 cycled through temperature variations from room temperature 22 to operational temperatuxes, 23 With reference to FIGURE ~, a irst reaction zone 24 6Z is formed by t~e interior of the second outer metal cas ing 42 and the interior of the inner casing 18. ~his reac-26 tion zone may contain an anodic reactant. The anodic reac-27 tant is heated by any conventional source and may be vlewed : : 28 as the anode proper or conductor through which electron fIow ~29 to an external circuit (not shown) is achieved. Molten :~ :
~: - 8 -.
~L076Z~)~
l sodium is employed as the anodic reactant in most preferred 2 embodiments of such alkali metal batteries. However, 3 potassiumt lithium, other alkali metals, mixtures of such 4 alkali metals or alloys containing such alkali metals can be used.
6 A second reaction zone 64 (shown only in FIGUR~
7 2~ is formed in the volume between the interior surface of 8 the first outer metal'casing 24 and the exterior surface 9 of the inner casing 18~ T~is reactant zone can contain the cathodic reactant. The cathodic reactant of the fully 11 charged battery is molten sulfur, which is electrode 12 chemically reversibly reactive with the anodic reactant.
13 As the battery is discharged, the mold fraction of elemental 14 sulfur drops until the open circuit voltage remains constant During this portion of the discharge cycle as the mold frac-16 tion of sulfur drops from 1.0 to approximately 0.72, the 17 cathodic reactant displays two phases, one being essentially 18 pure ~ulfur and the other ~eing sulfur saturated'with alkali 19 metal polysulfide in which the molar ratio of sulfur to alkali metal is about 5.2:2. When the battery is discharsed 21 to the'point where the ~old fraction of sulfur is about 0.72 22 the cathodic reaatant becomes one phase in nature since all 23 elemental sulfur has formed polysulfide salts. As the 24 battery is dlscharged further, the cathodic reactant remains one phase in nature and as the mold fraction of sulfur drops 26 so does the open circuit voltage corresponding to the change 27 in the potential determining reaction. Thus, the battery 28 continues to discharge from a point where polysulfide salts 2g containing sulfur and `alkali metal in a molar ratio of _ g _ .
l~q6Z~
1 approximately 5.2:2 to the point where polysulfide salts 2 contain sulfur and alkali metal in a ratio of about 3:2.
3 At this point the battery is fully discharged.
4 There has been disclosed herein a hermetically sealed alkali metal battery. In view of t~is specification, 6 those skilled in the art will be able to make variations of 7 the invention which fall within the true spirit and scope 8 of the invention. It is intended that all such modifica-g tions fall within the scope of ~he appended claims.
_ lQ -
12 A first outer metal casing 24 with an open end 26 13 and a closed end 28 surrounds the inner casing 18 and is 14 spaced therefrom.
A first metal ring 30 encircles and is welded b~
16 weldment 32 to the first outer ~etal casing 24. This first 17 metal ring 30 is formed of a metal such as and has a 18 raised annular ridge 34 encircling the open end 26 of the 19 ~ first outer metal casing 24 for a purpose described in detail herein below. The first metal ring also has at 21 least a pair of openings 36 ~only one sIlown) or receiving 22 bolts therethrough. In its assembled condition the firs~
23 metal ring is located adjacent the bottom surface 16 of the 24 ceramic ring 12.
A irst pair of thin metal washers 38 and 40 are 26 positioned ~etween the raised annular ridge 34 of the first 27 metal ring 30 and the bottom surace 16 of the ceramic ring 2a ~ 12. The washers have a thickn ss in the range of 0.003 to 29 0.005 inches. The washer 38 adjacent the first metal ring 30 may be formed of hardened polished steel and has a coeffi 31 cient of thermal expansion closely matching that o the ~7620~
l first metal ring. The metal washer 40 adjacent the ceramic e~9 ~
2 ring 12 may be formed from "Radar", a product name for a 3 cobalt, nickel, iron alloy which has a coefficient of ther-4 mal expansion closely matching that of the ceramic ring.
A second outer metal casing 42 has an open end 44 6 (shown only in FIGU~E ll. A second metal 48 encircles the 7 open end 44 of the second outer metal casing 42 and is 8 secured thereto by weldment 50 (shown in FIGURE 1 only).
9 This second metal ring is formed from the same material as the first metal ring and it also has a raised annular ridge ll 52 encircling the open end 44 of the second outer metal 12 casing 42. In its assem~led condition, the second metal 13 ring 48 is adjacent the top surface 14 of the ceramic 14 ring 12 whereby the second outer casing 42 is spaced from and extends in an opposite direction from the ceramic ring 16 than does the fixst outer casing 24.
17 A second pair of thin metal washers 38 and 40 are 18 positioned between the raised annular ridge 52 of the 19 second metal ring 48 and the top sur~ace 14 of the ceramic ring 12 for the same purposes as the washers were placed 21 between the raised annular ridge 34 o the first metal 22 ring 30 and the bottom surace 16 of the ceramic ring 12.
23 A Belleville spring 54 encircles the second outer 24 metal casing 42. This spring also engages an upper surface of the second metal ring 48.
26 A third metal ring 56 also encircles the second 27 outer metal casing 42. This third metal rîng engages an 28 upper surface of the Belleville spring 54. The third metal 29 ring also has at least a pair of spaced openings 58 (only one shown in the drawing) aligned with the openings 36 in 31 the first metal ring 30 for receiving bolts therethrough.
~ 7~ ~d~ ~nQ~ k 7 -.
~L~76201D
1 At least a pair of nut and bolt assemblies 60 2 (only one shown in each figure) are shown in their un-3 assembled condition in FIGURE 1 and in a securely tightened 4 position in FIGURE 2. In the securely tightened position, the nut and bolt assemblies draw toyether the annular ridges 6 34 and 52 to compress the irst and second pair of thin 7 metal washers 38 and 40 tightly into engagement with one 8 another and with the bottom surface 16 and the top surface 9 14 of the ceramic xing 12 to provide a hermetic seal for the alkali metal battery 10. Pressure is placed on this assembly 11 through the action of the selleville spring 5~ when the nut 12 and bolt assemblies are tightened down.
13 ~y uti.lizing the two pairs of metal washers 38 14 and 40, the mismatch in coefficient of thermal expansion between the ceramic ring 12 and the first metal ring 30 16 and second metal ring 48 are compensated for. The first 17 and second washers 38 and 40 may at their interface slide 18 back and forth su~ficiently to adjust for the differences g in coeicient of thermal expansion. Thus, the hermetic 2b seal of the battery remains even though the battery is 21 cycled through temperature variations from room temperature 22 to operational temperatuxes, 23 With reference to FIGURE ~, a irst reaction zone 24 6Z is formed by t~e interior of the second outer metal cas ing 42 and the interior of the inner casing 18. ~his reac-26 tion zone may contain an anodic reactant. The anodic reac-27 tant is heated by any conventional source and may be vlewed : : 28 as the anode proper or conductor through which electron fIow ~29 to an external circuit (not shown) is achieved. Molten :~ :
~: - 8 -.
~L076Z~)~
l sodium is employed as the anodic reactant in most preferred 2 embodiments of such alkali metal batteries. However, 3 potassiumt lithium, other alkali metals, mixtures of such 4 alkali metals or alloys containing such alkali metals can be used.
6 A second reaction zone 64 (shown only in FIGUR~
7 2~ is formed in the volume between the interior surface of 8 the first outer metal'casing 24 and the exterior surface 9 of the inner casing 18~ T~is reactant zone can contain the cathodic reactant. The cathodic reactant of the fully 11 charged battery is molten sulfur, which is electrode 12 chemically reversibly reactive with the anodic reactant.
13 As the battery is discharged, the mold fraction of elemental 14 sulfur drops until the open circuit voltage remains constant During this portion of the discharge cycle as the mold frac-16 tion of sulfur drops from 1.0 to approximately 0.72, the 17 cathodic reactant displays two phases, one being essentially 18 pure ~ulfur and the other ~eing sulfur saturated'with alkali 19 metal polysulfide in which the molar ratio of sulfur to alkali metal is about 5.2:2. When the battery is discharsed 21 to the'point where the ~old fraction of sulfur is about 0.72 22 the cathodic reaatant becomes one phase in nature since all 23 elemental sulfur has formed polysulfide salts. As the 24 battery is dlscharged further, the cathodic reactant remains one phase in nature and as the mold fraction of sulfur drops 26 so does the open circuit voltage corresponding to the change 27 in the potential determining reaction. Thus, the battery 28 continues to discharge from a point where polysulfide salts 2g containing sulfur and `alkali metal in a molar ratio of _ g _ .
l~q6Z~
1 approximately 5.2:2 to the point where polysulfide salts 2 contain sulfur and alkali metal in a ratio of about 3:2.
3 At this point the battery is fully discharged.
4 There has been disclosed herein a hermetically sealed alkali metal battery. In view of t~is specification, 6 those skilled in the art will be able to make variations of 7 the invention which fall within the true spirit and scope 8 of the invention. It is intended that all such modifica-g tions fall within the scope of ~he appended claims.
_ lQ -
Claims
The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
A hermetically sealed alkali metal battery container comprising:
a ceramic ring having top and bottom surfaces;
an inner casing of a solid alkali ion-conductive material with one open end;
a glass seal sealing said inner casing adjacent its open end to said ceramic ring so that said inner casing extends downwardly from the bottom surface of said ceramic ring;
a first outer casing with an open end and a closed end, said outer casing surrounding said inner casing and spaced therefrom;
a first ring encircling and bonded to said open end of said first outer casing, said ring (a) having a raised annular ridge encircling said open end of said first outer casing, (b) having at least a pair of openings for receiving bolts therethrough, and (c) being adjacent said bottom surface of said ceramic ring;
a first pair of thin washers positioned between said raised annular ridge of said first ring and said bottom surface of said ceramic ring, said washer adjacent said first ring having a coefficient of thermal expansion closely matching that of said first ring and said washer adjacent said ceramic ring having a coefficient of thermal expansion closely matching that of said ceramic ring;
- 1 - (Cont'd.) a second outer casing with an open end and a closed end;
a second ring encircling and bonded to said open end of said second outer casing, said second ring (a) having a raised annular ridge encir-cling said open end of said second outer casing, and (b) being adjacent said top surface of said ceramic ring, whereby said second outer casing is spaced from and extends in an opposite direction to said first outer casing;
a second pair of thin washers positioned between said raised annular ridge of said second ring and said top surface of said ceramic ring, said washer adjacent said second ring having a coefficient of thermal expansion closely matching that of said second ring and said washer adjacent said ceramic ring having a coefficient of thermal expansion closely matching that of said ceramic ring;
a Belleville spring encircling said second outer casing and engaging an upper surface of said second ring;
a third ring encircling said second outer casing: and both (a) engaging an upper edge of said Belleville spring, and (b) having at least a pair of spaced openings aligned with said openings of said first ring for receiving bolts therethrough; and at least a pair of nut and bolt assem-blies extending through said openings in said first and said third rings and securely tightened together - 1 - (Cont'd.) to draw said annular ridges on said first and said second rings tightly into engagement with said first and said second pair of washers to provide a hermeti-cally sealed alkali metal battery container.
A hermetically sealed alkali metal battery container comprising:
a ceramic ring having top and bottom surfaces;
an inner casing of a solid alkali ion-conductive material with one open end;
a glass seal sealing a portion of an outer wall of said inner casing adjacent its open end within and to an interior surface of said ceramic ring so that said inner casing extends downwardly from the bottom surface of said ceramic ring;
a first outer metal casing with an open end and a closed end, said outer metal casing surround-ing said inner casing and spaced therefrom;
a first metal ring encircling and welded to said open end of said first outer metal casing, said metal ring (a) having a raised annular ridge encircling said open end of said first outer metal casing, (b) having at least a pair of openings for receiving bolts therethrough, and (c) being adja-cent said bottom surface of said ceramic ring;
- 2 - (Cont'd.) a first pair of thin metal washers positioned between said raised annular ridge of said first metal ring and said bottom surface of said ceramic ring, said washer adjacent said first metal ring having a coefficient of thermal expansion closely matching that of said first metal ring and said washer adjacent said ceramic ring having a coefficient of thermal expansion closely matching that of said ceramic ring;
a second outer metal casing with an open end and a closed end;
a second metal ring encircling and welded to said open end of said second outer metal casing, said second metal ring (a) having a raised annular ridge encircling said open end of said second outer metal casing, and (b) being adjacent said top surface of said ceramic ring, whereby said second outer casing is spaced from and extends in an opposite direction to said first outer casing;
a second pair of thin metal washers positioned between said raised annular ridge of said second metal ring and said top surface of said ceramic ring, said washer adjacent said second metal ring hav-ing a coefficient of thermal expansion closely match-ing that of said second metal ring and said washer adjacent said ceramic ring having a coefficient of thermal expansion closely matching that of said ceramic ring;
a Belleville spring encircling said second outer metal casing and engaging an upper sur-face of said second metal ring;
- 2 - (Cont'd.) a third metal ring encircling said second outer metal casing and both (a) engaging an upper edge of said Belleville spring, and (b) having at least a pair of spaced openings aligned with said openings of said first metal ring for receiving bolts therethrough; and at least a pair of nut and bolt assem-blies extending through said openings in said first and said third metal rings and securely tightened together to draw said annular ridges on said first and said second metal rings tightly into engagement with said first and said second pair of metal washers to provide a hermetically sealed alkali metal battery container.
The container of Claim 2 wherein each of said washers have a thickness in the range from 0.003 to 0.005 inches.
The container of Claim 3 wherein said washer adjacent said metal rings are formed of hardened and polished steel and said washers adja-cent said ceramic ring are formed of a nickel, cobalt, iron alloy.
A hermetically sealed alkali metal battery container comprising:
a ceramic ring having top and bottom surfaces;
an inner casing of a solid alkali ion-conductive material with one open end;
a glass seal sealing said inner casing adjacent its open end to said ceramic ring so that said inner casing extends downwardly from the bottom surface of said ceramic ring;
a first outer casing with an open end and a closed end, said outer casing surrounding said inner casing and spaced therefrom;
a first ring encircling and bonded to said open end of said first outer casing, said ring (a) having a raised annular ridge encircling said open end of said first outer casing, (b) having at least a pair of openings for receiving bolts therethrough, and (c) being adjacent said bottom surface of said ceramic ring;
a first pair of thin washers positioned between said raised annular ridge of said first ring and said bottom surface of said ceramic ring, said washer adjacent said first ring having a coefficient of thermal expansion closely matching that of said first ring and said washer adjacent said ceramic ring having a coefficient of thermal expansion closely matching that of said ceramic ring;
- 1 - (Cont'd.) a second outer casing with an open end and a closed end;
a second ring encircling and bonded to said open end of said second outer casing, said second ring (a) having a raised annular ridge encir-cling said open end of said second outer casing, and (b) being adjacent said top surface of said ceramic ring, whereby said second outer casing is spaced from and extends in an opposite direction to said first outer casing;
a second pair of thin washers positioned between said raised annular ridge of said second ring and said top surface of said ceramic ring, said washer adjacent said second ring having a coefficient of thermal expansion closely matching that of said second ring and said washer adjacent said ceramic ring having a coefficient of thermal expansion closely matching that of said ceramic ring;
a Belleville spring encircling said second outer casing and engaging an upper surface of said second ring;
a third ring encircling said second outer casing: and both (a) engaging an upper edge of said Belleville spring, and (b) having at least a pair of spaced openings aligned with said openings of said first ring for receiving bolts therethrough; and at least a pair of nut and bolt assem-blies extending through said openings in said first and said third rings and securely tightened together - 1 - (Cont'd.) to draw said annular ridges on said first and said second rings tightly into engagement with said first and said second pair of washers to provide a hermeti-cally sealed alkali metal battery container.
A hermetically sealed alkali metal battery container comprising:
a ceramic ring having top and bottom surfaces;
an inner casing of a solid alkali ion-conductive material with one open end;
a glass seal sealing a portion of an outer wall of said inner casing adjacent its open end within and to an interior surface of said ceramic ring so that said inner casing extends downwardly from the bottom surface of said ceramic ring;
a first outer metal casing with an open end and a closed end, said outer metal casing surround-ing said inner casing and spaced therefrom;
a first metal ring encircling and welded to said open end of said first outer metal casing, said metal ring (a) having a raised annular ridge encircling said open end of said first outer metal casing, (b) having at least a pair of openings for receiving bolts therethrough, and (c) being adja-cent said bottom surface of said ceramic ring;
- 2 - (Cont'd.) a first pair of thin metal washers positioned between said raised annular ridge of said first metal ring and said bottom surface of said ceramic ring, said washer adjacent said first metal ring having a coefficient of thermal expansion closely matching that of said first metal ring and said washer adjacent said ceramic ring having a coefficient of thermal expansion closely matching that of said ceramic ring;
a second outer metal casing with an open end and a closed end;
a second metal ring encircling and welded to said open end of said second outer metal casing, said second metal ring (a) having a raised annular ridge encircling said open end of said second outer metal casing, and (b) being adjacent said top surface of said ceramic ring, whereby said second outer casing is spaced from and extends in an opposite direction to said first outer casing;
a second pair of thin metal washers positioned between said raised annular ridge of said second metal ring and said top surface of said ceramic ring, said washer adjacent said second metal ring hav-ing a coefficient of thermal expansion closely match-ing that of said second metal ring and said washer adjacent said ceramic ring having a coefficient of thermal expansion closely matching that of said ceramic ring;
a Belleville spring encircling said second outer metal casing and engaging an upper sur-face of said second metal ring;
- 2 - (Cont'd.) a third metal ring encircling said second outer metal casing and both (a) engaging an upper edge of said Belleville spring, and (b) having at least a pair of spaced openings aligned with said openings of said first metal ring for receiving bolts therethrough; and at least a pair of nut and bolt assem-blies extending through said openings in said first and said third metal rings and securely tightened together to draw said annular ridges on said first and said second metal rings tightly into engagement with said first and said second pair of metal washers to provide a hermetically sealed alkali metal battery container.
The container of Claim 2 wherein each of said washers have a thickness in the range from 0.003 to 0.005 inches.
The container of Claim 3 wherein said washer adjacent said metal rings are formed of hardened and polished steel and said washers adja-cent said ceramic ring are formed of a nickel, cobalt, iron alloy.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/719,881 US4049889A (en) | 1976-09-01 | 1976-09-01 | Hermetically sealed alkali metal battery container |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1076200A true CA1076200A (en) | 1980-04-22 |
Family
ID=24891754
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA281,047A Expired CA1076200A (en) | 1976-09-01 | 1977-06-21 | Hermetically sealed alkali metal battery |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4049889A (en) |
| JP (1) | JPS5330740A (en) |
| CA (1) | CA1076200A (en) |
| DE (1) | DE2730981C2 (en) |
| FR (1) | FR2363909A1 (en) |
| GB (1) | GB1583784A (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4124744A (en) * | 1977-11-17 | 1978-11-07 | General Electric Company | Composite solid electrolyte body |
| US4169919A (en) * | 1978-10-26 | 1979-10-02 | Ford Motor Company | Double seal for sodium sulfur battery |
| US4197363A (en) * | 1978-10-26 | 1980-04-08 | Ford Motor Company | Seal for sodium sulfur battery |
| US4192911A (en) * | 1978-11-01 | 1980-03-11 | Ford Motor Company | Sodium sulfur battery seal |
| US4170694A (en) * | 1978-12-04 | 1979-10-09 | Ford Aerospace & Communications Corp. | Hermetically sealed alkali metal battery container |
| 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 |
| DE3033130A1 (en) * | 1980-09-03 | 1982-04-01 | Brown, Boveri & Cie Ag, 6800 Mannheim | ELECTROCHEMICAL STORAGE CELL |
| US4377256A (en) * | 1981-06-22 | 1983-03-22 | Gusmer Corporation | Apparatus for dispensing a mixture of mutually reactive liquids |
| US4469251A (en) * | 1981-09-02 | 1984-09-04 | Sealed Air Corporation | Detachable mixing chamber for a fluid dispensing apparatus |
| DE3446779A1 (en) * | 1984-12-21 | 1986-07-03 | Brown, Boveri & Cie Ag, 6800 Mannheim | ELECTROCHEMICAL STORAGE CELL |
| JPH0793150B2 (en) * | 1986-08-29 | 1995-10-09 | 株式会社日立製作所 | Sodium-sulfur battery |
| US5529858A (en) * | 1994-10-24 | 1996-06-25 | Saft America, Inc. | Hermetically sealed thermocompression feedthrough and peripheral seal for high temperature lithium based battery applications |
| US5707758A (en) * | 1995-09-27 | 1998-01-13 | Nissan Motor Co., Ltd. | Secondary battery |
| US5578394A (en) * | 1996-02-15 | 1996-11-26 | Saft America, Inc. | Seal assembly for high temperature bipolar Li alloy metal sulfide battery |
| JP2961100B2 (en) * | 1997-09-16 | 1999-10-12 | 三菱重工業株式会社 | Sodium secondary battery |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3475220A (en) * | 1967-06-22 | 1969-10-28 | Ford Motor Co | Secondary battery |
| FR2119117A5 (en) * | 1970-12-21 | 1972-08-04 | Comp Generale Electricite | |
| US3826685A (en) * | 1972-03-31 | 1974-07-30 | Gen Electric | Sealed primary sodium-halogen 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
- 1976-09-01 US US05/719,881 patent/US4049889A/en not_active Expired - Lifetime
-
1977
- 1977-06-21 CA CA281,047A patent/CA1076200A/en not_active Expired
- 1977-07-08 DE DE2730981A patent/DE2730981C2/en not_active Expired
- 1977-08-09 GB GB33351/77A patent/GB1583784A/en not_active Expired
- 1977-08-24 FR FR7725792A patent/FR2363909A1/en active Granted
- 1977-08-30 JP JP10329177A patent/JPS5330740A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| US4049889A (en) | 1977-09-20 |
| DE2730981A1 (en) | 1978-03-02 |
| JPS5330740A (en) | 1978-03-23 |
| DE2730981C2 (en) | 1982-03-25 |
| GB1583784A (en) | 1981-02-04 |
| FR2363909B1 (en) | 1980-10-17 |
| FR2363909A1 (en) | 1978-03-31 |
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| MKEX | Expiry |