CA1040703A - Sodium-mixture of metal halides, sulfur battery - Google Patents
Sodium-mixture of metal halides, sulfur batteryInfo
- Publication number
- CA1040703A CA1040703A CA249,143A CA249143A CA1040703A CA 1040703 A CA1040703 A CA 1040703A CA 249143 A CA249143 A CA 249143A CA 1040703 A CA1040703 A CA 1040703A
- Authority
- CA
- Canada
- Prior art keywords
- halide
- positive
- sodium
- aluminum
- reactant
- 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
- 239000011593 sulfur Substances 0.000 title claims abstract description 32
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 32
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000000203 mixture Substances 0.000 title claims abstract description 20
- 229910001507 metal halide Inorganic materials 0.000 title claims abstract description 12
- 150000005309 metal halides Chemical class 0.000 title claims abstract description 12
- 239000000376 reactant Substances 0.000 claims abstract description 51
- 239000011734 sodium Substances 0.000 claims abstract description 29
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 29
- 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 claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003792 electrolyte Substances 0.000 claims abstract description 12
- -1 sodium cations Chemical class 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- 150000004820 halides Chemical class 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- 229910052787 antimony Inorganic materials 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 claims description 5
- 150000001649 bromium compounds Chemical class 0.000 claims description 5
- 150000001805 chlorine compounds Chemical class 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- 229910052714 tellurium Inorganic materials 0.000 claims description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000000155 melt Substances 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000011521 glass Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- 235000002639 sodium chloride Nutrition 0.000 description 5
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000005297 pyrex Substances 0.000 description 4
- RBWSWDPRDBEWCR-RKJRWTFHSA-N sodium;(2r)-2-[(2r)-3,4-dihydroxy-5-oxo-2h-furan-2-yl]-2-hydroxyethanolate Chemical compound [Na+].[O-]C[C@@H](O)[C@H]1OC(=O)C(O)=C1O RBWSWDPRDBEWCR-RKJRWTFHSA-N 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910000792 Monel Inorganic materials 0.000 description 2
- 229910020275 Na2Sx Inorganic materials 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000004945 silicone rubber Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- XXBNLUKLCXTTPH-LECHCGJUSA-N (2S,3R,4S,5R)-2,3,4,5,6-pentahydroxyhexanoyl chloride Chemical compound ClC(=O)[C@@H](O)[C@H](O)[C@@H](O)[C@H](O)CO XXBNLUKLCXTTPH-LECHCGJUSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 241000689227 Cora <basidiomycete fungus> Species 0.000 description 1
- 208000032139 Halitosis Diseases 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 241001296096 Probles Species 0.000 description 1
- 101100176490 Rhizobium sp. (strain MTP-10005) graD gene Proteins 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- COOGPNLGKIHLSK-UHFFFAOYSA-N aluminium sulfide Chemical compound [Al+3].[Al+3].[S-2].[S-2].[S-2] COOGPNLGKIHLSK-UHFFFAOYSA-N 0.000 description 1
- BBNUKMKBNHKOES-UHFFFAOYSA-K antimony(3+) trichlorite Chemical compound [Sb+3].[O-][Cl]=O.[O-][Cl]=O.[O-][Cl]=O BBNUKMKBNHKOES-UHFFFAOYSA-K 0.000 description 1
- RPJGYLSSECYURW-UHFFFAOYSA-K antimony(3+);tribromide Chemical compound Br[Sb](Br)Br RPJGYLSSECYURW-UHFFFAOYSA-K 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229940000425 combination drug Drugs 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- QYQIKTBQNRWCEW-UHFFFAOYSA-K dichlorosyloxyalumanyl chlorite Chemical compound [Al+3].[O-]Cl=O.[O-]Cl=O.[O-]Cl=O QYQIKTBQNRWCEW-UHFFFAOYSA-K 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000010442 halite Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 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)
Abstract
ABSTRACT OF THE DISCLOSURE
A secondary battery utilizing a molten sodium negative reactant, a mixture of metal halides, sulfur positive reactant melt having a carbon powder dispersed within the melt, a molten sodium haloaluminate electrolyte, and a selectively ionically-conductive separator positioned between the negative and positive reactants.
A secondary battery utilizing a molten sodium negative reactant, a mixture of metal halides, sulfur positive reactant melt having a carbon powder dispersed within the melt, a molten sodium haloaluminate electrolyte, and a selectively ionically-conductive separator positioned between the negative and positive reactants.
Description
This invention relates to secondary electrochemical cells and more particularly to secondary electrochenical cells utilizing a molten sodium negative reactant, a solid ionically-contuctive separator, a molten sulfur and mixture of molten metal or metal-like halides positive reactant, and a molten sodium haloaluminate electrolyte.
It may be explained here that Unitet States Patent No. 3,404,035 discloses a secondary battery that in its fully charged condition has a olten sodium negative reactant, a molten sulfur positive roactant and a solid eloctrolyte-separator of beta alumina or its terivative disposed between tho positive and negative reactants. In its discharged or partially discharged condition, it has an additional electrolyte comprising a sodium polysulfido tNa2Sx) on tho positive roactant sido of the bcta alumina soparator.
The potontial of this battory is typically in tho rango of fro about 2 to 2.2 volts and tho oporating tomporaturo of this battory is in tho rango of 265 to 350 C. in ortor to koop tho tischargo products, Na2Sx, "~olton at all tis. It is rocognized by those skillod in the art, howover, that oporation of this type battory at about or abovo 265C. cannot be carriod out without attondant problems. For exa ple, Na2Sx is a strong oxidizing agent at thoso olevated temperatures ant will tend to effect rapid corrosion and - 20 chomic-l attack of containers, current collectors, seals and soparators of tho battory, thus soriously roducing the usoful lifo of tho battory.
In Unitod Statos Patent No. 3,877,984, there is toscribet a battory which utilizos a otal chloride positive reactant, e.g. antimony chloride, in contact with a molten alkali metal chloroalu inate electrolyto, e.g. sotiu~
chloroaluminato. Tho nogative reactant of this battory is an alkali metal, o.g. sodium, is positioned between the positive and negative reactants. This battery can operate at a temperature as low as from about 150&. to about 225 C. and greatly reduce the corrosion proble s since sotium chloroaluminate at te peratures of from about 150C. to about 225C. is not a strong oxidizing agent. Additionally, the voltago potential of this battery approaches or . ~
~040703 exceeds 3 volts. se~,^al ~ C/,/~ 2 In our Canadian patent application/filed on evon date herewith a~
entitled "Sodium-Aluminum Halide, Sulfur Battery~', there is disclosed a novel secondary battery which utilizes a molten sotium negative reactant, and a molten sulfur ant molten aluminum halide, e.g. aluminum chloride, positive reactant in contact with a molten sotium haloaluminate (molten sodium halide-aluoinum halide) e.g. molten sodium chloroaluminste electrolyte. This battery can operato at a temperature as low as fro~ about 150C. to about 225C. and thus also groatly reducos the corrosion and chemical attack problems associated with sodiu~-sulfur batteries of the type described above with referonce to U. S. Patent 3,404,035. The potential of the battery described in this co-pending application approaches or exceeds 2.66 volts.
Ono of the di$foroncos botwoon the battery described in U. S. Patent No. 3,877,984 and tho coponding application just doscribod is that the major dischargo products of tho battory of U.S. Patent 3,877,984 aro antimony motal ant sotium chloride, whilo in tho battory of tho coponding application doscribot abo~o, tho ajor dischargo products aro, for oxa plo, sodium chloride and alu inum sulfite. Tho anti~ony motal and sodiu~ chloride dischargo products have no deloterious effect on the bota alumina separator or other co~pononts o the coll. In early colls constructed in accortance with the toaching of sait coponting application thero appeared to be a continual dogradation of tho battory with cycling. I spoculatod that tho aluminum sulfido, for od on dischargo, attacked tho bota alumina separator and/or cur-ront colloctors of tho cell, or at least for ed a rosistive phase around them.
;~ Working on the assu ption that one of the reaction products of the battery of the copending application tescribed above, namely aluninum sulfide, was attacking the beta aluoina, or at least forming a solid rosistive layer at its surface, I hypothesized that perhaps by adding a motal, such as for oxa plo antimony, to tho positivo reactant melt of this battery, then the ajor discharge protuct would be antimony sulfido or a mixed antimony ~040~03 aluminum salt rather than aluminum sulfide, and thus it would be possible to cycle the cell with no degradation. I subsequently discovered that my assump-tion was incorrect, the cell of said copending application, in fact, was not degrading in the manner speculated but, I had discovered a novel and, in some respects, a superior cell.
Cells were constructed according to the teaching of the copending application described above, and antimony was added to the positive reactant in chloride form (Sb C13) in the ratio of 5 parts Sb C13 to 2 parts of sulfur.
This battery can operate at a temperature as low as from about 150C. to about 225C. The potential of this novel battery ranges between approximately 2.5 and 3.5 volts.
This invention is directed to a secondary battery comprising in com-bination: (a) a molten sodium negative reactant; (b) a positive reactant com-prising molten sulfur and a mixture of halides, said mixture of halides select-ed from the group consisting of halides of metals at least as noble as aluminum, halides of metal-like elements and mixtures thereof; (c) a solid member separ-ating the negative and pos-itive reactants, said member being selectively ioni-cally conductive to sodium cations; (d) a molten sodium halide-aluminum halide electrolyte on the positive reactant side of the solid member; (e) a carbon powder dispersed within the molten sulfur and mixture of metal halides; and - (f) a current collector disposed in each the positive and negative reactants.
Embodiments of the invention will be described, by way of example, with reference to the accompanying drawings, in which:
Figure 1 is a schematic, cross-sectional view of a simple cell; and Figures 2 and 3 are graphic representations of the charge-discharge cycles of cells.
In the operation of the secondary or rechargeable battery of this invention, a high potential is achieved by utilizing a molten sodium negative - reactant and a molten sulfur and molten metal halides positive reactant melt having a carbon powder dispersed therein, separating the two reactants by means of a solid member which is selectively-ionically conductive to sodium B
cations and maintaining on the positive reactant side of the solid separating member a molten electrolyte comprising molten sodium haloaluminate.
In accordance with this invention, the negative reactant or relUctant is sodium maintained above its melting point when the cell is in operation. The negative reactant is initially heated by any conventional means such as induction heating by electrical means, direct heating, or indirect heat exchange with a suitable heated fluid oxchange means. The negative react-ant functions as a conductor through which electrons flow to the external circuit during discharge.
The positive reactant of the present invention comprises molten sulfur and a molten mixture of metal halides. The specific metal halides selectet for use will be determined by such factors as the end use to which the battery is to be put; the economics involved, e.g, the cost of starting materials; the desiret operating pressuro of the cell; ant the specific sotium haloaluminate electrolyte selectet for use in the battery. ~ne criterion ust however be satisfiet by the metal halites selectet. They ust be soluble to some extent in the sotium haloaluminate electrolyte of the battery.
So long as this criterion is satisfiet, the selection of the specific motal halides to be utilized becomes a practical question rather than a critical one, i.e. depenting on economics, ent use and the like. Use-ful materials from which the positive reactant etal halides can be formed inclute metals at least as noble as aluminum ant metal-like eleaents. By metal-like elements, it is meant elements Such as boron, silicon, selenium, arsenic, tellurium, ant antimony which are also known as metalloits and which are intermediate in properties between typical etals and non-metals. The preferret metal halides for use in combination with sulfur in the positive reactant melt are aluminum chlorite ant antimony chlorite.
The solit member which separates the negative reactant and the positive reactant in the instant invention must be solectively-ionically-~045~703 conductive to sodium cations. Materials suitable for use as the solid separ-ator inclute glass, beta aluminas and other cation conductive crystalline and/or glassy materials that are resistant to the negative reactant and have satisfactorily low resistivities. The prefe D d separator comprisos a beta alumina cationically-conductive crystalline structure consisting essentially of a structural lattice and sodium cati s which are mobile in rolation to said lattice. The solid separator member may be prepared by any art known means, see for oxamplo, U.S. 3,535,163, so long as the useful end product is solectivoly ionically-conductive to sotium cations.
The oloctrolyte utilizod in the present in~ention makes possible a substantial reduction in the operating temperature of molten sulfur batteries as co parod with those presently known and uset in the art. For examplo, tho operating tomporaturo of the nor~al molten sodium-molten sulfur secontary battory whoroin tho olten cathodic electrolyto is an ionizet combination of sotium ~nd sulfur, i.o. ions of sodium polysulfido, Na2S5, the operating tomporaturo is rocognizod to be woll about 200&. and closor to 300 &., the lting tomporature of sodiu~ pentasulfito boing as high as 265 &. In markot contrast, tho battory of the prosent invention utilizod an oloctrolyte on the positive reactant site of the solid separating mo ber which comprisos molton sotium haloalu inate ant por its the oporation of the instant battery to be carriot out at te~poraturos of about 150&. to about 225&. The advantages of oporating t a retucet to perature are of course apparont, e.g. retucet corrosion, increased battery life, and reduced cost of containers ant seals, e.g. silicone rubber may be used as a negative gaskot seal.
By tho ter~ molten sotium hsloaluminste ss uset herein is meant matorisls which include sodium hslites, as for exa~ple, chloridos, bromides, fluorides, or iodides of sotium, ant sluminum hslides, for exs~ple chlorides, bromides, fluorides or iotides of aluminum. All of theso metal halidos will form the corresponting sotium haloaluminate olectrolytes of the invention.
Tho preforred electrolyte is sodium chloroaluminate.
1040'703 In the battery of the present invention, the positive reactant (sulfur and a mixture of metal halides) is mixed with the metal haloaluminate by any means in the art, o.g. it is possible to mix sulfur, sodium chloride, aluminum chloride and antimony chloride together with the positive reactant and heat the resultant mix until sodium chloroaluminate and the positive react-ant aro formed within the cell. It should be noted that while the battery of this invention is a sotium-mixed metal halites sulfur battery, the metal halite reactants which are present in the cell, i.e. present in the sotium haloalu inate^positive roactant melt within this cell, may be atded initially as tho motals themselves, picking up halide ions from the ionized sodium haloaluminate upon charging. Therefore, even though metals were attet init-ially, tho positive reactant of tho cell will comprise sulfur ant a mixturo of otal halitos in tho charged state.
Roforring now to Figure 1, a single coll socondary battory accorting ; to tho invontion is diagrammatically shown having a nogativo roactant coll compartmont 10 which aro not attackot by lton sotium motal at tho oporating tomporaturo of tho coll (about 150 & to 225 & .), o.g. carbon stool, alu inum, certain cora ics, cortain hoat ant chemical resistant polymers, a suitable glass or an alpha alumina or derivativo thoroof, all thermally insulated with ; 20 fiberglass, rockwool, or other insulation. Insido compartment 10 is a molten sotiu~ nogativo roactant 12. Insido a positivo reactant compartment 13 is an oloctrolyte-sulfur mixturo of metal halidos positivc reactant molt 14, o.g.
sodiu chloroalu inato-sulfur, aluminum chloride and antimonr chloride melt.
A carbon powder is in the melt 14 and sorvos thc purpose of a dis-porsod current colloctor.
The positivo reactant compartment 13 ay be made of any suitable material such as glass, ceramic, tungsten and tho like. Current collectors 18 ant 20 are disposod within the negativo ant positive reactant compartmonts 10 and 13, respoctively, and may be made of any suitable material such as for example, tungsten wire, carbon rods and the like. A solit separating member 22 is disposed between the compartments 10 and 13. The requirements of the separating member 22 have been described above. The current collectors 18 and 20 provide means for connecting the cell with an external circuit 24 which closed the circuit of the cell. The external circuit 24 may include any suitable utilization device or load, voltmeter, ammeter, etc. which have not been shown other than as indicated in Figure 1.
A better understanding of the battery in accordance with the in-vention can be obtained from the following Examples which are intended to be merely illustrative of the invention and not in limitation thereof.
EXAMPLES
The following information applies to all cells tested in the Examples unless otherwise indicated. Also, unless otherwise indicated, all quantities are by weight.
1. Makeup of Cells: The cells comprised a Pyrex* glass positive container, a carbon steel negative container and a beta alumina separator tisc. The negative seal was silicone rubber, and the positive seal was .. ~
Teflon. The negative current collector was the steel sodium container. The positive current collector varied as to type and configuration, as described in the examples, but in all cases it was sealed to the Pyrex glass with a - 20 Monel* Gyralok* fitting containing Teflon* ferrules. In all cases the car-bon was Cabot Vulcon* XC-72R. This carbon has a relatively low surface area of approximately 200 square meters/gram.
Example 1 - Cell Assembly: A tungsten coil current collector was sealed to a 1/4" glass tube then inserted into the positive Pyrex glass con-tainer. The cell was then assembled and sealed to the beta-alumina separator.
The following positive ingredients were then added in powder form after which the Pyrex container was sealed with a Monel Swagelok-0.5 grams of sulfur 0.5 grams of XC-72R conductive carbon 0.5 grams of Na Cl * trademarks ~040703
It may be explained here that Unitet States Patent No. 3,404,035 discloses a secondary battery that in its fully charged condition has a olten sodium negative reactant, a molten sulfur positive roactant and a solid eloctrolyte-separator of beta alumina or its terivative disposed between tho positive and negative reactants. In its discharged or partially discharged condition, it has an additional electrolyte comprising a sodium polysulfido tNa2Sx) on tho positive roactant sido of the bcta alumina soparator.
The potontial of this battory is typically in tho rango of fro about 2 to 2.2 volts and tho oporating tomporaturo of this battory is in tho rango of 265 to 350 C. in ortor to koop tho tischargo products, Na2Sx, "~olton at all tis. It is rocognized by those skillod in the art, howover, that oporation of this type battory at about or abovo 265C. cannot be carriod out without attondant problems. For exa ple, Na2Sx is a strong oxidizing agent at thoso olevated temperatures ant will tend to effect rapid corrosion and - 20 chomic-l attack of containers, current collectors, seals and soparators of tho battory, thus soriously roducing the usoful lifo of tho battory.
In Unitod Statos Patent No. 3,877,984, there is toscribet a battory which utilizos a otal chloride positive reactant, e.g. antimony chloride, in contact with a molten alkali metal chloroalu inate electrolyto, e.g. sotiu~
chloroaluminato. Tho nogative reactant of this battory is an alkali metal, o.g. sodium, is positioned between the positive and negative reactants. This battery can operate at a temperature as low as from about 150&. to about 225 C. and greatly reduce the corrosion proble s since sotium chloroaluminate at te peratures of from about 150C. to about 225C. is not a strong oxidizing agent. Additionally, the voltago potential of this battery approaches or . ~
~040703 exceeds 3 volts. se~,^al ~ C/,/~ 2 In our Canadian patent application/filed on evon date herewith a~
entitled "Sodium-Aluminum Halide, Sulfur Battery~', there is disclosed a novel secondary battery which utilizes a molten sotium negative reactant, and a molten sulfur ant molten aluminum halide, e.g. aluminum chloride, positive reactant in contact with a molten sotium haloaluminate (molten sodium halide-aluoinum halide) e.g. molten sodium chloroaluminste electrolyte. This battery can operato at a temperature as low as fro~ about 150C. to about 225C. and thus also groatly reducos the corrosion and chemical attack problems associated with sodiu~-sulfur batteries of the type described above with referonce to U. S. Patent 3,404,035. The potential of the battery described in this co-pending application approaches or exceeds 2.66 volts.
Ono of the di$foroncos botwoon the battery described in U. S. Patent No. 3,877,984 and tho coponding application just doscribod is that the major dischargo products of tho battory of U.S. Patent 3,877,984 aro antimony motal ant sotium chloride, whilo in tho battory of tho coponding application doscribot abo~o, tho ajor dischargo products aro, for oxa plo, sodium chloride and alu inum sulfite. Tho anti~ony motal and sodiu~ chloride dischargo products have no deloterious effect on the bota alumina separator or other co~pononts o the coll. In early colls constructed in accortance with the toaching of sait coponting application thero appeared to be a continual dogradation of tho battory with cycling. I spoculatod that tho aluminum sulfido, for od on dischargo, attacked tho bota alumina separator and/or cur-ront colloctors of tho cell, or at least for ed a rosistive phase around them.
;~ Working on the assu ption that one of the reaction products of the battery of the copending application tescribed above, namely aluninum sulfide, was attacking the beta aluoina, or at least forming a solid rosistive layer at its surface, I hypothesized that perhaps by adding a motal, such as for oxa plo antimony, to tho positivo reactant melt of this battery, then the ajor discharge protuct would be antimony sulfido or a mixed antimony ~040~03 aluminum salt rather than aluminum sulfide, and thus it would be possible to cycle the cell with no degradation. I subsequently discovered that my assump-tion was incorrect, the cell of said copending application, in fact, was not degrading in the manner speculated but, I had discovered a novel and, in some respects, a superior cell.
Cells were constructed according to the teaching of the copending application described above, and antimony was added to the positive reactant in chloride form (Sb C13) in the ratio of 5 parts Sb C13 to 2 parts of sulfur.
This battery can operate at a temperature as low as from about 150C. to about 225C. The potential of this novel battery ranges between approximately 2.5 and 3.5 volts.
This invention is directed to a secondary battery comprising in com-bination: (a) a molten sodium negative reactant; (b) a positive reactant com-prising molten sulfur and a mixture of halides, said mixture of halides select-ed from the group consisting of halides of metals at least as noble as aluminum, halides of metal-like elements and mixtures thereof; (c) a solid member separ-ating the negative and pos-itive reactants, said member being selectively ioni-cally conductive to sodium cations; (d) a molten sodium halide-aluminum halide electrolyte on the positive reactant side of the solid member; (e) a carbon powder dispersed within the molten sulfur and mixture of metal halides; and - (f) a current collector disposed in each the positive and negative reactants.
Embodiments of the invention will be described, by way of example, with reference to the accompanying drawings, in which:
Figure 1 is a schematic, cross-sectional view of a simple cell; and Figures 2 and 3 are graphic representations of the charge-discharge cycles of cells.
In the operation of the secondary or rechargeable battery of this invention, a high potential is achieved by utilizing a molten sodium negative - reactant and a molten sulfur and molten metal halides positive reactant melt having a carbon powder dispersed therein, separating the two reactants by means of a solid member which is selectively-ionically conductive to sodium B
cations and maintaining on the positive reactant side of the solid separating member a molten electrolyte comprising molten sodium haloaluminate.
In accordance with this invention, the negative reactant or relUctant is sodium maintained above its melting point when the cell is in operation. The negative reactant is initially heated by any conventional means such as induction heating by electrical means, direct heating, or indirect heat exchange with a suitable heated fluid oxchange means. The negative react-ant functions as a conductor through which electrons flow to the external circuit during discharge.
The positive reactant of the present invention comprises molten sulfur and a molten mixture of metal halides. The specific metal halides selectet for use will be determined by such factors as the end use to which the battery is to be put; the economics involved, e.g, the cost of starting materials; the desiret operating pressuro of the cell; ant the specific sotium haloaluminate electrolyte selectet for use in the battery. ~ne criterion ust however be satisfiet by the metal halites selectet. They ust be soluble to some extent in the sotium haloaluminate electrolyte of the battery.
So long as this criterion is satisfiet, the selection of the specific motal halides to be utilized becomes a practical question rather than a critical one, i.e. depenting on economics, ent use and the like. Use-ful materials from which the positive reactant etal halides can be formed inclute metals at least as noble as aluminum ant metal-like eleaents. By metal-like elements, it is meant elements Such as boron, silicon, selenium, arsenic, tellurium, ant antimony which are also known as metalloits and which are intermediate in properties between typical etals and non-metals. The preferret metal halides for use in combination with sulfur in the positive reactant melt are aluminum chlorite ant antimony chlorite.
The solit member which separates the negative reactant and the positive reactant in the instant invention must be solectively-ionically-~045~703 conductive to sodium cations. Materials suitable for use as the solid separ-ator inclute glass, beta aluminas and other cation conductive crystalline and/or glassy materials that are resistant to the negative reactant and have satisfactorily low resistivities. The prefe D d separator comprisos a beta alumina cationically-conductive crystalline structure consisting essentially of a structural lattice and sodium cati s which are mobile in rolation to said lattice. The solid separator member may be prepared by any art known means, see for oxamplo, U.S. 3,535,163, so long as the useful end product is solectivoly ionically-conductive to sotium cations.
The oloctrolyte utilizod in the present in~ention makes possible a substantial reduction in the operating temperature of molten sulfur batteries as co parod with those presently known and uset in the art. For examplo, tho operating tomporaturo of the nor~al molten sodium-molten sulfur secontary battory whoroin tho olten cathodic electrolyto is an ionizet combination of sotium ~nd sulfur, i.o. ions of sodium polysulfido, Na2S5, the operating tomporaturo is rocognizod to be woll about 200&. and closor to 300 &., the lting tomporature of sodiu~ pentasulfito boing as high as 265 &. In markot contrast, tho battory of the prosent invention utilizod an oloctrolyte on the positive reactant site of the solid separating mo ber which comprisos molton sotium haloalu inate ant por its the oporation of the instant battery to be carriot out at te~poraturos of about 150&. to about 225&. The advantages of oporating t a retucet to perature are of course apparont, e.g. retucet corrosion, increased battery life, and reduced cost of containers ant seals, e.g. silicone rubber may be used as a negative gaskot seal.
By tho ter~ molten sotium hsloaluminste ss uset herein is meant matorisls which include sodium hslites, as for exa~ple, chloridos, bromides, fluorides, or iodides of sotium, ant sluminum hslides, for exs~ple chlorides, bromides, fluorides or iotides of aluminum. All of theso metal halidos will form the corresponting sotium haloaluminate olectrolytes of the invention.
Tho preforred electrolyte is sodium chloroaluminate.
1040'703 In the battery of the present invention, the positive reactant (sulfur and a mixture of metal halides) is mixed with the metal haloaluminate by any means in the art, o.g. it is possible to mix sulfur, sodium chloride, aluminum chloride and antimony chloride together with the positive reactant and heat the resultant mix until sodium chloroaluminate and the positive react-ant aro formed within the cell. It should be noted that while the battery of this invention is a sotium-mixed metal halites sulfur battery, the metal halite reactants which are present in the cell, i.e. present in the sotium haloalu inate^positive roactant melt within this cell, may be atded initially as tho motals themselves, picking up halide ions from the ionized sodium haloaluminate upon charging. Therefore, even though metals were attet init-ially, tho positive reactant of tho cell will comprise sulfur ant a mixturo of otal halitos in tho charged state.
Roforring now to Figure 1, a single coll socondary battory accorting ; to tho invontion is diagrammatically shown having a nogativo roactant coll compartmont 10 which aro not attackot by lton sotium motal at tho oporating tomporaturo of tho coll (about 150 & to 225 & .), o.g. carbon stool, alu inum, certain cora ics, cortain hoat ant chemical resistant polymers, a suitable glass or an alpha alumina or derivativo thoroof, all thermally insulated with ; 20 fiberglass, rockwool, or other insulation. Insido compartment 10 is a molten sotiu~ nogativo roactant 12. Insido a positivo reactant compartment 13 is an oloctrolyte-sulfur mixturo of metal halidos positivc reactant molt 14, o.g.
sodiu chloroalu inato-sulfur, aluminum chloride and antimonr chloride melt.
A carbon powder is in the melt 14 and sorvos thc purpose of a dis-porsod current colloctor.
The positivo reactant compartment 13 ay be made of any suitable material such as glass, ceramic, tungsten and tho like. Current collectors 18 ant 20 are disposod within the negativo ant positive reactant compartmonts 10 and 13, respoctively, and may be made of any suitable material such as for example, tungsten wire, carbon rods and the like. A solit separating member 22 is disposed between the compartments 10 and 13. The requirements of the separating member 22 have been described above. The current collectors 18 and 20 provide means for connecting the cell with an external circuit 24 which closed the circuit of the cell. The external circuit 24 may include any suitable utilization device or load, voltmeter, ammeter, etc. which have not been shown other than as indicated in Figure 1.
A better understanding of the battery in accordance with the in-vention can be obtained from the following Examples which are intended to be merely illustrative of the invention and not in limitation thereof.
EXAMPLES
The following information applies to all cells tested in the Examples unless otherwise indicated. Also, unless otherwise indicated, all quantities are by weight.
1. Makeup of Cells: The cells comprised a Pyrex* glass positive container, a carbon steel negative container and a beta alumina separator tisc. The negative seal was silicone rubber, and the positive seal was .. ~
Teflon. The negative current collector was the steel sodium container. The positive current collector varied as to type and configuration, as described in the examples, but in all cases it was sealed to the Pyrex glass with a - 20 Monel* Gyralok* fitting containing Teflon* ferrules. In all cases the car-bon was Cabot Vulcon* XC-72R. This carbon has a relatively low surface area of approximately 200 square meters/gram.
Example 1 - Cell Assembly: A tungsten coil current collector was sealed to a 1/4" glass tube then inserted into the positive Pyrex glass con-tainer. The cell was then assembled and sealed to the beta-alumina separator.
The following positive ingredients were then added in powder form after which the Pyrex container was sealed with a Monel Swagelok-0.5 grams of sulfur 0.5 grams of XC-72R conductive carbon 0.5 grams of Na Cl * trademarks ~040703
2.5 grams of Al C13 1.15 grams of Sb C13 The cell was heated to and held at 210C then put on discharge.
Cycle Mode CurrentPolarization CaPacity C#~~h~rge (MA) ~MN) (A-hrs.) De discharge 1 D 50 190 0.7S
; C 50 190 0.55 2 D 50 190 0.60 C 50 190 0.62
Cycle Mode CurrentPolarization CaPacity C#~~h~rge (MA) ~MN) (A-hrs.) De discharge 1 D 50 190 0.7S
; C 50 190 0.55 2 D 50 190 0.60 C 50 190 0.62
3 D 50 190 0.62 C 50 190 0.63
4 D 50 190 0.63 C 50 190 0.64 D 50 190 0.63 C 50 190 0.63 Tho capacity of this coll oquallod 1250 joulos por gra~ of positivo mix. Tho turnaround officiency was 88%. Also, soe Piguro 2 for chargo dis-chargo cyclo of this coll.
Exa~ple II
Tho coll assembly procoture was the sa e as described in Example I.
The following positive ingredients wero addet in powder form:
0.5 grams of sulfur 0.75 grams XC-72R conductivo carbon 1.25 gra s of Na Cl 4.50 gra s of Al C13 1.25 grams of Sb C13 ; Tho coll was hoatod to 210& and discharged.
Cyclo Modo CurrentPolarization Capacity C# charge (MA) (MV) (Amp.-hrs.) D~ discharge : 1 D 50 205 0.78 C 50 205 0.70 2 D 50 205 0.71 : 30 C 50 205 0.69 "
1~40703 Cycle Mode Current Polarization Capacity C~charge (M~) (MV) (Amp.-hrs.) D~dischargo 3 D S0 205 0.69 C S0 205 0.69 4 D 50 205 0.69 C 50 205 0.69 ` 5 D 50 205 0.69 C 50 205 0.69 The capacity of this coll equalled 850 joules/gram of positive d x.
The turnarount efficiency was 85%.
This coll was asso~bled and tosted as in the previous two Examplos oxcept that liquid titanium tetrachlorido was usod instoad of antimony trichlorido.
Tho positi~o ingrodionts woro:
0.25 gra s of sulfur 0.75 graDs of XC-72R conducti~o carbon 1.00 grams of Na Cl 4.00 grars of Al C13 ; 1.27 gra s (0.75 cc) of Ti C14 Cyclo do CurrentPolarization caPacity C~ chargo (MA) (MV) (A~p.-hrs.) ` D~ discharge 1 D 50 100 0.95 C 50 100 0.95 2 D 50 100 0.65 C 50 100 0.60 3 D 50 100 0.64 C 50 100 0.65 .
The capacity of this cell equallod 1020 joulos/grams of positivo ~; d x. Tho turnaround officiency was 90%. Also, see Figure 3 for chargo dis-charge cycle of this coll.
~Low cutoff ~oltago was raisod fro~ 1.62 to 2.3v. The original cutoff ~oltage for cycle 1 would have maintained 0.95 a~p hours.
Exa ple IV
~040703 A coll can be assomblet ss in Example I. The following positive ingredients can be atded:
0.5 grams of sulfur 0.5 grams of XC-72R conductive carbon 0.9 gra~s of Na Br
Exa~ple II
Tho coll assembly procoture was the sa e as described in Example I.
The following positive ingredients wero addet in powder form:
0.5 grams of sulfur 0.75 grams XC-72R conductivo carbon 1.25 gra s of Na Cl 4.50 gra s of Al C13 1.25 grams of Sb C13 ; Tho coll was hoatod to 210& and discharged.
Cyclo Modo CurrentPolarization Capacity C# charge (MA) (MV) (Amp.-hrs.) D~ discharge : 1 D 50 205 0.78 C 50 205 0.70 2 D 50 205 0.71 : 30 C 50 205 0.69 "
1~40703 Cycle Mode Current Polarization Capacity C~charge (M~) (MV) (Amp.-hrs.) D~dischargo 3 D S0 205 0.69 C S0 205 0.69 4 D 50 205 0.69 C 50 205 0.69 ` 5 D 50 205 0.69 C 50 205 0.69 The capacity of this coll equalled 850 joules/gram of positive d x.
The turnarount efficiency was 85%.
This coll was asso~bled and tosted as in the previous two Examplos oxcept that liquid titanium tetrachlorido was usod instoad of antimony trichlorido.
Tho positi~o ingrodionts woro:
0.25 gra s of sulfur 0.75 graDs of XC-72R conducti~o carbon 1.00 grams of Na Cl 4.00 grars of Al C13 ; 1.27 gra s (0.75 cc) of Ti C14 Cyclo do CurrentPolarization caPacity C~ chargo (MA) (MV) (A~p.-hrs.) ` D~ discharge 1 D 50 100 0.95 C 50 100 0.95 2 D 50 100 0.65 C 50 100 0.60 3 D 50 100 0.64 C 50 100 0.65 .
The capacity of this cell equallod 1020 joulos/grams of positivo ~; d x. Tho turnaround officiency was 90%. Also, see Figure 3 for chargo dis-charge cycle of this coll.
~Low cutoff ~oltago was raisod fro~ 1.62 to 2.3v. The original cutoff ~oltage for cycle 1 would have maintained 0.95 a~p hours.
Exa ple IV
~040703 A coll can be assomblet ss in Example I. The following positive ingredients can be atded:
0.5 grams of sulfur 0.5 grams of XC-72R conductive carbon 0.9 gra~s of Na Br
5.0 gra s of Al Br 1.8 grams of Sb Br3 Such a cell would behave similarly to the cell described in Exsmple 1.
Tho foregoing Examplos and detailed descriptions have boon given for clarity of untorstanding only snd no unnocessary limitations are to be undorstoot thorofrom. The in~ention is not li ited to exact details shown ant toscribed for obvious modificstions will occur to one skilled in the art.
Tho foregoing Examplos and detailed descriptions have boon given for clarity of untorstanding only snd no unnocessary limitations are to be undorstoot thorofrom. The in~ention is not li ited to exact details shown ant toscribed for obvious modificstions will occur to one skilled in the art.
Claims (8)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A secondary battery comprising in combination (a) a molten sodium negative reactant;
(b) a positive reactant comprising molten sulfur and a mixture of halides, said mixture of halides selected from the group consisting of halides of metals at least as noble as aluminum, halides of metal-like elements and mixtures thereof;
(c) a solid member separating the negative and positive reactants, said member being selectively ionically conductive to sodium cations;
(d) a molten sodium halide-aluminum halide electrolyte on the positive reactant side of the solid member;
(e) a carbon powder dispersed within the molten sulfur and mixture of metal halides; and (f) a current collector disposed in each the positive and negative reactants.
(b) a positive reactant comprising molten sulfur and a mixture of halides, said mixture of halides selected from the group consisting of halides of metals at least as noble as aluminum, halides of metal-like elements and mixtures thereof;
(c) a solid member separating the negative and positive reactants, said member being selectively ionically conductive to sodium cations;
(d) a molten sodium halide-aluminum halide electrolyte on the positive reactant side of the solid member;
(e) a carbon powder dispersed within the molten sulfur and mixture of metal halides; and (f) a current collector disposed in each the positive and negative reactants.
2. A battery according to claim 1 wherein the operating temperature of the battery is from about 150°C. to 225°C.
3. A battery according to claim 1 wherein the solid member is beta alumina.
4. A battery according to claim 1 wherein the positive reactant comprises molten sulfur and mixture of metal halides.
5. A battery according to claim 4 wherein the positive reactant com-prises molten sulfur and a mixture of aluminum halide and at least one metal halide selected from the group consisting of antimony halide, arsenic halide, tellurium halide, titanium halide and mixtures thereof.
6. A battery according to claim 5 wherein the positive reactant com-prises molten sulfur and wherein the aluminum halide is selected from the group consisting of chlorides and bromides of aluminum and the metal halide selected is antimony halide, said antimony halide being selected from the group consist-ing of chlorides and bromides of antimony.
7. A battery according to claim 1 wherein the sodium halide-aluminum halide electrolyte is selected from the group consisting of chlorides and bromides of sodium and aluminum and mixtures thereof.
8. A battery according to claim 1 wherein the positive reactant comprises molten sulfur and a mixture of aluminum chloride and antimony chloride and wherein molten sodium chloride-aluminum chloride is the elec-trolyte.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/584,987 US3988163A (en) | 1975-06-09 | 1975-06-09 | Sodium-mixture of metal halides, sulfur battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1040703A true CA1040703A (en) | 1978-10-17 |
Family
ID=24339595
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA249,143A Expired CA1040703A (en) | 1975-06-09 | 1976-03-30 | Sodium-mixture of metal halides, sulfur battery |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US3988163A (en) |
| JP (1) | JPS51150029A (en) |
| BR (1) | BR7603200A (en) |
| CA (1) | CA1040703A (en) |
| DE (1) | DE2613903A1 (en) |
| FR (1) | FR2314588A1 (en) |
| GB (1) | GB1496648A (en) |
| SE (1) | SE7602995L (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4117207A (en) * | 1977-10-14 | 1978-09-26 | Nardi John C | Molybdenum chloride-tetrachloroaluminate thermal battery |
| CA1149865A (en) * | 1979-08-22 | 1983-07-12 | Margaretha J. Nolte | Electrolyte for an electrochemical cell, and an electrochemical cell including the electrolyte |
| AU566856B2 (en) * | 1984-05-28 | 1987-10-29 | Lilliwyte Societe Anonyme | Electrochemcial cell with fluoride in electrolyte |
| GB8423961D0 (en) * | 1984-09-21 | 1984-10-31 | Lilliwyte Sa | Electrochemical cells |
| GB8523444D0 (en) * | 1985-09-23 | 1985-10-30 | Lilliwyte Sa | Electrochemical cell |
| US6815105B2 (en) * | 2000-10-23 | 2004-11-09 | The Regents Of The University Of California | Fuel cell apparatus and method thereof |
| US20130171487A1 (en) * | 2011-12-30 | 2013-07-04 | Roger Bull | Rechargeable battery and method |
| US8980459B1 (en) | 2014-01-02 | 2015-03-17 | Dynantis Corporation | Secondary metal chalcogenide batteries |
| EP3227951B1 (en) * | 2014-12-04 | 2019-08-28 | Field Upgrading USA, Inc. | Sodium-halogen secondary cell |
| US10601062B2 (en) | 2015-10-01 | 2020-03-24 | Dynantis Corp. | Sodium metal batteries with intercalating cathode |
| JP6701122B2 (en) * | 2016-05-17 | 2020-05-27 | 財團法人工業技術研究院Ｉｎｄｕｓｔｒｉａｌ Ｔｅｃｈｎｏｌｏｇｙ Ｒｅｓｅａｒｃｈ Ｉｎｓｔｉｔｕｔｅ | Metal ion battery and manufacturing method thereof |
| CN106711464B (en) * | 2017-01-20 | 2023-07-21 | 江南山 | Multitube sodium-sulfur battery |
| CN110911690B (en) * | 2019-12-06 | 2023-05-30 | 武汉大学 | A cathode current collector for a liquid metal battery with a carbide coating |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3463670A (en) * | 1967-05-26 | 1969-08-26 | Mallory & Co Inc P R | High energy density thermal cell |
| US3716403A (en) * | 1969-10-20 | 1973-02-13 | Molecular Energy Corp | A method of making semi-conductive cathodes |
| US3635765A (en) * | 1970-06-05 | 1972-01-18 | Nasa | Method of making e m f cell |
| US3751298A (en) * | 1971-05-21 | 1973-08-07 | Union Carbide Corp | Thermal, rechargeable electrochemical cell having lithium monoaluminide electrode and lithium tetrachloroaluminate electrolyte |
| US3879224A (en) * | 1974-04-05 | 1975-04-22 | Gen Electric | Sealed primary sodium-halogen cell |
| US3877984A (en) * | 1974-04-24 | 1975-04-15 | Esb Inc | Alkali metal-metal chloride battery |
-
1975
- 1975-06-09 US US05/584,987 patent/US3988163A/en not_active Expired - Lifetime
-
1976
- 1976-03-03 SE SE7602995A patent/SE7602995L/en unknown
- 1976-03-11 JP JP51026586A patent/JPS51150029A/en active Pending
- 1976-03-30 CA CA249,143A patent/CA1040703A/en not_active Expired
- 1976-03-31 DE DE19762613903 patent/DE2613903A1/en not_active Withdrawn
- 1976-04-28 FR FR7612590A patent/FR2314588A1/en active Granted
- 1976-05-20 BR BR7603200A patent/BR7603200A/en unknown
- 1976-06-09 GB GB23798/76A patent/GB1496648A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| FR2314588B1 (en) | 1981-06-19 |
| JPS51150029A (en) | 1976-12-23 |
| US3988163A (en) | 1976-10-26 |
| DE2613903A1 (en) | 1976-12-23 |
| FR2314588A1 (en) | 1977-01-07 |
| GB1496648A (en) | 1977-12-30 |
| BR7603200A (en) | 1977-02-15 |
| SE7602995L (en) | 1976-12-10 |
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