Process For Press-Contacting A Lithium Anode Onto The Inner Surface Of A Cylindrical Cell Casing
20240047757 ยท 2024-02-08
Inventors
- Brian D. Panzer (Williamsville, NY, US)
- Jordan A. Hartwig (East Aurora, NY, US)
- Gregory A. Voss (Alden, NY, US)
- Joshua C. Ulrich (East Aurora, NY, US)
- David Oddy (Clarence, NY, US)
- Alycia Kassian (Buffalo, NY, US)
- Zachary Klein (Buffalo, NY, US)
Cpc classification
H01M50/154
ELECTRICITY
H01M50/179
ELECTRICITY
Y02E60/10
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
H01M50/188
ELECTRICITY
H01M50/198
ELECTRICITY
International classification
H01M4/36
ELECTRICITY
H01M4/583
ELECTRICITY
Abstract
An electrochemical cell has a cylindrically-shaped casing tube with at least first and second lithium sheets swaged onto its inner surface. The first lithium sheet has respective spaced apart first right and left edges, and the second lithium sheet has spaced apart second right and left edges. The first and second right edges and the first and second left edges of the swaged first and second lithium sheets are adjacent to but spaced apart from each other by about 0.5 to about 1 about the inner circumference of the cylindrically-shaped casing tube. A novel process for swaging the first and second lithium sheets onto the inner surface of the casing tube is also described.
Claims
1. An electrochemical cell, comprising: a) a casing comprising a cylindrically-shaped casing tube having an inner surface with an inner circumference; b) a glass-to-metal seal (GTMS) comprising a ferrule supporting an insulator glass contacting a terminal pin residing inside the ferrule, wherein the ferrule of the GTMS is secured in an opening in the casing; c) an electrode assembly housed inside the casing, the electrode assembly comprising: i) an anode comprising lithium contacted to the inner surface of the casing tube; ii) a cathode current collector; iii) a cathode comprising a cathode active material contact to the cathode current collector, wherein the cathode resides in the casing tube, spaced from the anode; and iv) a separator segregating the lithium from directed physical contact with the cathode; and d) an electrolyte in the casing activating the electrode assembly, e) wherein the casing tube contacting the lithium serves as a negative terminal, and wherein the cathode current collector contacted to the cathode active material and being connected to the terminal pin electrically isolated from the casing by the GTMS serves as a positive terminal for the cell.
2. The electrochemical cell of claim 1, wherein the anode comprises at least a first lithium sheet and a second lithium sheet contacted to the inner surface of the cylindrically-shaped casing tube.
3. The electrochemical cell of claim 2, wherein the first lithium sheet comprises spaced apart first right and left edges and the second lithium sheet comprises spaced apart second right and left edges, and wherein the first and second right edges of the first and second lithium sheets contacted to the inner surface of the cylindrically-shaped casing tube are adjacent to but spaced apart from each other, and wherein the first and second left edges of the first and second lithium sheets contacted to the inner surface of the casing tube are adjacent to but spaced apart from each other.
4. The electrochemical cell of claim 3, wherein the first and second right edges of the respective first and second lithium sheets are spaced apart from each other by about 0.5 to about 1 about the inner circumference of the cylindrically-shaped casing tube, and wherein the first and second left edges of the respective first and second lithium sheets are spaced apart from each other by about 0.5 to about 1 about the inner circumference of the casing tube.
5. The electrochemical cell of claim 1, wherein the cathode current collector has a thickness and at least one opening through its thickness, and wherein the cathode active material contacted to the cathode current collector is locked to itself through the at least one opening.
6. The electrochemical cell of claim 5, wherein the cathode current collector is selected from titanium coated with carbon, tantalum, platinum, gold, aluminum, cobalt nickel alloys, highly alloyed ferritic stainless steel containing molybdenum and chromium, and nickel-, chromium- and molybdenum-containing alloys.
7. The electrochemical cell of claim 1, wherein the cathode active material is selected from fluorinated carbon (CF.sub.x), silver vanadium oxide (SVO), copper silver vanadium oxide, copper vanadium oxide, manganese dioxide, titanium disulfide, copper oxide, copper sulfide, iron sulfide, iron disulfide, lithium cobalt oxide, and mixtures thereof.
8. An electrochemical cell, comprising: a) a casing, comprising: i) a cylindrically-shaped casing tube extending from a lower open end to an upper open end, the casing tube comprising an outer surface spaced from an inner surface having an inner circumference; ii) a closure plate closing the lower open end of the casing tube; iii) a lid secured to the casing tube at the upper open end; and iv) a glass-to-metal seal (GTMS) comprising a ferrule supporting an insulator glass contacting a terminal pin centered inside the ferrule, wherein the GTMS resides in a lid opening where the ferrule is secured to the lid; and b) an electrode assembly housed inside the casing, the electrode assembly comprising: i) an anode comprising at least a first lithium sheet and a second lithium sheet contacted to the inner surface of the cylindrically-shaped casing tube; ii) a cathode current collector; iii) a cathode comprising fluorinated carbon (CF.sub.x) contacted to the cathode current collector, wherein the cathode has a cylindrical shape and resides in the casing tube, spaced from the first and second lithium sheets; and iv) a separator segregating the first and second lithium sheets from directed physical contact with the cathode; and c) an electrolyte in the casing activating the electrode assembly, d) wherein the casing tube contacting the first and second lithium sheets serves as a negative terminal, and wherein the cathode current collector contacted to the cathode active material and being connected to the terminal pin electrically isolated from the casing by the GTMS serves as a positive terminal for the cell.
9. The electrochemical cell of claim 8, wherein the first lithium sheet comprises spaced apart first right and left edges and the second lithium sheet comprises spaced apart second right and left edges, and wherein the first and second right edges of the first and second lithium sheets contacted to the inner surface of the cylindrically-shaped casing tube are adjacent to but spaced apart from each other, and wherein the first and second left edges of the first and second lithium sheets contacted to the inner surface of the casing tube are adjacent to but spaced apart from each other.
10. The electrochemical cell of claim 9, wherein the first and second right edges of the respective first and second lithium sheets are spaced apart from each other by about 0.5 to about 1 about the inner circumference of the cylindrically-shaped casing tube, and wherein the first and second left edges of the respective first and second lithium sheets are spaced apart from each other by about 0.5 to about 1 about the inner circumference of the casing tube.
11. A method for providing an electrochemical cell, comprising the steps of: a) providing a casing comprising a cylindrically-shaped casing tube having an inner surface with an inner circumference; b) providing a glass-to-metal seal (GTMS) comprising a ferrule supporting an insulator glass contacting a terminal pin residing inside the ferrule; c) contacting at least a first lithium sheet and a second lithium sheet to the inner surface of the casing tube; d) providing a cathode comprising a cathode active material contacted to a cathode current collector; e) connecting the terminal pin of the GTMS to the cathode current collector of the cathode; f) moving the ferrule of the GTMS into an opening in the casing and securing the ferrule to the casing with the cathode facing the first and second lithium sheets, wherein an intermediate separator prevents the first and second lithium sheets from physically contacting the cathode; g) providing an electrolyte in the casing to activate the first and second lithium sheets in electrochemical association with the cathode; and h) closing the casing, i) wherein the casing tube contacting the first and second lithium sheets comprises a negative terminal, and wherein the cathode current collector contacted to the cathode active material and being connected to the terminal pin electrically isolated from the casing by the GTMS serves as a positive terminal for the cell.
12. The method of claim 11, including providing the first lithium sheet comprising spaced apart first right and left edges and the second lithium sheet comprising spaced apart second right and left edges, and contacting the first and second lithium sheets to the inner surface of the cylindrically-shaped casing tube so that the first and second right edges of the first and second lithium sheets are adjacent to but spaced apart from each other, and so that the first and second left edges of the first and second lithium sheets are adjacent to but spaced apart from each other.
13. The method of claim 12, including providing the first and second right edges of the respective first and second lithium sheets being spaced apart from each other by about 0.5 to about 1 about the inner circumference of the cylindrically-shaped casing tube, and providing the first and second left edges of the respective first and second lithium sheets being spaced apart from each other by about 0.5 to about 1 about the inner circumference of the casing tube.
14. The method of claim 11, further including: a) providing the cylindrically-shaped casing tube extending from a lower open end to an upper open end; b) providing a lid having a lid opening; c) securing the ferrule of the GTMS to the lid in the lid opening; d) including providing the cathode current collector as an elongate plate-shaped current collector comprising a plurality of openings; e) connecting the terminal pin of the GTMS to the cathode current collector of the cathode; f) moving the ferrule of the GTMS into the lid opening and securing the ferrule to the lid; g) securing the lid to the casing tube at the upper open end with the cathode facing the first and second lithium sheets, wherein the intermediate separator prevents the first and second lithium sheets from physically contacting the cathode; and h) after providing the electrolyte in the casing tube to activate the first and second lithium sheets in electrochemical association with the cathode, closing the lower open end of the casing tube with a closure plate.
15. The method of claim 11, including selecting the cathode active material from fluorinated carbon (CF.sub.x), silver vanadium oxide (SVO), copper silver vanadium oxide, copper vanadium oxide, manganese dioxide, titanium disulfide, copper oxide, copper sulfide, iron sulfide, iron disulfide, lithium cobalt oxide, and mixtures thereof.
16. The method of claim 11, including enveloping the cathode in a separator prior to moving the ferrule of the GTMS into the opening in the casing and securing the ferrule to the casing with the cathode facing the first and second lithium sheets.
17. The method of claim 11, including selecting the cathode current collector from titanium coated with carbon, tantalum, platinum, gold, aluminum, cobalt nickel alloys, highly alloyed ferritic stainless steel containing molybdenum and chromium, and nickel-, chromium- and molybdenum-containing alloys.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0037] As used herein, the term swage means that a sheet of lithium is press-contacted to the inner surface of a casing under sufficient force so that the lithium sheet has a somewhat reduced thickness and a somewhat greater width and height as the force deforms the lithium from its original shape and thickness.
[0038] Referring back again to
[0039] Referring now to
[0040] As shown in
[0041]
[0042] As shown in
[0043] As next shown in
[0044] As shown in
[0045]
[0046] In a similar manner as previously described with respect to
[0047] The swaged second lithium sheet 14 extends from about 179 to about 179.5 around the inner surface 16E. This means that there are opposed gaps 26 and 28 (
[0048] Referring back to
[0049] Preferably, the electrochemical cell 10 is built in a case-negative design with the casing tube 16, bottom closure plate 22, lid 24 and ferrule 32 for the GTMS 30 serving as the negative terminal for the anode sheets 12, 14. However, the cell 10 can also be built in a case-positive design with the positions of the anode and the cathode being reversed or switched, as is well known by those skilled in the art.
[0050]
[0051] The cathode 18 is then assembled by contacting a cathode active material, for example, fluorinated carbon CF.sub.x, to the undulating portion 44 of the current collector 38. The cathode active material 18 as a unitary body is supported in a surrounding and contact relationship with the undulating portion 44 so that the active material fills in and around the crests and troughs 44A, 44B of the opposed undulating edges, and in the openings 46 where the active material locks to itself. The undulating edges of crests and troughs 44A, 44B, and the openings 46 serve as irregularly-shaped surfaces that prevent the cathode active material 18 from losing contact with the current collector 38. That way, the cathode active material 18 is incapable of sliding in an axial direction along the longitudinal axis B-B of the current collector 38 as well as being prevented from separating and delaminating from the front and back major sides and the opposed undulating edges of crests and troughs 44A, 44B. As shown in
[0052] While the cathode active material comprising the cathode 18 is preferably fluorinated carbon (CF.sub.x), other suitable active materials include silver vanadium oxide (SVO), copper silver vanadium oxide, copper vanadium oxide, manganese dioxide, titanium disulfide, copper oxide, copper sulfide, iron sulfide, iron disulfide, lithium cobalt oxide, and mixtures thereof.
[0053] As shown further in
[0054] Next, the cathode 18 is enveloped in an ionically porous polymeric material serving as the previously described separator 20 (
[0055] The height of the anode sheets 12, 14 along the axial length of the casing tube 16 is somewhat longer than the height of the cathode 18 along the longitudinal axis of the current collector 38. The greater height of the anode sheets 12, 14 in comparison to the cathode 18 accommodates for some misalignment between the electrodes while maintaining anode active material always being opposite the cathode active material.
[0056] As previously described, the terminal pin 36 is supported in the GTMS 30 by the insulator glass 34. The ferrule 32 of the glass-to-metal seal 30 is fit into the lid opening 24A and welded to the lid 24, for example, by laser welding. The lid 24 supporting the GTMS 30 is then welded to the proximal open end 16C of the casing tube 16 to hermetically close the casing tube at that end. The terminal pin 36 connected to the cathode current collector 38 supporting the cathode active material 18, and electrically isolated from the casing tube 16, lid 24 and ferrule 32 by the insulator glass 34 serves as the positive terminal for the electrochemical cell 10.
[0057] An electrolyte (not shown) is then filled into the casing tube 16 through the lower open end 16B thereof to activate the electrode assembly before the lower closure plate 22 is hermetically secured in the casing tube by a laser weld 52. Preferably, the bottom closure plate 22 is of the same material as the casing tube 16, and the bottom plate 20 along with the casing tube 16, lid 24 and ferrule 28 comprises part of the negative terminal for the cell 10.
[0058] By way of example, in an illustrative primary cell, the lithium sheets 12, 14 contacted to the inner surface 16E of the casing tube 16 serves as the negative terminal for the electrochemical cell 10. The preferred cathode active material is CF.sub.x contacted to the cathode current collector 38. This electrochemical couple is preferably activated with an exemplary electrolyte comprising a 1.0M to 1.4M solution of LiAsF.sub.6 or LiPF.sub.6 in -butyrolactone. A lithium/silver vanadium oxide (Li/SVO) couple is typically activated with an electrolyte comprising 1.0M to 1.4M of LiAsF.sub.6 or LiPF.sub.6 in a 50:50 mixture of, by volume, 1,2-dimethoxyethene and propylene carbonate.
[0059] Thus, a novel anode construction for an electrochemical cell is described by the present invention. The novel anode is formed of at least a first lithium sheet 12 and a second lithium sheet 14 contacted to the inner surface 16E of a cylindrically-shaped casing tube 16. Importantly, the first lithium sheet 12 has spaced apart first right and left edges 12A, 12B and the second lithium sheet 14 has spaced apart second right and left edges 14A, 14B. The first and second right edges 12A, 14A of the first and second lithium sheets 12, 14 contacted to the inner surface 16E of the cylindrically-shaped casing tube 16 are adjacent to but spaced apart from each other by about 0.5 to about 1 about the inner circumference of the cylindrically-shaped casing tube, and the first and second left edges 12B, 14B of the first and second lithium sheets 12, 14 contacted to the inner surface 16E of the casing tube 16 are adjacent to but spaced apart from each other by about 0.5 to about 1 about the inner circumference of the cylindrically-shaped casing tube. The first and second lithium sheets 12, 14 are press-contacted or swaged onto the inner surface 16E of the casing tube 16 under sufficient force so that the swaged lithium sheets each have a somewhat reduced thickness and a somewhat greater width and height than their original shape and thickness. That is done without the first and second lithium sheets 12, 14 ever touching each ever. Lithium is a relatively sticky material, especially to itself, so should there be contact between the first and second lithium sheets, it could lead to undesirable deformation of the lithium.
[0060] Finally, while the present process has been described for contacting two lithium sheets to the inner surface of a cylindrically-shaped casing tube, the present invention should not be so limited. Those skilled in the art will readily recognize that the novel swaging process described above can be used to swage three, four, or more lithium sheets onto the inner surface of the casing. The only requirement is that the lithium sheets do not contact each other during the swaging process and that after swaging, their adjacent edges are close to but spaced apart for each other.
[0061] It is appreciated that various modifications to the inventive concepts described herein may be apparent to those of ordinary skill in the art without departing from the scope of the present invention as defined by the appended claims.