Patent Grant
12021248
The present invention relates to the conversion of chemical energy to electrical energy. More particularly, the present invention relates to an electrochemical cell having a total size or volume that is less than 0.5 cc. Such so-called miniaturized electrochemical cells enable numerous new and improved medical device therapies. Miniature electrochemical cells are defined as those having a size or total volume that is less than 0.5 cc.
The casing for a miniature electrochemical cell according to the present invention consists of three main components: a lower plate supporting a cylindrically-shaped annular sidewall having an open upper end closed with a cover plate. The lower plate, annular sidewall and cover plate are each of a metal material, for example of titanium.
The annular sidewall is selectively coated with a dielectric material to provide electrical isolation of the to-be-housed first active material, for example, an anode active material, from the annular sidewall. A sealing glass is applied to the perimeter of the lower plate with the annular sidewall supported on the glass. The annular sidewall and lower plate are heated to a temperature that is sufficient to achieve a glass-to-metal seal between them. The thickness of the sealing glass combined with the glass seal bonds at the lower plate and at the annular sidewall are sufficient to ensure electrical isolation between the lower plate and the supported annular sidewall.
A layer of a first active material, for example, an anode active material, is deposited into the cavity formed by the lower plate/annular sidewall subassembly. In this position, the anode active material is in electrical contact with the exposed inner surface of the lower plate, which serves as the negative terminal for the cell, but which is electrically isolated from the annular sidewall by the above-described sealing glass. A separator is supported on the anode active material.
Separately, a current collector, for example, a cathode current collector, is contacted to an inner surface of the cover plate. A layer of a second active material, for example, a cathode active material, is then contacted to the current collector opposite the cover plate. The metallic cover plate/current collector/second active material subassembly is then seated on an inner step of the annular sidewall, and the cover plate and sidewall are welded together. In this construction, the cover plate connected to the annular sidewall is in electrical continuity with the cathode active material through the cathode current collector to thereby serve as the positive terminal for the cell.
Finally, the electrode assembly is activated with an electrolyte filled into the casing through a fill port in the cover plate. The fill port is sealed with a closure member welded therein or by melting the material of the cover plate into a solid mass closing the fill port.
However, a vexing problem with this type of cell construction, particularly for a miniature electrochemical cell having a size or total volume that is less than 0.5 cc, is that there is very limited internal space in the casing for electrolyte. There simply isn't any extra internal space that can serve as an avenue for electrolyte to effectively wet the opposite polarity active materials to an extent that is sufficient to promote desirable cell discharge. In addition to a lack of extra internal space, the cathode current collector contacted to the cathode active material substantially blocks or covers the electrolyte fill port in the cover plate.
Thus, there is a need for an improved miniature electrochemical cell that is designed to readily permit electrolyte to flow into the casing to activate the electrode assembly during the filling operation.
To help ameliorate the electrolyte filling problem described above, the current collector, for example, the cathode current collector, contacted to the inner surface of the cover plate, and the active material, for example, the cathode active material, contacted to the current collector are each provided with at least one opening. The current collector opening and the active material opening reside inwardly from their respective peripheral edges. Importantly, the current collector and active material openings are axially aligned with each other and with the electrolyte fill port in the cover plate. The aligned fill port, current collector opening and the active material opening readily permit activating electrolyte to flow through the cathode active material to the separator and then to the anode active material.
In that respect, the axially aligned fill port, current collector opening and the active material opening eliminate flow problems when filling electrolyte into the casing. Instead, the axially aligned fill port, and the current collector and active material openings enable free flow of the prescribed amount of electrolyte into the casing. Not only does this speed up the time needed for electrolyte filling, but the axially aligned fill port and current collector and active material openings also reduce the need for reworking cells or for a second filling operation.
While the present cell designs are adapted for miniature electrochemical cells, they are also applicable to cells that have a total volume that is greater than 0.5 cc and are not classified as “miniature”. Moreover, the present electrochemical cells are not limited to any one chemistry; they can be an alkaline cell, a primary lithium cell, a rechargeable lithium cell, a Ni/cadmium cell, a Ni/metal hydride cell, a supercapacitor, a thin film solid-state cell, and the like. One preferred chemistry is a lithium-ion electrochemical cell comprising a carbon-based or Li4Ti5O12-based anode and a lithium metal oxide-based cathode, such as of LiCoO2 or lithium nickel manganese cobalt oxide (LiNiaMnbCo1-a-bO2). The lithium-ion electrochemical cell is activated with a liquid electrolyte.
These and other aspects of the present invention will become increasingly more apparent to those skilled in the art by reference to the following detailed description and to the appended drawings.
Turning now to the drawings, an electrochemical cell 10 according to the present invention comprises an electrode assembly housed in a hermetically sealed casing. The casing comprises a lower plate 12 supporting an annular sidewall 14 having an open end closed by a plate-shaped lid or cover 16. The lower plate 12, annular sidewall 14 and cover plate 16 are each of a biocompatible metal, for example titanium. In addition to titanium, suitable materials for the lower plate 12, annular sidewall 14 and cover plate 16 include stainless steel, mild steel, nickel-plated mild steel, but not limited thereto, so long as the metallic material is compatible for use with the other cell components.
An inner surface of the annular sidewall 14 has a first or lower cylindrically-shaped portion 14D extending upwardly part-way along the height of the sidewall 14 from the lower annular edge 14C to a step 14E. A second or upper cylindrically-shaped portion 14F extends upwardly from the step 14E to the upper annular edge 14B.
An annular layer of dielectric material 22, for example an alumina (Al2O3) material, is coated on the lower edge 14C and the inner surface of the lower cylindrically-shaped portion 14D of the annular sidewall 14. For ease in manufacturing, the dielectric layer 22 may also be coated on the outer surface 14A.
While the dielectric material 22 is shown in
Depositing the sealing glass 24 is achieved by several suitable methods including screen printing, dispensing, dipping into a frit paste or the use of a preformed endless glass ring. Suitable sealing glasses include both vitreous and crystallizing compositions that exhibit good electrical isolation properties and form mechanical bonds with good wetting characteristics to the metals of the lower plate 12 and the annular sidewall 14. Exemplary sealing glasses include, but are not limited to, Ferro IP510, Corning 1890, Schott 8422 and Schott 8629.
The lower plate 12, sealing glass 24 and annular sidewall 14 comprising the casing first subassembly 18 are then heated to a temperature that is sufficient to burn off any organic binders that may be present in the glass 24 and to flow the glass to achieve a glass-to-metal seal between the lower plate 12 and the annular sidewall 14. The sealing glass 24 has a thickness that ranges from about 0.002 inches to about 0.0025 inches, which is sufficient to ensure electrical isolation between the lower plate 12 and the annular sidewall 14.
After the lower plate 12 and the annular sidewall 14 are secured together by the intermediate sealing glass 24, a first electrode active material 26, for example, an anode active material, is supported on the upper surface 12B of the lower plate. The anode active material 26 preferably extends to the dielectric coating 22 on the inner surface of the lower cylindrically-shaped portion 14D of the annular sidewall 14. The anode active material 26 is deposited on the lower plate 12 using any one of many suitable techniques including being pressed into contact with the plate, preformed into a sheet that is pressed into contact with the plate, sprayed onto the plate, sputtered onto the plate, or coated on the plate. While not intending to limit the present electrochemical cell 10, the anode active material 26 has a thickness that ranges from about-5 μm to about 1 mm. In other embodiments, the anode active material 26 has a thickness that is greater than 1 mm.
Illustrative anode active materials include carbon-based materials selected from coke, graphite, acetylene black, carbon black, glass carbon, hairy carbon, and mixtures thereof, or lithiated materials selected from Li4Ti5O12, lithiated silver vanadium oxide, lithiated copper silver vanadium oxide, lithiated copper sulfide, lithiated iron sulfide, lithiated iron disulfide, lithiated titanium disulfide, lithiated copper vanadium oxide, LixCuwAgyV2Oz with 0.5≤x≤4.0, 0.01≤w≤1.0, 0.01≤y≤1.0 and 5.01≤z≤6.5, and mixtures thereof. Lithium is also a suitable anode active material.
A separator 28 (
Illustrative separator materials include non-woven glass, polypropylene, polyethylene, microporous materials, glass fiber materials, ceramics, the polytetrafluorethylene membrane commercially available under the designations ZITEX (Chemplast Inc.), the polypropylene membrane commercially available under the designation CELGARD (Celanese Plastic Company Inc.) and DEXIGLAS (C. H. Dexter, Div., Dexter Corp.). Other separator materials that are useful with the present invention include woven fabrics comprising halogenated polymeric fibers, as described in U.S. Pat. No. 5,415,959 to Pyszczek et al., which is assigned to the assignee of the present invention and incorporated herein by reference. Examples of halogenated polymeric materials that are suitable for the present invention include, but are not limited to, polyethylene tetrafluoroethylene, which is commercially available under the name Tefzel, a trademark of the DuPont Company, polyethylenechlorotrifluoroethylene which is commercially available under the name Halar, a trademark of the Allied Chemical Company, and polyvinylidene fluoride.
Separately, a current collector 32 is contacted to the lower surface 16C of the cover plate 16. At least one opening 32A extends completely through the thickness of the current collector 32. The at least one current collector opening 32A has a diameter that ranges from about 0.005 inches to about 0.016 inches, which is sufficient to allow electrolyte to readily flow therethrough. The cathode current collector 32 has a thickness that ranges from about 0.1 μm to about 50 μm, and is deposited on the lower surface 16C of the cover plate 16 by any one of many suitable processes including by a physical vapor deposition (PVD) process, for example, sputter deposition or evaporation deposition. Cathode current collector 32 can also be physically attached to the cover plate 16 by a weld. Exemplary current collector materials include nickel, titanium, copper, and Ti/NiV composites.
A second electrode active material, for example, a cathode active material 34 is contacted to the current collector 32 opposite the cover plate 16. The cathode active material 34 has an outer annular edge 34A extending to an active material upper face 34B spaced from an active material lower face 34C. That way, the exemplary cathode active material 34 is in electrical continuity with the cathode current collector 32 and the cover plate 16.
The cathode active material 34 is deposited using any one of many suitable methods (i.e., dispensed, pressed, preformed, sprayed, sputter deposition, evaporation deposition, tape casted, and as a coating). While not intending to limit the present electrochemical cell 10, the cathode active material 34 has a thickness extending to its upper and lower faces 34B and 34C that ranges from about 5 μm to about 1 mm. In other embodiments, the cathode active material 34 has a thickness that is greater than 1 mm. Suitable cathode active materials 34 are selected from lithium nickel manganese cobalt oxide (LiNiaMnbCo1-a-bO2), LiCoO2, LiNiO2, LiMnO2, TiS, FeS, FeS2, CFx, Ag2O, Ag2O2, Ag2CrO4, silver vanadium oxide (SVO), copper silver vanadium oxide (CSVO), V2O5, MnO2.
If desired, the cathode active material 34 is mixed with a binder material and a solvent prior to being deposited on the cover plate 16. Binders such as, but not limited to, a powdered fluoro-polymer, more preferably powdered polytetrafluoroethylene or powdered polyvinylidene fluoride and solvents, such as but not limited to, trimethylphosphate (TMP), dimethylformamide (DMF), dimethylacetamide (DMAc), tetramethylurea (TMU), dimethylsulfoxide (DMSO), or n-methyl-2-pyrrolidone (NMP) may be used.
In addition, up to about 10 weight percent of a conductive diluent may be added to the cathode active material 34 to improve conductivity. Suitable materials for this purpose include acetylene black, carbon black, and graphite or, a metallic powder such as powdered nickel, aluminum, titanium, and stainless steel.
As shown in
It is often the case that a current collector having an active material contacted to both of its opposed major surfaces has a plurality of openings. These openings provide the current collector with a structure similar to that of a screen. The openings help the opposed sheets or layers of active material lock to each other through the openings.
However, in the present electrochemical cell 10, since the active material 34 only contacts the current-collector 32 on one side (the side opposite the cover plate 16), a current collector screen is not needed. In fact, having the current collector 32 as a continuous sheet of electrically conductive material saves processing costs generally associated with providing the plurality of perforations. In that respect, if the current collector 32 is a screen, the opening 32A represents at least one of the screen openings. On the other hand, if the current collector 32 is a continuous un-perforated sheet of electrically conductive material, the at least one opening 32A is provided in axial alignment with the electrolyte fill port 30 and the active material opening 34D. In an exemplary embodiment, the cathode active material has a diameter of about 0.068 inches, or about 0.005 inches less than the inside diameter of the annular sidewall 14. In an exemplary embodiment, the cathode active material has a diameter of about 0.068 inches. In another exemplary embodiment, the cathode active material has a diameter that is about 0.005 inches less than the inside diameter of the annular sidewall 14. The opening 34D has a diameter that ranges from about 0.005 inches to about 0.016 inches.
The cover plate 16 has a diameter that is sized to fit into the second or upper cylindrically-shaped portion 14F of the annular sidewall 14, supported on the step 14E. In this seated position, the upper planar surface 16B of the cover plate 16 is substantially co-planar with the upper annular edge 14B of the sidewall 14. As shown in
An activating electrolyte (not shown) is then filled into the casing through the fill port 30. The fill port 30 is preferably closed with a closure plug (not shown) that has been press-fit into the opening followed by being welded to the cover plate 16. Alternately, the fill port 30 is closed by directing a laser beam at the cover plate 16 to cause material of the plate to flow into and hermetically seal the port 30. Suitable closure systems for sealing an electrolyte fill port are described in U.S. Pat. No. 6,610,443 to Paulot et al., U.S. Pat. No. 7,128,765 to Paulot et al. and 10,446,825 to Voss et al. These patents are assigned to the assignee of the present invention and incorporated herein by reference.
The activating electrolyte is a nonaqueous and ionically conductive material mixture serving as a medium for migration of ions between the anode and cathode active materials during conversion of ions in atomic or molecular forms which migrate from the anode active material 26 to the cathode active material 34. Nonaqueous electrolytes that are suitable for the present electrochemical cell 10 are substantially inert to the anode and cathode active materials, and they exhibit those physical properties necessary for ionic transport, namely, low viscosity, low surface tension and wettability.
A suitable electrolyte has an inorganic, ionically conductive lithium salt dissolved in a mixture of aprotic organic solvents comprising a low viscosity solvent and a high permittivity solvent. The inorganic, ionically conductive lithium salt serves as the vehicle for migration of the anode ions to intercalate or react with the cathode active material 34. Suitable lithium salts include LiPF6, LiBF4, LiAsF6, LiSbF6, LiClO4, LiO2, LiAlCl4, LiGaCl4, LiC(SO2CF3)3, LiN(SO2CF3)2, LiSCN, LiO3SCF3, LiC6F5SO3, LiO2CCF3, LiSO6F, LiB(C6H5)4 and LiCF3SO3, and mixtures thereof.
Low viscosity solvents useful with the present electrochemical cell 10 include esters, linear and cyclic ethers and dialkyl carbonates such as tetrahydrofuran (THF), methyl acetate (MA), diglyme, trigylme, tetragylme, dimethyl carbonate (DMC), 1,2-dimethoxyethane (DME), 1,2-diethoxyethane (DEE), 1-ethoxy, 2-methoxyethane (EME), ethyl methyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, diethyl carbonate, dipropyl carbonate, and mixtures thereof, and high permittivity solvents include cyclic carbonates, cyclic esters and cyclic amides such as propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate, acetonitrile, dimethyl sulfoxide, dimethyl formamide, dimethyl acetamide, γ-valerolactone, γ-butyrolactone (GBL), N-methyl-pyrrolidinone (NMP), and mixtures thereof.
In the present electrochemical cell 10, the preferred anode active material 26 is lithium metal and the preferred electrolyte is 0.8M to 1.5M LiAsF6 or LiPF6 dissolved in a 30:70 mixture, by volume, of propylene carbonate as the preferred high permittivity solvent and 1,2-dimethoxyethane as the preferred low viscosity solvent.
The axially aligned fill port 30, current collector opening 32A and the active material opening 34D allows the casing to be filled using a vacuum filling process. Without the axially aligned openings 30, 32A and 34D, the electrode assembly would need to be soaked in electrolyte and the remaining casing void volume filled with additional electrolyte prior to welding the cover plate 16 to the annular sidewall 14. This creates multiple problems. First, internal voids within the opposite polarity electrode active materials are not optimally filled with electrolyte without a vacuum drawing electrolyte into all available porosity. A second issue relates to the difficulty in welding of the cover plate 16 to the annular sidewall 14 in the presence of electrolyte. Heat generated by the welding process can cause electrolyte to evaporate and form out-gassing byproducts that can contaminate the weld 36, thereby reducing weld integrity.
When the present electrochemical cell 10 is of a primary chemistry, the combined thicknesses of the anode active material 26, separator 28, the cathode active material 34 and the cathode current collector 32 is substantially equal to or slightly greater than the combined height of the sealing glass 24 and the lower inner cylindrically-shaped portion 14D of the annular sidewall 14 as measured from the lower plate 12 to the step 14E.
That way, there is sufficient stack pressure inside the electrochemical cell 10 to provide intimate contact between the anode/cathode electrode assembly to thereby ensure acceptable discharge for the primary chemistry cell.
Alternatively, when the electrochemical cell 10 is of a secondary chemistry, the combined thicknesses of the anode active material 26, the separator 28, the cathode active material 34 and the cathode current collector 32 is somewhat less than the combined height of the sealing glass 24 and the lower inner cylindrically-shaped portion 14D of the annular sidewall 14 as measured from the lower plate 12 to the step 14E. That way, there is sufficient free space inside the casing to accommodate expansion and contraction of the electrode stack or anode/cathode electrode assembly as the electrochemical cell 10 of the secondary chemistry is subjected to charge and discharge cycles.
With the electrochemical cell 10 comprising the electrode assembly of the anode active material 26/cathode active material 34 activated with the electrolyte and housed inside the casing comprising the casing lower subassembly 18 (
As those skilled in the art will readily appreciate, the cathode active material 34 can be switched with the anode active material 26. In this alternate embodiment, the cathode active material 34 in contact with cathode current collector 32 contacting the lower plate 12 serves as the positive terminal and the anode active material 26 in contact with the cover plate 16 welded to the annular sidewall 14 serves as the negative terminal.
However, the preferred cell design has the cathode current collector 32 and cathode active material 34 in electrical continuity with the cover plate 16. This construction is desirable because cathode active materials 34 that are useful with the present electrochemical cell 10 generally have better structure integrity than the anode active materials 26, particularly when the anode active material is lithium. Lithium is a relatively soft material. Forming an accurate opening through lithium is difficult due to the soft nature of the material. In contrast, a body of the cathode active materials described above is better able to have an opening formed therethrough without compromising structural integrity.
Thus, with the lower plate 12 having a surface area ranging from about 1 mm2 to about 1 cm2 (surface area of either of the upper and lower surfaces 12b, 12C), the upper surface 16B of the cover plate 16 and the upper edge 14B of the annular sidewall 14 having a combined surface area ranging from about 1 mm2 to about 1 cm2, and with the height of the casing as measured from the lower surface 12C of the lower plate 12 to the upper edge 14B of the annular sidewall 14 ranging from about 250 μm to about 2.5 mm, the present electrochemical cell 10 represents an advancement in electrochemical technology. The cell can be built with a total volume that is less than 0.5 cc but, as a hermetically sealed enclosure, is capable of being implanted in human or animal body tissue for extended periods of time.
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 spirit and scope of the present invention as defined by the appended claims.
This application claims priority to U.S. provisional application Ser. No. 63/041,147, filed on Jun. 19, 2020.
| Number | Name | Date | Kind |
|---|---|---|---|
| 5415959 | Pyszczek et al. | May 1995 | A |
| 6610443 | Paulot et al. | Aug 2003 | B2 |
| 7128765 | Paulot et al. | Oct 2006 | B2 |
| 9905819 | Saimaru | Feb 2018 | B2 |
| 10446825 | Voss | Oct 2019 | B2 |
| 10461308 | Kobayashi | Oct 2019 | B2 |
| 10957884 | Dianetti | Mar 2021 | B1 |
| 20110097623 | Marinis et al. | Apr 2011 | A1 |
| 20180138463 | Bruch | May 2018 | A1 |
| 20210111382 | Rubino | Apr 2021 | A1 |
| Number | Date | Country |
|---|---|---|
| 112016003117 | Apr 2018 | DE |
| 20170124302 | Nov 2017 | KR |
| 20170124302 | Nov 2017 | KR |
| Entry |
|---|
| Glass ceramic as evidenced by Wikipedia (Year: 2023). |
| Modofied translation KR20170124302A as taught by Sung (Year: 2017). |
| KR 20170124302 A, englsh translation as taught by Sung et al. (Year: 2017). |
| “Extended European Search Report, Application No. 21180130.3, dated Nov. 11, 2021”. |
| Number | Date | Country | |
|---|---|---|---|
| 20210399367 A1 | Dec 2021 | US |
| Number | Date | Country | |
|---|---|---|---|
| 63041147 | Jun 2020 | US |
