CA2138115C - Cylindrical air-cell - Google Patents
Cylindrical air-cell Download PDFInfo
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- CA2138115C CA2138115C CA002138115A CA2138115A CA2138115C CA 2138115 C CA2138115 C CA 2138115C CA 002138115 A CA002138115 A CA 002138115A CA 2138115 A CA2138115 A CA 2138115A CA 2138115 C CA2138115 C CA 2138115C
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- positive electrode
- cup
- cylindrical
- layer
- collector
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/183—Sealing members
- H01M50/184—Sealing members characterised by their shape or structure
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/183—Sealing members
- H01M50/186—Sealing members characterised by the disposition of the sealing members
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/183—Sealing members
- H01M50/19—Sealing members characterised by the material
- H01M50/193—Organic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/183—Sealing members
- H01M50/19—Sealing members characterised by the material
- H01M50/197—Sealing members characterised by the material having a layered structure
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Hybrid Cells (AREA)
- Sealing Battery Cases Or Jackets (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Inert Electrodes (AREA)
Abstract
The sealing of the top and/or bottom of the cylindrical positive electrode of an air-cell is improved and leakage of the electrolyte from the jellied zinc negative electrode disposed within the positive electrode which is constituted of a collector layer, catalyst layer, and a porous layer is prevented. By utilizing a positive electrode constituted of a metallic collector layer made of a metal mesh or such, a catalyst layer disposed around said collector, and a fluororesin porous layer as an air diffusion layer, an outer cup and an inner cup are pressed on the top of the positive electrode in order to prevent the leakage of the electrolyte. The possible leakage of electrolyte from the bottom of the positive electrode can be prevented by providing a resin sealing body with a ring shaped indentation fitted to the bottom of a positive electrode, and by inserting this resin sealing body into the positive electrode cannister, and by pressing the side wall. of the positive electrode cannister against the side of the resin sealing body, in order to fit the bottom of the positive electrode to the indentation of the resin sealing body.
Description
21381 1 ~
SPECIFICATION
TITLE OF THE INVENTION
Cylindrical Air-Cell FIELD OF THE INVENTION
This invention relates to a cylindrical- air-cell of which top of positive electrode cor:taining electrolyr_e a=nd cathode active material or sealing of the bottom of said air-cell is made liquid tight.
BACKGROUND OF THE INVENTION
A structure of conventional cylindrical. air-cell is explained below by referring Fig. 14 which shows a partly cutout side view of said air-cell. In Fig. 14, 101 is a cylindrical negative electrode containing an active mat=er~al of so-called "jelli_ed zinc" in which zinc powder is dispersed in jellied electrolyte, and 102 is a collector provided at the center of negative electrode 101. 103 is a multi-layered cylindrical positive electrode comprised of catalyst layer 104 containing mangar_ese oxide and carbon material, collector layer 105 buried within catalyst layer 109, and a water-repellant porous layer 106 made of fluororesin contacting with a surface of catalyst layer 104.
The other surface of said catalyst layer 109 is faced to negative electrode 102 through separator 1G7, and is operated by utilizing the oxygen contained in air as an active material. 108 is a cylindrical positive eleca rede-can containing air-diffusing layer made of non-woven fabric covering the surface of said positive electrode 103, and other electricity generating elements including negative electrode 101 and positive elect=rode 103, and is provided with air-intake hole 110. 111 is an insulation tube covering the entire surface of said cylindrical positive elec-trode can 109, provided with air-intak:>_ hole 110 and air-intake window 112 which are connected to said air-intake hole 110.
113 is a seal closing said air-intake window 112 and 114 is a resin seal to which the bot;.tom of positive electrode can 109 is bent and clamped. 115 is a bottom plate of the negative electrode terminal contacted with collector J.02, 116 ~s a positive electrode cap-terminal contacted with the top ef_ positive electrode 103, 117 is a cell cover, 118 is a grooved part, and 119 is a sealing material preventing the leakage of electrolyte.
Explaining this cell structure further, the upper edge of positive electrode 103 ~ws inwardly bent at t=he rim of grooved part 118, and the bent part is contacted wittu the rim of positive electrode cap-terminal J_16, and these are inserted into cell-cover 11'7, and the upper edge of positive electrode canister 109 is bent and clamped at the r.im of call-cover 117. The 1_ower edge of positive electrode 103 is sealed by inserting the bottom of water repellant porous layer 106 of positive electrode 103 between the sealing body 114 and the positive electrode canister 109, and clamped.
By employing the abc>ve explained cell-structure, leakage of jellied electrolyte filled within the cylindrical positive electrode 103 and leakage of E;lect:rol.yte containing trif~- zinc powder filled in the negative electrode from the top to t=he bottom end of positive electrode canister 109 can x>e prevented.
However, when t:he top end o.f <-ylindrical positive electrode 103 consisted o.f collector 105, catalyst layer 104, and water repellant porous layer 106, is bent at a rim of groove 118 provided for the sealing, cracks of catalyst layer 104 may apt to be produced at the bending of wrinkles of watr~r-repellant porous layer 106 are apt to take place, and as a result of this, complete seal of cell-cover 117 had been hard to accomplish.
Furthermore, since the: sealing of bottom edge of positive "~, electrode canister 109 is performed by clamping only the edge of water repellant porous layer 108 between the sealing body 114 and the positive electrode canister 109, cracks of edge of water repellant porous layer 109 are apt to be produced so that perfect seal had been hard to obtain.
Since the alkaline electrolyte has a strong tendency of creeping and leakage through minute wrinkles or cracks of seal if produced, leakage of electrolyte may take place easily during the storage period or during the usage thereof.
1o Moreover, the conduction from positive electrode 103 to positive electrode canister 109 is performed by the mechanical contact of positive electrode 103 and positive electrode cap terminal 116 accomplished by the bending of the top rim of positive electrode canister 109, these contacts may become unstable by vibration or shock applied on the cell, making the electric-current supply unstable.
SUMMARY OF THE INVENTION
The purpose of this invention is to offer a new air-cell structure by which the top and bottom of the cylindrical positive electrode consisted of collector and catalyst layers and water-repellant porous layer are sealed liquid tight, preventing the external leakage of electrolyte held within the positive electrode.
Therefore, according to a first broad aspect, the invention seeks to provide a cylindrical air-cell provided with a cylindrical positive electrode comprised of a metallic collector layer, a catalyst layer disposed on a side wall of a metallic collector, and a porous layer disposed on an external surface of the catalyst layer. An outer cap-shaped metal cup is fitted to an outer wall of an upper edge of the porous layer and an inner cap-shaped metal cup is fitted to an inner wall or an upper edge of the catalyst layer.
-3a-According to a second broad aspect, the invention also seeks to provide a cylindrical air-cell provided with a cylindrical positive electrode comprised of a cylindrical metallic collector layer having a bent part formed on a top edge of the collector layer by bending an upper edge of the collector layer inwardly, a catalyst layer disposed on a side wall of a metallic collector, and a porous layer disposed on an external surface of the catalyst layer. An outer cap-shaped metal cup is fitted to an outer wall of an upper edge of the porous layer and an inner cap-shaped metal cup is fitted to an inner wall of an upper edge of the catalyst layer, and the bent part of the collector layer is held between the outer cup and the inner cup.
The invention seeks to provide, in accordance with a third broad aspect, a cylindrical air-cell provided with a cylindrical positive electrode comprised of a cylindrical metallic collector layer having a bent part formed on a top edge of the collector layer by bending an upper edge of the collector layer inwardly, a catalyst layer disposed on a side wall of a metallic collector, a gas diffusion layer disposed on an external surface of the catalyst layer, and a porous layer disposed on an external surface of the gas diffusion layer. An outer cap-shaped metal cup is fitted to an outer wall of an upper edge of the porous layer and an inner cap-shaped metal cup is fitted to an inner wall of an upper edge of the catalyst layer, and the bent part of the 2o collector layer is held between the outer cup and the inner cup.
According to a fourth broad aspect, the present invention seeks to provide a cylindrical air-cell provided with a cylindrical positive electrode comprised of a metallic collector layer, a catalyst layer disposed on a side wall of a metallic collector, and a porous layer disposed on an external surface of the catalyst layer, wherein an outer cap-shaped metal cup is fitted to an outside wall of an upper edge of the porous layer and an inner cap-shaped metal cup is fitted to an inner side wall of an upper edge of the catalyst layer, and the positive electrode equipped with a terminal part on top of the positive electrode, is housed in a cylindrical positive electrode canister, and the terminal part and the outer cup are welded together, and an outer rim of the outer cup located outside of a welded part of the terminal part and the outer cup and an inner rim surface of the positive electrode canister facing to the outer rim of the outer cup is electrically insulated.
-3b-The invention also seeks to provide, in accordance with a fifth broad aspect, a cylindrical air-cell provided with a cylindrical positive electrode comprised of a cylindrical metallic collector layer having a bent part formed on a top edge of the collector layer by bending an upper edge of the collector layer inwardly, a catalyst layer disposed on a side wall of a metallic collector, and a porous layer disposed on an external surface of the catalyst layer. An outer cap-shaped metal cup is fitted to an outer wall of an upper edge of the porous layer and an inner cap-shaped metal cup is fitted to an inner wall of an upper edge of the catalyst layer, and the positive electrode is housed in a cylindrical electrode canister provided with a terminal part on 1o top of the positive electrode, and the terminal part and the outer cup are welded together, and an outer rim of the outer cup located outside of a welded part of the terminal part and the outer cup and an inner rim surface of positive electrode canister facing the outer rim of the outer cup is electrically insulated.
According to a sixth broad aspect, the invention seeks to provide a cylindrical air-cell provided with a cylindrical positive electrode comprised of a metallic collector layer, a catalyst layer disposed on a side wall of the metallic collector layer, and a layer disposed on an external surface of the catalyst layer, wherein a resin sealing body provided with a ring-shaped indentation is disposed on an edge of a positive 2o electrode canister holding the positive electrode, and a side of the positive electrode canister is pressed against an outer sidewall of the resin sealing body.
According to a seventh broad aspect, the following invention also seeks to provide a cylindrical air-cell provided with a cylindrical positive electrode comprised of a cylindrical metallic collector layer, a catalyst layer disposed on a side wall of the metallic collector layer, and a porous layer disposed on an external surface of the catalyst layer. A resin sealing body consisting of a resin mold body provided with a ring-shaped indentation is fitted to a bottom of the positive electrode and another resin mold body holding the resin mold body, is disposed on an edge of a positive electrode 3o canister in which the positive electrode is held, and a side of the positive electrode canister is pressed against an outer sidewall of the resin sealing body.
3c -The following invention also seeks to provide with an eighth broad aspect, a cylindrical air-cell provided with a cylindrical positive electrode comprised of a cylindrical metallic collector layer, a catalyst layer disposed on a side wall of the metallic collector layer, and a porous layer disposed on an external surface of the catalyst layer. A separator is disposed on an inner surface of the positive electrode, and a resin mold body holding both a ring-shaped resin sealing body on which a ring shaped indentation fitted to the bottoms of the positive electrode and the separator is provided and another resin sealing body holding the resin mold body, and a side of a positive electrode canister is pressed against an outer sidewall of the resin sealing 1 o body.
According to a ninth broad aspect, this inventions seeks to provide a cylindrical air-cell comprising a cylindrical positive electrode that comprises a metallic collector layer, a catalyst layer disposed on the side wall of the metallic collector, a porous layer disposed on the external surface of the catalyst layer, a first resin mold element provided with a ring-shaped indentation, a second resin mold element and a positive electrode canister. 'The ring-shaped indentation holds an end of the positive electrode, the second resin mold element holds the first resin mold element, the first resin mold element, the second resin mold element and the cylindrical positive electrode are fitted within the positive electrode canister which is arranged to press against the outer side wall of the first and the second resin mold elements to provide a seal therewith.
In order to accomplish the present purposes, the cylindrical mufti-layer positive electrode of the invented air-cell is constituted of a metallic collector, catalyst layers disposed on both sides of the metallic collector, and a porous layer disposed on the catalyst layer wherein an external cup and an internal cup are pressed on the external top rim of the porous layer and internal top rim of catalyst layer of the positive electrode respectively.
' 9 4~ 12~ 12 ~ (~j) 14 :15 ~l; ~, 7 I~ ~ - 3~ 1s fl; F ~x ill I~ is 'J - t 1, b~ 3~ z #1 F 0 5 ~~~a~ ~~
Moreover, as s metallic collector constitutl.ng Raid positive electrode, a cylindrical metallic collector layer of which top is inwardly bent can be employed, and said external metal cup pressed on the external top rim of said porous layer and Bald internal metal cup pressed on the internal top rim of catalyst layer are closely contacted on said inwardly bent part of said metallic collector.
Likewise, said cylindrical positive electrode may well be constituted of a gas diffusion layer disposed on the outer sur-faee of said catalyst layer and a porous layer disposed on the outer surface of said gas diffusion layer, and a cap-shaped external metal cup may be pressed on the external top rims of said porous 7.ayer and a cap-shaped internal metal cup may be pressed on the internal top rim of said catalyst layer respec-tively. though said the bent part of said metallic collector may well be held and clamped between said external and internal metal cups.
In another structure of the invented air-cell, a metallic external cup is disposed on the outer top rim of said porous layer, a metallic external cup is disposed on t;he internal top rim of said catalyst layer of said positive electrode, said positive electrode is inserted in a cylindrical positive elec-trode canister, and then the said outer metallic cup i.s welded to said terminal, and the outer rim of said outer cup positioned outside of the welded part of said outer cup and said terminal and the internal surface of said positive electrode canister facing to the outer rim of said outer cup can be elecCricall.y insulated. In this case, a metallic collector layer of which top rim is bent inwardly, may be used.
In the still other structure of the invented air-cell, a resin seal provided with a ring-shaped indentation fitted to the bottom of said positive electrode is used as a bottom seal of said positive electrode. In this case, the bottom of said posi-tive electrode is inserted in said ring-shaped indentation, and 'q4~l~,~l~.~r,~l~aoh ~n:~ ~~t- _. ~f~;~F~itifi~~~~-Y~.~~=~t said resin seal is inserted in said positive electrode canister.
After this, the side of resin seal is so pressed against the opposing inner wall of the positive-electrode canister that the bottom of positive electrode and the indentation of resin seal are contacted c.l.osely.
Moreover, in another structure of the invented air-cell.
said resin seal provided with a ring-shaped indentation to which the bottom of separator disposed on the positive electrode or on the inner wall of positive electrode is fitted, can be employed.
In still another structure of the invented air-cell., said resin seal may well be constituted of two elements, 1.e., a seal provided with a ring-shaped indentation fitted to the bottom of said positive electrode or an indentation fitted to both the bottoms of positive electrode and said separator, and an in-dependent seal by which this seal can be held.
According to the above described explanations, the functions of the inventions are as follows.
The top of a positive electrode consists of a metallic collector layer, a catalyst layer disposed on the side of said collector layer, and a porous layer held between two metal cups of different inner diameters, and the sides of said metal cups are pressed against said positive electrode, and by this, the top of said positive electrode can be completely sealed without producing cracks or wrinkles poRSible on said positive electrode so that the leakage of electrolyte from the top of positive electrode can be completely prevented.
In another case, a high electrical conductivity between the positive electrode and the metal cups can be obtained by employ-ing a cylindrical collector layer of which top rim is inwardly bent, and by welding the bent rim to the inner wall of said outer cup, and by pressing said outer cup and inner cup to said bent rim of coll.eetor. Moreover, a high electrical conductivity or low 's~y2y2B(~)m:ii ~~C ~h~- ~r ~;~~~i~~~~!-t~bR~~~l Fog internal cell resistance can be obtained by welding the top of said outer cup to the inner wall of said positive electrode canister, preventing contact failures between the collector and the cups even if unexpected shocks or vibration are applied to the cell.
Moreover, the bottom of positive electrode can be sealed completely by pressing the bottom of positive electrode against the indentation of resin sealing, and by applying a mechanical pressure on the positive electrode canister at the side of indentation after the bottom of positive electrode is inserted into the indentation of resin seal.
Furthermore, by inserting the bottom of separator into the indentation of resin seal, not only the excessive stress applica-tion on the positive electrode at sealing process can be avoided.
but the sealing performance can also be improved. Thus, the leakage of electrolyte and the shorts between the positive and the negative electrodes can be prevented improving the cell reliability further.
BRIEF DESCRIPTION OF TfIE DRAIIINGS
Fig. 1 shows a side view of the partly cut--off cylindrical zinc air-cell which is a first embodiment of the invention.
Fig. 2 shows an enlargement of the part-A of Fig. 1.
Fig. 3 shows an enlarsed cross-section of the top edge of modified positive -electrode of the cylindrical zinc air-cell shown in Flg. 1.
Fig. 4 shows a top view of the outer cup of cyll.ndrical zinc air-cell shown in Fig. 1.
Fig. 5 shows a cross-section of the outer cup of cylindrical '94~.12~128~~)14:32 ~~ ~Fi'- ~F ~~~~i9~~a~'-~~~~~#~ F02 zinc air-cell shown in Flg. 4, sectioned at Line A-B.
Fig. 6 shows an enlarged cros9-section of the tap edge of positive electrode of the cylindrical zinc air-cell which is a second embodiment of the invention.
Fig. 7 shows a aide view of the partly cut-off cylindrical zinc air-cell which is a third embodiment of the invention.
Fig. 8 shows a side view of the partly cut--off cylindrical zinc air-cell which is a fourth embodiment of the invention.
Fig. 9 shows a side view of the partly cut-off zinc cylind-rieal~air-cell which is a Tifth embodiment of the invention.
Fig. 10 shows a side cross-section of the ring-shaped resin mold employed in the cylindrleal air-cell shown in ~lg. 9.
Fig. 11 shows a side view of the partly cut-off modified cylindrical zinc air-cell which is a fifth embodiment of the invention.
Fig. 12 shows a side view of the partly cut-off cylindrical zinc air-cell which is a sixth embodiment of the invention.
Fig. 13 shows a side view of the partly cut-off modifled cylindrical zinc air-cell which is shown in Fig. 1.2.
Fig. 14 shows a side view of the partly cut-off conventional cylindrical zinc air-cell.
DESCRIPTION OF TIiF ~ PREI%EBRCD CMBODxI~NTS
(L~'mbod.iment-1 Fig. 1 shows a side view of the partly cut-aft cylindrical ~13~1 1 ~
zinc air-cell which is a first embodiment of the invention. Fig. 2 shows an enlargement of the part-A of Fig. 1, and Fig. 3 shows an enlarged cross-section of the top end of modified positive electrode of the cylindrical zinc air-cell shown in Fig. 1.
In Figs. 1 to 3, 1 is a cylindrical negative electrode in which an active material of so-called jellied zinc and collector 2 are incorporated, 3 is a multilayered c~yl.indrica.l positive electrode comprised of a catalyst layer 4 employing manganese oxide and carbon materials as main element,, collector layer 5 consisted of nickel plated stainless steel mesh disposed within catalyst layer 4, and a water-repellant porous layer b consisted of fluororesin contacting with a surface of catalyst layer 4, 7 is a separator disposed within catalyst layer 4 of positive electrode 3, within which negative electrode 1 is disposed, 8 is an air diffusion layer made of non-woven polypropylene fabric, 9 is a pos.i.tive electrode canister on which positive elecarode cap terminal 16 is integrally molded at its top, 10 is an air-intake hole provided on the positive electrode canister 9, 11 is an insulation tube, 12 is an air-intake window provided on insulation tube 11., 13 is a seal sealing the air-intake window until the cell operation, 14 is a seal made of resin, 15 is a bottom plate for negative electrode terminal, 17 is a sealing material, and 18 is a base paper. In place of metal mesh, an expanded metal or a punched metal may be used.
The manufacturing process of positive electrode 3, is began with a spot welding process overlapping the both ends of long collector layer forming collector 5 into a cylindrical shape and placing the overlapped part at a surface comm«n with the side surface of collector 5, and a preformed catalyst layer 4 is then pressed on the both surfaces of cylinde>.r-shaped collector 5.
The material of catalyst layer 4 is prepared by mixing activated carbon, manganese oxide, acetylene-black, and fluororesin powder at a predetermined mixing ratio, and b~Y~ further. kneading of the mixture after a proper amount of ethylal.cohol is added. Then, this kneaded mixture is extruded into a strip sheet having r.::
fl '94~12~12H(~114:33 ~~ ~~t- ~~ ~~~~~~~t-ez~~nft Po4 2~.~g~.~~
a thickness of about 0.6 mm. Said manganese oxide is prepared by applylna a beat-treatment on y-MnOOii 1n a nitrogen atmosphere at a temperature of 400°C. and said fluororesin powder is derived from polytetrafluoroethylene (PTF'E~ resin. Granulated or chained activated carbon having a particle diameter of 10 1:0 40 microns is used in this case.
On the other hand, a fluororesin dispersant containing PTFfi resin is coated on a surface of catalyst layer 4 and is dried at a temperature of 230°C. By this. the electrolyte can be easily permeated into the electrode. and obstruction of oxygen gas supply to the positive electrode can be prevented, The reason of the employment of a drying temperature of 230°C is to disperse the surface active agent coni:ained in the dispersant.
A gas-permeable water-repellant fluororesin layer is then pressed on the surface coated with fluororesin dispersant in order to obtain porous layer B of positive electrode 3 act as an air electrode. Thus prepared positive electrode 3 is wound involute in a form of cylinder to face catalyst layer 4 inwardly.
Then. inner cup 20 and outer cups 19 both made of nickel plated steel plate are disposed on the top of cylindrical posi-tive electrode 3, so that outer cup 19 is contacted with the outer rim while inner cup 20 is contacted with the Inner rim of the top edge oP said porous layer 5. As a result oP this, posi-tive electrode 3 can be sealed at a condition where the top edge of positive electrode 3 is held between the outer cup 19 and inner cup 20. Since the outside of outer cup rim is grooved by using a roller and is pressed against the outer surface of positive electrode 3 while inner cup 20 is widened within a space of catalyst layer 4 and pressed against the inner wall of posi-tive electrode 3, positive electrode 3 is held and clamped between the inner cup 20 and the outer cup 19 forming an air-tight and leakage-free sealing.
Furthermore. as shown in Fig. 3, the entire inner surface '94~12~128(~?14:34 ~~ ~~i~- ~ ~;~F~~i~~~~-e~~~~ff F05 of outer cup 19 is coated with a synthetic rubber sealing material made mainly of chlorosulionated-polyethylene for example forming a sealing lnyer 22, in order to improve the air-tightness and leakage-proof performance realizing high reliability of the sealing.
Thus, after sealing the top of positive electrode 3, the external surface of porous layer 8 and the area from the outer rim of outer cup 1S to the upper round-oti part nre wrapped h9 air-diffusion layer e.
As shown ltz Figs. 4 and 6. ~~nsi l pra~;ru5~icr~8 23 ere ~1sp09e~
o~ the ext~er~$1 ~Qp ~~e~f~c~e off' out~f cup ~9 at ~hro~ counts 8va.ldlng a strs~ght line disposition, and these small protrusions 23 are spot-welded on the inner surface of terminal ).6 of posi-tive electrode cap, disposed on the top of positive electrode canister 9.
Moreover, the top of said air-diffusion layer a is disposed between the outer rim of outer cup 18 located outside oP said small protrusions 23 and the inner side surface of positive elec-trode canister 9 opposing to these protrusions in order to avoid the contact of outer cup 18 to positive electrode canister e.
8y employing the above-described cell construction, since the eddy current produced at welding of small protrusions onto the top inner surface of positive electrode canister 9 is concentrated only to the small protrusions of outer cup 19. a higher welding strength and better appearance welding between the positive electrode canister a and the small protrusions can be obtained. Moreover, because of an opening 21 provided on the top center of inner cup 20, a welding rod can be inserted through opening 21 when positive e).ectrode canister 9 is welded to the outer cup I9 so that the welding bar can be contacted with outer cup 18 and the welding oP these components cnn be performed easily at a better stabilized condition.
-~. ~C~ '-z~3~~ 15_ Furthermore, instead of the non-wooer. fabric, air diffusion layer 6 covering the outside surface of porous layer 8 and the area from the outer side surface to the top of ~::up 19 can be formed by using a heat-shrinking porous resin tube ma de of a resin material such as air-permeable polyethylene terephtha.Late (PET) or a heat shrinking tube with small openings prepared in advance.
The bottom edge of positive electrode 3 is formed by bending the bottom edge of positive electrode 9 against the rim of sealing body 14 and by clamping, and by placing the lower edge of porous layer 6 between the sealing body 14 and the positive electrode canister 9 and by filling the gap with a seal:i.ng material 17.
Ten of the cylindrical zinc air-cells ~ are constructed according to Embodiment-7. shown in Fig. l, ten conventional cylindrical zinc air-cells C are constructed by bending the top edge of positive electrode inwardly and contacted with the bent part as shown in Fig. 14. Ten cylindrical zinc air-cells B are constructed according to Embodiment-1 shown in Fig. 3 but with sealing layer 22 is formed on the inner surface of outer cup ~-9, and ten conventional cylindrical zinc air-cells D with sealing layer 22 formed at the top edge of positive electrode, are prepared.
The storage characteristics of these cells are comparatively tested at a storage temper<~ture of 60°C and the result o:E these are shown in Table 1.
~3~115_ Table 1 Storage Period(at 60C) Tested cellsSealing 1 week 2 weeks 3 weeks 1 month applied on outer cup Cell A None 2/10 8/10 10/i0 -(Fig. 1) Cell B Yes C/10 0/10 0/10 0/10 (F.ig. 3) Cell C None 10/10 - - -(conventional) Cell D Yes 10/10 - - -(conventional) As shown in Table l, the conventional zinc air-cells C and D
showed very severe electrolyte leakages within very short periods, regardless of the coating of sealing material.
On the other hand, none of the zinc air-cells B of Embodiment-1 showed leakage after a storage period of one month at ~0°C while all of the zinc air-cells ~~ showed leakage after a storage period of three weeks.
Therefore, significant improvements of leakage stopping characteristics obtained by the invented zinc air-cells over those of conventional zinc air-cell:, are confirmed, in addition to further improvements obtained with sealing layer 22 formed on the internal surface of outer cup 19.
However, when the width of overlapped region of the cylindrically formed col-'-ect_or is inadequate, ar_ insufficient tensile strength of the overlappE:d region would be produced.
Therefore, when a volume expansion of the zinc negative electrode 1 is produced at discharge, breakage of: welded points at the edges of collector may take place, causing electrolyte leakage. Thus, at least an overlap width of 1.3$ of the circumference of collector layer 5 has to be provided.
On the other hand, wPen said overlapped width is too large, the collector area providing minute holes ar_e plugged, sacrificing the discharge capacity somewhat. The sacrifice cf discharge capacity can be minimized by setting the overlapped width at less than 9°s of the total circumference of collector layer 5.
Although a case where the both ends of long stainless steel mesh strip are over-lapped to constitute a cylindrical collector is shown here, the collector of the same function can be obtained by weaving a long horizontal. metal thread into a number of independent vertical fine metal wires formed into a shape of cylinder.
Both the horizontal and vertical met<31 wires in this case, could be nickel plated stainless steel wire or nickel ware, and in this case, erosion of c:ol.l.ector by the al_ka!ine electrolyte can be minimized so that the storage characteristics of cell can be improved.
(Embodiment-2) A bent part 2.4 formed by bending the top edge inwardly is provided on cylindrical collector 5 as shown in Fig. 6. By pressing and fitting outer cup 19 onto both the upper surface of bent part 24 and the upper edge rim of porous layer 6, and by pressing and fitting the inner cup 20 onto both the lower surface of bent part 24 and the inner rim o:f upper edge of catalyst .Laye.r 4, the bent part 24 can be held and clamped between the inner cup 1y and the outer_ cup 20. At this condition, outer cup 1'a and bent part 24 can be welded together.
A cylindrical air-cell acco;.-ding to the above shown cell construction yet having a cell construe~ion identical with those shown in Fig 1 for the rest of the cell, is fabrir_ated, and this cell is named as cell E of the embodiment of the invention.
,,'"''. 13 '94~12~128(~)14:36 ~~ ~ht- ~fi ~;~F~~'~~~'-~~~~~~t P09 Ten each of Cells E and A are prepared and the internal cell resistances are determined, and the results of these are listed in Table 2.
Table 2 Right after cell After 20 day storng~s assembly (in A) at fi0°C (.1n n) Invented Cell-F. x 0.1.54 ~c 0.186 (Fig. 6) Max 0.17 Max 0.20 Min 0 . 14 Min O , l.6 0~_1 0.010 on_1 0 .015 Invented Cell-A x 0.216 x 0.352 (Fig. 1) Max 0.27 Max 0.37 Min 0,18 Min 0.31 oA_1 O. 218 aA_1 O .
As shown in Table 2, substantial decreases of the internal.
resistance resulted from the closer contacts of bent part 24 of collector layer 5 to outer cup 19 and inner cup 20 is proved by cell F which is an embodiment of the invention.
This result proved that the internal resistance can be kept at low even after a storage period of 20 days at 60°C. The advan-tages of cell G have been confirmed with the cells assembled by using no welding of bent part 24 to collector layer 5 but is merely held between these two elements.
(Embodiment-3) Resin sealing body 14 sealJ.ng the bottom of c:yllndrlcal positive electrode 3 l.iqui.cf t.l.ght, may be provided w1 th a ring-'94~12~128(~)14:41 ~i~ ~ht- ~1~ ~;~~~fi~~~'-e~~~~ff P02 shaped indentation 25 to which the bottom of positive electrode 3 is fitted as shown in Fig. '7. After sealing body 1.4 provided with indentation 14 to which the bottom of positive electrode is fitted, i.s inserted into positive electrode canister 9, groove 26 is formed on the side wall of positive electrode canister 9 by applying an external mechanical pressure on sealing body 14.
Hy this, the side wall of sealing body 14 is pressed closely against positive electrode canister a and at the same time, the lower edge of positive electrode 3 is fitted liquid tight to indentation 25 of sealing body 14, sealing tlae bottom of positive electrode 3 completely.
In addition to the above, the sealing condition of the bottom of positive electrode canister can be further improved by applying a sealing agent in a gap between the side of resin sealing body 14 and the side of positive electrode canister. The zinc air-cell assembled by using the above-explained aeallng body 25 is named as cell F is shown in Fig. 7. Ten each cells F and C are assembled and these are submitted to comparative three-mcinth storage tests conducted at a temperature of 60°C testing the leakage from the bottom of positive electrodes 3, and the results are tabulated in Table 3.
Table 3 Storage Period (at 60°C) Tested cells 10 days 20 days 1 month 2 months a months Cell r 0/10 0/10 0/10 0/10 0/10 Cell G O/10 0/10 0/10 0/10 O/10 Cell II 0/10 0/1.0 0/1.0 0/10 O/10 Cell I 0/10 0/10 0/10 0/10 0/10 Conventional 10/10 - - -Cell C
is '94'~12~12A(~114:42 ~~ ~ht- ~~ ~;~F~;~;fi~~~t-e'z~~r~t Po3 As shown in Table 3, as for the ten F cells wttlch are an embodiment of the invention, no leakage have beerx detected even after a three month storage period conducted at a temperature of 60°C .
(Embodiment-4) As shown in Fig. 8, resin sealing body 14 may be constituted of a ring-shaped resin mold element 27 provided with indentation 25 to which the bottom of positive electrode 3 is fitted, and a convex resin mold element 28 holding said resin mold element 27.
The zinc air-cell assembled by employing sea:line body 14 of this construction is named as cell G which is an embodiment of the invention and is shown in Fig. 8.
Table 3 shows a result of the storage test same as the case of Embodiment-3 conducted by usl.ng cell G, Likewise. no cell leakage have been found even after three month storage period conducted at a temperature of 60°C.
( Gmbodirnen t-a ) As shown in I~ig. 9, metal ring 29 may be disposed between the resin mold element 27 and resin mold body 28 in Embodiment-4.
The cylindrical air-cell assembled by using the thus constructed sea:llng body 14 is designated as cell Ii of Embodiment-5 of the invention, and this is shown in Fig. 9.
The results of the test of cell 1l, conducted under a condition same as the one in Embodiment-3 is shown in Table 3 which shows no leaked cells after a three month storage test conducted at a temperature of 60°C.
Moreover, in the cased of Embodiments -4 and -5, the work to insert the bottom of positive electrode into indentation 25 can be simplified and easier by making the ring-shaped i_nden-2 '~ 3 ~ 1 1 5 _.
tation 25 of resin mold element 27 in a form of tapered side-wall 30 which is expanded gradual:l.y upward.
When the cylindrir.:al zinc air-cell of the invention is assembled by using the above explained sealing body 14, after air diffusion layer 8 is disposed on the outside of positive electrode 3 to which outer cup 19 and inrner cup 20 are fitted to the top of said positive electrode, these are inserted into positive electrode canister 9, the bottom <:af positive electrode 3 is inserted into indentation 25 of said resin mold element 2';', and the concave metal-ring holding part 31 provided on the side of resin mold element 27 is positioned at metal ring 29.
Then, by using a roller, a mechanical pressure is applied on the side of positive electrode canister 9 facing to the side of resin mold element 27, and by this groove 2n is formed. Although a pressure is applied on both the resin mold element 27 and the positive electrode r_aniste:r 9, movements of resin mold element 27 in the direction of pressure application can be blocked by means of metal ring 29, and the sealing between the resin :hold element 27 and the bottom of positive electrode 3 can be further improved.
By providing step part 32 at the upper part of the inner sidewall of indentation 25 as shown in fig. 10 ir_ order to hold the lower edge 33 of separator 7, a cell structure shown in Fig. 11 can be obtained, and the pos:>ibility of shorts between the positive electrode 3 and the negative electrode 1 can be completely eliminated.
(Embodiment-6) As shown in Fig. 1.2, a cylindrical air-cell of which top edge of positive electrode 3 have a structure shown i.n Fig. 6 is prepared, and this cell is specified as cell I of Embodiment-~6 of the invention here. This cell I is submitted to test the same as the previously conducted one, and the resu-i.t of this is shown ,. 1 '7 in Table 3.
Again as shown in Table 3, no cells I showed electrolyte leakage after a three month storage test conducted at a temperature of 60°C.
Moreover, as shown in Figure 1.3, although the resin mold element 28 consists of pi.Llar shaped base 34 and pillar 35 having a diameter smaller than the base 34 disposed c>n the center of base 34, by providing concave part 36 at a position under base 34 and outer side of pillar 35, and by inserting metal washer 37 therein as shown, the position of resin mold element 28 can be fixed more tightly when the bottom of positive electrode canister is bent and clamped on the resin mold element 28, and thus the positive electrode canister 9 and the resin mold element can be pressed more tightly.
Although a fluororesin porous layer is disposed at the outside of positive electrode 3 in this embodiment of the invention, a better effect can be obtained by employing a gas diffusion layer made of a sheet made of acetylene-black and fluorores.in powder improving the oxygen gas supply to positive electrode 3.
As above explained >o far, the cylindrical air-cell of the invention consists of a metallic collector Layer, a catalyst layer disposed on the side of said metal l.i.c collect: or layer, and a porous layer acting as a cylindri<:al ai.r electrode di sposed on the outside of said catalyst layer, and is provided with an outer metal cup pressed on the outer top ed<7e of said positive electrode and an inner metal cup pressed on the ir:ner top edge of said positive electrode.
Since the top of positive electrode is pressed and clamped by said outer and inner cups, the sealing of the top of positive electrode can be substantially improved, offering air-cells having excellent sealing and leak-proof charar_teristics.
'94~12~12~(~)14:43 ~'~ 7~~'- ~fa "~~~~~~~'-l''7,~"~,~ff P06 Moreover, by providing a bent part at the top edge of metallic collector layer, by holding and claroplng said bent part against between said outer metal cup and inner metal cup, and by welding said collector layer and outer cup, the contacts between these elements can be held at a best condition, nullifying the possibility of internal resistance increase due to poor contacts between the collector layer and the outer and inner cups.
Furthermore, a resin mold body having a ring-shaped inden-tation fitted to the lower edge of positive electrode is disposed at the bottom of positive electrode, and after said resin mold body is inserted into the positive electrode canister, the aide of said positive electrode canister is inward:Ly pressed against the side of said resin mold body in order to improve the sealing between the bottom of positive electrode and the ring-shaped indentation of said resin mold body, thus improving the leak-proof characteristics of the bottom of positive electrode.
SPECIFICATION
TITLE OF THE INVENTION
Cylindrical Air-Cell FIELD OF THE INVENTION
This invention relates to a cylindrical- air-cell of which top of positive electrode cor:taining electrolyr_e a=nd cathode active material or sealing of the bottom of said air-cell is made liquid tight.
BACKGROUND OF THE INVENTION
A structure of conventional cylindrical. air-cell is explained below by referring Fig. 14 which shows a partly cutout side view of said air-cell. In Fig. 14, 101 is a cylindrical negative electrode containing an active mat=er~al of so-called "jelli_ed zinc" in which zinc powder is dispersed in jellied electrolyte, and 102 is a collector provided at the center of negative electrode 101. 103 is a multi-layered cylindrical positive electrode comprised of catalyst layer 104 containing mangar_ese oxide and carbon material, collector layer 105 buried within catalyst layer 109, and a water-repellant porous layer 106 made of fluororesin contacting with a surface of catalyst layer 104.
The other surface of said catalyst layer 109 is faced to negative electrode 102 through separator 1G7, and is operated by utilizing the oxygen contained in air as an active material. 108 is a cylindrical positive eleca rede-can containing air-diffusing layer made of non-woven fabric covering the surface of said positive electrode 103, and other electricity generating elements including negative electrode 101 and positive elect=rode 103, and is provided with air-intake hole 110. 111 is an insulation tube covering the entire surface of said cylindrical positive elec-trode can 109, provided with air-intak:>_ hole 110 and air-intake window 112 which are connected to said air-intake hole 110.
113 is a seal closing said air-intake window 112 and 114 is a resin seal to which the bot;.tom of positive electrode can 109 is bent and clamped. 115 is a bottom plate of the negative electrode terminal contacted with collector J.02, 116 ~s a positive electrode cap-terminal contacted with the top ef_ positive electrode 103, 117 is a cell cover, 118 is a grooved part, and 119 is a sealing material preventing the leakage of electrolyte.
Explaining this cell structure further, the upper edge of positive electrode 103 ~ws inwardly bent at t=he rim of grooved part 118, and the bent part is contacted wittu the rim of positive electrode cap-terminal J_16, and these are inserted into cell-cover 11'7, and the upper edge of positive electrode canister 109 is bent and clamped at the r.im of call-cover 117. The 1_ower edge of positive electrode 103 is sealed by inserting the bottom of water repellant porous layer 106 of positive electrode 103 between the sealing body 114 and the positive electrode canister 109, and clamped.
By employing the abc>ve explained cell-structure, leakage of jellied electrolyte filled within the cylindrical positive electrode 103 and leakage of E;lect:rol.yte containing trif~- zinc powder filled in the negative electrode from the top to t=he bottom end of positive electrode canister 109 can x>e prevented.
However, when t:he top end o.f <-ylindrical positive electrode 103 consisted o.f collector 105, catalyst layer 104, and water repellant porous layer 106, is bent at a rim of groove 118 provided for the sealing, cracks of catalyst layer 104 may apt to be produced at the bending of wrinkles of watr~r-repellant porous layer 106 are apt to take place, and as a result of this, complete seal of cell-cover 117 had been hard to accomplish.
Furthermore, since the: sealing of bottom edge of positive "~, electrode canister 109 is performed by clamping only the edge of water repellant porous layer 108 between the sealing body 114 and the positive electrode canister 109, cracks of edge of water repellant porous layer 109 are apt to be produced so that perfect seal had been hard to obtain.
Since the alkaline electrolyte has a strong tendency of creeping and leakage through minute wrinkles or cracks of seal if produced, leakage of electrolyte may take place easily during the storage period or during the usage thereof.
1o Moreover, the conduction from positive electrode 103 to positive electrode canister 109 is performed by the mechanical contact of positive electrode 103 and positive electrode cap terminal 116 accomplished by the bending of the top rim of positive electrode canister 109, these contacts may become unstable by vibration or shock applied on the cell, making the electric-current supply unstable.
SUMMARY OF THE INVENTION
The purpose of this invention is to offer a new air-cell structure by which the top and bottom of the cylindrical positive electrode consisted of collector and catalyst layers and water-repellant porous layer are sealed liquid tight, preventing the external leakage of electrolyte held within the positive electrode.
Therefore, according to a first broad aspect, the invention seeks to provide a cylindrical air-cell provided with a cylindrical positive electrode comprised of a metallic collector layer, a catalyst layer disposed on a side wall of a metallic collector, and a porous layer disposed on an external surface of the catalyst layer. An outer cap-shaped metal cup is fitted to an outer wall of an upper edge of the porous layer and an inner cap-shaped metal cup is fitted to an inner wall or an upper edge of the catalyst layer.
-3a-According to a second broad aspect, the invention also seeks to provide a cylindrical air-cell provided with a cylindrical positive electrode comprised of a cylindrical metallic collector layer having a bent part formed on a top edge of the collector layer by bending an upper edge of the collector layer inwardly, a catalyst layer disposed on a side wall of a metallic collector, and a porous layer disposed on an external surface of the catalyst layer. An outer cap-shaped metal cup is fitted to an outer wall of an upper edge of the porous layer and an inner cap-shaped metal cup is fitted to an inner wall of an upper edge of the catalyst layer, and the bent part of the collector layer is held between the outer cup and the inner cup.
The invention seeks to provide, in accordance with a third broad aspect, a cylindrical air-cell provided with a cylindrical positive electrode comprised of a cylindrical metallic collector layer having a bent part formed on a top edge of the collector layer by bending an upper edge of the collector layer inwardly, a catalyst layer disposed on a side wall of a metallic collector, a gas diffusion layer disposed on an external surface of the catalyst layer, and a porous layer disposed on an external surface of the gas diffusion layer. An outer cap-shaped metal cup is fitted to an outer wall of an upper edge of the porous layer and an inner cap-shaped metal cup is fitted to an inner wall of an upper edge of the catalyst layer, and the bent part of the 2o collector layer is held between the outer cup and the inner cup.
According to a fourth broad aspect, the present invention seeks to provide a cylindrical air-cell provided with a cylindrical positive electrode comprised of a metallic collector layer, a catalyst layer disposed on a side wall of a metallic collector, and a porous layer disposed on an external surface of the catalyst layer, wherein an outer cap-shaped metal cup is fitted to an outside wall of an upper edge of the porous layer and an inner cap-shaped metal cup is fitted to an inner side wall of an upper edge of the catalyst layer, and the positive electrode equipped with a terminal part on top of the positive electrode, is housed in a cylindrical positive electrode canister, and the terminal part and the outer cup are welded together, and an outer rim of the outer cup located outside of a welded part of the terminal part and the outer cup and an inner rim surface of the positive electrode canister facing to the outer rim of the outer cup is electrically insulated.
-3b-The invention also seeks to provide, in accordance with a fifth broad aspect, a cylindrical air-cell provided with a cylindrical positive electrode comprised of a cylindrical metallic collector layer having a bent part formed on a top edge of the collector layer by bending an upper edge of the collector layer inwardly, a catalyst layer disposed on a side wall of a metallic collector, and a porous layer disposed on an external surface of the catalyst layer. An outer cap-shaped metal cup is fitted to an outer wall of an upper edge of the porous layer and an inner cap-shaped metal cup is fitted to an inner wall of an upper edge of the catalyst layer, and the positive electrode is housed in a cylindrical electrode canister provided with a terminal part on 1o top of the positive electrode, and the terminal part and the outer cup are welded together, and an outer rim of the outer cup located outside of a welded part of the terminal part and the outer cup and an inner rim surface of positive electrode canister facing the outer rim of the outer cup is electrically insulated.
According to a sixth broad aspect, the invention seeks to provide a cylindrical air-cell provided with a cylindrical positive electrode comprised of a metallic collector layer, a catalyst layer disposed on a side wall of the metallic collector layer, and a layer disposed on an external surface of the catalyst layer, wherein a resin sealing body provided with a ring-shaped indentation is disposed on an edge of a positive 2o electrode canister holding the positive electrode, and a side of the positive electrode canister is pressed against an outer sidewall of the resin sealing body.
According to a seventh broad aspect, the following invention also seeks to provide a cylindrical air-cell provided with a cylindrical positive electrode comprised of a cylindrical metallic collector layer, a catalyst layer disposed on a side wall of the metallic collector layer, and a porous layer disposed on an external surface of the catalyst layer. A resin sealing body consisting of a resin mold body provided with a ring-shaped indentation is fitted to a bottom of the positive electrode and another resin mold body holding the resin mold body, is disposed on an edge of a positive electrode 3o canister in which the positive electrode is held, and a side of the positive electrode canister is pressed against an outer sidewall of the resin sealing body.
3c -The following invention also seeks to provide with an eighth broad aspect, a cylindrical air-cell provided with a cylindrical positive electrode comprised of a cylindrical metallic collector layer, a catalyst layer disposed on a side wall of the metallic collector layer, and a porous layer disposed on an external surface of the catalyst layer. A separator is disposed on an inner surface of the positive electrode, and a resin mold body holding both a ring-shaped resin sealing body on which a ring shaped indentation fitted to the bottoms of the positive electrode and the separator is provided and another resin sealing body holding the resin mold body, and a side of a positive electrode canister is pressed against an outer sidewall of the resin sealing 1 o body.
According to a ninth broad aspect, this inventions seeks to provide a cylindrical air-cell comprising a cylindrical positive electrode that comprises a metallic collector layer, a catalyst layer disposed on the side wall of the metallic collector, a porous layer disposed on the external surface of the catalyst layer, a first resin mold element provided with a ring-shaped indentation, a second resin mold element and a positive electrode canister. 'The ring-shaped indentation holds an end of the positive electrode, the second resin mold element holds the first resin mold element, the first resin mold element, the second resin mold element and the cylindrical positive electrode are fitted within the positive electrode canister which is arranged to press against the outer side wall of the first and the second resin mold elements to provide a seal therewith.
In order to accomplish the present purposes, the cylindrical mufti-layer positive electrode of the invented air-cell is constituted of a metallic collector, catalyst layers disposed on both sides of the metallic collector, and a porous layer disposed on the catalyst layer wherein an external cup and an internal cup are pressed on the external top rim of the porous layer and internal top rim of catalyst layer of the positive electrode respectively.
' 9 4~ 12~ 12 ~ (~j) 14 :15 ~l; ~, 7 I~ ~ - 3~ 1s fl; F ~x ill I~ is 'J - t 1, b~ 3~ z #1 F 0 5 ~~~a~ ~~
Moreover, as s metallic collector constitutl.ng Raid positive electrode, a cylindrical metallic collector layer of which top is inwardly bent can be employed, and said external metal cup pressed on the external top rim of said porous layer and Bald internal metal cup pressed on the internal top rim of catalyst layer are closely contacted on said inwardly bent part of said metallic collector.
Likewise, said cylindrical positive electrode may well be constituted of a gas diffusion layer disposed on the outer sur-faee of said catalyst layer and a porous layer disposed on the outer surface of said gas diffusion layer, and a cap-shaped external metal cup may be pressed on the external top rims of said porous 7.ayer and a cap-shaped internal metal cup may be pressed on the internal top rim of said catalyst layer respec-tively. though said the bent part of said metallic collector may well be held and clamped between said external and internal metal cups.
In another structure of the invented air-cell, a metallic external cup is disposed on the outer top rim of said porous layer, a metallic external cup is disposed on t;he internal top rim of said catalyst layer of said positive electrode, said positive electrode is inserted in a cylindrical positive elec-trode canister, and then the said outer metallic cup i.s welded to said terminal, and the outer rim of said outer cup positioned outside of the welded part of said outer cup and said terminal and the internal surface of said positive electrode canister facing to the outer rim of said outer cup can be elecCricall.y insulated. In this case, a metallic collector layer of which top rim is bent inwardly, may be used.
In the still other structure of the invented air-cell, a resin seal provided with a ring-shaped indentation fitted to the bottom of said positive electrode is used as a bottom seal of said positive electrode. In this case, the bottom of said posi-tive electrode is inserted in said ring-shaped indentation, and 'q4~l~,~l~.~r,~l~aoh ~n:~ ~~t- _. ~f~;~F~itifi~~~~-Y~.~~=~t said resin seal is inserted in said positive electrode canister.
After this, the side of resin seal is so pressed against the opposing inner wall of the positive-electrode canister that the bottom of positive electrode and the indentation of resin seal are contacted c.l.osely.
Moreover, in another structure of the invented air-cell.
said resin seal provided with a ring-shaped indentation to which the bottom of separator disposed on the positive electrode or on the inner wall of positive electrode is fitted, can be employed.
In still another structure of the invented air-cell., said resin seal may well be constituted of two elements, 1.e., a seal provided with a ring-shaped indentation fitted to the bottom of said positive electrode or an indentation fitted to both the bottoms of positive electrode and said separator, and an in-dependent seal by which this seal can be held.
According to the above described explanations, the functions of the inventions are as follows.
The top of a positive electrode consists of a metallic collector layer, a catalyst layer disposed on the side of said collector layer, and a porous layer held between two metal cups of different inner diameters, and the sides of said metal cups are pressed against said positive electrode, and by this, the top of said positive electrode can be completely sealed without producing cracks or wrinkles poRSible on said positive electrode so that the leakage of electrolyte from the top of positive electrode can be completely prevented.
In another case, a high electrical conductivity between the positive electrode and the metal cups can be obtained by employ-ing a cylindrical collector layer of which top rim is inwardly bent, and by welding the bent rim to the inner wall of said outer cup, and by pressing said outer cup and inner cup to said bent rim of coll.eetor. Moreover, a high electrical conductivity or low 's~y2y2B(~)m:ii ~~C ~h~- ~r ~;~~~i~~~~!-t~bR~~~l Fog internal cell resistance can be obtained by welding the top of said outer cup to the inner wall of said positive electrode canister, preventing contact failures between the collector and the cups even if unexpected shocks or vibration are applied to the cell.
Moreover, the bottom of positive electrode can be sealed completely by pressing the bottom of positive electrode against the indentation of resin sealing, and by applying a mechanical pressure on the positive electrode canister at the side of indentation after the bottom of positive electrode is inserted into the indentation of resin seal.
Furthermore, by inserting the bottom of separator into the indentation of resin seal, not only the excessive stress applica-tion on the positive electrode at sealing process can be avoided.
but the sealing performance can also be improved. Thus, the leakage of electrolyte and the shorts between the positive and the negative electrodes can be prevented improving the cell reliability further.
BRIEF DESCRIPTION OF TfIE DRAIIINGS
Fig. 1 shows a side view of the partly cut--off cylindrical zinc air-cell which is a first embodiment of the invention.
Fig. 2 shows an enlargement of the part-A of Fig. 1.
Fig. 3 shows an enlarsed cross-section of the top edge of modified positive -electrode of the cylindrical zinc air-cell shown in Flg. 1.
Fig. 4 shows a top view of the outer cup of cyll.ndrical zinc air-cell shown in Fig. 1.
Fig. 5 shows a cross-section of the outer cup of cylindrical '94~.12~128~~)14:32 ~~ ~Fi'- ~F ~~~~i9~~a~'-~~~~~#~ F02 zinc air-cell shown in Flg. 4, sectioned at Line A-B.
Fig. 6 shows an enlarged cros9-section of the tap edge of positive electrode of the cylindrical zinc air-cell which is a second embodiment of the invention.
Fig. 7 shows a aide view of the partly cut-off cylindrical zinc air-cell which is a third embodiment of the invention.
Fig. 8 shows a side view of the partly cut--off cylindrical zinc air-cell which is a fourth embodiment of the invention.
Fig. 9 shows a side view of the partly cut-off zinc cylind-rieal~air-cell which is a Tifth embodiment of the invention.
Fig. 10 shows a side cross-section of the ring-shaped resin mold employed in the cylindrleal air-cell shown in ~lg. 9.
Fig. 11 shows a side view of the partly cut-off modified cylindrical zinc air-cell which is a fifth embodiment of the invention.
Fig. 12 shows a side view of the partly cut-off cylindrical zinc air-cell which is a sixth embodiment of the invention.
Fig. 13 shows a side view of the partly cut-off modifled cylindrical zinc air-cell which is shown in Fig. 1.2.
Fig. 14 shows a side view of the partly cut-off conventional cylindrical zinc air-cell.
DESCRIPTION OF TIiF ~ PREI%EBRCD CMBODxI~NTS
(L~'mbod.iment-1 Fig. 1 shows a side view of the partly cut-aft cylindrical ~13~1 1 ~
zinc air-cell which is a first embodiment of the invention. Fig. 2 shows an enlargement of the part-A of Fig. 1, and Fig. 3 shows an enlarged cross-section of the top end of modified positive electrode of the cylindrical zinc air-cell shown in Fig. 1.
In Figs. 1 to 3, 1 is a cylindrical negative electrode in which an active material of so-called jellied zinc and collector 2 are incorporated, 3 is a multilayered c~yl.indrica.l positive electrode comprised of a catalyst layer 4 employing manganese oxide and carbon materials as main element,, collector layer 5 consisted of nickel plated stainless steel mesh disposed within catalyst layer 4, and a water-repellant porous layer b consisted of fluororesin contacting with a surface of catalyst layer 4, 7 is a separator disposed within catalyst layer 4 of positive electrode 3, within which negative electrode 1 is disposed, 8 is an air diffusion layer made of non-woven polypropylene fabric, 9 is a pos.i.tive electrode canister on which positive elecarode cap terminal 16 is integrally molded at its top, 10 is an air-intake hole provided on the positive electrode canister 9, 11 is an insulation tube, 12 is an air-intake window provided on insulation tube 11., 13 is a seal sealing the air-intake window until the cell operation, 14 is a seal made of resin, 15 is a bottom plate for negative electrode terminal, 17 is a sealing material, and 18 is a base paper. In place of metal mesh, an expanded metal or a punched metal may be used.
The manufacturing process of positive electrode 3, is began with a spot welding process overlapping the both ends of long collector layer forming collector 5 into a cylindrical shape and placing the overlapped part at a surface comm«n with the side surface of collector 5, and a preformed catalyst layer 4 is then pressed on the both surfaces of cylinde>.r-shaped collector 5.
The material of catalyst layer 4 is prepared by mixing activated carbon, manganese oxide, acetylene-black, and fluororesin powder at a predetermined mixing ratio, and b~Y~ further. kneading of the mixture after a proper amount of ethylal.cohol is added. Then, this kneaded mixture is extruded into a strip sheet having r.::
fl '94~12~12H(~114:33 ~~ ~~t- ~~ ~~~~~~~t-ez~~nft Po4 2~.~g~.~~
a thickness of about 0.6 mm. Said manganese oxide is prepared by applylna a beat-treatment on y-MnOOii 1n a nitrogen atmosphere at a temperature of 400°C. and said fluororesin powder is derived from polytetrafluoroethylene (PTF'E~ resin. Granulated or chained activated carbon having a particle diameter of 10 1:0 40 microns is used in this case.
On the other hand, a fluororesin dispersant containing PTFfi resin is coated on a surface of catalyst layer 4 and is dried at a temperature of 230°C. By this. the electrolyte can be easily permeated into the electrode. and obstruction of oxygen gas supply to the positive electrode can be prevented, The reason of the employment of a drying temperature of 230°C is to disperse the surface active agent coni:ained in the dispersant.
A gas-permeable water-repellant fluororesin layer is then pressed on the surface coated with fluororesin dispersant in order to obtain porous layer B of positive electrode 3 act as an air electrode. Thus prepared positive electrode 3 is wound involute in a form of cylinder to face catalyst layer 4 inwardly.
Then. inner cup 20 and outer cups 19 both made of nickel plated steel plate are disposed on the top of cylindrical posi-tive electrode 3, so that outer cup 19 is contacted with the outer rim while inner cup 20 is contacted with the Inner rim of the top edge oP said porous layer 5. As a result oP this, posi-tive electrode 3 can be sealed at a condition where the top edge of positive electrode 3 is held between the outer cup 19 and inner cup 20. Since the outside of outer cup rim is grooved by using a roller and is pressed against the outer surface of positive electrode 3 while inner cup 20 is widened within a space of catalyst layer 4 and pressed against the inner wall of posi-tive electrode 3, positive electrode 3 is held and clamped between the inner cup 20 and the outer cup 19 forming an air-tight and leakage-free sealing.
Furthermore. as shown in Fig. 3, the entire inner surface '94~12~128(~?14:34 ~~ ~~i~- ~ ~;~F~~i~~~~-e~~~~ff F05 of outer cup 19 is coated with a synthetic rubber sealing material made mainly of chlorosulionated-polyethylene for example forming a sealing lnyer 22, in order to improve the air-tightness and leakage-proof performance realizing high reliability of the sealing.
Thus, after sealing the top of positive electrode 3, the external surface of porous layer 8 and the area from the outer rim of outer cup 1S to the upper round-oti part nre wrapped h9 air-diffusion layer e.
As shown ltz Figs. 4 and 6. ~~nsi l pra~;ru5~icr~8 23 ere ~1sp09e~
o~ the ext~er~$1 ~Qp ~~e~f~c~e off' out~f cup ~9 at ~hro~ counts 8va.ldlng a strs~ght line disposition, and these small protrusions 23 are spot-welded on the inner surface of terminal ).6 of posi-tive electrode cap, disposed on the top of positive electrode canister 9.
Moreover, the top of said air-diffusion layer a is disposed between the outer rim of outer cup 18 located outside oP said small protrusions 23 and the inner side surface of positive elec-trode canister 9 opposing to these protrusions in order to avoid the contact of outer cup 18 to positive electrode canister e.
8y employing the above-described cell construction, since the eddy current produced at welding of small protrusions onto the top inner surface of positive electrode canister 9 is concentrated only to the small protrusions of outer cup 19. a higher welding strength and better appearance welding between the positive electrode canister a and the small protrusions can be obtained. Moreover, because of an opening 21 provided on the top center of inner cup 20, a welding rod can be inserted through opening 21 when positive e).ectrode canister 9 is welded to the outer cup I9 so that the welding bar can be contacted with outer cup 18 and the welding oP these components cnn be performed easily at a better stabilized condition.
-~. ~C~ '-z~3~~ 15_ Furthermore, instead of the non-wooer. fabric, air diffusion layer 6 covering the outside surface of porous layer 8 and the area from the outer side surface to the top of ~::up 19 can be formed by using a heat-shrinking porous resin tube ma de of a resin material such as air-permeable polyethylene terephtha.Late (PET) or a heat shrinking tube with small openings prepared in advance.
The bottom edge of positive electrode 3 is formed by bending the bottom edge of positive electrode 9 against the rim of sealing body 14 and by clamping, and by placing the lower edge of porous layer 6 between the sealing body 14 and the positive electrode canister 9 and by filling the gap with a seal:i.ng material 17.
Ten of the cylindrical zinc air-cells ~ are constructed according to Embodiment-7. shown in Fig. l, ten conventional cylindrical zinc air-cells C are constructed by bending the top edge of positive electrode inwardly and contacted with the bent part as shown in Fig. 14. Ten cylindrical zinc air-cells B are constructed according to Embodiment-1 shown in Fig. 3 but with sealing layer 22 is formed on the inner surface of outer cup ~-9, and ten conventional cylindrical zinc air-cells D with sealing layer 22 formed at the top edge of positive electrode, are prepared.
The storage characteristics of these cells are comparatively tested at a storage temper<~ture of 60°C and the result o:E these are shown in Table 1.
~3~115_ Table 1 Storage Period(at 60C) Tested cellsSealing 1 week 2 weeks 3 weeks 1 month applied on outer cup Cell A None 2/10 8/10 10/i0 -(Fig. 1) Cell B Yes C/10 0/10 0/10 0/10 (F.ig. 3) Cell C None 10/10 - - -(conventional) Cell D Yes 10/10 - - -(conventional) As shown in Table l, the conventional zinc air-cells C and D
showed very severe electrolyte leakages within very short periods, regardless of the coating of sealing material.
On the other hand, none of the zinc air-cells B of Embodiment-1 showed leakage after a storage period of one month at ~0°C while all of the zinc air-cells ~~ showed leakage after a storage period of three weeks.
Therefore, significant improvements of leakage stopping characteristics obtained by the invented zinc air-cells over those of conventional zinc air-cell:, are confirmed, in addition to further improvements obtained with sealing layer 22 formed on the internal surface of outer cup 19.
However, when the width of overlapped region of the cylindrically formed col-'-ect_or is inadequate, ar_ insufficient tensile strength of the overlappE:d region would be produced.
Therefore, when a volume expansion of the zinc negative electrode 1 is produced at discharge, breakage of: welded points at the edges of collector may take place, causing electrolyte leakage. Thus, at least an overlap width of 1.3$ of the circumference of collector layer 5 has to be provided.
On the other hand, wPen said overlapped width is too large, the collector area providing minute holes ar_e plugged, sacrificing the discharge capacity somewhat. The sacrifice cf discharge capacity can be minimized by setting the overlapped width at less than 9°s of the total circumference of collector layer 5.
Although a case where the both ends of long stainless steel mesh strip are over-lapped to constitute a cylindrical collector is shown here, the collector of the same function can be obtained by weaving a long horizontal. metal thread into a number of independent vertical fine metal wires formed into a shape of cylinder.
Both the horizontal and vertical met<31 wires in this case, could be nickel plated stainless steel wire or nickel ware, and in this case, erosion of c:ol.l.ector by the al_ka!ine electrolyte can be minimized so that the storage characteristics of cell can be improved.
(Embodiment-2) A bent part 2.4 formed by bending the top edge inwardly is provided on cylindrical collector 5 as shown in Fig. 6. By pressing and fitting outer cup 19 onto both the upper surface of bent part 24 and the upper edge rim of porous layer 6, and by pressing and fitting the inner cup 20 onto both the lower surface of bent part 24 and the inner rim o:f upper edge of catalyst .Laye.r 4, the bent part 24 can be held and clamped between the inner cup 1y and the outer_ cup 20. At this condition, outer cup 1'a and bent part 24 can be welded together.
A cylindrical air-cell acco;.-ding to the above shown cell construction yet having a cell construe~ion identical with those shown in Fig 1 for the rest of the cell, is fabrir_ated, and this cell is named as cell E of the embodiment of the invention.
,,'"''. 13 '94~12~128(~)14:36 ~~ ~ht- ~fi ~;~F~~'~~~'-~~~~~~t P09 Ten each of Cells E and A are prepared and the internal cell resistances are determined, and the results of these are listed in Table 2.
Table 2 Right after cell After 20 day storng~s assembly (in A) at fi0°C (.1n n) Invented Cell-F. x 0.1.54 ~c 0.186 (Fig. 6) Max 0.17 Max 0.20 Min 0 . 14 Min O , l.6 0~_1 0.010 on_1 0 .015 Invented Cell-A x 0.216 x 0.352 (Fig. 1) Max 0.27 Max 0.37 Min 0,18 Min 0.31 oA_1 O. 218 aA_1 O .
As shown in Table 2, substantial decreases of the internal.
resistance resulted from the closer contacts of bent part 24 of collector layer 5 to outer cup 19 and inner cup 20 is proved by cell F which is an embodiment of the invention.
This result proved that the internal resistance can be kept at low even after a storage period of 20 days at 60°C. The advan-tages of cell G have been confirmed with the cells assembled by using no welding of bent part 24 to collector layer 5 but is merely held between these two elements.
(Embodiment-3) Resin sealing body 14 sealJ.ng the bottom of c:yllndrlcal positive electrode 3 l.iqui.cf t.l.ght, may be provided w1 th a ring-'94~12~128(~)14:41 ~i~ ~ht- ~1~ ~;~~~fi~~~'-e~~~~ff P02 shaped indentation 25 to which the bottom of positive electrode 3 is fitted as shown in Fig. '7. After sealing body 1.4 provided with indentation 14 to which the bottom of positive electrode is fitted, i.s inserted into positive electrode canister 9, groove 26 is formed on the side wall of positive electrode canister 9 by applying an external mechanical pressure on sealing body 14.
Hy this, the side wall of sealing body 14 is pressed closely against positive electrode canister a and at the same time, the lower edge of positive electrode 3 is fitted liquid tight to indentation 25 of sealing body 14, sealing tlae bottom of positive electrode 3 completely.
In addition to the above, the sealing condition of the bottom of positive electrode canister can be further improved by applying a sealing agent in a gap between the side of resin sealing body 14 and the side of positive electrode canister. The zinc air-cell assembled by using the above-explained aeallng body 25 is named as cell F is shown in Fig. 7. Ten each cells F and C are assembled and these are submitted to comparative three-mcinth storage tests conducted at a temperature of 60°C testing the leakage from the bottom of positive electrodes 3, and the results are tabulated in Table 3.
Table 3 Storage Period (at 60°C) Tested cells 10 days 20 days 1 month 2 months a months Cell r 0/10 0/10 0/10 0/10 0/10 Cell G O/10 0/10 0/10 0/10 O/10 Cell II 0/10 0/1.0 0/1.0 0/10 O/10 Cell I 0/10 0/10 0/10 0/10 0/10 Conventional 10/10 - - -Cell C
is '94'~12~12A(~114:42 ~~ ~ht- ~~ ~;~F~;~;fi~~~t-e'z~~r~t Po3 As shown in Table 3, as for the ten F cells wttlch are an embodiment of the invention, no leakage have beerx detected even after a three month storage period conducted at a temperature of 60°C .
(Embodiment-4) As shown in Fig. 8, resin sealing body 14 may be constituted of a ring-shaped resin mold element 27 provided with indentation 25 to which the bottom of positive electrode 3 is fitted, and a convex resin mold element 28 holding said resin mold element 27.
The zinc air-cell assembled by employing sea:line body 14 of this construction is named as cell G which is an embodiment of the invention and is shown in Fig. 8.
Table 3 shows a result of the storage test same as the case of Embodiment-3 conducted by usl.ng cell G, Likewise. no cell leakage have been found even after three month storage period conducted at a temperature of 60°C.
( Gmbodirnen t-a ) As shown in I~ig. 9, metal ring 29 may be disposed between the resin mold element 27 and resin mold body 28 in Embodiment-4.
The cylindrical air-cell assembled by using the thus constructed sea:llng body 14 is designated as cell Ii of Embodiment-5 of the invention, and this is shown in Fig. 9.
The results of the test of cell 1l, conducted under a condition same as the one in Embodiment-3 is shown in Table 3 which shows no leaked cells after a three month storage test conducted at a temperature of 60°C.
Moreover, in the cased of Embodiments -4 and -5, the work to insert the bottom of positive electrode into indentation 25 can be simplified and easier by making the ring-shaped i_nden-2 '~ 3 ~ 1 1 5 _.
tation 25 of resin mold element 27 in a form of tapered side-wall 30 which is expanded gradual:l.y upward.
When the cylindrir.:al zinc air-cell of the invention is assembled by using the above explained sealing body 14, after air diffusion layer 8 is disposed on the outside of positive electrode 3 to which outer cup 19 and inrner cup 20 are fitted to the top of said positive electrode, these are inserted into positive electrode canister 9, the bottom <:af positive electrode 3 is inserted into indentation 25 of said resin mold element 2';', and the concave metal-ring holding part 31 provided on the side of resin mold element 27 is positioned at metal ring 29.
Then, by using a roller, a mechanical pressure is applied on the side of positive electrode canister 9 facing to the side of resin mold element 27, and by this groove 2n is formed. Although a pressure is applied on both the resin mold element 27 and the positive electrode r_aniste:r 9, movements of resin mold element 27 in the direction of pressure application can be blocked by means of metal ring 29, and the sealing between the resin :hold element 27 and the bottom of positive electrode 3 can be further improved.
By providing step part 32 at the upper part of the inner sidewall of indentation 25 as shown in fig. 10 ir_ order to hold the lower edge 33 of separator 7, a cell structure shown in Fig. 11 can be obtained, and the pos:>ibility of shorts between the positive electrode 3 and the negative electrode 1 can be completely eliminated.
(Embodiment-6) As shown in Fig. 1.2, a cylindrical air-cell of which top edge of positive electrode 3 have a structure shown i.n Fig. 6 is prepared, and this cell is specified as cell I of Embodiment-~6 of the invention here. This cell I is submitted to test the same as the previously conducted one, and the resu-i.t of this is shown ,. 1 '7 in Table 3.
Again as shown in Table 3, no cells I showed electrolyte leakage after a three month storage test conducted at a temperature of 60°C.
Moreover, as shown in Figure 1.3, although the resin mold element 28 consists of pi.Llar shaped base 34 and pillar 35 having a diameter smaller than the base 34 disposed c>n the center of base 34, by providing concave part 36 at a position under base 34 and outer side of pillar 35, and by inserting metal washer 37 therein as shown, the position of resin mold element 28 can be fixed more tightly when the bottom of positive electrode canister is bent and clamped on the resin mold element 28, and thus the positive electrode canister 9 and the resin mold element can be pressed more tightly.
Although a fluororesin porous layer is disposed at the outside of positive electrode 3 in this embodiment of the invention, a better effect can be obtained by employing a gas diffusion layer made of a sheet made of acetylene-black and fluorores.in powder improving the oxygen gas supply to positive electrode 3.
As above explained >o far, the cylindrical air-cell of the invention consists of a metallic collector Layer, a catalyst layer disposed on the side of said metal l.i.c collect: or layer, and a porous layer acting as a cylindri<:al ai.r electrode di sposed on the outside of said catalyst layer, and is provided with an outer metal cup pressed on the outer top ed<7e of said positive electrode and an inner metal cup pressed on the ir:ner top edge of said positive electrode.
Since the top of positive electrode is pressed and clamped by said outer and inner cups, the sealing of the top of positive electrode can be substantially improved, offering air-cells having excellent sealing and leak-proof charar_teristics.
'94~12~12~(~)14:43 ~'~ 7~~'- ~fa "~~~~~~~'-l''7,~"~,~ff P06 Moreover, by providing a bent part at the top edge of metallic collector layer, by holding and claroplng said bent part against between said outer metal cup and inner metal cup, and by welding said collector layer and outer cup, the contacts between these elements can be held at a best condition, nullifying the possibility of internal resistance increase due to poor contacts between the collector layer and the outer and inner cups.
Furthermore, a resin mold body having a ring-shaped inden-tation fitted to the lower edge of positive electrode is disposed at the bottom of positive electrode, and after said resin mold body is inserted into the positive electrode canister, the aide of said positive electrode canister is inward:Ly pressed against the side of said resin mold body in order to improve the sealing between the bottom of positive electrode and the ring-shaped indentation of said resin mold body, thus improving the leak-proof characteristics of the bottom of positive electrode.
Claims (18)
1. A cylindrical air-cell provided with a cylindrical positive electrode comprised of a metallic collector layer, a catalyst layer disposed on a side wall of a metallic collector, and a porous layer disposed on an external surface of said catalyst layer, wherein an outer cap-shaped metal cup is fitted to an outer wall of an upper edge of said porous layer and an inner cap-shaped metal cup is fitted to an inner wall or an upper edge of said catalyst layer.
2. A cylindrical air-cell provided with a cylindrical positive electrode comprised of a cylindrical metallic collector layer having a bent part formed on a top edge of said collector layer by bending an upper edge of said collector layer inwardly, a catalyst layer disposed on a side wall of a metallic collector, and a porous layer disposed on an external surface of said catalyst layer, wherein an outer cap-shaped metal cup is fitted to an outer wall of an upper edge of said porous layer and an inner cap-shaped metal cup is fitted to an inner wall of an upper edge of said catalyst layer, and said bent part of said collector layer is held between said outer cup and the inner cup.
3. A cylindrical air-cell provided with a cylindrical positive electrode comprised of a cylindrical metallic collector layer having a bent part formed on a top edge of said collector layer by bending an upper edge of said collector layer inwardly, a catalyst layer disposed on a side wall of a metallic collector, a gas diffusion layer disposed on an external surface of said catalyst layer, and a porous layer disposed on an external surface of said gas diffusion layer, wherein an outer cap-shaped metal cup is fitted to an outer wall of an upper edge of said porous layer and an inner cap-shaped metal cup is fitted to an inner wall of an upper edge of said catalyst layer, and said bent part of said collector layer is held between said outer cup and the inner cup.
4. A cylindrical air-cell according to claims 1, 2 or 3 wherein said metallic collector is formed into a cylindrical form by overlapping and welding both ends of a long metal sheet selected out of metal mesh, expanded metal or punched metal sheet, and an area of said overlap is coplanar with said collector layer.
5. A cylindrical air-cell according to claims l, 2 or 3 wherein said metallic collector is formed into a cylindrical form by overlapping and welding both ends of a long metal sheet selected out of metal mesh, expanded metal, or punched metal, and a length of said overlap is within a range from 1.3% to less than 9.0% of the total circumference of said cylindrical collector layer.
6. A cylindrical air-cell according to claims 1, 2 or 3 wherein said metallic collector is formed by spirally weaving a single metal wire horizontally into a number of vertically disposed independent metal wires.
7. A cylindrical air-cell according to claims 1, 2, or 3 wherein said metallic collector is formed by spirally weaving a single metal wire horizontally into a number of vertically disposed independent metal wires, and at least one of said vertical wires or said horizontal wire is a nickel plated metal wire or nickel wire.
8. A cylindrical air-cell according to claims 1, 2, or 3 wherein an inner wall of said outer metal cup is coated with a sealing agent.
9. A cylindrical air-cell according to claims l, 2, or 3 wherein plural protrusions are provided on a top of said outer metal cup.
10. A cylindrical air-cell according to claims 1, 2, or 3 wherein an opening is provided on a top of said inner metal cup.
11. A cylindrical air-cell according to claims 2, or 3 wherein an opening is provided at a center of said inner metal cup, and said bent part of said metallic collector layer and said outer metal cup is welded together.
12. A cylindrical air-cell according to claims 1, 2, or 3 wherein said catalyst layer includes manganese oxide and carbon material.
13. A cylindrical air-cell provided with a cylindrical positive electrode comprised of a metallic collector layer, a catalyst layer disposed on a side wall of a metallic collector, and a porous layer disposed on an external surface of said catalyst layer, wherein an outer cap-shaped metal cup is fitted to an outside wall of an upper edge of said porous layer and an inner cap-shaped metal cup is fitted to an inner side wall of an upper edge of said catalyst layer, and said positive electrode equipped with a terminal part on top of said positive electrode, is housed in a cylindrical positive electrode canister, and said terminal part and said outer cup are welded together, and an outer rim of said outer cup located outside of a welded part of said terminal part and said outer cup and an inner rim surface of said positive electrode canister facing to said outer rim of said outer cup is electrically insulated.
14. A cylindrical air-cell provided with a cylindrical positive electrode comprised of a cylindrical metallic collector layer having a bent part formed on a top edge of said collector layer by bending an upper edge of said collector layer inwardly, a catalyst layer disposed on a side wall of a metallic collector, and a porous layer disposed on an external surface of said catalyst layer, wherein an outer cap-shaped metal cup is fitted to an outer wall of an upper edge of said porous layer and an inner cap-shaped metal cup is fitted to an inner wall of an upper edge of said catalyst layer, and said positive electrode is housed in a cylindrical electrode canister provided with a terminal part on top of said positive electrode, and said terminal part and said outer cup are welded together, and an outer rim of said outer cup located outside of a welded part of said terminal part and said outer cup and an inner rim surface of positive electrode canister facing said outer rim of said outer cup is electrically insulated.
15. A cylindrical air-cell according to claims 13 or 14 wherein a protrusion is provided on a top of said outer metal cup and said protrusion is welded on an internal surface of said terminal part on positive electrode canister.
16. A cylindrical air-cell according to claims 13 or 14 wherein a non-woven fabric is disposed between the outer rim of the outer cup locating at an outside of a protrusion provided at a top edge of metal outer cup and an outer surface of said porous layer, and an internal surface of said positive electrode canister.
17. A cylindrical air-cell according to claims 13 or 14 wherein a heat-shrinking porous resin tube having a high air permeability is disposed between the outer rim of the outer cup located at the outside of a protrusion provided at a top edge of the outer cup and an outer surface of said porous layer, and an internal surface of said positive electrode canister.
18. A cylindrical air-cell according to claims 13 or 14 wherein a heat-shrinking porous resin tube having a high air permeability is disposed between the outer rim of the outer cup located at the outside of a protrusion provided at a top edge of said outer cup and an outer surface of said porous layer, and an internal surface of said positive electrode canister, and openings are provided on a side wall of the heat-shrinking porous resin tube.
Applications Claiming Priority (18)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31315693 | 1993-12-14 | ||
| JP734194 | 1994-01-27 | ||
| JP1094094 | 1994-02-02 | ||
| JP1204294 | 1994-02-04 | ||
| JP1911694 | 1994-02-16 | ||
| JP2228194 | 1994-02-21 | ||
| JP2956794 | 1994-02-28 | ||
| JP5-313156 | 1994-10-05 | ||
| JP6-19116 | 1994-10-05 | ||
| JP24123194 | 1994-10-05 | ||
| JP6-7341 | 1994-10-05 | ||
| JP6-10940 | 1994-10-05 | ||
| JP6-12042 | 1994-10-05 | ||
| JP6-22281 | 1994-10-05 | ||
| JP6-29567 | 1994-10-05 | ||
| JP6-241231 | 1994-10-05 | ||
| JP6-283353 | 1994-11-17 | ||
| JP28335394A JP3475527B2 (en) | 1993-12-14 | 1994-11-17 | Cylindrical air battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2138115A1 CA2138115A1 (en) | 1995-06-15 |
| CA2138115C true CA2138115C (en) | 2007-01-30 |
Family
ID=27576548
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002138115A Expired - Fee Related CA2138115C (en) | 1993-12-14 | 1994-12-14 | Cylindrical air-cell |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US5518834A (en) |
| EP (2) | EP0920066B1 (en) |
| JP (1) | JP3475527B2 (en) |
| CA (1) | CA2138115C (en) |
| DE (2) | DE69433697T2 (en) |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6261709B1 (en) | 1998-03-06 | 2001-07-17 | Rayovac Corporation | Air depolarized electrochemical cell having mass-control chamber in anode |
| US6368738B1 (en) | 1998-03-06 | 2002-04-09 | Rayovac Corporation | Air depolarized electrochemical cell |
| US6436571B1 (en) * | 1998-03-06 | 2002-08-20 | Rayovac Corporation | Bottom seals in air depolarized electrochemical cells |
| US6294283B1 (en) * | 1998-08-21 | 2001-09-25 | Eveready Battery Company, Inc. | Electrochemical cell having low profile seal assembly |
| JP2000277178A (en) * | 1999-03-26 | 2000-10-06 | Sony Corp | Air battery |
| US6265104B1 (en) | 1999-08-13 | 2001-07-24 | The Gillette Company | Hot-melt seal for metal-air battery |
| US6479188B1 (en) | 1999-10-13 | 2002-11-12 | The Gillette Company | Cathode tube and method of making the same |
| US6372370B1 (en) * | 2000-01-19 | 2002-04-16 | The Gillette Company | Air recovery battery |
| US6423438B1 (en) | 2000-01-31 | 2002-07-23 | The Gillette Company | Method for sealing battery container |
| US6399243B1 (en) * | 2000-04-06 | 2002-06-04 | The Gillette Company | Air recovery battery |
| US7238448B1 (en) | 2000-04-26 | 2007-07-03 | The Gillette Company | Cathode for air assisted battery |
| US20040048146A1 (en) * | 2002-09-06 | 2004-03-11 | David Adamson | Electrochemical cells and systems |
| US7332238B2 (en) * | 2002-09-06 | 2008-02-19 | The Gillette Company | Electrochemical cells and systems |
| US7455929B2 (en) * | 2003-11-26 | 2008-11-25 | Eveready Battery Company, Inc. | Air cell with improved leakage resistance |
| JP4927071B2 (en) * | 2005-03-10 | 2012-05-09 | エバレデイ バツテリ カンパニー インコーポレーテツド | Air cell with improved leakage resistance |
| US20070141440A1 (en) * | 2005-12-21 | 2007-06-21 | General Electric Company | Cylindrical structure fuel cell |
| WO2013161253A1 (en) * | 2012-04-25 | 2013-10-31 | Hitachi Zosen Corporation | Functional porous material, metal-air battery, and method for manufacturing functional porous material |
| BR112017007901B1 (en) * | 2014-10-16 | 2021-07-13 | Spectrum Brands, Inc | ZINC-AIR BATTERY |
| CN107579312B (en) * | 2017-08-03 | 2020-01-31 | 中国科学技术大学 | zinc-air battery with winding structure |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1317214A (en) * | 1970-08-12 | 1973-05-16 | Hitachi Maxell | Metal/air or metal/oxygen cells |
| GB1350495A (en) * | 1971-09-14 | 1974-04-18 | Energy Conversion Ltd | Electrochemical cells |
| GB1459135A (en) * | 1974-04-02 | 1976-12-22 | Nabiullin Faat Khatovich | Alkaline galvanic cell |
| US4066822A (en) * | 1976-09-28 | 1978-01-03 | P. R. Mallory & Co. Inc. | Self sealing microporous membrane for electrochemical cells and method of forming same |
| JPS5889772A (en) * | 1981-11-20 | 1983-05-28 | Matsushita Electric Ind Co Ltd | Production method of button type air cell |
| JPS5999656A (en) * | 1982-11-30 | 1984-06-08 | Toshiba Corp | Cylindrical air cell |
| JPS5999657A (en) * | 1982-11-30 | 1984-06-08 | Toshiba Corp | Cylindrical air cell |
| JPS6054164A (en) * | 1983-09-05 | 1985-03-28 | Toshiba Corp | Zinc air battery |
| US4666799A (en) * | 1983-09-19 | 1987-05-19 | Medtronic, Inc. | Current collectors for batteries having cathode-electrolytes and batteries incorporating same |
| CA1265189A (en) * | 1984-08-17 | 1990-01-30 | Gregory S. Kulibert | Seal for alkaline primary battery |
| US4756983A (en) * | 1987-11-23 | 1988-07-12 | Eveready Battery Company | Cell circuit interrupter |
| US5008161A (en) * | 1989-02-01 | 1991-04-16 | Johnston Lowell E | Battery assembly |
| JPH0834098B2 (en) * | 1989-02-07 | 1996-03-29 | 日立マクセル株式会社 | Cylindrical organic electrolyte battery with PTC element |
| JPH0547388A (en) * | 1991-08-08 | 1993-02-26 | Matsushita Electric Ind Co Ltd | Cylindrical air zinc battery |
| JP3039055B2 (en) * | 1991-11-25 | 2000-05-08 | 松下電器産業株式会社 | Manufacturing method of cylindrical air cell and cylindrical air electrode |
-
1994
- 1994-11-17 JP JP28335394A patent/JP3475527B2/en not_active Expired - Fee Related
- 1994-12-14 EP EP98204139A patent/EP0920066B1/en not_active Expired - Lifetime
- 1994-12-14 DE DE69433697T patent/DE69433697T2/en not_active Expired - Fee Related
- 1994-12-14 CA CA002138115A patent/CA2138115C/en not_active Expired - Fee Related
- 1994-12-14 EP EP94309312A patent/EP0662731B1/en not_active Expired - Lifetime
- 1994-12-14 US US08/355,600 patent/US5518834A/en not_active Expired - Fee Related
- 1994-12-14 DE DE69425722T patent/DE69425722T2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| EP0662731A3 (en) | 1996-06-12 |
| EP0920066A2 (en) | 1999-06-02 |
| JP3475527B2 (en) | 2003-12-08 |
| CA2138115A1 (en) | 1995-06-15 |
| US5518834A (en) | 1996-05-21 |
| EP0920066A3 (en) | 2002-03-13 |
| DE69433697T2 (en) | 2004-09-16 |
| EP0920066B1 (en) | 2004-04-07 |
| JPH08162173A (en) | 1996-06-21 |
| EP0662731A2 (en) | 1995-07-12 |
| DE69425722D1 (en) | 2000-10-05 |
| DE69433697D1 (en) | 2004-05-13 |
| EP0662731B1 (en) | 2000-08-30 |
| DE69425722T2 (en) | 2000-12-28 |
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