CA1043869A - Thin flat cell construction having a gas-permeable coated perforated anode - Google Patents
Thin flat cell construction having a gas-permeable coated perforated anodeInfo
- Publication number
- CA1043869A CA1043869A CA230,884A CA230884A CA1043869A CA 1043869 A CA1043869 A CA 1043869A CA 230884 A CA230884 A CA 230884A CA 1043869 A CA1043869 A CA 1043869A
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- CA
- Canada
- Prior art keywords
- cell
- anode
- cathode
- electrolyte
- openings
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/06—Electrodes for primary cells
- H01M4/08—Processes of manufacture
- H01M4/12—Processes of manufacture of consumable metal or alloy electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/04—Cells with aqueous electrolyte
- H01M6/06—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
- H01M6/12—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid with flat electrodes
-
- 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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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Primary Cells (AREA)
- Gas Exhaust Devices For Batteries (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inert Electrodes (AREA)
- Hybrid Cells (AREA)
Abstract
CONDUCTIVE COATED VENTED CATHODE
COLLECTOR FOR THIN FLAT CELLS
ABSTRACT OF THE DISCLOSURE
A thin flat cell employing a metal anode (zinc), a cathode (manganese dioxide) an electrolyte (ammonium chloride) and a perforated cathode collector (steel); said cathode collector being coated with a continuous layer of a gas-permeable, electrolyte-impermeable polymeric material which allows the venting of undesirable gases formed within the cell while preventing any electrolyte loss from said cell.
1.
COLLECTOR FOR THIN FLAT CELLS
ABSTRACT OF THE DISCLOSURE
A thin flat cell employing a metal anode (zinc), a cathode (manganese dioxide) an electrolyte (ammonium chloride) and a perforated cathode collector (steel); said cathode collector being coated with a continuous layer of a gas-permeable, electrolyte-impermeable polymeric material which allows the venting of undesirable gases formed within the cell while preventing any electrolyte loss from said cell.
1.
Description
3 ~
Field of the Invention This in~ention relates to an improved con~
struction for ~hin flat cells or batteries and particularly to thin flat cells or batteries employing a gas-permeable coated vented anode. -. . .. . .. . . . . .
~'~ Description o~ the Prior Ar~
The collti~uing developDIent of portable elec~rically powered devices of compact design such as ~ape recorders and playback maohines, radio trans-10 ~nitters and receivers, shavers, watc~hes, and motionpicture or ~till cameras creates a continuing ~eman~
. for the development of reliable, compact batteries for i their operztion. The power needs of such devices are .~, . .
~ varied. Thus, a watch requires a battery which will "k,,~ perfor~ uniformly for ~t least a year at low drain;
:~
~ : recorders and radios require batteries which will -, opera~e intermittently for perhaps a half hour to several ~' hours at substantially hi~ller drains ollowed by langer .. . . .
perlods o~ nonuse~ A moti.on picture camera in which a ba~tery may oper~te exposure control means as wel.l . as drive a mo~or usually requires ~he ~ttery to opeirate . ~ .
. in a repetitive series of rel~tively short periods o~ .
~ime in ~ given day, but may not be used fo~ weeks ? ~
' .. . .
,~:
. .
or months. A still camera in which a battery may be used to fire a flash bulb and in some cases ~o control exposure means and advance the film after each exposure requires the battery to deliver a series of pulses of rather high current~ frequently in rapid succession.
While the battery industry has been quite successful in providing batterie~ to satisfy these dlvér~e demands, the vast majority of the batteries produced for and used in devices of the type discu~sed are cylindrical, They may range in height from the familiar .... . . .
"button" cells to as much as one-half inch to one . :
inch or even more and in diameter from roughly about one-half inch to one inch or more. Although they are excellent ~ources of electricityg their shape has llmited to some extent the size and ~hape of the devices for : . , .
which they are intended. As design concepts change ~ . ,.. .... :.. , there i9 increa3ing emphasi~ placed on thin, ~lat shap0s. ~, !
Devices of thin, flat shape cannot be made to accommodate the amiliar cyllndrical battery without devoting more space to the battery than i8 desired. Accordingly, there is an increasing demand or t~in, flat batteries.
~; The problem associat0d wi~h maintaining good electrical contact between cell elements i.8 particularly .: , :.... . :
~;~ notable in thin flat cell constructions where external ~ -supports are generally impractical since such mem~er~
may be many time~ the thickness of the cell itself. In :
addition, ~lnce such flat cells possess a large ,' .' ,:
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.
unsupported surface, the usual means employed for maintaining cell integrity along the periphery of the cell may not be sufficient to maintain good electrical contact between cell elements at the center of the flat cell because o the formation of gases within the cell which has a tendency to separate the cell components thereby increasing the resistance of the ^ell to a degree that the cell could become inoperative for its intended use.
` 10 It has previously been suggested in the prior flat cell art that adhesives be used in assembling specific cell components, for example, between cathode and cathode collector, between collector and the outer ~
envelope, and between cells in a stack. These bonding ~ -techniques are set forth in detail in U.S. Patent Nos. 2,870,235 to Soltis, 3,379,574 to Grulke et al, -~
Field of the Invention This in~ention relates to an improved con~
struction for ~hin flat cells or batteries and particularly to thin flat cells or batteries employing a gas-permeable coated vented anode. -. . .. . .. . . . . .
~'~ Description o~ the Prior Ar~
The collti~uing developDIent of portable elec~rically powered devices of compact design such as ~ape recorders and playback maohines, radio trans-10 ~nitters and receivers, shavers, watc~hes, and motionpicture or ~till cameras creates a continuing ~eman~
. for the development of reliable, compact batteries for i their operztion. The power needs of such devices are .~, . .
~ varied. Thus, a watch requires a battery which will "k,,~ perfor~ uniformly for ~t least a year at low drain;
:~
~ : recorders and radios require batteries which will -, opera~e intermittently for perhaps a half hour to several ~' hours at substantially hi~ller drains ollowed by langer .. . . .
perlods o~ nonuse~ A moti.on picture camera in which a ba~tery may oper~te exposure control means as wel.l . as drive a mo~or usually requires ~he ~ttery to opeirate . ~ .
. in a repetitive series of rel~tively short periods o~ .
~ime in ~ given day, but may not be used fo~ weeks ? ~
' .. . .
,~:
. .
or months. A still camera in which a battery may be used to fire a flash bulb and in some cases ~o control exposure means and advance the film after each exposure requires the battery to deliver a series of pulses of rather high current~ frequently in rapid succession.
While the battery industry has been quite successful in providing batterie~ to satisfy these dlvér~e demands, the vast majority of the batteries produced for and used in devices of the type discu~sed are cylindrical, They may range in height from the familiar .... . . .
"button" cells to as much as one-half inch to one . :
inch or even more and in diameter from roughly about one-half inch to one inch or more. Although they are excellent ~ources of electricityg their shape has llmited to some extent the size and ~hape of the devices for : . , .
which they are intended. As design concepts change ~ . ,.. .... :.. , there i9 increa3ing emphasi~ placed on thin, ~lat shap0s. ~, !
Devices of thin, flat shape cannot be made to accommodate the amiliar cyllndrical battery without devoting more space to the battery than i8 desired. Accordingly, there is an increasing demand or t~in, flat batteries.
~; The problem associat0d wi~h maintaining good electrical contact between cell elements i.8 particularly .: , :.... . :
~;~ notable in thin flat cell constructions where external ~ -supports are generally impractical since such mem~er~
may be many time~ the thickness of the cell itself. In :
addition, ~lnce such flat cells possess a large ,' .' ,:
3. ~-., ~ : ,, -.. .
;:
., .., ., ~ ... .
L3f~
.
unsupported surface, the usual means employed for maintaining cell integrity along the periphery of the cell may not be sufficient to maintain good electrical contact between cell elements at the center of the flat cell because o the formation of gases within the cell which has a tendency to separate the cell components thereby increasing the resistance of the ^ell to a degree that the cell could become inoperative for its intended use.
` 10 It has previously been suggested in the prior flat cell art that adhesives be used in assembling specific cell components, for example, between cathode and cathode collector, between collector and the outer ~
envelope, and between cells in a stack. These bonding ~ -techniques are set forth in detail in U.S. Patent Nos. 2,870,235 to Soltis, 3,379,574 to Grulke et al, -~
2,762,858 to Wood, 3,223,555 to Solomon et al, 2,658,0Y8 to Coleman et al and 2,487,985 to Ruben. The adhesives .
described in these patents have been sui~able for use . ' .
! 20 only in a limited portion of the cell and could not be used to maintain the entire cell structure as an integral unit. For example, none of the adhesives previously suggested has been entirely suitable for use in providing permanent adhesion to the corroding face of the cell.
anode. In this connection, it is well known that during discharge of the cell, the anode metal is consumed, and .;, .
~i if consumed in a nonuniform manner, physical voids could ! occur on and in the anode surface. Proper wetting of the .1 .
anode surface by the adhesive must be maintained for the adhesive to be effective.
~1:: , ,.;
.~ .
. . ~ . .
, ., .,.,, .. ~ . - , . . ~ ~
described in these patents have been sui~able for use . ' .
! 20 only in a limited portion of the cell and could not be used to maintain the entire cell structure as an integral unit. For example, none of the adhesives previously suggested has been entirely suitable for use in providing permanent adhesion to the corroding face of the cell.
anode. In this connection, it is well known that during discharge of the cell, the anode metal is consumed, and .;, .
~i if consumed in a nonuniform manner, physical voids could ! occur on and in the anode surface. Proper wetting of the .1 .
anode surface by the adhesive must be maintained for the adhesive to be effective.
~1:: , ,.;
.~ .
. . ~ . .
, ., .,.,, .. ~ . - , . . ~ ~
3~j3 .
U~ S. Patent 3,563~805 to Deierhoi~ Jr.
discloses a flat cell having an anode, a cathode, a separator, an immobilized adhesive electrolyte and a cathode collector, all of which ~re appropria~ely arr3nged and adhesively secured together by a conven~
tional sealing means which effectively main~ains a : .
relatlvely low electrical resistance contac~ between : ; :
all the individual cell components.
In U. S. Patent 3,617,387 to Grulke et al, a ~ ~.
lat cell is disclo~ed which ha8 all its components -completely internally bonded together wlth a polymeric .. adhesive, said adhesive maintaining physical and eiectrical J~ contact between the components.
Another approach to produce a flat multicell ,!~ bat~ery is disclosed in UO S. Patent No~. 3,770,504 to .
Bergum e~ al and 3,770,505 to Bergum, wherein the con~
. . . ~, .
.~ fron~ing faces of each ad~acen~ pair of eonductive layers for~lng the ba~tery are adhered and electrically bonded 20 one to the other~ In addition, ad~acent cells o~ the : bat~ery are electrically connected one to the other by :~
~ means o an electrolyte impcrvious intercell connector ..
3~;~ layer which extends beyond ~he electrodes of ,the cell.s :
~ o that the peripheral faces o the ln~ereell connec~or : .:
¦:~: layer~ can be 8uita~1y sealed to provide a liquid im-p~rviou5 ~eal around each cell.
Although all of the above approaches work to ,: .
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9382 .
f~LV43B~
some degree in producing a flat cell, a buildup of undesirable gas pres~ure generally occurs within a cell during shelf storage or during discharging which could be sufficient to separate two or more of the cell's ~-; components thereby greatly increasing the internal re- ,-sistance of the cell to a point where the cell become~ :
, ineffective for its intended u~e. ..
i` ;.''~,':
~: U. S. Patent No. 37902~922 issued to ; T. Kalnoki-Kis discloses another approach to producing ~
; 10 a thin, flat cell or battery wherein the cathode collector .
j of the cell is perforated for the purpose of venting . ~ .
J undesirable gQses formed during ~torage and discharge of the cell or battery. ;:
~ It is an object of ~he pre~ent invention to i provide a thin9 flat cell or battery having novel means for venting undesirable ~as formed wi~hin ~he cell 80 , as to effectively minimiæe any ga~ pres~ure buildup i. ~ wlthin the cell~
~ Another object o~ the present in~en~ion i9 to : . .
:1 20 pro~ide a ~hin, ~ cell or battery having a perforated ., .. ,: .~
;~ anode which i~ coated on one side with a ga3-permeable, ! ~ electrolyte-impermeable adhe~ive or paint. .,;-1 : ~
Another ob~ect of the present invention i~
to provide a thin, flat cell or bat~ery h~lng good ionic and/or electronic conductivi~y at ~he in~erface3 ' .
, ~ .
' 6.
', , 31~
of each of the cell's components throughout storage and discharge of the cell.
Another object of the present invention is -- to provide a thin, flat cell or battery having a perfor-ated anode and a perforated cathode collector, the former --of which is coated on one of its sides while the latter is coated on at least one of its sides with a ~as-permeable, electrolyte~impermeable paint or adhesive. ;,~ !
Summary of the Invention The invention relates to a thin, flat cell ;~
having a metal anode, a cathode of depolarizer . .. .
mix, an electrolyte-permeable separator between said anode and said cathode, an electrolyte in contact with said anode and said cathode, and a cathode collector; ~-said anode having a plurality of openings for venting ~ undesirable gases formed in the cell anid having on one of ;l its surfaces a substantially continuous layer of a gas-.,j .: .
permeable, electrolyte-impermeable paint; and wherein said cathode, said separator, and said electrolyte are bounded by a peripheral rame of electrolyte-impervious sealirlg material, said frame being bonded to at least a portion of the inner marginal faces o~ the anode and the cathode collector which extends beyond the area defined by said cathode, said separator and said electrolyte. ,~
The invention also relates to a thin, flat cell having a metal anode; a cathode of depolar-izer mix; an electrolyte-permeable separator between said anode and said cathode; an electrolyte in contact with said anode and said cathode; and a cathode ~ , . , ,;', ' .
,~; ,. ...
~3 collector; said anode having a plurality of openings for venting undesirable gases in the cell and having on ..
one of its surfaces a substantially continuous layer o-E
a gas-permeable, electrolyte-impermeable paint; and wherein all of said components of said cell are.substantially adhesively secured together so as to maintain a relatively low electrical resistance contact between said individual ::
.
cell componen~s. ThP invention also relateæ to either of the above thin flat cell constructions wherein the cathode collector is perforated so as to contain a plurality of .
openings for venting undesirable gases formed in the cell and wherein said cathode collector has on at least one of . ::
its surfaces a substantially continuous layer of a gas-permeable, electrolyte-impermeable conductive paint.
As used herein, a substan~ially continuous -~ .
layer shall mean at least a layer that effectLvely covers ~
the openings on the surface of the anode, and.when - ~.
applicable, the cathode collector. In addi~ion, when the ~ :
material o the anode, and when applicable, the cathode collector, i8 such tha~ it would be subject to excessive ~i corrosi.on in a cell environment, then at least ~he surface oP the anode and the cathode collec~or subject to such corrosion will be substanti.ally covered wikh the layer.
. . .
, The paint for use in this invention has to ,` be a gas-permeable~ electrolyte-impermeable adhesive ~:
paint, as for example, disclosed in U.S. Paten~s .. . .
- 2,759,038; 2,745,774; 2,834,826; 3,072,55~; 3,353,~99;
; 3,343,995; 3,510,448; 3,563,851; 3,547,771 and . 3,575,905. An additional paint or adhesive for use ~.
in thi~ invention could comprise a solution of . ~ :
a copolymer o vin~l chloride and vinyl acetate in an ..
..
~ 8~
,.... .. .. . ..
,,, .. .. ,',: .. , .,~ :.............. : ,.................. .
~ 3~
~ . ' organic solvent containing a suitable stabilizer for high temperature conditions and a plasticizer for flexibility.
In one embodiment of this invention, the cell's separator, electrolyte and cathode of depolarizer `
; mix are bounded at one end by a metal anode and at the other end by a metallic cathode collector, said anode ~-~
and cathode collector ex~ending beyond the area defined `
by the cathode, separator and electrolyte thereby forming ~ a peripheral recess between the marginal inner faces of ., said anode and said cathode collector into which a frame of electrolyte impervious sealing material is deposited.
~ In this type cell construction, any gases formed during ~, ; storage or during discharge of the cell will have a `;
' tendency to separate the components of the cell, i.e., ~.
:, the cathode collector from the cathode, or the separator - from the anode, which will have the effect of increasing ` `
the intsrnal resistance of the cell to a degree that the `j cell may become inoperative for its intended use.
According to this invention, a plurality of openings are ~`
placed in the anode, and in some applications a plurality o openings are placed in the cathode collec~or also, for venting any undesirable gases formed within the cell.
In addition to perforating the anode and when applicable, the cathode collector, a gas-permeable, electrolyte-imper-meable ~aint is deposited on one surface of the anod~ and a gas-permeable, electrolyte-impermeable conductive paint ~; is deposited on at least one surface of the cathode ;. collector so as to prevent the loss of any electrolyke ., .
;' through the openings in the anode and cathode collector ,~ ' . ' ' ;~' ~' , , ' , , ; ~ ... ~ ~ , . .... . . . . . .
, ,.,. , .. , . ,, , , . ~ , , . , : ~ .. ,, . . :
.
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while sLmultaneously allowing for the escape of undesir- , able gases. By having the combination of a perforated anode, or a perforated anode and a perforated cathode -collector, and a coating of a gas-permeable, electrolyte-i . .
impermeable pain~ on one or both cell components, respec-tively, t'ne bonding strength provided by the peripheral frame of electrolyte impervious sealing material will be sufficient to maintain the physical and electrical ~: contact between adjacent cell components during cell storage and discharge since any gases formed within the cell will be able to escape through the openings in one or both of the cell perforated components, respectively. ~ -Thus according to this invention, all components of the cell are secured in intimate contact, and no external pressure-exerting means need be employed. The frame of sealing material surrounding the cathode, s~parator ~ and elec~rolyte, aids to rigidify the cell and in main-;.!~ taining low electrical resistance contacts between the cell components in cooperation with the metal anode and the cathode collector to which the frame o~ sealing material i8 marginally sealed.
The size of the opening in the anode or the anode and cathode collector can vary between about 10 microns in diameter and about 250 microns in diameter, preferably between about 75 microns in diameter and about ~ :
175 microns in dia~eter. Openings larger than 250 microns in diameter will be unsuitable because of the tendency of -:
the gas-permeable, electrolyte-impermeable conducting adhesive to shrink and crack on drying, thereby providing .: '. , .' ,;
., .
, 10.
~, . .
, . ,. : ": . , . , " . . :,, : .,, , ~ .. ,, : .
' openings through which the electrolyte can escape. When using a conductive paint, openings smaller than 10 microns in diame~er will be unsuitable because the particles of the conductive material may be sufficiently large enough ~ :
.. ..
to plug or subs~antially plug the openings thereby pre-venting the effective venting of the gases formed within ~:
the cell. In addition, it would be difficult using -conventional perforating means to form openings smaller .
than about 10 microns. . .
The opening instead of being circular can be square, rectangular or any shape as long as the size of the opening is between about 78 square microns and about ` i.
65,000 square microns (~,0.0006 cm2), preferably between about 4200 square microns (~fO.00004 cm2) and about 25,000 square microns ~O.00025 cm2). In some instances, :~
it may be easible and advantageous to impart slits in the anode and/or cathode collector with any sharp instru-ment, such slits being at least about 0.0025 centimeter, preferably about 0.0075 centimeter, in width and up to about 1.0 centimeter in length.
The number of openings in the anode can vary depending on such features as the cell system. However, a minimum o at l~ast one opening ~or every eight square ~ : .
centimeters of the anode is necessary if the gases formed :
~: within the cell are to escape without disrupting the :. .
contact between the cell components. The maximum number - .
of openings in the ~node would be limited to the number .;.
whereby the ~mount of anode material removed by providing :~
openings would effectively decrease the amount of anode ' 11. ;, , . .
~V~ 3 ~
: material needed for a proper electrochemical reaction within the cell. For the case of the cathode collector, a minimum of at least one opening every three square ;~ centimeters of cathode collector is necessary while the maximum number of openings in the cathode collector would be limited to the number whereby the cathode i collector would effectively lose its conductive charac-i teristics and/or integrity and strength required to i t maintain the cell as a structural power unit. Preferably - 10 the openings should be uniformly disposed throughout the cell's component and, where not uniformly disposed, the ;. , .
op~nings should be disposed at or near the center of the cell's component where mechanical support is at a minimum.
It is apparen~ that if a rather dense, low porosity cathode mix is used in ~he cell, then the number ~ -of openings in the cathode collector would have to berather :
large to insure that any gas reaching the interface of the cathode mix and coated cathode collector would have an . .i .
opening available through which the gas could escape. On ;~ 20 the other hand, when a rather porous cathode mix is employed, then the num~er of openings requirPd would not be great since any gas reaching the interface of the cathode mix and the coated cathode collector could easily clrculate to a nearby opening and escape therefrom.
When employing a perforated cathode collector ,~ and a rather dense cathode mix, then the mix may be scored, perforated or suitably divided so as to provide adequate gas channels or passages within the mix leading ., .
to the interface of the cathode mix and the coated cathode collector. ~ -12.
.' g382 3~ 3 ., Another embodiment of this invention would be -similar to the above-described cell construction except that the anode and cathode collector would not extend -beyond, but would be coextensive with, the area defined by the separator, electrolyte and cathode mix. In addition, all the cell components would be adhesively secured together as disclosed, for example, in U.S.
Patents 3,563,805 and 3,617,387. The additional require- ~ ~;
ment that the adhesive means employed to secure the cell components together be gas-permeable is necessary O as to allow any gas formed within the cell to cir-culate to the openings in the anode and, when applicable, the cathode collector. In this embodiment, all of the components of the cell ara substantially adhesively . : , secured in intimate contact so that no external pressure-~, exerting means is necessary.
'2!~ Another embodiment of thls invention would be -~ , a multicell battery comprising an outer negative ~node) electrode having a plurality of openings for venting ;
gases formed within the battery and having on its outer ... .. .
surface a layer of a gas-permeable electrolyte--impermeable paint;;an outer positive (cathod~ electrode; at least one duplex electrode between the outer positive electrode and the outer negative electrode a separator and an electro-ly~e between each positive and negative electrode; and a cathode collector with or without a plurality of openings for venting undesirable gases formed within the battery and, at least for the former, having on at least one of its surfaces a substantially continuous layer of a gas-, : , ,',,'~ ~ ' : ,.
! 13.
'~ '', , .
.1 .
permeable, elec~rolyte-impermeable conductive paint; said d~plex electrode comprising a positive electrode bonded ~o a porous negative electrode via an electronically conductive layer of a gas-permeable, electrolyte-imperme-able adhesive; and whereinall of said components of said battery are substantially secured together so as to main-` tain a relatively low electrical resistance contact be-tween said individual cell components.
-, The positive electrode, electrolyte and separa-tor of each cell could be bounded by a peripheral frame of electrolyte-impervious sealing ma~erial which could also be marginally bonded to each negativé electrode and i the adjacent conductive layer of the duplex electrode or j the cathode collector whichever defines each such cell.
Or, if desired, all of the components of the battery could be substantially adhesively secured together as disclosed in U.S. Patent Nos. 3,563,805 and 3,617,387. If the latter construction is employed, then all the adhesive layers would have to be gas-permeable so as to permit any gases ormed within the cell to circulate to ~he anode and when applicable, the cathode collector, where the gases could be vented.
In the multicell embodiment of this invention, it iæ preferable to have the cathode collector perforated in addition to the anode so as to provide maximt~ openings for venting any gases formed within the cell. When a perorated cathode collec~or is employed in a multlcell .
embodiment having on~ duplex electrode, then it may not be necessary to have a porous negative electrode in the ' :.. "''.
: 14-.
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duplex electrode since any gas forming within the battery can be vented at the anode at one end and the cathode collector at the other end. When a porous negative electrode is employed, said porous negative electrode could be perforated in the same manner as the -~ outer negative electrode of the multicell battery.
'`! There are many conductive adhesives or paints which have been used,or are suitable for use,in the battery industry for bonding cell components together .i , .
or for providing a cell cnmponent with a conductive layer. Examples o adhesives or paints, conductive or non-conductive, are set forth, as for example, in IJ.S. -~ :
Patents 2,745,774; 2,759,038; 2,834,826; 3,072,558;
3,353,999; 3,343,995; 3,510,448; 3,563,851; 3,547,771 ~ -and 3,575,905. . , Plasticizers, including those materials which~ ~;
function as both a plasticizer and as a stabilizer, :
~ould be added in a minor amount to a conductive adhesive or paint to obt~in specific chemical and ~j . ... .
~ 20 mechanical properties desirable for a particular appli- ;
. .. . .
cation. For ~.xample, stabili2ers are generally added to maintain chemical s~ability at high temperatures and in oxidizing enviro~ments. Plasticizer~ are generally added to impart viscoelastic properties to the formed film. In many cases, a si~gl~ materlal will unction both as a i~tabilizer and ai~i a plaisticizer when added to an adhe~Lve or ~ain~.
.. . .
,, .
~ 15.
, . .
, , ,:, .
'.,, ; , ,; . '' ~ ~ ' .'' .' , '. . '' To render an adhesive or paint conductive, some electrically conductive particulate material, such as acetylene black, graphite or mixtures thereof, should be added. Preferably, a mixture having a ratio of 1 part by weight acetylene black ~o 3 parts by weigh~
graphite would be suitable for use on perforated cathode collectors of this invention. The conductive material shall not be added to the paint when the paint is -used to coat a perforated metal anode, such as a zinc anode, ~;
since it would provide a direct short with the metal . .. .. .
anode in the pres~nce of the cell's electrolyte. However, ~ ~
:~ ... .
in a duplex electrode construction for a multicell battery, the negative electrode would have to be coated with a conductive paint to insure electronic contact ~o the cathode of the duplex electrode. In the preferred . . .
embodiment of a m~lticell battery', the negative electrode of the duplex electrode would be a porous nega~ive eLectrode.
.,.. ~, .
' , ':
Lirief D~
Figo 1 is an ~somet~ic view of ~ cell made ln acco~d~nce ~o this invention.
~ig, 2 lllu~rates a par~al cross-~ection of a cell wherein the componen~s o ~he cell are shvwn greatly .
.
'~ .
.
- 93~2 ':. ' .
~ 3'~
magnified for purposes of illustra~ion.
Fig. 3 illustrates a partial cross-section of a battery wherein the components of the cell are shown greatly magnified.
Fig 4 ,s a cross-section of another embodiment . ~ .. . . .
of a cell wherein the components of the cell are shown : -.j , . .. . .
greatly magnified.
Referring in more detail to the drawings, there is shown in Figures 1 and 2 a thin, flat cell 1 having a vented anode 3, electrolyte-impregnated separ- ;
ator 5, cathode 7, conductive layer 9 and vented cathode ' :
-, , collector 11. Electrolyte-impregnated separator 5 and .::
-i cathode 7 are contained within and bound by anode 3 and cathode collector 11 forming a peripheral recess 13 which is filled with a frame of sealing material which ~ -~,; , marginally bounds cathode 7 and is secured to the inner ~-~-~ marginal face 17 of anode 3 and the inner marginal face 19 of cathode collector 11 via the conductive .: . . : ,.
,~ layer 9. The adhesive used to form the frame must not ; 20 react with the cell components or react,ion products, should be electrolyte-proof and impermeable to water and vapor transfer and should retain these properties . .
and its adhesi~ity over the range of cell temperature operations. Suitable adhesives which can be used as J!:~ the sealing material include the conventional vinyl ,~ adhesives or hot melt adhesives of vinyl wax mixtures.
Anode 3 is shown as having opening 23 for vent-ing any undesirable gases formed within the cell during stroage or dlscharge. A tab 27 provides external - ~ .
' ' . .
3 ~
electrical contact to the anode 3, said tab could be an integral part of the anode or a discrete, conductive member secured to the anode by conventional means. A
gas-permeable coating 25 is applied to the top surface -; of anode 3 so as to enable gases to be vented through openings 23 while blocking~the escape of any electrolyte - from the cell. ' -~
Cathode collector 11 is shown as having open-` ings 21 (optionalj for venting any undesirable gases formed within the cell during storage or discharge. The -composition of conductive layer 9 is as described above and i8 characterized as being conductive, gas-permeable and electrolyte-impermeable. Thus any gases formed within the cell can be vented at anode 3 through openings 23 or through openings 21 in cathode collector 11. Since most gas is formed at the vicinity o the anode, the openings in the anode will vent most of the gas ormed within the cell. In some~applications, the perforated anode will be sufficient to vent the gases formed within the cell and thus the cathode collector could be a solid plate as is conventional in the art.
~ To provide a battery of cells, it is necessary l~ merely to place the anode of one cell in intimate elec- ~
tronic contact with the cathode collector o another thus ~ ;
effecting a series connection.
Generally, the surface contact pressure between the anode and the cathode collector of two adjacent superimposed cells required to provide good electronic contact therebetween will be insuficient to block venting fi~
, ' ' "
.~ '.
18 ~ -~' ..
~ 3 ~
from the cathode collector. However, if desired, addi-tional horizontal venting passages may be disposed between sald components of the adjacent cells.
An al~ernate construc~ion for a series stack battery is one having a "duplex" electrode in which one --surface of a metal anode is provided with a conductive - :
coating according to this invention and as shown in Figure 3.
- .
As seen in Figure 3, two cells are arranged one above the other and adhesively secured together.
The upper cell 30 comprises vented anode 34 having openings 60, electrolyte-impregnated separator 36 and cathode 3B. A gas-permeable coating 58 i8 applied to the top surface of anoda 34 so as to enable gases formed~-wi~hin the battery to be vented through openings 60 while blocking the escape of any electrolyte from the battery.
When the anode 34 is zinc, a non-conductive adhesive or , . .
paint coating compositlon i8 employed. A conductive layer 40, as described above for layer 9 in Figure 2.
is then disposed between, and bonded to, porous anode 42 and cathode 38. The lower cell 32 compriges a porous anode 42, electrolyte-impregna~ed separator 44, and cathode 46.
Di~posed between and bonded to cathode 46 and cathode collector 50 is conductive layer 48 which is identical to the conductive layer 9 of Figure 2. The peripheral recesses 54 and 54' are filled with a sealing material 56 and 56l, respectively, as described in conjunction with Figure 2. Cathode collector 50 is shown as having .
... .
~ 19.
, .... . . .
, ~ . : .. . . :
openings 52 for venting gases formed within the cell during storage and discharge, I~ desired, although not shown anode 42 may be fabricated w~th openings similar to those shown for anode 34~ F~r this type battery construction, layers 40, 48 and 58 should be gas-permea~le so as to ~ .
permit the gases within~the cell to circulate to the .
openings 60 in the anode, and when appIicable, to openings 52 in the cathode collector 50. Although not :
...
shown, an anode ~ab, as described above in con~unction :
with Figures 1 and 2, can be used as a terminal for providing external electrical contact to the anode. .
Figure 4 shows another embodiment of a cell -of this invent~on wherein all of the cell components ~ :
are substantially adhesively secured together as dîlsclosed, for example, in U.S. Patent Wos. 3,563,805 and 3,617,387. . .
Specifically, cell 41 comprises a ~ented anode 43, having ~:
openings 59 and a top coated layer 61 as described above, ..
a first layer 45 of immobilized elec~rolyte, an electrolyte-absorbent separator 47, a second layer 49 of immobilized electrolyte, cathode 51, a conductive layer 53 and cathode collector 55 having openings 57. The layers 45 and 49 of immobilized electrolyte provide the el~ctrolyte which is in ionlc or electrolytic contact with the anode and cathode of the cell. The electrolyte ln this embodiment-can be a viscous, tacky or "sticky" mass which can be h ld within the bounds of the cell by having ~:
a quitable electrolyte-impermeable coating placed around the sides of the cell. This mass, in addition to providing the electrolyte of the cell, will ~erve to hold the cell components together.
20 , , -~
., .
..
The preferred embodiment of this invention would employe the LeClanche electrochemical system comprising manganese dioxide positive active material, zinc negative active material, preferably sheet zinc, and an electrolyte comprising ammonium chloride and/or zinc chloride. The cathode collector could be any conducting material such as steel, copper, zinc, nickel --and nickel alloys, Grafoil* and the like, preferably steel becaase of its relatively low cost and good physical properties, such as strength.
The perforated anode and/or perforated cathode collector of this invention, i.e., anode and/or cathode ~ ;
collector having a plurality of~openings,~could be porous conductive substrates having pores within the range of the openings specified above. Examples of such ma~erials are compressed metal wools, sintered metals .
and the like.
. ~
`~ Although the preferred electrochemical system ~` is LeClanche, there are a wide variety of electrochemical systems that can be used in this invention. ~mong the positive electrode materials that are suitable for use ~; in this invention are such materials as manganese dioxide, lead dioxide, nlckel oxyhydroxide, mercuric oxide, silver oxide, inorganic metal halides such as ~ *Grafoil is a trademark for flexible graphite material l~ of expanded graphite particles compressed together.
Grafoil i8 manuactured by Union Carbide Corporation, New York, New York and is the subject matter of U.S.
Patent No. 3,404,061.
:1~"' ' 21.
,',~ . .''.
~, .
93~2 silver chloride and lead chloride, and organic materials which are capable of being reduced such as dinitrobenzene and azodicarbonamide compounds. Among the negative electrode materials that are suitable for use in this inven~ion are zinc, zinc-clad steel, aluminum, lead, cadmium &nd iron. Suitable electrolytes are ammonium chloride and/or zinc chloride, various alkaline electro- -lytes such as the hydroxides of potassium, sodium and/or lithium, acidic electrolytes such as sulfuric or phosphoric acid, and non-aqueous electrolytes, said electrolytes being chosen to be compatible with the negative and positive electrodes. The electrolytes may be either gelled or liquid depending on the particu-lar cell construction and the electrochemical system used. The separator may be made from a wide variety o~
materials including the fibrous and cellulosic materials which are conventional in battery construction as well as from woven or non-woven fibrous materials such as , I polyester, nylon, polyethylene and glass.
Preferred electrochemical systems for use in this invention are those in which the positive electrode comprises manganese dioxide, the negative electrode comprises metals such as zinc, zinc-clad steel or aluminum, and the electrolyte substantially comprises an acidic solution of inorganic salts. Another pre~erred j, electrochemical system is the alkaline manganese system il~ in which the po~itive electrode comprises manganese -~ dioxide, the negative electrode comprises zinc, and 22.
.i .
:
: ' , ''' ' the electrolyte substantially comprises a solution oE
pota~sium hydroxide. Other aqueous electrolyte systems suitable for use with this invention are nickel-zinc, silver-zinc, mercury-zinc, mercury-cadmium and nickel-cadmium.
EXAMPLE
:, Thin flat LeClanche cells, as shown in Figure 2, except that the cathode collector was a solid steel plate, were prepared using a positive electrode mix of manganese dioxide, graphite and acet~lene black, a negative zinc sheet electrode, and an elec--,~ trolyte o~ ammonium chloride and zinc chloride. A
7~ cellulosic separator was diQposéd between the zinc anode and cathode mix of each cell as shown in Figure 2 and wa~ saturated with the electrolyte of each cell.
, A vinyl gas-permeabl~, electrolyte-impermeable paint, comprising a solution of a copolymer of vinyl chloride and vinyl acetate in an organic solvent containing a plasticizer and an epoxy resin stabilizer, was applied to the outer surface of the zinc anode sheet ha~ing openings disposed therein. A similar paint ; with the addition of acetylene black and graphite was applied to the cakhode collector. After the ! paints dried, the coated anode and the conductively 1 coated steel cathode collector were assembled with the other cell components, in a manner as ~ 23.
,~ , . . .
,.,, ~ :
'' ''; , ... ,.",.,. , ,.... ~ ..... : - ~ ' ...... , ,, " ., 93~2 :
shown in Figure 2, and then a hot melt adhesive, obtained commercially as Swift Z-863 from the Swift Company, was ~ .
deposited in the peripheral recesses formed between the ; extending anode and the cathode plates to produce a thin rectangular flat cell. Each cell measured 1.75 inches .~ wide and 2.75 inches long with the active cathode mix , component of each cell measuring 1.48 inches by 2.25 inches. :
Each cell was then tested by being successively discharged across a 0.312 ohm load for 0.1 sec~nd, a 0.832 ohm load for 1.5 seconds and then across a ;~
6.250 ohm load for 1.0 second. This cycle of discharge was repeated after a three-second rest period until the closed circuit voltage-of the cell reached 1.08 volts.
The data obtained from the cells, after being stored .
at 25C or 11 weeks, are shown in Table 2.
i: . : . .
1 Table 2 ': 1st Cycle Cell Impedance Open Circuit Closed Circuit .::. ;.!''~'.. "' ,~: 20 ohm at l-kHz. Voltage Voltage (volts) No bf Cycles ~-,~ 2.3 1.62 1.~2 29 2.5 1.64 1.43 26 0.6 1,62 1.39 19 10.1 1.63 1,44 39 0.6 1.61 1.44 47 ~ .
2.9 1.66 1.~5 37 ~, .
.. ~, ~ ..
. . ' 24. .
~' ' '' -'.
. - . .
. ~. ,-,.
,,- - : . .
,, . . , : : . . -~
3~
It is thus shown by the above example that using the teachings of this invention, flat cells can be constructed which can deliver a series of pulses of rather high current in a rapid succession without the need for all the cell components to be completely bonded together, It is to be understood that other modifications and ch~inges to the preferrQd embodiments of the inven-tion herein shown and described can àlso be made without . .
~ 10 departing from the spirit and scope of the invention.
i . . . .
..
.
.
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' ' .. .
25.
l~ , - i .' ~ .
. .
ij . .
U~ S. Patent 3,563~805 to Deierhoi~ Jr.
discloses a flat cell having an anode, a cathode, a separator, an immobilized adhesive electrolyte and a cathode collector, all of which ~re appropria~ely arr3nged and adhesively secured together by a conven~
tional sealing means which effectively main~ains a : .
relatlvely low electrical resistance contac~ between : ; :
all the individual cell components.
In U. S. Patent 3,617,387 to Grulke et al, a ~ ~.
lat cell is disclo~ed which ha8 all its components -completely internally bonded together wlth a polymeric .. adhesive, said adhesive maintaining physical and eiectrical J~ contact between the components.
Another approach to produce a flat multicell ,!~ bat~ery is disclosed in UO S. Patent No~. 3,770,504 to .
Bergum e~ al and 3,770,505 to Bergum, wherein the con~
. . . ~, .
.~ fron~ing faces of each ad~acen~ pair of eonductive layers for~lng the ba~tery are adhered and electrically bonded 20 one to the other~ In addition, ad~acent cells o~ the : bat~ery are electrically connected one to the other by :~
~ means o an electrolyte impcrvious intercell connector ..
3~;~ layer which extends beyond ~he electrodes of ,the cell.s :
~ o that the peripheral faces o the ln~ereell connec~or : .:
¦:~: layer~ can be 8uita~1y sealed to provide a liquid im-p~rviou5 ~eal around each cell.
Although all of the above approaches work to ,: .
~: -- 5.
..... ... . . .. . . . . .
9382 .
f~LV43B~
some degree in producing a flat cell, a buildup of undesirable gas pres~ure generally occurs within a cell during shelf storage or during discharging which could be sufficient to separate two or more of the cell's ~-; components thereby greatly increasing the internal re- ,-sistance of the cell to a point where the cell become~ :
, ineffective for its intended u~e. ..
i` ;.''~,':
~: U. S. Patent No. 37902~922 issued to ; T. Kalnoki-Kis discloses another approach to producing ~
; 10 a thin, flat cell or battery wherein the cathode collector .
j of the cell is perforated for the purpose of venting . ~ .
J undesirable gQses formed during ~torage and discharge of the cell or battery. ;:
~ It is an object of ~he pre~ent invention to i provide a thin9 flat cell or battery having novel means for venting undesirable ~as formed wi~hin ~he cell 80 , as to effectively minimiæe any ga~ pres~ure buildup i. ~ wlthin the cell~
~ Another object o~ the present in~en~ion i9 to : . .
:1 20 pro~ide a ~hin, ~ cell or battery having a perforated ., .. ,: .~
;~ anode which i~ coated on one side with a ga3-permeable, ! ~ electrolyte-impermeable adhe~ive or paint. .,;-1 : ~
Another ob~ect of the present invention i~
to provide a thin, flat cell or bat~ery h~lng good ionic and/or electronic conductivi~y at ~he in~erface3 ' .
, ~ .
' 6.
', , 31~
of each of the cell's components throughout storage and discharge of the cell.
Another object of the present invention is -- to provide a thin, flat cell or battery having a perfor-ated anode and a perforated cathode collector, the former --of which is coated on one of its sides while the latter is coated on at least one of its sides with a ~as-permeable, electrolyte~impermeable paint or adhesive. ;,~ !
Summary of the Invention The invention relates to a thin, flat cell ;~
having a metal anode, a cathode of depolarizer . .. .
mix, an electrolyte-permeable separator between said anode and said cathode, an electrolyte in contact with said anode and said cathode, and a cathode collector; ~-said anode having a plurality of openings for venting ~ undesirable gases formed in the cell anid having on one of ;l its surfaces a substantially continuous layer of a gas-.,j .: .
permeable, electrolyte-impermeable paint; and wherein said cathode, said separator, and said electrolyte are bounded by a peripheral rame of electrolyte-impervious sealirlg material, said frame being bonded to at least a portion of the inner marginal faces o~ the anode and the cathode collector which extends beyond the area defined by said cathode, said separator and said electrolyte. ,~
The invention also relates to a thin, flat cell having a metal anode; a cathode of depolar-izer mix; an electrolyte-permeable separator between said anode and said cathode; an electrolyte in contact with said anode and said cathode; and a cathode ~ , . , ,;', ' .
,~; ,. ...
~3 collector; said anode having a plurality of openings for venting undesirable gases in the cell and having on ..
one of its surfaces a substantially continuous layer o-E
a gas-permeable, electrolyte-impermeable paint; and wherein all of said components of said cell are.substantially adhesively secured together so as to maintain a relatively low electrical resistance contact between said individual ::
.
cell componen~s. ThP invention also relateæ to either of the above thin flat cell constructions wherein the cathode collector is perforated so as to contain a plurality of .
openings for venting undesirable gases formed in the cell and wherein said cathode collector has on at least one of . ::
its surfaces a substantially continuous layer of a gas-permeable, electrolyte-impermeable conductive paint.
As used herein, a substan~ially continuous -~ .
layer shall mean at least a layer that effectLvely covers ~
the openings on the surface of the anode, and.when - ~.
applicable, the cathode collector. In addi~ion, when the ~ :
material o the anode, and when applicable, the cathode collector, i8 such tha~ it would be subject to excessive ~i corrosi.on in a cell environment, then at least ~he surface oP the anode and the cathode collec~or subject to such corrosion will be substanti.ally covered wikh the layer.
. . .
, The paint for use in this invention has to ,` be a gas-permeable~ electrolyte-impermeable adhesive ~:
paint, as for example, disclosed in U.S. Paten~s .. . .
- 2,759,038; 2,745,774; 2,834,826; 3,072,55~; 3,353,~99;
; 3,343,995; 3,510,448; 3,563,851; 3,547,771 and . 3,575,905. An additional paint or adhesive for use ~.
in thi~ invention could comprise a solution of . ~ :
a copolymer o vin~l chloride and vinyl acetate in an ..
..
~ 8~
,.... .. .. . ..
,,, .. .. ,',: .. , .,~ :.............. : ,.................. .
~ 3~
~ . ' organic solvent containing a suitable stabilizer for high temperature conditions and a plasticizer for flexibility.
In one embodiment of this invention, the cell's separator, electrolyte and cathode of depolarizer `
; mix are bounded at one end by a metal anode and at the other end by a metallic cathode collector, said anode ~-~
and cathode collector ex~ending beyond the area defined `
by the cathode, separator and electrolyte thereby forming ~ a peripheral recess between the marginal inner faces of ., said anode and said cathode collector into which a frame of electrolyte impervious sealing material is deposited.
~ In this type cell construction, any gases formed during ~, ; storage or during discharge of the cell will have a `;
' tendency to separate the components of the cell, i.e., ~.
:, the cathode collector from the cathode, or the separator - from the anode, which will have the effect of increasing ` `
the intsrnal resistance of the cell to a degree that the `j cell may become inoperative for its intended use.
According to this invention, a plurality of openings are ~`
placed in the anode, and in some applications a plurality o openings are placed in the cathode collec~or also, for venting any undesirable gases formed within the cell.
In addition to perforating the anode and when applicable, the cathode collector, a gas-permeable, electrolyte-imper-meable ~aint is deposited on one surface of the anod~ and a gas-permeable, electrolyte-impermeable conductive paint ~; is deposited on at least one surface of the cathode ;. collector so as to prevent the loss of any electrolyke ., .
;' through the openings in the anode and cathode collector ,~ ' . ' ' ;~' ~' , , ' , , ; ~ ... ~ ~ , . .... . . . . . .
, ,.,. , .. , . ,, , , . ~ , , . , : ~ .. ,, . . :
.
~4~
while sLmultaneously allowing for the escape of undesir- , able gases. By having the combination of a perforated anode, or a perforated anode and a perforated cathode -collector, and a coating of a gas-permeable, electrolyte-i . .
impermeable pain~ on one or both cell components, respec-tively, t'ne bonding strength provided by the peripheral frame of electrolyte impervious sealing material will be sufficient to maintain the physical and electrical ~: contact between adjacent cell components during cell storage and discharge since any gases formed within the cell will be able to escape through the openings in one or both of the cell perforated components, respectively. ~ -Thus according to this invention, all components of the cell are secured in intimate contact, and no external pressure-exerting means need be employed. The frame of sealing material surrounding the cathode, s~parator ~ and elec~rolyte, aids to rigidify the cell and in main-;.!~ taining low electrical resistance contacts between the cell components in cooperation with the metal anode and the cathode collector to which the frame o~ sealing material i8 marginally sealed.
The size of the opening in the anode or the anode and cathode collector can vary between about 10 microns in diameter and about 250 microns in diameter, preferably between about 75 microns in diameter and about ~ :
175 microns in dia~eter. Openings larger than 250 microns in diameter will be unsuitable because of the tendency of -:
the gas-permeable, electrolyte-impermeable conducting adhesive to shrink and crack on drying, thereby providing .: '. , .' ,;
., .
, 10.
~, . .
, . ,. : ": . , . , " . . :,, : .,, , ~ .. ,, : .
' openings through which the electrolyte can escape. When using a conductive paint, openings smaller than 10 microns in diame~er will be unsuitable because the particles of the conductive material may be sufficiently large enough ~ :
.. ..
to plug or subs~antially plug the openings thereby pre-venting the effective venting of the gases formed within ~:
the cell. In addition, it would be difficult using -conventional perforating means to form openings smaller .
than about 10 microns. . .
The opening instead of being circular can be square, rectangular or any shape as long as the size of the opening is between about 78 square microns and about ` i.
65,000 square microns (~,0.0006 cm2), preferably between about 4200 square microns (~fO.00004 cm2) and about 25,000 square microns ~O.00025 cm2). In some instances, :~
it may be easible and advantageous to impart slits in the anode and/or cathode collector with any sharp instru-ment, such slits being at least about 0.0025 centimeter, preferably about 0.0075 centimeter, in width and up to about 1.0 centimeter in length.
The number of openings in the anode can vary depending on such features as the cell system. However, a minimum o at l~ast one opening ~or every eight square ~ : .
centimeters of the anode is necessary if the gases formed :
~: within the cell are to escape without disrupting the :. .
contact between the cell components. The maximum number - .
of openings in the ~node would be limited to the number .;.
whereby the ~mount of anode material removed by providing :~
openings would effectively decrease the amount of anode ' 11. ;, , . .
~V~ 3 ~
: material needed for a proper electrochemical reaction within the cell. For the case of the cathode collector, a minimum of at least one opening every three square ;~ centimeters of cathode collector is necessary while the maximum number of openings in the cathode collector would be limited to the number whereby the cathode i collector would effectively lose its conductive charac-i teristics and/or integrity and strength required to i t maintain the cell as a structural power unit. Preferably - 10 the openings should be uniformly disposed throughout the cell's component and, where not uniformly disposed, the ;. , .
op~nings should be disposed at or near the center of the cell's component where mechanical support is at a minimum.
It is apparen~ that if a rather dense, low porosity cathode mix is used in ~he cell, then the number ~ -of openings in the cathode collector would have to berather :
large to insure that any gas reaching the interface of the cathode mix and coated cathode collector would have an . .i .
opening available through which the gas could escape. On ;~ 20 the other hand, when a rather porous cathode mix is employed, then the num~er of openings requirPd would not be great since any gas reaching the interface of the cathode mix and the coated cathode collector could easily clrculate to a nearby opening and escape therefrom.
When employing a perforated cathode collector ,~ and a rather dense cathode mix, then the mix may be scored, perforated or suitably divided so as to provide adequate gas channels or passages within the mix leading ., .
to the interface of the cathode mix and the coated cathode collector. ~ -12.
.' g382 3~ 3 ., Another embodiment of this invention would be -similar to the above-described cell construction except that the anode and cathode collector would not extend -beyond, but would be coextensive with, the area defined by the separator, electrolyte and cathode mix. In addition, all the cell components would be adhesively secured together as disclosed, for example, in U.S.
Patents 3,563,805 and 3,617,387. The additional require- ~ ~;
ment that the adhesive means employed to secure the cell components together be gas-permeable is necessary O as to allow any gas formed within the cell to cir-culate to the openings in the anode and, when applicable, the cathode collector. In this embodiment, all of the components of the cell ara substantially adhesively . : , secured in intimate contact so that no external pressure-~, exerting means is necessary.
'2!~ Another embodiment of thls invention would be -~ , a multicell battery comprising an outer negative ~node) electrode having a plurality of openings for venting ;
gases formed within the battery and having on its outer ... .. .
surface a layer of a gas-permeable electrolyte--impermeable paint;;an outer positive (cathod~ electrode; at least one duplex electrode between the outer positive electrode and the outer negative electrode a separator and an electro-ly~e between each positive and negative electrode; and a cathode collector with or without a plurality of openings for venting undesirable gases formed within the battery and, at least for the former, having on at least one of its surfaces a substantially continuous layer of a gas-, : , ,',,'~ ~ ' : ,.
! 13.
'~ '', , .
.1 .
permeable, elec~rolyte-impermeable conductive paint; said d~plex electrode comprising a positive electrode bonded ~o a porous negative electrode via an electronically conductive layer of a gas-permeable, electrolyte-imperme-able adhesive; and whereinall of said components of said battery are substantially secured together so as to main-` tain a relatively low electrical resistance contact be-tween said individual cell components.
-, The positive electrode, electrolyte and separa-tor of each cell could be bounded by a peripheral frame of electrolyte-impervious sealing ma~erial which could also be marginally bonded to each negativé electrode and i the adjacent conductive layer of the duplex electrode or j the cathode collector whichever defines each such cell.
Or, if desired, all of the components of the battery could be substantially adhesively secured together as disclosed in U.S. Patent Nos. 3,563,805 and 3,617,387. If the latter construction is employed, then all the adhesive layers would have to be gas-permeable so as to permit any gases ormed within the cell to circulate to ~he anode and when applicable, the cathode collector, where the gases could be vented.
In the multicell embodiment of this invention, it iæ preferable to have the cathode collector perforated in addition to the anode so as to provide maximt~ openings for venting any gases formed within the cell. When a perorated cathode collec~or is employed in a multlcell .
embodiment having on~ duplex electrode, then it may not be necessary to have a porous negative electrode in the ' :.. "''.
: 14-.
g38~ ~:
3 ~
duplex electrode since any gas forming within the battery can be vented at the anode at one end and the cathode collector at the other end. When a porous negative electrode is employed, said porous negative electrode could be perforated in the same manner as the -~ outer negative electrode of the multicell battery.
'`! There are many conductive adhesives or paints which have been used,or are suitable for use,in the battery industry for bonding cell components together .i , .
or for providing a cell cnmponent with a conductive layer. Examples o adhesives or paints, conductive or non-conductive, are set forth, as for example, in IJ.S. -~ :
Patents 2,745,774; 2,759,038; 2,834,826; 3,072,558;
3,353,999; 3,343,995; 3,510,448; 3,563,851; 3,547,771 ~ -and 3,575,905. . , Plasticizers, including those materials which~ ~;
function as both a plasticizer and as a stabilizer, :
~ould be added in a minor amount to a conductive adhesive or paint to obt~in specific chemical and ~j . ... .
~ 20 mechanical properties desirable for a particular appli- ;
. .. . .
cation. For ~.xample, stabili2ers are generally added to maintain chemical s~ability at high temperatures and in oxidizing enviro~ments. Plasticizer~ are generally added to impart viscoelastic properties to the formed film. In many cases, a si~gl~ materlal will unction both as a i~tabilizer and ai~i a plaisticizer when added to an adhe~Lve or ~ain~.
.. . .
,, .
~ 15.
, . .
, , ,:, .
'.,, ; , ,; . '' ~ ~ ' .'' .' , '. . '' To render an adhesive or paint conductive, some electrically conductive particulate material, such as acetylene black, graphite or mixtures thereof, should be added. Preferably, a mixture having a ratio of 1 part by weight acetylene black ~o 3 parts by weigh~
graphite would be suitable for use on perforated cathode collectors of this invention. The conductive material shall not be added to the paint when the paint is -used to coat a perforated metal anode, such as a zinc anode, ~;
since it would provide a direct short with the metal . .. .. .
anode in the pres~nce of the cell's electrolyte. However, ~ ~
:~ ... .
in a duplex electrode construction for a multicell battery, the negative electrode would have to be coated with a conductive paint to insure electronic contact ~o the cathode of the duplex electrode. In the preferred . . .
embodiment of a m~lticell battery', the negative electrode of the duplex electrode would be a porous nega~ive eLectrode.
.,.. ~, .
' , ':
Lirief D~
Figo 1 is an ~somet~ic view of ~ cell made ln acco~d~nce ~o this invention.
~ig, 2 lllu~rates a par~al cross-~ection of a cell wherein the componen~s o ~he cell are shvwn greatly .
.
'~ .
.
- 93~2 ':. ' .
~ 3'~
magnified for purposes of illustra~ion.
Fig. 3 illustrates a partial cross-section of a battery wherein the components of the cell are shown greatly magnified.
Fig 4 ,s a cross-section of another embodiment . ~ .. . . .
of a cell wherein the components of the cell are shown : -.j , . .. . .
greatly magnified.
Referring in more detail to the drawings, there is shown in Figures 1 and 2 a thin, flat cell 1 having a vented anode 3, electrolyte-impregnated separ- ;
ator 5, cathode 7, conductive layer 9 and vented cathode ' :
-, , collector 11. Electrolyte-impregnated separator 5 and .::
-i cathode 7 are contained within and bound by anode 3 and cathode collector 11 forming a peripheral recess 13 which is filled with a frame of sealing material which ~ -~,; , marginally bounds cathode 7 and is secured to the inner ~-~-~ marginal face 17 of anode 3 and the inner marginal face 19 of cathode collector 11 via the conductive .: . . : ,.
,~ layer 9. The adhesive used to form the frame must not ; 20 react with the cell components or react,ion products, should be electrolyte-proof and impermeable to water and vapor transfer and should retain these properties . .
and its adhesi~ity over the range of cell temperature operations. Suitable adhesives which can be used as J!:~ the sealing material include the conventional vinyl ,~ adhesives or hot melt adhesives of vinyl wax mixtures.
Anode 3 is shown as having opening 23 for vent-ing any undesirable gases formed within the cell during stroage or dlscharge. A tab 27 provides external - ~ .
' ' . .
3 ~
electrical contact to the anode 3, said tab could be an integral part of the anode or a discrete, conductive member secured to the anode by conventional means. A
gas-permeable coating 25 is applied to the top surface -; of anode 3 so as to enable gases to be vented through openings 23 while blocking~the escape of any electrolyte - from the cell. ' -~
Cathode collector 11 is shown as having open-` ings 21 (optionalj for venting any undesirable gases formed within the cell during storage or discharge. The -composition of conductive layer 9 is as described above and i8 characterized as being conductive, gas-permeable and electrolyte-impermeable. Thus any gases formed within the cell can be vented at anode 3 through openings 23 or through openings 21 in cathode collector 11. Since most gas is formed at the vicinity o the anode, the openings in the anode will vent most of the gas ormed within the cell. In some~applications, the perforated anode will be sufficient to vent the gases formed within the cell and thus the cathode collector could be a solid plate as is conventional in the art.
~ To provide a battery of cells, it is necessary l~ merely to place the anode of one cell in intimate elec- ~
tronic contact with the cathode collector o another thus ~ ;
effecting a series connection.
Generally, the surface contact pressure between the anode and the cathode collector of two adjacent superimposed cells required to provide good electronic contact therebetween will be insuficient to block venting fi~
, ' ' "
.~ '.
18 ~ -~' ..
~ 3 ~
from the cathode collector. However, if desired, addi-tional horizontal venting passages may be disposed between sald components of the adjacent cells.
An al~ernate construc~ion for a series stack battery is one having a "duplex" electrode in which one --surface of a metal anode is provided with a conductive - :
coating according to this invention and as shown in Figure 3.
- .
As seen in Figure 3, two cells are arranged one above the other and adhesively secured together.
The upper cell 30 comprises vented anode 34 having openings 60, electrolyte-impregnated separator 36 and cathode 3B. A gas-permeable coating 58 i8 applied to the top surface of anoda 34 so as to enable gases formed~-wi~hin the battery to be vented through openings 60 while blocking the escape of any electrolyte from the battery.
When the anode 34 is zinc, a non-conductive adhesive or , . .
paint coating compositlon i8 employed. A conductive layer 40, as described above for layer 9 in Figure 2.
is then disposed between, and bonded to, porous anode 42 and cathode 38. The lower cell 32 compriges a porous anode 42, electrolyte-impregna~ed separator 44, and cathode 46.
Di~posed between and bonded to cathode 46 and cathode collector 50 is conductive layer 48 which is identical to the conductive layer 9 of Figure 2. The peripheral recesses 54 and 54' are filled with a sealing material 56 and 56l, respectively, as described in conjunction with Figure 2. Cathode collector 50 is shown as having .
... .
~ 19.
, .... . . .
, ~ . : .. . . :
openings 52 for venting gases formed within the cell during storage and discharge, I~ desired, although not shown anode 42 may be fabricated w~th openings similar to those shown for anode 34~ F~r this type battery construction, layers 40, 48 and 58 should be gas-permea~le so as to ~ .
permit the gases within~the cell to circulate to the .
openings 60 in the anode, and when appIicable, to openings 52 in the cathode collector 50. Although not :
...
shown, an anode ~ab, as described above in con~unction :
with Figures 1 and 2, can be used as a terminal for providing external electrical contact to the anode. .
Figure 4 shows another embodiment of a cell -of this invent~on wherein all of the cell components ~ :
are substantially adhesively secured together as dîlsclosed, for example, in U.S. Patent Wos. 3,563,805 and 3,617,387. . .
Specifically, cell 41 comprises a ~ented anode 43, having ~:
openings 59 and a top coated layer 61 as described above, ..
a first layer 45 of immobilized elec~rolyte, an electrolyte-absorbent separator 47, a second layer 49 of immobilized electrolyte, cathode 51, a conductive layer 53 and cathode collector 55 having openings 57. The layers 45 and 49 of immobilized electrolyte provide the el~ctrolyte which is in ionlc or electrolytic contact with the anode and cathode of the cell. The electrolyte ln this embodiment-can be a viscous, tacky or "sticky" mass which can be h ld within the bounds of the cell by having ~:
a quitable electrolyte-impermeable coating placed around the sides of the cell. This mass, in addition to providing the electrolyte of the cell, will ~erve to hold the cell components together.
20 , , -~
., .
..
The preferred embodiment of this invention would employe the LeClanche electrochemical system comprising manganese dioxide positive active material, zinc negative active material, preferably sheet zinc, and an electrolyte comprising ammonium chloride and/or zinc chloride. The cathode collector could be any conducting material such as steel, copper, zinc, nickel --and nickel alloys, Grafoil* and the like, preferably steel becaase of its relatively low cost and good physical properties, such as strength.
The perforated anode and/or perforated cathode collector of this invention, i.e., anode and/or cathode ~ ;
collector having a plurality of~openings,~could be porous conductive substrates having pores within the range of the openings specified above. Examples of such ma~erials are compressed metal wools, sintered metals .
and the like.
. ~
`~ Although the preferred electrochemical system ~` is LeClanche, there are a wide variety of electrochemical systems that can be used in this invention. ~mong the positive electrode materials that are suitable for use ~; in this invention are such materials as manganese dioxide, lead dioxide, nlckel oxyhydroxide, mercuric oxide, silver oxide, inorganic metal halides such as ~ *Grafoil is a trademark for flexible graphite material l~ of expanded graphite particles compressed together.
Grafoil i8 manuactured by Union Carbide Corporation, New York, New York and is the subject matter of U.S.
Patent No. 3,404,061.
:1~"' ' 21.
,',~ . .''.
~, .
93~2 silver chloride and lead chloride, and organic materials which are capable of being reduced such as dinitrobenzene and azodicarbonamide compounds. Among the negative electrode materials that are suitable for use in this inven~ion are zinc, zinc-clad steel, aluminum, lead, cadmium &nd iron. Suitable electrolytes are ammonium chloride and/or zinc chloride, various alkaline electro- -lytes such as the hydroxides of potassium, sodium and/or lithium, acidic electrolytes such as sulfuric or phosphoric acid, and non-aqueous electrolytes, said electrolytes being chosen to be compatible with the negative and positive electrodes. The electrolytes may be either gelled or liquid depending on the particu-lar cell construction and the electrochemical system used. The separator may be made from a wide variety o~
materials including the fibrous and cellulosic materials which are conventional in battery construction as well as from woven or non-woven fibrous materials such as , I polyester, nylon, polyethylene and glass.
Preferred electrochemical systems for use in this invention are those in which the positive electrode comprises manganese dioxide, the negative electrode comprises metals such as zinc, zinc-clad steel or aluminum, and the electrolyte substantially comprises an acidic solution of inorganic salts. Another pre~erred j, electrochemical system is the alkaline manganese system il~ in which the po~itive electrode comprises manganese -~ dioxide, the negative electrode comprises zinc, and 22.
.i .
:
: ' , ''' ' the electrolyte substantially comprises a solution oE
pota~sium hydroxide. Other aqueous electrolyte systems suitable for use with this invention are nickel-zinc, silver-zinc, mercury-zinc, mercury-cadmium and nickel-cadmium.
EXAMPLE
:, Thin flat LeClanche cells, as shown in Figure 2, except that the cathode collector was a solid steel plate, were prepared using a positive electrode mix of manganese dioxide, graphite and acet~lene black, a negative zinc sheet electrode, and an elec--,~ trolyte o~ ammonium chloride and zinc chloride. A
7~ cellulosic separator was diQposéd between the zinc anode and cathode mix of each cell as shown in Figure 2 and wa~ saturated with the electrolyte of each cell.
, A vinyl gas-permeabl~, electrolyte-impermeable paint, comprising a solution of a copolymer of vinyl chloride and vinyl acetate in an organic solvent containing a plasticizer and an epoxy resin stabilizer, was applied to the outer surface of the zinc anode sheet ha~ing openings disposed therein. A similar paint ; with the addition of acetylene black and graphite was applied to the cakhode collector. After the ! paints dried, the coated anode and the conductively 1 coated steel cathode collector were assembled with the other cell components, in a manner as ~ 23.
,~ , . . .
,.,, ~ :
'' ''; , ... ,.",.,. , ,.... ~ ..... : - ~ ' ...... , ,, " ., 93~2 :
shown in Figure 2, and then a hot melt adhesive, obtained commercially as Swift Z-863 from the Swift Company, was ~ .
deposited in the peripheral recesses formed between the ; extending anode and the cathode plates to produce a thin rectangular flat cell. Each cell measured 1.75 inches .~ wide and 2.75 inches long with the active cathode mix , component of each cell measuring 1.48 inches by 2.25 inches. :
Each cell was then tested by being successively discharged across a 0.312 ohm load for 0.1 sec~nd, a 0.832 ohm load for 1.5 seconds and then across a ;~
6.250 ohm load for 1.0 second. This cycle of discharge was repeated after a three-second rest period until the closed circuit voltage-of the cell reached 1.08 volts.
The data obtained from the cells, after being stored .
at 25C or 11 weeks, are shown in Table 2.
i: . : . .
1 Table 2 ': 1st Cycle Cell Impedance Open Circuit Closed Circuit .::. ;.!''~'.. "' ,~: 20 ohm at l-kHz. Voltage Voltage (volts) No bf Cycles ~-,~ 2.3 1.62 1.~2 29 2.5 1.64 1.43 26 0.6 1,62 1.39 19 10.1 1.63 1,44 39 0.6 1.61 1.44 47 ~ .
2.9 1.66 1.~5 37 ~, .
.. ~, ~ ..
. . ' 24. .
~' ' '' -'.
. - . .
. ~. ,-,.
,,- - : . .
,, . . , : : . . -~
3~
It is thus shown by the above example that using the teachings of this invention, flat cells can be constructed which can deliver a series of pulses of rather high current in a rapid succession without the need for all the cell components to be completely bonded together, It is to be understood that other modifications and ch~inges to the preferrQd embodiments of the inven-tion herein shown and described can àlso be made without . .
~ 10 departing from the spirit and scope of the invention.
i . . . .
..
.
.
:.- -''~ ' '.
'1 ' . :"' ',~ . ' ' , . , f , . . .
' ' .. .
25.
l~ , - i .' ~ .
. .
ij . .
Claims (8)
1. A thin, flat cell having a metal anode, a cathode of depolarizer mix, a separator between said anode and said cathode, an electrolyte in contact with said anode and said cathode, and a cathode collector; said anode having a plurality of openings for venting undesirable gases formed within the cell and having on its outer surface a substantially continuous layer of a gas-permeable, electrolyte-impermeable paint; and wherein said cathode, said separator and said electrolyte are within and bounded by a peripheral frame of electrolyte-impermeable sealing material, said frame being marginally adhered to said anode and said cathode collector.
2. The cell of claim 1 wherein the cathode collector has a plurality of openings for venting undesirable gases formed within the cell and has on at least one of its surfaces a substantially continuous layer of a gas-permeable, electrolyte-impermeable conductive paint.
3. The cell of claim 1 wherein the openings in said anode are sized between about 78 square microns and about 65,000 square microns.
4. The cell of claim 3 wherein the openings are sized between about 4200 square microns and about 25,000 square microns.
5. The cell of claim 1 wherein said anode is zinc, said cathode comprises manganese dioxide, and said 26.
electrolyte comprises ammonium chloride.
electrolyte comprises ammonium chloride.
6. The cell of claim 1 wherein said anode is zinc, said cathode comprises manganese dioxide, and said electrolyte comprises zinc chloride.
7. The cell of claim 2 wherein the openings in said cathode collector are sized between about 78 square microns and about 65,000 square microns, said anode is zinc 9 said cathode comprises manganese dioxide and said electrolyte comprises ammonium chloride.
8. The cell of claim 2 wherein the openings in said cathode collector are sized between about 78 square microns and about 65,000 square microns, said anode is zinc, said cathode comprises manganese dioxide and said electrolyte comprises zinc chloride.
27.
27.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA298,008A CA1087685A (en) | 1974-07-18 | 1978-03-01 | Thin flat cell construction having a gas-permeable coated perforated anode |
| CA298,007A CA1087684A (en) | 1974-07-18 | 1978-03-01 | Thin flat cell construction having a gaspermeable coated perforated anode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US489843A US3901732A (en) | 1974-07-18 | 1974-07-18 | Thin flat cell construction having a gas-permeable coated perforated anode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1043869A true CA1043869A (en) | 1978-12-05 |
Family
ID=23945494
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA230,884A Expired CA1043869A (en) | 1974-07-18 | 1975-07-07 | Thin flat cell construction having a gas-permeable coated perforated anode |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US3901732A (en) |
| JP (1) | JPS5626111B2 (en) |
| CA (1) | CA1043869A (en) |
| DE (1) | DE2531274C3 (en) |
| FR (1) | FR2279229A1 (en) |
| GB (1) | GB1517744A (en) |
Families Citing this family (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4457990A (en) * | 1982-03-19 | 1984-07-03 | Union Carbide Corporation | Thin miniature cell construction with reshaped gasket |
| US5348820A (en) * | 1992-07-10 | 1994-09-20 | Nippon Oil Company, Limited | Zinc electrode for alkaline storage battery |
| US5733676A (en) * | 1995-05-05 | 1998-03-31 | Rayovac Corporation | Metal-air cathode can and electrochemical cell made therewith |
| KR0138556B1 (en) * | 1995-06-14 | 1998-06-15 | 김광호 | Water-proof case assembly of battery electronic device |
| US5652043A (en) * | 1995-12-20 | 1997-07-29 | Baruch Levanon | Flexible thin layer open electrochemical cell |
| US5897522A (en) | 1995-12-20 | 1999-04-27 | Power Paper Ltd. | Flexible thin layer open electrochemical cell and applications of same |
| US6248463B1 (en) | 1997-05-05 | 2001-06-19 | Rayovac Corporation | Metal-air cathode can and electrochemical cell made therewith |
| US6855441B1 (en) | 1999-04-14 | 2005-02-15 | Power Paper Ltd. | Functionally improved battery and method of making same |
| WO2000062365A1 (en) * | 1999-04-14 | 2000-10-19 | Power Paper Ltd. | Functionally improved battery and method of making same |
| US7022431B2 (en) * | 2001-08-20 | 2006-04-04 | Power Paper Ltd. | Thin layer electrochemical cell with self-formed separator |
| US7335441B2 (en) * | 2001-08-20 | 2008-02-26 | Power Paper Ltd. | Thin layer electrochemical cell with self-formed separator |
| US20050181275A1 (en) * | 2004-02-18 | 2005-08-18 | Jang Bor Z. | Open electrochemical cell, battery and functional device |
| US8722235B2 (en) | 2004-04-21 | 2014-05-13 | Blue Spark Technologies, Inc. | Thin printable flexible electrochemical cell and method of making the same |
| EP1769426B1 (en) * | 2004-07-01 | 2011-05-25 | Powerid Ltd. | Battery-assisted backscatter rfid transponder |
| US8029927B2 (en) | 2005-03-22 | 2011-10-04 | Blue Spark Technologies, Inc. | Thin printable electrochemical cell utilizing a “picture frame” and methods of making the same |
| US8722233B2 (en) | 2005-05-06 | 2014-05-13 | Blue Spark Technologies, Inc. | RFID antenna-battery assembly and the method to make the same |
| JP5110619B2 (en) * | 2006-08-29 | 2012-12-26 | パナソニック株式会社 | Non-aqueous electrolyte secondary battery and manufacturing method thereof. |
| CN101802848A (en) * | 2007-07-18 | 2010-08-11 | 蓝色火花科技有限公司 | Integrated electronic device and methods of making the same |
| US8574754B2 (en) * | 2007-12-19 | 2013-11-05 | Blue Spark Technologies, Inc. | High current thin electrochemical cell and methods of making the same |
| WO2013044224A2 (en) | 2011-09-22 | 2013-03-28 | Blue Spark Technologies, Inc. | Cell attachment method |
| US8765284B2 (en) | 2012-05-21 | 2014-07-01 | Blue Spark Technologies, Inc. | Multi-cell battery |
| WO2014070254A1 (en) | 2012-11-01 | 2014-05-08 | Blue Spark Technologies, Inc. | Body temperature logging patch |
| WO2014085604A1 (en) | 2012-11-27 | 2014-06-05 | Blue Spark Technologies, Inc. | Battery cell construction |
| US9693689B2 (en) | 2014-12-31 | 2017-07-04 | Blue Spark Technologies, Inc. | Body temperature logging patch |
| US10849501B2 (en) | 2017-08-09 | 2020-12-01 | Blue Spark Technologies, Inc. | Body temperature logging patch |
| CN212099364U (en) * | 2020-04-02 | 2020-12-08 | 山东顶峰航空科技有限公司 | Energy load assembly and unmanned aerial vehicle |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2762858A (en) * | 1954-11-18 | 1956-09-11 | Reuben E Wood | Punched-cell wax electrolyte batteries |
| US3489616A (en) * | 1967-11-14 | 1970-01-13 | Berliner Akku & Elementefab | Galvanic atmospheric-oxygen cell |
| US3607430A (en) * | 1969-02-20 | 1971-09-21 | Union Carbide Corp | Manufacture of flat primary galvanic cells with two half cells |
| US3563805A (en) * | 1969-02-20 | 1971-02-16 | Union Carbide Corp | Thin,flat primary cells and batteries |
| US3741813A (en) * | 1971-11-03 | 1973-06-26 | Esb Inc | Battery having gas pervious liquid impervious member sealed over holein top |
| JPS5242628B2 (en) * | 1973-06-20 | 1977-10-25 |
-
1974
- 1974-07-18 US US489843A patent/US3901732A/en not_active Expired - Lifetime
-
1975
- 1975-07-07 CA CA230,884A patent/CA1043869A/en not_active Expired
- 1975-07-11 FR FR7522009A patent/FR2279229A1/en active Granted
- 1975-07-12 DE DE2531274A patent/DE2531274C3/en not_active Expired
- 1975-07-14 GB GB29432/75A patent/GB1517744A/en not_active Expired
- 1975-07-15 JP JP8663675A patent/JPS5626111B2/ja not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE2531274C3 (en) | 1980-01-17 |
| DE2531274A1 (en) | 1976-01-29 |
| US3901732A (en) | 1975-08-26 |
| JPS5133825A (en) | 1976-03-23 |
| FR2279229B1 (en) | 1979-05-11 |
| DE2531274B2 (en) | 1979-05-23 |
| GB1517744A (en) | 1978-07-12 |
| FR2279229A1 (en) | 1976-02-13 |
| JPS5626111B2 (en) | 1981-06-16 |
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