CA1186374A - Gelling agents for alkaline cells - Google Patents
Gelling agents for alkaline cellsInfo
- Publication number
- CA1186374A CA1186374A CA000422079A CA422079A CA1186374A CA 1186374 A CA1186374 A CA 1186374A CA 000422079 A CA000422079 A CA 000422079A CA 422079 A CA422079 A CA 422079A CA 1186374 A CA1186374 A CA 1186374A
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- CA
- Canada
- Prior art keywords
- anode
- cross
- carboxymethyl cellulose
- cell
- comprised
- 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.)
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Classifications
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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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/22—Immobilising of electrolyte
-
- 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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
-
- 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)
- Battery Electrode And Active Subsutance (AREA)
- Primary Cells (AREA)
Abstract
NOVEL GELLING AGENT FOR ALKALINE CELLS
ABSTRACT
A novel gelling agent comprised of cross-linked CMC (carboxymethyl cellulose) is utilized as a gelling agent in the anode of alkaline elec-trochemical cells with improved cell performance and reduced cell gassing as compared to the commonly utilized non cross-linked CMC.
ABSTRACT
A novel gelling agent comprised of cross-linked CMC (carboxymethyl cellulose) is utilized as a gelling agent in the anode of alkaline elec-trochemical cells with improved cell performance and reduced cell gassing as compared to the commonly utilized non cross-linked CMC.
Description
~637~
This invention relate6 to gelled anodes for alkaline electrochemical cell6 and more par~icularly to 6uch cell6 having ~inc anodes and CMC
(carboxymethyl cellulose) gelling agents.
In order to maintal~ homogenei~y with the anodes of alkaline cells ~hereby anodlc materials ~uch as amalgamated zinc powder6 are kept uniformr ly disper6ed or ~aximum electrochemlcal actlvity~ such anodes have been kept in a gelled 6tate. The most co~mon material utillzed ln or~1n~ such gelled anodes has been CMC. However, while widely ut~lized, such CMC
gelling agents have exhibited ~everal well recognized ~hortcomings. Anodes made with the CMC gelllng agent6 tend to 8ettle upon 6torage with liquid separation from the anodes and resul~nt loss of homogene$~y and reduced cell capaci~y. Other dra~backs o~ ~he CMC lnclude exce6æive cell gassing and transport of cell reaction products wi~h precipitatlon which may re6ult ln internal cell 6hort clrcuiting and reduced cell life.
It is an ob~ect of ~he p~e~ent invention to provide a novel ~elling agen~ for anodes of alkaline cell6 based upon CMC bu~ wherein the problems inherent with CMC u6age are ~ubstantially obviated. m i6 and o~her ob~ec-tive~9 feature~ and advantages of the present invention will become more evident from the followln~ di6cus6ion.
2Q Gene~ally, the present invention co~prl6es a method of ~aking gelled anode6 ~or alk~line cell6 with the use of cross-linked ~MG as a gelling agent, the anod2~ ~o formed and the cell6 containing such anodes. Cross-linked CMC ha~ been widely u~ilized in the pharmaceutical field as being a t~blet disinte~rPnt and in contra6t to ~on croes-linked CMC l~ sub6~an-tially insoluble in aqueou6 solution6. Structurally the non cross-linked ÇMC utlllzed a a gellin~ agent in alkaline cells is a long chain ~olecule (~w. between a~out 90,nOO-l,OOO,QQO~ llav~n~ repeating un~t6:
3~7 , _ ~ ~FQ a ~.
~ ~ CU,OC~10 The mo~t co~mon form of commercially available CMC i~ the sodium 6alt and i8 ormed by reactlng a~kali cellulo6e (made by steeplng wood pulp or cotton fiber ln 60dium hydroxide) ~ith sodium monochloroacet2te. The xe~ultant N~CMC has a degree of 6u~sti~ution of between 0.4% to 1.2% and generally sbout 0.7~ of every 3 available ~ubstitution ~ites. Formation of the cross-linked CMG utilized in the pre~ene invention t~kes place with an additional atep. After the sub6titution of the sodium CMC i~ complete~ the e~ces~ 60dium monochloroacetate i6 hydrolyzed to glycolic acid which changes a few of the sodium csrboxym2~chyl groups to the free acid thereby catalyzlng the ~ormatioll of cross-linkages via a condensation r~action wi~h result~n~
~ster form~tion:
r~ ~
h~u~ _ D- a~
~ ca ~ s~ r, The crofi6~ ked C~C i6 markedly di~ferent from the ~ingle chaln non cross~l~nked CMC utillzed a~ th~ anode gelling ~gent in prior art cells.
The cross-l~nked CMC iB BubBt~ntially insoluble in aqueou6 ~olu~lons thereby provid~ng it with gre~ter gel 6trength than ~he non cros~-linkPd CMC and h~s ~180 been dl~covere~ to i~prove homogeneity on standlng of anodes gelled therewith thereby lmproving cell performance. Additionally, the cross-l~nked CMC pr3Yldes cells having reduced gassing and reduced incidence ~f ~hort circul~lng.
The degree of cro~s li~king based upon the number of indlvidual glucose anhydride unit~ 1~ between 0.01% to ln% a~d pre~erably between 0.1% to 4%.
~63~7~
A lesser degree of cross linking provides a soluble material subs~antially the ~ame a6 the non-cross-linked CMC. A greater degree of cross linking provide6 a too tightly bound molecule ~ith llttle room for expansion and accomodation o~ water to form the deslred gel.
Examples of eommerclally ava~lable cros6-linked CMC include those designated by the trademarks CLD-2, AQ~ALON and Ac-Di-Sol ~all Eodium salt6) from Buckeye Cellulo6e Corp.~ Hercules Corp. and FMC respect-lvely.
The gelled anodes of the presen~ inventlon are made in accordance wi~h the prior ~rt practlce of either pregelling the anode and ~hereafter dis~
pensing the gel into cells or forming the ~el in 6itu. In the former ln.~tnnce, the cross linked CMC is admlxed with an active anode ~terial ~uch as powdered ~inc or amalg~mated zinc and a con~rolled amount of the cell electrolyte which iB generally an alkaline 30-40~ KOH aqueous solution.
Xn the in situ proces6ing, the anodic m~terial and the cross-linked CMC are mlxc~ an~ dispensed lnto the cell contalner in the dr~J state and then ~ctivated into a gel by the ~ddition of the cell ~lectroly~e. Lubr$cants ~nd additives Ruch a~ glycerlne or polyhydric alcohol~ to facllitate hand ling and proce~sing, may be sddltlonally added ~o ~he anode mixture.
2Q The amount of cross-llnked CMC utilized in the gelled anode may range from sbout 0.5~ to 7% by weight of ~he total anode~ More ~referably ~he effective range is between abou~ 1~6% tv 4~ with the most preferred percen-t~e being between sbout 2.5 to 3% by weight. Particle ~ize of the cross-linked CMC generally ranges between-30 to -400 mesh and 1B preferably between -100 to -400. Of the commercially avail~ble cross-linked CMC, CLD-
This invention relate6 to gelled anodes for alkaline electrochemical cell6 and more par~icularly to 6uch cell6 having ~inc anodes and CMC
(carboxymethyl cellulose) gelling agents.
In order to maintal~ homogenei~y with the anodes of alkaline cells ~hereby anodlc materials ~uch as amalgamated zinc powder6 are kept uniformr ly disper6ed or ~aximum electrochemlcal actlvity~ such anodes have been kept in a gelled 6tate. The most co~mon material utillzed ln or~1n~ such gelled anodes has been CMC. However, while widely ut~lized, such CMC
gelling agents have exhibited ~everal well recognized ~hortcomings. Anodes made with the CMC gelllng agent6 tend to 8ettle upon 6torage with liquid separation from the anodes and resul~nt loss of homogene$~y and reduced cell capaci~y. Other dra~backs o~ ~he CMC lnclude exce6æive cell gassing and transport of cell reaction products wi~h precipitatlon which may re6ult ln internal cell 6hort clrcuiting and reduced cell life.
It is an ob~ect of ~he p~e~ent invention to provide a novel ~elling agen~ for anodes of alkaline cell6 based upon CMC bu~ wherein the problems inherent with CMC u6age are ~ubstantially obviated. m i6 and o~her ob~ec-tive~9 feature~ and advantages of the present invention will become more evident from the followln~ di6cus6ion.
2Q Gene~ally, the present invention co~prl6es a method of ~aking gelled anode6 ~or alk~line cell6 with the use of cross-linked ~MG as a gelling agent, the anod2~ ~o formed and the cell6 containing such anodes. Cross-linked CMC ha~ been widely u~ilized in the pharmaceutical field as being a t~blet disinte~rPnt and in contra6t to ~on croes-linked CMC l~ sub6~an-tially insoluble in aqueou6 solution6. Structurally the non cross-linked ÇMC utlllzed a a gellin~ agent in alkaline cells is a long chain ~olecule (~w. between a~out 90,nOO-l,OOO,QQO~ llav~n~ repeating un~t6:
3~7 , _ ~ ~FQ a ~.
~ ~ CU,OC~10 The mo~t co~mon form of commercially available CMC i~ the sodium 6alt and i8 ormed by reactlng a~kali cellulo6e (made by steeplng wood pulp or cotton fiber ln 60dium hydroxide) ~ith sodium monochloroacet2te. The xe~ultant N~CMC has a degree of 6u~sti~ution of between 0.4% to 1.2% and generally sbout 0.7~ of every 3 available ~ubstitution ~ites. Formation of the cross-linked CMG utilized in the pre~ene invention t~kes place with an additional atep. After the sub6titution of the sodium CMC i~ complete~ the e~ces~ 60dium monochloroacetate i6 hydrolyzed to glycolic acid which changes a few of the sodium csrboxym2~chyl groups to the free acid thereby catalyzlng the ~ormatioll of cross-linkages via a condensation r~action wi~h result~n~
~ster form~tion:
r~ ~
h~u~ _ D- a~
~ ca ~ s~ r, The crofi6~ ked C~C i6 markedly di~ferent from the ~ingle chaln non cross~l~nked CMC utillzed a~ th~ anode gelling ~gent in prior art cells.
The cross-l~nked CMC iB BubBt~ntially insoluble in aqueou6 ~olu~lons thereby provid~ng it with gre~ter gel 6trength than ~he non cros~-linkPd CMC and h~s ~180 been dl~covere~ to i~prove homogeneity on standlng of anodes gelled therewith thereby lmproving cell performance. Additionally, the cross-l~nked CMC pr3Yldes cells having reduced gassing and reduced incidence ~f ~hort circul~lng.
The degree of cro~s li~king based upon the number of indlvidual glucose anhydride unit~ 1~ between 0.01% to ln% a~d pre~erably between 0.1% to 4%.
~63~7~
A lesser degree of cross linking provides a soluble material subs~antially the ~ame a6 the non-cross-linked CMC. A greater degree of cross linking provide6 a too tightly bound molecule ~ith llttle room for expansion and accomodation o~ water to form the deslred gel.
Examples of eommerclally ava~lable cros6-linked CMC include those designated by the trademarks CLD-2, AQ~ALON and Ac-Di-Sol ~all Eodium salt6) from Buckeye Cellulo6e Corp.~ Hercules Corp. and FMC respect-lvely.
The gelled anodes of the presen~ inventlon are made in accordance wi~h the prior ~rt practlce of either pregelling the anode and ~hereafter dis~
pensing the gel into cells or forming the ~el in 6itu. In the former ln.~tnnce, the cross linked CMC is admlxed with an active anode ~terial ~uch as powdered ~inc or amalg~mated zinc and a con~rolled amount of the cell electrolyte which iB generally an alkaline 30-40~ KOH aqueous solution.
Xn the in situ proces6ing, the anodic m~terial and the cross-linked CMC are mlxc~ an~ dispensed lnto the cell contalner in the dr~J state and then ~ctivated into a gel by the ~ddition of the cell ~lectroly~e. Lubr$cants ~nd additives Ruch a~ glycerlne or polyhydric alcohol~ to facllitate hand ling and proce~sing, may be sddltlonally added ~o ~he anode mixture.
2Q The amount of cross-llnked CMC utilized in the gelled anode may range from sbout 0.5~ to 7% by weight of ~he total anode~ More ~referably ~he effective range is between abou~ 1~6% tv 4~ with the most preferred percen-t~e being between sbout 2.5 to 3% by weight. Particle ~ize of the cross-linked CMC generally ranges between-30 to -400 mesh and 1B preferably between -100 to -400. Of the commercially avail~ble cross-linked CMC, CLD-
2 i8 ~100 mesh, ~QUALON i8 -60 to -325 mesh and Ac-D~-Sol 16 -400 mesh.
The cro60-linXed CMC m~y ~e utilized either alone a~ the sole gellln~
agen~ or ln ~dmixtu~e with o~her gelling agent~ ~uch as 6tarch graft co-p~lymers, methyl cellulo6e and even non cro~s-linked CMC wi~h varying d~grees oP effectlvenes~.
The cro60-linXed CMC m~y ~e utilized either alone a~ the sole gellln~
agen~ or ln ~dmixtu~e with o~her gelling agent~ ~uch as 6tarch graft co-p~lymers, methyl cellulo6e and even non cro~s-linked CMC wi~h varying d~grees oP effectlvenes~.
3~
In the present invention9 the anode 16 a gelled ~xt~re of the elec-trolyte ~olution ~nd a metal in a particulste or porous form. The metal useful in the ~node of the present inventinn can be any metal generally used ln cells havi~g an aqueous electrolyte. Such metal~ can include aluminum, cadmium, calcium, copper, indium, lron, lead, magnesium, ~anganese, mercury, nickel, tin, zlnc and other metals well known ln ~he ar~9 u~ed either alone or in alloys, amalgamations and admixtures. The anode metal can be used in ~he cell ~s a powder, granules or ~ny other particulate form.
In the preferred cell, the ~node metal comprises powdered amalgamated zLnc Powdered me~ls provide the l~rgest exposure of anode surface area to the electrolyte. Further, the finer the snode metal powder, the ~reater the ability of the ~el to ret~in ~he particles unlformly ~hroughout the ~el, which acts to ~aintain the exposure of the anode me~al to the elec-trolyte. The preferred ar,ode metal powder i6 of the order of from about 0.03 to 0.9 millimeter ln diameter. I~e most preferred size of powder to be used depends on many factors an~ it can be readlly determlned by one skilled in the art.
The electrolyte 601ution~ ~hich can be gelled by the agents of ~he Z0 present inventlon, include all ~queous electrolyte ~olutions usable 1~
electrochemical cell~. In the preferred embodiments of the present inven-tion ~lkaline electrolyte 801ut$0ns are employed. These include, but are ~ot limited to~ hydroxldes of alkali ~nd alkaline earth me~als. Sodium andfor pota~ium hydroxide are the 6t commonly u~ed alkaline electrolytes.
The cros~-linked CMC g~lling agent of t~e present invention can be sed with ~11 cathodes here~ofore useful in aqueou~ electrochemlcal cells.
l~ese cathode6 include7 but are no~ lted to oxidized metals, ~uch as c:~dmium oxide and hydroxidea mercurlc o~lde, lead oxide~ mQnganese diDxid~, ick~l o~ide and hydroxlde, eilver oxide ~nd alr.
In order ~o more fully illustrate ~he efficacy o the pre6ent lnvention the foll~ing example~ are pre~ented. It ls u~der6tood~ however, that 6uch example~ are lllu~trative in na~ure and any enumeration of de~ail therein should not be cons~rued ~6 limitation6 on the pre6ent invention.
Unless othe~7ise indica~ed~ all parts are par~s by ~eight.
~XAMPLES 1-9 Three zlnc anode powder blends were made using 2500 gm zinc powder9 188 g~ HG, 0.25% acetic Acid (percentage based upon the Zn ~ Hg weight);
and water, glycerin and cro~s-llnked CMC in the amounts and of the character ,given in Tabl~s I, II and III bel~w. Fifteen "D" aize cells were then made :from each of the blends with each cell being compri6ed of about 18.4 grams of the zinc anode powder blend a5 the anode, about 15 cm3 of 40% KOH
.~queous ~olution as electrolyte and MnO2 sta~dard depolsrizer powder and ~eparator wlth the cell~ being anode llmited. Pive cells o each an~de blend were discharged ~resh a~ 2 l./4 ohms, five cells at 2 l/4 ohms after one week storage ~t 130JF (54.4C) and the rem~inlng flve fresh ~ 10 ohms with the result~ given ln Tables I, II and III respecti~ely:
TABLE I*(2 1/4~- F~P-Bh) ~0 ~7pe of Example Cros~- Dischar~e hours % Zinc Ns~ (5 Anode linked %Gly~ tc cutcff volts utili-~ell~ ea.)Blend CMC & % cerine %H O 1~1 1.0 0.9 0.8 0.65 zation ,__ _ _ _ :l A Aqualon 0.25 0.25 7.1 11.3 15.1 19.7 24.5 78.2 2~U
'2 ~ CLD~2 0.25 0.25 7.8 12.3 lS.9 19.~ 24.3 78.3 2.5 :3 C Ac~Dl-Sol 0.35 0.35 6.8 11.4 ~4.8 18.0 20.6 69.5 3.0 * Percenta~e6 based on tot~l Zn ~ ~ ~eight. Re6ult6 given are a~erages.
3~
T~BLE II*(2 l/4 3~ - 130F ~torage for week~
Typ~ of Example Cro6s- Di~charge hour6 ~ Zinc Mo.5 Anode llnked %Gly- to cutoff vvlts u~
cells ea)Blend ~IC & % eer~ne ~ 1.1 1.0 0.9 0~8 0065 za~ion
In the present invention9 the anode 16 a gelled ~xt~re of the elec-trolyte ~olution ~nd a metal in a particulste or porous form. The metal useful in the ~node of the present inventinn can be any metal generally used ln cells havi~g an aqueous electrolyte. Such metal~ can include aluminum, cadmium, calcium, copper, indium, lron, lead, magnesium, ~anganese, mercury, nickel, tin, zlnc and other metals well known ln ~he ar~9 u~ed either alone or in alloys, amalgamations and admixtures. The anode metal can be used in ~he cell ~s a powder, granules or ~ny other particulate form.
In the preferred cell, the ~node metal comprises powdered amalgamated zLnc Powdered me~ls provide the l~rgest exposure of anode surface area to the electrolyte. Further, the finer the snode metal powder, the ~reater the ability of the ~el to ret~in ~he particles unlformly ~hroughout the ~el, which acts to ~aintain the exposure of the anode me~al to the elec-trolyte. The preferred ar,ode metal powder i6 of the order of from about 0.03 to 0.9 millimeter ln diameter. I~e most preferred size of powder to be used depends on many factors an~ it can be readlly determlned by one skilled in the art.
The electrolyte 601ution~ ~hich can be gelled by the agents of ~he Z0 present inventlon, include all ~queous electrolyte ~olutions usable 1~
electrochemical cell~. In the preferred embodiments of the present inven-tion ~lkaline electrolyte 801ut$0ns are employed. These include, but are ~ot limited to~ hydroxldes of alkali ~nd alkaline earth me~als. Sodium andfor pota~ium hydroxide are the 6t commonly u~ed alkaline electrolytes.
The cros~-linked CMC g~lling agent of t~e present invention can be sed with ~11 cathodes here~ofore useful in aqueou~ electrochemlcal cells.
l~ese cathode6 include7 but are no~ lted to oxidized metals, ~uch as c:~dmium oxide and hydroxidea mercurlc o~lde, lead oxide~ mQnganese diDxid~, ick~l o~ide and hydroxlde, eilver oxide ~nd alr.
In order ~o more fully illustrate ~he efficacy o the pre6ent lnvention the foll~ing example~ are pre~ented. It ls u~der6tood~ however, that 6uch example~ are lllu~trative in na~ure and any enumeration of de~ail therein should not be cons~rued ~6 limitation6 on the pre6ent invention.
Unless othe~7ise indica~ed~ all parts are par~s by ~eight.
~XAMPLES 1-9 Three zlnc anode powder blends were made using 2500 gm zinc powder9 188 g~ HG, 0.25% acetic Acid (percentage based upon the Zn ~ Hg weight);
and water, glycerin and cro~s-llnked CMC in the amounts and of the character ,given in Tabl~s I, II and III bel~w. Fifteen "D" aize cells were then made :from each of the blends with each cell being compri6ed of about 18.4 grams of the zinc anode powder blend a5 the anode, about 15 cm3 of 40% KOH
.~queous ~olution as electrolyte and MnO2 sta~dard depolsrizer powder and ~eparator wlth the cell~ being anode llmited. Pive cells o each an~de blend were discharged ~resh a~ 2 l./4 ohms, five cells at 2 l/4 ohms after one week storage ~t 130JF (54.4C) and the rem~inlng flve fresh ~ 10 ohms with the result~ given ln Tables I, II and III respecti~ely:
TABLE I*(2 1/4~- F~P-Bh) ~0 ~7pe of Example Cros~- Dischar~e hours % Zinc Ns~ (5 Anode linked %Gly~ tc cutcff volts utili-~ell~ ea.)Blend CMC & % cerine %H O 1~1 1.0 0.9 0.8 0.65 zation ,__ _ _ _ :l A Aqualon 0.25 0.25 7.1 11.3 15.1 19.7 24.5 78.2 2~U
'2 ~ CLD~2 0.25 0.25 7.8 12.3 lS.9 19.~ 24.3 78.3 2.5 :3 C Ac~Dl-Sol 0.35 0.35 6.8 11.4 ~4.8 18.0 20.6 69.5 3.0 * Percenta~e6 based on tot~l Zn ~ ~ ~eight. Re6ult6 given are a~erages.
3~
T~BLE II*(2 l/4 3~ - 130F ~torage for week~
Typ~ of Example Cro6s- Di~charge hour6 ~ Zinc Mo.5 Anode llnked %Gly- to cutoff vvlts u~
cells ea)Blend ~IC & % eer~ne ~ 1.1 1.0 0.9 0~8 0065 za~ion
4 A Aqualon 0.25 0.25 6.0 10.2 13.8 17.6 21.9 69.6 2.0 S B CLD-2 0.25 0.25 6.2 10.6 14.4 17.8 21.4 68.9 2.5 6 C Ac-Di-Sol 0.35 0.35 7.1 11.3 14.8 18.1 20.4 68.0 3.0 T~BLE III*(loJ~ Fresh) Type of ~x~ple Cross- Dl6charge hours % zinc No. (5 Anode linked %Gly- to cutoff ~olts utili-cells ea) Blend CMC L % cerine YH 0 1 1 1 0 0 9 0 8 0 65 zation O
7 A hqtlalon 0.25 0.25 57.6 70.8 8406 108.0 117.4 93.7 ~PX1148 2.0 B CLD-2 0.25 0.25 ** 76.7 88.2 106.5 117 99.1 2.5 9 C Ac-Di- 0.3S 0.35 60.6 74.6 87.0 105.4 115.2 94.3 Sol 3.0 * Percent~ges based on total Zn & Hg we~gh~. Results given are averages.
** Not recorded.
i3~7~
The cro6s-linked CMC provldes cells having lmproved di6charge capabil~ty compared to the prior art ~on cross-linked CMC. Cell~ ~ade ~i~h anodes pelled with the cro~s-linked CMC are compara~le to cells having anodes gelled with starch-graft-copoly~ers 6u~h a~ SGP which have been shown to be superior to the non-cro6s-linked CMC. However~ ~he cross-linked CMC
~elling agent of the pre6ent inventlon hss an advantage over the starch-graft-copolymer in that lt e~n be more effectively u~ilized in but~on type cell6 such a6 those containing 6ilver oxide anode~. The cros~-llnked CMC of the present invention does not oontain any ammonia (a n re~ldual product fou~d 1~ 6tarch-graft-copolymer6) ~hich way detri~en-tally react with the s~lver oxlde commonly u~ed as the depolarlzer in button cells.
It is under~tood that the above examples are merely illustrative of tlle pre~ent inVentiOTI and that different fo~ulation6 and ratlo6 of components as well a~ the actual componeTIts themselves may provide dlferent results under varying condition6. However, changes in cell components and component ratios are within the 6cope of the present invention as deflned in the following claims.
7 A hqtlalon 0.25 0.25 57.6 70.8 8406 108.0 117.4 93.7 ~PX1148 2.0 B CLD-2 0.25 0.25 ** 76.7 88.2 106.5 117 99.1 2.5 9 C Ac-Di- 0.3S 0.35 60.6 74.6 87.0 105.4 115.2 94.3 Sol 3.0 * Percent~ges based on total Zn & Hg we~gh~. Results given are averages.
** Not recorded.
i3~7~
The cro6s-linked CMC provldes cells having lmproved di6charge capabil~ty compared to the prior art ~on cross-linked CMC. Cell~ ~ade ~i~h anodes pelled with the cro~s-linked CMC are compara~le to cells having anodes gelled with starch-graft-copoly~ers 6u~h a~ SGP which have been shown to be superior to the non-cro6s-linked CMC. However~ ~he cross-linked CMC
~elling agent of the pre6ent inventlon hss an advantage over the starch-graft-copolymer in that lt e~n be more effectively u~ilized in but~on type cell6 such a6 those containing 6ilver oxide anode~. The cros~-llnked CMC of the present invention does not oontain any ammonia (a n re~ldual product fou~d 1~ 6tarch-graft-copolymer6) ~hich way detri~en-tally react with the s~lver oxlde commonly u~ed as the depolarlzer in button cells.
It is under~tood that the above examples are merely illustrative of tlle pre~ent inVentiOTI and that different fo~ulation6 and ratlo6 of components as well a~ the actual componeTIts themselves may provide dlferent results under varying condition6. However, changes in cell components and component ratios are within the 6cope of the present invention as deflned in the following claims.
Claims (18)
1. A method of gelling anodes for alkaline cells comprising the step of gelling an anode active material with cross-linked carboxymethyl cellulose and an alkaline electrolyte solution.
2. The method of claim 1 wherein said anode active material is comprised of zinc.
3. The method of claim 1 wherein said alkaline electrolyte solution is comprised of a KOH solution.
4. The method of claim 1 wherein the degree of cross linking in said cross-linked carboxymethyl cellulose is between 0,01 to 10% based upon the number of individual glucose anhydride units therein.
5. The method of claim 1 wherein said cross-linked carboxymethyl cellulose comprises between 0.5% to 7% by weight of said anode.
6, An anode blend for an electrochemical cell comprising an anode active powder and cross-linked carboxymethyl cellulose.
7. The anode blend of claim 6 wherein said active anode powder is comprised of zinc.
8. The anode blend of claim 7 wherein said blend further includes an aqueous KOH solution.
9. The anode blend of claim 7 wherein the degree of cross linking of said cross-linked carboxymethyl cellulose is between 0.01 to 10% based upon the number of individual glucose anhydride units therein.
10. The anode blend of claim 7 wherein said cross-linked carboxymethyl cellulose comprises between 0.5% to 7% by weight of said anode blend.
11. An electrochemical cell comprising a gelled anode, a cathode and an aqueous alkaline electrolyte characterized in that said gelled anode comprises an anode active powder and cross-linked carboxymethyl cellulose.
12. The electrochemical cell of claim 11, where said active anode powder is comprised of zinc.
13 The electrochemical cell of claim 12, where said gelled anode further includes an aqueous KOH solution.
14. The cell of claim 11, 12 or 13 wherein said aqueous alkaline electrolyte is comprised of a KOH solution.
15. The cell of claim 11, 12 or 13 wherein said cathode is comprised of a member of the group consisting of manganese dioxide, silver oxide and mercury oxide.
16. The cell of claim 11, 12 or 13 wherein said cathode is comprised of a member of the group consisting of manganese dioxide, silver oxide and mercury oxide; and wherein said aqueous alkaline electrolyte is comprised of a KOH solution.
17. The cell of claim 11, 12 or 13 wherein the degree of cross linking in said cross-linked carboxymethyl cellulose is between 0.01 to 10% based upon the number of individual glucose anhydride units therein.
18. The cell of claim 11, 12 or 13 wherein the degree of cross linking in said cross-linked carboxymethyl cellulose is between 0.01 to 10% based upon the number of individual glucose anhydride units therein; and wherein said cross-linked carboxymethyl cellulose comprises between 0.5% to 7% by weight of said anode.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/355,784 US4435488A (en) | 1982-03-08 | 1982-03-08 | Gelling agent for alkaline cells |
| US355,784 | 1982-03-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1186374A true CA1186374A (en) | 1985-04-30 |
Family
ID=23398833
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000422079A Expired CA1186374A (en) | 1982-03-08 | 1983-02-22 | Gelling agents for alkaline cells |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US4435488A (en) |
| JP (1) | JPS58166650A (en) |
| AU (1) | AU550081B2 (en) |
| BE (1) | BE895825A (en) |
| BR (1) | BR8301094A (en) |
| CA (1) | CA1186374A (en) |
| DE (1) | DE3308221A1 (en) |
| ES (1) | ES8406801A1 (en) |
| FR (1) | FR2523372B1 (en) |
| GB (1) | GB2118356B (en) |
| IT (1) | IT1193695B (en) |
| MX (1) | MX162738A (en) |
| ZA (1) | ZA83359B (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59160967A (en) * | 1983-03-04 | 1984-09-11 | Daicel Chem Ind Ltd | Gelling agent for alkaline battery |
| US4563404A (en) * | 1984-06-18 | 1986-01-07 | Duracell Inc. | Cell gelling agent |
| FR2583580B1 (en) * | 1985-06-18 | 1987-08-07 | Wonder | PROCESS FOR THE STABILIZATION OF PRIMARY ELECTROCHEMICAL GENERATORS WITH REACTIVE ANODES OF ZINC, ALUMINUM OR MAGNESIUM; STABILIZED ANODE OBTAINED BY THIS METHOD AND GENERATOR COMPRISING SUCH ANODE |
| US4906539A (en) * | 1987-07-08 | 1990-03-06 | Sanyo Electric Co., Ltd. | Sintered type negative cadmium electrode for an alkaline storage cell and method of manufacturing the same |
| US6087030A (en) * | 1995-05-05 | 2000-07-11 | Rayovac Corporation | Electrochemical cell anode and high discharge rate electrochemical cell employing same |
| US5721065A (en) * | 1995-05-05 | 1998-02-24 | Rayovac Corporation | Low mercury, high discharge rate electrochemical cell |
| US6521378B2 (en) | 1997-08-01 | 2003-02-18 | Duracell Inc. | Electrode having multi-modal distribution of zinc-based particles |
| US6472103B1 (en) | 1997-08-01 | 2002-10-29 | The Gillette Company | Zinc-based electrode particle form |
| US6596431B1 (en) * | 2000-01-20 | 2003-07-22 | Matsushita Electric Industrial Co., Ltd. | Battery and method for generating an electric power |
| WO2004114442A2 (en) * | 2003-06-17 | 2004-12-29 | The Gillette Company | Anode for battery |
| US20070218339A1 (en) * | 2006-03-14 | 2007-09-20 | More Energy Ltd. | Leak-proof liquid fuel cell |
| CN115141285B (en) * | 2022-08-11 | 2023-09-01 | 湖北亿纬动力有限公司 | A kind of modified carboxymethyl cellulose salt binder and its preparation method and application |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3918989A (en) | 1971-01-18 | 1975-11-11 | Gates Rubber Co | Flexible electrode plate |
| JPS4826494A (en) * | 1971-08-11 | 1973-04-07 | ||
| FR2186741B1 (en) * | 1972-05-30 | 1978-03-03 | Cipel | |
| US3877983A (en) | 1973-05-14 | 1975-04-15 | Du Pont | Thin film polymer-bonded cathode |
| JPS5247812B2 (en) * | 1973-08-30 | 1977-12-05 | ||
| US3954501A (en) | 1974-01-10 | 1976-05-04 | Guy Rampel | Rechargeable electrodes utilizing unsintered fluorocarbon binder |
| US3884722A (en) | 1974-03-18 | 1975-05-20 | Union Carbide Corp | Alkaline galvanic cells |
| JPS53129825A (en) * | 1977-04-19 | 1978-11-13 | Hitachi Maxell | Zinc alkali battery |
| US4175052A (en) * | 1978-03-31 | 1979-11-20 | Union Carbide Corporation | Alkaline-MnO2 cell having a zinc powder-gel anode containing P-N-V-P or PMA |
| US4209577A (en) * | 1978-03-31 | 1980-06-24 | Union Carbide Corporation | Alkaline-MnO2 cell having a zinc powder-gel anode containing methyl cellulose |
| JPS5628469A (en) * | 1979-08-16 | 1981-03-20 | Matsushita Electric Ind Co Ltd | Silver-oxide battery |
-
1982
- 1982-03-08 US US06/355,784 patent/US4435488A/en not_active Expired - Lifetime
-
1983
- 1983-01-19 ZA ZA83359A patent/ZA83359B/en unknown
- 1983-01-20 AU AU10630/83A patent/AU550081B2/en not_active Ceased
- 1983-02-04 BE BE0/210061A patent/BE895825A/en not_active IP Right Cessation
- 1983-02-08 ES ES519608A patent/ES8406801A1/en not_active Expired
- 1983-02-10 FR FR8302128A patent/FR2523372B1/en not_active Expired
- 1983-02-16 GB GB08304289A patent/GB2118356B/en not_active Expired
- 1983-02-22 CA CA000422079A patent/CA1186374A/en not_active Expired
- 1983-02-24 MX MX196368A patent/MX162738A/en unknown
- 1983-03-01 IT IT19849/83A patent/IT1193695B/en active
- 1983-03-04 BR BR8301094A patent/BR8301094A/en not_active IP Right Cessation
- 1983-03-07 JP JP58037233A patent/JPS58166650A/en active Pending
- 1983-03-08 DE DE19833308221 patent/DE3308221A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| GB8304289D0 (en) | 1983-03-23 |
| ES519608A0 (en) | 1984-07-16 |
| BR8301094A (en) | 1983-11-22 |
| ZA83359B (en) | 1983-10-26 |
| FR2523372A1 (en) | 1983-09-16 |
| DE3308221A1 (en) | 1983-09-22 |
| FR2523372B1 (en) | 1987-05-29 |
| AU1063083A (en) | 1983-09-15 |
| US4435488A (en) | 1984-03-06 |
| IT1193695B (en) | 1988-07-21 |
| GB2118356A (en) | 1983-10-26 |
| JPS58166650A (en) | 1983-10-01 |
| ES8406801A1 (en) | 1984-07-16 |
| AU550081B2 (en) | 1986-02-27 |
| MX162738A (en) | 1991-06-24 |
| BE895825A (en) | 1983-05-30 |
| GB2118356B (en) | 1985-04-11 |
| DE3308221C2 (en) | 1991-08-22 |
| IT8319849A0 (en) | 1983-03-01 |
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