CA2221603A1 - Electroactive high storage capacity polycarbon-sulfide materials and electrolytic cells containing same - Google Patents
Electroactive high storage capacity polycarbon-sulfide materials and electrolytic cells containing same Download PDFInfo
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- CA2221603A1 CA2221603A1 CA002221603A CA2221603A CA2221603A1 CA 2221603 A1 CA2221603 A1 CA 2221603A1 CA 002221603 A CA002221603 A CA 002221603A CA 2221603 A CA2221603 A CA 2221603A CA 2221603 A1 CA2221603 A1 CA 2221603A1
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
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- 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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- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49108—Electric battery cell making
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- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49108—Electric battery cell making
- Y10T29/49115—Electric battery cell making including coating or impregnating
Abstract
The present invention relates to novel electroactive energy storing polycarbon sulfide (PCS) materials of general formula: (CSx)n wherein x is greater than 2.3 to about 50, and n is equal to or greater than 2. This invention also relates to novel rechargeable electrochemical cells containing positive electrode materials comprised of said polycarbon-sulfide materials with improved storage capacity at ambient and sub-ambient temperatures. This invention also relates to novel gel type solid electrolytes useful in high energy storages batteries.
Description
CA 02221603 1997-12-0~
W O96/41387 PCT~US96/06750 ELECTROACTIVE HIGH STORAGE CAPACITY POLYCARBON-SULFIDE
MATF.RTAT.S AND ELECTROLYTIC CELLS CONTAINING SAME
BACKGROU~D OF T~IE INVENTION
This invention relates to novel electroactive energy storing polycarbon-sulfide (PCS) materials of general formula (CSx)n wherein x is greater than 2.3 to about 50, and n is equ~l to or S greater than 2. This invention also relates to novel l~char~able ele~l-ocl ~..ic~l cells cont~ininE
positive electrode m~t-~ri~lc comprised of said polycarbon-sulfide materials with improved storage capacity and eycle life at ambient and sub-ambient temperatures. This invention also relates to novel gel electrolytes developed for high energy density recl,~geable non-aqueous b~ttet~irc Batteries are used in almost all portable concnm~-r electronic products from flash lights to lap top computers. Over the years, considerable interest has been shown in developing lighter weight high energy-density rechargeable. batteries for many applications inrlllrling electric vehicles.
In this regard, thin film solid state batteries using the polycarbon-sulfur cathode materials of this invention are particularly well suited for use in many consumer applications beeause of their high 15 energy to weight ratio.
Two main types of cathode materials used in the m~ntlf:lr~llre of thin film li~hium and sodium batteries are known in the art. The first materials include transition metal chalcogenides, such as titanium t~ llfi~le with alkali metals as the anode. For e~mple, among the cathode active 20 chaleogenides, U.S. Patent No. 4,049,879 lists transition metal phosphorous ehaleogenides.
Other U.S. patents, sueh as U.S. Patent Nos. 4,143,214, 4,152,491 and 4,664,991 describe eells wherein the eathode is a earbon/sulfur based material, generally of the C,~S formula where x is typieally 10 or larger.
U.S. Patent No. 4,143,294 to Chang, et al. describes cells having cathodes cont~ining C,~S
wherein x is a mlm~c~ll value from about 4 to about 50. U.S. Patent No. 4,152,491 to Chang et al. relates to eleetric current produeing cells where the cathode-active materials include one or more ULE 2~) CA 02221603 1997-12-0~
W O 96/41387 PCTrUS96/067~0 polymer co,.lpoul.ds having a plurality of carbon monosulr~de units. The carbon monnsnlfifle uni~
is generally described as (CS),~, wherein x is an integer of at least 5, and may be at least 50. and is preferably at least 100. In both cells developed by Chang, et al. the energy storage capacity is limited because there is a low density of sulfur-sulfur bonds.
s U.S. Patent No. 4,664,991 to Perichaud, et al. describes a substance contnining a one-tlimencionnl electric conducting polymer and at least one polysulfurated chain forming a charge-transfer cnmrl~Y with the polymer. Pcrichaud, et al. use a material which has two components One is the conducting polymer, which is selected from a group consisting of polyacetylenes, 10 polyparaphenylenes, polythiophenes, polypyrroles, polyanilines and their suhstitnt~d derivatives.
The other is a polysulfurated chain which is in a chnrge transfer relntion to the con~ rting polymer.
The polysulfurated chain is formed by high temperature heating of sulfur with the conjugated polymer. As a result of using this material, the cell of Perichaud, et al. exhibits a fairly low voltage of only 2.0 V against lithium.
-U.S. Patents 4,833,048 and 4,917,974 to De Jonghe, et al. describe a class of cathode mnt~rinlc made of organo-sulfur compounds of the formula (R(S)y)n where y = 1 to 6; n = 2 to 20, and R is one or more different :~liphntir or aromatic organic moieties having one to twen~y carbon atoms. One or more oxygen, sulfur, nitrogen or fluorine atoms associated with the chain can also 20 be inr~ ed when R is an nliph~t jc chain. The aliphatic chain may be linear or branched, s~tu~.-ted or unsaturated. The aliphatic chain or the aromatic rings may have substituent groups. The p-cfe.-~;~ form of the cathode material is a simple dimer or (RS)2. When the organic moiety R is a straight or a ~ --nllcd :~liphnti~ chain, such moieties as alkyl, alkenyl, alkynyl, alkoxyalkyl, alkythioalkyl, or :~minonlkyl groups and their fluorine dcrivatives may be included. When the 25 organic moiety comprises an aromatic group, the group may comprise an aryl, arylalkyl or alkylaryl group, innluciing fluorine substituted derivatives, and the ring may also contain one or more nitrogen, sulfur, or oxygen heteroatoms as well.
~ E SHEET ~Ut ~:: 2~!
CA 02221603 1997-12-0~
W O 96/41387 PCTrUS96/06750 In the cell developed by De Jonghe. et al. the main cathode reaction during dischar~e of the b~ttery is the breaking and reforming of ~licnlfitle bonds. The breaking of a disulfide bond is associated with the formation of an RS-M+ ionic complex. The organo-sulfur materials 5 investigated by De Jonghe, et al. undergo polymerization (dimerization) and de-polymerization (disulfide cleavage) upon the formation and breaking of the disulfide bonds. The de-polym~ri7: ~ion which occurs during the discharging of the cell results in lower weight ml~nomt3~ic species which can dissolve into the electrolyte, thereby severely reducing the utility of the organo-sulfur material as cathode-active material. The result is an ~lnc-tticf~ ory cycle life having a 10m~imllm of about 200 deep dischargc-charge cycles, more typically less than 100 cycles as described in J. ~ectroche~ Soc., Vol. 138, pp. 1891-1895 (1991) In particul~r, the organo-sulfur materials developed by De Jonghe, et al., are highly unstable in the presence of high cnnfiuctivity liquid, p~ d polymer, or gel electrolytes.
15A 5jgnifir~nt nd~litiorlnl drawback with the organo-sulfur mnterials developed by De Jonghe; et al. is the slow kinetics of oxidation and reduction at ambient temperatures, severely reducing the power output of cells i.-co,~o-,lting cathodes made with these organo-sulfur materials.
The slow kinetics result from the oxidation and reduction being related to the formation and breaking"~.ecti~ely, of ~iiculfide bonds on non-conjugated, non-conductive materials. Such~0 breaking and reforming of said tiiC--lfi.l~ bonds results in depolymerization and repolymeriz ation, ely, wherein such processes are kint~tic~lly very slow.
U.S. Patent Application Ser. No. 145,091 describes polycarbon disulfide materials of general formula -(CS,c)n-, wherein x ranges from 1.7 to 2.3 and n is greater than 2. These 25 compositions are prepared by the re~inction of carbon dic--lfide with alkali metals using relatively short reaction times that produce polymers with structures co---p.;sed of SUBSTITUTE SHEET ~RULE 26) ' S ' - ,S, ,S, --C--S-- and --C-C--S--. n . . n Such m~7t~ri~1c suffer from a limited sulfur content and thus. limited capacity r~lative to the materials of the present invention. Materi~ls described in U.S. Patent Application Ser. No.
145,091 have sulfur contents less than 86 wt%.
Despite the various ap~ua.-l.es proposed for organo-sulfur cathode mn-f~ri: lc, there remains a need for in ~ c;ve cathode materials having high storage capacity, high dischar~e rates and very long cycle lives at ambient and sub-ambien~ tempe,L~tu~es~
It is, therefore, a primary object of this invention to provide new polycarbon-sulfur based cathode m~teri~llC for thin film solid state batteries which are in~oypl~ncive~ yet avoid the limit~tinnc existing in the prior art, while offering perforrnance characteristics much higher than those of known m~t~rinlc It is another obiect of this invention to provide new cathode materials having as the active materi~l polycarbon-sulfide (PCS) polymers which need not undergo polymerization and de-polymeri7~tic n upon ox~ n and re~luction It is yet another object of this invention to provide a method of making a solid state 20 rechargeable battery including the novel c;~thode of the invention.
SUBSTlTUTE SHEET (RULE 26) CA 02221603 1997-12-0~
SUMMARY OF THE PRESENT INVENTION
It is an object of the present invention to provide a novel electroactive energy storing polycarbon-sulfide (PCS) m~terial useful as a solid state c;~thode malerial in rechargeable batteries.
S In its fully charged or oxi~li7~d state. the PCS material can be represented by the formula I, ~ C(SX)~
I
wherein x ranges from greater than 2.3 to about 50, n is equal to or greater than 2, and said PCS
10 material does not contain nlirhnti~ or aromatic mQif'tit~~ Said PCS material is further ~h~l...~ t~ .od by the incorporation of large fractions of polysulfur components, which on clectrochemir:~l reduc tion in an electrolytic cell, provides the exceptionnlly high storage capacity per unit weight of mnterinl In contrnst to materials presently known in the art, the PCS materials of the present invention undergo oxi(lntion and reduction with the formntion and bre3~ing, respectively, of many 15 sulfur-sulfur bonds which are attached to conjugated ~ U~UIGS that provide good electron transport and fast electrorhemi~nl kinetics at ambient temperatures and below Said PCS materials when used as cathode materials in battery cells, may be optionally mixed with conductive components and binders to further improve electrochemic ~I recycleability and cnpacity of said cathode active mnt~o i nl One embodiment of this invention relntes to PCS compositions of formula I pl~p...~d by the reductior of carbon ~ -lfide with alknli metals, such ~s sodium or lithium, in an appropliate solvent such as dimethyl sulfoxide, dimethyl formamide (DME:), N-methyl pyrrolidinon-o.
h~ th~l pho~rhoramide, and the like, incorporating long reaction times before workup. It has 25 been ~ul~;sillgly discovered that reaction times greater than about 41 hrs provide PCS materials of the present invenlion with clP-- ~--t~l compositions contnining between aboul 86 wl% and 98 wt%
SUBSmUrE Sl~ RULE 26~
sulfur. Preferred PCS compositions are Ihose lhat have element;ll composi~ions c-~nt~ining between about 90 wt% and 98 wt% sulfur.
Although the detailed ~llu.~u.~s of the PCS materials made by this method have not been S completely determin~-l available structural information suggests that compositions of gener~l for~nul~ I of the present invention are comprised of one or more of the sl- uutu-.~l units of formulas II- VI, ~C=C~ _C=C-- ~(C=C)~ ~S ~ ~S~
~ III IV V VI
wherein m is the s:~me or different at e;leh occurrence and is gre:~ter than 2, y is the s~me or different at each oc~u--G,-ce and is equal to or greater than 1. and the relative amounts of a, b, c, d, and e eomprising said PCS material ean vary widely and depend on the method of synthesis.
Preferred PCS compositions with high eleetrochemic: l eapacity are those co~r:~ining 5l-hst~nti~1 15 amounts of polysulfide speeies -(Sm)- and -(Sy)- incorporated in and ~tt~ched to the polymer baekbone. ~peei~lly preferred compositions are those wherein m is on the average equal to or greater than 6, and y is on the average equal to or greater than 1. A key feature of these compocitionc is that ele-,~-ucl-c.--ieal redue~ion and o~ tion need not lead to depolymeri7: tir n and repol~ io~ of the polymerie backbone. Further, ~he polymer backbone strueture contains 20 eonjugated se~ u tc whieh may f;lcilir~t~ eleetron transport during eleetroch~omir ~1 o~ tion and red--c-ion of the polysulfur side groups, wherein eleetrochemic ~I re~uction and o~ til~n of the eonjugated bacLL.one segments does not oeeur.
~ f ~E S~ET ~F~ULE 26.~
W O 96/41387 PCTrUS96/06750 It is ~nother object of this invention to provide ~ rech~rge~ble, solid st~te electric current producing cell capable of operating at ambient temper;ltures and below, which is comprised of:
(a) an anode which is co. "p, ;cPd of one or more ~lkali or aL~line earth met~ls;
s (b) a novel c~thode having as the cathode active m~teri~l one or more polycarbon-sulfur co, pou~ c which c2n be formulated as (CS,~)n wherein x is from greater than 2.3 to about 50, and n is equ~l to or greater than 2; and (c) ~n electrolyte which is chemically inert with respect to the ~node and the cathode and which permits the trans~o~ iu-, of ions between the anode and the c;3thode.
The anode materi~l may be an ~lPm~n~l alkali metal or an alk~ metal alloy including the mixture of an el~om~ont~l ~lkali meul ~nd one or more alloys made from an element selected from the 15 Periodic T~ble Group IA and IIA metals. Lithium and sodium are useful m~t~.rinl.c for the anode of the battery of the invention. The anode may also be ~Ikali-metal intercalated carbon such 2s LiC,~
where x is equ~l to 6 or greater. Also useful as anode mnt~ri:llC of the present invention are alkali-metal intercalated conjugnted polymers, such as lithium7 sodium or potassium doped polyacetylene, polyphenylene, and the like.
The cathode employed in the battery of the invention as the c;lthode active m~terial is comprised of a PCS material of the formula (CS,~)n, wherein x is from greater th~n 2.3 to about 50, and n is ~ numerical value gre~ter th~n or equal to 2, and preferably gre~ter than 10.
The electrolytes used in battery cells function as a medium for storage and transport of ions, and in the special case of solid electrolytes these materials additionally function ~c sep~rator m~ tPrinlc between the anodes and ca-hodPc In principle, any liquid, solid, or solid-like material SUBSTITUTE SHEET (RULE 26) CA 02221603 1997-12-0~
capable of storing and transporting ions may be used. Particularly preferr~d are solid electrolyte separators comprised of polyethers, polyimides, polyphosph~7t~n~c, polyacrylonitriles (PAN), polysiloxanes, polyether grafted polysiloxanes. blends of the foregoing, derivatives of the foregoing, copolymers of the foregoing, crocclink~d and networl; structures of the foregoing, and S the like to which is ~dded an approp-;~te electrolyte salt.
New types of electrolytes have been discovered in the practice of the present invention that are gener~lly useful in non-nqueous high energy density batteries. These electrolytes are "gel-type"
solid electrolytes that consist of a high molecular weight polymer matrix into which is dissolved an 10 electrolyte salt, then subsequently swollen with ~ low molecular weight liquid which effectively acts as a pl~ctici7~r for the salt-polymer matrix. 1'hese low mol~c~ r weight liquids are referred to as gelation agents and are generally common organic solvcnts or liquid oligomers. Any organic liquid capable of swelling said salt-polymer matrix can be used as a gelation agent so long as it is stable to the selected cathode and anode in the battery cell. A snbst~nti:ll increase in electrolyte 15 cond~,ct;viLy can be achieved by introducing these gelation agents into said salt-polymer blends.
Gel-polymer electrolytes of this type have been found to be f~cpeni~lly useful in lithium and sodium (anode) b~sed high energy density batteries.
A variety of solid gel-type elcctrolytes havc becn found to be vcry useful in the practice of 20 this invention. Illustrative of useful gel-type electrolytes are polyacrylonitriles, sulfonated polyimides, cured divinyl polyethylene glycols, cured polyethylene glycol-bis-(methyl acrylates), and cured polyethylene glycol-bis-(methyl methacrylate) which have been swollen with propylene carbonate (PC), ethylene carbonate (EC), glymes. low molecular weight polysiloxanes, and mixtures thereof. Especially useful solid and gel-type electrolytes are those comprising 25 polyethylene glycol-bis-(methyl meth~crylate) which has bcen cured (crosclinkPd) using UV, x-ray, gamma ray, electron beam, or other ionizing r~ on SUBSTITUTE SHEET (RULE 2B) CA 0222l603 l997-l2-0~
W O 96/41387 PCTrUS96/067~0 It is another object of this invention to provide a method of m~;ing the solid state batteri~s h,co,l,ol,lting the novel cathode m~terials of the present invention. The method of making the cells ~ of the present invention is particularly preferred for use in applications requiring high energy storage cap~city.
s It is still another object of this invention to provide solid state b~tteries having higher specific energy and higher current than h~s been previously nchieved with organo-sulfur cathode materinls.
It is a further object of this invention to provide b~tteries having long shelf life and a low rate of self-discharge.
These and other objects of this invention will be apparent from the following description and the accompanying drawings.
BRIEF DESCRIPTION OF T~E DRAWINGS
Figure 1 shows a cyclic voltammogram of PCS (made from the reaction of carbon disulfide 20 with an alkali met:ll) in an electrolyte concicting of dimethylsul~oxide wilh 0.1 molarconcentration of ~e~ l,yl~mmonillm perchlorate at ~ sweep rate of 50 mVlsec at room temperature.
Figure 2 shows the cyclic voltammogram of ((C2H5)2NCSS)2 in an electrolyte conci~tin~
of dimethylsulfoxide with 0.1 molar con~ tl.ltion of tetraethylammonium perchlorate at a sweep 25 rate of 50 mV/sec at room t.omrerat~lre.
SUBSTITUTE SHEET (RULE 26) WO 96/41387 PCTnUS96/06750 Figure 3 shows speeific cathodec eapaeity during eharge and discharge cycles for a PCS
eathode material made from the reaction of carbon ~liclllfide with an alkali metal using long reaction times.
DETATLED DESCRTPTTON OF T~E INVENTTON
The eyelic voltammograms shown in Figures 1 and 2 illustrate the fun~l~mrnt~l difference between PCS m~t-~ri~lc of the present invention and organo-sulfur materials ~licclosed in the art 10 whose cle~,l,u~ I f ..;r:ll activity is based on breaking and reforming of dicnlfirle bonds. In the ease of PCS m:~teri~lc ehe o~ tio~ and reductiQn peaks are closely aligned on the voltage axis indieative of fast, reversible electroehemir~l kinetic5 In the ease of ((C2H5)2NCSS)2, whieh is ~c~.cse.-l~Livc of the m~tPri~lc diceloced by De Jonge et al. co.-t~;n;l-g ~liculfide bonds, and which polymerizes (dimerizes) and de-polymerizes (ele~ves) by the forming and breaking of said 15 ~liclllfi~P bonds, r~s~euLively, during eleu~,ucllc,,lieal n~id~tion and rednctir,n, there is a spread of about 2 vol~s between the n~ tion and the reduction peaks. This is indie~tive of very slow eleuL,url.~ 1 kineties ~csoc~ d with bond breaking and fc-rm~tinn It is elear from these e,~e.i,--ental results ~hat PCS behaves like a conjugated polymeric 20 material whieh is fun-l~m~n~:llly different in its ~L~UU~LIIC and eleetrochPmir:~l function eompared with the m~tPri~lc developed by De Jonghe et al. This fim~:lmen~l difference st~u-,Lul.llly and ele-,L,o,..cdlly is the eause for the suhct~nti~lly higher eapacity and much improved electrorh~mir: 1 kineties at room Le,,,pc,~t~
Novel reehargeable battery cells of the present invention eomprise three essenti:-l eomponents. One eSsenti~l eomponent is an anode material. The anode may eomprise any metal eapable of funrtiorling as a negative eleetrode in eombination with the eathode materials of the ~0 W O 96/41387 PCT~US96/06750 present invention. Illus~rative of useful ~node m~terials of this invention ~re one or more met~ls selected from the group concicting of metals belonging to Group IA and Group IIA in the Periodic Table of the ~l~mentc, such as lithium. sodium, potassium, m~n.ocillm, ~lrillm, and the like.
Also useful in the practice of this invention are ~nodes comprised of alloys, mixtures, composites, intercalated carbons, intercalated conjugated polymers, and the like, of the aforem~ntioned alkali and aLkaline earth metals. Illustrative of such compositions are sodium-lithium alloys, lead-sodium alloys, lithium-tin alloys, lithium-silicon alloys, lithium intercalated carbons, lithium doped polyacetylene, sodium doped polyphenylene, and lithium intercalated graphite. Preferred anodes in the practice of this invention are those comprised of alkali metals. More preferred are those 10 comprised of lithium andlor sodium. Most preferred are anodes comprised of lithium foils of from about 2 microns to about 250 microns.
Another ecc~n~ component in the novel battery cells of the present invention is a cathode material comprised of a polycarbon-sulfide materinl of gener 1 formula I;
~ C(sx)~
wherein x can range from greater ~h~n 2.3 to about 50, and n is equal to or grenter than 2.
Preferred anode materials are those wherein x is greater than 3, and n is equal to or greater than 5.
20 Particularly preferred cathode m:lt~ri~15 are those wherein x is equal to or greater than 6, and n is greater th~n 5.
Also illustrative of useful cathode m~r~ l.C of the present invention are composite c~thod~c co".p.i ,ed of:
(a) PCS materials of formula I, (b~ a non-aqueous electrolyte, and SUBSTlTUTE SHEET (RULE 26) CA 0222l603 l997-l2-0~
(e) a eon~ ctive filler.
Useful non-aqueous electrolytes in said composite cathodes c~n be the same or different from those used in the construction of complete b~uery cells. A complete description of useful 5 electrolytes in the composite cnthod~c of the present invention is presented below.
Useful conductive fillers are any conductive materials that can enhance the electrical co~n~ul;-/ity between the current collectors and the electroactive cathode components in the cell. I~
is desirable th~t said eon~lctive fillers be inert to the components of the cell under lhe int~d~d 10 opera~ing con~iitiorl~ of the cell. Particularly preferred con~iu~tive fillers are c~n~l~lrtive c~rbons;
conductive acetylene bl~cks; gr~phites; metal powders, flakes and fibers; and electrically conduetive polymers such as polynniline~, poly~cetylenes, polypyrroles, polythiophenes, polyphenylenes, polyphenylene-vinylenes, polythienylene-vinylenes, and derivatives thereof.
Additionally, eomposite cathodes useful in this invention may contain other polymeric or non-15 polymeric binder m~teri~ls that fncilit~t~ the formation, f:lbric~tion, and assembly of b~ttery cells indesired configurations. Such optional materials are known to those skilled in the art of cathode fabrication an inelude materials sueh as polytetra~luoroethylene and other fluorinated polymers, SBR rubbers, EPDM rubbers, and the like.
The third ~cc~nti ll component of tl e battery cells of the present invention is an electrolyte.
IIIu~Ll,LLive of useful eleetrolytes in the practice of this invention are electrolytes that ~re ch~omirnlly and electroch~minnlly inert with respect to the anode and cathode materials and which permit the migration of ions between the anode and c:~thode at desired use temperatures. Preferred electrolytes are those that allow for transport of ions at ambient temperatures and below.
25 Partieularly p~,L~Icd are those e~pable of operating between about 40'C and +120'C.
SUBSTltllTE SHEEt (RU~E 26~
CA 02221603 1997-12-0~
W O96/41387 PCT~US96/06750 Elec~roly~e systems which have application ~o both lithium ~nd sodium bascd le.:h~geable b~tteries can be employed in the fabrication of the cell of the invcntion, such as solid polymer electrolytes; single-ion con~cting polymer electrolytes, high cond~lctivity gel polymcr electrolytes, and liquid organic electrolytes. Particularly useful electrolytes for use in cells of the present 5 invention are single ion conrlllrting polymer electrolytes with highly delocalized anionic moieties covalently attached to the polymer backbone to achieve high specific lithium ion condu~ivity~ as descrihed in U.S. P~tent No. 4,882,243. The adv:~ntages of polymer electrolytes with exclusive cation cnntluction ~re reduced cell polarization deriving from low anion mobility, reduced volume changes in the cathode from intercalation of ion clusters, and reduced salt-induced corrosion on the 10 current coll~ctor~ Room temperatur~ co-~-luctivities for single ion co~d~lcting polymer electrolytes described in U.S. Pa~ent No. 4,882,243 are in the range of 10-4 to 10-5 S/cm.
A variety of gel-polymer electrolytcs have been discovered to be generally useful in non-aqueous high energy density batteries. Illustr~tive of useful polymer matrices for gel polymer 15 electrolytes in high energy density batteries are those derived from polyethylene oxides, poly~.op~lene oxides, polyacrylonitriles, polysilox~nes, polyimides, polyethers, sulfonated polyimides, NafionTM resins, divinyl polyethylene glycols. polyethylene glycol-bis-(methyl acrylates), polyethylene glycol-bis(methyl methacryla~e), blcnds of the foregoing, d~ tives of the foregoing, copolymers of thc forcgoing, croc~in~-ed and nc~work structures of thc foregoing, 20 and the like. Useful ionic electrolyte salts for gel-polymcr electrolytes include MC104, MAsF6, MS03CF3, MS03CH3, MBF4, MB(Ph)4, MPF6, Mc(so2cF3)37 MN(SO2CF3)2.
so2CF3 F3cso2~so2cF3 F3CSO2~;~ SO2CF3 MNSO2CF2CF2cF2cF2s02 ~ OM , M and the like, where M is Li or Na. Other electrolytes useful in the practice of this invention are r~ oc.od in U.S. Patent Application Ser. No. 192,008.
SUBSTITUTE SI~EET (Rl ILE 26 CA 0222l603 l997-l2-05 W O 96/41387 pcTrus96/o67so Useful ~el~non agen~s ~or ~el-polymer elec~rolytes include ethylene carbonate (FC), propylene carbonate ~PC), N-me~2yl aret~ nide. ~ce;oniT-ile,sulfolane.1.2-dimcthoxye~2ne.
polye1hyl~ne ~Iyc~ls, 1.3-dioxolanes, glyrnes, siloxanes, and e~hylene oxide ~rafted s;lo~n~c Particularly preferred gelation agen~s are tho.se denved from ~raft cnpolymers of e~ylene oxide 5 and oligomers of poly~dirne~hyl siloxane) of genes~l formula ~II, ~ Me 1 r Me t(CH ~ ~w I Me (~C~2CH2)~~Cf~3 YII
wherein u is an integer egual to or greater thanl, v is an int~er equaL to or gre~ter than O and less ~han 3bout 30, and the rariG zlw is ~ual to or ~reater lh3n 5~
V~ues ~or u, v, w, ~nd z can Yar,Y widely 2nd depend on the desi~cd properties for said liquid gel~tion agen~. P,eh,.~1 gel3tion a~ents of this type are ~hose wl2ere~n u rang~s from about 1 tO 5, v ran~es from ~ou~ 1 to ~0, and the r~ho z/w is equal to or grealer than 0.5 An especially 15 pre~rr~ coTnpoc;rion of fo~nula VII is that in whlch u i5 equ~ lo 3, v is equal to 7, and the rasio of zsowis 1.
These liquid ~el3tion ~ents themselYes are useful solvents to for~n liquid electrolytes which provide o~her ~rreclive electrolyt~ syst~ms for Ihe ceJls of the in~ention For ex~mple.
20 glymes with lithium salts. such as LiAsF6, are useful liquid elect~olytcs. ~i~cewise, composi~ions of ~;~2~ula VII together wi~ Li(SO~ 3) a~e ~c~e~i 311y useful as liquid ~ lcc~rolyte5.
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W O 96/41387 PCT~US96/06750 Battery cells comprising PCS cathodes can be made in a variety of si~s and configur~7~ir,nc which are known to those skilled in the art. Illustrative of useful battery design configurations are planar, prismatic, jelly-}oll, W-fold, and the like. These configurations are not to be construed as limi~tinnc on the scope of this invention as other designs are :m~icir~
s In batteries of the present invention, the main design concerns are the kine~ics and chPmir:ll and electrochPmir -l reversibility of the re~uc~ion/nYi~tirn rt~:lrtic-nc, the densi~y of available sulfur atoms, and the miscibili~y of oxidation and reduc~ion produc~s wi~h the polymer elec~roly~e.
During ~he discharge of the, cells Or this invenLion, ~hc PCS polymcr is reduccd accomr ~nied by thc 10 insertion of Li+ ions into the cathode from ~he elec~rolyte ~o m~in~in charge neutrali~y. In contras~
to the m~erials disclosed in U.S Pa~en~s 4,833,048 and 4,917,974, ~he polycarbon-sulfide m~Pri:~lc of the present inven~ion undcrgo oxida~ion and n:duc~ion wi~h thc form:ltion and brcal;ing of multiple sulfur-sulfur bonds ~ rhpd to conjugated s~ru~tul~s which provide good electron h~-S~OIL and fact electrochPmir~l kinetics at ambient temperaturec and below. An advantage of lS using PCS as the cathode active material is the high density of sulfur atoms which results in a high chal~e ~o~..ge density during oxidation-reduction. This is accompanied by a high densi~y of Li~
ions inserted for ch~rge neutrality, resulting in a high capacity. Figure 3 demonstrates the high capacity for the PCS materials of the present invention. In all PCS compounds used for the cathode of the present invention, the sulfur concentration is always greater than 86 wt%
In contrast to the organo-sulfur materials developed by Dc Jonghe, et al. PCS need not undergo polymPri7~inn/de-polymerization upon ch:~rge and discharge, thereby m~in~nining the hltt;~;~;ty of the polymcr backbonc and improving cathode utilization during repeated charge and discharge.
Table 1 snmm~ri7Ps the superior performance of bat~ery cells compriscd of PCS anodes of formula I relative to state-of-the-art rechargeable battery systems presen~ly commercialized or SUBSTITUTE SHEET (RULE 26~
CA 0222l603 l997-l2-05 W O96/41387 PCTrUS96/06750 under development. The PCS base(l cells exhibil ~ volumetric energy densi~y ndvantage of from 2 to 3 ~imes, and a gravimetric energy density advantage of from 1.7 to 3.5 times better than presently known l~l,.u~,~able cells in a AA configuration 5 Table 1. Performance comparisons of PCS based rechargeable cells relative to other advanced ~l.a~ able systems in AA cell configurations Volumetric EnergyGravimetric Energy Electrochemic~l SystemDensity (~Vhr/L)Density (Whr/K~) Li/PCS cells of formula I 430 - 500 175 - 260 Lithium Ion 215 100 Nickel Metal Hydride 180 - 200 60 - 75 Mckel~ lmi--m (~I~C~liUlll) 120 - 150 40- 50 The following specific examples are prcsented to more particularly illustrate the invention, 10 and should not be collaLLued as limitations on the scope and spirit of the invention.
EXA MPLES
Preparation of Polvcarbon-Slllfide From Carbon Dislllfide Example l To 26.2 g of sodium metal in 274 mL of boiling carbon ~iicnlfide with stirring was added dropwise 400 mL of dimethylsulfoxide (DMSO) during S hours, and the reaction mixture was 20 refluxed for 68 hr. Unreacted carbon disul~lde was dictille(l out and to the rem:-inin~ residue was added 400 mL of w~ter and 105 mL of concentrated hydrochloric acid. The polymer layer was ~UBSTITUTE $~EET (RIJLE 26 W O 96/41387 PCTAUS96/067~0 dec~n~Pd and w~shed with water (3 x 550 mL), then ac~tone (3 x 300 mL), and vacuum dried for 2 hours at 180 - 195'C. The yield of dry polymer was 92.4 g with a softening temperature of 68-80'C. Fl~-m~nt:ll analysis gave %C: 11.0, %S: 89.0, which corresponds to an empiric~l formul~
of -(cs30)n Ex3mple 2 The procedure of loy~lmrle 1 was repealed using 331~ (260 mL) of carbon rlic~llfi~e 25g of 10sodium metal, 400 mL of dimethyl sulfoxide, and a reflux time of 133 hr. The yield of polymer was 139 g with an el~ment:ll analysis of 7.9% carbon and 92.1% sulfur corresponding to an empirical formula Of -(CS4 37)n~.
15Ex~mple 3 For comr:~r.~tive purposes, ~he procedures of Examples 1 and 2 were repe~ted using reaction time less than 42 hours with the following results:
Carbon SodiumSolventReflux YieldElement~lEmpirical disulfide (g) (mL) time (g)Compositionformul~
(g) (hrs) %S
463 35 DMSO 39 92 83.9 CSI 95 (450) lS9 12 DMSO 41 52 85.0 CS2.12 (200) SUBSTITUTE SHEET (RULE 26~
W O 96/41387 PCTrUS96/06750 Preparation Or Polycarbon-Sulride Composite Cathodes l~:xample 4 A mixture of 40% by weight PCS prepared by the general procedure of FY~mple 1, 50%
polyacrylonitrile and 10% acetylene black was s~cpen~led in dimethylsulfoxide to form a slurry.
The slurry was ground into fine particles and was then cast as a film 25-lOO~lm thick on a 2511m thick nickel foil. The entire unit was dried in a vacuum oven at 40'C - 80AC for 24 hours.
Example S
A mixture of 40% by weight PCS from FY~mple 2, 45% by weight electrolyle and 15%acetylene black was s~cp~n~ied in dimethylsulfoxide to form a slurry. The electrolyte was a gel 15 electrolyte made from polyethylene oxide, propylene carbonate, ethylene carbonnte, and LiS03CF3. The slurry was finaliy ground and then cast as a film onto a nickel foil. The entire unit was then dried in a vacuum oven at 40'C - 80'C ~or 24 hours.
Preparation of Rechar~eable Batteries Example fi A rechargeable lithium battery of unipolar sandwich design was prcpared by sandwiching a 25 polymer electrolyte of about 25 micron thi~ n~c.c beLween a lithium foil of 125 micron thirl~nl~.cc and the composite cathode (FY:1mP1e. 4) of abou~ 25-75 microns thick. To obtain labor~tory prototype cells, the above components were sandwichcd between two 5~inl~cc steel circul~r disks S~IBSllTllTE S~EET ~ E 2~
CA 02221603 1997-12-0~
W O96/41387 PCTrUS96/06750 having 0.5 cm thirknPcc A typical material used for the anode was lithium metal. The PCS of the invention prepared in accord;mce wilh the procedure of Examples 1 or 2 was used for the cathode.
The electrolyte employed in preparing the battery of this example was a branched polysiloxane eont~ining grafted ethylene oxide side chains (formula VII, u = 3, v = 7, z/w = 1, molecular S weight of 1000) and a LiS03CF3 snlt.
Ex~mple 7 Following the general procedure of Exnmple 6, a rechargeable lithium/polymer electrolyte/PCS battery was prepared, using the composite cathode of example 4, a lithium foil anode, 9.8 mg of polymer gel electrolyte and 2.3 mg of ultrafine graphite powder The composite anode eont~ined 7.1 mg of PCS. The polymer gel electrolyte con-:linc d polyacrylonitrile, ethylene carbonate, propylene carbonate and LiCl04 with a conductivity of 3 x 10-3 S/cm at 25'C.
At 0.10 mA/cm2 current density, a practical capacity of 4.4 mAh has been achieved with a cut-off voltage at 1.5 volts. This translates into 87% of practical cathode l~tili7:ltion at a storage energy of 8.8 mWhr.
Ex~mple 8 Another rechargeable li~hium cell was prepared having a composite cathode cont:lining 5.4 mg of polymer gel electrolyte, 12.0 mg of PCS of Example I and 1.9 mg of graphite powder.
~ccllming a mid cell potential of 2.5V, a stor~ge energy of 12.6 mWh was obtained.
~.UBSTITUTE SHEET (RULE 26) CA 0222l603 l997-l2-05 W O 96/41387 PCT~US96/06750 The perfonn~nce eh~racteristics of the cells prep~red in F-r~mpl~ 7 ~nd 8 ~lrmQnctrate th~t by using the cathode of the invention a very high c~thode utilization is r~adily achieved resulting in energy capncity stor~ge mueh higher than those ~chieved by commerci~lly nvailabl~ batteries.
Example 9 A reehargeable lithium battery w~s prepared having a lithium foil anode of 125 micron thir~nf~cc, a polyethylene oxide (PEO)/LiS03CF3 solid elec~rolyle along with a siloxane (from 10 Example 6)/LiSO3CF3 liquid electrolyte, a composite cathode cont~ining 50 wt% PCS from rY:lmpllo.1 along with 30 wt% conduetive earbon and 20 w~% of the PEO/LiS03CF3 eleetrolyte, wherein the anode and eathode were separ~ted with Cel~rdTM 250Q. This lem x lem pl~n~r battery t-Yhihit~d 103 cycles at a charge/disch~rge current of 0.05 mA/cm2 with a capacity of 729 mAhr/g for the first several cycles, which then decayed to a final capacity of 243 mAhr/g at eyele 15 103.
Example 1 0 A reehargeable lithium battery w~s prepared h~ving a lithium foil anode of 125 micron shirknr5s, a eomposite eathode eort~ining 50 wt% PCS from example 2 along with 30 wt%
cn~nd~lctive c~rbon and 20 wt% of PEO/LiSO3CF3 electrolyte, ~ solid frPest~n(iing film electrolyte of polyethylene glycol-bis-(methyl methacryl~te) /silox~ne/LiSO3CF3 which was UV cured (cros~linkrd)~ and to the eell was added a sm~ll amount of liquid electrolyte corl~ining silox~ne 25 (from Example 6)/LiS03CF3. This lcm x lcm pl~n~r battery w~s ch~rged and disch~rged at a current density of 0.05 mA/cm2 and exhibited a capaeity of 1324 mAhr/g for the first sever~l eyeles, which then decayed to a final e~p~city of 296 mAhr/g al cycle 56.
SUBSIT~ SHEET (F~ULE 2~i) Ex~mple 1 1 A composite cathode was prepared from a physical mixture of 48 wt% PCS materi31 from example 1, 12 wt% of polyaniline powder in the fo.~ of Versico~ m lnllrlntllred by Allied-Signal, Inc., 20 wt% acetylene black, and 20 wt% polymer electrolyte. The polymer electrolyte used to form the composi~e cathode concict~od of a mixture of poiy(ethylene oxide) and a br~nched polysiloxane with ethylene oxide side chains (polysiloxane-graft-(ethylene oxide)7) and LiC104 in the ratio of 24 ethylene oxide units per lithium. The polymer electrolytes were dissolved in 10 a~ .;n ;il' and added to the mixture of PCS, polyaniline and acetylene black to form a viscous slurry. Co---pos-~ cnthodes of ti.i~ approximately 100 microns were cast onto Ni foil sn~str~t~-s and the solvent evaporated. Cells were assembled co n~; .;..g composite c~thodes, br~nl~h~d polysiloxane electrolytes and lithium foil anodes. The open circuit potentials of the cells were about 3.23 volts.
~UBSIlT~ ~EET (F~LE :~
W O96/41387 PCT~US96/06750 ELECTROACTIVE HIGH STORAGE CAPACITY POLYCARBON-SULFIDE
MATF.RTAT.S AND ELECTROLYTIC CELLS CONTAINING SAME
BACKGROU~D OF T~IE INVENTION
This invention relates to novel electroactive energy storing polycarbon-sulfide (PCS) materials of general formula (CSx)n wherein x is greater than 2.3 to about 50, and n is equ~l to or S greater than 2. This invention also relates to novel l~char~able ele~l-ocl ~..ic~l cells cont~ininE
positive electrode m~t-~ri~lc comprised of said polycarbon-sulfide materials with improved storage capacity and eycle life at ambient and sub-ambient temperatures. This invention also relates to novel gel electrolytes developed for high energy density recl,~geable non-aqueous b~ttet~irc Batteries are used in almost all portable concnm~-r electronic products from flash lights to lap top computers. Over the years, considerable interest has been shown in developing lighter weight high energy-density rechargeable. batteries for many applications inrlllrling electric vehicles.
In this regard, thin film solid state batteries using the polycarbon-sulfur cathode materials of this invention are particularly well suited for use in many consumer applications beeause of their high 15 energy to weight ratio.
Two main types of cathode materials used in the m~ntlf:lr~llre of thin film li~hium and sodium batteries are known in the art. The first materials include transition metal chalcogenides, such as titanium t~ llfi~le with alkali metals as the anode. For e~mple, among the cathode active 20 chaleogenides, U.S. Patent No. 4,049,879 lists transition metal phosphorous ehaleogenides.
Other U.S. patents, sueh as U.S. Patent Nos. 4,143,214, 4,152,491 and 4,664,991 describe eells wherein the eathode is a earbon/sulfur based material, generally of the C,~S formula where x is typieally 10 or larger.
U.S. Patent No. 4,143,294 to Chang, et al. describes cells having cathodes cont~ining C,~S
wherein x is a mlm~c~ll value from about 4 to about 50. U.S. Patent No. 4,152,491 to Chang et al. relates to eleetric current produeing cells where the cathode-active materials include one or more ULE 2~) CA 02221603 1997-12-0~
W O 96/41387 PCTrUS96/067~0 polymer co,.lpoul.ds having a plurality of carbon monosulr~de units. The carbon monnsnlfifle uni~
is generally described as (CS),~, wherein x is an integer of at least 5, and may be at least 50. and is preferably at least 100. In both cells developed by Chang, et al. the energy storage capacity is limited because there is a low density of sulfur-sulfur bonds.
s U.S. Patent No. 4,664,991 to Perichaud, et al. describes a substance contnining a one-tlimencionnl electric conducting polymer and at least one polysulfurated chain forming a charge-transfer cnmrl~Y with the polymer. Pcrichaud, et al. use a material which has two components One is the conducting polymer, which is selected from a group consisting of polyacetylenes, 10 polyparaphenylenes, polythiophenes, polypyrroles, polyanilines and their suhstitnt~d derivatives.
The other is a polysulfurated chain which is in a chnrge transfer relntion to the con~ rting polymer.
The polysulfurated chain is formed by high temperature heating of sulfur with the conjugated polymer. As a result of using this material, the cell of Perichaud, et al. exhibits a fairly low voltage of only 2.0 V against lithium.
-U.S. Patents 4,833,048 and 4,917,974 to De Jonghe, et al. describe a class of cathode mnt~rinlc made of organo-sulfur compounds of the formula (R(S)y)n where y = 1 to 6; n = 2 to 20, and R is one or more different :~liphntir or aromatic organic moieties having one to twen~y carbon atoms. One or more oxygen, sulfur, nitrogen or fluorine atoms associated with the chain can also 20 be inr~ ed when R is an nliph~t jc chain. The aliphatic chain may be linear or branched, s~tu~.-ted or unsaturated. The aliphatic chain or the aromatic rings may have substituent groups. The p-cfe.-~;~ form of the cathode material is a simple dimer or (RS)2. When the organic moiety R is a straight or a ~ --nllcd :~liphnti~ chain, such moieties as alkyl, alkenyl, alkynyl, alkoxyalkyl, alkythioalkyl, or :~minonlkyl groups and their fluorine dcrivatives may be included. When the 25 organic moiety comprises an aromatic group, the group may comprise an aryl, arylalkyl or alkylaryl group, innluciing fluorine substituted derivatives, and the ring may also contain one or more nitrogen, sulfur, or oxygen heteroatoms as well.
~ E SHEET ~Ut ~:: 2~!
CA 02221603 1997-12-0~
W O 96/41387 PCTrUS96/06750 In the cell developed by De Jonghe. et al. the main cathode reaction during dischar~e of the b~ttery is the breaking and reforming of ~licnlfitle bonds. The breaking of a disulfide bond is associated with the formation of an RS-M+ ionic complex. The organo-sulfur materials 5 investigated by De Jonghe, et al. undergo polymerization (dimerization) and de-polymerization (disulfide cleavage) upon the formation and breaking of the disulfide bonds. The de-polym~ri7: ~ion which occurs during the discharging of the cell results in lower weight ml~nomt3~ic species which can dissolve into the electrolyte, thereby severely reducing the utility of the organo-sulfur material as cathode-active material. The result is an ~lnc-tticf~ ory cycle life having a 10m~imllm of about 200 deep dischargc-charge cycles, more typically less than 100 cycles as described in J. ~ectroche~ Soc., Vol. 138, pp. 1891-1895 (1991) In particul~r, the organo-sulfur materials developed by De Jonghe, et al., are highly unstable in the presence of high cnnfiuctivity liquid, p~ d polymer, or gel electrolytes.
15A 5jgnifir~nt nd~litiorlnl drawback with the organo-sulfur mnterials developed by De Jonghe; et al. is the slow kinetics of oxidation and reduction at ambient temperatures, severely reducing the power output of cells i.-co,~o-,lting cathodes made with these organo-sulfur materials.
The slow kinetics result from the oxidation and reduction being related to the formation and breaking"~.ecti~ely, of ~iiculfide bonds on non-conjugated, non-conductive materials. Such~0 breaking and reforming of said tiiC--lfi.l~ bonds results in depolymerization and repolymeriz ation, ely, wherein such processes are kint~tic~lly very slow.
U.S. Patent Application Ser. No. 145,091 describes polycarbon disulfide materials of general formula -(CS,c)n-, wherein x ranges from 1.7 to 2.3 and n is greater than 2. These 25 compositions are prepared by the re~inction of carbon dic--lfide with alkali metals using relatively short reaction times that produce polymers with structures co---p.;sed of SUBSTITUTE SHEET ~RULE 26) ' S ' - ,S, ,S, --C--S-- and --C-C--S--. n . . n Such m~7t~ri~1c suffer from a limited sulfur content and thus. limited capacity r~lative to the materials of the present invention. Materi~ls described in U.S. Patent Application Ser. No.
145,091 have sulfur contents less than 86 wt%.
Despite the various ap~ua.-l.es proposed for organo-sulfur cathode mn-f~ri: lc, there remains a need for in ~ c;ve cathode materials having high storage capacity, high dischar~e rates and very long cycle lives at ambient and sub-ambien~ tempe,L~tu~es~
It is, therefore, a primary object of this invention to provide new polycarbon-sulfur based cathode m~teri~llC for thin film solid state batteries which are in~oypl~ncive~ yet avoid the limit~tinnc existing in the prior art, while offering perforrnance characteristics much higher than those of known m~t~rinlc It is another obiect of this invention to provide new cathode materials having as the active materi~l polycarbon-sulfide (PCS) polymers which need not undergo polymerization and de-polymeri7~tic n upon ox~ n and re~luction It is yet another object of this invention to provide a method of making a solid state 20 rechargeable battery including the novel c;~thode of the invention.
SUBSTlTUTE SHEET (RULE 26) CA 02221603 1997-12-0~
SUMMARY OF THE PRESENT INVENTION
It is an object of the present invention to provide a novel electroactive energy storing polycarbon-sulfide (PCS) m~terial useful as a solid state c;~thode malerial in rechargeable batteries.
S In its fully charged or oxi~li7~d state. the PCS material can be represented by the formula I, ~ C(SX)~
I
wherein x ranges from greater than 2.3 to about 50, n is equal to or greater than 2, and said PCS
10 material does not contain nlirhnti~ or aromatic mQif'tit~~ Said PCS material is further ~h~l...~ t~ .od by the incorporation of large fractions of polysulfur components, which on clectrochemir:~l reduc tion in an electrolytic cell, provides the exceptionnlly high storage capacity per unit weight of mnterinl In contrnst to materials presently known in the art, the PCS materials of the present invention undergo oxi(lntion and reduction with the formntion and bre3~ing, respectively, of many 15 sulfur-sulfur bonds which are attached to conjugated ~ U~UIGS that provide good electron transport and fast electrorhemi~nl kinetics at ambient temperatures and below Said PCS materials when used as cathode materials in battery cells, may be optionally mixed with conductive components and binders to further improve electrochemic ~I recycleability and cnpacity of said cathode active mnt~o i nl One embodiment of this invention relntes to PCS compositions of formula I pl~p...~d by the reductior of carbon ~ -lfide with alknli metals, such ~s sodium or lithium, in an appropliate solvent such as dimethyl sulfoxide, dimethyl formamide (DME:), N-methyl pyrrolidinon-o.
h~ th~l pho~rhoramide, and the like, incorporating long reaction times before workup. It has 25 been ~ul~;sillgly discovered that reaction times greater than about 41 hrs provide PCS materials of the present invenlion with clP-- ~--t~l compositions contnining between aboul 86 wl% and 98 wt%
SUBSmUrE Sl~ RULE 26~
sulfur. Preferred PCS compositions are Ihose lhat have element;ll composi~ions c-~nt~ining between about 90 wt% and 98 wt% sulfur.
Although the detailed ~llu.~u.~s of the PCS materials made by this method have not been S completely determin~-l available structural information suggests that compositions of gener~l for~nul~ I of the present invention are comprised of one or more of the sl- uutu-.~l units of formulas II- VI, ~C=C~ _C=C-- ~(C=C)~ ~S ~ ~S~
~ III IV V VI
wherein m is the s:~me or different at e;leh occurrence and is gre:~ter than 2, y is the s~me or different at each oc~u--G,-ce and is equal to or greater than 1. and the relative amounts of a, b, c, d, and e eomprising said PCS material ean vary widely and depend on the method of synthesis.
Preferred PCS compositions with high eleetrochemic: l eapacity are those co~r:~ining 5l-hst~nti~1 15 amounts of polysulfide speeies -(Sm)- and -(Sy)- incorporated in and ~tt~ched to the polymer baekbone. ~peei~lly preferred compositions are those wherein m is on the average equal to or greater than 6, and y is on the average equal to or greater than 1. A key feature of these compocitionc is that ele-,~-ucl-c.--ieal redue~ion and o~ tion need not lead to depolymeri7: tir n and repol~ io~ of the polymerie backbone. Further, ~he polymer backbone strueture contains 20 eonjugated se~ u tc whieh may f;lcilir~t~ eleetron transport during eleetroch~omir ~1 o~ tion and red--c-ion of the polysulfur side groups, wherein eleetrochemic ~I re~uction and o~ til~n of the eonjugated bacLL.one segments does not oeeur.
~ f ~E S~ET ~F~ULE 26.~
W O 96/41387 PCTrUS96/06750 It is ~nother object of this invention to provide ~ rech~rge~ble, solid st~te electric current producing cell capable of operating at ambient temper;ltures and below, which is comprised of:
(a) an anode which is co. "p, ;cPd of one or more ~lkali or aL~line earth met~ls;
s (b) a novel c~thode having as the cathode active m~teri~l one or more polycarbon-sulfur co, pou~ c which c2n be formulated as (CS,~)n wherein x is from greater than 2.3 to about 50, and n is equ~l to or greater than 2; and (c) ~n electrolyte which is chemically inert with respect to the ~node and the cathode and which permits the trans~o~ iu-, of ions between the anode and the c;3thode.
The anode materi~l may be an ~lPm~n~l alkali metal or an alk~ metal alloy including the mixture of an el~om~ont~l ~lkali meul ~nd one or more alloys made from an element selected from the 15 Periodic T~ble Group IA and IIA metals. Lithium and sodium are useful m~t~.rinl.c for the anode of the battery of the invention. The anode may also be ~Ikali-metal intercalated carbon such 2s LiC,~
where x is equ~l to 6 or greater. Also useful as anode mnt~ri:llC of the present invention are alkali-metal intercalated conjugnted polymers, such as lithium7 sodium or potassium doped polyacetylene, polyphenylene, and the like.
The cathode employed in the battery of the invention as the c;lthode active m~terial is comprised of a PCS material of the formula (CS,~)n, wherein x is from greater th~n 2.3 to about 50, and n is ~ numerical value gre~ter th~n or equal to 2, and preferably gre~ter than 10.
The electrolytes used in battery cells function as a medium for storage and transport of ions, and in the special case of solid electrolytes these materials additionally function ~c sep~rator m~ tPrinlc between the anodes and ca-hodPc In principle, any liquid, solid, or solid-like material SUBSTITUTE SHEET (RULE 26) CA 02221603 1997-12-0~
capable of storing and transporting ions may be used. Particularly preferr~d are solid electrolyte separators comprised of polyethers, polyimides, polyphosph~7t~n~c, polyacrylonitriles (PAN), polysiloxanes, polyether grafted polysiloxanes. blends of the foregoing, derivatives of the foregoing, copolymers of the foregoing, crocclink~d and networl; structures of the foregoing, and S the like to which is ~dded an approp-;~te electrolyte salt.
New types of electrolytes have been discovered in the practice of the present invention that are gener~lly useful in non-nqueous high energy density batteries. These electrolytes are "gel-type"
solid electrolytes that consist of a high molecular weight polymer matrix into which is dissolved an 10 electrolyte salt, then subsequently swollen with ~ low molecular weight liquid which effectively acts as a pl~ctici7~r for the salt-polymer matrix. 1'hese low mol~c~ r weight liquids are referred to as gelation agents and are generally common organic solvcnts or liquid oligomers. Any organic liquid capable of swelling said salt-polymer matrix can be used as a gelation agent so long as it is stable to the selected cathode and anode in the battery cell. A snbst~nti:ll increase in electrolyte 15 cond~,ct;viLy can be achieved by introducing these gelation agents into said salt-polymer blends.
Gel-polymer electrolytes of this type have been found to be f~cpeni~lly useful in lithium and sodium (anode) b~sed high energy density batteries.
A variety of solid gel-type elcctrolytes havc becn found to be vcry useful in the practice of 20 this invention. Illustrative of useful gel-type electrolytes are polyacrylonitriles, sulfonated polyimides, cured divinyl polyethylene glycols, cured polyethylene glycol-bis-(methyl acrylates), and cured polyethylene glycol-bis-(methyl methacrylate) which have been swollen with propylene carbonate (PC), ethylene carbonate (EC), glymes. low molecular weight polysiloxanes, and mixtures thereof. Especially useful solid and gel-type electrolytes are those comprising 25 polyethylene glycol-bis-(methyl meth~crylate) which has bcen cured (crosclinkPd) using UV, x-ray, gamma ray, electron beam, or other ionizing r~ on SUBSTITUTE SHEET (RULE 2B) CA 0222l603 l997-l2-0~
W O 96/41387 PCTrUS96/067~0 It is another object of this invention to provide a method of m~;ing the solid state batteri~s h,co,l,ol,lting the novel cathode m~terials of the present invention. The method of making the cells ~ of the present invention is particularly preferred for use in applications requiring high energy storage cap~city.
s It is still another object of this invention to provide solid state b~tteries having higher specific energy and higher current than h~s been previously nchieved with organo-sulfur cathode materinls.
It is a further object of this invention to provide b~tteries having long shelf life and a low rate of self-discharge.
These and other objects of this invention will be apparent from the following description and the accompanying drawings.
BRIEF DESCRIPTION OF T~E DRAWINGS
Figure 1 shows a cyclic voltammogram of PCS (made from the reaction of carbon disulfide 20 with an alkali met:ll) in an electrolyte concicting of dimethylsul~oxide wilh 0.1 molarconcentration of ~e~ l,yl~mmonillm perchlorate at ~ sweep rate of 50 mVlsec at room temperature.
Figure 2 shows the cyclic voltammogram of ((C2H5)2NCSS)2 in an electrolyte conci~tin~
of dimethylsulfoxide with 0.1 molar con~ tl.ltion of tetraethylammonium perchlorate at a sweep 25 rate of 50 mV/sec at room t.omrerat~lre.
SUBSTITUTE SHEET (RULE 26) WO 96/41387 PCTnUS96/06750 Figure 3 shows speeific cathodec eapaeity during eharge and discharge cycles for a PCS
eathode material made from the reaction of carbon ~liclllfide with an alkali metal using long reaction times.
DETATLED DESCRTPTTON OF T~E INVENTTON
The eyelic voltammograms shown in Figures 1 and 2 illustrate the fun~l~mrnt~l difference between PCS m~t-~ri~lc of the present invention and organo-sulfur materials ~licclosed in the art 10 whose cle~,l,u~ I f ..;r:ll activity is based on breaking and reforming of dicnlfirle bonds. In the ease of PCS m:~teri~lc ehe o~ tio~ and reductiQn peaks are closely aligned on the voltage axis indieative of fast, reversible electroehemir~l kinetic5 In the ease of ((C2H5)2NCSS)2, whieh is ~c~.cse.-l~Livc of the m~tPri~lc diceloced by De Jonge et al. co.-t~;n;l-g ~liculfide bonds, and which polymerizes (dimerizes) and de-polymerizes (ele~ves) by the forming and breaking of said 15 ~liclllfi~P bonds, r~s~euLively, during eleu~,ucllc,,lieal n~id~tion and rednctir,n, there is a spread of about 2 vol~s between the n~ tion and the reduction peaks. This is indie~tive of very slow eleuL,url.~ 1 kineties ~csoc~ d with bond breaking and fc-rm~tinn It is elear from these e,~e.i,--ental results ~hat PCS behaves like a conjugated polymeric 20 material whieh is fun-l~m~n~:llly different in its ~L~UU~LIIC and eleetrochPmir:~l function eompared with the m~tPri~lc developed by De Jonghe et al. This fim~:lmen~l difference st~u-,Lul.llly and ele-,L,o,..cdlly is the eause for the suhct~nti~lly higher eapacity and much improved electrorh~mir: 1 kineties at room Le,,,pc,~t~
Novel reehargeable battery cells of the present invention eomprise three essenti:-l eomponents. One eSsenti~l eomponent is an anode material. The anode may eomprise any metal eapable of funrtiorling as a negative eleetrode in eombination with the eathode materials of the ~0 W O 96/41387 PCT~US96/06750 present invention. Illus~rative of useful ~node m~terials of this invention ~re one or more met~ls selected from the group concicting of metals belonging to Group IA and Group IIA in the Periodic Table of the ~l~mentc, such as lithium. sodium, potassium, m~n.ocillm, ~lrillm, and the like.
Also useful in the practice of this invention are ~nodes comprised of alloys, mixtures, composites, intercalated carbons, intercalated conjugated polymers, and the like, of the aforem~ntioned alkali and aLkaline earth metals. Illustrative of such compositions are sodium-lithium alloys, lead-sodium alloys, lithium-tin alloys, lithium-silicon alloys, lithium intercalated carbons, lithium doped polyacetylene, sodium doped polyphenylene, and lithium intercalated graphite. Preferred anodes in the practice of this invention are those comprised of alkali metals. More preferred are those 10 comprised of lithium andlor sodium. Most preferred are anodes comprised of lithium foils of from about 2 microns to about 250 microns.
Another ecc~n~ component in the novel battery cells of the present invention is a cathode material comprised of a polycarbon-sulfide materinl of gener 1 formula I;
~ C(sx)~
wherein x can range from greater ~h~n 2.3 to about 50, and n is equal to or grenter than 2.
Preferred anode materials are those wherein x is greater than 3, and n is equal to or greater than 5.
20 Particularly preferred cathode m:lt~ri~15 are those wherein x is equal to or greater than 6, and n is greater th~n 5.
Also illustrative of useful cathode m~r~ l.C of the present invention are composite c~thod~c co".p.i ,ed of:
(a) PCS materials of formula I, (b~ a non-aqueous electrolyte, and SUBSTlTUTE SHEET (RULE 26) CA 0222l603 l997-l2-0~
(e) a eon~ ctive filler.
Useful non-aqueous electrolytes in said composite cathodes c~n be the same or different from those used in the construction of complete b~uery cells. A complete description of useful 5 electrolytes in the composite cnthod~c of the present invention is presented below.
Useful conductive fillers are any conductive materials that can enhance the electrical co~n~ul;-/ity between the current collectors and the electroactive cathode components in the cell. I~
is desirable th~t said eon~lctive fillers be inert to the components of the cell under lhe int~d~d 10 opera~ing con~iitiorl~ of the cell. Particularly preferred con~iu~tive fillers are c~n~l~lrtive c~rbons;
conductive acetylene bl~cks; gr~phites; metal powders, flakes and fibers; and electrically conduetive polymers such as polynniline~, poly~cetylenes, polypyrroles, polythiophenes, polyphenylenes, polyphenylene-vinylenes, polythienylene-vinylenes, and derivatives thereof.
Additionally, eomposite cathodes useful in this invention may contain other polymeric or non-15 polymeric binder m~teri~ls that fncilit~t~ the formation, f:lbric~tion, and assembly of b~ttery cells indesired configurations. Such optional materials are known to those skilled in the art of cathode fabrication an inelude materials sueh as polytetra~luoroethylene and other fluorinated polymers, SBR rubbers, EPDM rubbers, and the like.
The third ~cc~nti ll component of tl e battery cells of the present invention is an electrolyte.
IIIu~Ll,LLive of useful eleetrolytes in the practice of this invention are electrolytes that ~re ch~omirnlly and electroch~minnlly inert with respect to the anode and cathode materials and which permit the migration of ions between the anode and c:~thode at desired use temperatures. Preferred electrolytes are those that allow for transport of ions at ambient temperatures and below.
25 Partieularly p~,L~Icd are those e~pable of operating between about 40'C and +120'C.
SUBSTltllTE SHEEt (RU~E 26~
CA 02221603 1997-12-0~
W O96/41387 PCT~US96/06750 Elec~roly~e systems which have application ~o both lithium ~nd sodium bascd le.:h~geable b~tteries can be employed in the fabrication of the cell of the invcntion, such as solid polymer electrolytes; single-ion con~cting polymer electrolytes, high cond~lctivity gel polymcr electrolytes, and liquid organic electrolytes. Particularly useful electrolytes for use in cells of the present 5 invention are single ion conrlllrting polymer electrolytes with highly delocalized anionic moieties covalently attached to the polymer backbone to achieve high specific lithium ion condu~ivity~ as descrihed in U.S. P~tent No. 4,882,243. The adv:~ntages of polymer electrolytes with exclusive cation cnntluction ~re reduced cell polarization deriving from low anion mobility, reduced volume changes in the cathode from intercalation of ion clusters, and reduced salt-induced corrosion on the 10 current coll~ctor~ Room temperatur~ co-~-luctivities for single ion co~d~lcting polymer electrolytes described in U.S. Pa~ent No. 4,882,243 are in the range of 10-4 to 10-5 S/cm.
A variety of gel-polymer electrolytcs have been discovered to be generally useful in non-aqueous high energy density batteries. Illustr~tive of useful polymer matrices for gel polymer 15 electrolytes in high energy density batteries are those derived from polyethylene oxides, poly~.op~lene oxides, polyacrylonitriles, polysilox~nes, polyimides, polyethers, sulfonated polyimides, NafionTM resins, divinyl polyethylene glycols. polyethylene glycol-bis-(methyl acrylates), polyethylene glycol-bis(methyl methacryla~e), blcnds of the foregoing, d~ tives of the foregoing, copolymers of thc forcgoing, croc~in~-ed and nc~work structures of thc foregoing, 20 and the like. Useful ionic electrolyte salts for gel-polymcr electrolytes include MC104, MAsF6, MS03CF3, MS03CH3, MBF4, MB(Ph)4, MPF6, Mc(so2cF3)37 MN(SO2CF3)2.
so2CF3 F3cso2~so2cF3 F3CSO2~;~ SO2CF3 MNSO2CF2CF2cF2cF2s02 ~ OM , M and the like, where M is Li or Na. Other electrolytes useful in the practice of this invention are r~ oc.od in U.S. Patent Application Ser. No. 192,008.
SUBSTITUTE SI~EET (Rl ILE 26 CA 0222l603 l997-l2-05 W O 96/41387 pcTrus96/o67so Useful ~el~non agen~s ~or ~el-polymer elec~rolytes include ethylene carbonate (FC), propylene carbonate ~PC), N-me~2yl aret~ nide. ~ce;oniT-ile,sulfolane.1.2-dimcthoxye~2ne.
polye1hyl~ne ~Iyc~ls, 1.3-dioxolanes, glyrnes, siloxanes, and e~hylene oxide ~rafted s;lo~n~c Particularly preferred gelation agen~s are tho.se denved from ~raft cnpolymers of e~ylene oxide 5 and oligomers of poly~dirne~hyl siloxane) of genes~l formula ~II, ~ Me 1 r Me t(CH ~ ~w I Me (~C~2CH2)~~Cf~3 YII
wherein u is an integer egual to or greater thanl, v is an int~er equaL to or gre~ter than O and less ~han 3bout 30, and the rariG zlw is ~ual to or ~reater lh3n 5~
V~ues ~or u, v, w, ~nd z can Yar,Y widely 2nd depend on the desi~cd properties for said liquid gel~tion agen~. P,eh,.~1 gel3tion a~ents of this type are ~hose wl2ere~n u rang~s from about 1 tO 5, v ran~es from ~ou~ 1 to ~0, and the r~ho z/w is equal to or grealer than 0.5 An especially 15 pre~rr~ coTnpoc;rion of fo~nula VII is that in whlch u i5 equ~ lo 3, v is equal to 7, and the rasio of zsowis 1.
These liquid ~el3tion ~ents themselYes are useful solvents to for~n liquid electrolytes which provide o~her ~rreclive electrolyt~ syst~ms for Ihe ceJls of the in~ention For ex~mple.
20 glymes with lithium salts. such as LiAsF6, are useful liquid elect~olytcs. ~i~cewise, composi~ions of ~;~2~ula VII together wi~ Li(SO~ 3) a~e ~c~e~i 311y useful as liquid ~ lcc~rolyte5.
CA 02221603 1997-12-0~
W O 96/41387 PCT~US96/06750 Battery cells comprising PCS cathodes can be made in a variety of si~s and configur~7~ir,nc which are known to those skilled in the art. Illustrative of useful battery design configurations are planar, prismatic, jelly-}oll, W-fold, and the like. These configurations are not to be construed as limi~tinnc on the scope of this invention as other designs are :m~icir~
s In batteries of the present invention, the main design concerns are the kine~ics and chPmir:ll and electrochPmir -l reversibility of the re~uc~ion/nYi~tirn rt~:lrtic-nc, the densi~y of available sulfur atoms, and the miscibili~y of oxidation and reduc~ion produc~s wi~h the polymer elec~roly~e.
During ~he discharge of the, cells Or this invenLion, ~hc PCS polymcr is reduccd accomr ~nied by thc 10 insertion of Li+ ions into the cathode from ~he elec~rolyte ~o m~in~in charge neutrali~y. In contras~
to the m~erials disclosed in U.S Pa~en~s 4,833,048 and 4,917,974, ~he polycarbon-sulfide m~Pri:~lc of the present inven~ion undcrgo oxida~ion and n:duc~ion wi~h thc form:ltion and brcal;ing of multiple sulfur-sulfur bonds ~ rhpd to conjugated s~ru~tul~s which provide good electron h~-S~OIL and fact electrochPmir~l kinetics at ambient temperaturec and below. An advantage of lS using PCS as the cathode active material is the high density of sulfur atoms which results in a high chal~e ~o~..ge density during oxidation-reduction. This is accompanied by a high densi~y of Li~
ions inserted for ch~rge neutrality, resulting in a high capacity. Figure 3 demonstrates the high capacity for the PCS materials of the present invention. In all PCS compounds used for the cathode of the present invention, the sulfur concentration is always greater than 86 wt%
In contrast to the organo-sulfur materials developed by Dc Jonghe, et al. PCS need not undergo polymPri7~inn/de-polymerization upon ch:~rge and discharge, thereby m~in~nining the hltt;~;~;ty of the polymcr backbonc and improving cathode utilization during repeated charge and discharge.
Table 1 snmm~ri7Ps the superior performance of bat~ery cells compriscd of PCS anodes of formula I relative to state-of-the-art rechargeable battery systems presen~ly commercialized or SUBSTITUTE SHEET (RULE 26~
CA 0222l603 l997-l2-05 W O96/41387 PCTrUS96/06750 under development. The PCS base(l cells exhibil ~ volumetric energy densi~y ndvantage of from 2 to 3 ~imes, and a gravimetric energy density advantage of from 1.7 to 3.5 times better than presently known l~l,.u~,~able cells in a AA configuration 5 Table 1. Performance comparisons of PCS based rechargeable cells relative to other advanced ~l.a~ able systems in AA cell configurations Volumetric EnergyGravimetric Energy Electrochemic~l SystemDensity (~Vhr/L)Density (Whr/K~) Li/PCS cells of formula I 430 - 500 175 - 260 Lithium Ion 215 100 Nickel Metal Hydride 180 - 200 60 - 75 Mckel~ lmi--m (~I~C~liUlll) 120 - 150 40- 50 The following specific examples are prcsented to more particularly illustrate the invention, 10 and should not be collaLLued as limitations on the scope and spirit of the invention.
EXA MPLES
Preparation of Polvcarbon-Slllfide From Carbon Dislllfide Example l To 26.2 g of sodium metal in 274 mL of boiling carbon ~iicnlfide with stirring was added dropwise 400 mL of dimethylsulfoxide (DMSO) during S hours, and the reaction mixture was 20 refluxed for 68 hr. Unreacted carbon disul~lde was dictille(l out and to the rem:-inin~ residue was added 400 mL of w~ter and 105 mL of concentrated hydrochloric acid. The polymer layer was ~UBSTITUTE $~EET (RIJLE 26 W O 96/41387 PCTAUS96/067~0 dec~n~Pd and w~shed with water (3 x 550 mL), then ac~tone (3 x 300 mL), and vacuum dried for 2 hours at 180 - 195'C. The yield of dry polymer was 92.4 g with a softening temperature of 68-80'C. Fl~-m~nt:ll analysis gave %C: 11.0, %S: 89.0, which corresponds to an empiric~l formul~
of -(cs30)n Ex3mple 2 The procedure of loy~lmrle 1 was repealed using 331~ (260 mL) of carbon rlic~llfi~e 25g of 10sodium metal, 400 mL of dimethyl sulfoxide, and a reflux time of 133 hr. The yield of polymer was 139 g with an el~ment:ll analysis of 7.9% carbon and 92.1% sulfur corresponding to an empirical formula Of -(CS4 37)n~.
15Ex~mple 3 For comr:~r.~tive purposes, ~he procedures of Examples 1 and 2 were repe~ted using reaction time less than 42 hours with the following results:
Carbon SodiumSolventReflux YieldElement~lEmpirical disulfide (g) (mL) time (g)Compositionformul~
(g) (hrs) %S
463 35 DMSO 39 92 83.9 CSI 95 (450) lS9 12 DMSO 41 52 85.0 CS2.12 (200) SUBSTITUTE SHEET (RULE 26~
W O 96/41387 PCTrUS96/06750 Preparation Or Polycarbon-Sulride Composite Cathodes l~:xample 4 A mixture of 40% by weight PCS prepared by the general procedure of FY~mple 1, 50%
polyacrylonitrile and 10% acetylene black was s~cpen~led in dimethylsulfoxide to form a slurry.
The slurry was ground into fine particles and was then cast as a film 25-lOO~lm thick on a 2511m thick nickel foil. The entire unit was dried in a vacuum oven at 40'C - 80AC for 24 hours.
Example S
A mixture of 40% by weight PCS from FY~mple 2, 45% by weight electrolyle and 15%acetylene black was s~cp~n~ied in dimethylsulfoxide to form a slurry. The electrolyte was a gel 15 electrolyte made from polyethylene oxide, propylene carbonate, ethylene carbonnte, and LiS03CF3. The slurry was finaliy ground and then cast as a film onto a nickel foil. The entire unit was then dried in a vacuum oven at 40'C - 80'C ~or 24 hours.
Preparation of Rechar~eable Batteries Example fi A rechargeable lithium battery of unipolar sandwich design was prcpared by sandwiching a 25 polymer electrolyte of about 25 micron thi~ n~c.c beLween a lithium foil of 125 micron thirl~nl~.cc and the composite cathode (FY:1mP1e. 4) of abou~ 25-75 microns thick. To obtain labor~tory prototype cells, the above components were sandwichcd between two 5~inl~cc steel circul~r disks S~IBSllTllTE S~EET ~ E 2~
CA 02221603 1997-12-0~
W O96/41387 PCTrUS96/06750 having 0.5 cm thirknPcc A typical material used for the anode was lithium metal. The PCS of the invention prepared in accord;mce wilh the procedure of Examples 1 or 2 was used for the cathode.
The electrolyte employed in preparing the battery of this example was a branched polysiloxane eont~ining grafted ethylene oxide side chains (formula VII, u = 3, v = 7, z/w = 1, molecular S weight of 1000) and a LiS03CF3 snlt.
Ex~mple 7 Following the general procedure of Exnmple 6, a rechargeable lithium/polymer electrolyte/PCS battery was prepared, using the composite cathode of example 4, a lithium foil anode, 9.8 mg of polymer gel electrolyte and 2.3 mg of ultrafine graphite powder The composite anode eont~ined 7.1 mg of PCS. The polymer gel electrolyte con-:linc d polyacrylonitrile, ethylene carbonate, propylene carbonate and LiCl04 with a conductivity of 3 x 10-3 S/cm at 25'C.
At 0.10 mA/cm2 current density, a practical capacity of 4.4 mAh has been achieved with a cut-off voltage at 1.5 volts. This translates into 87% of practical cathode l~tili7:ltion at a storage energy of 8.8 mWhr.
Ex~mple 8 Another rechargeable li~hium cell was prepared having a composite cathode cont:lining 5.4 mg of polymer gel electrolyte, 12.0 mg of PCS of Example I and 1.9 mg of graphite powder.
~ccllming a mid cell potential of 2.5V, a stor~ge energy of 12.6 mWh was obtained.
~.UBSTITUTE SHEET (RULE 26) CA 0222l603 l997-l2-05 W O 96/41387 PCT~US96/06750 The perfonn~nce eh~racteristics of the cells prep~red in F-r~mpl~ 7 ~nd 8 ~lrmQnctrate th~t by using the cathode of the invention a very high c~thode utilization is r~adily achieved resulting in energy capncity stor~ge mueh higher than those ~chieved by commerci~lly nvailabl~ batteries.
Example 9 A reehargeable lithium battery w~s prepared having a lithium foil anode of 125 micron thir~nf~cc, a polyethylene oxide (PEO)/LiS03CF3 solid elec~rolyle along with a siloxane (from 10 Example 6)/LiSO3CF3 liquid electrolyte, a composite cathode cont~ining 50 wt% PCS from rY:lmpllo.1 along with 30 wt% conduetive earbon and 20 w~% of the PEO/LiS03CF3 eleetrolyte, wherein the anode and eathode were separ~ted with Cel~rdTM 250Q. This lem x lem pl~n~r battery t-Yhihit~d 103 cycles at a charge/disch~rge current of 0.05 mA/cm2 with a capacity of 729 mAhr/g for the first several cycles, which then decayed to a final capacity of 243 mAhr/g at eyele 15 103.
Example 1 0 A reehargeable lithium battery w~s prepared h~ving a lithium foil anode of 125 micron shirknr5s, a eomposite eathode eort~ining 50 wt% PCS from example 2 along with 30 wt%
cn~nd~lctive c~rbon and 20 wt% of PEO/LiSO3CF3 electrolyte, ~ solid frPest~n(iing film electrolyte of polyethylene glycol-bis-(methyl methacryl~te) /silox~ne/LiSO3CF3 which was UV cured (cros~linkrd)~ and to the eell was added a sm~ll amount of liquid electrolyte corl~ining silox~ne 25 (from Example 6)/LiS03CF3. This lcm x lcm pl~n~r battery w~s ch~rged and disch~rged at a current density of 0.05 mA/cm2 and exhibited a capaeity of 1324 mAhr/g for the first sever~l eyeles, which then decayed to a final e~p~city of 296 mAhr/g al cycle 56.
SUBSIT~ SHEET (F~ULE 2~i) Ex~mple 1 1 A composite cathode was prepared from a physical mixture of 48 wt% PCS materi31 from example 1, 12 wt% of polyaniline powder in the fo.~ of Versico~ m lnllrlntllred by Allied-Signal, Inc., 20 wt% acetylene black, and 20 wt% polymer electrolyte. The polymer electrolyte used to form the composi~e cathode concict~od of a mixture of poiy(ethylene oxide) and a br~nched polysiloxane with ethylene oxide side chains (polysiloxane-graft-(ethylene oxide)7) and LiC104 in the ratio of 24 ethylene oxide units per lithium. The polymer electrolytes were dissolved in 10 a~ .;n ;il' and added to the mixture of PCS, polyaniline and acetylene black to form a viscous slurry. Co---pos-~ cnthodes of ti.i~ approximately 100 microns were cast onto Ni foil sn~str~t~-s and the solvent evaporated. Cells were assembled co n~; .;..g composite c~thodes, br~nl~h~d polysiloxane electrolytes and lithium foil anodes. The open circuit potentials of the cells were about 3.23 volts.
~UBSIlT~ ~EET (F~LE :~
Claims (34)
1. An electrochemically active polycarbon-sulfide material, which in its oxidized state, is of the general formula I
I
wherein x ranges from greater than 2.5 to about 50, and n is greater than or equal to 2.
I
wherein x ranges from greater than 2.5 to about 50, and n is greater than or equal to 2.
2. The material of claim 1 wherein said polycarbon-sulfide electroactive material is of formula I, wherein x is greater than 3 and n is greater than 5.
3. The material of claim 1 wherein said polycarbon-sulfide electroactive material is of formula I, wherein x is greater than or equal to about 6 and n is greater than or equal to about 10.
4. The polycarbon-sulfide material of claim 1 prepared from the reduction of carbon disulfide with an alkali metal having a sulfur content greater than 87% wt.
5. The polycarbon-sulfide material of claim 1 wherein said material of general formula I is comprised of one or more of the structural moieties of formulas II-V, II III IV V
wherein m is the same or different at each occurrence and is greater than 2, and y is the same or different at each occurrence and is equal to or greater than 1.
wherein m is the same or different at each occurrence and is greater than 2, and y is the same or different at each occurrence and is equal to or greater than 1.
6. The polycarbon-sulfide material of claim 5 wherein m is the same or different at each occurrence and is equal to or greater than 6.
7. The composition of claim 5 wherein said composition is comprised of structural moieties II-VI. wherein m is the same or different at each occurrence and is greater than 2.
8. The polycarbon-sulfide material of claim 1 which upon electrochemical reduction and oxidation does not undergo depolymerization and repolymerization of the polymer backbone.
9. An electric current producing cell comprising:
(a) an anode comprised of a metal selected from the group consisting of metals belonging to group IA and group IIA of the Periodic Table of the elements;
(b) a cathode material comprised of a polycarbon-sulfide material of the general formula I, I
wherein values for x can range from greater than 2.5 to about 50, and n is equal to or greater than 2; and (c) an electrolyte.
(a) an anode comprised of a metal selected from the group consisting of metals belonging to group IA and group IIA of the Periodic Table of the elements;
(b) a cathode material comprised of a polycarbon-sulfide material of the general formula I, I
wherein values for x can range from greater than 2.5 to about 50, and n is equal to or greater than 2; and (c) an electrolyte.
10. The cell of claim 9 wherein said electrolyte provides an operating temperature range for the cell of -40°C to +120°C.
11. The cell of claim 9 wherein said electrolyte provides an operating temperature range for the cell of -20°C to + 100°C.
12. The cell of claim 9 wherein said electrolyte provides an operating temperature range for the cell of 0°C to + 100°C.
13. The cell of claim 9, wherein said anode material is comprised of one or more materials selected from the group of alkali metals, alkaline earth metals, alloys containing alkali metals, carbons intercalated with alkali metals, and conjugated polymers intercalated with alkali metals.
14. The cell of claim 13 wherein said anode material is comprised of one or more materials selected from the group consisting of lithium-aluminum alloys, lithium intercalated carbons, sodium intercalated carbons. sodium-lead alloys, lithium-lead alloys, lithium-tin alloys, lithium-silicon alloys, lithium-aluminum alloys, lithium doped polyacetylenes, sodium doped polyacetylenes, sodium doped polyphenylenes, and lithium doped polyphenylenes.
15. The cell of claim 9 wherein said cathode material is comprised of a polycarbon-sulfide material of general formula I, wherein x ranges from about 3 to about 20, and n is greater than 5.
16. The cell of claim 9 wherein said cathode material is comprised of a polycarbon-sulfide material of general formula I, wherein x is equal to or greater than 6 but less than about 20, and n is greater than 5.
17. The cell of claim 9 wherein said cathode material is comprised of n polycarbon-sulfide obtained by the reduction of carbon disulfide with an alkali metal.
18. The cell of claim 9 wherein said cathode material is comprised of one or more of the structural moieties of formulas II-V, II III IV Y
wherein m is the same or different at each occurrence and is greater than 2; and y is the same or different at each occurrence and is greater than 1.
wherein m is the same or different at each occurrence and is greater than 2; and y is the same or different at each occurrence and is greater than 1.
19. The cell of claim 18 wherein m is the same or different at each occurrence and is equal to or greater than 6.
20. The cell of claim 9 wherein said cathode material does not undergo polymerization and depolymerization of the polymer backbone on charging and discharging the cell.
21. The cell of claim 9 wherein said cathode material is a composite cathode comprised of a polycarbon-sulfide material of general formula I where x is greater than 2.5 to about 50, and n is equal to or greater than 2, and one or more of the materials selected from the group consisting of non-aqueous electrolytes, conductive fillers, and inert binders.
22. The cell of claim 21 wherein said composite cathode comprises a conductive filler selected from the group consisting of conductive carbons, graphites, conductive acetylene blacks, metal powders, metal flakes, metal fibers, and electrically conductive polymers.
23. The cell of claim 22 wherein said electrically conductive polymer is one or more polymers selected from the group of polyanilines, polyacetylenes, polypyrroles, polythiophenes, polyphenylenes, polyphenylene-vinylenes, polythienylene-vinylenes; and their derivatives.
24. The cell of claim 21 wherein said composite cathode comprises one or more binders selected from the group consisting of polytetrafluoroethylene, fluorinated polymers, EPDM
rubber, and SBR rubber.
rubber, and SBR rubber.
25. The cell of claim 9 wherein said electrolyte is one or more materials selected from the group consisting of solid polymer electrolytes, single-ion-containing polymer electrolytes, gel polymer electrolytes, and liquid electrolytes.
26. The cell of claim 25 wherein said electrolyte is a solid electrolyte comprised of one or more materials selected from the group of polysiloxanes, polyphosphazenes, polyethylene oxides, polypropylene oxides, polyacrylonitriles, polyimides, divinyl polyethylene glycols, polyethylene glycol-bis-(methyl acrylates), polyethylene glycol-bis-(methyl methacrylate);
copolymers of the foregoing; derivatives of the foregoing; and crosslinked and networked structures of the foregoing.
copolymers of the foregoing; derivatives of the foregoing; and crosslinked and networked structures of the foregoing.
27. The cell of claim 25 wherein said electrolyte is comprised of one or more single-ion-conducting polymer electrolytes substituted with anionic moieties covalently attached to the polymer backbone.
28. The cell of claim 25 wherein said gel-polymer electrolyte is comprised of one or more materials selected from the group consisting of polyethylene oxides, polypropylene oxides, polyacrylonitriles, polysiloxanes, polyphosphazenes, polyimides, sulfonated polyimides, Nafion TM resins, sulfonated polystyrenes, divinyl polyethylene glycols, polyethylene glycol-bis-(methyl acrylates), polyethylene glycol-bis(methyl methacrylate); blends of the foregoing; derivatives of the foregoing; copolymers of the foregoing; and crosslinked and network structures of the foregoing; to which has been added one or more gel-forming agents selected from the group of ethylene carbonate, propylene carbonate, acetonitrile, N-methyl acetamide, sulfolane, 1,2-dimethoxyethane, polyethylene glycols, 1,3-dioxanes, glymes, siloxanes, ethylene oxide grafted siloxanes, and methoxy tetrahydrofuran; and which said gel electrolyte further comprises one or more ionic salts selected from the group consisting of MClO4, MAsF6, MSO3CF3, MSO3CH3, MBF4, MB(Ph)4, MPF6. MC(SO2CF3)3. MN(SO2CF3)2. .
, and , where M is Li or Na.
, and , where M is Li or Na.
29. The cell of claim 28 wherein said gel forming agent is comprised of a material of formula VI
VI
wherein u is an integer equal to or greater than 1, v is an integer equal to or greater than 0 and less than about 30, and the ratio z/w is equal to or greater than 0.
VI
wherein u is an integer equal to or greater than 1, v is an integer equal to or greater than 0 and less than about 30, and the ratio z/w is equal to or greater than 0.
30. The cell of claim 25 wherein said electrolyte comprises one or more alkali-metal salts selected from the group consisting of MClO4, MASF6, MSO3CF3, MSO3CH3, MBF4, MB(Ph)4, MPF6, MC(SO2CF3)3, MN(SO2CF3)2. .
, and , where M is Li or Na.
, and , where M is Li or Na.
31. An electric current producing cell comprising:
(a) an anode comprising one or more materials selected from the group of alkali metals, alkali metal intercalated carbons, alloys containing alkali metals, and alkali metal doped conjugated polymers;
(b) a cathode material comprised of a polycarbon-sulfide material of general formula I, I
wherein x is greater than 2.5 to about 50, n is equal to or greater than 2, and said polycarbon-sulfide material is derived from the reduction of carbon disulfide with an alkali metal; and (c) an electrolyte comprised of one or more gel-polymer electrolytes selected from the group consisting of polyethyiene oxides, polypropylent: oxides, polyacrylonitriles, poly-phosphazenes, polysiloxanes, polyimides, sulfonated polyimides, Nafion TM resins, sulfonated polyatyrenes, polyethers. divinyl polyethylene glycols, polyethylene glycol-bis-(methyl acrylates), polyethylene glycol-bis(methyl methacrylate); blends of the foregoing; derivatives of the foregoing; copolymers of the foregoing; and crosslinked and network structures of the foregoing;
to which has been added one or more gel-forming agents selected from the group of ethylene carbonate, propylene carbonate, acetonitrile, N-methyl acetamide, sulfolane, 1,2-dimethoxyethane, polyethylene glycols, 1,3-dioxane, glymes, siloxanes, ethylene oxide grafted siloxanes, and methoxy tetrahydrofuran; and which further comprises one or more ionic salts selected from the group consisting of MClO4, MAsF6, MSO3CF3, MSO3CH3, MBF4, MB(Ph)4, MPF6, MC(SO2CF3)3, MN(SO2CF3)2, , , , where M is Li or Na.
(a) an anode comprising one or more materials selected from the group of alkali metals, alkali metal intercalated carbons, alloys containing alkali metals, and alkali metal doped conjugated polymers;
(b) a cathode material comprised of a polycarbon-sulfide material of general formula I, I
wherein x is greater than 2.5 to about 50, n is equal to or greater than 2, and said polycarbon-sulfide material is derived from the reduction of carbon disulfide with an alkali metal; and (c) an electrolyte comprised of one or more gel-polymer electrolytes selected from the group consisting of polyethyiene oxides, polypropylent: oxides, polyacrylonitriles, poly-phosphazenes, polysiloxanes, polyimides, sulfonated polyimides, Nafion TM resins, sulfonated polyatyrenes, polyethers. divinyl polyethylene glycols, polyethylene glycol-bis-(methyl acrylates), polyethylene glycol-bis(methyl methacrylate); blends of the foregoing; derivatives of the foregoing; copolymers of the foregoing; and crosslinked and network structures of the foregoing;
to which has been added one or more gel-forming agents selected from the group of ethylene carbonate, propylene carbonate, acetonitrile, N-methyl acetamide, sulfolane, 1,2-dimethoxyethane, polyethylene glycols, 1,3-dioxane, glymes, siloxanes, ethylene oxide grafted siloxanes, and methoxy tetrahydrofuran; and which further comprises one or more ionic salts selected from the group consisting of MClO4, MAsF6, MSO3CF3, MSO3CH3, MBF4, MB(Ph)4, MPF6, MC(SO2CF3)3, MN(SO2CF3)2, , , , where M is Li or Na.
32. An electric current producing cell comprising:
(a) an anode comprising one or more metals selected from the group of lithium metal and sodium metal (b) a composite cathode comprised of:
(i) a polycarbon-sulfide material of general formula (CSx)n, wherein x is greater than 2.5 to about 50 and n is equal to or greater than 2;
(ii) an electrolyte comprising an ionic salt selected from the group of Li(SO3CF3), MC(SO2CF3)3, MN(SO2CF3)2. , , ; and a polymer comprising a material selected from lhe group of divinyl polyethylene glycols, polyethyleneglycol-bis-(methyl acrylates), and polyethylene glycol-bis(methyl methacrylate) cured by UV, x-ray, gamma ray, electron beam, or other ionizing radiation;
polysiloxanes, ethylene oxide grafted siloxanes, and polyethylene oxide; which optionally further conains a liquid gelation agent;
(iii) a conductive filler selected from the group of conductive carbons, acetylene blacks, and graphite; and (c) an electrolyte comprised of one or more materials selected from the group ofpolysiloxanes, polyphosphazenes, polyethers, polyethylene oxides, poly-propylene oxides, cured divinyl polyethylene glycols, cured polyethylene glycol-bis-(methyl acrylates), and cured polyethylene glycol dimethyl acrylates; which electrolyte further comprises a liquid gelation agent and one or more alkali metal salts selected from the group consisting of MClO4, MAsF6, MSO3CF3, MSO3CH3, MBF4. MB(Ph)4. MPF6, MC(SO2CF3)3, MN(SO2CF3)2, , , and where M is Li or Na.
(a) an anode comprising one or more metals selected from the group of lithium metal and sodium metal (b) a composite cathode comprised of:
(i) a polycarbon-sulfide material of general formula (CSx)n, wherein x is greater than 2.5 to about 50 and n is equal to or greater than 2;
(ii) an electrolyte comprising an ionic salt selected from the group of Li(SO3CF3), MC(SO2CF3)3, MN(SO2CF3)2. , , ; and a polymer comprising a material selected from lhe group of divinyl polyethylene glycols, polyethyleneglycol-bis-(methyl acrylates), and polyethylene glycol-bis(methyl methacrylate) cured by UV, x-ray, gamma ray, electron beam, or other ionizing radiation;
polysiloxanes, ethylene oxide grafted siloxanes, and polyethylene oxide; which optionally further conains a liquid gelation agent;
(iii) a conductive filler selected from the group of conductive carbons, acetylene blacks, and graphite; and (c) an electrolyte comprised of one or more materials selected from the group ofpolysiloxanes, polyphosphazenes, polyethers, polyethylene oxides, poly-propylene oxides, cured divinyl polyethylene glycols, cured polyethylene glycol-bis-(methyl acrylates), and cured polyethylene glycol dimethyl acrylates; which electrolyte further comprises a liquid gelation agent and one or more alkali metal salts selected from the group consisting of MClO4, MAsF6, MSO3CF3, MSO3CH3, MBF4. MB(Ph)4. MPF6, MC(SO2CF3)3, MN(SO2CF3)2, , , and where M is Li or Na.
33. An electric current producing cell comprising:
(a) a positive electrode;
(b) a negative electrode comprising a material selected from the group consisting of alkali metals, alkali-metal alloys, alkali-metal intercalated carbons, and alkali-metal intercalated conjugated polymers; and (c) a gel electrolyte.
(a) a positive electrode;
(b) a negative electrode comprising a material selected from the group consisting of alkali metals, alkali-metal alloys, alkali-metal intercalated carbons, and alkali-metal intercalated conjugated polymers; and (c) a gel electrolyte.
34. The cell of claim 33 wherein said gel electrolyte is comprised of:
(a) a solid polymer selected from the group consisting of polyethylene oxides, polypropylene oxides, polyacrylonitriles. polyphosphazenes, polyethers, polysiloxanes, polyimides, sulfonated polyimides, Nafion TM resins, divinyl polyethylene glycols, polyethylene glycol-bis-(methyl acrylates), polyethylene glycol-bis(methyl methacrylate), sulfonated polystyrenes; blends of the foregoing; derivatives of the foregoing; copolymers of the foregoing;
and crosslinked and network structures of the foregoing;
(b) an electrolyte salt comprising one or more ionic salts selected from the group consisting of MClO4, MAsF6, MSO3CF3, MSO3CH3, MBF4, MB(Ph)4, MPF6, MC(SO2CF3)3, MN(SO2CF3)2, , , and , where M is Li or Na; and (c) one or more gel forming agents selected from the group consisting of ethylene carbonate (EC), propylene carbonate (PC), N-methyl acetamide, acetonitrile, sulfolane, 1,2-dimethoxyethane, polyethylene glycols, 1,3-dioxolanes, glymes, siloxanes, and ethylene oxide grafted siloxanes of general formula VII, VII
wherein u is an integer equal to or greater than 1, v is an integer equal to or greater than 0 and less than about 30, and the ratio z/w is equal to or greater than 0.
(a) a solid polymer selected from the group consisting of polyethylene oxides, polypropylene oxides, polyacrylonitriles. polyphosphazenes, polyethers, polysiloxanes, polyimides, sulfonated polyimides, Nafion TM resins, divinyl polyethylene glycols, polyethylene glycol-bis-(methyl acrylates), polyethylene glycol-bis(methyl methacrylate), sulfonated polystyrenes; blends of the foregoing; derivatives of the foregoing; copolymers of the foregoing;
and crosslinked and network structures of the foregoing;
(b) an electrolyte salt comprising one or more ionic salts selected from the group consisting of MClO4, MAsF6, MSO3CF3, MSO3CH3, MBF4, MB(Ph)4, MPF6, MC(SO2CF3)3, MN(SO2CF3)2, , , and , where M is Li or Na; and (c) one or more gel forming agents selected from the group consisting of ethylene carbonate (EC), propylene carbonate (PC), N-methyl acetamide, acetonitrile, sulfolane, 1,2-dimethoxyethane, polyethylene glycols, 1,3-dioxolanes, glymes, siloxanes, and ethylene oxide grafted siloxanes of general formula VII, VII
wherein u is an integer equal to or greater than 1, v is an integer equal to or greater than 0 and less than about 30, and the ratio z/w is equal to or greater than 0.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/478,330 US5601947A (en) | 1995-06-07 | 1995-06-07 | Electroactive high storage capacity polycarbon-sulfide materials and electrolytic cells containing same |
| US08/478,330 | 1995-06-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2221603A1 true CA2221603A1 (en) | 1996-12-19 |
Family
ID=23899499
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002221603A Abandoned CA2221603A1 (en) | 1995-06-07 | 1996-05-02 | Electroactive high storage capacity polycarbon-sulfide materials and electrolytic cells containing same |
Country Status (7)
| Country | Link |
|---|---|
| US (2) | US5601947A (en) |
| EP (1) | EP0840945A4 (en) |
| JP (1) | JPH11514128A (en) |
| KR (1) | KR19990022715A (en) |
| AU (1) | AU5743296A (en) |
| CA (1) | CA2221603A1 (en) |
| WO (1) | WO1996041387A1 (en) |
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|---|---|---|---|---|
| BR8407077A (en) * | 1983-09-20 | 1985-08-13 | Elf Aquitaine | NEW POLYCARBON SULPHECT DERIVATIVES, THEIR PREPARATION AND THEIR APPLICATIONS, ESPECIALLY IN ELECTROCHEMISTRY |
| US4917974A (en) * | 1989-04-14 | 1990-04-17 | The United States Of America As Represented By The Department Of Energy | Lithium/organosulfur redox cell having protective solid electrolyte barrier formed on anode and method of making same |
| US5441831A (en) * | 1992-12-17 | 1995-08-15 | Associated Universities, Inc. | Cells having cathodes containing polycarbon disulfide materials |
| US5460905A (en) * | 1993-06-16 | 1995-10-24 | Moltech Corporation | High capacity cathodes for secondary cells |
| US5601947A (en) * | 1995-06-07 | 1997-02-11 | Moltech Corporation | Electroactive high storage capacity polycarbon-sulfide materials and electrolytic cells containing same |
-
1995
- 1995-06-07 US US08/478,330 patent/US5601947A/en not_active Expired - Fee Related
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1996
- 1996-05-02 JP JP9500549A patent/JPH11514128A/en active Pending
- 1996-05-02 WO PCT/US1996/006750 patent/WO1996041387A1/en not_active Application Discontinuation
- 1996-05-02 CA CA002221603A patent/CA2221603A1/en not_active Abandoned
- 1996-05-02 EP EP96915730A patent/EP0840945A4/en not_active Withdrawn
- 1996-05-02 KR KR1019970709157A patent/KR19990022715A/en not_active Application Discontinuation
- 1996-05-02 AU AU57432/96A patent/AU5743296A/en not_active Abandoned
- 1996-10-07 US US08/729,713 patent/US5690702A/en not_active Expired - Fee Related
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| EP0840945A1 (en) | 1998-05-13 |
| EP0840945A4 (en) | 1999-11-10 |
| US5690702A (en) | 1997-11-25 |
| AU5743296A (en) | 1996-12-30 |
| US5601947A (en) | 1997-02-11 |
| WO1996041387A1 (en) | 1996-12-19 |
| JPH11514128A (en) | 1999-11-30 |
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