CA1157515A - Charge transfer complex cathodes for solid electrolyte cells - Google Patents
Charge transfer complex cathodes for solid electrolyte cellsInfo
- Publication number
- CA1157515A CA1157515A CA000354946A CA354946A CA1157515A CA 1157515 A CA1157515 A CA 1157515A CA 000354946 A CA000354946 A CA 000354946A CA 354946 A CA354946 A CA 354946A CA 1157515 A CA1157515 A CA 1157515A
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- CA
- Canada
- Prior art keywords
- cathode
- iodine
- lithium
- halogen
- charge transfer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
- H01M6/182—Cells with non-aqueous electrolyte with solid electrolyte with halogenide as solid electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Primary Cells (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
CHARGE TRANSFER COMPLEX CATHODES
FOR SOLID ELECTROLYTE CELLS
ABSTRACT OF THE DISCLOSURE
Charge transfer complex cathodes for use in solid cell systems wherein the cathodes are the reaction products of a halogen such as iotine or bromine with a carbonaceous pitch such as mesophase pitch.
S P E C I F I C A T I O N
1.
FOR SOLID ELECTROLYTE CELLS
ABSTRACT OF THE DISCLOSURE
Charge transfer complex cathodes for use in solid cell systems wherein the cathodes are the reaction products of a halogen such as iotine or bromine with a carbonaceous pitch such as mesophase pitch.
S P E C I F I C A T I O N
1.
Description
~15'~5~$ 1224 Field of the Invention The invention relate~ to a c~thode for u8e, primarily9 in ~olid atate cell systems ~nd wherein the cathode compri~es a ch~rge tran8fer complex in which the co~plex i8 the rcac~cion product of ~t least one halogesl with 2 cArbonaceou~ pitch, 8ueh ~8 mesQphase pitch.
Background of the Invention Ionic conductivity i~ usually a~sociated wlth the flow of. ions through an aqueous 801UtlOrl of metallic salts. In the vast ~a~ority of p~actical uses of ion~c conduc~ors, e.g., as electrolytes for dxy cell batteries, the aqueou~ ~olution i~ immobilized in a pa~te or gelled matrix to overcome the difficulties a~sociated wi~h handl~ng and packaging a llquid. However, even after immobilization, the ~ys~m is ~ ubject to po~sible leakage, has a limited shelf life due to drying out or cry tallization of ~hë 8alt8 and i~ ~uitable ~or ~se only within a limited temperature range corresponding to ~he liquid range o~ the electrolyteO In addi~cion, the neces~ity of including a large ~olume of i~mnobilizing ~terial has hindered the aims of miniaturi~ation.
In att~ting to o~rercome the ~hortcoming~ of liquid ~yst~ms, lnvestigator3 ha~te sur~eyed a large nusnber of ~olid compounds hopirlg to ind c~mpounds ~hich ~re ~olid a~ room ~empersture snd hav2 ionic conductance~
approaching ~hose exhibi~ed by ~he c~monly u~ed liquid ~ystem~O Such cGmpound~ ha~e speciflc conduc~ances at room tempera~ure (20C~) in ~he range of 10 6 to 10 15 okm cm 8S compared to aqueous ~olutions of ~81t8 which typ~cally have a specific conductance of
Background of the Invention Ionic conductivity i~ usually a~sociated wlth the flow of. ions through an aqueous 801UtlOrl of metallic salts. In the vast ~a~ority of p~actical uses of ion~c conduc~ors, e.g., as electrolytes for dxy cell batteries, the aqueou~ ~olution i~ immobilized in a pa~te or gelled matrix to overcome the difficulties a~sociated wi~h handl~ng and packaging a llquid. However, even after immobilization, the ~ys~m is ~ ubject to po~sible leakage, has a limited shelf life due to drying out or cry tallization of ~hë 8alt8 and i~ ~uitable ~or ~se only within a limited temperature range corresponding to ~he liquid range o~ the electrolyteO In addi~cion, the neces~ity of including a large ~olume of i~mnobilizing ~terial has hindered the aims of miniaturi~ation.
In att~ting to o~rercome the ~hortcoming~ of liquid ~yst~ms, lnvestigator3 ha~te sur~eyed a large nusnber of ~olid compounds hopirlg to ind c~mpounds ~hich ~re ~olid a~ room ~empersture snd hav2 ionic conductance~
approaching ~hose exhibi~ed by ~he c~monly u~ed liquid ~ystem~O Such cGmpound~ ha~e speciflc conduc~ances at room tempera~ure (20C~) in ~he range of 10 6 to 10 15 okm cm 8S compared to aqueous ~olutions of ~81t8 which typ~cally have a specific conductance of
2.
5 ~ ~ 122bt5 0 . 5 t o 0 . 05 ohm cm Improved microelectronlc c~rclllt designs ha~Je generally decrea~ed the current requirements for alectronlc dev~ce~,, This ~n turn has enhanced the ~pplicabllity of solid el2c~rolyte power source3 wllich u~ually c~n only deliver currents in ~che a~icro~mpere range. These solid electrolyte a5~8tem8 have the inherent ~dvantages o~ being free of electrolyte leakage ~nd ino~ernal gass~ng problems due to the sbsence of a liquid phase and corro~ion phenomena. In addition, they al~o have a ~uch longer shelf life tharl the con-ventional liquid elec~rolyte power source8.
Gutman et al, J~ Electrochem. SOCO, 114, 323 (1967) discloses solid stat0 cells utilizing cathodes of electronically conducting charge transfer complexes and anodes of ~elected divalent metals. U. S. P~tent
5 ~ ~ 122bt5 0 . 5 t o 0 . 05 ohm cm Improved microelectronlc c~rclllt designs ha~Je generally decrea~ed the current requirements for alectronlc dev~ce~,, This ~n turn has enhanced the ~pplicabllity of solid el2c~rolyte power source3 wllich u~ually c~n only deliver currents in ~che a~icro~mpere range. These solid electrolyte a5~8tem8 have the inherent ~dvantages o~ being free of electrolyte leakage ~nd ino~ernal gass~ng problems due to the sbsence of a liquid phase and corro~ion phenomena. In addition, they al~o have a ~uch longer shelf life tharl the con-ventional liquid elec~rolyte power source8.
Gutman et al, J~ Electrochem. SOCO, 114, 323 (1967) discloses solid stat0 cells utilizing cathodes of electronically conducting charge transfer complexes and anodes of ~elected divalent metals. U. S. P~tent
3 ,660,163 dis loses ~olid s~ate lithium-iodine primary cells employing a lithium anode, a ~olid s~cate lithium halide ~lectrolyte snd A conductive cathode of organic materials, ~uch a~ polycyclic aro~satic compounds, organic polymers, he~cerocyclic ni~rogen ccrntaining compounds, and ~che lik~, and iodine . U ~ S . Patent 3, 660, 1~4 di~clo~e~ solid e;tate cell~ utiliz~ng as a cathode a chss:ge ~ran~fer complex in whlch the Rccep~o~ c~snponent i8 the halogen and the donor compones~ an organic -- compound, ~cypic~lly aromatic or he~erocyclig.
~l~hough~variou~ cathode material~ have been recited in the art for u~e in variou~ ~ell oystem~, ~n object of the pres n~ in~ention i~ to provide a novel cathode for u~e in solid electrolyte cell ~y~t~s.
Arlo~cher o~ ~ ect of the pre~ent invenSion i~ ~o prsvide a cathode compri 3ing a charge ~ran~fer ¢omplex ln which the complex is the reaction product of at least 3~
122~5 ~ :1 5 ~S l ~
one h~logen with a ~ar~onsceous pltch.
~ nother ob~ect of ~he pre~ent invention ~ 8 to prov~de a eathode comprl~ing ~ chQrge tran~fer complex ln which th~ complex ~8 the reaction product o~ iodin~
or bromlne with ~esophase pitch~
~ nother ob~ect of ~he present in~ention i6 to pro~de a cathode c~mprisin~ a charge transfer complex in wh~ch the complex ~5 the reaetion product of iodine with ~esophase pitch for u8e in a ~olld ~tate cell emplo~ing R lithium anode and ~ solid lithlum iodide elec~rolyte.
The foregoing and additiona~ ob~ects will become more fully apparent fr~m the following descrip~ion.
Summary of the Invention The in~ention relates to a cathode for u~e in an electrochemical cell compri~ing a charge transfer complex in which the complex is the reaction product of ~t least one halogen ~ith a carbonaceo~s pitch and wherein the donor component is the carbonaceous pitch and the acceptor component is the at least one halogen.
A5 used herein, at least one halogen shall ~an a halogen ~uch as iodine, bromine, ehlorine sr 1uorine, a mi~ture of t~o or more halogens or a com~ound ~in~erhalogen) of two or more h~lo~ens~
Chnrge trans~er omplexes are a well-known cla~s of ~aterials tha~ have two component~ - o~e a~ an electron d~nor, thc other as ~n electron acceptor -th2t form weakly bonded complexe~ that e~hibit eleotronic conductiv~ty ~igher than ei~her eomponen~. Chaxge ~ransfer 3U complexes for this inYention compri~e a carbonacesus pitch ~ the electron donor and a~ least one h~logen as the electron acceptbr. The preferred c~ rge transfer ~omplexes of this in~ention would be the reaction product .
~ 3. r)'~ 12245 of a me~ophafie-cont~ining pi~ch wi~h lodine or bromine.
Although ~he ~onducti~vity of the charge ~cransfer com-plexes of th~ ~ in~vention will be ~ufficiently high for most cell applic~tions, the cDnductivity could be m~de higher by adding a conductive material ~uch fi5 carbon, graphi~e or 8n inert conduct~ve ~etal. ~referably, the conductivity of the charge tran8:Eer complexe~ for most cell applications should be greater than sbout lob Diho/cm.
Natural and syntheti c carbonaceou~ pitche~ 9 as i8 well knawn, are complex mixtures of orgsnic compounds which, except for certain rare para~finicbase pitches derived from certain petroleums, ~uch ~8 Pennsylvania crude, sre msde up essentially of fu~ed ring aromatic hydrocarbons ~nd are9 therefore, ~aid to have an aromatic base. Since the molecule6 which mske up ~hese organic c~mpounds are compara~ively ~mall (average molecular weight not ~ore ~han 8 few hundred) and interac~ only weakly with one ~nother, such pitches are i80tropic in ~0 ns ure. On heatin8 the~e pitches under quie~cent con-ditions at a temperature of about 3500-4500CG, howe~er, ei~her a~ ::onstan'c temperature or with gradually increasing t~mpera~ure, 8mall insoluble liquid ~pheres begin to .-appear ~n the pltch which gradually increa~e in s~ze ~s heating i8 continued. ~en ~xamined by electrDn difrac-'cion and polarized llg~t techniques, these ~phere~ are 8hown to ~onsi8t of layer~ of or~ented molecule~ aligned iFl t~e 8ame direction. A~ the6e 8pheres con~inue to grow in size as heating ~ ~ corltinued, they come in contact wlth one another ~nd gradually coalesce wlth each o~her to produce ~he larger masses of aligned layer~. A~
11~ 751$ 1224~
co~lescQnce con~inue~, d~m~ins of aligned molecules much larger than those of ~he or~gin~l sphere~ are fo~med. These domalns coue tsgether ~o form a bulk mesopha~e wherein the transition from one oriented do~ain to another sometime~ oCCUr8 smoothly and ~on-tinuously through grsdually curving ~dmell~e and ~ome-times ~hrough ~ore 8hssply curv~g læmellae. The differences in orientstion between the domains cr~ate a complex array of polar~zed light extincti~n c~ntours in the bulk mesoph~se corresponding to varlous types of linear ti~continui~y in molecular alignment. The ultimate 81ze of ~he oriented domains produced $s dependent upon the Vi~c08ity, and ~he rate of increa~e of the ~i~co~ity, of the mesophase from which they are formed, which, in ~urn, are dependent.upon ~he par~icular pitch and th~
heatlng rate~ In certain pitches, domain~ h~viag ~zes in excess of two kundr.ed microns up to several hundred microns are produ~edO In other pitches, th~ vi~cosity of the me~ophase i8 BUCh that only limited coalescence ~nd structural rearrangem~nt o~ layer~ occur, 80 that the ulti~ate domain ~ize does not e~ceed one h~ndred microns.
The highly oriented, optically anifiotropic, ins01ub}e ma~erial produced by treating pitches in this -- ~nanner has been g~en the ~cerm "mesophase"g and pltches conta~ing such material are known as l~mesophase pltches".
Such pitches, when heated above sheir ~oftening point~, are ~i$~res of ewo ~ cible liquid~, one the op~icall an~sotropiC~ oriented mesophas~ port~ , and the other the iBo~ropic non~mesopha~e portion. The ter~ "mesophase"
is derived from the Greek ilmesos" or "intermediate" and 6.
5'~51~
indicates the ~pseudocrystalline nature of this highly-oriented, optically anisotropic material. As used herein, "mesophase pitchl' or "mesophase" shall mean a carbonaceous pitch containing mesophase.
A detailed description for producing mesophase pitch can be found in U. S. Patents 4,005,183, 4,017,327 and 4,026,788.
The preferable carbonaceous pitches for use in this invention are mesophase pitches and more preferable would be mesophase pitches having a mesophase content of above 40 per cent by weight and preferably would be mesophase pitches having a mesophase content of above 90 per cent by weight and most preferably above 95 per cent by weight.
Specific preferable iodine-containing and bromine-containing charge transfer complexes for use in this invention are as follows:
X I2 where X is mesophase pitch and the amount of iodine varies between about 50% and about 97%
by weight and preferably between about 80% and about 90%
by weight;
X Br2 where X is mesophase pitch and the amount of bromine varies between about 50% and about 97%
by weight and preferably between about 80% and about 90%
by weight.
The above solid charge transfer complexes have been found to have vapor pressures below those of iodine and bromine.
~ i, ~ 5~ 245 Anode materials suitable for use wi~h the cathodes of this invention include lithium, ~iLver, ~odium, potassium, rubidium, magnesium and calcium. The pre-ferred anode m~terial is lithium.
Solid electrolytes for use in this in~ention would lnclude lithium iodide, silver iodide, silver bromide, lithium bromide, tetras~ver rubidium pentaiodide, lithium aluminum tetrachloride, te~rasilver potassium tetraiodide cyanide, te~rasilver rubidium tetraiodide cyanide, sodium iodide and sodium bromide. The preferred solid electrolytes or use in this invention are lithium iodide and tetrasilver potassium tetraiodide cyanide.
As disclosed in U. S. Patent No. 3~660,163, ln a lithium anode cell, lithium iodide can be formed in ~itu by contacting the lithium anode with the iodine-containing cathode surface whereupon the lithium will react with the iodine in the cathode to form a lithium iodide electroly~e layer that will contact both the anode and the ca~hode.
Alternately, the lithium iodide could be formed by reactin~
lithium and iodine and then applying the lithium iodide as a coating on the surface of the a~ode or cathode.
Preferable cell systems using the cathode of this invention would be as follows:
Anode Elec~rolyte .
lithium lithium iodide lithium li~hium br~mide silver silver iodide silver tetrasilver potassium tetraiodide cyanide silver ~etrasilver rubidium tetraiodide cyanide 5 ~ ~ 12245 ~XA~I E 1 .
Several cha~ge tran~er csmplexes were prepared by blending ~esoph~e pitch (containing about 85 per cent slesophase~ with iodine ln the weigh~ ratio8 ~hQwn in Table I. The blends ~ere then ~eslèd irl an e~cuated glas tube where they wese then either aged ~It room tempera~ure ~20C) or heated to the eemper~ture shawn In Table I for 16 hours, The ~nesophsse/iodfne ch~rge transfer complexe~ ~o formed and lodine (I2) wer~ then testet for iodine v~por pres~ure and the data ob~ain~d ~re shawn in Table I.
1 ~ 5 '~
~ 1 ~ ~ o ~ r~
s~ ,. . . . . . . . o ~ o ~ ~ CO ~ X 1 _, ,~
oo al ~ ~ I~
P~ C~ . . . . . . . . . . ..
o _I ~I C'~l C~l ~ C~l t~ M
h ~
C .
_, ~ e~ ~ ~ C~l o ~ . . . . . . . .
O Q O O O O O O O O O
t-~ ~I
a~
C~
~ C ~ ~ P~ .
_I ~U O O O O O O D O 0 0 . O O O O Q C~ O O O ~U
U ~ ~ O C:~ O C`~ ~ O t'`l :~1 0 ~ ~3 ~
- 0 0 0 a~
~ 3 ~C 3 ~
ac ~ P
0 .n ~ ~ ~n ,a ~ ~ ~ ~ ~11 ~ ~ 0 .l~
v ~ ~ ~a ~ ~ ~ ~ ~a O 0 3~ O ~
~:
- o sl~ a a~ o) ,c ~C ~ ~ .C ~c ~ ~ ,c 0 .C
_~ o O O o o ~ o O o ~ o ~c ~ o a~ 0 ~ ~ 0 ~ o 10.
~5'~5~5 1224S
~ ~vid2nt from the t~ta 4hown ~n T~ble I, the ~e~opha~e/iodlne-containlng charge trans~er com-pl~ces h~lve indine vapor pres~ures depresRed below tb~t o~ iodtne9 pa~ticul~rly ~t ~le~t~d test tempe~tures.
15~LE 2 A ch~rge tr4nsfer comple~ consi~ting of ~ne~o*lase pitch ~ont ining ~bout ~5% mesopha~e aTld bromine 1~8 for~ed as ~n Example 1 in w~lch a chemical ~nalys~s revealed that bromine was pre~ent in a 52 we~ght per cent 1~ propostion. The me~ophase/brom~ne charge ~craIIsfer complea~
~o formed ~nd bromine were t~sted or bromirle v~por pressure at variou~ t~mperatures ~md the data ob~erved are ~hown in Table II.
TABLE II
Bromine Vapor Pressure ~mm H~) M~terial 20C. 54C. 71C
O
~esophase.Br~mine 5.2 9.7 33 Bromine 220 640 1200 As evide~t from ~he data sh~wn in Table II, the mesophase/~romine-containing charge tran~fer comp~ex had a bromine vapor pre~sure ~ubstanti~lly below that of bromine~
EX~PLE 3 Samples of ~he mesophase/iodine-containing -- charge tran~fer complexes were prep~red as in Example 1 200C. uz~ng ~he ~eight ratio ~8 ~h~w~ ~ Table III.
The conductances of the~e ~R~ples ~long wlth ~e~oph~se pi ch and lodine ~I2) were fou~d and the da a obserYed are ~hown in Table III.
L15 tS15 ~BIE: III
Materisl nduct~nce (ohm 1 cm 1) me80phaAe under 10-~
iodine 1. 7 ~ ll1 7 slesopha~e~67% ~odine* 6.0 x 10 4 mesoph~se- 94% iodine* 2 . 2 x 10 5 *by weigh~ .
XA~L~ 4 Two ~.457-inch d~meter butt~ cells were lU constructed a~ follows. ~ me~opha~e (about 857.
mesophssa)/iodine charge ~ransfes comple~ wa prepared by ~rinding the me~oph~e pltch and iodine componenta followed by drying them UBiTlg phosphoru~ pe~toxide for a week ln an argon dry box. Thereaf~er the me~opha~e pitch and iodine were blended together in a weight ratio of one mesopha~e pitch to 1~ iod~ne (me80ph~8e- ~Z lod~ne~ ~nd - then sealed in an eYacuated tube whereupon it wBs heated at 20()C~ for 16 hours, The re~ulting charge transfer complex ~as a85embled in a nickel-plated cold-rolled steel container, A llthium ~node strlp was placed in a eo~7er wt~ h wa~ then a8~embled slong with ~ ga~ket on ~ p of the container in a conventlotlal manner 8uch thllt the ~urface of the anode made contact with the 8urface of the c~thodee, The electrolyte~ lithium iodide, was ~ormed in - ~itu by the reaction of the lithlum in ~he a~ode and the ~odine ln the c~thode. The two ~ells were ths~n di~charged for 10 second period~ across ~ario~ resls~iv2 load~ and the voltages observed were recorded, Based OJl ~he total surfaee area of the c~thode . facing the arlode, ~he current densi~y was calculated for each voltage readlng arld the data obtained are shown ln Table IV.
12, ll5'~5~S 12245 TABLE IV
Cell 1 Cell ~ _ . .. ~
Voltage Cu~r~nt d ~ity Voltage Current d~nsity ~Yolts~ ~4A/cm (volts) ~ ~/cm 2~75 2.6 2.7 ~.7 ~.6 5.6 ~.55 5"~
2.5 8.4 2.4s 8 2 . 35 11 2 . 3 2.2s 15 2.~ 14 2. 1 20 1.95 18.5 1.6 30 1.5 30 0.8 50 0.65 6 EXA~LE 5 r._ : . ~
A 0.457 inch di~meter button cell was con-~truc~ed a~ in ~xample 4 except that the can was ~tainless steel and the mesophase pl~ch snd iodine of the charge trans-fer complex were in a weight rstio of one mesophase pitch to 16 iodine (mesophase-34~/O lodine). The cell was continu-ously discharged across a l-megohm load and the data obtained ~re ~h~wn in Table VO
TABLE ~ .
Time Yolt~ge 100 2.7S
250 2.65 300 2.60 6~0 2.50 700 2~45 800 2~40 gO0 2.35 1100 2,30 -~XA~PLE 6 Two 0.457 ~nch disme~er bu$ton cell~ were con~trucked a8 follows. A mesopha~e (85% mesoph~se)/
br~m~e charge transfer complex ~as prepared by grinding the mesopha~e p~tch and d~y~ng ~t u8ing ph9SphOrU~
pento~lde for a week ~n an argon dry box~ Thereafter the ~c~ophase pl~ch and br~mine were mixed toge~her ln weight rat~o of one mesophase pitch ~o 1 bromlne. The 13.
5 ~ ~
re~ulting charge tr~nsfer comple~ w~ e~led in 8 nickel pl~t~d colt ~olled steel c~n. A lithlum ~node ~trip wa~ pl~ced ~n a cover w~lch ~as ~hen ~embled ~long wlth ~ ga~ket on top of the c~ a cçmrentlonal manner such that the ~usface of the ~node D~.ode 0n~ct ~ith the ~urface o~ the cathode. The electrolyte, lithium b~omide, ~!18 formed iSl ~itu by the rgaction of the lithil3m ln the anode l~nd the bromine ln the cathode.
The cell wa8 then discharged for lû-second period~ BCrO21S
various resist~ve loads ~nd the voltAge~ observed ~e$e recorded. Bs~ed on the total surface ~rea of the ca~chote faclng the amode, the current density wa~ c~lculated ~or each voltsge readlng and ~he da~a obtained are ahown in Table VI~
TABLE VI
Voltage Curren~c De~s ity ~At~m 3 3 3.4 3 1 7,0 ~0 2. 9 10 2. 7 1.6 32 Oc5 ~2 Two cells were cz~st~uc~ed a~ in Ea~ple 4 except that t~e charge t~sfer eo~plex employet waR a blend of 67Z by weigh~ iodine wlth 33% mesopha~e pi~ch - ~labout 85% me~o~se3" E~ch cell 6?a~ te~ted 8~ desc~ibed ~n ~xEmp~e ~, and the data obtained are ~ho~ in 30 . T~ble VIX.
122~5 5'~5i ~LE VII
Cell 1 Cell 2 VoltageCurrent d~n~ity ~lolta~eCur~ent d~nsity ~volts~ ~ (~t A/cm ).
2.72 2.7 2.69 2,7 2. 71 6 2. 6~ 6 2. 71 g 2. ~7 g 2 . 70 ~3 2 . 6~ 13 2 . 651 1~ 2. 65 18 2 . 68 27 2, ~3 26 2. 63 52 2. 5~ 51 2. 31 231 2, 10 219 l~he two cell~ were then t~ted ~!18 te~cribed in E2cample 5, The data obtained ~e shown in Table VIII, TABLE VIII
Cell 1 Cell 2 ~ . ;.
Time Volt~ge Time Voltage ~!~ (vol~
1~0 2, 77 10 ~, 77 100 ~ 77 100 2.76 200 2 76 200 2,75 300 2, 75 ~ 3ûO 2. 75 500 2, 73 500 2, 72 1000 ~ . ~ 7 1000 Z . ~7 2û00 2, ~0 . ~000 2. 50 EXA~LE 8 Two ~ell8 were co~structed a~ in E~ple 4 except that the charge l:ran~fer complex employed ~8 a blend of 86% by weight iodine with 14% me~opha~e pi~ch (~bout ~5% mesopha~e). Each ~ell WEI~ te~ted a~ described in E~cample 4, ~nd the d~ta obtained axe shown in Table I2.
~ABT F ~ X
Cell 1 Cell 2 Voltag2 Current d~nsity Voltage Cu~rent d~n~lSy ~volt~) ~i_ ~ ~9 2. 76 2. 76 ~, 75 2., 75 2 75 6 2.13 2 75 5~ 2.71 2,74 13,7 ~,6~ 13 2 74 18 2. ~5 18 2 72 27 2,~ 26 2,S9 54 2~41 4~
~,43 243 ï, 57 157 1~ ., 1~$'~$
The ewo e211~ ~ere ~hen t~3~d a~ d~cribed ln E:~ca~Dple 5. The data obta~n~d ~re sh~ n T~le X.
SABLE X
-Cs!ll 1 Cell 2 Time Voltage T~e Yoltage ~!~ (voLt~) ~our~) 2. t7 lU ~. 7~
100 2. 77 ~00 2. 73 - ~0 2. ~7 2~0 2. 71 300 2. 76 30~) 2. 71 ~00 2. 75 500 2. ~9 lO0(~ 2072 ~ 1000 2.b~
1~00 ~. 6~ 1~00 2. 63 A cell W~18 constructed a~ in EsaD~ple 4 ~:RC¢pt that the charge transfer complex omployed was a blend of 75%, by weight iodine with 25% me20ph~se pi~c~h (abou~ ~570 mesopha~e), The cell ~as te~ted ll8 describ~ in E~c~mple 4 and the data obtained ar2 shown in T~ble ~ TALLE XI
Voltage . Cus~nt d~n~ ity 2.6~ 2,7 2.65 2.~4 9 ~,64 . 13 2. ~4 18 2, 63 2~
2. ~0 52 2. 3~ 23 The cell ~as then ~e~ed a8 desGrlbed in E~campl~ 5. The data obPained are ~hown in Tabl~
~ABLE XII
T~e Vol~age (hour ~
~0 ~,77 100 ~. 76 2û0 2. 75 500 ~, 72 00 2. 7 16 ,.
. . ' ' .. .
.
11,5'~5~; 12~4~
hould be under~tood tha~t the foreg~ing dlsclosure relates to pref~rr~d embodiments of the inventioTI 8nd ~ t i~ intended to cc~ er ~11 chan~se8 snd modiflcatl.on~ of the invention w~ich do not depart rom the ~pirit and 3cope of the ~ppended clsim8.
17 ~
~l~hough~variou~ cathode material~ have been recited in the art for u~e in variou~ ~ell oystem~, ~n object of the pres n~ in~ention i~ to provide a novel cathode for u~e in solid electrolyte cell ~y~t~s.
Arlo~cher o~ ~ ect of the pre~ent invenSion i~ ~o prsvide a cathode compri 3ing a charge ~ran~fer ¢omplex ln which the complex is the reaction product of at least 3~
122~5 ~ :1 5 ~S l ~
one h~logen with a ~ar~onsceous pltch.
~ nother ob~ect of ~he pre~ent invention ~ 8 to prov~de a eathode comprl~ing ~ chQrge tran~fer complex ln which th~ complex ~8 the reaction product o~ iodin~
or bromlne with ~esophase pitch~
~ nother ob~ect of ~he present in~ention i6 to pro~de a cathode c~mprisin~ a charge transfer complex in wh~ch the complex ~5 the reaetion product of iodine with ~esophase pitch for u8e in a ~olld ~tate cell emplo~ing R lithium anode and ~ solid lithlum iodide elec~rolyte.
The foregoing and additiona~ ob~ects will become more fully apparent fr~m the following descrip~ion.
Summary of the Invention The in~ention relates to a cathode for u~e in an electrochemical cell compri~ing a charge transfer complex in which the complex is the reaction product of ~t least one halogen ~ith a carbonaceo~s pitch and wherein the donor component is the carbonaceous pitch and the acceptor component is the at least one halogen.
A5 used herein, at least one halogen shall ~an a halogen ~uch as iodine, bromine, ehlorine sr 1uorine, a mi~ture of t~o or more halogens or a com~ound ~in~erhalogen) of two or more h~lo~ens~
Chnrge trans~er omplexes are a well-known cla~s of ~aterials tha~ have two component~ - o~e a~ an electron d~nor, thc other as ~n electron acceptor -th2t form weakly bonded complexe~ that e~hibit eleotronic conductiv~ty ~igher than ei~her eomponen~. Chaxge ~ransfer 3U complexes for this inYention compri~e a carbonacesus pitch ~ the electron donor and a~ least one h~logen as the electron acceptbr. The preferred c~ rge transfer ~omplexes of this in~ention would be the reaction product .
~ 3. r)'~ 12245 of a me~ophafie-cont~ining pi~ch wi~h lodine or bromine.
Although ~he ~onducti~vity of the charge ~cransfer com-plexes of th~ ~ in~vention will be ~ufficiently high for most cell applic~tions, the cDnductivity could be m~de higher by adding a conductive material ~uch fi5 carbon, graphi~e or 8n inert conduct~ve ~etal. ~referably, the conductivity of the charge tran8:Eer complexe~ for most cell applications should be greater than sbout lob Diho/cm.
Natural and syntheti c carbonaceou~ pitche~ 9 as i8 well knawn, are complex mixtures of orgsnic compounds which, except for certain rare para~finicbase pitches derived from certain petroleums, ~uch ~8 Pennsylvania crude, sre msde up essentially of fu~ed ring aromatic hydrocarbons ~nd are9 therefore, ~aid to have an aromatic base. Since the molecule6 which mske up ~hese organic c~mpounds are compara~ively ~mall (average molecular weight not ~ore ~han 8 few hundred) and interac~ only weakly with one ~nother, such pitches are i80tropic in ~0 ns ure. On heatin8 the~e pitches under quie~cent con-ditions at a temperature of about 3500-4500CG, howe~er, ei~her a~ ::onstan'c temperature or with gradually increasing t~mpera~ure, 8mall insoluble liquid ~pheres begin to .-appear ~n the pltch which gradually increa~e in s~ze ~s heating i8 continued. ~en ~xamined by electrDn difrac-'cion and polarized llg~t techniques, these ~phere~ are 8hown to ~onsi8t of layer~ of or~ented molecule~ aligned iFl t~e 8ame direction. A~ the6e 8pheres con~inue to grow in size as heating ~ ~ corltinued, they come in contact wlth one another ~nd gradually coalesce wlth each o~her to produce ~he larger masses of aligned layer~. A~
11~ 751$ 1224~
co~lescQnce con~inue~, d~m~ins of aligned molecules much larger than those of ~he or~gin~l sphere~ are fo~med. These domalns coue tsgether ~o form a bulk mesopha~e wherein the transition from one oriented do~ain to another sometime~ oCCUr8 smoothly and ~on-tinuously through grsdually curving ~dmell~e and ~ome-times ~hrough ~ore 8hssply curv~g læmellae. The differences in orientstion between the domains cr~ate a complex array of polar~zed light extincti~n c~ntours in the bulk mesoph~se corresponding to varlous types of linear ti~continui~y in molecular alignment. The ultimate 81ze of ~he oriented domains produced $s dependent upon the Vi~c08ity, and ~he rate of increa~e of the ~i~co~ity, of the mesophase from which they are formed, which, in ~urn, are dependent.upon ~he par~icular pitch and th~
heatlng rate~ In certain pitches, domain~ h~viag ~zes in excess of two kundr.ed microns up to several hundred microns are produ~edO In other pitches, th~ vi~cosity of the me~ophase i8 BUCh that only limited coalescence ~nd structural rearrangem~nt o~ layer~ occur, 80 that the ulti~ate domain ~ize does not e~ceed one h~ndred microns.
The highly oriented, optically anifiotropic, ins01ub}e ma~erial produced by treating pitches in this -- ~nanner has been g~en the ~cerm "mesophase"g and pltches conta~ing such material are known as l~mesophase pltches".
Such pitches, when heated above sheir ~oftening point~, are ~i$~res of ewo ~ cible liquid~, one the op~icall an~sotropiC~ oriented mesophas~ port~ , and the other the iBo~ropic non~mesopha~e portion. The ter~ "mesophase"
is derived from the Greek ilmesos" or "intermediate" and 6.
5'~51~
indicates the ~pseudocrystalline nature of this highly-oriented, optically anisotropic material. As used herein, "mesophase pitchl' or "mesophase" shall mean a carbonaceous pitch containing mesophase.
A detailed description for producing mesophase pitch can be found in U. S. Patents 4,005,183, 4,017,327 and 4,026,788.
The preferable carbonaceous pitches for use in this invention are mesophase pitches and more preferable would be mesophase pitches having a mesophase content of above 40 per cent by weight and preferably would be mesophase pitches having a mesophase content of above 90 per cent by weight and most preferably above 95 per cent by weight.
Specific preferable iodine-containing and bromine-containing charge transfer complexes for use in this invention are as follows:
X I2 where X is mesophase pitch and the amount of iodine varies between about 50% and about 97%
by weight and preferably between about 80% and about 90%
by weight;
X Br2 where X is mesophase pitch and the amount of bromine varies between about 50% and about 97%
by weight and preferably between about 80% and about 90%
by weight.
The above solid charge transfer complexes have been found to have vapor pressures below those of iodine and bromine.
~ i, ~ 5~ 245 Anode materials suitable for use wi~h the cathodes of this invention include lithium, ~iLver, ~odium, potassium, rubidium, magnesium and calcium. The pre-ferred anode m~terial is lithium.
Solid electrolytes for use in this in~ention would lnclude lithium iodide, silver iodide, silver bromide, lithium bromide, tetras~ver rubidium pentaiodide, lithium aluminum tetrachloride, te~rasilver potassium tetraiodide cyanide, te~rasilver rubidium tetraiodide cyanide, sodium iodide and sodium bromide. The preferred solid electrolytes or use in this invention are lithium iodide and tetrasilver potassium tetraiodide cyanide.
As disclosed in U. S. Patent No. 3~660,163, ln a lithium anode cell, lithium iodide can be formed in ~itu by contacting the lithium anode with the iodine-containing cathode surface whereupon the lithium will react with the iodine in the cathode to form a lithium iodide electroly~e layer that will contact both the anode and the ca~hode.
Alternately, the lithium iodide could be formed by reactin~
lithium and iodine and then applying the lithium iodide as a coating on the surface of the a~ode or cathode.
Preferable cell systems using the cathode of this invention would be as follows:
Anode Elec~rolyte .
lithium lithium iodide lithium li~hium br~mide silver silver iodide silver tetrasilver potassium tetraiodide cyanide silver ~etrasilver rubidium tetraiodide cyanide 5 ~ ~ 12245 ~XA~I E 1 .
Several cha~ge tran~er csmplexes were prepared by blending ~esoph~e pitch (containing about 85 per cent slesophase~ with iodine ln the weigh~ ratio8 ~hQwn in Table I. The blends ~ere then ~eslèd irl an e~cuated glas tube where they wese then either aged ~It room tempera~ure ~20C) or heated to the eemper~ture shawn In Table I for 16 hours, The ~nesophsse/iodfne ch~rge transfer complexe~ ~o formed and lodine (I2) wer~ then testet for iodine v~por pres~ure and the data ob~ain~d ~re shawn in Table I.
1 ~ 5 '~
~ 1 ~ ~ o ~ r~
s~ ,. . . . . . . . o ~ o ~ ~ CO ~ X 1 _, ,~
oo al ~ ~ I~
P~ C~ . . . . . . . . . . ..
o _I ~I C'~l C~l ~ C~l t~ M
h ~
C .
_, ~ e~ ~ ~ C~l o ~ . . . . . . . .
O Q O O O O O O O O O
t-~ ~I
a~
C~
~ C ~ ~ P~ .
_I ~U O O O O O O D O 0 0 . O O O O Q C~ O O O ~U
U ~ ~ O C:~ O C`~ ~ O t'`l :~1 0 ~ ~3 ~
- 0 0 0 a~
~ 3 ~C 3 ~
ac ~ P
0 .n ~ ~ ~n ,a ~ ~ ~ ~ ~11 ~ ~ 0 .l~
v ~ ~ ~a ~ ~ ~ ~ ~a O 0 3~ O ~
~:
- o sl~ a a~ o) ,c ~C ~ ~ .C ~c ~ ~ ,c 0 .C
_~ o O O o o ~ o O o ~ o ~c ~ o a~ 0 ~ ~ 0 ~ o 10.
~5'~5~5 1224S
~ ~vid2nt from the t~ta 4hown ~n T~ble I, the ~e~opha~e/iodlne-containlng charge trans~er com-pl~ces h~lve indine vapor pres~ures depresRed below tb~t o~ iodtne9 pa~ticul~rly ~t ~le~t~d test tempe~tures.
15~LE 2 A ch~rge tr4nsfer comple~ consi~ting of ~ne~o*lase pitch ~ont ining ~bout ~5% mesopha~e aTld bromine 1~8 for~ed as ~n Example 1 in w~lch a chemical ~nalys~s revealed that bromine was pre~ent in a 52 we~ght per cent 1~ propostion. The me~ophase/brom~ne charge ~craIIsfer complea~
~o formed ~nd bromine were t~sted or bromirle v~por pressure at variou~ t~mperatures ~md the data ob~erved are ~hown in Table II.
TABLE II
Bromine Vapor Pressure ~mm H~) M~terial 20C. 54C. 71C
O
~esophase.Br~mine 5.2 9.7 33 Bromine 220 640 1200 As evide~t from ~he data sh~wn in Table II, the mesophase/~romine-containing charge tran~fer comp~ex had a bromine vapor pre~sure ~ubstanti~lly below that of bromine~
EX~PLE 3 Samples of ~he mesophase/iodine-containing -- charge tran~fer complexes were prep~red as in Example 1 200C. uz~ng ~he ~eight ratio ~8 ~h~w~ ~ Table III.
The conductances of the~e ~R~ples ~long wlth ~e~oph~se pi ch and lodine ~I2) were fou~d and the da a obserYed are ~hown in Table III.
L15 tS15 ~BIE: III
Materisl nduct~nce (ohm 1 cm 1) me80phaAe under 10-~
iodine 1. 7 ~ ll1 7 slesopha~e~67% ~odine* 6.0 x 10 4 mesoph~se- 94% iodine* 2 . 2 x 10 5 *by weigh~ .
XA~L~ 4 Two ~.457-inch d~meter butt~ cells were lU constructed a~ follows. ~ me~opha~e (about 857.
mesophssa)/iodine charge ~ransfes comple~ wa prepared by ~rinding the me~oph~e pltch and iodine componenta followed by drying them UBiTlg phosphoru~ pe~toxide for a week ln an argon dry box. Thereaf~er the me~opha~e pitch and iodine were blended together in a weight ratio of one mesopha~e pitch to 1~ iod~ne (me80ph~8e- ~Z lod~ne~ ~nd - then sealed in an eYacuated tube whereupon it wBs heated at 20()C~ for 16 hours, The re~ulting charge transfer complex ~as a85embled in a nickel-plated cold-rolled steel container, A llthium ~node strlp was placed in a eo~7er wt~ h wa~ then a8~embled slong with ~ ga~ket on ~ p of the container in a conventlotlal manner 8uch thllt the ~urface of the anode made contact with the 8urface of the c~thodee, The electrolyte~ lithium iodide, was ~ormed in - ~itu by the reaction of the lithlum in ~he a~ode and the ~odine ln the c~thode. The two ~ells were ths~n di~charged for 10 second period~ across ~ario~ resls~iv2 load~ and the voltages observed were recorded, Based OJl ~he total surfaee area of the c~thode . facing the arlode, ~he current densi~y was calculated for each voltage readlng arld the data obtained are shown ln Table IV.
12, ll5'~5~S 12245 TABLE IV
Cell 1 Cell ~ _ . .. ~
Voltage Cu~r~nt d ~ity Voltage Current d~nsity ~Yolts~ ~4A/cm (volts) ~ ~/cm 2~75 2.6 2.7 ~.7 ~.6 5.6 ~.55 5"~
2.5 8.4 2.4s 8 2 . 35 11 2 . 3 2.2s 15 2.~ 14 2. 1 20 1.95 18.5 1.6 30 1.5 30 0.8 50 0.65 6 EXA~LE 5 r._ : . ~
A 0.457 inch di~meter button cell was con-~truc~ed a~ in ~xample 4 except that the can was ~tainless steel and the mesophase pl~ch snd iodine of the charge trans-fer complex were in a weight rstio of one mesophase pitch to 16 iodine (mesophase-34~/O lodine). The cell was continu-ously discharged across a l-megohm load and the data obtained ~re ~h~wn in Table VO
TABLE ~ .
Time Yolt~ge 100 2.7S
250 2.65 300 2.60 6~0 2.50 700 2~45 800 2~40 gO0 2.35 1100 2,30 -~XA~PLE 6 Two 0.457 ~nch disme~er bu$ton cell~ were con~trucked a8 follows. A mesopha~e (85% mesoph~se)/
br~m~e charge transfer complex ~as prepared by grinding the mesopha~e p~tch and d~y~ng ~t u8ing ph9SphOrU~
pento~lde for a week ~n an argon dry box~ Thereafter the ~c~ophase pl~ch and br~mine were mixed toge~her ln weight rat~o of one mesophase pitch ~o 1 bromlne. The 13.
5 ~ ~
re~ulting charge tr~nsfer comple~ w~ e~led in 8 nickel pl~t~d colt ~olled steel c~n. A lithlum ~node ~trip wa~ pl~ced ~n a cover w~lch ~as ~hen ~embled ~long wlth ~ ga~ket on top of the c~ a cçmrentlonal manner such that the ~usface of the ~node D~.ode 0n~ct ~ith the ~urface o~ the cathode. The electrolyte, lithium b~omide, ~!18 formed iSl ~itu by the rgaction of the lithil3m ln the anode l~nd the bromine ln the cathode.
The cell wa8 then discharged for lû-second period~ BCrO21S
various resist~ve loads ~nd the voltAge~ observed ~e$e recorded. Bs~ed on the total surface ~rea of the ca~chote faclng the amode, the current density wa~ c~lculated ~or each voltsge readlng and ~he da~a obtained are ahown in Table VI~
TABLE VI
Voltage Curren~c De~s ity ~At~m 3 3 3.4 3 1 7,0 ~0 2. 9 10 2. 7 1.6 32 Oc5 ~2 Two cells were cz~st~uc~ed a~ in Ea~ple 4 except that t~e charge t~sfer eo~plex employet waR a blend of 67Z by weigh~ iodine wlth 33% mesopha~e pi~ch - ~labout 85% me~o~se3" E~ch cell 6?a~ te~ted 8~ desc~ibed ~n ~xEmp~e ~, and the data obtained are ~ho~ in 30 . T~ble VIX.
122~5 5'~5i ~LE VII
Cell 1 Cell 2 VoltageCurrent d~n~ity ~lolta~eCur~ent d~nsity ~volts~ ~ (~t A/cm ).
2.72 2.7 2.69 2,7 2. 71 6 2. 6~ 6 2. 71 g 2. ~7 g 2 . 70 ~3 2 . 6~ 13 2 . 651 1~ 2. 65 18 2 . 68 27 2, ~3 26 2. 63 52 2. 5~ 51 2. 31 231 2, 10 219 l~he two cell~ were then t~ted ~!18 te~cribed in E2cample 5, The data obtained ~e shown in Table VIII, TABLE VIII
Cell 1 Cell 2 ~ . ;.
Time Volt~ge Time Voltage ~!~ (vol~
1~0 2, 77 10 ~, 77 100 ~ 77 100 2.76 200 2 76 200 2,75 300 2, 75 ~ 3ûO 2. 75 500 2, 73 500 2, 72 1000 ~ . ~ 7 1000 Z . ~7 2û00 2, ~0 . ~000 2. 50 EXA~LE 8 Two ~ell8 were co~structed a~ in E~ple 4 except that the charge l:ran~fer complex employed ~8 a blend of 86% by weight iodine with 14% me~opha~e pi~ch (~bout ~5% mesopha~e). Each ~ell WEI~ te~ted a~ described in E~cample 4, ~nd the d~ta obtained axe shown in Table I2.
~ABT F ~ X
Cell 1 Cell 2 Voltag2 Current d~nsity Voltage Cu~rent d~n~lSy ~volt~) ~i_ ~ ~9 2. 76 2. 76 ~, 75 2., 75 2 75 6 2.13 2 75 5~ 2.71 2,74 13,7 ~,6~ 13 2 74 18 2. ~5 18 2 72 27 2,~ 26 2,S9 54 2~41 4~
~,43 243 ï, 57 157 1~ ., 1~$'~$
The ewo e211~ ~ere ~hen t~3~d a~ d~cribed ln E:~ca~Dple 5. The data obta~n~d ~re sh~ n T~le X.
SABLE X
-Cs!ll 1 Cell 2 Time Voltage T~e Yoltage ~!~ (voLt~) ~our~) 2. t7 lU ~. 7~
100 2. 77 ~00 2. 73 - ~0 2. ~7 2~0 2. 71 300 2. 76 30~) 2. 71 ~00 2. 75 500 2. ~9 lO0(~ 2072 ~ 1000 2.b~
1~00 ~. 6~ 1~00 2. 63 A cell W~18 constructed a~ in EsaD~ple 4 ~:RC¢pt that the charge transfer complex omployed was a blend of 75%, by weight iodine with 25% me20ph~se pi~c~h (abou~ ~570 mesopha~e), The cell ~as te~ted ll8 describ~ in E~c~mple 4 and the data obtained ar2 shown in T~ble ~ TALLE XI
Voltage . Cus~nt d~n~ ity 2.6~ 2,7 2.65 2.~4 9 ~,64 . 13 2. ~4 18 2, 63 2~
2. ~0 52 2. 3~ 23 The cell ~as then ~e~ed a8 desGrlbed in E~campl~ 5. The data obPained are ~hown in Tabl~
~ABLE XII
T~e Vol~age (hour ~
~0 ~,77 100 ~. 76 2û0 2. 75 500 ~, 72 00 2. 7 16 ,.
. . ' ' .. .
.
11,5'~5~; 12~4~
hould be under~tood tha~t the foreg~ing dlsclosure relates to pref~rr~d embodiments of the inventioTI 8nd ~ t i~ intended to cc~ er ~11 chan~se8 snd modiflcatl.on~ of the invention w~ich do not depart rom the ~pirit and 3cope of the ~ppended clsim8.
17 ~
Claims (11)
1. A cathode for use in an electrochemical cell comprising a charge transfer complex in which the complex is the reaction product of at least one halogen with mesophase pitch and wherein the donor component is the mesophase pitch and the acceptor component is the at least one halogen.
2. The cathode of claim 1 wherein the at least one halogen is selected from the group consisting of iodine, bromine, chlorine and fluorine.
3. The cathode of claim 1 wherein the at least one halogen is iodine.
4. The cathode of claim 1 wherein the at least one halogen is bromine.
5. The cathode of claim 1 wherein the charge transfer complex is X-I2 where X is mesophase pitch and wherein the amount of iodine varies between about 50% and about 97% by weight.
6. The cathode of claim 5 wherein the iodine varies between about 80% and about 87% by weight.
7. The cathode of claim 1 wherein the charge transfer complex is X-Br2 where X is mesophase pitch and wherein the amount of bromine varies between about 50 and about 97% by weight.
8. The cathode of claim 1 for use in a solid electrolyte cell employing an anode selected from the group consisting of lithium, silver, sodium, potassium, rubidium, magnesium and calcium.
9. The cathode of claim 1 or 8 for use in a solid electrolyte cell employing an electrolyte selected from the group consisting of lithium iodide, tetrasilver potassium tetraiodide cyanide, lithium bromide and tetra-18.
silver rubidium pentaiodide.
silver rubidium pentaiodide.
10. The cathode of claim 2 for use in a solid electrolyte cell wherein the halogen is iodine, the anode is lithium and the electrolyte is lithium iodide.
11. The cathode of claim 2 for use in a solid electrolyte cell wherein the halogen is bromine, the anode is lithium and the electrolyte is lithium bromide.
19.
19.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US052,846 | 1979-06-28 | ||
| US06/052,846 US4243732A (en) | 1979-06-28 | 1979-06-28 | Charge transfer complex cathodes for solid electrolyte cells |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1157515A true CA1157515A (en) | 1983-11-22 |
Family
ID=21980276
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000354946A Expired CA1157515A (en) | 1979-06-28 | 1980-06-26 | Charge transfer complex cathodes for solid electrolyte cells |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US4243732A (en) |
| JP (1) | JPS5619868A (en) |
| BE (1) | BE884035A (en) |
| BR (1) | BR8004052A (en) |
| CA (1) | CA1157515A (en) |
| CH (1) | CH638643A5 (en) |
| DE (1) | DE3023969C2 (en) |
| FR (1) | FR2460549A1 (en) |
| GB (1) | GB2053877B (en) |
| HK (1) | HK23084A (en) |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4333996A (en) * | 1980-09-29 | 1982-06-08 | Union Carbide Corporation | Solid state cell in which an inert nonconductive material is dispersed in the cathode |
| US4409303A (en) * | 1982-03-04 | 1983-10-11 | Duracell Inc. | Catalytic cathode for primary and secondary fluid cathode depolarized cells |
| US4477545A (en) * | 1983-06-29 | 1984-10-16 | Union Carbide Corporation | Isostatic compression method for producing solid state electrochemical cells |
| US5015544A (en) | 1989-02-08 | 1991-05-14 | Strategic Energy Ltd. | Battery with strength indicator |
| US5156931A (en) | 1991-12-31 | 1992-10-20 | Strategic Energy Ltd. | Battery with strength indicator |
| CA2098248C (en) * | 1993-06-11 | 1999-03-16 | Jeffrey Raymond Dahn | Electron acceptor substituted carbons for use as anodes in rechargeable lithium batteries |
| US9742008B2 (en) | 2013-12-03 | 2017-08-22 | Ionic Materials, Inc. | Solid, ionically conducting polymer material, and methods and applications for same |
| US10559827B2 (en) | 2013-12-03 | 2020-02-11 | Ionic Materials, Inc. | Electrochemical cell having solid ionically conducting polymer material |
| US11251455B2 (en) | 2012-04-11 | 2022-02-15 | Ionic Materials, Inc. | Solid ionically conducting polymer material |
| US9819053B1 (en) | 2012-04-11 | 2017-11-14 | Ionic Materials, Inc. | Solid electrolyte high energy battery |
| US12074274B2 (en) | 2012-04-11 | 2024-08-27 | Ionic Materials, Inc. | Solid state bipolar battery |
| US11319411B2 (en) | 2012-04-11 | 2022-05-03 | Ionic Materials, Inc. | Solid ionically conducting polymer material |
| US11152657B2 (en) | 2012-04-11 | 2021-10-19 | Ionic Materials, Inc. | Alkaline metal-air battery cathode |
| DE102013017594A1 (en) * | 2013-09-27 | 2015-04-02 | Forschungszentrum Jülich GmbH | Production method for electrochemical cells of a solid-state battery |
| HUE053572T2 (en) | 2014-04-01 | 2021-07-28 | Ionic Mat Inc | High capacity polymer cathode and high energy density rechargeable cell containing the cathode |
| EP3304620A4 (en) | 2015-06-04 | 2018-11-07 | Ionic Materials, Inc. | Solid state bipolar battery |
| KR102640010B1 (en) | 2015-06-04 | 2024-02-22 | 아이오닉 머터리얼스, 인코퍼레이션 | Lithium metal battery with solid polymer electrolyte |
| KR102607433B1 (en) | 2015-06-08 | 2023-11-27 | 아이오닉 머터리얼스, 인코퍼레이션 | Battery with aluminum anode and solid polymer |
| US11342559B2 (en) | 2015-06-08 | 2022-05-24 | Ionic Materials, Inc. | Battery with polyvalent metal anode |
| CN110337746A (en) | 2017-01-26 | 2019-10-15 | 离子材料公司 | Alkaline cell cathode with solid polymer electrolyte |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1162747A (en) * | 1966-06-13 | 1969-08-27 | California Inst Res Found | Primary Cells Containing Halogen Charge Transfer Complexes |
| US3660164A (en) * | 1969-07-02 | 1972-05-02 | California Inst Res Found | Primary cell utilizing halogen-organic charge tranfer complex |
| JPS5533588B1 (en) * | 1970-03-04 | 1980-09-01 | ||
| US3660163A (en) * | 1970-06-01 | 1972-05-02 | Catalyst Research Corp | Solid state lithium-iodine primary battery |
| US3895962A (en) * | 1972-03-01 | 1975-07-22 | Greatbatch W Ltd | Solid state battery and method of making the same |
| US4017327A (en) * | 1973-12-11 | 1977-04-12 | Union Carbide Corporation | Process for producing mesophase pitch |
| US4026788A (en) * | 1973-12-11 | 1977-05-31 | Union Carbide Corporation | Process for producing mesophase pitch |
| US4049890A (en) * | 1975-04-03 | 1977-09-20 | Catalyst Research Corporation | Lithium-iodine cells and method for making same |
-
1979
- 1979-06-28 US US06/052,846 patent/US4243732A/en not_active Expired - Lifetime
-
1980
- 1980-06-26 BE BE0/201200A patent/BE884035A/en not_active IP Right Cessation
- 1980-06-26 DE DE3023969A patent/DE3023969C2/en not_active Expired
- 1980-06-26 CA CA000354946A patent/CA1157515A/en not_active Expired
- 1980-06-27 CH CH498680A patent/CH638643A5/en not_active IP Right Cessation
- 1980-06-27 FR FR8014387A patent/FR2460549A1/en active Granted
- 1980-06-27 BR BR8004052A patent/BR8004052A/en unknown
- 1980-06-27 JP JP8768480A patent/JPS5619868A/en active Pending
- 1980-06-27 GB GB8021057A patent/GB2053877B/en not_active Expired
-
1984
- 1984-03-15 HK HK230/84A patent/HK23084A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5619868A (en) | 1981-02-24 |
| FR2460549B1 (en) | 1985-02-01 |
| CH638643A5 (en) | 1983-09-30 |
| FR2460549A1 (en) | 1981-01-23 |
| BR8004052A (en) | 1981-01-21 |
| DE3023969A1 (en) | 1981-01-08 |
| HK23084A (en) | 1984-03-23 |
| BE884035A (en) | 1980-12-29 |
| DE3023969C2 (en) | 1982-07-01 |
| US4243732A (en) | 1981-01-06 |
| GB2053877A (en) | 1981-02-11 |
| GB2053877B (en) | 1983-03-30 |
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| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |