CA1264416A - Composites for use in electrical applications such as electrodes in solid state energy storage devices - Google Patents
Composites for use in electrical applications such as electrodes in solid state energy storage devicesInfo
- Publication number
- CA1264416A CA1264416A CA000467307A CA467307A CA1264416A CA 1264416 A CA1264416 A CA 1264416A CA 000467307 A CA000467307 A CA 000467307A CA 467307 A CA467307 A CA 467307A CA 1264416 A CA1264416 A CA 1264416A
- Authority
- CA
- Canada
- Prior art keywords
- ionic
- electronic
- conductor
- conducting material
- energy storage
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 22
- 238000004146 energy storage Methods 0.000 title claims description 8
- 239000007787 solid Substances 0.000 title description 6
- 239000004020 conductor Substances 0.000 claims abstract description 53
- 239000000463 material Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
- -1 polyphenylene Polymers 0.000 claims description 19
- 229920000642 polymer Polymers 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 16
- 229920000233 poly(alkylene oxides) Polymers 0.000 claims description 14
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 13
- 229920001197 polyacetylene Polymers 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000010416 ion conductor Substances 0.000 claims description 6
- 239000011532 electronic conductor Substances 0.000 claims description 5
- 229920000265 Polyparaphenylene Polymers 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000007784 solid electrolyte Substances 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 238000005266 casting Methods 0.000 claims description 3
- 239000011877 solvent mixture Substances 0.000 claims description 3
- 230000001427 coherent effect Effects 0.000 claims description 2
- 210000000352 storage cell Anatomy 0.000 claims 3
- JRXXLCKWQFKACW-UHFFFAOYSA-N biphenylacetylene Chemical group C1=CC=CC=C1C#CC1=CC=CC=C1 JRXXLCKWQFKACW-UHFFFAOYSA-N 0.000 claims 1
- 238000005191 phase separation Methods 0.000 claims 1
- 229920006389 polyphenyl polymer Polymers 0.000 claims 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 239000002019 doping agent Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 3
- 239000002322 conducting polymer Substances 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 230000002844 continuous effect Effects 0.000 description 2
- 238000004455 differential thermal analysis Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical group CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- VOVZXURTCKPRDQ-CQSZACIVSA-N n-[4-[chloro(difluoro)methoxy]phenyl]-6-[(3r)-3-hydroxypyrrolidin-1-yl]-5-(1h-pyrazol-5-yl)pyridine-3-carboxamide Chemical compound C1[C@H](O)CCN1C1=NC=C(C(=O)NC=2C=CC(OC(F)(F)Cl)=CC=2)C=C1C1=CC=NN1 VOVZXURTCKPRDQ-CQSZACIVSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/122—Ionic conductors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
- H01B1/125—Intrinsically conductive polymers comprising aliphatic main chains, e.g. polyactylenes
-
- 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
-
- 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
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Secondary Cells (AREA)
- Laminated Bodies (AREA)
- Manufacturing Of Electric Cables (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Novel composite conductors are provided comprising interpenetrating networks of a continuous electronic conducting material and a continuous ionic conducing material. Also provided is a method of producing films of the same.
Novel composite conductors are provided comprising interpenetrating networks of a continuous electronic conducting material and a continuous ionic conducing material. Also provided is a method of producing films of the same.
Description
~26~
The presen~ invention relates to novel compos:ite materials and a method for preparing films of such composite materials. The composite materials herein are useful in electrical applications such as electrodes in solid state energy storage devices.
It is known to produce energy storage devices which use an electrode of a conducting polymer and an electrolyte which may be either a solid or a liquid. Solid-~tate energy skoraye devices have been prepared having a composite or laminar structure comprising a layer of eleetrolyte beiny sandwiched, either as such or impregnated in a matrix, between two electrodes. It is also known that by electrochemically doping the conducting polymers with a dopant anion or cation, the polymers of this type can be used to store electric charge.
In such solid-state devices, the conducting polymer acts as the electronic conduckor and the electrolyte ~atrix as the ionic conductor. One of the major drawbacks of using composites in such devices is that the migration of ions from the electrolyte to the polymer electrode ls hindered by the relatively low 2Q diffusion rate of the dopant ion into khe polymer electrode, and the resulting high internal resistance reduces the devices performance.
It has now been found that the ion diffusion rate characteris~ically found in conventional conductivs composite materials can be si~nificantly increased by preparing an ionic/
electronic composite conductor comprising interpene~ra~ing networks of a continuous electronic conduc~ing polymeric material and a g~ ~
!IIID~J
' "'",, `
~:6~6 continuous ionlc conducting material. Sucb composite conduceors can be used in a varlety of electrical applications but are partlcularly suited for use in solid state energy storage devices.
Accordingly, the present lnvention provides an ionic/electronic composite conductor comprislng interpenetrating networks o a coneinuous electronic conductlng material and a continuous ionic conducting maeerial.
In a preferred embodiment 9 the compoæite conductor i9 a coherent film.
The present invention also provides a method for preparing a film of a composite conductor comprising interpenetratlng networks oP a continuous electronic conducting material and a continuous ionic conducting materisl, the method comprising i) preparing ln a common sovlent or solvent mlxture a solution o~
an ionic conducting material and an electronic conducting material or a precursor thereof, li) intimately mixing the solution, and iii) casting the solution on a substrate, and iv) removing the solvent.
According to another embodiment of this invention, an energy storage device i8 provided containing at least one electrode comprising interprenetrating net~orks oE a continuous electronic conducting material and a continuous ion~c conducting material.
By lnterpenetratlng networks is meant herein that each material of the composite conductor i~ continuous and intimately mixed with the other materlal throughout the composite. In order to determine that the mate~lals are intlmate and continuou~, thermal analysi~ can be conducted in accordance with known differential thermal analysis (DTA) techniques. Such technique~ will show an increased ~elting point for the lonic conducting material~ as compared to its normal meltlng point, when the electronic conducting material and the lonic conducting material are interpenetrating.
The electronic conducting material of the ionic/elec~ronic composlte conductor according to the present invention is ormed 3S from a conducting hydrocarbon polymer which i~ soluble in the .' ' :
~6~L6 solvent employed. For example~ the6e materials include but are not limited to soluble precursor polymers of polyacetylene and polyphenylene whlch can be s~bsequently converted tG polyacetylene and polyphenylene; soluble electronic conductlng polymers s~ch as polyphenylene diphenyl vinylene; or soluble substieuted electronlc conduceing polymers such as phenyl substituted poLyacetylene~
Polyacetylene precursors are preferredO
The ionlc conducting material of the composlte conductor is a mlxture or a complex of an ionic salt, containing anions such as 0 ASF6 9 PF6 , BF4 or C10~ , and catlons such as a:Lkall metal cations, e.g. Li~, with a poly~eric solvating agent capable of solvating the ionic sale such as a polyalkylene o~cide. Preferred polyalkylene oxides are polyethylene o~ide and polypropylene oxide.
The ionic conducting material comprising the mixture or complex of the ionic salt and the polymeric solvating agent may be $ormed by doplng the polymeric ~olvating agent with an appropriate ionic salt before, during or after the production of the composite conductor.
Any of the well known doping techniques for incorporating anions or cation into polymer materials can be used.
The lonic/electronic compo~lte conductor of the present invention is prepared by tntimately mixing the electronic conducting material wlth the ionic conductlng material. The electronic conducting msterial and the ionic conducting material are dissolved in a commo-l solvent or solvent mixture. The solvent or solvent mixture must be capable of solubilising both material~ in sufficient concentrations and must not substantially react with either material. The solvents used herein are polar organic solvents or mixture th~reofO Preferred is tetrahydrofuran. The solution of the electronic conducting msterial and the lonic conducting material should be throughly mixed.
A fllm of the composite can be cast from solution by pouring the solu~ion onto a substrate and removing the solvent by heating at elevated temperatures from 20 to 150~C, typlcally about 50C, or by spinning the substrate at high rates of revolutionO The solvent should be removed quic~ly, preferably by evaporation, so that phase , ~6~6 separatlon of the component materlals ls ~nhibited.
In a variation of the abovY process, the ionic salt may be added to a 801ution of the electronic conductlng ma~erial and a polymeric ~olvating agent prior to ca~ting the film.
The relativ~ molar concentratlons ~in terms of the polymerl~ed unlts in the respective monomers) of the electronic conducting material and the pol~meric solvatlng agent in the composite is suitably from l:lO to lO:l, preferably from 1:2 to 2:l and most preferably l:l.
The molar concentration of the dopant ionic salt in the polymeric solvating agent is preferably from 2:l to 5:1 based on moles of salt per mole of ~otal polymerised unlts in ~he polymer.
'Ln a preferred embodiment of this invention, the electronic conducting materlal is a,poly~acetylene) precursor polymer of 7,8-bis(trifluoromethyl) tricyclo-~4,2,2,02~5]-deca-3,7,9-triene which is described ln European Patent publication No 0080329. The ionlctelectronic conductor containing the precursor polymer is prepared as discussed above. The resultant product is then cast into a film and then converted by heat treatment lnto a film of a composite comprising interpenetrating networks of a continuous electronic conducting polyacetylene and a continuou~ ionic conducting material. The composi~e film is subsequen~ly ~eeped in a solution of an lonic salt to orm the ionic/electronic composite conductor.
The precursor poly~er is convsrted to polyacetylene by heating the polymer at a temperatures below 130C, preferably 70 to 120C, under vacuum or in ~e-~ec7e~R=r~-an inert atmosphere~ T,he specific temperature and duration of heating will depend on the raee of transformation desired. Typically, the heating is conducted for a period from 1 to abou~ 100 hours, preferably between lO and 50 hours~
The polyaceeylene prepared from the precursor polymer can be doped after casting by known chemical or electrochemical techniques. Suitable dopants are ~ell known to chose skilled ln the 3S art.
~" .
~, :
.
The ener~y storage device of this inventlon co~pri~e~ at least one lonlc/electronic conductor employsd a~ an electrode and a solid eletrolyte. The preferred embodiment comprises two ionic/electronic conductors wlth a solld electrolyte therebet~een.
The solid electrolyte should be lonlcally conducting but not electronically conducting such a~ a polyalkylene oxide.
In a more preferred embodiment, polyalkylene oxide (PA0), preferably polyethylene oxide, i~ sandwiched between two layers of a polyacetylene/PA0 composlte conductor film prepared according to the pxe~ent invention and incorporating a suitahle ionic salt. The PA0 solid elecerolyte al~o incorporates an ionic ~alt. The 6tructure can be built up by succe6sive evaporation~ from a solution of polyacetylene precursor, PA0 and ionic ~alc on the one hand and a solution of PA0 and ionic salt only o~ the other hand, combined wieh a heating 8tep to convert the precursor polymer into an electronically conducting poly~cetylene polymer, (CH)X.
As constructed, the cell is in a dlscharged ~tate. It i8 charged by pas~ing current through lt, in elther directlon. The (CH)X initially has relatively low conductlvity~ but ionic conductlon allows reasonable charging rates until the electronic conduction becomes high. At the anode, anions are removed from the PA0 matrix and dope the (CH)X so that the anode (CH)X beco~es p-type. Simllarly, at the cathode, catlona are removed from the PA0 matri~, and dope the (C~)x electrode to become n-type. Charging 1~
complete when a suitable doping level in the (C~)x i9 achleved (ior instance 20% per (CH~ unit). Discharge of the cell rever~es the composite conductor with a large area for large electrical contact pads, to reduce the internal impedence of the cell. Specific example~ of contact pad~ include those made from gold, platlnum and silver although any metal capable of giving ohmic contact with the elctronic conducting poly~er may be used.
Since the cell i8 ln the for~ of a flexlble film ~before charging~ it can be, for example9 conv~niently rolled up into a cylindrical ~hape~ The combin~tion of the thin cell and he large surface area readily gives very low internal impedences3 and ~akes ' , . ~ . :
... ~ , .
possible the con3truction of cells with relatively high power denslties.
The present invention is illustrated by the following examples. However, the scope of ~his invent10n should not be limited to the examples but includes modifications, variationæ and equivalent embodiments ~hat fall ~lthin the æcope of the attached claimæ.
~xample 1 Preparation of CHx/P~O Composites .
Two equivalent molar concentration solutions were prepared containlng approximately 5.0 x 106 molecular welght polyethylene oxide and poly(acetylene) precursor polymer of 7t8-bls(trlfluror-methyl) trichloro-[4,2,2,02-5]-deca-3,7,9-trlene each in tetrahydrofuran. The two solutions were then mixed uRing a magnet:Lc stirrer to en~ure thorough mixing. The resultlng mixture was cast onto a preprepared and heated substrste at about 60C in a inert atmosphere. Once the solvent had evaporated, the film was then evacuated under reduced pressure to remove any remaining solvent and 20 then heated to about 80C for 11 hour3 to tran6form the precursor pol~mer to poly(acetylene).
Conductivlty measurements were taken of the above film using a Keithley 220 current source, Keithley 619 DMM/electrometer in a Van der Pauw configuration which gave a conductivity of about ~6~ohmg 1 cm~l-/v The film was ehen doped by contacting it wlth g~aeous iodinefor about 60 minutes. The conductivity was again meas~red and found to be about 10-3 ohms ~lcm~l.
A film of the poly(acetylene) precursor/polyethylene oxide was prepared aæ above and differential scanning calorimetry measurements were preformed using a Perkin-Elmer DSC-2C. The thermagram showed the characterlstic melting point of polyethylene oxide and a characteristic dual exothermæ of the precuræor polymer. Howevar, the melting point of the polyethylene oxlde was obæerved to have . ., ~Z6~
increased by about 20C in a sample containlng a 1:1 molar ratio of polyethylene oxide and precursor in the film.
Hot stage mlcro~copy of che same film was prefor~ed to observe the rphology of the film during evaporation and transfor~atlon.
c In a sample contain~ng a 1:1 molar ratio of polyethylene oxide/poly(acetylene) presursor, it was ob~erved that no separation occurred between the two materials when a film wa3 casted at 60C
and the precursor was transformed to poly(acetylene) at 80C.
"~s, " .~;~
:
The presen~ invention relates to novel compos:ite materials and a method for preparing films of such composite materials. The composite materials herein are useful in electrical applications such as electrodes in solid state energy storage devices.
It is known to produce energy storage devices which use an electrode of a conducting polymer and an electrolyte which may be either a solid or a liquid. Solid-~tate energy skoraye devices have been prepared having a composite or laminar structure comprising a layer of eleetrolyte beiny sandwiched, either as such or impregnated in a matrix, between two electrodes. It is also known that by electrochemically doping the conducting polymers with a dopant anion or cation, the polymers of this type can be used to store electric charge.
In such solid-state devices, the conducting polymer acts as the electronic conduckor and the electrolyte ~atrix as the ionic conductor. One of the major drawbacks of using composites in such devices is that the migration of ions from the electrolyte to the polymer electrode ls hindered by the relatively low 2Q diffusion rate of the dopant ion into khe polymer electrode, and the resulting high internal resistance reduces the devices performance.
It has now been found that the ion diffusion rate characteris~ically found in conventional conductivs composite materials can be si~nificantly increased by preparing an ionic/
electronic composite conductor comprising interpene~ra~ing networks of a continuous electronic conduc~ing polymeric material and a g~ ~
!IIID~J
' "'",, `
~:6~6 continuous ionlc conducting material. Sucb composite conduceors can be used in a varlety of electrical applications but are partlcularly suited for use in solid state energy storage devices.
Accordingly, the present lnvention provides an ionic/electronic composite conductor comprislng interpenetrating networks o a coneinuous electronic conductlng material and a continuous ionic conducting maeerial.
In a preferred embodiment 9 the compoæite conductor i9 a coherent film.
The present invention also provides a method for preparing a film of a composite conductor comprising interpenetratlng networks oP a continuous electronic conducting material and a continuous ionic conducting materisl, the method comprising i) preparing ln a common sovlent or solvent mlxture a solution o~
an ionic conducting material and an electronic conducting material or a precursor thereof, li) intimately mixing the solution, and iii) casting the solution on a substrate, and iv) removing the solvent.
According to another embodiment of this invention, an energy storage device i8 provided containing at least one electrode comprising interprenetrating net~orks oE a continuous electronic conducting material and a continuous ion~c conducting material.
By lnterpenetratlng networks is meant herein that each material of the composite conductor i~ continuous and intimately mixed with the other materlal throughout the composite. In order to determine that the mate~lals are intlmate and continuou~, thermal analysi~ can be conducted in accordance with known differential thermal analysis (DTA) techniques. Such technique~ will show an increased ~elting point for the lonic conducting material~ as compared to its normal meltlng point, when the electronic conducting material and the lonic conducting material are interpenetrating.
The electronic conducting material of the ionic/elec~ronic composlte conductor according to the present invention is ormed 3S from a conducting hydrocarbon polymer which i~ soluble in the .' ' :
~6~L6 solvent employed. For example~ the6e materials include but are not limited to soluble precursor polymers of polyacetylene and polyphenylene whlch can be s~bsequently converted tG polyacetylene and polyphenylene; soluble electronic conductlng polymers s~ch as polyphenylene diphenyl vinylene; or soluble substieuted electronlc conduceing polymers such as phenyl substituted poLyacetylene~
Polyacetylene precursors are preferredO
The ionlc conducting material of the composlte conductor is a mlxture or a complex of an ionic salt, containing anions such as 0 ASF6 9 PF6 , BF4 or C10~ , and catlons such as a:Lkall metal cations, e.g. Li~, with a poly~eric solvating agent capable of solvating the ionic sale such as a polyalkylene o~cide. Preferred polyalkylene oxides are polyethylene o~ide and polypropylene oxide.
The ionic conducting material comprising the mixture or complex of the ionic salt and the polymeric solvating agent may be $ormed by doplng the polymeric ~olvating agent with an appropriate ionic salt before, during or after the production of the composite conductor.
Any of the well known doping techniques for incorporating anions or cation into polymer materials can be used.
The lonic/electronic compo~lte conductor of the present invention is prepared by tntimately mixing the electronic conducting material wlth the ionic conductlng material. The electronic conducting msterial and the ionic conducting material are dissolved in a commo-l solvent or solvent mixture. The solvent or solvent mixture must be capable of solubilising both material~ in sufficient concentrations and must not substantially react with either material. The solvents used herein are polar organic solvents or mixture th~reofO Preferred is tetrahydrofuran. The solution of the electronic conducting msterial and the lonic conducting material should be throughly mixed.
A fllm of the composite can be cast from solution by pouring the solu~ion onto a substrate and removing the solvent by heating at elevated temperatures from 20 to 150~C, typlcally about 50C, or by spinning the substrate at high rates of revolutionO The solvent should be removed quic~ly, preferably by evaporation, so that phase , ~6~6 separatlon of the component materlals ls ~nhibited.
In a variation of the abovY process, the ionic salt may be added to a 801ution of the electronic conductlng ma~erial and a polymeric ~olvating agent prior to ca~ting the film.
The relativ~ molar concentratlons ~in terms of the polymerl~ed unlts in the respective monomers) of the electronic conducting material and the pol~meric solvatlng agent in the composite is suitably from l:lO to lO:l, preferably from 1:2 to 2:l and most preferably l:l.
The molar concentration of the dopant ionic salt in the polymeric solvating agent is preferably from 2:l to 5:1 based on moles of salt per mole of ~otal polymerised unlts in ~he polymer.
'Ln a preferred embodiment of this invention, the electronic conducting materlal is a,poly~acetylene) precursor polymer of 7,8-bis(trifluoromethyl) tricyclo-~4,2,2,02~5]-deca-3,7,9-triene which is described ln European Patent publication No 0080329. The ionlctelectronic conductor containing the precursor polymer is prepared as discussed above. The resultant product is then cast into a film and then converted by heat treatment lnto a film of a composite comprising interpenetrating networks of a continuous electronic conducting polyacetylene and a continuou~ ionic conducting material. The composi~e film is subsequen~ly ~eeped in a solution of an lonic salt to orm the ionic/electronic composite conductor.
The precursor poly~er is convsrted to polyacetylene by heating the polymer at a temperatures below 130C, preferably 70 to 120C, under vacuum or in ~e-~ec7e~R=r~-an inert atmosphere~ T,he specific temperature and duration of heating will depend on the raee of transformation desired. Typically, the heating is conducted for a period from 1 to abou~ 100 hours, preferably between lO and 50 hours~
The polyaceeylene prepared from the precursor polymer can be doped after casting by known chemical or electrochemical techniques. Suitable dopants are ~ell known to chose skilled ln the 3S art.
~" .
~, :
.
The ener~y storage device of this inventlon co~pri~e~ at least one lonlc/electronic conductor employsd a~ an electrode and a solid eletrolyte. The preferred embodiment comprises two ionic/electronic conductors wlth a solld electrolyte therebet~een.
The solid electrolyte should be lonlcally conducting but not electronically conducting such a~ a polyalkylene oxide.
In a more preferred embodiment, polyalkylene oxide (PA0), preferably polyethylene oxide, i~ sandwiched between two layers of a polyacetylene/PA0 composlte conductor film prepared according to the pxe~ent invention and incorporating a suitahle ionic salt. The PA0 solid elecerolyte al~o incorporates an ionic ~alt. The 6tructure can be built up by succe6sive evaporation~ from a solution of polyacetylene precursor, PA0 and ionic ~alc on the one hand and a solution of PA0 and ionic salt only o~ the other hand, combined wieh a heating 8tep to convert the precursor polymer into an electronically conducting poly~cetylene polymer, (CH)X.
As constructed, the cell is in a dlscharged ~tate. It i8 charged by pas~ing current through lt, in elther directlon. The (CH)X initially has relatively low conductlvity~ but ionic conductlon allows reasonable charging rates until the electronic conduction becomes high. At the anode, anions are removed from the PA0 matrix and dope the (CH)X so that the anode (CH)X beco~es p-type. Simllarly, at the cathode, catlona are removed from the PA0 matri~, and dope the (C~)x electrode to become n-type. Charging 1~
complete when a suitable doping level in the (C~)x i9 achleved (ior instance 20% per (CH~ unit). Discharge of the cell rever~es the composite conductor with a large area for large electrical contact pads, to reduce the internal impedence of the cell. Specific example~ of contact pad~ include those made from gold, platlnum and silver although any metal capable of giving ohmic contact with the elctronic conducting poly~er may be used.
Since the cell i8 ln the for~ of a flexlble film ~before charging~ it can be, for example9 conv~niently rolled up into a cylindrical ~hape~ The combin~tion of the thin cell and he large surface area readily gives very low internal impedences3 and ~akes ' , . ~ . :
... ~ , .
possible the con3truction of cells with relatively high power denslties.
The present invention is illustrated by the following examples. However, the scope of ~his invent10n should not be limited to the examples but includes modifications, variationæ and equivalent embodiments ~hat fall ~lthin the æcope of the attached claimæ.
~xample 1 Preparation of CHx/P~O Composites .
Two equivalent molar concentration solutions were prepared containlng approximately 5.0 x 106 molecular welght polyethylene oxide and poly(acetylene) precursor polymer of 7t8-bls(trlfluror-methyl) trichloro-[4,2,2,02-5]-deca-3,7,9-trlene each in tetrahydrofuran. The two solutions were then mixed uRing a magnet:Lc stirrer to en~ure thorough mixing. The resultlng mixture was cast onto a preprepared and heated substrste at about 60C in a inert atmosphere. Once the solvent had evaporated, the film was then evacuated under reduced pressure to remove any remaining solvent and 20 then heated to about 80C for 11 hour3 to tran6form the precursor pol~mer to poly(acetylene).
Conductivlty measurements were taken of the above film using a Keithley 220 current source, Keithley 619 DMM/electrometer in a Van der Pauw configuration which gave a conductivity of about ~6~ohmg 1 cm~l-/v The film was ehen doped by contacting it wlth g~aeous iodinefor about 60 minutes. The conductivity was again meas~red and found to be about 10-3 ohms ~lcm~l.
A film of the poly(acetylene) precursor/polyethylene oxide was prepared aæ above and differential scanning calorimetry measurements were preformed using a Perkin-Elmer DSC-2C. The thermagram showed the characterlstic melting point of polyethylene oxide and a characteristic dual exothermæ of the precuræor polymer. Howevar, the melting point of the polyethylene oxlde was obæerved to have . ., ~Z6~
increased by about 20C in a sample containlng a 1:1 molar ratio of polyethylene oxide and precursor in the film.
Hot stage mlcro~copy of che same film was prefor~ed to observe the rphology of the film during evaporation and transfor~atlon.
c In a sample contain~ng a 1:1 molar ratio of polyethylene oxide/poly(acetylene) presursor, it was ob~erved that no separation occurred between the two materials when a film wa3 casted at 60C
and the precursor was transformed to poly(acetylene) at 80C.
"~s, " .~;~
:
Claims (12)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. An ionic/electronic composite conductor comprising interpenetrating networks of a continuous electronic conducting polymeric material and a continuous ionic conducting material.
2. The conductor of claim 1 wherein the conductor is a coherent film.
3. The conductor of claim 1 wherein the electronic conducting material is selected from polyacetylene, polyphenylene, polyphenyl diphenyl vinylene, or a substituted polyacetylene.
4. The conductor of claim 3 wherein the ionic conducting material is a mixture or a complex of an ionic salt and a poly-meric solvating agent.
5. The conductor of claim 4 wherein the polymeric solvating agent is a polyalkylene oxide.
6. The conductor of claim 5 wherein the electronic conducting material is polyacetylene prepared by heating a polymer of 7,8-bis-(trifluoromethyl) tricyclo-[4,2,3,02.5]-deca-3,7,9-triene.
7. A method for preparing a film of an ionic/electronic composite conductor having interpenetrating networks of a continuous electronic conducting polymeric material and a continuous ionic conducting material, the method comprising:
(i) preparing in a common solvent or solvent mixture a solution of an ionic conducting material and an electronic conducting polymeric material, (ii) intimately mixing the solution, (iii) casting the solution on a substrate, and (iv) removing the solvent quickly, so that phase separation of the component materials is inhibited.
(i) preparing in a common solvent or solvent mixture a solution of an ionic conducting material and an electronic conducting polymeric material, (ii) intimately mixing the solution, (iii) casting the solution on a substrate, and (iv) removing the solvent quickly, so that phase separation of the component materials is inhibited.
8. The method of claim 7 wherein the electronic conducting material results from a precursor of the electronic conducting material which is transformed into the electronic conducting material after step (iv) by heating at temperatures below 130°C
under vacuum or in an inert atmosphere.
under vacuum or in an inert atmosphere.
9. The method of claim 8 wherein the ionic conducting material is a polyalkylene oxide containing an ionic salt and the precursor electronic conducting material is a polymer of 7,8-bis-(trifluoromethyl) tricyclo-[4,2,3,02.5]-deca-3,7,9-triene.
10. An energy storage cell comprising two electrodes, at least one of which is an ionic/electronic conductor comprising interpenetrating networks of an ionic conducting material and an electronic conducting polymeric material, and a solid electrolyte therebetween, the solid electrolyte being an ionic conductor but not an electronic conductor.
11. The energy storage cell of claim 10 wherein the two electrodes are each an ionic/electronic conductor.
12. The energy storage cell of claim 11 wherein the ionic conductor is a polyalkylene oxide containing an ionic salt, the electronic conducting material is polyacetylene or polyphenylene and the solid electrolyte is a polyalkylene oxide containing an ionic salt.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8329906 | 1983-11-09 | ||
| GB838329906A GB8329906D0 (en) | 1983-11-09 | 1983-11-09 | Composites |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1264416A true CA1264416A (en) | 1990-01-16 |
Family
ID=10551503
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000467307A Expired - Fee Related CA1264416A (en) | 1983-11-09 | 1984-11-08 | Composites for use in electrical applications such as electrodes in solid state energy storage devices |
Country Status (6)
| Country | Link |
|---|---|
| US (2) | US4681822A (en) |
| EP (1) | EP0145275A3 (en) |
| JP (1) | JPS61500362A (en) |
| CA (1) | CA1264416A (en) |
| GB (1) | GB8329906D0 (en) |
| WO (1) | WO1985002294A1 (en) |
Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3201482A1 (en) * | 1982-01-20 | 1983-09-08 | Bayer Ag, 5090 Leverkusen | MULTI-LAYER AREA |
| US4849311A (en) * | 1986-09-24 | 1989-07-18 | Toa Nenryo Kogyo Kabushiki Kaisha | Immobilized electrolyte membrane |
| US4824745A (en) * | 1987-02-25 | 1989-04-25 | Bridgestone Corporation | Electric cell comprising a polymeric material film electrode having a collection integrated therewith |
| US4830939B1 (en) * | 1987-10-30 | 1996-10-08 | Mhb Joint Venture | Radiation cured solid electrolytes and electrochemical devices employing the same |
| US5238758A (en) * | 1987-10-30 | 1993-08-24 | Mhb Joint Venture | Badiation cured solid electrolytes and electrochemical devices employing the same |
| JPH0773061B2 (en) * | 1987-11-20 | 1995-08-02 | 三菱化学株式会社 | Secondary battery manufacturing method |
| US5008040A (en) * | 1988-02-09 | 1991-04-16 | Director-General Of Agency Of Industrial Science And Technology | Process for preparation of polyacetylene film |
| US4990413A (en) * | 1989-01-18 | 1991-02-05 | Mhb Joint Venture | Composite solid electrolytes and electrochemical devices employing the same |
| WO1991006132A1 (en) * | 1989-10-13 | 1991-05-02 | The Regents Of The University Of California | Cell for making secondary batteries |
| US5162175A (en) * | 1989-10-13 | 1992-11-10 | Visco Steven J | Cell for making secondary batteries |
| US5362493A (en) * | 1990-05-04 | 1994-11-08 | Associated Universities, Inc. | Preparation of redox polymer cathodes for thin film rechargeable batteries |
| US5071721A (en) * | 1990-09-28 | 1991-12-10 | Rosemount Inc. | Matrix immobilized electrolyte |
| JP2851722B2 (en) * | 1991-07-26 | 1999-01-27 | 日本石油株式会社 | Polymer solid electrolyte and method for producing the same |
| US5917693A (en) * | 1992-10-26 | 1999-06-29 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Electrically conductive polymer composition |
| WO1995007552A1 (en) * | 1993-09-07 | 1995-03-16 | Motorola, Inc. | Conductive polymer matrix electrodes and electrochemical cells |
| US5868966A (en) | 1995-03-30 | 1999-02-09 | Drexel University | Electroactive inorganic organic hybrid materials |
| US6210537B1 (en) * | 1995-06-19 | 2001-04-03 | Lynntech, Inc. | Method of forming electronically conducting polymers on conducting and nonconducting substrates |
| US6096453A (en) * | 1998-06-19 | 2000-08-01 | Adven Polymers, Inc. | Polymeric thin-film reversible electrochemical charge storage devices |
| US6277512B1 (en) | 1999-06-18 | 2001-08-21 | 3M Innovative Properties Company | Polymer electrolyte membranes from mixed dispersions |
| WO2002026489A1 (en) * | 2000-09-26 | 2002-04-04 | Clemson University | Chaotic mixing method and structured materials formed therefrom |
| KR101257439B1 (en) * | 2011-06-27 | 2013-04-23 | 한국철도기술연구원 | Direct driven traction motor for upgrading maintenances of railroad car |
| GB201712274D0 (en) * | 2017-07-31 | 2017-09-13 | Cambridge Entpr Ltd | Polymer-based energy storage device |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US448115A (en) * | 1891-03-10 | Garbage-furnace | ||
| FR78505E (en) * | 1959-10-08 | 1962-08-03 | Int Standard Electric Corp | Multiple conductor cables |
| FR2442514A1 (en) * | 1978-11-22 | 1980-06-20 | Anvar | Ionically and pref. electronically conductive electrode - comprising agglomerate of active electrode material and solid soln. of ionic cpd. in polymer pref. polyoxyalkylene |
| FR2442512A1 (en) * | 1978-11-22 | 1980-06-20 | Anvar | NEW ELASTOMERIC MATERIALS WITH ION CONDUCTION |
| US4321114A (en) * | 1980-03-11 | 1982-03-23 | University Patents, Inc. | Electrochemical doping of conjugated polymers |
| DE3048445A1 (en) * | 1980-12-22 | 1982-07-22 | Basf Ag, 6700 Ludwigshafen | METHOD FOR THE PRODUCTION OF ELECTRICALLY CONDUCTIVE POLYMERIC SYSTEMS AND THEIR USE IN ELECTROTECHNICS AND FOR THE ANTISTATIC EQUIPMENT OF PLASTICS |
| US4525440A (en) * | 1981-05-13 | 1985-06-25 | Duracell Inc. | Solid state cell with anolyte |
| DE3129679A1 (en) * | 1981-07-28 | 1983-02-17 | Varta Batterie Ag, 3000 Hannover | GALVANIC ELEMENT WITH A POROUS, SOLID SOLID ELEMENTROLYTE CONTAINING THE CATHODE SUBSTANCE |
| DE3139400A1 (en) * | 1981-10-03 | 1983-04-14 | Varta Batterie Ag, 3000 Hannover | Galvanic solid-state cell |
| DE3277830D1 (en) * | 1981-11-03 | 1988-01-21 | Comp Generale Electricite | Process for manufacturing a polymeric solid electrolyte for an electrochemical generator |
| US4496702A (en) * | 1981-11-20 | 1985-01-29 | The British Petroleum Company P.L.C. | Polyacetylene production |
| US5378402A (en) * | 1982-08-02 | 1995-01-03 | Raychem Limited | Polymer compositions |
| GB8412304D0 (en) * | 1984-05-14 | 1984-06-20 | Atomic Energy Authority Uk | Composite cathode |
| US4654279A (en) * | 1986-07-10 | 1987-03-31 | The United States Of America As Represented By The Secretary Of The Navy | Interpenetrating-network polymeric electrolytes |
| US9556614B2 (en) * | 2015-05-13 | 2017-01-31 | Awi Licensing Llc | Mounting apparatus for suspended ceiling system |
-
1983
- 1983-11-09 GB GB838329906A patent/GB8329906D0/en active Pending
-
1984
- 1984-11-08 JP JP59504090A patent/JPS61500362A/en active Pending
- 1984-11-08 EP EP84307719A patent/EP0145275A3/en not_active Ceased
- 1984-11-08 WO PCT/GB1984/000382 patent/WO1985002294A1/en not_active Ceased
- 1984-11-08 US US06/752,047 patent/US4681822A/en not_active Expired - Fee Related
- 1984-11-08 CA CA000467307A patent/CA1264416A/en not_active Expired - Fee Related
-
1986
- 1986-10-02 US US06/914,360 patent/US4734343A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| US4681822A (en) | 1987-07-21 |
| WO1985002294A1 (en) | 1985-05-23 |
| EP0145275A3 (en) | 1985-07-03 |
| GB8329906D0 (en) | 1983-12-14 |
| JPS61500362A (en) | 1986-03-06 |
| US4734343A (en) | 1988-03-29 |
| EP0145275A2 (en) | 1985-06-19 |
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