GB2518837A - Electrolyte and photovoltaic cell comprising the same - Google Patents
Electrolyte and photovoltaic cell comprising the same Download PDFInfo
- Publication number
- GB2518837A GB2518837A GB1317358.8A GB201317358A GB2518837A GB 2518837 A GB2518837 A GB 2518837A GB 201317358 A GB201317358 A GB 201317358A GB 2518837 A GB2518837 A GB 2518837A
- Authority
- GB
- United Kingdom
- Prior art keywords
- electrolyte
- ionic liquid
- electrolyte according
- viscosity
- reducing agent
- 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.)
- Withdrawn
Links
- 239000003792 electrolyte Substances 0.000 title claims abstract description 177
- 239000002608 ionic liquid Substances 0.000 claims abstract description 123
- -1 hexafluorophosphate Chemical compound 0.000 claims abstract description 58
- 150000001450 anions Chemical class 0.000 claims abstract description 42
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims abstract description 9
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 claims abstract description 7
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 claims abstract description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000007983 Tris buffer Substances 0.000 claims abstract description 4
- 150000008051 alkyl sulfates Chemical class 0.000 claims abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims abstract description 4
- JFZKOODUSFUFIZ-UHFFFAOYSA-N trifluoro phosphate Chemical compound FOP(=O)(OF)OF JFZKOODUSFUFIZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- XOHZHMUQBFJTNH-UHFFFAOYSA-N 1-methyl-2h-tetrazole-5-thione Chemical compound CN1N=NN=C1S XOHZHMUQBFJTNH-UHFFFAOYSA-N 0.000 claims abstract description 3
- PWKSKIMOESPYIA-UHFFFAOYSA-N 2-acetamido-3-sulfanylpropanoic acid Chemical compound CC(=O)NC(CS)C(O)=O PWKSKIMOESPYIA-UHFFFAOYSA-N 0.000 claims abstract description 3
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims abstract description 3
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 34
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 26
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 150000001768 cations Chemical class 0.000 claims description 14
- 239000003349 gelling agent Substances 0.000 claims description 14
- 229910052697 platinum Inorganic materials 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 9
- WRTMQOHKMFDUKX-UHFFFAOYSA-N triiodide Chemical compound I[I-]I WRTMQOHKMFDUKX-UHFFFAOYSA-N 0.000 claims description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 claims description 8
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 7
- ZRALSGWEFCBTJO-UHFFFAOYSA-O guanidinium Chemical compound NC(N)=[NH2+] ZRALSGWEFCBTJO-UHFFFAOYSA-O 0.000 claims description 7
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 125000000304 alkynyl group Chemical group 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 125000001905 inorganic group Chemical group 0.000 claims description 4
- WVDDUSFOSWWJJH-UHFFFAOYSA-N 1-methyl-3-propylimidazol-1-ium Chemical compound CCCN1C=C[N+](C)=C1 WVDDUSFOSWWJJH-UHFFFAOYSA-N 0.000 claims description 3
- PPDFQRAASCRJAH-UHFFFAOYSA-N 2-methylthiolane 1,1-dioxide Chemical compound CC1CCCS1(=O)=O PPDFQRAASCRJAH-UHFFFAOYSA-N 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 150000002892 organic cations Chemical class 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 3
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 claims description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 3
- JBOIAZWJIACNJF-UHFFFAOYSA-N 1h-imidazole;hydroiodide Chemical compound [I-].[NH2+]1C=CN=C1 JBOIAZWJIACNJF-UHFFFAOYSA-N 0.000 claims description 2
- SFPQDYSOPQHZAQ-UHFFFAOYSA-N 2-methoxypropanenitrile Chemical compound COC(C)C#N SFPQDYSOPQHZAQ-UHFFFAOYSA-N 0.000 claims description 2
- 241000284156 Clerodendrum quadriloculare Species 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- 229920002873 Polyethylenimine Polymers 0.000 claims description 2
- 150000003998 acyclic ketones Chemical class 0.000 claims description 2
- 229940045713 antineoplastic alkylating drug ethylene imines Drugs 0.000 claims description 2
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 claims description 2
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 150000003997 cyclic ketones Chemical class 0.000 claims description 2
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 claims description 2
- 229920000075 poly(4-vinylpyridine) Polymers 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims 2
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 claims 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims 1
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 claims 1
- 229940124530 sulfonamide Drugs 0.000 claims 1
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- QYTDEUPAUMOIOP-UHFFFAOYSA-N TEMPO Chemical group CC1(C)CCCC(C)(C)N1[O] QYTDEUPAUMOIOP-UHFFFAOYSA-N 0.000 abstract 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 24
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 12
- 229910052740 iodine Inorganic materials 0.000 description 12
- 239000011630 iodine Substances 0.000 description 12
- FGYADSCZTQOAFK-UHFFFAOYSA-N 1-methylbenzimidazole Chemical compound C1=CC=C2N(C)C=NC2=C1 FGYADSCZTQOAFK-UHFFFAOYSA-N 0.000 description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 9
- 239000000499 gel Substances 0.000 description 9
- XREPTGNZZKNFQZ-UHFFFAOYSA-M 1-butyl-3-methylimidazolium iodide Chemical compound [I-].CCCCN1C=C[N+](C)=C1 XREPTGNZZKNFQZ-UHFFFAOYSA-M 0.000 description 8
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical group C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- CZPWVGJYEJSRLH-UHFFFAOYSA-O hydron;pyrimidine Chemical group C1=CN=C[NH+]=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-O 0.000 description 6
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical group C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 6
- MCTWTZJPVLRJOU-UHFFFAOYSA-O 1-methylimidazole Chemical compound CN1C=C[NH+]=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-O 0.000 description 5
- WTKZEGDFNFYCGP-UHFFFAOYSA-O Pyrazolium Chemical group C1=CN[NH+]=C1 WTKZEGDFNFYCGP-UHFFFAOYSA-O 0.000 description 5
- SDTAXUVLXYGRNE-UHFFFAOYSA-O bis(trifluoromethylsulfonyl)azanide;3-methyl-1h-imidazol-3-ium Chemical compound C[N+]=1C=CNC=1.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F SDTAXUVLXYGRNE-UHFFFAOYSA-O 0.000 description 5
- ZCQWOFVYLHDMMC-UHFFFAOYSA-O hydron;1,3-oxazole Chemical group C1=COC=[NH+]1 ZCQWOFVYLHDMMC-UHFFFAOYSA-O 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 125000001425 triazolyl group Chemical group 0.000 description 5
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 4
- VFLYBWGSQGMWHP-UHFFFAOYSA-N 3-methyl-1h-imidazol-3-ium;iodide Chemical compound [I-].C[N+]=1C=CNC=1 VFLYBWGSQGMWHP-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 150000003949 imides Chemical class 0.000 description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- HVVRUQBMAZRKPJ-UHFFFAOYSA-N 1,3-dimethylimidazolium Chemical compound CN1C=C[N+](C)=C1 HVVRUQBMAZRKPJ-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical group C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 3
- NIHOUJYFWMURBG-UHFFFAOYSA-N 1-ethyl-1-methylpyrrolidin-1-ium Chemical compound CC[N+]1(C)CCCC1 NIHOUJYFWMURBG-UHFFFAOYSA-N 0.000 description 2
- JMUSPDQIRHNZLT-UHFFFAOYSA-O 2,2-dicyanoethenylideneazanide 3-methyl-1H-imidazol-3-ium Chemical compound C(#N)[C-](C#N)C#N.C[NH+]1C=NC=C1 JMUSPDQIRHNZLT-UHFFFAOYSA-O 0.000 description 2
- LWMDPZVQAMQFOC-UHFFFAOYSA-N 4-butylpyridine Chemical compound CCCCC1=CC=NC=C1 LWMDPZVQAMQFOC-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002879 Lewis base Substances 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- HFWIMJHBCIGYFH-UHFFFAOYSA-N cyanoform Chemical compound N#CC(C#N)C#N HFWIMJHBCIGYFH-UHFFFAOYSA-N 0.000 description 2
- BTBRORIXZPYPDC-UHFFFAOYSA-O cyanoiminomethylideneazanide 3-methyl-1H-imidazol-3-ium Chemical compound N#C[N-]C#N.C[NH+]1C=CN=C1 BTBRORIXZPYPDC-UHFFFAOYSA-O 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 150000007527 lewis bases Chemical class 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 125000000547 substituted alkyl group Chemical group 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- PXELHGDYRQLRQO-UHFFFAOYSA-N 1-butyl-1-methylpyrrolidin-1-ium Chemical compound CCCC[N+]1(C)CCCC1 PXELHGDYRQLRQO-UHFFFAOYSA-N 0.000 description 1
- SHPPDRZENGVOOR-UHFFFAOYSA-N 1-butylbenzimidazole Chemical compound C1=CC=C2N(CCCC)C=NC2=C1 SHPPDRZENGVOOR-UHFFFAOYSA-N 0.000 description 1
- FXPLCAKVOYHAJA-UHFFFAOYSA-N 2-(4-carboxypyridin-2-yl)pyridine-4-carboxylic acid Chemical compound OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C(O)=O)=C1 FXPLCAKVOYHAJA-UHFFFAOYSA-N 0.000 description 1
- UUIMDJFBHNDZOW-UHFFFAOYSA-N 2-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=CC=N1 UUIMDJFBHNDZOW-UHFFFAOYSA-N 0.000 description 1
- AWVNJBFNHGQUQU-UHFFFAOYSA-N 3-butoxypropanenitrile Chemical compound CCCCOCCC#N AWVNJBFNHGQUQU-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LEVWYRKDKASIDU-IMJSIDKUSA-N L-cystine Chemical compound [O-]C(=O)[C@@H]([NH3+])CSSC[C@H]([NH3+])C([O-])=O LEVWYRKDKASIDU-IMJSIDKUSA-N 0.000 description 1
- 235000019393 L-cystine Nutrition 0.000 description 1
- 239000004158 L-cystine Substances 0.000 description 1
- 229920003182 Surlyn® Polymers 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- BOXSCYUXSBYGRD-UHFFFAOYSA-N cyclopenta-1,3-diene;iron(3+) Chemical compound [Fe+3].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 BOXSCYUXSBYGRD-UHFFFAOYSA-N 0.000 description 1
- 229960003067 cystine Drugs 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000010952 in-situ formation Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000000858 thiocyanato group Chemical group *SC#N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
- H01G9/2013—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte the electrolyte comprising ionic liquids, e.g. alkyl imidazolium iodide
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
- H01G9/2018—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte characterised by the ionic charge transport species, e.g. redox shuttles
-
- 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
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Hybrid Cells (AREA)
Abstract
An electrolyte for a photovoltaic device is provided, the electrolyte comprising: a first ionic liquid comprising a first redox active species and a redox-inert, substantially water immiscible second ionic liquid. A photovoltaic device comprising the electrolyte is also disclosed. Further disclosed is a similar electrolyte wherein the second ionic liquid is weakly coordinating. The first redox active species may comprise iodide, an Fe[2+] complex a Co[2+] complex, a viologen, L-cysteine, ferrocene, 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO), Ni(III) bis(dicarbollide) complexes or 5-mercapto, 1-methyltetrazole. The second ionic liquid may contain an anion comprising one or more of a bis(trifluoromethanesulfonyl)imide, tris(pentafluoroethyl)trifluorophosphate, trifluoromethansulfonate, heptachlorodialuminate, hydrogen sulfate, alkylsulfate, methane sulfonate, dimethylphosphate, diethylphosphate, hexafluorophosphate and nonaflate.
Description
Electrolyte and photovoltaic cell comprising the same
Field of the invention
The present invention relates to an electrolyte for use in a photovoltaic device and a photovoltaic device comprising the same.
Background of the invehtion
Dye sensitised photovoltaic devices are well known to those skilled in the art. They are prone to many problems, however, such as corrosion of one or more of the electrodes (particularly corrosion of platinum electrodes) and leakage of liquid from the cell. The present invention seeks to ameliorate one or more of the problems identified above.
Summary of the invention
In accordance with a first aspect of the present invention, thereis provided an electrolyte for a photovoltaic device, the electrolyte domprising: a first ionic liquid comprising a first redox active species and a redox-inert, substantially water-immiscible. second ionic liquid.
Without wishing to be bound by theory, the applicant believes that the use of a redox-inert, substantially water-immiscible second ionic liquid produces an electrolyte that is less aggressive towards platinum electrodes with which the electrode may contact.
Those skilled in the art will realise that in the context of electrolytes for photovoltaic devices, "redox-inert" indicates that the second ionic liquid does not take part in the redox process associated with the operation of a photovoltaic device.
The presence of a redox inactive anion helps reduce the corrosive nature of the electrolyte, particularly towards platinum counter electrodes which are typically used in photovoltaic devices. The applicant has also unexpectedly discovered that the use of a second ionic liquid which is substantially immiscible with water helps reduce the cbrrosive nature of the electrolyte. Without wishing to be bound by theory, the applicant believes that the second ionic liquid comprises a non-or low-coordinating anion. In this connection, the second ionic liquid optionally comprThes an anion which hasa low affinity for platinum in an oxidation state of zero, ±1, +2, +3 and/or +4.
The second ionic liquid is optionally substantially hydrolytically stable. This may be desirable to increase the operational lifetime of the electrolyte.
The second ionic liquid optionally has a lower viscosity than the first ionic liquid. This has the effect of producing an electrolyte with a lower viscosity which improves certain aspects of performance of th electrolyte and the photovoltaic cell in which the electrolyte will typically be used.
Unless otherwise noted, the viscosities noted herein are at 25°C. Viscosities ar typically measured using a rheometer, typically a rotational rheometer, an example of which is a Brookfielcl ultra rheometer. The viscosity of the first ionic liquid is optionally from 300 to 6000cP, optionally from 300 to 2000cP, optionally from 800 to 2000cF.
The viscosity of the second ionic liquid is optionally from 1 to 200c9, optionally from 10 to lOOcP and optionally from 20 to 80cP.
The viscosity of the electrolyte is optionally from 1 to lOOaP, optionally from 2 to 6OcP and optionally from 5 to 30cP.
The electrolyte may comprise a viscosity-reducing agent. The viscosity-reducing agent typically has a viscosity less than that of any of the ionic liquids present in the electrolyte.
The viscosity-reducing agent may comprise a polar liquid, such as a polar organic liquid. The viscosity-reducing agent optionally comprises one or more of gamma butyrolactone, cyclic and acyclic lactones, sulfolane, methyl sulfolane, cyclic and acyclic sulfoxides, cyclic and acyclic ketones, alkoxypropionitriles including butoxy and methoxy propionitrile and dinitrile compounds including glutaro, adiponitriles, óligo and poly-glymes, oligo-and poly-ethyleneimines, dentrimers and star-burst compounds.
The viscosity-reducing agent optionally has a boiling point of at least 150°C, optionally at least 170°C and optionally at least 200°C. Without wishing to be bound by theory, it is believed that a viscosity-reducing agent with a high boiling point is less likely to diffuse out of any device provided with the electrolyte.
The viscosity of the viscosity-reducing agent is optionally no more than lOcB and optionally no more than 3cP. It is preferred thatthe viscosity of the viscosity-reducing agent is relatively low because this decreases the viscosity of the electrolyte, thereby aiding the diffusion of components of the electrolyte into the mesoporous titanium dioxide layer which is typically used in a photovoltaic device.
The volume of the viscosity-reducing agent may be from 10 to 60% (and optionally from 20 to 50% and optionally from 10 to 30% and optionally from 40 to 60%) of the total volume of the viscosity-reducing agent, first ionic liquid, second ionic liquid and any further ionic liquids present in the electrolyte.
It has been *found that, in certain cases, an effective electrolyte composition is formed when the volume of the viscosity-reducing agent is from 10-30% of the total volume of the viscosity-reducing agent, first ionic liquid, second ionic liquid and any further ionic liquids present in the electrolyte: lEt has also been found that, in certain cases, an effective electrolyte composition is formed when the volume of the viscosity-reducing agent is from 40-60% of the total volume of the viscosity-reducing agent, first ionic liquid, second ionic liquid and any further ionic liquids present in the electrolyte.
The volume of the first ionic liquid may be from 20 to 60% (and optionally from 30 to 60% and optionally from 30 to 55%) of the total volume of the viscosity-reducing agent, first ionic liquid, second ionic liquid and any further ionic liquids present in the electrolyte.
The volume of the second ionic liquid may be from 5 to 50% (and optionally from 10 to 35%) of the total volume of the viscosity-reducing agent, first ionic liquid, second ionic liquid and any further ionic liquids present in the electrolyte.
The first redox active species optionally comprises iodide, an Fe2 complex, a 0o2+ complex, a viologen, L-cysteine, ferrocene, 2,2,6,6-tetramethyl-l-piperidinyloxy (TEMPO), Ni(III) bis(dicarbollide) complexes or 5-mercapto, l-methyltetrazole.
The electrolyte optionally comprises a second redox active species for pairing or coupling with the first redox active species. Those skilled in the art will be aware of such redox active species. Examples of such redox active species which are "paired" to the first redox active species listed above are triiodide, co3 complex, viologen, L-cystine, ferrocenium, TEMPO compound, Ni(IV) bis(dicarbollide) complexes and a dimer of 5-mercapto, 1-methyltetrazole.
If the first redox active species is iodide and the. second redox active species is triiodide, typical ranges.of iodide to triiodide mole ratioà are 1 to 10 to 1 to 200. Low triiodide concentration is critical for indoor light to electricity cOnversion devices. Triiodide could be formed by external addition of iodine to the electrolyte or by in-situ formation using reduction of photo-oxidized dye molecules by iodide.
The first ionic liquid and/or the second ionic liquid optionally comprise an organic cation. The organic cation may comprise a heterocyclic moiety, optionally comprising 5 or 6 atoms, one or two of which are optionally not carbon, and which are optionally individually selected from 0, N, Se, and S. The ffrst ionic liquid and/or the second ionic liquid optionally comprise a cation comprising a pyridinium, guaftidiniuiu, imidazolium, amrnonium, sulfonium, pyridazinium, pyrimidinium, pyrazinium, pyrazolium, thizolium, oxazolium or triazolium moiety, which may be optionally substituted, optionally by one or more of F, phenyl or C16 alkyl group which is optionally substituted, optionally by one or more electron withdrawing grcup, such as halogen, CE3, SF5, CF3S, (CF3)2CHS or (CF3)3CS. The first ionic liquid and/or the second ionic liquid optionally comprise a cation comprising a py±idinium, guanidinium, imidazolium, arrimonium, sulfonium, pyridazinium, pyrimidinium, pyrazinium, pyrazolium, thizolium, oxazoiium or triazolium moiety, optionally substituted by one or more C16 alkyl group.
The first ionic liquid and/or the second ionic liquid optionally comprises a cation selected from the group consisting of 1,3-dimethylimidazolium, 1-methylimidazolium, 3- propyl-l-methylimidazolium, 3-èthyl-l-methylimidazolium, 4- butyl pyridiriium, N-dimethyl pyrrolidinium, N-Methyl-N-ethylpyrrolidinium, N-Nethyl-N-butylpyrrolidinium, and tetraethylarnmonium.
The first ionic liquid optionally comprises a cation comprising apyridinium, guanidinium, imidazolium, ammonium, sulfonium, pyridazinium, pyrimidinium, pyrazinium, pyrazolium, thizolium, oxazolium or triazolium moiety, which may be optionally substituted, optionally by one or more of F, phenyl or 016 alkyl group which is optionally substituted, optionally by one or more electron withdrawing group, such as halogen, OF3, SF5, CF3S, (CF3)20H5 or (0F3)30S. The first ionic liquid optionally comprises a cation comprising a pyridiniun, guanidinium, imidazolium, ammonium, sulfonium, pyridazinium, pyrimidinium, pyrazinium, pyrazoliurn, thizolium, oxazolium or triazollum moiety, optionally substituted by one or more 016 alkyl group; The first ionic liquid optionally comprises a cation selected from the group consisting of 1,3- dimethylimidazolium, 1-methylimidazolium, 3-propyl-l-methylimidazolium, 3-ethyl-l-methylimidazoiium, 4-butyl pyridinium, N-dimethyl pyrrolidinium, N-Methyl-N-ethylpyrrolidinium, N-Methyl--N-butylpyrrolidiriium and tetraethylammonium.
The second ionic liquid optionally comprises a cation comprising a pyridinium, guanidinium, imidazolium, amrnonium, sulfonium, pyridazinium, pyrimidinium, pyrazinium, pyrazolium, thizolium, oxazolium or triazolium moiety, which may be S optionally substituted, optionally by one or more of F, phenyl or O alkyl group which is optionally substituted, optionally by one or more electron withdrawing group, such as halogen, CE3, SF5, OF3S, (OF3) 2CHS or (OF3) 30S. The second ionic liquid optionally comprises a cation comprising a pyridinium, guanidinium, imidazolium, arru'nonium, sulfonium, pyridazinium, pyrimidinium, pyrazinium, pyrazolium, thizolium, oxazolium or triazolium moiety, substituted by one or more O16 alkyl group.
The second ionic liquid optionally comprises a cation selected from the group consisting of 1,3-dimethylimidazolium, 1- methylimidazolium, 3-propyl-l--methylimidazoliun, 3-ethyl-l-methylimidazolium, 4-butyl pyridinium, N-dimethyl pyrrolidinium, N-Methyl-N-ethylpyrrolidihium, N-Methyl-N-butylpyrrolidinium and tetraethylammonium.
The second ionic liquid optionally comprises a fluorinated anion. The second ionic liquid optionally comprises an anion comprising one or more of a fluorinated organic moiety and a fluorinated inorganic group, for example, an anion comprising one or more of a perfluorinated organic moiety and a perfluorinated inorganic group. The second ionic liquid optionally comprises an anion comprising one or more of a fluorinated alkyl, alkenyl, aLkynyl, aryl, borate and phosphate, for exarnple an anion comprising one or more of a perfluorinated alkyl, lkenyl, alkynyl, aryl, borate an phosphate. The second ionic liquid may comprise an anion comprising one or more sulphonyl groups, at least one sulphonyl group being attached to a fluorinated alkyl group, optionally a perfluoroakyl group, optionally with fewer than 5 carbon atoms. The second ionic liquid may comprise an anion comprising two suiphonyl groups, each of which is attached to a fluorinated alkyl group, optionally a perfluoroakyl group, optionally with fewer than 5 carbon atoms.
The anion of the second ionic liquid may comprise an optionally substituted imide ion, optionally comprising one or more 002 or 502 groups connected to the N of the imide ion.
Said 002 or SO2 groups may be connected to an optionally substituted alkyl group, optionally a fluorinated alkyl group, optionally a perfluoroakyl group, optionally with fewer than 5 carbon atoms.
Optionally, the anion of the second ionic liquid has a Van der Waals volume of more than lOOM.
Optionally, the anion of the second ionic liquid is a weakly-effective Lewis base.
The second ionic liquid optionally comprises an anion comprising one or more of an isocyanate, thiocyanate, dicyanamide, tricyanomethane, bis (trifluoromethanesuifonyl) imide, tetracyanoborate, tris (pentafluoroethyl) trifluorophosphate, trifluoromethanesulfonate, heptachlorodialuminate, hydrogensulfate, alkylsulfate, methanesulfonate, dimethylphosphate, diethylphosphate, diethylphosphate, hexafluorophoshate and nonaflate.
The eleutrolyte may be a binary mixture of ionic liquids.
Alternatively, the electrolyte may comprise more than two ionic liquids. For example, the electrolyte may comprise a third ionic liquid.
The electrolyte optionally comprises one or more gelling agents. Such gelling agents may help reduce leakage of electrolyte from a cell in which the electrolyte is to be placed. Furthermore, gels may assist in applying the electrolyte to a cell in liquid form and subsequently cooling the cell, thereby forming a solid gel at operating S temperature. The gelling agent optionally comprises one or more of high surface area particles (such as silica nanoparticles) , polyacrylonitrile, poly(4-vinylimidazole) poly(4-vinylpyridine), poly(vinyl pyrrolidone) poly(vinylidine fluoride), poly(ethyelenoxide), polyethyleneimine, polyrnethylmethacrylates and poly(organophosphate), *or one or more precursors thereof, such as monomers which react to form a gelling agent, for example, on exposure to certain wavelengths of radiation. The gel so formed typically has a gel-to-liquid transition at 80°c or higher. The electrolyte optionally comprises 2 to 2Owt% (optionally 2-lGwt%, optionally 2 to 6wt%) gelling agent (or one or more precursors thereof) The electrolyte of the first aspect of the present invention may be in a liquid state comprising a gelling agent which has yet to be activated to form a gel or in a gel state.
The electrolyte may comprise further components, such as one or more passivating agents, such as n-methylbenzimidazole, t-butylpyridine and n-butylbenzimidazole. Such passivating agents typically comprise free electron pairs and are capable of adsorbing onto a porous oxide electrode surface (such as is provided by titanium dioxide) . The concentration of the passivating agent is optionally from 0.05 to SM, optionally from 0.1 to 2M and optionally from 0.2 to lM.
The electrolyte may optionally comprise other components, such as dye enhancement additives, such as those which facilitate theassembly of a dye layer, for example, guanidium thocyanate. Guanidium thiocyanate is optionally typically added to the electrolyte in 0.1 to 0.4 N quantities.
The electrolyte may comprise from 50 ho 90 vol% of a mixture of first and second ionic liquids, the first ionic liquid comprising an imidazolium iodide, the second ionic liquid comprising an imidazolium bis(trifluoromethane sulphonamide) and 20 to 50 vol% of a viscosity-reducing agent having a boiling point of more than 150°C.
In accordance with a second aspect of the present invention, there is provided an electrolyte for a photovoltic device, the electrolyte comprising: a first ionic liquid comprising a first redox active species and a redox-inert second ionic liquid which is hydrophobic.
The electrolyte of the second aspect of the present invention may comprise the features described above in relation to the electroLyte of the first aspect of the present invention.
In accordance with a third aspect of the ptesent invention, there is provided an electrolyte for a photovoltaic device, the electrolyte comprising: a first ionic liquid comprising a first redox active species and a redox-inert second ionic liquid comprising a weakly co-ordinating anion.
The weakly co-ordinating anion may comprise a fluorinated anion. The weakly co-ordinating anion may comprise one or mOre of a fluorinated organic moiety and a fluorinated inorganiè group, for example, an anion comprising one or more of a :ii perfluorinated organic moiety and a perfluorinated inorganic group. The weakly co-ordinating anion may comprise one or more of a fluorinated alkyl, alkenyl, alkynyl, aryl, borate and phosphate, for example, an anion comprising one or more of a S perfluorinated alkyl, alkenyl, alkynyl, aryl,. borate and phosphate. the second ionic liquid may comprise an anion comprising one or more suiphonyl groups, at least one sulphonyl group being attached to a fluorinated alkyl group, optionally a perfluoroakyl group, optionally with fewer than 5 carbon atoms. The second ionic liquid may comprise an anion comprising two sulphonyl groups, each of which isattached to a fluorinated alkyl group, optionally a perfluoroakyl group, optionally with fewer than 5 carbon atoms.
The anion df the second ionic liquid may comprise an optionally substituted imide ion, optionally comprising one or more 002 or S0 groups connected to the N of the imide ion.
Said 002 or °2 groups may be connected to an bptiorially substituted alkyl group, optionally a fluorinated alkyl group, optionally a perfluoroakyl group, optionally with fewer than 5 carbon atoms. . Optionally, the anion of the second ionic liquid has a Van der Waals volume of more than lOOM.
Optionally, th anion of the second ionic liquid is a weakly-effective Lewis base.
The weakly co-ordinating anion may comprise one or more of an isocyanate, thiocyanate, dicyanamide, tricyanomethane, big (trifluoromethanesulfonyl) imide, tetracyanoborate, tris(pentafluoroethyl)trifluorophosphate, trifluoromethanesulfonate, heptachlorodialuminate, hydrogensulfate, alkylsulfate, methanesulfonate, dimethylphosphate, diethylphosphate, diethylphosphate, hexafluorophoshate and nonaflate.
The weakly co-ordinating anion may be provided by the second, redox inert ionic liquid of the electrolyte of the first aspect of the present invention. Therefore, the weakly co-S ordinating anion may be the anion of the second, redox inert ionic liquid of the electrolyte of the first aspect of the present invention.
The electrolytes of the first and second aspects of the present invention are typically suitable for use in dye-sensitised solar cells.
In accordance with a fourth aspect of the present invention, there is provided a photovoltaic device comprising an electrolyte according to the first, second and/or third aspects of the present invention.
The photovoltaic device may comprise a first electrode optionally comprising platinum and a second, photo-sensitised electrode, the electrolyte disposed between the first and second electrodes. The electrolyte is typically in contact with the platinum provided ifl the first electrode. The second, photo-sensitised electrode optionally comprises a photosensitive dye.
The photovoltaic device is dptionaliy a flexible photovoltaic cell comprising first and second flexible substrates. The first substrate is typically provided with a first electrode* (optionally comprising platinum) and the second substrate is typically provided with a second electrode (typically comprising a photo-sensitised dye) . It will of course be appreciated that features described in relation to one aspect of the present invention may be incorporated into other aspects of the present invention.
Description of the drawings
An example of an electrolyte in accordance with the present invention will now be described by way of example only of which: Figure 1 shows the current stability of a flexible dye sensitized photovoltaic cell comprising an example of an electrolyte in accordance with the present invention as a function of time at elevated temperature (65°C); Figure 2 shows the efficiency stability of a flexible dye sensitized photovoltaic cell comprising an example of an electrolyte in accordance with the present invention as a function of time at elevated temperature (65°C); Figure 3 shows the cathodic charge transfer resistance of a flexible dye sensitized photovoltaic cell comprising an example of an electrolyte. in accordance with the present invention as a function of time at elevated temperature (65°C) ; Figure 4 shows the cathodic charge transfer resistance of a flexible dye sensitized photovoltaic cell comprising an example of an electrolyte in accordance with the present invention as a function of time at a higher elevated temperature (85°C); and Figure 5 is a schematic cross-section through a photovoltaic cell showing the structure thereof. 25.
Detailed description
Various example electrolytes were produced, along with several comparative example electrolytes. . . Electrolyte 1 0.1M iodine, and 0.5 M of N-methyl benzimidazole were dissolved in ionic liquid mixture containing 2/1 v/v l-butyl, 3-methyl imidazolium iodide and 1-ethyl, 3-Methyl imidazolium bis(trifluoromethylsulfonyl)imide (Sigma Aldrich). Those skilled in the art will realize that iodine provides the iodine for the formation of the redox active species triiodide. The ionic liquid 1-butyl, 3-methyl imldazolium iodide provides the redox active species iodide. The ionic liquid 1-ethyl, 3-Methyl imidazolium lois (trifluoromethylsulfony) imide is substantially water-immiscible, is hydrophobic and redox inactive in a photochemical cell.
Comparative Example 1 0.114 iodine;, and 0.5 N of N-methyl benzimidazole were dissolved in 1-butyl, 3-methyl imidazolium iodide. This electrolyte does not comprise the second, redox inert ionic liquid.
Comparative Example 2 0.lM iodine, and 0.5 N of N-methyl benzimidazole were dissolved in ionic liquid mixture containing 2/1 v/v l-butyl, 3-methyl imidazolium iodide and 1-ethyl, 3-Methyl imidazolium dicyanamide. The ionic liquid 1-ethyl, 3-Methyl imidazolium dicyanamide is redox inactive in a photochemical cell, but is not hydrophobic or water-immiscible.
Comparative Example 3 0.114 iodine, and 0.5 N of N-methyl benzimidazole were dissolved in ionic liquid mixture containing 2/1 v/v 1-butyl, 3-methyl imidazolium iodide and 1-ethyl, 3-Methyl imidazolium tricyanomethanide. The ionic liquid 1-ethyl, 3-Methyl imidazolium tricyanomethanide is redox inactive in a photochemical cell, but is not hydrophobic or water-immiscible Photovoltaic cells comprising the Electrolyte 1 and Comparative Examples 1 to 3 were produced as follows. An aqueous titanium oxide colloid was made using hydrothermal process, which had average particle size of 23 nm. The titanium oxide colloid was coated on cleaned Ti foil using meyer rods. The typical thickness of titanium oxide coating is around 8 im. The coated slides were air dried at room temperature and sintered at 450 °C for 30 minutes. After cooling the slides to about 80 °C, the slides were immersed into 3x10 M cis-di(thiocyanato) (2,2'-bipyridyl-4,4'-dicarboxylate) ( 2,2'-bipyridyl-4,4'-dinonyl) ruthenium (II) (herein referred to as Z907) dye solution in 1/1 v/v acetonitrile/t-butanol for overnight. The photoelectrodes on titanium foil were removed and rinsed with ethanol and dried over slide warmer at 40 °C for about 10 minutes. The foils were cut into about Q.9x4 cm2 size active area cells. The electrolytes were applied onto the photoelectrodes using a glass pipette and sandwiched with a platinum-sputtered (1-5 nm thick) indium tin oxide coated PET substrate (28 ohms/sq) using a 25 micron thick surlyn polymer adhesive film. The general structure of the cells so made is shown schematically in Figure 5. The cell, denoted generally by reference numeral 1, comprises the titanium foil 6 provided with a coating of dye-sensitized, porous titanium oxide 5 and an electrolyte 4 sandwiched between the titanium oxide 5 and the platinum electrode 3, the platinum electrode 3 being supported by the plastic PET substrate 2.
The performance of each cell was measured at AM 1.5 solar simulator conditions (i.e., irradiation with light having an intensity of 1000 W/m2) , and is noted in Table 1 below.
Electrolyte Short Open Fill Efficiency circuit circuit factor (%) current voltage density (V) (mA/cm2) Comparative Example 1 4.15 0.65 0.75 2.02 Electrolyte 1 8.40 0.66 0.72 3.99 Comparative Example 3 7.95 0.66 0.73 3.83 Comparative Ekample 3 7.45 0.72 0.74 3.97 Table 1 -electrical performance of Electrolyte 1 compared to
Comparative Examples
The fill factor is calculated from the ratio of the solar conversion efficiency to the product of the open circuit voltage and the average short circuit current, i.e. FT = Efficiency (%)/[Open circuit voltage (V) x Short circuit current density (mA/cm2) Table 1 demonstrates that Electrolyte 1 performs well compared to the Comparative Examples.
The effect of prolonged exposure to heat was studied using cells comprising Electrolyte 1 and Comparative Examples 1 to 3. Cells were placed in a dry oven at 65 °C and current voltage characteristics were periodically monitored by testing them using at AM 1.5 solar simulator conditibns (i.e., irradiation with light having an intensity of 1000 W/m2) . The results are shown in Figures 1 and 2 (square -Electrolyte 1; diamond -Comparative Example 2; triangle -Comparative Example 3) . It can clearly be seen that the cell containing Electrolyte 1 performed better than the cells containing the electrolytes of Comparative Examples 2 and 3. Electrolyte 1 maintained a higher current density and higher efficiency than the S Comparative Examples.
The harge transfer resistance between triioide and platinum catalyst at the cathode was studied using electrical impedance spectroscopic (FIS) technique for cells containing Electrolyte 1 and Comparative Examples 2 and 3 as a function of time at elevated temperature. Cells were placed in dry ovens at 65°C or 85°C and platinum dissolution was monitored using the cathodic charge transfer resistance measurements. As can be seen from Figures 3 and 4 (square -Electrolyte 1; diamond -Comparative Example 2; triangle -Comparative Example 3), the cathodic charge transfer resistance increased for all cells with increased time exposed to elevated temperature. The increase in resistance for cells containing Electrolyte 1 was far less than that shown by cells containing the electrolytes of Comparative Examples 2 and 3. This suggests that there is less platinum corrosion by Electrolyte 1 than the electrolytes of Comparative Examples 2 and 3.
Further exathple electrolytes were made with a viscosity-reducing additive, in this case, y-butyrolactone.
E1ectro1yte 2 The elecErolyte was prepared by mixing 35/15/50 parts by volume of 3-Butyl 1-methyl imidazolium iodide, 1-ethyl, 3 Methyl imidazolium bis(trifluoromethylsulfonyl)imide (Sigma Aldrich) and y-butyrolactone, respectively. 0.1M iodine and 0.5M N-Methylbenzimidazole were also present in the electrolyte.
Electrolyte 3 The electrolyte was prepared by mixing 60/20/20 parts by volume of 3-Butyl 1-methyl imidazolium iodide, 1-ethyl, 3-Methyl imidazolium bis(trifluoromethylsulfonyl)imide (Sigma Aldrich) and y-butyrolactone, respectively. 0.1M iodine and 0.5M N-Meth.ylbenzimidazole were also present in the electrolyte.
Electrolyte 4 The electrolyte was prepared, by mixing 55/25/20 parts by volume of 3-Butyl 1-methyl imidazolium iodide, 1-ethyl, 3-Methyl imidazolium bis (trifluoromethylsulfonyl) imide (Sigma Aldrich) and y-butyrolactone, respectively. 0.TM iodine and 0.5M N-Methylbenzimidazole were also present in the electrolyte.
Comparative Example 4 The electrolyte was prepared by mixing 80/20 parts by volume of 3-Butyl 1-methyl imidazolium iodide, and y-butyrolactone, resective1y. 0.1M iodine and 05M N-Methylbenzimidazole were also present in the electrolyte. Comparative Example 4 does not comprise an inert second ionic liquid.
Photovoltaic cells containing Electrolytes 2, 3 and 4, and Comparative Example 4 were made substantially as described above in relation to Electrolyte 1, although a different dye (K19) was used.. 1(19 was synthesized based on procedure described in P. Wang, C. Klein, R. Humphry-Baker, S.M.
Zakeeruddin and M. Gratzel, J. Am. Chem. Soc. Vol. 127, issue 3 (2005) 808-809) The elLectrochemical performance of each cell was studied, and the results shown in Table 2.
Electrolyte Short Open Fill Efficiency circuit circuit factor (%) current voltage (mA/cm2) (V) Electrolyte 2 11.0±0.4 0.680 0.62 4.7±0.2 ±0.004 ±0.16 Comparative 10.6±0.5 0.659 0.60 4.2±0.2 Example 4 ±0.004 ±0.12 Electrolyte 3 10.6±0.5 0.657 0.61 4.2±0.2 ±0.005 ±0.12 Table 2 -electrical performance of Electrolytes 2 and 3 compared to Comparative Example The data from Table 2 indicate that Electrolytes 2 and 3 perform well compared to the electrolyte of Comparative
Example 4.
The effect of prolonged exposure to elevated temperature and high relative humidity was investigated. Cells containing Electrolyte 4 and Comparative Example 4 were heated to 65°C at 85% relative humidity. The cell containing Electroite 4 suffered a decrease in efficiency of about 3% whereas the cell containing the electrolyte of Comparative Example 4 suffered a decrease in efficiency of about 37%. This indicates that the electrolyte of the present invention is particularly resilient to elevated temperature.
Further example electrolytes were made comprising a gelling agent as follows.
Electrolyte 5 A 6 % polyacryionitrile (MW BOOK from Aldrich chemicals) in y-butyrolactone was prepared by heating 6 g of polyacrylonitrile in 100 mL of y-butyrolactone at 120°C. To this were added 75 g 3-butyl 1-methyl imidazolium iodide and 25 g 3-ethyl 1-methyl imidazolium bis(trifluoromethylsulfonyl) imide (TF'SI) (Sigma Aldrich) . 0.1 M iodine and 0.5 N N-methylbenzirnidazole were added to the above electrolyte solution. Cooling the electrolyte forms hard gel. The gel shows a gel-to-liquid transition temperature of 105°C.
The properties of Electrolyte 5 were compared to those of a corresponding electrolyte, Electrolyte 6, which did not contain the gelling agent.
Electrolyte 6 The electrolyte was prepared by mixing 30/20/50 parts by volume of 3-Butyl 1-methyl imidazolium iodide, 1-ethyl, 3-Methyl imidazolium bis(trifluoromethylsuifonyl)imide (Sigma Aldrich) and y-butyrolactone, respectively. 0.1M iodine and 0.5M N-Methylbenzimidazole were also present in the electrolyte.
-Triiodide diffusion Electrolyte [1210 (mol cm 3) 2 coefficient (cm s') Electrolyte 6 7.5*10-5 4.34*10 Electrolyte 5 7.5*10-5 3.71*106 Table 3.-triiodide diffusion coefficients for electrolyte with and without gellirig agent The data from Table 3 indicate that addition of the gelling agent does not severely adversely affect the triiodide diffusion coefficient.
Further example electrolytes were made comprising an alternative gelling agent as follows.
Electrolyte 7 An HSA-Silica gel based gel eleOtrolyte was prepared as follows: A 5 % USA-Silica (surface area 20 m2/g) was vigorously stirred with an electrolyte containing 10 mL g-butyrolactone 7.5 mL 3-butyl 1-methyl imidazolium iodide and 2.5 mL 3-ethyl 1-methyl imidazolium bis(trifluoromethylsulfonyl) imide (TESI) (Sigma Aldrich).
0.1 M iodine and 0.5 P4 N-methylbenzimidazole were added to he above electrolyte solution. Gelling is observed, and the gel was used to make dye sensitized solar cells The properties of Electrolyte 7 were compared to those of a corresponding electrolyte, Electrolyte 8, which did not contain the gelling agent.
Electrolyte 8 The electrolyte was prepared by mixing 37.5/12.5/50 parts by volume of 3-Butyl 1-methyl imidazolium iodide, 1-ethyl, 3-Methyl imidazolium bis (trifluoromethylsulfonyl) imide (Sigma Aldrich) and y-butyrolactone, respectively. 0.1M iodine and 0.5M N-Methylbenzimidazole were also present in the electrolyte.
Electrolyfes 7 and 8 were used to make photovoltaic cells substantially as mentioned above in relation to Electrolyte 1.
Open circuit Short circuit voltage current Efficiency Fill Electrolyte (V) (mA/cia2) (%) factor Electrolyte 8 0.645±0.005 11.4±0.3 3.8±0.2 52±3 Electrolyte 7 0.644±0.005 9.0±0.5 3.6±1 62±1 Table 4 -electrical data for Electrolytes 7 and 8 The data from Table 3 indicate that addition of the gelling agent does not severely affect the performance of the cell.
Some of the examples above use y-butyrolactone as a viscosity-reducing agent. Those skilled in the art will realise that other viscosity-reducing agents may be used, such as y- octalactone, methyl sulfolane, sulfolane, adiponitrile and 3-butoxy propionitrile.
The examples above illustrate the use of a redox-inert ionic liquid comprising a bis(trifluoromethylsulfbny) imide anion.
Those skilled in the art will realise that other anions may be used. Such anions would typically be fluorinated anions, although certain non-fluorinated anions would be capable of producing hydrophobic, water-immiscible, redox inert ionic liquids.
The examples above illustrate the use of a redox-inert ionic liquid comprising a 1-Butyl, 3-Methyl imidaolium cation.
Those skilled in the art will realise that other cations may be used.
Where in the foregoing description, integers or elements are mentioned whith have known, obvious or foreseeable equivalents, then such equivalents are herein incorporated as S if. individually set forth. Reference should be made to the claims for determining the true scope of the present invention, which should be construed so as to encompass any such equivalents. It will also be appreciated by the reader that integers or features of the invention that are described as preferable, advantageous, convenient or the like are optional and do not limit the scope of the independent claims.
Moreover, it is to be understood that such optional integers or features, whilst of possible benefit in some embodiments of the invention, may not be desirable, and may therefore be absent, in other embodiments. .
Claims (24)
- Claims 1. Ar electrolyte for a photovoltaic device, the electrolyte comprising: A first ionic liquid comprising a first redox active species and A redox-iriert, substantially water-immiscible second ionic liquid.
- 2. An electrolyte according to any preceding claim wherein the second ionic liquid is substantially hydrolyticallystable.
- 3. An electrolyte according to any preceding claim wherein the second ionic liquid has a lower viscosity than the first ionic liquid.
- 4. An electrolyte according to any preceding claim wherein the viscosity of the first ionic liquid is from 300 to 6000cP at 25°C.
- 5. An electrolyte according to any preceding claim wherein the viscosity of the second ionic liquid is from 1 to 200cP at 25°C.
- 6. An electrolyte according to any preceding claim wherein the viscosity of the electrolyte is from 1 to lOOcP at 25°C.
- 7. An electrolyte according to any preceding claim wherein the first redox active species comprises iodide, an Fe2 complex, a Co2 complex, a viologen, L-cysteine, ferrocene, 2,2,6, 6-tetramethyl-l-piperidinyloxy (TEMPO), Ni(III) bis(dicarbollide) complexes or 5-mercapto, 1-methyltetrazole.
- 8. An electrolyte according to any preceding claim wherein the first ionic liquid and/or the second ionic liquid comprises an organic cation.
- 9. An electrolyte according to any preceding claim wherein the first ionic liquid and/or the second ionic liquid comprise a cation selected from the group consisting of derivatives of pyridinium, guanidinium, imidazolium, ammonium and sulfonium.
- 10. An electrolyte according to claim 9 wherein the first ionic liquid and/or the second ionic liquid comprise a cation selected from the group consisting of alkyl or dialkyl derivatives of pyridinium, guanidinium, imidazolium, ammonium and sulfonium.
- 11. An electrolyte according to any preceding claim wherein the first ionic liquid and/or the second ionic * liquid comprises a cation selected from the group * consisting of 1,3-dirnethylimidazoliuth,3-butyl-1- methylimidazolium, 3-propyl-l-methylimidazolium, 3-ethyl- * l-methylimidazolium, 4'-butyl pyridinium, N-dimethyl pyrrolidinium, N-Methyl-N-ethylpyrroiidinium and N-Nethyl-N--butylpyrrolidinium tetraethylammonium
- 12. An electrolyte accordIng to any preceding claim wherein the second ionic liquid comprises a fluorinated anion.
- 13. An electrolyte according to claim 12 wherein the second ionic liquid comprises an anion comprising one or more of a fluorinated organic moiety and a fluorinated inorganic* group.
- 14. An electrolyte according to claim 13 wherein the second ionic liquid comprises an anion comprising one or more of a perfluorinated organic moiety and a perfluorinated inorganic group
- 15. An electrolyte according to claim 13 or claim 14 wherein the second ionic liquid comprises an anion comprising one or more of a fluorinated alkyl, alkenyl, alkynyl, aryl, borate and phosphate.
- 16. An electrolyte according to claim 15 wherein the second ionic liquid comprises an anion comprising one or more of a perfluorinated alkyl, alkenyl, alkynyl, aryl, borate and phosphate
- 17. An electrolyte according to any of claims 1 to 11 wherein the second ionic liquid comprises an anion comprising one or mote of an bis (trifluoromethanesulfonyl) imide, tris (pentafluoroethyl) trifluorophosphate, trifluoromethanesulfonate, heptachlorodialuminate, hydrogensulfate, alkylsulfate, methanesulfonate, dimethylphosphate, diethylphosphate, diethylphosphate, hexafluorophoshate and nonaflate.
- 18. An electrolyte according to any preceding claim comprising a second redox active species for pairing or coupling with the first redox active species.
- 19. An electrolyte according to claim 18 wherein the first redox active species comprises iodide, and the second redox active species comprises triiodide (13)
- 20. An electrolyte according to any preceding claim being a binary mixture of ionic liquids.
- 21. An electrolyte according to any of claims 1 to 19 comprising a third ionic liquid.
- 22. An electrolyte according to any preceding claim comprising one or more gelling agents.
- 23. An electrolyte according to claim 22 wherein the gelling agent comprises one or more of high surface area particles, polyacrylonitrile, poly(4-vinylimidazole), poly(4-vinylpyridine) , poly(vinyl pyrrolidone) poly(vinylidine fluoride), poly(ethyelenoxide) polyethyleneimine, polymethylmethacrylates and poly(organophosphate) .
- 24. An electrolyte according to any preceding claim comprising a viscosity-reducing agent.25.. An electrolyte according to claim 24 wherein the viscosity-reducing agent has a viscosity less than that of any of the ionic liquids present in the electrolyte.26. An electrolyte according to claim 2 or 25 wherein the viscosity-reducing agent comprises a polar liquid.27. An electrolyte according to claim 26 wherein the viscosity-reducing agent comprises a polar organic liquid.28. An electrolyte according to any of claims 24 to 27 wherein the viscosity reducing agent has a boiling point of at least 150°C.29. An electrolyte according to claim 28 wherein the viscosity-reducing agent has a boiling point of at least °C.An electrolyte according to claim 29 wherein the viscosity-reducing agent has a boiling point of at least 2000.31. An electrolyte according to any of claims 24 to 30 wherein the viscosity of the viscosity-reducing agent is no more than lOoP.2. An electrolyte according to any of claims 24 to 30 wherein the viscosity of the viscosity-reducing agent is no more than 3cP.33. , An electrolyte according to any of claims 24 to 32, wherein the viscosity-reducing agent comprises one or more of gamma butyrolactone, cyclic lactone, sulfolane, methyl sulfolane, cyclic and acyclic sulfoxides, cyclic and acyclic ketones and alkoxyproplonitriles including butoxy and methoxy propionitrile, dinitrile compounds including glutaro, adiponitriles, oligo and poly-glymes, oligo-and poly-ethyleneimines, dentrimers and star-burst compounds.34. An electrolyte acco±ding to any of claims 24 to 33 wherein the volume of the viscosity-reducing agent is from 10 to 60% of the total volume of the viscosity-reducing agent, first ionic liquid, second ionic liquid and any further ionic liquids present in the electrolyte.35. An electrolyte according to any preceding claim wherein the volume of the first ionic liquid is from 20 to 60% of the total volume of the viscosity-reducing agent (if present) , first ionic liquid, second ionic liquid and any further ionic liquids present in the electrolyte.36. An electrolyte according to any preceding claim wherein the volume of the second ionic liquid is from 5 to 50% of tIe total volume of the visbosity-reducing agent (if present) , first ipnic liquid,, second ionic liquid and any further ionic liquids present in the electrolyte.37. An electrolyte according to any precedin claim comprising from 50 to 9Owt% of a mixture of first and second ionic liquids, the first ionic liquid comprising an imidazolium iodide, the second ionic liquid comprising an imidazolium bis(trifluoromethane) sulphonamide and -10 to SOwt% of a viscosity-reducing agent having a boiling point of more than 150°C.38. An electrolyte for a photovoltaic device, the electrolyte comprising: A first ionic liquid comprising a first redox active species and A redox-inert second lonip liquid comprising a weakly co-qrdinating anion.39. A photovoltaic cell comprising an elect±olyte according to any preceding claim.40. A hotovoltaic cell according to claim 39 comprising a first electrode comprising platinum and a second, photo-sensitised electrode, the electrolyte being disposed between the two electrodes.41. A photovoltaic cell according to claim 40 wherein the second, photo-sensitised electrode comprises a photosensitive dye.
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CN112086683A (en) * | 2019-06-14 | 2020-12-15 | 比亚迪股份有限公司 | Lithium ion battery electrolyte, preparation method thereof, high-voltage lithium ion battery and battery module |
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WO2005055286A2 (en) * | 2003-12-01 | 2005-06-16 | Konarka Technologies, Inc. | Zwitterionic compounds and photovoltaic cells containing same |
US20050189014A1 (en) * | 2004-02-19 | 2005-09-01 | Konarka Technologies, Inc. | Photovoltaic cell with spacers |
US20070204904A1 (en) * | 2004-07-20 | 2007-09-06 | Keith Brooks | Photoactive layer containing macroparticles |
WO2007111763A2 (en) * | 2006-03-20 | 2007-10-04 | General Electric Company | Opto-electronic devices exhibiting enhanced efficiency |
WO2012017872A1 (en) * | 2010-08-03 | 2012-02-09 | 富士フイルム株式会社 | Metal complex dye, photoelectric conversion element and photoelectrochemical cell |
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US20050045851A1 (en) * | 2003-08-15 | 2005-03-03 | Konarka Technologies, Inc. | Polymer catalyst for photovoltaic cell |
WO2005055286A2 (en) * | 2003-12-01 | 2005-06-16 | Konarka Technologies, Inc. | Zwitterionic compounds and photovoltaic cells containing same |
US20050189014A1 (en) * | 2004-02-19 | 2005-09-01 | Konarka Technologies, Inc. | Photovoltaic cell with spacers |
US20070204904A1 (en) * | 2004-07-20 | 2007-09-06 | Keith Brooks | Photoactive layer containing macroparticles |
WO2007111763A2 (en) * | 2006-03-20 | 2007-10-04 | General Electric Company | Opto-electronic devices exhibiting enhanced efficiency |
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