CN107406985B - 在基底上超声喷雾热解沉积一个或更多个电致变色膜和/或电解质膜的改善方法 - Google Patents
在基底上超声喷雾热解沉积一个或更多个电致变色膜和/或电解质膜的改善方法 Download PDFInfo
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- CN107406985B CN107406985B CN201580073496.8A CN201580073496A CN107406985B CN 107406985 B CN107406985 B CN 107406985B CN 201580073496 A CN201580073496 A CN 201580073496A CN 107406985 B CN107406985 B CN 107406985B
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- lithium
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- 239000000758 substrate Substances 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 56
- 239000003792 electrolyte Substances 0.000 title claims abstract description 49
- 238000000151 deposition Methods 0.000 title claims abstract description 38
- 230000008021 deposition Effects 0.000 title claims abstract description 33
- 238000003764 ultrasonic spray pyrolysis Methods 0.000 title claims abstract description 33
- 239000002243 precursor Substances 0.000 claims abstract description 44
- 239000007921 spray Substances 0.000 claims abstract description 31
- 239000012528 membrane Substances 0.000 claims abstract description 15
- 239000004094 surface-active agent Substances 0.000 claims abstract description 15
- 238000009718 spray deposition Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 229910000502 Li-aluminosilicate Inorganic materials 0.000 claims description 26
- 239000011521 glass Substances 0.000 claims description 26
- -1 silicon alkoxide Chemical class 0.000 claims description 17
- 229910052744 lithium Inorganic materials 0.000 claims description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 12
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 12
- 229920001223 polyethylene glycol Polymers 0.000 claims description 11
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 10
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 8
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 8
- 229910001887 tin oxide Inorganic materials 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- 229910001416 lithium ion Inorganic materials 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 4
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 239000010955 niobium Substances 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001422 barium ion Inorganic materials 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 229910001424 calcium ion Inorganic materials 0.000 claims description 2
- 239000012159 carrier gas Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- 229910052805 deuterium Inorganic materials 0.000 claims description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910021432 inorganic complex Inorganic materials 0.000 claims description 2
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910000457 iridium oxide Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 2
- 229910001453 nickel ion Inorganic materials 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 2
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 2
- 229910000487 osmium oxide Inorganic materials 0.000 claims description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 2
- JIWAALDUIFCBLV-UHFFFAOYSA-N oxoosmium Chemical compound [Os]=O JIWAALDUIFCBLV-UHFFFAOYSA-N 0.000 claims description 2
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 claims description 2
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 claims description 2
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 claims description 2
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910003445 palladium oxide Inorganic materials 0.000 claims description 2
- 229910003446 platinum oxide Inorganic materials 0.000 claims description 2
- 229910001414 potassium ion Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910003450 rhodium oxide Inorganic materials 0.000 claims description 2
- 229910001419 rubidium ion Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- 229910001427 strontium ion Inorganic materials 0.000 claims description 2
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- 229910001936 tantalum oxide Inorganic materials 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910001456 vanadium ion Inorganic materials 0.000 claims description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 239000010410 layer Substances 0.000 description 73
- 239000010408 film Substances 0.000 description 42
- 239000000243 solution Substances 0.000 description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 230000008569 process Effects 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- 238000002834 transmittance Methods 0.000 description 7
- 239000003513 alkali Substances 0.000 description 6
- 238000000970 chrono-amperometry Methods 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 6
- 238000002845 discoloration Methods 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 238000003556 assay Methods 0.000 description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
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- 229910052738 indium Inorganic materials 0.000 description 3
- 229910003437 indium oxide Inorganic materials 0.000 description 3
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
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- 238000000197 pyrolysis Methods 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 229910001868 water Inorganic materials 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910013553 LiNO Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
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- 230000005518 electrochemistry Effects 0.000 description 2
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- 238000000605 extraction Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
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- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 239000002563 ionic surfactant Substances 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000000877 morphologic effect Effects 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
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- 239000003960 organic solvent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
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- 150000003839 salts Chemical class 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
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- 229910052718 tin Inorganic materials 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
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- 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
- H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
本发明提供通过在基底上超声喷雾热解(USP)沉积制备电致变色膜或电解膜的方法，其包括：将表面活性剂混合至包含电致变色组分或电解质组分的水性前体溶液中，以提供喷雾溶液；将所述喷雾溶液以介于0.1 mL/min和2 mL/min之间的恒定流速引入超声喷雾沉积喷嘴中，并施加介于80和120 kHz之间的超声频率以产生所述前体溶液的雾化液滴；用在介于0.50至2.0 psi之间的压力下的受控空气射流作为气体载体夹带所述雾化液滴至200至450°C的温度下的预热基底上；在沉积到所述预热基底上时使所述雾化液滴热转化，以产生电致变色膜或电解质膜。还通过根据本发明的方法提供了多层堆叠结构。
Description
本发明涉及通过在大气压下、在基底上超声喷雾热解(USP)沉积来制备电致变色膜或电解质膜的方法。本发明还涉及在该基底上的电致变色膜和电解质膜的多层堆叠结构(stacking construction)。
背景：
超声喷雾热解在本领域中是众所周知的且最近已被Tenent(特别在US 2011/0260124中)应用于电致变色金属氧化物膜的沉积。
然而，所得膜的质量不是最佳的，特别地就均质性和电致变色性能如着色对比度、着色效率、可逆性、耐久性、转换动力学(switching kinetics)、表面/界面缺陷而言。此外，工艺条件也有待改善，以在中等成本下，在大规模基底上有效。多层结构也需要关于在基底上的各层的特性(behaviour)(稳定性、性能…)以及不同层之间的界面而被改善。
R.C. Tenent在US 2011/0260124中教导了在大气压下沉积到FTO(氟掺杂的氧化锡)覆盖的玻璃基底的表面上的电致变色膜，如锂掺杂的氧化镍(Li-NiO)，其中所述氧化物通过水基前体溶液的热解反应产生。液体前体溶液的雾化液滴通常被氮气流携带至受热玻璃基底，让该前体溶液在所述受热玻璃基底上干燥。在干燥期间，在该基底上产生涂层。该涂层可为完全或部分结晶的或无定形的。
R.C. Tenent还在ECS Electrochemistry Letters 1 (2012) H24-H27和SolarEnergy Materials and Solar Cells 99 (2012) 50-55中教导了实现氧化钨WO3的电致变色膜的方法。
所述膜通过两步法产生。通过热丝化学气相沉积合成晶体氧化钨纳米颗粒。收集该纳米颗粒并将其分散于乙醇中，并随后用于在室温下使用超声喷雾沉积、接着在2小时期间在300°C下进行退火步骤以改善结晶度来形成电致变色薄膜。WO3膜是介孔性的，这是由于它们由纳米颗粒堆叠产生。
R.C. Tenent在Electrochemistry Communications 25 (2012) 62-6和SolarEnergy Materials and Solar Cells 121 (2014) 163-170中进一步教导了实现氧化钨的电致变色膜的又一种方法。
所述方法将在无水乙醇(EtOH)中的三嵌段聚合物——聚(乙二醇)-嵌段-聚(丙二醇)-嵌段-聚(乙二醇)添加到六氯化钨(WCl6)在EtOH中的前体溶液中，并使用室温下的超声喷雾沉积、接着在水蒸气室中进行水解和在300-400°C下进行退火来完成WCl6向WO3的转化。
发明内容：
发明人现在已发现用于在大气压下在基底上进行改善的USP沉积方法的特定条件，所述方法使用空气作为由水性前体溶液组成的液滴的气体载体，以通过雾化液滴热解在预热基底上产生一个或更多个电致变色膜或电解质膜。有利地进行该方法(其通常用于电致变色膜和电解质膜制备)而没有任何额外的退火步骤。
也已在大规模基底上获得改善的均质的薄电致变色层或电解质层，其具有高的层均匀性、完美的覆盖和改善的电致变色性能如着色效率、着色对比度、低光扩散率(雾度)、良好的循环可逆性、耐久性、转换动力学。
最后，根据本发明的方法产生在基底上包含至少一个电致变色层和至少一个电解质层的多层堆叠结构，其具有出乎意料地良好的循环可逆性。
根据本发明的电致变色膜是包含选自以下的金属氧化物的金属氧化物膜：氧化钨、氧化钼、氧化铌、氧化钛、氧化铜、氧化铬、氧化锰、氧化钒、氧化钽、氧化铁、氧化钴、氧化镍、氧化钌、氧化铑、氧化钯、氧化锇、氧化铱、氧化铂及其组合。
所述电致变色膜也可包含掺杂元素。
用于所述电致变色膜的掺杂元素选自氢离子、氘离子、锂离子、钠离子、钾离子、铷离子、铯离子、钼离子、钛离子、钒离子、钙离子、钡离子、镁离子、锶离子、钨离子、镍离子或其组合。
根据本发明的电解质膜是包含选自如下的碱(金属)离子(alkali ion)的金属氧化物基质：锂、钠、钾、铷、铯或其组合。该碱金属离子可以供选地被质子替代。所述金属氧化物基质通常由主要氧化物(由主要氧化物前体提供)、次要氧化物(也称为改性氧化物，由次要氧化物前体提供)和质子或碱(金属)离子源如锂源材料制成。
所述碱(金属)离子源、主要氧化物和次要氧化物前体是所述电解质前体溶液的电解质组分。
所述锂源材料可为锂盐，例如硝酸锂LiNO3、氯化锂LiCl或硫酸锂Li2SO4或锂的有机可溶性盐、络合物如乙酸锂和柠檬酸锂。
钠源材料可为钠盐，例如硝酸钠NaNO3、氯化钠NaCl或硫酸钠Na2SO4或钠的 有机可溶性盐、络合物如乙酸钠和柠檬酸钠。类似的碱(金属)源材料可用于其它上述碱。
所述主要氧化物前体可为例如原硅酸四乙酯，也称为四乙氧基硅，并由Si(OC2H5)4或TEOS表示。供选地，烃氧基硅(silicon alkoxide) Si(OR)4也可是合适的，其中R为烷基，如例如甲基、丙基等等。
所述次要氧化物前体可为例如Al(NO3)3.9H2O、H3BO3或H3PO4，分别用于产生铝硅酸锂(LAS)、硼硅酸锂(LBS)和磷硅酸锂(LPS)或其组合。也可考虑其它氧化物如Ti、Zn、Ge、Se、Zr、Nb、Mo、In、Sn、La和Ta的氧化物或其组合作为次要氧化物前体。
例如，所述电解质膜可由氧化锂、氧化硅和氧化铝/氧化硼/氧化磷(分别在LAS/LBS/LPS的情况下)构成。氧化锂Li2O中包含的Li+离子是可移动的，并因此在该膜内产生离子导电性。
作为第一步骤，根据本发明的方法包括优选在室温下将表面活性剂混合到水性前体溶液中。所述水性前体溶液也可被具有有机溶剂如乙醇、甲醇、二甲基甲酰胺、四氢呋喃等等或其组合的有机前体溶液替代。
前体溶液通常定义为有机或无机溶剂如水或其组合，其包含分散的组分。所述组分为可作为可溶性或胶态种类分散的电致变色组分或电解质组分。前体溶液可为例如溶液或胶态悬浮液或乳液或其混合物。
所述电致变色膜的水性前体溶液包含电致变色组分，其可为选自如下的有机或无机盐或络合物：硝酸盐、盐酸盐、乙酸盐、乙酰丙酮化物、柠檬酸盐、硫酸盐，其含有选自如下的金属：钨、钼、铌、钛、铜、铬、锰、钒、钽、铁、钴、镍、钌、铑、钯、锇、铱、铂或其组合。
所述电解质膜的水性前体溶液包含电解质组分，如质子源或碱(金属)离子源。例如，锂离子源材料选自硝酸锂、氯化锂、硫酸锂或其组合。所述电解质膜的水性前体溶液还包含主要氧化物前体如烃氧基硅；和次要氧化物前体(也称为改性氧化物前体)如硝酸铝、氯化铝、硝酸锌、氯化锌、硝酸、硼酸、磷酸或其组合。
根据本发明的表面活性剂选自非离子型化合物或离子型化合物。非离子型表面活性剂可为具有不同分子量(优选具有400、600、1500的分子量)的聚乙二醇或其组合。离子型表面活性剂可为阴离子型(例如十二烷基硫酸钠)或阳离子型(例如溴化十六烷基三甲基铵)化合物或其组合。也可使用离子型表面活性剂和非离子型表面活性剂的组合。将表面活性剂加入前体溶液中，用于形成电致变色膜以及电解质膜。
最优选的是具有400的分子量(Mw)的聚乙二醇。
当使用聚乙二醇时，所述电致变色组分与聚乙二醇的重量比介于10:1和1:10之间， 优选当使用PEG Mw 400时，对于WO3膜，所述重量比为1:10，且对于Li-NiO膜，所述重量比为1:3。当使用PEG Mw 400时，对于LAS膜，所述电解质组分(如LiNO3)与聚乙二醇的重量比优选为1:300。
表面活性剂结合到所述水性或有机前体溶液中旨在降低表面张力，以在超声喷雾喷嘴处产生较小的液滴并改善它们在沉积到受热基底上时的润湿性。所述前体溶液中的表面活性剂还影响溶液粘度并可在将要形成膜时防止颗粒的聚结或聚集。
因此，将这种包含表面活性剂的前体溶液作为喷雾溶液引入超声喷雾喷嘴中。
一旦所述喷雾溶液被引入超声喷雾喷嘴中，将介于80和120 kHz之间，优选120kHz的频率施加至喷嘴，以产生所述前体溶液的雾化液滴。
取决于喷嘴设计，将所述喷雾溶液维持在可从0.1至2.0 mL/min变化的恒定流速下。对于具有顶端或水平几何结构的雾化喷嘴而言，所述恒定流速优选介于0.1至0.4 mL/min之间，且最优选为0.25 mL/min。
通过受控的空气气体(air gas)流使所述雾化液滴进一步从喷雾喷嘴的孔移动至预热基底。
空气气体可为纯空气、干燥空气或与另一气体如氩气混合的空气气体。
低压空气气体介于0.50和2.0 psi之间，优选为0.90 psi。
所述喷嘴具有特定喷雾几何结构，相对所述基底，其可为在顶端的(如对于来自Sono-Tek的AccuMist喷雾喷嘴而言)或水平的(如对于来自Sono-Tek的Impact Edge喷雾喷嘴而言)。此外，可使用平面射流空气转向器来控制雾化液滴向基底的移动。
将基底在介于200和450°C之间，优选350°C的温度下预热。液滴在沉积到该预热基底上时热转变并进一步产生均匀的电致变色膜或电解质膜。
通过热转化或热转变，人们表示在USP工艺期间当雾化液滴沉积在预热基底上时发生的受热促进的整套化学、物理化学反应和物理转变。例如，热转化可包括热解、热分解(thermolysis)、水解、缩合(condensation)、燃烧、分解、氧化、化学平衡移动、干燥、脱水、膨胀、泡腾、任何相转变(熔化、冷凝(condensation)、汽化、升华、沉积、固相转变、结晶)、稠化、收缩、烧结等等。
根据本发明的基底可为玻璃(经回火或未经回火)，其可被由氧化铟、掺杂的氧化铟、氧化锡、掺杂的氧化锡、氧化锌、掺杂的氧化锌、氧化钌、掺杂的氧化钌或具有足够表面电阻性质的任何其它透明导电氧化物制得的透明导电氧化物(TCO)层覆盖。掺杂元素可为氟、锌、铟、铝。玻璃基底可进一步在玻璃块基底和导电层之间包含(content)钠扩散屏障。该基底也可为聚合物或金属片。
该基底可具有任何种类的表面几何结构如平面和非平面，如例如用于窗户、挡风玻璃、曲面镜、透镜、玻璃制品或装饰物品的平板玻璃。
在本发明的优选实施方案中，超声喷雾沉积的方法使用三维沉积图案以产生电致变色膜或电解质膜。该三维图案设计优选通过具有顶端或水平几何结构的雾化喷嘴、根据在x,y-平面内移动的S形弧线进行。
可重复超声喷雾热解沉积的过程2至16次，优选介于6至10次之间，以产生薄的、均匀的电致变色层或电解质层，其厚度介于100至1000 nm之间、优选200-400 nm。
在由掺杂锂的氧化镍(Li-NiO)制得的电致变色层的情况下，优选进行10次沉积通过(passage)，产生260-270 nm的厚度，而在由氧化钨(WO3)制得的电致变色层的情况下，优选进行6次沉积通过，产生220-230 nm的厚度。至于铝硅酸锂电解质层的情况，优选进行6至8次沉积通过，产生360-370 nm的厚度。
沉积根据具有S形移动的弧形图案(1-6 mm间距，优选4 mm间距；间距意指两个喷嘴行进路线之间的距离)以5-50 mm/s、优选40 mm/s的恒定速度在基底表面上方依照”x,y”图案，其中喷嘴和基底之间的恒定z距离为3-6 cm、优选5.5 cm。可重复”x,y”沉积2-16次，每奇数次通过(表示第1、3、5次通过等)保持完全相同的图案，并且每偶数次通过(表示第2、4、6次通过等)改变”x”或”y”坐标一半间距值，这是为了促进形成均质且光滑的沉积层而不是有沟槽的沉积层。
根据本发明的方法进一步包括多个沉积步骤，以产生电致变色层和电解质层的多层堆叠结构。例如，所述方法可产生电致变色/电解质的双层或电致变色/电解质/电致变色的三层，优选锂掺杂的氧化镍/LAS或氧化钨/LAS双层，或锂掺杂的氧化镍/LAS/氧化钨或氧化钨/LAS/锂掺杂的氧化镍三层。
当产生电致变色/电解质的双层时，根据本发明的方法可进一步包括膜的第三沉积步骤，所述膜充当电致变色第一层(充当工作电极)的对电极。该对电极可为第二电致变色膜。合适的电致变色工作电极和对电极材料的选择依赖于它们的电学、电化学和光学互补性，并且是本领域技术人员众所周知的。
本发明的另一目的涉及电致变色层和电解质层的多层堆叠结构。
这种双层或三层结构(特别在其上沉积导电顶层之后)的一个优点是呈现优异的视觉外观(具有高均质性和几乎没有或没有视觉形态缺陷)的全功能“全固态”多层堆叠结构在大气压下的简单制作(straightforward elaboration)。就着色对比度、着色效率、低光散射(通过雾度定量)、可逆性、耐久性和转换动力学而言，所述多层堆叠结构还显示优异的电化学、电致变色和光学特性。
导电顶层通常是透明的，优选对于中性(neutral)材料具有大于80%的透射百分比，但使用有色材料可能较低。该导电顶层可由不同材料如薄的金属涂层包括金、银、铂，或导电氧化物包括氧化铟、氧化锡、氧化锌制得。此类导电氧化物可掺杂诸如氟、铝、锡、铟、锑或锌的元素。透明导电氧化物的典型实例是氧化铟锡(ITO)、氟掺杂的氧化锡(FTO)、铝掺杂的氧化锌(AZO)、锑掺杂的氧化锡(ATO)。供选地，当不要求透明度时，如对于磨砂玻璃、乳白玻璃(opalin glass)等等，该顶层可为半透明的。
所述导电顶层可通过不同方法沉积在基底上，所述方法包括化学气相沉积(CVD)和物理气相沉积(PVD)方法，如金属有机化学气相沉积、磁控溅射、脉冲激光沉积、喷雾热解和超声喷雾热解。
为解释本说明书的目的，以下术语应被给予下文阐述的含义：
着色效率(CE)意指由CE = log(Tb/Tc)/Q定义的参数(以cm²/C表示)，其中Tb和Tc代表褪色状态和着色状态(分别地)的透射率，而Q代表单位面积的电荷(以C/cm²表示)。但是，一些作者更喜欢使用以下等式：CE = ln(Tb/Tc)/Q (以cm²/C表示)，其导致不同的CE值。下文中所有的报导值均依照基于对数的定义获得。
着色对比度(或透射率调制(transmittance modulation))意指Tb和Tc之间的透射率差异。
可逆性意指抽取的电荷(或阳极电荷，Qa)和插入的电荷(或阴极电荷，Qc)之间的比率。
耐久性意指可逆性值随着电化学循环(循环伏安法)的变化(evolution)。经过大量循环后可逆性越稳定且越接近100%，认为该器件越耐久。
转换动力学或着色和褪色时间意指达到总透射率变化的90%所需的持续时间。
光散色定量或雾度意指褪色的氧化物膜的漫射透射率百分比，其根据ASTM D1003评价。
附图简述
图1例示了在超声喷雾沉积过程期间，超声喷雾喷嘴根据其在基底表面上方移动的弧线图案。两根弧线之间的典型间距值为4 mm。可重复该沉积图案2-16次，每奇数次通过时保持完全相同的图案，并且每偶数次通过时移动”x”或”y”坐标间距值的一半(这里是2mm)。
图2例示了AccuMist喷雾喷嘴及其示意图(由Sono-Tek制造)。该喷嘴用于根据本发明的方法。
图3例示了Impact Edge喷雾喷嘴及其示意图(由Sono-Tek制造)。该喷嘴也可用于根据本发明的方法，尤其在大规模基底上。
图4例示了通过根据本发明的方法沉积的电致变色膜所获得的循环伏安图(虚线)/透射率(实线)曲线。
报导了在350°C下通过USP沉积在玻璃/FTO基底上的Li-NiO(上)和WO3(下)电致变色膜在0.5 M LiClO4/碳酸丙烯酯中、从-1.74至+1.06 V/Ag-AgNO3的透射率(λ=550 nm)和电流密度相对电势的变化(10次循环，20 mV/s)。
图5例示了进行循环伏安法(20 mV/s，从-1.74至+1.06 V/Ag-AgNO3，100次循环，0.5 M LiClO4/碳酸丙烯酯溶液)期间，在350°C下通过USP沉积在玻璃/FTO基底上的Li-NiO(带圆点的黑色曲线)和WO3(带三角的红色曲线)电致变色膜的可逆性的变化。
图6例示了在350°C下通过USP沉积在玻璃/FTO基底上的Li-NiO(上)和WO3(下)电致变色膜在0.5 M LiClO4/碳酸丙烯酯溶液中测定的与双阶跃计时电流法(电流密度相对时间)曲线相关的透射率(λ=550 nm)的变化。连续施加+1.06和-1.74 V/Ag-AgNO3的电势值3 min(各阶跃)，以促进Li-NiO膜的着色和褪色(分别地)，而连续施加-1.74和+1.06 V/Ag-AgNO3的电势值3 min(各阶跃)，以促进WO3膜的着色和褪色(分别地)。每种情况下记录4次测定循环。
图7例示了在350°C下通过USP沉积在玻璃/FTO基底上的Li-NiO(左)、LAS(中)和WO3(右)膜的扫描电子显微术图像。所有层均证实了高的均质性、均匀性和光滑度。
图8例示了在完整样品制备1天之后(图8a)和1年之后(图8b)记录的与双阶跃计时电流法曲线相关的550 nm处透射率的变化。连续施加-2.0和+2.0V的电势值5 min(1天；图8a)或3 min(1年；图8b)(各阶跃)，以促进器件的着色和褪色(分别地)。每种情况下记录6次测定循环。
详述
现在在使用玻璃/TCO作为基底的以下实施例中例示根据本发明的方法，其中TCO为氟掺杂的氧化锡(FTO)。
根据以下方案获得不同的单层或/和多层体系：
-单独的电致变色化学计量或非化学计量的锂化的氧化镍层Liy-NiOx(还表示为”Li-NiO”)、电致变色化学计量或非化学计量的氧化钨层WO(3-y)(还表示为”WO3”) 和电解质铝硅酸锂(还表示为”LAS”)层的超声喷雾热解(USP)沉积(参见方案1 的步骤I)；
-电致变色+电解质的双层的USP沉积，依照不同的组合：Li-NiO/LAS或 WO3/LAS(参见方案1的步骤II)；
-电致变色+电解质+电致变色的三层的USP沉积，依照不同沉积次序： Li-NiO/LAS/WO3或WO3/LAS/Li-NiO(参见方案1的步骤III)。
方案1：在锂掺杂的氧化镍/铝硅酸锂/氧化钨多层堆叠的代表性情况下，通过根据本发明的USP(代表超声喷雾热解)沉积方法获得的电致变色层和电解质层逐渐堆叠。TCO代表透明导电氧化物层。
根据本发明的方法可包括以下步骤：
1. 由电致变色层或电解质层的前体溶液制备喷雾溶液；一种或更多种表面活性剂可合并到该前体溶液中；
2. 根据在整个基底上方以恒定z距离的喷雾喷嘴的x,y-移动弧线图案将喷雾溶液超声喷雾到预热的玻璃/TCO基底上(其可重复若干次)：超声产生的喷雾在气流(空气)中被夹带到受热表面上，其中沉积的雾化液滴经历热转化反应，导致产生呈现电致变色或电解质特征的氧化物薄膜；
3. 在堆叠步骤的情况下，其旨在制作全固态无机电致变色器件，用电致变色层(WO3或Li-NiO；步骤1)和电解质层(LAS；步骤2)的前体溶液重复以上步骤1和2，以在玻璃/TCO基底上产生双层(电致变色层+电解质层)或三层(电致变色层+电解质层+电致变色层)堆叠。但是，单一电致变色单层(Li-NiO或WO3)也可用作用于电致变色器件的另一堆叠结构的构成部分(例如，通过与另一电致变色层和基于聚合物凝胶或其它材料的电解质层层合–层合意指通过压力、热或粘合强度的作用将两种分开的材料永久性组装；对于这种堆叠结构，本领域技术人员将参考例如Zelazowska等人，Journal of Non-Crystalline Solids354 (2008) 4500-4505；Al-Kahlout等人，Ionics 16 (2010) 13-19，...)。
4. 将如上所述的导电顶层沉积在该多层堆叠上。
根据本发明的我方的方法的实验方案
实验方案涉及2.0x2.0x0.4 cm玻璃/FTO基底(Planibel GFast，15欧姆/平方)。USP沉积的“标准”参数依赖于使用来自Sono-Tek的Exactacoat USP设备，其具有AccuMist超声喷嘴(具有顶端喷雾几何结构)、在120 kHz下运行。溶液流动速率保持恒定在0.25 mL/min，使用0.90 psi的干净空气作为载气。然后将在喷嘴末端处超声产生的喷雾在顶端夹带在低压空气流中，以最终到达基底，该基底的温度设定在350°C。沉积根据具有S形移动的弧形图案(4 mm间距)以40 mm/s的恒定速度在表面上方依照”x,y”图案，其中喷嘴和基底之间的恒定z距离为5.5 cm。将基底在喷雾之前和之后在加热板上保持5分钟，以在喷雾之前在基底表面处达到350°C的所需温度并在喷雾之后促进前体的分解。重复”x,y”沉积若干次，每奇数次通过保持完全相同的图案，并且每偶数次通过移动”x”或”y”坐标2 mm(参见图1)。
对于各单独层合适的参数：
· Li-NiO电致变色层(方案1上的I)：前体溶液由0.1 M NiNO3.6H2O + LiNO3 5%wt/纯化的H2O + Mw为400的聚乙二醇(PEG)表面活性剂(重量比mNiNO3 : mPEG = 1 : 3)组成。在整个玻璃/FTO表面上方经由AccuMist喷嘴的10次连续通过进行USP沉积。所得层的性质描述于下表1中并例示了这种电致变色Li-NiO层的高可逆性、非常快的着色和褪色时间、高着色对比度、非常高的着色效率和相当低的雾度。
· LAS电解质层(方案1上的II)：该层在重量比为0.13的EtOH/(纯化的)H2O溶液中由溶胶-凝胶方案合成，并且由Al2O3 25%mol (来自Al(NO3)3.9H2O ~1.1 M)、Li2O 25%mol(来自LiNO3 ~1.1 M)和SiO2 50%mol (来自TEOS Si(OCH2CH3)4 ~1.1 M; H2O/TEOS =32.43)构成。前体溶液pH固定在0.22(用HNO3调节)，之后在H2O中稀释50倍。然后将Mw为400的PEG表面活性剂(6.0 g)加入20.0 mL稀释过的溶液中。经由6至8次连续通过进行USP沉积。所得层的性质描述于下表2中并例示了这种电致变色固态LAS层的低雾度与高电导率。
· WO3电致变色层(方案1上的III)：前体溶液由0.01 M偏钨酸铵AMT ((NH4)6W12O39.4H2O)/纯化的H2O + Mw为400的PEG表面活性剂(重量比mAMT : mPEG = 1 : 10)组成。经由6次连续通过进行USP 沉积。所得层的性质描述于下表3中并例示了这种电致变色WO3层的非常高的可逆性、适度快的着色和褪色时间、非常高的着色对比度、高着色效率和适度低的雾度。
使用不同喷嘴的实施例：
测试两种不同的喷嘴类型。AccuMist喷嘴(Sono-Tek)(参见图2)包含顶端喷雾几何结构，在如上所述的3D图案中非常有用，而Impact Edge喷嘴(Sono-Tek)(参见图3)产生扇形喷雾图案，其可能更适合于(至少)10x10x0.4 cm的较大尺寸表面(玻璃/FTO基底)。
通过根据本发明的我方的方法获得的各个层的主要特性
表1：通过使用喷雾喷嘴进行的根据本发明的方法获得的Li-NiO层的性质(室温下的最佳性能)。
表2：通过使用喷雾喷嘴进行的根据本发明的方法获得的LAS层的性质(室温下的最佳性能)。
表3：通过使用喷雾喷嘴进行的根据本发明的方法获得的WO3层的性质(室温下的最佳性能)。
(*)循环伏安图/透射率曲线和循环时可逆性的变化分别呈现于图4和图5上。
(**)双阶跃计时电流法/透射率曲线呈现于图6上。
通过根据本发明的方法获得的电致变色膜的可逆性和稳定性的实施例
在0.5 M LiClO4/碳酸丙烯酯溶液中在于350°C下通过USP沉积在玻璃/FTO基底上的Li-NiO和WO3的电致变色膜上进行循环伏安法和透射率测定。
图4例示了从-1.74至+1.06 V/Ag-AgNO3报导的λ=550 nm处的透射率和电流密度相对电势(10次循环，20 mV/s)，并例示了对于根据本发明的方法制备的Li-NiO和WO3电致变色膜分别为84和94%的良好的可逆性。
图5例示了20 mV/s下、从-1.74至+1.06 V/Ag-AgNO3的循环伏安法测定期间，Li-NiO和WO3电致变色膜在100次循环期间的可逆性的变化。在100次循环测试期间两种膜均保持稳定(可逆性值总是较接近100%)。
通过根据本发明的方法获得的电致变色膜的着色/褪色性能的实施例
电致变色器件的普遍工作原理基于WO3(工作电极，WE)和Li-NiO(对电极，CE)层的网络内部和外部的正离子(Li+)和电子的可逆双电化学注入。着色机理涉及与CE处Ni的氧化和Li+抽取(阳极着色)同时进行的WE处W的还原和Li+插入(阴极着色)。褪色机理基于相反过程，并且两种机理是完全可逆的。
在0.5 M LiClO4/碳酸丙烯酯溶液中在于350°C下通过USP沉积在玻璃/FTO基底上的Li-NiO和WO3的电致变色膜上进行计时电流法测定。图6例示了与双阶跃计时电流法(电流密度相对时间)曲线相关的550 nm处的透射率的变化，其中连续施加+1.06和-1.74V/Ag-AgNO3的电势值3 min(各阶跃)以促进Li-NiO膜的着色和褪色(分别地)，而连续施加-1.74和+1.06 V/Ag-AgNO3的电势值3 min(各阶跃)以促进WO3膜的着色和褪色(分别地)。每种情况下记录4次测定循环。
着色和褪色动力学证实了Li-NiO的分别为6和5s、以及WO3的分别为28和11s的非常快的着色和褪色时间。此外，分别针对Li-NiO和WO3测得54和 83%的高光学对比度。
通过根据本发明的方法获得的电致变色膜和电解质膜的形态性质的实施例
在于350°C下通过USP沉积在玻璃/FTO基底上的Li-NiO、LAS和WO3膜上进行扫描电子显微术测定。图7例示了各情况下和在整个表面上的非常高的光滑度、均匀性和均质性，以及介于1和2%之间的较低的雾度值。
通过根据本发明的方法获得的多层堆叠的实施例
因此，我们可以不同构造使用WO3工作电极和Li-NiO对电极(或以相反顺序)的“串联”组合。在堆叠结构的特定情况下，经由中间电解质层实现Li+插入/抽取过程，所述中间电解质层因此充当Li+离子槽。
因此，根据本发明的USP沉积方法(在大气压下)可有利地用于通过不同层的逐渐堆叠制备多层堆叠结构，所述不同层的逐渐堆叠可例如依照沉积次序Li-NiO/LAS/WO3(如方案1上所呈现)以及WO3/LAS/Li-NiO进行。
这种“全固态”多层堆叠结构的电致变色评价可通过在WO3/LAS/Li-NiO堆叠(例示的情况)上进行的计时电流法测定实现，所述堆叠在350°C下通过USP连续沉积在玻璃/FTO基底上，并出于导电目的被Au薄层覆盖(阴极电弧沉积)。因此，玻璃/FTO基底上的WO3层充当工作电极，而与Au顶涂层相连的Li-NiO层充当对电极。图8例示在完整样品制备1天之后(图8a)和1年之后(图8b)记录的与双阶跃计时电流法曲线相关的550 nm处的透射率的变化。连续施加-2.0和+2.0V的电势值5 min (1天；图8a)或3 min (1年；图8b)(各阶跃)，以促进器件的着色和褪色(分别地)。每种情况下记录6次测定循环。获得良好的整体着色对比度(高达54%)，而着色/褪色动力学保持在几十秒内，其中着色的最快值为12 s而褪色的最快值为32 s。在环境气氛中样品老化1年之后，此类性能整体上保持稳定(图8a相对图8b)，其证明了器件的耐久性。该器件还证实了高伏安循环稳定性和可逆性。已经实现至少1500次循环(光学监测)。
本发明还考虑到依照其它方法制备多层堆叠，例如通过在经USP沉积在玻璃/FTO基底上的WO3和 Li-NiO电致变色层之间包封由聚合物凝胶制得的电解质层。
本发明还考虑到制备基于通过USP沉积在玻璃/FTO基底上的单一电致变色Li-NiO或WO3层且充当工作电极的器件。这可进一步用充当对电极的在玻璃/FTO基底上的电解质层(例如，聚合物凝胶)包封。
Claims (18)
1.一种通过在基底上超声喷雾热解(USP)沉积制备选自铝硅酸锂(LAS)、硼硅酸锂(LBS)或磷硅酸锂(LPS)的电解质膜的方法，其包括：
- 将表面活性剂与包含电解质组分的水性前体溶液混合，以提供喷雾溶液；
- 将所述喷雾溶液以介于0.1 mL/min和2 mL/min之间的恒定流速引入超声喷雾沉积喷嘴中，并施加介于80和120 kHz之间的超声频率以产生所述前体溶液的雾化液滴；
- 在介于0.50至2.0 psi之间的压力下的作为气体载体的受控空气射流中夹带所述雾化液滴至200至450°C的温度下的预热基底上；
- 在沉积到所述预热基底上时使所述雾化液滴热转化，以产生电解质膜；
其中，所述水性前体溶液包含选自质子源或锂离子源的电解质组分；选自四乙氧基硅或烃氧基硅的主要氧化物前体和选自Al(NO3)3.9H2O、H3BO3、H3PO4或其组合的次要氧化物前体。
2.根据权利要求1所述的方法，其中对于喷雾喷嘴，所述恒定流速介于0.1和0.4 mL/min之间。
3.根据权利要求1所述的方法，其中通过所述超声喷雾沉积喷嘴根据三维图案设计至所述预热基底上的所述膜沉积。
4.根据权利要求3所述的方法，其中所述三维图案在X-Y平面中依照S形弧线移动。
5.根据权利要求1所述的方法，其中将夹带所述雾化液滴至所述预热基底上和使它们在所述预热基底上热转化的两个步骤重复介于2至16次之间，以便产生均质的电解质层。
6.根据权利要求1所述的方法，其中所述表面活性剂是聚乙二醇。
7.根据权利要求1所述的方法，其中所述超声频率为120 kHz。
8.根据权利要求1所述的方法，其中所述载体空气气压为0.90 psi。
9.根据权利要求1所述的方法，其中所述基底在350°C的温度下预热。
10.根据权利要求1所述的方法，其中所述基底是氟掺杂的氧化锡涂布的玻璃。
11.根据权利要求1所述的方法，其中所述超声喷雾沉积喷嘴和预热基底之间的距离为3-6 cm。
12.根据权利要求1所述的方法，其中所述电解质组分是选自硝酸锂、氯化锂、硫酸锂或其组合的锂离子源。
13.根据权利要求1所述的方法，其进一步包括：
- 将表面活性剂与包含电致变色组分的水性前体溶液混合，以提供喷雾溶液；
- 将所述喷雾溶液以介于0.1 mL/min和2 mL/min之间的恒定流速引入超声沉积喷嘴中并施加介于80和120 kHz之间的超声频率以产生所述前体溶液的雾化液滴；
- 在介于0.50至2.0 psi之间压力下的作为气体载体的受控空气射流中夹带所述雾化液滴至200至450°C的温度下的预热基底上；
- 在沉积到所述预热基底上时使所述雾化液滴热转化，以产生电致变色膜。
14.根据权利要求13所述的方法，其中所述电致变色膜包含选自如下的金属氧化物：氧化钨、氧化钼、氧化铌、氧化钛、氧化铜、氧化铬、氧化锰、氧化钒、氧化钽、氧化铁、氧化钴、氧化镍、氧化钌、氧化铑、氧化钯、氧化锇、氧化铱、氧化铂或其组合。
15.根据权利要求14所述的方法，其中所述电致变色膜还包含选自如下的掺杂元素：氢离子、氘离子、锂离子、钠离子、钾离子、铷离子、铯离子、钼离子、钛离子、钒离子、钙离子、钡离子、镁离子、锶离子、钨离子、镍离子及其组合。
16.根据权利要求13所述的方法，其中所述水性前体溶液包含电致变色组分，所述电致变色组分包含选自如下的有机或无机盐或络合物：硝酸盐、氯化物、乙酸盐、乙酰丙酮化物、柠檬酸盐、硫酸盐、过氧金属化物，其含有选自如下的金属：钨、钼、铌、钛、铜、铬、锰、钒、钽、铁、钴、镍、钌、铑、钯、锇、铱、铂或其组合。
17.根据权利要求13所述的方法，其中所述电致变色层为锂掺杂的氧化镍或三氧化钨。
18.根据权利要求13所述的方法，其中所述表面活性剂是聚乙二醇并且其中在所述水性前体溶液中所述电致变色组分与聚乙二醇的重量比介于10:1和1:10之间。
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| JP7021533B2 (ja) * | 2017-12-22 | 2022-02-17 | セイコーエプソン株式会社 | 電解質前駆体溶液の製造方法および電極複合体の製造方法 |
| CN108191257A (zh) * | 2018-01-05 | 2018-06-22 | 东华大学 | 一种利用喷雾热解法制备电致变色薄膜的方法 |
| RU2671362C1 (ru) * | 2018-04-04 | 2018-10-30 | Федеральное государственное унитарное предприятие "Центральный научно-исследовательский институт химии и механики" (ФГУП "ЦНИИХМ") | Электрохромная пленка триоксида вольфрама и способ ее получения |
| US11223066B2 (en) | 2018-08-01 | 2022-01-11 | Samsung Electronics Co., Ltd. | Solid-state electrolyte and method of manufacture thereof |
| US11251460B2 (en) | 2018-08-01 | 2022-02-15 | Samsung Electronics Co., Ltd. | Solution-processed solid-state electrolyte and method of manufacture thereof |
| KR102180882B1 (ko) * | 2018-09-12 | 2020-11-20 | 주식회사 보야스에너지 | 초음파 분무 열분해법을 이용한 수전해 촉매 합성방법 |
| KR102157489B1 (ko) * | 2018-12-13 | 2020-09-18 | 서울과학기술대학교 산학협력단 | 전자파 차폐형 산화물 반도체 박막 제조방법 |
| CN109704592B (zh) * | 2019-01-29 | 2021-12-17 | 西安理工大学 | 氟掺杂二氧化钛的纳米阵列电致变色薄膜及其制备方法 |
| IL266281A (en) * | 2019-04-27 | 2020-10-28 | Yeda Res & Dev | Electrochromic devices of different colors |
| US11757127B2 (en) | 2019-06-18 | 2023-09-12 | Samsung Electronics Co., Ltd. | Lithium solid electrolyte and method of manufacture thereof |
| JP7379306B2 (ja) * | 2020-09-28 | 2023-11-14 | 東芝マテリアル株式会社 | エレクトロクロミック素子 |
| CN112285981B (zh) * | 2020-10-27 | 2022-11-01 | 哈尔滨工业大学 | 一种具有高电荷储存能力的电致变色器件的制备方法 |
| CN113568235A (zh) * | 2021-06-28 | 2021-10-29 | 浙江工业大学 | 一种基于多功能水凝胶电解质的电致变色器件及制备方法 |
| CN114163139B (zh) * | 2021-12-23 | 2024-02-20 | 合肥工业大学 | 一种两层不同结构的复合氧化镍薄膜的制备方法 |
| CN115079481A (zh) * | 2022-05-24 | 2022-09-20 | 湘潭大学 | 一种电致变色用硝酸根离子电解质及其应用 |
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