CN101989499A - Asymmetric electrochemical supercapacitor and method of manufacture thereof - Google Patents
Asymmetric electrochemical supercapacitor and method of manufacture thereof Download PDFInfo
- Publication number
- CN101989499A CN101989499A CN2010102438883A CN201010243888A CN101989499A CN 101989499 A CN101989499 A CN 101989499A CN 2010102438883 A CN2010102438883 A CN 2010102438883A CN 201010243888 A CN201010243888 A CN 201010243888A CN 101989499 A CN101989499 A CN 101989499A
- Authority
- CN
- China
- Prior art keywords
- metal
- active material
- asymmetric ultracapacitor
- ultracapacitor
- described asymmetric
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title description 39
- 238000004519 manufacturing process Methods 0.000 title description 2
- 239000000463 material Substances 0.000 claims abstract description 44
- 239000011149 active material Substances 0.000 claims abstract description 41
- 239000003792 electrolyte Substances 0.000 claims abstract description 41
- 229910052751 metal Inorganic materials 0.000 claims abstract description 39
- 239000002184 metal Substances 0.000 claims abstract description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000007864 aqueous solution Substances 0.000 claims abstract description 34
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 9
- 150000001450 anions Chemical class 0.000 claims abstract description 6
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 6
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 6
- 239000010439 graphite Substances 0.000 claims abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 46
- 229910052799 carbon Inorganic materials 0.000 claims description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 17
- 229920001940 conductive polymer Polymers 0.000 claims description 16
- 239000002322 conducting polymer Substances 0.000 claims description 15
- 239000010949 copper Substances 0.000 claims description 13
- 239000011572 manganese Substances 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 229910044991 metal oxide Inorganic materials 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 11
- 239000002388 carbon-based active material Substances 0.000 claims description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims description 10
- 229910052709 silver Inorganic materials 0.000 claims description 10
- 239000000853 adhesive Substances 0.000 claims description 9
- 230000001070 adhesive effect Effects 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- 150000004706 metal oxides Chemical class 0.000 claims description 8
- 239000010944 silver (metal) Substances 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 150000004767 nitrides Chemical class 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 229910013733 LiCo Inorganic materials 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 6
- -1 poly(ethylene oxide) Polymers 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 5
- 239000002086 nanomaterial Substances 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 5
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 4
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 4
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 150000003949 imides Chemical class 0.000 claims description 4
- 150000002823 nitrates Chemical class 0.000 claims description 4
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 4
- 229920000767 polyaniline Polymers 0.000 claims description 4
- 229920000128 polypyrrole Polymers 0.000 claims description 4
- 229910012851 LiCoO 2 Inorganic materials 0.000 claims description 3
- 229910001513 alkali metal bromide Inorganic materials 0.000 claims description 3
- 229910001514 alkali metal chloride Inorganic materials 0.000 claims description 3
- 229910052936 alkali metal sulfate Inorganic materials 0.000 claims description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910001511 metal iodide Inorganic materials 0.000 claims description 3
- 239000002121 nanofiber Substances 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052755 nonmetal Inorganic materials 0.000 claims description 3
- 229920001197 polyacetylene Polymers 0.000 claims description 3
- 229920000123 polythiophene Polymers 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical group [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052946 acanthite Inorganic materials 0.000 claims description 2
- 239000003011 anion exchange membrane Substances 0.000 claims description 2
- SKKMWRVAJNPLFY-UHFFFAOYSA-N azanylidynevanadium Chemical compound [V]#N SKKMWRVAJNPLFY-UHFFFAOYSA-N 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
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 claims description 2
- 229960004643 cupric oxide Drugs 0.000 claims description 2
- 229940095991 ferrous disulfide Drugs 0.000 claims description 2
- 229910003437 indium oxide Inorganic materials 0.000 claims description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 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
- 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
- 239000012528 membrane Substances 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229940056910 silver sulfide Drugs 0.000 claims description 2
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 claims description 2
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 claims description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001887 tin oxide Inorganic materials 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims 2
- 239000004917 carbon fiber Substances 0.000 claims 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 2
- 239000002041 carbon nanotube Substances 0.000 claims 1
- 229910021393 carbon nanotube Inorganic materials 0.000 claims 1
- 239000007770 graphite material Substances 0.000 claims 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 abstract 2
- 229910019098 CoSx Inorganic materials 0.000 abstract 1
- 229910032387 LiCoO2 Inorganic materials 0.000 abstract 1
- 229910011380 LiCoxNiyMn Inorganic materials 0.000 abstract 1
- 229910011393 LiCoxNiyO2 Inorganic materials 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 55
- 239000003990 capacitor Substances 0.000 description 25
- 230000008569 process Effects 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000007772 electrode material Substances 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 238000002484 cyclic voltammetry Methods 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000011255 nonaqueous electrolyte Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 239000002048 multi walled nanotube Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 229910002640 NiOOH Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 235000019241 carbon black Nutrition 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- CHLISLWBOOKYGY-UHFFFAOYSA-N 3-fluoro-2-phenylthiophene Chemical compound C1=CSC(C=2C=CC=CC=2)=C1F CHLISLWBOOKYGY-UHFFFAOYSA-N 0.000 description 1
- 229920013683 Celanese Polymers 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000003542 behavioural effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 206010061592 cardiac fibrillation Diseases 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002600 fibrillogenic effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- VUFYPLUHTVSSGR-UHFFFAOYSA-M hydroxy(oxo)nickel Chemical compound O[Ni]=O VUFYPLUHTVSSGR-UHFFFAOYSA-M 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- UBNZXCZZENTUCE-UHFFFAOYSA-K potassium nickel(2+) trihydroxide Chemical compound [K+].[OH-].[Ni+2].[OH-].[OH-] UBNZXCZZENTUCE-UHFFFAOYSA-K 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000013014 purified material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000007582 slurry-cast process Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The disclosure relates to asymmetric supercapacitors containing: a positive electrode comprising a current collector and a first active material selected from a layered double hydroxide of formula [M2+1-xMx3+(OH)2]An-x/n.mH2O where M2+ is at least one divalent metal, M3+ is at least one trivalent metal and A is an anion of charge n-, where x is greater than zero and less than 1, n is 1, 2, 3 or 4 and m is 0 to 10; LiCoO2; LiCoxNiyO2 where x and y are greater than zero and less than 1; LiCoxNiyMn(1-x-y)O2 where x and y are greater than zero and less than 1; CoSx where x is from 1 to 1.5; MoS; Zn; activated carbon and graphite; a negative electrode containing a material selected from a carbonaceous active material, MoO3 and Li1xMoO6-x/2; an aqueous electrolyte solution or a non-aqueous ionic conducting electrolyte solution containing a salt and a salt and a non-aqueous solution; and a separator plate. Alternatively, the electrolyte can be a solid electrolyte.
Description
The cross reference of related application
The application is the U.S. Patent application No.11/711 that submitted on February 27th, 2007,376 continuation application also requires its priority, described at first to file No.11/711,376 is the U.S. Patent application No.09/590 that submitted on June 9th, 2000,496 continuation application also requires its priority, and is described at first to file No.09/590, and 496 require the U.S. Provisional Application No.60/138 of submission on June 11st, 1999,857 priority is incorporated their full text into this paper by reference.
The statement of government's rights and interests
The present invention makes under the government of the award of contract NAS 3-99054 of NASA supports.Government has certain rights and interests in the present invention.
Technical field
The present invention relates to electrochemical capacitor.The method that the present invention is specifically related to asymmetric electrochemical capacitor and improves its energy density and power density.
Background technology
Electrochemical capacitor (EC) can be stored per unit weight energy (weight energy density) and the unit volume energy (volume energy density) than the high hundred times of traditional electrical electrolysis condenser.Herein energy density be meant the weight and volume energy density both.Other advantages of EC comprise high cycle life (＞300k), high rate discharge (from minute to microsecond), two-forty charging, the fail safe tolerance limit of discharging and overcharging, good charged state indication in wide working temperature and the charge and discharge process.Under many circumstances, need in the scope in a few minutes to several seconds in the application of high power density and discharge rate, EC can surmount the performance of battery, for example those that are run in pulsed discharge is used.
The application of asymmetric electrochemical capacitor comprises digital dock backup, defibrillator, power supply (UPS), portable electric appts, telephonic communication system, Portable X-ray device power supply and the remote telemetry device power supply in storage backup device, apparatus and the military electronic equipment of computer.Automobile is used the load adjustment comprise in the electric motor car to prolong the useful life of battery, and being acceleration, automobile start, illumination and igniting (SLI), automobile power steering, preheating catalyst and pulse power demand such as electric door lock and power windows provide electric power.
Electrochemical double layer capacitor is also referred to as ultracapacitor, the charging by electrode/electrolyte interface (double layer capacitor) or by coming stored energy at electrode surface or near take place it faraday's reaction (fake capacitance).The active material that research at present is used for the electrode material of these devices comprises that active carbon (has 1000-3000m usually
2The surface area of/g), conducting polymer such as the polypyrrole and the polyaniline of mixed-metal oxides (as ruthenium-oxide and yttrium oxide) and doping.Use aqueous electrolyte and nonaqueous electrolyte.
The material that is used for two electrodes that the ultracapacitor of symmetry adopts has the response of about par to applied voltage, and asymmetric ultracapacitor uses two kinds of different electrode materials, the response that separately applied voltage is had different magnitudes.Perhaps symmetrical ultracapacitor can be described as at two electrodes and uses the identical energy memory mechanisms, and asymmetric ultracapacitor can be described as at each electrode and uses the different-energy memory mechanism.The mechanism of energy storage comprises separation of charge and faraday's process (electron transfer).
Compared to battery, low but ultracapacitor has very high power density energy density.Studied distinct methods and do not influenced its high power performance with the energy density that increases ultracapacitor.Thereby the operating voltage that a kind of method is to use nonaqueous electrolyte to improve ultracapacitor increases the energy of storage.Such as the value of the operating voltage of the commercial ultracapacitor with nonaqueous electrolyte of PANASONIC development up to 2.5 volts (V).
The second method that improves the energy density of ultracapacitor is all to use conductive polymer electrodes in two electrodes, for example the fluorophenyl thiophene.These systems are approximately working under the 2.8V.By its present state of development, it is 6-10 watt hour/kilogram (Wh/kg) that the energy density of practical devices is designed at about 2 kilowatts/kilogram (kW/kg) following power level, but long-time stability and cycle life are not clear.Because high battery operated voltage, this method require to use very highly purified material and technology, therefore increased the cost of ultracapacitor.
The third method that improves the energy density of ultracapacitor is to use fake capacitance device electrode material, for example based on the mixed oxidization objects system of ruthenium-oxide and yttrium oxide.Usually, most of fake capacitance modulator material need the aqueous electrolyte of limit battery voltage for about 1.2V.The energy density that improves in these systems is not because higher voltage, but because the use of fake capacitance and double-deck charge storage on the electrode of high surface.Reported recently by using the aqua oxidation ruthenium electrode to significantly improve energy density (twice).This obviously allows the storage of volume (bulk) and surface charge.But,, still too high based on method price for automobile is used of ruthenium even energy density doubles.For example, in hybrid vehicle was used, this method only cost of raw material just substantially exceeded 100000 dollars.
Sought the low-cost substitute of ruthenium based system, for example as metal oxide, nitride and the sulfide of molybdenum and tungsten.Equally, all these material require aqueous electrolytes are used for the fake capacitance charge storage.The operating voltage of this material is low fallaciously, and stable working range is 0.6～0.8V.This greatly reduces the energy and the power density of material.Material still keeps high relatively cost, and the super capacitor material such as the active carbon of suitable performance especially can be provided with respect to other.
U.S. Patent No. 5,986,876 disclose a kind of asymmetric ultracapacitor.In this design, hydroxy nickel oxide (NiOOH) anodal coupling activated carbon negative electrode and potassium hydroxide (KOH) electrolyte.Asymmetric ultracapacitor is because several are former thereby the energy density advantage is provided.At first, because 1/C
T=1/C
1+ 1/C
2, device capacitor has the electric capacity of the electrode of minimum capacity no better than.This is because other electrodes are formed by having more the material of height ratio capacity.On the contrary, the plot ratio of symmetrical ultracapacitor is about 1, produces device capacitor and is 1/2nd of each electrode approximately.Secondly, because a kind of electrode material has high power capacity like this, its quality and volume can be more much smaller than other electrodes.Therefore high-capacity electrode can have insignificant quality or volume with respect to other electrodes, and this further improves the energy density of asymmetric ultracapacitor.At last, have the asymmetric ultracapacitor of aqueous electrolyte can be under the voltage more than the 1.22V reliably working and do not have gas to emit.For example, known asymmetric ultracapacitor can almost be the twice of commercially available symmetrical water-based ultracapacitor in 1.7～1.8V work.This high voltage makes energy density be increased to nearly four times.These three factors can combine the energy density to 8 times that improves asymmetric ultracapacitor or more high power in symmetrical ultracapacitor.
Although above-mentioned improvement is significant, this area still needs to have more high density, high power performance and the asymmetric ultracapacitor of long-life improvement.
Summary of the invention
Disclosed asymmetric ultracapacitor overcomes or has subdued above-mentioned shortcoming and defect among the present invention.According to an embodiment, asymmetric ultracapacitor comprises:
Positive pole comprises the current-collector and first active material, and first active material is selected from following material:: formula [M
2+ 1-xN
x 3+(OH)
2] A
N- X/nMH
2The layered double-hydroxide of O, wherein M
2+Be at least a divalent metal, N
3+Be at least a trivalent metal/nonmetal, A is that electric charge is the anion of n-, and wherein x is greater than 0 and less than 1; LiCoO
2, LiCo
xNi
yO
2And LiCo
xNi
yMn
(1-x-y)O
2, wherein x and y are greater than 0 and less than 1; Formula MS
xSulfide, wherein x is 1～10, M is selected from least a among Co, Ni, Fe, Cu, Ag, Mo and the W; Li
xCo
y(PO
4)
zAnd Li
xNi
y(PO
4)
z, wherein x, y and z are greater than 0 and less than 1; Active carbon and graphite; And the combination that contains at least a aforementioned active material;
Negative pole comprises being selected from following at least a material: carbon active material, Zn, Al, Mg, Ca, Cr, La, V, Ti, Li, Na; Formula MO
xMetal oxide, wherein 0＜x＜3 and M are be selected from Ti, V, Nb, Cr, Mo, W, Mn, Fe, Co, Ni, Pd, Pt, Cu and Ag at least a, formula MS
xSulfide, wherein x is 1～10, M is be selected from Co, Ni, Fe, Cu, Ag, Mo and W at least a; Li
xMoO
(6-x)/2Wherein x and y are greater than 0 and less than 1; And conducting polymer;
Be selected from following electrolyte aqueous solution: the aqueous solution of the aqueous solution of alkali metal hydroxide aqueous solution, alkali carbonate, the aqueous solution of alkali metal chloride, alkali metal bromide, the aqueous solution of alkaline metal iodide, the aqueous solution of alkali metal sulfates, the aqueous solution of alkali nitrates, and the combination that comprises at least a above-mentioned aqueous solution; Or the nonaqueous ionic conducting electrolyte solution of saliferous and non-aqueous solution; With
Dividing plate.
In another embodiment, asymmetric ultracapacitor comprises: the positive pole that contains the current-collector and first active material; Negative pole; Solid electrolyte; And dividing plate.
Asymmetric ultracapacitor by with the positive pole of high faraday's capacity with by improving energy density coming the negative electricity of stored charge to be coupled such as the electric double layer place separation of charge of carbon containing.Asymmetric ultracapacitor also improves power density by the nano structure electrode material that uses high surface.
Asymmetric ultracapacitor is except more also providing other practical advantage the high-energy-density.The electric capacity of asymmetric ultracapacitor is near the electric capacity of two-layer electrode electric capacity, because anodal electric capacity is big usually doubly a lot.In addition, asymmetric ultracapacitor is more cheap, is the active carbon of common tip heigh material because have only an electrode.In addition, the balance of voltage in series connection aqueous electrolyte asymmetrical cell lacks than the problem in the symmetrical battery, because the successfully operating gas circulation under the condition of overcharging of these batteries.Therefore when charging, the ceiling voltage battery at first reaches the gassing condition and the voltage that tops out, and makes other batteries can be charged to identical voltage.Voltage of serially-connected cells was identical when therefore, each system charged fully.Therefore, be unwanted as the cell voltage reduction rated value seen in the symmetrical battery, in fact do not expect.This has created energy and power density and the minimum possible cost of chance to realize maximum possible.
Description of drawings
Fig. 1 is the schematic diagram of the potential change of each electrode in charging and discharge process.
Fig. 2 is at the schematic diagram that charges and the discharge process intermediate ion moves.
Fig. 3 is the schematic diagram of asymmetric ultracapacitor.
Fig. 4 is [Co in selected electrolyte
0.36Ni
0.24Al
0.4(OH)
2] (CO
3)
0.2Figure.
Fig. 5 is the [Co of heat treated in selected electrolyte
0.36Ni
0.24Al
0.4(OH)
2] (CO
3)
0.2Cyclic voltammogram.
Fig. 6 is illustrated in [Co among the 4.8M KOH
0.4Ni
0.29Al
0.31(OH)
2] (CO
3)
0.155Constant charge-discharge performance.
Fig. 7 A illustrates by [the Co among the 4.8M KOH
0.36Ni
0.24Al
0.4(OH)
2] (CO
3)
0.2The asymmetric capacitor of positive pole and activated carbon negative electrode preparation is at Nyquist (Nyquist) figure of different charging voltages.
Fig. 7 B illustrates by [the Co among the 4.8M KOH
0.36Ni
0.24Al
0.4(OH)
2] (CO
3)
0.2The asymmetric capacitor of positive pole and activated carbon negative electrode preparation is at baud (Bode) the magnitude figure of different charging voltages.
Specific embodiments
The invention discloses a kind of asymmetric ultracapacitor, comprise positive pole, negative pole and electrolyte with current-collector and active material, described electrolyte can be the form of solid, the aqueous solution or non-aqueous solution.
Asymmetric ultracapacitor by with the positive pole of high faraday's capacity with by improving energy density coming the negative electricity of stored charge to be coupled such as the electric double layer place separation of charge of carbon containing negative pole.Asymmetric ultracapacitor also improves power density by the nano structure electrode material that uses high surface.
In order to make the promptly anodal and negative pole acquisition high-energy-density of electrochemistry coupling, one of electrode is anodal in present case, must have the hypopolarization degree; Electrode potential changes very little with respect to its reversible potential during electric current passes through.In addition, non-Faraday process must minimize, and faraday's process (electron transfer) is passed electrode surface with high reaction rate and taken place.Should have high polarizability and under ideal conditions to electrode (negative pole), in charge and discharge process, should obtain the potential change of big window.The charge storage of polarizable electrode is through double-deck separation of charge.Be the explanation this point, the potential change that takes place at each electrode in the charge and discharge process is schematically shown in Figure 1.As can be seen, when charging, asymmetric ultracapacitor forms big voltage window.For the electrolytical asymmetric unit of the property of water-bearing, potential window can limit by discharging at electrode place hydrogen and oxygen.Current potential with electrode of hypopolarization degree all keeps constant substantially in charge and discharge process.
Except high-energy-density more, asymmetric ultracapacitor also provides other practical advantage.The electric capacity of asymmetric ultracapacitor is near the electric capacity of two-layer electrode electric capacity, because anodal electric capacity is big usually doubly a lot.In addition, asymmetric ultracapacitor is more cheap, is common tip heigh material activity charcoal because have only an electrode.In addition, the balance of voltage in series connection aqueous electrolyte asymmetrical cell lacks than the problem in the symmetrical battery, because the successfully operating gas circulation under the condition of overcharging of these batteries.Therefore when charging, the ceiling voltage battery at first reaches the gassing condition and the voltage that tops out, and makes other batteries can be charged to identical voltage.Voltage of serially-connected cells was identical when therefore, each system charged fully.Therefore, be unwanted such as the cell voltage reduction rated value seen in the symmetrical battery, in fact do not expect.This has created energy and power density and the minimum possibility cost of chance to realize maximum possible.
The example of suitable positive electrode active materials comprises formula [M
2+ 1-xN
x 3+(OH)
2] A
N- X/nMH
2The layered double-hydroxide of O, wherein M
2+Be at least a divalent metal, N
3+Be at least a trivalent metal/nonmetal, A is that electric charge is the anion of n-, wherein x greater than 0 and less than 1 and n be 1,2,3 or 4; LiCoO
2, LiCo
xNi
yO
2And LiCo
xNi
yMn
(1-x-y)O
2, wherein x and y are greater than 0 and less than 1; Formula MS
xSulfide, wherein x is 1～10, M is selected from least a among Co, Ni, Fe, Cu, Ag, Mo and the W; Li
xCo
y(PO
4)
zAnd Li
xNi
y(PO
4)
z, wherein x, y and z are greater than 0 and less than 1; Active carbon and graphite, and the combination that contains at least a aforementioned active material;
Layered double-hydroxide can comprise the M of any number
2+And N
3+Metal.Usually use 2～5 kinds of metals.Metal M
2+And N
3+Can include but not limited to alkaline-earth metal, transition metal, main group metal and lanthanide series metal.Divalent metal M
2+Can comprise Ca
2+, Mg
2+, Mn
2+, Fe
2+, Co
2+, Ni
2+, Cu
2+And Zn
2+Trivalent metal N
3+Can comprise B
3+, Al
3+, Mn
3+, Fe
3+, Co
3+, Ni
3+, Cr
3+, Ga
3+, Y
3+, La
3+And Ti
3+Anion A
N-Can include but not limited to HCO
3 -, CO
3 2-, NO
3 2-, SO
3 2-, SO
4 2-, F
-, Cl
-, Br
-, I
-, PO
4 3-And tetrasodium ethylenediamine tetraacetate (Na
4EDTA).
Active material is generally graininess, and the average single linear size of described particle is less than about 100 microns, and is preferably nanostructure.The grain shape of active material depends on estimated performance, cost and other characteristics of asymmetric ultracapacitor.Expection can be used various ways.For example, active material can be taked irregular or regular shape, as amorphous, fibrous, oval, rhombus etc., nest like is as U.S. Patent No. 6,036,774 disclosed nanotubes or nanometer rods and U.S. Patent No. 6,162,530 disclosed other forms, these patents are incorporated this paper by reference into.Nano structural material is suitable for electrode very much, because they have high surface activity and high useable surface area.Long-pending to be included in the profound and subtle hole therefore in capacitor application disabled to a great extent other high surface area materials opposite with most surfaces wherein for this.Nano structural material used herein is meant to have the material that granularity is about 1～100 nanometer (wherein 1nm=10 dust).Therefore being characterized as of nano structural material has a high proportion of material atom that is present in crystal grain or granule boundary.For example, when granularity in 5 nanometer range, only about half of atom is present in crystal grain or granule boundary place in the nanocrystalline or nanophase solid.
Above-mentioned nano structural material can be made by the aqueous chemical solution method, comprises the initial aqueous solution and reactant aqueous solution are provided, and one of at least comprises at least a precursor metal salts in the two, and aqueous slkali.
Nanostructured powders can wear out or heat treatment a period of time effectively all or part of crystal nanometer powder is changed into the crystalline state of expection.This process is used for the stabilized nanoscale crystal structure.Influence the form of manocrystalline powders product and the technological parameter of productive rate and comprise heating-up temperature, heating time and pH value of solution.
After the aging and heat treatment, nano-crystalline granule usually by isolated by filtration and washing to remove accessory substance, preferably use deionized water, distilled water or other suitable solvents.
Current-collector is well known in the art.They can comprise any electric conducting material that has electrochemical stability in the ultracapacitor environment.The example of this material includes but not limited to metal forming, wire netting, conducting polymer, conducting polymer composite material and expanding metal (expanded metal).As required, current-collector can be porous or non-porous.The thickness of current-collector must be enough to electric current collection is provided equably and enough rate capabilities (promptly keeping current capability) are provided for the active material in all electrodes.Current-collector have usually about 10 microns to about 75 microns thickness.
Active material can put on current-collector by any methods known in the art.A kind of such method is known as coating.Active material mixes with adhesive to form slurry and puts on current-collector then.The example of adhesive includes but not limited to PVDF and fibrillation PTFE.If adhesive is a solid, then it at first is dissolved in follow-up then current-collector, the evaporating solvent of being applied to of suitable solvent.Active material is depended in the selection of adhesive, and choice of Solvent depends on the selection of adhesive.Those skilled in the art can easily determine adhesive and choice of Solvent and not need excessive experiment.
Electrode can form by thermal spraying on current-collector.Plasma spray technology is at U.S. Patent application No.09/485, and 424 is U.S. Patent No. 5,599, and open in 644, it incorporates this paper by reference into.At this preparation of nanostructure thermal spray feedstock is described.Use strong ultrasonic probe that the suspended substance of nano-crystalline granule is carried out ultrasonic Treatment.Ultrasonic Treatment makes that all powder aggregation is cracked and introduce lattice defect to nano-crystalline granule.For example, when as the active material in the nickel electrode, these defectives can apply material impact to the performance of nickel hydroxide.The parameter that influences final products comprises ultrasonic power and processing time.
The final step of thermal spray feedstock preparation generally is a spray drying through the nanoparticle suspension of sonicated to produce nanoporous globular powder agglomerate.This method produces the agglomerate of nano-structured particles, and wherein the diameter of agglomerate is about 0.1～200 micron, and preferred 1～100 micron, most preferably from about 20 microns.In spray-drying process, rapid evaporation takes place to produce saturated steam blanket when spray droplets contact hot-air steam.Continuous evaporation depends on the diffusion rate through the moisture of surperficial shell.When the thickness of shell increased in time, evaporation rate is corresponding to be reduced.Because evaporation is an endothermic process, even gas stream can be quite warm, but the drop surface also keeps cooling to finish until evaporation.Use the aerosol spray drying to guarantee the phase that the end product powder is not expected, and when heating more than 200 ℃, may produce these phases.Relevant technological parameter comprises the precursor transmission speed, entrance and exit gas temperature and suspended substance concentration.
Useful anodal thickness is about 10 microns to about 250 microns.Preferred anodal thickness is less than about 50 microns.
The example of suitable negative pole carbon active material includes but not limited to carbon such as graphite, as U.S. Patent No. 6,031, disclosed functionalization carbon such as gnf and nanotube in 711 (incorporating this paper by reference into), carbon composite is as carbon that is coated with metal and metal oxide such as ruthenium-oxide and the combination that contains at least a above-mentioned active material.Be particle on the active material properties, the averaged particles radius is less than about 100 microns.Can comprise fiber at this term " particle ".Fiber can be loose (dispersing) fiber or nonwoven mat or woven cloths form.And the two-dimentional sheet that contains carbonized polymers within the scope of the invention.Useful fibre diameter is less than about 10 microns.Nano-fiber material is a diameter less than the fiber of 100nm owing to its high surface can be used in the electrode.Fibre diameter less than the nanofiber carbon of about 50nm since its more high surface be considered to more suitable.
When the active material of negative pole contained bulk particulate material, it can put on the optional current-collector by any known method in this area (comprising coating (as mentioned above) and casting).In casting, will have in the slurry casting film of active material of optional adhesive.The film of gained is applied to current-collector, preferably uses adhesive.If active material is the form of nonwoven mat, woven cloths or two-dimentional sheet, active material can put on the current-collector in the ultracapacitor or closely contact with current-collector simply.If active material is the form that can support oneself, then it can be used for the dual purpose of active material and current-collector.The carbon active material must be through overactivation, and activation can realize by any known method in this area.The gained electrode is a porous, and porosity is usually greater than about 80%.Porosity is even more important when using liquid electrolyte, more closely contacts between active material and the electrolyte because hole makes.In addition, can come electrode coated with collecting (current collection) coating in the current-collector side to improve electric current collection.The selection of coating is decided by the stability of coating under the condition of ultracapacitor, especially about electrolyte corrosion.For example, when being electrolyte, uses in potassium hydroxide nickel coating usually, because nickel is not subjected to the influence of potassium hydroxide relatively.Useful thickness of electrode is about 50 microns to about 375 microns.
Electrolyte can be solid or liquid.Suitable solid electrolyte example includes but not limited to the isopolyacid and the different polyacid of open (incorporating this paper by reference into) in polyacid such as the U.S. Patent No. 5,986,878.Liquid electrolyte can be a water-based or nonaqueous.Before the electrochemical decomposition that water takes place, aqueous electrolyte can only keep being up to the current potential of about 1～2V in device.This can be by arranging single capacitors in series or by using nonaqueous electrolyte to overcome, and nonaqueous electrolyte can bear the current potential that applies up to～3V.But suitable nonaqueous electrolyte is the organic or nonaqueous solvents that contains the ion on intercalation electrode surface.Ion can be anion or cation, depends on the active material of electrode.
Other non-water or organic bath also are fit to, if satisfy following standard: the current potential (" puncture voltage ") that (1) electrolyte applies when decomposing is 1V～10V, (2) electrolytical conductivity is enough high to promote the swift electron between the electrode to shift, be preferably 0.1～1000, preferred 0.1～500 milli Siemens/cm and (3) electrolyte chelated mineral or the ability that metal is extracted from film surface are low or do not have.Electrolyte should or remove less than 5% with preferably less than 1% metal from the film chelated surface.
Suitable aqueous electrolyte comprises the aqueous solution of alkali metal hydroxide, alkali carbonate, alkali halide, alkali nitrates, sulfuric acid, or its mixture.Thereby electrolytical selection minimizes equivalent series resistance (ESR) with the composition of matched electrodes.Need not excessive experiment, those skilled in the art can make these decisions.Electrolytical amount is by the size decision of capacitor.Electrolytical concentration is to realize the concentration of maximum ion conductivity under the working temperature of capacitor.Usually aqueous electrolyte concentration is generally about 25wt% to about 45wt%.
Dividing plate comprises thin non-conductive porous material.It can be by anyly not being subjected to the condition of ultracapacitor, promptly being exposed to electric charge and the electrolytical material that influences is formed.Porosity is generally about 40% to about 87%.Preferred porosity is about 65% to about 85%.Thickness is generally about 25 microns to about 75 microns.Preferred separator is the CELGARD that Hoechst Celanese Corp company sells
TM3501.
Asymmetric ultracapacitor can be assembled with all methods known in the art by said modules.When electrolyte is liquid, must soak (" wetting ") electrode material before the electrode construction or after the electrode construction.Can be before electrode make up, electrode makes up afterwards or the moulding (activation) of electrode material is carried out in the ultracapacitor assembling afterwards.When electrolyte was solid, it was set to adjacent with electrode.Electrode, electrolyte and current-collector (if existence) constitute half-cell.A half-cell is put on dividing plate make two half-cell pairings and sealing then, preferably by heating.
In order to make the electrochemistry coupling is anodal and negative pole acquisition high-energy-density, an electrode, and the positive pole in present case must have the hypopolarization degree; Electrode potential changes very little with respect to its reversible potential during electric current passes through.In addition, non-Faraday process must minimize, and faraday's process (electron transfer) is passed electrode surface with high reaction rate and taken place.Should have high degree of polarization performance and under ideal conditions to electrode (negative pole), in charge and discharge process, should obtain the potential change of big window.The charge storage of polarizable electrode is through double-deck separation of charge.Be the explanation this point, the potential change that takes place at each electrode in the charge and discharge process is schematically shown in Figure 1.As can be seen, when charging, asymmetric ultracapacitor forms big voltage window.For the electrolytical asymmetric unit of the property of water-bearing, potential window can limit by discharging at electrode place hydrogen and oxygen.Current potential with electrode of hypopolarization degree all keeps constant substantially in charge and discharge process.
Be not bound by theory, the general mechanism of expection asymmetric capacitor is similar to its water-based analog, faraday's process occurs and the double-deck charging at the carbon electrode place at the manganese electrode.This illustrates in Fig. 2, and the ion that is presented in the charge and discharge process of the asymmetric ultracapacitor that contains manganese and carbon among the water-based KOH moves.In charging process, come the proton of self poling manganese electrode to be released and to move to electrolyte (deprotonation) electric double layer that formation is made of hydration K ion on carbon electrode simultaneously.This process is oppositely running in discharge process.
Fig. 3 is the schematic diagram of ultracapacitor.The 1st, be used for anodal active material, the 2nd, be used for the active material of negative pole, the 3rd, dividing plate and 4 is current-collectors.
Although material with carbon element is low cost and the chemically stable material that is used for negative pole, can use other active materials to replenish or alternative carbon-based material.The example of other active cathode material comprises and comprises the negative pole that is selected from following at least a material: carbon active material, Zn, Al, Mg, Ca, Cr, La, V, Ti, Li, Na; Formula MO
xMetal oxide, wherein 0＜x＜3 and M are be selected from Ti, V, Nb, Cr, Mo, W, Mn, Fe, Co, Ni, Pd, Pt, Cu and Ag at least a; Formula MS
xSulfide, wherein x is 1～10, M is be selected from Co, Ni, Fe, Cu, Ag, Mo and W at least a; Li
xMoO
(6-x)/2Wherein x and y are greater than 0 and less than 1; And conducting polymer.The example of other active materials includes but not limited to: conducting polymer, metal, metal oxide, metal nitride, other metal sulfides and comprise at least a combination of above-mentioned active material.The example of suitable conducting polymer includes but not limited to polyacetylene, polypyrrole, polyaniline, polythiophene and contains at least a combination of above-mentioned polymer.This conducting polymer also can be used in the anodal current-collector.The example of suitable metal includes but not limited to manganese, iron, zinc, cobalt, nickel, copper, zinc, ruthenium, iridium, palladium, silver, platinum and comprises at least a combination of above-mentioned metal.The example of suitable metal oxide includes but not limited to ruthenium-oxide, yttrium oxide, cupric oxide, nickel oxide, indium oxide, tin oxide and comprises at least a combination of above-mentioned metal oxide.The example of suitable metal nitride includes but not limited to titanium nitride, vanadium nitride and comprises at least a combination of above-mentioned metal nitride.The example of suitable metal sulfide includes but not limited to ferrous disulfide, cobalt sulfide, nickel sulfide, silver sulfide and comprises at least a combination of above-mentioned metal sulfide.
Asymmetric therein ultracapacitor comprises in the embodiment of electrolyte aqueous solution, except the aqueous solution of alkali metal hydroxide and carbonate, electrolytical example also includes but not limited to the aqueous solution of alkali metal chloride, the aqueous solution of alkaline metal iodide, the aqueous solution of alkali metal bromide, the aqueous solution of alkali metal sulfates, the aqueous solution of alkali nitrates, and at least a combination that comprises the above-mentioned aqueous solution.
Asymmetric therein ultracapacitor comprises that in the embodiment of nonaqueous ionic conducting electrolyte, electrolytical example includes but not limited to contain the inorganic solution of solvent and salt, contains the organic solution of solvent and salt, perhaps contains the combination of at least a above-mentioned solution.Inorganic solution can be selected from SOCl
2, SO
2, NH
3With at least a combination that comprises above-mentioned solvent.The salt of inorganic solution can be selected from LiAlCl
3, LiAlF
3, LiPF
6, LiBF
4, [N (CH
3CH
2)
4] BF
4, two (trifyl) acid imide and comprise at least a combination of above-mentioned salt.Organic solvent can be selected from ethylene carbonate (PC), propylene carbonate (EC), butylene carbonate (BC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylene methyl esters (EMC), carbonic acid first propyl ester (MPC), acetonitrile (CH
3CN) and comprise at least a combination of above-mentioned solvent.The salt of organic solution can be selected from LiAlCl
3, LiAlF
3, LiPF
6, LiBF
4, [N (CH
3CH
2)
4] BF
4, two (trifyl) acid imide and comprise at least a combination of above-mentioned salt.
Asymmetric therein ultracapacitor comprises in the embodiment of solid electrolyte that solid electrolyte can be a polymer.The example of the polymer that is fit to includes but not limited to poly(ethylene oxide), polyacrylate, polystyrene and comprises at least a combination of above-mentioned polymer.The example of the polymer that other are fit to includes but not limited to proton exchange membrane and anion-exchange membrane.
The present invention also describes by following non-limiting example.
Embodiment:
Layered double-hydroxide (LDH) active material is by at constant pH (8-10) down co-precipitation and interpolation/hybrid metal nitrate and aqueous slkali (NaOH+Na simultaneously
2CO
3) and prepare.Products therefrom aging and crystallization in synthetic solvent is spent the night (75 ℃) then, separates by centrifugal/sedimentation then and washs to there not being Na
+Drying material is also used mortar and the grinding rod grinding.Prepare a series of stratiform double-hydroxide compounds, see Table 1.
Table 1
[Co
0.36Ni
0.24Al
0.4(OH)
2] (CO
3)
0.2Sample is mixed and made into electrode by multi-walled carbon nano-tubes (MWNT) and the 3 weight %PTFE (Dupont type 6C) with 20 weight %.Material is with mortar and grinding rod mixing and be rolled into sheet.Make the electrode of 12mm diameter by this sheet punching press, and be pressed on the nickel wire net current-collector.With cyclic voltammetry (CV) half-cell that the double-hydroxide of preparation like this carries out in various electrolyte (6M KOH, 4M LiOH) is measured.Carbon-point and saturated calomel electrode (SCE) are used separately as electrode and reference electrode.The CV experimental result is illustrated among Fig. 4.In air at 160 ℃ of following heat treated [Co after 5 hours
0.36Ni
0.24Al
0.4(OH)
2] (CO
3)
0.2A series of cyclic voltammetry curves in different electrolyte are illustrated among Fig. 5.Fig. 6 illustrates the [Co among the 6M KOH
0.4Ni
0.29Al
0.31(OH)
2] (CO
3)
0.155Constant current under different discharge rates discharges and recharges performance.Layered double-hydroxide mixes with 2.5 weight %PTFE (Dupont 6C) and 19.5 weight % graphite (Lonza KS6).The fake capacitance of LDH passes through H
+Inject/go out and (be similar to Ni (OH)
2-NiOOH redox couple) lattice and obtaining.It should be noted that owing to the high proton mobility, LDH shows the two-forty performance.
Use LDH to assemble as electrolyte with 4.8M KOH for anodal and active carbon asymmetric capacitor as negative pole.Positive pole contains [Co
0.36Ni
0.24Al
0.4(OH)
2] (CO
3)
0.2With 20 weight % carbon blacks and 3 weight %PTFE (Dupont 6C).The impedance spectrogram of the asymmetric capacitor device of assembling respectively with the form of Nyquist and Bode magnitude figure shown in Fig. 7 a and the 7b.Device illustrates the typical capacitance characteristic of expection.
Fig. 4 illustrates the layered double-hydroxide (LDH) of above-mentioned preparation, [Co
0.36Ni
0.24Al
0.4(OH)
2] (CO
3)
0.2Representative cyclic voltammetry curve in containing different cationic water-based KOH electrolyte.The LDH material mixes with 20 weight %MWNT and 3 weight %PTFE.Sweep speed is 1mV/s.SCE is as reference electrode.For every kind of electrolyte, LDH shows oxidation and reduction wave, is similar to the faraday who finds in the general active anode compartment material used in the secondary cell and discharges and recharges.LDH is presented at the maximum faraday's electric capacity (maximum area of oxidation and reduction peak in the cyclic voltammetric) in the KOH electrolyte.The electric capacity of other dielectrics LiOH and NaOH acquisition similar (but being lower than KOH).The dielectric invertibity that discharges and recharges of LiOH is the highest.That is, oxidation shows that with reduction wave or peak minimum Δ E separates.
Fig. 5 is illustrated in the air under 160C heat treated layered double-hydroxide (LDH) after 5 hours, [Co
0.36Ni
0.24Al
0.4(OH)
2] (CO
3)
0.2Representative cyclic voltammetry curve in containing different cationic water-based KOH electrolyte.The LDH material mixes with 20 weight %MWNT and 3 weight %PTFE.Sweep speed is 1mV/s.SCE is as reference electrode.As the LDH material (Fig. 4) of above-mentioned preparation, this LDH material shows oxidation and reduction wave, is similar to the faraday who finds in the general active anode compartment material used in the secondary cell and discharges and recharges.Heat treated LDH is presented at the maximum faraday's electric capacity in the KOH electrolyte, is NaOH and LiOH then, and LiOH shows the minimum capacitance (or the area under the volt-ampere curve).The electric capacity of heat treated LDH among the KOH is lower than the electric capacity of preparation as mentioned above identical among Fig. 4 (nonheat-treated material).The shape of the oxidation wave of heat treated LDH is compared also with the LDH (Fig. 4) for preparing as mentioned above and is changed, and the oxygen overvoltage (or analysing oxygen starting voltage E) after the expression heat treatment changes.
Fig. 6 illustrates the [Co of preparation as mentioned above
0.4Ni
0.29Al
0.31(OH)
2] (CO
3)
0.155LDH (not heat treatment).Prepare electrode by mixing LDH material and 19.5 weight %KS-6 and 2.5 weight %PTFE.Electrolyte is 6M KOH.SCE is as reference electrode.In all situations, the LDH electrode is with same current charging (397mA/g).Electrode is with 4 different current discharges (397,595,794 and 992mA/g) then.All just come in the LDH active material of every gram than electric current.The discharge capacity of electrode (mAh/g) measures and is converted to F/g after each discharge rate.Usually, that as was expected to cell type faraday material is similar for discharge voltage profile.When the discharging current increase, also as expectedly reduce the discharge time of electrode (or capacity).Usually, LDH demonstrates considerable two-forty performance and is attributable to H
+Inject/go out the high proton mobility of lattice, be similar to Ni (OH)
2-NiOOH redox couple.The voltage drop of LDH (IR) is also high relatively, at about 80mV, may be the poor conductivity owing to the LDH material for preparing as mentioned above.In all situations (discharge rate), LDH shows the fake capacitance that surpasses 1000F/g.It should be noted that except used minimum discharge rate (397mA/g), charge rate (gained charging coulomb is charging current X charging interval (500s)) is less than discharge rate.In these situations, LDH still shows fabulous discharge capacity.
Fig. 7 a shows the complex plane impedance behavior of asymmetric LDH/KOH/ active carbon capacitor.LDH be not heat treated as mentioned above the preparation [Co
0.4Ni
0.29Al
0.31(OH)
2] (CO
3)
0.155By being mixed with 20 weight % carbon blacks and 3 weight %PTFE, this material prepares the LDH positive pole.Negative pole is commercially available active carbon, contains the LDH positive pole of 2 times of effective masses.Electrolyte is 4.8M KOH.The asymmetric capacitor charging also remains on each constant voltage 0.5,0.75,1.0 and 1.1V.Under each specific voltage, after the asymmetric capacitor charging, obtain and the anti-resistance of record spectrogram.Asymmetric capacitor is also tested under 0V or full discharge scenario.Impedance spectrum to each voltage conditions gained is shown.Usually, the complex plane impedance shows the double-deck charge storage of expection with typical case's diffusion and charging saturation region.Data show, when asymmetric capacitor was charged to more high voltage, the ESR of device (equivalent series resistance) also as corresponding raising expectedly.The maximum ESR of this device is about 120 milliohms.
Fig. 7 b illustrates the anti-resistance of corresponding Bode magnitude of the data that obtained among Fig. 7 a.Equally, these data obtain from asymmetric LDH/KOH/ active carbon capacitor.As was expected, and the Bode magnitude demonstrates typical double layer electric capacity behavioral trait under each charging voltage.
By foregoing description and example as can be known, described herein asymmetric ultracapacitor shows energy and the power density of improving compared to symmetrical ultracapacitor.In addition, asymmetric ultracapacitor provides the energy and the power density of improvement with the cost effective and efficient manner.
Though illustrated and described preferred embodiment, can carry out various modifications and alternative to it, and not deviate from the spirit and scope of the present invention.Therefore, it should be understood that description of the invention is an illustrative and nonrestrictive.
As used herein, the noun that countless measure word limit comprises the implication of odd number and plural number, unless clearly demonstrate in addition in the literary composition.What it should also be clear that is that term " comprises " and/or " comprising " when being used for this specification, refer in particular to and have described characteristic, integral body, step, operation, element and/or composition, but do not get rid of the existence of one or more other characteristics, integral body, step, operation, element, composition and/or its combination or replenish.
Claims (24)
1. asymmetric ultracapacitor comprises:
The positive pole that comprises the current-collector and first active material, described first active material is selected from following material: formula [M
2+ 1-xN
x 3+(OH)
2] A
N- X/nMH
2The layered double-hydroxide of O, wherein M
2+Be at least a divalent metal, N
3+Be at least a trivalent metal and/or nonmetal, A is that electric charge is the anion of n-, and wherein x and y are greater than 0 and less than 1, and n is 1,2,3 or 4; LiCoO
2LiCo
xNi
yO
2LiCo
xNi
yMn
(1-x-y)O
2, wherein x and y are greater than 0 and less than 1; Formula MS
xSulfide, wherein x is 1～10, M is selected from least a among Co, Ni, Fe, Cu, Ag, Mo and the W; Li
xCo
y(PO
4)
zAnd Li
xNi
y(PO
4)
z, wherein x, y and z are greater than 0 and less than 1; Active carbon and graphite, and the combination that comprises at least a aforementioned active material;
Negative pole comprises being selected from following at least a material: carbon active material, Zn, Al, Mg, Ca, Cr, La, V, Ti, Li, Na; Formula MO
xMetal oxide, 0＜x＜3 wherein, M is selected from least a among Ti, V, Nb, Cr, Mo, W, Mn, Fe, Co, Ni, Pd, Pt, Cu and the Ag; Formula MS
xSulfide, wherein x is 1～10, M is selected from least a among Co, Ni, Fe, Cu, Ag, Mo and the W; Li
xMoO
(6-x)/2Wherein x and y are greater than 0 and less than 1; And conducting polymer;
Solid electrolyte, or the nonaqueous ionic conducting electrolyte solution of saliferous and non-aqueous solution, or be selected from following electrolyte aqueous solution: the aqueous solution of the aqueous solution of alkali metal hydroxide aqueous solution, alkali carbonate, the aqueous solution of alkali metal chloride, alkali metal bromide, the aqueous solution of alkaline metal iodide, the aqueous solution of alkali metal sulfates, the aqueous solution of alkali nitrates, and the combination that comprises at least a above-mentioned aqueous solution; With
Dividing plate.
2. the described asymmetric ultracapacitor of claim 1, wherein said negative pole also comprises another current-collector and second active material, the combination that described second active material is selected from conducting polymer, metal, metal oxide, metal nitride, metal sulfide and comprises at least a above-mentioned active material.
3. the described asymmetric ultracapacitor of claim 2, wherein said another current-collector is selected from metal forming, wire netting, conducting polymer composite material and expanding metal.
4. the described asymmetric ultracapacitor of claim 1, wherein said asymmetric ultracapacitor contains the carbon active material, and described carbon active material comprises nano-fiber material, carbon nano-tube, graphite material and the combination that comprises at least a above-mentioned material.
5. the described asymmetric ultracapacitor of claim 4, wherein said carbon active material comprises that diameter is less than about 10 microns discrete carbon fiber.
6. the described asymmetric ultracapacitor of claim 5, wherein said carbon active material comprises the carbon fiber of diameter less than about 100nm.
7. the described asymmetric ultracapacitor of claim 1, wherein said negative pole have about 50 microns to about 375 microns thickness.
8. the described asymmetric ultracapacitor of claim 4, wherein said carbon active material is nonwoven mat, woven cloths or the two-dimentional sheet that comprises carbonized polymers.
9. the described asymmetric ultracapacitor of claim 1, wherein said negative pole also comprises the collection coating.
10. the described asymmetric ultracapacitor of claim 1, wherein said first active material is a nanostructure.
11. the described asymmetric ultracapacitor of claim 1, wherein said positive pole also comprises adhesive.
12. the described asymmetric ultracapacitor of claim 1, wherein said current-collector is selected from metal forming, wire netting, conducting polymer composite material and expanding metal.
13. the described asymmetric ultracapacitor of claim 1, the thickness of wherein said positive pole is less than about 250 microns.
14. the described asymmetric ultracapacitor of claim 2, wherein said another current-collector comprises conducting polymer, and described conducting polymer is selected from polyacetylene, polypyrrole, polyaniline, polythiophene and comprises the combination of at least a above-mentioned polymer.
15. the described asymmetric ultracapacitor of claim 2, wherein said conducting polymer are selected from polyacetylene, polypyrrole, polyaniline, polythiophene and comprise the combination of at least a above-mentioned polymer.
16. the described asymmetric ultracapacitor of claim 2, the metal of wherein said negative pole are selected from manganese, iron, zinc, cobalt, nickel, copper, zinc, ruthenium, iridium, palladium, silver, platinum and comprise the combination of at least a above-mentioned metal.
17. the described asymmetric ultracapacitor of claim 2, the metal oxide of wherein said negative pole are selected from ruthenium-oxide, yttrium oxide, cupric oxide, nickel oxide, indium oxide, tin oxide and comprise the combination of at least a above-mentioned metal oxide.
18. the described asymmetric ultracapacitor of claim 2, the metal nitride of wherein said negative pole is selected from titanium nitride, vanadium nitride and comprises the combination of at least a above-mentioned metal nitride, and the metal sulfide of wherein said negative pole is selected from ferrous disulfide, cobalt sulfide, nickel sulfide, silver sulfide and comprises the combination of at least a above-mentioned metal sulfide.
19. the described asymmetric ultracapacitor of claim 1, wherein said nonaqueous ionic conducting electrolyte solution comprises solvent and salt, and wherein said solvent is selected from SOCl
2, SO
2, NH
3With the combination that comprises at least a above-mentioned solvent, wherein said salt is selected from LiAlCl
3, LiAlF
3, LiPF
6, LiBF
4, [N (CH
3CH
2)
4] BF
4, two (trifyl) acid imide and comprise the combination of at least a above-mentioned salt.
20. the described asymmetric ultracapacitor of claim 1, wherein said nonaqueous ionic conducting electrolyte solution comprises solvent and salt, and wherein said solvent is selected from PC, EC, BC, DMC, DEC, EMC, MPC, CH
3CN and the combination that comprises at least a above-mentioned solvent, wherein said salt is selected from LiAlCl
3, LiAlF
3, LiPF
6, LiBF
4, [N (CH
3CH
2)
4] BF
4, two (trifyl) acid imide and comprise the combination of at least a above-mentioned salt.
21. the described asymmetric ultracapacitor of claim 1, wherein said solid electrolyte are the combination of polymers that is selected from poly(ethylene oxide), polyacrylate, polystyrene and comprises at least a above-mentioned polymer.
22. the described asymmetric ultracapacitor of claim 21, wherein said solid electrolyte is a proton exchange membrane.
23. the described asymmetric ultracapacitor of claim 21, wherein said solid electrolyte is an anion-exchange membrane.
24. the described asymmetric ultracapacitor of claim 1, wherein said divalent metal M
2+Be to be selected from Co
2+, Mg
2+, Mn
2+, Fe
2+, Co
2+, Ni
2+, Cu
2+And Zn
2+In at least a, wherein said trivalent metal N
3+Be to be selected from Al
3+, B
3+, Mn
3+, Fe
3+, Co
3+, Ni
3+, Cr
3+, Ga
3+, Y
3+, La
3+, Ce
3+And Ti
3+In at least a.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US12/511,568 | 2009-07-29 | ||
| US12/511,568 US8107223B2 (en) | 1999-06-11 | 2009-07-29 | Asymmetric electrochemical supercapacitor and method of manufacture thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101989499A true CN101989499A (en) | 2011-03-23 |
Family
ID=43745988
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010102438883A Pending CN101989499A (en) | 2009-07-29 | 2010-07-29 | Asymmetric electrochemical supercapacitor and method of manufacture thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101989499A (en) |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102800493A (en) * | 2012-08-18 | 2012-11-28 | 中北大学 | Micro-capacitor with asymmetric 3D structure and producing method thereof |
| CN103384905A (en) * | 2010-08-11 | 2013-11-06 | 诺丁汉大学 | Charge storage device and method of manufacturing it |
| CN103474250A (en) * | 2012-06-08 | 2013-12-25 | 海洋王照明科技股份有限公司 | Super capacitor and manufacturing method thereof |
| CN104299797A (en) * | 2014-11-06 | 2015-01-21 | 中南大学 | Aqueous asymmetric supercapacitor based on NiCo2S4 and its composites |
| CN105097295A (en) * | 2015-07-23 | 2015-11-25 | 武汉理工大学 | High-performance miniature supercapacitor and fabrication method thereof |
| CN105399145A (en) * | 2014-08-18 | 2016-03-16 | 中国科学院理化技术研究所 | Trivalent nickel doped nickel-based hydrotalcite nanosheet, preparation method thereof and application thereof in supercapacitor |
| CN105810445A (en) * | 2015-10-29 | 2016-07-27 | 钰邦电子（无锡）有限公司 | High-energy-storage capacitive unit |
| WO2018072457A1 (en) * | 2016-10-21 | 2018-04-26 | 北京化工大学 | Method for preparing multi-ion embedded supercapacitor with electrochemical alkaline activation |
| CN109065368A (en) * | 2018-09-04 | 2018-12-21 | 北京邮电大学 | The flexible super capacitor and preparation method thereof of the heterogeneous nano-chip arrays structure of nickel sulfide-molybdenum sulfide based on carbon cloth load |
| CN110078130A (en) * | 2019-05-19 | 2019-08-02 | 东北电力大学 | A kind of preparation method of hollow structure Fe-base compound and its application as super capacitor anode material |
| CN110476213A (en) * | 2016-09-29 | 2019-11-19 | 巴黎科技与文学-拉丁区 | Improvement supercapacitor containing electrolyte |
| CN110818035A (en) * | 2019-12-16 | 2020-02-21 | 嘉兴市众盛环保科技有限公司 | TiN/activated carbon three-dimensional particle electrode and preparation method thereof |
| CN110853928A (en) * | 2018-12-29 | 2020-02-28 | 熵零技术逻辑工程院集团股份有限公司 | Capacitor implementation method and capacitor thereof |
| CN111137928A (en) * | 2019-11-18 | 2020-05-12 | 江汉大学 | A kind of preparation method of two-dimensional carbon nanosheet supported metal nickel sulfide electrode material |
| CN111584243A (en) * | 2020-04-30 | 2020-08-25 | 璧靛悍 | A kind of Mn3O4-carbon nanotube-polyaniline supercapacitor material and preparation method thereof |
| CN111883370A (en) * | 2020-07-21 | 2020-11-03 | 南京邮电大学 | Asymmetric printed super capacitor and preparation method thereof |
| CN112400243A (en) * | 2018-07-13 | 2021-02-23 | 弗朗索瓦·吉尼恩 | Double-layer hydroxide (DLH) type compounds and their use in electrodes for energy storage devices with graphite and resin composites and electrolytes |
| CN112563040A (en) * | 2020-12-10 | 2021-03-26 | 西安交通大学 | Ceramic double electric layer capacitor and preparation method thereof |
| CN114784358A (en) * | 2016-03-23 | 2022-07-22 | 加利福尼亚大学董事会 | Apparatus and method for high voltage and solar energy applications |
| CN116313543A (en) * | 2018-04-17 | 2023-06-23 | 艾尼股份公司 | Energy storage device for high temperature applications |
| US12153032B2 (en) | 2011-12-21 | 2024-11-26 | The Regents Of The University Of California | Interconnected corrugated carbon-based network |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1941238A (en) * | 2005-09-26 | 2007-04-04 | 日清纺织株式会社 | Electric double layer capacitor |
| CN101017736A (en) * | 2007-03-07 | 2007-08-15 | 中南大学 | A polyaniline/carbon mixed super capacitor |
| CN101088132A (en) * | 2004-12-21 | 2007-12-12 | 帝人株式会社 | Electric double layer capacitor |
| CN101165827A (en) * | 2007-08-29 | 2008-04-23 | 李青海 | Mixed electrochemical capacitor and its manufacture method |
| JP2008300667A (en) * | 2007-05-31 | 2008-12-11 | Fuji Heavy Ind Ltd | Power storage device |
-
2010
- 2010-07-29 CN CN2010102438883A patent/CN101989499A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101088132A (en) * | 2004-12-21 | 2007-12-12 | 帝人株式会社 | Electric double layer capacitor |
| CN1941238A (en) * | 2005-09-26 | 2007-04-04 | 日清纺织株式会社 | Electric double layer capacitor |
| CN101017736A (en) * | 2007-03-07 | 2007-08-15 | 中南大学 | A polyaniline/carbon mixed super capacitor |
| JP2008300667A (en) * | 2007-05-31 | 2008-12-11 | Fuji Heavy Ind Ltd | Power storage device |
| CN101165827A (en) * | 2007-08-29 | 2008-04-23 | 李青海 | Mixed electrochemical capacitor and its manufacture method |
Non-Patent Citations (2)
| Title |
|---|
| 王庆伟: "凝胶电解质的研究进展", 《化学进展》 * |
| 肖超: "超级电容器电极材料的研究进展", 《绝缘材料》 * |
Cited By (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103384905B (en) * | 2010-08-11 | 2017-03-22 | 诺丁汉大学 | Charge storage device and method of manufacturing it |
| CN103384905A (en) * | 2010-08-11 | 2013-11-06 | 诺丁汉大学 | Charge storage device and method of manufacturing it |
| US12153032B2 (en) | 2011-12-21 | 2024-11-26 | The Regents Of The University Of California | Interconnected corrugated carbon-based network |
| CN103474250A (en) * | 2012-06-08 | 2013-12-25 | 海洋王照明科技股份有限公司 | Super capacitor and manufacturing method thereof |
| CN102800493B (en) * | 2012-08-18 | 2015-04-08 | 中北大学 | Micro-capacitor with asymmetric 3D structure and producing method thereof |
| CN102800493A (en) * | 2012-08-18 | 2012-11-28 | 中北大学 | Micro-capacitor with asymmetric 3D structure and producing method thereof |
| CN105399145B (en) * | 2014-08-18 | 2017-11-28 | 中国科学院理化技术研究所 | Trivalent nickel doped nickel-based hydrotalcite nanosheet, preparation method thereof and application thereof in supercapacitor |
| CN105399145A (en) * | 2014-08-18 | 2016-03-16 | 中国科学院理化技术研究所 | Trivalent nickel doped nickel-based hydrotalcite nanosheet, preparation method thereof and application thereof in supercapacitor |
| CN104299797B (en) * | 2014-11-06 | 2017-10-17 | 中南大学 | One kind is based on NiCo2S4And its water system asymmetrical type ultracapacitor of composite |
| CN104299797A (en) * | 2014-11-06 | 2015-01-21 | 中南大学 | Aqueous asymmetric supercapacitor based on NiCo2S4 and its composites |
| CN105097295B (en) * | 2015-07-23 | 2017-10-24 | 武汉理工大学 | A kind of high-performance micro ultracapacitor and preparation method thereof |
| CN105097295A (en) * | 2015-07-23 | 2015-11-25 | 武汉理工大学 | High-performance miniature supercapacitor and fabrication method thereof |
| CN105810445A (en) * | 2015-10-29 | 2016-07-27 | 钰邦电子（无锡）有限公司 | High-energy-storage capacitive unit |
| CN114784358A (en) * | 2016-03-23 | 2022-07-22 | 加利福尼亚大学董事会 | Apparatus and method for high voltage and solar energy applications |
| CN110476213A (en) * | 2016-09-29 | 2019-11-19 | 巴黎科技与文学-拉丁区 | Improvement supercapacitor containing electrolyte |
| CN110476213B (en) * | 2016-09-29 | 2023-06-13 | 巴黎科学与文学基金会 | Improved supercapacitor with electrolyte |
| WO2018072457A1 (en) * | 2016-10-21 | 2018-04-26 | 北京化工大学 | Method for preparing multi-ion embedded supercapacitor with electrochemical alkaline activation |
| CN116313543A (en) * | 2018-04-17 | 2023-06-23 | 艾尼股份公司 | Energy storage device for high temperature applications |
| CN112400243A (en) * | 2018-07-13 | 2021-02-23 | 弗朗索瓦·吉尼恩 | Double-layer hydroxide (DLH) type compounds and their use in electrodes for energy storage devices with graphite and resin composites and electrolytes |
| CN109065368A (en) * | 2018-09-04 | 2018-12-21 | 北京邮电大学 | The flexible super capacitor and preparation method thereof of the heterogeneous nano-chip arrays structure of nickel sulfide-molybdenum sulfide based on carbon cloth load |
| CN110853928A (en) * | 2018-12-29 | 2020-02-28 | 熵零技术逻辑工程院集团股份有限公司 | Capacitor implementation method and capacitor thereof |
| CN110078130B (en) * | 2019-05-19 | 2021-11-26 | 东北电力大学 | Preparation method of hollow-structure iron-based compound and application of hollow-structure iron-based compound as cathode material of supercapacitor |
| CN110078130A (en) * | 2019-05-19 | 2019-08-02 | 东北电力大学 | A kind of preparation method of hollow structure Fe-base compound and its application as super capacitor anode material |
| CN111137928A (en) * | 2019-11-18 | 2020-05-12 | 江汉大学 | A kind of preparation method of two-dimensional carbon nanosheet supported metal nickel sulfide electrode material |
| CN110818035A (en) * | 2019-12-16 | 2020-02-21 | 嘉兴市众盛环保科技有限公司 | TiN/activated carbon three-dimensional particle electrode and preparation method thereof |
| CN111584243A (en) * | 2020-04-30 | 2020-08-25 | 璧靛悍 | A kind of Mn3O4-carbon nanotube-polyaniline supercapacitor material and preparation method thereof |
| CN111584243B (en) * | 2020-04-30 | 2021-12-17 | 郭米娟 | Mn (manganese)3O4-carbon nano tube-polyaniline super capacitor material and preparation method thereof |
| CN111883370A (en) * | 2020-07-21 | 2020-11-03 | 南京邮电大学 | Asymmetric printed super capacitor and preparation method thereof |
| CN112563040A (en) * | 2020-12-10 | 2021-03-26 | 西安交通大学 | Ceramic double electric layer capacitor and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8107223B2 (en) | Asymmetric electrochemical supercapacitor and method of manufacture thereof | |
| CN101989499A (en) | Asymmetric electrochemical supercapacitor and method of manufacture thereof | |
| US7576971B2 (en) | Asymmetric electrochemical supercapacitor and method of manufacture thereof | |
| Zhang et al. | Self-assembling hierarchical NiCo2O4/MnO2 nanosheets and MoO3/PPy core-shell heterostructured nanobelts for supercapacitor | |
| EP1876663B1 (en) | Negative electrode active material for charging device | |
| Brousse et al. | Materials for electrochemical capacitors | |
| Li et al. | One-dimension MnCo2O4 nanowire arrays for electrochemical energy storage | |
| US7199997B1 (en) | Asymmetric electrochemical supercapacitor and method of manufacture thereof | |
| Aravindan et al. | High power lithium-ion hybrid electrochemical capacitors using spinel LiCrTiO 4 as insertion electrode | |
| Zhang et al. | Nanowire Na0. 35MnO2 from a hydrothermal method as a cathode material for aqueous asymmetric supercapacitors | |
| Kalubarme et al. | Electrochemical characteristics of two-dimensional nano-structured MnO2 for symmetric supercapacitor | |
| Puthusseri et al. | Improving the energy density of Li-ion capacitors using polymer-derived porous carbons as cathode | |
| Zhao et al. | Cobalt carbonate dumbbells for high-capacity lithium storage: a slight doping of ascorbic acid and an enhancement in electrochemical performances | |
| US20130171502A1 (en) | Hybrid electrode and surface-mediated cell-based super-hybrid energy storage device containing same | |
| US10650984B2 (en) | Metal oxide nanostructured material and an electrochemical cell comprising the same | |
| Malak et al. | Hybrid materials for supercapacitor application | |
| Guo et al. | Multifunctional nanocomposites for energy and environmental applications | |
| Jing et al. | Electrochemically alternating voltage tuned Co2MnO4/Co hydroxide chloride for an asymmetric supercapacitor | |
| Adhikari et al. | Template-free synthesis of hierarchical mixed-metal cobaltites: Electrocapacitive and Theoretical study | |
| US20190006122A1 (en) | Electrochemical energy storage devices | |
| Liang et al. | H2O/Ni2+ intercalated lamellar vanadium oxide as cathode materials for aqueous zn-ion hybrid supercapacitors | |
| Liao et al. | Hierarchical self-supported Ni (OH) 2@ Ni12P5 for supercapacitor electrodes with ultra-high area ratio capacitance | |
| Chen et al. | Low-temperature performance of aqueous electrochemical capacitors based on manganese oxides | |
| Wang et al. | One-pot synthesis of MnX2O4 (X= Co, Ni)/graphite nanoflakes composites as high-performance supercapacitor electrodes | |
| Keshari et al. | Sucrose-assisted one step hydrothermal synthesis of MnCO3/Mn3O4 hybrid materials for electrochemical energy storage |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| AD01 | Patent right deemed abandoned |
Effective date of abandoning: 20151118 |
|
| C20 | Patent right or utility model deemed to be abandoned or is abandoned |