US20090253025A1 - Sodium ion based aqueous electrolyte electrochemical secondary energy storage device - Google Patents
Sodium ion based aqueous electrolyte electrochemical secondary energy storage device Download PDFInfo
- Publication number
- US20090253025A1 US20090253025A1 US12/385,277 US38527709A US2009253025A1 US 20090253025 A1 US20090253025 A1 US 20090253025A1 US 38527709 A US38527709 A US 38527709A US 2009253025 A1 US2009253025 A1 US 2009253025A1
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- United States
- Prior art keywords
- active cathode
- cathode electrode
- electrolyte
- electrode
- anode
- Prior art date
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 82
- 238000004146 energy storage Methods 0.000 title claims abstract description 48
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 229910001415 sodium ion Inorganic materials 0.000 title claims description 26
- 239000011734 sodium Substances 0.000 claims abstract description 76
- 239000007772 electrode material Substances 0.000 claims abstract description 33
- -1 sodium cations Chemical class 0.000 claims abstract description 22
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 21
- 238000009830 intercalation Methods 0.000 claims abstract description 20
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 9
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 5
- 229910001413 alkali metal ion Inorganic materials 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 108
- 239000006182 cathode active material Substances 0.000 claims description 102
- 239000000463 material Substances 0.000 claims description 85
- 239000007832 Na2SO4 Substances 0.000 claims description 57
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 57
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 57
- 239000002131 composite material Substances 0.000 claims description 47
- 229910052596 spinel Inorganic materials 0.000 claims description 47
- 239000011029 spinel Substances 0.000 claims description 47
- 150000001768 cations Chemical class 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 40
- 239000010405 anode material Substances 0.000 claims description 37
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 29
- 229910014485 Na0.44MnO2 Inorganic materials 0.000 claims description 25
- 239000011230 binding agent Substances 0.000 claims description 23
- 229910052744 lithium Inorganic materials 0.000 claims description 22
- 239000008151 electrolyte solution Substances 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 230000002441 reversible effect Effects 0.000 claims description 15
- 229910052723 transition metal Inorganic materials 0.000 claims description 15
- 150000003624 transition metals Chemical class 0.000 claims description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 229910052749 magnesium Inorganic materials 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 229910019338 NaMnO2 Inorganic materials 0.000 claims description 13
- 229910052791 calcium Inorganic materials 0.000 claims description 13
- 238000009831 deintercalation Methods 0.000 claims description 13
- 229910052700 potassium Inorganic materials 0.000 claims description 13
- 239000003513 alkali Substances 0.000 claims description 11
- 239000006229 carbon black Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 229910001416 lithium ion Inorganic materials 0.000 claims description 11
- 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 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 10
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- 239000003990 capacitor Substances 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 229910052720 vanadium Inorganic materials 0.000 claims description 8
- 229910014235 MyOz Inorganic materials 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 150000001450 anions Chemical class 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011888 foil Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910015232 LixMn2-z Inorganic materials 0.000 claims description 5
- 229910052790 beryllium Inorganic materials 0.000 claims description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 229910010293 ceramic material Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- 239000010450 olivine Substances 0.000 claims description 5
- 229910052609 olivine Inorganic materials 0.000 claims description 5
- 239000004800 polyvinyl chloride Substances 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 5
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 238000012546 transfer Methods 0.000 claims description 5
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 5
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 5
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 230000001747 exhibiting effect Effects 0.000 claims description 4
- 230000003993 interaction Effects 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000036961 partial effect Effects 0.000 claims description 4
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 229920001940 conductive polymer Polymers 0.000 claims description 3
- 229910001512 metal fluoride Inorganic materials 0.000 claims description 3
- 229910001463 metal phosphate Inorganic materials 0.000 claims description 3
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 239000002861 polymer material Substances 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910004617 Na2MPO4F Inorganic materials 0.000 claims description 2
- 229910018893 NaMPO4 Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 238000005342 ion exchange Methods 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 8
- 239000011777 magnesium Substances 0.000 claims 8
- 239000011591 potassium Substances 0.000 claims 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 3
- 239000002482 conductive additive Substances 0.000 claims 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims 2
- 229910001424 calcium ion Inorganic materials 0.000 claims 2
- 239000010936 titanium Substances 0.000 claims 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims 1
- 229940096405 magnesium cation Drugs 0.000 claims 1
- 238000012360 testing method Methods 0.000 description 26
- 239000011572 manganese Substances 0.000 description 23
- 229940021013 electrolyte solution Drugs 0.000 description 20
- 239000003085 diluting agent Substances 0.000 description 13
- 239000008188 pellet Substances 0.000 description 13
- 230000002687 intercalation Effects 0.000 description 12
- 235000019241 carbon black Nutrition 0.000 description 10
- 230000015556 catabolic process Effects 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 9
- 238000006731 degradation reaction Methods 0.000 description 9
- 230000007774 longterm Effects 0.000 description 8
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000010406 cathode material Substances 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 6
- 230000001351 cycling effect Effects 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 239000011255 nonaqueous electrolyte Substances 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000002336 sorption--desorption measurement Methods 0.000 description 4
- 229910004591 Na2FePO4F Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052745 lead Inorganic materials 0.000 description 3
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- DOBUSJIVSSJEDA-UHFFFAOYSA-L 1,3-dioxa-2$l^{6}-thia-4-mercuracyclobutane 2,2-dioxide Chemical compound [Hg+2].[O-]S([O-])(=O)=O DOBUSJIVSSJEDA-UHFFFAOYSA-L 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- 229910015329 LixMn2O4 Inorganic materials 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 229910019898 NaxMnO2 Inorganic materials 0.000 description 2
- 229910018487 Ni—Cr Inorganic materials 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000003466 anti-cipated effect Effects 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000779 depleting effect Effects 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Chemical compound [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- MINVSWONZWKMDC-UHFFFAOYSA-L mercuriooxysulfonyloxymercury Chemical compound [Hg+].[Hg+].[O-]S([O-])(=O)=O MINVSWONZWKMDC-UHFFFAOYSA-L 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910000370 mercury sulfate Inorganic materials 0.000 description 2
- 229910000371 mercury(I) sulfate Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910018862 CoN Inorganic materials 0.000 description 1
- 229910015140 FeN Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910017286 LixM2O4 Inorganic materials 0.000 description 1
- 229910019330 NaMn2O4 Inorganic materials 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000002083 X-ray spectrum Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 230000022131 cell cycle Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910001120 nichrome Inorganic materials 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 229910001487 potassium perchlorate Inorganic materials 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002062 proliferating effect Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- 238000009718 spray deposition Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- QXKXDIKCIPXUPL-UHFFFAOYSA-N sulfanylidenemercury Chemical compound [Hg]=S QXKXDIKCIPXUPL-UHFFFAOYSA-N 0.000 description 1
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention is generally directed to aqueous electrolyte electrochemical secondary energy storage devices and materials for use therein.
- Small renewable energy harvesting and power generation technologies such as solar arrays, wind turbines, micro sterling engines, and solid oxide fuel cells
- Batteries for these stationary applications typically store between 1 and 50 kWh of energy (depending on the application) and have historically been based on the lead-acid (Pb-acid) chemistry.
- Banks of deep-cycle lead-acid cells are assembled at points of distributed power generation and are known to last 1 to 10 years depending on the typical duty cycle.
- Embodiments of the present invention provide a secondary hybrid aqueous energy storage device comprising an anode electrode, a cathode electrode which is capable of reversibly intercalating sodium cations, a separator, and a sodium cation containing aqueous electrolyte, wherein an initial active cathode electrode material comprises an alkali metal containing active cathode electrode material which deintercalates alkali metal ions during initial charging of the device.
- electronegativity is used to describe the ability of an atom to attract electrons in a covalent bond to itself.
- Several different scales may be used to describe electronegativity. Unless otherwise indicated, electronegativity values indicated herein are according to the Pauling scale.
- the term faradaic reaction indicates a reaction that results in oxidation or reduction of an involved species.
- the active cathode materials when Na cations intercalate in to active cathode materials, the active cathode materials must be reduced (that is electrons must be transferred to the active cathode materials) in order to preserve electroneutrality of the bulk material.
- nonfaradaic processes involve the accumulation of charge at the surface of an electrode/solution interface resulting in the formation of an electrical double layer.
- secondary energy storage device may be used interchangeably with the term secondary battery.
- FIG. 1 shows an illustration of one possible charge/discharge mechanism employed by hybrid energy storage devices of the embodiments of the present invention.
- FIG. 2 shows a schematic representation of a secondary energy storage device according to an embodiment of the present invention.
- FIG. 3 shows the X-ray diffraction pattern obtained from spinel structure Li 1.05 Mn 1.89 Al 0.06 O 4 synthesized according the method described in Example 1.
- FIG. 4 shows the X-ray diffraction pattern obtained from spinel structure Mn 1.89 Al 0.06 O 4 (Al-doped ⁇ -MnO 2 ) after deintercalation of Li from spinel Li 1.05 Mn 1.89 Al 0.06 O 4 as described in Example 1.
- FIGS. 5A and 5B show the overlap of a portion of the X-ray diffraction patterns from FIGS. 3 and 4 .
- FIG. 6 shows data from three sequential cyclic voltammargrams for de-lithiated Al-doped ⁇ -MnO 2 active cathode material in aqueous Na 2 SO 4 electrolyte obtained after ten conditioning cycles.
- FIG. 7 shows cyclic voltammargram data for activated carbon anode material in aqueous Na 2 SO 4 electrolyte. No distinct reduction-oxidation peaks are observed.
- FIG. 8 shows the charge/discharge behavior (i.e., cell potential versus time through charge/discharge cycles) of a full aqueous Na-ion hybrid energy storage device based on a de-lithiated Al-doped ⁇ -MnO 2 active cathode material in aqueous Na 2 SO 4 electrolyte at C/24 and 2C rates.
- FIGS. 9A and 9B show single C/5 discharge behavior versus time and specific energy (Wh/kg), respectively, for Al-doped ⁇ -MnO 2 active cathode material in aqueous Na 2 SO 4 electrolyte from 1.7 to 0.8 V cell potential.
- FIG. 10 shows data from a single C/10 discharge cycle as a function of time for Al-doped ⁇ -MnO 2 active cathode material in aqueous Na 2 SO 4 electrolyte from 1.7 to 0.6 V cell potential.
- FIGS. 11A and 11B show data showing the cycling performance of Al-doped ⁇ -MnO 2 active cathode material made via electrochemical Li/Na ion exchange in aqueous Na 2 SO 4 electrolyte from 2.0 to 0.8 V cell potential
- FIGS. 12A and 12B show specific energy and specific capacity, respectively, versus cycle number for long term testing (up to 40 cycles) of a full aqueous Na-ion hybrid energy storage device based on a de-lithiated Al-doped ⁇ -MnO 2 active cathode material in aqueous Na 2 SO 4 electrolyte.
- FIG. 12C shows extended high rate cycling performance (cell capacity versus cycle number) for more than 540 cycles at 5C rate across a potential range of 1.8 to 0.8 V.
- FIG. 13 shows the energy density as a function of cycle number for Al-doped ⁇ -MnO 2 active cathode material in aqueous 1 M Na 2 SO 4 electrolyte with C/5 cycling rate across a potential range of 1.9 to 0.8 V.
- FIG. 14 shows specific energy versus discharge rate for a cell with Al-doped ⁇ -MnO 2 active cathode material versus activated carbon anode material in aqueous Na 2 SO 4 electrolyte.
- FIG. 15 shows specific energy versus specific power for a cell with Al-doped ⁇ -MnO 2 active cathode material versus activated carbon anode material in aqueous Na 2 SO 4 electrolyte.
- FIG. 16 shows the temperature dependency of specific energy versus discharge rates for cells with Al-doped ⁇ -MnO 2 active cathode material versus activated carbon anode material in aqueous Na 2 SO 4 electrolyte.
- FIG. 17 shows long term cell capacity performance for a cell with Al-doped ⁇ -MnO 2 active cathode material versus activated carbon anode material in aqueous Na 2 SO 4 electrolyte over about 5000 cycles.
- FIG. 18 shows the cell potential versus cell energy for a two cell stack constructed with Al-doped ⁇ -MnO 2 active cathode material versus activated carbon anode material in aqueous Na 2 SO 4 electrolyte.
- FIG. 19 shows the charge/discharge behavior (i.e., cell potential versus time through charge/discharge cycles) of a full aqueous Na-ion hybrid energy storage device based on a NaMnO 2 (birnassite phase) active cathode material in aqueous Na 2 SO 4 electrolyte.
- charge/discharge behavior i.e., cell potential versus time through charge/discharge cycles
- FIG. 20A shows data from four sequential cyclic voltammograms for Na 2 Mn 3 O 7 active cathode material in aqueous Na 2 SO 4 electrolyte solution.
- FIG. 20B shows a potential versus time profile from a portion of the cyclic voltammogram testing shown in FIG. 20A .
- FIG. 21 shows discharge behavior of a test cell with a Na 2 FePO 4 F active cathode material, an activated carbon anode material, and aqueous Na 2 SO 4 electrolyte.
- FIG. 22 shows a structural representation of the crystal structure of Na 0.44 MnO 2 perpendicular to the ab plane.
- FIG. 23 shows a cyclic voltammogram of a composite Na 0.44 MnO 2 electrode in an aqueous Na 2 SO 4 electrolyte.
- FIG. 24 shows a cyclic voltammogram of a composite activated carbon electrode in an aqueous Na 2 SO 4 electrolyte.
- FIG. 25 shows charge/discharge behavior of a composite Na 0.44 MnO 2 /Na 2 SO 4(aq) /composite activated carbon hybrid electrical energy storage device through five cycles over about 15 hours.
- FIG. 26 shows specific capacity across a typical discharge cycle of a composite Na 0.44 MnO 2 /Na 2 SO 4(aq) /composite activated carbon hybrid electrical energy storage device.
- FIG. 27 shows long-term charge/discharge behavior of a composite Na 0.44 MnO 2 /Na 2 SO 4(aq) /composite activated carbon hybrid electrical energy storage device after 40 continuous hours of testing to about 60 continuous hours of testing.
- FIG. 28 shows a plot of charge and discharge capacity as a function of cycle for a composite Na 0.44 MnO 2 /Na 2 SO 4(aq) /composite activated carbon hybrid electrical energy storage device over 180 cycles.
- FIG. 29 shows a plot of charge and discharge energy as a function of cycle for a composite Na 0.44 MnO 2 /Na 2 SO 4(aq) /composite activated carbon hybrid electrical energy storage device over 110 cycles.
- FIG. 30A shows cell potential versus specific capacity for a full aqueous Na-ion hybrid energy storage device based on a composite Na 0.44 MnO 2 cathode (made with hydrated NaMnO 2 (birnassite) as a binder) in aqueous Na 2 SO 4 electrolyte.
- FIG. 30B shows specific capacity versus cycle number for long term testing (over about 25 cycles) of a full aqueous Na-ion hybrid energy storage device based on a composite Na 0.44 MnO 2 cathode (made with hydrated NaMnO 2 (birnassite) as a binder) in aqueous Na 2 SO 4 electrolyte.
- Hybrid electrochemical energy storage systems of embodiments of the present invention include a double-layer capacitor electrode coupled with an active electrode.
- the capacitor electrode stores charge through a reversible nonfaradiac reaction of Na cations on the surface of the electrode (double-layer), while the active electrode undergoes a reversible faradic reaction in a transition metal oxide that intercalates and deintercalates Na cations similar to that of a battery.
- Li-based system has been described by Wang, et al., which utilizes a spinel structure LiMn 2 O 4 battery electrode, an activated carbon capacitor electrode, and an aqueous Li 2 SO 4 electrolyte.
- Wang, et al. Electrochemistry Communications, 7:1138-42 (2005).
- the negative anode electrode stores charge through a reversible nonfaradiac reaction of Li-ion on the surface of an activated carbon electrode.
- the positive cathode electrode utilizes a reversible faradiac reaction of Li-ion intercalation/deintercalation in spinel LiMn 2 O 4 .
- the charge/discharge processes of a device are associated with the transfer of Na cations between the active cathode electrode material and the anode electrode, with a Na cation containing electrolyte acting primarily as an ionic conductor between the two electrodes. That is, the cation concentration in the electrolyte stays relatively constant through a charge/discharge cycle. As the system is charged, cations in the electrolyte solution are adsorbed onto the surface of the anode material. At the same time, cations deintercalate from the active cathode material, thus keeping cation electrolyte concentration roughly constant through the charging process.
- Highly purified solvent-based non-aqueous electrolytes are typically necessary in Li-based systems because Li-ion systems are designed to have a relatively high operating potential, typically between about 3.3 and 4.2 V. Such high operating potentials are problematic for aqueous systems because water is electrolyzed at ⁇ 1.3 V, so non-aqueous (i.e., solvent-based) electrolytes that are stable to >4 V are needed. This results in several undesirable consequences.
- Li-ion batteries are either significantly rate limited, or must be fabricated in such a way that they have very thin porous electrodes.
- the latter design is selected despite being a much more complicated design with high surface area current collectors, very thin roll-coated electrodes, and a large-area polymer separator.
- Much of the cost associated with state of the art Li-ion batteries is a result of this design paradigm.
- the cost of handling and fabrication is elevated since a moisture-free environment must be maintained during battery assembly.
- Third, a controlled moisture-free fabrication environment is required, which also increases cost and complexity.
- embodiments of the present invention provide a secondary (rechargeable) energy storage system which uses a water-based (aqueous) electrolyte, such as a Na-based aqueous electrolyte.
- a water-based (aqueous) electrolyte such as a Na-based aqueous electrolyte.
- This allows for use of much thicker electrodes, much less expensive separator and current collector materials, and benign and more environmentally friendly materials for electrodes and electrolyte salts.
- energy storage systems of embodiments of the present invention can be assembled in an open-air environment, resulting in a significantly lower cost of production.
- Secondary (rechargeable) energy storage systems of embodiments of the present invention comprise an anode (i.e., negative) electrode, an anode side current collector, a cathode (i.e., positive) electrode, a cathode side current collector, a separator, and a Na-ion containing aqueous electrolyte.
- Any material capable of reversible intercalation/deintercalation of Na-ions may be used as an active cathode material.
- Any material capable of reversible adsorption/desorption of Na-ions and can function together with such an active cathode material and an appropriate electrolyte solution may be used as an anode material. As shown in the schematic of an exemplary device in FIG.
- the cathode side current collector 1 is in contact with the cathode electrode 3 .
- the cathode electrode 3 is in contact with the electrolyte solution 5 , which is also in contact with the anode electrode 9 .
- the separator 7 is located in the electrolyte solution 5 at a point between the cathode electrode 3 and the anode electrode 9 .
- the anode electrode is also in contact with the anode side current collector 11 .
- the components of the exemplary device are shown as not being in contact with each other. The device was illustrated this way to clearly indicate the presence of the electrolyte solution relative to both electrodes.
- the cathode electrode 3 is in contact with the separator 7 , which is in contact with the anode electrode 9 .
- active cathode materials capable of reversible Na-ion intercalation/deintercalation.
- Materials suitable for use as active cathode materials in embodiments of the present invention preferably contain alkali atoms, such as sodium, lithium, or both, prior to use as active cathode materials. It is not necessary for an active cathode material to contain Na and/or Li in the as-formed state (that is, prior to use in an energy storage device). However, Na cations from the electrolyte must be able to incorporate into the active cathode material by intercalation during operation of the energy storage device.
- materials that may be used as cathodes in the present invention comprise materials that do not necessarily contain. Na in an as-formed state, but are capable of reversible intercalation/deintercalation of Na-ions during discharging/charging cycles of the energy storage device without a large overpotential loss.
- the active cathode material contains alkali-atoms (preferably Na or Li) prior to use, some or all of these atoms are deintercalated during the first cell charging cycle.
- Alkali cations from the electrolyte primarily Na cations
- cations from the electrolyte are adsorbed on the anode during a charging cycle.
- the counter-anions, such as hydrogen ions, in the electrolyte intercalate into the active cathode material, thus preserving charge balance, but depleting ionic concentration, in the electrolyte solution.
- Suitable active cathode materials may have the following general formula during use: A x M y O z , where A is Na or a mixture of Na and one or more of Li, K, Be, Mg, and Ca, where x is within the range of 0 to 1, inclusive, before use and within the range of 0 to 10, inclusive, during use; M comprises any one or more transition metal, where y is within the range of 1 to 3, inclusive; preferably within the range of 1.5 and 2.5, inclusive; and O is oxygen, where z is within the range of 2 to 7, inclusive; preferably within the range of 3.5 to 4.5, inclusive.
- A comprises at least 50 at % of at least one or more of Na, K, Be, Mg, or Ca, optionally in combination with Li; M comprises any one or more transition metal; O is oxygen; x ranges from 3.5 to 4.5 before use and from 1 to 10 during use; y ranges from 8.5 to 9.5 and z ranges from 17.5 to 18.5.
- A preferably comprises at least 51 at % Na, such as at least 75 at % Na, and 0 to 49 at %, such as 0 to 25 at %, Li, K, Be, Mg, or Ca; M comprises one or more of Mn, Ti, Fe, Co, Ni, Cu, V, or Sc; x is about 4 before use and ranges from 0 to 10 during use; y is about 9; and z is about 18.
- A comprises Na or a mix of at least 80 atomic percent Na and one or more of Li, K, Be, Mg, and Ca.
- x is preferably about 1 before use and ranges from 0 to about 1.5 during use.
- M comprises one or more of Mn, Ti, Fe, Co, Ni, Cu, and V, and may be doped (less than 20 at %, such as 0.1 to 10 at %; for example, 3 to 6 at %) with one or more of Al, Mg, Ga, In, Cu, Zn, and Ni.
- Suitable active cathode materials include (but are not limited to) the layered/orthorhombic NaMO 2 (birnessite), the cubic spinel based manganate (e.g., MO 2 , such as ⁇ -MnO 2 based material where M is Mn, e.g., Li x M 2 O 4 (where 1 ⁇ x ⁇ 1.1) before use and Na y Mn 2 O 4 in use), the Na 2 M 3 O 7 system, the NaMPO 4 system, the NaM 2 (PO 4 ) 3 system, the Na 2 MPO 4 F system, and the tunnel-structured Na 0.44 MO 2 , where M in all formula comprises at least one transition metal.
- MO 2 such as ⁇ -MnO 2 based material where M is Mn, e.g., Li x M 2 O 4 (where 1 ⁇ x ⁇ 1.1) before use and Na y Mn 2 O 4 in use
- M M 3 O 7 system
- the NaMPO 4 system the NaM 2 (PO 4 ) 3 system
- Typical transition metals may be Mn or Fe (for cost and environmental reasons), although Co, Ni, Cr, V, Ti, Cu, Zr, Nb, W, Mo (among others), or combinations thereof, may be used to wholly or partially replace Mn, Fe, or a combination thereof.
- Mn is a preferred transition metal.
- cathode electrodes may comprise multiple active cathode materials, either in a homogenous or near homogenous mixture or layered within the cathode electrode.
- the initial active cathode material comprises NaMnO 2 (birnassite structure) optionally doped with one or more metals, such as Li or Al.
- the initial active cathode material comprises ⁇ -MnO 2 (i.e., the cubic isomorph of manganese oxide) based material, optionally doped with one or more metals, such as Li or Al.
- cubic spinel ⁇ -MnO 2 may be formed by first forming a lithium containing manganese oxide, such as lithium manganate (e.g., cubic spinel LiMn 2 O 4 or non-stoichiometric variants thereof.
- a lithium containing manganese oxide such as lithium manganate
- cubic spinel LiMn 2 O 4 e.g., cubic spinel LiMn 2 O 4 or non-stoichiometric variants thereof.
- cubic spinel ⁇ -MnO 2 active cathode material most or all of the Li may be extracted electrochemically or chemically from the cubic spinel LiMn 2 O 4 to form cubic spinel ⁇ -MnO 2 type material (i.e., material which has a 1:2 Mn to O ratio, and/or in which the Mn may be substituted by another metal, and/or which also contains an alkali metal, and/or in which the Mn to O ratio is not exactly 1:2).
- Li-ions are deintercalated from the as-formed cubic spinel LiMn 2 O 4 during the first charging cycle.
- Na-ions from the electrolyte intercalate into the cubic spinel ⁇ -MnO 2 .
- the formula for the active cathode material during operation is Na y Li x Mn 2 O 4 (optionally doped with one or more additional metal as described above, preferably Al), with 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, and x+y ⁇ 1.1.
- the quantity x+y changes through the charge/discharge cycle from about 0 (fully charged) to about 1 (fully discharged). However, values above 1 during full discharge may be used.
- Non-stoichiometric Li x Mn 2 O 4 materials with more than 1 Li for every2 Mn and 4 O atoms may be used as initial materials from which cubic spinel ⁇ -MnO 2 may be formed (where 1 ⁇ x ⁇ 1.1 for example).
- the cubic spinel ⁇ -manganate may have a formula Al z Li x Mn 2-z O 4 where 1 ⁇ x ⁇ 1.1 and 0 ⁇ z ⁇ 0.1 before use, and Al z Li x Na y Mn 2 O 4 where 0 ⁇ x ⁇ 1.1, 0 ⁇ x ⁇ 1, 0 ⁇ x+y ⁇ 1.1, and 0 ⁇ z ⁇ 0.1 in use (and where Al may be substituted by another dopant).
- the initial cathode material comprises Na 2 Mn 3 O 7 , optionally doped with one or more metals, such as Li or Al.
- the initial cathode material comprises Na 2 FePO 4 F, optionally doped with one or more metals, such as Li or Al.
- the cathode material comprises Na 0.44 MnO 2 , optionally doped with one or more metals, such as Li or Al.
- This active cathode material may be made by thoroughly mixing Na 2 CO 3 and Mn 2 O 3 to proper molar ratios and firing, for example at about 800° C. The degree of Na content incorporated into this material during firing determines the oxidation state of the Mn and how it bonds with O 2 locally. This material has been demonstrated to cycle between 0.33 ⁇ x ⁇ 0.66 for Na x MnO 2 in a non-aqueous electrolyte.
- the cathode electrode may be in the form of a composite cathode comprising one or more active cathode materials, a high surface area conductive diluent (such as conducting grade graphite, carbon blacks, such as acetylene black, non-reactive metals, and/or conductive polymers), a binder, a plasticizer, and/or a filler.
- a high surface area conductive diluent such as conducting grade graphite, carbon blacks, such as acetylene black, non-reactive metals, and/or conductive polymers
- Exemplary binders may comprise polytetrafluoroethylene (PTFE), a polyvinylchloride (PVC)-based composite (including a PVC-SiO 2 composite), cellulose-based materials, polyvinylidene fluoride (PVDF), hydrated birnassite (when the active cathode material comprises another material), other non-reactive non-corroding polymer materials, or a combination thereof.
- PTFE polytetrafluoroethylene
- PVC polyvinylchloride
- PVDF polyvinylidene fluoride
- hydrated birnassite when the active cathode material comprises another material
- a composite cathode may be formed by mixing a portion of one or more preferred active cathode materials with a conductive diluent, and/or a polymeric binder, and pressing the mixture into a pellet.
- a composite cathode electrode may be formed from a mixture of about 50 to 90 wt % active cathode material, with the remainder of the mixture comprising a combination of one or more of diluent, binder, plasticizer, and/or filler.
- a composite cathode electrode may be formed from about 80 wt % active cathode material, about 10 to 15 wt % diluent, such as carbon black, and about 5 to 10 wt % binder, such as PTFE.
- One or more additional functional materials may optionally be added to a composite cathode to increase capacity and replace the polymeric binder.
- These optional materials include but are not limited to Zn, Pb, hydrated NaMnO 2 (birnassite), and hydrated Na 0.44 MnO 2 (orthorhombic tunnel structure).
- hydrated NaMnO 2 (birnassite) and/or hydrated Na 0.44 MnO 2 (orthorhombic tunnel structure) is added to a composite cathode, the resulting device has a dual functional material composite cathode.
- a cathode electrode will generally have a thickness in the range of about 40 to 800 ⁇ m.
- the anode may comprise any material capable of reversibly storing Na-ions through surface adsorption/desorption (via an electrochemical double layer reaction and/or a pseudocapacitive reaction (i.e., a i.e. partial charge transfer surface interaction)) and have sufficient capacity in the desired voltage range.
- exemplary materials meeting these requirements include porous activated carbon, graphite, mesoporous carbon, carbon nanotubes, disordered carbon, Ti-oxide (such as titania) materials, V-oxide materials, phospho-olivine materials, other suitable mesoporous ceramic materials, and a combinations thereof.
- activated carbon is used as the anode material.
- the anode electrode may be in the form of a composite anode comprising one or more anode materials, a high surface area conductive diluent (such as conducting grade graphite, carbon blacks, such as acetylene black, non-reactive metals, and/or conductive polymers), a binder, such as PTFE, a PVC-based composite (including a PVC-SiO 2 composite), cellulose-based materials, PVDF, other non-reactive non-corroding polymer materials, or a combination thereof, plasticizer, and/or a filler.
- a high surface area conductive diluent such as conducting grade graphite, carbon blacks, such as acetylene black, non-reactive metals, and/or conductive polymers
- a binder such as PTFE, a PVC-based composite (including a PVC-SiO 2 composite), cellulose-based materials, PVDF, other non-reactive non-corroding polymer materials, or a
- a composite anode may be formed my mixing a portion of one or more preferred anode materials with a conductive diluent, and/or a polymeric binder, and pressing the mixture into a pellet.
- a composite anode electrode may be formed from a mixture from about 50 to 90 wt % anode material, with the remainder of the mixture comprising a combination of one or more of diluent, binder, plasticizer, and/or filler.
- a composite cathode electrode may be formed from about 80 wt % activated carbon, about 10 to 15 wt % diluent, such as carbon black, and about 5 to 10 wt % binder, such as PTFE.
- One or more additional functional materials may optionally be added to a composite anode to increase capacity and replace the polymeric binder.
- These optional materials include but are not limited to Zn, Pb, hydrated NaMnO 2 (birnassite), and hydrated Na 0.44 MnO 2 (orthorhombic tunnel structure).
- An anode electrode will generally have a thickness in the range of about 80 to 1600 ⁇ m.
- the cathode and anode materials may be mounted on current collectors.
- current collectors are desirable that are electronically conductive and corrosion resistant in the electrolyte (aqueous Na-cation containing solutions, described below) at operational potentials.
- an anode current collector must be stable in a range of approximately ⁇ 1.2 to ⁇ 0.5 V vs. a standard Hg/Hg 2 SO 4 reference electrode, since this is the nominal potential range that the anode half of the electrochemical cell is exposed during use.
- a cathode current collector must be stable in a range of approximately 0.1 to 0.7 V vs. a standard Hg/Hg 2 SO 4 reference electrode.
- Suitable uncoated current collector materials for the anode side include stainless steel, Ni, Ni—Cr alloys, Al, Ti, Cu, Pb and Pb alloys, refractory metals, and noble metals.
- Suitable uncoated current collector materials for the cathode side include stainless steel, Ni, Ni—Cr alloys, Ti, Pb-oxides (PbO x ), and noble metals.
- Current collectors may comprise solid foils or mesh materials.
- a metal foil current collector of a suitable metal such as Al
- a thin passivation layer that will not corrode and will protect the foil onto which it is deposited.
- Such corrosion resistant layers may be, but are not limited to, TiN, CrN, C, CN, NiZr, NiCr, Mo, Ti, Ta, Pt, Pd, Zr, W, FeN, CoN, etc.
- These coated current collectors may be used for the anode and/or cathode sides of a cell.
- the cathode current collector comprises Al foil coated with TiN, FeN, C, or CN.
- the coating may be accomplished by any method known in the art, such as but not limited to physical vapor deposition such as sputtering, chemical vapor deposition, electrodeposition, spray deposition, or lamination.
- Electrolytes useful in embodiments of the present invention comprise a salt dissolved fully in water.
- the electrolyte may comprise a 0.1 M to 10 M solution of at least one anion selected from the group consisting of SO 4 2 ⁇ , NO 3 ⁇ , ClO 4 ⁇ , PO 4 3 ⁇ , CO 3 2 ⁇ , Cl ⁇ , and/or OH ⁇ .
- Na cation containing salts may include (but are not limited to) Na 2 SO 4 , NaNO 3 , NaClO 4 , Na 3 PO 4 , Na 2 CO 3 , NaCl, and NaOH, or a combination thereof.
- the electrolyte solution may be substantially free of Na.
- cations in salts of the above listed anions may be an alkali other than Na (such as K) or alkaline earth (such as Ca, or Mg) cation.
- alkali other than Na cation containing salts may include (but are not limited to) K 2 SO 4 , KNO 3 , KClO 4 , K 3 PO 4 , K 2 CO 3 , KCl, and KOH.
- Exemplary alkaline earth cation containing salts may include CaSO 4 , Ca(NO 3 ) 2 , Ca(ClO 4 ) 2 , CaCO 3 , and Ca(OH) 2 , MgSO 4 , Mg(NO 3 ) 2 , Mg(ClO 4 ) 2 , MgCO 3 , and Mg(OH) 2 .
- Electrolyte solutions substantially free of Na may be made from any combination of such salts.
- the electrolyte solution may comprise a solution of a Na cation containing salt and one or more non-Na cation containing salt.
- Molar concentrations preferably range from about 0.05 M to 3 M, such as about 0.1 to 1 M, at 100° C. for Na 2 SO 4 in water depending on the desired performance characteristics of the energy storage device, and the degradation/performance limiting mechanisms associated with higher salt concentrations. Similar ranges are preferred for other salts.
- a blend of different salts may result in an optimized system.
- Such a blend may provide an electrolyte with sodium cations and one or more cations selected from the group consisting of alkali (such as K), alkaline earth (such as Mg and Ca), lanthanide, aluminum, and zinc cations.
- the pH of the electrolyte may be altered by adding some additional OH ⁇ ionic species to make the electrolyte solution more basic, for example by adding NaOH other OH-containing salts, or by adding some other OH ⁇ concentration-affecting compound (such as H 2 SO 4 to make the electrolyte solution more acidic).
- the pH of the electrolyte affects the range of voltage stability window (relative to a reference electrode) of the cell and also can have an effect on the stability and degradation of the active cathode material and may inhibit proton (H + ) intercalation, which may play a role in active cathode material capacity loss and cell degradation.
- the pH can be increased to 11 to 13, thereby allowing different active cathode materials to be stable (than were stable at neutral pH 7).
- the pH may be within the range of about 3 to 13, such as between about 3 and 6 or between about 8 and 13.
- the electrolyte solution contains an additive for mitigating degradation of the active cathode material, such as birnassite material.
- An exemplary additive may be, but is not limited to, Na 2 HPO 4 , in quantities sufficient to establish a concentration ranging from 0.1 mM to 100 mM.
- a separator for use in embodiments of the present invention may comprise a cotton sheet, PVC (polyvinyl chloride), PE (polyethylene), glass fiber or any other suitable material.
- the active cathode material contains alkali-atoms (preferably Na or Li) prior to use, some or all of these atoms are deintercalated during the first cell charging cycle.
- Alkali cations from the electrolyte primarily Na cations
- cations from the electrolyte are adsorbed on the anode during a charging cycle.
- the counter-anions in the electrolyte intercalate into the active cathode material, thus preserving charge balance, but depleting ionic concentration, in the electrolyte solution.
- a hybrid energy storage device may be capable of operating over 500 cycles, such as over 5000 cycles, such as between 5000 and 10000 cycles at full discharge with less than 20% loss of initial capacity; preferably less than or equal to 10% loss of initial capacity; preferably less than or equal to about 5% loss of initial capacity, such as between 0 and 10% loss of initial capacity; such as between 1 and 5%.
- a hybrid energy storage device comprises an activated carbon anode material exhibiting greater than or equal to about 60 mAh/g specific capacity (cathode basis), such as 60 to 130 mAh/g (cathode basis), with Na 2 SO 4 electrolyte.
- a hybrid energy storage device comprises a Na 0.44 MnO 2 -type active cathode material exhibiting greater than or equal to about 20 mAh/g specific capacity with Na 2 SO 4 electrolyte, such as about 45 to 80 mAh/g (cathode basis).
- a hybrid energy storage device comprises a Na 0.44 MO 2 -type active cathode material, an activated carbon anode material, and exhibits a specific energy (normalized to active cathode and anode material mass) of greater than 20 Wh/kg, such as between 20 and 35 Wh/kg, when cycled between potentials of 0.35 and 1.5 V in 1 M Na 2 SO 4 at C/5 rate or slower.
- a hybrid energy storage device comprises a cubic spinel ⁇ -MO 2 -NaM 2 O 4 -type active cathode material exhibiting greater than or equal to about 75 mAh/g specific capacity (cathode basis) with Na 2 SO 4 electrolyte.
- a hybrid energy storage device comprises a cubic spinel ⁇ -MO 2 -NaM 2 O 4 -type active cathode material, an activated carbon anode material, and exhibits a specific energy (normalized to active cathode and anode material mass) of greater than 20 Wh/kg, such as between about 20 and 105 Wh/kg (when cycled between potentials of 0.60 and 1.55 V in 1 M Na 2 SO 4 at C/10 rate or slower); preferably as greater than 40 Wh/kg, such as between 40 and 105 Wh/kg (when cycled between potentials of 0.60 and 1.9 V in 1 M Na 2 SO 4 at C/10 rate or slower).
- a hybrid energy storage device comprises a cubic spinel ⁇ -MO 2 -NaM 2 O 4 -type active cathode material, an activated carbon anode material, and exhibits a specific energy (normalized to active cathode and anode material mass) of between 10 and 105 Wh/kg (cathode basis), for a specific power of between 20 to 1100 W/kg, such as between about 70 and about 105 Wh/kg for between 20 and 100 W/kg, at 23° C. at 0.1C rate.
- a hybrid energy storage device comprises a cubic spinel ⁇ -MO 2 -NaM 2 O 4 -type active cathode material, an activated carbon anode material, and exhibits a specific energy (normalized to active cathode and anode material mass) of between 30 and 50 Wh/kg, at ⁇ 5 to 23° C. at 1 C rate.
- the specific energy is between 65 and 100 Wh/kg, at ⁇ 5 to 23° C. at 0.5 C rate.
- a hybrid energy storage device comprises a cathode electrode that is able to support greater than 1 kW of discharge power per kg of active cathode material.
- the active cathode material may comprise Na 0.44 MnO 2 or ⁇ -NaMnO 2 (cubic spinel NaMn 2 O 4 )
- test cell was constructed with a ⁇ -MO 2 -type active cathode material versus an activated carbon anode material in 1 M Na 2 SO 4 in DI H 2 O electrolyte.
- the active cathode material was made from Al-doped, Li-containing, cubic spinel MnO 2 .
- the Li-containing cubic spinel was synthesized by thoroughly mixing Li 2 CO 3 , Mn 2 O 3 , and Al(OH) 3 to proper mole ratios and firing at 750° C. for 24 hours.
- This material resulted in a spinel structure with the formula Li 1.05 Mn 1.89 Al 0.06 O 4 , as verified by X-ray diffraction analysis.
- X-ray spectra is shown in FIG. 3 .
- a composite cathode was formed by mixing about 80 wt % Li 0.05 Mn 1.89 Al 0.06 O 4 initial active material, 10 wt % carbon black conductive diluent, and about 10% PTFE polymeric binder. This mixture was then pressed into a pellet, which was placed into a large electrochemical cell and biased to remove most of the Li. The cell was held at greater than 4.1 V for at least 5 hours to electrochemically extract the Li, although chemical extraction could have been used instead.
- FIG. 4 show that the material is a close match to ⁇ -MnO 2 as described by JCPDS card # 00-044-0992.
- the diffraction patterns shown in FIGS. 3 and 4 are superimposed in FIG. 5 to demonstrate the difference.
- the resulting Al-doped ⁇ -MnO 2 material was then placed as a working electrode (cathode) into an electrochemical half cell environment with a Pt counter electrode, and a mercury/mercury sulfate reference electrode, and a Na 2 SO 4 aqueous electrolyte.
- the half-cell was cycled between ⁇ 0.3 and 0.6 V vs. SME.
- the data indicate that the cathode does display Na-ion intercalation/deintercalation events and is stable over many cycles.
- the data shown in FIG. 6 show three sequential cyclic voltammargrams obtained after ten conditioning cycles. This result indicates that Al-doped ⁇ -MnO 2 is able to reversibly intercalate Na cations from a Na cation containing electrolyte with virtually no Li or Li cations present.
- a pellet was pressed of the composite Li-containing active cathode material described above and placed in a coin cell.
- the anode, separator, and electrolyte in the coin cell are described below.
- Activated carbon was used as the anode material. This material is known to reversibly store Li cations through surface adsorption/desorption and also has sufficient capacity in the desired voltage range. It was anticipated that this material could store between 40 and 100 mAh/g of Na + in the voltage range of 1.5 to 2 V vs. Na metal.
- a composite anode was formed by mixing about 80 wt % activated carbon, 10 wt % carbon black conductive diluent, and 10 wt % PTFE polymeric binder and pressing the mixture into a pellet.
- the density of the pellet was at least 0.35 g/cm 3 .
- the mass of the pressed anode pellet was matched to the mass of the cathode pellet so that both electrodes could hold sufficient Na cations to make maximum use of the active material present.
- This composite anode material was placed as a working electrode into an electrochemical half cell environment with a Pt counter electrode, and a mercury/mercury sulfate reference electrode.
- the half-cell was cycled between ⁇ 0.6 and 0.7 V vs. SME, with a 1 M Na 2 SO 4 electrolyte solution.
- the data indicate that the anode material does not display Na-ion intercalation/deintercalation events, exhibited symmetrical behavior indicative of a reversible Na cation storage process via a surface adsorption/electrochemical double layer capacitance effect.
- a cyclic voltammargram obtained from this half cell is shown in FIG. 7 .
- the anode and cathode material pellets were fitted into standard stainless steel 2032 coin cell test fixtures. Cotton sheeting was used as a separator material, and Ni mesh served a current collectors for both electrodes. After some irreversible capacity loss on the first several formation cycles, typical charge/discharge behavior was observed to be very consistent and stable in the voltage range between 0.8 and 1.8 V, at least, as shown in FIG. 8 . The cell delivered uniform charge/discharge behavior during both C/24 and 2 C cycling and little obvious decay was observed.
- FIGS. 9A and 9B Data showing a single C/5 discharge curve as a function of time and as a function of specific energy are shown in FIGS. 9A and 9B , respectively. Data showing a single C/10 discharge curve as a function of specific energy is shown in FIG. 10 .
- FIGS. 12A and 12B show specific energy and specific capacity, respectively, versus cycle number for long term testing (up to 40 cycles). After the formation cycling is complete, a near-100% columbic efficiency is observed.
- FIG. 12C shows extended high rate cycling performance, with little cell capacity degradation observed over 570 cycles at 5° C. As seen in FIG. 17 , such cells exhibit little to no degradation for 1000 or more charge/discharge cycles and less than 10% degradation over 5000 or more cycles, such as 5000 to 10,000 cycles.
- FIG. 13 shows the energy density of such cells as a function of cycle number
- FIG. 14 shows the specific energy versus discharge rate
- FIG. 15 shows the specific energy versus specific power.
- FIG. 16 shows the temperature dependency of the specific energy versus discharge rates for a cell with this active cathode material.
- a large scale cell i.e., a two cell stack
- the active cathode material composite electrode versus an activated carbon anode electrode.
- the cell potential versus the cell energy is shown in FIG. 18 .
- a separate test cell was constructed from a fully de-lithiated, Al doped cubic spinel active cathode material (where Li was removed in a half cell environment described above and replaced with Na electrochemically in a half cell before assembling in the test cell) to demonstrate that this material is fully functional as an active cathode material.
- Cell cycle characteristics for this cell are shown in FIGS. 11A and 11B .
- the cell showed significant capacity and a similar characteristic charge discharge profile as the cell where the starting material was Al doped LiMn 2 O 4 , described above.
- Li could have been removed chemically with a Br containing solution followed by washing. Additionally, Na could have also been added to a de-lithiated, cubic spinel active cathode material chemically by treatment with molten Na salt or Na containing solution.
- a test cell similar to that described in Example 1 above was constructed with a NaMnO 2 (birnassite structure) active cathode material, activated carbon anode material, and 1 M Na 2 SO 4 in DI H 2 O electrolyte.
- NaMnO 2 birnassite structure
- FIG. 19 shows the charge/discharge behavior (i.e., cell potential versus time through charge/discharge cycles) of the NaMnO 2 (birnassite phase) active cathode material test cell.
- the system demonstrated a potential range of about 0.0 V to about 1.7 V.
- a half cell similar to that described in Example 1 above was constructed with a Na 2 Mn 3 O 7 (JCPDS structure: 078-0193) working electrode, a SCE reference electrode, and a Pt counter electrode.
- the half-cell was cycled between about ⁇ 0.5 and 0.6 V vs. SCE.
- the data indicate that Na 2 Mn 3 O 7 does display Na cation intercalation/deintercalation events and is stable between the potential range studied.
- the data shown in FIG. 20A show cyclic voltammargrams which demonstrate reversible capacity for Na 2 Mn 3 O 7 in 1 M Na 2 SO 4 in DI H 2 O electrolyte solution.
- FIG. 20B shows a potential versus time profile from a portion of the same test.
- FIG. 21 shows the discharge behavior of the test cell over time. As seen in FIG. 21 , significant capacity was observed at about 0.8 V.
- a test cell and a half cell similar to those described in Example 1 were constructed with Na 0.44 MnO 2 active cathode material.
- the Na 0.44 MnO 2 active cathode material was as synthesized by thoroughly mixing Na 2 CO 3 and Mn 2 O 3 to proper molar ratios and firing at 800° C. for 12 hours. The degree of Na content during firing determines the oxidation state of the Mn and how it bonds with O 2 locally. This material is known to cycle between 0.33 ⁇ x ⁇ 0.66 for Na x MnO 2 in a Na cation containing non-aqueous electrolyte. The specific capacity of this material is as much as 160 mAh/g in an organic electrolyte, with a voltage of 2 to 3 V vs. Na metal.
- a structural representation of the crystal structure is shown in FIG. 22 .
- a composite cathode was formed according to a similar procedure as outlined in Example 1. In this case, 80 wt % Na 0.44 MnO 2 , 15 wt % carbon black conductive diluent, and 5 wt % PTFE polymeric binder were mixed and pressed into a pellet. The redox potential associated with Na-ion intercalation/deintercalation is below the breakdown potential (oxygen reduction) of water, demonstrating that the material is suitable for use with an aqueous electrolyte.
- Activated carbon was used as the anode material. This material is known to reversibly store Li cations through surface adsorption/desorption and have sufficient capacity in the desired voltage range. It was anticipated that this material could store between 40 and 100 mAh/g of Na + in the voltage range of 1.5 to 2 V vs. Na metal.
- a composite anode was formed according to a similar procedure as outlined in Example 1. In this case, 80 wt % activated carbon, 15 wt % carbon black conductive diluent, and 5 wt % PTFE polymeric binder were mixed and pressed into a pellet.
- the electrolyte for the half cell was 2 N Na 2 SO 4 in DI H 2 O, and for the test cell was 1.5 M Na 2 SO 4 in DI H 2 O.
- Other work has shown that the same effect is present in salt concentrations ranging from 0.05 to 5 M.
- the reversible nature of the Na 0.44 MnO 2 active cathode material was examined using a three electrode half-cell set-up, with the pressed composite Na 0.44 MnO 2 electrode affixed to Ni mesh and immersed into an open beaker of electrolyte.
- a standard sulfur-mercury electrode was used (Koslow scientific) as a reference electrode, and Pt wire as a counter electrode.
- Example 2 A series of the full cells similar to those described in Example 1 was then made and tested for a composite Na 0.44 MnO 2 cathode, composite activated carbon anode, and aqueous Na 2 SO 4 electrolyte. After some irreversible capacity loss on the formation cycle(s), typical charge/discharge behavior was very consistent and was stable in the voltage range between 0.35 and 1.8 V, at least, as seen in FIG. 25 . The cells demonstrated little obvious decay over about 15 hours.
- FIG. 26 shows a typical discharge curve.
- a specific capacity between 15 and 36 mAh/g was observed for between 1.0 and 0.4 V cell potential. Further study indicated that the cells are stable and can be cycled repeatedly to 1.8 V, at least. The cells also exhibit excellent long-term stability.
- FIG. 27 shows a portion of a long-duration cycle-life test. The cycle life behavior of this cell shows that there was no degradation over at least 180 cycles (over at least 40 continuous hours of testing) between 0.4 and 1.6 V cell potential.
- the charge and discharge energy of these cells is shown in FIG. 29 as a function of cycle index. Minimal system fade was observed over the first 180 cycles, and even at a rate of greater than 2 C, the cell delivered a roundtrip energy efficiency of over 85% (about 87%). Efficiency would increase significantly at lower rates of charge/discharge, because nearly all efficiency loss is due to overpotential loss at higher currents.
- Example 5 Another test cell similar to that described in Example 1 was constructed with Na 0.44 MnO 2 active cathode material and hydrated NaMnO 2 (birnassite) as a binder material.
- the Na 0.44 MnO 2 active cathode material was synthesized as described in Example 5.
- the composite cathode was formed according to a similar procedure as outlined in Example 1. In this case, 80 wt % Na 0.44 MnO 2 , 15 wt % carbon black conductive diluent, and 5 wt % hydrated NaMnO 2 (birnassite) binder were mixed and pressed into a pellet.
- FIGS. 30A and 30B Performance data of this test cell is shown in FIGS. 30A and 30B .
- FIG. 30A shows a plot of the cell potential versus specific capacity
- FIG. 30B shows the capacity versus cycle number for long term testing (over about 25 cycles).
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WO2011127384A1 (fr) | 2010-04-09 | 2011-10-13 | Massachussetts Institute Of Technology | Transfert d'énergie utilisant des fluides isolés électrochimiquement |
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US8137830B2 (en) * | 2011-07-19 | 2012-03-20 | Aquion Energy, Inc. | High voltage battery composed of anode limited electrochemical cells |
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US20110311846A1 (en) | 2011-12-22 |
JP5431452B2 (ja) | 2014-03-05 |
KR20110017850A (ko) | 2011-02-22 |
CA2720600C (fr) | 2017-09-12 |
CN102027625B (zh) | 2017-05-03 |
TWI463720B (zh) | 2014-12-01 |
US20110052945A1 (en) | 2011-03-03 |
JP2011519122A (ja) | 2011-06-30 |
US8741455B2 (en) | 2014-06-03 |
IL208581A0 (en) | 2010-12-30 |
EP2274789B1 (fr) | 2016-12-07 |
US9088046B2 (en) | 2015-07-21 |
CN102027625A (zh) | 2011-04-20 |
KR101693602B1 (ko) | 2017-01-06 |
TW201001784A (en) | 2010-01-01 |
AU2009233974A1 (en) | 2009-10-15 |
WO2009126525A3 (fr) | 2010-01-21 |
WO2009126525A2 (fr) | 2009-10-15 |
AU2009233974B2 (en) | 2013-10-17 |
CA2720600A1 (fr) | 2009-10-15 |
EP2274789A4 (fr) | 2014-10-15 |
EP2274789A2 (fr) | 2011-01-19 |
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