EP3785318A1 - New sodium-based material and its use as positive electrode material or na-ion cells - Google Patents
New sodium-based material and its use as positive electrode material or na-ion cellsInfo
- Publication number
- EP3785318A1 EP3785318A1 EP19721240.0A EP19721240A EP3785318A1 EP 3785318 A1 EP3785318 A1 EP 3785318A1 EP 19721240 A EP19721240 A EP 19721240A EP 3785318 A1 EP3785318 A1 EP 3785318A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- positive electrode
- cell
- sodium
- formula
- ion
- 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
- 239000000463 material Substances 0.000 title claims abstract description 103
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 61
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 10
- 239000011734 sodium Substances 0.000 title claims description 66
- 229910052708 sodium Inorganic materials 0.000 title claims description 41
- 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 title claims description 40
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 229910001428 transition metal ion Inorganic materials 0.000 claims abstract description 4
- 230000007704 transition Effects 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 23
- 239000003792 electrolyte Substances 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 17
- 229910021385 hard carbon Inorganic materials 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 239000006258 conductive agent Substances 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- -1 sodium hexafluorophosphate Chemical compound 0.000 claims description 8
- 229910001373 Na3V2(PO4)2F3 Inorganic materials 0.000 claims description 7
- 239000007772 electrode material Substances 0.000 claims description 7
- 229910052720 vanadium Inorganic materials 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 238000003869 coulometry Methods 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- VCCATSJUUVERFU-UHFFFAOYSA-N sodium bis(fluorosulfonyl)azanide Chemical compound FS(=O)(=O)N([Na])S(F)(=O)=O VCCATSJUUVERFU-UHFFFAOYSA-N 0.000 claims description 4
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims description 4
- YLKTWKVVQDCJFL-UHFFFAOYSA-N sodium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Na+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F YLKTWKVVQDCJFL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 3
- 229910019398 NaPF6 Inorganic materials 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- 238000005266 casting Methods 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 2
- 229910021201 NaFSI Inorganic materials 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 238000010280 constant potential charging Methods 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 229940017219 methyl propionate Drugs 0.000 claims description 2
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 2
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 2
- QSTITLHDMBEKHE-UHFFFAOYSA-N sodium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Na+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F QSTITLHDMBEKHE-UHFFFAOYSA-N 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 10
- 238000000605 extraction Methods 0.000 description 8
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 230000002441 reversible effect Effects 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 230000002427 irreversible effect Effects 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920005596 polymer binder Polymers 0.000 description 3
- 239000002491 polymer binding agent Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 239000006231 channel black Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000002051 biphasic effect Effects 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000022131 cell cycle Effects 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
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- 230000001627 detrimental effect Effects 0.000 description 1
- 229920005994 diacetyl cellulose Polymers 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 239000000835 fiber Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001205 potentiostatic coulometry Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/455—Phosphates containing halogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/043—Processes of manufacture in general involving compressing or compaction
- H01M4/0435—Rolling or calendering
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0438—Processes of manufacture in general by electrochemical processing
- H01M4/044—Activating, forming or electrochemical attack of the supporting material
- H01M4/0445—Forming after manufacture of the electrode, e.g. first charge, cycling
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
- H01M4/13915—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx containing halogen atoms, e.g. LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to the field of Na-ion cells and provides a new Na- based material.
- the present invention also relates to a method of preparation of said material and its use as a positive electrode material.
- the present invention also relates to a positive electrode material comprising said Na-based material, and to a Na-ion cell comprising said positive electrode.
- Li-ion batteries The most appealing alternative to Li-ion batteries regarding chemical element abundance and cost is by all means sodium. Batteries using sodium ions as shuttling ions in place of lithium ions are employed for use in place of lithium in applications where the stored energy density is less critical than for portable electronics or automotive transport, more particularly for the management of renewable energies. Such awareness has prompted the revival of the Na-ion battery concept with intense activity devoted to the search of highly performing electrode material.
- the performance of the Na-ion batteries is related to the capacity of the positive electrode material which today mostly uses the Na 3 V 2 (P0 4 ) 2 F 3 material (NVPF). Said material is capable of inserting and de-inserting two sodium ions per formula unit leading to a reversible capacity of 120 mAh/g.
- NVPF Na 3 V 2 (P0 4 ) 2 F 3 material
- Bianchini et al. ( Chemistry of Materials, 2014, 26(14) : 4238-47) discloses the preparation of Na 3 V 2 (P04)2F 3 material and its use as a positive electrode material, and explains that only the reversible extraction of two sodium ions may be achieved in a Na- ion cell.
- the aim of the present invention is to provide a Na-ion cell which presents an increased reversible capacity, and an increased energy density in comparison of the Na- cell ion described in the prior art.
- Another aim of the present invention is to provide a positive electrode material which presents a better cycle life in comparison to the prior art.
- ⁇ represents a vacancy
- M represents a transition or a non-transition metal ion.
- M is selected from the group consisting of magnesium, zinc, iron, aluminum, nickel, cobalt, chromium, titanium, manganese and mixtures thereof, preferably M is aluminum.
- x, y and z are chosen so as to ensure the electroneutrality of the compound.
- x is 2.25, 2.35, 2.5 or 2.75.
- the material of formula (I) can reversibly uptake and remove more than two sodium ions.
- the material of formula (I) is disordered, meaning that sodium ions adopt a disordered arrangement. Accordingly, the material of formula (I) presents a structure of tetragonal space group 14/mmm. Said disordering is irreversible.
- the structure of the material of formula (I) can be spotted by XRD diffraction. The higher the x value, the higher the disordered phase formation is observed.
- the present invention also relates to a method of preparation of the material of formula (I), comprising the following steps:
- a Na-ion cell comprising at least one positive electrode, at least one negative electrode, and at least one electrolyte, said positive electrode comprising a Na-based material (A) selected from the group consisting of: o Na 3 V 2 (P04)2F3;
- step ii) galvanostatically and constant-voltage charging of the Na-ion cell obtained at the end of step i) at a potential comprised between 4.3 V and 4.8 V (Na + /Na°), preferably at 4.8 V, and maintaining said cell at such potential till more than two Na ions are extracted from the material (A), in which the amount of Na ions is determined by coulometry; and
- up to three sodium ions may be reversibly extracted from the material (A) in order to obtain the material of formula (I).
- the amount of the sodium ions extracted is measured by coulometry, especially by controlled-potential coulometry, i.e., the potential applied to the cell is constant.
- Coulometry enables counting the number of electron which has passed through a material. Specifically, the current is monitored as a function of time so as to calculate the total charges which have passed through the materials.
- Said technique may be implemented either in a galvanostatic mode (i.e. a current value is fixed) or potentiostatic mode (constant voltage mode). Said charges are proportional to the amount of sodium ions extracted from the material (A).
- the potential applied in step ii) is comprised between 4.3 V and 4.8 V (Na + /Na°). (Na + /Na°) meaning that the potential is defined with respects to the potential of Na + /Na°, which is the reference potential.
- step ii) of this method a galvanostat or a potentiostat such as Bio-Logic ⁇ may be used.
- the material of formula (I) is prepared in-situ.
- the sodium ions (more than 2) that have been extracted from the material (A) to form the material of formula (I) can be re-inserted back into said newly formed material of formula (I) by discharging the potential applied to the Na-ion cell from between 4.3 V and 4.8 V down to 1 V.
- the material of formula (I) obtained at the end of step iii) of the method of the invention may be used immediately or stored, preferably under an inert atmosphere.
- the positive electrode implemented in the above-mentioned method comprises the material (A), a current collector, a polymer binder and an electronic conductive agent.
- the positive electrode further comprises a Na-based oxide material (B) such as Na x -MO 2 (0 ⁇ x’ ⁇ 1 ) in which M’ represents at least one metal ion selected from the group consisting of nickel, zinc, cobalt, manganese, iron, chromium, titanium, copper, vanadium, aluminum, magnesium, and mixtures thereof.
- M represents at least one metal ion selected from the group consisting of nickel, zinc, cobalt, manganese, iron, chromium, titanium, copper, vanadium, aluminum, magnesium, and mixtures thereof.
- the material (B) is
- the polymer binder as mentioned above confers mechanical strength to the electrode material, and is preferably a polymer which has a high modulus of elasticity (e.g. of the order of several hundred MPa), and which is stable under the temperature and voltage conditions in which the positive electrode is intended to operate.
- the binder provides high adhesive strength between the electrode materials and the current collector, maintains the electron conductivity, and facilitates the electrolyte wetting into the electrode materials so as to form a stable interface between the electrodes and the electrolyte.
- the binder may be selected from polyvinylidene difluoride and poly(tetrafluoroethylene), cellulose fibers, cellulose derivatives such as starch, carboxymethyl cellulose (CMC), diacetyl cellulose, hydroxyethyl cellulose or hydroxypropyl cellulose, styrene butadiene rubber (SBR), and mixtures thereof.
- CMC carboxymethyl cellulose
- SBR styrene butadiene rubber
- the amount of binder may vary from 0 to 40 wt. %, preferably, from 1 to 10 wt. % with regard to the total weight of the materials of formula (A) and (B).
- the electronically conductive agent may be selected from the group consisting of carbon black, Super P® carbon black, acetylene black, ketjen black®, channel black, natural or synthetic graphite, carbon fibers, carbon nanotubes, vapor grown carbon fibers or a mixture thereof.
- “carbon black” is a material having a form of paracrystalline carbon, presenting a high ratio of surface area/volume, and is mostly issued from the incomplete combustion of heavy petroleum products.
- Acetylene black and channel black are subtypes of carbon black.
- carbon fibers, carbon nanotubes and vapor grown carbon fibers are cylindrical nanostructures of carbon comprising graphene layers arranged as stacks cones, cups or plates.
- the amount of electronically conductive agent may vary from 0 to 40 w%, preferably, from 1 to 10 wt. % with regard to the total weight of the materials of formula (A) and (B).
- the current collector is a material characterized by a high electrical conductivity; a resistance to corrosion, a mechanical strength and flexibility allowing it withstands manufacturing operations (e.g., pasting and rolling), etc.
- the current collector may be composed of an electron conductive material, more particularly of a metallic material which may be selected from aluminium, copper, nickel, steel, titanium, tungsten, tantalum and carbon foil.
- the amount of material (A) varies from 0.1 wt. % to 100 wt. %, and the amount of material (B) varies from 0 to 99.9 wt. % with regard to the total amount of the electrode material.
- the amount of material (A) varies from 45 to 100 wt. %, and the amount of material (B) varies from 0 to 55 wt. % with regard to the total amount (weight) of the electrode material.
- the positive electrode as defined above and implemented in the method of the invention may be prepared according to the following steps:
- step b) dispersing the mixture obtained at step a) in a solvent and forming a slurry; c) casting the slurry obtained at the end of step b) onto the current collector, and obtaining a positive electrode;
- step c) drying the positive electrode obtained at the end of step c) at a temperature comprised between 60°C and 300°C, preferably at 120°C;
- step d) pressing the dried positive electrode obtained at the end of step d) with a roller machine.
- the mixing step a) may be implemented by mixing in a mortar with pestle or by a ball- milling process.
- step b) the mixture obtained at step a) is preferably dispersed in a solvent selected from the group consisting of N-Methyl-2-pyrrolidone (NMP), acetonitrile, ethanol, water and mixtures thereof.
- NMP N-Methyl-2-pyrrolidone
- step c) is carried out using an electrode coating machine.
- step e) is carried out with a calendaring machine such as CIS® CLP 2025H.
- the above-mentioned negative electrode of the invention may comprise a material (C).
- the negative electrode may also comprise a current collector, a polymer binder and an electronic conductive agent as previously defined.
- Such negative electrode may be prepared according to the following steps:
- step b’ dispersing the mixture obtained at step a’) in a solvent and forming a slurry; c’) casting the slurry obtained at the end of step b’) onto a current collector, and obtaining a negative electrode;
- step d’ pressing the dried negative electrode obtained at the end of step d’) with a roller machine.
- the mixing step a’) may be implemented by mixing in a mortar with pestle or by a ball- milling process.
- Steps b’)-e’) are similar to steps b)-e) previously defined.
- the material (C) of the negative electrode may be selected from the group consisting of hard carbon, antimony, tin, sodium, phosphorus and mixtures thereof.
- a "hard carbon” is a carbonaceous compound obeying to a “falling cards model”, in which the graphene layers (2 or 3 layers) are randomly stacked to form nanoscale pores. Said material has been described in Stevens et al. ( Journal of the Electrochemical Society, 147(4) 1271-1273 (2000)) and in Dhan et al. ( Carbon Vol. 35, n°6, pp.825-830 ).
- the binder and the electronic conductive agent comprised in the negative electrode are similar to the binder and the electronic conductive agent comprised in the positive electrode and as previously defined.
- the amount of the material (C) varies from 80 to XX 99% with regard to the total amount of the negative electrode material.
- the current collector of the negative electrode preferably comprises aluminum.
- the electrolyte implemented in the method of the invention is generally a solution comprising a solvent and a salt, preferably a sodium salt.
- the solvent may be a liquid solvent, optionally gelled by a polymer, or a polar polymer solvent which is optionally plasticized by a liquid.
- the liquid solvent may comprise a polar aprotic solvent and may be selected from the group consisting of dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, propylene carbonate, ethylene carbonate and esters such as ethyl acetate, ethyl propionate and methyl propionate, and mixtures thereof.
- Said liquid solvent may optionally be gelled by addition of a polymer obtained, for example, from one or more monomers selected from ethylene oxide, propylene oxide, methyl methacrylate, methyl acrylate, acrylonitrile, methacrylonitrile, N-vinylpyrrolidone and vinylidene fluoride, said polymer having a linear, comb, random, alternating, or block structure, and being crosslinked or not.
- a polymer obtained, for example, from one or more monomers selected from ethylene oxide, propylene oxide, methyl methacrylate, methyl acrylate, acrylonitrile, methacrylonitrile, N-vinylpyrrolidone and vinylidene fluoride, said polymer having a linear, comb, random, alternating, or block structure, and being crosslinked or not.
- the proportion of liquid solvent in the solvent may vary from about 2% by volume (corresponding to a plasticized solvent) to about 98% by volume (corresponding to a gelled solvent).
- the electrolyte comprises at least one salt selected from the group consisting of sodium hexafluorophosphate (NaPF 6 ), sodium perchlorate (NaCIC ), sodium bis (fluorosulfonyl) imide (NaFSI), sodium bis(trifluoromethanesulfonyl)imide (NaTFSI), sodium bis(pentafluoroethanesulfonyl)imide (NaBETI), sodium tetrafluoroborate (NaBF 4 ), and mixtures thereof.
- NaPF 6 sodium hexafluorophosphate
- NaCIC sodium perchlorate
- NaFSI sodium bis (fluorosulfonyl) imide
- NaTFSI sodium bis(trifluoromethanesulfonyl)imide
- NaBETI sodium bis(pentafluoroethanesulfonyl)imide
- NaBF 4 sodium tetrafluoroborate
- the electrolyte When the electrolyte is a liquid electrolyte, said liquid electrolyte will be injected into the cell having a separator.
- the separator may be a conventional polymer-based separator such as a Celgard® separator or a Whatman® borosilicate glass fiber separator, or a cellulose-based separator, such as Dreamweaver® nonwoven nanofiber separator.
- the electrolyte is a solution comprising a salt of sodium and one or more carbonates selected from ethylene carbonate, propylene carbonate, dimethylcarbonate, ethyl methyl carbonate, diethyl carbonate, vinylene carbonate, and fluoroethylene carbonate.
- the electrolyte may further comprise an additive selected from the group consisting of vinylene carbonate (VC) (in an amount ranging from 0.1 to 10 wt.%, preferably from 0.5 to 5.0 wt.%), 1 ,3-Propanesultone (PS) (in an amount ranging from 0.1 to 5 wt.%, preferably from 0.5 to 3.0 wt.%), Succinonitrile (SN) (in an amount ranging from 0.1 to 5 wt.%, preferably from 0.5 to 2.0 wt.%), Sodium difluoro(oxalato)borate (NaODFB) (in an amount ranging from 0.05 to 10 wt.%, preferably from 0.2 to 1 .0 wt.%).
- Additives can be used individually or mixture of them, in order to achieve the high temperature performance and low self-discharge performance of the Na ion battery.
- the electrolyte may be prepared by adding the salt in the solvent under stirring, and then adding the additive into the obtained solution.
- the adding sequence may be changed, like adding additives into solvent first, then adding salt.
- the whole preparation is carried out in inert atmosphere (under argon or nitrogen).
- the present invention also relates to the use of the material of formula (I) as defined above, as positive electrode active material for Na-ion batteries.
- the present invention also relates to a positive electrode comprising at least one material of formula (I).
- Said positive electrode may further comprise a current collector.
- the invention also relates to a Na-ion cell comprising at least one positive electrode as previously defined, at least one negative electrode, and at least one electrolyte as previously defined, and is prepared as previously described.
- the Na-ion cell implemented in the method of the invention may be a half-cell using metallic sodium as negative electrode, or a full cell using hard carbon as negative electrode.
- the Na-ion cell is a coin cell, a pouch cell, a cylindrical cell or a prismatic cell.
- Said Na-ion cell may also comprise at least one separator selected from the group consisting of glass fiber, polyolefin separators, including polypropylene (PP), polyethylene (PE) or a polypropylene/polyethylene/polypropylene film.
- separators selected from the group consisting of glass fiber, polyolefin separators, including polypropylene (PP), polyethylene (PE) or a polypropylene/polyethylene/polypropylene film.
- Said Na-ion cell may be composed of a single electrochemical cell comprising two electrodes (i.e. one positive electrode and one negative electrode) separated by an electrolyte; or of a plurality of chemical cells assembled in series; or of a plurality of chemical cells assembled in parallel; or of a combination of the two assembly types.
- the positive electrode, separator, and negative electrode may be stacked layer by layer (one layer of electrodes by one layer of separator), before being folded and winded to a cell core.
- the core is then placed inside of the cell shell. After this, the cell is drought at 85°C under vacuum for about 24 hours.
- the electrolyte is then injected into the cell before said cell is sealed to assembling a Na-ion cell.
- Figure 1 concerns the evolution of the voltage (V) with the discharge potential limited to 3 V, as a function of amount of sodium in material of formula (I) for a sodium half-cell having NVPF positive electrode.
- Figure 2 concerns the derivative plots of the discharge curves in figure 1 which are used as finger prints to follow the extent of in-situ electrochemical modifications caused in the material of formula (I).
- Figure 3 concerns the evolution of the voltage (V), as a function of amount of sodium in the material of formula (I) (cycled between 3 and 4.3 V) for a sodium half-cell having NVPF positive electrode according to the invention.
- Figure 4 concerns the evolution of the capacity (in mAh g _1 ) as a function of the number of cycles for a for a sodium half-cell (cycled between 3 and 4.3 V) having NVPF positive electrode according to the invention.
- Figure 5 concerns the evolution of the voltage (V) with the discharge potential limited to 2 V, as a function of amount of sodium in the material of formula (I) in sodium ion full cells using hard carbon negative electrode and NVPF positive electrode, according to the invention.
- Figure 6 concerns the evolution of the energy (in Wh.Kg 1 ) as a function of the number of cycles for a for a sodium ion full cell (cycled between 2 and 4.3 V) having hard carbon negative electrode and NVPF positive electrode according to the invention.
- Figure 7 concerns the evolution of the voltage (V) with the discharge potential limited to 1 V, as a function of amount of sodium in the material of formula (I) for a sodium half cell having NVPF positive electrode, according to the invention.
- Figure 8 concerns the evolution of the voltage (V), as a function of amount of sodium in the material of formula (I) (cycled between 1 - 4.3 V) for a sodium half-cell having NVPF positive electrode according to the invention.
- Figure 9 concerns the evolution of the capacity (in mAh g _1 ) as a function of the number of cycles for a for a sodium half-cell (cycled between 1 - 4.3 V) having NVPF positive electrode according to the invention.
- Figure 10 concerns the evolution of the voltage (V) with the discharge potential down to 0 V, as a function of amount of sodium in the material of formula (I) in sodium ion full cells using hard carbon negative electrode and NVPF positive electrode, according to the invention.
- Figure 1 1 concerns the evolution of the voltage (V) with the discharge potential limited to 1.8 V, as a function of capacity (in mAh.g 1 ) for a sodium half-cell having NVPF mixed with layered oxide Na x M0 2 positive electrode, according to the invention.
- the materials (A) were modified electrochemically by charging said material to potential higher than 4.3 V and de-inserting more than 2 sodium from the structure.
- the electrochemical sodium de-insertion was carried out in half cells with metallic sodium as negative electrode or full cells using Na host material such as hard carbon, antimony, phosphorus, etc. as negative electrode.
- Na host material such as hard carbon, antimony, phosphorus, etc.
- 1 M (mol/litre) NaPF 6 dissolved in propylene carbonate was used as electrolyte.
- the charge curves represented in Figure 1 show that the extraction of the third sodium from the structure of material (A) happens through a third plateau at 4.75 V.
- the charge process was controlled by limiting the amount of sodium that is removed from the NVPF structure on the first charge to 2, 2.25, 2.5 and 2.75 etc.
- the material of formula (I) thus formed is represented here after as ‘NVPF Dc’ where Dc is the amount of sodium that is removed from the structure of the material (A) on first charge to introduce the electrochemical modifications.
- discharge curves in Figure 1 On subsequent discharge (discharge curves in Figure 1 ), a change in curve shape from biphasic plateau (NVPF 2.0) to S-shape (NVPF 2.25 and so on) is observed and the extent of modification increases with increasing sodium extraction on first charge.
- Such change in discharge curve shape indicates a structural modification that is caused by the extraction of more than 2 sodium ions from the material (A).
- the derivative plots of the discharge curves in Figure 2 are used as finger print to follow the extent of structural modifications. The modifications thus produced are irreversible and the cell cycles through S-shape curve on continuous cycling with comparable capacity retention as shown in Figures 3 and 4.
- Example 3 Application of the material of formula (I) for over-discharge protection of the sodium ion cells.
- Example 4 Usage of the material of formula (I) for achieving mixed electrodes of high gravimetric and volumetric energy densities.
- the layered sodium transition metal oxides provide higher density (typically 4 to 5 g/cm 3 ) in comparison to that of NVPF ( ⁇ 3.1 g/cm 3 ) material.
- the sodium layered oxides offers a better advantage in terms of volumetric energy density.
- the P2, P3 and certain 03 layered oxides e.g.
- Na x CuyFe z Mni- y-z 0 2 are non-stoichiometric and require extra sodium source in the cells for the electrochemical conversion of Na x M02 to NaiM0 2 in order to improve their gravimetric energy density. This was achieved by mixing NVPF with sodium layered oxides and activating the NVPF beyond 2 Na extractions. The sodium thus removed from the NVPF (beyond 2) is used for the electrochemical conversion of Na x M0 2 to NaiM0 2 ( Figure 1 1 ).
- the P2 type Na 2/ 3Mgo 3Mn 0 70 2 is used here to explain the proof of concept; similar principle can be extended to other P2, P3 Na x M0 2 phases and also for 03 phases for which the Na/M ratio is ⁇ 1 (e.g. Na x Cu y Fe z Mni- y-z 0 2 ).
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Abstract
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