CN113078298A - Sodium-magnesium-iron-manganese-based layered oxide material, preparation method and application - Google Patents
Sodium-magnesium-iron-manganese-based layered oxide material, preparation method and application Download PDFInfo
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- CN113078298A CN113078298A CN202010010825.7A CN202010010825A CN113078298A CN 113078298 A CN113078298 A CN 113078298A CN 202010010825 A CN202010010825 A CN 202010010825A CN 113078298 A CN113078298 A CN 113078298A
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- manganese
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- 239000000463 material Substances 0.000 title claims abstract description 127
- -1 Sodium-magnesium-iron-manganese Chemical compound 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 72
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 44
- 239000011734 sodium Substances 0.000 claims abstract description 41
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 35
- 239000001301 oxygen Substances 0.000 claims abstract description 34
- 229910052742 iron Inorganic materials 0.000 claims abstract description 24
- 239000013078 crystal Substances 0.000 claims abstract description 11
- 229910001437 manganese ion Inorganic materials 0.000 claims abstract description 10
- 239000007774 positive electrode material Substances 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 8
- 230000002441 reversible effect Effects 0.000 claims abstract description 6
- 238000007599 discharging Methods 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- 102100029469 WD repeat and HMG-box DNA-binding protein 1 Human genes 0.000 claims abstract description 4
- 101710097421 WD repeat and HMG-box DNA-binding protein 1 Proteins 0.000 claims abstract description 4
- 239000002243 precursor Substances 0.000 claims description 89
- 239000000843 powder Substances 0.000 claims description 59
- 238000010438 heat treatment Methods 0.000 claims description 36
- 239000002002 slurry Substances 0.000 claims description 36
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 30
- 239000011777 magnesium Substances 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 26
- 238000000227 grinding Methods 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 22
- 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 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000004146 energy storage Methods 0.000 claims description 19
- 238000001694 spray drying Methods 0.000 claims description 18
- 239000011572 manganese Substances 0.000 claims description 17
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 16
- 229910052708 sodium Inorganic materials 0.000 claims description 16
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 238000010248 power generation Methods 0.000 claims description 13
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 230000008859 change Effects 0.000 claims description 11
- 239000000395 magnesium oxide Substances 0.000 claims description 11
- 229910002651 NO3 Inorganic materials 0.000 claims description 10
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 8
- 238000010532 solid phase synthesis reaction Methods 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 7
- 238000004891 communication Methods 0.000 claims description 6
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 6
- 239000000347 magnesium hydroxide Substances 0.000 claims description 6
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 6
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004317 sodium nitrate Substances 0.000 claims description 6
- 235000010344 sodium nitrate Nutrition 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000000975 co-precipitation Methods 0.000 claims description 5
- 238000003980 solgel method Methods 0.000 claims description 5
- 239000002738 chelating agent Substances 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000002572 peristaltic effect Effects 0.000 claims description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 238000000498 ball milling Methods 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 239000002482 conductive additive Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 9
- 238000012360 testing method Methods 0.000 description 17
- 239000010405 anode material Substances 0.000 description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 10
- 239000002033 PVDF binder Substances 0.000 description 10
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 10
- 239000010447 natron Substances 0.000 description 10
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 10
- 229910018434 Mn0.5O2 Inorganic materials 0.000 description 9
- 239000013543 active substance Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 231100000252 nontoxic Toxicity 0.000 description 8
- 230000003000 nontoxic effect Effects 0.000 description 8
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 229910052723 transition metal Inorganic materials 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 239000006230 acetylene black Substances 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- 238000012983 electrochemical energy storage Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- 229910014103 Na-S Inorganic materials 0.000 description 2
- 229910014147 Na—S Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910001447 ferric ion Inorganic materials 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910018416 Mn0.33O2 Inorganic materials 0.000 description 1
- 229910003307 Ni-Cd Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 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 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- 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
- H01M4/366—Composites as layered products
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
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- 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
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
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Abstract
The invention discloses a sodium-magnesium-iron-manganese-based layered oxide material, a preparation method and application, wherein the material has a chemical general formula as follows: na (Na)a[MgbFeCMnd]O2+β(ii) a a, b, c, d and beta are respectively the mol percentage of the corresponding elements; the space group of the layered oxide material is
Oxygen ion changeThe valence layered oxide material is used for a positive electrode active material of a sodium ion secondary battery, when the positive electrode active material is charged for the first week, iron ions in crystal lattices lose electrons, the average valence state is increased from +3 to +4, oxygen ions in the crystal lattices lose electrons, and the average valence state is increased from-2 to a valence state between-2 and-1; during the first cycle of discharge, oxygen ions with higher valence state obtain electrons again, then iron ions obtain electrons and are reduced, along with the deep discharge, part of manganese ions can obtain electrons, and the average valence state is changed from quadrivalence to trivalence; from the second week, iron, oxygen and manganese ions participate in reversible electron gain and loss processes during charging and discharging.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a sodium-magnesium-iron-manganese-based layered oxide material with variable valence of oxygen ions, a preparation method and application thereof.
Background
Along with the development and progress of society, the demand of human beings for energy is increasing, but the application of traditional fossil energy such as coal, oil, natural gas is gradually limited in many aspects due to the gradual depletion of resources and the increasingly severe urban environmental pollution and greenhouse effect problems caused by the traditional fossil energy, so that the development of sustainable clean energy is always a direction of concern of various countries. However, in the process of converting wind energy, solar energy, tidal energy and the like into electric energy, the renewable energy sources are greatly limited by natural conditions and have the characteristics of obvious time discontinuity, spatial distribution nonuniformity and the like, so that the electric power provided by the renewable energy sources is poor in controllability and stability and cannot be directly input into a power grid for use. Therefore, only by matching with a high-performance large-scale energy storage system, the problem of time difference contradiction between power generation and power utilization is solved, and the quality of electric energy is adjusted, so that reliable power supply of a power system can be ensured. At present, the sustainable development of energy in China has urgent need for large-scale energy storage technology, and the method is also a research hotspot in all countries in the world.
The existing energy storage modes at present are physical energy storage and chemical energy storage. Pumped storage in physical energy storage is the most used at present, the energy storage is the largest, but pumped storage is limited by geographical positions, the construction period is long, and other physical energy storage such as compressed air energy storage, flywheel energy storage and the like are not on a large scale. Electrochemical energy storage refers to the storage or release of electricity by reversible chemical reactions, and is widely concerned by people with its advantages of high energy conversion efficiency and power density, long cycle life, short construction period, low maintenance cost, etc.
At present, electrochemical energy storage mainly includes high-temperature sodium-sulfur batteries, flow batteries, lead-acid batteries, lithium ion batteries and the like. The working temperature of the Na-S battery is 300 ℃, the metal sodium and elemental sulfur are in a molten state, and if the materials are damaged at high temperature, fire is easily caused in a battery module, so that the safety problem is great, and the Na-S battery cannot be applied in a large scale. The flow battery has low energy density and large volume. Compared with Ni-Cd batteries, lead-acid batteries have no memory effect and low cost, always account for most of the energy storage market at present, and are widely applied. But the disadvantages are obvious, such as lead pollution to environment, low energy density of the battery, heavy mass, large volume and increased maintenance cost. Because the energy storage system needs to have the characteristics of low cost, environmental protection, long service life, high safety performance and the like, among numerous electrochemical energy storage materials, lithium ion secondary batteries and sodium ion secondary batteries become important technologies in energy storage technology.
The lithium ion battery used as electrochemical energy storage has the advantages of high energy density, high cycle stability, long cycle life, small volume, light weight, no pollution and the like, and is widely applied to daily life. Sodium is considered to be an alkali metal element in the periodic table with lithium and therefore has similar physicochemical properties. The sodium ion battery and the lithium ion battery have similar charge-discharge storage mechanisms, more importantly, the sodium is abundant and widely distributed in nature, and has a very obvious price advantage. Besides the low price of sodium ions, aluminum foils can be used as the positive and negative current collectors of the sodium ion battery, while the negative electrode of the lithium ion battery can only use copper, which is obviously more expensive than aluminum, so that the raw material cost is low and the raw material is easy to obtain, and the sodium ion battery is more and more widely concerned worldwide due to the advantages.
However, currently, sodium-ion batteries are still in the research stage, no commercial sodium-ion battery cathode material is available, and researches on sodium-ion batteries by researchers are mainly focused on an oxide cathode material Na with a layered structurexMO2(M represents a 3d transition metal element and may contain one or more of Ti, V, Cr, Fe, Mn, Cr, Mn, or a combination thereof,Co, Ni, Cu, Nb, Ru, Mo, Zn, etc.). The basis of the cell is a redox reaction, which is essentially a valence change, i.e., a transfer and shift of electrons. The half reaction of electron loss is oxidation reaction, and the valence of the anode material is increased; the half reaction of obtaining electrons is a reduction reaction, and the valence in the anode material is reduced. The above-described layered oxide positive electrode materials of the sodium ion battery all have transition metal materials capable of undergoing redox reactions, and the variable valence transition metal in the initial state of the materials is in a lower valence state.
Disclosure of Invention
The embodiment of the invention provides a sodium-magnesium-iron-manganese-based layered oxide material with oxygen ion valence change, a preparation method and application. The material not only has higher specific capacity and specific energy, the specific capacity is 1.5 to 2 times of that of the anode material of the common sodium-ion battery, but also has better cycle life and great practical value, and can be used for large-scale energy storage equipment of solar power generation, wind power generation, smart grid peak regulation, distributed power stations, backup power supplies or communication base stations.
In a first aspect, the invention discloses a sodium-magnesium-iron-manganese-based layered oxide material with oxygen ion valence change, which has a chemical general formula: na (Na)a[MgbFeCMnd]O2+β；
The a, b, c, d and beta are respectively the mol percentage of the corresponding elements; the relationship between them satisfies b + c + d ═ 1, and a +2b +3c +4d × (2+ β); wherein a is more than or equal to 0.67 and less than or equal to 1; b is more than or equal to 0.083 and less than or equal to 0.33; c is more than or equal to 0.16 and less than or equal to 0.67; d is more than or equal to 0.25 and less than or equal to 0.5; beta is more than or equal to minus 0.02 and less than or equal to 0.02;
the space group of the layered oxide material is
The sodium-magnesium-iron-manganese-based layered oxide material with the oxygen ion valence change is used for a positive electrode active material of a sodium ion secondary battery, when the material is charged for the first week, iron ions in crystal lattices lose electrons, the average valence state is increased from +3 valence to +4 valence, oxygen ions in the crystal lattices lose electrons, and the average valence state is increased from-2 to a valence state between-2 and-1; during the first cycle of discharge, oxygen ions with higher valence state obtain electrons again, then iron ions obtain electrons and are reduced, along with the deep discharge, part of manganese ions can obtain electrons, and the average valence state is changed from quadrivalence to trivalence; from the second week, iron ions, oxygen ions and manganese ions participate in reversible electron gaining and losing processes during charging and discharging.
In a second aspect, embodiments of the present invention provide a method for preparing a layered oxide material as described in the first aspect, where the method is a solid phase method, and the method includes:
mixing 100-108 wt% of sodium carbonate with the stoichiometric amount of required sodium, and magnesium hydroxide and/or magnesium oxide, ferric oxide and/or ferroferric oxide and manganese dioxide with the stoichiometric amount of required sodium according to a proportion to form a precursor;
uniformly mixing the precursors by adopting a ball milling method to obtain precursor powder;
placing the precursor powder in a muffle furnace, and carrying out heat treatment for 2-24 hours at 600-1000 ℃ in an air atmosphere;
and grinding the precursor powder after the heat treatment to obtain the layered oxide material.
In a third aspect, an embodiment of the present invention provides a method for preparing a layered oxide material according to the first aspect, where the method is a spray drying method, and includes:
mixing 100-108 wt% of sodium carbonate with the stoichiometric amount of required sodium, and magnesium hydroxide and/or magnesium oxide, ferric oxide and/or ferroferric oxide and manganese dioxide with the stoichiometric amount of required sodium according to a proportion to form a precursor;
adding ethanol or water into the precursor, and uniformly stirring to form slurry;
spray drying the slurry to obtain precursor powder;
placing the precursor powder in a muffle furnace, and carrying out heat treatment for 2-24 hours at 600-1000 ℃ in an air atmosphere;
and grinding the precursor powder after the heat treatment to obtain the layered oxide material.
In a fourth aspect, an embodiment of the present invention provides a method for preparing a layered oxide material according to the first aspect, where the method is a spray drying method, and includes:
sodium nitrate, magnesium nitrate, manganese nitrate, ferric nitrate and/or ferrous nitrate in stoichiometric ratio are/is adopted as precursors;
adding ethanol or water into the precursor, and uniformly stirring to form slurry;
spray drying the slurry to obtain precursor powder;
placing the precursor powder in a muffle furnace, and carrying out heat treatment for 2-24 hours at 600-1000 ℃ in an air atmosphere;
and grinding the precursor powder after the heat treatment to obtain the layered oxide material.
In a fifth aspect, embodiments of the present invention provide a method for preparing a layered oxide material according to the first aspect, where the method is a sol-gel method, and the method includes:
dissolving one or more of sodium acetate, sodium nitrate, sodium carbonate or sodium sulfate with the stoichiometric quantity of 100-108 wt% of the required sodium and nitrate or sulfate respectively containing magnesium, manganese and iron in water or ethanol according to the stoichiometric ratio to form precursor solution;
stirring at 50-100 ℃, adding a proper amount of chelating agent, and evaporating to dryness to form precursor gel;
placing the precursor gel in a crucible, and presintering for 2 hours at the temperature of 200-500 ℃ in the air atmosphere;
then carrying out heat treatment for 2-24 hours at 600-1000 ℃;
and grinding the precursor powder after the heat treatment to obtain the layered oxide material.
In a sixth aspect, embodiments of the present invention provide a method for preparing a layered oxide material as described in the first aspect, where the method is a co-precipitation method, and the method includes:
respectively dissolving nitrate or sulfate or carbonate or hydroxide respectively containing magnesium, iron and manganese in required stoichiometric ratio in deionized water with certain volume to respectively form solutions;
respectively adding the solution into ammonia water solution with certain concentration and pH value in a dropwise manner by using a peristaltic pump to generate precipitate;
cleaning the obtained precipitate with deionized water, drying, and uniformly mixing with sodium carbonate according to a stoichiometric ratio to obtain a precursor;
placing the precursor in a crucible, and carrying out heat treatment for 2-24 hours at 600-1000 ℃ in an air atmosphere to obtain precursor powder;
and grinding the precursor powder after the heat treatment to obtain the layered oxide material.
In a seventh aspect, an embodiment of the present invention provides a positive electrode plate of a sodium ion secondary battery, where the positive electrode plate includes:
a current collector, a conductive additive and a binder coated on the current collector, and a layered oxide material as described above in the first aspect.
In an eighth aspect, an embodiment of the present invention provides a sodium-ion secondary battery including the positive electrode sheet described in the seventh aspect.
In a ninth aspect, embodiments of the present invention provide a use of the sodium ion secondary battery according to the seventh aspect, where the sodium ion secondary battery is used in solar power generation, wind power generation, smart grid peak shaving, distributed power plants, backup power sources, or large-scale energy storage equipment of communication base stations.
The sodium-magnesium-iron-manganese-based layered oxide material provided by the embodiment of the invention is simple to prepare, and the contained elements, namely sodium, magnesium, iron and manganese, are nontoxic and safe elements and have high abundance in the earth crust, so that the manufacturing cost is low. In the sodium ion secondary battery using the layered oxide material, first-cycle charging electrons are provided by oxidation of ferric ions and lattice oxygen ions; during first-cycle discharge, firstly, the part of higher-valence oxygen ions losing electrons obtain electrons again, the higher-valence oxygen ions are changed into negative divalent from the higher-valence state, then the iron ions obtain electrons changed from quadrivalent to trivalent, and along with deep discharge, part of manganese ions can obtain electrons changed from quadrivalent to trivalent; from the second week, iron ions, oxygen ions and manganese ions can jointly participate in a reversible electron gaining and losing process in the charging and discharging process, and finally, relatively high discharge capacity is achieved. The material has good cycle performance and safety performance, has great practical value, and can be used for large-scale energy storage equipment of solar power generation, wind power generation, smart grid peak regulation, distributed power stations, backup power supplies or communication base stations.
Drawings
The technical solutions of the embodiments of the present invention are further described in detail with reference to the accompanying drawings and embodiments.
Fig. 1 is a schematic diagram of a crystal structure and a coordination diagram of sodium ions of a layered oxide of a sodium ion battery provided by an embodiment of the invention;
FIG. 2 is a schematic diagram of the operating potential of a redox couple provided by an embodiment of the present invention in a sodium metal half cell;
FIG. 3 is an XRD pattern of a plurality of layered oxide materials of varying elemental mole percentages provided by embodiments of the present invention;
FIG. 4 is a flow chart of a method for preparing a layered oxide material by a solid phase method according to example 2 of the present invention;
FIG. 5 is a flow chart of a method for preparing a layered oxide material by a spray drying method according to embodiment 3 of the present invention;
FIG. 6 is a flow chart of another method for preparing a layered oxide material by a spray drying method according to example 4 of the present invention;
FIG. 7 is a flowchart of a method for preparing a layered oxide material by a sol-gel method according to example 5 of the present invention;
FIG. 8 is a flow chart of a method for preparing a layered oxide material by co-precipitation as provided in example 6 of the present invention;
fig. 9 is a charge-discharge curve diagram of a sodium ion battery at 1.5-4.5V according to embodiment 7 of the present invention;
fig. 10 is a charge-discharge curve diagram of a sodium ion battery at 1.5-4.5V according to embodiment 8 of the present invention;
fig. 11 is a charge-discharge curve diagram of a sodium ion battery at 1.5-4.5V according to embodiment 9 of the present invention;
fig. 12 is a charge-discharge curve diagram of a sodium ion battery at 1.5-4.5V according to embodiment 10 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples, but the present invention is not limited thereto.
Example 1
The embodiment of the invention provides a sodium-magnesium-iron-manganese-based layered oxide material with oxygen ion valence change, a preparation method and application. The layered oxide material is simple to prepare, and the contained elements of sodium, magnesium, iron and manganese are nontoxic and safe elements, and have high abundance in the earth crust, so the manufacturing cost is low. The sodium ion secondary battery using the sodium-magnesium-iron-manganese-based layered oxide material is simple in material preparation, and the material is found to have high specific mass capacity and specific energy in a half-battery test, wherein the specific capacity is 1.5 to 2 times of that of a common sodium ion battery anode material, the cycle life is long, the material has high practical value, and the material can be used for large-scale energy storage equipment of solar power generation, wind power generation, peak regulation of an intelligent power grid, a distributed power station, a backup power supply or a communication base station.
The invention provides a sodium-magnesium-iron-manganese-based layered oxide material with oxygen ion valence change, which has a chemical general formula as follows: na (Na)a[MgbFeCMnd]O2+β；
a, b, c, d and beta are respectively the mol percentage of the corresponding elements; the relationship between them satisfies b + c + d ═ 1, and a +2b +3c +4d × (2+ β); wherein a is more than or equal to 0.67 and less than or equal to 1; b is more than or equal to 0.083 and less than or equal to 0.33; c is more than or equal to 0.16 and less than or equal to 0.67; d is more than or equal to 0.25 and less than or equal to 0.5; beta is more than or equal to minus 0.02 and less than or equal to 0.02;
the space group of the sodium-magnesium-iron-manganese-based layered oxide material is
A sodium magnesium iron manganese-based layered oxide material having oxygen ion valence change is used for a positive electrode active material of a sodium ion secondary battery. During the first charging cycle (corresponding to the extraction of sodium ions), the iron ions in the crystal lattice lose electrons, represented by Fe3+Conversion to Fe4+Oxygen ions in the crystal lattice lose electrons, from O2-Conversion to O2 x-Wherein 0 < x < 4, the average valence state increasing from-2 to a valence state between-2 and-1; during the first cycle of discharge (corresponding to the intercalation of sodium ions), oxygen ions with higher valence state obtain electrons again, then iron ions obtain electrons and are reduced, along with the deepening of discharge (the intercalation of sodium ions is increased), part of manganese ions can obtain electrons, and the average valence state can be changed from quadrivalence to trivalence; from the second week, iron, oxygen and manganese ions participate in reversible electron gain and loss processes during charging and discharging.
In particular, the sodium-magnesium-iron-manganese-based layered oxide material of the embodiment introduces variable valence transition metal Fe, which plays an especially important role in the layered oxide material.
In the positive electrode material, the introduction of anion valence change makes it possible for the material to break through the theoretical capacity limit, but it is noted that the capacity contributed by lattice oxygen as a structural skeleton participating in valence change will undoubtedly cause great damage to the entire junction structure, such as causing structural distortion, collapse of the layered structure, and the like.
By introducing variable-valence transition metal Fe, the variable-valence transition metal shares part of capacity contribution tasks while oxygen participates in capacity contribution, and the sodium ion layered cathode material with stable structure and considerable capacity and anion variable valence can be obtained. In this patent it can be seen that the cycling becomes significantly better over a wide voltage interval.
The addition of Fe makes the material more prone to an O3 structure, with space group being R-3m, which is different from the common layered oxide cathode material structure with anion valence change (usually P2 structure, space group P63/mmc). The O3 structure has more Na content and therefore also has a relatively higher capacity. For a specific comparison, see fig. 1 and table 1.
TABLE 1
Lamellar with anionic valencyThe positive electrode material often needs higher oxygen activation voltage (usually about 4.5V), and the lower potential Fe is introduced3+So that the oxygen activity is activated at 4.0V and the oxygen reaction is completed within 4.3V. The operating potential of a redox couple common in batteries in sodium metal half-cells can be seen in figure 2.
The introduction of Fe breaks the ordered distribution of the transition metal layer of the common oxygen valence-variable material, so that the mixed discharge of anions and cations is caused, and the reversibility of oxygen is promoted.
Example 2
The embodiment provides a preparation method of a sodium-magnesium-iron-manganese-based layered oxide material, specifically a solid-phase method, as shown in fig. 4, including:
and 204, grinding the precursor powder after heat treatment to obtain the sodium-magnesium-iron-manganese-based layered oxide material.
The preparation method of the natron-based layered oxide material provided in this example can be used to prepare the natron-based layered oxide material described in example 1 above. The method provided by the embodiment is simple and easy to implement, low in cost, safe and nontoxic in used materials, and suitable for large-scale manufacturing.
Example 3
The embodiment provides a preparation method of a sodium-magnesium-iron-manganese-based layered oxide material, specifically a spray drying method, as shown in fig. 5, including:
301, mixing sodium carbonate with the stoichiometric quantity of 100-108 wt% of the required sodium, magnesium hydroxide and/or magnesium oxide, ferric oxide and/or ferroferric oxide and manganese dioxide with the required stoichiometric quantity according to a proportion to form a precursor;
304, placing the precursor powder in a muffle furnace, and carrying out heat treatment for 2-24 hours in an air atmosphere at 600-1000 ℃;
and 305, grinding the precursor powder after heat treatment to obtain the sodium-magnesium-iron-manganese-based layered oxide material.
The preparation method of the natron-based layered oxide material provided in this example can be used to prepare the natron-based layered oxide material described in example 1 above. The method provided by the embodiment is simple and easy to implement, low in cost, safe and nontoxic in used materials, and suitable for large-scale manufacturing.
Example 4
The embodiment provides a preparation method of a sodium-magnesium-iron-manganese-based layered oxide material, specifically a spray drying method, as shown in fig. 6, including:
and 405, grinding the precursor powder after heat treatment to obtain the sodium-magnesium-iron-manganese-based layered oxide material.
The preparation method of the natron-based layered oxide material provided in this example can be used to prepare the natron-based layered oxide material described in example 1 above. The method provided by the embodiment is simple and easy to implement, low in cost, safe and nontoxic in used materials, and suitable for large-scale manufacturing.
Example 5
The embodiment provides a method for preparing a sodium-magnesium-iron-manganese-based layered oxide material, specifically a sol-gel method, as shown in fig. 7, including:
and 505, grinding the precursor powder after heat treatment to obtain the sodium-magnesium-iron-manganese-based layered oxide material.
The preparation method of the natron-based layered oxide material provided in this example can be used to prepare the natron-based layered oxide material described in example 1 above. The method provided by the embodiment is simple and easy to implement, low in cost, safe and nontoxic in used materials, and suitable for large-scale manufacturing.
Example 6
The embodiment provides a preparation method of a sodium-magnesium-iron-manganese-based layered oxide material, specifically a coprecipitation method, as shown in fig. 8, including:
specifically, the concentration of the ammonia water solution is within the range of 2-12 mol/L, and the pH value is 8-13.
and 605, grinding the precursor powder obtained by the heat treatment to obtain the sodium-magnesium-iron-manganese-based layered oxide material.
The preparation method of the natron-based layered oxide material provided in this example can be used to prepare the natron-based layered oxide material described in example 1 above. The method provided by the embodiment is simple and easy to implement, low in cost, safe and nontoxic in used materials, and suitable for large-scale manufacturing.
In order to better understand the technical scheme provided by the invention, the following specific examples respectively illustrate the specific processes for preparing the sodium-magnesium-iron-manganese-based layered oxide material by using the methods provided by the above embodiments of the invention, and the methods for applying the material to the secondary battery and the battery characteristics.
Example 7
In this embodiment, the solid-phase method described in embodiment 2 is used to prepare the sodium-magnesium-iron-manganese-based layered oxide material, and the method includes:
mixing Na2CO3(analytically pure), MgO (analytically pure), Fe2O3(analytically pure), MnO2(analytically pure) mixing according to the required stoichiometric ratio; grinding for half an hour in an agate mortar to obtain a precursor; tabletting the precursor and transferring to Al2O3Treating in a crucible at 900 deg.C for 15 hr to obtain black powder of layered oxide material Na0.83Mg0.083Fe0.67Mn0.25O2The XRD pattern is shown in figure 3, and from the XRD pattern, Na is seen0.83Mg0.083Fe0.67Mn0.25O2The crystal structure of (a) is an oxide of O3 phase layered structure.
The prepared layered oxide material is used as an active substance of a battery positive electrode material for a sodium ion batteryThe preparation method comprises the following specific steps: the prepared Na0.83Mg0.083Fe0.67Mn0.25O2Mixing the powder with acetylene black and a binder polyvinylidene fluoride (PVDF) according to a mass ratio of 80:10:10, adding a proper amount of N-methylpyrrolidone (NMP) solution, grinding the mixture in a normal-temperature drying environment to form slurry, then uniformly coating the slurry on a current collector aluminum foil, drying the slurry under an infrared lamp, and cutting the dried slurry into (8 x 8) mm2The pole piece of (2). The pole piece is dried for 10 hours at 110 ℃ under vacuum condition, and then transferred to a glove box for standby.
The assembly of the simulated cell was carried out in a glove box under Ar atmosphere, with sodium metal as the counter electrode and NaClO as the counter electrode4Diethyl carbonate (EC: DEC) solution was used as an electrolyte to assemble a CR2032 button cell. The charge and discharge test was performed at a current density of C/10 using a constant current charge and discharge mode. The test results are shown in FIG. 9 under the conditions of a discharge cutoff voltage of 1.5V and a charge cutoff voltage of 4.3V. The charge-discharge cycle curves for the first and second weeks are shown in fig. 9, and it can be seen that the specific discharge capacity for the first week can reach 142.5mAh/g, the coulombic efficiency for the second week is about 94.98%, and the cycle is stable.
Example 8
In this example, the solid-phase method described in the foregoing example 2 was used to prepare a sodium-magnesium-iron-manganese-based layered oxide material.
The procedure of the preparation of the example is as in example 6, but the precursor compound Na is used2CO3(analytically pure), MgO (analytically pure), Fe2O3(analytically pure), MnO2(analytically pure) stoichiometry differs from that in example 6, the heat treatment was carried out at 900 ℃ for 15 hours to obtain a black powder of Na as the layered oxide material0.83Mg0.17Fe0.50Mn0.33O2The XRD pattern is shown in figure 3.
The prepared layered oxide material is used as an active substance of a battery anode material for preparing a sodium ion battery, and an electrochemical charge and discharge test is carried out. The procedure and test method were the same as in example 6. The test voltage range is 1.5V-4.3V, and the test result is shown in figure 10. The first and second week charge and discharge curves are shown in fig. 10. It can be seen that the specific discharge capacity at the first cycle can reach 141.8mAh/g, and the coulomb efficiency at the second cycle is about 95.20%.
Example 9
In this example, the layered oxide material was prepared using the solid phase method described in example 2 above.
The procedure of the preparation of the example is as in example 6, but the precursor compound Na is used2CO3(analytically pure), MgO (analytically pure), Fe2O3(analytically pure), MnO2(analytically pure) stoichiometry differs from that in example 6, the heat treatment was carried out at 900 ℃ for 15 hours to obtain a black powder of Na as the layered oxide material0.83Mg0.25Fe0.333Mn0.417O2The XRD pattern is shown in figure 3.
The prepared layered oxide material is used as an active substance of a battery anode material for preparing a sodium ion battery, and an electrochemical charge and discharge test is carried out. The procedure and test method were the same as in example 6. The test voltage range is 1.5V-4.3V, and the test result is shown in figure 11. The first and second week charge and discharge curves are shown in fig. 11. It can be seen that the specific discharge capacity at the first cycle can reach 192.3mAh/g, and the coulomb efficiency at the second cycle is about 96.66%.
Example 10
In this example, the layered oxide material was prepared using the solid phase method described in example 2 above.
The procedure of the preparation of the example is as in example 6, but the precursor compound Na is used2CO3(analytically pure), MgO (analytically pure), Fe2O3(analytically pure), MnO2(analytically pure) stoichiometry differs from that in example 6, the heat treatment was carried out at 900 ℃ for 15 hours to obtain a black powder of Na as the layered oxide material0.83Mg0.33Fe0.17Mn0.5O2The XRD pattern is shown in figure 3.
The prepared layered oxide material is used as an active substance of a battery anode material for preparing a sodium ion battery, and an electrochemical charge and discharge test is carried out. The procedure and test method were the same as in example 6. The test voltage range is 1.5V-4.3V, and the test result is shown in figure 12. The first and second week charge and discharge curves are shown in fig. 12. It can be seen that the specific discharge capacity at the first cycle can reach 207.4mAh/g, and the coulomb efficiency at the second cycle is about 96.55%.
Example 11
In this embodiment, the spray drying method described in embodiment 3 is used to prepare the sodium-magnesium-iron-manganese-based layered oxide material, and the method includes:
mixing Na2CO3(analytically pure), MgO (analytically pure), Fe2O3(analytically pure), MnO2(analytically pure) mixing according to the required stoichiometric ratio; adding ethanol or water into the mixed powder, uniformly stirring to form slurry, carrying out spray drying on the slurry to obtain precursor powder, placing the precursor powder in a muffle furnace, treating for 15 hours at 900 ℃ in an air atmosphere, and grinding the layered oxide material of the black powder in an agate mortar for half an hour to obtain a precursor; tabletting the precursor and transferring to Al2O3The crucible was treated at 900 ℃ for 15 hours in a muffle furnace to obtain a black powder of O3-type layered oxide material Na0.83Mg0.33Fe0.17Mn0.5O2。
The prepared layered oxide material is used for preparing a sodium ion battery as an active substance of a battery anode material, and the preparation method comprises the following specific steps: the prepared Na0.83Mg0.33Fe0.17Mn0.5O2Mixing the powder with acetylene black and a binder polyvinylidene fluoride (PVDF) according to a mass ratio of 80:10:10, adding a proper amount of N-methylpyrrolidone (NMP) solution, grinding the mixture in a normal-temperature drying environment to form slurry, then uniformly coating the slurry on a current collector aluminum foil, drying the slurry under an infrared lamp, and cutting the dried slurry into (8 x 8) mm2The pole piece of (2). The pole piece is dried for 10 hours at 110 ℃ under vacuum condition, and then transferred to a glove box for standby.
The assembly of the simulated cell was carried out in a glove box under Ar atmosphere, with sodium metal as the counter electrode and NaClO as the counter electrode4Diethyl carbonate (EC: DEC) solution was used as an electrolyte to assemble a CR2032 button cell. Using constant currentIn the charge/discharge mode, a charge/discharge test was performed at a current density of C/10. Under the conditions that the discharge cutoff voltage is 1.5V and the charge cutoff voltage is 4.3V, the first-cycle discharge specific capacity can reach 207.4mAh/g, the second-cycle coulombic efficiency is about 96.55 percent, and the cycle is stable.
Example 12
In this embodiment, the spray drying method described in embodiment 4 is used to prepare the sodium-magnesium-iron-manganese-based layered oxide material, and the method includes:
mixing Na2NO3(analytically pure), Mg (NO)3)2(analytically pure), Fe (NO)3)3(analytically pure), Mn (NO)3)2(analytically pure) mixing according to the required stoichiometric ratio; adding ethanol or water into the mixed powder, uniformly stirring to form slurry, carrying out spray drying on the slurry to obtain precursor powder, placing the precursor powder in a muffle furnace, treating for 15 hours at 900 ℃ in an air atmosphere, and grinding the layered oxide material of the black powder in an agate mortar for half an hour to obtain a precursor; tabletting the precursor and transferring to Al2O3The crucible was treated at 900 ℃ for 15 hours in a muffle furnace to obtain a black powder of O3-type layered oxide material Na0.83Mg0.33Fe0.17Mn0.5O2。
The prepared layered oxide material is used for preparing a sodium ion battery as an active substance of a battery anode material, and the preparation method comprises the following specific steps: the prepared Na0.83Mg0.33Fe0.17Mn0.5O2Mixing the powder with acetylene black and a binder polyvinylidene fluoride (PVDF) according to a mass ratio of 80:10:10, adding a proper amount of N-methylpyrrolidone (NMP) solution, grinding the mixture in a normal-temperature drying environment to form slurry, then uniformly coating the slurry on a current collector aluminum foil, drying the slurry under an infrared lamp, and cutting the dried slurry into (8 x 8) mm2The pole piece of (2). The pole piece is dried for 10 hours at 110 ℃ under vacuum condition, and then transferred to a glove box for standby.
The assembly of the simulated cell was carried out in a glove box under Ar atmosphere, with sodium metal as the counter electrode and NaClO as the counter electrode4Diethyl carbonate (EC: DEC) solution as electricityAnd (4) decomposing the solution to assemble the CR2032 button cell. The charge and discharge test was performed at a current density of C/10 using a constant current charge and discharge mode. Under the conditions that the discharge cutoff voltage is 1.5V and the charge cutoff voltage is 4.3V, the first-cycle discharge specific capacity can reach 207.4mAh/g, the second-cycle coulombic efficiency is about 96.55 percent, and the cycle is stable.
Example 13
In this embodiment, the sol-gel method described in the foregoing embodiment 5 is adopted to prepare a sodium-magnesium-iron-manganese-based layered oxide material, including:
mixing Na2NO3(analytically pure), Mg (NO)3)2(analytically pure), Fe (NO)3)3(analytically pure), Mn (NO)3)2(analytically pure) dissolving the components in water according to the required stoichiometric ratio to form a precursor solution; stirring at 80 ℃, adding a proper amount of chelating agent, evaporating to dryness to form precursor gel, placing the precursor gel in a crucible, presintering for 2 hours at 400 ℃ in air atmosphere, and then performing heat treatment for 15 hours at 900 ℃; grinding the precursor powder after heat treatment to obtain O3-type layered oxide material Na of black powder0.83Mg0.33Fe0.17Mn0.5O2。
The prepared layered oxide material is used for preparing a sodium ion battery as an active substance of a battery anode material, and the preparation method comprises the following specific steps: the prepared Na0.83Mg0.33Fe0.17Mn0.5O2Mixing the powder with acetylene black and a binder polyvinylidene fluoride (PVDF) according to a mass ratio of 80:10:10, adding a proper amount of N-methylpyrrolidone (NMP) solution, grinding the mixture in a normal-temperature drying environment to form slurry, then uniformly coating the slurry on a current collector aluminum foil, drying the slurry under an infrared lamp, and cutting the dried slurry into (8 x 8) mm2The pole piece of (2). The pole piece is dried for 10 hours at 110 ℃ under vacuum condition, and then transferred to a glove box for standby.
The assembly of the simulated cell was carried out in a glove box under Ar atmosphere, with sodium metal as the counter electrode and NaClO as the counter electrode4Diethyl carbonate (EC: DEC) solution was used as an electrolyte to assemble a CR2032 button cell. Using constant current charge-discharge mode, at C/10 current densityAnd (5) carrying out charge and discharge tests at the same time. Under the conditions that the discharge cutoff voltage is 1.5V and the charge cutoff voltage is 4.3V, the first-cycle discharge specific capacity can reach 207.4mAh/g, the second-cycle coulombic efficiency is about 96.55 percent, and the cycle is stable.
Example 14
In this embodiment, the coprecipitation method described in the foregoing embodiment 6 is used to prepare the sodium-magnesium-iron-manganese-based layered oxide material, and the method includes:
mixing Mg (NO)3)2(analytically pure), Fe (NO)3)3(analytically pure), Mn (NO)3)2(analytically pure) dissolving the components in deionized water according to the required stoichiometric ratio to form a solution; the solution was slowly added dropwise to a 1mol/L aqueous ammonia solution using a peristaltic pump to form a precipitate. Cleaning the obtained precipitate with deionized water, drying, uniformly mixing with sodium carbonate according to a stoichiometric ratio to obtain precursor powder, placing the precursor powder in a crucible, carrying out heat treatment for 15 hours at 900 ℃ in an air atmosphere, grinding the heat-treated precursor powder to obtain O3-type layered oxide material Na of black powder0.83Mg0.33Fe0.17Mn0.5O2。
The prepared layered oxide material is used for preparing a sodium ion battery as an active substance of a battery anode material, and the preparation method comprises the following specific steps: the prepared Na0.83Mg0.33Fe0.17Mn0.5O2Mixing the powder with acetylene black and a binder polyvinylidene fluoride (PVDF) according to a mass ratio of 80:10:10, adding a proper amount of N-methylpyrrolidone (NMP) solution, grinding the mixture in a normal-temperature drying environment to form slurry, then uniformly coating the slurry on a current collector aluminum foil, drying the slurry under an infrared lamp, and cutting the dried slurry into (8 x 8) mm2The pole piece of (2). The pole piece is dried for 10 hours at 110 ℃ under vacuum condition, and then transferred to a glove box for standby.
The assembly of the simulated cell was carried out in a glove box under Ar atmosphere, with sodium metal as the counter electrode and NaClO as the counter electrode4Diethyl carbonate (EC: DEC) solution was used as an electrolyte to assemble a CR2032 button cell. Charge and discharge tests were performed at C/10 current density using a constant current charge and discharge mode. Under the conditions that the discharge cutoff voltage is 1.5V and the charge cutoff voltage is 4.3V, the first-cycle discharge specific capacity can reach 207.4mAh/g, the second-cycle coulombic efficiency is about 96.55 percent, and the cycle is stable.
The sodium-magnesium-iron-manganese-based layered oxide material provided by the embodiment of the invention is simple to prepare, and the contained elements of sodium, magnesium, iron and manganese are nontoxic and safe elements, so that the abundance in the earth crust is high, and the manufacturing cost is low. The sodium ion secondary battery using the sodium-magnesium-iron-manganese-based layered oxide material is simple in material preparation, and the material is found in a half battery test to have ultrahigh specific mass capacity and specific energy, wherein the specific capacity is 1.5 to 2 times of that of a common sodium ion battery anode material, the cycle life is long, the material has great practical value, and the material can be used for large-scale energy storage equipment of solar power generation, wind power generation, peak regulation of an intelligent power grid, a distributed power station, a backup power supply or a communication base station.
Claims (10)
1. A sodium-magnesium-iron-manganese-based layered oxide material with oxygen ion valence change is characterized in that the layered oxide material has a chemical general formula: na (Na)a[MgbFeCMnd]O2+β；
The a, b, c, d and beta are respectively the mol percentage of the corresponding elements; the relationship between them satisfies b + c + d ═ 1, and a +2b +3c +4d × (2+ β); wherein a is more than or equal to 0.67 and less than or equal to 1; b is more than or equal to 0.083 and less than or equal to 0.33; c is more than or equal to 0.16 and less than or equal to 0.67; d is more than or equal to 0.25 and less than or equal to 0.5; beta is more than or equal to minus 0.02 and less than or equal to 0.02;
the space group of the layered oxide material is
The oxygen ion valence-variable layered oxide material is used for a positive electrode active material of a sodium ion secondary battery, when the material is charged for the first week, iron ions in crystal lattices lose electrons, the average valence state is increased from +3 to +4, oxygen ions in the crystal lattices lose electrons, and the average valence state is increased from-2 to a valence state between-2 and-1; during the first cycle of discharge, oxygen ions with higher valence state obtain electrons again, then iron ions obtain electrons and are reduced, along with the deep discharge, part of manganese ions can obtain electrons, and the average valence state is changed from quadrivalence to trivalence; from the second week, iron ions, oxygen ions and manganese ions participate in reversible electron gaining and losing processes during charging and discharging.
2. The layered oxide material of claim 1, wherein upon first cycle charging, oxygen ions in the crystal lattice are replaced by O2-To be converted into
Wherein x is more than 0 and less than 4.
3. A method for preparing the layered oxide material of claim 1, wherein the method is a solid phase method comprising:
mixing 100-108 wt% of sodium carbonate with the stoichiometric amount of required sodium, and magnesium hydroxide and/or magnesium oxide, ferric oxide and/or ferroferric oxide and manganese dioxide with the stoichiometric amount of required sodium according to a proportion to form a precursor;
uniformly mixing the precursors by adopting a ball milling method to obtain precursor powder;
placing the precursor powder in a muffle furnace, and carrying out heat treatment for 2-24 hours at 600-1000 ℃ in an air atmosphere;
and grinding the precursor powder after the heat treatment to obtain the layered oxide material.
4. A method for preparing the layered oxide material of claim 1, wherein the method is a spray drying method comprising:
mixing 100-108 wt% of sodium carbonate with the stoichiometric amount of required sodium, and magnesium hydroxide and/or magnesium oxide, ferric oxide and/or ferroferric oxide and manganese dioxide with the stoichiometric amount of required sodium according to a proportion to form a precursor;
adding ethanol or water into the precursor, and uniformly stirring to form slurry;
spray drying the slurry to obtain precursor powder;
placing the precursor powder in a muffle furnace, and carrying out heat treatment for 2-24 hours at 600-1000 ℃ in an air atmosphere;
and grinding the precursor powder after the heat treatment to obtain the layered oxide material.
5. A method for preparing the layered oxide material of claim 1, wherein the method is a spray drying method comprising:
sodium nitrate, magnesium nitrate, manganese nitrate, ferric nitrate and/or ferrous nitrate in stoichiometric ratio are/is adopted as precursors;
adding ethanol or water into the precursor, and uniformly stirring to form slurry;
spray drying the slurry to obtain precursor powder;
placing the precursor powder in a muffle furnace, and carrying out heat treatment for 2-24 hours at 600-1000 ℃ in an air atmosphere;
and grinding the precursor powder after the heat treatment to obtain the layered oxide material.
6. A method for preparing the layered oxide material of claim 1, wherein the method is a sol-gel method comprising:
dissolving one or more of sodium acetate, sodium nitrate, sodium carbonate or sodium sulfate with the stoichiometric quantity of 100-108 wt% of the required sodium and nitrate or sulfate respectively containing magnesium, manganese and iron in water or ethanol according to the stoichiometric ratio to form precursor solution;
stirring at 50-100 ℃, adding a proper amount of chelating agent, and evaporating to dryness to form precursor gel;
placing the precursor gel in a crucible, and presintering for 2 hours at the temperature of 200-500 ℃ in the air atmosphere;
then carrying out heat treatment for 2-24 hours at 600-1000 ℃;
and grinding the precursor powder after the heat treatment to obtain the layered oxide material.
7. A method for preparing the layered oxide material of claim 1, wherein the method is a co-precipitation method comprising:
respectively dissolving nitrate or sulfate or carbonate or hydroxide respectively containing magnesium, iron and manganese in required stoichiometric ratio in deionized water with certain volume to respectively form solutions;
respectively adding the solution into ammonia water solution with certain concentration and pH value in a dropwise manner by using a peristaltic pump to generate precipitate;
cleaning the obtained precipitate with deionized water, drying, and uniformly mixing with sodium carbonate and lithium hydroxide according to a stoichiometric ratio to obtain a precursor;
placing the precursor in a crucible, and carrying out heat treatment for 2-24 hours at 600-1000 ℃ in an air atmosphere to obtain precursor powder;
and grinding the precursor powder after the heat treatment to obtain the layered oxide material.
8. A positive electrode sheet for a sodium ion secondary battery, comprising:
a current collector, a conductive additive and a binder coated on said current collector, and a layered oxide material as defined in claim 1 above.
9. A sodium ion secondary battery comprising the positive electrode sheet as defined in claim 8.
10. Use of the sodium ion secondary battery according to claim 9 for solar power generation, wind power generation, smart grid peak shaving, distributed power plants, backup power sources or large-scale energy storage devices of communication base stations.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114784241A (en) * | 2022-04-13 | 2022-07-22 | 河北光兴半导体技术有限公司 | Sodium ion battery positive electrode material, preparation method thereof and sodium ion battery |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120020962A (en) * | 2010-08-31 | 2012-03-08 | 경상대학교산학협력단 | Sodium battery and the method manufacturing thereof |
| CN103840149A (en) * | 2012-11-27 | 2014-06-04 | 中国科学院物理研究所 | Sodium ion secondary battery, layered manganese-containing oxide active substance and anode active substance used in sodium ion secondary battery, and preparation method of layered manganese-containing oxide active substance |
| US20170025678A1 (en) * | 2015-07-21 | 2017-01-26 | Sharp Kabushiki Kaisha | Layered oxide materials for batteries |
| US20200112023A1 (en) * | 2017-03-29 | 2020-04-09 | Sumitomo Chemical Company, Limited | Composite metal oxide, positive electrode active material, positive electrode, sodium secondary battery, and method for producing composite metal oxide |
| CN111952579A (en) * | 2020-08-25 | 2020-11-17 | 东华理工大学 | High-energy-density sodium ion battery iron-manganese-based positive electrode material and preparation method thereof |
-
2020
- 2020-01-06 CN CN202010010825.7A patent/CN113078298A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120020962A (en) * | 2010-08-31 | 2012-03-08 | 경상대학교산학협력단 | Sodium battery and the method manufacturing thereof |
| CN103840149A (en) * | 2012-11-27 | 2014-06-04 | 中国科学院物理研究所 | Sodium ion secondary battery, layered manganese-containing oxide active substance and anode active substance used in sodium ion secondary battery, and preparation method of layered manganese-containing oxide active substance |
| US20170025678A1 (en) * | 2015-07-21 | 2017-01-26 | Sharp Kabushiki Kaisha | Layered oxide materials for batteries |
| US20200112023A1 (en) * | 2017-03-29 | 2020-04-09 | Sumitomo Chemical Company, Limited | Composite metal oxide, positive electrode active material, positive electrode, sodium secondary battery, and method for producing composite metal oxide |
| CN111952579A (en) * | 2020-08-25 | 2020-11-17 | 东华理工大学 | High-energy-density sodium ion battery iron-manganese-based positive electrode material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 阮艳莉;郑斌;刘萍;: "钠离子电池正极材料Na(Mn_(0.4)Fe_(0.2)Ni_(0.35)Mg_(0.05))O_2的制备及电化学性能研究", 现代化工 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114784241A (en) * | 2022-04-13 | 2022-07-22 | 河北光兴半导体技术有限公司 | Sodium ion battery positive electrode material, preparation method thereof and sodium ion battery |
| CN114784241B (en) * | 2022-04-13 | 2023-11-28 | 河北光兴半导体技术有限公司 | Sodium ion battery positive electrode material, preparation method thereof and sodium ion battery |
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