CN117334887A - Layered oxide composite positive electrode material, preparation method thereof and sodium battery - Google Patents
Layered oxide composite positive electrode material, preparation method thereof and sodium battery Download PDFInfo
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- CN117334887A CN117334887A CN202311630714.6A CN202311630714A CN117334887A CN 117334887 A CN117334887 A CN 117334887A CN 202311630714 A CN202311630714 A CN 202311630714A CN 117334887 A CN117334887 A CN 117334887A
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- Prior art keywords
- layered oxide
- sodium
- positive electrode
- lithium
- electrode material
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 62
- 239000011734 sodium Substances 0.000 title claims abstract description 61
- 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 abstract description 54
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 39
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000003513 alkali Substances 0.000 claims abstract description 34
- 239000010405 anode material Substances 0.000 claims abstract description 21
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 7
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 6
- 238000005245 sintering Methods 0.000 claims description 64
- 239000000203 mixture Substances 0.000 claims description 47
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- 239000002002 slurry Substances 0.000 claims description 10
- 239000011572 manganese Substances 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 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
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(iii) oxide Chemical compound O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 3
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 2
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 2
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 claims description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 2
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 14
- 238000012545 processing Methods 0.000 abstract description 9
- 230000000052 comparative effect Effects 0.000 description 32
- 239000010410 layer Substances 0.000 description 17
- 238000000875 high-speed ball milling Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229910001415 sodium ion Inorganic materials 0.000 description 6
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910013716 LiNi Inorganic materials 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 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 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910015866 LiNi0.8Co0.1Al0.1O2 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910003289 NiMn Inorganic materials 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002345 surface coating layer Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing 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
- 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
- H01M4/36—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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a layered oxide composite positive electrode material, a preparation method thereof and a sodium battery, and belongs to the technical field of sodium battery materials. The layered oxide composite positive electrode material provided by the invention comprises the following components: the sodium-electricity layered oxide and the lithium-electricity layered oxide layer coated on the surface of the sodium-electricity layered oxide comprise the following components: liN 1‑a M a O 2 N is selected from at least one of Ni, co, mn, al, M is selected from at least one of Mg, ca, ba, sr, Y, zr, ti, sn, V, mo, ru, nb, sb, a is more than or equal to 0 and less than or equal to 0.05, and lithium battery layered oxideThe layer accounts for 0.1% -2% of the total mass of the layered oxide composite anode material. According to the invention, the lithium battery layered oxide layer is coated on the surface of the sodium battery layered oxide, so that the air stability of the sodium battery layered oxide can be improved, the residual alkali on the surface can be reduced, and the processing performance can be improved.
Description
Technical Field
The invention relates to the technical field of sodium battery materials, in particular to a layered oxide composite positive electrode material, a preparation method thereof and a sodium battery.
Background
When the high-temperature solid phase method is adopted to sinter and prepare the layered oxide anode material of the sodium ion battery, after the sodium salt and the metal oxide are formed into a layered structure through the rupture and recombination of chemical bonds, part of the sodium salt does not enter the bulk phase structure of the material, but remains on the surface of the material to form alkaline substances, so that the material is over-strong in alkalinity, sodium in the bulk phase is easy to deviate from the alkaline substances such as sodium carbonate, sodium hydroxide and the like formed on the surfaces of particles when the material is stored in an air environment containing water and carbon dioxide, and the capacity of the sodium-electricity layered oxide is reduced, so that the anode material needs to be stored in a vacuum or protective atmosphere environment, and the storage cost is high. Meanwhile, the increase of the residual alkali on the surface can also lead to gel formation in the process of homogenizing the sodium-electricity layered oxide, so that the processing performance of the material is affected, and how to effectively reduce the residual alkali on the surface of the sodium-ion battery layered oxide positive electrode material and improve the processing performance of the material is needed to be solved.
In view of this, the present invention has been proposed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a layered oxide composite positive electrode material, a preparation method thereof and a sodium battery.
The invention solves the technical problems by adopting the following technical scheme.
The invention provides a layered oxide composite anode material, which comprises a sodium-electricity layered oxide and a lithium-electricity layered oxide layer coated on the surface of the sodium-electricity layered oxide, wherein the composition of the lithium-electricity layered oxide is as follows: liN 1-a M a O 2 N is selected from Ni, co, MAt least one of n and Al, M is at least one of Mg, ca, ba, sr, Y, zr, ti, sn, V, mo, ru, nb, sb, a is more than or equal to 0 and less than or equal to 0.05, and the lithium battery layered oxide layer accounts for 0.1-2% of the total mass of the layered oxide composite anode material.
The invention also provides a preparation method of the layered oxide composite anode material, which comprises the following steps: and mixing the sodium-electricity layered oxide with a lithium source and a metal source in proportion, and sintering at high temperature to obtain the layered oxide composite anode material.
The invention also provides a sodium battery, and the positive electrode of the sodium battery comprises the layered oxide composite positive electrode material.
The invention has the following beneficial effects:
the invention provides a layered oxide composite positive electrode material, a preparation method thereof and a sodium battery, wherein the layered oxide composite positive electrode material comprises sodium electric layered oxide and a lithium electric layered oxide layer coated on the surface of the sodium electric layered oxide, and the composition of the lithium electric layered oxide is as follows: liN 1-a M a O 2 N is selected from at least one of Ni, co, mn, al, M is selected from at least one of Mg, ca, ba, sr, Y, zr, ti, sn, V, mo, ru, nb, sb, a is more than or equal to 0 and less than or equal to 0.05, and the lithium battery layered oxide layer accounts for 0.1-2% of the total mass of the layered oxide composite anode material. The lithium battery layered oxide has good air stability compared with sodium battery layered oxide and excellent processability. Therefore, the lithium battery layered oxide layer is coated on the surface of the sodium battery layered oxide, the problem of poor air stability of the sodium battery layered oxide positive electrode material is fundamentally solved, the residual alkali content on the surface of the composite positive electrode material can be obviously reduced, the processing performance is improved, the structural stability of the sodium battery layered oxide can be improved through coating modification, and the electrochemical performance of the layered oxide composite positive electrode material is comprehensively improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an SEM image of the product obtained in example 1;
FIG. 2 is an SEM image of the product obtained in example 1 after 5 days in air;
FIG. 3 is an SEM image of the product of comparative example 2;
fig. 4 is an SEM image of the product obtained in comparative example 2 after 5 days of standing in air.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The layered oxide composite positive electrode material, the preparation method thereof and the sodium battery provided by the embodiment of the invention are specifically described below.
In a first aspect, an embodiment of the present invention provides a layered oxide composite positive electrode material, including a sodium-electricity layered oxide and a lithium-electricity layered oxide layer coated on the surface of the sodium-electricity layered oxide, where the composition of the lithium-electricity layered oxide is as follows: liN 1- a M a O 2 N is selected from at least one of Ni, co, mn, al, M is selected from at least one of Mg, ca, ba, sr, Y, zr, ti, sn, V, mo, ru, nb, sb, a is more than or equal to 0 and less than or equal to 0.05, and the lithium battery layered oxide layer accounts for 0.1-2% of the total mass of the layered oxide composite anode material.
The current method for reducing the residual alkali content on the surface of the layered oxide positive electrode material of the sodium ion battery is to wash the positive electrode material with water, acid or alcohol. Although the method can reduce the residual alkali content on the surface of the positive electrode material, soaking and washing can possibly cause certain ions on the surface of the positive electrode active material to be dissolved out to damage the surface structure of the positive electrode active material, and meanwhile, residual water molecules can be slightly diffused into particles to be difficult to remove, so that waste liquid pollution can be caused, and the subsequent material drying can increase the production cost. Although the residual alkali content on the surface of the positive electrode material can be reduced by washing, the defect of poor air stability of the layered oxide positive electrode material of the sodium ion battery cannot be fundamentally solved, the problem of poor processing performance still occurs, and the structural damage and the accelerated performance degradation of the sodium electric oxide positive electrode material can be caused by washing.
The inventor finds that the lithium battery layered oxide has good air stability compared with sodium battery layered oxide and excellent processability through long-term practice. The embodiments of the present invention therefore propose: and coating a lithium battery layered oxide layer on the surface of the sodium battery layered oxide to obtain the layered oxide composite anode material. According to the scheme provided by the embodiment of the invention, the lithium electric layered oxide layer is coated on the surface of the sodium electric layered oxide, so that the problem of poor air stability of the sodium electric layered oxide positive electrode material is fundamentally solved, the air stability of the sodium electric layered oxide is obviously improved, sodium in the sodium electric layered positive electrode material inside the composite positive electrode material is not easy to deviate from alkaline substances such as sodium carbonate and sodium hydroxide formed on the particle surface when the composite positive electrode material is stored in an air environment containing water and carbon dioxide, the generation amount of residual alkali on the surface is obviously reduced, and the processing performance of the material is improved. The practice proves that: the coating modification mode provided by the embodiment of the invention can improve the air stability of the sodium-electricity layered oxide, obviously reduce the generation amount of residual alkali on the surface of the composite positive electrode material, and ensure that the residual alkali of the composite positive electrode material is not increased even when the composite positive electrode material is placed in the air for a long time, so that the layered oxide composite positive electrode material has good processing performance, namely, the viscosity of the material is smaller after the material is homogenized and placed, and the material can be normally coated.
In an alternative embodiment, D of the sodium-electric layered oxide 50 The thickness of the lithium battery layered oxide layer is 2nm-50nm and is 1 μm-15 μm.
In an alternative embodiment, the layered oxide composite positive electrode material slurry having a solids content of 60% has a viscosity of no more than 6000Pa/s after standing under continuous agitation for 24 hours in a 25% relative humidity environment.
In an alternative embodiment, the layered oxide composite positive electrode material has a surface residual alkali NaOH content of 300ppm to 700ppm, and after 10 days of standing in air, the surface residual alkali NaOH content is 800ppm to 1600ppm.
In a second aspect, an embodiment of the present invention further provides a method for preparing the layered oxide composite cathode material, including: and mixing the sodium-electricity layered oxide with a lithium source, an M source and an N source in proportion, and performing high-temperature sintering to prepare the layered oxide composite anode material.
The embodiment of the invention also provides a preparation method of the layered oxide composite anode material, which comprises the following steps: and preparing the sodium-electricity layered oxide by adopting a high-temperature sintering method, mixing the prepared sodium-electricity layered oxide with a lithium source, an M source and an N source according to a proportion, and performing high-temperature sintering to finally obtain the layered oxide composite anode material. In the secondary sintering process, the lithium source, the M source and the N source can generate a lithium electric layered oxide layer on the surface of the sodium electric layered oxide, and the lithium electric layered oxide layer is formed on the surface of the sodium electric layered oxide particles by an in-situ coating method. The experimental results show that: the lithium electric layered oxide layer is coated on the surface of the sodium electric layered oxide particles, so that the problem of poor air stability of the sodium electric layered oxide positive electrode material is fundamentally solved, the stability of the sodium electric layered oxide in the air is improved, and residual alkali is not easy to generate in a high-humidity environment, so that the residual alkali content on the surface of the sodium electric layered oxide is obviously reduced, the processing performance is optimized, the surface or the internal structure of the sodium electric layered oxide positive electrode material is not damaged by coating modification, and the electrochemical performance of the layered oxide composite positive electrode material is more improved.
In an alternative embodiment, the mass ratio of the sodium-electric layered oxide to the lithium source, the M source, and the N source is 1 (0.0003 to 0.006): (0.0003-0.012): (0-0.00005).
In an alternative embodiment, the high temperature sintering is performed at a temperature of 500 ℃ to 900 ℃ for a time of 4 hours to 18 hours.
In an alternative embodiment, the sodium-electricity layered oxide is prepared by mixing a sodium source and a corresponding metal source (one or more of a nickel source, an iron source and a manganese source) according to a certain proportion, and then sintering the mixture in an air atmosphere of a high-temperature furnace. The sodium source comprises one or more of sodium carbonate, sodium citrate, sodium acetate and sodium nitrate, and the metal source comprises one or more of nickel source selected from nickel oxide, nickel hydroxide, nickel acetate and nickel nitrate; the manganese source is selected from one or more of manganese trioxide, manganese acetate, manganese nitrate and manganese hydroxide; the iron source is selected from one or more of ferric oxide, ferrous oxide, ferric hydroxide, ferric acetate and ferric nitrate.
In an alternative embodiment, the sodium-electrical layered oxide is prepared by the following preparation method: the sodium source and the precursor (NiMn (OH) 2 、NiFeMn(OH) 2 ) Mixing according to a certain proportion, and sintering in the air atmosphere of a high-temperature furnace.
In an alternative embodiment, the M source comprises at least one of a Ni source, a Co source, a Mn source, and an Al source, and the Ni source comprises at least one of nickel oxide, nickel hydroxide, nickel acetate, and nickel nitrate, the Co source comprises at least one of cobalt oxide, cobalt hydroxide, and cobalt nitrate, the Al source comprises at least one of aluminum oxide, aluminum hydroxide, and aluminum nitrate, and the Mn source comprises at least one of manganese dioxide, manganese trioxide, manganese acetate, manganese nitrate, and manganese hydroxide; the N source is selected from one or more of oxide, hydroxide, nitrate and acetate; the lithium source includes at least one of anhydrous lithium hydroxide, lithium hydroxide monohydrate, lithium carbonate, lithium nitrate, lithium oxide, lithium acetate, and lithium oxalate.
In a third aspect, the embodiment of the invention also provides a sodium battery, wherein the positive electrode of the sodium battery comprises the layered oxide composite positive electrode material.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
Na is mixed with 2 CO 3 And NiFeMn (OH) 2 The high ratio is carried out in a molar ratio of 0.5:1Mixing by rapid ball milling, sintering in air atmosphere in a high temperature furnace at 1000 deg.C for 10h to obtain NaNiFeMnO 2 Sodium-electric layered oxide.
1000g of NaNiFeMnO 2 And 1.13gLi 2 CO 3 、2.86gCo(OH) 2 Performing high-speed ball milling and mixing to obtain a mixture, and sintering the mixture in an oxygen atmosphere of a high-temperature furnace: the sintering temperature is 700 ℃, the sintering time is 6 hours, and the composition of NaNiFeMnO is obtained after the sintering is completed 2 @LiCoO 2 Is a layered oxide composite positive electrode material.
Example 2
Na is mixed with 2 CO 3 And NiFeMn (OH) 2 High-speed ball milling and mixing are carried out according to the mol ratio of 0.5:1, the mixture is placed in a high-temperature furnace to be sintered in the air atmosphere after the mixture is mixed, the sintering temperature is 1000 ℃, the sintering time is 10 hours, and NaNiFeMnO is obtained after the sintering is completed 2 Sodium-electric layered oxide.
1000g of NaNiFeMnO 2 And 0.378gLi 2 CO 3 Ball milling and mixing 0.765g of NiO at a high speed to obtain a mixture, and sintering the mixture in a high-temperature furnace oxygen atmosphere: the sintering temperature is 800 ℃, the sintering time is 6 hours, and the composition of NaNiFeMnO is obtained after the sintering is completed 2 @LiNiO 2 Is a layered oxide composite positive electrode material.
Example 3
Na is mixed with 2 CO 3 And NiFeMn (OH) 2 High-speed ball milling and mixing are carried out according to the mol ratio of 0.5:1, the mixture is placed in a high-temperature furnace to be sintered in the air atmosphere after the mixture is mixed, the sintering temperature is 1000 ℃, the sintering time is 10 hours, and NaNiFeMnO is obtained after the sintering is completed 2 Sodium-electric layered oxide.
An amount of 1000g NaNiFeMnO 2 And 0.377gLi 2 CO 3 、0.820gCo 3 O 4 Performing high-speed ball milling and mixing to obtain a mixture, and sintering the mixture in an oxygen atmosphere of a high-temperature furnace: the sintering temperature is 800 ℃, the sintering time is 6 hours, and the composition of NaNiFeMnO is obtained after the sintering is completed 2 @LiCoO 2 Is a layered oxide composite positive electrode material.
Example 4
Na is mixed with 2 CO 3 And NiFeMn (OH) 2 High-speed ball milling and mixing are carried out according to the mol ratio of 0.5:1, the mixture is placed in a high-temperature furnace to be sintered in the air atmosphere after the mixture is mixed, the sintering temperature is 1000 ℃, the sintering time is 10 hours, and NaNiFeMnO is obtained after the sintering is completed 2 Sodium-electric layered oxide.
An amount of 1000g NaNiFeMnO 2 And 0.377gLi 2 CO 3 Ball milling and mixing 0.766g CoO at high speed to obtain a mixture, and sintering the mixture in a high-temperature furnace oxygen atmosphere: the sintering temperature is 800 ℃, the sintering time is 6 hours, and the composition of NaNiFeMnO is obtained after the sintering is completed 2 @LiCoO 2 Is a layered oxide composite positive electrode material.
Example 5
Na is mixed with 2 CO 3 And NiFeMn (OH) 2 High-speed ball milling and mixing are carried out according to the mol ratio of 0.5:1, the mixture is placed in a high-temperature furnace to be sintered in the air atmosphere after the mixture is mixed, the sintering temperature is 1000 ℃, the sintering time is 10 hours, and NaNiFeMnO is obtained after the sintering is completed 2 Sodium-electric layered oxide.
1000g of NaNiFeMnO 2 And 0.384gLi 2 CO 3 、0.388gNiO、0.367gMnO 2 Ball milling and mixing 0.078g CoO at high speed to obtain a mixture, and sintering the mixture in a high-temperature furnace oxygen atmosphere: the sintering temperature is 800 ℃, the sintering time is 6 hours, and the composition of NaNiFeMnO is obtained after the sintering is completed 2 @LiNi 0.5 Co 0.1 Mn 0.4 O 2 Is a layered oxide composite positive electrode material.
Example 6
Na is mixed with 2 CO 3 And NiFeMn (OH) 2 High-speed ball milling and mixing are carried out according to the mol ratio of 0.5:1, the mixture is placed in a high-temperature furnace to be sintered in the air atmosphere after the mixture is mixed, the sintering temperature is 1000 ℃, the sintering time is 10 hours, and NaNiFeMnO is obtained after the sintering is completed 2 Sodium-electric layered oxide.
1000g of NaNiFeMnO 2 And 0.279gLi 2 CO 3 、0.452gNiO、0.057gCoO、0.077gAl 2 O 3 Performing high-speed ball milling and mixing to obtain a mixture, and sintering the mixture in an oxygen atmosphere of a high-temperature furnace: the sintering temperature is 800 ℃, the sintering time is 6 hours, and the composition of NaNiFeMnO is obtained after the sintering is completed 2 @LiNi 0.8 Co 0.1 Al 0.1 O 2 Is a layered oxide composite positive electrode material.
Example 7
Na is mixed with 2 CO 3 And NiFeMn (OH) 2 High-speed ball milling and mixing are carried out according to the mol ratio of 0.5:1, the mixture is placed in a high-temperature furnace to be sintered in the air atmosphere after the mixture is mixed, the sintering temperature is 1000 ℃, the sintering time is 10 hours, and NaNiFeMnO is obtained after the sintering is completed 2 Sodium-electric layered oxide.
1000g NaNiFeMnO 2 With 0.385g Li 2 CO 3 、0.623g NiO、0.078g CoO、0.045g MnO 2 、0.053gZrO 2 Performing high-speed ball milling and mixing to obtain a mixture, and sintering the mixture in an oxygen atmosphere of a high-temperature furnace: the sintering temperature is 800 ℃, the sintering time is 6 hours, and the composition of NaNiMnO is obtained after the sintering is completed 2 @LiNi 0.8 Co 0.1 Mn 0.05 Zr 0.05 O 2 Is a layered oxide composite positive electrode material.
Comparative example 1
The composition NaNiFeMnO was obtained by the method of example 1 2 Sodium-electric layered oxide of (a).
The NaNiFeMnO is prepared 2 The layered oxide is put into ethanol solution for washing to obtain NaNiFeMnO after alcohol washing 2 Layered oxides.
Comparative example 2
The composition NaNiFeMnO was obtained by the method of example 1 2 Sodium-electric layered oxide of (a).
SEM image of the sample obtained in comparative example 2 is shown in FIG. 3, SEM image of the sample after being left in air for 5 days is shown in FIG. 4, the sodium-electric layered oxide prepared in comparative example 2 is not coated on the surface, and it can be seen that the uncoated material is left in air for 5 daysThe surface becomes extremely rough with many small particles, which are just residual bases. This phenomenon is in sharp contrast to the examples, which give SEM images of samples of FIG. 1, SEM images of 5 days in air of FIG. 2, liCoO 2 The surface of the coated sample after being placed in the air is smoother than that of comparative example 2, so that the air stability of the sodium-electricity positive electrode material coated by the lithium-electricity layered oxide layer is obviously improved.
Comparative example 3
The composition NaNiFeMnO was obtained by the method of example 1 2 Sodium-electric layered oxide of (a).
NaNiFeMnO 2 With Al 2 O 3 High-speed ball milling and mixing to obtain a mixture, and NaNiFeMnO 2 With Al 2 O 3 The mass ratio of (2) is 1:0.001892 sintering the mixture in a high-temperature furnace oxygen atmosphere: the sintering temperature is 550 ℃, the sintering time is 6 hours, and NaNiFeMnO is obtained after the sintering is completed 2 @Al 2 O 3 Is a layered oxide composite positive electrode material.
Comparative example 4
Similar to the procedure of example 1, the only difference is that: the composition of the surface coating layer of the sodium-electricity layered oxide is only Li 2 CO 3 。
Comparative example 5
Similar to the procedure of example 1, the only difference is that: the secondary sintering temperature or time is 1020 DEG C
Comparative example 6
Similar to the procedure of example 1, the only difference is that: the temperature of the secondary sintering was 200 ℃.
Residual alkali (NaOH) test: absolute ethyl alcohol is used as a solvent, and the potential titration method is adopted to measure the NaOH content on the surface of the anode material; viscosity test: the positive electrode material is adopted: carbon black: pvdf=19:0.5:0.5, slurry was prepared, and the slurry solids content was adjusted to 60% with NMP; the above ratio slurry was transferred to a 25% relative humidity environment, mechanically stirred, and after stirring for 24 hours, the viscosity was measured with a viscometer.
The composite positive electrode materials obtained in examples 1 to 7 and comparative examples 1 to 6 were prepared as followsThe formula is prepared into a button cell: and mixing and grinding the prepared composite positive electrode material finished product serving as an active substance with a binder polyvinylidene fluoride (PVDF) and a conductive agent acetylene black in a mass ratio of 90:5:5 uniformly, adding a certain amount of Nitrogen Methyl Pyrrolidone (NMP) serving as a dispersing agent to disperse the mixture, grinding the mixture into uniform slurry again, and coating the slurry on an aluminum foil. The coated electrode material was dried in a vacuum oven at 110 c, after which the dried electrode material was rolled by a twin-roll machine and dried in a vacuum oven at 120 c for 12 hours. And punching the dried electrode material, weighing, and assembling the battery in a glove box. Wherein the electrolyte used for assembling the battery is prepared from a solution containing 1M NaPF 6 And the electrolyte formed by DMC+EC solvent of sodium source takes the electrode plate and sodium plate of the composite material as working electrode and counter electrode respectively. The composite positive plate and the sodium plate are assembled into a button type half battery through a glove box.
The experimental results of the products obtained in examples 1 to 7 and comparative examples 1 to 6 above are shown in tables 1 and 2 below.
TABLE 1
| pH in water | Residual alkali NaOH/ppm | Residual alkali NaOH/ppm after 10 days of air standing | viscosity/Pa/s of 60% solids slurry after continuous stirring for 24 hours at 25% relative humidity | |
| Example 1 | 12.33 | 364 | 832 | 3689 |
| Example 2 | 12.43 | 482 | 901 | 3892 |
| Example 3 | 12.12 | 433 | 889 | 4031 |
| Example 4 | 12.08 | 506 | 802 | 5129 |
| Example 5 | 12.45 | 482 | 965 | 4369 |
| Example 6 | 12.41 | 400 | 1052 | 5678 |
| Example 7 | 12.01 | 397 | 926 | 5012 |
| Comparative example 1 | 12.36 | 501 | 1085 | Gel |
| Comparative example 2 | 13.44 | 1656 | 7895 | Gel |
| Comparative example 3 | 12.89 | 781 | 2301 | 19810 |
| Comparative example 4 | 13.01 | 1389 | 8657 | Gel |
| Comparative example 5 | 12.34 | 1056 | 3568 | Gel |
| Comparative example 6 | 13.36 | 1546 | 6985 | Gel |
TABLE 2
| 2-4V,0.1C initial discharge specific capacity mAh/g | First discharge efficiency% | 1C cycle 50 cycles capacity retention | |
| Example 1 | 135.3 | 96.5 | 96.3 |
| Example 2 | 134.2 | 94.8 | 95.5 |
| Example 3 | 132.4 | 94.6 | 94.8 |
| Example 4 | 133.1 | 94.9 | 95.7 |
| Example 5 | 134.1 | 95.0 | 95.1 |
| Example 6 | 133.7 | 94.2 | 94.9 |
| Example 7 | 134.8 | 95.4 | 95.2 |
| Comparative example 1 | 134.4 | 94.7 | 93.2 |
| Comparative example 2 | 133.9 | 94.8 | 93.5 |
| Comparative example 3 | 132.1 | 94.2 | 92.7 |
| Comparative example 4 | 130.6 | 94.2 | 90.2 |
| Comparative example 5 | 131.1 | 94.1 | 91.2 |
| Comparative example 6 | 131.8 | 94.0 | 92.0 |
As can be seen from tables 1 and 2 above: naNiFeMnO coated with lithium battery layered oxide 2 The layered oxides of examples 1-7 all had less than 700ppm residual alkali and had a pH of less than 13 in water. The residual alkali increase after 5 days of air standing was 652ppm at the most, but the residual alkali increase of the positive electrode material of comparative example 4, which was not coated with the lithium battery layered oxide, was 7268ppm. From the viewpoint of the viscosity of the slurry with 60% solid content under the 25% humidity environment after 24 hours of continuous stirring, the slurries of examples 1 to 7 all have the viscosity lower than 6000Pa/s and can be normally coated, but the viscosity of the positive electrode material without the lithium battery layered oxide is very high, even the positive electrode material is directly gelled. In the comparative example 1, the residual alkali is removed by adopting a direct alcohol washing mode, and the surface is not modified, sodium ions between layers can still be replaced by water and carbon dioxide in the air, so that the residual alkali is increased, and the air stability is not improved; comparative example 2 did not undergo the residual alkali reduction process, the residual alkali was relatively high, and the air stability was relatively poor, and the problem of gelation during the homogenization process occurred; comparative examples 3 and 4 were coated with a common oxide, and we found that the air stability after coating was not significantly improved, because the oxide still exists on the surface as sodium ion related salts after reaction with the residual alkali on the surface, and the residual alkali still increases during the homogenization process. Comparative examples 5 and 6 are sintering temperatures too high or too low, the metal compound added too low in temperature cannot react to form lithium battery layered oxide, and too high in temperature is unfavorable for forming lithium battery layered oxide. The above results show that NaNiFeMnO coated by lithium battery layered oxide 2 Has the advantages of low residual alkali, good air stability, good processing performance and the like. The existing lithium battery anode material almost needs to undergo a water washing process in order to remove residual alkali, but the sodium battery anode material is poor in air stability and is often caused by moisture in the environment, so that the defects of high residual alkali and poor air stability of the sodium battery anode material are ingeniously overcome by introducing water-resistant lithium battery layered oxide on the surface of the sodium battery anode material. The electrochemical performance test is carried out on the examples and the comparative examples, and the lithium battery layered oxide coated sodium-electricity positive electrode material is found not to deteriorate the electrochemical performance, so that the practicability is further proved. Examples 1 to 7 exhibited excellent cycle stability compared to the comparative examples, since the residual alkali was significantly reduced after the surface modification, and the air stability was improved, resulting in good cycle stability.
In summary, the embodiment of the invention provides a layered oxide composite positive electrode material, a preparation method thereof and a sodium battery, wherein the provided layered oxide composite positive electrode material comprises the following components: the sodium-electricity layered oxide and the lithium-electricity layered oxide layer coated on the surface of the sodium-electricity layered oxide comprise the following components: liN 1-a M a O 2 N is selected from at least one of Ni, co, mn, al, M is selected from at least one of Mg, ca, ba, sr, Y, zr, ti, sn, V, mo, ru, nb, sb, a is more than or equal to 0 and less than or equal to 0.05, and the lithium battery layered oxide layer accounts for 0.1-2% of the total mass of the layered oxide composite anode material. The lithium battery layered oxide with good stability and processability is coated on the surface of the sodium battery layered oxide, so that the stability of the sodium battery layered oxide is improved, residual alkali is not easy to generate on the surface of the sodium battery layered oxide under a high-humidity environment, the content of the residual alkali on the surface of the sodium battery layered oxide is obviously reduced, and the processability of the sodium battery layered oxide is improved.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The layered oxide composite positive electrode material is characterized by comprising a sodium-electricity layered oxide and a lithium-electricity layered oxide layer coated on the surface of the sodium-electricity layered oxide, wherein the composition of the lithium-electricity layered oxide is as follows: liN 1-a M a O 2 N is selected from at least one of Ni, co, mn, al, M is selected from at least one of Mg, ca, ba, sr, Y, zr, ti, sn, V, mo, ru, nb, sb, a is more than or equal to 0 and less than or equal to 0.05, and the layered oxide layer of the lithium battery accounts for 0.1-2% of the total mass of the layered oxide composite anode material.
2. The layered oxide composite positive electrode material according to claim 1, wherein the composition of the sodium-electric layered metal oxide is NaNi x Fe y Mn z R 1-x-y-z O 2 Wherein R is at least one of Li, mg, cu, zn, co, ca, ba, sr, al, B, cr, zr, ti, sn, V, mo, ru, nb, sb, x is more than or equal to 0.1 and less than or equal to 0.9, y is more than or equal to 0.1 and less than or equal to 0.9, z is more than or equal to 0.1 and less than or equal to 0.9, and x+y+z=1.
3. The layered oxide composite positive electrode material according to claim 1, wherein D of the sodium-electric layered oxide 50 The thickness of the lithium battery layered oxide layer is between 2nm and 50nm and is between 1 and 15 mu m.
4. The layered oxide composite positive electrode material according to claim 1, wherein the layered oxide composite positive electrode material slurry having a solid content of 60% has a viscosity of not more than 6000Pa/s after being left for 24 hours in a 25% humidity environment.
5. The layered oxide composite positive electrode material according to any one of claims 1 to 4, wherein the layered oxide composite positive electrode material has a surface residual alkali NaOH content of 300ppm to 700ppm and a surface residual alkali NaOH content of 800ppm to 1600ppm after being left in air for 5 days.
6. A method for producing the layered oxide composite positive electrode material according to any one of claims 1 to 5, comprising: and mixing the sodium-electricity layered oxide with a lithium source, an M source and an N source in proportion, and performing high-temperature sintering to obtain the layered oxide composite anode material.
7. The method according to claim 6, wherein the mass ratio of the sodium-electric layered oxide, the lithium source, the N source, and the M source is 1 (0.0003 to 0.006): (0.0003-0.012): (0-0.00005).
8. The method according to claim 6, wherein the high-temperature sintering is performed at a temperature of 500 ℃ to 900 ℃ for a time of 4 hours to 15 hours.
9. The method according to claim 6, wherein the M source comprises at least one of a Ni source, a Co source, a Mn source, and an Al source, and the Ni source comprises at least one of nickel oxide, nickel hydroxide, nickel acetate, and nickel nitrate, the Co source comprises at least one of cobalt oxide, cobalt hydroxide, and cobalt nitrate, the Al source comprises at least one of aluminum oxide, aluminum hydroxide, and aluminum nitrate, and the Mn source comprises at least one of manganese dioxide, manganese trioxide, manganese acetate, manganese nitrate, and manganese hydroxide; the N source is selected from one or more of oxide, hydroxide, nitrate and acetate; the lithium source includes at least one of anhydrous lithium hydroxide, lithium hydroxide monohydrate, lithium carbonate, lithium nitrate, lithium oxide, lithium acetate, and lithium oxalate.
10. A sodium battery, characterized in that the positive electrode of the sodium battery comprises the layered oxide composite positive electrode material according to any one of claims 1 to 5 or the layered oxide composite positive electrode material according to any one of claims 6 to 9.
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