CN117117197B - Nickel-manganese-based layered oxide positive electrode material for sodium ion battery and preparation method thereof - Google Patents
Nickel-manganese-based layered oxide positive electrode material for sodium ion battery and preparation method thereof Download PDFInfo
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- CN117117197B CN117117197B CN202311368286.4A CN202311368286A CN117117197B CN 117117197 B CN117117197 B CN 117117197B CN 202311368286 A CN202311368286 A CN 202311368286A CN 117117197 B CN117117197 B CN 117117197B
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- nickel
- manganese
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- ions
- layered oxide
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- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 57
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 50
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000011572 manganese Substances 0.000 claims abstract description 73
- 239000011734 sodium Substances 0.000 claims abstract description 69
- 239000000126 substance Substances 0.000 claims abstract description 39
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 20
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 15
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 14
- 150000001340 alkali metals Chemical group 0.000 claims abstract description 14
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 14
- 150000003624 transition metals Chemical group 0.000 claims abstract description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 86
- 150000002500 ions Chemical class 0.000 claims description 57
- 239000000463 material Substances 0.000 claims description 49
- 239000010406 cathode material Substances 0.000 claims description 46
- 239000011777 magnesium Substances 0.000 claims description 33
- 239000013078 crystal Substances 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 26
- 238000001354 calcination Methods 0.000 claims description 24
- 239000011701 zinc Substances 0.000 claims description 23
- 229910052760 oxygen Inorganic materials 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000002994 raw material Substances 0.000 claims description 19
- 239000001301 oxygen Substances 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000008139 complexing agent Substances 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 13
- 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 12
- 239000012298 atmosphere Substances 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000013067 intermediate product Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 9
- 229910002651 NO3 Inorganic materials 0.000 claims description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 8
- 229910001416 lithium ion Inorganic materials 0.000 claims description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 7
- 238000004146 energy storage Methods 0.000 claims description 7
- -1 oxygen ions Chemical class 0.000 claims description 7
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 6
- 229910001437 manganese ion Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910001453 nickel ion Inorganic materials 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical group O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000010000 carbonizing Methods 0.000 claims description 5
- 229960002303 citric acid monohydrate Drugs 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 5
- 238000003980 solgel method Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 238000003763 carbonization Methods 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 238000004891 communication Methods 0.000 claims description 3
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 3
- 229940071125 manganese acetate Drugs 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
- 229940078494 nickel acetate Drugs 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
- 238000010248 power generation Methods 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 239000007784 solid electrolyte Substances 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 2
- 230000001351 cycling effect Effects 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 64
- 230000014759 maintenance of location Effects 0.000 description 34
- 230000000052 comparative effect Effects 0.000 description 28
- 238000002441 X-ray diffraction Methods 0.000 description 22
- 238000011056 performance test Methods 0.000 description 11
- 150000001450 anions Chemical class 0.000 description 10
- 238000010998 test method Methods 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 4
- 229910004838 Na2/3Ni1/3Mn2/3O2 Inorganic materials 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000002482 conductive additive Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 241000234314 Zingiber Species 0.000 description 2
- 235000006886 Zingiber officinale Nutrition 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000011363 dried mixture Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 235000008397 ginger Nutrition 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 125000004436 sodium atom Chemical group 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007040 multi-step synthesis reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012956 testing procedure Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 230000003442 weekly effect Effects 0.000 description 1
Classifications
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M4/485—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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- 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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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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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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- Chemical & Material Sciences (AREA)
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- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
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- Secondary Cells (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a nickel-manganese-based layered oxide positive electrode material for a sodium ion battery and a preparation method thereof, wherein the chemical general formula of the nickel-manganese-based layered oxide positive electrode material is Na x L y [Ni a Mn b M c N d ]O 2+δ‑γ F γ Wherein x is more than or equal to 0.5 and less than or equal to 0.8, y is more than or equal to 0 and less than or equal to 0.2, a+b+c+d=1, a is more than or equal to 0 and less than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.3, d is more than or equal to 0 and less than or equal to 0.3, -0.2 and less than or equal to 0.2, and gamma is more than or equal to 0 and less than or equal to 0.2; l is an element for doping and substituting Na at an alkali metal position; m is an element for doping and substituting transition metal position Ni or Mn; n is an element for doping and substituting transition metal Ni or Mn; the nickel-manganese-based layered oxide positive electrode material is used for a sodium ion battery, can stably work under a high voltage of 2V-4.5V, and has high specific capacity under high multiplying power and good safety and cycling stability.
Description
Technical Field
The invention relates to the technical field of sodium ion battery materials, in particular to a nickel-manganese-based layered oxide positive electrode material for a sodium ion battery and a preparation method thereof.
Background
The energy storage system is clearly an important component of intelligent power grid management for implementing intermittent renewable energy sources in the power grid and realizing electric energy balance in peak and valley periods. Electrochemical energy storage can efficiently convert electric energy into chemical energy for storage, and can be converted into electric energy again for output. Therefore, rechargeable batteries having high safety factor, high capacity, good rate capability, suitable voltage range, and low price have been widely studied. Lithium ion batteries are currently the most successful and advanced secondary batteries. With the rapid increase of the requirements of portable electronic products, electric automobiles and the like on high-performance batteries, the reserves of lithium resources in all countries of the world are uneven, the content of lithium elements in the crust is small, and the price of the lithium elements with deficient resources is rapidly increased, so that the cost of the lithium ion battery is continuously increased, and the practical large-scale application of the lithium ion battery is not facilitated. The Na element is in the same main group as Li in the periodic table, the Na element and Li have similar physical and chemical properties, na is abundant in the crust (2.83 percent and the sixth position), and a large amount of developable sodium resources exist in seawater. So developing a low cost and practical sodium ion battery has attracted attention and interest.
The currently reported positive electrode materials of sodium ion batteries are mainly divided into four types: layered transition metal oxides, polyanion compounds, prussian blue analogues and organic positive electrode materials. The layered oxide material has the following advantages over other classes of positive electrode materials: firstly sodium ions are transported relatively fast in the material (they possess a two-dimensional transport channel); and secondly, the energy density is high (the compaction density of the layered material is higher). There has been a great deal of attention because of the relatively high energy density exhibited by layered oxide cathode materials. Layered oxides are mainly classified into P2, P3, O2 and O3. Wherein O and P represent different positions of an alkali metal element, O and P respectively represent Na atoms to form octahedral coordination with surrounding six O atoms, and the octahedral coordination with a triangular prism (in the triangular prism coordination, the Na atoms are positioned at the center of the triangular prism); 2 and 3 represent the stacking repeat period of the minimum atomic layer, respectively.
A classical material system of the layered oxide anode is nickel-manganese-based layered oxide which has strong oxidation-reduction capability of anionic oxygen and Ni 3+ /Ni 4+ Redox couples, which provide a higher specific capacity, have received much attention from researchers. However, nickel-manganese-based layered oxides are susceptible to phase transition from P2 phase to O2 phase during electrochemical process, and as anions participate in redox process, this causes larger volume change (about 20%), too many anions participate in redox and cause oxygen precipitation to destroy structure, resulting in specific capacity of material with circulation The increase in the number of times decreases dramatically, rendering the nickel manganese-based layered material inoperable at too high a voltage. This is alleviated by reducing the Ni to Mn ratio in the material, but results in Mn in the structure 3+ The content of (c) increases, thereby causing taylor distortion of the ginger to adversely affect the electrode material.
The nickel-manganese-based material has poor stability under high voltage, and the anion redox is irreversible, so that the practical application of the high-energy-density sodium ion battery is limited. The slow redox kinetics of oxygen, how to improve reversibility, reduce anion loss, and how to regulate the redox degree of oxygen anions are significant challenges facing nickel-manganese-based layered anodes.
The anions of nickel manganese-based layered oxides can be valence-shifted, providing higher specific capacity, but such valence-shift is difficult to stabilize, and previous work reported improvement of valence-shift stability of anions by doping transition metal layers, such as Na 0.67 Ni 0.23 Mg 0.1 Mn 0.67 O 2 、Na 0.67 Ni 0.23 Zn 0.1 Mn 0.67 O 2 And the like, but the above work still has no obvious improvement on the cycle stability under high voltage and has poor multiplying power performance, if the transition metal layer of the material is continuously doped with more inert metal to change the stability, the specific capacity is inevitably reduced, and the basic capacity advantage of the nickel-manganese-based layered oxide is weakened by the method.
The previous patent reports that the alkali metal site doping substitution synthesis method of the sodium ion battery layered oxide has more complicated steps, generally adopts a multi-step synthesis mode, greatly improves the cost of the sodium ion battery layered oxide in production and application, and is not beneficial to practical application.
Disclosure of Invention
Aiming at the existing problems, the invention provides a nickel-manganese-based layered oxide positive electrode material for a sodium ion battery and a preparation method thereof, which greatly simplify the existing multi-step calcination method of doping sodium sites of layered materials and are easy for commercial application and large-scale production. The nickel-manganese-based layered oxide positive electrode material prepared by the preparation method provided by the invention has excellent cycling stability, can stably work under high voltage, has high specific capacity under high multiplying power, is good in safety, and has practical application value for a sodium ion battery system.
To this end, in a first aspect, embodiments of the present invention provide a nickel-manganese-based layered oxide cathode material for a sodium-ion battery, where the nickel-manganese-based layered oxide cathode material has a chemical formula Na x L y [Ni a Mn b M c N d ]O 2+δ-γ F γ Wherein x is more than or equal to 0.5 and less than or equal to 0.8, y is more than or equal to 0 and less than or equal to 0.2, a+b+c+d=1, a is more than or equal to 0 and less than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.3, d is more than or equal to 0 and less than or equal to 0.3, -0.2 and less than or equal to 0.2, and gamma is more than or equal to 0 and less than or equal to 0.2;
L is an element for doping and substituting Na at an alkali metal position, and the ions of L comprise K + 、Li + 、Mg 2+ One or more of the following;
m is an element for doping and substituting transition metal position Ni or Mn, and the ion of M specifically comprises Mg 2+ 、Zn 2+ 、Li + In (a) and (b);
n is an element for doping and substituting transition metal position Ni or Mn, and the ion of N specifically comprises Nb 5+ 、Ca 2+ 、B 3+ 、Co 3+ 、Fe 3+ 、Cu 2+ 、Al 3+ 、Co 2+ 、Zr 4+ 、Sn 4+ 、Ti 4+ 、Ru 4+ 、Nb 4+ 、Te 6+ 、Sb 5+ Or Mo (Mo) 6+ One or more of the following;
the nickel-manganese-based layered oxide positive electrode material has an operating voltage of 2V-4.5V when used in a sodium ion battery.
Preferably, the crystal structure of the nickel-manganese-based layered oxide positive electrode material is a P2 phase, and the space group is P63/mmc; preferably, the nickel-manganese-based layered oxide positive electrode material is used in a sodium ion battery, nickel ions are converted from positive divalent to positive trivalent when charged at the first week, manganese ions of positive trivalent are converted from positive trivalent to positive tetravalent, and oxygen ions are converted from negative divalent to negative monovalent; when the lithium ion battery discharges in the first week, nickel ions are converted into positive bivalent from positive trivalent, oxygen ions are converted into negative monovalent from negative bivalent, manganese ions in the positive trivalent are converted into positive tetravalent from positive trivalent, magnesium ions, lithium ions and zinc ions are not changed in valence, and the valence changing process after the first week is consistent with the first week.
In a second aspect, an embodiment of the present invention provides a method for preparing the nickel-manganese-based layered oxide cathode material for a sodium ion battery according to the first aspect, where the preparation method is a sol-gel method, and includes the following steps:
Step S1, weighing a sodium source material, a nickel source material, a manganese source material, a compound containing L ions, a compound containing M ions, a compound containing N ions and NaF as raw materials according to stoichiometric ratio, dissolving the raw materials in deionized water, stirring and mixing, adding a complexing agent, and continuously stirring at a certain temperature to form precursor gel;
step S2, placing the precursor gel in a muffle furnace, and carbonizing in an air atmosphere to obtain intermediate product powder;
and step S3, pressing the intermediate product powder into a wafer, calcining in a single step in an oxygen atmosphere, and naturally cooling to room temperature after calcining to obtain the nickel-manganese-based layered oxide cathode material.
Preferably, the sodium source material comprises: sodium nitrate and/or sodium acetate; the nickel source material comprises: nickel nitrate and/or nickel acetate; the manganese source material comprises: manganese nitrate and/or manganese acetate;
the compound containing L ions comprises nitrate and/or acetate containing L ions; the L ions include: k (K) + 、Li + 、Mg 2+ One or more of the following;
the M ion-containing compound comprises nitrate and/or acetate containing M ions; the M ion includes: mg of 2+ 、Zn 2+ 、Li + In (a) and (b);
the N-ion containing compound comprises nitrate and/or acetate containing N ions; the N ions include: nb (Nb) 5+ 、Ca 2+ 、B 3+ 、Co 3+ 、Fe 3+ 、Cu 2+ 、Al 3+ 、Co 2+ 、Zr 4+ 、Sn 4+ 、Ti 4+ 、Ru 4+ 、Nb 4+ 、Te 6+ 、Sb 5+ Or Mo (Mo) 6+ One or more of the following.
Preferably, the mass ratio of the raw materials to the deionized water is 3:50;
the complexing agent is citric acid monohydrate; the mass ratio of the complexing agent to the deionized water is 2:25.
Preferably, the temperature of continuous stirring at a certain temperature is between 90 ℃ and 100 ℃, and the stirring time is 9 hours to 12 hours;
the specific conditions of carbonization are as follows: heating to 300-500 ℃ at a heating rate of 2-8 ℃/min;
the single-step calcination temperature is 1000-1050 ℃, the heating rate is 2-8 ℃/min, and the calcination time is 12-14 hours.
In a third aspect, an embodiment of the present invention provides a positive electrode, where the positive electrode includes the nickel-manganese-based layered oxide positive electrode material described in the first aspect.
In a fourth aspect, an embodiment of the present invention provides a sodium ion battery, where the sodium ion battery includes the positive electrode, the separator, the electrolyte or the solid electrolyte, and the negative electrode described in the third aspect;
the operating voltage range of the sodium ion battery is between 2V and 4.5V.
In a fifth aspect, an embodiment of the present invention provides a use of the sodium ion battery according to the fourth aspect, where the sodium ion battery is used for a large-scale energy storage device for solar energy and wind energy generation, or any one of smart grid peak shaving, a distribution power station, a backup power source, a communication base station, and an energy storage device of an electric automobile.
The embodiment of the invention provides a preparation method of a nickel-manganese-based layered oxide positive electrode material for a sodium ion battery, which is characterized in that precursor gel is formed from raw materials by a sol-gel method, and then the nickel-manganese-based layered oxide positive electrode material is obtained by carbonization and single-step calcination processes.
The nickel-manganese-based layered oxide positive electrode material prepared by the sol-gel method disclosed by the invention has the advantages that the alkali metal layer is doped, so that the stability of anion valence variation is enhanced, the cycle stability of the nickel-manganese-based layered oxide is greatly improved, the rate capability of the nickel-manganese-based layered oxide is also greatly improved, and the capacity of the nickel-manganese-based layered oxide is not influenced.
The nickel-manganese-based layered oxide positive electrode material provided by the invention is applied to a sodium ion battery, can excite more anions to participate in redox reaction, can stabilize oxygen in electrochemical reaction, can increase the proportion of oxygen to participate in electrochemical reaction, and further improves the specific capacity and the cycling stability of the sodium ion battery.
Drawings
The technical scheme of the embodiment of the invention is further described in detail through the drawings and the embodiments.
Fig. 1 is a flowchart of a preparation method of a nickel-manganese-based layered oxide cathode material according to an embodiment of the present invention.
Fig. 2 is an X-ray diffraction (XRD) pattern of the nickel manganese-based layered oxide cathode materials prepared in examples 1 to 7 of the present invention.
Fig. 3 is an X-ray diffraction (XRD) pattern of the nickel manganese-based layered oxide cathode materials prepared in examples 11 to 15 of the present invention.
Fig. 4 is an X-ray diffraction (XRD) pattern of the nickel manganese-based layered oxide cathode materials prepared in examples 17 to 20 according to the present invention.
Fig. 5 is an X-ray diffraction (XRD) pattern of the nickel manganese-based layered oxide cathode materials prepared in examples 24 to 27 of the present invention.
Fig. 6 is a crystal structure diagram of nickel manganese-based layered oxide cathode materials prepared in example 6, example 13 and example 19 according to the present invention.
Fig. 7 is a first cycle charge-discharge curve of the assembled batteries of example 6, example 22 and example 23.
Fig. 8 is a graph of the 120 cycle capacity of the assembled batteries of example 6, example 22 and example 23.
FIG. 9 is a Na prepared in example 6 0.62 K 0.05 [Ni 0.23 Mn 0.67 Mg 0.1 ]O 2 Charge-discharge curves for the first to fifth weeks of assembled battery.
Fig. 10 is a graph of cycle capacity of the assembled batteries of examples 2-9 and comparative example 1.
Fig. 11 is a graph of the rate performance test of the assembled batteries of example 6 and comparative example 1.
FIG. 12 is a Na prepared in example 13 0.62 K 0.05 [Ni 0.21 Mn 0.71 Li 0.08 ]O 2 Charge-discharge curves for the first to fifth weeks of assembled battery.
Fig. 13 is a graph of cycle capacity of the assembled batteries of examples 10-15 and comparative example 1.
Fig. 14 is a graph showing the rate performance test of the assembled batteries of example 13 and comparative example 1.
FIG. 15 is a Na prepared in example 19 0.62 K 0.05 [Ni 0.25 Mn 0.69 Zn 0.08 ]O 2 Charge-discharge curves for the first to fifth weeks of the assembled battery.
Fig. 16 is a 400-week cycle capacity graph of the assembled batteries of examples 16-21 and comparative example 1.
Fig. 17 is a graph showing the rate performance test of the assembled batteries of example 19 and comparative example 1.
Fig. 18 is a comparison of the first cycle charge-discharge curves of the batteries assembled in example 6, example 13, example 19 and comparative example 1.
FIG. 19 is a Na prepared in example 26 0.6 K 0.05 [Ni 0.15 Mn 0.85 ]O 2 Charge-discharge curves for the first to fifth weeks of the assembled battery.
Fig. 20 is a comparative graph of the first cycle charge-discharge curves of the assembled batteries of example 26 and comparative example 2.
Fig. 21 is a graph of the 100 cycle electrochemical performance of the assembled cells of example 26 and comparative example 2.
Fig. 22 is a comparative plot of the rate performance test of the assembled batteries of example 26 and comparative example 2.
FIG. 23 is a Na prepared in example 27 0.62 K 0.05 [Ni 0.21 Mn 0.71 Li 0.08 ]O 1.98 F 0.02 Charge-discharge curves for the first to fifth weeks of assembled battery.
Detailed Description
The invention is further illustrated by the drawings and the specific examples, which are to be understood as being for the purpose of more detailed description only and are not to be construed as limiting the invention in any way, i.e. not intended to limit the scope of the invention.
The embodiment of the invention provides a nickel-manganese-based layered oxide positive electrode material for a sodium ion battery, which has a chemical formula of Na x L y [Ni a Mn b M c N d ]O 2+δ-γ F γ Wherein x is more than or equal to 0.5 and less than or equal to 0.8, y is more than or equal to 0 and less than or equal to 0.2, a+b+c+d=1, a is more than or equal to 0 and less than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.3, d is more than or equal to 0 and less than or equal to 0.3, delta is more than or equal to 0.2 and less than or equal to 0.2, y is more than or equal to 0.03 and less than or equal to 0.7, a is more than or equal to 0.1 and less than or equal to 0.35,0.05, and c is more than or equal to 0.15.
Specifically, L is an element for doping and substituting Na at an alkali metal position, and the ions of L specifically comprise K + 、Li + 、Mg 2+ One or more of the following.
M is an element for doping and substituting transition metal position Ni or Mn, and the ion of M specifically comprises Mg 2+ 、Zn 2+ 、Li + Is a kind of medium.
N is an element for doping and substituting transition metal position Ni or Mn, and the ion of N specifically comprises Nb 5+ 、Ca 2+ 、B 3+ 、Co 3+ 、Fe 3+ 、Cu 2+ 、Al 3+ 、Co 2+ 、Zr 4+ 、Sn 4+ 、Ti 4+ 、Ru 4+ 、Nb 4+ 、Te 6+ 、Sb 5+ Or Mo (Mo) 6+ One or more of the following. The crystal structure of the nickel-manganese-based layered oxide positive electrode material is P2, and the space group is P63/mmc.
When the nickel-manganese-based layered oxide positive electrode material is used in a sodium ion battery, nickel ions are converted from positive divalent to positive trivalent during first-week charging, manganese ions of positive trivalent are converted from positive trivalent to positive tetravalent, and oxygen ions are converted from negative divalent to negative monovalent; when the first week discharges, nickel ions are converted from positive trivalent to positive divalent again, oxygen ions are converted from negative divalent to negative monovalent again, manganese ions of positive trivalent are converted from positive trivalent to positive tetravalent, magnesium ions, lithium ions and zinc ions are not changed in valence, and the valence changing process after the first week is consistent with the first week; the working voltage of the nickel-manganese-based layered oxide positive electrode material used for the sodium ion battery is between 2V and 4.5V.
K of the invention + 、Li + 、Mg 2+ The alkali metal position plays a role of a support, inhibits interlayer sliding in the charge-discharge process and stabilizes anionic oxygen; mg of 2+ 、Zn 2+ 、Li + The average working voltage can be improved in transition metal potential, the Taylor distortion of ginger can be reduced, and the anion oxidation reduction can be excited.
When the nickel-manganese-based layered oxide positive electrode material contains F element, the F ion is partially doped to replace O ion, and the F ion can form stronger chemical bonds with other elements, so that the crystal structure can be stabilized, and the stability of the material is improved.
The Na and the alkali metal site doping element L are the same as the alkali metal layer and are arranged in disorder. The Ni, mn and transition metal bit doping elements M, N are the same as the transition metal layer and are arranged in disorder.
The embodiment of the invention provides a preparation method of a nickel-manganese-based layered oxide positive electrode material for a sodium ion battery, which is a sol-gel method, as shown in fig. 1, and specifically comprises the following steps.
Step S1, weighing a sodium source material, a nickel source material, a manganese source material, a compound containing L ions, a compound containing M ions, a compound containing N ions and NaF as raw materials according to stoichiometric ratio, dissolving the raw materials in deionized water, stirring and mixing, adding a complexing agent, and continuously stirring at a certain temperature to form precursor gel.
Wherein the sodium source material comprises: sodium nitrate and/or sodium acetate; the nickel source material includes: nickel nitrate and/or nickel acetate; the manganese source material includes: manganese nitrate and/or manganese acetate.
The compound containing L ions comprises nitrate and/or acetate containing L ions; the L ions include: k (K) + 、Li + 、Mg 2+ One or more of the following.
The M ion-containing compound comprises nitrate and/or acetate containing M ions; the M ions include: mg of 2+ 、Zn 2+ 、Li + Is a kind of medium.
The N-ion containing compound comprises nitrate and/or acetate containing N ions; the N ions include: nb (Nb) 5+ 、Ca 2+ 、B 3+ 、Co 3+ 、Fe 3+ 、Cu 2+ 、Al 3+ 、Co 2+ 、Zr 4+ 、Sn 4+ 、Ti 4+ 、Ru 4+ 、Nb 4+ 、Te 6+ 、Sb 5+ Or Mo (Mo) 6+ One or more of the following.
The mass ratio of the raw materials to the deionized water is 3:50; the complexing agent is citric acid monohydrate (C) 6 H 10 O 8 ) The method comprises the steps of carrying out a first treatment on the surface of the The mass ratio of complexing agent to deionized water was 2:25.
The temperature of continuous stirring at a certain temperature is between 90 ℃ and 100 ℃, and the stirring time is 9 hours to 12 hours.
And S2, placing the precursor gel in a muffle furnace, and carbonizing in an air atmosphere to obtain intermediate product powder.
The specific conditions of carbonization are as follows: heating to 300-500 ℃ at a heating rate of 2-8 ℃/min, carbonizing for 2-5 hours to remove complexing agent, preferably carbonizing at 400 ℃ for 2 hours.
And step S3, pressing the intermediate product powder into a wafer, calcining in a single step in an oxygen atmosphere, and naturally cooling to room temperature after calcining to obtain the nickel-manganese-based layered oxide cathode material.
Wherein the single-step calcination temperature is 1000-1050 ℃, the heating rate is 2-8 ℃/min, and the calcination time is 12-14 hours.
The preparation method provided by the invention has a simple calcination mode, and the final nickel-manganese-based layered oxide positive electrode material can be obtained only by one calcination process, which is obviously superior to the existing multi-step calcination method for preparing the layered oxide positive electrode material, and greatly simplifies the synthesis steps; the method is suitable for the positive electrode of the invention Material chemical formula Na x L y [Ni a Mn b M c N d ]O 2+δ-γ F γ All nickel-manganese-based layered oxide cathode materials contained in the lithium ion battery have universality.
The present inventors have found that when the calcination temperature in the above step S3 is in the range of 1000℃to 1050℃and any value in the above range, such as 1000℃1010℃1020℃1030℃1040℃1050℃and the like, is possible, but not limited to the values listed, the crystal structure of the material prepared in this calcination temperature range is P2 phase, and has a good specific capacity and cycle stability.
The nickel-manganese-based layered oxide positive electrode material provided by the embodiment of the invention can be used as a positive electrode active material to prepare slurry together with a conductive additive and a binder, and the slurry is coated on a current collector to obtain a positive electrode; the positive electrode, the negative electrode and a diaphragm, electrolyte or solid electrolyte arranged between the positive electrode and the negative electrode are combined together to form a sodium ion battery according to a conventional process; specifically, the negative electrode adopts sodium metal, or the negative electrode comprises a negative electrode current collector and a negative electrode material on the negative electrode current collector, wherein the negative electrode material comprises a negative electrode active substance, a conductive agent and a binder.
The preparation method of the positive electrode and the assembly method of the sodium ion battery are specifically as follows.
(1) The nickel-manganese-based layered oxide positive electrode material provided by the embodiment of the invention is ground and mixed with conductive additive carbon black (super p) powder with the proportion of 0-30wt% (the conductive additive can also be other common conductive agents in sodium ion batteries, such as acetylene black, graphite and the like).
(2) Adding the binder polyvinylidene fluoride (PVDF) into the uniformly mixed powder in the step (1), uniformly grinding the final mixed slurry, coating the mixture on an aluminum foil current collector, drying the mixture, placing the dried mixture in an oven, and drying the dried mixture in vacuum at 100-120 ℃ for 10 hours.
(3) Cutting the electrode plate obtained in the process (2) into 8 multiplied by 8mm 2 Is then quickly transferred to an argon filled glove box for later use.
(4) Forming a sodium ion battery by the obtained anode, a diaphragm, electrolyte and a cathode in a glove box filled with argon; wherein, the electrolyte of the sodium ion battery is preferably NaPF of 1M 6 Dissolved in 100Vol% Polycarbonate (PC) and 5Vol% (fluoroethylene carbonate) FEC is added, the negative electrode material is preferably metallic sodium sheet.
The working voltage range of the sodium ion battery is between 2V and 4.5V, preferably between 2V and 4.3V, and the sodium ion battery has excellent multiplying power performance and higher specific capacity, and particularly has good cycle performance under high voltage and good practical application prospect.
The sodium ion battery can be used for large-scale energy storage equipment for solar energy and wind energy power generation, or energy storage equipment of a smart grid peak shaving, a distributed power station, a backup power supply, a communication base station or an electric automobile.
In order to better understand the technical scheme provided by the invention, the following specific processes for preparing the nickel-manganese-based layered oxide positive electrode material by applying the method provided by the embodiment of the invention, and the method for applying the nickel-manganese-based layered oxide positive electrode material to a sodium ion battery and the battery characteristics are respectively described in a plurality of specific examples.
Example 1
The embodiment provides a preparation process and performance test of a nickel-manganese-based layered oxide positive electrode material, wherein the prepared positive electrode material has a chemical formula of Na 0.62 K 0.05 [Ni 0.33 Mn 0.67 ]O 2 (wherein, corresponding to the general formula a=0.33, b=0.67, c=0, d=0, x=0.62, y=0.05, l is the K element), the specific preparation and test procedure are as follows.
(1) Weighing sodium source material CH according to stoichiometric ratio 3 COONa, nickel Source Material (CH) 3 COO) 2 Ni, mn source material (CH) 3 COO) 2 Mn·4H 2 O, K ion-containing compound CH 3 COOK is taken as a raw material, the raw material is dissolved in deionized water, the complexing agent citric acid monohydrate is added after stirring and mixing for 60min, and then stirring is continued for 9 hours at 90 ℃ to form precursor gel; wherein the mass ratio of the raw materials to the deionized water is 3:50, and the mass ratio of the complexing agent to the deionized water is 2:25.
(2) And (3) placing the precursor gel in a muffle furnace, and heating to 400 ℃ at a heating rate of 5 ℃/min in an air atmosphere to carbonize for 2 hours to obtain intermediate product powder.
(3) Pressing the intermediate product powder into a wafer, and in an oxygen atmosphere, heating to 1000 ℃ at a heating rate of 5 ℃/min for single-step calcination for 12 hours, and naturally cooling to room temperature after the calcination is completed to obtain the nickel-manganese-based layered oxide positive electrode material with a chemical formula of Na 0.62 K 0.05 [Ni 0.33 Mn 0.67 ]O 2 。
Nickel-manganese-based layered oxide positive electrode material Na prepared in this example 0.62 K 0.05 [Ni 0.33 Mn 0.67 ]O 2 As shown in fig. 2, the crystal structure is seen to be P2 phase.
Example 2
The embodiment provides a preparation process and performance test of a nickel-manganese-based layered oxide positive electrode material, wherein the prepared positive electrode material has a chemical formula of Na 0.62 K 0.05 [Ni 0.31 Mn 0.67 Mg 0.02 ]O 2 (wherein, corresponding to the general formula a=0.31, b=0.67, c=0.02, x=0.62, y=0.05, l is K) + M is Mg 2+ ) The specific preparation and testing procedures are as follows.
(1) Weighing sodium source material CH according to stoichiometric ratio 3 COONa, nickel Source Material (CH) 3 COO) 2 Ni, mn source material (CH) 3 COO) 2 Mn·4H 2 O, K ion-containing compound CH 3 COOK and M ion-containing compound Mg (CH 3 COO) 2 Dissolving the raw materials in deionized water, stirring and mixing for 60min, adding complexing agent citric acid monohydrate, and then continuously stirring at 90 ℃ for 11 hours to form precursor gel; wherein the mass ratio of the raw materials to the deionized water is 3:50, and the mass ratio of the complexing agent to the deionized water is 2:25.
(2) And (3) placing the precursor gel in a muffle furnace, and heating to 400 ℃ at a heating rate of 5 ℃/min in an air atmosphere to carbonize for 2 hours to obtain intermediate product powder.
(3) Powder compacting the intermediate productForming a wafer, heating to 1050 ℃ at a heating rate of 5 ℃/min under an oxygen atmosphere, calcining for 13 hours in a single step, and naturally cooling to room temperature after calcining to obtain the nickel-manganese-based layered oxide positive electrode material, wherein the chemical formula is Na 0.62 K 0.05 [Ni 0.31 Mn 0.67 Mg 0.02 ]O 2 。
XRD of the nickel-manganese-based layered oxide cathode material prepared in this example, as shown in FIG. 2, can see that the crystal structure is P2 phase.
The preparation method for preparing the sodium ion battery by taking the nickel-manganese-based layered oxide positive electrode material as the active substance of the battery positive electrode material comprises the following specific steps of.
Mixing the prepared nickel-manganese-based layered oxide positive electrode material powder with carbon black and a binder PVDF according to the following ratio of 80:10:10, adding a proper amount of N-methyl pyrrolidone (NMP) solution, grinding in a normal-temperature drying environment to form slurry, uniformly coating the slurry on a current collector aluminum foil, and drying under an infrared lamp to obtain the pole piece. Drying at 110deg.C under vacuum for 10 hr, and cutting into 8×8mm 2 And then quickly transferred to an argon filled glove box for later use.
The assembly of the simulated cell was performed in a glove box under argon atmosphere with metallic sodium as the counter electrode and 1mol/L NaPF 6 An electrolyte solution of 100% Vol Polycarbonate (PC) and 5% Vol fluoroethylene carbonate (FEC) was added thereto, and as an electrolyte solution, a glass fiber film was used as a battery separator, and a CR2032 button battery was fabricated according to a conventional process.
The battery testing method specifically comprises the following steps: the charge and discharge test was performed at a current density of 1C using a constant current charge and discharge mode, with a discharge cutoff voltage of 2.0V and a charge cutoff voltage of 4.3V. The test cycle capacity graph is shown in FIG. 10, the first week specific capacity is 93.6mAh/g, the 120 week capacity retention is 90%, and the test data are shown in Table 1.
The preparation method of the nickel-manganese-based layered oxide cathode material, the CR2032 button cell assembly and the test method provided in examples 3 to 9 were the same as in example 2, except that the contents of Ni element and doped Mg element were different, as follows.
The nickel-manganese-based layered oxide cathode material prepared in example 3 has the chemical formula Na 0.62 K 0.05 [Ni 0.29 Mn 0.67 Mg 0.04 ]O 2 (wherein, corresponding to the general formula a=0.29, b=0.67, c=0.04, x=0.62, y=0.05, l is K) + M is Mg 2+ ) XRD thereof, as shown in fig. 2, can see the crystal structure as P2 phase; the cycle capacity curve of the test battery, as shown in FIG. 10, has an operating voltage interval of 2-4.3V, a first week specific capacity of 96mAh/g at 1C, a 120 week capacity retention of 79%, and the test data are summarized in Table 1.
The nickel-manganese-based layered oxide cathode material prepared in example 4 has the chemical formula Na 0.62 K 0.05 [Ni 0.27 Mn 0.67 Mg 0.06 ]O 2 (wherein, corresponding to the general formula a=0.27, b=0.67, c=0.06, x=0.62, y=0.05, l is K) + M is Mg 2+ ) XRD thereof, as shown in fig. 2, can see the crystal structure as P2 phase; the cycle capacity curve of the test cell, as shown in FIG. 10, had a first week specific capacity of 110.6mAh/g at 1C and a 120 week capacity retention of 74%, and the test data are summarized in Table 1.
The nickel-manganese-based layered oxide cathode material prepared in example 5 has the chemical formula Na 0.62 K 0.05 [Ni 0.25 Mn 0.67 Mg 0.08 ]O 2 (wherein, corresponding to the general formula a=0.25, b=0.67, c=0.08, x=0.62, y=0.05, l is K) + M is Mg 2+ ) XRD thereof, as shown in fig. 2, can see the crystal structure as P2 phase; the cycle capacity curve of the test battery, as shown in FIG. 10, the working voltage interval is 2V-4.3V, the initial week specific capacity is 110.8mAh/g at 1C, the 120 week capacity retention rate is 80%, and the test data are summarized in Table 1.
The nickel-manganese-based layered oxide cathode material prepared in example 6 has the chemical formula Na 0.62 K 0.05 [Ni 0.23 Mn 0.67 Mg 0.1 ]O 2 (wherein, corresponding to the general formula a=0.23, b=0.67, c=0.1, x=0.62, y=0.05, l is K) + M is Mg 2 + ) XRD thereof, as shown in FIG. 2, can see crystal junctionThe structure of the phase P2 is shown in FIG. 6 (a); the charge-discharge curve graph of the test battery in the first five weeks is shown in fig. 9, the cycle capacity curve graph of the test battery is shown in fig. 10, the working voltage interval is 2V-4.3V, the first week specific capacity is 110.8mAh/g at 1C, the 120 week capacity retention rate is 80%, and the test data are summarized in table 1; the discharge capacity of example 6 was 132.6mAh/g, 125.1mAh/g, 118.1mAh/g, 108.8mAh/g and 96.4mAh/g at 0.2C, 0.5C, 1C, 2C and 5C, respectively, as shown in FIG. 11, the specific capacity at 5C was 73% of that at 0.2C, the rate performance was excellent, and the rate test data were summarized in Table 2.
The nickel-manganese-based layered oxide cathode material prepared in example 7 has the chemical formula Na 0.62 K 0.05 [Ni 0.21 Mn 0.67 Mg 0.12 ]O 2 (wherein, corresponding to the general formula a=0.21, b=0.67, c=0.12, x=0.62, y=0.05, l is K) + M is Mg 2+ ) XRD thereof, as shown in fig. 2, can see the crystal structure as P2 phase; the cycle capacity curve of the test battery, as shown in FIG. 10, the working voltage interval is 2V-4.3V, the initial cycle specific capacity at 1C is 113.1mAh/g, the 120-cycle capacity retention rate is 78%, and the test data are summarized in Table 1.
The nickel-manganese-based layered oxide cathode material prepared in example 8 has the chemical formula Na 0.62 K 0.05 [Ni 0.19 Mn 0.67 Mg 0.14 ]O 2 (wherein, corresponding to the general formula a=0.19, b=0.67, c=0.14, x=0.62, y=0.05, l is K) + M is Mg 2+ ) The method comprises the steps of carrying out a first treatment on the surface of the The cycle capacity curve of the test battery is shown in fig. 10, the working voltage interval is 2V-4.3V, the first week specific capacity is 103.9mAh/g at 1C, the 120 week capacity retention rate is 72%, and the test data are summarized in table 1.
The nickel-manganese-based layered oxide cathode material prepared in example 9 has the chemical formula Na 0.62 K 0.05 [Ni 0.17 Mn 0.67 Mg 0.16 ]O 2 (wherein, corresponding to the general formula a=0.17, b=0.67, c=0.16, x=0.62, y=0.05, l is K) + M is Mg 2+ ) The method comprises the steps of carrying out a first treatment on the surface of the The cycle capacity curve of the test cell, as shown in FIG. 10, has an operating voltage range of 2V-4.3V, at 1CThe weekly specific capacity was 96.7mAh/g, the 120-week capacity retention was 88%, and the test data are summarized in Table 1.
Example 10
The embodiment provides a preparation process and performance test of a nickel-manganese-based layered oxide positive electrode material, wherein the prepared positive electrode material has a chemical formula of Na 0.62 K 0.05 [Ni 0.3 Mn 0.68 Li 0.02 ]O 2 (wherein, corresponding to the general formula a=0.3, b=0.68, c=0.02, x=0.62, y=0.05, l is K) + M is Li + ) The specific preparation method is the same as that of the substrate of the example 1, except that the raw material is also added with a compound CH containing M ions 3 COOLi。
The battery assembly and test method were the same as in example 2, the cycle capacity graph of the test battery was shown in FIG. 13, the initial cycle specific capacity was 125mAh/g, the 300 cycle capacity retention rate was 51%, the operating voltage interval was 2V-4.3V, and the test data were summarized in Table 1.
The preparation method of the nickel-manganese-based layered oxide cathode material, the CR2032 button cell assembly and the test method provided in examples 11 to 15 were the same as in example 10, except that the contents of Ni element and doped Li element were different, as follows.
The nickel-manganese-based layered oxide cathode material prepared in example 11 has the chemical formula Na 0.62 K 0.05 [Ni 0.27 Mn 0.69 Li 0.04 ]O 2 (wherein, corresponding to the general formula a=0.27, b=0.69, c=0.04, x=0.62, y=0.05, l is K) + M is Li + ) XRD thereof, as shown in fig. 3, can see the crystal structure as P2 phase; the graph of the cyclic capacity of the test battery is shown in FIG. 13, the initial cycle specific capacity at 1C is 127mAh/g, the capacity retention rate at 300 weeks is 44%, the working voltage interval is 2V-4.3V, and the summary of the test data is shown in Table 1.
The nickel-manganese-based layered oxide cathode material prepared in example 12 has the chemical formula Na 0.62 K 0.05 [Ni 0.24 Mn 0.7 Li 0.06 ]O 2 (wherein, corresponding to the general formula a=0.24, b=0.7, c=0.06, x=0.62, y=0.05, l is K) + M is Li + ) XR of it D, as shown in FIG. 3, the crystal structure can be seen to be the P2 phase; the cycle capacity graph of the test battery is shown in FIG. 13, the first week specific capacity at 1C is 126.3mAh/g, the 220 week capacity retention rate is 38%, the working voltage interval is 2V-4.3V, and the test data are summarized in Table 1.
The nickel-manganese-based layered oxide cathode material prepared in example 13 has the chemical formula Na 0.62 K 0.05 [Ni 0.21 Mn 0.71 Li 0.08 ]O 2 (wherein, corresponding to the general formula a=0.21, b=0.71, c=0.08, x=0.62, y=0.05, l is K) + M is Li + ) XRD thereof, as shown in fig. 3, can see the crystal structure as P2 phase; the structure is shown in FIG. 6 (b); the charge-discharge curve for the first five weeks of the test cell is shown in fig. 12; the cycle capacity curve chart of the test battery is shown in FIG. 13, the initial cycle specific capacity at 1C is 122mAh/g, the capacity retention rate at 300 weeks is 70%, the working voltage interval is 2V-4.3V, and the summary of the test data is shown in Table 1; the rate graphs are shown in FIG. 14, and the discharge capacities are 133.2mAh/g, 127mAh/g, 119.7mAh/g, 106.9mAh/g and 95.8mAh/g respectively at the rates of 0.2C, 0.5C, 1C, 2C and 5C, the specific capacities at the rate of 5C can reach 72% at the rate of 0.2C, the rate performance is excellent, and the rate test data are summarized in Table 2.
The nickel-manganese-based layered oxide cathode material prepared in example 14 has the chemical formula Na 0.62 K 0.05 [Ni 0.18 Mn 0.72 Li 0.1 ]O 2 (wherein, corresponding to the general formula a=0.18, b=0.72, c=0.1, x=0.62, y=0.05, l is K) + M is Li + ) XRD thereof, as shown in fig. 3, can see the crystal structure as P2 phase; the cycle capacity graph of the test battery is shown in FIG. 13, the initial cycle specific capacity at 1C is 118.9mAh/g, the 300 cycle capacity retention rate is 56%, the working voltage interval is 2V-4.3V, and the test data are summarized in Table 1.
The nickel-manganese-based layered oxide cathode material prepared in example 15 has the chemical formula Na 0.62 K 0.05 [Ni 0.15 Mn 0.73 Li 0.12 ]O 2 (wherein, corresponding to the general formula a=0.15, b=0.73, c=0.12, x=0.62, y=0.05, l is K) + M is Li + ) XRD of which, as shown in FIG. 3, canTo see the crystal structure as P2 phase; the cycle capacity graph of the test battery is shown in FIG. 13, the initial cycle specific capacity at 1C is 116.2mAh/g, the 200 cycle capacity retention rate is 46%, the working voltage interval is 2V-4.3V, and the test data are summarized in Table 1.
Example 16
The embodiment provides a preparation process and performance test of a nickel-manganese-based layered oxide positive electrode material, wherein the prepared positive electrode material has a chemical formula of Na 0.62 K 0.05 [Ni 0.31 Mn 0.67 Zn 0.02 ]O 2 (wherein, corresponding to the general formula a=0.31, b=0.67, c=0.02, x=0.62, y=0.05, l is K) + M is Zn 2+ ) The same substrate as in example 1 was prepared specifically, except that the raw material was further added with a Compound (CH) containing M ions 3 COO) 2 Zn. The battery assembly and test procedure was the same as in example 2.
The test cycle capacity graph is shown in FIG. 16, the initial cycle specific capacity is 103.8mAh/g, the 200-cycle capacity retention rate is 50%, the working voltage interval is 2V-4.3V, and the test data are summarized in Table 1.
The preparation method of the nickel-manganese-based layered oxide cathode material, the CR2032 button cell assembly and the test method provided in examples 17 to 21 were the same as in example 16, except that the Ni element and the doped Zn element were different in content, as follows.
The nickel-manganese-based layered oxide cathode material prepared in example 17 has the chemical formula Na 0.62 K 0.05 [Ni 0.29 Mn 0.67 Zn 0.04 ]O 2 (wherein, corresponding to the general formula a=0.29, b=0.67, c=0.04, x=0.62, y=0.05, l is K) + M is Zn 2+ ) XRD thereof, as shown in fig. 4, can see the crystal structure as P2 phase; the test cycle capacity graph is shown in FIG. 16, the first week specific capacity at 1C is 117.7mAh/g, the 200 week capacity retention rate is 60%, the working voltage interval is 2V-4.3V, and the test data are summarized in Table 1.
The nickel-manganese-based layered oxide cathode material prepared in example 18 has the chemical formula Na 0.62 K 0.05 [Ni 0.27 Mn 0.67 Zn 0.06 ]O 2 (wherein, corresponding to the general formula a=0.27, b=0.67, c=0.06, x=0.62, y=0.05, l is K) + M is Zn 2+ ) XRD thereof, as shown in fig. 4, can see the crystal structure as P2 phase; the cycle capacity graph of the test battery is shown in FIG. 16, the first week specific capacity at 1C is 114mAh/g, the 300 week capacity retention rate is 47%, the working voltage interval is 2V-4.3V, and the summary of the test data is shown in Table 1.
The nickel-manganese-based layered oxide cathode material prepared in example 19 has the chemical formula Na 0.62 K 0.05 [Ni 0.25 Mn 0.67 Zn 0.08 ]O 2 (wherein, corresponding to the general formula a=0.25, b=0.67, c=0.08, x=0.62, y=0.05, l is K) + M is Zn 2+ ) The specific preparation and test procedure was the same as in example 16; XRD thereof, as shown in fig. 4, can see the crystal structure as P2 phase; the structure is shown in fig. 6. The charge-discharge curve graph of the first five weeks of the test battery is shown in fig. 15, the cycle capacity curve graph is shown in fig. 16, the first week specific capacity at 1C is 109mAh/g, the 400 week capacity retention rate is 74%, the working voltage interval is 2-4.3V, and the test data are summarized in table 1; the rate graphs are shown in FIG. 17, the discharge capacities of example 19 are 109.3mAh/g, 109mAh/g, 107mAh/g, 100.1mAh/g and 86.9mAh/g at rates of 0.2C, 0.5C, 1C, 2C and 5C, respectively, the specific capacities at 5C rate can reach 80% at 0.2C rate, the rate performance is excellent, and the rate test data are summarized in Table 2.
Preparation process and performance test of Nickel-manganese-based layered oxide cathode material prepared in example 20, the prepared cathode material has a chemical formula of Na 0.62 K 0.05 [Ni 0.23 Mn 0.67 Zn 0.1 ]O 2 (wherein, corresponding to the general formula a=0.23, b=0.67, c=0.1, x=0.62, y=0.05, l is K) + M is Zn 2+ ) XRD thereof, as shown in fig. 4, can see the crystal structure as P2 phase; the test cycle capacity graph is shown in FIG. 16, the first week specific capacity at 1C is 104mAh/g, the 400 week capacity retention rate is 73%, the working voltage interval is 2V-4.3V, and the test data are summarized in Table 1.
The nickel-manganese-based layered oxide cathode material prepared in example 21 has the chemical formula Na 0.62 K 0.05 [Ni 0.21 Mn 0.67 Zn 0.12 ]O 2 (wherein, corresponding to the general formula a=0.21, b=0.67, c=0.12, x=0.62, y=0.05, l is K) + M is Zn 2+ ) The cycle capacity graph of the test battery is shown in fig. 16, the initial cycle specific capacity at 1C is 105.1mAh/g, the 200 cycle capacity retention rate is 18%, the working voltage interval is 2V-4.3V, and the test data are summarized in table 1.
The preparation methods of the nickel-manganese-based layered oxide cathode materials, CR2032 button cell assembly and test methods provided in examples 22 and 23 were the same as in example 6, except that the content of the alkali metal site doping element K was different, as follows.
The nickel-manganese-based layered oxide cathode material prepared in example 22 has the chemical formula Na 0.64 K 0.03 [Ni 0.23 Mn 0.67 Mg 0.1 ]O 2 (wherein, corresponding to the general formula a=0.23, b=0.67, c=0.1, x=0.64, y=0.03, l is K) + M is Mg 2 + ) The crystal structure is P2 phase, the first cycle charge-discharge curve of the test battery is shown in figure 7, the cycle capacity curve is shown in figure 8, the first cycle specific capacity is 108.9mAh/g, the 120 cycle capacity retention rate is 79%, the working voltage interval is 2V-4.3V, and the summary of the test data is shown in table 1.
The nickel-manganese-based layered oxide cathode material prepared in example 23 has the chemical formula Na 0.6 K 0.07 [Ni 0.23 Mn 0.67 Mg 0.1 ]O 2 (wherein, corresponding to the general formula a=0.23, b=0.67, c=0.1, x=0.6, y=0.07, l is K) + M is Mg 2 + ) The crystal structure is P2 phase, the first-week charge-discharge curve of the test battery is shown in FIG. 7, the cyclic capacity curve is shown in FIG. 8, the first-week specific capacity is 110.7mAh/g, the 120-week capacity retention rate is 78%, the working voltage interval is 2V-4.3V, and the summary of the test data is shown in Table 1.
The preparation methods of the nickel-manganese-based layered oxide cathode materials provided in examples 24 to 27 were the same as those in example 1, except that the contents of the doping elements were different, and the CR2032 button cell assembly and test methods of examples 26 and 27 were the same as those in example 2, respectively, as follows.
The nickel-manganese-based layered oxide cathode material prepared in example 24 has the chemical formula Na 0.64 K 0.01 [Ni 0.15 Mn 0.85 ]O 2 (wherein, corresponding to the formula a=0.15, b=0.85, x=0.64, y=0.01, l is K) + ) XRD thereof, as shown in FIG. 5, can see the crystal structure as P2 phase.
The nickel-manganese-based layered oxide cathode material prepared in example 25 has the chemical formula Na 0.62 K 0.03 [Ni 0.15 Mn 0.85 ]O 2 (wherein, corresponding to the formula a=0.15, b=0.85, x=0.62, y=0.03, l is K) + ) XRD thereof, as shown in FIG. 5, can see the crystal structure as P2 phase.
The nickel-manganese-based layered oxide cathode material prepared in example 26 has the chemical formula Na 0.6 K 0.05 [Ni 0.15 Mn 0.85 ]O 2 (wherein, for the general formula, a=0.15, b=0.85, x=0.6, y=0.05, l is K) + ) XRD thereof, as shown in fig. 5, can see the crystal structure as P2 phase; the charge-discharge curve of the first five weeks of the test battery is shown in fig. 19, the charge-discharge curve of the first week under 0.2C multiplying power is shown in fig. 20, the long-cycle capacity curve is shown in fig. 21, the first week specific capacity of the long-cycle capacity curve under 0.2C is 180.7mAh/g, the capacity retention rate of the long-cycle capacity curve under 100 weeks is 90%, the working voltage interval is 2V-4.2V, and the test data are summarized in table 1; the rate graphs are shown in FIG. 22, and the discharge capacities at the rates of 0.2C, 0.5C, 1C, 2C and 5C are 194.2mAh/g, 158.2mAh/g, 139.4mAh/g, 126.2mAh/g and 103.6mAh/g, respectively, and the specific capacities at the rate of 5C can reach 54% at the rate of 0.2C, and the rate test data are summarized in Table 2.
Example 27
The embodiment provides a preparation process and performance test of a nickel-manganese-based layered oxide positive electrode material, wherein the prepared positive electrode material has a chemical formula of Na 0.62 K 0.05 [Ni 0.21 Mn 0.71 Li 0.08 ]O 1.98 F 0.02 (wherein, corresponding to the general formula a=0.21, b=0.71, c=0.08, x=0.62, y=0.05, γ=0.02, l is K) + M is Li + ) The crystal structure is P2 phase, and the specific preparation method and the test method are the same as those of the matrix in the embodiment 1 and are the same as those of the embodimentExample 1 differs in that the starting material is also added with a compound CH containing M ions 3 COOLi and F-containing compound NaF. Na prepared in example 27 0.62 K 0.05 [Ni 0.21 Mn 0.71 Li 0.08 ]O 1.98 F 0.02 Charge-discharge graphs for the first to fifth weeks of the assembled battery are shown in fig. 23.
To better illustrate the effect of the examples of the present invention, the materials prepared in comparative examples 1-2 were compared with the above examples.
Comparative example 1
With undoped Na 2/3 Ni 1/3 Mn 2/3 O 2 For comparative example 1, the preparation was essentially the same as in example 1, except that the starting materials and the calcination were such that CH was stoichiometrically taken 3 COONa(CH 3 COO) 2 Ni、(CH 3 COO) 2 Mn·4H 2 O, the precursor gel is prepared subsequently, the precursor gel is the same as that of the example 1, then the intermediate product powder is pressed into a wafer, the wafer is heated to 900 ℃ at the heating rate of 2 ℃/min under the air atmosphere, the wafer is calcined for 12 hours after the heating is finished, and the wafer is cooled to the room temperature to obtain the anode active substance Na 2/3 Ni 1/ 3 Mn 2/3 O 2 The crystal structure is P2 phase.
Prepared Na 2/3 Ni 1/3 Mn 2/3 O 2 The method for assembling the battery is the same as that of the example 2, a test cycle capacity curve chart is shown in fig. 10, the first week specific capacity at 1C is 120.1mAh/g, the 100 week capacity retention rate is only 46%, the working voltage interval is 2V-4.3V, and the test data are summarized in table 1; the magnification chart is shown in FIG. 11, na at the magnifications of 0.2C, 0.5C, 1C, 2C and 5C 2/3 Ni 1/3 Mn 2/3 O 2 The discharge capacities of (3) were 114.1, 84, 71, 60.1 and 44.3mAh/g, respectively, and the specific capacities at 5C rate were only 36% at 0.2C rate, the rate performance was poor, and the rate test data are summarized in Table 2.
Comparative example 2
Preparation of Na without elemental doping Using Sol gel 0.65 Ni 0.15 Mn 0.85 O 2 Accurately weigh CH of chemical formula metering ratio 3 COONa、(CH 3 COO) 2 Ni、(CH 3 COO) 2 Mn·4H 2 O, the preparation method is basically the same as that of example 1, the difference is that the raw materials are used, the precursor gel is prepared in the following way, the precursor wafer is heated to 900 ℃ at the heating rate of 5 ℃/min under the air atmosphere, calcined for 12 hours after the heating is finished, and cooled to room temperature to obtain the anode active material Na 0.65 Ni 0.15 Mn 0.85 O 2 The crystal structure is P2 phase.
Prepared Na 0.65 Ni 0.15 Mn 0.85 O 2 The method for assembling the battery is the same as that of the example 2, the first-week charge-discharge curve is shown in fig. 20, the test cycle capacity curve is shown in fig. 21, the first-week specific capacity at 0.2C is 151.4mAh/g, the 100-week capacity retention rate is only 23%, and the test data are summarized in table 1; the magnification graphs are shown in FIG. 22, na at magnifications of 0.2C, 0.5C, 1C, 2C and 5C 0.65 Ni 0.15 Mn 0.85 O 2 The discharge capacities of (3) were 151.8, 131.8, 121.2, 109.4 and 77.2mAh/g, respectively, and the specific capacities at 5C rate were only 50.8% at 0.2C rate, and the rate performance was poor, and the rate test data are summarized in Table 2.
Table 1 shows a summary of the material formulas and crystal structures prepared in examples 2-23, examples 26-27 and comparative examples 1-2, and a summary of test data for assembled batteries.
Table 2 is a summary of the rate test data for examples 6, 13, 19, 26 and comparative examples 1-3:
the performance of the nickel manganese-based layered oxide positive electrode materials of the present invention is illustrated by the test data of table 1, as well as by the accompanying figures 1-22.
By XRD of the materials of figures 2-5, it can be seen that the obtained nickel-manganese-based layered oxide positive electrode materials are all of a pure phase structure, which proves that L ions are successfully doped into alkali metal sites in the structure.
As can be seen from fig. 7 and 8, the K ions doped with alkali metal sites in different proportions of examples 6, 22 and 23 have different electrochemical effects on the material, the 120-week capacity retention rate of example 6 is 81%, the 120-week capacity retention rate of example 22 is 79%, and the 120-week capacity retention rate of example 23 is 78%, which proves that the doping of K ions has a beneficial improvement on the structure of the nickel-manganese-based layered oxide cathode material, and the study finds that the performance of the material is optimal when the mole number of K ions is 0.05.
As can be seen from the long cycle capacity graphs and test data of the assembled batteries of examples 2 to 9 and comparative example 1 of FIG. 10, the optimal cycle performance of examples 2 to 9 is that of example 6, the 120-cycle capacity retention of example 6 is 81%, and comparative example 1 does not have any doped layered oxide material Na 2/3 Ni 1/3 Mn 2/3 O 2 The capacity retention rate is only 46% after 100 weeks of circulation, which indicates that the co-doping of L ions and M ions on the nickel-manganese-based layered oxide greatly improves the long-circulating performance of the material.
As can be seen from a comparison of the rate performance of the assembled batteries of example 6 and comparative example 1 of fig. 11, the specific capacity of example 6 at different rates was always higher than that of comparative example 1, and the specific capacity of example 6 at 5C rate could reach 72% at 0.2C rate, while comparative example 1 was only 36%. Similarly, in examples 10 to 15, the performance was optimal in example 13 by fig. 13 and 14, and the 300-week capacity retention rate of example 13 was 70%, and the specific capacity at 5C rate could reach 71% at 0.2C rate. In contrast, in examples 16 to 21, example 19 was preferred in fig. 16 and 17, and the 400-week capacity retention rate of example 19 was 74%, and the specific capacity at 5C rate was 78% at 0.2C rate, which was excellent in rate performance. Such results demonstrate that alkali and transition metal site doping is effective in stabilizing anions of nickel manganese-based layered oxides, improving cycle performance, rate performance, and stability at high voltages without reducing capacity.
The embodiment of the invention provides a combination The chemical formula of the preparation method is Na x L y [Ni a Mn b M c N d ]O 2 Is common to all materials. To demonstrate this, the invention was prepared synthetically in materials of different nickel to manganese ratios, FIGS. 19-22 by Na of example 26 and comparative example 2 0.65 Ni 0.15 Mn 0.85 O 2 Electrochemical performance tests of first week charge and discharge, long cycle performance, and rate capability were performed, the 100 week capacity retention of example 26 was 90%, and the Na of comparative example 2 0.65 Ni 0.15 Mn 0.85 O 2 The 90-week capacity retention of (2) was only 23%, the capacity of example 26 was higher at different rates than that of the battery of comparative example 2, the specific capacity at 5C rate could reach 54% at 0.2C rate, and comparative example 2 used Na 0.65 Ni 0.15 Mn 0.85 O 2 Only 50% of the assembled cells were assembled. The electrochemical properties of example 26 are significantly higher than those of the comparative materials, confirming that the synthetic preparation method of the invention can significantly improve the electrochemical properties of the existing nickel-manganese-based layered oxide.
In summary, the invention provides a very simple preparation method, a series of nickel-manganese-based layered oxide positive electrode materials for sodium ion batteries, which have very excellent cycle life and multiplying power capability and very high specific capacity, are obtained, the raw materials are cheap and easy to obtain, and the preparation method is suitable for commercial production, has very excellent practical application prospect, and can be applied to the fields of solar energy, wind power generation, electric automobiles and the like on a large scale.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the scope of the invention, but to limit the invention to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (9)
1. A nickel-manganese-based layered oxide positive electrode material for a sodium ion battery, characterized in that the nickel-manganese-based layered oxide positive electrodeThe chemical general formula of the material is Na x L y [Ni a Mn b M c N d ]O 2+δ-γ F γ Wherein x is more than or equal to 0.5 and less than or equal to 0.8, y is more than or equal to 0 and less than or equal to 0.2, a+b+c+d=1, a is more than or equal to 0 and less than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.3, d is more than or equal to 0 and less than or equal to 0.3, -0.2 and delta is more than or equal to 0 and less than or equal to 0.2;
l is an element for doping and substituting Na at an alkali metal position, and the ion of L is K + ；
M is an element for doping and substituting transition metal position Ni or Mn, and the ion of M specifically comprises Mg 2+ 、Zn 2+ 、Li + Any one of them;
n is an element for doping and substituting transition metal position Ni or Mn, and the ion of N specifically comprises Nb 5+ 、Ca 2+ 、B 3+ 、Co 3+ 、Fe 3+ 、Cu 2+ 、Al 3+ 、Co 2+ 、Zr 4+ 、Sn 4+ 、Ti 4+ 、Ru 4+ 、Nb 4+ 、Te 6+ 、Sb 5+ Or Mo (Mo) 6+ One or more of the following;
the working voltage of the nickel-manganese-based layered oxide positive electrode material when the nickel-manganese-based layered oxide positive electrode material is used for a sodium ion battery is between 2V and 4.5V;
The nickel-manganese-based layered oxide positive electrode material is used in a sodium ion battery, nickel ions are converted from positive bivalent to positive trivalent when charged in the first week, manganese ions of positive trivalent are converted from positive trivalent to positive tetravalent, and oxygen ions are converted from negative bivalent to negative monovalent; when the discharge is carried out in the first week, nickel ions are converted into positive bivalent again from positive trivalent, oxygen ions are converted into negative bivalent again from negative monovalent, positive tetravalent manganese ions are converted into positive trivalent from positive tetravalent, magnesium ions, lithium ions or zinc ions are not changed in valence, and the valence changing process after the first week is consistent with the first week.
2. The nickel manganese-based layered oxide cathode material for a sodium ion battery according to claim 1, wherein the crystal structure of the nickel manganese-based layered oxide cathode material is P2 phase and the space group is P63/mmc.
3. A method for preparing the nickel-manganese-based layered oxide positive electrode material for a sodium ion battery according to any one of claims 1 to 2, wherein the preparation method is a sol-gel method, comprising the steps of:
step S1, weighing a sodium source material, a nickel source material, a manganese source material, a compound containing L ions, a compound containing M ions, a compound containing N ions and NaF as raw materials according to stoichiometric ratio, dissolving the raw materials in deionized water, stirring and mixing, adding a complexing agent, and continuously stirring at a certain temperature to form precursor gel;
Step S2, placing the precursor gel in a muffle furnace, and carbonizing in an air atmosphere to obtain intermediate product powder;
and step S3, pressing the intermediate product powder into a wafer, calcining in a single step in an oxygen atmosphere, and naturally cooling to room temperature after calcining to obtain the nickel-manganese-based layered oxide cathode material.
4. A method of preparing as claimed in claim 3, wherein the sodium source material comprises: sodium nitrate and/or sodium acetate; the nickel source material comprises: nickel nitrate and/or nickel acetate; the manganese source material comprises: manganese nitrate and/or manganese acetate;
the compound containing L ions comprises nitrate and/or acetate containing L ions; the L ion is K + ；
The M ion-containing compound comprises nitrate and/or acetate containing M ions; the M ion includes: mg of 2+ 、Zn 2+ 、Li + Any one of them;
the N-ion containing compound comprises nitrate and/or acetate containing N ions; the N ions include: nb (Nb) 5+ 、Ca 2+ 、B 3+ 、Co 3+ 、Fe 3+ 、Cu 2+ 、Al 3+ 、Co 2+ 、Zr 4+ 、Sn 4+ 、Ti 4+ 、Ru 4+ 、Nb 4+ 、Te 6+ 、Sb 5+ Or Mo (Mo) 6+ One or more of the following.
5. The method of claim 3, wherein the mass ratio of the raw materials to the deionized water is 3:50;
the complexing agent is citric acid monohydrate; the mass ratio of the complexing agent to the deionized water is 2:25.
6. A method according to claim 3, wherein the temperature at which stirring is continued is between 90 ℃ and 100 ℃ for a period of 9 hours to 12 hours;
the specific conditions of carbonization are as follows: heating to 300-500 ℃ at a heating rate of 2-8 ℃/min;
the single-step calcination temperature is 1000-1050 ℃, the heating rate is 2-8 ℃/min, and the calcination time is 12-14 hours.
7. A positive electrode comprising the nickel manganese-based layered oxide positive electrode material according to any one of claims 1 to 2.
8. A sodium ion battery comprising a positive electrode, a separator, an electrolyte or a solid electrolyte, a negative electrode according to claim 7;
the operating voltage range of the sodium ion battery is between 2V and 4.5V.
9. Use of the sodium ion battery according to claim 8, wherein the sodium ion battery is used for large-scale energy storage equipment for solar energy and wind power generation, or any one of smart grid peak shaving, distribution power stations, backup power sources, communication base stations and energy storage equipment of electric automobiles.
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| CN116845229A (en) * | 2023-05-25 | 2023-10-03 | 多助科技(武汉)有限公司 | Double-doped P2 type layered oxide composite material and preparation method and application thereof |
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| CN111162250A (en) * | 2018-11-07 | 2020-05-15 | 中国科学院物理研究所 | Pure cation valence-change high-sodium-content P2 phase layered oxide material, preparation method and application |
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