CN116443951A - Sodium-embedded lithium ion battery positive electrode material and preparation method thereof - Google Patents
Sodium-embedded lithium ion battery positive electrode material and preparation method thereof Download PDFInfo
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- CN116443951A CN116443951A CN202310483990.8A CN202310483990A CN116443951A CN 116443951 A CN116443951 A CN 116443951A CN 202310483990 A CN202310483990 A CN 202310483990A CN 116443951 A CN116443951 A CN 116443951A
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- Prior art keywords
- sodium
- reaction
- ion battery
- lithium ion
- hydroxide
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 56
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 102
- 238000006243 chemical reaction Methods 0.000 claims abstract description 98
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 87
- 239000002243 precursor Substances 0.000 claims abstract description 61
- 239000011734 sodium Substances 0.000 claims abstract description 59
- 229910052742 iron Inorganic materials 0.000 claims abstract description 51
- 239000011572 manganese Substances 0.000 claims abstract description 39
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 38
- 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 abstract description 37
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 37
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000002156 mixing Methods 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 34
- 239000012702 metal oxide precursor Substances 0.000 claims abstract description 33
- 239000007788 liquid Substances 0.000 claims abstract description 32
- 238000000926 separation method Methods 0.000 claims abstract description 28
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 28
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 24
- 238000001354 calcination Methods 0.000 claims abstract description 24
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 11
- 239000010405 anode material Substances 0.000 claims abstract description 10
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 7
- 230000035484 reaction time Effects 0.000 claims abstract description 7
- 239000007800 oxidant agent Substances 0.000 claims abstract description 6
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 42
- 229910052759 nickel Inorganic materials 0.000 claims description 41
- 239000000243 solution Substances 0.000 claims description 26
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- 238000005245 sintering Methods 0.000 claims description 16
- 229910044991 metal oxide Inorganic materials 0.000 claims description 15
- 150000004706 metal oxides Chemical class 0.000 claims description 15
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 14
- 239000013078 crystal Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 238000000975 co-precipitation Methods 0.000 claims description 11
- 238000002425 crystallisation Methods 0.000 claims description 11
- 230000008025 crystallization Effects 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 239000006104 solid solution Substances 0.000 claims description 11
- 235000002639 sodium chloride Nutrition 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 239000008139 complexing agent Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000010406 cathode material Substances 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 230000014759 maintenance of location Effects 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 3
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride 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
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical class [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 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
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- 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 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 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 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 2
- 229940039790 sodium oxalate Drugs 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 235000015424 sodium Nutrition 0.000 claims 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 26
- 238000005303 weighing Methods 0.000 description 21
- 238000009830 intercalation Methods 0.000 description 17
- 230000002687 intercalation Effects 0.000 description 17
- 239000000463 material Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 14
- 238000000498 ball milling Methods 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- VVNXEADCOVSAER-UHFFFAOYSA-N lithium sodium Chemical compound [Li].[Na] VVNXEADCOVSAER-UHFFFAOYSA-N 0.000 description 6
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 235000015842 Hesperis Nutrition 0.000 description 1
- 235000012633 Iberis amara Nutrition 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 239000006257 cathode slurry Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000010998 test method 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
- H01M4/48—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
-
- 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
-
- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a positive electrode material of a sodium-embedded lithium ion battery and a preparation method thereof, comprising the following steps: obtaining a hydroxide or carbonate precursor containing metallic nickel, iron and manganese; mixing the hydroxide or carbonate precursor, an oxidizing agent, and a sodium-containing metal compound, controlling reaction conditions includes: the reaction pressure is 0.1-3 MPa, the reaction temperature is 20-250 ℃, the reaction time is 4-50 h, and the concentration of sodium metal ions in the reaction system is 0.5-10 mol/L, so that the sodium ions and the hydroxide or carbonator precursor undergo a physical-chemical reaction; carrying out solid-liquid separation on the reaction product to obtain a sodium-embedded metal oxide precursor; and mixing and calcining the sodium-intercalated metal oxide precursor and a lithium source to obtain the sodium-intercalated lithium ion battery anode material, wherein the first discharge capacity and the cycle performance are obviously improved.
Description
Technical Field
The invention relates to a preparation technology of a lithium ion battery, in particular to a sodium-embedded lithium ion battery positive electrode material and a preparation method thereof.
Background
Lithium ion batteries are currently the main energy storage devices and are widely applied to the fields of mobile phones, notebook computers, electric tools, automobiles, aerospace and the like. In order to make up for the deficiency of the lithium ion battery, doping the lithium ion battery is a current research hot spot.
In which, the lithium ion battery is doped with multiple metals, so that great progress has been made at present, for example, CN114447309A discloses a sodium ion doped lithium ion battery positive electrode material, the chemical formula of the positive electrode material is Lix-yNayNizM1-zO 2 Wherein M is one or more of Mn, mg, ti, al, co. The preparation method comprises the following steps: s1, preparing NaxNizM1-zO 2 Precursor: uniformly mixing a metal M source, a Ni source and a sodium source, sintering, and cooling to obtain a precursor material NaxNizM1-zO 2 The method comprises the steps of carrying out a first treatment on the surface of the S2, mixing the obtained NaxNizM1-zO 2 Mixing the precursor with a lithium source, and then carrying out molten salt ion exchange to obtain a bulk material; s3, cleaning the obtained block material, and performing solid-liquid separation and drying to obtain a powder material; and S4, performing heat treatment on the obtained powder material to obtain the positive electrode material.
The method adopts a solid-phase ball milling mixing mode to carry out sodium ion doping, so that the mixing level at the particle level can be realized, the prepared material is a mixed phase crystal mixture, the doping elements are unevenly distributed, the effect of improving the first charge and discharge efficiency of the material during charge and discharge is not obvious, and the performance attenuation of the material is aggravated.
Disclosure of Invention
The invention aims to solve the problems of low first discharge capacity and low cycle performance of the existing lithium ion battery, and provides a sodium-intercalated lithium ion battery positive electrode material, sodium is intercalated into hydroxide or carbonator crystal lattice through chemical reaction, and sodium is more uniform in the material to reach atomic level; the mixing of sodium in the conventional sodium-embedded lithium battery cathode material adopts mechanical and physical mixing, and the mixing effect only reaches the particle level; the sodium reaction kettle is made to perform in wet reaction through a wet sodium embedding scheme, so that the energy consumption is lower, sodium elements in the product are uniform and better, the consistency of phase components is improved, and the first discharge capacity and the cycle performance are obviously improved in the charge and discharge process.
Further, due to the radius of Na ionRadius +.>The c-axis and c/a ratio of the material can be slightly increased by adopting sodium ion doping, which is favorable for Li ion diffusion, and the polarization of the material can be reduced after sodium doping, which is favorable for further improving the first discharge capacity and the cycle performance of the material.
The specific scheme is as follows:
the preparation method of the sodium-embedded lithium ion battery positive electrode material comprises the following steps:
(1) Obtaining a hydroxide or carbonate precursor containing metallic nickel, iron and manganese;
(2) Mixing the hydroxide or carbonate precursor, an oxidizing agent, and a sodium-containing metal compound, controlling reaction conditions includes: the reaction pressure is 0.1-3 MPa, the reaction temperature is 20-250 ℃, the reaction time is 1-50 h, and the concentration of sodium metal ions in the reaction system is 0.5-10 mol/L, so that the sodium ions and the hydroxide or carbonator precursor undergo a physical-chemical reaction; by controlling the conditions in the step, the intercalation of sodium into hydroxide or carbonator crystal lattice through chemical reaction can realize atomic-level dispersion;
(3) Carrying out solid-liquid separation on the reaction product in the step (2) to obtain a sodium-embedded metal oxide precursor;
(4) And (3) mixing the sodium-intercalated metal oxide precursor obtained in the step (3) with a lithium source, and calcining to obtain the sodium-intercalated lithium ion battery anode material.
Further, in the step (1), the preparation method of the hydroxide or carbonator precursor comprises the following steps: adding water, complexing agent, precipitant, optional additive and mixed metal solution, performing coprecipitation crystallization reaction, and obtaining hydroxide or carbonator precursor containing metallic nickel, iron and manganese through solid-liquid separation;
preferably, the mixed metal solution is a mixed solution of metal compounds containing nickel, iron and manganese, wherein the metal compounds containing nickel are selected from one or more of nickel sulfate, nickel nitrate, nickel chloride or nickel acetate, the metal compounds containing iron are selected from one or more of ferrous sulfate, ferrous nitrate or ferrous chloride, and the metal compounds containing manganese are selected from one or more of manganese sulfate, manganese nitrate, manganese chloride or manganese acetate;
preferably, the complexing agent is one of ammonia water, ammonium bicarbonate or sodium carbonate;
preferably, the precipitant is sodium hydroxide;
preferably, the additive is at least one of aluminum, titanium, magnesium, niobium, tungsten, zirconium metal compounds;
preferably, the complexing agent: the precipitant: the mass ratio of the mixed metal feed liquid is 1:1-3:4-8, preferably 1:1.5-2.5:4.5-6.5, and more preferably 1:2:5;
further, in the coprecipitation crystallization reaction, the reaction temperature is 30-80 ℃, preferably 35-60 ℃, more preferably 50 ℃;
preferably, the complexing agent concentration is 2-15 g/L, preferably 3-12g/L, more preferably 5-10g/L;
preferably, the pH of the solution is from 10 to 13, preferably from 10.5 to 12, more preferably 11;
preferably, the stirring strength is 0.5-1.0 kw/m of input power 2 H, preferably 0.6-0.9kw/m 2 H, more preferably 0.8kw/m 2 ·h；
Preferably, the percentage saturation of dissolved oxygen in the solution is 5-50%, preferably 10-40%, more preferably 35%;
preferably, the reaction time is from 30 to 100 hours, preferably from 40 to 90 hours, more preferably from 50 to 80 hours.
Further, in the step (2), the sodium-containing metal compound is at least one of sodium oxide, sodium carbonate, sodium oxalate, sodium sulfate, sodium nitrate and sodium chloride;
preferably, in the physicochemical reaction, the metal Me in the hydroxide or carbonate precursor forms a solid solution structure with sodium ions, me represents at least one metal element of nickel, iron and manganese, preferably Me represents nickel, iron and manganese;
preferably, the molar ratio of metal Me to the oxidant in the hydroxide or carbonate precursor is 1: (0.5 to 4), preferably 1 to 3, more preferably 1.5 to 2.5; the full progress of the physical and chemical reaction is ensured by controlling the dosage of the oxidant.
Preferably, the molar ratio of the sodium-containing metal compound to the metal Me in the hydroxide or carbonate precursor is from (0.001 to 0.05): 1, preferably from (0.005 to 0.04): 1, more preferably from (0.01 to 0.03): 1;
preferably, the reaction pressure is 0.5 to 2.5MPa, preferably 0.8 to 2MPa, more preferably 1.5MPa;
preferably, the reaction temperature is 20 to 250 ℃, preferably 50 to 200 ℃, more preferably 100 to 180 ℃;
preferably, the reaction time is from 4 to 50 hours, preferably from 6 to 48 hours, more preferably from 10 to 24 hours;
preferably, the sodium metal ion concentration in the reaction system is 0.5 to 10mol/L, preferably 0.8 to 8mol/L, more preferably 1.0 to 6.0mol/L. In the reaction system of the invention, the concentration of sodium metal ions is the key to influence the crystal structure, and when the concentration of sodium metal ions is lower than 0.5mol/L, the entropy requirement cannot be met, and a sodium-embedded solid solution structure cannot be formed.
In the step (3), the solid-liquid separation mode is centrifugal separation, and the centrifugal separation is followed by drying treatment, wherein the drying temperature is 100-200 ℃ and the drying time is 6-24 hours.
Preferably, the sodium-intercalated metal oxide precursor has the chemical formula Na 2 O·Me 2 O 3 Sodium ions are located in the crystal lattice of the metal oxide without changing its original structure.
Further, in the step (4), the lithium source is selected from one or more of lithium carbonate, lithium hydroxide and lithium acetate;
preferably, the conditions of the calcination include: the calcination temperature is 500-950 ℃, preferably 600-900 ℃; the calcination time is 6-36 h, preferably 10-30h; the sintering atmosphere is air atmosphere or oxygen atmosphere;
preferably, the calcination comprises at least 2 stages, pre-calcination is performed at 500-650 ℃ for 3-10 hours, and then sintering is performed at 800-950 ℃ for 10-30 hours;
preferably, the sodium-intercalated metal oxide precursor is mixed with a lithium source according to Li: me molar ratio = 1.01-1.1:1, preferably 1.05-1.1:1.
The invention also protects the sodium-embedded lithium ion battery anode material prepared by the preparation method of the sodium-embedded lithium ion battery anode material.
Further, the sodium-intercalated lithium ion battery cathode material has any 1 or more of the following (1) to (3):
(1) The monocrystal particles of the positive electrode material of the sodium-embedded lithium ion battery are complete in morphology and round in particle surface;
(2) The first discharge capacity of the positive electrode material of the sodium-embedded lithium ion battery under the multiplying power of 3-4.4V and 0.1C is improved by 4-6 mAh/g compared with the corresponding positive electrode material of the lithium ion battery without sodium embedding;
(3) The capacity retention rate of the positive electrode material of the sodium-embedded lithium ion battery for 50 circles under the 1C multiplying power is more than or equal to 94%.
The invention also provides a battery, which comprises the positive electrode material of the sodium-intercalated lithium ion battery.
The invention also provides a power device comprising the battery.
The beneficial effects are that:
according to the invention, the sodium-embedded metal oxide precursor prepared by the wet method is a sodium-embedded solid solution, so that atomic-level sodium element dispersion is realized, and the sodium-embedded metal oxide precursor is used as a precursor to be mixed and calcined with a lithium source, so that the first discharge capacity and the cycle performance of the positive electrode material of the sodium-embedded lithium ion battery are improved, and the sodium-embedded metal oxide precursor has an excellent application prospect and can be widely applied to power devices such as ships, vehicles, terminal equipment, airplanes, rockets and the like.
Drawings
In order to more clearly illustrate the technical solutions of the present invention, the following brief description will be made on the accompanying drawings, which are given by way of illustration only and not limitation of the present invention.
FIG. 1 is an SEM image of a sodium-inlaid metal oxide precursor provided by one embodiment 1 of the present invention;
fig. 2 is an SEM image of a positive electrode material of a sodium-intercalated lithium ion battery according to embodiment 1 of the present invention.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the preferred embodiments of the present invention are described below, it should be understood that the present invention may be embodied in various forms and should not be limited to the embodiments set forth herein. The specific techniques or conditions are not identified in the examples and are performed according to techniques or conditions described in the literature in this field or according to the product specifications. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention. In the following examples, "%" means weight percent and parts means parts by weight unless otherwise specified.
The test methods used below included:
(1) First charge and discharge test: the charge-discharge test voltage interval is 3.0-4.4V, and the charge-discharge current is 0.1C (1C=200 mAh/g);
(2) Cycle stability test: the charge-discharge test voltage interval is 3.0-4.4V, and the charge-discharge current is 1C
(1c=200 mAh/g), and charge and discharge were cycled for 50 weeks.
Example 1
S1, adding non-salt water into a reaction kettle, controlling the ammonia content to be 7g/L, pH value to be 12.0 and the stirring strength to be 1.0kw/m of input power 2 H, under the condition that the temperature is 60 ℃ and the percentage saturation degree of dissolved oxygen in the solution is 10%, ammonia water, sodium hydroxide solution and the molar ratio are as follows: iron: manganese=0.45:0.10:0.45Sequentially adding the metal solution into a reaction kettle for coprecipitation crystallization reaction for 80 hours, and obtaining hydroxide precursors containing nickel, iron and manganese after solid-liquid separation, wherein the precursors are in a similar spherical shape;
s2, weighing hydroxide precursors containing nickel, iron and manganese, hydrogen peroxide and sodium hydroxide according to a molar ratio of 1:2:0.01, adding the mixture into a reactor, uniformly mixing the mixture, carrying out sodium intercalation reaction, controlling the concentration of sodium ions in the reaction process to be 4mol/L, controlling the temperature to be 220 ℃, controlling the reaction pressure to be 2MPa, and carrying out solid-liquid separation after continuous reaction for 2 hours to obtain a molar ratio Na: me=1% of metal oxide precursor, me represents nickel, iron, manganese.
The sodium-inlaid metal oxide precursor has Na 2 O·Me 2 O 3 The solid solution structure shows a single peak in the XRD spectrum, and no sodium oxide diffraction peak is seen, which shows that sodium ions are located in the crystal lattice of the metal oxide without changing the original shape and structure, and the scanning electron microscope picture is shown in figure 1, and it can be seen from figure 1 that the metal oxide precursor shape after embedding sodium is still kept to be in a similar spherical structure formed by stacking and arranging flaky primary particles, and no pulverization and fragmentation phenomenon exists.
S3, according to Li: me molar ratio=1.05:1, lithium hydroxide and a sodium-intercalated metal oxide precursor are weighed, ball-milled and mixed, placed in an air atmosphere, pre-calcined at 500 ℃ for 6 hours, and sintered at 900 ℃ for 12 hours, so that the positive electrode material of the sodium-intercalated lithium ion battery is finally obtained, and is marked as QNaNFM1, and a scanning electron microscope photo is shown as a graph in fig. 2, and the consistency of material particles is narrow, the particle surfaces are round and smooth, and the crystallinity of the material is good.
Example 2
S1, adding non-salt water into a reaction kettle, controlling the ammonia content to be 6g/L, pH value to be 12.0 and the stirring strength to be 1.0kw/m of input power 2 H, under the condition that the temperature is 60 ℃ and the percentage saturation degree of dissolved oxygen in the solution is 20%, ammonia water, sodium hydroxide solution and the molar ratio are as follows: iron: sequentially adding the metal solution of Mn=0.35:0.30:0.35 into a reaction kettle for coprecipitation crystallization reaction for 80 hours, and obtaining hydroxide containing Ni, fe and Mn after solid-liquid separationA precursor, wherein the morphology of the precursor is similar to a sphere;
s2, weighing hydroxide precursors containing nickel, iron and manganese, hydrogen peroxide and sodium hydroxide according to a molar ratio of 1:2:0.03, adding the mixture into a reactor, uniformly mixing the mixture, performing sodium intercalation reaction, controlling the concentration of sodium ions in the reaction process to be 4mol/L, controlling the temperature to be 200 ℃, controlling the reaction pressure to be 2MPa, continuously reacting for 1 hour, and performing solid-liquid separation to obtain a molar ratio Na: me=1% of metal oxide precursor, me represents nickel, iron, manganese; the sodium-inlaid metal oxide precursor has Na 2 O·Me 2 O 3 Solid solution structure, sodium ions are located in the crystal lattice of the metal oxide without changing its original morphology and structure.
S3, according to Li: me molar ratio=1.05:1, weighing a precursor containing lithium hydroxide and sodium-intercalated metal oxide, ball-milling and mixing, placing in an air atmosphere, pre-calcining at 500 ℃ for 6 hours, and sintering at 920 ℃ for 12 hours to finally obtain the positive electrode material of the sodium-intercalated lithium ion battery, namely QNaNFM2.
Example 3
S1, adding non-salt water into a reaction kettle, controlling the ammonia content to be 7.1 according to the 5g/L, pH value and the stirring strength to be 1.0kw/m of input power 2 H, under the condition that the temperature is 45 ℃ and the percentage saturation of dissolved oxygen in the solution is 5%, ammonia water, liquid alkali and mole ratio are as follows: iron: sequentially adding metal solutions of manganese=0.35:0.30:0.35 into a reaction kettle to perform coprecipitation crystallization reaction for 100 hours, and obtaining carbonate precursors containing nickel, iron and manganese after solid-liquid separation, wherein the precursors are in a similar spherical shape;
s2, weighing carbonate precursors containing nickel, iron and manganese, hydrogen peroxide and sodium hydroxide according to a molar ratio of 1:2:0.02, adding the carbonate precursors into a reactor, uniformly mixing the carbonate precursors and the hydrogen peroxide to perform sodium intercalation reaction, controlling the sodium ion concentration in the reaction process to be 4mol/L, controlling the temperature to be 220 ℃, controlling the reaction pressure to be 2MPa, and performing solid-liquid separation after continuous reaction for 1 hour to obtain a molar ratio Na: me=2% of metal oxide precursor, me represents nickel, iron, manganese; the sodium-inlaid metal oxide precursor has Na 2 O·Me 2 O 3 Solid solution structure, sodium ions are located in the crystal lattice of metal oxide without modificationChanging the original shape and structure.
S3, according to Li: me molar ratio=1.05:1, weighing a precursor containing lithium hydroxide and sodium-intercalated metal oxide, ball-milling and mixing, placing in an air atmosphere, pre-calcining at 500 ℃ for 6 hours, and sintering at 920 ℃ for 12 hours to finally obtain the positive electrode material of the sodium-intercalated lithium ion battery, namely QNaNFM3.
Example 4
S1, adding non-salt water into a reaction kettle, controlling the ammonia content to be 12g/L, pH value to be 11.6 and the stirring strength to be 0.9kw/m of input power 2 H, under the condition that the temperature is 50 ℃ and the percentage saturation of dissolved oxygen in the solution is 20%, ammonia water, liquid alkali and mole ratio are as follows: iron: sequentially adding metal solutions of manganese=0.50:0.20:0.30 into a reaction kettle to perform coprecipitation crystallization reaction for 90 hours, and obtaining hydroxide precursors containing nickel, iron and manganese after solid-liquid separation, wherein the precursors are in a similar spherical shape;
s2, weighing hydroxide precursors containing nickel, iron and manganese, hydrogen peroxide and sodium hydroxide according to a molar ratio of 1:3:0.04, adding the mixture into a reactor, uniformly mixing the mixture, carrying out sodium intercalation reaction, controlling the concentration of sodium ions in the reaction process to be 1mol/L, controlling the temperature to be 150 ℃, controlling the reaction pressure to be 1.5MPa, and carrying out solid-liquid separation after continuous reaction for 10 hours to obtain a molar ratio Na: me=4% of metal oxide precursor, me represents nickel, iron, manganese; the sodium-inlaid metal oxide precursor has Na 2 O·Me 2 O 3 Solid solution structure, sodium ions are located in the crystal lattice of the metal oxide without changing its original morphology and structure.
S3, according to Li: me molar ratio=1.08:1, weighing a precursor containing lithium hydroxide and sodium-intercalated metal oxide, ball-milling and mixing, placing in an air atmosphere, pre-calcining at 650 ℃ for 5 hours, and sintering at 900 ℃ for 10 hours to finally obtain the positive electrode material of the sodium-intercalated lithium ion battery, namely QNaNFM4.
Example 5
S1, adding non-salt water into a reaction kettle, controlling the ammonia content to be 5g/L, pH value to be 11.2 and the stirring strength to be 0.6kw/m of input power 2 H, percentage saturation of dissolved oxygen in solution at 45 DEG CAt 20%, ammonia water, liquid alkali and mole ratio of nickel: iron: sequentially adding metal solutions of manganese=0.40:0.20:0.40 into a reaction kettle to perform coprecipitation crystallization reaction for 60 hours, and obtaining hydroxide precursors containing nickel, iron and manganese after solid-liquid separation, wherein the precursors are in a similar spherical shape;
s2, weighing hydroxide precursors containing nickel, iron and manganese, hydrogen peroxide and sodium hydroxide according to a molar ratio of 1:1.5:0.02, adding the mixture into a reactor, uniformly mixing the mixture, performing sodium intercalation reaction, controlling the concentration of sodium ions in the reaction process to be 8mol/L, controlling the temperature to be 100 ℃, controlling the reaction pressure to be 1.2MPa, and performing solid-liquid separation after continuous reaction for 6 hours to obtain a molar ratio Na: me=2% of metal oxide precursor having Na 2 O·Me 2 O 3 Solid solution structure, me represents nickel, iron and manganese; the sodium ions are located in the crystal lattice of the metal oxide without changing its original morphology and structure.
S3, according to Li: me molar ratio=1.03:1, weighing a precursor containing lithium hydroxide and sodium-intercalated metal oxide, ball-milling and mixing, placing in an air atmosphere, pre-calcining at 600 ℃ for 5 hours, and sintering at 800 ℃ for 15 hours to finally obtain the positive electrode material of the sodium-intercalated lithium ion battery, namely QNaNFM5.
Example 6
S1, adding non-salt water into a reaction kettle, controlling the ammonia content to be 7.0 at a value of 3g/L, pH and the stirring strength to be 0.5kw/m of input power 2 H, under the condition that the temperature is 35 ℃ and the percentage saturation of dissolved oxygen in the solution is 5%, ammonia water, liquid alkali and mole ratio are as follows: iron: sequentially adding metal solutions of manganese=0.40:0.20:0.40 into a reaction kettle to perform coprecipitation crystallization reaction for 50 hours, and obtaining carbonate precursors containing nickel, iron and manganese after solid-liquid separation, wherein the precursors are in a similar spherical shape;
s2, weighing carbonate precursors containing nickel, iron and manganese, hydrogen peroxide and sodium hydroxide according to a molar ratio of 1:1.5:0.04, adding the carbonate precursors into a reactor, uniformly mixing the carbonate precursors and the hydrogen peroxide to the sodium hydroxide, performing sodium intercalation reaction, controlling the concentration of sodium ions in the reaction process to be 0.8mol/L, controlling the temperature to be 180 ℃, controlling the reaction pressure to be 2MPa, and performing solid-liquid separation after continuous reaction for 2 hoursThe molar ratio Na: me=4% of metal oxide precursor having Na 2 O·Me 2 O 3 Solid solution structure, me represents nickel, iron and manganese; the sodium ions are located in the crystal lattice of the metal oxide without changing its original morphology and structure.
S3, according to Li: me molar ratio=1.05:1, weighing a precursor containing lithium hydroxide and sodium-intercalated metal oxide, ball-milling and mixing, placing in an air atmosphere, pre-calcining at 550 ℃ for 6 hours, and sintering at 880 ℃ for 12 hours to finally obtain the positive electrode material of the sodium-intercalated lithium ion battery, namely QNaNFM6.
Example 7
S1, adding non-salt water into a reaction kettle, controlling the ammonia content to be 7.1 according to the 5g/L, pH value and the stirring strength to be 1.0kw/m of input power 2 H, under the condition that the temperature is 45 ℃ and the percentage saturation of dissolved oxygen in the solution is 5%, ammonia water, liquid alkali and mole ratio are as follows: iron: sequentially adding metal solutions of manganese=0.35:0.30:0.35 into a reaction kettle to perform coprecipitation crystallization reaction for 100 hours, and obtaining carbonate precursors containing nickel, iron and manganese after solid-liquid separation, wherein the precursors are in a similar spherical shape;
s2, weighing carbonate precursors containing nickel, iron and manganese, hydrogen peroxide and sodium hydroxide according to a molar ratio of 1:2:0.02, adding the carbonate precursors into a reactor, uniformly mixing the carbonate precursors and the hydrogen peroxide to perform sodium intercalation reaction, controlling the sodium ion concentration in the reaction process to be 4mol/L, controlling the temperature to be 220 ℃, controlling the reaction pressure to be 2MPa, and performing solid-liquid separation after continuous reaction for 1 hour to obtain a molar ratio Na: me=2% of metal oxide precursor having Na 2 O·Me 2 O 3 Solid solution structure, me represents nickel, iron and manganese; the sodium ions are located in the crystal lattice of the metal oxide without changing its original morphology and structure.
S3, according to Li: me molar ratio=1.02:1, weighing a precursor containing lithium hydroxide and sodium-intercalated metal oxide, ball-milling and mixing, placing in an air atmosphere, pre-calcining at 580 ℃ for 6 hours, and sintering at 850 ℃ for 12 hours to finally obtain the positive electrode material of the sodium-intercalated lithium ion battery, namely QNaNFM7.
Comparative example 1
The molar ratio of nickel was prepared as in step S1 of example 1: iron: manganese=0.45:0.10:0.45, except that the sodium intercalation reaction of step S2 was not performed, finally according to the molar ratio Li: me=1.05:1, weighing lithium hydroxide and a hydroxide precursor, ball-milling and mixing, placing in an air atmosphere, pre-calcining for 6 hours at 500 ℃, and sintering for 12 hours at 900 ℃, thereby finally obtaining the lithium ion battery anode material, which is marked as NFM1.
Comparative example 2
The molar ratio of nickel was prepared as in step S1 of example 1: iron: manganese=0.35:0.30:0.35, except that the sodium intercalation reaction of step S2 was not performed, finally according to the molar ratio Li: me=1.05:1, weighing lithium hydroxide and a hydroxide precursor, ball-milling and mixing, placing in an air atmosphere, pre-calcining for 6 hours at 500 ℃, and then sintering for 12 hours at 900 ℃, thus finally obtaining the lithium ion battery anode material, which is marked as NFM2.
Comparative example 3
The molar ratio of nickel was prepared as in step S1 of example 1: iron: manganese=0.45:0.10:0.4
5, except for step S2, the sodium intercalation reaction is carried out according to the following conditions:
weighing hydroxide precursors containing nickel, iron and manganese, hydrogen peroxide and sodium hydroxide according to a molar ratio of 1:2:0.01, adding the mixture into a reactor, uniformly mixing the mixture, carrying out sodium intercalation reaction, controlling the concentration of sodium ions in the reaction process to be 0.3mol/L, controlling the temperature to be 220 ℃, controlling the reaction pressure to be 2MPa, continuously reacting for 2 hours, and carrying out solid-liquid separation to obtain a molar ratio Na: me=1% of metal oxide precursor, which is Na 2 O and MeO x Me represents nickel, iron, manganese.
Finally, according to the mole ratio of Li: me=1.05:1, namely, weighing lithium hydroxide and a metal oxide precursor, ball-milling and mixing, placing in an air atmosphere, pre-calcining for 6 hours at 500 ℃, and then sintering for 12 hours at 900 ℃, thus finally obtaining the lithium ion battery anode material which is marked as NFM3.
Comparative example 4
The molar ratio of nickel was prepared as in step S1 of example 1: iron: manganese=0.45:0.10:0.45, except for step S2, the sodium intercalation reaction is carried out according to the following conditions:
weighing hydroxide precursors containing nickel, iron and manganese, hydrogen peroxide and sodium hydroxide according to a molar ratio of 1:2:0.01, adding the mixture into a reactor, uniformly mixing the mixture, carrying out sodium intercalation reaction, controlling the concentration of sodium ions in the reaction process to be 4mol/L, controlling the temperature to be normal temperature, controlling the reaction pressure to be 2MPa, and carrying out solid-liquid separation after continuous reaction for 2 hours to obtain a molar ratio Na: me=1% of metal oxide precursor, which is Na 2 O and MeO x Me represents nickel, iron, manganese.
Finally, according to the mole ratio of Li: me=1.05:1, namely, weighing lithium hydroxide and a metal oxide precursor, ball-milling and mixing, placing in an air atmosphere, pre-calcining for 6 hours at 500 ℃, and then sintering for 12 hours at 900 ℃, thus finally obtaining the lithium ion battery anode material which is marked as NFM4.
Comparative example 5
The molar ratio of nickel was prepared as in step S1 of example 1: iron: manganese=0.45:0.10:0.45, except for step S2, the sodium intercalation reaction is carried out according to the following conditions:
weighing hydroxide precursors containing nickel, iron and manganese, hydrogen peroxide and sodium hydroxide according to a molar ratio of 1:2:0.01, adding the mixture into a reactor, uniformly mixing the mixture, carrying out sodium intercalation reaction, controlling the concentration of sodium ions in the reaction process to be 4mol/L, controlling the temperature to be 220 ℃, controlling the reaction pressure to be normal pressure, continuously reacting for 2 hours, and carrying out solid-liquid separation to obtain a molar ratio Na: me=1% of metal oxide precursor, which is Na 2 O and MeO x Me represents nickel, iron, manganese.
Finally, according to the mole ratio of Li: me=1.05:1, namely, weighing lithium hydroxide and a metal oxide precursor, ball-milling and mixing, placing in an air atmosphere, pre-calcining for 6 hours at 500 ℃, and then sintering for 12 hours at 900 ℃, thus finally obtaining the lithium ion battery anode material which is marked as NFM5.
Performance detection
The materials prepared in examples and comparative examples were prepared into batteries under the following conditions:
the materials obtained in examples 1 to 6 and the materials obtained in comparative examples 1 to 5 are used as lithium ion cathode materials, the conductive carbon black and the polyvinylidene fluoride (PVDF) are respectively weighed according to the mass ratio of 8:1:1, a proper amount of NMP solvent is added under the inert atmosphere condition to be sufficiently ground to prepare cathode slurry, the slurry is uniformly coated on an aluminum foil current collector with the thickness of 16 mu m, and the aluminum foil current collector is dried for 12 hours at the temperature of 120 ℃ in vacuum and then cut into pieces, so that the cathode pole piece with the diameter of 19mm is prepared. Finally, a metallic lithium sheet was used as a negative electrode in an argon-filled glove box together with the positive electrode sheet, glass fiber separator paper (Whatman GF/D), an electrolyte (1 mol/L LiPF 6 Together, EC: PC (1:1)) assembled into a CR2025 button lithium ion battery.
As shown in Table 1, the first discharge capacity of the positive electrode material of the lithium ion battery after sodium doping is improved by about 4-6 mAh/g, meanwhile, the capacity retention rate under 1C circulation is obviously improved, and the sodium intercalation effect under high temperature and high pressure conditions is better.
Table 1 battery charge and discharge test results table
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner without contradiction. The various possible combinations of the invention are not described in detail in order to avoid unnecessary repetition.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (10)
1. A preparation method of a sodium-embedded lithium ion battery positive electrode material is characterized by comprising the following steps: the method comprises the following steps:
(1) Obtaining a hydroxide or carbonate precursor containing metallic nickel, iron and manganese;
(2) Mixing the hydroxide or carbonate precursor, an oxidizing agent, and a sodium-containing metal compound, controlling reaction conditions includes: the reaction pressure is 0.1-3 MPa, the reaction temperature is 20-250 ℃, the reaction time is 1-50 h, and the concentration of sodium metal ions in the reaction system is 0.5-10 mol/L, so that the sodium ions and the hydroxide or carbonator precursor undergo a physical-chemical reaction;
(3) Carrying out solid-liquid separation on the reaction product in the step (2) to obtain a sodium-embedded metal oxide precursor;
(4) And (3) mixing the sodium-intercalated metal oxide precursor obtained in the step (3) with a lithium source, and calcining to obtain the sodium-intercalated lithium ion battery anode material.
2. The method for preparing the positive electrode material of the sodium-embedded lithium ion battery according to claim 1, which is characterized in that: in step (1), the method for preparing the hydroxide or carbonator precursor comprises the following steps: adding water, complexing agent, precipitant, optional additive and mixed metal solution, performing coprecipitation crystallization reaction, and obtaining hydroxide or carbonator precursor containing metallic nickel, iron and manganese through solid-liquid separation;
preferably, the mixed metal solution is a mixed solution of metal compounds containing nickel, iron and manganese, wherein the metal compounds containing nickel are selected from one or more of nickel sulfate, nickel nitrate, nickel chloride or nickel acetate, the metal compounds containing iron are selected from one or more of ferrous sulfate, ferrous nitrate or ferrous chloride, and the metal compounds containing manganese are selected from one or more of manganese sulfate, manganese nitrate, manganese chloride or manganese acetate;
preferably, the complexing agent is one of ammonia water, ammonium bicarbonate or sodium carbonate;
preferably, the precipitant is sodium hydroxide;
preferably, the additive is at least one of aluminum, titanium, magnesium, niobium, tungsten, zirconium metal compounds;
preferably, the complexing agent: the precipitant: the mass ratio of the mixed metal feed liquid is 1:1-3:4-8, preferably 1:1.5-2.5:4.5-6.5, and more preferably 1:2:5.
3. The method for preparing the positive electrode material of the sodium-embedded lithium ion battery according to claim 2, which is characterized in that: in the coprecipitation crystallization reaction, the reaction temperature is 30-80 ℃, preferably 35-60 ℃, more preferably 50 ℃; preferably, the complexing agent concentration is 2-15 g/L, preferably 3-12g/L, more preferably 5-10g/L;
preferably, the pH of the solution is from 10 to 13, preferably from 10.5 to 12, more preferably 11;
preferably, the stirring strength is 0.5-1.0 kw/m of input power 2 H, preferably 0.6-0.9kw/m 2 H, more preferably 0.8kw/m 2 ·h；
Preferably, the percentage saturation of dissolved oxygen in the solution is 5-50%, preferably 10-40%, more preferably 35%; preferably, the reaction time is from 30 to 100 hours, preferably from 40 to 90 hours, more preferably from 50 to 80 hours.
4. The method for preparing the positive electrode material of the sodium-embedded lithium ion battery according to claim 1, which is characterized in that: in the step (2), the sodium-containing metal compound is at least one of sodium oxide, sodium carbonate, sodium oxalate, sodium sulfate, sodium nitrate and sodium chloride;
preferably, in the physicochemical reaction, the metal Me in the hydroxide or carbonate precursor forms a solid solution structure with sodium ions, me represents at least one metal element of nickel, iron and manganese, preferably Me represents nickel, iron and manganese;
preferably, the molar ratio of metal Me to the oxidant in the hydroxide or carbonate precursor is 1: (0.5 to 4), preferably 1 to 3, more preferably 1.5 to 2.5;
preferably, the molar ratio of the sodium-containing metal compound to the metal Me in the hydroxide or carbonate precursor is from (0.001 to 0.05): 1, preferably from (0.005 to 0.04): 1, more preferably from (0.01 to 0.03): 1; preferably, the reaction pressure is 0.5 to 2.5MPa, preferably 0.8 to 2MPa, more preferably 1.5MPa; preferably, the reaction temperature is 20 to 250 ℃, preferably 50 to 200 ℃, more preferably 100 to 180 ℃; preferably, the reaction time is from 4 to 50 hours, preferably from 6 to 48 hours, more preferably from 10 to 24 hours;
preferably, the sodium metal ion concentration in the reaction system is 0.5 to 10mol/L, preferably 0.8 to 8mol/L, more preferably 1.0 to 6.0mol/L.
5. The method for preparing the positive electrode material of the sodium-embedded lithium ion battery according to claim 4, which is characterized in that: in the step (3), the solid-liquid separation mode is centrifugal separation, and drying treatment is carried out after the centrifugal separation, wherein the drying temperature is 100-200 ℃ and the time is 6-24 hours;
preferably, the sodium-intercalated metal oxide precursor has the chemical formula Na 2 O·Me 2 O 3 Sodium ions are located in the crystal lattice of the metal oxide without changing its original structure.
6. The method for preparing the positive electrode material of the sodium-embedded lithium ion battery according to claim 4 or 5, which is characterized in that: in the step (4), the lithium source is selected from one or more of lithium carbonate, lithium hydroxide and lithium acetate;
preferably, the conditions of the calcination include: the calcination temperature is 500-950 ℃, preferably 600-900 ℃; the calcination time is 6-36 h, preferably 10-30h; the sintering atmosphere is air atmosphere or oxygen atmosphere;
preferably, the calcination comprises at least 2 stages, pre-calcination is performed at 500-650 ℃ for 3-10 hours, and then sintering is performed at 800-950 ℃ for 10-30 hours;
preferably, the sodium-intercalated metal oxide precursor is mixed with a lithium source according to Li: me molar ratio = 1.01-1.1:1, preferably 1.05-1.1:1.
7. The positive electrode material for sodium-embedded lithium ion battery prepared by the preparation method of the positive electrode material for sodium-embedded lithium ion battery of any one of claims 1 to 6.
8. The sodium-intercalated lithium ion battery cathode material according to claim 7, characterized in that any 1 or more of the following (1) to (3):
(1) The monocrystal particles of the positive electrode material of the sodium-embedded lithium ion battery are complete in morphology and round in particle surface;
(2) The first discharge capacity of the positive electrode material of the sodium-embedded lithium ion battery under the multiplying power of 3-4.4V and 0.1C is improved by 4-6 mAh/g compared with the corresponding positive electrode material of the lithium ion battery without sodium embedding;
(3) The capacity retention rate of the positive electrode material of the sodium-embedded lithium ion battery for 50 circles under the 1C multiplying power is more than or equal to 94%.
9. A battery comprising the sodium-intercalated lithium ion battery positive electrode material of claim 7 or 8.
10. A power plant comprising the battery of claim 9.
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| CN111977707A (en) * | 2020-08-24 | 2020-11-24 | 厦门厦钨新能源材料股份有限公司 | Lithium-intercalated nickel-containing metal oxide and preparation method and application thereof |
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| CN111977707A (en) * | 2020-08-24 | 2020-11-24 | 厦门厦钨新能源材料股份有限公司 | Lithium-intercalated nickel-containing metal oxide and preparation method and application thereof |
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