CN117049610A - Sodium ion battery anode material precursor and preparation method and application thereof - Google Patents
Sodium ion battery anode material precursor and preparation method and application thereof Download PDFInfo
- Publication number
- CN117049610A CN117049610A CN202311067811.9A CN202311067811A CN117049610A CN 117049610 A CN117049610 A CN 117049610A CN 202311067811 A CN202311067811 A CN 202311067811A CN 117049610 A CN117049610 A CN 117049610A
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- electrode material
- precursor
- ion battery
- sodium ion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002243 precursor Substances 0.000 title claims abstract description 133
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 103
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 239000010405 anode material Substances 0.000 title claims description 11
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 239000007774 positive electrode material Substances 0.000 claims abstract description 133
- 239000000463 material Substances 0.000 claims abstract description 70
- 239000002228 NASICON Substances 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000000126 substance Substances 0.000 claims abstract description 22
- 239000011734 sodium Substances 0.000 claims abstract description 16
- 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 15
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000007864 aqueous solution Substances 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- 239000010936 titanium Substances 0.000 claims description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- 159000000003 magnesium salts Chemical class 0.000 claims description 7
- 150000003608 titanium Chemical class 0.000 claims description 7
- 150000003754 zirconium Chemical class 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 238000000975 co-precipitation Methods 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 13
- 239000011248 coating agent Substances 0.000 abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- 239000011247 coating layer Substances 0.000 abstract description 9
- 238000013508 migration Methods 0.000 abstract description 9
- 230000005012 migration Effects 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 8
- 238000005245 sintering Methods 0.000 abstract description 7
- 230000002829 reductive effect Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- 239000008139 complexing agent Substances 0.000 description 18
- 239000010949 copper Substances 0.000 description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- 239000011572 manganese Substances 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 239000003513 alkali Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- OANFWJQPUHQWDL-UHFFFAOYSA-N copper iron manganese nickel Chemical compound [Mn].[Fe].[Ni].[Cu] OANFWJQPUHQWDL-UHFFFAOYSA-N 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 239000010406 cathode material Substances 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 239000012716 precipitator Substances 0.000 description 5
- 229910000365 copper sulfate Inorganic materials 0.000 description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 239000011790 ferrous sulphate Substances 0.000 description 4
- 235000003891 ferrous sulphate Nutrition 0.000 description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- 235000019341 magnesium sulphate Nutrition 0.000 description 4
- 229940099596 manganese sulfate Drugs 0.000 description 4
- 239000011702 manganese sulphate Substances 0.000 description 4
- 235000007079 manganese sulphate Nutrition 0.000 description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 4
- 229940048086 sodium pyrophosphate Drugs 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 4
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 4
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000006256 anode slurry Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000002696 manganese Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 241000510672 Cuminum Species 0.000 description 1
- 235000007129 Cuminum cyminum Nutrition 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [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
- 239000010410 layer Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- -1 nickel-iron-manganese-copper hydroxide Chemical compound 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a precursor of a positive electrode material of a sodium ion battery, and a preparation method and application thereof. The sodium ion battery positive electrode material precursor comprises a positive electrode material precursor and a NASICON type material precursor; the precursor of the NASICON type material is a substance which is converted into the NASICON type material after calcination. According to the invention, the NASICON material precursor and the positive electrode material precursor are matched for use, so that the sodium ion migration efficiency and the sodium storage performance are effectively improved. The NASICON type material is preferably coated on the surface of the positive electrode material, so that the uniformity of a coating layer is improved, and the cycle performance and the multiplying power performance of the material are greatly improved. Meanwhile, the common positive electrode material precursor and the NASICON type material precursor are matched at the precursor end, so that the defect of poor air and water stability existing in the coating of the rear positive electrode material in the sintering stage is overcome, the complexity of the subsequent process is reduced, and the production cost is reduced.
Description
Technical Field
The invention belongs to the technical field of sodium ion batteries, and relates to a precursor of a positive electrode material of a sodium ion battery, and a preparation method and application thereof.
Background
Lithium, sodium and potassium are similar to alkali metal elements belonging to group IA of the periodic table of elements in physical and chemical properties, and can be theoretically used as metal ion carriers of secondary batteries. Among them, lithium has a smaller ionic radius, a higher standard potential, and a much higher specific capacity than sodium and potassium, and thus has been used earlier and more widely in secondary batteries. However, the global reserve of lithium resources is limited, the demand of batteries is greatly increased along with the development of new energy automobiles, the bottleneck of the resource end is gradually revealed, and the large-scale application of lithium ion batteries is limited by higher cost.
Sodium resources are very abundant, crust abundance is 2.64%, which is 440 times of lithium resources, and sodium resources are widely distributed and are simple to refine. The role of sodium as a substitute for lithium has emerged and has gained increasing attention in the battery field. Through development in recent years, the comprehensive performance and demonstration application of the sodium ion battery achieve remarkable effects, the sodium ion battery as a beneficial supplement of the lithium ion battery is greatly developed in the fields of large-scale energy storage and miniature electric vehicles, and an electrode material with high specific energy is still a target required by people for cumin.
The key technology of the sodium ion battery is mainly material technology, and the key of the battery with long service life is to develop a material with high stability. Because of the difference of ion characteristics, it is not suitable to directly change lithium in the electrode material of the lithium ion battery into sodium, so finding an electrode material suitable for the sodium ion battery is a key to the practical realization of the lithium ion battery.
In recent decades, cathode materials, which are one of the key components of sodium ion batteries, such as layered oxides, polyanion-based compounds, prussian blue-based compounds, organic compounds, and the like, have been widely studied. Sodium ion layered transition metal oxide (Na x TMO 2 TM is generally transition metal, x is less than or equal to 1), is similar to a lithium ion layered oxide successfully applied in commercialization, has the advantages of higher specific capacity, simple preparation, high compaction density, adjustable voltage range and the like, and is greatly studied. However, when the sodium ion layered oxide positive electrode material realizes more reversible extraction/intercalation of sodium ions, the system faces complex structural evolution, and the capacity retention rate in the long-cycle process is seriously affected.
Although doping or replacing transition metal sites can significantly inhibit phase transition, inhibit transition metal ion migration, and improve the chemical and electrochemical stability of the sodium-free material, the content of the redox couple of the system is inevitably reduced, thereby affecting the energy density of the system, and the content of doped ions is too small to stabilize the structure of the layered oxide material. In addition, K can be doped with sodium ion + 、Mg 2+ 、Ca 2+ Or Zn 2+ The method has the advantages that the method plays a role of a strut, thereby effectively relieving the electrostatic repulsive force between the sodium layers O-O and inhibiting the occurrence of phase transition, but the doping amount is difficult to be large, and the energy density of the system is also sacrificed.
The coating modification has many applications and remarkable effects in lithium ion layered oxide cathode materials, but has little research in sodium-electric layered oxides. Mainly because the air and water stability of the sodium ion layered oxide is poor, the aqueous solution coating method commonly used in lithium batteries is not applicable to sodium ion batteries any more, and the preparation cost of electrode materials can be obviously increased due to the complex operation flow.
Therefore, development of a coating method which is simple and effective and can improve the cycle performance of the sodium-electricity layered oxide material under the condition of higher specific capacity is imperative.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a precursor of a positive electrode material of a sodium ion battery, and a preparation method and application thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a sodium ion battery positive electrode material precursor, which comprises a positive electrode material precursor and a NASICON type material precursor;
the precursor of the NASICON type material is a substance which is converted into the NASICON type material after calcination.
In the "calcining" process of the "the precursor of the NASICON-type material is a material that is converted into the NASICON-type material after calcining", sodium is added and then sintering is performed, for example, the precursor of the NASICON-type material is mixed with sodium salt and then calcined, so as to obtain the NASICON-type material.
In the invention, the existence forms of the positive electrode material precursor and the NASICON type material precursor are not limited, and the positive electrode material precursor and the NASICON type material precursor can exist in a mixture form or can be in a coating state, for example, the NASICON type material precursor is coated on the surface of the positive electrode material precursor to form the sodium ion battery positive electrode material precursor.
The NASICON type material has conductivity far higher than that of lithium ions, and the NASICON structure has flexibility and can accommodate transition metal ions, so that electron conductivity can be introduced and sodium ions can be stored, and the sodium ion migration efficiency is effectively improved. Further, NASICON type materials are preferably coated on the surface of the positive electrode material, so that uniformity of a coating layer is improved, and cycle performance and rate performance of the material are greatly improved. Meanwhile, the common positive electrode material precursor and the NASICON material precursor are matched at the precursor end, so that the defect of poor air and water stability existing in the coating of the rear positive electrode material in the sintering stage is overcome.
The sodium ion battery positive electrode material prepared by adopting the precursor of the sodium ion battery positive electrode material can effectively improve the cycle stability and the multiplying power performance of the sodium ion battery and has the advantage of low cost.
As a preferable scheme, the NASICON type material precursor is coated on the surface of the positive electrode material precursor to form the sodium ion battery positive electrode material precursor, and in the positive electrode material prepared by adopting the sodium ion battery positive electrode material precursor, the NASICON type material is coated on the surface of the sodium ion battery positive electrode material, so that the sodium ion migration efficiency can be better improved.
The following preferred technical solutions are used as the present invention, but not as limitations on the technical solutions provided by the present invention, and the technical objects and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solutions.
Preferably, the positive electrode material precursor is a layered oxide positive electrode material precursor, preferably a quaternary layered oxide positive electrode material precursor.
Preferably, the quaternary layered oxide positive electrode material has a chemical formula of Ni a Fe b Cu c Mn d (OH) 2 Wherein 0 is<a≤0.4，0<b≤0.4，0<c≤0.3，0<d is less than or equal to 0.6, and a+b+c+d=1. Illustratively, a may be 0.001, 0.005, 0.01, 0.02, 0.05, 0.08, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, or 0.4, etc., b may be 0.001, 0.005, 0.01, 0.02, 0.05, 0.08, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, or 0.4, etc., c may be 0.001, 0.005, 0.01, 0.02, 0.05, 0.08, 0.1, 0.15, 0.2, 0.25, or 0.3, etc., d may be 0.001, 0.005, 0.01, 0.02, 0.05, 0.08, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, or 0.55, etc. The quaternary layered oxide positive electrode material is called a nickel-iron-copper-manganese quaternary precursor for short.
The air and water stability of the layered oxide sodium ion positive electrode material is poor, so that the process of coating the positive electrode stage by sintering is extremely complex. The invention coats the precursor end, which can reduce the complexity of the subsequent process and the production cost.
Preferably, the NASICON type material is NaMg x Zr y Ti 1-x-y (PO 4 ) 3 Wherein x is more than or equal to 0.1 and less than or equal to 0.3,0.1, and y is more than or equal to 0.3.x may be, for example, 0.1, 0.15, 0.2, 0.25, or 0.3, and y may be, for example, 0.1, 0.15, 0.2, 0.25, or 0.3.
In a second aspect, the present invention provides a method for preparing a precursor of a positive electrode material of a sodium ion battery according to the first aspect, the method comprising the steps of:
(1) Preparing raw materials of the NASICON type material precursor into aqueous solutions respectively, and adding the aqueous solutions and the aqueous ammonia solution into a reaction system containing the positive electrode material precursor in parallel flow for reaction to obtain the positive electrode material precursor of the sodium ion battery.
According to the invention, a precursor with a NASICON structure is uniformly coated on the surface of a positive electrode material precursor (such as a nickel-iron-copper-manganese quaternary precursor) by adopting a wet coating method, the positive electrode material is prepared by adopting the precursor, and the NASICON type material coated sodium-ion battery positive electrode material can be obtained by one-step sintering. The NASICON type material has stable structural framework, high electronic conductivity and good thermal stability, and can effectively improve the migration efficiency of sodium ions, thereby improving the electrochemical performance of the positive electrode material of the sodium ion battery.
As a preferable technical scheme of the preparation method of the precursor of the positive electrode material of the sodium ion battery, the raw materials of the precursor of the NASICON material comprise phosphoric acid, magnesium salt, zirconium salt and titanium salt.
The invention is not limited to the specific types of magnesium salts, zirconium salts, and titanium salts, and the magnesium salts may be magnesium sulfate, the zirconium salts may be zirconium sulfate, and the titanium salts may be titanyl sulfate by way of example and not limitation.
Preferably, the concentration of the aqueous solution of step (1) is independently from 0.1mol/L to 1mol/L, for example 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L, 0.6mol/L, 0.8mol/L or 1mol/L, etc.
Preferably, the aqueous solution formulated with phosphoric acid is fed at a rate of 30L/h to 90L/h, for example 30L/h, 35L/h, 38L/h, 40L/h, 43L/h, 46L/h, 48L/h, 50L/h, 55L/h, 60L/h, 65L/h, 70L/h, 75L/h, 80L/h, 85L/h or 90L/h, etc.
Preferably, the aqueous solution formulated with magnesium salt is fed at a rate of 10L/h to 30L/h, for example 10L/h, 15L/h, 18L/h, 20L/h, 23L/h, 26L/h, 28L/h or 30L/h, etc.
Preferably, the aqueous solution formulated with the zirconium salt is fed at a rate of 10L/h to 30L/h, for example 10L/h, 15L/h, 18L/h, 20L/h, 23L/h, 26L/h, 28L/h, 30L/h, etc.
Preferably, the aqueous solution prepared using the titanium salt is fed at a rate of 50L/h to 200L/h, for example, 50L/h, 80L/h, 100L/h, 120L/h, 140L/h, 160L/h, 180L/h, 200L/h, or the like.
Preferably, the ammonia solution has a mass concentration of 15% to 30%, for example, 15%, 16%, 18%, 20%, 22%, 23%, 25%, 27%, 28%, 30%, or the like.
Preferably, the aqueous ammonia solution is fed at a rate of 5L/h to 30L/h, for example, 5L/h, 10L/h, 15L/h, 18L/h, 20L/h, 23L/h, 26L/h, 28L/h, 30L/h, or the like.
Preferably, the time of the co-current addition is 1h to 15h, for example 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h or 15h, etc.
Preferably, the positive electrode material precursor is a layered oxide positive electrode material, preferably a quaternary layered oxide positive electrode material.
The air and water stability of the layered oxide sodium ion positive electrode material is poor, so that the process of coating the positive electrode stage by sintering is extremely complex. The invention carries out wet coating on the precursor end, can greatly improve the uniformity of the coating layer, reduce the complexity of the subsequent process and reduce the production cost.
Preferably, the reaction system comprising the positive electrode material precursor is: and (3) preparing a reaction system of the positive electrode material precursor by coprecipitation.
The method for preparing the precursor of the positive electrode material is not particularly limited, and a person skilled in the art can prepare the precursor by referring to the methods disclosed in the prior art.
Chemical formula Ni of positive electrode material precursor a Fe b Cu c Mn d (OH) 2 (wherein 0<a≤0.4，0<b≤0.4，0<c≤0.3，0<d is less than or equal to 0.6, and a+b+c+d=1), and a preparation method of a precursor of the positive electrode material of the sodium ion battery is exemplarily provided, and the method comprises the following steps:
step 1: preparing a nickel-iron-copper-manganese metal salt solution A with the total concentration of metal ions of 0.5-2.5 mol/L by using soluble nickel salt, soluble ferric salt, soluble copper salt and soluble manganese salt according to a certain proportion;
preparing complexing agent solution B with the concentration of 0.05mol/L to 0.1 mol/L;
industrial liquid alkali is used as a precipitator C;
step 2: adding a certain amount of pure water into a reaction kettle, adding liquid alkali and complexing agent to prepare base solution, continuously introducing nitrogen for protection, respectively adding the mixed solution A, the complexing agent solution B and the precipitator C into the reaction kettle according to a certain flow, reacting at 30-60 ℃, maintaining the pH of the reaction at 8.5-12 and the concentration of the complexing agent at 0.01-0.1 mol/L, stirring at 200-500 rpm, and suspending feeding after a period of reaction to obtain a nickel-iron-manganese-copper hydroxide precursor;
step 3: and (3) preparing phosphoric acid, magnesium salt, zirconium salt and titanium salt into aqueous solution with certain concentration, and continuously feeding the aqueous solution and the aqueous ammonia solution for a period of time according to certain flow simultaneously to obtain the precursor of the coated sodium ion battery anode material.
In one embodiment, in step 1, the soluble nickel salt includes, but is not limited to, at least one of nickel sulfate, nickel chloride, and nickel nitrate.
In one embodiment, in step 1, the soluble iron salt includes, but is not limited to, at least one of ferrous sulfate, ferrous chloride, and ferrous nitrate.
In one embodiment, in step 1, the soluble copper salt includes, but is not limited to, at least one of copper sulfate, copper chloride, and copper nitrate.
In one embodiment, in step 1, the soluble manganese salt includes, but is not limited to, at least one of manganese sulfate, manganese chloride, and manganese nitrate.
In one embodiment, in step 1, the complexing agent in complexing agent solution B is selected from at least one of ammonia, EDTA, ammonium bicarbonate, and sodium pyrophosphate.
In one embodiment, in step 1, the concentration of industrial liquid base is 32%.
In one embodiment, in step 2, the volume of the reaction vessel is 8000L.
In a third aspect, the invention provides a positive electrode material of a sodium ion battery, which is prepared from the positive electrode material precursor of the sodium ion battery in the first aspect, and comprises a positive electrode material core and a NASICON type material coated on the surface of the positive electrode material core.
Preferably, the NASICON-type material has a mass content of 1% -10%, for example 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9% or 10%, etc., based on 100% of the total mass of the sodium ion battery cathode material.
In a fourth aspect, the present invention provides a method for preparing a positive electrode material for a sodium ion battery according to the third aspect, the method comprising the steps of:
and mixing and calcining the sodium ion battery anode material precursor and a sodium source to obtain the sodium ion battery anode material.
The kind of the sodium source is not particularly limited in the present invention, and sodium carbonate may be used, for example.
Preferably, the calcination temperature is 800 ℃ to 1000 ℃, for example 800 ℃, 825 ℃, 850 ℃, 870 ℃, 880 ℃, 900 ℃, 950 ℃, 1000 ℃, or the like.
Preferably, the calcination is for a period of time ranging from 12h to 20h, such as 12h, 13h, 14h, 15h, 16h, 18h, or 20h, etc.
In a fifth aspect, the present invention provides a sodium-ion battery comprising the sodium-ion battery cathode material of the third aspect.
The numerical ranges recited herein include not only the recited point values, but also any point values between the recited numerical ranges that are not recited, and are limited to, and for the sake of brevity, the invention is not intended to be exhaustive of the specific point values that the recited range includes.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, the NASICON type material precursor and the positive electrode material precursor are matched to form the positive electrode material precursor of the sodium ion battery, so that the sodium ion migration efficiency and the sodium storage performance are effectively improved. Further, NASICON type materials are preferably coated on the surface of the positive electrode material, so that uniformity of a coating layer is improved, and cycle performance and rate performance of the material are greatly improved. Meanwhile, the common positive electrode material precursor and the NASICON type material precursor are matched at the precursor end, so that the defect of poor air and water stability existing in the coating of the rear positive electrode material in the sintering stage is overcome, the complexity of the subsequent process is reduced, and the production cost is reduced.
(2) The sodium ion battery positive electrode material prepared by adopting the precursor of the sodium ion battery positive electrode material can effectively improve the cycle stability and the multiplying power performance of a sodium ion battery, the multiplying power performance is more than 90%, and the capacity retention rate of 500 cycles is more than 91%.
Drawings
Fig. 1 is an SEM image of a coated sodium ion battery positive electrode material precursor in example 1.
Detailed Description
The technical scheme of the invention is further described below by the specific embodiments with reference to the accompanying drawings.
In the embodiment of the invention, the precursor of the positive electrode material is Ni 0.25 Fe 0.25 Cu 0.25 Mn 0.25 (OH) 2 By way of example, and not limitation, this chemical formula, other positive electrode material precursors commonly used in the art are also suitable for use in the present invention.
Example 1
The embodiment provides a precursor of a positive electrode material of a sodium ion battery, which comprises a precursor of the positive electrode material and a precursor of a NASICON type material; the NASICON section barThe material precursor is a substance which is converted into a NASICON type material after being calcined. Wherein the positive electrode material precursor is a quaternary layered oxide positive electrode material precursor, and the chemical formula is Ni 0.25 Fe 0.25 Cu 0.25 Mn 0.25 (OH) 2 (noted as NFCM precursor), the NASICON type material has the chemical formula of NaMg 0.2 Zr 0.2 Ti 1.6 (PO 4 ) 3 。
The embodiment also provides a preparation method of the precursor of the positive electrode material of the sodium ion battery, which comprises the following steps:
step 1: preparing nickel sulfate, ferrous sulfate, copper sulfate and manganese sulfate into a nickel-iron-copper-manganese metal salt solution A with the total concentration of metal ions of 1mol/L according to the metal molar ratio of 1:1:1:1;
preparing EDTA solution with the concentration of 0.05mol/L as a complexing agent B;
32% of industrial liquid alkali is used as a starch agent C.
Step 2: 6000L of pure water and liquid alkali and complexing agent EDTA are added into a 8000L reaction kettle to prepare base solution until the pH value is 11.6, the concentration of EDTA is 0.01mol/L, the temperature is raised to 38 ℃ and nitrogen is continuously introduced for protection. Continuously adding the mixed solution A, the complexing agent B and the precipitator C into a reaction kettle according to the flow rates of 400L/h, 100L/h and 130L/h respectively, maintaining the pH of the reaction at 11.6, the concentration of the complexing agent at 0.01mol/L, stirring at 500rpm, and suspending feeding after reacting for 50h to obtain Ni 0.25 Fe 0.25 Cu 0.25 Mn 0.25 (OH) 2 A precursor.
Step 3: preparing 0.5mol/L aqueous solution of phosphoric acid, magnesium sulfate, zirconium sulfate and titanyl sulfate respectively, and continuously feeding with 17% ammonia aqueous solution for 1h according to 60L/h, 20L/h, 160L/h and 30L/h to obtain the precursor of the coated sodium ion battery anode material.
The embodiment also provides a positive electrode material of a sodium ion battery, and the preparation method comprises the following steps:
uniformly mixing the precursor of the coated sodium ion battery positive electrode material with sodium carbonate, and calcining at 800 ℃ for 20 hours to obtain the sodium ion battery positive electrode material, wherein the sodium ion battery positive electrodeThe material comprises NFCM1111 quaternary layered oxide positive electrode material (chemical formula is NaNi 0.25 Fe 0.25 Cu 0.25 Mn 0.25 O 2 ) And NaMg coated on the surface thereof 0.2 Zr 0.2 Ti 1.6 (PO 4 ) 3 . NaMg based on 100% of total mass of the sodium ion battery positive electrode material 0.2 Zr 0.2 Ti 1.6 (PO 4 ) 3 The mass content of (2%).
Fig. 1 is an SEM image of a coated precursor, from which it can be seen that NASICON-type material precursor is uniformly coated on NFCM precursor.
Example 2
The embodiment provides a precursor of a positive electrode material of a sodium ion battery, which comprises a precursor of the positive electrode material and a precursor of a NASICON type material; the precursor of the NASICON type material is a substance which is converted into the NASICON type material after calcination. Wherein the positive electrode material precursor is a quaternary layered oxide positive electrode material precursor, and the chemical formula is Ni 0.25 Fe 0.25 Cu 0.25 Mn 0.25 (OH) 2 The chemical formula of the NASICON type material is NaMg 0.2 Zr 0.2 Ti 1.6 (PO 4 ) 3 。
The embodiment also provides a preparation method of the precursor of the positive electrode material of the sodium ion battery, which comprises the following steps:
step 1: preparing nickel sulfate, ferrous sulfate, copper sulfate and manganese sulfate into a nickel-iron-copper-manganese metal salt solution A with the total concentration of metal ions of 2mol/L according to the metal molar ratio of 1:1:1:1;
preparing EDTA solution with the concentration of 0.1mol/L as a complexing agent B;
32% of industrial liquid alkali is used as a starch agent C.
Step 2: 6000L of pure water and liquid alkali and complexing agent EDTA are added into a 8000L reaction kettle to prepare base solution until the pH value is 11.0, the concentration of EDTA is 0.05mol/L, the temperature is raised to 50 ℃ and nitrogen is continuously introduced for protection. Continuously adding the mixed solution A, the complexing agent B and the precipitator C into a reaction kettle according to the flow rates of 400L/h, 100L/h and 130L/h respectively, and maintaining the pH of the reaction at 11.0 and the concentration of the complexing agent at 0.05mol/L, stirring at 300rpm, and stopping feeding after 40h of reaction to obtain Ni 0.25 Fe 0.25 Cu 0.25 Mn 0.25 (OH) 2 A precursor.
Step 3: preparing 1mol/L aqueous solution of phosphoric acid, magnesium sulfate, zirconium sulfate and titanyl sulfate respectively, and continuously feeding with 25% ammonia water solution for 10h according to 30L/h, 10L/h, 100L/h and 18L/h to obtain the precursor of the coated sodium ion battery anode material.
The embodiment also provides a positive electrode material of a sodium ion battery, and the preparation method comprises the following steps:
the precursor of the coated sodium ion battery positive electrode material and sodium carbonate are uniformly mixed and calcined for 15 hours at 950 ℃ to obtain the sodium ion battery positive electrode material, wherein the sodium ion battery positive electrode material comprises NFCM1111 quaternary layered oxide positive electrode material (the chemical formula is NaNi 0.25 Fe 0.25 Cu 0.25 Mn 0.25 O 2 ) And NaMg coated on the surface thereof 0.2 Zr 0.2 Ti 1.6 (PO 4 ) 3 . NaMg based on 100% of total mass of the sodium ion battery positive electrode material 0.2 Zr 0.2 Ti 1.6 (PO 4 ) 3 The mass content of (2) was 7%.
Example 3
The embodiment provides a precursor of a positive electrode material of a sodium ion battery, which comprises a precursor of the positive electrode material and a precursor of a NASICON type material; the precursor of the NASICON type material is a substance which is converted into the NASICON type material after calcination. Wherein the positive electrode material precursor is a quaternary layered oxide positive electrode material precursor, and the chemical formula is Ni 0.25 Fe 0.25 Cu 0.25 Mn 0.25 (OH) 2 The chemical formula of the NASICON type material is NaMg 0.2 Zr 0.2 Ti 1.6 (PO 4 ) 3 。
The embodiment also provides a preparation method of the precursor of the positive electrode material of the sodium ion battery, which comprises the following steps:
step 1: preparing nickel sulfate, ferrous sulfate, copper sulfate and manganese sulfate into a nickel-iron-copper-manganese metal salt solution A with the total concentration of metal ions of 2.5mol/L according to the metal molar ratio of 1:1:1:1;
preparing sodium pyrophosphate solution with the concentration of 0.08mol/L as a complexing agent B;
32% of industrial liquid alkali is used as a starch agent C.
Step 2: 6000L of pure water, liquid alkali and complexing agent sodium pyrophosphate are added into a 8000L reaction kettle to prepare base solution until the pH value is 12.0, the concentration of sodium pyrophosphate is 0.07mol/L, the temperature is raised to 45 ℃ and nitrogen is continuously introduced for protection. Continuously adding the mixed solution A, the complexing agent B and the precipitator C into a reaction kettle according to the flow rates of 400L/h, 100L/h and 130L/h respectively, maintaining the pH of the reaction at 12.0, the concentration of the complexing agent at 0.07mol/L, stirring at 350rpm, and suspending feeding after reacting for 35h to obtain Ni 0.25 Fe 0.25 Cu 0.25 Mn 0.25 (OH) 2 A precursor.
Step 3: preparing 0.6mol/L aqueous solution of phosphoric acid, magnesium sulfate, zirconium sulfate and titanyl sulfate respectively, and continuously feeding with 20% ammonia water solution for 8h according to 45L/h, 15L/h, 140L/h and 20L/h to obtain the precursor of the coated sodium ion battery anode material.
The embodiment also provides a positive electrode material of a sodium ion battery, and the preparation method comprises the following steps:
the precursor of the coated sodium ion battery positive electrode material and sodium carbonate are uniformly mixed and calcined for 17 hours at 900 ℃ to obtain the sodium ion battery positive electrode material, wherein the sodium ion battery positive electrode material comprises NFCM1111 quaternary layered oxide positive electrode material (the chemical formula is NaNi 0.25 Fe 0.25 Cu 0.25 Mn 0.25 O 2 ) And NaMg coated on the surface thereof 0.2 Zr 0.2 Ti 1.6 (PO 4 ) 3 . NaMg based on 100% of total mass of the sodium ion battery positive electrode material 0.2 Zr 0.2 Ti 1.6 (PO 4 ) 3 The mass content of (2) was 10%.
Example 4
The difference from example 1 is that the preparation parameters are adjusted so that the total mass of the positive electrode material of the sodium ion battery is 100%, naMg 0.2 Zr 0.2 Ti 1.6 (PO 4 ) 3 The mass content of (2) was 0.5%.
Example 5
The difference from example 1 is that the preparation parameters are adjusted so that the total mass of the positive electrode material of the sodium ion battery is 100%, naMg 0.2 Zr 0.2 Ti 1.6 (PO 4 ) 3 The mass content of (2) was 10.5%.
Comparative example 1
The difference from example 1 is that the external coating layer has the chemical formula of NaMg 0.4 Zr 0.4 Ti 1.0 (PO 4 ) 3 。
Comparative example 2
The difference from example 1 is that the preparation stage of the precursor of the positive electrode material of the sodium ion battery is not performed in step 3, but Ni prepared directly in step 2 0.25 Fe 0.25 Cu 0.25 Mn 0.25 (OH) 2 The precursor is used as a precursor of a positive electrode material of the sodium ion battery.
And (3) testing:
1. preparation of a cell
The positive electrode sheet is prepared by adopting the positive electrode materials prepared in each example and comparative example, and the preparation method comprises the following steps:
mixing the anode material with a conductive agent (carbon black) and a binder (PVDF) according to a mass ratio of 90:5:5 to prepare anode slurry, and coating the anode slurry on an aluminum foil to obtain the anode plate. And after the half-cell is assembled by using sodium metal as a counter electrode and glass fiber as a diaphragm and using an organic solution with sodium perchlorate as an electrolyte, the electrochemical performance of the positive electrode material is tested.
2. And (3) multiplying power performance test: at 25deg.C, charging and discharging at 0.2C for three times in a voltage range of 2V to 4.1V to obtain discharge capacity C of the last circle 0 The method comprises the steps of carrying out a first treatment on the surface of the Then, charging and discharging are carried out for three times by 1C to obtain the discharge capacity C of the last circle 2 ；C 2 /C 0 The ratio of (2) is the multiplying power performance.
3. And (3) testing the cycle performance: at 25 ℃, in a voltage interval of 2.0V to 4.1V, the cycle performance test is carried out by charging at 0.5C and discharging at 0.5C, and the capacity retention rate after 500 cycles is calculated according to the following formula: capacity retention = 500 th discharge specific capacity/first discharge specific capacity x 100%.
The test results are shown in Table 1.
TABLE 1
| Numbering device | Rate performance (%) | Capacity retention (%) |
| Example 1 | 95.4 | 98.3 |
| Example 2 | 91.7 | 93.3 |
| Example 3 | 90.2 | 91.5 |
| Example 4 | 96.3 | 93.2 |
| Example 5 | 93.8 | 99.9 |
| Comparative example 1 | 87.3 | 89.2 |
| Comparative example 2 | 85.9 | 79.3 |
As shown in Table 1, the precursor of the NASICON material and the precursor of the positive electrode material are matched to form the precursor of the positive electrode material of the sodium ion battery, so that the migration efficiency and the sodium storage performance of sodium ions are effectively improved. Further, NASICON type materials are preferably coated on the surface of the positive electrode material, so that uniformity of a coating layer is improved, and cycle performance and rate performance of the material are greatly improved.
As can be seen from comparative example 1 and examples 4-5, naMg in the cathode material 0.2 Zr 0.2 Ti 1.6 (PO) 3 The coating amount of (2) is in a preferable range, and less than 1% adversely affects the capacity retention and more than 10% adversely affects the rate performance.
As can be seen from comparative examples 1 and 1, the composition of the external coating layer also affects the electrochemical performance, the coating layer can improve the interface between the material and the electrolyte, reduce side reactions, and the NASICON-type material can effectively improve the sodium ion migration efficiency.
As can be seen from comparative examples 1 and 2, the present invention combines NASICON-type material precursor and positive electrode material precursor to form sodium ion battery positive electrode material precursor, thereby effectively improving sodium ion migration efficiency and sodium storage performance. Further, NASICON type materials are preferably coated on the surface of the positive electrode material, so that uniformity of a coating layer is improved, and cycle performance and rate performance of the material are greatly improved.
The applicant states that the detailed method of the present invention is illustrated by the above examples, but the present invention is not limited to the detailed method described above, i.e. it does not mean that the present invention must be practiced in dependence upon the detailed method described above. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (10)
1. The positive electrode material precursor of the sodium ion battery is characterized by comprising a positive electrode material precursor and a NASICON material precursor;
the precursor of the NASICON type material is a substance which is converted into the NASICON type material after calcination.
2. The sodium ion battery positive electrode material precursor according to claim 1, wherein the positive electrode material precursor is a layered oxide positive electrode material precursor, preferably a quaternary layered oxide positive electrode material precursor;
preferably, the quaternary layered oxide positive electrode material has a chemical formula of Ni a Fe b Cu c Mn d (OH) 2 Wherein 0 is<a≤0.4，0<b≤0.4，0<c≤0.3，0<d is less than or equal to 0.6, and a+b+c+d=1;
preferably, the NASICON type material is NaMg x Zr y Ti 1-x-y (PO 4 ) 3 Wherein x is more than or equal to 0.1 and less than or equal to 0.3,0.1, and y is more than or equal to 0.3.
3. A method for preparing a precursor of a positive electrode material for a sodium ion battery according to claim 1 or 2, comprising the steps of:
preparing raw materials of the NASICON type material precursor into aqueous solutions respectively, and adding the aqueous solutions and the aqueous ammonia solution into a reaction system containing the positive electrode material precursor in parallel flow for reaction to obtain the positive electrode material precursor of the sodium ion battery.
4. A method according to claim 3, wherein the raw materials of the NASICON-type material precursor include phosphoric acid, magnesium salts, zirconium salts and titanium salts;
preferably, the concentration of the aqueous solution in step (1) is independently 0.1mol/L to 1mol/L;
preferably, the feeding speed of the aqueous solution prepared by phosphoric acid is 30L/h-90L/h;
preferably, the feeding speed of the aqueous solution prepared by magnesium salt is 10L/h-30L/h;
preferably, the feeding speed of the aqueous solution prepared by adopting the zirconium salt is 10L/h-30L/h;
preferably, the feeding speed of the aqueous solution prepared by adopting the titanium salt is 50L/h-200L/h;
preferably, the mass concentration of the ammonia water solution is 15% -30%;
preferably, the feeding speed of the ammonia water solution is 5L/h-30L/h;
preferably, the parallel flow adding time is 1-15 h;
preferably, the positive electrode material precursor is a layered oxide positive electrode material, preferably a quaternary layered oxide positive electrode material.
5. The method of claim 3 or 4, wherein the reaction system comprising the positive electrode material precursor is: and (3) preparing a reaction system of the positive electrode material precursor by coprecipitation.
6. The positive electrode material of the sodium ion battery is characterized in that the positive electrode material of the sodium ion battery is prepared by adopting the positive electrode material precursor of the sodium ion battery according to any one of claims 1-3, and the positive electrode material of the sodium ion battery comprises a positive electrode material inner core and a NASICON type material coated on the surface of the positive electrode material inner core.
7. The positive electrode material for sodium ion battery according to claim 6, wherein the NASICON-type material has a mass content of 1% to 10% based on 100% of the total mass of the positive electrode material for sodium ion battery.
8. A method for preparing the positive electrode material of sodium ion battery as claimed in claim 6 or 7, comprising the steps of:
and mixing and calcining the sodium ion battery anode material precursor and a sodium source to obtain the sodium ion battery anode material.
9. The method of claim 8, wherein the temperature of calcination is 800 ℃ to 1000 ℃;
preferably, the calcination time is 12-20 hours.
10. A sodium ion battery, characterized in that the sodium ion battery comprises the sodium ion battery positive electrode material of claim 6 or 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311067811.9A CN117049610A (en) | 2023-08-23 | 2023-08-23 | Sodium ion battery anode material precursor and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311067811.9A CN117049610A (en) | 2023-08-23 | 2023-08-23 | Sodium ion battery anode material precursor and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117049610A true CN117049610A (en) | 2023-11-14 |
Family
ID=88658624
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311067811.9A Pending CN117049610A (en) | 2023-08-23 | 2023-08-23 | Sodium ion battery anode material precursor and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117049610A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103078105A (en) * | 2013-01-23 | 2013-05-01 | 宁德新能源科技有限公司 | Lithium ion battery, positive active material thereof and preparation method of positive active material |
| CN111342049A (en) * | 2020-03-04 | 2020-06-26 | 溧阳中科海钠科技有限责任公司 | Modified sodium ion battery positive electrode material, preparation method and battery |
| CN114709404A (en) * | 2022-04-22 | 2022-07-05 | 宁波市稻禾科技有限公司 | NASICON titanium sodium phosphate coated sodium iron phosphate cathode material and preparation method thereof |
| CN114824269A (en) * | 2022-03-30 | 2022-07-29 | 北京当升材料科技股份有限公司 | Composite positive electrode material, preparation method and application thereof, sodium ion battery pack and equipment |
| CN115939390A (en) * | 2022-11-30 | 2023-04-07 | 格林美（无锡）能源材料有限公司 | Sodium electrode material with sodium fast ion conductor as coating layer and preparation method and application thereof |
| CN116375111A (en) * | 2023-06-06 | 2023-07-04 | 宜宾锂宝新材料有限公司 | Sodium ion battery, positive electrode material and precursor thereof and preparation method |
-
2023
- 2023-08-23 CN CN202311067811.9A patent/CN117049610A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103078105A (en) * | 2013-01-23 | 2013-05-01 | 宁德新能源科技有限公司 | Lithium ion battery, positive active material thereof and preparation method of positive active material |
| CN111342049A (en) * | 2020-03-04 | 2020-06-26 | 溧阳中科海钠科技有限责任公司 | Modified sodium ion battery positive electrode material, preparation method and battery |
| CN114824269A (en) * | 2022-03-30 | 2022-07-29 | 北京当升材料科技股份有限公司 | Composite positive electrode material, preparation method and application thereof, sodium ion battery pack and equipment |
| CN114709404A (en) * | 2022-04-22 | 2022-07-05 | 宁波市稻禾科技有限公司 | NASICON titanium sodium phosphate coated sodium iron phosphate cathode material and preparation method thereof |
| CN115939390A (en) * | 2022-11-30 | 2023-04-07 | 格林美（无锡）能源材料有限公司 | Sodium electrode material with sodium fast ion conductor as coating layer and preparation method and application thereof |
| CN116375111A (en) * | 2023-06-06 | 2023-07-04 | 宜宾锂宝新材料有限公司 | Sodium ion battery, positive electrode material and precursor thereof and preparation method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104577093A (en) | Surface coating modified lithium ion battery cathode material and preparation method thereof | |
| CN108878827B (en) | High-nickel ternary positive electrode material coated by dioxygen compound and preparation method thereof | |
| CN104332629B (en) | The preparation method of a kind of lithium manganese phosphate hollow nanospheres and product | |
| EP4439716A1 (en) | Positive electrode material and preparation method therefor | |
| CN105206815B (en) | A kind of carbon coating Li4Ti5O12‑TiO2/ Sn nano composite materials and its preparation and application | |
| CN113903884B (en) | Positive electrode active material, preparation method thereof, positive electrode and lithium ion battery | |
| CN102344356A (en) | Battery grade nano ferrous oxalate, its preparation method and application | |
| CN113314700A (en) | Dual-action modified high-nickel positive electrode material of lithium ion battery and preparation method of dual-action modified high-nickel positive electrode material | |
| CN110993923B (en) | Carbon-coated auxiliary sodium-titanium double-doped lithium iron silicate positive electrode material and preparation method and application thereof | |
| CN106129383B (en) | A kind of ball-shaped lithium-ion battery anode material and its synthetic method with two phase gradient distributed architecture of nanoscale | |
| CN110911652B (en) | Nano spherical alpha-MnO 2 /Bi 2 O 3 Material, preparation method and application thereof | |
| CN117334857B (en) | Sodium ion battery positive electrode material and preparation method thereof | |
| CN106252592A (en) | Preparation method of micro-nano structure lithium ion battery carbon composite niobium pentoxide material | |
| CN114649528A (en) | Electrode additive, preparation method thereof and positive plate | |
| CN116344763B (en) | Metal/carbon coated lithium oxide composite positive electrode material, preparation method thereof, positive electrode plate containing positive electrode material and battery | |
| CN117476858A (en) | Modified sodium ferric sulfate positive electrode material and preparation method and application thereof | |
| CN117154046A (en) | Sodium-rich tunnel transition metal oxide positive electrode material and preparation method and application thereof | |
| CN117049610A (en) | Sodium ion battery anode material precursor and preparation method and application thereof | |
| CN115224259A (en) | Titanium-doped lithium nickel manganese oxide positive electrode material, preparation method and application thereof, and lithium ion battery | |
| CN115188958A (en) | Spherical porous sodium-ion battery material and preparation method thereof | |
| CN115395011A (en) | Aqueous chloride ion battery | |
| CN113140808A (en) | Water-based battery | |
| CN114031124B (en) | Tungsten double-coated positive electrode material and preparation method and application thereof | |
| CN118486815B (en) | Organic complexing coated lithium manganate and preparation method and application thereof | |
| CN116666582B (en) | Metal oxide coated lithium oxide composite positive electrode material, preparation method thereof, positive electrode plate containing positive electrode material and battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |