CN117855462A - Ternary positive electrode material of sodium ion battery with composite structure, and preparation method and application thereof - Google Patents
Ternary positive electrode material of sodium ion battery with composite structure, and preparation method and application thereof Download PDFInfo
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- CN117855462A CN117855462A CN202311780564.7A CN202311780564A CN117855462A CN 117855462 A CN117855462 A CN 117855462A CN 202311780564 A CN202311780564 A CN 202311780564A CN 117855462 A CN117855462 A CN 117855462A
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- positive electrode
- ion battery
- electrode material
- sodium
- sodium ion
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- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 56
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 51
- 239000002131 composite material Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 22
- 239000010410 layer Substances 0.000 claims abstract description 12
- 239000011734 sodium Substances 0.000 claims abstract description 12
- 239000011572 manganese Substances 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000011247 coating layer Substances 0.000 claims abstract description 5
- 230000007935 neutral effect Effects 0.000 claims abstract description 3
- 239000002243 precursor Substances 0.000 claims description 70
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 22
- 229920000447 polyanionic polymer Polymers 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000005245 sintering Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 238000000498 ball milling Methods 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 11
- 235000017550 sodium carbonate Nutrition 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000008139 complexing agent Substances 0.000 claims description 7
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 238000000975 co-precipitation Methods 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- 150000002696 manganese Chemical class 0.000 claims description 4
- 150000002815 nickel Chemical class 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
- 159000000000 sodium salts Chemical class 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- 238000001694 spray drying Methods 0.000 claims description 3
- BDOYKFSQFYNPKF-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;sodium Chemical compound [Na].[Na].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O BDOYKFSQFYNPKF-UHFFFAOYSA-N 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-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
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- IREHHCMIJCTSKK-UHFFFAOYSA-H [OH-].[Fe+2].[Mn+2].[Ni+2].[OH-].[OH-].[OH-].[OH-].[OH-] Chemical group [OH-].[Fe+2].[Mn+2].[Ni+2].[OH-].[OH-].[OH-].[OH-].[OH-] IREHHCMIJCTSKK-UHFFFAOYSA-H 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
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- 239000011656 manganese carbonate Substances 0.000 claims description 2
- 235000006748 manganese carbonate Nutrition 0.000 claims description 2
- 229940093474 manganese carbonate 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
- 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
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 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
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 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
- 239000002994 raw material Substances 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 235000002639 sodium chloride Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- XFLNVMPCPRLYBE-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate;tetrahydrate Chemical compound O.O.O.O.[Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O XFLNVMPCPRLYBE-UHFFFAOYSA-J 0.000 claims description 2
- URQWOSCGQKPJCM-UHFFFAOYSA-N [Mn].[Fe].[Ni] Chemical compound [Mn].[Fe].[Ni] URQWOSCGQKPJCM-UHFFFAOYSA-N 0.000 abstract description 4
- ZMVMBTZRIMAUPN-UHFFFAOYSA-H [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZMVMBTZRIMAUPN-UHFFFAOYSA-H 0.000 abstract description 4
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 3
- 150000004706 metal oxides Chemical class 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 13
- 238000007873 sieving Methods 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 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
- 239000010405 anode material Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
Abstract
The invention discloses a ternary positive electrode material of a sodium ion battery with a composite structure, and a preparation method and application thereof, wherein the ternary positive electrode material of the sodium ion battery has a chemical formula of Na a Ni x Fe y Mn z O 2 ‑NVP，0.5<a≤1，0<x≤0.5，0<y≤0.5，0<z is less than or equal to 0.5, and the values of a, x, y and z lead the chemical formula to be electrically neutral; wherein Na is a Ni x Fe y Mn z O 2 Is an inner layer particle of ternary positive electrode material of sodium ion battery, NVP is coated on the surface of the inner layer particleIs coated with a coating layer. The inner layer particles of the ternary positive electrode material of the sodium ion battery with the composite structure provided by the invention are nickel-iron-manganese layered metal oxides, and the surface of the inner layer particles is coated with sodium vanadium phosphate, so that the ternary positive electrode material of the sodium ion battery has the advantages of good air stability, high specific capacity and excellent cycle stability under the synergistic effect of the inner layer particles and the sodium vanadium phosphate.
Description
Technical Field
The invention belongs to the technical field of sodium ion battery material preparation, and particularly relates to a ternary positive electrode material of a sodium ion battery with a composite structure, and a preparation method and application thereof.
Background
The application field of lithium ion batteries is very wide in the current society, and the application scene is varied. However, as a country with poor lithium and rich sodium, more than 80% of lithium resources are imported annually. Therefore, in order to alleviate social development and energy crisis, other novel energy sources need to be developed greatly, wherein the sodium ion battery can replace the lithium ion battery in part of application scenes so as to alleviate the demand of China on lithium resources.
Sodium ion batteries, in which the positive electrode materials that have been commercialized at present are the Prussian series, the layered oxide series, and the polyanion series, have similar electrochemical properties to lithium ion batteries. Among them, layered transition metal oxide has become the first choice for realizing mass production of sodium-electricity anode because of its advantages of high specific capacity, good conductivity, simple synthesis process, etc. However, the ternary positive electrode material with higher specific capacity has poor air stability, is easy to react with moisture, carbon dioxide and the like, so that the material is deteriorated, the cycle stability is poor, and the further development of the sodium ion battery is limited.
The polyanion compound has excellent air stability and electrochemical circulation stability, higher plateau voltage, but poor electric conductivity and lower theoretical capacity.
Therefore, it is necessary to develop a positive electrode material for sodium ion batteries which has excellent air stability, high specific capacity and excellent cycle stability.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a ternary positive electrode material of a sodium ion battery with a composite structure.
The invention also aims to provide a preparation method of the ternary positive electrode material of the sodium ion battery.
The invention also aims to provide an application of the ternary positive electrode material of the sodium ion battery.
The technical scheme of the invention is as follows:
ternary positive electrode material of sodium ion battery with composite structure, and chemical formula of ternary positive electrode material of sodium ion battery is Na a Ni x Fe y Mn z O 2 -NVP，0.5<a≤1，0<x≤0.5，0<y≤0.5，0<z is less than or equal to 0.5, and the values of a, x, y and z lead the chemical formula to be electrically neutral;
wherein Na is a Ni x Fe y Mn z O 2 The NVP is a coating layer coated on the surface of the inner layer particles.
In one possible implementation, the ternary positive electrode material of the sodium ion battery has a particle size of 1 μm to 10 μm.
In one possible implementation, the thickness of the cladding layer is 1nm-2 μm.
The preparation method of the ternary positive electrode material of the sodium ion battery comprises the following steps:
(1) The ternary precursor and the polyanion precursor are mixed with m: the mass ratio of (1-m) is fully ground and mixed to obtain a pre-mixed uniform precursor, wherein m is more than or equal to 0.2 and less than or equal to 0.8, and the ternary precursor is nickel-iron-manganese hydroxide Nix ' Fey ' Mnz ' (OH) 2 ，0<x’≤0.5，0<y’≤0.5，0<z ' is less than or equal to 0.5, x ' +y ' +z ' =1, and the values of x ', y ' and z ' satisfy charge balance, and the polyanion precursor is NVP@C;
(2) And fully sintering the pre-mixed uniform precursor and a sodium source in an oxygen-containing atmosphere to obtain the ternary positive electrode material of the sodium ion battery.
In one possible implementation, the preparation method of the ternary precursor is as follows: mixing nickel salt, manganese salt, ferrous salt, an alkaline precipitant and a complexing agent, performing crystal nucleus generation at a first pH value, and performing coprecipitation reaction at a second pH value to obtain a ternary precursor;
wherein the nickel salt is at least one selected from nickel nitrate, nickel sulfate, nickel carbonate, nickel acetate and nickel chloride;
the manganese salt is at least one of manganese nitrate, manganese sulfate, manganese carbonate, manganese acetate and manganese chloride;
the ferrous salt is at least one selected from ferrous nitrate, ferrous sulfate and ferrous chloride;
the alkaline precipitant is at least one of sodium hydroxide aqueous solution, potassium hydroxide aqueous solution and calcium hydroxide aqueous solution, and the concentration of the alkaline precipitant is 1mol/L-4mol/L;
the complexing agent is at least one of an ammonia water solution, an ethylene diamine tetraacetic acid disodium solution and an ethylene diamine tetraacetic acid tetrasodium solution, and the concentration of the complexing agent is 0.5mol/L-2mol/L;
the first pH is 10.8;
the second pH is 9.2-10.4.
In one possible implementation, the polyanionic precursor is prepared by: and (3) completely dissolving ammonium metavanadate, ammonium hydrogen phosphate and sodium salt, adding a carbon source, maintaining the system temperature at 65-80 ℃, fully reacting to obtain NVP@C slurry, and carrying out spray drying on the NVP@C slurry to obtain the polyanion precursor NVP@C.
It is further preferred that the carbon content in the polyanionic precursor is 5wt% to 15wt%.
In one possible implementation, the operation of sufficient grinding is physical mechanical mixing using a ball mill, wherein the ball mass ratio of the ball mill is 100-200:1, the rotating speed is 500rmp-1000rmp, and the ball milling time is 1h-2h.
In one possible implementation, the sodium source is at least one of sodium hydroxide, sodium carbonate, sodium nitrate, sodium acetate, sodium chloride;
the temperature of the full sintering is 400-1000 ℃, and the time of the full sintering is 12-30 h.
A raw material of the positive electrode of the sodium ion battery comprises the ternary positive electrode material of the sodium ion battery.
The beneficial effects of the invention are as follows:
1. the inner layer particles of the ternary positive electrode material of the sodium ion battery with the composite structure provided by the invention are nickel-iron-manganese layered metal oxides, and the surface of the inner layer particles is coated with sodium vanadium phosphate, so that the ternary positive electrode material of the sodium ion battery has the advantages of good air stability, high specific capacity and excellent cycle stability under the synergistic effect of the inner layer particles and the sodium vanadium phosphate.
2. The preparation method provided by the invention has the advantages that the ternary precursor and the polyanion precursor are premixed uniformly and then sintered, the preparation method is simple, the cost is low, and the large-scale production is easy.
Drawings
FIG. 1 is a flow chart of a ternary precursor preparation process;
FIG. 2 is an SEM image of a ternary precursor prepared by a co-precipitation method;
FIG. 3 is a process flow diagram of a composite structure of a sodium ion battery positive electrode material;
fig. 4 is an SEM image of the positive electrode of the sodium ion battery of the composite structure obtained in example 2;
FIG. 5 is an SEM image of the nickel-iron-manganese ternary positive electrode obtained in comparative example 1;
FIG. 6 is an X-ray diffraction pattern of comparative example 1 and example 2;
fig. 7 is a graph showing the first-turn discharge specific capacity of the positive electrode material obtained in example 2;
fig. 8 is a cycle performance chart of the positive electrode material obtained in example 2.
Detailed Description
The technical scheme of the invention is further illustrated and described through the following specific embodiments.
In the following examples, the water used may be one or more of distilled water, purified water, and drinking water; unless otherwise specified, the detection methods in the following embodiments are all conventional detection methods; the reagents in the examples described below were purchased commercially unless otherwise specified.
Preparation of ternary precursor
The ternary precursors used in the following embodiments are prepared in the following manner, but in other possible implementations are also directly available.
The preparation process flow of the ternary precursor is shown in figure 1.
Weighing nickel sulfate, manganese sulfate and ferrous sulfate in a molar ratio of 1:1:1, and preparing a mixed salt solution with a mol/L ratio;
adding 0.5L of ammonia water with the concentration of 0.8mol/L as a base solution at the bottom of a reaction kettle of a coprecipitation device, heating to 60 ℃, introducing nitrogen for protection, adjusting the pH value to 10.8, introducing inert gas for protection (in the embodiment, the inert gas is nitrogen), pumping 1mol/L of mixed salt solution, 2mol/L of sodium hydroxide solution (alkali liquor) and 0.8mol/L of ammonia water (complexing agent) solution into the coprecipitation reaction kettle through peristaltic pumps at constant speed, nucleating and growing crystals at the pH value of 10.8, and performing precipitation treatment at the pH value of 10.4; then aging for 4 hours, and sequentially washing, suction filtering, drying, crushing and sieving the obtained precursor slurry to obtain a ternary precursor, wherein the chemical formula of the ternary precursor is Ni 1/3 Fe 1/3 Mn 1/3 (OH) 2 The prepared ternary precursor was subjected to scanning electron microscopy (sem) with a particle size of 6 μm-10 μm, as shown in fig. 2.
Preparation of polyanionic precursors
Dissolving ammonium metavanadate, ammonium hydrogen phosphate and sodium salt in a mass ratio of 0.7:1:1 in deionized water, magnetically stirring at 65 ℃ in a water bath to enable the ammonium metavanadate, the ammonium hydrogen phosphate and the sodium salt to be completely dissolved, adding 0.9g of carbon source into the solution, magnetically stirring continuously, maintaining the system temperature at 65 ℃, fully reacting to obtain NVP@C slurry, and carrying out spray drying on the NVP@C slurry to obtain the polyanion precursor NVP@C.
Example 1
Fig. 3 is a process flow diagram of a composite structure of a sodium ion battery positive electrode material.
At 0.2: weighing polyanion precursor and ternary precursor according to the mass ratio of 0.8, ball-milling for 2 hours at the rotating speed of 1000rmp under a ball mill to obtain a pre-mixed uniform precursor, and mixing the pre-mixed uniform precursor with sodium carbonate according to the mass ratio of 1:1.1, heating to 500 ℃ in oxygen atmosphere, maintaining the temperature for 2 hours, heating to 900 ℃ and sintering for 12 hours, cooling, taking out a sample, and sieving to obtain the ternary positive electrode material of the sodium ion battery with the particle size of 6-10 mu m.
Example 2
At 0.25: weighing polyanion precursor and ternary precursor according to a mass ratio of 0.75, ball-milling for 2 hours at a rotating speed of 1000rmp under a ball mill to obtain a pre-mixed uniform precursor, and mixing the pre-mixed uniform precursor with sodium carbonate according to a mass ratio of 1:1.1, heating to 500 ℃ in oxygen atmosphere, maintaining the temperature for 2 hours, heating to 900 ℃ and sintering for 12 hours, cooling, taking out a sample, and sieving to obtain the ternary positive electrode material of the sodium ion battery with the particle size of 6-10 mu m.
Example 3
At 0.2: weighing polyanion precursor and ternary precursor according to the mass ratio of 0.8, ball-milling for 2 hours at the rotating speed of 1000rmp under a ball mill to obtain a pre-mixed uniform precursor, and mixing the pre-mixed uniform precursor with sodium carbonate according to the mass ratio of 1: mixing in a molar ratio of 1.05, heating to 500 ℃ in an oxygen atmosphere, maintaining the temperature for 2 hours, heating to 900 ℃ and sintering for 12 hours, cooling, taking out a sample, and sieving to obtain the ternary positive electrode material of the sodium ion battery with the particle size of 6-10 mu m.
Example 4
At 0.3: weighing polyanion precursor and ternary precursor according to the mass ratio of 0.7, ball-milling for 2 hours at the rotational speed of 800rmp under a ball mill to obtain a pre-mixed uniform precursor, and mixing the pre-mixed uniform precursor with sodium carbonate according to the mass ratio of 1:1.1, heating to 500 ℃ in oxygen atmosphere, maintaining the temperature for 2 hours, heating to 900 ℃ and sintering for 12 hours, cooling, taking out a sample, and sieving to obtain the ternary positive electrode material of the sodium ion battery with the particle size of 6-10 mu m.
Example 5
At 0.3: weighing polyanion precursor and ternary precursor according to the mass ratio of 0.7, ball-milling for 1h at the rotating speed of 1000rmp under a ball mill to obtain a pre-mixed uniform precursor, and mixing the pre-mixed uniform precursor with sodium carbonate according to the mass ratio of 1:1.1, heating to 500 ℃ in oxygen atmosphere, maintaining the temperature for 2 hours, heating to 900 ℃ and sintering for 12 hours, cooling, taking out a sample, and sieving to obtain the ternary positive electrode material of the sodium ion battery with the particle size of 6-10 mu m.
Example 6
At 0.25: weighing polyanion precursor and ternary precursor according to a mass ratio of 0.75, ball-milling for 2 hours at a rotating speed of 1000rmp under a ball mill to obtain a pre-mixed uniform precursor, and mixing the pre-mixed uniform precursor with sodium carbonate according to a mass ratio of 1:1.06, heating to 500 ℃ in oxygen atmosphere, maintaining the temperature for 2 hours, heating to 900 ℃ and sintering for 12 hours, cooling, taking out a sample, and sieving to obtain the ternary positive electrode material of the sodium ion battery with the particle size of 6-10 mu m.
Example 7
At 0.2: weighing polyanion precursor and ternary precursor according to the mass ratio of 0.8, ball-milling for 2 hours at the rotating speed of 900rmp under a ball mill to obtain a pre-mixed uniform precursor, and mixing the pre-mixed uniform precursor with sodium carbonate according to the mass ratio of 1: mixing in a molar ratio of 1.08, heating to 500 ℃ in an oxygen atmosphere, maintaining the temperature for 2 hours, heating to 900 ℃ and sintering for 12 hours, cooling, taking out a sample, and sieving to obtain the ternary positive electrode material of the sodium ion battery with the particle size of 6-10 mu m.
Example 8
At 0.35: weighing polyanion precursor and ternary precursor according to a mass ratio of 0.65, ball-milling for 2 hours at a rotating speed of 1000rmp under a ball mill to obtain a pre-mixed uniform precursor, and mixing the pre-mixed uniform precursor with sodium carbonate according to a mass ratio of 1: mixing in a molar ratio of 1.08, heating to 500 ℃ in an oxygen atmosphere, maintaining the temperature for 2 hours, heating to 900 ℃ and sintering for 12 hours, cooling, taking out a sample, and sieving to obtain the ternary positive electrode material of the sodium ion battery with the particle size of 6-10 mu m.
Comparative example 1
Ball-milling the ternary precursor for 2 hours at a rotating speed of 1000rmp under a ball mill, and mixing the ground ternary precursor with sodium carbonate according to a ratio of 1: mixing in a molar ratio of 1.08, heating to 500 ℃ in an oxygen atmosphere, maintaining the temperature for 2 hours, heating to 900 ℃ and sintering for 12 hours, cooling, taking out a sample, and sieving to obtain the comparative anode material with the particle size of 6-10 mu m.
Electrochemical performance test
1. The ternary precursor and the sodium ion battery cathode materials prepared in example 2 and comparative example 1 were subjected to scanning electron microscope test, and the results are shown in fig. 2, fig. 4 and fig. 5, respectively. It can be seen that the nickel-iron-manganese layered metal oxide and the ternary positive electrode material of the sodium ion battery prepared by the method have uniform granularity, wherein as can be seen from fig. 4, a uniform coating layer is formed on the surface of the inner layer particles of the ternary positive electrode material of the sodium ion battery coated by the single ion conductor prepared by the method in example 2.
2. The ternary positive electrode material of the sodium ion battery prepared in example 2 and the comparative positive electrode material prepared in comparative example 1 were subjected to an X-ray diffraction powder test, and the results are shown in fig. 6. XRD results show that the coated ternary positive electrode material of the sodium ion battery has a good layered structure.
The ternary positive electrode materials of the sodium ion batteries prepared in examples 1-8 and the comparative positive electrode material prepared in comparative example 1 are respectively mixed with acetylene black and PVDF binder according to the following ratio of 8:1:1, and adding the N-methyl pyrrolidone solution to prepare slurry. The slurry was uniformly coated on a carbon-coated aluminum foil with a coating thickness of 150 μm. And (3) drying overnight in a vacuum drying oven at 100 ℃, cutting into round pole pieces with the diameter of 12mm, taking metal sodium as a negative electrode, taking 1mol/L NaClO4PC (100 percent) and 5 percent FEC as electrolyte in a glove box, assembling the CR2016 button cell, and carrying out electrochemical performance test.
The testing method comprises the following steps: the charge and discharge test was carried out at a 1C rate in a voltage range of 2.0V-4.0V with a current density of 150mA/g.
Test results: the electrochemical properties of examples 1 to 8 and comparative example are shown in table 1, and the first-cycle charge-discharge specific capacity result of the sodium ion battery prepared from the ternary cathode material of the sodium ion battery obtained in example 2 is shown in fig. 7, and the cycle performance after 100 cycles is shown in fig. 8.
Table 1 electrochemical properties of examples 1-8 and comparative example 1
As can be seen from table 1, the sodium ion batteries prepared from the ternary positive electrode materials of the sodium ion batteries of the composite structures prepared in examples 1 to 8 have significantly improved initial coulombic efficiency and higher capacity retention after long cycles, compared to the uncoated comparative positive electrode material prepared in comparative example 1.
The above examples are only for illustrating the technical solution of the present invention, but not for limiting the scope of the present invention, and it should be pointed out that those skilled in the art may make any modification to the specific embodiments described in the foregoing examples, or make equivalent substitutions and improvements on some or all of the technical features thereof, and are included in the scope of the present invention.
Claims (10)
1. A ternary positive electrode material of a sodium ion battery with a composite structure is characterized in that the ternary positive electrode material of the sodium ion battery has a chemical formula of Na a Ni x Fe y Mn z O 2 -NVP，0.5<a≤1，0<x≤0.5，0<y≤0.5，0<z is less than or equal to 0.5, and the values of a, x, y and z lead the chemical formula to be electrically neutral;
wherein Na is a Ni x Fe y Mn z O 2 And NVP is a coating layer coated on the surface of the inner layer particles.
2. The ternary positive electrode material of a sodium ion battery of claim 1, wherein the ternary positive electrode material of the sodium ion battery has a particle size of 1 μm to 10 μm.
3. The ternary positive electrode material of a sodium ion battery of claim 1, wherein the coating layer has a thickness of 1nm to 2 μm.
4. A method for preparing the ternary positive electrode material of the sodium ion battery as claimed in claims 1-3, which is characterized by comprising the following steps:
(1) The ternary precursor and the polyanion precursor are mixed with m: the mass ratio of (1-m) is fully ground and mixed to obtain a pre-mixed uniform precursor, wherein m is more than or equal to 0.2 and less than or equal to 0.8, and the ternary precursor is nickel-iron-manganese hydroxide Nix ' Fey ' Mnz ' (OH) 2 ，0<x’≤0.5，0<y’≤0.5，0<z’≤0.5, x '+y' +z '=1 and values of x', y 'and z' satisfy charge balance, the polyanion precursor is nvp@c;
(2) And fully sintering the pre-mixed uniform precursor and a sodium source in a molar ratio of 1:1.05-1.15 in an oxygen-containing atmosphere to obtain the ternary positive electrode material of the sodium ion battery.
5. The method of claim 4, wherein the ternary precursor is prepared by: mixing nickel salt, manganese salt, ferrous salt, an alkaline precipitant and a complexing agent, performing crystal nucleus generation at a first pH value, and performing coprecipitation reaction at a second pH value to obtain the ternary precursor;
wherein the nickel salt is selected from at least one of nickel nitrate, nickel sulfate, nickel carbonate, nickel acetate and nickel chloride;
the manganese salt is selected from at least one of manganese nitrate, manganese sulfate, manganese carbonate, manganese acetate and manganese chloride;
the ferrous salt is at least one selected from ferrous nitrate, ferrous sulfate and ferrous chloride;
the alkaline precipitant is at least one of sodium hydroxide aqueous solution, potassium hydroxide aqueous solution and calcium hydroxide aqueous solution, and the concentration of the alkaline precipitant is 1mol/L-4mol/L;
the complexing agent is at least one of an ammonia water solution, an ethylene diamine tetraacetic acid disodium solution and an ethylene diamine tetraacetic acid tetrasodium solution, and the concentration of the complexing agent is 0.5mol/L-2mol/L;
the first pH is 10.6-10.9.
The second pH is 9.2-10.4.
6. The method of claim 4, wherein the polyanionic precursor is prepared by: and (3) completely dissolving ammonium metavanadate, ammonium hydrogen phosphate and sodium salt, adding a carbon source, maintaining the system temperature at 65-80 ℃, fully reacting to obtain NVP@C slurry, and carrying out spray drying on the NVP@C slurry to obtain the polyanion precursor NVP@C.
7. The method of claim 6, wherein the polyanionic precursor contains carbon in an amount of 5 wt.% to 15 wt.%.
8. The method of claim 4, wherein the sufficient grinding is performed by physical mechanical mixing using a ball mill having a ball mass ratio of 100 to 200:1, the rotating speed is 500rmp-1000rmp, and the ball milling time is 1h-2h.
9. The method according to claim 4, wherein the sodium source is at least one of sodium hydroxide, sodium carbonate, sodium nitrate, sodium acetate, and sodium chloride;
the temperature of the full sintering is 400-1000 ℃, and the time of the full sintering is 12-30 h.
10. A sodium ion battery, characterized in that the raw material of the positive electrode of the sodium ion battery comprises the ternary positive electrode material of the sodium ion battery as claimed in claims 1-3.
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