CN111082058B - Nasicon structure sodium titanium phosphate surface modified P2 type manganese-based sodium ion battery positive electrode material and preparation method thereof - Google Patents
Nasicon structure sodium titanium phosphate surface modified P2 type manganese-based sodium ion battery positive electrode material and preparation method thereof Download PDFInfo
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- 239000011572 manganese Substances 0.000 title claims abstract description 69
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 68
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 55
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 51
- MJEPCYMIBBLUCJ-UHFFFAOYSA-K sodium titanium(4+) phosphate Chemical compound P(=O)([O-])([O-])[O-].[Ti+4].[Na+] MJEPCYMIBBLUCJ-UHFFFAOYSA-K 0.000 title claims abstract description 32
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000010405 anode material Substances 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 24
- 239000011734 sodium Substances 0.000 claims abstract description 21
- 238000005245 sintering Methods 0.000 claims abstract description 14
- 239000002345 surface coating layer Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 23
- 239000000725 suspension Substances 0.000 claims description 16
- 238000005303 weighing Methods 0.000 claims description 14
- 238000001704 evaporation Methods 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 12
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 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 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 150000002696 manganese Chemical class 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 235000010344 sodium nitrate Nutrition 0.000 claims description 6
- 239000004317 sodium nitrate Substances 0.000 claims description 6
- 159000000000 sodium salts Chemical class 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 4
- 239000011363 dried mixture Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000001632 sodium acetate Substances 0.000 claims description 4
- 235000017281 sodium acetate Nutrition 0.000 claims description 4
- 239000011975 tartaric acid Substances 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 4
- 239000004254 Ammonium phosphate Substances 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 abstract description 8
- 230000004048 modification Effects 0.000 abstract description 8
- 238000012986 modification Methods 0.000 abstract description 8
- 238000009792 diffusion process Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000003795 desorption Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 238000003980 solgel method Methods 0.000 abstract description 2
- 239000007790 solid phase Substances 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 18
- 238000000634 powder X-ray diffraction Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Natural products OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 1
- 229910004838 Na2/3Ni1/3Mn2/3O2 Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—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
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a sodium titanium phosphate surface modified P2 type manganese-based sodium ion battery anode material with a Nasicon structure and a preparation method thereof. The material consists of a surface coating layer and a P2 type manganese-based sodium ion battery anode material; the surface coating layer is NaTi 2 (PO 4 ) 3 The positive electrode material of the P2 type manganese-based sodium ion battery is Na x Mn a M 1‑a O 2 . The method prepares a precursor by a sol-gel method, and prepares the P2 type manganese-based sodium ion battery anode material with the surface modified by the sodium titanium phosphate through high-temperature solid-phase sintering reaction and surface modification. The surface coating layer is provided with a rapid sodium ion diffusion channel, which is beneficial to the desorption of sodium ions. Using NaTi 2 (PO 4 ) 3 The surface modified P2 type manganese-based sodium ion battery cathode material can effectively improve the cycle performance and the rate performance of the material, and the preparation method disclosed by the invention is simple to operate, low in cost, environment-friendly and easy to realize industrial large-scale production.
Description
Technical Field
The invention belongs to the technical field of preparation of sodium ion battery electrode materials, and particularly relates to a sodium titanium phosphate surface modified P2 type manganese-based sodium ion battery anode material with a Nasicon structure and a preparation method thereof.
Background
In recent years, with the rise of research on cheaper and more efficient electrochemical energy storage technology, people pay attention to sodium ion batteries again, and research and development are carried out on a series of positive and negative electrode materials for the sodium ion batteries. The positive electrode material of the sodium-ion battery is a key material of the sodium-ion battery, and a great deal of research work is carried out on the positive electrode material of the sodium-ion battery. The P2 type manganese-based sodium ion battery anode material has the advantages of relatively low cost, high capacity and long cycle life, and has a huge application prospect. But also has the inherent defects that the structure change is complex in the process of sodium deintercalation, the crystal structure is easy to damage, and the application of the P2 type manganese-based sodium ion battery anode material is limited. At present, the electrochemical performance of the material is improved mainly by means of surface modification, metal doping with chemical activity or substitution of inert elements, improvement of the preparation process (morphology and crystal structure) and the like.
The sodium titanium phosphate has an open three-dimensional framework and a rapid ion diffusion rate, is often used for a solid electrolyte and a sodium electric negative electrode, is an ideal coating material, and no literature reports that the surface of the sodium titanium phosphate is modified to prepare the sodium electric positive electrode material at present. Therefore, the surface of the positive electrode material of the P2 type manganese-based sodium ion battery is modified with the sodium titanium phosphate, so that the embedding and the separation of sodium ions are facilitated, the direct contact between the material and an electrolyte can be reduced, the side reaction is reduced, the irreversible phase transformation of the material is inhibited, and the rate capability and the cycling stability of the material are finally improved.
Disclosure of Invention
The invention aims to provide a sodium titanium phosphate surface modified P2 type manganese-based sodium ion battery cathode material with a Nasicon structure and a preparation method thereof, which improve the preparation process of the existing sodium ion battery cathode material, can inhibit the irreversible phase transformation of the material, and improve the diffusion rate of sodium ions of the material, thereby effectively improving the cycle performance and the rate capability of the material, and being suitable for industrial application.
The purpose of the invention is realized by the following technical scheme.
A sodium titanium phosphate surface modified P2 type manganese-based sodium ion battery anode material with a Nasicon structure is composed of a surface coating layer and a P2 type manganese-based sodium ion battery anode material; the surface coating layer is NaTi 2 (PO 4 ) 3 The positive electrode material of the P2 type manganese-based sodium ion battery is Na x Mn a M 1-a O 2 Wherein x and a are mole numbers, x is more than 0.44 and less than 1,0.4 and a is more than or equal to 1,M is one or more of metal ions Ni, co, mg, al, zn, ti, cu and Fe.
Further, the NaTi 2 (PO 4 ) 3 With Na x Mn a M 1-a O 2 In the mass ratio of (0.0005-0.20): 1.
the preparation method of the Nasicon structure sodium titanium phosphate surface modified P2 type manganese-based sodium ion battery anode material comprises the following steps:
1) According to the chemical formula Na x Mn a M 1-a O 2 Weighing manganese salt and M salt according to the molar ratio of Mn and M elements in the solution, dissolving the manganese salt and the M salt in a proper amount of water, adding 1-5 mol% of sodium salt in excess, stirring and dissolving to prepare a mixed solution;
2) Heating and stirring the mixed solution obtained in the step 1), adding an additive, stirring and evaporating to dryness to obtain gel;
3) Drying and crushing the gel obtained in the step 2), pre-sintering for 4-6 hours at 400-600 ℃ in the air atmosphere, then sintering for 12-18 hours at 850-1000 ℃, and cooling to room temperature to obtain a pure-phase P2 type manganese-based sodium ion battery anode material;
4) Dispersing the pure-phase P2 type manganese-based sodium ion battery anode material obtained in the step 3) in an organic solvent, stirring to obtain a uniformly dispersed suspension, and then according to the NaTi 2 (PO 4 ) 3 With Na x Mn a M 1-a O 2 In the mass ratio of (0.0005-0.20): 1, weighing a titanium source, adding the titanium source into a suspension, preparing a phosphorus source solution and a sodium source solution by using water, dropwise adding the phosphorus source solution and the sodium source solution into the suspension, continuously stirring, and evaporating the solvent to obtain a mixture;
5) And (3) placing the dried mixture obtained in the step 4) into a tubular furnace, sintering for 5-15 h at 400-900 ℃ in an air atmosphere, and cooling to room temperature to obtain the Nasicon structure sodium titanium phosphate surface modified P2 type manganese-based sodium ion battery anode material.
Further, the sodium salt, the manganese salt and the metal M salt in the step 1) are one or more of sulfate, nitrate and acetate.
Further, the additive in the step 2) is one or more of citric acid, glycol and tartaric acid; the dosage of the additive is 20-50% of the total mass of the sodium salt, the manganese salt and the M salt.
Further, the temperature for evaporating in the step 2) and the step 4) is 80-100 ℃.
Further, the organic solvent in the step 4) is one or more of ethanol and acetone.
Further, the stirring time of the step 4) is 1-3 hours.
Further, the titanium source in the step 4) is one or more of tetrabutyl titanate, titanium isopropoxide, titanium sulfate and titanyl sulfate.
Further, the phosphorus source in the step 4) is one or more of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, phosphoric acid and hypophosphorous acid; the sodium source is one or more of sodium acetate, sodium carbonate, sodium nitrate and sodium hydroxide.
Compared with the prior art, the invention has the following advantages and technical effects:
1. the invention prepares the precursor by a simple sol-gel method, and prepares the P2 type manganese-based sodium ion battery anode material with the surface modified by the sodium titanium phosphate through high-temperature solid-phase sintering reaction and surface modification. NaTi 2 (PO 4 ) 3 The surface coating layer has a rapid sodium ion diffusion channel, which is beneficial to the desorption of sodium ions, and NaTi 2 (PO 4 ) 3 The surface coating layer can reduce the direct contact of the material and the electrolyte and reduce the side reaction of the electrode material and the electrolyte. In addition thereto, by PO 4 -3 Partially replacing oxygen sites and Ti in octahedron 4+ The material structure can be stabilized by partially replacing sodium ions, and irreversible phase transformation of the material under high voltage is inhibited, so that the cycle stability and the rate capability of the material are improved.
2. The preparation method has the advantages of easily available raw materials, simple operation, low cost and good reproducibility, can meet various requirements of practical application of the sodium-ion battery, and can realize industrial large-scale production.
Drawings
Fig. 1 is an XRD chart of the surface-modified P2-type manganese-based sodium-ion battery positive electrode material of sodium titanium phosphate obtained in example 1 of the present invention and the pure-phase P2-type manganese-based sodium-ion battery positive electrode material in the comparative example.
Fig. 2a and 2b are SEM images of the surface-modified P2-type mn-based na-ion battery positive electrode material of sodium titanium phosphate obtained in example 1 of the present invention and the pure-phase P2-type mn-based na-ion battery positive electrode material in the comparative example, respectively.
Fig. 3 is a comparison graph of first cycle charge and discharge curves of the sodium titanium phosphate surface-modified P2-type manganese-based sodium ion battery positive electrode material obtained in example 1 of the present invention and the pure-phase P2-type manganese-based sodium ion battery positive electrode material in the comparative example.
Fig. 4 is a comparison graph of cycle performance curves of the sodium titanium phosphate surface-modified P2-type manganese-based sodium ion battery positive electrode material obtained in example 1 of the present invention and the pure-phase P2-type manganese-based sodium ion battery positive electrode material in the comparative example.
Fig. 5 is a graph comparing the rate performance of the sodium titanium phosphate surface-modified P2-type manganese-based sodium ion battery positive electrode material obtained in example 1 of the present invention and the pure-phase P2-type manganese-based sodium ion battery positive electrode material obtained in the comparative example under different current densities.
Detailed Description
Specific embodiments of the present invention will be further described below with reference to the following examples and drawings, but the present invention is not limited thereto.
Example 1:
(1) According to the synthesis of 10g of Na 0.65 Ni 0.16 Co 0.14 Mn 0.7 O 2 Weighing manganese nitrate, nickel nitrate and cobalt nitrate according to the molar ratio of Mn, ni and Co elements, dissolving the manganese nitrate, the nickel nitrate and the cobalt nitrate in 200mL of deionized water, adding 1mol% of sodium nitrate in excess, continuously stirring, weighing 1g of citric acid after metal salts are dissolved, adding the citric acid into the solution, stirring and evaporating at 80 ℃ to dryness, and obtaining the gel substance.
(2) And (2) drying the gel obtained in the step (1) at 80 ℃ in vacuum, crushing, presintering for 4 hours at 400 ℃ in an air atmosphere, then sintering for 12 hours at 850 ℃, and cooling to room temperature to obtain the pure-phase P2 type manganese-based sodium ion battery anode material NaNCM.
(3) 5g of pure-phase product NaNCM was weighed out and dispersed in 50mL of absolute ethanol, stirred for 1 hour to give a uniformly dispersed suspension, and then the suspension was stirred as NaTi 2 (PO 4 ) 3 Weighing tetrabutyl titanate in a mass ratio of 0.0005 to NaNCM of 1, adding the tetrabutyl titanate into the suspension, preparing ammonium dihydrogen phosphate and sodium carbonate solution by using deionized water, dropwise adding the solution into the suspension, continuously stirring, evaporating the solvent at 80 ℃, drying, and then adding the solutionThe mixture is put into a tube furnace, sintered for 5 hours at the temperature of 400 ℃ in the air atmosphere, and cooled to room temperature to obtain the sodium titanium phosphate surface modified P2 type manganese-based sodium ion battery anode material NaNCM/NTP.
(4) X-ray powder diffraction (XRD) analysis shows that the obtained product NaNCM/NTP and pure NaNCM have consistent structures, high crystallinity, and belong to P2 type lamellar structures, and the space group is P6 3 And/mmc (as shown in figure 1). It can be seen from the Scanning Electron Microscope (SEM) image that the material has a flaky morphology, and the modified flaky surface becomes rough from smooth (as shown in fig. 2 a).
(5) At 25 ℃, the initial discharge specific capacity of the sodium titanium phosphate surface modified P2 type manganese-based sodium ion battery anode material NaNCM/NTP at a multiplying power of 0.1C of 1.5-4.3V is 201.7mAh/g (as shown in figure 3), the initial discharge specific capacity at a multiplying power of 1C is 154.7mAh/g, the discharge specific capacity after 50 cycles at a multiplying power of 1C is 139.6mAh/g, and the capacity retention rate is 90.2% (as shown in figure 4). The specific discharge capacity at different rates was also higher than that of the unmodified material, naNCM (as shown in fig. 5). From the above results, it can be seen that the P2-type manganese-based sodium ion battery cathode material surface-modified by titanium sodium phosphate has stable structure, high specific capacity, good cycle stability, and excellent electrochemical performance.
Example 2:
(1) According to the synthesis of 10g of Na 2/3 Ni 1/3 Mn 2/3 O 2 Weighing manganese acetate and nickel acetate according to the molar ratio of Mn and Ni elements, dissolving the manganese acetate and the nickel acetate in 200mL of deionized water, adding 3mol% of excessive sodium acetate, continuously stirring, weighing 2g of citric acid after the metal salts are dissolved, adding the citric acid into the solution, stirring and evaporating at 90 ℃ to dryness, and thus obtaining the gel substance.
(2) And (2) drying the gel obtained in the step (1) at 90 ℃ in vacuum, crushing, presintering for 5 hours at 500 ℃ in an air atmosphere, then sintering for 15 hours at 925 ℃, and cooling to room temperature to obtain the pure-phase P2 type manganese-based sodium ion battery anode material NaNM.
(3) 5g of the pure-phase product NaNM was weighed out and dispersed in 20mL of acetone, stirred for 2 hours to give a homogeneously dispersed suspension, then according to NaTi 2 (PO 4 ) 3 The mass ratio of NaNM to NaNM is 0.1Adding titanium isopropoxide into the suspension, then preparing a diammonium hydrogen phosphate solution and a sodium acetate solution by using deionized water, dropwise adding the solution into the suspension, continuously stirring, evaporating the solvent to dryness at 90 ℃, putting the dried mixture into a tubular furnace, sintering for 10 hours at 650 ℃ in an air atmosphere, and cooling to room temperature to obtain the sodium titanium phosphate surface modified P2 type manganese-based sodium ion battery cathode material NaNM/NTP.
(4) X-ray powder diffraction (XRD) analysis shows that the obtained product NaNM/NTP and pure NaNM have the same structure and high crystallinity, belong to a P2-type layered structure, and have a space group of P6 3 And/mmc. It can be seen from the Scanning Electron Microscope (SEM) picture that the material has a flaky shape, and the flaky surface becomes rough from smooth after modification.
(5) At 25 ℃, the initial discharge specific capacity of the sodium titanium phosphate surface modified P2 type manganese-based sodium ion battery anode material NaNM/NTP at 0.1C multiplying power of 1.5-4.3V is 153.1mAh/g, the initial discharge specific capacity at 1C multiplying power is 139.8mAh/g, the discharge specific capacity after 100 cycles at 1C multiplying power is 130.6mAh/g, and the capacity retention rate is 93.4%. The specific discharge capacity under different multiplying powers is higher than that of the material NaNM before modification. From the above results, it can be seen that the P2-type manganese-based sodium ion battery cathode material surface-modified by titanium sodium phosphate has stable structure, high specific capacity, good cycle stability, and excellent electrochemical performance.
Example 3:
(1) According to the synthesis of 10g of Na 0.5 Ni 0.23 Fe 0.13 Mn 0.63 O 2 Weighing manganese nitrate, nickel nitrate and ferrous nitrate according to the molar ratio of Mn, ni and Fe elements, dissolving the manganese nitrate, the nickel nitrate and the ferrous nitrate in 200mL of deionized water, adding 5mol% of excessive sodium nitrate, continuously stirring, weighing 5g of tartaric acid, adding the tartaric acid into the solution after the metal salts are dissolved, stirring and evaporating at 100 ℃, and obtaining the gel substance.
(2) And (2) drying the gel obtained in the step (1) at 100 ℃ in vacuum, crushing, presintering at 600 ℃ for 6 hours in the air atmosphere, sintering at 1000 ℃ for 18 hours, and cooling to room temperature to obtain the pure-phase P2 type manganese-based sodium ion battery positive electrode material NaNFM.
(3) 5g of the pure phase product NaNFM were weighed out and dispersed in 25mL of anhydrous ethyl acetateMixing the solution with 25mL acetone, stirring for 3 hours to obtain a uniformly dispersed suspension, and then adding the solution according to NaTi 2 (PO 4 ) 3 And (2) weighing titanyl sulfate according to the mass ratio of 0.2 to NaNFM, adding the titanyl sulfate into the suspension, then preparing ammonium phosphate and sodium nitrate solution by using deionized water, dropwise adding the solution into the suspension, continuously stirring, evaporating the solvent at 100 ℃, placing the dried mixture into a tubular furnace, sintering for 15 hours at 900 ℃ in an air atmosphere, and cooling to room temperature to obtain the sodium titanium phosphate surface modified P2 type manganese-based sodium ion battery positive electrode material NaNFM/NTP.
(4) X-ray powder diffraction (XRD) analysis shows that the obtained product NaNFM/NTP and pure NaNFM have consistent structures, high crystallinity, belong to P2 type lamellar structures, and have a space group of P6 3 And/mmc. It can be seen from the Scanning Electron Microscope (SEM) picture that the material has a flaky shape, and the flaky surface becomes rough from smooth after modification.
(5) At 25 ℃, the initial discharge specific capacity of the sodium titanium phosphate surface modified P2 type manganese-based sodium ion battery anode material NaNFM/NTP at 0.1C multiplying power of 1.5-4.3V is 210.5mAh/g, the initial discharge specific capacity at 1C multiplying power is 170.6mAh/g, the discharge specific capacity after 100 cycles at 1C multiplying power is 150.3mAh/g, and the capacity retention rate is 88.1%. The specific discharge capacity under different multiplying powers is also higher than that of the material NaNFM before modification. From the above results, it can be seen that the P2-type manganese-based sodium ion battery cathode material surface-modified by titanium sodium phosphate has stable structure, high specific capacity, good cycle stability, and excellent electrochemical performance.
Comparative example 1:
(1) According to the synthesis of 10g of Na 0.65 Ni 0.16 Co 0.14 Mn 0.7 O 2 Weighing manganese nitrate, nickel nitrate and cobalt nitrate according to the molar ratio of Mn, ni and Co elements, dissolving the manganese nitrate, the nickel nitrate and the cobalt nitrate in 200mL of deionized water, adding 1mol% of sodium nitrate in excess, continuously stirring, weighing 2g of citric acid after the metal salts are dissolved in the step, adding the citric acid into the solution, stirring and evaporating at 80 ℃, and obtaining the gel substance.
(2) And (2) drying the gel obtained in the step (1) at 80 ℃ in vacuum, crushing, presintering for 4 hours at 400 ℃ in an air atmosphere, then sintering for 12 hours at 850 ℃, and cooling to room temperature to obtain the pure-phase P2 type manganese-based sodium ion battery anode material NaNCM.
(3) X-ray powder diffraction (XRD) analysis shows that the obtained product NaNCM has high crystallinity, belongs to a P2 type layered structure and has a space group of P6 3 And/mmc (as shown in figure 1). It can be seen in the Scanning Electron Microscope (SEM) image that the material exhibits a lamellar morphology, with the front lamellar surface being relatively smooth upon modification (as shown in figure 2 b).
(5) At 25 ℃, the primary specific discharge capacity of the positive electrode material NaNCM of the pure-phase P2 type manganese-based sodium ion battery at 0.1C multiplying power of 1.5-4.3V is 176.5mAh/g (shown in figure 3), the primary specific discharge capacity at 1C multiplying power is 145.9mAh/g, the specific discharge capacity after 50 cycles at 1C multiplying power is 92.6mAh/g, and the capacity retention rate is 63.5% (shown in figure 4). The specific discharge capacity at different rates is also lower than that of the modified material NaNCM/NTP (shown in figure 5). From the above results, it can be seen that the P2-type manganese-based sodium ion battery cathode material surface-modified by titanium sodium phosphate has stable structure, high specific capacity, good cycle stability, and excellent electrochemical performance.
Claims (10)
1. A preparation method of a Nasicon structure sodium titanium phosphate surface modified P2 type manganese-based sodium ion battery anode material is characterized by comprising the following steps:
1) According to the chemical formula Na x Mn a M 1-a O 2 Weighing manganese salt and M salt according to the molar ratio of Mn and M elements in the solution, dissolving the manganese salt and the M salt in water, adding 1-5 mol% of sodium salt in excess, stirring and dissolving to prepare a mixed solution, wherein the positive electrode material of the P2 type manganese-based sodium ion battery is Na x Mn a M 1-a O 2 Wherein x and a are mole numbers, x is more than 0.44 and less than 1,0.4 and less than or equal to 1, M is one or more of metal ions Ni, co, mg, al, zn, ti, cu and Fe;
2) Heating and stirring the mixed solution obtained in the step 1), adding an additive, stirring and evaporating to dryness to obtain gel;
3) Drying and crushing the gel obtained in the step 2), pre-sintering for 4-6 hours at 400-600 ℃ in the air atmosphere, then sintering for 12-18 hours at 850-1000 ℃, and cooling to room temperature to obtain a pure-phase P2 type manganese-based sodium ion battery anode material;
4) Dispersing the pure-phase P2 type manganese-based sodium ion battery anode material obtained in the step 3) in an organic solvent, stirring to obtain a uniformly dispersed suspension, and then according to the NaTi 2 (PO 4 ) 3 With Na x Mn a M 1-a O 2 In the mass ratio of (0.0005-0.20): 1, weighing a titanium source, adding the titanium source into a suspension, preparing a phosphorus source solution and a sodium source solution by using water, dropwise adding the phosphorus source solution and the sodium source solution into the suspension, continuously stirring, and evaporating the solvent to obtain a mixture;
5) And (3) putting the dried mixture obtained in the step (4) into a tubular furnace, sintering the mixture at 400-900 ℃ in an air atmosphere for 5-15 h, and cooling the mixture to room temperature to obtain the Nasicon structure sodium titanium phosphate surface modified P2 type manganese-based sodium ion battery anode material.
2. The preparation method of claim 1, wherein the sodium salt, the manganese salt and the metal M salt in the step 1) are one or more of sulfate, nitrate and acetate.
3. The preparation method of claim 1, wherein the additive in step 2) is one or more of citric acid, ethylene glycol and tartaric acid; the dosage of the additive is 20-50% of the total mass of the sodium salt, the manganese salt and the M salt.
4. The method according to claim 1, wherein the temperature for evaporating in step 2) and step 4) is 80-100 ℃.
5. The preparation method according to claim 1, wherein the organic solvent in step 4) is one or more of ethanol and acetone.
6. The method according to claim 1, wherein the stirring time in the step 4) is 1 to 3 hours.
7. The preparation method according to claim 1, wherein the titanium source in step 4) is one or more of tetrabutyl titanate, titanium isopropoxide, titanium sulfate and titanyl sulfate.
8. The preparation method according to claim 1, wherein the phosphorus source in step 4) is one or more of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, phosphoric acid and hypophosphorous acid; the sodium source is one or more of sodium acetate, sodium carbonate, sodium nitrate and sodium hydroxide.
9. The Nasicon structure sodium titanium phosphate surface modified P2 type manganese-based sodium ion battery positive electrode material prepared by the preparation method of any one of claims 1 to 8, characterized in that the material consists of a surface coating layer and a P2 type manganese-based sodium ion battery positive electrode material; the surface coating layer is NaTi 2 (PO 4 ) 3 。
10. The Nasicon structure sodium titanium phosphate surface modified P2 type manganese-based sodium ion battery positive electrode material as claimed in claim 9, wherein the NaTi is 2 (PO 4 ) 3 With Na x Mn a M 1-a O 2 In the mass ratio of (0.0005-0.20): 1.
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