CN117673295A - Sodium ion battery positive electrode composite material, preparation method thereof and sodium ion battery - Google Patents
Sodium ion battery positive electrode composite material, preparation method thereof and sodium ion battery Download PDFInfo
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- CN117673295A CN117673295A CN202311598750.9A CN202311598750A CN117673295A CN 117673295 A CN117673295 A CN 117673295A CN 202311598750 A CN202311598750 A CN 202311598750A CN 117673295 A CN117673295 A CN 117673295A
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- sodium
- ion battery
- sodium ion
- positive electrode
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 112
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 86
- 239000011734 sodium Substances 0.000 claims abstract description 61
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 33
- 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 27
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims abstract description 19
- -1 sodium orthophosphate ion Chemical class 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 42
- 239000002243 precursor Substances 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 27
- 239000000126 substance Substances 0.000 claims description 25
- 238000001354 calcination Methods 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 21
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 12
- 229910015177 Ni1/3Co1/3Mn1/3 Inorganic materials 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 7
- 239000012798 spherical particle Substances 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- 229910015207 Ni1/3Co1/3Mn1/3O Inorganic materials 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 239000002105 nanoparticle Substances 0.000 claims description 4
- 239000004317 sodium nitrate Substances 0.000 claims description 4
- 235000010344 sodium nitrate Nutrition 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- 229910014507 Na0.67Ni0.33Mn0.67O2 Inorganic materials 0.000 claims description 3
- 229910015228 Ni1/3Mn1/3CO1/3 Inorganic materials 0.000 claims description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical class OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 claims description 3
- 150000002823 nitrates Chemical class 0.000 claims description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 238000012360 testing method Methods 0.000 description 42
- 239000010410 layer Substances 0.000 description 27
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 21
- 238000007599 discharging Methods 0.000 description 21
- 238000011056 performance test Methods 0.000 description 21
- 239000000243 solution Substances 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000011248 coating agent Substances 0.000 description 16
- 238000000576 coating method Methods 0.000 description 16
- 239000003792 electrolyte Substances 0.000 description 16
- 230000014759 maintenance of location Effects 0.000 description 16
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 239000002033 PVDF binder Substances 0.000 description 14
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 14
- 229910001437 manganese ion Inorganic materials 0.000 description 14
- 229910021645 metal ion Inorganic materials 0.000 description 14
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 14
- 238000002441 X-ray diffraction Methods 0.000 description 13
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 13
- 239000010936 titanium Substances 0.000 description 13
- 239000006256 anode slurry Substances 0.000 description 12
- 239000006183 anode active material Substances 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 239000011572 manganese Substances 0.000 description 11
- 239000007774 positive electrode material Substances 0.000 description 11
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 10
- 235000019837 monoammonium phosphate Nutrition 0.000 description 10
- 230000004913 activation Effects 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 8
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 229910017052 cobalt Inorganic materials 0.000 description 7
- 239000010941 cobalt Substances 0.000 description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 7
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 7
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000012467 final product Substances 0.000 description 7
- 239000011888 foil Substances 0.000 description 7
- 235000006748 manganese carbonate Nutrition 0.000 description 7
- 239000011656 manganese carbonate Substances 0.000 description 7
- 229940093474 manganese carbonate Drugs 0.000 description 7
- 229940099596 manganese sulfate Drugs 0.000 description 7
- 235000007079 manganese sulphate Nutrition 0.000 description 7
- 239000011702 manganese sulphate Substances 0.000 description 7
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 7
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 7
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 7
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 7
- 230000005855 radiation Effects 0.000 description 7
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 7
- 235000017557 sodium bicarbonate Nutrition 0.000 description 7
- 239000011247 coating layer Substances 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 6
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 5
- VQBIMXHWYSRDLF-UHFFFAOYSA-M sodium;azane;hydrogen carbonate Chemical compound [NH4+].[Na+].[O-]C([O-])=O VQBIMXHWYSRDLF-UHFFFAOYSA-M 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 230000002035 prolonged effect Effects 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 229910021550 Vanadium Chloride Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000011883 electrode binding agent Substances 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009210 therapy by ultrasound 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 relates to the technical field of sodium ion batteries, in particular to a sodium ion battery positive electrode composite material, a preparation method thereof and a sodium ion battery. The positive electrode composite material of the sodium ion battery comprises a layered oxide and a sodium orthophosphate material layer coated on the surface of the layered oxide. The surface of the layered oxide in the sodium ion battery positive electrode composite material is coated with the sodium-rich sodium orthophosphate ion material layer, so that the surface of the layered material is protected, the capacity attenuation rate of the sodium ion battery positive electrode in the circulating process is reduced, and the circulating stability of the sodium ion battery is improved.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a sodium ion battery positive electrode composite material, a preparation method thereof and a sodium ion battery.
Background
Sodium ion batteries are considered to have great application prospects in electrochemical energy storage due to their lower raw material cost than lithium ion batteries. The positive electrode material of the existing sodium ion battery is mainly layered oxide and has the characteristics of high energy density and the like. However, sodium ion batteries using layered oxides as the positive electrode active material have a rapid capacity fade during cycling, and result in a similarly rapid energy density fade, resulting in poor cycling performance.
Disclosure of Invention
The embodiment of the invention mainly aims to provide a positive electrode composite material of a sodium ion battery, and aims to solve the problems of high capacity attenuation and high energy density attenuation of a layered oxide positive electrode material of an existing sodium ion battery.
In a first aspect, an embodiment of the present invention provides a positive electrode composite material for a sodium ion battery, where the positive electrode composite material for a sodium ion battery includes a layered oxide and a sodium orthophosphate material layer coated on the surface of the layered oxide, and the sodium orthophosphate material layer is composed of a substance represented by a chemical formula as shown in a general formula I:
Na 7 M 4 (P 2 O 7 ) 4 PO 4 (I)；
wherein M comprises one or more of Al, cr, fe and V.
In some embodiments, the layered oxide has a formula as shown in formula II:
Na x TMO 2-y F y (II)；
wherein x is more than or equal to 0.44 and less than or equal to 1.0; y is more than or equal to 0 and less than or equal to 0.2;
the TM includes one or more of Li, ni, mn, fe, co, cu, zn, sn, mg, sb, K, zr and Ti.
In some embodiments, the spherical particles of the layered oxide of the sodium ion battery positive electrode composite have an average particle size between 10nm and 200 μm; and/or the average thickness of the sodium orthophosphate ion material layer is between 2nm and 200 nm.
In some embodiments, the layered oxide comprises NaNi 1/3 Co 1/3 Mn 1/3 O 2 、Na 2/3 Ni 1/3 Co 1/3 Mn 1/ 3 O 2 、Na 0.9 Ti 0.1 [Ni 1/3 Co 1/3 Mn 1/3 ] 0.9 O 2 、Na 0.8 [Ni 1/3 Co 1/3 Mn 1/3 ] 0.8 Ti 0.1 Li 0.1 O 2 、Na 0.67 Ni 0.33 Mn 0.67 O 2 、Na 0.8 Fe 0.4 Mn 0.6 O 2 、NaNi 0.1 Li 0.2 Mn 0.7 O 2 Na and Na 0.67 (Ni 1/3 Mn 1/3 Co 1/3 ) 0.8 Ti 0.1 Li 0.1 O 1.95 F 0.05 At least one of them.
Compared with the prior art, the sodium ion battery positive electrode composite material provided by the embodiment of the invention comprises the layered oxide and the orthophosphate sodium ion material layer, and the orthophosphate sodium ion material layer is coated on the surface of the layered oxide, so that the exposure area of the layered oxide is effectively reduced, the stability of the sodium ion battery positive electrode composite material is improved, the discharge specific capacity attenuation rate is mild when the sodium ion battery is assembled, the cycle performance of the sodium ion battery can be effectively improved, and the service life of the sodium ion battery is prolonged.
In a second aspect, the embodiment of the invention also provides a preparation method of the positive electrode composite material of the sodium ion battery, which adopts the following technical scheme:
the preparation method of the positive electrode composite material of the sodium ion battery comprises the following steps:
mixing the precursor with a first sodium source, and tabletting to obtain a lamellar material;
calcining the lamellar material at 500-1100 ℃ to obtain lamellar oxide;
dissolving phosphate, a second sodium source and metal M salt in a solvent to obtain a mixed solution; wherein the ratio of phosphorus in the phosphate, metal M in the metal salt, and sodium in the second sodium source is 9:4:7.
Putting the layered oxide into the mixed solution, heating to dryness at the temperature of 120-150 ℃ to enable solute in the mixed solution to be deposited on the surface of the layered oxide, calcining at the temperature of 780-900 ℃, and finally washing and drying to obtain the sodium ion battery anode composite material;
wherein, the sodium orthophosphate ion material layer coated on the surface of the layered oxide in the sodium ion battery positive electrode composite material consists of substances represented by chemical formula as shown in a general formula I:
Na 7 M 4 (P 2 O 7 ) 4 PO 4 (I)；
wherein M comprises one or more of Al, cr, fe and V.
In some embodiments, the precursor comprises TM (OH) 2 At least one of TM metal carbonates, wherein TM is selected from one or more of Li, ni, mn, fe, co, cu, zn, sn, mg, sb, K, zr, ti;
the first sodium source and the second sodium source are respectively and independently selected from at least one of sodium carbonate, sodium nitrate, sodium chlorate and sodium sulfate.
In some embodiments, the molar ratio of the precursor to sodium of the first sodium source is 1 (0.44-1.0).
In some embodiments, the metal salt of M is selected from at least one of a sulfate salt of M, a chlorate salt of M, a nitrate salt of M.
In some embodiments, the calcination is for a period of time ranging from 1h to 72h;
and/or, before the layered oxide is put into the mixed solution, the layered oxide is crushed into micro-nano-sized powder with spherical particles with average particle diameter ranging from 20nm to 500 mu m.
Compared with the prior art, the preparation method of the sodium ion battery positive electrode composite material provided by the embodiment of the invention has the characteristics of simple preparation process, high material purity, few impurities and the like, and the sodium ion material layer can be effectively coated on the surface of the layered oxide by adopting the method, so that the exposed area of the layered oxide is effectively reduced, the discharge specific capacity attenuation rate is relatively mild when the obtained sodium ion battery positive electrode composite material is assembled into a sodium ion battery, and the service life of the sodium ion battery can be effectively prolonged.
In a third aspect, the embodiment of the invention also provides a sodium ion battery, which comprises a positive plate and a negative plate, wherein the positive plate contains the positive composite material of the sodium ion battery;
or the positive plate contains the sodium ion battery positive electrode composite material prepared by the preparation method of the sodium ion battery positive electrode composite material.
Compared with the prior art, the positive plate of the sodium ion battery provided by the embodiment contains the positive electrode composite material of the sodium ion battery, so that the discharge specific capacity decay rate is mild in the use process, the sodium ion battery has excellent cycle performance, and the service life of the sodium ion battery can be effectively prolonged.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present application, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an XRD pattern of a first sample provided in example 1 of the present invention;
FIG. 2 is an SEM image of a first sample according to example 1 of the present invention;
FIG. 3 is a TEM image of a first sample according to example 1 of the present invention;
FIG. 4 is an XRD pattern for a second sample provided in example 2 of the present invention;
FIG. 5 is an SEM image of a second sample according to example 2 of the present invention;
FIG. 6 is an XRD pattern of a third sample according to example 3 of the present invention
FIG. 7 is a graph showing the specific capacity retention rate of 100 cycles in application example 1 and comparative example 1 of the present invention;
Fig. 8 is a graph showing the rate performance of the present invention at different current densities of application example 2 and comparative example 2.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It is to be understood that the terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used in this specification and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The embodiment of the invention provides a sodium ion battery positive electrode composite material, which comprises a layered oxide and a sodium orthophosphate material layer coated on the surface of the layered oxide, wherein the sodium orthophosphate material layer consists of substances with chemical formulas shown in a general formula I:
Na 7 M 4 (P 2 O 7 ) 4 PO 4 (I)；
Wherein M comprises one or more of Al, cr, fe and V.
Specifically, the layered oxide has a chemical formula as shown in formula II:
Na x TMO 2-y F y (II)；
wherein x is more than or equal to 0.44 and less than or equal to 1.0; y is more than or equal to 0 and less than or equal to 0.2;
the TM includes one or more of Li, ni, mn, fe, co, cu, zn, sn, mg, sb, K, zr and Ti.
According to the sodium ion battery positive electrode composite material provided by the embodiment of the invention, as the surface of the layered oxide is coated with the sodium orthophosphate material layer, the stability of the material can be effectively improved, and when the sodium ion battery is assembled, the specific capacity decay rate of the battery is relaxed, the cycling stability of the sodium ion battery is improved, and the service life of the sodium ion battery is prolonged.
In some embodiments, the average particle size of the spherical particles of the layered oxide is between 10nm and 200 μm, and the excessively large particle size of the spherical particles of the layered oxide increases the coating difficulty of the sodium orthophosphate material layer, and the coating layer is easy to break due to the stress of the coated coating layer, which is not beneficial to obtaining a good coating effect and a stable coating layer. In some embodiments, the layer of sodium orthophosphate ionic material has an average thickness between 2nm and 200 nm. In some embodiments, the layer of sodium orthophosphate material is uniformly coated on the surface of the layered oxide, and the thickness of the layer of sodium orthophosphate material has a D50 between 50nm and 100 nm. It should be noted that the conventional definition of D50 is that the particle size corresponds to a cumulative particle size distribution percentage of one sample reaching 50%, and in the embodiment of the present invention, the cumulative thickness distribution percentage of the sodium orthophosphate material layer coated on the surface of the layered oxide reaches 50% by using D50 as the definition.
In some embodiments, the layered oxide comprises NaNi 1/3 Co 1/3 Mn 1/3 O 2 、Na 2/3 Ni 1/3 Co 1/3 Mn 1/3 O 2 、Na 0.9 Ti 0.1 [Ni 1/3 Co 1/3 Mn 1/3 ] 0.9 O 2 、Na 0.8 [Ni 1/3 Co 1/3 Mn 1/3 ] 0.8 Ti 0.1 Li 0.1 O 2 、Na 0.67 Ni 0.33 Mn 0.67 O 2 、Na 0.8 Fe 0.4 Mn 0.6 O 2 、NaNi 0.1 Li 0.2 Mn 0.7 O 2 Na and Na 0.67 (Ni 1/3 Mn 1/3 Co 1/3 ) 0.8 Ti 0.1 Li 0.1 O 1.95 F 0.05 At least one of them.
Based on the provided sodium ion battery anode composite material, the embodiment of the invention also provides a preparation method of the sodium ion battery anode composite material.
Specifically, the sodium ion battery positive electrode composite material can be prepared according to the following steps:
(1) And mixing the precursor with a first sodium source, and tabletting to obtain the sheet material.
In step (1), the precursor comprises TM (OH) 2 At least one of TM metal carbonates, wherein TM is selected from one or more of Li, ni, mn, fe, co, cu, zn, sn, mg, sb, K, zr, ti; the first sodium source is at least one selected from sodium carbonate, sodium nitrate, sodium chlorate and sodium sulfate.
In some embodiments, the molar ratio of the precursor to sodium of the first sodium source is 1 (0.44-1.0), thereby facilitating the assurance of sufficient or even excessive sodium ions.
In some embodiments, the tabletting process may be performed by loading the powder in a die with an applied pressure of 5 to 3000MPa, the die may have a cylindrical cavity in which the powder is placed.
(2) And (3) calcining the lamellar material at 500-1100 ℃ to obtain the lamellar oxide.
In the step (2), the calcination treatment may be performed in an air atmosphere.
(3) And dissolving phosphate, a second sodium source and metal M salt in a solvent to obtain a mixed solution, wherein the ratio of phosphorus in the phosphate, metal M in the metal M salt and sodium in the second sodium source is 9:4:7.
In step (3), the metal salt of M is selected from at least one of a sulfate salt of M, a chlorate salt of M, and a nitrate salt of M.
In some embodiments, the second sodium source is selected from at least one of sodium carbonate, sodium nitrate, sodium chlorate, sodium sulfate.
In some embodiments, the molar ratio of metal M in the metal M salt to sodium of the second sodium source is about 4:7 to effectively ensure the amount of sodium ions of the coating.
In some embodiments, the solvent is selected from deionized water.
(4) Putting the layered oxide into the mixed solution, heating to dryness at the temperature of 120-150 ℃ to enable solute in the mixed solution to be deposited on the surface of the layered oxide, calcining at the temperature of 780-900 ℃, and finally washing and drying to obtain the sodium ion battery anode composite material;
Wherein, the sodium orthophosphate ion material layer coated on the surface of the layered oxide in the sodium ion battery positive electrode composite material consists of substances represented by chemical formula as shown in a general formula I:
Na 7 M 4 (P 2 O 7 ) 4 PO 4 (I)；
wherein M comprises one or more of Al, cr, fe and V.
In the step (4), before the layered oxide is put into the mixed solution, a step of crushing the layered oxide into micro-nano-sized powder is further included.
In some embodiments, the layered oxide is crushed using a crushing device such as a planetary ball mill so that the layered oxide becomes micro-nano sized powder. For example, when ball milling is performed by a ball mill, the ball milling speed is 200 r/min-1000 r/min. The average particle size of the spherical particles of the layered oxide is between 10nm and 200 mu m through crushing, so that the coating rate is improved, and the exposed surface area of the layered oxide is reduced.
In some embodiments, after the layered oxide is added to the mixed solution, stirring is performed first, so that the materials are uniformly mixed to facilitate uniform dispersion and uniform precipitation.
In some embodiments, the calcination time is between 1h and 72h, which is advantageous for improving the coating effect by extending the calcination time from 780 ℃ to 900 ℃. In some embodiments, the calcination temperature is between 795 ℃ and 900 ℃ to facilitate a purer phase and denser coating.
In some embodiments, the heating process at 120-150 ℃ also comprises the application of ultrasonic conditions, so that a uniform sodium orthophosphate ion material layer is generated on the surface of the layered oxide by ultrasonic treatment, the coating uniformity of the sodium orthophosphate ion material layer is improved, and the coating effect is improved.
In some embodiments, when the ultrasonic condition is applied, the frequency of the ultrasonic wave is between 20kHz and 120kHz, and the ultrasonic wave in the frequency range can effectively inhibit aggregation of crystal nuclei of the sodium orthophosphate ion material in the deposition process, and is beneficial to uniformly dispersing the crystal nuclei of the sodium orthophosphate ion material on the surface of the layered oxide, so that a uniform coating layer is obtained, and the coating effect is effectively improved.
In some embodiments, the metal M salt and the second sodium source added to the reaction system are both in excess, improving the coating effect.
In some embodiments, the washing and drying of step (4) comprises washing with deionized water or the like, filtering, drying to obtain a dried sodium ion battery positive electrode composite.
Based on the sodium ion battery positive electrode composite material and the preparation method of the sodium ion battery positive electrode composite material, the embodiment of the invention also provides a sodium ion battery.
Specifically, the sodium ion battery comprises a positive plate and a negative plate, wherein the positive plate contains the sodium ion battery positive electrode composite material, or the positive plate contains the sodium ion battery positive electrode composite material prepared by the preparation method of the sodium ion battery positive electrode composite material.
In some embodiments, the positive plate of the sodium ion battery comprises a positive current collector and a positive active layer overlapped on the surface of the positive current collector, wherein the positive active layer comprises a positive conductive agent, a positive binder and the positive composite material of the sodium ion battery. Wherein the mass content of the sodium ion battery positive electrode composite material in the active layer is more than 60%. The positive electrode current collector, the positive electrode conductive agent and the positive electrode binder are materials commonly used in the field of secondary batteries, and therefore, the description thereof will not be repeated.
In some embodiments, the negative active material in the negative electrode sheet may be any one of sodium metal, hard carbon, or soft carbon. In some embodiments, the sodium ion battery further comprises a separator or solid electrolyte layer for separating the positive electrode sheet from the negative electrode sheetThe negative electrode plate is used for preventing the positive electrode plate and the negative electrode plate from being short-circuited, and the solid electrolyte layer is also used for conducting sodium ions. The separator or the solid electrolyte layer is a material well known in the art of secondary batteries, and thus, will not be described in detail herein. In some embodiments, the sodium ion battery further comprises an electrolyte, e.g., the electrolyte may be 0.4 to 1.5M NaClO 4 Or NaPF 6 Of course, the solvent of the electrolyte may be a mixed solution of Propylene Carbonate (PC)/fluoroethylene carbonate (FEC) (the volume ratio of PC to FEC is 95:5), and the volume ratio of PC to PC is 1:1.
In order to better illustrate the solution of the present invention, a number of specific examples are set forth below for further explanation.
Example 1
A preparation method of a positive electrode composite material of a sodium ion battery comprises the following steps:
dissolving manganese sulfate in water to prepare a metal ion solution with the concentration of 2 mol/L; 2mol/L sodium bicarbonate aqueous solution is added to 16.7ml of metal ion (manganese ion) solution as a precipitant until the manganese ions are completely precipitated, and a manganese carbonate precursor is obtained.
Mixing cobalt carbonate and nickel carbonate according to the stoichiometric ratio of the final product (the molar ratio of cobalt to nickel is 1:1), and then adopting microwave radiation to perform constant-temperature sintering for 30min at 400 ℃ to obtain the heat-treatment oxide precursor.
Mixing the oxide precursor with sodium carbonate at a ratio of 1: the mixture was uniformly mixed at a molar ratio of 0.5, and then pressed into a cylindrical sheet shape under a pressure of 400 MPa. Calcining cylindrical material at 1100deg.C for 12 hr, taking out, and grinding into powder, wherein the chemical formula of the obtained powder material is NaNi 1/3 Co 1/3 Mn 1/3 O 2 。
Mixing all the obtained powder with sodium carbonate and ammonium dihydrogen phosphate, wherein the sodium carbonate: ammonium dihydrogen phosphate molar ratio = 3.5:9, wherein the content of sodium carbonate is 0.371g, then dissolving and dispersing in deionized water, adding 4mL of 1M vanadium chloride solution, drying at 140 ℃ for 40 hours, taking out, calcining at 800 ℃ for 6 hours, filtering, and washing and filtering with deionized water3 times, drying at 120deg.C for 24h to obtain first sample NaNi 1/3 Co 1/3 Mn 1/3 O 2 @Na 7 V 4 (P 2 O 7 ) 4 PO 4 。
XRD (X-ray diffraction), SEM (Scanning Electron Microscope ) and TEM (Transmission Electron Microscope, transmission electron microscope) were performed on the sample obtained in example 1, and specific test results are shown in FIGS. 1, 2 and 3.
As can be seen from fig. 1, the main characteristic peaks (marked with crystal plane indices) of the sample of example 1 in the XRD spectrum are consistent with the standard XRD spectrum of the layered oxide, demonstrating that the obtained material is of layered oxide structure, but that there are few other peaks of other substances in the graph, which peaks are marked with asterisks, which are diffraction peaks of the sodium orthophosphate material (which can be seen in conjunction with fig. 3), and no other impurity peaks are found, indicating that the purity of the coated sodium orthophosphate material is higher.
From fig. 2 it is demonstrated that the surface of the material prepared has a large number of particles, confirming the presence of two different particles: respectively large particles in a block shape and small particles attached to the surface of the block shape.
From fig. 3 it is evident that the surface of the material contains materials of different structure, with a more pronounced demarcation between the two structural materials, indicating that the sodium orthophosphate material is coated onto the layered oxide material.
According to the physical properties of the materials, it can be determined that the material prepared in the embodiment 1 is a composite material with a layered oxide material surface coated with a sodium orthophosphate ion material layer, and the sodium orthophosphate ion material layer has higher purity.
Example 2
A preparation method of a layered oxide of a sodium ion battery comprises the following steps:
dissolving manganese sulfate in water to prepare a metal ion solution with the concentration of 2 mol/L; 2mol/L sodium bicarbonate aqueous solution is used as a precipitator to be added into 16.7ml of metal ion (manganese ion) solution dropwise until the manganese ions are completely precipitated, and a manganese carbonate precursor is obtained.
Mixing cobalt carbonate and nickel carbonate according to the stoichiometric ratio of the final product (the molar ratio of cobalt to nickel is 1:1), and then adopting microwave radiation to sinter at the constant temperature of 400 ℃ for 30min to obtain the heat treatment oxide precursor.
Mixing the oxide precursor with sodium carbonate at a ratio of 1: the mixture was uniformly mixed at a molar ratio of 0.5, and then pressed into a cylindrical sheet shape under a pressure of 400 MPa. The cylindrical material is calcined at 1000 ℃ for 12 hours and then taken out to be ground into powder. Obtaining a first sample with a chemical formula of NaNi 1/3 Co 1/3 Mn 1/3 O 2 。
Mixing all the obtained powder with sodium carbonate and ammonium dihydrogen phosphate, wherein the sodium carbonate: ammonium dihydrogen phosphate molar ratio = 3.5:9, wherein the content of sodium carbonate is 0.371g, then dissolving and dispersing in deionized water, then adding 4mL of 1M chromium nitrate solution, drying at 140 ℃ for 40 hours, taking out, calcining at 800 ℃ for 6 hours, filtering, washing with deionized water, filtering for 3 times, drying at 120 ℃ for 24 hours, and obtaining a second sample NaNi 1/3 Co 1/3 Mn 1/3 O 2 @Na 7 Cr 4 (P 2 O 7 ) 4 PO 4 。
XRD and SEM tests were carried out on the samples obtained in example 2, and the specific test results are shown in FIGS. 4 and 5.
As can be seen from the XRD spectrum of fig. 4, the main characteristic peak (marked with crystal face index) of the sample is consistent with the standard XRD spectrum of the layered oxide, and it is proved that the obtained material has a layered oxide structure, and a small amount of peaks of other substances exist in the figure, and the peaks are marked with asterisks, and the asterisks are diffraction peaks of the sodium orthophosphate material.
From fig. 5, it was confirmed that the surface of the prepared material had a large number of particles, and the presence of two different particles was confirmed, so that it was confirmed that the material prepared in example 2 was a layered material coated with a sodium orthophosphate ion material.
Example 3
The preparation method of the positive electrode composite material of the sodium ion battery comprises the following steps:
dissolving manganese sulfate in water to prepare a metal ion solution with the concentration of 2 mol/L; 2mol/L sodium bicarbonate aqueous solution is added to 16.7ml of metal ion (manganese ion) solution as a precipitant until the manganese ions are completely precipitated, and a manganese carbonate precursor is obtained.
Mixing cobalt carbonate and nickel carbonate according to the stoichiometric ratio of the final product (the molar ratio of cobalt to nickel is 1:1), and then adopting microwave radiation to sinter at the constant temperature of 400 ℃ for 30min to obtain the heat treatment oxide precursor.
An oxide precursor is adopted, and the following components are mixed with sodium carbonate according to the proportion of 1: the 0.34 molar ratio was mixed homogeneously and then pressed into a cylindrical sheet shape under a pressure of 15 MPa. Calcining cylindrical material at 900 deg.C for 24 hr, and grinding into powder, wherein the chemical formula of the obtained powder material is Na 2/3 Ni 1/3 Co 1/3 Mn 1/3 O 2 。
Mixing all the obtained powder with sodium carbonate and ammonium dihydrogen phosphate, wherein the sodium carbonate: ammonium dihydrogen phosphate molar ratio = 3.5:9, wherein the content of sodium carbonate is 0.371g, then dissolving and dispersing in deionized water, then adding 4mL of 1M ferric chloride solution, drying at 140 ℃ for 40 hours, taking out, calcining at 800 ℃ for 6 hours, filtering, washing with deionized water, filtering for 3 times, drying at 120 ℃ for 24 hours, obtaining a third sample Na 2/3 Ni 1/3 Co 1/ 3 Mn 1/3 O 2 @Na 7 Fe 4 (P 2 O 7 ) 4 PO 4 。
XRD testing was performed on the sample obtained in example 3, and the specific test results are shown in FIG. 6. The XRD pattern of fig. 6 is consistent with the standard XRD pattern of the layered oxide, demonstrating that the material obtained is a layered oxide structure, but that there are small amounts of peaks of other substances present in the pattern, which peaks are marked with asterisks, which are diffraction peaks of the sodium orthophosphate material. It was thus determined that the material prepared in example 3 was a layered material coated with a sodium orthophosphate ion material.
Example 4
The preparation method of the positive electrode composite material of the sodium ion battery comprises the following steps:
dissolving manganese sulfate in water to prepare a metal ion solution with the concentration of 2 mol/L; 2mol/L sodium bicarbonate aqueous solution is added to 16.7ml of metal ion (manganese ion) solution as a precipitant until the manganese ions are completely precipitated, and a manganese carbonate precursor is obtained.
Mixing cobalt carbonate and nickel carbonate according to the stoichiometric ratio of the final product (the molar ratio of cobalt to nickel is 1:1), and then adopting microwave radiation to perform constant-temperature sintering for 30min at 400 ℃ to obtain the heat-treatment oxide precursor.
Mixing the oxide precursor with titanium oxide and sodium carbonate according to 0.9:0.1: the mixture was uniformly mixed at a molar ratio of 0.45, and then pressed into a cylindrical sheet shape under a pressure of 200 MPa.
Calcining cylindrical material at 1100deg.C for 12 hr, taking out, grinding into powder, and collecting powder material with chemical formula of Na 0.9 Ti 0.1 [Ni 1/3 Co 1/3 Mn 1/3 ] 0.9 O 2 。
Mixing all the obtained powder with sodium carbonate and ammonium dihydrogen phosphate, wherein the sodium carbonate: ammonium dihydrogen phosphate molar ratio = 3.5:9, wherein the content of sodium carbonate is 0.371g, then dissolving and dispersing in deionized water, then adding 4mL of 1M aluminum nitrate solution, drying at 140 ℃ for 40 hours, taking out, calcining at 900 ℃ for 6 hours, then washing and filtering with deionized water for 3 times, drying at 120 ℃ for 12 hours, and obtaining a fourth sample Na 0.9 Ti 0.1 [Ni 1/3 Co 1/ 3 Mn 1/3 ] 0.9 O 2 @Na 7 Al 4 (P 2 O 7 ) 4 PO 4 。
Example 5
The preparation method of the positive electrode composite material of the sodium ion battery comprises the following steps:
dissolving manganese sulfate in water to prepare a metal ion solution with the concentration of 2 mol/L; 2mol/L sodium bicarbonate aqueous solution is added to 16.7ml of metal ion (manganese ion) solution as a precipitant until the manganese ions are completely precipitated, and a manganese carbonate precursor is obtained.
Mixing cobalt carbonate and nickel carbonate according to the stoichiometric ratio of the final product (the molar ratio of cobalt to nickel is 1:1), and then adopting microwave radiation to sinter at the constant temperature of 400 ℃ for 30min to obtain the heat treatment oxide precursor.
Mixing the oxide precursor with titanium oxide, lithium carbonate and sodium carbonate according to a ratio of 0.8:0.1:0.05: the mixture was uniformly mixed at a molar ratio of 0.4, and then pressed into a cylindrical sheet shape under a pressure of 200 MPa.
Calcining cylindrical material at 1100deg.C for 12 hr, taking out, grinding into powder, and collecting powder material with chemical formula of Na 0.8 [Ni 1/3 Co 1/3 Mn 1/3 ] 0.8 Ti 0.1 Li 0.1 O 2 。
Mixing all the obtained powder with sodium carbonate and ammonium dihydrogen phosphate, wherein the sodium carbonate: ammonium dihydrogen phosphate molar ratio = 3.5:9, wherein the content of sodium carbonate is 0.371g, then dissolving and dispersing in deionized water, then adding 4mL of 1M aluminum nitrate solution, drying at 140 ℃ for 40 hours, taking out, calcining at 900 ℃ for 6 hours, filtering, washing with deionized water for 3 times, drying at 120 ℃ for 12 hours to obtain a coating layer, thus obtaining a fifth sample Na 0.8 [Ni 1/3 Co 1/3 Mn 1/3 ] 0.8 Ti 0.1 Li 0.1 O 2 @Na 7 Al 4 (P 2 O 7 ) 4 PO 4 。
Example 6
A preparation method of a layered oxide of a sodium ion battery comprises the following steps:
dissolving manganese sulfate in water to prepare a metal ion solution with the concentration of 2 mol/L; 2mol/L sodium bicarbonate aqueous solution is added to 16.7ml of metal ion (manganese ion) solution as a precipitant until the manganese ions are completely precipitated, and a manganese carbonate precursor is obtained.
Mixing cobalt carbonate and nickel carbonate according to the stoichiometric ratio of the final product (the molar ratio of cobalt to nickel is 1:1), and then adopting microwave radiation to perform constant-temperature sintering for 30min at 400 ℃ to obtain the heat-treatment oxide precursor.
Mixing the oxide precursor with sodium carbonate at a ratio of 1: the mixture was uniformly mixed at a molar ratio of 0.5, and then pressed into a cylindrical sheet shape under a pressure of 400 MPa. The cylindrical material is calcined at 1100 ℃ for 12 hours and then taken out to be ground into powder. Obtaining a sixth sample with a chemical formula of NaNi 1/3 Co 1/3 Mn 1/3 O 2 。
Example 7
The preparation method of the positive electrode composite material of the sodium ion battery comprises the following steps:
dissolving manganese sulfate in water to prepare a metal ion solution with the concentration of 2 mol/L; 2mol/L sodium bicarbonate aqueous solution is added to 16.7ml of metal ion (manganese ion) solution as a precipitant until the manganese ions are completely precipitated, and a manganese carbonate precursor is obtained.
Mixing cobalt carbonate and nickel carbonate according to the stoichiometric ratio of the final product (the molar ratio of cobalt to nickel is 1:1), and then adopting microwave radiation to perform constant-temperature sintering for 30min at 400 ℃ to obtain the heat-treatment oxide precursor.
Mixing the oxide precursor with titanium oxide, lithium carbonate and sodium carbonate according to a ratio of 0.8:0.1:0.05: the mixture was uniformly mixed at a molar ratio of 0.4, and then pressed into a cylindrical sheet shape under a pressure of 200 MPa.
Calcining the cylindrical material at 1100 ℃ for 12 hours, taking out and grinding the cylindrical material into powder to obtain a seventh sample, wherein the seventh sample has a chemical formula of Na 0.8 [Ni 1/3 Co 1/3 Mn 1/3 ] 0.8 Ti 0.1 Li 0.1 O 2 。
In order to demonstrate the performance of the materials obtained in the present invention, the materials prepared in examples 1 to 5 were used as positive electrode materials for sodium ion batteries, respectively, and assembled into sodium ion batteries, and the corresponding performance was tested.
Application example 1
A preparation method of the sodium ion battery comprises the following steps:
(1) The first sample obtained in example 1 is used as a positive electrode active material, is mixed with conductive carbon black and polyvinylidene fluoride (PVDF) binder according to the mass ratio of 7:2:1, is dissolved in N-methyl pyrrolidone (NMP) solvent to prepare positive electrode slurry, is coated on aluminum foil, and is dried and cut to obtain a positive electrode plate.
(2) Assembling the positive plate obtained in the step (1) with a sodium metal and Celgard diaphragm to form a sodium ion battery, wherein the electrolyte of the sodium ion battery is 1M NaPF 6 An electrolyte formed by dissolving in a mixture of EC (ethylene carbonate) and DMC (dimethyl carbonate) (in volume ratio EC: dmc=1:1). And standing for 24 hours after assembly, and then carrying out charge-discharge activation test on the materials.
Specifically, the test mode is: three charges and discharges were performed in the voltage range of 2.0-4.5V at a current density of 0.2C (1c=100 mA/g), while the cycle performance was tested. The specific test mode is as follows: the cycle performance test was performed by charging and discharging three times in a voltage range of 2.0 to 4.5V at a current density of 0.2C and sequentially charging and discharging to 100 cycles at a current density of 0.5C, and the capacity retention rate is shown in table 1 and the cycle effect at 0.5C is shown in fig. 7.
And simultaneously, the multiplying power performance test is carried out on the alloy.
Specifically, the test mode is: charging was performed at a current density of 0.2C in a voltage range of 2.0-4.5V, and the rate performance test was performed by sequentially discharging 5 cycles at current densities of 0.2C, 0.5C, 1C, 2C and 5C, and the results of the first cycle specific capacity test at different rates are shown in table 1.
As can be seen from table 1 and fig. 7, the first sample positive electrode material obtained in example 1 had a first-turn discharge specific capacity of 187mAh/g (charge-discharge current density of 20mA/g, 0.2C) at 0.2C; the specific discharge capacity of the lithium ion battery is as high as 173mAh/g under the current density of 0.5 ℃; at a current density of 5C, the discharge specific capacity is as high as 121mAh/g; the specific capacity retention was about 89% over 100 charge and discharge cycles at a current density of 0.5C.
Application example 2
A preparation method of the sodium ion battery comprises the following steps:
(1) And (3) taking the second sample obtained in the example 2 as an anode active material, mixing the anode active material with conductive carbon black and polyvinylidene fluoride (PVDF) binder according to the mass ratio of 7:2:1, dissolving the mixture in N-methylpyrrolidone (NMP) solvent to prepare anode slurry, coating the anode slurry on aluminum foil, drying and cutting to obtain the anode plate.
(2) Assembling the positive plate obtained in the step (1) with a sodium metal and Celgard diaphragm to form a sodium ion battery, wherein the electrolyte of the sodium ion battery is 1M NaPF 6 An electrolyte formed by dissolving in a mixture of EC (ethylene carbonate) and DMC (dimethyl carbonate) (in volume ratio EC: dmc=1:1). And standing for 24 hours after assembly, and then carrying out charge-discharge activation test on the materials.
Specifically, the test mode is: three charges and discharges were performed in the voltage range of 2.0-4.5V at a current density of 0.2C (1c=100 mA/g), while the cycle performance was tested. The specific test mode is as follows: the cycle performance test was performed by charging and discharging three times in a voltage range of 2.0 to 4.5V at a current density of 0.2C and sequentially charging and discharging to 100 cycles at a current density of 0.5C, and the capacity retention rate was shown in table 1.
And simultaneously, the multiplying power performance test is carried out on the alloy.
Specifically, the test mode is: charging was performed at a current density of 0.2C in a voltage range of 2.0-4.5V, and the rate performance test was performed by sequentially discharging 5 cycles at current densities of 0.2C, 0.5C, 1C, 2C and 5C, and the results of the first cycle specific capacity test at different rates are shown in table 1 and the complete rate test data are shown in fig. 8.
As can be seen from table 1 and fig. 8, the second sample positive electrode material obtained in example 2 had a specific capacity of 183mAh/g (charge-discharge current density of 20mA/g, 0.2C) at the first turn of discharge; the specific capacity of discharge is up to 158mAh/g under the current density of 0.5C; at a current density of 5C, the discharge specific capacity is up to 118mAh/g; the specific capacity retention was about 83% over 100 charge and discharge cycles at a current density of 0.5C.
Application example 3
A preparation method of the sodium ion battery comprises the following steps:
(1) And taking the third sample obtained in the example 3 as an anode active material, mixing the anode active material with conductive carbon black and polyvinylidene fluoride (PVDF) binder according to the mass ratio of 7:2:1, dissolving the mixture in N-methyl pyrrolidone (NMP) solvent to prepare anode slurry, coating the anode slurry on aluminum foil, drying and cutting to obtain the anode plate.
(2) Assembling the positive plate obtained in the step (1) with a sodium metal and Celgard diaphragm to form a sodium ion battery, wherein the electrolyte of the sodium ion battery is 1M NaPF 6 An electrolyte formed by dissolving in a mixture of EC (ethylene carbonate) and DMC (dimethyl carbonate) (in volume ratio EC: dmc=1:1). And standing for 24 hours after assembly, and then carrying out charge-discharge activation test on the materials.
Specifically, the test mode is: three charges and discharges were performed in the voltage range of 2.0-4.5V at a current density of 0.2C (1c=100 mA/g), while the cycle performance was tested. The specific test mode is as follows: the cycle performance test was performed by charging and discharging three times in a voltage range of 2.0 to 4.5V at a current density of 0.2C and sequentially charging and discharging to 100 cycles at a current density of 0.5C, and the capacity retention rate was shown in table 1.
And simultaneously, the multiplying power performance test is carried out on the alloy.
Specifically, the test mode is: charging was performed at a current density of 0.2C in a voltage range of 2.0-4.5V, and the rate performance test was performed by sequentially discharging 5 cycles at current densities of 0.2C, 0.5C, 1C, 2C and 5C, and the results of the first cycle specific capacity test at different rates are shown in table 1.
As can be seen from Table 1, the third sample positive electrode material obtained in example 3 had a specific capacity of 142mAh/g (charge-discharge current density of 20mA/g, 0.2C) at the first turn of discharge; the specific discharge capacity of the high-voltage power supply is up to 141mAh/g under the current density of 0.5 ℃; at a current density of 5C, the discharge specific capacity is up to 116mAh/g; the specific capacity retention was about 87% over 100 charge and discharge cycles at a current density of 0.5C.
Application example 4
A preparation method of the sodium ion battery comprises the following steps:
(1) And taking the fourth sample obtained in the example 4 as an anode active material, mixing the anode active material with conductive carbon black and polyvinylidene fluoride (PVDF) binder according to the mass ratio of 7:2:1, dissolving the mixture in N-methyl pyrrolidone (NMP) solvent to prepare anode slurry, coating the anode slurry on aluminum foil, drying and cutting to obtain the anode plate.
(2) Combining the positive plate obtained in the step (1) with sodium metal and Celgard diaphragm groupIs assembled into a sodium ion battery, the electrolyte of the sodium ion battery is 1M NaPF 6 An electrolyte formed by dissolving in a mixture of EC (ethylene carbonate) and DMC (dimethyl carbonate) (in volume ratio EC: dmc=1:1). And standing for 24 hours after assembly, and then carrying out charge-discharge activation test on the materials.
Specifically, the test mode is: three charges and discharges were performed in the voltage range of 2.0-4.5V at a current density of 0.2C (1c=100 mA/g), while the cycle performance was tested. The specific test mode is as follows: the cycle performance test was performed by charging and discharging three times in a voltage range of 2.0 to 4.5V at a current density of 0.2C and sequentially charging and discharging to 100 cycles at a current density of 0.5C, and the capacity retention rate was shown in table 1.
And simultaneously, the multiplying power performance test is carried out on the alloy.
Specifically, the test mode is: charging was performed at a current density of 0.2C in a voltage range of 2.0-4.5V, and the rate performance test was performed by sequentially discharging 5 cycles at current densities of 0.2C, 0.5C, 1C, 2C and 5C, and the results of the first cycle specific capacity test at different rates are shown in table 1.
As can be seen from Table 1, the positive electrode material of the fourth sample obtained in example 4 had a specific capacity of 150mAh/g (charge-discharge current density of 20mA/g, 0.2C) at the first turn of discharge; the specific discharge capacity of the lithium ion battery is up to 148mAh/g under the current density of 0.5 ℃; at a current density of 5C, the discharge specific capacity is as high as 115mAh/g; the specific capacity retention was about 90% over 100 charge and discharge cycles at a current density of 0.5C.
Application example 5
A preparation method of the sodium ion battery comprises the following steps:
(1) And taking the fifth sample obtained in the example 5 as an anode active material, mixing the fifth sample with conductive carbon black and polyvinylidene fluoride (PVDF) binder according to the mass ratio of 7:2:1, dissolving the mixture in N-methyl pyrrolidone (NMP) solvent to prepare anode slurry, coating the anode slurry on aluminum foil, drying and cutting to obtain the anode plate.
(2) Assembling the positive plate obtained in the step (1) with a sodium metal and Celgard diaphragm to form a sodium ion battery, wherein the electrolyte of the sodium ion battery is 1M NaPF 6 Dissolved in EC (ethylene carbonate) and DMC (carbonDimethyl acid) mixture (in terms of volume ratio EC: dmc=1:1). And standing for 24 hours after assembly, and then carrying out charge-discharge activation test on the materials.
Specifically, the test mode is: three charges and discharges were performed in the voltage range of 2.0-4.5V at a current density of 0.2C (1c=100 mA/g), while the cycle performance was tested. The specific test mode is as follows: the cycle performance test was performed by charging and discharging three times in a voltage range of 2.0 to 4.5V at a current density of 0.2C and sequentially charging and discharging to 100 cycles at a current density of 0.5C, and the capacity retention rate was shown in table 1.
And simultaneously, the multiplying power performance test is carried out on the alloy.
Specifically, the test mode is: charging was performed at a current density of 0.2C in a voltage range of 2.0-4.5V, and the rate performance test was performed by sequentially discharging 5 cycles at current densities of 0.2C, 0.5C, 1C, 2C and 5C, and the results of the first cycle specific capacity test at different rates are shown in table 1.
As can be seen from Table 1, the fifth sample positive electrode material obtained in example 5 had a specific capacity of 190mAh/g (charge-discharge current density of 20mA/g, 0.2C) at the first turn of discharge; the specific discharge capacity of the lithium ion battery is up to 181mAh/g under the current density of 0.5 ℃; at a current density of 5C, the specific discharge capacity is up to 128mAh/g; the specific capacity retention was about 83% over 100 charge and discharge cycles at a current density of 0.5C.
Comparative example 1
A preparation method of the sodium ion battery comprises the following steps:
(1) And taking the sixth sample obtained in the example 6 as an anode active material, mixing the anode active material with conductive carbon black and polyvinylidene fluoride (PVDF) binder according to the mass ratio of 7:2:1, dissolving the mixture in N-methylpyrrolidone (NMP) solvent to prepare anode slurry, coating the anode slurry on aluminum foil, drying and cutting to obtain the anode plate.
(2) Assembling the positive plate obtained in the step (1) with a sodium metal and Celgard diaphragm to form a sodium ion battery, wherein the electrolyte of the sodium ion battery is 1M NaPF 6 An electrolyte formed by dissolving in a mixture of EC (ethylene carbonate) and DMC (dimethyl carbonate) (in volume ratio EC: dmc=1:1). Standing for 24h after assembly, and then feedingAnd (5) performing a row charge-discharge activation test.
Specifically, the test mode is: three charges and discharges were performed in the voltage range of 2.0-4.5V at a current density of 0.2C (1c=100 mA/g), while the cycle performance was tested. The specific test mode is as follows: the cycle performance test was performed by charging and discharging three times in a voltage range of 2.0 to 4.5V at a current density of 0.2C and sequentially charging and discharging to 100 cycles at a current density of 0.5C, and the capacity retention rate is shown in table 1 and the cycle effect at 0.5C is shown in fig. 7.
And simultaneously, the multiplying power performance test is carried out on the alloy.
Specifically, the test mode is: charging was performed at a current density of 0.2C in a voltage range of 2.0-4.5V, and the rate performance test was performed by sequentially discharging 5 cycles at current densities of 0.2C, 0.5C, 1C, 2C and 5C, and the results of the first cycle specific capacity test at different rates are shown in table 1.
As can be seen from fig. 7, application example 1 had a capacity retention of about 89% after 100 charge and discharge cycles at a current density of 50mA/g (0.5C) after activation; while comparative example 1 had a capacity retention of about 63% after 100 charge and discharge cycles at a current density of 50mA/g (0.5C) after activation, application example 1 had a higher cycle retention during the cycle; it can also be seen from fig. 3 that the surface of the sample of application example 1 (first sample) has a certain coating layer (shown as a more distinct boundary line between the two structural materials) to protect the positive electrode material. Therefore, the sodium orthophosphate ion material layer can improve the stability of lamellar oxidation and the circulation stability of the material.
Comparative example 2
A preparation method of the sodium ion battery comprises the following steps:
(1) And taking the seventh sample obtained in the example 7 as an anode active material, mixing the anode active material with conductive carbon black and polyvinylidene fluoride (PVDF) binder according to the mass ratio of 7:2:1, dissolving the mixture in N-methylpyrrolidone (NMP) solvent to prepare anode slurry, coating the anode slurry on aluminum foil, drying and cutting to obtain the anode plate.
(2) Assembling the positive plate obtained in the step (1) with a sodium metal and Celgard diaphragm to form a sodium ion battery, wherein the electrolyte of the sodium ion battery is 1M NaPF 6 An electrolyte formed by dissolving in a mixture of EC (ethylene carbonate) and DMC (dimethyl carbonate) (in volume ratio EC: dmc=1:1). And standing for 24 hours after assembly, and then carrying out charge-discharge activation test on the materials.
Specifically, the test mode is: three charges and discharges were performed in the voltage range of 2.0-4.5V at a current density of 0.2C (1c=100 mA/g), while the cycle performance was tested. The specific test mode is as follows: the cycle performance test was performed by charging and discharging three times in a voltage range of 2.0 to 4.5V at a current density of 0.2C and sequentially charging and discharging to 100 cycles at a current density of 0.5C, and the capacity retention rate was shown in table 1.
And simultaneously, the multiplying power performance test is carried out on the alloy.
Specifically, the test mode is: charging was performed at a current density of 0.2C in a voltage range of 2.0-4.5V, and the rate performance test was performed by sequentially discharging 5 cycles at current densities of 0.2C, 0.5C, 1C, 2C and 5C, and the results of the first cycle specific capacity test at different rates are shown in table 1 and the complete rate test data are shown in fig. 8.
As can be seen from FIG. 8, application example 2, which has a discharge specific capacity of up to 183mAh/g at a current density of 20mA/g (0.2C); at a current density (5C) of 500mA/g, the specific discharge capacity is up to 118mAh/g; whereas comparative example 2, which had a specific discharge capacity of 208mAh/g at a current density of 20mA/g (0.2C); at a current density (5C) of 500mA/g, the specific discharge capacity was 83mAh/g. From this, it is clear that the high rate performance of the layered oxide coated with the sodium orthophosphate material is significantly better than that of comparative example 2.
Table 1 electrochemical properties of each application example
While the invention has been described with reference to certain preferred embodiments, it will be understood by those skilled in the art that various changes and substitutions may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. Therefore, the protection scope of the invention is subject to the protection scope of the claims.
Claims (10)
1. The positive electrode composite material of the sodium ion battery is characterized by comprising a layered oxide and a sodium orthophosphate material layer coated on the surface of the layered oxide, wherein the sodium orthophosphate material layer is composed of substances represented by a chemical formula shown in a general formula I:
Na 7 M 4 (P 2 O 7 ) 4 PO 4 (I)；
wherein M comprises one or more of Al, cr, fe and V.
2. The positive electrode composite for sodium ion battery according to claim 1, wherein the layered oxide has a chemical formula as shown in formula II:
Na x TMO 2-y F y (II)；
wherein x is more than or equal to 0.44 and less than or equal to 1.0; y is more than or equal to 0 and less than or equal to 0.2;
TM comprises one or more of Li, ni, mn, fe, co, cu, zn, sn, mg, sb, K, zr and Ti;
and/or the average particle diameter of spherical particles of the layered oxide of the sodium ion battery positive electrode composite material is between 10nm and 200 mu m;
and/or the thickness of the sodium orthophosphate ion material layer is between 2nm and 200 nm.
3. The positive electrode composite material of sodium ion battery according to claim 2, wherein the layered oxide comprises NaNi 1/3 Co 1/3 Mn 1/3 O 2 、Na 2/3 Ni 1/3 Co 1/3 Mn 1/3 O 2 、Na 0.9 Ti 0.1 [Ni 1/3 Co 1/3 Mn 1/3 ] 0.9 O 2 、Na 0.8 [Ni 1/3 Co 1/ 3 Mn 1/3 ] 0.8 Ti 0.1 Li 0.1 O 2 、Na 0.67 Ni 0.33 Mn 0.67 O 2 、Na 0.8 Fe 0.4 Mn 0.6 O 2 、NaNi 0.1 Li 0.2 Mn 0.7 O 2 Na and Na 0.67 (Ni 1/ 3 Mn 1/3 Co 1/3 ) 0.8 Ti 0.1 Li 0.1 O 1.95 F 0.05 At least one of them.
4. A method for preparing the positive electrode composite material of the sodium ion battery as claimed in any one of claims 1 to 3, comprising the following steps:
Mixing the precursor with a first sodium source, and tabletting to obtain a lamellar material;
calcining the lamellar material at 500-1100 ℃ to obtain lamellar oxide;
according to the chemical formula shown in the general formula I, according to the proportion relation of P, M and sodium of 9:4:7, dissolving phosphate, a second sodium source and metal M salt in a solvent to obtain a mixed solution;
putting the layered oxide into the mixed solution, heating to dryness at the temperature of 120-150 ℃ to enable solute in the mixed solution to be deposited on the surface of the layered oxide, calcining at the temperature of 780-900 ℃, and finally washing and drying to obtain the sodium ion battery anode composite material;
wherein the chemical formula shown in the general formula I shows the composition of the substance:
Na 7 M 4 (P 2 O 7 ) 4 PO 4 (I)；
wherein M comprises one or more of Al, cr, fe and V.
5. The method of claim 4, wherein the precursor comprises TM (OH) 2 At least one of TM metal carbonates, wherein TM is selected from one or more of Li, ni, mn, fe, co, cu, zn, sn, mg, sb, K, zr, ti;
the first sodium source and the second sodium source are respectively and independently selected from at least one of sodium carbonate, sodium nitrate, sodium chlorate and sodium sulfate.
6. The method according to any one of claims 4 and 5, wherein the molar ratio of the precursor to sodium of the first sodium source is 1 (0.44 to 1.0).
7. The method according to any one of claims 4 or 5, wherein the metal salt of M is selected from at least one of a sulfate salt of M, a chlorate salt of M, and a nitrate salt of M.
8. The method according to any one of claims 4 or 5, wherein the calcination time is 1 to 72 hours.
9. The method according to any one of claims 4 and 5, wherein the layered oxide further comprises a step of crushing the layered oxide into micro-nano-sized powder having an average particle diameter of 20nm to 500 μm in a spherical particle size range, before the layered oxide is put into the mixed solution.
10. A sodium ion battery comprising a positive plate and a negative plate, wherein the positive plate contains the sodium ion battery positive composite material of any one of claims 1 to 3;
or the positive plate contains the sodium ion battery positive electrode composite material prepared by the preparation method of the sodium ion battery positive electrode composite material according to any one of claims 4 to 9.
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