CN115172695B - Surface-coated layered transition metal oxide positive electrode material and preparation method thereof - Google Patents
Surface-coated layered transition metal oxide positive electrode material and preparation method thereof Download PDFInfo
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- 229910000314 transition metal oxide Inorganic materials 0.000 title claims abstract description 51
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000011734 sodium Substances 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 19
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 6
- 150000003624 transition metals Chemical class 0.000 claims abstract description 5
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 21
- 238000000498 ball milling Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 12
- 229920000877 Melamine resin Polymers 0.000 claims description 11
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 11
- 239000012300 argon atmosphere Substances 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 5
- 239000001488 sodium phosphate Substances 0.000 claims description 5
- 235000011008 sodium phosphates Nutrition 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 5
- 235000011152 sodium sulphate Nutrition 0.000 claims description 5
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 3
- MOMKYJPSVWEWPM-UHFFFAOYSA-N 4-(chloromethyl)-2-(4-methylphenyl)-1,3-thiazole Chemical compound C1=CC(C)=CC=C1C1=NC(CCl)=CS1 MOMKYJPSVWEWPM-UHFFFAOYSA-N 0.000 claims description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 2
- 235000019983 sodium metaphosphate Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000012071 phase Substances 0.000 abstract 2
- 238000005245 sintering Methods 0.000 abstract 1
- 239000007790 solid phase Substances 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000010405 anode material Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 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 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000005280 amorphization Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M4/366—Composites as layered products
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
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- C01G45/00—Compounds of manganese
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Abstract
The invention discloses a surface-coated layered transition metal oxide positive electrode material and a preparation method thereof. The surface of the surface-coated layered transition metal oxide positive electrode material consists of S-doped or P-doped amorphous carbon, and the near surface consists of N-doped layered transition metal oxide Na α MO 2‑z N z The material phase is layered transition metal oxide Na β MO 2 The composition is that the near-surface and bulk phases of the material have no transition metal offset or vacancy, and the material is prepared by adopting a solid phase sintering method. The preparation process is simple, and the prepared surface-coated layered transition metal oxide positive electrode material is applied to sodium ion batteries, and the batteries show excellent multiplying power performance and cycle stability.
Description
Technical Field
The invention belongs to the technical field of sodium ion battery anode materials, and relates to a surface-coated layered transition metal oxide anode material and a preparation method thereof.
Background
Layered transition metal oxide Na x MO 2 (M is a transition metal element) sodium resources are considered to be one of the most promising positive electrode materials of sodium-ion batteries because of the advantages of low price, wide sources, high theoretical specific capacity and the like. Layered transition metal oxide Na x MO 2 Mainly comprises O3 and P2 type layered transition metal oxides, but the reported O3 and P2 type layered oxides Na x MO 2 There are disadvantages in electrochemical properties. Such as O3-NaMnO 2 The positive electrode material is capable of providing discharge capacities up to 197mAh/g (j. Electrochem. Soc.,2011,158, a 1307), but over-charges and dischargesDuring the process, the lattice structure is easily distorted due to the sliding of the oxygen layer, resulting in rapid capacity fade. Compared with O3-NaMnO 2 ，P2-Na 0.67 MnO 2 The positive electrode material has good rate performance, but when charged to a high potential, the P2 phase also generates a slip of the oxygen layer, a phase transition from P2 to O2 occurs, and a drastic unit cell volume change occurs therewith, which is very unfavorable as a commercial sodium ion battery electrode material (angel. Chem. Int. Ed.,2016,128,12952). Therefore, the modification of the layered transition metal oxide positive electrode material for the sodium ion battery is important for improving the electrochemical stability of the layered transition metal oxide positive electrode material.
Surface coating is a common material modification method, but the currently reported surface coating mode still has certain defects in electrochemical performance. Such as Al 2 O 3 P2 phase material N after surface coating a0.5 Mn 0.5 Co 0.5 O 2 (Hari Vignesh Ramasamy,2019,564,467) can be increased from 154mAh/g to 174mAh/g at 0.5C, but can only be increased from 75% to 78% in terms of cycling. P3 phase material Na coated by phosphate surface 0.65 Mn 0.75 Ni 0.25 O 2 (Yu Wang,2019,372,1066) the circulation of material can be increased from 76.4% to 92.4% at 0.2C, but only from 130.2mAh/g to 133.6mAh/g in capacity.
Disclosure of Invention
The invention aims to provide a surface-coated layered transition metal oxide positive electrode material for a sodium ion battery and a preparation method thereof. The method adopts a composite surface coating technology to effectively inhibit the problems of transition metal migration, dissolution, surface amorphization and the like on the surface of the layered transition metal oxide material, and prepares the layered transition metal oxide anode material for the sodium ion battery with low cost and long cycle life.
The technical solution for realizing the purpose of the invention is as follows:
the surface of the material is coated with a layered transition metal oxide positive electrode material, the surface of the material consists of S or P doped amorphous carbon, and the near surface of the material consists of N doped layered transition metal oxide Na α MO 2-z N z Composition, materialThe material phase is layered transition metal oxide Na β MO 2 Composition, near-surface and bulk phase of the material are free of transition metal offset or vacancy, wherein M is transition metal ion Ni 2+ 、Ni 3 + 、Fe 3+ 、Cu 2+ 、Co 3+ 、Cr 3+ 、Zn 2+ 、Ti 4+ 、V 5+ 、Nb 5+ 、Li + 、Mn 3+ 、Mn 4+ Z is more than or equal to 0.05 and less than or equal to 0.1,0.6, alpha is more than or equal to 1,0.55 and beta is more than or equal to 0.95.
Preferably, the thickness of the surface and the near surface of the surface coated layered transition metal oxide positive electrode material is 2-10 nm.
The preparation method of the surface-coated layered transition metal oxide cathode material comprises the following specific steps:
the preparation method comprises the steps of taking transition metal oxide and sodium carbonate as raw materials, uniformly ball-milling and mixing according to stoichiometric ratio, performing heat treatment for 15-18 h in an air atmosphere at 900+/-10 ℃, cooling to obtain precursor powder, uniformly mixing and ball-milling the precursor powder, melamine, a sulfur source and/or a phosphorus source, and performing heat treatment for 2-5 h in a nitrogen or argon atmosphere at 300-600 ℃ to obtain the surface-coated layered transition metal oxide.
Preferably, the transition metal oxide is NiO, ni 2 O 3 、Fe 2 O 3 、CuO、Co 2 O 3 、Cr 2 O 3 、ZnO、TiO 2 、V 2 O 5 、Nb 2 O 5 、Li 2 O、Mn 2 O 3 Or MnO 2 。
Preferably, the phosphorus source is one or more of sodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium hypophosphite and sodium metaphosphate.
Preferably, the sulfur source is one or more of thiourea, sodium sulfate, sodium bisulfate.
Preferably, the mass of melamine is 2% -5% of the total mass of the transition metal oxide and sodium carbonate.
Preferably, the mass of the sulfur source or the phosphorus source is 1 to 5% of the total mass of the transition metal oxide and sodium carbonate.
Compared with the prior art, the invention has the following advantages:
(1) The surface of the layered transition metal oxide is coated with amorphous carbon, so that the electronic conductivity and the multiplying power performance of the material are improved; (2) The surface of the invention is coated with the layered transition metal oxide, which inhibits the dissolution of transition metal, improves the material circulation performance, and can be used as the positive electrode material of sodium ion batteries.
Drawings
FIG. 1 is a scanning electron microscope image of a sample prepared in example 1.
FIG. 2 is a scanning electron microscope image of the sample prepared in example 2.
FIG. 3 is a scanning electron microscope image of the sample prepared in example 3.
Detailed Description
The present invention is further illustrated below with reference to examples and drawings, but the content of the present invention is not limited thereto.
The preparation method of the surface-coated layered transition metal oxide electrode and the electrochemical performance test thereof comprise the following specific steps:
the surface-coated layered transition metal oxide powder prepared by the invention, superconducting carbon black (Super P) and polyvinylidene fluoride (PVDF) are mixed according to the mass ratio of 8:1:1 are evenly mixed and then dissolved in N-methyl pyrrolidone (NMP) and coated on the surface of an aluminum foil, and then dried in a vacuum oven at 80 ℃ for 10 hours, thus obtaining the surface-coated layered transition metal oxide electrode.
The surface-coated layered transition metal oxide electrode is used as a positive electrode, a sodium metal sheet is used as a negative electrode, and 1.0mol/LNaPF is used 6 And (3) taking propylene carbonate as electrolyte, assembling the propylene carbonate into a half cell in a glove box in an argon atmosphere, and detecting electrochemical properties of the surface-coated layered transition metal oxide electrode material, wherein the electrochemical properties comprise specific capacity, rate capability, cycle stability and first coulombic efficiency, and the test voltage range is 2.5-4.5V.
In the examples described below, the amount of melamine added is calculated as the percentage of the mass of melamine relative to the total mass of transition metal oxide and sodium carbonate.
Example 1
MnO is added to 2 Ball milling and mixing sodium carbonate in proportion, heating at 900 deg.c for 15 hr to obtain Na 0.67 MnO 2 . Na is mixed with 0.67 MnO 2 Powder, 3wt% of melamine and 1wt% of thiourea are taken as raw materials, the powder is obtained after ball milling and mixing, and the surface-coated layered transition metal oxide powder is obtained after heating treatment for 5 hours in an argon atmosphere at 300 ℃.
Example 2
MnO is added to 2 Ball milling and mixing sodium carbonate in proportion, heating at 900 deg.c for 15 hr to obtain Na 0.67 MnO 2 . Na is mixed with 0.67 MnO 2 Powder, 3wt% of melamine and 1wt% of disodium hydrogen phosphate are taken as raw materials, the raw materials are ball-milled and mixed uniformly to obtain powder, and the powder is heated for 5 hours in an argon atmosphere at 300 ℃ to obtain the surface-coated layered transition metal oxide powder.
Example 3
MnO is added to 2 Ball milling and mixing sodium carbonate in proportion, heating at 900 deg.c for 15 hr to obtain Na 0.67 MnO 2 . Na is mixed with 0.67 MnO 2 Powder, 3wt% of melamine, 1wt% of sodium sulfate and 1wt% of sodium phosphate are taken as raw materials, the powder is obtained after ball milling and uniform mixing, and the surface-coated layered transition metal oxide powder is obtained after heating treatment for 5 hours in an argon atmosphere at 300 ℃.
Example 4
MnO is added to 2 Ball milling and mixing sodium carbonate in proportion, heating at 900 deg.c for 18 hr to obtain Na 0.67 MnO 2 . Na is mixed with 0.67 MnO 2 Powder, 5wt% of melamine, 5wt% of sodium sulfate and 5wt% of sodium phosphate are taken as raw materials, the powder is obtained after ball milling and uniform mixing, and the surface-coated layered transition metal oxide powder is obtained after heating treatment for 5 hours in an argon atmosphere at 600 ℃.
Example 5
MnO is added to 2 Ball milling and mixing sodium carbonate in proportion, heating at 900 deg.c for 18 hr to obtain Na 0.67 MnO 2 . Na is mixed with 0.67 MnO 2 Powder, 2wt% of melamine, 1wt% of sodium sulfate and 1wt% of sodium phosphate are taken as raw materials, the powder is obtained after ball milling and uniform mixing, and the surface-coated layered transition metal oxide powder is obtained after heating treatment for 2 hours in an argon atmosphere at 300 ℃.
Comparative example
Comparative example with Na 0.67 MnO 2 As a positive electrode material, the capacity retention rate after 100 cycles in the voltage range of 0.02A/g and 2.5 to 4.5V was 43.5%.
TABLE 1
Claims (9)
1. The surface-coated layered transition metal oxide positive electrode material is characterized in that the surface of the material consists of S or P doped amorphous carbon, and the near surface of the material consists of N doped layered transition metal oxide Na α MnO 2-z N z The material phase is layered transition metal oxide Na β MnO 2 The composition is that the near-surface and bulk phases of the material have no transition metal offset or vacancy, and z is more than or equal to 0.05 and less than or equal to 0.1,0.6, alpha is more than or equal to 1,0.55 and beta is more than or equal to 0.95.
2. The surface-coated layered transition metal oxide positive electrode material according to claim 1, wherein the thickness of the surface and the near surface of the surface-coated layered transition metal oxide positive electrode material is 2 to 10nm.
3. The method for preparing a surface-coated layered transition metal oxide positive electrode material according to claim 1 or 2, characterized by comprising the specific steps of:
the preparation method comprises the steps of taking transition metal oxide and sodium carbonate as raw materials, uniformly ball-milling and mixing according to stoichiometric ratio, performing heat treatment for 15-18 h in an air atmosphere at 900+/-10 ℃, cooling to obtain precursor powder, uniformly mixing and ball-milling the precursor powder, melamine, a sulfur source and/or a phosphorus source, and performing heat treatment for 2-5 h in a nitrogen or argon atmosphere at 300-600 ℃ to obtain the surface-coated layered transition metal oxide.
4. The process according to claim 3, wherein the transition metal oxide is Mn 2 O 3 Or MnO 2 。
5. The method according to claim 3, wherein the phosphorus source is one or more of sodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium hypophosphite, and sodium metaphosphate.
6. A method of preparing according to claim 3, wherein the sulfur source is one or more of thiourea, sodium sulfate, sodium bisulfate.
7. A production method according to claim 3, characterized in that the mass of melamine is 2% -5% of the total mass of transition metal oxide and sodium carbonate.
8. The method according to claim 3, wherein the mass of the sulfur source or the phosphorus source is 1 to 5% of the total mass of the transition metal oxide and the sodium carbonate.
9. Use of the surface-coated layered transition metal oxide positive electrode material according to claim 1 or 2 in sodium ion batteries.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107946564A (en) * | 2017-11-16 | 2018-04-20 | 武汉理工大学 | Rich sodium manganese base Na4Mn2O5/Na0.7MnO2Composite material and its preparation method and application |
| CN112830521A (en) * | 2019-11-22 | 2021-05-25 | 南京理工大学 | F-doped P2-Na0.7MnO2Electrode material and preparation method thereof |
| KR20220008612A (en) * | 2020-07-14 | 2022-01-21 | 한국과학기술연구원 | Cathode active material for sodium ion battery and method for preparing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107946564A (en) * | 2017-11-16 | 2018-04-20 | 武汉理工大学 | Rich sodium manganese base Na4Mn2O5/Na0.7MnO2Composite material and its preparation method and application |
| CN112830521A (en) * | 2019-11-22 | 2021-05-25 | 南京理工大学 | F-doped P2-Na0.7MnO2Electrode material and preparation method thereof |
| KR20220008612A (en) * | 2020-07-14 | 2022-01-21 | 한국과학기술연구원 | Cathode active material for sodium ion battery and method for preparing the same |
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