CN117457889A - Na (Na) 2 Ti 7 O 15 Doped with Na 2 Ti 3 O 7 Sodium titanate electrode material, and preparation method and application thereof - Google Patents
Na (Na) 2 Ti 7 O 15 Doped with Na 2 Ti 3 O 7 Sodium titanate electrode material, and preparation method and application thereof Download PDFInfo
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- 239000011734 sodium Substances 0.000 title claims abstract description 171
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000007772 electrode material Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims description 17
- 239000010936 titanium Substances 0.000 claims abstract description 178
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 56
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 40
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 26
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 239000013078 crystal Substances 0.000 claims abstract description 20
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 20
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000002073 nanorod Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 9
- 238000000498 ball milling Methods 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 9
- 230000000630 rising effect Effects 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000012071 phase Substances 0.000 abstract description 30
- 239000000463 material Substances 0.000 abstract description 21
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 8
- 238000009792 diffusion process Methods 0.000 abstract description 8
- 229910052708 sodium Inorganic materials 0.000 abstract description 8
- 238000003860 storage Methods 0.000 abstract description 8
- 238000009830 intercalation Methods 0.000 abstract description 5
- 230000002687 intercalation Effects 0.000 abstract description 5
- 238000009831 deintercalation Methods 0.000 abstract description 4
- 230000003247 decreasing effect Effects 0.000 abstract description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 3
- 238000009768 microwave sintering Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 7
- 238000000713 high-energy ball milling Methods 0.000 description 7
- 238000003837 high-temperature calcination Methods 0.000 description 7
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 5
- 238000013508 migration Methods 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229910001414 potassium ion Inorganic materials 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000731 high angular annular dark-field scanning transmission electron microscopy Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000000851 scanning transmission electron micrograph Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a Na 2 Ti 7 O 15 Doped with Na 2 Ti 3 O 7 The electrode material is a porous block structure formed by stacking nano rods; synthesized by a simple solid phase method, precursor sodium carbonate and anatase phase titanium dioxide are ball-milled according to a proportion, and then are obtained by microwave sintering in air, na 2 Ti 7 O 15 Is added to Na 2 Ti 3 O 7 Sodium titanate (100) has increased sodium storage crystal face exposure while (003) crystal face exposure is decreased; na (Na) 2 Ti 7 O 15 There are 4 TiO in one structural unit 6 Octahedron with more sodium storage sites and wider sodium ion diffusion channels improves the specific capacity and rate capability of the material. Na (Na) 2 Ti 7 O 15 Upper and lower layers of TiO 6 The octahedrons are connected with each other, and the structure of the octahedrons is more stable in the sodium ion intercalation/deintercalation process, so that the long-cycle stability of the material is improved.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to Na 2 Ti 7 O 15 Doped with Na 2 Ti 3 O 7 Sodium titanate electrode material, and preparation method and application thereof.
Background
In recent years, lithium ion batteries have achieved great success in the fields of portable electronic devices and electric automobiles, resulting in an increasing demand for lithium resources. With the great increase of the cost of lithium resources, sodium ion batteries are considered as ideal substitutes for lithium ion batteries due to the advantages of abundant resources, low cost, high efficiency and the like. For sodium ion batteries, a large number of electrode materials have been explored but low voltage negative electrode materials comparable to graphite negative electrodes in lithium ion batteries are severely deficient. Titanium-based materials due to their abundant crystal forms, moderate Ti 3+ /Ti 4+ Low potential redox couples, and low cost have led to a great deal of research interest as negative electrode materials for sodium ion batteries.
In various titanium-based anode materials of sodium ion batteries, na 2 Ti 3 O 7 Due to its special titanyl octahedral zigzag layered structure, 0.3V (vs. Na/Na + ) Average low sodium intercalation plateau and 177mAh g -1 Is considered to be a very potential negative electrode material. Research has found that Na 2 Ti 3 O 7 Is not high and sodium ions migrate preferably along these zigzag layers rather than through these layers in order to meet the minimum energy principle, so the number and length of sodium ion migration channels and the stability of the channels are limiting Na 2 Ti 3 O 7 Key factors for migration and intercalation/deintercalation of sodium ions.
In recent years, in order to shorten the sodium ion migration path, the ion diffusion channel is widened and the interlayer structure is stabilized during charge and discharge to obtain Na 2 Ti 3 O 7 The nano design and doping of other elements are mainstream strategies, but the nano preparation method is high in cost and low in yield, is difficult to realize in industrial production, and cannot well solve the problem of structural collapse caused by the sliding and expanding of the layered material in the charge and discharge process due to simple ion doping.
The patent application of the subject group is a potassium-doped sodium titanate electrode material, a preparation method and application thereof (202211220673.9) which are characterized in that potassium ions are used for doping the sodium titanate electrode material, and pure-phase potassium-doped Na is obtained after calcination due to the existence of the potassium ions 2 Ti 3 O 7 Crystalline phase, na 2 Ti 3 O 7 Part of sodium ions in the crystal phase are replaced by potassium ions, and the method is a method for shortening the migration path of sodium ions by utilizing ion doping.
The application adopts completely different doping directions and adopts a crystal phase doping mode, and adopts the method of doping Na 2 Ti 7 O 15 Doped to Na 2 Ti 3 O 7 The strategy of increasing sodium ion storage sites, widening sodium ion diffusion channels and stabilizing structural changes in the charge-discharge process is not reported before. And the strategy adopts a microwave-assisted solid phase method to synthesize the material. The preparation method is simple, the yield is high, and the industrial production is easy to realize.
Disclosure of Invention
In view of the above problems in the prior art, the present invention provides a Na 2 Ti 7 O 15 Doped with Na 2 Ti 3 O 7 Sodium titanate electrode material, and preparation method and application thereof.
In order to achieve the above purpose, the present invention provides the following technical solutions:
na (Na) 2 Ti 7 O 15 Doped with Na 2 Ti 3 O 7 The structure of the sodium titanate electrode material is a porous block structure formed by stacking nano rods, and the diameter of the sodium titanate electrode material is 100-400nm.
Preferably Na 2 Ti 7 O 15 Crystalline phase is regularly doped in Na 2 Ti 3 O 7 And (3) a crystal phase.
Microwave-assisted Na 2 Ti 7 O 15 Doped with Na 2 Ti 3 O 7 The sodium titanate negative electrode material has preferential orientation, and the (100) crystal face exposure is increased and the (003) crystal face exposure is reduced. Na (Na) 2 Ti 7 O 15 The presence of (a) results in an increase in the sodium storage sites of the materialIn this case, the diffusion channel of sodium ions is widened, and the interlayer structure can be stabilized in the charge and discharge process.
The invention also provides a method for preparing Na 2 Ti 7 O 15 Doped with Na 2 Ti 3 O 7 A method of sodium titanate electrode material comprising the steps of:
(1) Ball milling and mixing are carried out on sodium carbonate and anatase phase titanium dioxide, and a precursor mixture which is uniformly mixed is obtained;
(2) Placing the precursor mixture which is uniformly mixed into a microwave tube furnace, and calcining in an air atmosphere to obtain Na 2 Ti 7 O 15 Doped with Na 2 Ti 3 O 7 Sodium titanate electrode material.
Preferably, the sodium carbonate: molar ratio of anatase phase titanium dioxide= (1.5-1.99): 6.
preferably, the temperature rising rate of calcination in a microwave tube furnace is 5-10 ℃/min, the calcination temperature is 800-1100 ℃, and the calcination time is 20-60 min.
In addition, the invention also provides Na as above 2 Ti 7 O 15 Doped with Na 2 Ti 3 O 7 The application of the sodium titanate electrode material in sodium ion batteries.
The beneficial effects of the invention are as follows:
(1) The precursors of the electrode material are low-cost sodium carbonate and titanium dioxide;
(2) The preparation method of the material is simple, the solid phase method is adopted for synthesis, the precursor is obtained by microwave sintering in the air after ball milling according to a proportion, and the phase doped sodium titanate electrode material can be obtained by reducing the ratio of sodium carbonate;
(3) Na is mixed with 2 Ti 7 O 15 Doped with Na 2 Ti 3 O 7 Sodium titanate used as negative electrode material applied to sodium ion battery due to Na 2 Ti 7 O 15 Is added to Na 2 Ti 3 O 7 The sodium titanate (100) has increased sodium storage crystal face exposure and decreased (003) crystal face exposure. At the same time due to Na 2 Ti 7 O 15 There are 4 TiO in one structural unit 6 Octahedron, compared with Na 2 Ti 3 O 7 In one structural unit, 3 TiO are present 6 Octahedron with more sodium storage sites and wider sodium ion diffusion channels improves the specific capacity and rate capability of the material. Compared with Na 2 Ti 3 O 7 TiO with upper and lower layers separated from layered material 6 Octahedron, na 2 Ti 7 O 15 Upper and lower layers of TiO 6 The octahedrons are connected with each other, and the structure of the octahedrons is more stable in the sodium ion intercalation/deintercalation process, so that the long-cycle stability of the material is improved.
Drawings
FIG. 1 is a Na prepared in example 5 2 Ti 7 O 15 Doped with Na 2 Ti 3 O 7 Sodium titanate electrode Material 1.9Na 2 Ti 3 O 7 &Na 2 Ti 7 O 15 And Na prepared in comparative example 1 2 Ti 3 O 7 X-ray diffraction pattern of sodium titanate electrode material.
FIG. 2 is a Na prepared in example 5 2 Ti 7 O 15 Doped with Na 2 Ti 3 O 7 Sodium titanate electrode Material 1.9Na 2 Ti 3 O 7 &Na 2 Ti 7 O 15 Is a field emission scanning electron microscope image of (1).
FIG. 3 is a Na prepared in example 5 2 Ti 7 O 15 Doped with Na 2 Ti 3 O 7 Sodium titanate electrode Material 1.9Na 2 Ti 3 O 7 &Na 2 Ti 7 O 15 Is a high angle annular dark field spherical aberration correcting scanning transmission electron microscopy image.
FIG. 4 is a Na prepared in example 1 2 Ti 7 O 15 Doped with Na 2 Ti 3 O 7 Sodium titanate electrode material 1.5Na 2 Ti 3 O 7 &Na 2 Ti 7 O 15 First charge-discharge voltage versus specific capacity.
FIG. 5 is a Na prepared in example 2 2 Ti 7 O 15 Doped with Na 2 Ti 3 O 7 Sodium titanate electrode Material 1.6Na 2 Ti 3 O 7 &Na 2 Ti 7 O 15 First charge-discharge voltage versus specific capacity.
FIG. 6 is a Na prepared in example 3 2 Ti 7 O 15 Doped with Na 2 Ti 3 O 7 Sodium titanate electrode Material 1.7Na 2 Ti 3 O 7 &Na 2 Ti 7 O 15 First charge-discharge voltage versus specific capacity.
FIG. 7 is a Na prepared in example 4 2 Ti 7 O 15 Doped with Na 2 Ti 3 O 7 Sodium titanate electrode Material 1.8Na 2 Ti 3 O 7 &Na 2 Ti 7 O 15 First charge-discharge voltage versus specific capacity.
FIG. 8 is a Na prepared in example 5 2 Ti 7 O 15 Doped with Na 2 Ti 3 O 7 Sodium titanate electrode Material 1.9Na 2 Ti 3 O 7 &Na 2 Ti 7 O 15 First charge-discharge voltage versus specific capacity.
FIG. 9 is a Na prepared in example 6 2 Ti 7 O 15 Doped with Na 2 Ti 3 O 7 Sodium titanate electrode material 1.99Na 2 Ti 3 O 7 &Na 2 Ti 7 O 15 First charge-discharge voltage versus specific capacity.
FIG. 10 is a Na prepared in comparative example 1 2 Ti 3 O 7 And a graph of the first charge-discharge voltage and specific capacity of the sodium titanate electrode material.
FIG. 11 is a Na prepared in example 5 2 Ti 7 O 15 Doped with Na 2 Ti 3 O 7 Sodium titanate electrode Material 1.9Na 2 Ti 3 O 7 &Na 2 Ti 7 O 15 And Na prepared in comparative example 1 2 Ti 3 O 7 The rate performance of the sodium titanate electrode material is shown in the graph (circle: example 5; triangle: comparative example 1).
Detailed Description
In order to make the technical solution of the present invention better understood by those skilled in the art, the technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings, and based on the embodiments in the present application, other similar embodiments obtained by those skilled in the art without making creative efforts should fall within the scope of protection of the present application.
Example 1:
the present example relates to Na 2 Ti 7 O 15 Doped with Na 2 Ti 3 O 7 The preparation method of the sodium titanate electrode material comprises the following steps: at room temperature, 0.795g of sodium carbonate and 2.396g of anatase phase titanium dioxide (the molar ratio of the sodium carbonate to the anatase phase titanium dioxide is 1.5:6) are placed in a high-energy ball milling tank for ball milling for 1 hour, and a precursor which is uniformly mixed is obtained; then placing the precursor in a microwave tube furnace for high-temperature calcination, specifically: the temperature rising rate is set to 5 ℃ per minute, and the mixture is calcined for 60 minutes in the air atmosphere at 800 ℃ to obtain Na 2 Ti 7 O 15 Doped with Na 2 Ti 3 O 7 Sodium titanate electrode material (1.5 Na 2 Ti 3 O 7 &Na 2 Ti 7 O 15 )。
Example 2:
the present example relates to Na 2 Ti 7 O 15 Doped with Na 2 Ti 3 O 7 The preparation method of the sodium titanate electrode material comprises the following steps: at room temperature, 0.848g of sodium carbonate and 2.396g of anatase phase titanium dioxide (the molar ratio of the sodium carbonate to the anatase phase titanium dioxide is 1.6:6) are placed in a high-energy ball milling tank for ball milling for 1 hour, and a precursor which is uniformly mixed is obtained; then placing the precursor in a microwave tube furnace for high-temperature calcination, specifically: the temperature rising rate is set to 6 ℃ per minute, and the mixture is calcined for 50 minutes in the air atmosphere at 850 ℃ to obtain Na 2 Ti 7 O 15 Doped with Na 2 Ti 3 O 7 Sodium titanate electrode material (1.6 Na 2 Ti 3 O 7 &Na 2 Ti 7 O 15 )。
Example 3:
the present example relates to Na 2 Ti 7 O 15 Doped with Na 2 Ti 3 O 7 The preparation method of the sodium titanate electrode material comprises the following steps: at room temperature, 0.901g of sodium carbonate and 2.396g of anatase phase titanium dioxide (the molar ratio of the sodium carbonate to the anatase phase titanium dioxide is 1.7:6) are placed in a high-energy ball milling tank for ball milling for 1 hour, and a precursor which is uniformly mixed is obtained; then placing the precursor in a microwave tube furnace for high-temperature calcination, specifically: the temperature rising rate is set to 7 ℃ per minute, and the mixture is calcined for 40 minutes in the air atmosphere at 900 ℃ to obtain Na 2 Ti 7 O 15 Doped with Na 2 Ti 3 O 7 Sodium titanate electrode material (1.7 Na 2 Ti 3 O 7 &Na 2 Ti 7 O 15 )。
Example 4:
the present example relates to Na 2 Ti 7 O 15 Doped with Na 2 Ti 3 O 7 The preparation method of the sodium titanate electrode material comprises the following steps: at room temperature, 0.954g of sodium carbonate and 2.396g of anatase phase titanium dioxide (the molar ratio of the sodium carbonate to the anatase phase titanium dioxide is 1.8:6) are placed in a high-energy ball milling tank for ball milling for 1 hour, and a precursor which is uniformly mixed is obtained; then placing the precursor in a microwave tube furnace for high-temperature calcination, specifically: the temperature rising rate is set to 8 ℃ per minute, and the mixture is calcined for 30 minutes in air atmosphere at 1000 ℃ to obtain Na 2 Ti 7 O 15 Doped with Na 2 Ti 3 O 7 Sodium titanate electrode material (1.8 Na 2 Ti 3 O 7 &Na 2 Ti 7 O 15 )。
Example 5:
the present example relates to Na 2 Ti 7 O 15 Doped with Na 2 Ti 3 O 7 The preparation method of the sodium titanate electrode material comprises the following steps: at room temperature, 1.007g of sodium carbonate and 2.396g of anatase phase titanium dioxide (the molar ratio of the sodium carbonate to the anatase phase titanium dioxide is 1.9:6) are placed in a high-energy ball milling tank for ball milling for 1 hour, and a precursor which is uniformly mixed is obtained; then the precursor isThe body is placed in a microwave tube type furnace for high-temperature calcination, and specifically comprises the following steps: the temperature rising rate is set to 10 ℃ per minute, and the mixture is calcined for 20 minutes in air atmosphere at 850 ℃ to obtain Na 2 Ti 7 O 15 Doped with Na 2 Ti 3 O 7 Sodium titanate electrode material (1.9 Na 2 Ti 3 O 7 &Na 2 Ti 7 O 15 )。
For Na prepared in this example 2 Ti 7 O 15 Doped with Na 2 Ti 3 O 7 Sodium titanate electrode Material 1.9Na 2 Ti 3 O 7 &Na 2 Ti 7 O 15 Characterization was performed. The material was structurally characterized by an X-ray diffractometer and the results are shown in figure 1. As can be seen from FIG. 1, the diffraction peaks of the prepared material are compared with Na 2 Ti 3 O 7 And Na (Na) 2 Ti 7 O 15 The DFT standard card of (C) shows consistent crystal phase, which indicates that the embodiment successfully prepares Na 2 Ti 7 O 15 Doped with Na 2 Ti 3 O 7 Sodium titanate material (1.9 Na 2 Ti 3 O 7 &Na 2 Ti 7 O 15 ). In fig. 1, it can be seen that the diffraction intensity of the 10.527 ° (100) crystal plane is enhanced, and the diffraction intensity of the 29.929 ° (003) crystal plane is relatively reduced, indicating Na 2 Ti 7 O 15 The addition of (3) causes a preferential orientation of the crystal such that the (100) crystal face exposure is increased and the (003) crystal face exposure is relatively decreased, which causes the diffusion channel of sodium ions to become shorter while being increased. Is favorable for the diffusion and storage of sodium ions.
1.9Na by field emission scanning electron microscopy (FE-SEM) 2 Ti 3 O 7 &Na 2 Ti 7 O 15 The morphology of the material was characterized and the results are shown in figure 2. As can be seen from FIG. 2, the prepared material has a porous block structure formed by stacking nano rods, and the diameter of the rods is 100-400nm.
Scanning transmission electron microscope (HAADF-STEM) pair 1.9Na by high angle annular dark field spherical aberration correction 2 Ti 3 O 7 &Na 2 Ti 7 O 15 Material feedThe rows are characterized and the results are shown in figure 3. As can be seen from FIG. 3, na was prepared 2 Ti 3 O 7 Regular appearance of Na in the crystalline phase 2 Ti 7 O 15 Is a crystal phase of (a) indicating Na 2 Ti 7 O 15 Successfully dope into Na 2 Ti 3 O 7 And (3) a crystal phase. Due to Na 2 Ti 7 O 15 There are 4 TiO in one structural unit 6 Octahedron, compared with Na 2 Ti 3 O 7 In one structural unit, 3 TiO are present 6 Octahedron with more sodium storage sites and wider sodium ion diffusion channels improves the specific capacity and rate capability of the material. Compared with Na 2 Ti 3 O 7 TiO with upper and lower layers separated from layered material 6 Octahedron, na 2 Ti 7 O 15 Upper and lower layers of TiO 6 The octahedrons are connected with each other, and the structure of the octahedrons is more stable in the sodium ion intercalation/deintercalation process, so that the long-cycle stability of the material is improved.
Example 6:
the present example relates to Na 2 Ti 7 O 15 Doped with Na 2 Ti 3 O 7 The preparation method of the sodium titanate electrode material comprises the following steps: 1.054g of sodium carbonate and 2.396g of anatase phase titanium dioxide (the molar ratio of sodium carbonate to anatase phase titanium dioxide is 1.99:6) are placed in a high-energy ball milling tank for ball milling for 1 hour at room temperature, and a precursor which is uniformly mixed is obtained; then placing the precursor in a microwave tube furnace for high-temperature calcination, specifically: the temperature rising rate is set to 10 ℃ per minute, and the mixture is calcined for 20 minutes in the air atmosphere at 1100 ℃ to obtain Na 2 Ti 7 O 15 Doped with Na 2 Ti 3 O 7 Sodium titanate electrode material (1.99 Na 2 Ti 3 O 7 &Na 2 Ti 7 O 15 )。
Comparative example 1:
this example relates to pure phase Na 2 Ti 3 O 7 The preparation method of the sodium titanate electrode material comprises the following steps: 1.060g of sodium carbonate and 2.396g of anatase phase titanium dioxide were placed in a high energy ball milling jar at room temperatureBall milling for 1 hour to obtain a precursor which is uniformly mixed; then placing the precursor in a microwave tube furnace for high-temperature calcination, specifically: the temperature rising rate is set to 10 ℃ per minute, and the mixture is calcined for 20 minutes in an air atmosphere at 850 ℃ to obtain the sodium titanate electrode material (Na 2 Ti 3 O 7 )。
For Na prepared in this example 2 Ti 3 O 7 The sodium titanate electrode material was subjected to structural characterization by an X-ray diffractometer, and the result is shown in fig. 1. As can be seen from FIG. 1, the diffraction peaks of the prepared material are compared with Na 2 Ti 3 O 7 The DFT standard card of (C) shows consistent crystal phase, which indicates that the embodiment successfully prepares pure phase Na 2 Ti 3 O 7 Sodium titanate material. For Na 2 Ti 7 O 15 Doped with Na 2 Ti 3 O 7 Sodium titanate electrode material and Na 2 Ti 3 O 7 The electrochemical performance test experiment of the sodium titanate electrode material comprises the following specific steps:
na obtained in examples 1 to 6 2 Ti 7 O 15 Doped with Na 2 Ti 3 O 7 Sodium titanate material and Na obtained in comparative example 1 2 Ti 3 O 7 Sodium titanate electrode material is used as negative electrode of sodium ion battery, metallic sodium is used as counter electrode, glass fiber is used as diaphragm, sodium perchlorate (NaPF is used 6 ) As an electrolyte, a CR2032 button cell case was packaged in an argon atmosphere glove box to obtain Na 2 Ti 7 O 15 Doped with Na 2 Ti 3 O 7 Half cell of sodium titanate electrode material and Na 2 Ti 3 O 7 Sodium titanate electrode material half cell. At 0.1C (1c=177 mA g -1 ) Electrochemical performance tests were performed at a rate of 0.01 to 2.5V, and the specific capacities obtained are shown in table 1. Electrochemical rate performance tests were performed at 0.1, 0.2, 0.5, 1, 2, 5, 10 and 20C rates, and voltage ranges of 0.01-2.5V, and the resulting rate performance is shown in fig. 11.
TABLE 1 EXAMPLES 1 to 6Na 2 Ti 7 O 15 Doped with Na 2 Ti 3 O 7 Sodium titanate electrode material and Na of comparative example 1 2 Ti 3 O 7 Specific charge capacity (mAh g) of sodium titanate electrode material -1 )。
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (6)
1. Na (Na) 2 Ti 7 O 15 Doped with Na 2 Ti 3 O 7 The sodium titanate electrode material is characterized in that the structure is a porous block structure formed by stacking nano rods, and the diameter of the porous block structure is 100-400nm.
2. The sodium titanate electrode material of claim 1, wherein Na 2 Ti 7 O 15 Crystalline phase is regularly doped in Na 2 Ti 3 O 7 And (3) a crystal phase.
3. A process for preparing Na according to claim 1 or 2 2 Ti 7 O 15 Doped with Na 2 Ti 3 O 7 A method of sodium titanate electrode material, comprising the steps of:
(1) Ball milling and mixing are carried out on sodium carbonate and anatase phase titanium dioxide, and a precursor mixture which is uniformly mixed is obtained;
(2) Placing the precursor mixture which is uniformly mixed into a microwave tube furnace, and calcining in an air atmosphere to obtain Na 2 Ti 7 O 15 Doped with Na 2 Ti 3 O 7 Sodium titanate electrode material.
4. A Na according to claim 3 2 Ti 7 O 15 Doped with Na 2 Ti 3 O 7 The preparation method of the sodium titanate electrode material is characterized in that the sodium carbonate: molar ratio of anatase phase titanium dioxide= (1.50-1.99): 6.
5. a Na according to claim 3 2 Ti 7 O 15 Doped with Na 2 Ti 3 O 7 The preparation method of the sodium titanate electrode material is characterized in that the temperature rising rate of calcination in a microwave tube furnace is 5-10 ℃/min, the calcination temperature is 800-1100 ℃, and the calcination time is 20-60 min.
6. Na as claimed in claim 1 or 2 2 Ti 7 O 15 Doped with Na 2 Ti 3 O 7 The application of the sodium titanate electrode material in sodium ion batteries.
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