CN114695855A - Lithium/titanium co-doped sodium ion battery composite cathode material and preparation method and application thereof - Google Patents
Lithium/titanium co-doped sodium ion battery composite cathode material and preparation method and application thereof Download PDFInfo
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- 239000010936 titanium Substances 0.000 title claims abstract description 92
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 33
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 29
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 28
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 28
- 239000002131 composite material Substances 0.000 title claims abstract description 16
- 239000010406 cathode material Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000011734 sodium Substances 0.000 claims abstract description 95
- 238000000498 ball milling Methods 0.000 claims abstract description 18
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- 229910052718 tin Inorganic materials 0.000 claims abstract description 6
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 6
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 239000011572 manganese Substances 0.000 claims description 80
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 77
- 150000001875 compounds Chemical class 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000007774 positive electrode material Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000010405 anode material Substances 0.000 claims description 3
- 238000003837 high-temperature calcination Methods 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 37
- 230000004888 barrier function Effects 0.000 abstract description 5
- 230000008859 change Effects 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 238000009831 deintercalation Methods 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 16
- 229910001416 lithium ion Inorganic materials 0.000 description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
- 238000010532 solid phase synthesis reaction Methods 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000004146 energy storage Methods 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 238000007605 air drying Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- SWAIALBIBWIKKQ-UHFFFAOYSA-N lithium titanium Chemical compound [Li].[Ti] SWAIALBIBWIKKQ-UHFFFAOYSA-N 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
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- 238000000227 grinding Methods 0.000 description 2
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052714 tellurium Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- 229910012465 LiTi Inorganic materials 0.000 description 1
- 229910003069 TeO2 Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000001000 micrograph 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
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000012254 powdered material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention discloses a lithium/titanium co-doped sodium ion battery composite cathode material and a preparation method and application thereof, wherein the cathode material has a chemical general formula as follows: na (Na)aLibTicMndNieMfO2Wherein a is more than or equal to 0.67 and less than or equal to 0.8, b is more than 0.05 and less than 0.20, c is more than 0.03 and less than 0.10, d is more than 0.50 and less than 0.67, e is more than 0.10 and less than 0.33, f is more than or equal to 0 and less than 0.08, b + c + d + e + f is 1, b/c is more than or equal to 1 and less than or equal to 4, M is one or more of Co, Fe, Mg, Zn, Cu, Al, Sn, Zr and Cr, and all metal sources are firstly mixed by ball milling; then tabletting is carried out; finally, the step ofCalcining at high temperature to obtain the catalyst. The invention obviously inhibits the phase change of the material under high pressure and inhibits Na through the codoping of lithium and titanium+The vacancy ordering phenomenon, thereby reducing the energy barrier of sodium ion deintercalation and obviously improving the multiplying power performance of the material.
Description
Technical Field
The invention relates to a lithium/titanium co-doped sodium-ion battery composite cathode material and a preparation method and application thereof, belonging to the technical field of sodium-ion batteries.
Background
With the increasing concern of people on global energy crisis and environmental protection problems, the demand for green and renewable energy sources is increasing, and the reserves of new energy sources such as solar energy, wind energy, geothermal energy, tidal energy and the like are large and environment-friendly, but the defects of being limited by natural conditions, namely discontinuity in time and nonuniformity in space, exist at the same time. These make direct grid-connected utilization of new energy sources hindered, so that the efficient energy storage system is very important as a storage medium of new energy sources. In the current energy storage field, lithium ion batteries occupy the main market share, however, in recent years, new energy automobiles and portable 3C electronic products have been developed rapidly, which makes the demand of lithium ion batteries increase sharply. However, global lithium resources are in a relatively scarce state, and the imbalance between market demand and supply causes the cost of lithium ion batteries to rise rapidly, which is very disadvantageous for large-scale energy storage devices requiring low-cost batteries. Therefore, a low-cost substitute for a lithium ion battery is urgently needed in the field of energy storage, a sodium ion battery which has the same working principle and similar chemical components with the lithium ion battery is widely concerned due to the advantages of abundant sodium resources, low cost, good comprehensive performance and the like, the problem of limited development of the energy storage battery caused by lithium resource shortage can be relieved to a certain extent, the sodium ion battery is an important supplement of the lithium ion battery, and meanwhile, the lithium ion battery can gradually replace a lead-acid battery and is expected to play an important role in novel energy storage application.
Layered oxide positive electrode material (Na) of sodium ion batteryxTMO2) And lithium ion battery cathode material (Li) which is already in commercial usexTMO2) The sodium ion battery cathode material has similar structure and synthesis process, has the advantages of environmental friendliness, higher energy density, simple synthesis process and the like, and is widely considered as the sodium ion battery cathode material which is most hopeful to be industrialized. However, sodium ions have a larger radius than lithium ions, so that there are certain differences in ion transport, bulk phase structure evolution, interface properties, and the like. During the diffusion process of sodium ions, a larger migration energy barrier needs to be overcome, and the rate performance of the material is influenced. Meanwhile, Na appears in the layered oxide cathode material+Vacancy ordering phenomena, mainly due to charge ordering in the transition metal layer and strong Na in the alkali metal layer+-Na+Caused by interaction, when Na is in the sodium layer+When the Fermi levels between adjacent TM1 and TM2 are close, the migration of Na layer sites frequently occurs, which usually shows higher Na content in the de-intercalation process+The migration energy barrier and the stepped voltage plateau in the electrochemical curve limit the rate capability and cycle capability.
Disclosure of Invention
The invention aims to provide a lithium/titanium co-doped sodium ion battery composite positive electrode material and a preparation method and application thereof+The vacancy ordering phenomenon, thereby improving the structural stability and the sodium ion diffusion coefficient, and further improving the multiplying power performance of the material.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a lithium/titanium co-doped sodium-ion battery composite cathode material is represented by a chemical general formula: na (Na)aLibTicMndNieMfO2Wherein a is more than or equal to 0.67 and less than or equal to 0.8, b is more than 0.05 and less than 0.20, c is more than 0.03 and less than 0.10, d is more than 0.50 and less than 0.67, e is more than 0.10 and less than 0.33, f is more than or equal to 0 and less than 0.08, b + c + d + e + f is 1, b/c is more than or equal to 1 and less than or equal to 4, and M is one or more of Co, Fe, Mg, Zn, Cu, Al, Sn, Zr and Cr.
The invention also provides a preparation method of the lithium/titanium co-doped sodium ion battery composite positive electrode material, which comprises the steps of firstly, ball-milling and uniformly mixing the sodium source compound, the lithium source compound, the titanium source compound, the manganese source compound, the nickel source compound and the M source compound according to the stoichiometric ratio to obtain a mixture; then tabletting the obtained mixture to obtain a sheet; and finally, calcining the obtained sheet at high temperature to obtain the lithium/titanium co-doped sodium ion battery composite anode material.
Preferably, the sodium source compound is one or more of sodium carbonate, sodium hydroxide and sodium bicarbonate.
Preferably, the lithium source compound is one or more of lithium carbonate and lithium hydroxide.
Preferably, the titanium source compound is titanium dioxide.
Preferably, the manganese source compound, the nickel source compound and the M source compound are one or more of corresponding oxides, carbonates and hydroxides.
Preferably, the ball milling speed is 200-. The ball milling can ensure that the raw materials are fully and uniformly mixed, thereby facilitating the full implementation of the subsequent reaction.
Preferably, the mixture is placed in an infrared tabletting mold with the thickness of 15mm for tabletting, and the pressure condition for tabletting is 5MPa-30 MPa. The mixture can be contacted more tightly by tabletting under the pressure, so that the reaction is more sufficient and uniform in the subsequent high-temperature calcination process.
Preferably, the atmosphere of the high-temperature calcination is an oxidizing atmosphere, such as oxygen or air, the temperature is 500-1000 ℃, the time is 5-12 h, and the temperature rise rate is 1-10 ℃/min.
The invention also provides application of the lithium/titanium co-doped sodium ion battery composite positive electrode material in preparation of a sodium ion battery.
The positive electrode material Na of the inventionaLibTicMndNieMfO2Still maintain the pure P2 phase layered crystal structure, present obvious plate crystal with high crystallinity and uniform appearance and particle size.
The key point of the invention is lithium/titanium co-doping, and the respective doping amounts of lithium and titanium and the molar ratio of lithium to titanium are strictly controlled, through the cooperation of the factors, the phase change of the material under high pressure can be obviously inhibited, and Na can be inhibited+The/vacancy ordering phenomenon reduces the energy barrier of sodium ion extraction, and shows excellent rate performance. When other doping modes are adopted, such as single lithium doping or single titanium doping, the material capacity is rapidly attenuated under the high current density (such as 10C and 20C), and is even close to 0 mAh/g; further, for example, Sn, Ca, Mo, V, Te, Zr, W are used in place of NaaLibTicMndNieMfO2In Ti or replacing Na by Mg or CuaLibTicMndNieMfO2Li in the alloy is obviously inferior to Na in rate capabilityaLibTicMndNieMfO2(ii) a If the molar ratio of Li/Ti does not satisfy the interval range of the present invention, the rate capability of the material is greatly influenced.
Compared with the prior art, the invention has the following advantages:
1. the lithium/titanium double-ion co-doping modification method can obviously inhibit the phase change of the material under high pressure and can inhibit Na+Vacancy ordering phenomenon, thereby lowering the energy barrier for sodium ion deintercalation and exhibiting excellent rate capability, such as Li+And Ti4+Codoped Na0.67Mn0.62Ni0.18Li0.15Ti0.05O2Can provide 123mAh g at the current density of 0.2C-1The reversible discharge specific capacity of the material can still release 95mAh g at 5C-1Even at an extreme rate of 20C, can still provide 52mAh g-1And once recovered from the limit rate of 20C to 0.1C, 125mAh g is rapidly recovered-1The specific capacity of (A).
2. The invention adopts a simple solid phase method to prepare the anode material NaaLibTicMndNieMfO2The crystal still maintains a pure P2 phase layered crystal structure, presents obvious plate-shaped crystals with high crystallinity and has uniform appearance and grain size.
Drawings
FIG. 1 shows Na obtained in example 1 of the present invention0.67Mn0.62Ni0.18Li0.15Ti0.05O2X-ray powder diffraction pattern of (a);
FIG. 2 shows Na obtained in example 1 of the present invention0.67Mn0.62Ni0.18Li0.15Ti0.05O2Scanning electron microscope images of (a);
FIG. 3 shows Na obtained in example 1 of the present invention0.67Mn0.62Ni0.18Li0.15Ti0.05O2Transmission electron microscopy images of;
FIG. 4 shows Na obtained in example 1 of the present invention0.67Mn0.62Ni0.18Li0.15Ti0.05O2X-ray energy spectrum analysis of (1);
FIG. 5 shows Na obtained in example 1 of the present invention0.67Mn0.62Ni0.18Li0.15Ti0.05O2The charge-discharge curve chart of (1);
FIG. 6 shows Na obtained in example 1 of the present invention0.67Mn0.62Ni0.18Li0.15Ti0.05O2(NaMNO-LiTi) with Na prepared in comparative example 10.67Mn0.67Ni0.33O2(NaMNO), Na prepared in comparative example 20.67Mn0.62Ni0.33Ti0.05O2(NaMNO-Ti), Na prepared in comparative example 30.67Mn0.67Ni0.18Li0.15O2Graph comparing rate performance of (NaMNO-Li);
FIG. 7 shows Na obtained in example 2 of the present invention0.8Mn0.62Ni0.18Li0.15Ti0.05O2Na prepared in comparative example 10.67Mn0.67Ni0.33O2A graph comparing the rate performance of (1);
FIG. 8 shows Na obtained in example 3 of the present invention0.67Mn0.6Ni0.18Li0.15Ti0.05Cu0.02O2、Na0.67Mn0.6Ni0.18Li0.15Ti0.05Fe0.02O2Na prepared in comparative example 10.67Mn0.67Ni0.33O2A graph comparing the rate performance of (1);
FIG. 9 shows Na obtained in example 4 of the present invention0.67Mn0.62Ni0.13Li0.2Ti0.05O2、Na0.67Mn0.57Ni0.18Li0.15Ti0.1O2Na prepared in example 10.67Mn0.62Ni0.18Li0.15Ti0.05O2A graph comparing the rate performance of (1);
FIG. 10 shows Na obtained in comparative example 4 of the present invention0.67Mn0.64Ni0.18Li0.15Ti0.03O2Na obtained in comparative example 50.6 7Mn0.66Ni0.18Li0.15Ti0.01O2Na prepared in example 10.67Mn0.62Ni0.18Li0.15Ti0.05O2A graph comparing the rate performance of (1);
FIG. 11 is a graph showing that different metal elements in comparative example 6 of the present invention are substituted for Na respectively0.67Mn0.62Ni0.18Li0.15Ti0.05O2Ti of (1) and Na of example 10.67Mn0.62Ni0.18Li0.15Ti0.05O2A graph comparing the rate performance of (1);
FIG. 12 shows comparative examples 7 of the present invention in which Mg and Cu are substituted for Na, respectively0.67Mn0.62Ni0.18Li0.15Ti0.05O2Li (Li) with Na (from example 1)0.67Mn0.62Ni0.18Li0.15Ti0.05O2Graph comparing the rate performance of (1).
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be merely illustrative of specific embodiments of the present invention and not to limit the scope of the claims. Modifications and substitutions to methods, steps or conditions of the present invention may be made without departing from the spirit and substance of the invention.
Example 1
(1) Accurately weighing Na with corresponding mass according to the molar ratio of 0.67:0.15:0.05:0.62:0.182CO3、Li2CO3、TiO2、Mn2O3And NiO, placing the NiO into an agate ball milling tank, adding a proper amount of agate ball milling beads into the tank, adding a proper amount of absolute ethyl alcohol into the tank, placing the ball milling tank into a planetary ball mill, and carrying out ball milling for 5 hours at the rotating speed of 450 r/min. And (4) taking out the ball milling tank after the ball milling is finished, placing the ball milling tank in a 60 ℃ forced air drying oven to dry ethanol, and scraping the ball milled powdery material.
(2) Putting the powdery material into an infrared tabletting mould with the thickness of 15mm, and pressing into a tablet under the pressure of 10MPa to obtain the sheet.
(3) And (3) transferring the sheet into a muffle furnace, pre-burning for 6h at 500 ℃, then calcining for 12h at 850 ℃, and raising the temperature at a rate of 3 ℃/min. After the material is naturally cooled to room temperature, taking out the material from the furnace, grinding the flaky material into fine powder by using an agate mortar to obtain the target product Na0.67Mn0.62Ni0.18Li0.15Ti0.05O2。
Comparative example 1
Na was prepared by the same solid phase method as in example 1 above0.67Mn0.67Ni0.33O2。
Comparative example 2
Na was prepared by the same solid phase method as in example 1 above0.67Mn0.62Ni0.33Ti0.05O2。
Comparative example 3
Na was prepared by the same solid phase method as in example 1 above0.67Mn0.67Ni0.18Li0.15O2。
Battery assembly and electrochemical performance testing.
Mixing the above prepared Na0.67Mn0.62Ni0.18Li0.15Ti0.05O2(Na0.67Mn0.67Ni0.33O2Or Na0.67Mn0.62Ni0.33Ti0.05O2Or Na0.67Mn0.67Ni0.18Li0.15O2) Mixing with polyvinylidene fluoride (PVDF) as a binder and a Super-P as a conductive agent in a mass ratio of 8:1:1, adding a proper amount of N-methylpyrrolidone (NMP) as a solvent to prepare a slurry, taking an aluminum foil as a current collector, uniformly coating the slurry on the aluminum foil, transferring the aluminum foil coated with the slurry into a 65 ℃ forced air drying oven to dry NMP, and then placing the aluminum foil at 100 ℃ to dry for 12 hours in vacuum to obtain Na0.67Mn0.62Ni0.18Li0.15Ti0.05O2And (3) a composite positive electrode. Subsequently, the prepared composite positive electrode, separator, electrolyte (1mol L)-1NaClO (NaClO)4The button sodium ion battery is assembled by adopting the following steps of/PC + FEC (95:5)), a negative pole piece (sodium blocks with the purity of 99.5 percent are cut off a surface oxidation layer in a glove box and rolled into a sheet, and metal sodium is cut into a circular sodium sheet by using a circular punch with the diameter of 12 mm), a positive pole shell and a negative pole shell. And finally, performing constant-current charge and discharge test on the battery at 25 ℃ and in a voltage range of 2-4.4V.
From the XRD fine-screen pattern of FIG. 1, Na can be obtained0.67Mn0.62Ni0.18Li0.15Ti0.05O2Maintain P63And the diffraction peaks of the/mmc space group correspond to the peaks of the standard P2 phase one by one. This shows that when Li is used+And Ti4+When the raw materials are doped, the prepared materials stillThe pure P2 phase lamellar crystal structure is kept.
From FIG. 2, Na was observed0.67Mn0.62Ni0.18Li0.15Ti0.05O2The material presents obvious plate-shaped crystals with high crystallinity, the grain diameter is about 1-2um, and the surface is very smooth.
The clear lattice fringes are observed in FIG. 3, which demonstrates that the material has a high degree of crystallinity and the lattice fringe spacing is 0.277nm, corresponding to P2-Na0.67Mn0.67Ni0.33O2Peak (004).
Confirmation of Na from EDS of FIG. 40.67Mn0.62Ni0.18Li0.15Ti0.05O2Na, Mn, Ni, Ti and O elements exist in the sample, each element is uniformly distributed in the material, and the Li element cannot be detected because the energy is too low.
From fig. 5, it is seen that the charge-discharge curve is very smooth and there is no significant voltage plateau, evidencing Li+、Ti4+Doping can make the material form a solid solution structure, and Na is inhibited+Vacancy ordering phenomena and phase transitions. Under the current density of 0.2C and the voltage window of 2.0-4.4V, the first discharge specific capacity is 123mAh g-1The capacity retention after 100 cycles was 89%.
FIG. 6 shows Na0.67Mn0.67Ni0.33O2、Na0.67Mn0.62Ni0.18Li0.15Ti0.05O2、Na0.67Mn0.62Ni0.33Ti0.05O2、Na0.67Mn0.67Ni0.18Li0.15O2Graph comparing the rate performance of (1). Starting material (Na)0.67Mn0.67Ni0.33O2) Titanium material (Na) alone0.67Mn0.62Ni0.33Ti0.05O2) Lithium-doped material (Na) alone0.67Mn0.67Ni0.18Li0.15O2) The capacity is rapidly attenuated under high current density, even close to 0 mAh/g. But lithium titanium codoped material (Na)0.67Mn0.62Ni0.18Li0.15Ti0.05O2) Can provide 123mAh g at the current density of 0.2C-1The reversible discharge specific capacity of the material can still release 95mAh g at 5C-1Even at extreme rates of 20C, Li+And Ti4+Codoped Na0.67Mn0.62Ni0.18Li0.15Ti0.05O2Can still provide 52mAh g-1When the specific capacity of the resin is recovered from the limit rate of 20C to 0.1C, 125mAh g is rapidly recovered-1Specific capacity of, this demonstrates Li+And Ti4+The doping of (2) greatly improves the diffusion rate of sodium ions and improves the stability of the crystal structure.
Example 2
Accurately weighing Na with corresponding mass according to the molar ratio of 0.80:0.15:0.05:0.62:0.182CO3、Li2CO3TiO2Mn2O3NiO, placing the NiO into an agate ball milling tank, adding a proper amount of agate ball milling beads into the tank, and then adding a proper amount of absolute ethyl alcohol. And (5) putting the ball mill pot into a planetary ball mill, and carrying out ball milling for 5h at the rotating speed of 450 r/min. And (4) taking out the ball milling tank after the ball milling is finished, and drying the ethanol in a 60 ℃ forced air drying oven. The ball-milled powdered material was then scraped off. Putting the powdery material into an infrared tabletting mould with the thickness of 15mm, and pressing into a tablet under the pressure of 10MPa to obtain the sheet. And (3) transferring the sheet into a muffle furnace, pre-burning for 6h at 500 ℃, then calcining for 12h at 850 ℃, and raising the temperature at a rate of 3 ℃/min. After the material is naturally cooled to room temperature, taking out the material from the furnace, grinding the flaky material into fine powder by using an agate mortar to obtain the target product Na0.8Mn0.62Ni0.18Li0.15Ti0.05O2。
FIG. 7 shows Na0.8Mn0.62Ni0.18Li0.15Ti0.05O2The rate capability of (2). Can provide 125mAh g at the current density of 0.1C-1The reversible discharge specific capacity of the lead-acid battery can provide 96mAh g at 5C-1Even at a large rate of 10C, the specific discharge capacity of (2) can still provide 83mAh g-1The specific capacity of (A). This proves that Li+And Ti4+The doping of the material greatly improves the diffusion rate of sodium ions and the stability of a crystal structure, thereby improving the rate capability of the material and showing that the rate capability of the material is not influenced by the improvement of the sodium content.
Example 3
The same solid phase method as in example 1 was followed (Cu source is CuO and Fe source is Fe)2O3) Preparation of Na0.67Mn0.6Ni0.18Li0.15Ti0.05Cu0.02O2And Na0.67Mn0.6Ni0.18Li0.15Ti0.05Fe0.02O2。
FIG. 8 shows Na0.67Mn0.6Ni0.18Li0.15Ti0.05Cu0.02O2And Na0.67Mn0.6Ni0.18Li0.15Ti0.05Fe0.0 2O2With Na0.67Mn0.67Ni0.33O2The experiment shows that on the basis of lithium and titanium codoping, other one or more heteroatoms are doped, and the modified material still shows excellent rate performance.
Example 4
A series of materials Na with different ratios of lithium to titanium were prepared according to the same solid phase method as in example 1 above0.67Mn0.62Ni0.13Li0.2Ti0.05O2、Na0.67Mn0.57Ni0.18Li0.15Ti0.1O2。
FIG. 9 shows both with Na0.67Mn0.62Ni0.18Li0.15Ti0.05O2Comparison of rate capability of (1), Na at a current density of 10C0.67Mn0.62Ni0.13Li0.2Ti0.05O2Still can provide 70mAh g-1Specific capacity of, Na0.67Mn0.57Ni0.18Li0.15Ti0.1O2Can provide 75mAh g-1The discharge specific capacity of the material shows excellent rate capability.
Comparative example 4
Na was prepared by the same solid phase method as in example 1 above0.67Mn0.64Ni0.18Li0.15Ti0.03O2。
Comparative example 5
Na was prepared by the same solid phase method as in example 1 above0.67Mn0.66Ni0.18Li0.15Ti0.01O2。
FIG. 10 shows a graph comparing the rate performance of Na at a current density of 10C0.67Mn0.66Ni0.18Li0.15Ti0.01O2Can only provide 44mAh g-1Specific discharge capacity, Na0.67Mn0.64Ni0.18Li0.15Ti0.03O2Can only provide 56mAh g-1Specific discharge capacity, and Na0.67Mn0.62Ni0.18Li0.15Ti0.05O2Then 80mAh g can be provided-1Specific discharge capacity. It can be seen that in the chemical formula NaaLibTicMndNieMfO2(a is more than or equal to 0.67 and less than or equal to 0.8, b is more than or equal to 0.05 and less than 0.20, c is more than or equal to 0.03 and less than or equal to 0.10, d is more than 0.50 and less than 0.67, e is more than 0.10 and less than 0.33, f is more than or equal to 0.08, b + c + d + e + f is 1, b/c is more than or equal to 1 and less than or equal to 4, and M is one or more of Co, Fe, Mg, Zn, Cu, Al, Sn, Zr and Cr).
Comparative example 6
Replacing Na with 7 elements of Sn, Ca, Mo, V, Te, Zr and W respectively0.67Mn0.62Ni0.18Li0.15Ti0.05O2The titanium element in (b) was prepared by the same solid phase method as in example 1 (the Sn source was SnO)2The Ca source is CaO and the Mo source is MoO3The source of V is V2O5Te source is TeO2The Zr source is ZrO2The W source is WO3) A series of materials co-doped with lithium and other different elements were prepared and their rate performance was compared, as shown in fig. 11. Research shows that the lithium-titanium co-doped material shows the optimal rate performance.
Comparative example 7
Respectively substituting Mg and Cu elements for Na0.67Mn0.62Ni0.18Li0.15Ti0.05O2In the lithium element (b), Na was prepared by the same solid phase method as in example 1 (MgO as Mg source and CuO as Cu source)0.67Mn0.62Ni0.18Mg0.15Ti0.05O2And Na0.67Mn0.62Ni0.18Cu0.15Ti0.05O2The materials were compared in terms of rate performance, as shown in fig. 12. Research shows that the lithium-titanium co-doped material shows the optimal rate performance.
Claims (10)
1. The composite cathode material of the lithium/titanium co-doped sodium-ion battery is characterized in that the chemical general formula of the cathode material is shown as follows: na (Na)aLibTicMndNieMfO2Wherein a is more than or equal to 0.67 and less than or equal to 0.8, b is more than 0.05 and less than 0.20, c is more than 0.03 and less than 0.10, d is more than 0.50 and less than 0.67, e is more than 0.10 and less than 0.33, f is more than or equal to 0 and less than 0.08, b + c + d + e + f is 1, b/c is more than or equal to 1 and less than or equal to 4, and M is one or more of Co, Fe, Mg, Zn, Cu, Al, Sn, Zr and Cr.
2. The preparation method of the lithium/titanium co-doped sodium ion battery composite positive electrode material of claim 1, wherein a sodium source compound, a lithium source compound, a titanium source compound, a manganese source compound, a nickel source compound and an M source compound are uniformly mixed by ball milling to obtain a mixture; then tabletting the obtained mixture to obtain a sheet; and finally, calcining the obtained sheet at high temperature to obtain the lithium/titanium co-doped sodium ion battery composite anode material.
3. The method of claim 2, wherein: the sodium source compound is one or more of sodium carbonate, sodium hydroxide and sodium bicarbonate.
4. The method of claim 2, wherein: the lithium source compound is one or more of lithium carbonate and lithium hydroxide.
5. The method of claim 2, wherein: the titanium source compound is titanium dioxide.
6. The method of claim 2, wherein: the manganese source compound, the nickel source compound and the M source compound are one or more of corresponding oxides, carbonates and hydroxides.
7. The method of claim 2, wherein: the ball milling speed is 200-.
8. The method of claim 2, wherein: and tabletting the obtained mixture in an infrared tabletting mold of 15mm under the pressure condition of 5-30 MPa.
9. The method of claim 2, wherein: the high-temperature calcination atmosphere is oxidizing atmosphere, the temperature is 500-1000 ℃, the time is 5-12 h, and the heating rate is 1-10 ℃/min.
10. The application of the lithium/titanium co-doped sodium-ion battery composite cathode material of claim 1 or the lithium/titanium co-doped sodium-ion battery composite cathode material prepared by the preparation method of any one of claims 2 to 9 is characterized in that: it is used for preparing sodium ion batteries.
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