CN115043430B - Preparation method and application of praseodymium-doped porous spherical titanium niobate material - Google Patents
Preparation method and application of praseodymium-doped porous spherical titanium niobate material Download PDFInfo
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- CN115043430B CN115043430B CN202210589044.7A CN202210589044A CN115043430B CN 115043430 B CN115043430 B CN 115043430B CN 202210589044 A CN202210589044 A CN 202210589044A CN 115043430 B CN115043430 B CN 115043430B
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000000463 material Substances 0.000 title claims abstract description 65
- 239000010936 titanium Substances 0.000 title claims abstract description 65
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 25
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 23
- 238000001354 calcination Methods 0.000 claims abstract description 21
- 239000010955 niobium Substances 0.000 claims abstract description 19
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 18
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 238000004140 cleaning Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000013049 sediment Substances 0.000 claims abstract description 3
- 238000001291 vacuum drying Methods 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- 239000011230 binding agent Substances 0.000 claims description 11
- 239000006258 conductive agent Substances 0.000 claims description 11
- -1 praseodymium ions Chemical class 0.000 claims description 10
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 9
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical group Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 239000006230 acetylene black Substances 0.000 claims description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 239000013543 active substance Substances 0.000 claims description 2
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 239000011889 copper foil Substances 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 239000011888 foil Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000002985 plastic film Substances 0.000 claims description 2
- 229920006255 plastic film Polymers 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000002105 nanoparticle Substances 0.000 abstract description 2
- 239000011164 primary particle Substances 0.000 description 9
- 238000009792 diffusion process Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 5
- WYOIGGSUICKDNZ-UHFFFAOYSA-N 2,3,5,6,7,8-hexahydropyrrolizin-1-one Chemical compound C1CCC2C(=O)CCN21 WYOIGGSUICKDNZ-UHFFFAOYSA-N 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- WCWKKSOQLQEJTE-UHFFFAOYSA-N praseodymium(3+) Chemical compound [Pr+3] WCWKKSOQLQEJTE-UHFFFAOYSA-N 0.000 description 1
- LHBNLZDGIPPZLL-UHFFFAOYSA-K praseodymium(iii) chloride Chemical compound Cl[Pr](Cl)Cl LHBNLZDGIPPZLL-UHFFFAOYSA-K 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G33/00—Compounds of niobium
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
- C01P2002/54—Solid solutions containing elements as dopants one element only
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
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- Organic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
A preparation method and application of praseodymium-doped porous spherical titanium niobate material, belonging to the field of lithium ion batteries. The method comprises the following steps: according to the titanium source, the niobium source and the praseodymium source being 1:2-x: taking material with the molar ratio of x of 0.01-0.1, dissolving a titanium source compound in absolute ethyl alcohol, controlling the concentration of the titanium source to be 0.05-0.2mol/L, then adding a niobium source and a praseodymium source compound, and uniformly mixing; reacting for 12-36 h at 150-200 ℃ in a homogeneous reactor to obtain a precursor; centrifugally separating and cleaning for three times, and collecting sediment and vacuum drying for 12 hours at 80 ℃; calcining the precursor in a high temperature furnace for 4-12h under the air condition of 700-800 ℃. According to the invention, due to the special porous spherical morphology and the requirement of primary nano particles, the calcining temperature is 700-800 ℃, and the energy consumption in the material preparation process is reduced.
Description
Technical Field
The invention belongs to the field of lithium ion batteries, and particularly relates to a preparation method and application of a praseodymium-doped porous spherical titanium niobate material.
Background
As a battery which is critical to the power of a new energy automobile, the endurance and the safety performance of the battery are critical, and the batteries of the main stream pure electric automobile and the hybrid electric automobile in the market at present are basically lithium ion batteries.
Titanium niobate (TiNb) 2 O 7 Abbreviated as TNO) is a lithium ion intercalation and deintercalation type negative electrode material, is first proposed by Goodenough to be applied to a lithium ion battery in 2011, has higher theoretical specific capacity than the lithium titanate material commercialized at the present stage, simultaneously has excellent multiplying power performance, has volume change less than 9% in the process of intercalating and deintercalating lithium, is similar to graphite, is a practical negative electrode material, is very compatible with the high-power discharging process of a power battery such as start-stop and the like, but has wide energy band gap (2.92 eV), and is limited by poor electronic conductivity and ion conductivity as a commercialized batteryTherefore, various scholars at home and abroad carry out various mechanism researches and modifications on the material with full prospect, hope to realize the application of the material as a commercial battery, and the Japanese Toshiba company has developed a carbon-coated modified TNO negative electrode/nickel-cobalt-manganese ternary positive electrode power battery, but the energy density of the TNO material is still lower than that of other power batteries at the present stage, so that the TNO material still needs to be further researched and improved, and particularly the capacity, the cycle rate performance and the like of the material are important solutions of the invention. The doping of elements is an effective means for improving the performance, lanthanide metal ions have large ionic radius and inner layer 4f or 5f electrons, and after doping into the material, the inter-plane distance can be widened, and the conductivity of the material can be improved. In the past study, we used neodymium element doping to replace titanium element to prepare Nd x Ti 1-x Nb 2 O 7 The element is doped at Ti site, the radius of trivalent neodymium ion is 0.1163nm, which is nearly one time larger than that of replaced tetravalent titanium ion (0.0605 nm), the volume is increased by several times, and huge energy is needed for doping the ion into crystal lattice to cross energy barrier, and the calcining temperature of the material must be higher (more than 900 ℃) to obtain the target product.
Disclosure of Invention
The invention aims to solve the problems of non-ideal performance of the existing pure-phase TNO material and high energy consumption of the existing doping modification process, and provides a preparation method and application of a praseodymium-doped porous spherical titanium niobate material with high specific surface area, wherein doping sites are selected to replace niobium element sites with lower energy barriers, the calcination temperature is reduced from more than 900 ℃ to 700-800 ℃, the crystal face spacing and the intrinsic conductivity of the material are improved through the doping of rare earth element praseodymium, and simultaneously oxygen vacancy defects are generated when tetravalent praseodymium ions replace pentavalent niobium ions, so that the capacity, the circulation rate and other performances of the material are improved.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a preparation method of praseodymium-doped porous spherical titanium niobate material, which comprises the following steps:
step one: according to the titanium source, the niobium source and the praseodymium source being 1:2-x: taking material with the molar ratio of x of 0.01-0.1, dissolving a titanium source compound in absolute ethyl alcohol, controlling the concentration of the titanium source to be 0.05-0.2mol/L, then adding a niobium source and a praseodymium source compound, and uniformly mixing;
step two: putting the solution obtained in the step one into an ultrasonic cleaner for ultrasonic dispersion for 1h to obtain a solution with uniform dispersion, transferring the solution into a reaction kettle, wherein the volume ratio of the mixed solution in the kettle is 30% -60%, sealing the reaction kettle, and reacting for 12h-36h at 150-200 ℃ in a homogeneous reactor to obtain a precursor; too low a Shui Rewen degree or too short a time may result in insufficient reaction of the material precursor;
step three: separating and cleaning the precursor for three times by a centrifugal machine, collecting sediment by deionized water as cleaning solution, and vacuum drying at 80 ℃ for 12 hours;
step four: calcining the precursor in a high-temperature furnace at 700-800 ℃ for 4-12 hours under the air condition, and obtaining the praseodymium-doped porous spherical titanium niobate anode material. The precursor is heated uniformly, the calcination temperature is 700-800 ℃, the incomplete oxidation of the precursor can be caused by the low calcination temperature, and the generated material contains various impurity phases such as niobium pentoxide, titanium dioxide, incomplete oxide and the like instead of target products. The temperature is higher than the interval, the primary particle structure of the material can be damaged, the experimental result shows that the size of the primary particles increases along with the increase of the calcining temperature, the volume of the primary particles is 5-10 times larger than that of the primary particles at 750 ℃ during the calcining at 900 ℃, the primary particles are converted into strip-shaped nano rods from spherical particles, the specific surface area of the material is greatly reduced, and the primary particles are excessively large when the calcining temperature is higher, so that the self-generated porous morphology structure is damaged. The calcination time interval is 4-12h, the influence on the material is similar to the temperature change, the target product cannot be obtained after too short, and the special morphology and structure can be damaged after too long.
In the first step, the titanium source is tetrabutyl titanate, and dissolution is accelerated under the stirring condition, so that insoluble impurity products are prevented from being generated after standing in the air for too long; the niobium source is niobium pentachloride, the niobium pentachloride is ensured to be rapidly weighed in a dry environment or carried out in an argon atmosphere of a glove box, and the niobium pentachloride can be decomposed by reaction with water and the like in the air; the praseodymium source is a stable compound of praseodymium acetate, praseodymium chloride and the like which are dissolved in solvent ethanol and do not react with the titanium source and the niobium source at normal temperature, a praseodymium ion doping site is selected as a niobium ion with lower doping energy barrier, the doping proportion is x, and the niobium source with corresponding proportion is replaced.
Further, in the second step, the temperature of the homogeneous reactor is 180 ℃ and the time is 24 hours.
Further, in the fourth step, the high temperature furnace is one of a tube furnace, a box furnace or a muffle furnace, and the calcining temperature is 750 ℃ and the calcining time is 6h.
The praseodymium element doped porous spherical titanium niobate material prepared by the method is applied to a lithium ion battery as an active substance, and specifically has the following two conditions:
case one: praseodymium-doped titanium niobate is used as a positive electrode and lithium metal combined assembled battery (short for half battery);
and a second case: praseodymium-doped titanium niobate is used as a cathode and a nickel cobalt manganese 811 anode to be combined and assembled into a battery (called a full battery for short).
Further, the battery consists of a positive plate, a negative plate, a diaphragm, electrolyte and an aluminum shell or an aluminum plastic film, and the specific combination mode is achieved according to the conventional battery assembly mode.
Further, the titanium niobate pole piece is prepared as follows: the slurry consists of 80% of praseodymium-doped titanium niobate material, 10% of conductive agent and 10% of binder by mass percentage, wherein the conductive agent is one or more of acetylene black, graphene, carbon nano tube or Super P, the binder is PVDF solvent, the concrete slurry component can be finely adjusted, and the current collector is copper foil.
Further, in case two, the nickel cobalt manganese 811 positive electrode sheet was prepared as: the slurry consists of 80% of nickel cobalt manganese 811 material, 10% of conductive agent and 10% of binder by mass percentage, wherein the conductive agent is one or more of acetylene black, graphene, carbon nano tube or Super P, the binder is PVDF solvent, the concrete slurry component can be finely adjusted, and the current collector is aluminum foil.
Compared with the prior art, the invention has the beneficial effects that:
(1) After praseodymium ions with large ion radius are doped into the material, the material is partially substituted for TiNb 2 O 7 Nb of (a) to form TiNb 2- x Pr x O 7 The intrinsic conductivity of the material can be improved, the lithium ion diffusion channel can be widened, further, higher reversible capacity, cycle performance and high-rate performance can be shown in the lithium ion battery, and further, the test of preparing the button-type full battery by using the positive electrode of the nickel cobalt manganese 811 shows excellent electrochemical performance, so that the hardness requirement of the negative electrode of the power battery can be met.
(2) In the invention, due to the special porous spherical morphology and the requirement of primary nano particles, the calcining temperature cannot exceed 800 ℃, thus praseodymium element in lanthanide is selected to prepare TiNb 2-x Pr x O 7 The ionic radius of tetravalent praseodymium ions is 0.085nm, and pentavalent niobium ions are 0.064nm, doping is selected to be doped at niobium element sites, doping energy barrier is reduced, calcining temperature is only required to be 700-800 ℃, and energy consumption in the material preparation process is reduced.
Drawings
FIG. 1 is a scanning electron microscope image of a praseodymium-doped porous spherical titanium niobate prepared;
FIG. 2 is an XRD diffraction pattern of a praseodymium-doped porous spherical titanium niobate prepared;
FIG. 3 shows the ultraviolet-visible absorption spectrum of praseodymium-doped porous spherical titanium niobate (A)hv) 1/2 And photon energyhvIs a graph of the relationship of (2);
FIG. 4 is a graph of three cycles of charge and discharge prior to 0.1C of a praseodymium-doped titanium niobate half cell;
FIG. 5 is a graph of 1C800 cycles performance of a praseodymium-doped titanium niobate half cell and a pure phase titanium niobate half cell;
FIG. 6 is a graph showing the variation of the diffusion coefficient of lithium ions with the delithiation process calculated from the constant current titration technique results for a praseodymium-doped titanium niobate half cell and a pure phase titanium niobate half cell;
FIG. 7 is a graph of 1C600 cycle performance of a praseodymium-doped titanium niobate full cell and a pure phase titanium niobate full cell (the specific energy of the cell only calculates the positive and negative electrode active materials);
FIG. 8 is a graph of the first cycle charge and discharge curves of a praseodymium-doped titanium niobate full cell and a pure phase titanium niobate full cell 1C (the specific energy of the cell only calculates the positive and negative electrode active materials);
fig. 9 is a scanning electron microscope image of a praseodymium-doped porous spherical titanium niobate prepared with a calcination time of 12 hours.
Detailed Description
The following description of the present invention refers to the accompanying drawings and examples, but is not limited to the same, and modifications and equivalents of the present invention can be made without departing from the spirit and scope of the present invention.
Example 1:
weighing 1g of tetrabutyl titanate, adding into a beaker, adding 20 ml absolute ethyl alcohol, controlling the concentration of a titanium source to be 0.05-0.2mol/L, and uniformly mixing; simultaneously, the mol ratio of titanium, niobium and praseodymium is 1:1.96:0.04 niobium pentachloride and praseodymium acetate were weighed into a beaker and stirred 6h by a magnetic stirrer until the solution became colorless. And then adding the solution into a hydrothermal reaction kettle to react at 180 ℃ for 24h, washing the obtained grey product with deionized water for three times, and drying 12h under the condition of vacuum 80 ℃ to obtain a uniformly mixed precursor. Grinding the obtained precursor material and calcining 6h under the air condition of 750 ℃ to obtain a yellow-white spherical praseodymium-doped titanium niobate material (TiNb) 1.96 Pr 0.04 O 7 ). As can be seen from fig. 1, the praseodymium-doped titanium niobate prepared in this embodiment is a porous sphere formed by agglomerating several tens of nanometer primary particles, and this structure provides a high specific surface area, and the primary particles have nanometer-scale pores therebetween, which provides an excellent path for lithium ion transport and electrolyte permeation. As can be seen from FIG. 2, the praseodymium doped titanium niobate material prepared in this example has a small shift in peak position relative to the pure phase titanium niobate material, and the refinement results indicate that the unit cell volume of the material is represented by 823A 3 To 826 a 3 The fact that the inter-crystal face distance of the praseodymium-doped titanium niobate material is increased is proved to be beneficial to the diffusion of ions among the crystal lattices. As can be seen from FIG. 3, the energy gap of the Pr-doped titanium niobate material prepared in the embodiment is 2.66eV, which is greatly reduced compared with that of the pure phase titanium niobate material (2.92 eV), indicating that Pr-doped titanium niobate materialThe intrinsic conductivity of the material is improved, which is beneficial to improving the electrochemical performance.
Example 2:
the material in example 1 is used as a positive electrode to be matched with lithium metal to prepare a button lithium ion battery, and the praseodymium-doped titanium niobate pole piece is composed of 80% of praseodymium-doped titanium niobate material, 10% of conductive agent and 10% of binder by mass percent. As can be seen from FIG. 4, the first discharge capacity and the first charge specific capacity of the lithium ion battery obtained in this example at 0.1C activation were 300.0 and 281.1 mAh g, respectively -1 The first coulomb efficiency is as high as 96.7%. As can be seen from fig. 5, the lithium ion battery obtained in this example has a first reversible specific capacity of 242.2 mAh g at 1C current -1 Is 40 mAh g higher than that of unmodified material -1 The capacity after 800 times of circulation is 217.5 mAh g -1 The capacity preservation rate is 89.8 percent, which is far higher than that of the pure phase TiNb 2 O 7 A material. As can be seen from FIG. 6, the lithium ion battery obtained in this example was subjected to TiNb measurement by the constant current titration technique (GITT) 1.96 Pr 0.04 O 7 And TiNb 2 O 7 Lithium ion diffusion coefficient of two materials, and TiNb in the process of removing lithium 1.96 Pr 0.04 O 7 Compared with a pure phase material, the lithium ion diffusion coefficient of the material is improved by 1 order of magnitude, namely about 10 times, and the fact that the interplanar distance and the lithium ion diffusion channel are increased caused by doping tetravalent praseodymium ions with large radius into crystal lattices is proved, and the improvement of the lithium ion diffusion coefficient is reflected.
Example 3:
the material in example 1 was used as a negative electrode and was matched with a nickel cobalt manganese 811 positive electrode to prepare a button lithium ion battery, and the praseodymium-doped titanium niobate sheet consisted of 80% of praseodymium-doped titanium niobate material, 10% of conductive agent and 10% of binder by mass, and the positive electrode sheet consisted of 80% of nickel cobalt manganese 811 material, 10% of conductive agent and 10% of binder by mass. As can be seen from fig. 7, after the lithium ion battery 0.1C obtained in this example was activated three times, the 1C first cycle exhibited 187.6Wh kg -1 The initial discharge specific energy (calculated according to the mass of positive and negative active materials) of the alloy is higher than that of the pure phase TiNb 2 O 7 Initial discharge specific energy of battery of materialThe amount is higher than 10 Wh kg -1 The doping of praseodymium improves the intrinsic conductivity of the material and the actual specific capacity. After 600 cycles of circulation, tiNb 1.96 Pr 0.04 O 7 The material performance is better and also 100.2 Wh kg -1 The specific discharge energy of (C) was 53.4% and the energy retention was TiNb 2 O 7 The material was only 64.7 Wh g -1 The specific discharge energy of (2) was 36.3%. As can be seen from fig. 8, the lithium ion battery obtained in this embodiment shows a gentle curve in the charge-discharge curve of 3-1.7V, and then the voltage drops rapidly in the interval of 1.7-1V, and the initial voltage is about 1.7V during the charging process, and the battery does not have any electrochemical reaction in this interval.
Example 4:
1g of tetrabutyl titanate is weighed and added into a beaker, 20 ml absolute ethyl alcohol is added, and meanwhile, the molar ratio of titanium, niobium and praseodymium is 1:1.96: and 0.04, weighing niobium pentachloride and praseodymium acetate, adding the niobium pentachloride and the praseodymium acetate into a beaker, and stirring for 4-6 hours until the solution becomes colorless. And then adding the solution into a hydrothermal reaction kettle to react at 180 ℃ for 24h, washing the obtained grey product with deionized water for three times, and drying 12h under the condition of vacuum 80 ℃ to obtain a uniformly mixed precursor. Grinding the obtained precursor material and calcining 12h under the air condition of 750 ℃ to obtain a yellow-white spherical praseodymium-doped titanium niobate material (TiNb) 1.96 Pr 0.04 O 7 -12 h). As shown in fig. 9, the praseodymium-doped titanium niobate primary particles prepared in this example have a length of more than 200nm and are interlinked, which results in a decrease in the specific surface area of the material.
Claims (8)
1. A preparation method of praseodymium element doped porous spherical titanium niobate material for lithium ion batteries is characterized by comprising the following steps: the method comprises the following steps:
step one: according to the titanium source, the niobium source and the praseodymium source being 1:2-x: taking material with the molar ratio of x of 0.01-0.1, dissolving a titanium source compound in absolute ethyl alcohol, controlling the concentration of the titanium source to be 0.05-0.2mol/L, then adding a niobium source and a praseodymium source compound, and uniformly mixing; the praseodymium source is a stable compound which is dissolved in ethanol and does not react with the titanium source and the niobium source at normal temperature;
step two: putting the solution obtained in the step one into an ultrasonic cleaner for ultrasonic dispersion for 1h to obtain a solution with uniform dispersion, transferring the solution into a reaction kettle, wherein the volume ratio of the mixed solution in the kettle is 30% -60%, sealing the reaction kettle, and reacting for 12h-36h at 150-200 ℃ in a homogeneous reactor to obtain a precursor;
step three: separating and cleaning the precursor for three times by a centrifugal machine, collecting sediment by deionized water as cleaning solution, and vacuum drying at 80 ℃ for 12 hours;
step four: calcining for 4-12 hours at 700-800 ℃ in a high-temperature furnace to obtain praseodymium-doped porous spherical titanium niobate material;
the praseodymium element exists in the form of tetravalent praseodymium ions, the ion radius of the niobium ions is 0.064nm, and the ion radius of the praseodymium ions is 0.085nm when the praseodymium element is doped at a niobium site.
2. The method according to claim 1, characterized in that: in the first step, the titanium source is tetrabutyl titanate, the dissolution is accelerated under the stirring condition, and insoluble impurity products are prevented from being generated after standing for a long time in the air; the niobium source is niobium pentachloride, and the niobium pentachloride is ensured to be rapidly weighed in a dry environment or carried out in an argon atmosphere of a glove box.
3. The method according to claim 1, characterized in that: in the second step, the temperature of the homogeneous reactor is 180 ℃ and the time is 24 hours.
4. The method according to claim 1, characterized in that: in the fourth step, the high temperature furnace is one of a tube furnace, a box furnace or a muffle furnace, the calcining temperature is 750 ℃, and the calcining time is 6 hours.
5. Use of praseodymium-doped porous spherical titanium niobate material prepared by the method of any one of claims 1 to 4, characterized in that: the material is applied to a lithium ion battery as an active substance, and specifically has the following two conditions:
case one: praseodymium element doped porous spherical titanium niobate is taken as a positive electrode to be combined with lithium metal to assemble a battery; or (b)
And a second case: and the praseodymium-doped porous spherical titanium niobate is taken as a negative electrode to be combined with the nickel cobalt manganese 811 positive electrode to assemble the battery.
6. The use according to claim 5, characterized in that: the battery consists of a positive plate, a negative plate, a diaphragm, electrolyte and an aluminum shell or an aluminum plastic film, and the specific combination mode is realized according to the conventional battery assembly mode.
7. The use according to claim 6, characterized in that: the preparation method of the titanium niobate pole piece comprises the following steps: the slurry consists of praseodymium-doped titanium niobate material, a conductive agent and a binder, wherein the conductive agent is one or more of acetylene black, graphene, carbon nano tubes or Super P, the binder is PVDF solvent, and the current collector is copper foil.
8. The use according to claim 6, characterized in that: in the second case, the nickel cobalt manganese 811 positive electrode sheet was prepared as: the slurry consists of nickel cobalt manganese 811 material, a conductive agent and a binder, wherein the conductive agent is one or more of acetylene black, graphene, carbon nano tubes or Super P, the binder is PVDF solvent, and the current collector is aluminum foil.
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