CN114084913A - Preparation method and application of pre-lithiation lithium cobalt oxide with core-shell structure - Google Patents
Preparation method and application of pre-lithiation lithium cobalt oxide with core-shell structure Download PDFInfo
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Abstract
The invention provides a preparation method and application of pre-lithiation lithium cobaltate with a core-shell structure, wherein the method comprises the following steps: (1) preparation of carbon nanotube-loaded doped lithium ferrite Li5FenX(1‑n)O4；（2）Preparation of surface self-assembled film modified carbon nanotube loaded doped lithium iron oxide Li5FenX(1‑n)O4(ii) a (3) Preparation of seed Cobaltate MCo of lithium cobaltate precursor2O4(ii) a (4) Preparing a lithium cobaltate precursor; (5) preparing lithium cobaltate; (6) preparation of surface-coated lithium cobaltate (7) preparation of surface nitride-coated lithium cobaltate. The pre-lithiation lithium cobaltate with the core-shell structure adopts cobaltate as a seed crystal, and a carbon nano tube loaded pre-lithiation anode material in an aqueous solution is doped with lithium ferrite to prepare a lithium cobaltate precursor in a self-assembly mode; preparing a titanium-containing oxide coating layer, and carrying out nitridation reaction to generate the coated lithium cobaltate containing titanium nitride and oxide.
Description
Technical Field
The invention belongs to the field of nano materials, and particularly relates to a preparation method and application of pre-lithiation core-shell structure lithium cobaltate.
Background
The positive and negative electrode materials of the lithium ion secondary battery have irreversible capacity during the first charge and discharge, and in order to improve the effective battery material capacity, the method for supplementing the active free migration lithium ion content of the positive and negative electrode materials is a good method for improving the battery capacity. The method is a feasible method for supplementing reversible capacity of the lithium ion anode and cathode materials by using the materials with high gram capacity and low irreversible capacity; no related products are seen in the market at present.
Disclosure of Invention
In view of this, the present invention provides a preparation method and application of a pre-lithiated core-shell structure lithium cobalt oxide, aiming at overcoming the defects in the prior art.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a preparation method of pre-lithiation lithium cobalt oxide with a core-shell structure comprises the following steps:
(1) preparation of carbon nanotube-loaded doped lithium iron oxide Li5FenX(1-n)O4：
Dissolving ferric salt and other metal salts in an aqueous solution, adding surfactant molecules, lithium compounds and carbon nano tubes, adjusting the pH value and temperature of the solution, stirring, filtering and washing after reaction to obtain a precursor, calcining the precursor in the air, crushing, sieving, washing and drying the calcined product to obtain the carbon nano tube loaded lithium iron doped Li5FenX(1-n)O4；
(2) Preparation of surface self-assembled film modified carbon nanotube loaded doped lithium iron oxide Li5FenX(1-n)O4：
Loading the obtained carbon nano tube with doped lithium iron oxide Li5FenX(1-n)O4Placing the mixture into an ionic liquid solution containing a surfactant, uniformly stirring, filtering and cleaning to obtain the surface self-assembled film modified carbon nanotube loaded doped lithium iron oxide Li5FenX(1-n)O4；
(3) Preparation of seed Cobaltate MCo of lithium cobaltate precursor2O4：
Dissolving cobalt salt and other metal salts in a non-aqueous solvent, adding surfactant molecules, performing ultrasonic treatment after reaction, filtering, cleaning, drying, and calcining in air to obtain a product, namely a lithium cobaltate precursor seed crystal cobaltate MCo2O4；
(4) Preparing a lithium cobaltate precursor:
loading lithium ferrate Li to the surface self-assembly film modified carbon nano tube obtained in the step (2)5FenX(1-n)O4And the cobaltate MCo obtained in the step (3)2O4Placing the mixture into an alkaline aqueous solution reaction kettle, uniformly stirring, introducing a cobalt ion aqueous solution, a doped metal ion aqueous solution and an alkaline aqueous solution into the reaction kettle, adjusting the pH value and the temperature of the solution, and filtering and cleaning a product after the reaction is finished to obtain a lithium cobaltate precursor;
(5) preparing lithium cobaltate:
mixing the obtained lithium cobaltate precursor with a lithium compound, and calcining to obtain lithium cobaltate;
(6) preparing surface-coated lithium cobaltate:
placing the obtained lithium cobaltate in an aqueous solution, stirring and mixing, adjusting the pH value and the temperature of the solution, adding a metal compound, keeping the reaction time constant, filtering and cleaning the reaction solution, and drying to prepare surface-coated lithium cobaltate;
(7) preparing surface nitride coated lithium cobaltate:
and mixing the obtained surface-coated lithium cobalt oxide with a nitrogen source, calcining and cooling in an inert atmosphere to obtain the nitride-coated lithium cobalt oxide.
Further, the ferric salt in the step (1) is at least one of ferric nitrate, ferric sulfate, ferric chloride, ferric perchlorate or ferric acetate; the other metal salt is water-soluble metal salt; the surfactant molecule is at least one of an ionic surfactant or a nonionic surfactant; the lithium compound is at least one of lithium hydroxide, lithium carbonate, lithium bicarbonate, lithium perchlorate, lithium nitrate, lithium sulfate, lithium chloride, lithium acetate or lithium fluoride; the carbon nano tube is a carbon nano tube with at least one open end; the diameter of the carbon nano tube is 0.01-500 microns; the pH value is 7-12; the temperature is 20-100 ℃; the reaction time is 0.5-5 hours; the calcining temperature is 100-500 ℃; the carbon nano tube load doped lithium ferrate Li5FenX(1-n)O4The structure of (1) is as follows: filling doped lithium iron oxide Li in carbon nano tube5FenX(1-n)O4Li generated by reaction outside carbon nanotube5FenX(1-n)O4Stripping from the carbon nano tube after washing; the doped lithium ferrate Li5FenX(1-n)O4Wherein n is 0 to 0.5.
Further, the concentration of the surfactant in the step (2) is 0.01-10 mol/L; the temperature is 10-40 ℃; the reaction time is 0.5-20 hours; the surfactant molecule is at least one of an ionic surfactant or a nonionic surfactant; the ionic liquid is soluble in water.
Further, the cobalt salt in the step (3) is at least one of cobalt nitrate, cobalt sulfate, cobalt chloride or cobalt acetate; the other metal salt is water-soluble other metal salt; the other metal salt is at least one of nitrate, sulfate, chloride or acetate; the surfactant molecule is at least one of an ionic surfactant or a nonionic surfactant; the ultrasonic frequency of the ultrasonic step is 20-80 kHz; the reaction temperature is 50-300 ℃; the reaction time is 2-50 hours; the temperature of the calcination is 200-800 ℃.
Further, in the step (4): surface self-assembly film modified carbon nanotube loaded lithium iron oxide doped Li in reaction kettle5FenX(1-n)O4The concentration of the solution is constant and is 0.01-5 mol/L; cobaltate MCo in reaction kettle2O4The concentration of the solution is constant and is 0.02-10 mol/L; the cobalt ion aqueous solution is at least one of cobalt nitrate, cobalt sulfate, cobalt chloride or cobalt acetate aqueous solution; the other metal is at least one of potassium, sodium, calcium, nickel, manganese, copper, silver, magnesium, aluminum, zirconium, vanadium, zinc, germanium, molybdenum, indium, antimony, bismuth, barium, tungsten, palladium, strontium, cerium, niobium, zirconium, scandium or gallium; the doped metal ion solution is at least one of water-soluble nitrate, sulfate, chloride or acetate aqueous solutions of other metal ions; the alkaline aqueous solution is at least one of aqueous solution of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, ammonium carbonate or ammonium bicarbonate; the pH value of the solution is 7-12; the temperature is 20-90 ℃; the reaction time is 1-60 hours.
Preferably, the pH value of the solution is 7-9; the temperature is 40-60 ℃; the reaction time is 5-10 hours.
Further, the lithium compound in the step (5) is at least one of lithium hydroxide, lithium carbonate or lithium acetate; the stoichiometric molar ratio of the lithium cobaltate precursor to the lithium compound is 1.20-1.0; the temperature of the calcination step is 400-1200 ℃, and the temperature is kept for 5-50 hours.
Further, the pH value in the step (6) is 7-12; the temperature is 10-90 ℃; the reaction time is 0.5-10 hours; the washing liquid in the washing step is at least one of ultrapure water, ethanol, propanol or isopropanol; the temperature of the drying step is 80-200 ℃; the surface-coated lithium cobaltate structure is that the surface of the lithium cobaltate is uniformly coated with titanium dioxide and/or other metal oxides.
Further, the metal compound in the step (6) is at least one of a titanium metal organic compound and/or at least one of other metal soluble salts and other metal organic compounds; the titanium metal organic compound is at least one of methyl titanate, ethyl titanate, n-propyl titanate, tetrabutyl titanate, tetraisopropyl titanate or titanyl phthalocyanine; the other metal organic compound is a coordination compound formed by other metals and organic compounds; the other metal soluble salt is at least one of other metal soluble salts except titanium metal; the other metal soluble salt is at least one of other metal nitrate, sulfate, chloride, acetate or perchlorate;
the stoichiometric molar ratio of the titanium element to the lithium cobaltate is (0-0.1): 1; the stoichiometric molar ratio of the other metal elements to the lithium cobaltate is (0-0.1): 1.
further, the stoichiometric molar ratio of the nitrogen source to the surface-coated lithium cobaltate in the step (7) is (0.001-0.2): 1; the nitrogen source is at least one of ammonia gas, urea, amino alkane-containing or nitrogen element-containing ionic liquid; the inert atmosphere is at least one of nitrogen, helium or argon; the temperature of the calcination step is 100-400 ℃, and the time is 1-30 hours.
The application of the pre-lithiated lithium cobaltate with the core-shell structure prepared by the method in a lithium ion secondary battery.
Compared with the prior art, the invention has the following advantages:
the pre-lithiation lithium cobaltate with the core-shell structure adopts cobaltate as a seed crystal, and a carbon nano tube loaded pre-lithiation anode material in an aqueous solution is doped with lithium ferrite to prepare a lithium cobaltate precursor in a self-assembly mode; preparing a titanium-containing oxide coating layer, and performing nitridation reaction to generate coated lithium cobaltate containing titanium nitride and oxide; the self-assembly film mode is to self-assemble a surfactant molecular film on the outer wall of the carbon nano tube loaded with the pre-lithiation anode material doped with lithium iron in the ionic liquid to prevent the hydrolysis reaction of the carbon nano tube loaded with the pre-lithiation anode material doped with lithium iron in an aqueous solution; and then forming a lithium cobaltate precursor containing the carbon nano tube loaded with the pre-lithiated positive electrode material doped with lithium iron through a self-assembly mode.
According to the pre-lithiation lithium cobalt oxide with the core-shell structure, the pre-lithiation anode material is loaded in the carbon nano tube to be doped with lithium iron oxide, so that the internal space of the carbon nano tube is effectively utilized, and the occupied effective volume of an active substance of the anode material is reduced; the first efficiency of the anode material can be improved, and the reversible gram capacity of the material can be improved.
The preparation method of the pre-lithiation lithium cobaltate with the core-shell structure adopts green dissolved ionic liquid, has an environment-friendly preparation process, is easy to control, and is a preparation method of a positive electrode material with a good prospect.
Drawings
FIG. 1 is a schematic diagram of the structures of the products of step (1) and step (2) in example 1 of the present invention: 1-A is the product of step (1), and 1-B is the product of step (2);
FIG. 2 is a schematic diagram of the structures of the products of steps (3) to (7) described in example 1 of the present invention: 2-A is the product of step (3), 2-B is the product of step (4), 2-C is the product of step (5), 2-D is the product of step (6), 2-E is the product of step (7);
FIG. 3 is a MgCo cobaltate prepared in step (3) of example 12O4The particle size distribution curve of (a);
fig. 4 is an SEM image of the surface-coated lithium cobaltate prepared in step (6) described in example 1;
FIG. 5 is an SEM image of surface-coated titanium nitride and lithium cobalt oxide alumina prepared in step (7) of example 1;
FIG. 6 is an SEM image of a thin film battery electrode sheet prepared in example 1;
FIG. 7 is an SEM image of a thin film battery electrode piece coated with titanium nitride and lithium cobalt oxide aluminum prepared in comparative example 1;
FIG. 8 is a graph of capacity retention of thin film batteries of example 1 and comparative example 1;
FIG. 9 is a graph of capacity retention of thin film batteries of examples 1 and 2;
FIG. 10 is a graph of capacity retention of thin film batteries of example 7 and comparative example 1;
fig. 11 is an SEM image of the thin film battery electrode sheet prepared in example 10.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
And (3) material performance characterization:
(1) the surface morphology of the material was carried out on a JSM-6510 scanning electron microscope, JEOL, Japan, and an EV018 scanning electron microscope, Zeiss, Germany, and the X-ray energy scattering EDS spectra and the elemental surface distribution maps were carried out on an Oxford X-MAX 20 energy spectrometer.
(2) The median particle size of the material particles was carried out on a malvern Mastersizer 2000 laser particle sizer in the uk.
(3) The mass percentage content of the element nickel is measured by a gravimetric method; the mass percentage content of the element cobalt is measured by adopting a potentiometric titration method; the mass percentage content of the element manganese is determined by a titration method; measuring the mass percentage of the element fluorine by adopting an ion selective electrode method; the content of other metal elements is measured by ICP method.
(4) The crystal structure test is carried out on a D/max 2500VL/PC type XRD diffractometer of Japan science company, a copper target is adopted, the test precision is +/-0.02 degrees, and the scanning range is from 5 degrees to 90 degrees.
(5) The specific surface area of the material is measured on a Bekedlan BSD-660 full-automatic high-performance physical adsorption instrument.
And (3) electrochemical performance testing:
(1) electricity withholding test
According to the mass ratio of 90: 2: 8, weighing an anode active material (the anode active material is amorphous powder formed after the silicon-titanium alloy prepared in the example 1 is ball-milled for 120 hours, and the carbon-coated silicon-titanium nitride alloy cathode material generated in the example 4), a conductive agent Super P and a binder PVDF (HSV900), adding a proper amount of N-methylpyrrolidone as a solvent, and stirring for 15 hours by using a magnetic stirrer in a glove box under the protection of argon to prepare slurry required for power-on. The coating machine is an automatic machine of Shenzhen science and technology Limited MSK-AFA-IIIA coating dryer with a coating gap of 25 micrometers and a speed of 5 cm/min, wherein the slurry is uniformly coated on a smooth copper foil with the thickness of 9 micrometers and the purity of 99.8 percent, which is produced by Jinxiang copper foil Limited in Meixian county, is dried in vacuum at 120 ℃ for 12 hours, and then is punched into an electrode slice with the diameter of about 16 millimeters by a Shenzhen Kejing MSK-T06 button cell punching machine. CR2032 coin cells were assembled in a german blaun glove box filled with 99.9% high purity argon. A Shenzhenjian crystal MSK-110 small-sized hydraulic button battery packaging machine is adopted. The cathode is a high-purity lithium sheet with the purity of 99.99 percent and the diameter of 15.8 millimeters, the diaphragm is a American ENTEK LP16 type PE diaphragm with the thickness of 16 micrometers, and the electrolyte is DMC: EMC (60:40, mass ratio), VC (2% of the total mass of DMC and EMC) and 1.3mol/L LiPF6. Button cell cycling and rate testing was performed on a CT2001A tester by wuhan blue electronics ltd.
2) Thin film battery testing
The mass ratio of the positive electrode material is as follows: conductive agent: binder (97.8:1.2: 2); the negative electrode is prepared from graphite G49: conductive agent: the adhesive (96:2:2) was used, and the test voltage was 3.0-4.53V.
The pre-lithiation lithium cobalt oxide with the core-shell structure prepared by the preparation method disclosed by the invention can improve the first efficiency and the cycle performance of a lithium cobalt oxide positive electrode material, and the preparation process is green and environment-friendly and is suitable for large-scale production.
A preparation method of pre-lithiation lithium cobalt oxide with a core-shell structure comprises the following steps:
(1) preparation of carbon nanotube-loaded doped lithium iron oxide Li5FenX(1-n)O4：
Dissolving ferric salt and other metal salts in an aqueous solution, adding surfactant molecules, lithium compounds and carbon nano tubes, adjusting the pH value and temperature of the solution, stirring, filtering and washing after reaction to obtain a precursor, calcining the precursor in the air, crushing, sieving, washing and drying the calcined product to obtain the carbon nano tube loaded lithium iron doped Li5FenX(1-n)O4；
(2) Preparation of surface self-assembled film modified carbon nanotube loaded doped lithium iron oxideLi5FenX(1-n)O4：
Loading the obtained carbon nano tube with doped lithium iron oxide Li5FenX(1-n)O4Placing the mixture into an ionic liquid solution containing a surfactant, uniformly stirring, filtering and cleaning to obtain the surface self-assembled film modified carbon nanotube loaded doped lithium iron oxide Li5FenX(1-n)O4；
(3) Preparation of seed Cobaltate MCo of lithium cobaltate precursor2O4：
Dissolving cobalt salt and other metal salts in a non-aqueous solvent, adding surfactant molecules, performing ultrasonic treatment after reaction, filtering, cleaning, drying, and calcining in air to obtain a product, namely a lithium cobaltate precursor seed crystal cobaltate MCo2O4；
(4) Preparing a lithium cobaltate precursor:
loading lithium ferrate Li to the surface self-assembly film modified carbon nano tube obtained in the step (2)5FenX(1-n)O4And the cobaltate MCo obtained in the step (3)2O4Placing the mixture into an alkaline aqueous solution reaction kettle, uniformly stirring, introducing a cobalt ion aqueous solution, a doped metal ion aqueous solution and an alkaline aqueous solution into the mixture, adjusting the pH value and the temperature of the solution, and filtering and cleaning a product after the reaction is finished to obtain a lithium cobaltate precursor;
(5) preparing lithium cobaltate:
mixing the obtained lithium cobaltate precursor with a lithium compound, and calcining to obtain lithium cobaltate;
(6) preparing surface-coated lithium cobaltate:
placing the obtained lithium cobaltate in an aqueous solution, stirring and mixing, adjusting the pH value and the temperature of the solution, adding a metal compound, keeping the reaction time constant, filtering and cleaning the reaction solution, and drying to prepare surface-coated lithium cobaltate;
(7) preparing surface nitride coated lithium cobaltate:
and mixing the obtained surface-coated lithium cobaltate with a nitrogen source, calcining and cooling in an inert atmosphere to obtain the nitride-coated lithium cobaltate.
The present invention will be described in detail with reference to examples.
Example 1
A preparation method of lithium cobaltate with a pre-lithiation core-shell structure comprises the following steps:
step (1): adding 300 g of polymer surfactant molecular polyvinyl alcohol (PVAL) into 5L of 5mol/L lithium nitrate solution, uniformly stirring until the solution is clear, adjusting the pH of the solution to 9.5 by using lithium hydroxide, adding 200 g of carbon nano tubes with the diameter of 80nm and the length of about 3 microns, stirring at a high speed of 1000rpm/min until the solution is uniformly mixed, adding 1L of 5mol/L ferric nitrate solution in the stirring process, keeping the reaction temperature of the solution constant at 90 ℃ for 10 hours, filtering the prepared slurry, washing by using hot deionized water until the washing solution is clear, drying in the air at 100 ℃, calcining the prepared product at 450 ℃ for 5 hours in the air atmosphere, naturally cooling, crushing and sieving by using a 150-mesh sieve, thus preparing the product, namely the carbon nano tube loaded lithium iron doped Li5FeO4；
Step (2): adding 20 g of surfactant molecule Cetyl Trimethyl Ammonium Bromide (CTAB) into 3L 1-methylimidazolium chloride, stirring, dissolving and mixing uniformly, keeping the solution temperature at 25 ℃, and adding 200 g of carbon nano tube loaded doping lithium iron oxide Li prepared in the step (1)5FeO4Stirring and mixing for 3 hours, filtering, washing with absolute ethyl alcohol until the solution is clear, and preparing the carbon nano tube loaded doped lithium iron oxide Li with the surface self-assembled CTAB membrane modified5FeO4；
And (3): mixing 1L of 2mol/L cobalt nitrate solution and 1L of 1mol/L magnesium nitrate solution, adding 20 g of polymer surfactant molecular polyethylene glycol (PEG), uniformly stirring until the solution is clear, placing the solution in a high-pressure reaction kettle, keeping the temperature at 150 ℃, stirring at a high speed at 1000rpm/min for reaction for 10 hours, filtering a product, washing the product with absolute ethyl alcohol until the solution is clear, drying the product at 80 ℃ in vacuum, calcining the product at 450 ℃ for 5 hours in a muffle furnace under air atmosphere, naturally cooling, crushing the product, and sieving the product with a 400-mesh sieve to obtain a magnesium cobaltate MgCo product with D50 of 3.05 microns2O4Magnesium cobaltate MgCo2O4The particle size distribution curve of (a) is shown in FIG. 3;
and (4): MCNT-Li prepared in the step (2)5FeO4And the magnesium cobaltate MgCo prepared in the step (3)2O4Putting the mixture into a reaction kettle of alkaline aqueous solution in 1.5mol/L ammonium bicarbonate aqueous solution, adding ammonia water to keep the pH value at 7.5, keeping the temperature at 40 ℃ under stirring, adding 1mol/L cobalt nitrate aqueous solution and 0.003mol/L aluminum sulfate aqueous solution in a concurrent flow manner through a peristaltic pump, reacting for 15 hours, standing and aging for 3 hours at 30 ℃ at constant temperature, filtering, washing with 0.1mol/L ammonium bicarbonate, and drying in vacuum to obtain the doped cobalt carbonate with D50 of 15.30 micron core-shell structure, wherein the inner core is a product of cobalt magnesium cobaltate MgCo with D50 of 3.05 micron2O4Inside the outer shell is MCNT-Li5FeO4Self-assembly in a crystal structure by electrostatic adsorption;
and (5): preparing lithium cobaltate;
mixing the lithium cobaltate precursor prepared in the step (4) with lithium carbonate according to the stoichiometric molar ratio of cobalt to lithium of 1:1.15, calcining for 5 hours at 450 ℃ in air, and calcining for 10 hours at 900 ℃ to prepare a product D50 which is 16.40 micron lithium cobaltate;
and (6): putting 500 g of the lithium cobaltate prepared in the step (5) into 2L of aqueous solution, stirring and mixing, keeping the pH of the solution at 11 and the temperature at 25 ℃, adding 10 g of n-butyl titanate and 0.01mol/L of aluminum sulfate, reacting for 2 hours, filtering and cleaning the reaction solution, drying in the air at 100 ℃, and preparing titanium dioxide and aluminum oxide coated lithium cobaltate, wherein an SEM image of the surface coated lithium cobaltate is shown in figure 4;
and (7): placing the surface-coated lithium cobaltate prepared in the step (6) in a tube furnace, introducing ammonia gas, keeping the temperature at 400 ℃ for 10 hours, cooling to 25 ℃ under the nitrogen protection atmosphere, and preparing titanium nitride and aluminum oxide-coated lithium cobaltate, wherein SEM images of the surface-coated titanium nitride and aluminum oxide-coated lithium cobaltate are shown in FIG. 5; the SEM image of the prepared thin film battery electrode sheet is shown in fig. 6.
Comparative example 1
The only difference from example 1 is that: the preparation of the prelithiation anode material not comprising the step (1) and the step (2) and the preparation of the carbon nano tube loaded doped lithium iron oxide Li not comprising the surface self-assembly film modification5FenX(1-n)O4。
FIG. 7 is an SEM image of a thin film battery electrode piece coated with titanium nitride and lithium cobalt oxide aluminum prepared in comparative example 1;
the capacity retention rate curves of the thin film batteries of example 1 and comparative example 1 are shown in fig. 8; example 1 loaded lithium iron oxide doped Li containing surface self-assembled film modified carbon nanotubes5FeO4In the latter-stage cycle, the capacity retention was better than that of comparative example 1.
Example 2
The only difference from example 1 is that: step (1): 200 g of polymer surfactant molecule polyethylene glycol (PEG) is added into 5L of 5mol/L lithium nitrate solution.
The capacity retention rate curves of the thin film batteries of the examples 1 and 2 are shown in FIG. 9; the capacity retention rates of example 1 and example 2 were the same after 250 cycles.
Example 3
The only difference from example 1 is that: step (2): 30 g of surfactant molecule sodium lauryl sulfate (SDS) is added into 3L of 1-methylimidazole tetrafluoroborate, and the mixture is stirred, dissolved and mixed evenly.
The capacity retention rate curves of the thin film batteries are the same in the embodiment 1 and the embodiment 3.
Example 4
The only difference from example 1 is that:
adding ammonia water with constant pH of 8.0, keeping the temperature at 45 ℃ under the stirring condition, and adding a 1.5mol/L cobalt sulfate aqueous solution in a concurrent flow manner through a peristaltic pump;
and (7): and (3) uniformly stirring and mixing the surface-coated lithium cobaltate prepared in the step (6) and ethylenediamine according to the stoichiometric molar ratio of 1:0.03, placing the mixture in a tube furnace, keeping the temperature at 450 ℃ for 10 hours, and cooling the mixture to 25 ℃ in a nitrogen protective atmosphere to prepare titanium nitride and alumina-coated lithium cobaltate.
Example 5
The only difference from example 1 is that:
step (5) mixing the lithium cobaltate precursor prepared in the step (4) with lithium carbonate according to the stoichiometric molar ratio of cobalt to lithium of 1:1.10, and calcining at the temperature of 950 ℃ when calcining for 5 hours at the temperature of 450 ℃ in air;
and (6): and (3) putting 500 g of the lithium cobaltate prepared in the step (5) into 2L of aqueous solution, stirring and mixing, keeping the pH value of the solution at 11 and the temperature at 25 ℃, adding 20 g of n-butyl titanate, reacting for 2 hours, filtering and cleaning the reaction solution, and drying in the air at 100 ℃ to prepare the titanium dioxide coated lithium cobaltate.
Example 6
The only difference from example 1 is that: and (6): and (3) placing 500 g of lithium cobaltate prepared in the step (5) in 2L of aqueous solution, stirring and mixing, keeping the pH of the solution at 11 and the temperature at 25 ℃, adding 10 g of n-butyl titanate and 10 g of aluminum isopropoxide, reacting for 2 hours, filtering and cleaning the reaction solution, and drying in the air at 100 ℃ to prepare the titanium dioxide and aluminum oxide coated lithium cobaltate.
Example 7
The only difference from example 1 is that:
and (7): and (3) uniformly stirring and mixing the surface-coated lithium cobaltate prepared in the step (6) and urea according to the stoichiometric molar ratio of 1:0.05, placing the mixture in a tube furnace, introducing high-purity nitrogen, keeping the temperature at 500 ℃ for 8 hours, and cooling to 25 ℃ under the nitrogen protective atmosphere to prepare titanium nitride and aluminum oxide-coated lithium cobaltate.
The capacity retention rate curves of the thin film batteries of example 7 and comparative example 1 are shown in fig. 10; example 7 has a higher capacity retention than comparative example 1.
Example 8
The only difference from example 1 is that:
step (1): adding 200 g of polyvinyl pyrrolidone PVP into 5L of 2mol/L lithium nitrate solution, uniformly stirring until the solution is clear, adjusting the pH of the solution to 9.0 by using lithium hydroxide, and adding 200 g of carbon nano tubes with the diameter of 200nm and the length of 2 microns;
step (2): adding 20 g of Cetyl Trimethyl Ammonium Bromide (CTAB) serving as a surfactant molecule and 10 g of polyethylene glycol (PEG) serving as a polymer surfactant molecule into 4L 1-ethylimidazole trifluoroacetate, stirring, dissolving and mixing uniformly, keeping the solution temperature at 25 ℃, adding 200 g of the carbon nano tube loaded doped lithium iron oxide Li prepared in the step (1)5FeO4。
Example 9
The only difference from example 1 is that: step (1): adding 400 g of polymer Polyaniline (PANI) into 4L of 3mol/L lithium perchlorate solution, uniformly stirring until the solution is clear, adjusting the pH value of the solution to 9.2 by using lithium carbonate, adding 300 g of carbon nano tubes with the diameter of 90nm and the length of about 2 microns, stirring at a high speed at 1000rpm/min until the solution is uniformly mixed, adding 1L of 5mol/L ferric nitrate solution and 1L of 0.1mol/L ferric aluminum nitrate solution during stirring, keeping the reaction temperature at 90 ℃, and reacting for 10 hours. Filtering the prepared slurry, washing the slurry with hot deionized water until a washing solution is clear, drying the slurry in the air at 100 ℃, calcining the prepared product for 5 hours at 450 ℃ under the air atmosphere, naturally cooling the calcined product, crushing the calcined product and sieving the crushed product with a 150-mesh sieve to obtain the carbon nano tube loaded doped lithium iron oxide Li5Fe0.9Al0.1O4。
First charge and discharge efficiencies of the thin film batteries of example 1, example 9 and comparative example 1 are shown in table 1; examples 1 and 9 contain pre-conditioned MCNT-Li5FeO4The first efficiency of lithium cobaltate is higher than the first efficiency of lithium cobaltate without pre-lithiation.
TABLE 1 first charge-discharge efficiency of thin film battery
The capacity retention rate curves of the thin film batteries are the same as those of the thin film batteries in example 9 and example 1.
Example 10
The only difference from the examples is: and (7): and (3) uniformly stirring and mixing the surface-coated lithium cobaltate prepared in the step (6) and the brown liquid hydrophilic ionic liquid 1-butylpyridinium dinitrile amine salt according to the stoichiometric molar ratio of 1:0.02:0.03 to 1-butyl-3-methylimidazolium dinitrile amine salt, placing the mixture in a tubular furnace, keeping the temperature at 500 ℃ for 12 hours, cooling the mixture to 25 ℃ under the nitrogen protection atmosphere, and preparing the titanium nitride and aluminum oxide-coated lithium cobaltate.
The capacity retention rate curves of the thin film batteries are the same in the embodiment 1 and the embodiment 10. An SEM image of the thin film battery electrode sheet prepared in example 10 is shown in fig. 11.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of lithium cobaltate with a pre-lithiation core-shell structure is characterized by comprising the following steps: the method comprises the following steps:
(1) preparation of carbon nanotube-loaded doped lithium iron oxide Li5FenX(1-n)O4：
Dissolving ferric salt and other metal salts in an aqueous solution, adding surfactant molecules, lithium compounds and carbon nano tubes, adjusting the pH value and temperature of the solution, stirring, filtering and washing after reaction to obtain a precursor, calcining the precursor in the air, crushing, sieving, washing and drying the calcined product to obtain the carbon nano tube loaded lithium iron doped Li5FenX(1-n)O4；
(2) Preparation of surface self-assembled film modified carbon nanotube loaded doped lithium iron oxide Li5FenX(1-n)O4：
Loading the obtained carbon nano tube with doped lithium iron oxide Li5FenX(1-n)O4Placing the mixture into an ionic liquid solution containing a surfactant, uniformly stirring, filtering and cleaning to obtain the surface self-assembled film modified carbon nanotube loaded doped lithium iron oxide Li5FenX(1-n)O4；
(3) Preparation of seed Cobaltate MCo of lithium cobaltate precursor2O4：
Dissolving cobalt salt and other metal salts in a non-aqueous solvent, adding surfactant molecules, performing ultrasonic treatment after reaction, filtering, cleaning, drying, and calcining in air to obtain a product, namely a lithium cobaltate precursor seed crystal cobaltate MCo2O4；
(4) Preparing a lithium cobaltate precursor:
loading lithium ferrate Li to the surface self-assembly film modified carbon nano tube obtained in the step (2)5FenX(1-n)O4And the cobaltate MCo obtained in the step (3)2O4Placing the mixture into an alkaline aqueous solution reaction kettle, uniformly stirring, introducing a cobalt ion aqueous solution, a doped metal ion aqueous solution and an alkaline aqueous solution into the mixture, adjusting the pH value and the temperature of the solution, and filtering and cleaning a product after the reaction is finished to obtain a lithium cobaltate precursor;
(5) preparing lithium cobaltate:
mixing the obtained lithium cobaltate precursor with a lithium compound, and calcining to obtain lithium cobaltate;
(6) preparing surface-coated lithium cobaltate:
placing the obtained lithium cobaltate in an aqueous solution, stirring and mixing, adjusting the pH value and the temperature of the solution, adding a metal compound, keeping the reaction time constant, filtering and cleaning the reaction solution, and drying to prepare surface-coated lithium cobaltate;
(7) preparing surface nitride coated lithium cobaltate:
and mixing the obtained surface-coated lithium cobaltate with a nitrogen source, calcining and cooling in an inert atmosphere to obtain the nitride-coated lithium cobaltate.
2. The method for preparing lithium cobaltate with a pre-lithiated core-shell structure according to claim 1, wherein the method comprises the following steps: the ferric salt in the step (1) is at least one of ferric nitrate, ferric sulfate, ferric chloride, ferric perchlorate or ferric acetate; the other metal salt is a water-soluble metal salt; the surfactant molecule is at least one of an ionic surfactant or a nonionic surfactant; the lithium compound is at least one of lithium hydroxide, lithium carbonate, lithium bicarbonate, lithium perchlorate, lithium nitrate, lithium sulfate, lithium chloride, lithium acetate or lithium fluoride; the carbon nano tube is a carbon nano tube with at least one open end; the diameter of the carbon nano tube is 0.01-500 microns; the pH value is 7-12; the temperature is 20-100 ℃; the reaction time is 0.5-5 hours; the calcining temperature is 100-500 ℃; what is needed isThe carbon nano tube loaded with doped lithium ferrate Li5FenX(1-n)O4The structure of (1) is as follows: filling doped lithium iron oxide Li in carbon nano tube5FenX(1-n)O4Li generated by reaction outside carbon nanotube5FenX(1-n)O4Stripping from the carbon nano tube after washing; the doped lithium ferrate Li5FenX(1-n)O4Wherein n is 0 to 0.5.
3. The method for preparing lithium cobaltate with a pre-lithiated core-shell structure according to claim 1, wherein the method comprises the following steps: the concentration of the surfactant in the step (2) is 0.01-10 mol/L; the temperature is 10-40 ℃; the reaction time is 0.5-20 hours; the surfactant molecule is at least one of an ionic surfactant or a nonionic surfactant; the ionic liquid is soluble in water.
4. The method for preparing lithium cobaltate with a pre-lithiated core-shell structure according to claim 1, wherein the method comprises the following steps: the cobalt salt in the step (3) is at least one of cobalt nitrate, cobalt sulfate, cobalt chloride or cobalt acetate; the other metal salt is water-soluble other metal salt; the other metal salt is at least one of nitrate, sulfate, chloride or acetate; the surfactant molecule is at least one of an ionic surfactant or a nonionic surfactant; the ultrasonic frequency of the ultrasonic step is 20-80 kHz; the reaction temperature is 50-300 ℃; the reaction time is 2-50 hours; the calcination temperature is 200-800 ℃.
5. The method for preparing lithium cobaltate with a pre-lithiated core-shell structure according to claim 1, wherein the method comprises the following steps: in the step (4): surface self-assembly film modified carbon nanotube loaded lithium iron oxide doped Li in reaction kettle5FenX(1-n)O4The concentration of the solution is constant and is 0.01-5 mol/L; cobaltate MCo in reaction kettle2O4The concentration of the solution is constantly 0.02-10 mol/L; the cobalt ion aqueous solution is at least one of cobalt nitrate, cobalt sulfate, cobalt chloride or cobalt acetate aqueous solution; the doped metal ion solution is at least one of water-soluble nitrate, sulfate, chloride or acetate aqueous solutions of other metal ions; the alkaline aqueous solution is at least one of aqueous solution of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, ammonium carbonate or ammonium bicarbonate; the other metal is at least one of potassium, sodium, calcium, nickel, manganese, copper, silver, magnesium, aluminum, zirconium, vanadium, zinc, germanium, molybdenum, indium, antimony, bismuth, barium, tungsten, palladium, strontium, cerium, niobium, zirconium, scandium or gallium; the pH value of the solution is 7-12; the temperature is 20-90 ℃; the reaction time is 1-60 hours.
6. The method for preparing lithium cobaltate with a pre-lithiated core-shell structure according to claim 1, wherein the method comprises the following steps: the lithium compound in the step (5) is at least one of lithium hydroxide, lithium carbonate or lithium acetate; the stoichiometric molar ratio of the lithium cobaltate precursor to the lithium compound is 1.20-1.0; the temperature of the calcination step is 400-1200 ℃, and the temperature is kept for 5-50 hours.
7. The method for preparing lithium cobaltate with a pre-lithiated core-shell structure according to claim 1, wherein the method comprises the following steps: the pH value in the step (6) is 7-12; the temperature is 10-90 ℃; the reaction time is 0.5-10 hours; the washing liquid in the washing step is at least one of ultrapure water, ethanol, propanol or isopropanol; the temperature of the drying step is 80-200 ℃; the surface-coated lithium cobaltate structure is that the surface of the lithium cobaltate is uniformly coated with titanium dioxide and/or other metal oxides.
8. The method for preparing lithium cobaltate with a pre-lithiated core-shell structure according to claim 1, wherein the method comprises the following steps: the metal compound in the step (6) is at least one of titanium metal organic compound and/or at least one of other metal soluble salt and other metal organic compound; the titanium metal organic compound is at least one of methyl titanate, ethyl titanate, n-propyl titanate, tetrabutyl titanate, tetraisopropyl titanate or titanyl phthalocyanine; the other metal organic compound is a coordination compound formed by other metals and organic compounds; the other metal soluble salt is at least one of other metal soluble salts except titanium metal; the other metal soluble salt is at least one of other metal nitrate, sulfate, chloride, acetate or perchlorate;
the stoichiometric molar ratio of the titanium element to the lithium cobaltate is (0-0.1): 1; the stoichiometric molar ratio of the other metal elements to the lithium cobaltate is (0-0.1): 1.
9. the method for preparing lithium cobaltate with a pre-lithiated core-shell structure according to claim 1, wherein the method comprises the following steps: the stoichiometric molar ratio of the nitrogen source to the surface-coated lithium cobaltate in the step (7) is (0.001-0.2): 1; the nitrogen source is at least one of ammonia gas, urea, amino alkane-containing or nitrogen element-containing ionic liquid; the inert atmosphere is at least one of nitrogen, helium or argon; the temperature of the calcination step is 100-400 ℃, and the time is 1-30 hours.
10. Use of a pre-lithiated lithium cobaltate with core-shell structure prepared by the method of any one of claims 1 to 9 in a lithium ion secondary battery.
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