CN108598458B - Nitrogen-doped lithium titanate composite material, preparation method thereof and lithium ion battery - Google Patents
Nitrogen-doped lithium titanate composite material, preparation method thereof and lithium ion battery Download PDFInfo
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- 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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Abstract
The invention discloses a nitrogen-doped lithium titanate composite material, a preparation method thereof and a lithium ion battery, wherein the preparation method comprises the following steps: dispersing the nanoparticles in a solvent containing a dispersant; dividing the solvent dispersed with the nano particles into two parts, adding a lithium source into one part of solution, adding a titanium source into the other part of solution, and mixing the two parts of solution to prepare sol; heating the sol to 40-100 ℃, and stirring for 4-10 hours at constant temperature to form gel; removing the solvent from the gel at 100-200 ℃ to obtain a precursor; and heating the precursor to 700-1000 ℃ in an inert atmosphere, calcining for 5-20 hours in a reducing atmosphere, and finally cooling and grinding to obtain the nitrogen-doped lithium titanate composite material. The nitrogen-doped lithium titanate composite material prepared by the invention has good electronic conductivity, high lithium ion diffusion speed and stable structure; the lithium ion battery has long service life.
Description
Technical Field
The invention relates to the technical field of battery materials, in particular to a nitrogen-doped lithium titanate composite material, a preparation method thereof and a lithium ion battery.
Background
At present, research on negative electrode materials for lithium ion batteries is mainly developing towards power type battery materials with high specific capacity, high rate, high cycle performance and high safety performance. A conventional anode material is a carbon anode material. Although carbon anodes have been successfully commercialized, the battery safety problems, particularly at high rates, have forced the search for new and reliable anode materials that intercalate lithium at a slightly higher potential than the intercalation potential of carbon anodes. Among them, low potential transition metal oxides and composite oxides have attracted wide attention as negative electrode materials of lithium ion batteries, especially zero strain material Li4Ti5O12At 1.5V (vs. Li/Li)+) The voltage, the charge-discharge efficiency close to 1 and the excellent cycle performance are widely concerned, and the lithium ion battery is an electrode which has great potential to be used as a negative electrode material of a power type lithium ion batteryA material.
Lithium titanate, however, has poor electronic conductivity, which limits its high rate capability. Therefore, it is required to modify the lithium titanate to improve the conductivity thereof, thereby improving the high rate performance of the lithium titanate while maintaining the high reversible electrochemical capacity and good cycle performance thereof. At present, the method for improving the rate capability of lithium titanate mainly comprises the following steps: preparing lithium titanate with nano particle size, doping the lithium titanate body and introducing a conductive phase. Carbon coating of lithium titanate by different methods is currently disclosed, and although some improvement in its performance is achieved, there is a limit to the improvement in its conductivity and no improvement in contrast capacity.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a nitrogen-doped lithium titanate composite material, a preparation method thereof and a lithium ion battery, and aims to solve the problems that the conductivity of lithium titanate is limited to be improved and the contrast capacity is not improved by carbon coating in the prior art.
The technical scheme of the invention is as follows:
a preparation method of a nitrogen-doped lithium titanate composite material comprises the following steps:
(1) dispersing the nanoparticles in a solvent containing a dispersant;
(2) dividing the solvent dispersed with the nano particles into two parts, adding a lithium source into one part of solution, adding a titanium source into the other part of solution, and mixing the two parts of solution to prepare sol;
(3) heating the sol to 40-100 ℃, and stirring for 4-10 hours at constant temperature to form gel;
(4) removing the solvent from the gel at 100-200 ℃ to obtain a precursor;
(5) and heating the precursor to 700-1000 ℃ in an inert atmosphere, calcining for 5-20 hours in a reducing atmosphere, and finally cooling and grinding to obtain the nitrogen-doped lithium titanate composite material.
The preparation method of the nitrogen-doped lithium titanate composite material comprises the step (1), wherein the nano particles are selected from one or more of nano titanium, nano aluminum, nano vanadium, nano zirconium, nano tantalum, nano magnesium, nano calcium, nano boron, nano manganese, nano tungsten, nano carbon nitride and nano titanium nitride.
The preparation method of the nitrogen-doped lithium titanate composite material comprises the step (1), wherein the dispersing agent is selected from one or more of polyethylene glycol, sodium dodecyl sulfate, triethylhexylphosphoric acid, methylpentanol, cellulose derivatives, polyacrylamide, Guel gum, fatty acid polyglycol ester and silane coupling agent.
The preparation method of the nitrogen-doped lithium titanate composite material comprises the step (2), wherein the lithium source is one or more selected from lithium hydroxide, lithium acetate and lithium nitrate.
The preparation method of the nitrogen-doped lithium titanate composite material comprises the step (2), wherein the titanium source is one or more selected from butyl titanate, titanium tetrachloride, metatitanic acid, n-propyl titanate, isopropyl titanate and acetylacetonato titanium oxide titanate coupling agent.
The preparation method of the nitrogen-doped lithium titanate composite material comprises the step (2), wherein the mass ratio of the lithium source to the titanium source to the nano particles is 0.75-0.90:1: 0.01-0.1.
The preparation method of the nitrogen-doped lithium titanate composite material comprises the step (5), wherein the inert atmosphere is selected from one of argon, nitrogen and helium.
The preparation method of the nitrogen-doped lithium titanate composite material comprises the step (5), wherein the reducing atmosphere is selected from one of ammonia gas and nitrogen-hydrogen mixed gas.
The invention discloses a nitrogen-doped lithium titanate composite material, which is prepared by the preparation method of the nitrogen-doped lithium titanate composite material.
A lithium ion battery comprises a negative electrode, wherein the material of the negative electrode is the nitrogen-doped lithium titanate composite material.
Has the advantages that: the nitrogen-doped lithium titanate composite material prepared by the invention has good electronic conductivity, high lithium ion diffusion speed and stable structure; the introduction of the auxiliary nitrogen-doped nano particles not only effectively inhibits the activity of tetravalent titanium ions, greatly relieves the problem of gas generation caused by the catalytic cracking of electrolyte by the tetravalent titanium ions, but also stabilizes the crystal structure of lithium titanate, increases the lattice stability of the lithium titanate material in the lithium deintercalation process, and prolongs the service life of the lithium titanate battery. In addition, the preparation method has the advantages of simple preparation process, easily controlled process parameters and lower production cost, and is suitable for industrial large-scale production.
Drawings
Fig. 1 is an XRD pattern of nitrogen-doped lithium titanate composite materials prepared in example 1, example 2 and example 3;
FIG. 2 is a graph comparing EIS of the nitrogen-doped lithium titanate composite material prepared in example 1 and a conventional non-nitrided lithium titanate material;
fig. 3 is a first charge-discharge curve diagram of 0.2C of the nitrogen-doped lithium titanate composite material prepared in example 1;
fig. 4 is a first charge-discharge curve diagram of the nitrogen-doped lithium titanate composite material 5C prepared in example 2;
fig. 5 is a cycle performance diagram of charging and discharging of the nitrogen-doped lithium titanate composite material 5C prepared in example 2.
Detailed Description
The invention provides a nitrogen-doped lithium titanate composite material, a preparation method thereof and a lithium ion battery, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a preparation method of a nitrogen-doped lithium titanate composite material, which comprises the following steps:
(1) dispersing the nanoparticles in a solvent containing a dispersant;
(2) dividing the solvent dispersed with the nano particles into two parts, adding a lithium source into one part of solution, adding a titanium source into the other part of solution, and mixing the two parts of solution to prepare sol;
(3) heating the sol to 40-100 ℃, and stirring for 4-10 hours at constant temperature to form gel;
(4) removing the solvent from the gel at 100-200 ℃ to obtain a precursor;
(5) and heating the precursor to 700-1000 ℃ in an inert atmosphere, calcining for 5-20 hours in a reducing atmosphere, and finally cooling and grinding to obtain the nitrogen-doped lithium titanate composite material.
The step (1) specifically comprises: firstly, adding a dispersing agent into a solvent (such as absolute ethyl alcohol), and then ultrasonically dispersing the nanoparticles into the solvent containing the dispersing agent for 1.5-2.5h (such as 2 h).
Preferably, the nano particles are selected from one or more of nano titanium, nano aluminum, nano vanadium, nano zirconium, nano tantalum, nano magnesium, nano calcium, nano boron, nano manganese, nano tungsten, nano carbon nitride, nano titanium nitride and the like.
Preferably, the dispersant is selected from one or more of polyethylene glycol, sodium dodecyl sulfate, triethylhexyl phosphoric acid, methyl amyl alcohol, cellulose derivatives, polyacrylamide, guar gum, fatty acid polyglycol ester, silane coupling agent and the like.
The step (2) specifically comprises: the solvent with dispersed nano particles is divided into two parts, lithium source is added into one part of solution, titanium source is added into the other part of solution, and the two parts of solution are mixed to prepare sol. If a lithium source and a titanium source are directly added into the solvent in which the nanoparticles are dispersed, the lithium source and the titanium source can be quickly reacted, and the particle size, the morphology and the performance of a target product are influenced. The invention adopts the steps of respectively adding the lithium source and the titanium source into the two parts of solution, and then mixing the two parts of solution, so that the sol can be better formed by separately adding the two parts of solution.
Preferably, the lithium source is selected from one or more of lithium hydroxide, lithium acetate, lithium nitrate, and the like.
Preferably, the titanium source is selected from one or more of butyl titanate, titanium tetrachloride, metatitanic acid, n-propyl titanate, isopropyl titanate, and titanium oxide acetylacetonate titanate coupling agent, and the like.
Preferably, the ratio of the amounts of the lithium source, titanium source and nanoparticles is 0.75-0.90:1: 0.01-0.1. The lithium ion is kept surplus by about 3 percent, so that the lithium loss in the sintering process can be supplemented, and the integrity of crystal grains is facilitated.
The step (5) specifically comprises: and heating the precursor to 700-1000 ℃ at a speed of 4-6 ℃/min in an inert atmosphere, switching the inert atmosphere to a reducing atmosphere, calcining at a constant temperature for 5-20 h, switching the reducing atmosphere to the inert atmosphere, naturally cooling to room temperature, grinding, and sieving to obtain the nitrogen-doped nano lithium titanate powder. The reducing atmosphere is used under the high-temperature condition to assist nitrogen doping, and the inert atmosphere is used in the heating and cooling processes to ensure the structural stability of the target product.
Preferably, the inert atmosphere is selected from one of argon, nitrogen, helium, and the like.
Preferably, the reducing atmosphere is selected from one of ammonia gas, nitrogen-hydrogen mixed gas and the like.
The nitrogen-doped nano particles release nitrogen to help lithium titanate to be nitrided, or react with the nitrogen to generate nitride with high electronic conductivity, or capture oxygen molecules in lithium titanate to form oxide to help lithium titanate to be converted into lithium titanate nitride.
The formation mechanism of the nitrogen-doped lithium titanate composite material of the present invention is further illustrated below: in the formation process of lithium titanate, due to the existence of reducing atmosphere, such as nitrogen atmosphere, part of oxygen positions can be occupied by active nitrogen during the crystallization process of product particles, so that nitrogen doping is realized. In addition, the doped nano ions release nitrogen elements to occupy partial oxygen positions, or oxygen atoms in the lithium titanate are abstracted to form oxides, and the oxygen positions in the lithium titanate are occupied by the nitrogen atoms to further assist nitrogen doping.
Compared with the prior art, the nitrogen-doped lithium titanate composite material with good electronic conductivity and high lithium ion diffusion speed is prepared by adopting the method of introducing the auxiliary nitrogen-doped nano particles, so that the problems of low electronic conductivity and large crystal boundary resistance in the process of applying the conventional lithium titanate material to high-rate charge and discharge are solved; the introduction of the auxiliary nitrogen-doped nano particles not only effectively inhibits the activity of tetravalent titanium ions, greatly relieves the problem of gas generation caused by the catalytic cracking of electrolyte by the tetravalent titanium ions, but also stabilizes the crystal structure of lithium titanate, increases the lattice stability of the lithium titanate material in the lithium deintercalation process, and prolongs the service life of the lithium titanate battery. In addition, the method is simple in preparation process, suitable for modification production of the existing lithium titanate material, low in production cost and suitable for industrial large-scale production.
The invention also provides a nitrogen-doped lithium titanate composite material, wherein the nitrogen-doped lithium titanate composite material is prepared by the preparation method of the nitrogen-doped lithium titanate composite material.
The invention also provides a lithium ion battery which comprises a negative electrode, wherein the material of the negative electrode is the nitrogen-doped lithium titanate composite material.
The invention is further illustrated by the following examples.
Example 1
The preparation method of the nitrogen-doped lithium titanate composite material comprises the following steps:
weighing 4.25g of lithium acetate, 17.36g of butyl titanate, 0.48g of nano metal titanium powder, 1g of polyethylene glycol and 25g of absolute ethyl alcohol.
Firstly, adding polyethylene glycol into absolute ethyl alcohol, then ultrasonically dispersing the nano titanium powder into the absolute ethyl alcohol containing the polyethylene glycol, and ultrasonically dispersing for 2 hours.
Taking 15g of absolute ethyl alcohol dispersed with nano titanium powder, adding butyl titanate into the absolute ethyl alcohol, adding lithium acetate into the rest of absolute ethyl alcohol dispersed with nano titanium powder, and mixing the two solutions under the stirring condition to obtain sol.
The sol is heated to 60 ℃, and stirred for 4 hours at constant temperature to form gel.
And drying the gel at 120 ℃ to obtain a precursor.
And heating the precursor to 700 ℃ at a speed of 5 ℃/min in an argon atmosphere, switching the argon atmosphere to an ammonia atmosphere, keeping the temperature for 5h, switching the ammonia atmosphere to the argon atmosphere, naturally cooling to room temperature, grinding, and sieving with a 150-mesh sieve to obtain the nitrogen-doped nano lithium titanate powder. The powder color is white. The lithium titanate is tested by X-ray powder diffraction (XRD) and has a single spinel structure, as shown in a in figure 1.
Electrochemical tests were performed under the following conditions: the prepared nitrogen-doped lithium titanate composite material is used as an active substance, Super P (Super carbon) is used as a conductive agent, PVDF (polyvinylidene fluoride) is used as a binder, NMP (N-methyl-2-pyrrolidone) is used as a solvent, prepared into slurry, and the slurry is coated on copper foil to prepare an electrode plate. And (3) assembling the test battery by taking a lithium sheet as a counter electrode, taking the concentration of the electrolyte as 1mol/L and taking a polypropylene microporous membrane as a diaphragm of the battery. Button cells were assembled in a glove box filled with argon and subjected to electrochemical testing. The charge-discharge voltage range is 1.0-2.5V. The product is assembled into a battery according to the method, the first discharge capacity is more than 190mAh/g at 0.2C, and the charge capacity is close to 180mAh/g, as shown in figure 3. The resistance of Lithium Titanate (LTON) after nitrogen doping is significantly reduced, and the electrochemical impedance is shown in fig. 2 compared to non-nitrided Lithium Titanate (LTO).
Example 2
The preparation method of the nitrogen-doped lithium titanate composite material comprises the following steps:
weighing 4.25g of lithium acetate, 17.36g of butyl titanate, 0.48g of nano metal titanium powder, 1g of polyethylene glycol and 25g of absolute ethyl alcohol.
Firstly, adding polyethylene glycol into absolute ethyl alcohol, then ultrasonically dispersing nano metal titanium powder into the absolute ethyl alcohol containing the polyethylene glycol, and ultrasonically dispersing for 2 hours.
Taking 15g of absolute ethyl alcohol dispersed with nano metal titanium powder, adding butyl titanate into the absolute ethyl alcohol, adding lithium acetate into the rest of absolute ethyl alcohol dispersed with nano metal titanium powder, and mixing the two solutions under stirring to obtain sol.
The sol is heated to 60 ℃, and stirred for 4 hours at constant temperature to form gel.
And drying the gel at 120 ℃ to obtain a precursor.
And heating the precursor to 800 ℃ at a speed of 5 ℃/min in an argon atmosphere, switching the argon atmosphere to an ammonia atmosphere, keeping the temperature for 5h, switching the ammonia atmosphere to the argon atmosphere, naturally cooling to room temperature, grinding, and sieving with a 150-mesh sieve to obtain the nitrogen-doped lithium titanate powder. The color of the nitrogen-doped lithium titanate powder is light gray. The lithium titanate is tested by X-ray powder diffraction (XRD) and has a single spinel structure, as shown in b in figure 1.
The prepared nitrogen-doped lithium titanate powder is assembled into a battery according to the method of example 1, the first discharge capacity is about 160mAh/g at 5C, and the charge capacity is about 155mAh/g, as shown in FIG. 4. The capacity retention after 12000 cycles was greater than 80%, as shown in fig. 5.
Example 3
The preparation method of the nitrogen-doped lithium titanate composite material comprises the following steps:
weighing 4.25g of lithium acetate, 17.36g of butyl titanate, 0.48g of nano metal titanium powder, 1g of polyethylene glycol and 25g of absolute ethyl alcohol.
Firstly, adding polyethylene glycol into absolute ethyl alcohol, then ultrasonically dispersing nano metal titanium powder into the absolute ethyl alcohol containing the polyethylene glycol, and ultrasonically dispersing for 2 hours.
Taking 15g of absolute ethyl alcohol dispersed with nano metal titanium powder, adding butyl titanate into the absolute ethyl alcohol, adding lithium acetate into the rest of absolute ethyl alcohol dispersed with nano metal titanium powder, and mixing the two solutions under stirring to obtain sol.
The sol is heated to 60 ℃, and stirred for 4 hours at constant temperature to form gel.
And drying the gel at 120 ℃ to obtain a precursor.
And heating the precursor to 900 ℃ at a speed of 5 ℃/min in an argon atmosphere, switching the argon atmosphere to an ammonia atmosphere, keeping the temperature for 5h, switching the ammonia atmosphere to the argon atmosphere, naturally cooling to room temperature, grinding, and sieving with a 150-mesh sieve to obtain the nitrogen-doped lithium titanate powder. The powder color is dark gray. The lithium titanate is tested by X-ray powder diffraction (XRD) and has a single spinel structure, as shown in c in figure 1.
Example 4
The other conditions are the same as the example 1, except that the nano metal titanium powder is replaced by the nano metal aluminum powder, and the calcination is carried out in the ammonia atmosphere at the temperature of 700 ℃ for 5 hours to obtain the nitrogen-doped lithium titanate powder. The resulting product was assembled into a battery according to the method of example 1, with a first charge/discharge capacity of about 150mAh/g at 5C and a capacity of about 110mAh/g after 100 cycles.
Example 5
The other conditions are the same as the example 1, except that the nano metal titanium powder is replaced by nano metal vanadium powder, and the calcination is carried out in the ammonia atmosphere at the temperature of 700 ℃ for 5 hours to obtain the nitrogen-doped lithium titanate powder. The resulting product was assembled into a battery according to the method of example 1, with a first charge/discharge capacity of about 152mAh/g at 5C and a capacity of about 115mAh/g after 100 cycles.
In summary, the invention provides a nitrogen-doped lithium titanate composite material, a preparation method thereof and a lithium ion battery. The method for preparing the nitrogen-doped lithium titanate composite material with good electronic conductivity and high lithium ion diffusion speed by introducing the auxiliary nitrogen-doped nano particles solves the problems of low electronic conductivity and large crystal boundary resistance when the conventional lithium titanate material is applied to a high-rate charge-discharge process; the introduction of the auxiliary nitrogen-doped nano particles not only effectively inhibits the activity of tetravalent titanium ions, greatly relieves the problem of gas generation caused by the catalytic cracking of electrolyte by the tetravalent titanium ions, but also stabilizes the crystal structure of lithium titanate, increases the lattice stability of the lithium titanate material in the lithium deintercalation process, and prolongs the service life of the lithium titanate battery. In addition, the preparation method is simple in preparation process, the lithium titanate can be synthesized by any method without affecting the performance of the composite material, the method is suitable for modification production of the existing lithium titanate material, the production cost is low, and the method is suitable for industrial large-scale production.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (8)
1. The preparation method of the nitrogen-doped lithium titanate composite material is characterized by comprising the following steps of:
(1) dispersing the nanoparticles in a solvent containing a dispersant;
(2) dividing the solvent dispersed with the nano particles into two parts, adding a lithium source into one part of solution, adding a titanium source into the other part of solution, and mixing the two parts of solution to prepare sol;
(3) heating the sol to 40-100 ℃, and stirring for 4-10 hours at constant temperature to form gel;
(4) removing the solvent from the gel at 100-200 ℃ to obtain a precursor;
(5) heating the precursor to 700-1000 ℃ in an inert atmosphere, calcining for 5-20 hours in a reducing atmosphere, and finally cooling and grinding to obtain the nitrogen-doped lithium titanate composite material;
in the step (1), the nano particles are selected from one or more of nano titanium, nano aluminum, nano vanadium, nano zirconium, nano tantalum, nano magnesium, nano calcium, nano boron, nano manganese, nano tungsten, nano carbon nitride and nano titanium nitride;
in the step (5), the reducing atmosphere is selected from one of ammonia gas and nitrogen-hydrogen mixed gas.
2. The method of preparing a nitrogen-doped lithium titanate composite material according to claim 1, wherein in the step (1), the dispersant is one or more selected from the group consisting of polyethylene glycol, sodium dodecyl sulfate, triethylhexylphosphoric acid, methylpentanol, cellulose derivatives, polyacrylamide, guar gum, fatty acid polyglycol ester, and silane coupling agent.
3. The method for preparing a nitrogen-doped lithium titanate composite material according to claim 1, wherein in the step (2), the lithium source is one or more selected from lithium hydroxide, lithium acetate and lithium nitrate.
4. The method for preparing a nitrogen-doped lithium titanate composite material according to claim 1, wherein in the step (2), the titanium source is selected from one or more of butyl titanate, titanium tetrachloride, metatitanic acid, n-propyl titanate, isopropyl titanate, and titanium oxide acetylacetonate titanate coupling agent.
5. The method for preparing a nitrogen-doped lithium titanate composite material according to claim 1, wherein in the step (2), the mass ratio of the lithium source, the titanium source and the nanoparticles is 0.75-0.90:1: 0.01-0.1.
6. The method of preparing a nitrogen-doped lithium titanate composite material according to claim 1, wherein in the step (5), the inert atmosphere is selected from one of argon gas and helium gas.
7. A nitrogen-doped lithium titanate composite material, which is characterized by being prepared by the preparation method of the nitrogen-doped lithium titanate composite material as claimed in any one of claims 1 to 6.
8. A lithium ion battery, comprising a negative electrode, wherein the material of the negative electrode is the nitrogen-doped lithium titanate composite material according to claim 7.
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