CN107732205B - Method for preparing sulfur-nitrogen co-doped carbon-coated nano flower-shaped lithium titanate composite negative electrode material - Google Patents

Method for preparing sulfur-nitrogen co-doped carbon-coated nano flower-shaped lithium titanate composite negative electrode material Download PDF

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CN107732205B
CN107732205B CN201710967819.9A CN201710967819A CN107732205B CN 107732205 B CN107732205 B CN 107732205B CN 201710967819 A CN201710967819 A CN 201710967819A CN 107732205 B CN107732205 B CN 107732205B
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lithium titanate
nitrogen
sulfur
doped carbon
nano flower
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CN107732205A (en
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任玉荣
肖慧
丁建宁
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Changzhou University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
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    • 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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Abstract

The invention relates to the technical field of lithium ion battery manufacturing, in particular to a method for preparing a sulfur-nitrogen co-doped carbon-coated nano flower-shaped lithium titanate composite negative electrode material, which comprises the following steps: the preparation method comprises the steps of dispersing polyvinylpyrrolidone, n-butyl titanate and lithium hydroxide monohydrate in an organic solvent, adding thiourea and polyacrylamide after hydrolysis and calcination, and carrying out plasma treatment at high temperature to obtain the sulfur-nitrogen co-doped carbon-coated nano flower-shaped lithium titanate composite negative electrode material. The preparation rate of the electrode material and the specific capacity of the electrode material under a high-rate condition are improved.

Description

Method for preparing sulfur-nitrogen co-doped carbon-coated nano flower-shaped lithium titanate composite negative electrode material
Technical Field
The invention relates to the technical field of lithium ion battery manufacturing, in particular to a method for preparing a sulfur-nitrogen co-doped carbon-coated nano flower-shaped lithium titanate composite negative electrode material.
Background
Spinel type lithium titanate (Li)4Ti5O12) The lithium ion battery cathode material has obvious advantages as a novel lithium ion battery cathode material: zero strain and excellent cycle performance; the high oxidation-reduction potential (1.5VvsLi) does not react with the common electrolyte, so that the safety is good; environment-friendly, easy preparation, low cost and the like. Despite Li4Ti5O12Has a plurality of advantages, but also has a prominent problem: the conductivity is low, so that the high rate performance of the battery is poor, and the battery is greatly limited if the battery is applied to the fields of power vehicles, large energy storage batteries and the like. It can be seen that Li is increased4Ti5The O rate capability being Li4Ti5O12One of the key issues for the application of the anode material.
At present, the common solution approaches of domestic and foreign research groups mainly comprise: firstly, a composite electrode is formed by coating a conductive carbon material on the surface to improve the electronic conductivity of the material; ② doping lithium titanate with ions, improving the stability of the main skeleton to make voids, expanding the ion diffusion channel and weakening the acting force between the main skeleton and the migrating ions, thereby helping Li+Migrating; in addition, appropriate ion doping can reduce the energy band gap of lithium titanate and improve the intrinsic electronic conductivity of the active material; ③ Synthesis of titanic acid with nanometer particle sizeLithium, shortening Li+Migration path and increase of contact area of electrode active material and electrolyte; and fourthly, the porous lithium titanate is prepared, so that the electrolyte can be directly filled in the pore channel, the transmission distance of lithium ions is shortened, and the damage of the structure of the material caused by volume expansion in the circulation process can be reduced.
Disclosure of Invention
To improve Li4Ti5O12The invention provides a method for preparing a sulfur-nitrogen co-doped carbon-coated nano flower-shaped lithium titanate composite negative electrode material, aiming at improving the preparation rate of the electrode material and the specific capacity of the electrode material under a high-rate condition.
The specific preparation process comprises the following steps:
(1) dispersing polyvinylpyrrolidone, tetrabutyl titanate and lithium hydroxide monohydrate in an organic solvent, reacting for 6-12 h at 150-180 ℃,
the organic solvent is a mixed solvent of anhydrous methanol and anhydrous DMF;
(2) filtering the suspension reacted in the step (1), fully washing a filter cake by using an organic solvent, and drying at 80 ℃ to obtain a lithium titanate precursor;
(3) performing plasma treatment on the lithium titanate precursor obtained in the step (2) at 600 ℃ for 30min to obtain nano flower-shaped lithium titanate;
(4) dispersing thiourea, polyacrylamide and the nano flower-shaped lithium titanate obtained in the step (3) in distilled water, evaporating the solvent to dryness at 100 ℃, and drying in vacuum at 100 ℃ to obtain a sulfur-nitrogen co-doped carbon-coated lithium titanate precursor;
(5) and (5) carrying out plasma treatment on the sulfur-nitrogen co-doped carbon-coated lithium titanate precursor obtained in the step (4) at 600 ℃ for 10min to obtain the sulfur-nitrogen co-doped carbon-coated nano flower-shaped lithium titanate composite negative electrode material.
The invention has the beneficial effects that: when the lithium titanate precursor is prepared, the rapid hydrolysis of the titanium source is realized by fully utilizing the crystal water in the lithium hydroxide monohydrate without additionally adding water through the synergistic selection and control of the titanium source, the additive, the solvent and the like, and the method is a special case of hydrolysis by utilizing the crystal water;
construction of Nanoplastic structures Li4Ti5O12The specific surface area, the shorter ion diffusion path and the electron transmission distance are favorably improved, and the specific capacity and the rate capability of the lithium ion battery can be obviously improved;
sulfur-nitrogen incorporation of Li4Ti5O12In the crystal lattice of the carbon coating layer, the semiconductor doping effect is favorably formed, and the defect degree of the carbon material is improved, so that the electrochemical activity and the electric conductivity of the carbon-based material are improved;
the plasma as the fourth state of the matter is produced by corona discharge of a gas medium to generate a large amount of plasmas of charged particles, excited particles, photons, free radicals and the like, and the high-energy plasmas are utilized to impact the surface of the material, so that the interface microscopic characteristics of the material are improved, the surface defects are increased, the reaction temperature is reduced, the reaction time is shortened, and meanwhile, the plasma-assisted sintering technology has an obvious promotion effect on non-metal doping of the material.
The sulfur-nitrogen co-doped carbon-coated nano flower-shaped lithium titanate composite negative electrode material prepared by the invention has high rate capability and good cycle performance. Wherein the material prepared in example 3 has discharge capacities of 173mAhg at 0.5C, 10C and 20C-1、153mAhg-1And 140mAhg-1(ii) a After 100 cycles at 10C, the discharge capacity retention was 97.4%.
Drawings
FIG. 1 is an X-ray diffraction diagram of the products prepared in example 1, comparative example 2 and comparative example 3 of this patent, with the abscissa being 2 θ/° and θ being the diffraction angle.
FIG. 2 is a scanning electron microscope photograph of the product prepared in example 2 of this patent.
FIG. 3 shows the cycling performance of the sulfur-nitrogen co-doped carbon-coated nano flower-like lithium titanate composite negative electrode material prepared in the examples 1, 2 and 3 and the sulfur-nitrogen co-doped carbon-coated nano flower-like lithium titanate composite negative electrode material prepared in the example 2 under different multiplying powers, wherein the abscissa is the cycle number, and the ordinate is the specific capacity/mAhg-1The charge and discharge multiplying power is respectively 0.5C, 1C, 2C, 5C, 10C and 2C0C。
FIG. 4 shows the cycle performance of the product prepared in example 2, namely the sulfur-nitrogen co-doped carbon-coated nano flower-shaped lithium titanate composite negative electrode material at 10 ℃, with the abscissa representing the cycle number and the ordinate representing the specific capacity/mAhg-1。
Detailed Description
Example 1
Fully dispersing 0.3g of polyvinylpyrrolidone, 0.015mol of n-butyl titanate and 0.01275mol of lithium hydroxide monohydrate in 200mL of mixed solvent of anhydrous methanol and anhydrous DMF (the volume ratio of the anhydrous methanol to the anhydrous DMF is 4: 1), transferring the mixture into a 250mL PPL reaction kettle with a lining, placing the reaction kettle in a constant-temperature infrared oven, and reacting for 8 hours at 180 ℃; and filtering the reacted suspension by using a sand core filtering device, fully washing a filter cake by using anhydrous methanol, drying at 80 ℃ to obtain a lithium titanate precursor, and carrying out plasma treatment on the precursor at 600 ℃ for 30min to obtain the nano flower-shaped lithium titanate.
Comparative example 1
The "n-butyl titanate" in example 1 was replaced with equimolar titanium tetrachloride, and the remaining operating parameters were not changed.
Comparative example 2
The "mixed solvent of anhydrous methanol and anhydrous DMF" in example 1 was replaced with an equal volume of anhydrous methanol, and the remaining operating parameters were not changed.
Comparative example 3
The "mixed solvent of anhydrous methanol and anhydrous DMF" in example 1 was replaced with an equal volume of anhydrous DMF, and the remaining operating parameters were not changed.
As can be seen from the accompanying FIG. 1, the product prepared in example 1 is a pure phase, while the products prepared in comparative example 1, comparative example 2 and comparative example 3 all contain a distinct peak of titanium dioxide impurity, indicating that the reactions of example 1, comparative example 1 and comparative example 3 are far from complete, which is also seen from the distinct difference in electrochemical properties of the samples in FIG. 3.
Example 2
Fully dispersing 0.2g of thiourea, 0.4g of polyacrylamide and the nano flower-shaped lithium titanate obtained in the example 1 in distilled water, evaporating the solvent to dryness at 100 ℃, and fully drying in vacuum at 100 ℃ to obtain a sulfur-nitrogen co-doped carbon-coated lithium titanate precursor; and then carrying out plasma treatment on the sulfur-nitrogen codoped carbon-coated lithium titanate precursor at 600 ℃ for 10min to obtain a sulfur-nitrogen codoped carbon-coated nano flower-shaped lithium titanate composite negative electrode material, wherein the specific morphology is shown in figure 2.
Electrochemical performance test
The products prepared in patent example 1, comparative example 2 and comparative example 3 and the negative electrode material prepared in example 2 are respectively used as active ingredients, and a coating method is adopted to prepare a negative electrode for a lithium ion battery, and the specific operations are as follows: mixing active ingredients, conductive agent Super-Pcarbonate and binder LA132 according to the mass ratio of 85:10:5, then uniformly coating the mixture on an aluminum foil, drying the mixture in vacuum at 100 ℃ to obtain a working electrode plate,
the electrode slice containing the active ingredients prepared above is used as a working electrode, a metal lithium slice is used as a counter electrode, Celgard2400 is used as a diaphragm, and 1mol/LLIPF6The EC/DEC/DMC (volume ratio is 1:1:1) solution is used as electrolyte to assemble a CR2032 button cell, and a constant-current charge-discharge performance test is carried out on a cell test system, wherein the charge voltage range is 1-3V.
Fig. 3 shows cycle performance of the products of example 1, comparative example 2, and comparative example 3 and the negative electrode material of example 2 at different rates, and it can be seen from fig. 3 that the product of example 1 has significantly higher rate performance than the products of comparative example 1, comparative example 2, and comparative example 3; compared with example 1, the modified example 2 has better rate capability, and the discharge capacities at 0.5C, 10C and 20C are 173mAhg respectively-1、153mAhg-1And 140mAhg-1；
Fig. 4 shows the cycle performance of the negative electrode material prepared in example 2 at 10C, and it can be seen that the discharge capacity retention after 100 cycles is 97.4%, which has better cycle performance.
Comparative example 4
The same procedure as in example 1 was repeated except that "lithium hydroxide monohydrate" in example 1 was replaced with equimolar anhydrous lithium hydroxide and sufficient water was added to the reaction system to promote sufficient hydrolysis.
The obtained lithium titanate product is used as an active ingredient, a working electrode plate is prepared by the process, and the charge and discharge performance tests of the same operation are carried out, so that the discharge capacities at 0.5C, 10C and 20C are 166mAhg respectively-1、140mAhg-1And 121mAhg-1Very close to example 1. This also illustrates that sufficient hydrolysis has been achieved in example 1.

Claims (3)

1. A method for preparing a sulfur-nitrogen co-doped carbon-coated nano flower-shaped lithium titanate composite negative electrode material is characterized by comprising the following steps: a particular operation of the method is that,
(1) 0.3g of polyvinylpyrrolidone, 0.015mol of n-butyl titanate and 0.01275mol of lithium hydroxide monohydrate are dispersed in 200mL of organic solvent and are heated to react; the organic solvent is a mixed solvent of anhydrous methanol and anhydrous DMF, and the volume ratio of the anhydrous methanol to the anhydrous DMF is 4: 1;
(2) filtering the suspension reacted in the step (1), fully washing a filter cake with anhydrous methanol, and drying to obtain a lithium titanate precursor;
(3) performing plasma treatment on the lithium titanate precursor obtained in the step (2) at 600 ℃ to obtain nano flower-shaped lithium titanate;
(4) dispersing 0.2g of thiourea, 0.4g of polyacrylamide and the nano flower-shaped lithium titanate obtained in the step (3) in distilled water, evaporating the solvent to dryness and performing vacuum drying to obtain a sulfur-nitrogen co-doped carbon-coated lithium titanate precursor;
(5) and (5) carrying out plasma treatment on the sulfur-nitrogen co-doped carbon-coated lithium titanate precursor obtained in the step (4) at 600 ℃ to obtain the sulfur-nitrogen co-doped carbon-coated nano flower-shaped lithium titanate composite negative electrode material.
2. The method for preparing the sulfur-nitrogen co-doped carbon-coated nano flower-shaped lithium titanate composite anode material as claimed in claim 1, wherein the method comprises the following steps: the heating reaction in the step (1) is carried out for 6-12 hours at the temperature of 150-180 ℃.
3. The method for preparing the sulfur-nitrogen co-doped carbon-coated nano flower-shaped lithium titanate composite anode material as claimed in claim 1, wherein the method comprises the following steps: in step (4), the solvent is evaporated to dryness at 100 ℃ and dried in vacuo at 100 ℃.
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CN108520953A (en) * 2018-04-17 2018-09-11 吉林大学 A kind of carbon coating lithium titanate negative material and preparation method thereof
CN108550831A (en) * 2018-05-15 2018-09-18 肇庆益晟商贸有限公司 A kind of lithium battery negative material and preparation method thereof
CN110620221B (en) * 2019-09-05 2022-03-25 常州大学 Sulfur-doped lithium titanate/graphene oxide composite material, and preparation method and application thereof
CN110745800B (en) * 2019-11-07 2021-05-11 南京师范大学 Nitrogen-doped nickel phosphide nanoflower and preparation method and application thereof
CN111370676B (en) * 2020-03-24 2022-05-03 电子科技大学 Method for preparing three-dimensional porous carbon doped lithium titanate coating on surface of copper foil
WO2021201319A1 (en) * 2020-03-31 2021-10-07 한국해양대학교 산학협력단 Method for producing nitrogen-carbon aggregate having hierarchical porous structure, nitrogen-carbon aggregate produced thereby, and sodium-ion battery comprising same
CN111403721B (en) * 2020-04-16 2021-06-29 旭派电源有限公司 Preparation method of lithium titanate negative electrode material of lithium ion battery
CN112551574A (en) * 2020-12-11 2021-03-26 桐乡市鸿信科技合伙企业(有限合伙) Sulfur-nitrogen doped porous carbon-coated Li4Ti5O12Lithium ion battery cathode material and preparation method thereof

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