CN112670470B - Lithium titanate/graphite single alkyne composite anode material and preparation method and application thereof - Google Patents
Lithium titanate/graphite single alkyne composite anode material and preparation method and application thereof Download PDFInfo
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- CN112670470B CN112670470B CN202011512793.7A CN202011512793A CN112670470B CN 112670470 B CN112670470 B CN 112670470B CN 202011512793 A CN202011512793 A CN 202011512793A CN 112670470 B CN112670470 B CN 112670470B
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Abstract
The invention belongs to the technical field of electrochemical materials, and particularly relates to a lithium titanate/graphite single alkyne composite material as well as a preparation method and application thereof. According to the invention, the gamma-type graphite monoalkyne two-dimensional nano carbon material is used as a carbon source for modifying lithium titanate for the first time, so that the high conductivity and ion transmission capability of the gamma-type graphite monoalkyne are fully exerted. The lithium titanate/graphite single alkyne composite material prepared by the method has excellent electrochemical performance and can be used as a lithium ion battery cathode material. Electrochemical test results show that the cathode material has excellent cycling stability and high rate characteristic, and has good practical application prospect.
Description
Technical Field
The invention belongs to the technical field of electrochemical materials, and particularly relates to a lithium titanate/graphite single-alkyne lithium ion battery cathode composite material as well as a preparation method and application thereof.
Background
Lithium titanate (Li) 4 Ti 5 O 12 ) Has the advantages of long cycle life, high safety and the like, has wide application prospect in the aspect of lithium ion battery cathodes in the fields of aerospace, electric automobiles, energy storage power stations and the like, however, li 4 Ti 5 O 12 The intrinsic conductivity is poor, the polarization is severe under the condition of large current, the multiplying power performance is poor, and the practical application of the composite material is limited to a certain extent.
The gamma-type graphite single alkyne is composed of sp and sp 2 The novel carbon allotrope formed by hybridized carbon atoms has a two-dimensional plane conjugated system, an electron-withdrawing alkynyl functional group, a unique large triangular hole structure and good chemical stability, shows excellent electron conduction and ion transmission capacity, and has wide application prospects in the fields of energy conversion and storage.
The invention takes the gamma-type graphite mono-alkyne two-dimensional carbon material as carbon for the first timeThe source modified lithium titanate fully exerts the high conductivity and ion transmission capability of the gamma-type graphite monoacyne. The invention provides a simple method for preparing Li 4 Ti 5 O 12 The graphite single alkyne composite material is applied to a lithium ion battery cathode material. Electrochemical test results show that the composite negative electrode material has excellent cycle stability and high rate characteristic, and has good practical application prospect.
Disclosure of Invention
The invention aims to provide a lithium titanate/graphite single alkyne composite material with large specific capacity and high rate capability, a preparation method thereof and application thereof in a lithium ion battery cathode material. Compared with a pure lithium titanate negative electrode material, the composite material can obviously improve the specific capacity and rate capability of the battery.
The lithium titanate/graphite single alkyne composite material provided by the invention is obtained by modifying lithium titanate by taking a gamma-type graphite single alkyne two-dimensional nano carbon material as a carbon source: the preparation method comprises the following specific steps:
weighing a certain amount of gamma-type graphite monoalkyne and lithium titanate powder, adding a proper amount of absolute ethyl alcohol, carrying out manual grinding or mechanical ball milling for a certain time, and drying at 40-60 ℃ to obtain the lithium titanate/gamma-type graphite monoalkyne composite material.
In the invention, the mass of the gamma-type graphite monoalkyne accounts for 2-10% of the total mass.
In the invention, manual grinding can be carried out by using an agate mortar, and the grinding time is 30 to 60 minutes.
In the invention, a planetary ball mill is used for mechanical ball milling, the ball-material ratio is 100 to 300, the rotating speed is 200 to 300 r/min, and the ball milling time is 8 to 12 hours.
In the invention, the volume of absolute ethyl alcohol added in the mechanical ball milling process is 5-10% of the volume of the ball milling tank.
The lithium titanate/gamma-graphite single alkyne composite material prepared by the invention has excellent electrochemical performance and can be used as a lithium ion battery cathode material.
Compared with the prior art, the invention has the following remarkable characteristics:
(1) Provides a novel lithium titanate/gamma-graphite single alkyne composite material;
(2) The preparation method disclosed by the invention has the advantages that the required equipment is simple, and the method is suitable for industrial production;
(3) The lithium titanate/gamma-graphite single alkyne composite material has excellent electrochemical performance, and compared with a pure lithium titanate negative electrode material, the composite material can obviously improve the specific capacity and the rate capability of a battery.
The salient features and significant improvements of the present invention can be seen in the following examples.
Drawings
FIG. 1 is an X-ray diffraction pattern of a sample of example 1 of the present invention and pure lithium titanate.
FIG. 2 is an SEM image of a sample of example 1 and pure lithium titanate of the invention, wherein a is the pure lithium titanate and b is the sample of example 1
FIG. 3 is a graph of rate capability of a sample of example 1 of the present invention and pure lithium titanate, wherein the current density at 1C rate is 175 mA g -1 The voltage ranges are 1.0 \8210and2.5V.
FIG. 4 is an X-ray diffraction pattern of a sample of example 2 of the invention and pure lithium titanate.
FIG. 5 is a graph of rate capability for ball-milled lithium titanate and samples of example 2 of the present invention, wherein the current density at 1C rate is 175 mA g -1 The voltage ranges are 1.0 \8210and2.5V.
FIG. 6 is an X-ray diffraction pattern of a sample of example 3 of the invention and pure lithium titanate.
FIG. 7 is a graph of rate capability of a sample and ball-milled lithium titanate of example 3 of the present invention, wherein the current density at 1C rate is 175 mA g -1 The voltage range is 1.0-8210and 2.5V.
Detailed Description
The practice of the invention is further illustrated, but is not limited, by the following examples and figures.
Example 1
392 mg of commercial lithium titanate and 8 mg of gamma-type graphite monoalkyne are weighed, forcefully ground for 30 minutes in agate grinding, and powder is collected to obtain the lithium titanate/gamma-type graphite monoalkyne composite material.
The XRD result (figure 1) shows that the composite gamma-type graphite monoalkyne does not change the crystal form of lithium titanate and still has a spinel crystal structure (corresponding to PDF standard card number 49-0207). The diffraction peak signal of the gamma-type graphite monoacyne is not detected in the sample, and the main reason is that the content of the gamma-type graphite monoacyne is lower than the detection limit of an instrument. As can be seen from the SEM image (figure 2), the pure lithium titanate is particles with a diameter of 200 to 500 nanometers, and the gamma-type graphite monoalkyne network in the lithium titanate/gamma-type graphite monoalkyne sample is coated on the surface of the lithium titanate.
Adding a lithium titanate/gamma-type graphite single alkyne composite material, super P conductive carbon black and a polyvinylidene fluoride binder into a 1-methyl-2-pyrrolidone solvent according to a mass ratio of 8. Wherein, metallic lithium is used as a counter electrode, 1.2 mol/L LiPF 6 The EC/DMC (volume ratio of 1. The charge and discharge test was performed on a LAND test system. Figure 3 compares the reversible specific capacity at different rates. Under the multiplying power of 0.2C, the specific capacity of the lithium titanate/gamma type graphite single alkyne composite material and the pure lithium titanate are both close to the theoretical specific capacity (175 mAh g) -1 ) The electrode polarization is small under this current density. Under the current densities of 0.5C \8210and10C, the specific capacities of the composite material are respectively 1.1, 1.4 and 2.5 times of those of pure lithium titanate, and the specific capacities of the composite material are respectively 1.1, 1.4 and 2.5 times of that of the pure lithium titanate, so that the polarization of the gamma-type graphite monoalkyne under the large current density can be reduced, and the reversible specific capacity of the lithium titanate material under the high-rate condition is improved.
Example 2
Weighing 950 mg of commercial lithium titanate and 50 mg of gamma-type graphite monoalkyne, placing the weighed materials in a 250 ml stainless steel ball milling tank, adding 20 ml of absolute ethyl alcohol, vacuumizing and sealing; the jar was transferred to a planetary ball mill set at 200 rpm for 10 hours of continuous operation. Collecting the ball-milled product, and drying in a 40 ℃ forced air drying oven for 24 hours to obtain the ball-milled-lithium titanate/gamma type graphite monoalkyne composite material.
The XRD result (fig. 4) indicates that the ball-milled-lithium titanate/γ -type graphite monoalkyne composite material maintains the crystal structure of spinel-type lithium titanate, and the characteristic diffraction peak of γ -type graphite monoalkyne is not detected.
Adding a ball-milling-lithium titanate/gamma type graphite single alkyne composite material, super P conductive carbon black and a polyvinylidene fluoride binder into a 1-methyl-2-pyrrolidone solvent according to a mass ratio of 8. Wherein, the metallic lithium is used as a counter electrode, and 1.2 mol/L LiPF 6 The EC/DMC (volume ratio: 1. And carrying out charge and discharge test on the LAND test system. Fig. 5 compares the reversible specific capacities of the ball-milled lithium titanate/gamma graphite monoalkyne composite material and the ball-milled lithium titanate electrode at different multiplying powers. The specific capacities of the ball-milled lithium titanate/gamma type graphite single alkyne composite material at the multiplying powers of 0.5C, 1C, 2C, 5C and 10C are 166 mAh g, 163 mAh g, 159 mAh g, 149 mAh g and 138 mAh g respectively -1 The ratio of the pure ball milling to the lithium carbonate is 1.24, 1.23 and 1.23 times, so that the multiplying power performance of the lithium titanate is obviously improved by the composite gamma type graphite monoalkyne.
Example 3
Weighing 900 mg of commercial lithium titanate and 100 mg of gamma-type graphite monoalkyne, placing the commercial lithium titanate and the gamma-type graphite monoalkyne in a 250 ml stainless steel ball milling tank, adding 25 ml of absolute ethyl alcohol, vacuumizing and sealing; the jar was transferred to a planetary ball mill set at 250 rpm for 8 hours of continuous operation. Collecting the ball-milled product, and drying in a 60 ℃ forced air drying oven for 12 hours to obtain the ball-milled-lithium titanate/gamma type graphite monoalkyne composite material.
XRD results (FIG. 6) show that the ball-milled lithium titanate/gamma type graphite monoalkyne composite material maintains the crystal structure of spinel type lithium titanate. The diffraction peak at the 26.5-degree position is the characteristic peak of gamma-type graphite monoalkyne.
Adding the ball-milled lithium titanate/gamma-type graphite single alkyne composite material, super P conductive carbon black and polyvinylidene fluoride binder into a 1-methyl-2-pyrrolidone solvent according to the mass ratio of 8The cells were dried for 12 hours, cut into circular disc electrodes of 14 mm diameter and assembled in a glove box filled with argon into CR2016 type button cells. Wherein, the metallic lithium is used as a counter electrode, and 1.2 mol/L LiPF 6 The EC/DMC (volume ratio: 1. And carrying out charge and discharge test on the LAND test system. Fig. 7 compares the reversible specific capacities of ball-milled lithium titanate/gamma graphite monoalkyne composites and ball-milled lithium titanate electrodes at different rates. The specific capacities of the ball-milled lithium titanate/gamma type graphite single alkyne composite material at the multiplying powers of 0.5C, 1C, 2C, 5C and 10C are 145 mAh g, 142 mAh g, 137 mAh g, 128 mAh g and 118 mAh g respectively -1 The ratio of the pure ball milling to the lithium carbonate is 1.08, 1.06 and 1.06 times, so that the multiplying power performance of the lithium titanate can be improved by the composite gamma type graphite monoalkyne.
Claims (6)
1. A preparation method of a lithium titanate/graphite single alkyne composite material is characterized in that a gamma-type graphite single alkyne two-dimensional carbon material is used as a carbon source to modify lithium titanate, and the preparation method specifically comprises the following steps:
taking gamma-type graphite monoalkyne and lithium titanate powder, adding a proper amount of absolute ethyl alcohol, carrying out manual grinding or mechanical ball milling for a certain time, and drying at the temperature of 40-60 ℃ to obtain a lithium titanate/gamma-type graphite monoalkyne composite material; wherein the mass of the gamma-type graphite monoalkyne accounts for 2-10% of the total mass.
2. The method according to claim 1, wherein the grinding is carried out by hand using an agate mortar, and the grinding time is 30 to 60 minutes.
3. The preparation method according to claim 1, wherein the mechanical ball milling is carried out by a planetary ball mill, the ball-to-material ratio is 100 to 1, the rotation speed is 200 to 300 revolutions per minute, and the ball milling time is 8 to 12 hours.
4. The preparation method of claim 1, wherein the volume of the absolute ethyl alcohol added in the mechanical ball milling process is 5-10% of the volume of the ball milling tank.
5. A lithium titanate/graphite monoalkyne composite material obtained by the preparation method according to any one of claims 1 to 4.
6. The use of the lithium titanate/graphite monoalkyne composite material according to claim 5 as a negative electrode material for lithium ion batteries.
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| WO2016165262A1 (en) * | 2015-04-15 | 2016-10-20 | 田东 | Preparation method for doped lithium titanate negative electrode material |
| CN107331850A (en) * | 2017-07-10 | 2017-11-07 | 河南大学 | A kind of preparation method of anode material for lithium-ion batteries |
| CN109888229A (en) * | 2019-03-01 | 2019-06-14 | 中山市华舜科技有限责任公司 | A kind of preparation method of the lithium ion battery negative material based on lithium titanate coated graphite composite material |
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| KR101519333B1 (en) * | 2013-10-17 | 2015-05-13 | 건국대학교 산학협력단 | LITHIUM ION BATTERY ANODE MATERIAL WITH α-GRAPHDIYNE |
| CN104638267A (en) * | 2013-11-12 | 2015-05-20 | 赵宽 | Graphene coated lithium titanate cathode and preparation method thereof |
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| WO2016165262A1 (en) * | 2015-04-15 | 2016-10-20 | 田东 | Preparation method for doped lithium titanate negative electrode material |
| CN107331850A (en) * | 2017-07-10 | 2017-11-07 | 河南大学 | A kind of preparation method of anode material for lithium-ion batteries |
| CN109888229A (en) * | 2019-03-01 | 2019-06-14 | 中山市华舜科技有限责任公司 | A kind of preparation method of the lithium ion battery negative material based on lithium titanate coated graphite composite material |
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