CN107910528B - Lithium titanate composite material, preparation method thereof, negative plate and lithium ion battery - Google Patents

Lithium titanate composite material, preparation method thereof, negative plate and lithium ion battery Download PDF

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CN107910528B
CN107910528B CN201711145359.8A CN201711145359A CN107910528B CN 107910528 B CN107910528 B CN 107910528B CN 201711145359 A CN201711145359 A CN 201711145359A CN 107910528 B CN107910528 B CN 107910528B
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lithium titanate
composite material
ruthenium
lithium
solution
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CN107910528A (en
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赵微
詹世英
马美品
李海军
蔡惠群
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Luoyang Gree Titanium New Energy Co ltd
Shijiazhuang Zhongbo Automobile Co ltd
Gree Altairnano New Energy Inc
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Yinlong New Energy Co Ltd
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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/626—Metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Engineering & Computer Science (AREA)
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Abstract

The invention relates to a lithium titanate composite material, a preparation method thereof, a negative plate and a lithium ion battery, and relates to the technical field of batteries. The main technical scheme adopted is as follows: a preparation method of a lithium titanate composite material comprises the following steps: 1) preparing a ruthenium dioxide/titanium dioxide composite; 2) the lithium titanate composite material is prepared by taking a ruthenium dioxide/titanium dioxide composite and a lithium source as raw materials. A lithium titanate composite material is prepared by the method. A negative plate comprises the lithium titanate composite material; a lithium ion battery comprises the negative plate. The invention is mainly used for providing the lithium titanate composite material with good conductivity, and when the lithium titanate composite material is used as a negative electrode active material of a lithium ion battery, the rate capability of the lithium ion battery can be improved.

Description

Lithium titanate composite material, preparation method thereof, negative plate and lithium ion battery
Technical Field
The invention relates to the technical field of batteries, in particular to a lithium titanate composite material and a preparation method thereof, a negative plate and a lithium ion battery.
Background
With the gradual depletion of fossil fuels such as coal, oil, natural gas and the like, people face an unprecedented energy crisis nowadays, and the search and development of renewable energy sources are imperative while the non-renewable resources are reasonably utilized and saved. However, lead-acid batteries, nickel-cadmium batteries, nickel-hydrogen batteries, lithium ion batteries, and other recyclable energy storage devices are inevitably used in the development and utilization of renewable energy sources such as solar energy, wind energy, and geothermal energy. Among the chemical energy storage batteries, lithium ion batteries have attracted attention because of their characteristics of high operating potential, high energy density, long cycle life, small self-discharge, wide temperature range of use, no memory effect, etc.
Currently, various lithium intercalation carbon materials are mostly used as negative electrode materials of lithium ion batteries. However, since the potential of the carbon electrode is very close to that of the metallic lithium, the metallic lithium is easily precipitated on the surface of the carbon electrode when the battery is overcharged, dendrite is formed to cause short circuit, and thermal runaway is easily caused when the temperature is too high. Spinel Li4Ti5O12The potential of the electrode relative to metal lithium is 1.55V, a very flat charging and discharging platform is formed in the reaction, and the safety performance is good; and Li4Ti5O12Is a zero strain insertion material, and has extremely stable structure and excellent cycle performance in the charge and discharge processes. Despite Li4Ti5O12The theoretical specific capacity of the lithium ion battery is only 175 mA.h/g, but the reversible lithium ion extraction proportion is close to 100 percent, so the actual specific capacity is generally kept at 150-160 mA.h/g. However, Li4Ti5O12The material has poor conductivity, and is easy to generate larger polarization in the high-rate charge and discharge process, so that the application of the material in the lithium ion battery is restricted.
For lithium titanate (Li)4Ti5O12) The above disadvantages of the materials exist, and the prior art mainly adopts the following two effective means to modify the lithium titanate material: first, ion doping modification, the doping ion studied at present mainly contains Mg2+、Al3+、Sn4+、W4+、Ni4+、V5+And F-Etc.; a small amount of metal elements are introduced, so that the conductivity of the lithium titanate material can be effectively improved, the voltage of the redox reaction can be reduced, or an additional voltage platform is generated under a lower potential; however, the prior art mainly adopts a solid phase method for ion doping; the traditional solid phase method is simple to operate and low in equipment requirement, but the synthesized product is uneven in particle size, irregular in crystal form, wide in particle size distribution range and long in synthesis period, and efficient utilization of the lithium titanate material is difficult to achieve. Secondly, carbon coating/composite modification, which mainly uses graphene, acetylene black, multi-walled carbon nanotubes and the like as carbon sources to coat lithium titanate or compound lithium titanate so as to improve the qualityElectron conductivity of the lithium titanate material; however, due to the limitations of affinity between materials and preparation and stirring equipment, the dispersion problem of carbon sources such as graphene and the composite effect of the carbon sources and the lithium titanate material are still not good, so that the battery capacity and rate capability of the prepared electrode are not ideal.
Disclosure of Invention
In view of the above, the invention provides a lithium titanate composite material, a preparation method thereof, a negative plate and a lithium ion battery, and mainly aims to provide a lithium titanate composite material with good conductivity, and when the lithium titanate composite material is used as a negative active material of the lithium ion battery, the rate capability of the lithium ion battery can be improved.
In order to achieve the purpose, the invention mainly provides the following technical scheme:
on one hand, the embodiment of the invention provides a preparation method of a lithium titanate composite material, which is characterized by comprising the following steps:
1) preparing a ruthenium dioxide/titanium dioxide composite;
2) the lithium titanate composite material is prepared by taking a ruthenium dioxide/titanium dioxide composite and a lithium source as raw materials.
The object of the present invention and the technical problems solved thereby can be further achieved by the following technical measures.
Preferably, the step 2) includes:
21) reacting the ruthenium dioxide/titanium dioxide composite with a lithium source to obtain a lithium titanate composite doped with ruthenium;
22) and enabling the ruthenium-doped lithium titanate composite to adsorb ruthenium ions to obtain the lithium titanate composite material.
Preferably, the step 2) includes: and reacting the ruthenium dioxide/titanium dioxide composite with a lithium source to obtain the lithium titanate composite material.
Preferably, said step 1) comprises:
11) modifying ruthenium dioxide by using a surfactant;
12) mixing the modified ruthenium dioxide with a solvent to prepare a dispersion liquid;
13) and mixing the dispersion, the buffer solution and the tetrabutyl titanate solution to prepare a mixture containing the ruthenium dioxide/titanium dioxide composite.
Preferably, the step 11) is specifically:
dispersing ruthenium dioxide powder in a surfactant solution;
separating the modified ruthenium dioxide from the solution;
wherein the size of the ruthenium dioxide powder is 10-15 nm.
Preferably, the surfactant solution is polyvinylpyrrolidone solution; wherein the mass ratio of the ruthenium dioxide to the polyvinylpyrrolidone is 1: (5-300); the mass fraction of the polyvinylpyrrolidone solution is 10-40 g/L.
Preferably, in said step 12):
the solvent comprises absolute ethyl alcohol and water; wherein the modified ruthenium dioxide, the absolute ethyl alcohol and the water are in a mass ratio of: (2-50): (5-20): 1.
preferably, the step 13) is specifically:
firstly, adding a buffer solution into the dispersion liquid, then adding a tetra-n-butyl titanate solution, stirring and uniformly mixing.
Preferably, in said step 13): the volume ratio of the buffer solution to the dispersion solution is 1: (400-800); the volume ratio of the tetra-n-butyl titanate solution to the dispersion is 1: (40-90);
wherein the buffer solution is tetramethylammonium hydroxide solution, and the volume fraction of the tetramethylammonium hydroxide solution is 5-15%; and/or the tetra-n-butyl titanate solution is a tetra-n-butyl titanate ethanol solution, and the volume fraction of the tetra-n-butyl titanate solution is 1-20%.
Preferably, the step 21) is specifically: and (3) reacting the ruthenium dioxide/titanium dioxide composite with a lithium source by using a sol-gel method to obtain the lithium titanate composite doped with ruthenium.
Preferably, when the step 1) includes the step 13), the step 21) is specifically:
dropwise adding a lithium source into the mixture containing the ruthenium dioxide/titanium dioxide composite, and continuously stirring for a set time to obtain wet gel;
sequentially carrying out aging treatment and drying treatment on the wet gel to obtain dry gel; wherein the xerogel is a lithium titanate composite material doped with ruthenium.
Preferably, the lithium source is lithium acetate ethanol solution; wherein the concentration of the lithium acetate ethanol solution is 0.4-1 mol/L; the molar ratio of lithium acetate in the lithium acetate ethanol solution to tetra-n-butyl titanate in the tetra-n-butyl titanate solution is (0.8-0.9): 1.
preferably, the conditions for aging the wet gel are: aging at 25-50 deg.C for 3-5 hr; and/or
The conditions for drying the wet gel are as follows: the drying temperature is 50-100 ℃, and the drying time is 10-30 hours.
Preferably, said step 22) comprises:
reacting the ruthenium-doped lithium titanate composite with a ruthenium salt solution to obtain a precipitate;
and calcining the precipitate to obtain the lithium titanate composite material.
Preferably, the ruthenium salt solution is a ruthenium nitrate solution with the concentration of 0.5-2 g/L; and the mass ratio of the ruthenium nitrate in the ruthenium nitrate solution to the ruthenium-doped lithium titanate composite is 1: (20-100); and/or reacting the ruthenium-doped lithium titanate composite with a ruthenium salt solution in an ultrasonic microwave mixed reaction system; and the conditions of the ultrasonic microwave reaction are as follows: the power is 50-100W, the reaction temperature is 500-1000 ℃, and the reaction time is 6-12 hours.
Preferably, the method further comprises the step of grinding the ruthenium doped lithium titanate complex into powder prior to the step of reacting the ruthenium doped lithium titanate complex with the ruthenium salt solution; and/or
The conditions under which the precipitate is calcined are: the calcination temperature is 500-1000 ℃, and the calcination time is 6-12 h.
In another aspect, an embodiment of the present invention provides a lithium titanate composite material, wherein the lithium titanate composite material is prepared by the method for preparing a lithium titanate composite material according to any one of the above aspects.
In another aspect, an embodiment of the present invention provides a negative electrode sheet, where the negative electrode sheet includes the lithium titanate composite material described above.
In another aspect, an embodiment of the present invention provides a lithium battery, wherein the lithium battery includes the negative electrode sheet described above.
Compared with the prior art, the lithium titanate composite material, the preparation method thereof, the negative plate and the lithium ion battery have at least the following beneficial effects:
on one hand, the embodiment of the invention provides a preparation method of a lithium titanate composite material, which mainly comprises the steps of preparing a ruthenium dioxide/titanium dioxide composite, and preparing the lithium titanate composite material with ruthenium doped inside by taking the ruthenium dioxide/titanium dioxide composite and a lithium source as raw materials; the lithium titanate composite material prepared by the method is doped with ruthenium, so that the conductivity of the lithium titanate composite material is improved, and the rate capability of a battery is improved.
Further, according to the preparation method of the lithium titanate composite material provided by the embodiment of the invention, after the lithium titanate composite with ruthenium doped inside is prepared, ruthenium ions are introduced to the outside of the lithium titanate composite, so that the conductivity of the lithium titanate composite material is further improved, and the rate capability of a battery is improved.
Further, in the preparation method of the lithium titanate composite material provided by the embodiment of the invention, when the ruthenium dioxide/titanium dioxide composite is prepared, PVP is firstly used for modifying ruthenium dioxide, so that the coating of titanium dioxide on ruthenium dioxide can be promoted. And when tetrabutyl titanate is hydrolyzed, a buffer solution is added to ensure that the ruthenium dioxide/titanium dioxide composite particles are uniform, and the lithium titanate composite material is prepared by adopting a sol-gel method, so that the lithium titanate composite material has uniform particle size and can be efficiently utilized.
On the other hand, the embodiment of the invention also provides a lithium titanate composite material prepared by the method, and the lithium titanate composite material is applied to a negative plate and a lithium ion battery, so that the rate capability of the battery is finally improved.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings.
Drawings
Fig. 1 is a preparation flow chart of a preparation method of a lithium titanate composite material according to an embodiment of the present invention;
fig. 2 is XRD patterns of lithium titanate composites prepared in examples 1 and 2 of the present invention;
FIG. 3 is a charge-discharge curve of 1C lithium titanate composite material prepared in example 1 of the present invention;
FIG. 4 is a charge-discharge curve of 2C lithium titanate composite material prepared in example 1 of the present invention;
fig. 5 is a graph comparing rate discharge performance of a lithium titanate composite material prepared by an embodiment of the invention and a pure phase lithium titanate material.
Detailed Description
To further explain the technical means and effects of the present invention adopted to achieve the predetermined object, the following detailed description of the embodiments, structures, features and effects according to the present invention will be made with reference to the accompanying drawings and preferred embodiments. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
In one aspect, an embodiment of the present invention provides a preparation method of a lithium titanate composite material, as shown in fig. 1, the preparation method includes the following steps:
firstly, preparing a ruthenium dioxide/titanium dioxide composite. Specifically, the steps mainly include:
11) modifying ruthenium dioxide by using a surfactant.
Dispersing ruthenium dioxide powder in a surfactant solution; after sufficient reaction, the modified ruthenium dioxide is separated from the solution. The size of the ruthenium dioxide powder is 10-15 nm.
Preferably, the surfactant solution is polyvinylpyrrolidone solution (PVP solution); wherein the mass ratio of the ruthenium dioxide to the polyvinylpyrrolidone is 1: (5-300); the mass fraction of the polyvinylpyrrolidone solution is 10-40 g/L.
The method comprises the following steps: dispersing nano-powder ruthenium dioxide in PVP (polyvinylpyrrolidone) solution, and fully reacting; the resulting PVP-modified ruthenium dioxide precipitate was isolated.
Here, the purpose of surface-modifying ruthenium dioxide with a surfactant in this step is to facilitate coating of ruthenium dioxide with titanium dioxide in step 13).
12) And mixing the modified ruthenium dioxide with a solvent to prepare a dispersion liquid.
In this step, the solvent includes absolute ethanol and water. Wherein the modified ruthenium dioxide, the absolute ethyl alcohol and the water have the mass ratio of: (2-50): (5-20): 1.
the method comprises the following steps: adding the PVP modified ruthenium dioxide precipitate separated in the step 11) into absolute ethyl alcohol, adding water, and uniformly dispersing to obtain a dispersion liquid.
13) The dispersion, the buffer and the tetrabutyl titanate solution were mixed to prepare a mixture containing a ruthenium dioxide/titanium dioxide complex.
The method comprises the following steps: adding the buffer solution into the dispersion solution, adding the tetrabutyl titanate solution, stirring and uniformly mixing.
Preferably, the volume ratio of the buffer to the dispersion is 1: (400-800); the volume ratio of the tetra-n-butyl titanate solution to the dispersion is 1: (40-90);
wherein, the buffer solution is tetramethylammonium hydroxide solution, and the volume fraction of the tetramethylammonium hydroxide solution is 5-15%, preferably 10%. The tetrabutyl titanate solution is tetrabutyl titanate ethanol solution, and the volume fraction of the tetrabutyl titanate solution is 1-20%.
In this step, the purpose of adding the buffer is as follows: since the solution of tetrabutyl titanate is hydrolyzed after being mixed with the dispersion liquid and the hydrolysis is severe, the rate of hydrolysis is moderated by adding a buffer solution, and finally, ruthenium dioxide/titanium dioxide composite particles with uniform size are formed.
And secondly, preparing the lithium titanate composite material by taking the ruthenium dioxide/titanium dioxide composite and a lithium source as two raw materials.
The method mainly comprises the following two schemes:
the first scheme is as follows: the ruthenium dioxide/titanium dioxide composite and a lithium source are reacted to directly prepare the lithium titanate composite material.
The scheme is that the lithium titanate composite material finally obtained is only internally doped with ruthenium.
The second scheme comprises the following steps:
21) the ruthenium dioxide/titanium dioxide composite is reacted with a lithium source to give a ruthenium doped lithium titanate composite (corresponding to the final product of the first embodiment).
22) And enabling the ruthenium-doped lithium titanate composite to adsorb ruthenium ions to obtain the lithium titanate composite material.
In the second scheme, on the basis of obtaining the lithium titanate composite doped with ruthenium inside, ruthenium ions are introduced outside the ruthenium-doped lithium titanate material to obtain the lithium titanate composite doped with ruthenium inside and outside.
Preferably, step 21) is specifically: and (3) reacting the ruthenium dioxide/titanium dioxide composite with a lithium source by using a sol-gel method to obtain the lithium titanate composite doped with ruthenium. Preferably, when step 1) includes step 13), the step 21) is specifically: dropwise adding a lithium source into the mixture containing the ruthenium dioxide/titanium dioxide composite, and continuously stirring for a set time to obtain wet gel; sequentially carrying out aging treatment and drying treatment on the wet gel to obtain dry gel; wherein the xerogel is a lithium titanate composite material doped with ruthenium. Preferably, the lithium source in the embodiment of the present invention is preferably a lithium acetate ethanol solution (alternatively, a lithium carbonate solution or a lithium oxalate solution may be used). Wherein the concentration of the lithium acetate ethanol solution is 0.4-1 mol/L; the molar ratio of lithium acetate in the lithium acetate ethanol solution to tetra-n-butyl titanate in the tetra-n-butyl titanate solution is (0.8-0.9): 1. preferably, the conditions for aging the wet gel are: the aging temperature is 25-50 ℃, and the aging time is 3-5 hours. Preferably, the conditions for drying the wet gel are as follows: the drying temperature is 50-100 ℃, and the drying time is 10-30 hours. Wherein, the preparation step of the first scheme can refer to step 21).
The step 21) is specifically as follows: uniformly mixing the dispersion liquid, the buffer solution and the tetrabutyl titanate solution obtained in the step 13), dropwise adding a lithium acetate ethanol solution into the mixture, and continuously stirring the mixture for 2 hours to obtain wet gel. And (3) aging the wet gel in an oven for a period of time, and then drying to obtain dry gel.
Step 22), specifically comprising:
221) the ruthenium-doped lithium titanate composite (xerogel) is reacted with a ruthenium salt solution to obtain a precipitate.
Preferably, the ruthenium salt solution is a ruthenium nitrate solution with the concentration of 0.5-2 g/L; and the mass ratio of the ruthenium nitrate to the lithium titanate composite doped with ruthenium in the ruthenium nitrate solution is 1: (20-100).
Preferably, the lithium titanate compound doped with ruthenium and the ruthenium salt solution react in an ultrasonic microwave mixed reaction system; and the conditions of the ultrasonic microwave reaction are as follows: the power is 50-100W, the reaction temperature is 500-1000 ℃, and the reaction time is 6-12 hours.
Preferably, the step of reacting the ruthenium doped lithium titanate complex with the ruthenium salt solution further comprises the step of grinding the ruthenium doped lithium titanate complex into powder.
222) And calcining the precipitate to obtain the lithium titanate composite material.
Preferably, the calcination conditions for the precipitate are: in the air, the calcining temperature is 500-1000 ℃, and the calcining time is 6-12 h. Because the precipitate obtained in the step 221) contains water and ethanol, and the step 222) of calcining is mainly used for removing the ethanol and the water and improving the crystallinity of the lithium titanate composite material.
On the other hand, the embodiment of the invention also provides a lithium titanate composite material, wherein the lithium titanate composite material is prepared by the preparation method of the lithium titanate composite material.
On the other hand, the embodiment of the invention also provides a negative electrode plate, wherein the negative electrode plate comprises the lithium titanate composite material.
On the other hand, the embodiment of the invention also provides a lithium battery, wherein the lithium battery comprises the negative electrode sheet.
This is further illustrated by the experimental examples below.
Example 1
The preparation method of the lithium titanate composite material comprises the following specific steps:
1) dispersing 0.02g of nano ruthenium dioxide powder into 100ml of 20g/L PVP solution, stirring for reaction for 10h, separating the generated pale yellow PVP modified ruthenium dioxide powder, adding the separated pale yellow PVP modified ruthenium dioxide powder into 100ml of absolute ethyl alcohol, adding 10ml of deionized water, and performing ultrasonic dispersion for 5min to obtain a dispersion liquid.
2) And (3) dropwise adding 200ul of TMAH solution with the volume fraction of 10% into the dispersion, adding 200ml of ethanol solution of tetra-n-butyl titanate with the volume fraction of 5%, stirring for 15min, and uniformly mixing to obtain a mixture containing the ruthenium dioxide/titanium dioxide composite.
3) 80ml of 0.4mol/L lithium acetate ethanol solution is dripped into the mixture obtained in the step 2), and yellow colloid is obtained after stirring for 2 hours. The yellow colloid was placed in a 35 ℃ oven for 3h to give a white gel. The white gel was dried in an oven at 80 ℃ for 20h to give a xerogel. Wherein the xerogel is a lithium titanate compound doped with ruthenium.
4) And grinding the dried gel into powder, adding the powder into 100ml of 0.5g/L ruthenium nitrate solution, placing the solution in an ultrasonic-microwave mixed reaction system to react for 1h at the temperature of 60 ℃ at 50W, separating out precipitates, placing the precipitates in a tubular furnace, and calcining the precipitates for 8h at the temperature of 800 ℃ in the air atmosphere to obtain the lithium titanate composite material.
Weighing 1.2g of the lithium titanate composite material prepared in the embodiment 1, adding a certain amount of conductive agent, adhesive and N-methyl pyrrolidone, ball-milling for 3 hours by using a planetary ball mill, coating the ball-milled powder on an aluminum foil to form a film with the thickness of 152um, cutting the film into wafers with the diameter of 12mm after vacuum drying, accurately weighing the mass of the pole piece after drying, and calculating the content of active substances. Selecting metal lithium sheets as a counter electrode and a reference electrode, selecting a polypropylene microporous membrane as a diaphragm, using 1mol/L of EC (ethylene carbonate) and DEC (diethyl carbonate) as an electrolyte solution (VEC: VDEC ═ 1: 1), assembling the button cell in a vacuum glove box, and sealing by using a button cell sealing machine to obtain the button cell.
Example 2
The preparation method of the lithium titanate composite material comprises the following specific steps:
1) dispersing 0.01g of nano ruthenium dioxide powder into 100ml of 20g/L PVP solution, stirring for reaction for 10h, separating the generated pale yellow PVP modified ruthenium dioxide powder, adding the separated pale yellow PVP modified ruthenium dioxide powder into 100ml of absolute ethyl alcohol, adding 15ml of deionized water, and performing ultrasonic dispersion for 5min to obtain a dispersion liquid.
2) Dropwise adding 180ul of TMAH solution with volume fraction of 10% into the dispersion, adding 120ml of ethanol solution of tetra-n-butyl titanate with volume fraction of 10%, stirring for 15min, and mixing uniformly to obtain a mixture containing the ruthenium dioxide/titanium dioxide composite.
3) 80ml of 0.5mol/L lithium acetate ethanol solution is dripped into the mixture obtained in the step 2), and yellow colloid is obtained after stirring for 2 hours. The yellow colloid was placed in an oven at 40 ℃ for 3h to give a white gel. The white gel was dried in an oven at 90 ℃ for 20h to give a xerogel. Wherein the xerogel is a lithium titanate compound doped with ruthenium.
4) And grinding the dried gel into powder, adding the powder into 100ml of 1g/L ruthenium nitrate solution, placing the solution in an ultrasonic-microwave mixed reaction system for reaction at the temperature of 70 ℃ for 1h, separating out precipitates, and placing the precipitates in a tubular furnace for calcination at the temperature of 800 ℃ in air for 10h to obtain the lithium titanate composite material.
Weighing 1.2g of the lithium titanate composite material prepared in the embodiment 2, adding a certain amount of conductive agent, adhesive and N-methyl pyrrolidone, ball-milling for 3 hours by using a planetary ball mill, coating the ball-milled powder on an aluminum foil to form a film with the thickness of 152um, cutting the film into wafers with the diameter of 12mm after vacuum drying, accurately weighing the mass of the pole piece after drying, and calculating the content of active substances. Selecting metal lithium sheets as a counter electrode and a reference electrode, selecting a polypropylene microporous membrane as a diaphragm, using 1mol/L of EC (ethylene carbonate) and DEC (diethyl carbonate) as an electrolyte solution (VEC: VDEC ═ 1: 1), assembling the button cell in a vacuum glove box, and sealing by using a button cell sealing machine to obtain the button cell.
Example 3
The preparation method of the lithium titanate composite material comprises the following specific steps:
1) dispersing 0.01g of nano ruthenium dioxide powder into 100ml of 25g/L PVP solution, stirring for reaction for 10h, separating the generated pale yellow PVP modified ruthenium dioxide powder, adding the separated pale yellow PVP modified ruthenium dioxide powder into 100ml of absolute ethyl alcohol, adding 20ml of deionized water, and performing ultrasonic dispersion for 5min to obtain a dispersion liquid.
2) 200ul of TMAH solution with volume fraction of 10% is added into the dispersion liquid dropwise, 150ml of ethanol solution of tetra-n-butyl titanate with volume fraction of 5% is added into the dispersion liquid, the mixture is stirred for 15min and mixed uniformly, and the mixture containing the ruthenium dioxide/titanium dioxide composite is obtained.
3) 50ml of 0.5mol/L lithium acetate ethanol solution is dripped into the mixture obtained in the step 2), and yellow colloid is obtained after stirring for 2 hours. The yellow colloid was placed in an oven at 45 ℃ for 3h to give a white gel. The white gel was dried in an oven at 70 ℃ for 15h to give a xerogel. Wherein the xerogel is a lithium titanate compound doped with ruthenium.
4) And grinding the dried gel into powder, adding the powder into 100ml of 0.8g/L ruthenium nitrate solution, placing the solution in an ultrasonic-microwave mixed reaction system for reaction at 50W and 60 ℃ for 2h, separating out precipitates, and placing the precipitates in a tubular furnace for calcination at the air atmosphere of 900 ℃ for 10h to obtain the lithium titanate composite material.
Weighing 1.2g of the lithium titanate composite material prepared in the embodiment 3, adding a certain amount of conductive agent, adhesive and N-methyl pyrrolidone, ball-milling for 3 hours by using a planetary ball mill, coating the ball-milled powder on an aluminum foil to form a film with the thickness of 152um, cutting the film into wafers with the diameter of 12mm after vacuum drying, accurately weighing the mass of the pole piece after drying, and calculating the content of active substances. Selecting metal lithium sheets as a counter electrode and a reference electrode, selecting a polypropylene microporous membrane as a diaphragm, using 1mol/L of EC (ethylene carbonate) and DEC (diethyl carbonate) as an electrolyte solution (VEC: VDEC ═ 1: 1), assembling the button cell in a vacuum glove box, and sealing by using a button cell sealing machine to obtain the button cell.
Example 4
The preparation method of the lithium titanate composite material comprises the following specific steps:
1) dispersing 0.01g of nano ruthenium dioxide powder into 100ml of 30g/L PVP solution, stirring for reaction for 10h, separating the generated pale yellow PVP modified ruthenium dioxide powder, adding the separated pale yellow PVP modified ruthenium dioxide powder into 100ml of absolute ethyl alcohol, adding 5ml of deionized water, and performing ultrasonic dispersion for 5min to obtain a dispersion liquid.
2) And dripping 230ul of TMAH solution with the volume fraction of 10% into the dispersion, adding 200ml of ethanol solution of tetra-n-butyl titanate with the volume fraction of 5%, stirring for 15min, and uniformly mixing to obtain a mixture containing the ruthenium dioxide/titanium dioxide composite.
3) And (3) dropwise adding 45ml of 0.7mol/L lithium acetate ethanol solution into the mixture obtained in the step 2), and stirring for 2 hours to obtain yellow colloid. The yellow colloid was placed in an oven at 40 ℃ for 4h to give a white gel. The white gel was dried in an oven at 80 ℃ for 25h to give a xerogel. Wherein the xerogel is a lithium titanate compound doped with ruthenium.
4) And grinding the dried gel into powder, adding the powder into 100ml of 0.9g/L ruthenium nitrate solution, placing the solution in an ultrasonic-microwave mixed reaction system for reaction at the temperature of 80 ℃ for 1h, separating out precipitates, and placing the precipitates in a tubular furnace for calcination at the temperature of 800 ℃ in the air atmosphere for 8h to obtain the lithium titanate composite material.
Weighing 1.2g of the lithium titanate composite material prepared in the embodiment 4, adding a certain amount of conductive agent, adhesive and N-methyl pyrrolidone, ball-milling for 3 hours by using a planetary ball mill, coating the ball-milled powder on an aluminum foil to form a film with the thickness of 152um, cutting the film into wafers with the diameter of 12mm after vacuum drying, accurately weighing the mass of the pole piece after drying, and calculating the content of active substances. Selecting metal lithium sheets as a counter electrode and a reference electrode, selecting a polypropylene microporous membrane as a diaphragm, using 1mol/L of EC (ethylene carbonate) and DEC (diethyl carbonate) as an electrolyte solution (VEC: VDEC ═ 1: 1), assembling the button cell in a vacuum glove box, and sealing by using a button cell sealing machine to obtain the button cell.
Example 5
The preparation method of the lithium titanate composite material comprises the following specific steps:
1) dispersing 0.02g of nano ruthenium dioxide powder into 100ml of 30g/L PVP solution, stirring for reaction for 10h, separating the generated pale yellow PVP modified ruthenium dioxide powder, adding the separated pale yellow PVP modified ruthenium dioxide powder into 100ml of absolute ethyl alcohol, adding 15ml of deionized water, and performing ultrasonic dispersion for 5min to obtain a dispersion liquid.
2) 150ul of TMAH solution with volume fraction of 10% is added into the dispersion liquid dropwise, 150ml of ethanol solution with volume fraction of 12% of tetra-n-butyl titanate is added into the dispersion liquid, the mixture is stirred for 15min and mixed uniformly, and the mixture containing the ruthenium dioxide/titanium dioxide composite is obtained.
3) 60ml of 1mol/L lithium acetate ethanol solution is dripped into the mixture obtained in the step 2), and yellow colloid is obtained after stirring for 2 hours. The yellow colloid was placed in a 35 ℃ oven for 5h to give a white gel. The white gel was dried in an oven at 90 ℃ for 25h to give a xerogel. Wherein the xerogel is a lithium titanate compound doped with ruthenium.
4) And grinding the dried gel into powder, adding the powder into 100ml of 2g/L ruthenium nitrate solution, placing the solution in an ultrasonic-microwave mixed reaction system for reaction at the temperature of 80 ℃ for 2h, separating out precipitates, and placing the precipitates in a tubular furnace for calcining at the temperature of 100 ℃ for 9h in the air atmosphere to obtain the lithium titanate composite material.
Weighing 1.2g of the lithium titanate composite material prepared in the embodiment 5, adding a certain amount of conductive agent, adhesive and N-methyl pyrrolidone, ball-milling for 3 hours by using a planetary ball mill, coating the ball-milled powder on an aluminum foil to form a film with the thickness of 152um, cutting the film into wafers with the diameter of 12mm after vacuum drying, accurately weighing the mass of the pole piece after drying, and calculating the content of active substances. Selecting metal lithium sheets as a counter electrode and a reference electrode, selecting a polypropylene microporous membrane as a diaphragm, using 1mol/L of EC (ethylene carbonate) and DEC (diethyl carbonate) as an electrolyte solution (VEC: VDEC ═ 1: 1), assembling the button cell in a vacuum glove box, and sealing by using a button cell sealing machine to obtain the button cell.
Comparative example
Weighing 1.2g of pure-phase lithium titanate composite material, adding a certain amount of conductive agent, adhesive and N-methyl pyrrolidone, ball-milling for 3h by using a planetary ball mill, coating the ball-milled powder on an aluminum foil to form a film with the thickness of 152um, cutting the film into wafers with the diameter of 12mm after vacuum drying, accurately weighing the mass of the pole piece after drying, and calculating the content of active substances. Selecting metal lithium sheets as a counter electrode and a reference electrode, selecting a polypropylene microporous membrane as a diaphragm, using 1mol/L of EC (ethylene carbonate) and DEC (diethyl carbonate) as an electrolyte solution (VEC: VDEC ═ 1: 1), assembling the button cell in a vacuum glove box, and sealing by using a button cell sealing machine to obtain the button cell.
The performance tests were performed as follows:
the lithium titanate composite material prepared in example 1 was subjected to an X-ray diffraction test (XRD test), and the details of the test pattern are shown in fig. 2.
No diffraction peak of metallic ruthenium was seen from the XRD pattern of fig. 2, because the amount of ruthenium in the lithium titanate composite material prepared in example 1 was very small.
Wherein, the 1C charging and discharging curve of the button cell prepared in example 1 is shown in fig. 3. The 2C charge-discharge cycle curve of the button cell prepared in example 1 is shown in fig. 4. The rate discharge performance of the lithium titanate material prepared in example 1 is compared with that of a pure phase lithium titanate material, as shown in fig. 5. As can be seen from fig. 3 to 5, the lithium titanate composite material prepared in example 2 has good conductivity and battery rate performance.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are still within the scope of the technical solution of the present invention.

Claims (22)

1. A preparation method of a lithium titanate composite material is characterized by comprising the following steps:
1) preparing a ruthenium dioxide/titanium dioxide composite;
2) preparing a lithium titanate composite material by using a ruthenium dioxide/titanium dioxide composite and a lithium source as raw materials;
wherein the step 1) comprises:
11) modifying ruthenium dioxide by using a surfactant;
12) mixing the modified ruthenium dioxide with a solvent to prepare a dispersion liquid;
13) mixing the dispersion, the buffer solution and the tetrabutyl titanate solution to prepare a mixture containing the ruthenium dioxide/titanium dioxide composite;
wherein the surfactant solution is polyvinylpyrrolidone solution; the solvent comprises absolute ethyl alcohol and water; the buffer solution is tetramethyl ammonium hydroxide solution.
2. The method for preparing a lithium titanate composite material according to claim 1, wherein the step 2) comprises:
21) reacting the ruthenium dioxide/titanium dioxide composite with a lithium source to obtain a lithium titanate composite doped with ruthenium;
22) and enabling the ruthenium-doped lithium titanate composite to adsorb ruthenium ions to obtain the lithium titanate composite material.
3. The method for preparing a lithium titanate composite material according to claim 1, wherein the step 2) comprises:
and reacting the ruthenium dioxide/titanium dioxide composite with a lithium source to obtain the lithium titanate composite material.
4. The method for preparing a lithium titanate composite material according to claim 1, wherein the step 11) is specifically:
dispersing ruthenium dioxide powder in a surfactant solution;
separating the modified ruthenium dioxide from the solution;
wherein the size of the ruthenium dioxide powder is 10-15 nm.
5. The method for preparing a lithium titanate composite material according to claim 4,
the mass ratio of the ruthenium dioxide to the polyvinylpyrrolidone is 1: (5-300); the mass fraction of the polyvinylpyrrolidone solution is 10-40 g/L.
6. The method for preparing a lithium titanate composite material according to claim 1, characterized in that, in the step 12):
the mass ratio of the modified ruthenium dioxide to the absolute ethyl alcohol to the water is as follows: (2-50): (5-20): 1.
7. the method for preparing a lithium titanate composite material according to claim 1, wherein the step 13) is specifically:
firstly, adding a buffer solution into the dispersion liquid, then adding a tetra-n-butyl titanate solution, stirring and uniformly mixing.
8. The method for preparing a lithium titanate composite material according to claim 1, characterized in that, in the step 13): the volume ratio of the buffer solution to the dispersion solution is 1: (400-800); the volume ratio of the tetra-n-butyl titanate solution to the dispersion is 1: (40-90);
wherein the volume fraction of the tetramethylammonium hydroxide solution is 5-15%.
9. The method for preparing a lithium titanate composite material according to claim 8,
the tetra-n-butyl titanate solution is a tetra-n-butyl titanate ethanol solution, and the volume fraction of the tetra-n-butyl titanate solution is 1-20%.
10. The method for preparing a lithium titanate composite material according to claim 2, wherein the step 21) is specifically: and (3) reacting the ruthenium dioxide/titanium dioxide composite with a lithium source by using a sol-gel method to obtain the lithium titanate composite doped with ruthenium.
11. The method for preparing a lithium titanate composite material according to claim 10, wherein the step 21) is specifically:
dropwise adding a lithium source into the mixture containing the ruthenium dioxide/titanium dioxide composite, and continuously stirring for a set time to obtain wet gel;
sequentially carrying out aging treatment and drying treatment on the wet gel to obtain dry gel; wherein the xerogel is a lithium titanate compound doped with ruthenium.
12. The method for preparing a lithium titanate composite material according to claim 11, wherein the lithium source is a lithium acetate ethanol solution; wherein the concentration of the lithium acetate ethanol solution is 0.4-1 mol/L; the molar ratio of lithium acetate in the lithium acetate ethanol solution to tetra-n-butyl titanate in the tetra-n-butyl titanate solution is (0.8-0.9): 1.
13. the method for preparing a lithium titanate composite material according to claim 11, wherein the wet gel is subjected to an aging treatment under the following conditions: the aging temperature is 25-50 ℃, and the aging time is 3-5 hours.
14. The method for preparing a lithium titanate composite material according to claim 11,
the conditions for drying the wet gel are as follows: the drying temperature is 50-100 ℃, and the drying time is 10-30 hours.
15. The method for preparing a lithium titanate composite material according to claim 2, wherein the step 22) includes:
reacting the ruthenium-doped lithium titanate composite with a ruthenium salt solution to obtain a precipitate;
and calcining the precipitate to obtain the lithium titanate composite material.
16. The method for preparing the lithium titanate composite material according to claim 15, wherein the ruthenium salt solution is a ruthenium nitrate solution with a concentration of 0.5-2 g/L; and the mass ratio of the ruthenium nitrate in the ruthenium nitrate solution to the ruthenium-doped lithium titanate composite is 1: (20-100).
17. The method for preparing a lithium titanate composite material according to claim 15,
reacting the ruthenium-doped lithium titanate compound with a ruthenium salt solution in an ultrasonic microwave mixed reaction system; and the conditions of the ultrasonic microwave reaction are as follows: the power is 50-100W, the reaction temperature is 500-1000 ℃, and the reaction time is 6-12 hours.
18. The method of preparing a lithium titanate composite material according to claim 15, further comprising a step of grinding the ruthenium doped lithium titanate composite into powder prior to the step of reacting the ruthenium doped lithium titanate composite with a ruthenium salt solution.
19. The method for preparing a lithium titanate composite material according to claim 15,
the conditions under which the precipitate is calcined are: the calcination temperature is 500-1000 ℃, and the calcination time is 6-12 h.
20. A lithium titanate composite material characterized by being produced by the method for producing a lithium titanate composite material according to any one of claims 1 to 19.
21. A negative electrode sheet, characterized in that the negative electrode sheet comprises the lithium titanate composite material according to claim 20.
22. A lithium battery comprising the negative electrode sheet of claim 21.
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