CN111446416B - Multi-level structure phase-combined TiO2Preparation and application of composite graphene negative electrode material - Google Patents
Multi-level structure phase-combined TiO2Preparation and application of composite graphene negative electrode material Download PDFInfo
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Abstract
The invention discloses TiO combined with a multilevel structure2The preparation method of the composite graphene negative electrode material comprises the following steps: preparing a precursor by a solvothermal method by using tetrabutyl titanate as a titanium source and an alcohol compound as a primary solvent; the precursor is converted into TiO phase with anatase phase and rutile phase by a two-step calcination method at the temperature lower than the phase transition temperature2(ii) a In combination with TiO2Uniformly mixing with graphene, placing in a secondary solvent, keeping constant temperature, and performing ultrasonic treatment to obtain TiO with a three-dimensional multi-level structure2A graphene composite material. TiO with multilevel structure2The composite graphene negative electrode material is prepared by the preparation method. A battery electrode is TiO combined with multi-level structure2The composite graphene negative electrode material is prepared. The finally prepared material of the invention also has nanometer TiO2High cycle life is imparted to the battery, and high conductivity and large current discharge capability are imparted to the electrode material by the graphene.
Description
Technical Field
The invention belongs to the field of electrochemical energy storage, and particularly relates to a three-dimensional multilevel structure TiO combined lithium ion battery cathode material2Preparation and application of the composite graphene material.
Background
In the past decades, lithium ion batteries have been widely used in the fields of portable electronic devices, electric vehicles, energy storage, and the like, due to their high energy density and long cycle life. Currently, graphite is used as the main negative electrode material in the industrial production of lithium ion batteries, however, the low discharge voltage (0.2V vs. Li/Li +) of the graphite electrode still affects the high rate performance and safety performance of the lithium ion battery(lithium is separated out during charging and discharging to generate lithium dendrites). The transition metal oxide is considered to be a potential high-energy-density lithium ion battery cathode material due to the characteristics of high discharge voltage, high specific discharge capacity and the like. Among the numerous transition metal oxides, TiO2The working voltage of the material is about 1.6V vs. Li/Li + (higher than that of a graphite cathode material), the volume of the material is slightly changed in the charging and discharging process (zero volume effect), and the material has stable structure and abundant sources and attracts wide attention. Multi-phase TiO2E.g. anatase, rutile and TiO phases2(B) The phase was studied as a negative electrode material. However, TiO2The low conductivity directly affects its practical application. In order to solve the problem, various strategies such as construction of a combined structure, construction of a multi-level structure, doping of equivalent ions, and compounding of other conductive materials are proposed. Among the numerous methods, the complexation with carbon materials is considered to be an effective measure for improving the electrochemical performance, since the complexation can establish a stable interface to reduce the side reactions between the active material and the electrolyte, and can promote TiO2Is conducted. Graphene is a typical carbon material, and its special network structure can provide a fast transport channel for electrons, and it has high gram capacity and lithium ion mobility. In addition, the multi-level structure composed of nanoparticles can shorten the lithium ion diffusion path while providing more lithium storage sites. Therefore, the performance of the cathode material can be improved by designing the material by combining the advantages of the combination, the multilevel structure and the material composition, and the method has important application value.
CN108511696A discloses a preparation method of a titanium dioxide/graphene composite material, the material is used as a negative electrode material, and 0.1C rate test results show that the first discharge specific capacity is 253.6mAh/g, the discharge specific capacity after 50 times of circulation is 183.6mAh/g, and the capacity retention rate is 72.40%, which improves the electrochemical performance to a certain extent, but because bulk TiO phase2The final cycle performance of the material cannot meet the requirement due to the characteristics of low conductivity and the like of the material.
Disclosure of Invention
In order to solve the defects of the prior art, the invention providesMulti-level structure phase-combined TiO2Preparation and application of the composite graphene negative electrode material.
In order to solve the technical problems, the invention adopts the technical scheme that: multi-level structure phase-combined TiO2The preparation method of the composite graphene negative electrode material comprises the following steps:
preparing three-dimensional multilevel structure TiO by a solvothermal method by using tetrabutyl titanate (TBOT) as a titanium source and an alcohol compound as a primary solvent2A precursor;
II, preparing the three-dimensional multilevel structure TiO prepared in the step I2The precursor is converted into TiO phase with anatase phase (A) and rutile phase (R) by a two-step calcination method at the temperature lower than the phase transition temperature (600℃)2Mixed phase of TiO2The appearance of (A) is a three-dimensional multilevel structure;
III combining the TiO prepared in step II2Uniformly mixing the composite material with graphene to obtain a composite material, placing the composite material in a secondary solvent, keeping the constant temperature at 40-80 ℃, performing ultrasonic treatment, and completely volatilizing the secondary solvent to obtain TiO with a three-dimensional multilevel structure2And compounding the graphene negative electrode material.
Further, in the step I, the primary solvent is a mixed solvent composed of glycerol and ethanol, and the volume ratio of the glycerol to the ethanol is 1: 4-1: 1.
Further, the volume ratio of the tetrabutyl titanate to the primary solvent in the step I is 2-10%.
Furthermore, the air introducing amount in the first calcining process and the air introducing amount in the second calcining process in the two-step calcining method are different, and the adopted heating process is different; wherein, TiO with three-dimensional multilevel structure2The precursor is finished in the first calcination process, and the second calcination process is started after the precursor is cooled to room temperature.
Further, the air inlet amount in the first calcination process is 1-25 ml/min; the heating process is carried out at a heating rate of 1-5 ℃/min, at a calcining temperature of 200-400 ℃ and for a calcining time of 1-4 h.
Further, the air inlet amount in the second calcination process is 30-100 ml/min; the heating speed is 2-10 ℃/min, the calcination temperature is preferably 300-550 ℃, and the calcination time is 1-3 h.
Further, TiO is added according to the mass ratio of 1-10% of graphene in the composite material2。
Further, in step III, the secondary solvent is one of ethanol, acetone or water.
TiO with multilevel structure2The composite graphene anode material is TiO combined by a multilevel structure2The composite graphene negative electrode material is prepared by the preparation method.
A battery electrode is TiO combined with multi-level structure2The composite graphene negative electrode material is prepared.
The invention has the following beneficial effects: the invention provides a TiO combined with a multilevel structure2A preparation method of the composite graphene negative electrode material; TiO in the composite material2The lithium ion battery has a combined phase (A/R) and three-dimensional multilevel structure, and the special structure can shorten a lithium ion diffusion path; in addition, the existence of graphene can better improve TiO2Electrochemical kinetics of (a); finally prepared three-dimensional multilevel structure combined TiO2The composite graphene negative electrode material has nano TiO2High cycle life is imparted to the battery, and high conductivity and large current discharge capability are imparted to the electrode material by the graphene.
Drawings
FIG. 1 shows three-dimensional multilevel TiO2The precursor (shown in a1 and a2) combines TiO with a three-dimensional multilevel structure2(FIG. b1, b 2).
FIG. 2 is a three-dimensional multilevel structure-combined TiO2XRD patterns of (a, b: primary calcination, secondary calcination).
FIG. 3 is a three-dimensional multilevel structure phase TiO2TEM images of composite graphene.
FIG. 4 is a three-dimensional multilevel structure phase TiO2Cycle profile of composite graphene materials.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
The first embodiment,
Three-dimensional multilevel structure phase-bonded TiO2The preparation method of the composite graphene negative electrode material comprises the following steps:
uniformly mixing glycerol and ethanol according to the volume ratio of 1:4 to prepare a primary solvent, and adding tetrabutyl titanate (TBOT) into the primary solvent according to the volume ratio of 10% of tetrabutyl titanate (TBOT) to the primary solvent. Uniformly stirring, putting into a reaction kettle, carrying out solvothermal reaction for 50h at 180 ℃ to obtain the three-dimensional multilevel structure TiO2And (3) precursor. As is clear from the SEM images a1 and a2 in FIG. 1, TiO with a three-dimensional multilevel structure2The precursor is a three-dimensional multi-stage flower type structure assembled by a similar belt structure.
II, preparing the three-dimensional multilevel structure TiO prepared in the step I2Placing the precursor in a furnace, introducing air at 25ml/min, heating to 200 ℃ at a heating rate of 1 ℃/min, keeping the temperature for calcining for 4h, and after the first calcining is finished, cooling the sample to room temperature and then carrying out secondary calcining. At the moment, the air introduction amount is changed to 30ml/min, the temperature is increased to 300 ℃ at the temperature rising speed of 10 ℃/min, the temperature is maintained, and the calcination is carried out for 3h, so that the TiO with the three-dimensional multi-level structure combination can be obtained2。
As shown in FIG. 1, the TiO obtained after calcination2The crystal still keeps the three-dimensional multi-stage pattern type morphology (figures b1, b 2). Comparing fig. a2 and b2, the difference is that after the calcination treatment, the ribbon structure with smooth surface is changed into a rod structure formed by stacking a plurality of nanoparticles, and the multi-stage structure formed by the nanoparticles can shorten the lithium ion diffusion path. In addition, the XRD pattern of FIG. 2 shows that the precursor is calcined to form a combined TiO of anatase and rutile2。
III, adding TiO with a three-dimensional multilevel structure according to the mass ratio of 1% of graphene in the composite material2Uniformly mixing, adding into ethanol solvent, setting the temperature at 40 ℃, performing ultrasonic treatment, and completely volatilizing the solvent to obtain TiO with a three-dimensional multilevel structure2A graphene composite material. As can be seen from the TEM image of FIG. 3, the TiO phase is combined2The composite graphene material is successfully prepared.
Example II,
Three-dimensional multilevel structure phase-bonded TiO2The preparation method of the composite graphene negative electrode material comprises the following steps:
and I, uniformly mixing glycerol and ethanol according to the volume ratio of 1:1 to prepare a primary solvent, and adding tetrabutyl titanate into the primary solvent according to the volume ratio of 2% of tetrabutyl titanate (TBOT) to the primary solvent. Uniformly stirring, putting into a reaction kettle, carrying out solvothermal reaction for 12h at 180 ℃ to obtain the three-dimensional multilevel structure TiO2And (3) precursor.
II, preparing the three-dimensional multilevel structure TiO prepared in the step I2Placing the precursor in a furnace, introducing air at the rate of 1ml/min, heating to 400 ℃ at the heating rate of 5 ℃/min, keeping the temperature for calcining for 1h, and after the first calcining is finished, cooling the sample to room temperature and then carrying out secondary calcining. At the moment, the air introduction amount is changed to 100ml/min, the temperature is increased to 550 ℃ at the temperature increase speed of 2 ℃/min, the temperature is maintained, and the calcination is carried out for 1h, so that the TiO with the three-dimensional multi-level structure combination can be obtained2。
III, adding TiO with a three-dimensional multilevel structure according to the mass ratio of 10% of graphene in the composite material2Uniformly mixing, adding into a hydrosolvent, setting the temperature at 80 ℃, performing ultrasonic treatment, and completely volatilizing the solvent to obtain TiO with a three-dimensional multilevel structure2And compounding the graphene negative electrode material.
Example III,
Three-dimensional multilevel structure phase-bonded TiO2The preparation method of the composite graphene negative electrode material comprises the following steps:
uniformly mixing glycerol and ethanol according to the volume ratio of 1:2 to prepare a primary solvent, and adding tetrabutyl titanate (TBOT) into the primary solvent according to the volume ratio of 5% of tetrabutyl titanate to the primary solvent. Uniformly stirring, putting into a reaction kettle, carrying out solvothermal reaction for 20h at 180 ℃ to obtain the three-dimensional multilevel structure TiO2And (3) precursor.
II, preparing the three-dimensional multilevel structure TiO prepared in the step I2Placing the precursor in a furnace, introducing air at 20ml/min, heating to 300 deg.C at a rate of 2 deg.C/min, calcining for 3 hr, and cooling to the temperatureAfter room temperature, secondary calcination is carried out. At the moment, the air introduction amount is changed to 80ml/min, the temperature is raised to 450 ℃ at the temperature rise speed of 4 ℃/min, the temperature is maintained, and the calcination is carried out for 2h, so that the TiO with the three-dimensional multi-level structure combination can be obtained2。
III, adding TiO with a three-dimensional multilevel structure according to the mass ratio of 5% of graphene in the composite material2Uniformly mixing, adding into acetone solvent, setting the temperature at 60 deg.C, ultrasonic treating, and volatilizing to obtain TiO with three-dimensional multilevel structure2And compounding the graphene negative electrode material.
Example four,
Three-dimensional multilevel structure phase-bonded TiO2The preparation method of the composite graphene negative electrode material comprises the following steps:
uniformly mixing glycerol and ethanol according to the volume ratio of 1:3 to prepare a primary solvent, and adding tetrabutyl titanate (TBOT) into the primary solvent according to the volume ratio of 7% of tetrabutyl titanate to the primary solvent. Uniformly stirring, putting into a reaction kettle, carrying out solvothermal reaction for 30h at 180 ℃ to obtain the three-dimensional multilevel structure TiO2And (3) precursor.
II, preparing the three-dimensional multilevel structure TiO prepared in the step I2Placing the precursor in a furnace, introducing air at a rate of 15ml/min, heating to 300 ℃ at a heating rate of 3 ℃/min, keeping the temperature for calcining for 2h, and after the first calcining is finished, cooling the sample to room temperature and then carrying out secondary calcining. At the moment, the air introduction amount is changed to 50ml/min, the temperature is increased to 350 ℃ at the temperature rising speed of 6 ℃/min, the temperature is kept for calcination for 2.5h, and the TiO with the three-dimensional multi-level structure combination can be obtained2。
III, adding TiO with a three-dimensional multilevel structure according to the mass ratio of 7% of graphene in the composite material2Uniformly mixing, adding into a water solvent, setting the temperature at 70 ℃, performing ultrasonic treatment, and completely volatilizing the solvent to obtain TiO with a three-dimensional multi-level structure2And compounding the graphene negative electrode material.
Example V,
Three-dimensional multilevel structure phase-bonded TiO2The preparation method of the composite graphene negative electrode material comprises the following steps:
uniformly mixing glycerol and ethanol according to the volume ratio of 1:1 to prepare a primary solvent, and adding tetrabutyl titanate (TBOT) into the primary solvent according to the volume ratio of 10%. Uniformly stirring, putting into a reaction kettle, and carrying out solvothermal reaction for 40h at 180 ℃ to obtain the three-dimensional multilevel structure TiO2And (3) precursor.
II, preparing the three-dimensional multilevel structure TiO prepared in the step I2Placing the precursor in a furnace, introducing 10ml/min of air, heating to 400 ℃ at the heating rate of 4 ℃/min, keeping the temperature for calcining for 1.5h, and after the first calcining is finished, cooling the sample to room temperature and then carrying out secondary calcining. At the moment, the air introduction amount is changed to 70ml/min, the temperature is raised to 500 ℃ at the temperature rise speed of 5 ℃/min, the temperature is maintained, and the calcination is carried out for 2h, so that the TiO with the three-dimensional multi-level structure combination can be obtained2。
III, adding TiO with a three-dimensional multilevel structure according to the mass ratio of 3% of graphene in the composite material2Uniformly mixing, adding into acetone solvent, setting the temperature at 50 deg.C, ultrasonic treating, and volatilizing to obtain TiO with three-dimensional multilevel structure2And compounding the graphene negative electrode material.
Example six,
Three-dimensional multilevel structure phase-bonded TiO2The preparation method of the composite graphene negative electrode material comprises the following steps:
and I, uniformly mixing glycerol and ethanol according to the volume ratio of 1:1 to prepare a primary solvent, and adding tetrabutyl titanate into the primary solvent according to the volume ratio of 2% of tetrabutyl titanate (TBOT) to the primary solvent. Uniformly stirring, putting into a reaction kettle, carrying out solvothermal reaction for 12h at 180 ℃ to obtain the three-dimensional multilevel structure TiO2And (3) precursor.
II, preparing the three-dimensional multilevel structure TiO prepared in the step I2Placing the precursor in a furnace, introducing air at 5ml/min, heating to 400 ℃ at the heating rate of 5 ℃/min, keeping the temperature for calcining for 1h, and after the first calcining is finished, cooling the sample to room temperature and then carrying out secondary calcining. At the moment, the air introduction amount is changed to 90ml/min, the temperature is increased to 550 ℃ at the temperature rising speed of 3 ℃/min, the temperature is maintained, and the three-dimensional multilevel structure can be obtained after the calcination for 1hIn combination with TiO2。
III, adding TiO with a three-dimensional multilevel structure according to the mass ratio of 9% of graphene in the composite material2Uniformly mixing, adding into a hydrosolvent, setting the temperature at 80 ℃, performing ultrasonic treatment, and completely volatilizing the solvent to obtain TiO with a three-dimensional multilevel structure2And compounding the graphene negative electrode material.
Example seven,
Three-dimensional multilevel structure phase-bonded TiO2The preparation method of the composite graphene negative electrode material comprises the following steps:
uniformly mixing glycerol and ethanol according to the volume ratio of 1:4 to prepare a primary solvent, and adding tetrabutyl titanate (TBOT) into the primary solvent according to the volume ratio of 9% of tetrabutyl titanate (TBOT) to the primary solvent. Uniformly stirring, putting into a reaction kettle, carrying out solvothermal reaction for 50h at 180 ℃ to obtain the three-dimensional multilevel structure TiO2And (3) precursor.
II, preparing the three-dimensional multilevel structure TiO prepared in the step I2Placing the precursor in a furnace, introducing air at 25ml/min, heating to 200 ℃ at a heating rate of 1 ℃/min, keeping the temperature for calcining for 4h, and after the first calcining is finished, cooling the sample to room temperature and then carrying out secondary calcining. At the moment, the air introduction amount is changed to 60ml/min, the temperature is increased to 350 ℃ at the temperature increase speed of 4 ℃/min, the temperature is maintained, and the calcination is carried out for 3h, so that the TiO with the three-dimensional multi-level structure combination can be obtained2。
III, adding TiO with a three-dimensional multi-level structure according to the mass ratio of 2% of graphene in the composite material2Uniformly mixing, adding into ethanol solvent, setting the temperature at 50 ℃, performing ultrasonic treatment, and completely volatilizing the solvent to obtain TiO with a three-dimensional multilevel structure2And compounding the graphene negative electrode material.
And (3) experimental results and detection:
the three-dimensional multilevel structure prepared in the first example is combined with TiO2The composite graphene material is used as a negative active material to be manufactured into a negative pole piece of the battery.
In the pole piece manufacturing process, conductive carbon black (SP) is selected as a conductive agent, a binder is carboxymethyl cellulose (CMC) and Styrene Butadiene Rubber (SBR), and the active substance, the SP, the CMC and the SBR are mixed according to a mass ratio of 80: 10: 5: and 5, adding a proper amount of water, mixing to prepare slurry, coating the slurry on a copper foil current collector, and performing vacuum drying at 80 ℃ for 24 hours to obtain the pole piece.
A metallic lithium sheet is used as a counter electrode, electrolyte is a solution of Ethyl Carbonate (EC) and dimethyl carbonate (DMC) (volume ratio is 1:1) of 1.0M LiPF6, a diaphragm is a celgard2400 membrane, a 2032 type button cell is assembled in a glove box filled with argon, the cell is kept stand for 12 hours, and electrochemical performance test is carried out.
And (3) testing results: under the conditions of 0.1C multiplying power and 0.01-3V charging and discharging interval, the first specific discharge capacity of the pole piece prepared from the composite material in the first embodiment reaches 434.8mAh/g, the specific discharge capacity after 400 cycles is 387mAh/g (as shown in figure 4), and the capacity retention rate is 89%. When under 5C high rate, the first discharge specific capacity of the material has 279 mAh/g.
The above embodiments are not intended to limit the present invention, and the present invention is not limited to the above examples, and those skilled in the art may make variations, modifications, additions or substitutions within the technical scope of the present invention.
Claims (8)
1. Multi-level structure phase-combined TiO2The preparation method of the composite graphene negative electrode material is characterized by comprising the following steps: the method comprises the following steps:
taking tetrabutyl titanate as a titanium source and a mixed solvent consisting of glycerol and ethanol as a primary solvent, and preparing the TiO with the three-dimensional multilevel structure by a solvothermal method2A precursor;
II, preparing the three-dimensional multilevel structure TiO prepared in the step I2The precursor is converted into TiO phase with anatase phase and rutile phase by a two-step calcination method at the temperature lower than the phase transition temperature2Mixed phase of TiO2The appearance of (A) is a three-dimensional multilevel structure;
the air inlet amount in the first calcination process is 1-25 ml/min; the heating process is carried out at a heating speed of 1-5 ℃/min, at a calcining temperature of 200-400 ℃ and for a calcining time of 1-4 h; the air inlet amount in the second calcination process is 30-100 ml/min; the heating process is carried out at the heating speed of 6-10 ℃/min, the calcining temperature of 300-550 ℃ and the calcining time of 1-3 h;
III combining the TiO prepared in step II2Uniformly mixing the composite material with graphene to obtain a composite material, placing the composite material in a secondary solvent, keeping the constant temperature at 40-80 ℃, performing ultrasonic treatment, and completely volatilizing the secondary solvent to obtain TiO with a three-dimensional multilevel structure2And compounding the graphene negative electrode material.
2. The multi-level structure phase TiO of claim 12The preparation method of the composite graphene negative electrode material is characterized by comprising the following steps: the volume ratio of the glycerol to the ethanol in the step I is 1: 4-1: 1.
3. The multi-level structure phase TiO of claim 12The preparation method of the composite graphene negative electrode material is characterized by comprising the following steps: the volume ratio of tetrabutyl titanate to the primary solvent in the step I is 2-10%.
4. The multi-level structure phase TiO of claim 12The preparation method of the composite graphene negative electrode material is characterized by comprising the following steps: three-dimensional multilevel structure TiO2The precursor is finished in the first calcination process, and the second calcination process is started after the precursor is cooled to room temperature.
5. The multi-level structure phase TiO of claim 12The preparation method of the composite graphene negative electrode material is characterized by comprising the following steps: in the step III, TiO is added according to the mass ratio of 1-10% of graphene in the composite material2。
6. The multi-level structure phase TiO of claim 12The preparation method of the composite graphene negative electrode material is characterized by comprising the following steps: and the secondary solvent in the step III is one of ethanol, acetone or water.
7. TiO with multilevel structure2Composite graphiteThe alkene negative pole material is characterized in that: the negative electrode material is TiO combined by the multilevel structure of any one of claims 1 to 62The composite graphene negative electrode material is prepared by the preparation method.
8. A battery electrode, characterized by: the battery electrode is TiO combined by the multilevel structure of claim 72The composite graphene negative electrode material is prepared.
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