CN108987720B - Carbon/zinc oxide composite material and preparation method and application thereof - Google Patents
Carbon/zinc oxide composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a carbon/zinc oxide composite material and a preparation method and application thereof. A preparation method of a carbon/zinc oxide composite material comprises the following steps: carrying out hydrothermal reaction on the biomass material in an alkali solution at the temperature of 150-200 ℃ to obtain a precipitate; refluxing the precipitate in an acid solution at the temperature of 80-90 ℃, and then washing the precipitate to be neutral to obtain a carbon skeleton; and carrying out hydrothermal reaction on the zinc acetate, sodium hydroxide and a growth auxiliary agent at the temperature of 150-200 ℃ to obtain a precursor. Carrying out hydrothermal reaction on the carbon skeleton and the precursor at the temperature of 200-250 ℃ to obtain a reactant; and calcining the reactant in the atmosphere of protective gas to obtain the carbon/zinc oxide composite material. The carbon/zinc oxide composite material prepared by the preparation method of the carbon/zinc oxide composite material has the advantages of low cost and good electrochemical performance.
Description
Technical Field
The invention relates to the technical field of electrochemistry, in particular to a carbon/zinc oxide composite material and a preparation method and application thereof.
Background
The lithium ion battery is a novel high-energy battery successfully developed in the 20 th century, and the traditional battery is gradually replaced by the unique advantages of high specific capacity, long cycle life, high working voltage, safety, no pollution and the like, and the traditional lithium ion battery material cannot meet the requirement of high energy density along with the wide application of electric vehicles and new energy vehicles and the rapid development of high and new technologies. Lithium ion batteries are a great research trend at present, and the improvement of the specific capacity, the cycle rate and the cycle stability of the batteries becomes a main focus of lithium ion battery research.
The carbon material is a typical lithium ion battery cathode material due to the fact that the potential of the carbon material in the intercalation process is close to the lithium potential, and has stable cycle performance, but the standard specific capacity of the carbon material is too low, the cost of the carbon material is relatively high, and the carbon material cannot meet the increasing energy and cost requirements.
Disclosure of Invention
Therefore, a preparation method of the carbon/zinc oxide composite material with lower cost and better electrochemical performance is needed.
In addition, a carbon/zinc oxide composite material and application thereof are also provided.
A preparation method of a carbon/zinc oxide composite material comprises the following steps:
carrying out hydrothermal reaction on a biomass material in an alkali solution at the temperature of 150-200 ℃ to obtain a precipitate, wherein the biomass material is selected from one of rice hulls and corn straws;
refluxing the precipitate in an acid solution at the temperature of 80-90 ℃, and then washing the precipitate to be neutral to obtain a carbon skeleton;
and carrying out hydrothermal reaction on the zinc acetate, sodium hydroxide and a growth auxiliary agent at the temperature of 150-200 ℃ to obtain a precursor.
Carrying out hydrothermal reaction on the carbon skeleton and the precursor at the temperature of 200-250 ℃ to obtain a reactant;
and calcining the reactant in the atmosphere of protective gas to obtain the carbon/zinc oxide composite material.
According to the preparation method of the carbon/zinc oxide composite material, the biomass material is prepared into the carbon skeleton, the carbon skeleton is reacted with the precursor, and the carbon/zinc oxide composite material is obtained through high-temperature calcination, wherein the biomass material is selected as the carbon source, and the carbon/zinc oxide composite material is widely and easily obtained based on the biomass material, so that the cost of the carbon/zinc oxide composite material is greatly reduced; meanwhile, the carbon skeleton made of the biomass material has a unique natural skeleton and pore channels, so that the lithium ion transmission is faster, the zinc oxide is embedded in the surface of the carbon made of the biomass material, the volume change in the zinc oxide charging and discharging process can be inhibited, the zinc oxide is prevented from being crushed, the integrity of the zinc oxide shape is kept, and the electrochemical performance of the carbon/zinc oxide composite material is improved.
In one embodiment, the alkali solution is selected from one of a sodium hydroxide solution and a potassium hydroxide solution.
In one embodiment, the concentration of the alkali solution is 1moL/L to 3 moL/L.
In one embodiment, the acid solution is hydrochloric acid.
In one embodiment, the concentration of the acid solution is 1moL/L to 3 moL/L.
In one embodiment, in the step of carrying out hydrothermal reaction on zinc acetate, sodium hydroxide and a growth auxiliary agent, the mass ratio of the zinc acetate to the sodium hydroxide to the growth auxiliary agent is 2:1: 1-2: 1: 3.
In one embodiment, the growth aid is selected from at least one of cetyltrimethylammonium bromide, sodium dodecylbenzene sulfonate, ethylenediamine, poly (oxyethylene) nonylphenol, polyvinylpyrrolidone, and hexamethylenetetramine.
In one embodiment, before the step of refluxing the precipitate in the acid solution, the step of washing the precipitate to neutrality is further included.
The carbon/zinc oxide composite material prepared by the preparation method of the carbon/zinc oxide composite material.
The carbon/zinc oxide composite material is applied to the preparation of lithium ion batteries.
Drawings
FIG. 1 is a Raman spectrum of the carbon/zinc oxide composite material obtained in example 1;
FIG. 2 is an X-ray diffraction spectrum of the carbon/zinc oxide composite material obtained in example 1;
FIG. 3 is a scanning electron microscope image at 35000 times magnification of the carbon/zinc oxide composite material prepared in example 3;
FIG. 4 is a scanning electron micrograph of the carbon/zinc oxide composite material obtained in example 3, magnified 70000 times;
FIG. 5 is a transmission electron micrograph of the carbon/zinc oxide composite material obtained in example 3, magnified 80000 times;
FIG. 6 is a transmission electron micrograph of the carbon/zinc oxide composite material prepared in example 3 magnified 100000 times;
FIG. 7 is a graph of the cycle performance of the carbon/zinc oxide composite prepared in example 2 with zinc oxide at a current density of 0.1A/g.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
A method of preparing a carbon/zinc oxide composite according to an embodiment includes the steps of:
step S110: the biomass material is subjected to hydrothermal reaction in an alkali solution at the temperature of 150-200 ℃ to obtain a precipitate.
Wherein the biomass material is selected from one of rice husk and corn stalk.
Wherein, in the step of carrying out hydrothermal reaction on the biomass material in an alkaline solution, the alkaline solution is selected from one of a sodium hydroxide solution and a potassium hydroxide solution. Further, the concentration of the alkali solution is 1 moL/L-3 moL/L.
Furthermore, in the step of carrying out hydrothermal reaction on the biomass material in the alkaline solution, the reaction time is 10-14 h.
Step S120: and refluxing the precipitate in an acid solution at the temperature of 80-90 ℃, and then washing the precipitate to be neutral to obtain the carbon skeleton.
Wherein, in the step of refluxing the precipitate in the acid solution, the acid solution is hydrochloric acid or hydrochloric acid to remove metal ions in the precipitate. Further, the concentration of the acid solution is 1 moL/L-3 moL/L.
Further, in the step of refluxing the precipitate in the acid solution, the refluxing time is 2 to 3 hours.
Wherein, in the step of washing to neutrality, the used water is deionized water.
The method further includes a step of washing the precipitate with water to neutrality, before the step of refluxing the precipitate in the acid solution. Specifically, the water used is deionized water.
Step S130: and carrying out hydrothermal reaction on the zinc acetate, sodium hydroxide and a growth auxiliary agent at the temperature of 150-200 ℃ to obtain a precursor.
Specifically, the hydrothermal reaction of zinc acetate, sodium hydroxide and a growth auxiliary agent comprises the following steps: dissolving zinc acetate, sodium hydroxide and a growth auxiliary agent in ethanol to obtain a mixed solution; then the mixed solution is reacted for 6 to 10 hours in a reaction kettle.
Wherein in the step of carrying out hydrothermal reaction on zinc acetate, sodium hydroxide and a growth auxiliary agent, the mass ratio of the zinc acetate to the sodium hydroxide to the growth auxiliary agent is 2:1: 1-2: 1: 3.
Wherein the growth auxiliary agent is at least one selected from Cetyl Trimethyl Ammonium Bromide (CTAB), sodium Dodecyl Benzene Sulfonate (DBS), Ethylenediamine (EDA), poly (oxyethylene) Nonylphenol (NP), polyvinylpyrrolidone (PVP) and Hexamethylenetetramine (HMT). Further, the growth assistant is a mixture of cetyltrimethylammonium bromide and ethylenediamine. Specifically, in the mixture of hexadecyl trimethyl ammonium bromide and ethylenediamine, the mass ratio of the hexadecyl trimethyl ammonium bromide to the ethylenediamine is 2: 1-3: 1.
Step S140: and carrying out hydrothermal reaction on the carbon skeleton and the precursor at the temperature of 200-250 ℃ to obtain a reactant.
Wherein in the step of carrying out hydrothermal reaction on the carbon skeleton and the precursor, the reaction time is 24-36 h. Specifically, the adopted equipment is a reaction kettle.
Wherein, the step of carrying out hydrothermal reaction on the carbon skeleton and the precursor comprises the following steps: and washing the precursor with deionized water to be neutral, and then carrying out hydrothermal reaction with the carbon skeleton.
Step S150: and calcining the reactant in the atmosphere of protective gas to obtain the carbon/zinc oxide composite material.
Wherein the protective gas is selected from one of nitrogen and argon.
Wherein in the step of calcining the reactant, the calcining temperature is 400-600 ℃; the calcining time is 2-4 h. In particular, the equipment used is a tube furnace.
The carbon/zinc oxide composite material prepared by the preparation method of the carbon/zinc oxide composite material. The carbon/zinc oxide composite material has the advantages of low cost and good electrochemical performance.
The carbon/zinc oxide composite material is applied to the preparation of lithium ion batteries. For example, in the preparation of negative electrodes for lithium ion batteries.
The preparation method of the carbon/zinc oxide composite material at least has the following advantages:
1) according to the preparation method of the carbon/zinc oxide composite material, the biomass material is prepared into the carbon skeleton, the carbon skeleton is reacted with the precursor, and the carbon/zinc oxide composite material is obtained through high-temperature calcination, wherein the biomass material is selected as the carbon source, and the carbon/zinc oxide composite material is widely and easily obtained based on the biomass material, so that the cost of the carbon/zinc oxide composite material is greatly reduced; meanwhile, the carbon skeleton made of the biomass material has a unique natural skeleton and pore channels, so that the lithium ion transmission is faster, the zinc oxide is embedded in the surface of the carbon made of the biomass material, the volume change in the zinc oxide charging and discharging process can be inhibited, the zinc oxide is prevented from being crushed, the integrity of the zinc oxide shape is kept, and the electrochemical performance of the carbon/zinc oxide composite material is improved.
2) The preparation method of the carbon/zinc oxide composite material takes the biomass material as the carbon source, thereby greatly reducing the environmental pressure, increasing the utilization rate of the biomass material and realizing the maximization of resource utilization.
3) The carbon/zinc oxide composite material prepared by the preparation method of the carbon/zinc oxide composite material has a larger specific surface area as a two-dimensional composite material, and is beneficial to improving the electrochemical active area, so that the rate capability of an electrode of a lithium ion battery is improved.
The following are specific examples:
example 1
The preparation steps of the carbon/zinc oxide composite material of the embodiment are as follows:
(1) 2g of rice hull and 30mL of 1moL/L sodium hydroxide solution are uniformly mixed, and then the mixture is transferred into a reaction kettle to react for 10 hours at 180 ℃ to obtain a precipitate.
(2) Washing the precipitate to neutrality, refluxing with 1moL/L hydrochloric acid solution at 80 deg.C for 2 hr in water bath, collecting white residue, and washing with deionized water to neutrality to obtain carbon skeleton.
(3) 1g of zinc acetate, 1.8g of hexadecyl trimethyl ammonium bromide, 0.4g of sodium hydroxide and 0.06mL of ethylenediamine are dissolved in 40mL of ethanol, and the mixture is uniformly mixed and then transferred into a reaction kettle to react for 6 hours at 180 ℃ to obtain a precursor.
(4) And (3) washing the precursor with deionized water to be neutral, transferring the precursor and the carbon skeleton into a reaction kettle, and reacting for 24 hours at 200 ℃ to obtain a reactant.
(5) And putting the reactants into a tubular furnace to calcine for 2 hours at 400 ℃ under the protection atmosphere of argon to obtain the carbon/zinc oxide composite material.
Raman spectrum analysis was performed on the carbon/zinc oxide composite material obtained in example 1, and the results are shown in fig. 1. 448cm can be seen from FIG. 1-1The peak at (a) is due to stretching of the Zn-O bond; at 1350cm-1And 1595cm-1The two characteristic peaks are respectively corresponding to a D peak and a G peak, the D peak is caused by defects and disordered structures in the amorphous carbon material, the G peak is corresponding to the vibration of sp2 hybridized carbon atoms, the intensity ratio of the D peak to the G peak is 0.84, and the defects in the carbon/zinc oxide composite material are increased, because the zinc oxide and the amorphous carbon are compounded, the defects can provide more active sites in the subsequent charging and discharging process, and further the lithium storage capacity of the carbon/zinc oxide composite material is improved.
The carbon/zinc oxide composite material obtained in example 1 was subjected to X-ray diffraction spectroscopic analysis, and the results are shown in fig. 2. As can be seen from fig. 2, the diffraction peaks of the X-ray diffraction spectrum appear at 31.80 °, 34.48 °, 36.21 °, 47.64 °, 56.60 °, 62.86 °, 66.45 °, 68.00 °, 69.04 °, 72.70 ° and 77.00 °, corresponding to the (100), (002), (100), (102), (110), (103), (200), (112), (201), (004) and (002) crystal planes of zinc oxide, indicating that zinc oxide in the carbon/zinc oxide composite is zinc oxide of a hexagonal wurtzite structure (JCPDS No. 36-1451). The diffraction peak of zinc oxide was sharp and intense, indicating that zinc oxide has high crystallinity, and no impurity peak was observed, confirming the high purity of zinc oxide. It is noteworthy that a large peak envelope of about 20 ° can be observed in the carbon/zinc oxide composite material, corresponding to amorphous carbon, indicating successful recombination of zinc oxide and carbon made from biomass material.
Example 2
The preparation steps of the carbon/zinc oxide composite material of the embodiment are as follows:
(1) 2g of rice hull and 30mL of 2moL/L sodium hydroxide solution are uniformly mixed, and then the mixture is transferred into a reaction kettle to react for 12 hours at 180 ℃ to obtain a precipitate.
(2) Washing the precipitate to neutrality, refluxing with 2moL/L hydrochloric acid solution at 80 deg.C for 2 hr in water bath, collecting white residue, and washing with deionized water to neutrality to obtain carbon skeleton.
(3) 1g of zinc acetate, 1.8g of hexadecyl trimethyl ammonium bromide, 0.4g of sodium hydroxide and 0.06mL of ethylenediamine are dissolved in 40mL of ethanol, and the mixture is uniformly mixed and then transferred into a reaction kettle to react for 8 hours at 180 ℃ to obtain a precursor.
(4) And (3) washing the precursor with deionized water to be neutral, transferring the precursor and the carbon skeleton into a reaction kettle, and reacting for 24 hours at 200 ℃ to obtain a reactant.
(5) And putting the reactants into a tubular furnace to calcine for 3 hours at 500 ℃ under the protective atmosphere of argon to obtain the carbon/zinc oxide composite material.
Example 3
The preparation steps of the carbon/zinc oxide composite material of the embodiment are as follows:
(1) 3g of rice hull and 30mL of 2moL/L sodium hydroxide solution are uniformly mixed, and then the mixture is transferred into a reaction kettle to react for 12 hours at 180 ℃ to obtain a precipitate.
(2) Washing the precipitate to neutrality, refluxing with 1moL/L hydrochloric acid solution at 90 deg.C for 3 hr in water bath, collecting white residue, and washing with deionized water to neutrality to obtain carbon skeleton.
(3) 2g of zinc acetate, 3.6g of hexadecyl trimethyl ammonium bromide, 0.5g of sodium hydroxide and 0.07mL of ethylenediamine are dissolved in 40mL of ethanol, and the mixture is uniformly mixed and then transferred into a reaction kettle to react for 8 hours at 190 ℃ to obtain a precursor.
(4) And washing the precursor with deionized water to be neutral, transferring the precursor and the carbon skeleton to a reaction kettle, and reacting for 30 hours at 200 ℃ to obtain a reactant.
(5) And putting the reactants into a tubular furnace to calcine for 3 hours at 500 ℃ under the protective atmosphere of argon to obtain the carbon/zinc oxide composite material.
Scanning electron microscope analysis was performed on the carbon/zinc oxide composite material obtained in example 3, and the results are shown in fig. 3 and 4. As can be seen from fig. 3 and 4, the carbon in the carbon/zinc oxide composite material is amorphous carbon and is a skeleton of the carbon/zinc oxide composite material, and the surface of the carbon in the carbon/zinc oxide composite material is connected with the rod-shaped zinc oxide.
The carbon/zinc oxide composite material obtained in example 3 was analyzed by transmission electron microscopy, and the results are shown in fig. 5 and 6. As can be seen from fig. 5 and 6, the dispersibility of zinc oxide is good at the surface of carbon in the carbon/zinc oxide composite material, and the zinc oxide nanorods are uniformly attached to the surface of the carbon skeleton, which makes the contact surface more stable, can suppress the pulverization of zinc oxide, and maintain the integrity of zinc oxide to achieve a stable charge and discharge cycle.
Example 4
The preparation steps of the carbon/zinc oxide composite material of the embodiment are as follows:
(1) 2g of rice hull and 30mL of 3moL/L sodium hydroxide solution are uniformly mixed, and then the mixture is transferred into a reaction kettle to react for 14 hours at 180 ℃ to obtain a precipitate.
(2) Washing the precipitate to neutrality, refluxing with 2moL/L hydrochloric acid solution at 90 deg.C for 2 hr in water bath, collecting white residue, and washing with deionized water to neutrality to obtain carbon skeleton.
(3) 2g of zinc acetate, 3.6g of hexadecyl trimethyl ammonium bromide, 0.5g of sodium hydroxide and 0.07mL of ethylenediamine are dissolved in 40mL of ethanol, and the mixture is uniformly mixed and then transferred into a reaction kettle to react for 8 hours at 180 ℃ to obtain a precursor.
(4) And (3) washing the precursor with deionized water to be neutral, transferring the precursor and the carbon skeleton into a reaction kettle, and reacting for 24 hours at 200 ℃ to obtain a reactant.
(5) And putting the reactants into a tubular furnace to calcine for 4 hours at 500 ℃ under the protection atmosphere of argon to obtain the carbon/zinc oxide composite material.
And (3) testing:
the cycle performance test was carried out on the carbon/zinc oxide composite material and zinc oxide obtained in example 2, respectively, and the results are shown in fig. 7, where RHC in fig. 7 represents carbon obtained from rice hulls.
The method for testing the cycle performance comprises the following steps: respectively taking the carbon/zinc oxide composite material and zinc oxide prepared in the embodiment 2 as initial raw materials, uniformly mixing the initial raw materials with acetylene black and PVDF according to the mass ratio of 8:1:1 to obtain a mixture, then dropwise adding NMP into the mixture, stirring for 6 hours to form uniformly mixed slurry, uniformly coating the slurry on a copper foil, drying at 120 ℃ in a vacuum drying oven for 12 hours, and stamping the copper foil into a wafer with the diameter of 12mm by using a stamping machine after drying; the wafer is made into a negative electrode of a lithium ion battery, and is applied to a CR2025 type lithium ion battery. Among them, the type CR2025 lithium ion battery uses a lithium sheet as a counter electrode, a diaphragm is PP, and an electrolyte is EC/DMC (1: 1). The lithium ion battery is subjected to charge and discharge tests, the tests are carried out on a blue CT2001A multi-channel battery test system, the termination voltage range is 0.02V-3.0V, and the test current density is 0.1A/g.
As can be seen from fig. 7, under the current density of 0.1A/g, the specific capacity of the carbon/zinc oxide composite material prepared in example 2 still has 920mA · h/g after 100 cycles, and the specific capacity of pure zinc oxide has only 45.5mA · h/g after 100 cycles, which indicates that the carbon skeleton prepared from the biomass material enhances the conductivity of the carbon/zinc oxide composite material, and meanwhile, the zinc oxide nanorod can improve the electrochemical dynamics, shorten the diffusion distance of lithium ions and electrons, and further improve the specific capacity of the carbon/zinc oxide composite material. Therefore, compared with zinc oxide, the lithium ion battery using the carbon/zinc oxide composite material prepared in example 2 as the negative electrode material has better cycle stability and higher specific discharge capacity, that is, the carbon/zinc oxide composite material prepared in example 2 has better electrochemical performance.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The preparation method of the carbon/zinc oxide composite material is characterized by comprising the following steps:
carrying out hydrothermal reaction on a biomass material in an alkali solution at the temperature of 150-200 ℃ to obtain a precipitate, wherein the biomass material is selected from one of rice hulls and corn straws;
refluxing the precipitate in an acid solution at the temperature of 80-90 ℃, and then washing the precipitate to be neutral to obtain a carbon skeleton;
carrying out hydrothermal reaction on zinc acetate, sodium hydroxide and a growth auxiliary agent at the temperature of 150-200 ℃ to obtain a precursor, wherein the growth auxiliary agent is at least one selected from cetyl trimethyl ammonium bromide, sodium dodecyl benzene sulfonate, ethylenediamine, poly (oxyethylene) nonyl phenol, polyvinylpyrrolidone and hexamethylenetetramine;
carrying out hydrothermal reaction on the carbon skeleton and the precursor at the temperature of 200-250 ℃ to obtain a reactant;
and calcining the reactant in the atmosphere of protective gas to obtain the carbon/zinc oxide composite material.
2. The method for preparing a carbon/zinc oxide composite material according to claim 1, wherein the alkali solution is one selected from a sodium hydroxide solution and a potassium hydroxide solution.
3. The method for preparing a carbon/zinc oxide composite material according to claim 2, wherein the concentration of the alkali solution is 1moL/L to 3 moL/L.
4. The method for preparing a carbon/zinc oxide composite material according to claim 1, wherein the acid solution is a hydrochloric acid solution.
5. The method for preparing a carbon/zinc oxide composite material according to claim 4, wherein the concentration of the acid solution is 1moL/L to 3 moL/L.
6. The method for preparing the carbon/zinc oxide composite material according to claim 1, wherein in the step of carrying out the hydrothermal reaction on the zinc acetate, the sodium hydroxide and the growth auxiliary agent, the mass ratio of the zinc acetate to the sodium hydroxide to the growth auxiliary agent is 2:1: 1-2: 1: 3.
7. The method of claim 1, wherein the growth aid is selected from the group consisting of a mixture of cetyltrimethylammonium bromide and ethylenediamine.
8. The method for preparing a carbon/zinc oxide composite material according to claim 1, wherein the step of refluxing the precipitate in an acid solution further comprises a step of washing the precipitate with water to neutrality.
9. The carbon/zinc oxide composite material prepared by the method for preparing the carbon/zinc oxide composite material according to any one of claims 1 to 8.
10. Use of the carbon/zinc oxide composite material according to claim 9 in the preparation of a lithium ion battery.
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