CN108987720A - Carbon/zinc oxide composite and its preparation method and application - Google Patents

Carbon/zinc oxide composite and its preparation method and application Download PDF

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CN108987720A
CN108987720A CN201810864419.XA CN201810864419A CN108987720A CN 108987720 A CN108987720 A CN 108987720A CN 201810864419 A CN201810864419 A CN 201810864419A CN 108987720 A CN108987720 A CN 108987720A
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carbon
zinc oxide
oxide composite
preparation
hydro
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CN108987720B (en
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李义
高岩
于开锋
曹兴刚
邹康迪
王中书
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NALON BATTERY (SHEN ZHEN) CO Ltd
Qiantai Technology (shenshan Special Cooperation Zone) Co Ltd
Shenzhen Dry Energy Recycling Technology Co Ltd
Jilin University
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NALON BATTERY (SHEN ZHEN) CO Ltd
Qiantai Technology (shenshan Special Cooperation Zone) Co Ltd
Shenzhen Dry Energy Recycling Technology Co Ltd
Jilin University
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/625Carbon or graphite
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M2004/021Physical characteristics, e.g. porosity, surface area
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M2004/026Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027Negative electrodes
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The present invention relates to a kind of carbon/zinc oxide composites and its preparation method and application.A kind of preparation method of carbon/zinc oxide composite, comprising the following steps: under conditions of 150 DEG C~200 DEG C, biological material is subjected to hydro-thermal reaction in aqueous slkali, obtains sediment;Under conditions of 80 DEG C~90 DEG C, sediment is flowed back in acid solution, neutrality is then washed to, obtains carbon skeleton;Under conditions of 150 DEG C~200 DEG C, zinc acetate and sodium hydroxide, growth adjuvant are subjected to hydro-thermal reaction, obtain presoma.Under conditions of 200 DEG C~250 DEG C, carbon skeleton and presoma are subjected to hydro-thermal reaction, obtain reactant;Under the atmosphere of protective gas, reactant is calcined, obtains carbon/zinc oxide composite.Carbon/zinc oxide composite made from the preparation method of above-mentioned carbon/zinc oxide composite has the advantages that cost is relatively low, chemical property is preferable.

Description

Carbon/zinc oxide composite and its preparation method and application
Technical field
The present invention relates to electrochemical technology fields, more particularly to a kind of carbon/zinc oxide composite and preparation method thereof And application.
Background technique
Lithium ion battery is that the novel high-energy battery succeeded in developing in 20th century is had extended cycle life due to its high specific capacity, Operating voltage is high, and the unique advantages such as safety non-pollution have gradually replaced conventional batteries, with electric vehicle, new-energy automobile it is extensive Using the rapid development with new and high technology, traditional lithium ion battery material can no longer meet the requirement of high-energy density.Lithium Ion battery becomes a current big research tendency, and improving battery specific capacity, circulating ratio and cyclical stability becomes lithium ion The principal concern of battery research.
Carbon material is typical lithium ion battery negative material since its current potential in telescopiny is close to lithium current potential, With stable cycle performance, but its standard specific volume amount is too low, and the cost is relatively high, is unable to satisfy the energy increasingly to increase severely And cost needs.
Summary of the invention
Based on this, it is necessary to which providing one kind, cost is relatively low, the preparation of the preferable carbon/zinc oxide composite of chemical property Method.
In addition, additionally providing a kind of carbon/zinc oxide composite and its application.
A kind of preparation method of carbon/zinc oxide composite, comprising the following steps:
Under conditions of 150 DEG C~200 DEG C, biological material is subjected to hydro-thermal reaction in aqueous slkali, obtains sediment, Wherein, the biological material is selected from one of rice husk and corn stover;
Under conditions of 80 DEG C~90 DEG C, the sediment is flowed back in acid solution, is then washed to neutrality, obtains carbon Skeleton;
Under conditions of 150 DEG C~200 DEG C, zinc acetate and sodium hydroxide, growth adjuvant are subjected to hydro-thermal reaction, obtained Presoma.
Under conditions of 200 DEG C~250 DEG C, the carbon skeleton and the presoma are subjected to hydro-thermal reaction, reacted Object;
Under the atmosphere of protective gas, the reactant is calcined, obtains the carbon/zinc oxide composite.
The preparation method of above-mentioned carbon/zinc oxide composite is by being prepared into carbon skeleton for biological material, and by carbon bone Frame and forerunner's precursor reactant, obtain carbon/zinc oxide composite using high-temperature calcination, wherein select biological material as carbon Source, based on biological material extensively and be easily obtained, greatly reduce carbon/zinc oxide composite cost;Meanwhile biomass There is carbon skeleton made from material unique natural skeleton and duct to inlay zinc oxide so that the transmission of lithium ion is more quick The surface of carbon made from embedding biomaterial, the volume change being able to suppress in zinc oxide charge and discharge process avoid the powder of zinc oxide It is broken, the integrality of zinc oxide pattern is kept, to improve carbon/zinc oxide composite chemical property.
The aqueous slkali is selected from one of sodium hydroxide solution and potassium hydroxide solution in one of the embodiments,.
The concentration of the aqueous slkali is 1moL/L~3moL/L in one of the embodiments,.
The acid solution is hydrochloric acid in one of the embodiments,.
The concentration of the acid solution is 1moL/L~3moL/L in one of the embodiments,.
The step that zinc acetate and sodium hydroxide, growth adjuvant are carried out to hydro-thermal reaction in one of the embodiments, In rapid, the mass ratio of the zinc acetate and the sodium hydroxide, the growth adjuvant is 2:1:1~2:1:3.
The growth adjuvant is selected from cetyl trimethylammonium bromide, detergent alkylate in one of the embodiments, At least one of sodium sulfonate, ethylenediamine, poly- (ethylene oxide) nonyl phenol, polyvinylpyrrolidone and hexa.
In one of the embodiments, before the described the step of sediment flows back in acid solution, further include by The sediment is washed to neutral step.
Carbon/zinc oxide composite made from above-mentioned carbon/zinc oxide composite preparation method.
Above-mentioned carbon/zinc oxide composite is preparing the application in lithium ion battery.
Detailed description of the invention
Fig. 1 is carbon/zinc oxide composite Raman spectrogram made from embodiment 1;
Fig. 2 is carbon/zinc oxide composite X-ray diffraction spectra figure made from embodiment 1;
Fig. 3 is the scanning electron microscope (SEM) photograph of 35000 times of carbon/zinc oxide composite amplification made from embodiment 3;
Fig. 4 is the scanning electron microscope (SEM) photograph of 70000 times of carbon/zinc oxide composite amplification made from embodiment 3;
Fig. 5 is the transmission electron microscope picture of 80000 times of carbon/zinc oxide composite amplification made from embodiment 3;
Fig. 6 is the transmission electron microscope picture of 100000 times of carbon/zinc oxide composite amplification made from embodiment 3;
Fig. 7 is the circulation of carbon/zinc oxide composite and zinc oxide under the current density of 0.1A/g made from embodiment 2 Performance chart.
Specific embodiment
To facilitate the understanding of the present invention, a more comprehensive description of the invention is given in the following sections with reference to the relevant attached drawings.In attached drawing Give preferred embodiment of the invention.But the invention can be realized in many different forms, however it is not limited to herein Described embodiment.On the contrary, purpose of providing these embodiments is keeps the understanding to the disclosure more saturating It is thorough comprehensive.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool Body embodiment purpose, it is not intended that in limitation the present invention.
Carbon/zinc oxide composite preparation method of one embodiment, comprising the following steps:
Step S110: under conditions of 150 DEG C~200 DEG C, biological material is subjected to hydro-thermal reaction in aqueous slkali, is obtained To sediment.
Wherein, biological material is selected from one of rice husk and corn stover.
Wherein, in the step of biological material to be carried out to hydro-thermal reaction in aqueous slkali, it is molten that aqueous slkali is selected from sodium hydroxide One of liquid and potassium hydroxide solution.Further, the concentration of aqueous slkali is 1moL/L~3moL/L.
Further, in the step of biological material to be carried out to hydro-thermal reaction in aqueous slkali, time of reaction be 10h~ 14h。
Step S120: under conditions of 80 DEG C~90 DEG C, sediment being flowed back in acid solution, is then washed to neutrality, Obtain carbon skeleton.
Wherein, in the step of sediment being flowed back in acid solution, acid solution is hydrochloric acid or, to remove the gold in sediment Belong to ion.Further, the concentration of acid solution is 1moL/L~3moL/L.
Further, in the step of sediment being flowed back in acid solution, the time of reflux is 2h~3h.
Wherein, it is washed in neutral step, the water used is deionized water.
It should be noted that further including in being washed to sediment before the step of sediment is flowed back in acid solution The step of property.It specifically, the use of water is deionized water.
Step S130: under conditions of 150 DEG C~200 DEG C, zinc acetate and sodium hydroxide, growth adjuvant are subjected to hydro-thermal Reaction, obtains presoma.
Specifically, the step of zinc acetate and sodium hydroxide, growth adjuvant being subjected to hydro-thermal reaction are as follows: by zinc acetate, hydrogen Sodium oxide molybdena and the dissolution of growth adjuvant in ethanol, obtain mixed liquor;Then mixed liquor is reacted into 6h~10h in a kettle.
Wherein, in the step of zinc acetate and sodium hydroxide, growth adjuvant being carried out hydro-thermal reaction, zinc acetate and hydroxide Sodium, the mass ratio for growing adjuvant are 2:1:1~2:1:3.
Wherein, growth adjuvant be selected from cetyl trimethylammonium bromide (CTAB), neopelex (DBS), In ethylenediamine (EDA), poly- (ethylene oxide) nonyl phenol (NP), polyvinylpyrrolidone (PVP) and hexa (HMT) extremely Few one kind.Further, growth adjuvant is the mixture of cetyl trimethylammonium bromide and ethylenediamine.Specifically, ten six In the mixture of alkyl trimethyl ammonium bromide and ethylenediamine, the mass ratio of cetyl trimethylammonium bromide and ethylenediamine is 2:1 ~3:1.
Step S140: under conditions of 200 DEG C~250 DEG C, carbon skeleton and presoma is subjected to hydro-thermal reaction, reacted Object.
Wherein, in the step of carbon skeleton and presoma being carried out hydro-thermal reaction, the time of reaction is for 24 hours~36h.Specifically Ground uses equipment for reaction kettle.
Wherein, the step of carbon skeleton and presoma being carried out hydro-thermal reaction includes: that presoma is washed with deionized water into Property, then hydro-thermal reaction is carried out with carbon skeleton.
Step S150: under the atmosphere of protective gas, reactant being calcined, and obtains carbon/zinc oxide composite.
Wherein, protective gas is selected from one of nitrogen and argon gas.
Wherein, in the step of reactant being calcined, the temperature of calcining is 400 DEG C~600 DEG C;The time of calcining be 2h~ 4h.Specifically, the equipment used is tube furnace.
Carbon/zinc oxide composite made from the preparation method of above-mentioned carbon/zinc oxide composite.Carbon/the zinc oxide is multiple Condensation material has the advantages that cost is relatively low, chemical property is preferable.
Upper carbon/zinc oxide composite is preparing the application in lithium ion battery.For example, preparing negative electrode of lithium ion battery In application.
The preparation method of above-mentioned carbon/zinc oxide composite at least has the advantages that
1) preparation method of above-mentioned carbon/zinc oxide composite is by being prepared into carbon skeleton for biological material, and by carbon Skeleton and forerunner's precursor reactant, obtain carbon/zinc oxide composite using high-temperature calcination, wherein select biological material as Carbon source, based on biological material extensively and be easily obtained, greatly reduce carbon/zinc oxide composite cost;Meanwhile biology Carbon skeleton made from material has unique natural skeleton and duct, so that the transmission of lithium ion is more quick, by zinc oxide The surface for inlaying carbon made from biomaterial, the volume change being able to suppress in zinc oxide charge and discharge process, avoids zinc oxide It crushes, the integrality of zinc oxide pattern is kept, to improve carbon/zinc oxide composite chemical property.
2) preparation method of above-mentioned carbon/zinc oxide composite significantly reduces environment pressure using biological material as carbon source Power increases the utilization rate of biological material, realizes maximum resource utilization.
3) carbon made from the preparation method of above-mentioned carbon/zinc oxide composite/zinc oxide composite is compound as two dimension Material has biggish specific surface area, helps to improve the active area of electrochemistry, thus improve the electrode of lithium ion battery High rate performance.
The following are specific embodiment parts:
Embodiment 1
Carbon/zinc oxide composite preparation step of the present embodiment is as follows:
(1) rice husk of 2g is uniformly mixed with the sodium hydroxide solution of the 1moL/L of 30mL, is then transferred into reaction kettle In 180 DEG C of reaction 10h, sediment is obtained.
(2) it after sediment being washed till neutrality, is flowed back 2h, is collected white at 80 DEG C with 1moL/L hydrochloric acid solution in water-bath Color residue is simultaneously washed with deionized water to neutrality, obtains carbon skeleton.
(3) by the second of the zinc acetate of 1g, the cetyl trimethylammonium bromide of 1.8g, the sodium hydroxide of 0.4g and 0.06mL Diamines is dissolved in the ethyl alcohol of 40mL, is transferred in reaction kettle after mixing in 180 DEG C of reaction 6h, is obtained presoma.
(4) it is transferred in reaction kettle after presoma being washed with deionized water to neutrality with carbon skeleton, for 24 hours in 200 DEG C of reactions, Obtain reactant.
(5) under the protective atmosphere of argon gas, reactant is put into tube furnace in 400 DEG C of calcining 2h, carbon/zinc oxide is obtained Composite material.
Raman spectrum analysis is carried out to carbon made from embodiment 1/zinc oxide composite, as a result as shown in Figure 1.From Fig. 1 In as can be seen that 448cm-1The peak at place is attributed to the stretching of Zn-O key;In 1350cm-1And 1595cm-1Locate existing two features Peak corresponds respectively to the peak D and the peak G, and the peak D is due to caused by defect in amorphous carbon material and chaotic structure, and the peak G is corresponding In the vibration of sp2 hydbridized carbon atoms, the intensity ratio at the peak D and the peak G is 0.84, shows that defect increases in carbon/zinc oxide composite, This is because zinc oxide and agraphitic carbon is compound, these defects can provide more activity in subsequent charge and discharge process Site, and then improve carbon/zinc oxide composite lithium storage content.
X-ray diffraction spectra analysis is carried out to carbon made from embodiment 1/zinc oxide composite, as a result as shown in Figure 2. From figure 2 it can be seen that the diffraction maximum of X-ray diffraction spectra appears in 31.80 °, and 34.48 °, 36.21 °, 47.64 °, 56.60 °, 62.86 °, 66.45 °, 68.00 °, 69.04 °, 72.70 ° and 77.00 °, corresponding to (100) of zinc oxide, (002), (100), (102), (110), (103), (200), (112), (201), (004) and (002) crystal face illustrate that carbon/zinc oxide is compound Zinc oxide in material is the zinc oxide (JCPDS No.36-1451) of hexagonal wurtzite structure.The diffraction maximum of zinc oxide is sharp With it is strong, show that zinc oxide has highly crystalline, and impurity peaks be not observed, it was demonstrated that the high-purity of zinc oxide.Value It obtains it is noted that it can be observed that about 20 ° of big Bao Feng, corresponds to amorphous carbon, say in carbon/zinc oxide composite material The success of carbon made from bright zinc oxide and biological material is compound.
Embodiment 2
Carbon/zinc oxide composite preparation step of the present embodiment is as follows:
(1) rice husk of 2g is uniformly mixed with the sodium hydroxide solution of the 2moL/L of 30mL, is then transferred into reaction kettle In 180 DEG C of reaction 12h, sediment is obtained.
(2) it after sediment being washed till neutrality, is flowed back 2h, is collected white at 80 DEG C with 2moL/L hydrochloric acid solution in water-bath Color residue is simultaneously washed with deionized water to neutrality, obtains carbon skeleton.
(3) by the second of the zinc acetate of 1g, the cetyl trimethylammonium bromide of 1.8g, the sodium hydroxide of 0.4g and 0.06mL Diamines is dissolved in the ethyl alcohol of 40mL, is transferred in reaction kettle after mixing in 180 DEG C of reaction 8h, is obtained presoma.
(4) it is transferred in reaction kettle after presoma being washed with deionized water to neutrality with carbon skeleton, for 24 hours in 200 DEG C of reactions, Obtain reactant.
(5) under the protective atmosphere of argon gas, reactant is put into tube furnace in 500 DEG C of calcining 3h, carbon/zinc oxide is obtained Composite material.
Embodiment 3
Carbon/zinc oxide composite preparation step of the present embodiment is as follows:
(1) rice husk of 3g is uniformly mixed with the sodium hydroxide solution of the 2moL/L of 30mL, is then transferred into reaction kettle In 180 DEG C of reaction 12h, sediment is obtained.
(2) it after sediment being washed till neutrality, is flowed back 3h, is collected white at 90 DEG C with 1moL/L hydrochloric acid solution in water-bath Color residue is simultaneously washed with deionized water to neutrality, obtains carbon skeleton.
(3) by the second of the zinc acetate of 2g, the cetyl trimethylammonium bromide of 3.6g, the sodium hydroxide of 0.5g and 0.07mL Diamines is dissolved in the ethyl alcohol of 40mL, is transferred in reaction kettle after mixing in 190 DEG C of reaction 8h, is obtained presoma.
(4) it is transferred in reaction kettle after presoma being washed with deionized water to neutrality with carbon skeleton, in 200 DEG C of reaction 30h, Obtain reactant.
(5) under the protective atmosphere of argon gas, reactant is put into tube furnace in 500 DEG C of calcining 3h, carbon/zinc oxide is obtained Composite material.
Electron microscope analysis is scanned to carbon/zinc oxide composite made from embodiment 3, as a result as shown in Figure 3 and Figure 4. It is agraphitic carbon from the carbon that can be seen that in Fig. 3 and Fig. 4 in carbon/zinc oxide composite, is carbon/zinc oxide composite Skeleton, meanwhile, the surface of the carbon in carbon/zinc oxide composite is connected with rodlike zinc oxide.
Transmission electron microscope analysis is carried out to carbon made from embodiment 3/zinc oxide composite, as a result as shown in Figure 5 and Figure 6. As can be known from Fig. 5 and Fig. 6, the favorable dispersibility of the zinc oxide on the surface of the carbon in carbon/zinc oxide composite, zinc oxide Nanometer rods are homogenously connected to the surface of carbon skeleton, this makes contact surface more stable, can inhibit the crushing of zinc oxide, and keep Zinc oxide integrality, to realize stable charge and discharge cycles.
Embodiment 4
Carbon/zinc oxide composite preparation step of the present embodiment is as follows:
(1) rice husk of 2g is uniformly mixed with the sodium hydroxide solution of the 3moL/L of 30mL, is then transferred into reaction kettle In 180 DEG C of reaction 14h, sediment is obtained.
(2) it after sediment being washed till neutrality, is flowed back 2h, is collected white at 90 DEG C with 2moL/L hydrochloric acid solution in water-bath Color residue is simultaneously washed with deionized water to neutrality, obtains carbon skeleton.
(3) by the second of the zinc acetate of 2g, the cetyl trimethylammonium bromide of 3.6g, the sodium hydroxide of 0.5g and 0.07mL Diamines is dissolved in the ethyl alcohol of 40mL, is transferred in reaction kettle after mixing in 180 DEG C of reaction 8h, is obtained presoma.
(4) it is transferred in reaction kettle after presoma being washed with deionized water to neutrality with carbon skeleton, for 24 hours in 200 DEG C of reactions, Obtain reactant.
(5) under the protective atmosphere of argon gas, reactant is put into tube furnace in 500 DEG C of calcining 4h, carbon/zinc oxide is obtained Composite material.
Test:
Cycle performance test is carried out to carbon/zinc oxide composite made from embodiment 2 and zinc oxide respectively, as a result as schemed Shown in 7, in Fig. 7, RHC indicates carbon made from rice husk.
Wherein, the method for cycle performance test are as follows: respectively with carbon/zinc oxide composite and oxidation made from embodiment 2 Zinc is starting material, is then mixed starting material and acetylene black, PVDF according to the ratio of mass ratio 8:1:1 Object is allowed to form uniformly mixed slurry, slurry is evenly coated on copper foil simultaneously then to NMP is added dropwise in mixture and stirs 6h In 120 DEG C of vacuum oven dry 12h, copper foil is struck out to the disk of diameter 12mm using press machine after dry;By disk system At the cathode of lithium ion battery, in the lithium ion battery applied to model CR2025 type.Wherein, the lithium of model CR2025 type Use lithium piece as to electrode in ion battery, diaphragm PP, electrolyte is EC/DMC (1:1).Lithium ion battery is filled Discharge test, test are carried out in blue electricity CT2001A multi-channel battery test system, and final voltage range is 0.02V ~3.0V, test current density are 0.1A/g.
From figure 7 it can be seen that under the current density of 0.1A/g, carbon/zinc oxide composite ratio made from embodiment 2 Capacity still has 920mAh/g after the circulation of 100 circles, and the specific capacity of pure zinc oxide only has after the circulation of 100 circles 45.5mAh/g illustrates that carbon skeleton made from biological material enhances carbon/zinc oxide composite conductivity, simultaneous oxidation Zinc nanometer rods can be improved electrochemical kinetics, shorten the diffusion length of lithium ion and electronics, and then it is compound to improve carbon/zinc oxide The specific capacity of material.Therefore, compared with zinc oxide, lithium of the carbon/zinc oxide composite as negative electrode material made from embodiment 2 The cyclical stability of ion battery is preferable, and specific discharge capacity is higher, i.e. carbon/zinc oxide composite electricity made from embodiment 2 Chemical property is more preferable.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.

Claims (10)

1. a kind of preparation method of carbon/zinc oxide composite, which comprises the following steps:
Under conditions of 150 DEG C~200 DEG C, biological material is subjected to hydro-thermal reaction in aqueous slkali, obtains sediment, In, the biological material is selected from one of rice husk and corn stover;
Under conditions of 80 DEG C~90 DEG C, the sediment is flowed back in acid solution, is then washed to neutrality, obtains carbon bone Frame;
Under conditions of 150 DEG C~200 DEG C, zinc acetate and sodium hydroxide, growth adjuvant are subjected to hydro-thermal reaction, obtain forerunner Body.
Under conditions of 200 DEG C~250 DEG C, the carbon skeleton and the presoma are subjected to hydro-thermal reaction, obtain reactant;
Under the atmosphere of protective gas, the reactant is calcined, obtains the carbon/zinc oxide composite.
2. the preparation method of carbon/zinc oxide composite according to claim 1, which is characterized in that the aqueous slkali choosing From one of sodium hydroxide solution and potassium hydroxide solution.
3. the preparation method of carbon/zinc oxide composite according to claim 2, which is characterized in that the aqueous slkali Concentration is 1moL/L~3moL/L.
4. the preparation method of carbon/zinc oxide composite according to claim 1, which is characterized in that the acid solution is Hydrochloric acid.
5. the preparation method of carbon/zinc oxide composite according to claim 4, which is characterized in that the acid solution Concentration is 1moL/L~3moL/L.
6. the preparation method of carbon/zinc oxide composite according to claim 1, which is characterized in that described by zinc acetate In the step of carrying out hydro-thermal reaction with sodium hydroxide, growth adjuvant, the zinc acetate and the sodium hydroxide, the growth are auxiliary The mass ratio of auxiliary agent is 2:1:1~2:1:3.
7. the preparation method of carbon/zinc oxide composite according to claim 1, which is characterized in that the growth auxiliary Agent is selected from cetyl trimethylammonium bromide, neopelex, ethylenediamine, poly- (ethylene oxide) nonyl phenol, polyethylene pyrrole At least one of pyrrolidone and hexa.
8. the preparation method of carbon/zinc oxide composite according to claim 1, which is characterized in that described described to sink Before the step of starch flows back in acid solution, include the steps that the sediment being washed to neutrality.
9. carbon/zinc oxide made from carbon/zinc oxide composite preparation method described in claim 1~8 any one is multiple Condensation material.
10. carbon/zinc oxide composite as claimed in claim 9 is preparing the application in lithium ion battery.
CN201810864419.XA 2018-08-01 2018-08-01 Carbon/zinc oxide composite material and preparation method and application thereof Active CN108987720B (en)

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