CN109962224A - A kind of three-dimensional carbon nanosheet-zinc oxide composites and the preparation method and application thereof - Google Patents

A kind of three-dimensional carbon nanosheet-zinc oxide composites and the preparation method and application thereof Download PDF

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CN109962224A
CN109962224A CN201910173322.9A CN201910173322A CN109962224A CN 109962224 A CN109962224 A CN 109962224A CN 201910173322 A CN201910173322 A CN 201910173322A CN 109962224 A CN109962224 A CN 109962224A
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zinc oxide
zinc
carbon nanosheet
dimensional carbon
preparation
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邵怀宇
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MACAO UNIV
University of Macau
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H01M4/36—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
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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

Abstract

The present invention provides a kind of three-dimensional carbon nanosheet-zinc oxide composites and the preparation method and application thereof, and preparation method mixes the following steps are included: high polymer and zinc source are added in solvent, obtains reaction solution；The pH value of obtained reaction solution is adjusted to 8-12, and is stirred, is precipitated；Obtained precipitating is dried, then is placed at 200-1200 DEG C and heats carbonization, obtains three-dimensional carbon nanosheet-zinc oxide composites.Three-dimensional carbon nanosheet-zinc oxide composites can be prepared in the preparation method, the compound shows three-dimensional manometer frame and hole configurations, Zinc oxide nanoparticle is packed in this structure, alleviate bulking effect of the zinc oxide in charge and discharge process, and remaining carbon material increases the electric conductivity of composite materials after presoma roasting, the composite material of acquisition has excellent charge-discharge performance and very strong cyclical stability.

Description

A kind of three-dimensional carbon nanosheet-zinc oxide composites and the preparation method and application thereof
Technical field
The invention belongs to the preparation technical fields of nano material, and in particular to a kind of three-dimensional carbon nanosheet-zinc oxide is compound Object and the preparation method and application thereof.
Background technique
Nowadays it depends on fossil fuel unduly and causes serious environmental problem and energy crisis.In this case, it seeks Clean, safe and efficient sustainable green energy resource is asked to become the problem of urgent need to resolve.Renewable energy refers to natural resources, Such as sunlight, wind, underground heat, they are that nature can be fed.However, these resources be it is intermittent, validity is unpredictable , which has limited them to become dependable energy resource supply.In contrast, the storage electric energy that rechargeable battery can be simple and efficient And it receives significant attention.Compared with lead-acid battery, Ni-Co or Ni-MH, lithium ion battery is because of its higher volume and weight energy Metric density, longer cycle life become being preferably selected for small device energy storage.
The composition of lithium ion battery includes positive electrode active materials, negative electrode active material, electrolyte and diaphragm, wherein anode The excellent performance for directly affecting lithium ion battery of the performance of active material and negative electrode active material.Lithium ion battery negative material Mainly there are carbon negative pole material and metal oxide negative electrode material two major classes.Wherein, carbon negative pole material mainly include graphite, hard carbon, Soft carbon and carbon nanomaterial commonly use graphite in practical application and are used as carbon negative pole material, however, the graphite of commercialization is because of its limited appearance Measure (372mAhg-1) it is not able to satisfy the high-energy density of powering device and the needs of high power density.With graphite-phase ratio, metal Transition metal oxide in oxide cathode material is because of its higher theoretical capacity (700~1000mAhg-1) show not The potentiality of custom.In these oxides, ZnO has higher conductivity as semiconductor；At the same time, ZnO because theoretical capacity compared with Height (978mAhg-1), it is abundance, cheap, environmental-friendly and receive significant attention.However, zno-based material is followed in charge and discharge Because biggish volume expansion causes destructurized during ring, keep its stable circulation performance poor, cycle life is short.
Summary of the invention
The technical problem to be solved by the present invention is to provide a kind of three-dimensional carbon nanosheet-zinc oxide composites and preparation method thereof with Using the three-dimensional carbon nanosheet-zinc oxide composites being prepared show three-dimensional manometer frame and hole configurations, alleviate oxygen Change bulking effect of the zinc in charge and discharge process, and remaining carbon material increases the conduction of composite materials after presoma roasting Property, the composite material of acquisition has excellent charge-discharge performance and very strong cyclical stability.
To solve the above-mentioned problems, the present invention provides a kind of preparation method of three-dimensional carbon nanosheet-zinc oxide composites, packet Include following steps:
The first step will mix in high polymer and zinc source addition solvent, obtain reaction solution；
The pH value for the reaction solution that the first step obtains is adjusted to 8-12, and stirred by second step, is precipitated；
Third step, the precipitating for obtaining second step are dried, then are placed at 200-1200 DEG C and heat carbonization, obtain three-dimensional Carbon nanosheet-zinc oxide composites.
This method is using high polymer and zinc source as raw material, by that can obtain being encapsulated in three-dimensional after precipitating, simple carburizing reagent Three-dimensional manometer frame and hole configurations is presented in Zinc oxide nanoparticle composite material in carbon nanosheet frame, the composite material, It limits, alleviate expansion reaction of the zinc oxide in charge and discharge process when as lithium ion battery negative material, and after being fired The carbon nanosheet of generation increases the electric conductivity of composite material, improves the transmission rate of lithium ion and electronics, so that with its work It is greatly improved for the chemical property and recycling storage lithium stability of the lithium ion battery of battery cathode active material.
Wherein, the optional organic solvent of solvent such as ethyl alcohol etc. or inorganic solvent such as water etc., it is preferred that solvent selection water.
Organic base or inorganic base, the optional ammonium hydroxide of inorganic base, sodium hydroxide, hydrogen can be used when correspondingly, adjusting reaction solution pH Potassium oxide etc., preferably ammonium hydroxide, the ammonium ion that ammonium hydroxide retains can be discharged in gaseous form in roasting process, will not be compound Foreign metal ion is generated in material.
Wherein, high polymer refers to the molecular weight formed by one or more of simple aggregated reactions of low-molecular-weight organic compound Biggish compound, also known as macromolecule or macromolecular compound.Preferably, high polymer selects water soluble polymer, high water solubility Polymers dissolves in aqueous solvent, evenly dispersed with molecular state in water, so as to carry out more evenly with the zinc source of molecular state Mixing.In technical solution, it is preferred that high polymer is polyvinyl alcohol, polyethyleneimine, polyvinyl butyral, polyvinyl pyrrole One or more of alkanone, polyethylene glycol oxide.
Wherein, zinc source refers to containing zinc atom, and the precursor compound of zinc oxide can be formed after high-temperature roasting.Zinc source is optional Select inorganic zinc salt or organic zinc salt.In technical solution, it is preferred that zinc source is zinc acetate, zinc nitrate, zinc sulfate, zinc citrate, hard One or more of resin acid zinc.
In technical solution, it is preferred that the mass ratio in high polymer and zinc source is (1~50): (0.1~20).
It is further preferred that high polymer and the mass ratio in zinc source are (0.4~0.5): 1.
In technical solution, it is preferred that the first step specifically includes:
S1, high polymer is dissolved in solvent, and stirred, obtain polymer reaction liquid；
S2, zinc source is dissolved in solvent, and stirred, obtain zinc source reaction solution；
S3, polymer reaction liquid obtained by step S1 is mixed with zinc source reaction solution obtained by step S2, obtains reaction solution.
Wherein, the solvent of step S1 and step S2 may respectively be organic solvent such as ethyl alcohol etc. or inorganic solvent such as water Deng, it is preferred that solvent selects water.
It is further preferred that the high polymer of 1-50 parts by weight to be dissolved in the solvent of 30-3000 parts by weight in step S1 In；In step S2, the zinc source of 0.1-20 parts by weight is dissolved in the solvent of 5-1000 parts by weight.
In technical solution, it is preferred that the concentration of polymer reaction liquid is 10-100g/L, zinc source in step S2 in step S1 The concentration of reaction solution is 60-300g/L.
It is furthermore preferred that high polymer is dissolved in solvent in S1, and stirs 0.5-2 hours and obtain polymer reaction liquid；S2 In, zinc source is dissolved in solvent, and stir and obtain within 0.5-2 hours zinc source reaction solution；In second step, what adjusting obtained the first step The pH value of reaction solution is adjusted to 8-12, and is stirred at room temperature 1-5 hours.
In technical solution, it is preferred that in third step will precipitating heating carbonization when heating temperature be 500-1000 DEG C, when heating Between be 1-6h.It is further preferred that the heating rate in heating process is 1~50 DEG C/min；It is furthermore preferred that heating rate is 1 ~8 DEG C/min.
In technical solution, it is preferred that be also passed through inert protective gas, inertia protection when in third step to precipitating heating carbonization Gas is one of argon gas, nitrogen, helium or a variety of.It is furthermore preferred that the flow for the inert protective gas being passed through be 20~ 100mL/min.Preferably, heating carburizing reagent is carried out using vacuum tube furnace.
It is a further object of the present invention to provide the preparation methods of above-mentioned three-dimensional carbon nanosheet-zinc oxide composites to be prepared into Three-dimensional carbon nanosheet-the zinc oxide composites arrived.
Another object of the present invention is to provide above-mentioned three-dimensional carbon nanosheet-zinc oxide composites as negative electrode of lithium ion battery The application of active material.
Compared with the prior art, the present invention has the following beneficial effects:
1. three-dimensional carbon nanosheet-zinc oxide composites preparation method, which can be prepared, is encapsulated in three-dimensional carbon nanosheet frame Three-dimensional carbon nanometer frame and hole configurations, zinc oxide nano is presented in Zinc oxide nanoparticle composite material in frame, the composite material Rice grain is packed in this structure, limits, alleviates when as lithium ion battery negative material zinc oxide in charge and discharge Expansion reaction in journey significantly improves the cyclical stability of lithium ion battery, hence it is evident that better than using pure zinc oxide material as cathode The lithium ion battery of active material；
2. the carbon nanosheet generated after being fired increases the electric conductivity of composite material, the biography of lithium ion and electronics is improved Defeated rate significantly improves the charge-discharge performance of lithium ion battery, hence it is evident that better than using pure zinc oxide material as negative electrode active material Lithium ion battery；
3. the preparation method passes through precipitation reaction and letter using abundance, cheap high polymer and zinc source as raw material Single carbonisation can be completed, and experimentation is simple, be easy to repeat, low in cost, be highly susceptible to industrial amplification, realize extensive Production.
Detailed description of the invention
Fig. 1 is three-dimensional carbon nanosheet-zinc oxide that preparation method described in the embodiment of the present invention one, two, three is prepared The XRD spectrum of compound；Wherein ZnO-C-600 represents the carbon nanosheet of three-dimensional obtained in embodiment one-zinc oxide composites, ZnO-C-700 represents the carbon nanosheet of three-dimensional obtained in embodiment two-zinc oxide composites, and ZnO-C-800 represents embodiment three Obtained in three-dimensional carbon nanosheet-zinc oxide composites, pure ZnO represents pure zinc oxide material；
Fig. 2 is three-dimensional carbon nanosheet-zinc oxide that preparation method described in the embodiment of the present invention one, two, three is prepared The SEM of compound schemes；Wherein (a1), (a2) are that three-dimensional carbon nanosheet-zinc oxide composites difference obtained in embodiment one is put SEM figure under big multiple, (b1), (b2) are three-dimensional carbon nanosheet obtained in embodiment two-zinc oxide composites difference amplification SEM figure under multiple, (c1), (c2) are three-dimensional carbon nanosheet-zinc oxide composites difference times magnification obtained in embodiment three SEM figure under several, (d1), (d2) are the SEM figure under the different amplification of pure zinc oxide material；
Fig. 3 is the three-dimensional carbon nanosheet-oxidation being prepared with preparation method described in the embodiment of the present invention one, two, three Zinc complexes are the cycle performance figure of the constant current charge-discharge of the lithium ion battery of negative electrode active material, and wherein ZnO-C-600 is represented The carbon nanosheet of three-dimensional obtained in embodiment one-zinc oxide composites, ZnO-C-700 represent three-dimensional carbon obtained in embodiment two Nanometer sheet-zinc oxide composites, ZnO-C-800 represents the carbon nanosheet of three-dimensional obtained in embodiment three-zinc oxide composites, pure ZnO represents pure zinc oxide material；
Fig. 4 is three-dimensional carbon nanosheet-zinc oxide that preparation method described in the embodiment of the present invention one, two, three is prepared The Raman spectrogram of compound；Wherein it is compound to represent the carbon nanosheet of three-dimensional obtained in embodiment one-zinc oxide by ZnO-C-600 Object, ZnO-C-700 represent the carbon nanosheet of three-dimensional obtained in embodiment two-zinc oxide composites, and ZnO-C-800 represents embodiment The carbon nanosheet of three-dimensional obtained in three-zinc oxide composites.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other Embodiment shall fall within the protection scope of the present invention.
In the description of the present invention, it should be noted that term " center ", "upper", "lower", "left", "right", "vertical", The orientation or positional relationship of the instructions such as "horizontal", "inner", "outside" be based on the orientation or positional relationship shown in the drawings, merely to Convenient for description the present invention and simplify description, rather than the device or element of indication or suggestion meaning must have a particular orientation, It is constructed and operated in a specific orientation, therefore is not considered as limiting the invention.
Embodiment one
The preparation method of three-dimensional carbon nanosheet-zinc oxide composites described in the present embodiment is specific as follows:
(1) 1.0g polyvinylpyrrolidone is placed in 200mL beaker, 30mL deionized water is added, stirred 1 hour, obtain To polyvinylpyrrolidone reaction solution.
(2) 2.09g zinc nitrate is placed in the beaker of 50mL, 20mL deionized water is added, stir about 30 minutes, obtains nitre Sour zinc reaction solution.
(3) product of step (1) and step (2) is mixed, adjusting pH with ammonium hydroxide is 10 or so, is stirred to react at room temperature 1 hour, precipitating, freeze-drying obtained polyvinylpyrrolidone and zinc hydroxide mixture.
(4) 1.0g step (3) obtained polyvinylpyrrolidone and zinc hydroxide mixture are placed in tube furnace, 600 DEG C are risen to the heating rate of 8 DEG C/min under argon gas (flow 100mL/min) protection, and is carbonized at a temperature of 600 DEG C 2 hours, it is down to room temperature to double temperature-area tubular furnace temperature, sample is removed, three-dimensional carbon nanosheet-zinc oxide composites can be obtained.
What ZnO-C-600 was indicated in Fig. 1 is the present embodiment system tested by Rigaku Smartlab X-ray diffractometer The XRD spectrum of obtained three-dimensional carbon nanosheet-zinc oxide composites.Its diffraction maximum and standard card as we can see from the figure (JCPDS:36-1451) it matching, this illustrates to generate zinc oxide in the preparation method final product of the present embodiment, and 31.6 °, 34.3 °, 36.1 °, 47.4 °, 56.5 °, 62.7 °, 66.3 °, 67.8 °, 69.0 °, 72.3 °, 76.9 °, 81.2 ° and 89.5 ° of (100) for corresponding respectively to zincite crystal, (002), (101), (102), (110), (103), (200), (112), (201), (004), (202), (104) and (203) face.
(a1) in Fig. 2, (a2) are the obtained three-dimensional carbon nanosheet-zinc oxide composites of the present embodiment in different amplification Under SEM figure；(d1), (d2) is SEM figure of the pure zinc oxide under different amplification.As can be seen that this reality from figure (a1) It applies the material that example is prepared and shows three-dimensional carbon nanosheet structure, and contain the hole of a large amount of tens micron-scales, from Scheme in (a2) as can be seen that the thickness of three-dimensional carbon nanosheet is probably in tens nanometers；It can from figure (d1), (d2) Out, in contrast, pure zinc oxide is in hexagonal structure, and particle is larger and uneven.
By preparation-obtained sample, Super P conductive carbon black, polyvinylidene fluoride mixed grinding according to a certain mass ratio Afterwards, it is made into uniform slurry with N-Methyl pyrrolidone, is uniformly coated on copper foil of affluxion body, cut-parts are as work after drying Electrode with metal lithium sheet is to be used as electrolyte using the ethylene carbonate of 1mol/L LiPF6 and dimethyl carbonate to electrode, poly- Propylene microcellular film (Celgard 2500) is diaphragm, is assembled into button cell in the glove box full of argon gas, is then carried out permanent Flow charge-discharge test.
Fig. 3 be by each material of the new prestige battery test system in Shenzhen test as lithium ion battery anode active material when The cycle performance comparison diagram of constant current charge-discharge, wherein ZnO-C-600 is that the resulting three-dimensional carbon nanosheet-zinc oxide of the present embodiment is multiple Close object；Pure ZnO is pure zinc oxide.When pure zinc oxide is as lithium ion battery anode active material it can be seen from experimental result First charge-discharge coulombic efficiency is 32.7%, is 500mAg in current density-1Under, after 1000 circle circulations, stablize specific volume Amount is 18mAhg-1；And the resulting three-dimensional carbon nanosheet-zinc oxide composites of the present embodiment are as negative electrode of lithium ion battery activity First charge-discharge coulombic efficiency is 62.6% when material, current density 500mAg-1Under, after 1000 circle circulations, stablize Specific capacity is 373.7mAhg-1, significantly improve, show after adding three-dimensional carbon nanosheet than pure zinc oxide, it is compound after oxidation The chemical property of Zinc material significantly improves, and has more high charge-discharge coulombic efficiency and very strong cyclical stability.
Embodiment two
The preparation method of three-dimensional carbon nanosheet-zinc oxide composites described in the present embodiment is specific as follows:
(1) 1.0g polyvinylpyrrolidone is placed in 200mL beaker, 30mL deionized water is added, stirred 1 hour, obtain To polyvinylpyrrolidone reaction solution.
(2) 2.09g zinc nitrate is placed in the beaker of 50mL, 20mL deionized water is added, stir about 30 minutes, obtains nitre Sour zinc reaction solution.
(3) product of step (1) and step (2) is mixed, adjusting pH with ammonium hydroxide is 10 or so, is stirred to react at room temperature 1 hour, precipitating, freeze-drying obtained polyvinylpyrrolidone and zinc hydroxide mixture.
(4) 1.0g step (3) obtained polyvinylpyrrolidone and zinc hydroxide mixture are placed in tube furnace, Rise to 700 DEG C under argon gas (flow 100mL/min) protection with the heating rate of 8 DEG C/min, and 700 DEG C at a temperature of be carbonized 2 hours, it is down to room temperature to double temperature-area tubular furnace temperature, sample is removed, three-dimensional carbon nanosheet-zinc oxide composites can be obtained.
What ZnO-C-700 was indicated in Fig. 1 is the present embodiment system tested by Rigaku Smartlab X-ray diffractometer The XRD spectrum of obtained three-dimensional carbon nanosheet-zinc oxide composites.Its diffraction maximum and standard card as we can see from the figure (JCPDS:36-1451) it matching, this illustrates to generate zinc oxide in the preparation method final product of the present embodiment, and 31.6 °, 34.3 °, 36.1 °, 47.4 °, 56.5 °, 62.7 °, 66.3 °, 67.8 °, 69.0 °, 72.3 °, 76.9 °, 81.2 ° and 89.5 ° of (100) for corresponding respectively to zincite crystal, (002), (101), (102), (110), (103), (200), (112), (201), (004), (202), (104) and (203) face.
(b1) in Fig. 2, (b2) are the obtained three-dimensional carbon nanosheet-zinc oxide composites of the present embodiment in different amplification Under SEM figure；(d1), (d2) is SEM figure of the pure zinc oxide under different amplification.As can be seen that this reality from figure (b1) It applies the material that example is prepared and shows three-dimensional carbon nanosheet structure, and contain the hole of a large amount of tens micron-scales, from Scheme in (b2) as can be seen that the thickness of three-dimensional carbon nanosheet is probably in tens nanometers；It can from figure (d1), (d2) Out, in contrast, pure zinc oxide is in hexagonal structure, and particle is larger and uneven.
By preparation-obtained sample, Super P conductive carbon black, polyvinylidene fluoride mixed grinding according to a certain mass ratio Afterwards, it is made into uniform slurry with N-Methyl pyrrolidone, is uniformly coated on copper foil of affluxion body, cut-parts are as work after drying Electrode with metal lithium sheet is to be used as electrolyte using the ethylene carbonate of 1mol/L LiPF6 and dimethyl carbonate to electrode, poly- Propylene microcellular film (Celgard 2500) is diaphragm, is assembled into button cell in the glove box full of argon gas, is then carried out permanent Flow charge-discharge test.
Fig. 3 be by each material of the new prestige battery test system in Shenzhen test as lithium ion battery anode active material when The cycle performance comparison diagram of constant current charge-discharge, wherein ZnO-C-700 is that the resulting three-dimensional carbon nanosheet-zinc oxide of the present embodiment is multiple Close object；Pure ZnO is pure zinc oxide.When pure zinc oxide is as lithium ion battery anode active material it can be seen from experimental result First charge-discharge coulombic efficiency is 32.7%, is 500mAg in current density-1Under, after 1000 circle circulations, stablize specific volume Amount is 18mAhg-1；And the resulting three-dimensional carbon nanosheet-zinc oxide composites of the present embodiment are as negative electrode of lithium ion battery activity First charge-discharge coulombic efficiency is 53.4% when material, current density 500mAg-1Under, after 1000 circle circulations, stablize Specific capacity is 770mAhg-1, significantly improve, show after adding three-dimensional carbon nanosheet than pure zinc oxide, it is compound after zinc oxide The chemical property of material significantly improves, and has higher charge and discharge coulombic efficiency and very strong cyclical stability.
Embodiment three
The preparation method of three-dimensional carbon nanosheet-zinc oxide composites described in the present embodiment is specific as follows:
(1) 1.0g polyvinylpyrrolidone is placed in 200mL beaker, 30mL deionized water is added, stirred 1 hour, obtain To polyvinylpyrrolidone reaction solution.
(2) 2.09g zinc nitrate is placed in the beaker of 50mL, 20mL deionized water is added, stir about 30 minutes, obtains nitre Sour zinc reaction solution.
(3) product of step (1) and step (2) is mixed, adjusting pH with ammonium hydroxide is 10 or so, is stirred to react at room temperature 1 hour, precipitating, freeze-drying obtained polyvinylpyrrolidone and zinc hydroxide mixture.
(4) 1.0g step (3) obtained polyvinylpyrrolidone and zinc hydroxide mixture are placed in tube furnace, 800 DEG C are risen to the heating rate of 8 DEG C/min under argon gas (flow 100mL/min) protection, and is carbonized at a temperature of 800 DEG C 2 hours, it is down to room temperature to double temperature-area tubular furnace temperature, sample is removed, three-dimensional carbon nanosheet-zinc oxide composites can be obtained.
What ZnO-C-800 was indicated in Fig. 1 is the present embodiment system tested by Rigaku Smartlab X-ray diffractometer The XRD spectrum of obtained three-dimensional carbon nanosheet-zinc oxide composites.Its diffraction maximum and standard card as we can see from the figure (JCPDS:36-1451) it matching, this illustrates to generate zinc oxide in the preparation method final product of the present embodiment, and 31.6 °, 34.3 °, 36.1 °, 47.4 °, 56.5 °, 62.7 °, 66.3 °, 67.8 °, 69.0 °, 72.3 °, 76.9 °, 81.2 ° and 89.5 ° of (100) for corresponding respectively to zincite crystal, (002), (101), (102), (110), (103), (200), (112), (201), (004), (202), (104) and (203) face.
(c1) in Fig. 2, (c2) are the obtained three-dimensional carbon nanosheet-zinc oxide composites of the present embodiment in different amplification Under SEM figure；(d1), (d2) is SEM figure of the pure zinc oxide under different amplification.As can be seen that this reality from figure (c1) It applies the material that example is prepared and shows three-dimensional carbon nanosheet structure, and contain the hole of a large amount of tens micron-scales, from Scheme in (c2) as can be seen that the thickness of three-dimensional carbon nanosheet is probably in tens nanometers；It can from figure (d1), (d2) Out, in contrast, pure zinc oxide is in hexagonal structure, and particle is larger and uneven.
By preparation-obtained sample, Super P conductive carbon black, polyvinylidene fluoride mixed grinding according to a certain mass ratio Afterwards, it is made into uniform slurry with N-Methyl pyrrolidone, is uniformly coated on copper foil of affluxion body, cut-parts are as work after drying Electrode with metal lithium sheet is to be used as electrolyte using the ethylene carbonate of 1mol/L LiPF6 and dimethyl carbonate to electrode, poly- Propylene microcellular film (Celgard 2500) is diaphragm, is assembled into button cell in the glove box full of argon gas, is then carried out permanent Flow charge-discharge test.
Fig. 3 be by each material of the new prestige battery test system in Shenzhen test as lithium ion battery anode active material when The cycle performance comparison diagram of constant current charge-discharge, wherein ZnO-C-800 is that the resulting three-dimensional carbon nanosheet-zinc oxide of the present embodiment is multiple Close object；Pure ZnO is pure zinc oxide.When pure zinc oxide is as lithium ion battery anode active material it can be seen from experimental result First charge-discharge coulombic efficiency is 32.7%, is 500mAg in current density-1Under, after 1000 circle circulations, stablize specific volume Amount is 18mAhg-1；And the resulting three-dimensional carbon nanosheet-zinc oxide composites of the present embodiment are as negative electrode of lithium ion battery activity First charge-discharge coulombic efficiency is 65.1% when material, current density 500mAg-1Under, after 1000 circle circulations, stablize Specific capacity is 302mAhg-1, significantly improve, show after adding three-dimensional carbon nanosheet than pure zinc oxide, it is compound after zinc oxide The chemical property of material significantly improves, and has higher charge and discharge coulombic efficiency and very strong cyclical stability.
Fig. 4 is the three-dimensional that the embodiment one, two, three tested by French Horiba LabRAM HR Raman spectrometer obtains Carbon nanosheet-zinc oxide composites Raman spectrum comparison diagram.From the figure, it can be seen that with the raising of maturing temperature, the peak D with The intensity ratio I at the peak GD/IGValue is first increased and is reduced afterwards, shows the order degree of three-dimensional carbon nanosheet-zinc oxide composites with roasting temperature The raising of degree first reduces to be increased afterwards.
Example IV
The preparation method of three-dimensional carbon nanosheet-zinc oxide composites described in the present embodiment is specific as follows:
(1) 2.8g polyethyleneimine is placed in 200mL beaker, 90mL deionized water is added, stirred 1 hour, gathered Aziridine reaction solution.
(2) 5.8g zinc nitrate is placed in the beaker of 50mL, 30mL deionized water is added, stir about 30 minutes, obtains nitre Sour zinc reaction solution.
(3) product of step (1) and step (2) is mixed, adjusting pH with ammonium hydroxide is 9 or so, is stirred to react 2 at room temperature Hour, precipitating is dried to obtain polyethyleneimine and zinc hydroxide mixture.
(4) 3.0g step (3) obtained polyethyleneimine and zinc hydroxide mixture are placed in tube furnace, in nitrogen 600 DEG C are risen to the heating rate of 5 DEG C/min under (flow 50mL/min) protection, and small in 600 DEG C of at a temperature of charing 3 When, it is down to room temperature to double temperature-area tubular furnace temperature, sample is removed, three-dimensional carbon nanosheet-zinc oxide composites can be obtained.
The carbon nanosheet of three-dimensional made from the present embodiment-zinc oxide composite XRD spectrum, SEM figure and Raman spectrogram It is similar to the embodiment three-dimensional carbon nanosheet-zinc oxide composite of one gained.
By preparation-obtained sample, Super P conductive carbon black, polyvinylidene fluoride mixed grinding according to a certain mass ratio Afterwards, it is made into uniform slurry with N-Methyl pyrrolidone, is uniformly coated on copper foil of affluxion body, cut-parts are as work after drying Electrode with metal lithium sheet is to be used as electrolyte using the ethylene carbonate of 1mol/L LiPF6 and dimethyl carbonate to electrode, poly- Propylene microcellular film (Celgard 2500) is diaphragm, is assembled into button cell in the glove box full of argon gas, is then carried out permanent Flow charge-discharge test.
Using the new prestige battery test system in Shenzhen, to the resulting three-dimensional carbon nanosheet-zinc oxide composite wood of the present embodiment Material is that the constant current charge-discharge cycle performance of the lithium ion battery of negative electrode active material is tested.Experimental result obtains, pure zirconia First charge-discharge coulombic efficiency is 32.7% when zinc is as lithium ion battery anode active material, is 500mA in current density g-1Under, after 1000 circle circulations, stablizing specific capacity is 18mAhg-1；And the resulting three-dimensional carbon nanosheet-oxygen of the present embodiment First charge-discharge coulombic efficiency is 61.5% when changing zinc complexes as lithium ion battery anode active material, and current density is 500mA·g-1Under, after 1000 circle circulations, stablizing specific capacity is 366.8mAhg-1, significantly improved than pure zinc oxide, Show after adding three-dimensional carbon nanosheet, it is compound after the chemical property of zinc oxide material significantly improve, there is higher charge and discharge Electric coulombic efficiency and very strong cyclical stability.
Embodiment five
The preparation method of three-dimensional carbon nanosheet-zinc oxide composites described in the present embodiment is specific as follows:
(1) 2.8g polyethyleneimine is placed in 200mL beaker, 90mL deionized water is added, stirred 1 hour, gathered Aziridine reaction solution.
(2) 5.8g zinc nitrate is placed in the beaker of 50mL, 30mL deionized water is added, stir about 30 minutes, obtains nitre Sour zinc reaction solution.
(3) product of step (1) and step (2) is mixed, adjusting pH with ammonium hydroxide is 9 or so, is stirred to react 1 at room temperature Hour, precipitating is dried to obtain polyethyleneimine and zinc hydroxide mixture.
(4) 3.0g step (3) obtained polyethyleneimine and zinc hydroxide mixture are placed in tube furnace, in nitrogen 700 DEG C are risen to the heating rate of 5 DEG C/min under (flow 50mL/min) protection, and small in 700 DEG C of at a temperature of charing 3 When, it is down to room temperature to double temperature-area tubular furnace temperature, sample is removed, three-dimensional carbon nanosheet-zinc oxide composites can be obtained.
The carbon nanosheet of three-dimensional made from the present embodiment-zinc oxide composite XRD spectrum, SEM figure and Raman spectrogram It is similar to the embodiment three-dimensional carbon nanosheet-zinc oxide composite of two gained.
By preparation-obtained sample, Super P conductive carbon black, polyvinylidene fluoride mixed grinding according to a certain mass ratio Afterwards, it is made into uniform slurry with N-Methyl pyrrolidone, is uniformly coated on copper foil of affluxion body, cut-parts are as work after drying Electrode with metal lithium sheet is to be used as electrolyte using the ethylene carbonate of 1mol/L LiPF6 and dimethyl carbonate to electrode, poly- Propylene microcellular film (Celgard 2500) is diaphragm, is assembled into button cell in the glove box full of argon gas, is then carried out permanent Flow charge-discharge test.
Using the new prestige battery test system in Shenzhen, to the resulting three-dimensional carbon nanosheet-zinc oxide composite wood of the present embodiment Material is that the constant current charge-discharge cycle performance of the lithium ion battery of negative electrode active material is tested.Experimental result obtains, pure zirconia First charge-discharge coulombic efficiency is 32.7% when zinc is as lithium ion battery anode active material, is 500mA in current density g-1Under, after 1000 circle circulations, stablizing specific capacity is 18mAhg-1；And the resulting three-dimensional carbon nanosheet-oxygen of the present embodiment First charge-discharge coulombic efficiency is 51.2% when changing zinc complexes as lithium ion battery anode active material, and current density is 500mA·g-1Under, after 1000 circle circulations, stablizing specific capacity is 756mAhg-1, significantly improved than pure zinc oxide, table After the three-dimensional carbon nanosheet of bright addition, it is compound after the chemical property of zinc oxide material significantly improve, there are higher charge and discharge Coulombic efficiency and very strong cyclical stability.
Embodiment six
The preparation method of three-dimensional carbon nanosheet-zinc oxide composites described in the present embodiment is specific as follows:
(1) 2.8g polyethyleneimine is placed in 200mL beaker, 90mL deionized water is added, stirred 1 hour, gathered Aziridine reaction solution.
(2) 5.8g zinc nitrate is placed in the beaker of 50mL, 30mL deionized water is added, stir about 30 minutes, obtains nitre Sour zinc reaction solution.
(3) product of step (1) and step (2) is mixed, adjusting pH with ammonium hydroxide is 9 or so, is stirred to react 1 at room temperature Hour, precipitating is dried to obtain polyethyleneimine and zinc hydroxide mixture.
(4) 3.0g step (3) obtained polyethyleneimine and zinc hydroxide mixture are placed in tube furnace, in nitrogen 800 DEG C are risen to the heating rate of 5 DEG C/min under (flow 50mL/min) protection, and small in 800 DEG C of at a temperature of charing 3 When, it is down to room temperature to double temperature-area tubular furnace temperature, sample is removed, three-dimensional carbon nanosheet-zinc oxide composites can be obtained.
The carbon nanosheet of three-dimensional made from the present embodiment-zinc oxide composite XRD spectrum, SEM figure and Raman spectrogram It is similar to the embodiment three-dimensional carbon nanosheet-zinc oxide composite of three gained.
By preparation-obtained sample, Super P conductive carbon black, polyvinylidene fluoride mixed grinding according to a certain mass ratio Afterwards, it is made into uniform slurry with N-Methyl pyrrolidone, is uniformly coated on copper foil of affluxion body, cut-parts are as work after drying Electrode with metal lithium sheet is to be used as electrolyte using the ethylene carbonate of 1mol/L LiPF6 and dimethyl carbonate to electrode, poly- Propylene microcellular film (Celgard 2500) is diaphragm, is assembled into button cell in the glove box full of argon gas, is then carried out permanent Flow charge-discharge test.
Using the new prestige battery test system in Shenzhen, to the resulting three-dimensional carbon nanosheet-zinc oxide composite wood of the present embodiment Material is that the constant current charge-discharge cycle performance of the lithium ion battery of negative electrode active material is tested.Experimental result obtains, pure zirconia First charge-discharge coulombic efficiency is 32.7% when zinc is as lithium ion battery anode active material, is 500mA in current density g-1Under, after 1000 circle circulations, stablizing specific capacity is 18mAhg-1；And the resulting three-dimensional carbon nanosheet-oxygen of the present embodiment First charge-discharge coulombic efficiency is 63.3% when changing zinc complexes as lithium ion battery anode active material, and current density is 500mA·g-1Under, after 1000 circle circulations, stablizing specific capacity is 300mAhg-1, significantly improved than pure zinc oxide, table After the three-dimensional carbon nanosheet of bright addition, it is compound after the chemical property of zinc oxide material significantly improve, there are higher charge and discharge Coulombic efficiency and very strong cyclical stability.
Embodiment seven
The preparation method of three-dimensional carbon nanosheet-zinc oxide composites described in the present embodiment is specific as follows:
(1) 1.0g polyvinylpyrrolidone is placed in 200mL beaker, 30mL deionized water is added, stirred 1 hour, obtain To polyvinylpyrrolidone reaction solution.
(2) 2.5g zinc acetate is placed in the beaker of 50mL, 25mL deionized water is added, stir about 30 minutes, obtains vinegar Sour zinc reaction solution.
(3) product of step (1) and step (2) is mixed, adjusting pH with ammonium hydroxide is 11 or so, is stirred to react at room temperature 3 hours, precipitating, freeze-drying obtained polyvinylpyrrolidone and zinc hydroxide mixture.
(4) 1.0g step (3) obtained polyvinylpyrrolidone and zinc hydroxide mixture are placed in tube furnace, 600 DEG C are risen to the heating rate of 20 DEG C/min under argon gas (flow 200mL/min) protection, and in 600 DEG C of at a temperature of carbon Change 4 hours, is down to room temperature to double temperature-area tubular furnace temperature, sample is removed, it is compound that three-dimensional carbon nanosheet-zinc oxide can be obtained Object.
The carbon nanosheet of three-dimensional made from the present embodiment-zinc oxide composite XRD spectrum, SEM figure and Raman spectrogram It is similar to the embodiment three-dimensional carbon nanosheet-zinc oxide composite of one gained.
By preparation-obtained sample, Super P conductive carbon black, polyvinylidene fluoride mixed grinding according to a certain mass ratio Afterwards, it is made into uniform slurry with N-Methyl pyrrolidone, is uniformly coated on copper foil of affluxion body, cut-parts are as work after drying Electrode with metal lithium sheet is to be used as electrolyte using the ethylene carbonate of 1mol/L LiPF6 and dimethyl carbonate to electrode, poly- Propylene microcellular film (Celgard 2500) is diaphragm, is assembled into button cell in the glove box full of argon gas, is then carried out permanent Flow charge-discharge test.
Using the new prestige battery test system in Shenzhen, to the resulting three-dimensional carbon nanosheet-zinc oxide composite wood of the present embodiment Material is that the constant current charge-discharge cycle performance of the lithium ion battery of negative electrode active material is tested.Experimental result obtains, pure zirconia First charge-discharge coulombic efficiency is 32.7% when zinc is as lithium ion battery anode active material, is 500mA in current density g-1Under, after 1000 circle circulations, stablizing specific capacity is 18mAhg-1；And the resulting three-dimensional carbon nanosheet-oxygen of the present embodiment First charge-discharge coulombic efficiency is 61.5% when changing zinc complexes as lithium ion battery anode active material, and current density is 500mA·g-1Under, after 1000 circle circulations, stablizing specific capacity is 365.2mAhg-1, significantly improved than pure zinc oxide, Show after adding three-dimensional carbon nanosheet, it is compound after the chemical property of zinc oxide material significantly improve, there is higher charge and discharge Electric coulombic efficiency and very strong cyclical stability.
Embodiment eight
The preparation method of three-dimensional carbon nanosheet-zinc oxide composites described in the present embodiment is specific as follows:
(1) 1.0g polyvinylpyrrolidone is placed in 200mL beaker, 30mL deionized water is added, stirred 1 hour, obtain To polyvinylpyrrolidone reaction solution.
(2) 2.5g zinc acetate is placed in the beaker of 50mL, 25mL deionized water is added, stir about 30 minutes, obtains vinegar Sour zinc reaction solution.
(3) product of step (1) and step (2) is mixed, adjusting pH with ammonium hydroxide is 11 or so, is stirred to react at room temperature 3 hours, precipitating, freeze-drying obtained polyvinylpyrrolidone and zinc hydroxide mixture.
(4) 1.0g step (3) obtained polyvinylpyrrolidone and zinc hydroxide mixture are placed in tube furnace, 700 DEG C are risen to the heating rate of 20 DEG C/min under argon gas (flow 200mL/min) protection, and in 700 DEG C of at a temperature of carbon Change 4 hours, is down to room temperature to double temperature-area tubular furnace temperature, sample is removed, it is compound that three-dimensional carbon nanosheet-zinc oxide can be obtained Object.
The carbon nanosheet of three-dimensional made from the present embodiment-zinc oxide composite XRD spectrum, SEM figure and Raman spectrogram It is similar to the embodiment three-dimensional carbon nanosheet-zinc oxide composite of two gained.
By preparation-obtained sample, Super P conductive carbon black, polyvinylidene fluoride mixed grinding according to a certain mass ratio Afterwards, it is made into uniform slurry with N-Methyl pyrrolidone, is uniformly coated on copper foil of affluxion body, cut-parts are as work after drying Electrode with metal lithium sheet is to be used as electrolyte using the ethylene carbonate of 1mol/L LiPF6 and dimethyl carbonate to electrode, poly- Propylene microcellular film (Celgard 2500) is diaphragm, is assembled into button cell in the glove box full of argon gas, is then carried out permanent Flow charge-discharge test.
Using the new prestige battery test system in Shenzhen, to the resulting three-dimensional carbon nanosheet-zinc oxide composite wood of the present embodiment Material is that the constant current charge-discharge cycle performance of the lithium ion battery of negative electrode active material is tested.Experimental result obtains, pure zirconia First charge-discharge coulombic efficiency is 32.7% when zinc is as lithium ion battery anode active material, is 500mA in current density g-1Under, after 1000 circle circulations, stablizing specific capacity is 18mAhg-1；And the resulting three-dimensional carbon nanosheet-oxygen of the present embodiment First charge-discharge coulombic efficiency is 52.8% when changing zinc complexes as lithium ion battery anode active material, and current density is 500mA·g-1Under, after 1000 circle circulations, stablizing specific capacity is 756mAhg-1, significantly improved than pure zinc oxide, table After the three-dimensional carbon nanosheet of bright addition, it is compound after the chemical property of zinc oxide material significantly improve, there are higher charge and discharge Coulombic efficiency and very strong cyclical stability.
Embodiment nine
The preparation method of three-dimensional carbon nanosheet-zinc oxide composites described in the present embodiment is specific as follows:
(1) 1.0g polyvinylpyrrolidone is placed in 200mL beaker, 30mL deionized water is added, stirred 1 hour, obtain To polyvinylpyrrolidone reaction solution.
(2) 2.5g zinc acetate is placed in the beaker of 50mL, 25mL deionized water is added, stir about 30 minutes, obtains vinegar Sour zinc reaction solution.
(3) product of step (1) and step (2) is mixed, adjusting pH with ammonium hydroxide is 11 or so, is stirred to react at room temperature 3 hours, precipitating, freeze-drying obtained polyvinylpyrrolidone and zinc hydroxide mixture.
(4) 1.0g step (3) obtained polyvinylpyrrolidone and zinc hydroxide mixture are placed in tube furnace, 800 DEG C are risen to the heating rate of 20 DEG C/min under argon gas (flow 200mL/min) protection, and in 800 DEG C of at a temperature of carbon Change 4 hours, is down to room temperature to double temperature-area tubular furnace temperature, sample is removed, it is compound that three-dimensional carbon nanosheet-zinc oxide can be obtained Object.
The carbon nanosheet of three-dimensional made from the present embodiment-zinc oxide composite XRD spectrum, SEM figure and Raman spectrogram It is similar to the embodiment three-dimensional carbon nanosheet-zinc oxide composite of three gained.
By preparation-obtained sample, Super P conductive carbon black, polyvinylidene fluoride mixed grinding according to a certain mass ratio Afterwards, it is made into uniform slurry with N-Methyl pyrrolidone, is uniformly coated on copper foil of affluxion body, cut-parts are as work after drying Electrode with metal lithium sheet is to be used as electrolyte using the ethylene carbonate of 1mol/L LiPF6 and dimethyl carbonate to electrode, poly- Propylene microcellular film (Celgard 2500) is diaphragm, is assembled into button cell in the glove box full of argon gas, is then carried out permanent Flow charge-discharge test.
Using the new prestige battery test system in Shenzhen, to the resulting three-dimensional carbon nanosheet-zinc oxide composite wood of the present embodiment Material is that the constant current charge-discharge cycle performance of the lithium ion battery of negative electrode active material is tested.Experimental result obtains, pure zirconia First charge-discharge coulombic efficiency is 32.7% when zinc is as lithium ion battery anode active material, is 500mA in current density g-1Under, after 1000 circle circulations, stablizing specific capacity is 18mAhg-1；And the resulting three-dimensional carbon nanosheet-oxygen of the present embodiment First charge-discharge coulombic efficiency is 66.2% when changing zinc complexes as lithium ion battery anode active material, and current density is 500mA·g-1Under, after 1000 circle circulations, stablizing specific capacity is 315mAhg-1, significantly improved than pure zinc oxide, table After the three-dimensional carbon nanosheet of bright addition, it is compound after the chemical property of zinc oxide material significantly improve, there are higher charge and discharge Coulombic efficiency and very strong cyclical stability.
Embodiment ten
The preparation method of three-dimensional carbon nanosheet-zinc oxide composites described in the present embodiment is specific as follows:
(1) 2.9g polyethyleneimine is placed in 200mL beaker, 90mL deionized water is added, stirred 1 hour, gathered Vinylpyrrolidone reaction solution.
(2) 6.0g zinc stearate is placed in the beaker of 50mL, 60mL deionized water is added, stir about 30 minutes, obtains Zinc stearate reaction solution.
(3) product of step (1) and step (2) is mixed, adjusting pH with ammonium hydroxide is 8 or so, is stirred to react 1 at room temperature Hour, precipitating is dried to obtain polyethyleneimine and zinc hydroxide mixture.
(4) 2.5g step (3) obtained polyethyleneimine and zinc hydroxide mixture are placed in tube furnace, in argon gas 600 DEG C are risen to the heating rate of 10 DEG C/min under (flow 100mL/min) protection, it is small in 600 DEG C of at a temperature of carbonization 2 When, it is down to room temperature to double temperature-area tubular furnace temperature, sample is removed, three-dimensional carbon nanosheet-zinc oxide composites can be obtained.
The carbon nanosheet of three-dimensional made from the present embodiment-zinc oxide composite XRD spectrum, SEM figure and Raman spectrogram It is similar to the embodiment three-dimensional carbon nanosheet-zinc oxide composite of one gained.
By preparation-obtained sample, Super P conductive carbon black, polyvinylidene fluoride mixed grinding according to a certain mass ratio Afterwards, it is made into uniform slurry with N-Methyl pyrrolidone, is uniformly coated on copper foil of affluxion body, cut-parts are as work after drying Electrode with metal lithium sheet is to be used as electrolyte using the ethylene carbonate of 1mol/L LiPF6 and dimethyl carbonate to electrode, poly- Propylene microcellular film (Celgard 2500) is diaphragm, is assembled into button cell in the glove box full of argon gas, is then carried out permanent Flow charge-discharge test.
Using the new prestige battery test system in Shenzhen, to the resulting three-dimensional carbon nanosheet-zinc oxide composite wood of the present embodiment Material is that the constant current charge-discharge cycle performance of the lithium ion battery of negative electrode active material is tested.Experimental result obtains, pure zirconia First charge-discharge coulombic efficiency is 32.7% when zinc is as lithium ion battery anode active material, is 500mA in current density g-1Under, after 1000 circle circulations, stablizing specific capacity is 18mAhg-1；And the resulting three-dimensional carbon nanosheet-oxygen of the present embodiment First charge-discharge coulombic efficiency is 61.5% when changing zinc complexes as lithium ion battery anode active material, and current density is 500mA·g-1Under, after 1000 circle circulations, stablizing specific capacity is 364.7mAhg-1, significantly improved than pure zinc oxide, Show after adding three-dimensional carbon nanosheet, it is compound after the chemical property of zinc oxide material significantly improve, there is higher charge and discharge Electric coulombic efficiency and very strong cyclical stability.
Embodiment 11
The preparation method of three-dimensional carbon nanosheet-zinc oxide composites described in the present embodiment is specific as follows:
(1) 2.9g polyethyleneimine is placed in 200mL beaker, 90mL deionized water is added, stirred 1 hour, gathered Vinylpyrrolidone reaction solution.
(2) 6.0g zinc stearate is placed in the beaker of 50mL, 60mL deionized water is added, stir about 30 minutes, obtains Zinc stearate reaction solution.
(3) product of step (1) and step (2) is mixed, adjusting pH with ammonium hydroxide is 8 or so, is stirred to react 1 at room temperature Hour, precipitating is dried to obtain polyethyleneimine and zinc hydroxide mixture
(4) 2.5g step (3) obtained polyethyleneimine and zinc hydroxide mixture are placed in tube furnace, in argon gas 700 DEG C are risen to the heating rate of 10 DEG C/min under (flow 100mL/min) protection, it is small in 700 DEG C of at a temperature of carbonization 2 When, it is down to room temperature to double temperature-area tubular furnace temperature, sample is removed, three-dimensional carbon nanosheet-zinc oxide composites can be obtained.
The carbon nanosheet of three-dimensional made from the present embodiment-zinc oxide composite XRD spectrum, SEM figure and Raman spectrogram It is similar to the embodiment three-dimensional carbon nanosheet-zinc oxide composite of two gained.
By preparation-obtained sample, Super P conductive carbon black, polyvinylidene fluoride mixed grinding according to a certain mass ratio Afterwards, it is made into uniform slurry with N-Methyl pyrrolidone, is uniformly coated on copper foil of affluxion body, cut-parts are as work after drying Electrode with metal lithium sheet is to be used as electrolyte using the ethylene carbonate of 1mol/L LiPF6 and dimethyl carbonate to electrode, poly- Propylene microcellular film (Celgard 2500) is diaphragm, is assembled into button cell in the glove box full of argon gas, is then carried out permanent Flow charge-discharge test.
Using the new prestige battery test system in Shenzhen, to the resulting three-dimensional carbon nanosheet-zinc oxide composite wood of the present embodiment Material is that the constant current charge-discharge cycle performance of the lithium ion battery of negative electrode active material is tested.Experimental result obtains, pure zirconia First charge-discharge coulombic efficiency is 32.7% when zinc is as lithium ion battery anode active material, is 500mA in current density g-1Under, after 1000 circle circulations, stablizing specific capacity is 18mAhg-1；And the resulting three-dimensional carbon nanosheet-oxygen of the present embodiment First charge-discharge coulombic efficiency is 54.1% when changing zinc complexes as lithium ion battery anode active material, and current density is 500mA·g-1Under, after 1000 circle circulations, stablizing specific capacity is 775mAhg-1, significantly improved than pure zinc oxide, table After the three-dimensional carbon nanosheet of bright addition, it is compound after the chemical property of zinc oxide material significantly improve, there are higher charge and discharge Coulombic efficiency and very strong cyclical stability.
Embodiment 12
The preparation method of three-dimensional carbon nanosheet-zinc oxide composites described in the present embodiment is specific as follows:
(1) 2.9g polyethyleneimine is placed in 200mL beaker, 90mL deionized water is added, stirred 1 hour, gathered Vinylpyrrolidone reaction solution.
(2) 6.0g zinc stearate is placed in the beaker of 50mL, 60mL deionized water is added, stir about 30 minutes, obtains Zinc stearate reaction solution.
(3) product of step (1) and step (2) is mixed, adjusting pH with ammonium hydroxide is 8 or so, is stirred to react 1 at room temperature Hour, precipitating is dried to obtain polyethyleneimine and zinc hydroxide mixture
(4) 2.5g step (3) obtained polyethyleneimine and zinc hydroxide mixture are placed in tube furnace, in argon gas 800 DEG C are risen to the heating rate of 10 DEG C/min under (flow 100mL/min) protection, it is small in 800 DEG C of at a temperature of carbonization 2 When, it is down to room temperature to double temperature-area tubular furnace temperature, sample is removed, three-dimensional carbon nanosheet-zinc oxide composites can be obtained.
The carbon nanosheet of three-dimensional made from the present embodiment-zinc oxide composite XRD spectrum, SEM figure and Raman spectrogram It is similar to the embodiment three-dimensional carbon nanosheet-zinc oxide composite of three gained.
By preparation-obtained sample, Super P conductive carbon black, polyvinylidene fluoride mixed grinding according to a certain mass ratio Afterwards, it is made into uniform slurry with N-Methyl pyrrolidone, is uniformly coated on copper foil of affluxion body, cut-parts are as work after drying Electrode with metal lithium sheet is to be used as electrolyte using the ethylene carbonate of 1mol/L LiPF6 and dimethyl carbonate to electrode, poly- Propylene microcellular film (Celgard 2500) is diaphragm, is assembled into button cell in the glove box full of argon gas, is then carried out permanent Flow charge-discharge test.
Using the new prestige battery test system in Shenzhen, to the resulting three-dimensional carbon nanosheet-zinc oxide composite wood of the present embodiment Material is that the constant current charge-discharge cycle performance of the lithium ion battery of negative electrode active material is tested.Experimental result obtains, pure zirconia First charge-discharge coulombic efficiency is 32.7% when zinc is as lithium ion battery anode active material, is 500mA in current density g-1Under, after 1000 circle circulations, stablizing specific capacity is 18mAhg-1；And the resulting three-dimensional carbon nanosheet-oxygen of the present embodiment First charge-discharge coulombic efficiency is 63.7% when changing zinc complexes as lithium ion battery anode active material, and current density is 500mA·g-1Under, after 1000 circle circulations, stablizing specific capacity is 298mAhg-1, significantly improved than pure zinc oxide, table After the three-dimensional carbon nanosheet of bright addition, it is compound after the chemical property of zinc oxide material significantly improve, there are higher charge and discharge Coulombic efficiency and very strong cyclical stability.
Embodiment 13
The preparation method of three-dimensional carbon nanosheet-zinc oxide composites described in the present embodiment is specific as follows:
(1) 1.8g polyvinyl alcohol is placed in 200mL beaker, 60mL deionized water is added, stirred 1 hour, obtain poly- second Enol reaction solution.
(2) 3.7g zinc stearate is placed in the beaker of 50mL, 40mL deionized water is added, stir about 30 minutes, obtains Zinc stearate reaction solution.
(3) product of step (1) and step (2) is mixed, adjusting pH with ammonium hydroxide is 12 or so, is stirred to react at room temperature 1 hour, precipitating was dried to obtain polyvinyl alcohol and zinc hydroxide mixture
(4) 1.8g step (3) obtained polyvinyl alcohol and zinc hydroxide mixture are placed in tube furnace, in argon gas With the heating rate of 20 DEG C/min rise to 600 DEG C under (flow 50mL/min) protection, 600 DEG C at a temperature of be carbonized 2 hours, It is down to room temperature to double temperature-area tubular furnace temperature, sample is removed, three-dimensional carbon nanosheet-zinc oxide composites can be obtained.
The carbon nanosheet of three-dimensional made from the present embodiment-zinc oxide composite XRD spectrum, SEM figure and Raman spectrogram It is similar to the embodiment three-dimensional carbon nanosheet-zinc oxide composite of one gained.
By preparation-obtained sample, Super P conductive carbon black, polyvinylidene fluoride mixed grinding according to a certain mass ratio Afterwards, it is made into uniform slurry with N-Methyl pyrrolidone, is uniformly coated on copper foil of affluxion body, cut-parts are as work after drying Electrode with metal lithium sheet is to be used as electrolyte using the ethylene carbonate of 1mol/L LiPF6 and dimethyl carbonate to electrode, poly- Propylene microcellular film (Celgard 2500) is diaphragm, is assembled into button cell in the glove box full of argon gas, is then carried out permanent Flow charge-discharge test.
Using the new prestige battery test system in Shenzhen, to the resulting three-dimensional carbon nanosheet-zinc oxide composite wood of the present embodiment Material is that the constant current charge-discharge cycle performance of the lithium ion battery of negative electrode active material is tested.Experimental result obtains, pure zirconia First charge-discharge coulombic efficiency is 32.7% when zinc is as lithium ion battery anode active material, is 500mA in current density g-1Under, after 1000 circle circulations, stablizing specific capacity is 18mAhg-1；And the resulting three-dimensional carbon nanosheet-oxygen of the present embodiment First charge-discharge coulombic efficiency is 62.3% when changing zinc complexes as lithium ion battery anode active material, and current density is 500mA·g-1Under, after 1000 circle circulations, stablizing specific capacity is 378.3mAhg-1, significantly improved than pure zinc oxide, Show after adding three-dimensional carbon nanosheet, it is compound after the chemical property of zinc oxide material significantly improve, there is higher charge and discharge Electric coulombic efficiency and very strong cyclical stability.
Embodiment 14
The preparation method of three-dimensional carbon nanosheet-zinc oxide composites described in the present embodiment is specific as follows:
(1) 1.8g polyvinyl alcohol is placed in 200mL beaker, 60mL deionized water is added, stirred 1 hour, obtain poly- second Enol reaction solution.
(2) 3.7g zinc stearate is placed in the beaker of 50mL, 40mL deionized water is added, stir about 30 minutes, obtains Zinc stearate reaction solution.
(3) product of step (1) and step (2) is mixed, adjusting pH with ammonium hydroxide is 12 or so, is stirred to react at room temperature 1 hour, precipitating was dried to obtain polyvinyl alcohol and zinc hydroxide mixture
(4) 1.8g step (3) obtained polyvinyl alcohol and zinc hydroxide mixture are placed in tube furnace, in argon gas With the heating rate of 20 DEG C/min rise to 700 DEG C under (flow 50mL/min) protection, 700 DEG C at a temperature of be carbonized 2 hours, It is down to room temperature to double temperature-area tubular furnace temperature, sample is removed, three-dimensional carbon nanosheet-zinc oxide composites can be obtained.
The carbon nanosheet of three-dimensional made from the present embodiment-zinc oxide composite XRD spectrum, SEM figure and Raman spectrogram It is similar to the embodiment three-dimensional carbon nanosheet-zinc oxide composite of two gained.
By preparation-obtained sample, Super P conductive carbon black, polyvinylidene fluoride mixed grinding according to a certain mass ratio Afterwards, it is made into uniform slurry with N-Methyl pyrrolidone, is uniformly coated on copper foil of affluxion body, cut-parts are as work after drying Electrode with metal lithium sheet is to be used as electrolyte using the ethylene carbonate of 1mol/L LiPF6 and dimethyl carbonate to electrode, poly- Propylene microcellular film (Celgard 2500) is diaphragm, is assembled into button cell in the glove box full of argon gas, is then carried out permanent Flow charge-discharge test.
Using the new prestige battery test system in Shenzhen, to the resulting three-dimensional carbon nanosheet-zinc oxide composite wood of the present embodiment Material is that the constant current charge-discharge cycle performance of the lithium ion battery of negative electrode active material is tested.Experimental result obtains, pure zirconia First charge-discharge coulombic efficiency is 32.7% when zinc is as lithium ion battery anode active material, is 500mA in current density g-1Under, after 1000 circle circulations, stablizing specific capacity is 18mAhg-1；And the resulting three-dimensional carbon nanosheet-oxygen of the present embodiment First charge-discharge coulombic efficiency is 51.6% when changing zinc complexes as lithium ion battery anode active material, and current density is 500mA·g-1Under, after 1000 circle circulations, stablizing specific capacity is 757mAhg-1, significantly improved than pure zinc oxide, table After the three-dimensional carbon nanosheet of bright addition, it is compound after the chemical property of zinc oxide material significantly improve, there are higher charge and discharge Coulombic efficiency and very strong cyclical stability.
Embodiment 15
The preparation method of three-dimensional carbon nanosheet-zinc oxide composites described in the present embodiment is specific as follows:
(1) 1.8g polyvinyl alcohol is placed in 200mL beaker, 60mL deionized water is added, stirred 1 hour, obtain poly- second Enol reaction solution.
(2) 3.7g zinc stearate is placed in the beaker of 50mL, 40mL deionized water is added, stir about 30 minutes, obtains Zinc stearate reaction solution.
(3) product of step (1) and step (2) is mixed, adjusting pH with ammonium hydroxide is 12 or so, is stirred to react at room temperature 1 hour, precipitating was dried to obtain polyvinyl alcohol and zinc hydroxide mixture
(4) 1.8g step (3) obtained polyvinyl alcohol and zinc hydroxide mixture are placed in tube furnace, in argon gas With the heating rate of 20 DEG C/min rise to 800 DEG C under (flow 50mL/min) protection, 800 DEG C at a temperature of be carbonized 2 hours, It is down to room temperature to double temperature-area tubular furnace temperature, sample is removed, three-dimensional carbon nanosheet-zinc oxide composites can be obtained.
The carbon nanosheet of three-dimensional made from the present embodiment-zinc oxide composite XRD spectrum, SEM figure and Raman spectrogram It is similar to the embodiment three-dimensional carbon nanosheet-zinc oxide composite of three gained.
By preparation-obtained sample, Super P conductive carbon black, polyvinylidene fluoride mixed grinding according to a certain mass ratio Afterwards, it is made into uniform slurry with N-Methyl pyrrolidone, is uniformly coated on copper foil of affluxion body, cut-parts are as work after drying Electrode with metal lithium sheet is to be used as electrolyte using the ethylene carbonate of 1mol/L LiPF6 and dimethyl carbonate to electrode, poly- Propylene microcellular film (Celgard 2500) is diaphragm, is assembled into button cell in the glove box full of argon gas, is then carried out permanent Flow charge-discharge test.
Using the new prestige battery test system in Shenzhen, to the resulting three-dimensional carbon nanosheet-zinc oxide composite wood of the present embodiment Material is that the constant current charge-discharge cycle performance of the lithium ion battery of negative electrode active material is tested.Experimental result obtains, pure zirconia First charge-discharge coulombic efficiency is 32.7% when zinc is as lithium ion battery anode active material, is 500mA in current density g-1Under, after 1000 circle circulations, stablizing specific capacity is 18mAhg-1；And the resulting three-dimensional carbon nanosheet-oxygen of the present embodiment First charge-discharge coulombic efficiency is 67.0% when changing zinc complexes as lithium ion battery anode active material, and current density is 500mA·g-1Under, after 1000 circle circulations, stablizing specific capacity is 313mAhg-1, significantly improved than pure zinc oxide, table After the three-dimensional carbon nanosheet of bright addition, it is compound after the chemical property of zinc oxide material significantly improve, there are higher charge and discharge Coulombic efficiency and very strong cyclical stability.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or It changes still within the protection scope of the invention.

Claims (10)

1. a kind of preparation method of three-dimensional carbon nanosheet-zinc oxide composites, which comprises the following steps:
The first step will mix in high polymer and zinc source addition solvent, obtain reaction solution；
The pH value for the reaction solution that the first step obtains is adjusted to 8-12, and stirred by second step, is precipitated；
Third step, the precipitating for obtaining second step are dried, then are placed at 200-1200 DEG C and heat carbonization, obtain described Three-dimensional carbon nanosheet-zinc oxide composites.
2. the preparation method of three-dimensional carbon nanosheet-zinc oxide composites according to claim 1, it is characterised in that: described High polymer is one of polyvinyl alcohol, polyethyleneimine, polyvinyl butyral, polyvinylpyrrolidone, polyethylene glycol oxide Or it is several.
3. the preparation method of three-dimensional carbon nanosheet-zinc oxide composites according to claim 1, it is characterised in that: described Zinc source is one or more of zinc acetate, zinc nitrate, zinc sulfate, zinc citrate, zinc stearate.
4. the preparation method of three-dimensional carbon nanosheet-zinc oxide composites according to claim 1, it is characterised in that: described High polymer and the mass ratio in the zinc source are (1~50): (0.1~20).
5. the preparation method of three-dimensional carbon nanosheet-zinc oxide composites according to claim 1, which is characterized in that described The first step specifically includes:
S1, the high polymer is dissolved in solvent, and stirred, obtain polymer reaction liquid；
S2, the zinc source is dissolved in solvent, and stirred, obtain zinc source reaction solution；
S3, polymer reaction liquid obtained by step S1 is mixed with zinc source reaction solution obtained by step S2, obtains the reaction solution.
6. the preparation method of three-dimensional carbon nanosheet-zinc oxide composites according to claim 5, it is characterised in that: step The concentration of polymer reaction liquid described in S1 is 10-100g/L, and the concentration in zinc source reaction solution described in step S2 is 60-300g/ L。
7. the preparation method of three-dimensional carbon nanosheet-zinc oxide composites according to claim 1, it is characterised in that: described The heating temperature that the precipitating heating is carbonized in third step is 500-1000 DEG C, heating time 1-6h.
8. the preparation method of three-dimensional carbon nanosheet-zinc oxide composites according to claim 1, it is characterised in that: described Inert protective gas is also passed through to precipitating heating carbonization in third step, the inert protective gas is argon gas, nitrogen, helium One of or it is a variety of.
9. the three-dimensional that the preparation method of any three-dimensional carbon nanosheet-zinc oxide composites of claim 1-8 is prepared Carbon nanosheet-zinc oxide composites.
10. three-dimensional carbon nanosheet-zinc oxide composites answering as lithium ion battery anode active material as claimed in claim 9 With.
CN201910173322.9A 2019-03-07 2019-03-07 A kind of three-dimensional carbon nanosheet-zinc oxide composites and the preparation method and application thereof Pending CN109962224A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110534728A (en) * 2019-08-07 2019-12-03 华南师范大学 A kind of self-assembly zinc oxide/trbasic zinc phosphate/carbon composite, electrode and preparation method thereof
CN112864365A (en) * 2021-04-20 2021-05-28 杭州芳闻新型材料有限公司 Nitrogen-sulfur co-doped porous carbon loaded zinc oxide negative electrode material and preparation method thereof
CN113782731A (en) * 2021-08-20 2021-12-10 中南大学 Cathode material for water-based zinc secondary battery and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20150063265A (en) * 2013-11-29 2015-06-09 한국과학기술연구원 ZnO-MnO-C COMPOSITE, MANUFACTURING METHOD OF COMPOSITE CONTAINING ZINC OXIDE AND MANGANESE OXIDE AND ANODE ACTIVE MATERIAL CONTAINING THE SAME
CN107464923A (en) * 2017-07-19 2017-12-12 成都理工大学 A kind of compound high-capacity lithium ion cell material of nano zine oxide/porous carbon in situ and preparation method thereof
CN108598414A (en) * 2018-04-23 2018-09-28 复旦大学 Amorphous zinc oxide/carbon composition lithium ion battery cathode material and preparation method thereof
CN108987720A (en) * 2018-08-01 2018-12-11 吉林大学 Carbon/zinc oxide composite and its preparation method and application
CN109065854A (en) * 2018-07-09 2018-12-21 华南师范大学 A kind of preparation method of nano-carbon coated zinc oxide composite and the preparation method of electrode
CN109309219A (en) * 2018-09-12 2019-02-05 肇庆市华师大光电产业研究院 A kind of zinc oxide/carbon composite preparation method for negative electrode of lithium ion battery

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20150063265A (en) * 2013-11-29 2015-06-09 한국과학기술연구원 ZnO-MnO-C COMPOSITE, MANUFACTURING METHOD OF COMPOSITE CONTAINING ZINC OXIDE AND MANGANESE OXIDE AND ANODE ACTIVE MATERIAL CONTAINING THE SAME
CN107464923A (en) * 2017-07-19 2017-12-12 成都理工大学 A kind of compound high-capacity lithium ion cell material of nano zine oxide/porous carbon in situ and preparation method thereof
CN108598414A (en) * 2018-04-23 2018-09-28 复旦大学 Amorphous zinc oxide/carbon composition lithium ion battery cathode material and preparation method thereof
CN109065854A (en) * 2018-07-09 2018-12-21 华南师范大学 A kind of preparation method of nano-carbon coated zinc oxide composite and the preparation method of electrode
CN108987720A (en) * 2018-08-01 2018-12-11 吉林大学 Carbon/zinc oxide composite and its preparation method and application
CN109309219A (en) * 2018-09-12 2019-02-05 肇庆市华师大光电产业研究院 A kind of zinc oxide/carbon composite preparation method for negative electrode of lithium ion battery

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PENG LI ET AL.: "Facile synthesis of ZnO/mesoporous carbon nanocomposites as high-performance anode for lithium-ion battery", 《CHEMICAL ENGINEERING JOURNAL》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110534728A (en) * 2019-08-07 2019-12-03 华南师范大学 A kind of self-assembly zinc oxide/trbasic zinc phosphate/carbon composite, electrode and preparation method thereof
CN112864365A (en) * 2021-04-20 2021-05-28 杭州芳闻新型材料有限公司 Nitrogen-sulfur co-doped porous carbon loaded zinc oxide negative electrode material and preparation method thereof
CN113782731A (en) * 2021-08-20 2021-12-10 中南大学 Cathode material for water-based zinc secondary battery and preparation method thereof
CN113782731B (en) * 2021-08-20 2022-11-22 中南大学 Cathode material for water-based zinc secondary battery and preparation method thereof

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Application publication date: 20190702