CN112436111A - Preparation method and application of graphene modified nickel oxide nanocomposite - Google Patents

Preparation method and application of graphene modified nickel oxide nanocomposite Download PDF

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CN112436111A
CN112436111A CN202011155919.XA CN202011155919A CN112436111A CN 112436111 A CN112436111 A CN 112436111A CN 202011155919 A CN202011155919 A CN 202011155919A CN 112436111 A CN112436111 A CN 112436111A
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nickel oxide
graphene
modified nickel
preparing
oxide nanocomposite
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姚玉洋
高丽
赵小娃
王光志
李海波
黄志强
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Binzhou Double Peaks Graphite Sealing Material Co ltd
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Binzhou Double Peaks Graphite Sealing Material Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/366—Composites as layered products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • 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
    • H01M4/58—Selection 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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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 invention provides a preparation method and application of a graphene modified nickel oxide nano composite material, which comprises the following steps: (1) preparing graphene oxide; (2) preparing black nickel oxide powder; (3) respectively preparing a graphene oxide solution and a nickel oxide nanoparticle dispersion liquid with the same concentration, stirring and mixing the graphene oxide solution and the nickel oxide nanoparticle dispersion liquid with the same volume, and performing ultrasonic treatment; (4) after the mixture in the step (3) is subjected to cold quenching treatment, spreading a sample subjected to cold quenching treatment in a culture dish, and dehydrating and drying the sample by freeze drying; and after removing the residual PVC fragments of the sample, reducing in a tubular furnace to obtain the graphene modified nickel oxide nanocomposite. According to the technical scheme, the prepared graphene modified nickel oxide nanocomposite has good electrochemical performance, has good reproducibility and reversibility in the oxidation-reduction reaction process, and the lithium ion battery prepared by using the graphene modified nickel oxide nanocomposite has good cycle stability.

Description

Preparation method and application of graphene modified nickel oxide nanocomposite
Technical Field
The invention relates to the technical field of nano composite material preparation, in particular to a preparation method and application of a graphene modified nickel oxide nano composite material.
Background
A battery is a chemical and electrical energy storage and conversion device that generally consists essentially of three parts, a positive (also called cathodic) electrolyte and a negative (also called anodic) electrode. The reactants of the battery reaction are a positive electrode and a negative electrode, and the electrolyte serves as a medium and provides a channel for the movement of positive and negative ions. During charging, lithium ions leave from the crystal lattice of the anode, pass through the electrolyte and the diaphragm, obtain an electron, are reduced into Li, and then reach the cathode graphite in a layered structure; during discharge, lithium in the negative electrode graphite loses one electron and becomes Li +, and the lithium moves to the positive electrode and enters the positive electrode material to be in an intercalation state. The charge-discharge process is a reversible process, namely, lithium ions continuously move between the positive electrode and the negative electrode to form a cyclic process. In the process, the performance is related to the structural stability of the positive and negative electrode materials in the embedding and stripping processes, and the better the stability is, the better the performance of the battery is. In the process of charging and discharging, the deposition and dissolution process of metal lithium is avoided, so that lithium dendrite is avoided, and the service life of the battery can be prolonged. Therefore, the improvement of the stability and other electrochemical properties of the electrode material in the lithium ion battery is of great importance to the research and development of future lithium battery materials.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art or the related art.
Therefore, the invention aims to provide a preparation method and application of a graphene modified nickel oxide nanocomposite, which can improve the electrochemical stability of the graphene modified nickel oxide nanocomposite, and can be applied to a lithium ion battery as a negative electrode, so that the lithium ion battery has a better cycle life.
In order to achieve the above object, the technical scheme of the present invention provides a preparation method of a graphene modified nickel oxide nanocomposite, comprising the following steps:
(1) in KMnO4、H2SO4As an oxidant, graphene oxide is prepared by weak ultrasonic dispersion and centrifuge centrifugation through a modified chemical stripping method;
(2) putting a mixture of nickel nitrate hexahydrate, hexamethylenetetramine and trisodium citrate into a polytetrafluoroethylene-lined stainless steel autoclave for reaction, and then carrying out heat treatment on the obtained powder in a muffle furnace to obtain nickel oxide black powder;
(3) respectively preparing a graphene oxide solution and a nickel oxide nanoparticle dispersion liquid with the same concentration, stirring and mixing the graphene oxide solution and the nickel oxide nanoparticle dispersion liquid with the same volume, and performing ultrasonic treatment;
(4) after the mixture obtained in the step (3) is subjected to mixed ultrasonic treatment and is subjected to cold quenching treatment, spreading a sample subjected to cold quenching treatment in a culture dish, and dehydrating and drying the sample by freeze drying; and after removing the residual PVC fragments of the sample, reducing in a tubular furnace to obtain the graphene modified nickel oxide nanocomposite.
Preferably, in the step (3), the method further comprises: and adding trisodium citrate into the mixture of the graphene oxide solution and the nickel oxide nanoparticle dispersion liquid, and carrying out ultrasonic treatment.
Preferably, the addition amount of the trisodium citrate is 8-15mg per 100ml of the mixed solution.
Preferably, in the step (3), the graphene oxide solution and the nickel oxide nanoparticle dispersion liquid are stirred and mixed, firstly ultrasonic treatment is carried out for 10min, and then ultrasonic treatment is carried out for 5min after trisodium citrate is added.
Preferably, in step (1), KMnO4、H2SO4The ratio of the components is 1:8, the centrifugal speed of a centrifugal machine is 3000rpm, and the centrifugal time is 5 min.
Preferably, in the step (2), the ratio of nickel nitrate hexahydrate, hexamethylenetetramine and trisodium citrate is 30:30:1, the reaction time in the autoclave is 24 hours, the reaction pressure is 2.8MPa, and the reaction temperature is 200 ℃.
Preferably, in the step (3), the concentration of the graphene oxide solution and the nickel oxide nanoparticle dispersion liquid is 1.0 mg/ml-1。
Preferably, in the step (4), the cold quenching treatment is specifically that the mixture is heated to 80 ℃ in a water bath, then is put into liquid nitrogen for cold quenching, and then the PVC fragments are removed by tweezers after the cold quenching.
The technical scheme of the invention also provides an application of the graphene modified nickel oxide nanocomposite prepared by the method, and the graphene modified nickel oxide nanocomposite is applied to a lithium ion battery as a negative electrode material, and specifically comprises the steps of preparing slurry from the graphene modified nickel oxide nanocomposite, and grinding the slurry in a mortar until the slurry can be coated; coating the prepared slurry on a copper foil, performing vacuum drying, punching, weighing, then loading in a distribution battery, and standing.
Preferably, when preparing the slurry, the mass ratio of the graphene modified nickel oxide nanocomposite, the binder and the conductive carbon black is 8:1:1, with N-methylpyrrolidone (NMP) as a dispersing agent.
The preparation method and the application of the graphene modified nickel oxide nanocomposite provided by the invention have the following beneficial technical effects:
(1) the graphene modified nickel oxide nanocomposite prepared by the method provided by the invention has good electrochemical performance, has good reproducibility and reversibility in the process of redox reaction, and the lithium ion battery prepared by using the graphene modified nickel oxide nanocomposite has good cycle stability, so that the lithium ion battery has good cycle life and the performance of the lithium ion battery as a lithium battery material is improved.
(2) The graphene modified nickel oxide nanocomposite prepared by the method provided by the invention not only effectively improves the phenomena of folds and the like caused by thermodynamic instability of graphene, but also reduces the magnetic influence of metal oxides, fully utilizes the performances of high electrochemical lithium storage specific capacity and good electrochemical stability of the metal oxides, and has higher specific capacity and safety performance.
(3) The graphene modified nickel oxide nanocomposite has a more uniform overall structure due to the addition of the trisodium citrate surfactant, the influence of the inherent magnetism of the nickel oxide on the composite structure is remarkably reduced, and the graphene modified nickel oxide nanocomposite has better conductivity and activity and larger charge-discharge specific capacity.
(4) The specific discharge capacity of the graphene modified nickel oxide nanocomposite prepared by the method reaches 720 mAh.g at the 1C multiplying power-1And after trisodium citrate is added, the specific capacity of the first discharge of 960 mAh.g can be achieved-1The first charging specific capacity under 1C multiplying power reaches 510 mAh.g-1And after trisodium citrate is added, the specific charge capacity of the lithium ion battery can reach 810 mAh.g-1The nickel oxide wraps the graphene to enhance the conductivity of the material, the specific capacity of the material still keeps good cycle performance after the cycle, the cycle specific capacity of the material keeps stable along with the increase of cycle times, and the problem of the conductivity reduction of the material caused by the volume expansion effect of secondary particles does not exist basically in the charging and discharging process.
(5) Through the cold quenching process, the graphene oxide is curled to form a nano roll, NiO nano particles are tightly wrapped between the graphene oxide layers, and trisodium citrate is added, so that the agglomeration and accumulation phenomena of the NiO nano particles due to magnetism are improved, the electrochemical performance of the NiO nano particles is improved, and the capacitance is increased. The average particle size of the graphene modified nickel oxide nanocomposite particles is about 25nm, the overlapping phenomenon is not obvious, the NiO nanoparticles inhibit the overlapping of the graphene, and meanwhile, the wrinkling phenomenon of the graphene is also obviously reduced due to the gravity action of the NiO nanoparticles.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 shows a scanning electron microscope image of a composite material wrapping structure prepared by the preparation method of the graphene modified nickel oxide nanocomposite material;
FIG. 2 shows a graph of the cycle stability of a composite material prepared by the method for preparing a graphene-modified nickel oxide nanocomposite material according to the present invention at a rate of 1C for 200 times;
FIG. 3 shows a cyclic voltammetry curve of a composite prepared by the method for preparing a graphene-modified nickel oxide nanocomposite provided by the invention;
fig. 4 shows an ac impedance curve of the composite material prepared by the method for preparing the graphene-modified nickel oxide nanocomposite material.
Detailed Description
The invention discloses a preparation method and application of a graphene modified nickel oxide nanocomposite, and a person skilled in the art can use the contents to appropriately improve process parameters for realization. It is expressly intended that all such similar substitutes and modifications which would be obvious to one skilled in the art are deemed to be included in the invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of this invention without departing from the spirit and scope of the invention.
The invention is further illustrated by the following examples:
example 1
The preparation method of the graphene modified nickel oxide nanocomposite comprises the following steps:
s1, preparing graphene oxide by using KMnO4、H2SO4As an oxidant, graphene oxide, KMnO is prepared by weak ultrasonic dispersion and centrifuge centrifugation through a modified chemical stripping method4、H2SO4The ratio of the components is 1:8, the centrifugal speed of a centrifugal machine is 3000rpm, and the centrifugal time is 5 min.
S2, preparing nickel oxide nanoparticles, putting a mixture of nickel nitrate hexahydrate, hexamethylene tetramine and trisodium citrate into a polytetrafluoroethylene-lined stainless steel autoclave for reaction, then carrying out heat treatment on the obtained powder in a muffle furnace to obtain nickel oxide black powder, wherein the ratio of the nickel nitrate hexahydrate, the hexamethylene tetramine and the trisodium citrate is 30:30:1, the reaction time in the autoclave is 24 hours, the reaction pressure is 2.8MPa, and the reaction temperature is 200 ℃.
S3, the preparation concentration is 1.0 mg/mL-1Taking 50mL1.0 mg/mL of graphene oxide solution and NiO nano-particle dispersion liquid respectively-1And putting the graphene oxide solution and the NiO nano-particle dispersion liquid into a container, stirring, mixing and ultrasonically treating for 15 min.
S4, heating the mixture subjected to ultrasonic treatment in a water bath to 80 ℃, putting the mixture into liquid nitrogen for cold quenching, removing PVC fragments inside the mixture by using forceps after the cold quenching, paving the sample subjected to cold quenching in a culture dish, and dehydrating and drying the sample by freeze drying; and after removing the residual PVC fragments of the sample, reducing in a tubular furnace to obtain the graphene modified nickel oxide nanocomposite.
Example 2
The preparation method of the graphene modified nickel oxide nanocomposite comprises the following steps:
s1, preparing graphene oxide by using KMnO4、H2SO4As an oxidant, graphene oxide, KMnO is prepared by weak ultrasonic dispersion and centrifuge centrifugation through a modified chemical stripping method4、H2SO4The ratio of the components is 1:8, the centrifugal speed of a centrifugal machine is 3000rpm, and the centrifugal time is 5 min.
S2, preparing nickel oxide nanoparticles, putting a mixture of nickel nitrate hexahydrate, hexamethylene tetramine and trisodium citrate into a polytetrafluoroethylene-lined stainless steel autoclave for reaction, then carrying out heat treatment on the obtained powder in a muffle furnace to obtain nickel oxide black powder, wherein the ratio of the nickel nitrate hexahydrate, the hexamethylene tetramine and the trisodium citrate is 30:30:1, the reaction time in the autoclave is 24 hours, the reaction pressure is 2.8MPa, and the reaction temperature is 200 ℃.
S3, the preparation concentration is 1.0 mg/mL-1Taking 50mL1.0 mg/mL of graphene oxide solution and NiO nano-particle dispersion liquid respectively-1And putting the graphene oxide solution and the NiO nano-particle dispersion liquid into a container, stirring, mixing and ultrasonically treating for 10min, adding trisodium citrate, wherein the adding amount of the trisodium citrate is 10mg, and then ultrasonically treating for 5 min.
S4, heating the mixture subjected to ultrasonic treatment in a water bath to 80 ℃, putting the mixture into liquid nitrogen for cold quenching, removing PVC fragments inside the mixture by using forceps after the cold quenching, paving the sample subjected to cold quenching in a culture dish, and dehydrating and drying the sample by freeze drying; and after removing the residual PVC fragments of the sample, reducing in a tubular furnace to obtain the graphene modified nickel oxide nanocomposite.
Scanning electron microscope scanning is performed on the graphene modified nickel oxide nanocomposite prepared in the above examples 1 and 2, and the coating structure thereof is shown in fig. 1, (a) is the coating structure scanning electron microscope image of the composite prepared in example 1 without trisodium citrate, and (b) is the coating structure scanning electron microscope image of the composite prepared in example 2 with trisodium citrate, and the graphene oxide is curled to form a nano roll through a cold quenching process, and at the same time, NiO nanoparticles are tightly coated between graphene oxide layers. In FIG. 1(a), NiO is magnetic and is in an agglomerated and stacked state, and is in a large amount of clusters, while in FIG. 1(b), trisodium citrate is added to reduce the agglomeration and stacking phenomenon. The average particle size of the graphene modified nickel oxide nano composite material particles is about 25nm, the overlapping phenomenon is not obvious, and the NiO nano particles inhibit the overlapping of graphene. Meanwhile, due to the gravity action of the NiO nano particles, the phenomenon of folding of the graphene is also obviously reduced.
Taking N-methylpyrrolidone (NMP) as a dispersing agent, preparing slurry from the graphene modified nickel oxide nanocomposite prepared in the example 1, an adhesive and conductive carbon black according to the mass ratio of 8:1:1, manually grinding the slurry in a mortar for 2 to 3 hours until the slurry can be coated, and stopping grinding; coating: coating on copper foil with a 20-micron scraper; drying: vacuum drying for 24h in a vacuum drying oven; punching, and reserving blank copper foil; and weighing, loading the sheet in a distribution cell, and standing for 24 hours.
The battery prepared from the graphene modified nickel oxide nanocomposite prepared in example 1 was subjected to 200 cycle stability tests at a magnification of 1C, and the test results are shown in the NiO @ GNS curve in fig. 2, so that the cycle performance was relatively stable, and the first discharge specific capacity reached 720mAh · g-1The first charging specific capacity reaches 510 mAh.g-1. The graphene modified nickel oxide nanocomposite prepared in the embodiment 1 basically has no problem of reduced conductivity of the material due to the volume expansion effect of secondary particles in the charging and discharging processes, and NiO wraps the graphene to enhance the conductivity of the material; and the specific capacity still keeps good cycle performance after the cycle. The specific circulation capacity of the material remains stable as the number of cycles increases.
An alternating current impedance spectrogram test is carried out on the battery prepared by the graphene modified nickel oxide nanocomposite prepared in the embodiment 1 under the state of the open-circuit potential of the primary battery, the test result is shown as a NiO @ GNS-2 curve in FIG. 4, the conductance of the electrode is good, and the high-frequency semicircle corresponds to the impedance formed by the reaction of an SEI film on the surface of the negative electrode material and the electrode; the diagonal straight line in the low frequency range is believed to be caused by the diffusion process of Li +, and as shown by the curve NiO @ GNS-2 in fig. 4, the impedance of the cell is small, and Li + is well diffused and not easily deposited and dissolved.
Taking N-methylpyrrolidone (NMP) as a dispersing agent, preparing slurry from the graphene modified nickel oxide nanocomposite prepared in the example 2, an adhesive and conductive carbon black according to the mass ratio of 8:1:1, manually grinding the slurry in a mortar for 2 to 3 hours until the slurry can be coated, and stopping grinding; coating: coating on copper foil with a 20-micron scraper; drying: vacuum drying for 24h in a vacuum drying oven; punching, and reserving blank copper foil; and weighing, loading the sheet in a distribution cell, and standing for 24 hours.
The battery prepared by using the graphene modified nickel oxide nanocomposite prepared in example 2 was processed at a rate of 1CThe test is carried out for 200 times of cycle stability tests, the test result is shown as a NiO @ NCs @ GNS curve in figure 2, the cycle performance is relatively stable, and the first discharge specific capacity reaches 960 mAh.g-1The first charging specific capacity reaches 810 mAh.g-1. The graphene modified nickel oxide nanocomposite prepared in the embodiment 2 basically has no problem of reduced conductivity of the material due to the volume expansion effect of secondary particles in the charging and discharging processes, and NiO wraps the graphene to enhance the conductivity of the material; and the specific capacity still keeps good cycle performance after the cycle. The specific circulation capacity of the material remains stable as the number of cycles increases. Meanwhile, trisodium citrate is added in the embodiment 2, so that the compounding is more uniform, the structure of the composite material is further improved, and the cycle stability, the first discharge specific capacity and the first charge specific capacity are all stronger than those of the composite material prepared in the embodiment 1.
When a cyclic voltammetry curve test of an electrode was performed on a battery prepared from the graphene-modified nickel oxide nanocomposite prepared in example 2, the test voltage interval was 0.01 to 3.00V, the scan rate was 0.5mV/s, and the test result is shown in fig. 3, and a strong reduction peak was observed around the voltage value of 0.57V during the first cycle. This peak appears in correspondence with the electrochemical reaction that occurs when the nickel oxide is first intercalated with lithium ions, and a solid electrolyte interface film is formed on the surface of the electrode material. Meanwhile, in the following reverse scanning process, a wide oxidation peak appears near the voltage value of 1.54V, and the reduction reaction product is re-oxidized to generate NiO. During the second cycle, the reduction peak at 0.57V disappeared, confirming that nickel oxide was reduced to metallic nickel upon first intercalation of lithium ions, accompanied by an amorphous compound Li2O formation, and the formation of a solid electrolyte interfacial film, all of which are irreversible. From the second cycle, a reduction peak at 0.76V and an oxidation peak at 1.71V were clearly observed, and their positions were hardly changed. Again, the excellent reproducibility and reversibility of the sample during the redox reaction process should be verified. Furthermore, it can be seen on the cyclic voltammogramThus, the first and second cycling profiles have a significant amount of change, i.e., the intensity of the reduction peak is significantly reduced. The reduction of the integrated area under the cyclic voltammetry curve means the degradation of the charge-discharge capacity during cycling, and this characteristic can be reflected on the charge-discharge curve.
An alternating current impedance spectrogram test is carried out on the battery prepared by the graphene modified nickel oxide nanocomposite prepared in the embodiment 2 under the state of the open-circuit potential of the primary battery, the test result is shown as a NiO @ GNS-1 curve in a figure 4, the conductance of the electrode is good, and the high-frequency semicircle corresponds to the impedance formed by the reaction of an SEI film on the surface of the negative electrode material and the electrode; the diagonal straight line in the low frequency range is believed to be caused by the diffusion process of Li +, and as shown by the curve NiO @ GNS-1 in fig. 4, the impedance of the cell is small, and Li + is well diffused and not easily deposited and dissolved. Meanwhile, trisodium citrate is added in the embodiment 2, so that the structure of the composite material is further improved, the resistance corresponding to the arc of the composite material electrode NiO @ GNS-1 in a high-frequency region is far smaller than that of NiO @ GNS-2, and the resistance at the moment is related to the conductivity and activity of the electrode, and the resistance of an electrolyte and a diaphragm. Under the condition that the material and the test condition are the same, the composite material NiO @ GNS-1 is known to have better performance than NiO @ GNS-2.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A preparation method of a graphene modified nickel oxide nanocomposite is characterized by comprising the following steps:
(1) in KMnO4、H2SO4As an oxidant, graphene oxide is prepared by weak ultrasonic dispersion and centrifuge centrifugation through a modified chemical stripping method;
(2) putting a mixture of nickel nitrate hexahydrate, hexamethylenetetramine and trisodium citrate into a polytetrafluoroethylene-lined stainless steel autoclave for reaction, and then carrying out heat treatment on the obtained powder in a muffle furnace to obtain nickel oxide black powder;
(3) respectively preparing a graphene oxide solution and a nickel oxide nanoparticle dispersion liquid with the same concentration, stirring and mixing the graphene oxide solution and the nickel oxide nanoparticle dispersion liquid with the same volume, and performing ultrasonic treatment;
(4) after the mixture obtained in the step (3) is subjected to mixed ultrasonic treatment and is subjected to cold quenching treatment, spreading a sample subjected to cold quenching treatment in a culture dish, and dehydrating and drying the sample by freeze drying; and after removing the residual PVC fragments of the sample, reducing in a tubular furnace to obtain the graphene modified nickel oxide nanocomposite.
2. The method for preparing graphene-modified nickel oxide nanocomposite according to claim 1,
in the step (3), the method further comprises: and adding trisodium citrate into the mixture of the graphene oxide solution and the nickel oxide nanoparticle dispersion liquid, and carrying out ultrasonic treatment.
3. The method for preparing graphene-modified nickel oxide nanocomposite according to claim 2,
the addition amount of the trisodium citrate is 8-15mg of trisodium citrate added into each 100ml of mixed solution.
4. The method for preparing a graphene-modified nickel oxide nanocomposite material according to claim 3,
in the step (3), stirring and mixing the graphene oxide solution and the nickel oxide nanoparticle dispersion liquid, firstly performing ultrasonic treatment for 10min, adding trisodium citrate, and then performing ultrasonic treatment for 5 min.
5. The method for preparing a graphene-modified nickel oxide nanocomposite material according to claim 4,
in step (1), KMnO4、H2SO4The ratio of the components is 1:8, the centrifugal speed of a centrifugal machine is 3000rpm, and the centrifugal time is 5 min.
6. The method for preparing a graphene-modified nickel oxide nanocomposite material according to claim 4,
in the step (2), the ratio of nickel nitrate hexahydrate, hexamethylenetetramine and trisodium citrate is 30:30:1, the reaction time in the autoclave is 24 hours, the reaction pressure is 2.8MPa, and the reaction temperature is 200 ℃.
7. The method for preparing a graphene-modified nickel oxide nanocomposite material according to claim 4,
in the step (3), the concentration of the graphene oxide solution and the nickel oxide nanoparticle dispersion liquid is 1.0 mg.ml -1。
8. The method for preparing a graphene-modified nickel oxide nanocomposite material according to claim 4,
in the step (4), the cold quenching treatment specifically comprises the steps of heating the mixture to 80 ℃ in a water bath, putting the mixture into liquid nitrogen for cold quenching, and removing PVC fragments inside the mixture by using forceps after the cold quenching.
9. Use of a graphene-modified nickel oxide nanocomposite material prepared by the method according to any one of claims 1 to 8,
the graphene modified nickel oxide nanocomposite is applied to a lithium ion battery as a negative electrode material, and specifically comprises the steps of preparing slurry from the graphene modified nickel oxide nanocomposite, and grinding the slurry in a mortar until the slurry can be coated; coating the prepared slurry on a copper foil, performing vacuum drying, punching, weighing, then loading in a distribution battery, and standing.
10. The use of the graphene-modified nickel oxide nanocomposite according to claim 9,
when the slurry is prepared, N-methyl pyrrolidone (NMP) is used as a dispersing agent, and the mass ratio of the graphene modified nickel oxide nano composite material to the adhesive to the conductive carbon black is 8:1: 1.
CN202011155919.XA 2020-10-26 2020-10-26 Preparation method and application of graphene modified nickel oxide nanocomposite Pending CN112436111A (en)

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