CN109244440B - NiO-ZnO composite material, preparation method thereof and lithium ion battery - Google Patents

NiO-ZnO composite material, preparation method thereof and lithium ion battery Download PDF

Info

Publication number
CN109244440B
CN109244440B CN201811453390.2A CN201811453390A CN109244440B CN 109244440 B CN109244440 B CN 109244440B CN 201811453390 A CN201811453390 A CN 201811453390A CN 109244440 B CN109244440 B CN 109244440B
Authority
CN
China
Prior art keywords
nio
composite material
zno composite
zno
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201811453390.2A
Other languages
Chinese (zh)
Other versions
CN109244440A (en
Inventor
孙灵娜
袁知洋
李少军
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenzhen University
Original Assignee
Shenzhen University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shenzhen University filed Critical Shenzhen University
Priority to CN201811453390.2A priority Critical patent/CN109244440B/en
Publication of CN109244440A publication Critical patent/CN109244440A/en
Application granted granted Critical
Publication of CN109244440B publication Critical patent/CN109244440B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • 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
    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a NiO-ZnO composite material, a preparation method thereof and a lithium ion battery. The invention prepares the bi-component NiO-ZnO composite material by combining a simple hydrothermal method with calcination treatment. Compared with single-component NiO and ZnO, the bi-component NiO-ZnO composite material has excellent electrochemical performance, and the main reason is that an internal electric field is formed at a heterojunction interface formed by NiO and ZnO, so that the electron transfer among nano particles is enhanced; meanwhile, the stress caused by volume change is buffered and the structural integrity is kept by utilizing the synergistic effect of the two components, so that the cycle performance of the material is improved; and a large amount of simple substance Ni and simple substance Zn are generated in the first discharging process, have electrochemical catalysis effect, and can promote the reaction, thereby improving the electrochemical performance of the material.

Description

NiO-ZnO composite material, preparation method thereof and lithium ion battery
Technical Field
The invention relates to the technical field of composite materials, in particular to a NiO-ZnO composite material, a preparation method thereof and a lithium ion battery.
Background
Since the 21 st century, energy and environmental problems caused by the rapid development of economy have become prominent, people have increasingly demanded clean and sustainable energy, and lithium ion batteries have attracted much attention as a new green energy. In a lithium ion battery, a negative electrode material is an important component of the lithium ion battery, and plays a decisive role in lithium ion electrochemical performance as a main body for storing lithium. Currently, the lithium ion battery cathode material in commercialization is mainly graphite, which has lower theoretical capacity (372 mAh. cndot.)g-1) The demand of people for high-energy density batteries is far from being met. Transition metal oxides due to their higher theoretical capacity: (> 600 mAh·g-1) And good ability to store lithium, are considered to be a very potential negative electrode material. However, low electronic conductivity, volume expansion, voltage hysteresis, etc. are three major problems to be faced by transition metal oxides as negative electrode materials of lithium ion batteries. The low electron conductivity limits the electron transport and hinders the electron transport capability of the electrode material, thereby affecting the conversion reaction of the transition metal oxide and lithium, resulting in large polarization, low energy efficiency and poor cycle performance. The volume expansion destroys the structure of the active material, resulting in poor cycling stability of the material. There is a voltage hysteresis between the discharge potential and the charge potential, resulting in low energy efficiency.
In order to solve the problems of the transition metal oxide and improve the electrochemical performance of the material, modification strategies such as nanocrystallization, structural optimization and compositing are generally adopted for the transition metal oxide. Wang et al deposited 0D Mn on copper foil by electrochemical deposition3O4Nanoparticles at 936 mA · g-1The first charge-discharge specific capacity under the current density is 622 and 919 mAh.g-1And the reversible specific capacity is maintained at 882 mAh g after 85 cycles of circulation-1(ii) a Liu et al prepared hollow NiO nanotube material by covering filter paper with a layer of nano NiO gel based on the sol-gel method and calcining in a muffle furnace. The high specific capacity and the good cycling stability of the electrode material are determined by the high specific surface and the stable hollow structure, and the current density is 1000 mA-g-1The reversible specific capacity is still 570 mAh g after the circulation is performed for 100 circles-1(ii) a Xiang et al form a CuO/Ni composite by coating Ni nanoparticles on the surface of flower-like CuO by an electrodeposition method in an alkaline nickel electroplating solution, the first coulombic efficiency of flower-like CuO is increased from 57% to 72.1% by the presence of a nickel simple substance, and the capacity retention rate is still 94.3% after 50 cycles.
It can be seen that although the research on the transition metal oxide negative electrode material has been developed to some extent, the application of the transition metal oxide negative electrode material to the lithium ion battery with high capacity and good cycle performance still needs further intensive research.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a NiO-ZnO composite material, a preparation method thereof and a lithium ion battery, and aims to solve the problem of poor electrochemical performance of the lithium ion battery caused by the defects of low electronic conductivity, volume expansion, voltage hysteresis and the like of the conventional negative electrode material.
The technical scheme of the invention is as follows:
a preparation method of a NiO-ZnO composite material comprises the following steps:
(1) firstly, dissolving nickel salt and zinc salt in deionized water, and stirring to form uniform mixed solution;
(2) adding urea into the uniform mixed solution, stirring, transferring to a polytetrafluoroethylene reaction kettle, and then placing into a uniform reactor for reaction at a high temperature of 160 ℃ and 200 ℃ for 8-16 h;
(3) after the reaction is finished, cooling to room temperature, sequentially carrying out suction filtration separation, washing and drying to obtain a NiO-ZnO composite material precursor;
(4) and finally, calcining the dried NiO-ZnO composite material precursor for 2-6h at the temperature of 400-700 ℃ in a muffle furnace to prepare the NiO-ZnO composite material.
The preparation method of the NiO-ZnO composite material comprises the following steps of (1) and (3): (1-3).
The preparation method of the NiO-ZnO composite material comprises the step (1) of preparing a NiO-ZnO composite material, wherein the nickel salt is nickel nitrate or nickel acetate.
The preparation method of the NiO-ZnO composite material comprises the step (1), wherein the zinc salt is zinc nitrate or zinc acetate.
The preparation method of the NiO-ZnO composite material comprises the following steps of (3): washed three times with deionized water and absolute ethyl alcohol respectively.
The preparation method of the NiO-ZnO composite material comprises the following steps of (3): drying in a forced air drying oven at 70 deg.C for 8 h.
The NiO-ZnO composite material is prepared by the preparation method of the NiO-ZnO composite material.
The NiO-ZnO composite material is characterized in that the NiO-ZnO composite material is nanoparticles, and the particle size of the nanoparticles is 80-120 nm.
The lithium ion battery comprises a negative electrode, wherein the negative electrode material comprises the NiO-ZnO composite material.
Has the advantages that: compared with single-component NiO and ZnO, the bi-component NiO-ZnO composite material has excellent electrochemical performance, and the main reason is that an internal electric field is formed at a heterojunction interface formed by NiO and ZnO, so that the electron transfer among nano particles is enhanced; meanwhile, the stress caused by volume change is buffered and the structural integrity is kept by utilizing the synergistic effect of the two components, so that the cycle performance of the material is improved; and a large amount of simple substance Ni and simple substance Zn are generated in the first discharging process, have electrochemical catalysis effect, and can promote the reaction, thereby improving the electrochemical performance of the material.
Drawings
FIG. 1 is a flow chart of the preparation of a NiO-ZnO composite material in embodiment 4 of the present invention.
FIG. 2 is a SEM image of the NiO-ZnO composite material, NiO and ZnO prepared in the embodiment 4 of the invention.
FIG. 3 is an XRD pattern of the NiO-ZnO composite material, NiO and ZnO prepared in the embodiment 4 of the present invention.
FIG. 4 is a graph showing the cycle performance of the NiO-ZnO composite material, NiO and ZnO prepared in example 4 of the present invention.
FIG. 5 is a graph showing rate capability of NiO and ZnO in the NiO-ZnO composite material obtained in example 4 of the present invention.
Detailed Description
The invention provides a NiO-ZnO composite material, a preparation method thereof and a lithium ion battery, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a preparation method of a NiO-ZnO composite material, which comprises the following steps:
(1) firstly, dissolving nickel salt and zinc salt in deionized water, and stirring to form uniform mixed liquor (light green);
(2) adding urea into the uniform mixed solution, stirring, transferring to a polytetrafluoroethylene reaction kettle, and then placing into a uniform reactor for reaction at a high temperature of 160 ℃ and 200 ℃ for 8-16 h;
(3) after the reaction is finished, cooling to room temperature, sequentially carrying out suction filtration separation, washing and drying to obtain a NiO-ZnO composite material precursor;
(4) and finally, calcining the dried NiO-ZnO composite material precursor for 2-6h at the temperature of 400-700 ℃ in a muffle furnace to prepare the NiO-ZnO composite material.
The embodiment of the invention adopts a simple hydrothermal method combined with calcination treatment to prepare the bi-component NiO-ZnO composite material. Compared with single-component NiO and ZnO, the bi-component NiO-ZnO composite material has excellent electrochemical performance, and the main reason is that an internal electric field is formed at a heterojunction interface formed by NiO and ZnO, so that the electron transfer among nano particles is enhanced; meanwhile, the stress caused by volume change is buffered and the structural integrity is kept by utilizing the synergistic effect of the two components, so that the cycle performance of the material is improved; and a large amount of simple substance Ni and simple substance Zn are generated in the first discharging process, have electrochemical catalysis effect, and can promote the reaction, thereby improving the electrochemical performance of the material.
The NiO-ZnO composite material utilizes the components in the multi-oxide composite material to have different electrochemical activities under different potentials. When a transition metal oxide is inserted into Li+Other oxides may be used as buffer matrices, and vice versa. Importantly, each oxide is an active material that can store lithium, and thus can provide a higher specific capacity, than the transition metal oxides and carbon composites.
In the step (1), preferably, the molar ratio of the nickel salt to the zinc salt is (1-3): (1-3), the molar ratio of different nickel salts and zinc salts has great influence on the appearance of the product, thereby further influencing the electrochemical performance of the battery. Within the above molar ratio range, the obtained battery has better electrochemical performance.
In the step (1), preferably, the nickel salt is nickel nitrate or nickel acetate.
In the step (1), preferably, the zinc salt is zinc nitrate or zinc acetate.
In the step (3), preferably, the washing process comprises: washed three times with deionized water and absolute ethyl alcohol respectively.
In the step (3), preferably, the drying process includes: drying in a forced air drying oven at 70 deg.C for 8 h.
In the step (4), the dried NiO-ZnO composite material precursor further comprises the following steps before high-temperature calcination: and grinding the dried NiO-ZnO composite material. The dried NiO-ZnO composite material is fully ground in a mortar, so that the subsequent calcination can be fully ensured.
The embodiment of the invention provides a NiO-ZnO composite material, wherein the NiO-ZnO composite material is prepared by the preparation method of the NiO-ZnO composite material. Wherein the NiO-ZnO composite material is nano-particles, and the particle size of the nano-particles is about 100 nm.
The embodiment of the invention provides a lithium ion battery which comprises a negative electrode, wherein the negative electrode material comprises the NiO-ZnO composite material.
Example 1:
(1) first, 2 mmol of Ni (CH) is weighed3COO)2•4H2O，1 mmol Zn(CH3COO)2•4H2Dissolving O in 120 mL of deionized water, and magnetically stirring for 10min to form a uniform mixed solution;
(2) dissolving 6 mmol urea in the uniform mixed solution, and magnetically stirring for 30 min; then transferring the mixed solution into a 150 mL polytetrafluoroethylene reaction kettle to react for 12 h at the high temperature of 160 ℃;
(3) after the reaction is finished, cooling to room temperature, performing suction filtration and separation on the product by using a Buchner funnel, washing the product for three times by using deionized water and absolute ethyl alcohol respectively, and then placing the product in a forced air drying oven at 70 ℃ for constant-temperature drying for 8 hours;
(4) and finally, grinding the dried precursor into powder by using a mortar, and then placing the powder in a muffle furnace to calcine for 4 hours at 400 ℃.
(5) For comparison, the preparation of NiO alone without the addition of Zn (CH)3COO)2•4H2O; similarly, when ZnO is prepared separately, Ni (CH) is not added3COO)2•4H2O; other conditions were unchanged.
The SEM image, XRD image, cycle performance image and rate performance image of the NiO-ZnO composite material prepared by the embodiment are not shown. Analysis shows that similar to example 4, the NiO-ZnO composite material obtained in the embodiment has similar performance advantages.
Example 2:
(1) first, 2 mmol of Ni (CH) is weighed3COO)2•4H2O，1 mmol Zn(CH3COO)2•4H2Dissolving O in 120 mL of deionized water, and magnetically stirring for 10min to form a uniform mixed solution;
(2) dissolving 6 mmol urea in the uniform mixed solution, and magnetically stirring for 30 min; then transferring the mixed solution into a 150 mL polytetrafluoroethylene reaction kettle to react for 12 h at the high temperature of 180 ℃;
(3) after the reaction is finished, cooling to room temperature, performing suction filtration and separation on the product by using a Buchner funnel, washing the product for three times by using deionized water and absolute ethyl alcohol respectively, and then placing the product in a forced air drying oven at 70 ℃ for constant-temperature drying for 8 hours;
(4) and finally, grinding the dried precursor into powder by using a mortar, and then placing the powder in a muffle furnace to calcine for 4 hours at 400 ℃.
(5) For comparison, the preparation of NiO alone without the addition of Zn (CH)3COO)2•4H2O; similarly, when ZnO is prepared separately, Ni (CH) is not added3COO)2•4H2O; other conditions were unchanged.
The SEM image, XRD image, cycle performance image and rate performance image of the NiO-ZnO composite material prepared by the embodiment are not shown. Analysis shows that similar to example 4, the NiO-ZnO composite material obtained in the embodiment has similar performance advantages.
Example 3:
(1) first, 2 mmol of Ni (CH) is weighed3COO)2•4H2O，1 mmol Zn(CH3COO)2•4H2Dissolving O in 120 mL of deionized water, and magnetically stirring for 10min to form a uniform mixed solution;
(2) dissolving 6 mmol urea in the uniform mixed solution, and magnetically stirring for 30 min; then transferring the mixed solution into a 150 mL polytetrafluoroethylene reaction kettle to react for 12 h at the high temperature of 200 ℃;
(3) after the reaction is finished, cooling to room temperature, performing suction filtration and separation on the product by using a Buchner funnel, washing the product for three times by using deionized water and absolute ethyl alcohol respectively, and then placing the product in a forced air drying oven at 70 ℃ for constant-temperature drying for 8 hours;
(4) and finally, grinding the dried precursor into powder by using a mortar, and then placing the powder in a muffle furnace to calcine for 4 hours at 400 ℃.
(5) For comparison, the preparation of NiO alone without the addition of Zn (CH)3COO)2•4H2O; similarly, when ZnO is prepared separately, Ni (CH) is not added3COO)2•4H2O; other conditions were unchanged.
The SEM image, XRD image, cycle performance image and rate performance image of the NiO-ZnO composite material prepared by the embodiment are not shown. Analysis shows that similar to example 4, the NiO-ZnO composite material obtained in the embodiment has similar performance advantages.
Example 4:
FIG. 1 is a flow chart of the preparation of the NiO-ZnO composite material of this example, wherein the preparation process of the NiO-ZnO composite material is as follows:
(1) first, 2 mmol of Ni (CH) is weighed3COO)2•4H2O，1 mmol Zn(CH3COO)2•4H2Dissolving O in 120 mL of deionized water, and magnetically stirring for 10min to form a uniform mixed solution;
(2) dissolving 6 mmol urea in the uniform mixed solution, and magnetically stirring for 30 min; then transferring the mixed solution into a 150 mL polytetrafluoroethylene reaction kettle to react for 12 h at the high temperature of 180 ℃;
(3) after the reaction is finished, cooling to room temperature, performing suction filtration and separation on the product by using a Buchner funnel, washing the product for three times by using deionized water and absolute ethyl alcohol respectively, and then placing the product in a forced air drying oven at 70 ℃ for constant-temperature drying for 8 hours;
(4) and finally, grinding the dried precursor into powder by using a mortar, and then placing the powder in a muffle furnace to calcine for 4 hours at 500 ℃.
(5) For comparison, the preparation of NiO alone without the addition of Zn (CH)3COO)2•4H2O; similarly, when ZnO is prepared separately, Ni (CH) is not added3COO)2•4H2O; other conditions were unchanged.
And carrying out corresponding characterization tests on the prepared NiO-ZnO composite material.
FIG. 2 is a SEM image of a NiO-ZnO composite material, NiO and ZnO under a field emission scanning electron microscope. FIGS. 2a and 2d are the morphology diagrams of the NiO-ZnO composite material under different magnifications, from which it can be clearly seen that the morphology of the NiO-ZnO composite material is nano-particles, and the size is about 100 nm; fig. 2b and 2e are the topography maps of NiO under different magnifications, fig. 2c and 2f are the topography maps of ZnO under different magnifications, it can be observed that the topography of NiO and ZnO is porous nanosheets, and it can be clearly observed that both NiO (fig. 2 e) and ZnO (fig. 2 f) are porous nanosheets stacked from nanoparticles under a large magnification.
FIG. 3 is an XRD spectrum of the NiO-ZnO composite material, NiO and ZnO. It can be clearly observed that the diffraction peaks of the NiO-ZnO composite material at 37.25 degrees, 43.28 degrees, 62.87 degrees, 75.41 degrees and 79.40 degrees respectively correspond to the (111), (200), (220), (311) and (222) crystal faces of NiO standard card PDF #65-5745 with a cubic crystal structure; diffraction peaks at 31.77 degrees, 34.42 degrees, 36.25 degrees and 62.86 degrees correspond to crystal faces (100), (002), (101) and (103) of ZnO standard card PDF #36-1451 of a wurtzite-type crystal structure, and weak diffraction peaks at 47.53 degrees, 56.60 degrees and 69.09 degrees correspond to crystal faces (102), (110) and (201); the diffraction peaks of NiO and ZnO can be respectively matched with PDF #65-5745 and PDF #36-1451 of standard cards, which shows that the NiO-ZnO composite material consists of cubic NiO and wurtzite ZnO.
FIG. 4 is a graph of the cycle performance of the NiO-ZnO composite, NiO and ZnO. The NiO-ZnO composite material is at 200 mA.g-1The reversible specific capacity after 200 cycles of circulation under the current density is 978.3mAh g-1Is obviously superior to 550.8 mAh.g of single-component NiO-1211.4 mAh.g. of one-component ZnO-1. This is because the synergistic effect generated by the bi-component NiO-ZnO composite material effectively relieves the Li extraction+The volume expansion in the process improves the conductivity of the material.
FIG. 5 is a graph of rate capability of the NiO-ZnO composite, NiO and ZnO. It is evident from the figure that the NiO-ZnO composite material has higher capacity after cycling for 10 circles under different current densities compared with the single-component NiO and ZnO, and returns to 0.1 A.g after cycling under different current densities-1During the process, the reversible specific capacity exceeds the reversible specific capacity of the initial 10 cycles, and good rate capability is shown. The bi-component NiO-ZnO composite material forms a heterostructure, and improves the conductivity of the material. Meanwhile, the volume expansion of the material in the circulation process is effectively relieved by the synergistic effect between the two-component NiO-ZnO composite materials, so that the material shows better rate performance.
Example 5:
(1) first, 2 mmol of Ni (CH) is weighed3COO)2•4H2O，1 mmol Zn(CH3COO)2•4H2Dissolving O in 120 mL of deionized water, and magnetically stirring for 10min to form a uniform mixed solution;
(2) dissolving 6 mmol urea in the uniform mixed solution, and magnetically stirring for 30 min; then transferring the mixed solution into a 150 mL polytetrafluoroethylene reaction kettle to react for 12 h at the high temperature of 180 ℃;
(3) after the reaction is finished, cooling to room temperature, performing suction filtration and separation on the product by using a Buchner funnel, washing the product for three times by using deionized water and absolute ethyl alcohol respectively, and then placing the product in a forced air drying oven at 70 ℃ for constant-temperature drying for 8 hours;
(4) and finally, grinding the dried precursor into powder by using a mortar, and then placing the powder in a muffle furnace to calcine for 4 hours at the temperature of 600 ℃.
(5) For comparison, the preparation of NiO alone without the addition of Zn (CH)3COO)2•4H2O; similarly, when ZnO is prepared separately, Ni (CH) is not added3COO)2•4H2O; other conditions were unchanged.
The SEM image, XRD image, cycle performance image and rate performance image of the NiO-ZnO composite material prepared by the embodiment are not shown. Analysis shows that similar to example 4, the NiO-ZnO composite material obtained in the embodiment has similar performance advantages.
Example 6:
(1) first, 2 mmol of Ni (CH) is weighed3COO)2•4H2O，1 mmol Zn(CH3COO)2•4H2Dissolving O in 120 mL of deionized water, and magnetically stirring for 10min to form a uniform mixed solution;
(2) dissolving 6 mmol urea in the uniform mixed solution, and magnetically stirring for 30 min; then transferring the mixed solution into a 150 mL polytetrafluoroethylene reaction kettle to react for 12 h at the high temperature of 180 ℃;
(3) after the reaction is finished, cooling to room temperature, performing suction filtration and separation on the product by using a Buchner funnel, washing the product for three times by using deionized water and absolute ethyl alcohol respectively, and then placing the product in a forced air drying oven at 70 ℃ for constant-temperature drying for 8 hours;
(4) and finally, grinding the dried precursor into powder by using a mortar, and then placing the powder in a muffle furnace to be calcined for 4 hours at 700 ℃.
(5) For comparison, the preparation of NiO alone without the addition of Zn (CH)3COO)2•4H2O; similarly, when ZnO is prepared separately, Ni (CH) is not added3COO)2•4H2O; other conditions were unchanged.
The SEM image, XRD image, cycle performance image and rate performance image of the NiO-ZnO composite material prepared by the embodiment are not shown. Analysis shows that similar to example 4, the NiO-ZnO composite material obtained in the embodiment has similar performance advantages.
In conclusion, the invention provides a NiO-ZnO composite material, a preparation method thereof and a lithium ion battery, and particularly provides a bi-component NiO-ZnO composite material prepared by combining a simple hydrothermal method and calcination treatment. Compared with single-component NiO and ZnO, the bi-component NiO-ZnO composite material has excellent electrochemical performance, and the main reason is that an internal electric field is formed at a heterojunction interface formed by NiO and ZnO, so that the electron transfer among nano particles is enhanced; meanwhile, the stress caused by volume change is buffered and the structural integrity is kept by utilizing the synergistic effect of the two components, so that the cycle performance of the material is improved; and a large amount of simple substance Ni and simple substance Zn are generated in the first discharging process, have electrochemical catalysis effect, and can promote the reaction, thereby improving the electrochemical performance of the material.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.

Claims (9)

1. A preparation method of a NiO-ZnO composite material is characterized by comprising the following steps:
(1) firstly, dissolving nickel salt and zinc salt in deionized water, and stirring to form uniform mixed solution;
(2) adding urea into the uniform mixed solution, stirring, transferring to a polytetrafluoroethylene reaction kettle, and then placing into a uniform reactor for reaction at a high temperature of 160 ℃ and 200 ℃ for 8-16 h;
(3) after the reaction is finished, cooling to room temperature, sequentially carrying out suction filtration separation, washing and drying to obtain a NiO-ZnO composite material precursor;
(4) finally, calcining the dried NiO-ZnO composite material precursor for 2-6h at the high temperature of 400-700 ℃ in a muffle furnace to prepare the NiO-ZnO composite material; the NiO-ZnO composite material is nanoparticles, and the particle size of the nanoparticles is 80-120 nm.
2. The method for preparing the NiO-ZnO composite material according to the claim 1, wherein in the step (1), the molar ratio of the nickel salt to the zinc salt is (1-3): (1-3).
3. The method for preparing the NiO-ZnO composite material according to claim 1, wherein in the step (1), the nickel salt is nickel nitrate or nickel acetate.
4. The method for preparing the NiO-ZnO composite material according to claim 1, wherein in the step (1), the zinc salt is zinc nitrate or zinc acetate.
5. The method for preparing the NiO-ZnO composite material according to the claim 1, wherein in the step (3), the washing process comprises the following steps: washed three times with deionized water and absolute ethyl alcohol respectively.
6. The method for preparing the NiO-ZnO composite material according to the claim 1, wherein in the step (3), the drying process comprises the following steps: drying in a forced air drying oven at 70 deg.C for 8 h.
7. A NiO-ZnO composite material characterized by being produced by the method for producing a NiO-ZnO composite material according to any one of claims 1 to 6.
8. The NiO-ZnO composite of claim 7, wherein the NiO-ZnO composite is nanoparticles, and the size of the nanoparticles is 80-120 nm.
9. A lithium ion battery comprising a negative electrode, characterized in that the negative electrode material comprises the NiO-ZnO composite according to any of claims 7 to 8.
CN201811453390.2A 2018-11-30 2018-11-30 NiO-ZnO composite material, preparation method thereof and lithium ion battery Active CN109244440B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811453390.2A CN109244440B (en) 2018-11-30 2018-11-30 NiO-ZnO composite material, preparation method thereof and lithium ion battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811453390.2A CN109244440B (en) 2018-11-30 2018-11-30 NiO-ZnO composite material, preparation method thereof and lithium ion battery

Publications (2)

Publication Number Publication Date
CN109244440A CN109244440A (en) 2019-01-18
CN109244440B true CN109244440B (en) 2021-09-28

Family

ID=65074375

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811453390.2A Active CN109244440B (en) 2018-11-30 2018-11-30 NiO-ZnO composite material, preparation method thereof and lithium ion battery

Country Status (1)

Country Link
CN (1) CN109244440B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111204822A (en) * 2020-01-08 2020-05-29 九江学院 Preparation method of NiO-ZnO/S lithium-sulfur battery positive electrode material with flower-like structure

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103435104A (en) * 2013-06-04 2013-12-11 东莞上海大学纳米技术研究院 Preparation method for lithium ion battery negative electrode material-nano zinc ferrite
US20160281004A1 (en) * 2013-12-30 2016-09-29 King Fahd University Of Petroleum And Minerals Novel method for preparing alumina-zinc oxide-nickel oxide composite for desulfurization
CN106076246A (en) * 2016-06-20 2016-11-09 江苏大学 A kind of have the compound except iodine material and preparation method of micro-nano hierarchy
CN106783186A (en) * 2016-12-22 2017-05-31 广东昭信光电科技有限公司 A kind of ZnO nanorod light anode and preparation method thereof, solar cell
CN111204822A (en) * 2020-01-08 2020-05-29 九江学院 Preparation method of NiO-ZnO/S lithium-sulfur battery positive electrode material with flower-like structure

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103435104A (en) * 2013-06-04 2013-12-11 东莞上海大学纳米技术研究院 Preparation method for lithium ion battery negative electrode material-nano zinc ferrite
US20160281004A1 (en) * 2013-12-30 2016-09-29 King Fahd University Of Petroleum And Minerals Novel method for preparing alumina-zinc oxide-nickel oxide composite for desulfurization
CN106076246A (en) * 2016-06-20 2016-11-09 江苏大学 A kind of have the compound except iodine material and preparation method of micro-nano hierarchy
CN106783186A (en) * 2016-12-22 2017-05-31 广东昭信光电科技有限公司 A kind of ZnO nanorod light anode and preparation method thereof, solar cell
CN111204822A (en) * 2020-01-08 2020-05-29 九江学院 Preparation method of NiO-ZnO/S lithium-sulfur battery positive electrode material with flower-like structure

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"Nanosheets- based ZnO-NiO microspheres for lithium-ion batteries";Cao tingting et al.;《JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS》;20150505;第26卷(第7期);第5287-5294页 *
"Synthesizing a flower-like NiO and ZnO composite for supercapacitor applications";Zheng J.H.et al.;《RESEARCH ON CHEMICAL INTERMEDIATES 》;20180425;第44卷(第9期);第5569-5582页 *

Also Published As

Publication number Publication date
CN109244440A (en) 2019-01-18

Similar Documents

Publication Publication Date Title
CN106784686A (en) A kind of doped lithium ion battery class monocrystalline multicomponent material and preparation method thereof
CN106299348B (en) A kind of method of composite material cladding nickel ion doped
CN111453776B (en) Phosphorus and tungsten co-doping modification preparation method of lithium-rich manganese-based cathode material of lithium ion battery
CN111916687A (en) Cathode material, preparation method thereof and lithium ion battery
CN1595687A (en) A positive electrode material for lithium secondary cell, and preparation and usage thereof
CN108400324B (en) Lithium ion battery cathode material zinc manganate nanorod and preparation method thereof
CN111129439B (en) High-performance zinc-cobalt battery positive electrode and preparation method thereof
CN109659519B (en) TiO2Preparation method of nanofiber-coated lithium ion battery ternary cathode material and product
CN109148828B (en) Comprises cluster Co-Fe of rice straw2O3Electrode of nano composite material and preparation method thereof
CN1595689A (en) Positive electrode material of manganese series, and preparation and usage thereof
CN112599743B (en) Carbon-coated nickel cobaltate multi-dimensional assembled microsphere negative electrode material and preparation method thereof
CN109935819B (en) Preparation method of negative electrode material for lithium ion battery
CN113998745B (en) Cobalt-free cathode material and preparation method and application thereof
CN106252594B (en) A kind of ball-shaped lithium-ion battery anode material and its synthetic method with nanoscale two-phase coexistent structure
CN106941158A (en) A kind of Zinc vanadate molybdenum trioxide nanosheet electrode material of lithium battery and preparation method
CN113845152A (en) Lithium nickel manganese oxide positive electrode material, preparation method thereof and lithium ion battery
CN115395007A (en) Layered-spinel composite phase monocrystal lithium-rich manganese-based positive electrode material and application thereof
CN112687875B (en) Preparation method and application of nickel molybdate flexible film composite material
CN108598463B (en) Preparation method of nano flaky lithium-rich manganese-based positive electrode material
CN112952056B (en) Lithium-rich manganese-based composite cathode material and preparation method and application thereof
CN108565454B (en) Lithium nickel manganese oxide positive electrode material with three-dimensional desert wave structure and preparation method and application thereof
CN112436136B (en) Cobalt molybdate nanorod containing oxygen vacancy as well as preparation method and application thereof
CN109244440B (en) NiO-ZnO composite material, preparation method thereof and lithium ion battery
CN110120519B (en) Precursor of lithium-rich manganese-based positive electrode material with stacking structure and preparation method of lithium-rich manganese-based positive electrode material with stacking structure
CN112624198A (en) Method for synthesizing high-activity layered zinc ion secondary battery anode material by one-step method at room temperature

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant