CN108314092B - Foam nickel loaded nano rod-shaped cobalt molybdate and preparation method and application thereof - Google Patents

Foam nickel loaded nano rod-shaped cobalt molybdate and preparation method and application thereof Download PDF

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CN108314092B
CN108314092B CN201711481258.8A CN201711481258A CN108314092B CN 108314092 B CN108314092 B CN 108314092B CN 201711481258 A CN201711481258 A CN 201711481258A CN 108314092 B CN108314092 B CN 108314092B
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molybdate
solution
nickel
cobalt
hydrothermal
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CN108314092A (en
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闫东伟
孙学敏
胡小萍
李艳萍
侯立婷
曾宏
武英
况春江
周少雄
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Advanced Technology and Materials Co Ltd
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    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • H—ELECTRICITY
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    • 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
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • H01M4/626—Metals
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
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    • 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 discloses foam nickel loaded nano rodlike cobalt molybdate and a preparation method and application thereof. The preparation method of the foam nickel-loaded nano rodlike cobalt molybdate comprises the following steps: cleaning foamed nickel; preparation steps of the reaction solution: respectively dissolving molybdate and cobalt salt in water, and stirring and dissolving to obtain molybdate solution and cobalt salt solution; then, dropwise adding the molybdate solution into the cobalt salt solution, and continuously stirring to obtain a uniformly mixed reaction solution; a hydrothermal treatment step; and a step of treating the hydrothermal product. According to the invention, a hydrothermal synthesis method is adopted, and the nano-rod-shaped cobalt molybdate grows on the surface of the foamed nickel, so that the conductivity of the cobalt molybdate is effectively improved; the uniform nanorod structure shortens the intercalation distance of lithium ions; the material is used for the lithium ion battery cathode material, and can effectively improve the conductivity, rate capability and the like of the lithium ion battery cathode material; in addition, the invention has the advantages of simple preparation process, convenient operation, good reproducibility and the like.

Description

Foam nickel loaded nano rod-shaped cobalt molybdate and preparation method and application thereof
Technical Field
The invention relates to foam nickel loaded nano rodlike cobalt molybdate and a preparation method and application thereof, belonging to the field of inorganic material synthesis and application thereof in the electrochemical field.
Background
The transition metal oxide is used as the cathode material of the lithium ion battery, and is expected to replace the traditional carbon-based cathode material by the high theoretical capacity and energy density, excellent cycle life and rate capability, abundant mineral resources, simple preparation process and the like. However, during charge and discharge, the structure is inevitably damaged by insertion and extraction of lithium ions, alloying and dealloying, oxidation and reduction reactions, and the like, and collapse of the structure, pulverization of the active material, and the like occur, resulting in adverse effects such as increase in internal resistance, capacity fade, and reduction in cycle life of the battery.
A conductive substrate is used as a carrier to grow binary or multi-element transition metal oxide with a nano structure. The special combination structure and the nanometer size can improve the electrochemical performance of the transition metal oxide in various aspects. (1) The conductive substrate is used as a carrier, so that the conductivity of the transition metal oxide can be enhanced, and no conductive agent is required to be added; (2) binary or multiple transition metal oxides. On one hand, due to the synergistic effect, the expansion of the structure can be relieved by different expansion coefficients of all transition metal elements in the process of storing lithium; on the other hand, binary or multi-element transition metal oxide is not mixed with simple oxide in the traditional sense, and the complex chemical structure of the binary or multi-element transition metal oxide can generate alloying reaction with more lithium, so that the capacity is improved; in addition, binary or multi-element transition metal oxides show higher conductivity than single oxides; (3) the nano structure has a high specific surface area, can improve the contact area of an active substance and an electrolyte, provides more active sites, and can shorten the intercalation/deintercalation distance of lithium ions, improve the electrochemical performance and the like.
Recently Wang Yu et al ("ports Iron cobalt nanoparticles Array on Nickel phosphor-ion Batteries Materials with Enhanced electrochemical Performance", ACS Appl. Mater. Interface, 2016,8(2), pp 1351-: under the current density of 0.01-3V and 100mA/g,1962 mAh.g-1Reversible specific capacity (coulombic efficiency 92-95%); at a current density of 2000mA/g, there was 875mAh g-1The discharge specific capacity of the material shows excellent rate performance. Cobalt molybdate is a lithium ion battery anode material with great potential in molybdate, and the search literature shows that: reports of foamed nickel loaded cobalt molybdate as a negative electrode material of a lithium ion battery are not published yet, and the foamed nickel loaded cobalt molybdate is currently reported as a positive electrode material of a supercapacitor, for example: GK Veerasaborani, improved biochemical performance of binder-free CoMoO4 nanoplate arrays @ Ni foamex using redox additive electrolyte, Journal of Power Source, 2016,306: 378-positive 386, Z Zhang, etc., Formation of hierarchical CoO 4@ MnO2 core-shell nanoshiettar on nic foam with market enhanced reactive properties, Journal of Power Source, 2015,296: 162-positive 168, and Chinese patent CN 104752071A. In the patent, a hydrothermal synthesis method is adopted for the first time to successfully prepare the foam nickel-loaded nano rodlike cobalt molybdate and the foam nickel-loaded nano rodlike cobalt molybdate is used for a lithium ion battery cathode material.
Disclosure of Invention
The invention provides a foam nickel loaded nano rodlike cobalt molybdate, and also provides a preparation method and application of the foam nickel loaded nano rodlike cobalt molybdate.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of foam nickel loaded nano rodlike cobalt molybdate comprises the following steps:
cleaning foamed nickel;
preparation steps of the reaction solution: respectively dissolving molybdate and cobalt salt in water, and stirring to obtain a molybdate solution and a cobalt salt solution; then dropwise adding the molybdate solution into the cobalt salt solution, and continuously stirring to obtain a uniformly mixed reaction solution;
a hydrothermal treatment step: transferring the reaction solution into a reaction kettle, placing the cleaned nickel foam, and carrying out hydrothermal treatment in a closed environment to obtain a hydrothermal product;
and (3) treating the hydrothermal product: and naturally cooling the hydrothermal product to room temperature, and washing and drying to obtain the foam nickel-loaded nano rodlike cobalt molybdate.
The invention makes molybdate and cobalt salt solution react under high pressure and high temperature to generate nano-rod-shaped cobalt molybdate which is loaded on the foam nickel.
In the above preparation method, as a preferred embodiment, in the step of cleaning the nickel foam, the nickel foam is sequentially put into ethanol, deionized water, hydrochloric acid, acetone, ethanol, and deionized water for ultrasonic cleaning to obtain cleaned nickel foam; this cleaning step allows very good removal of the various impurities adsorbed on the nickel foam, so as to obtain a higher purity nickel foam, in order to improve the properties of the final product. Preferably, the concentration of the hydrochloric acid is 0.5-1mol/L (such as 0.55mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L, 0.98 mol/L); the ultrasonic cleaning time is 10-20min (such as 11min, 12min, 13min, 14min, 15min, 17min, 18min, 19min), and the power is 2-5 Kw.
In the above-mentioned preparation method, as a preferred embodiment, in the step of preparing the reaction solution, the continuous stirring means that the stirring is continued while the molybdate solution is added dropwise; preferably, the duration of the continuous stirring is 8-15min (such as 9min, 12min, 13min, 14 min).
In the above preparation method, as a preferred embodiment, in the step of preparing the reaction solution, the molybdate is sodium molybdate or ammonium molybdate; the cobalt salt is cobalt acetate or cobalt nitrate.
In the above production method, as a preferred embodiment, in the step of producing the reaction solution, the molar ratio of molybdenum in the molybdate to cobalt in the cobalt salt in the reaction solution is 1 to 1.6:1 (e.g., 1.05:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.45:1), and more preferably 1 to 1.2:1 (e.g., 1.02:1, 1.05:1, 1.08:1, 1.12:1, 1.15:1, 1.18: 1).
In the above production method, as a preferable embodiment, the concentration of molybdenum in the reaction solution is 5 to 20mmol/L (e.g., 6mmol/L, 8mmol/L, 10mmol/L, 12mmol/L, 14mmol/L, 16mmol/L, 18 mmol/L).
In the above preparation method, as a preferred embodiment, in the hydrothermal treatment step, the ratio of the mass of the nickel foam to the total mass of the molybdate and the cobalt salt is 2:1 to 10:1 (e.g., 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9: 1).
In the above production method, as a preferred embodiment, in the hydrothermal treatment step, the heating method of the hydrothermal treatment is electric heating or microwave heating.
In the above preparation method, as a preferred embodiment, in the hydrothermal treatment step, the temperature of the hydrothermal treatment is 140-; more preferably, the temperature of the hydrothermal treatment is 170-190 ℃ (such as 172 ℃, 175 ℃, 180 ℃, 185 ℃ and 188 ℃), and the holding time is 6-10h (such as 6.5h, 7h, 7.5h, 8h, 8.5h, 9h and 9.5 h).
In the above preparation method, as a preferred embodiment, in the step of treating the hydrothermal product, the washing refers to washing with water and ethanol alternately for a total of six times.
In the above preparation method, as a preferred embodiment, in the step of treating the hydrothermal product, the temperature of the drying treatment is 50 to 180 ℃ (e.g., 52 ℃, 54 ℃, 60 ℃, 70 ℃, 90 ℃, 110 ℃, 130 ℃, 140 ℃, 145 ℃, 148 ℃, 150 ℃, 160 ℃, 170 ℃, 178 ℃), and the holding time is 6 to 15h (e.g., 6.5h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 14.5 h); more preferably, the drying treatment is carried out at a temperature of 70-90 deg.C (e.g., 72 deg.C, 75 deg.C, 80 deg.C, 85 deg.C, 88 deg.C) for a period of 8-12h (e.g., 8.5h, 9h, 9.5h, 10h, 10.5h, 11h, 11.5 h).
The foam nickel-supported nano-rod-shaped cobalt molybdate prepared by the method uniformly covers the surface of the foam nickel, and the size of the nano-rod-shaped cobalt molybdate supported on the foam nickel is as follows: the diameter of the nano rod is 60-80 nanometers, and the length is 200-300 nanometers.
The foam nickel-loaded nano rod-shaped cobalt molybdate is applied to a lithium ion battery as a negative electrode material.
Compared with the prior art, the invention has the beneficial effects that:
1) according to the invention, a hydrothermal synthesis method is adopted, and the nano-rod-shaped cobalt molybdate grows on the surface of the foamed nickel, so that the conductivity of the cobalt molybdate is effectively improved; the uniform nanorod structure shortens the intercalation distance of lithium ions; the material is used for the lithium ion battery cathode material, and can effectively improve the conductivity, rate capability and the like of the lithium ion battery cathode material;
2) the invention has the advantages of simple preparation process, convenient operation, good reproducibility and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is an X-ray diffraction (XRD) pattern of the foamed nickel-supported nano-rod-shaped cobalt molybdate prepared in example 1 of the present invention.
Fig. 2 is a Scanning Electron Microscope (SEM) photograph of the foamed nickel-supported nano-rod-shaped cobalt molybdate according to example 1 of the present invention, in which (a) is a low-magnification SEM of the foamed nickel-supported nano-rod-shaped cobalt molybdate, and (b) is a high-magnification SEM of the foamed nickel-supported nano-rod-shaped cobalt molybdate.
Fig. 3 is a CV curve diagram of an experimental battery assembled by using the foam nickel-supported nano rod-shaped cobalt molybdate as a raw material in example 1 of the present invention at 0.01 to 3.0V.
Fig. 4 is a capacity-voltage curve diagram of an experimental battery assembled by using the foam nickel-supported nano-rod-shaped cobalt molybdate as a raw material, which is prepared in example 1 of the present invention, at 0.01 to 3.0V.
Fig. 5 is a graph of capacity (coulombic efficiency) -cycle curve at 0.01-3.0V for an experimental battery assembled by using the foam nickel supported nano-rod-shaped cobalt molybdate prepared in example 1 of the present invention as a raw material.
FIG. 6 is a graph of capacity-cycle curves of the foam nickel supported nano-rod-shaped cobalt molybdate prepared in example 1 of the present invention at different currents.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments, which are not limited to the following embodiments.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The various reagents and starting materials used in the examples are all commercially available products.
Example 1
This example prepares the foamed nickel supported nanorod cobalt molybdate by a hydrothermal method.
The preparation method comprises the following steps:
(1) cleaning of foamed nickel: taking small pieces (1 cm) with aperture of about 250um2) The foamed nickel is sequentially put into 5ml of ethanol, 5ml of deionized water, 5ml of 1mol/L hydrochloric acid, 5ml of acetone, 5ml of ethanol and 5ml of deionized water, the ultrasonic cleaning time in each cleaning solution is 10min, and the ultrasonic power is 3 KW;
(2) preparation of reaction solution: 0.1694g of sodium molybdate dihydrate (0.7mmol) and 0.2037g of cobalt nitrate hexahydrate (0.7mmol) are respectively weighed and dissolved in 35ml of deionized water, and after stirring and dissolving, a sodium molybdate solution and a cobalt nitrate solution are obtained; then dropwise adding the sodium molybdate solution into the cobalt nitrate solution, stirring while dropwise adding, and continuing for 10min to obtain a uniformly mixed reaction solution;
(3) a hydrothermal treatment step: transferring the reaction solution into a 100ml sealed reaction kettle, placing the small piece of cleaned nickel foam in the step (1), and performing hydrothermal treatment by utilizing electric heating at the temperature of 180 ℃ for 8 hours to obtain a hydrothermal product;
(4) and (3) treating the hydrothermal product: and naturally cooling the obtained hydrothermal product to room temperature, alternately cleaning the hydrothermal product by using water and ethanol for six times, and drying the hydrothermal product in a constant-temperature drying oven at the temperature of 80 ℃ for 12 hours to obtain a target product, namely the foamed nickel loaded nano rod-shaped cobalt molybdate.
And (3) performing structural characterization on the finally prepared foam nickel-loaded nano rodlike cobalt molybdate sample by using an X-ray powder diffractometer, wherein the result is shown in figure 1.
The finally prepared foam nickel-loaded nano rodlike cobalt molybdate sample is characterized in morphology by adopting a scanning electron microscope, and the result is shown in fig. 2, wherein (a) in fig. 2 shows that a layer of cobalt molybdate covers the surface of the foam nickel, and excessive cobalt molybdate is attached to the surface layer of the cobalt molybdate in a rodlike manner; as can be seen from (b) in fig. 2, the nano-rod-shaped cobalt molybdate with uniform morphology uniformly covers the surface of the foamed nickel. The diameter of the nano rod is 60-70 nanometers, and the length is 200-250 nanometers.
The nickel foam loaded nano-rod-shaped cobalt molybdate negative electrode material prepared in the embodiment, acetylene black and polyvinylidene fluoride are ground in an N-methylpyrrolidone (NMP) medium according to the mass ratio of 7:2:1 to prepare slurry, and the slurry is coated on a copper foil, dried and sliced. 1M LiPF with metal lithium sheet as counter electrode and polypropylene film as diaphragm6And (EC + DMC + EMC) is electrolyte, and a 2032 model experimental battery is assembled for electrochemical performance test.
As shown in FIG. 3, it is a CV curve graph of the foamed nickel loaded nanorod cobalt molybdate measured at 0.01-3V at a scan rate of 0.1 mV/s. The second circle and the third circle are basically superposed except the first circle, and excellent cycle performance is shown; under the first cathode scanning mode, the cobalt molybdate structure is damaged, divalent cobalt ions and tetravalent molybdenum lithium ions are subjected to reduction reaction and are respectively reduced into metal cobalt and metal molybdenum, and the alloying performance with lithium is not obvious; under the anode scanning mode, the metal cobalt and the metal molybdenum are oxidized into bivalent cobalt ions, tetravalent molybdenum ions and hexavalent molybdenum ions respectively.
Fig. 4 and 5 are a graph of capacity-voltage curve and a graph of capacity (coulombic efficiency) -cycle curve of the prepared foam nickel supported nano-rod-shaped cobalt molybdate, respectively. As can be seen from FIGS. 4 and 5, the voltage is 500mA · g at 0.01-3V-1After 100 cycles, the capacity is still maintained at 760mAh g-1The reversible specific capacity of (a).
As shown in FIG. 6, is at 0.01-3V, respectivelyCapacity-cycle plot measured at current density. As can be seen from the figure, at 2000mA · g-1The foam nickel supported nano-rod-shaped cobalt molybdate shows 480 mAh.g at high current density-1When the current density is reduced to 100mA g-1The reversible specific capacity reaches 1500 mAh.g-1And excellent rate performance is shown.
Example 2
This example prepares the foamed nickel supported nanorod cobalt molybdate by a hydrothermal method.
The preparation method comprises the following steps:
(1) cleaning of foamed nickel: taking small pieces (1 cm) with aperture of about 250um2) The foamed nickel is sequentially put into 5ml of ethanol, 5ml of deionized water, 5ml of 1mol/L hydrochloric acid, 5ml of acetone, 5ml of ethanol and 5ml of deionized water, and the ultrasonic cleaning time in each cleaning solution is 10 min;
(2) preparation of reaction solution: respectively weighing 0.1694g of sodium molybdate dihydrate (0.7mmol) and 0.2037g of cobalt nitrate hexahydrate (0.7mmol) and dissolving in 35ml of deionized water, stirring and dissolving, then dropwise adding the sodium molybdate solution into the cobalt nitrate solution, stirring while dropwise adding, and continuing for 10min to obtain a uniformly mixed reaction solution;
(3) a hydrothermal treatment step: transferring the reaction solution into a 100ml sealed reaction kettle, placing a piece of cleaned foamed nickel in the step (1), and performing hydrothermal treatment by using electric heating at 160 ℃ for 12 hours to obtain a hydrothermal product;
(4) and (3) treating the hydrothermal product: and naturally cooling the obtained hydrothermal product to room temperature, alternately cleaning with water and ethanol for six times in total, and drying in a constant-temperature drying oven at the temperature of 80 ℃ for 12 hours to obtain the target product, namely the foamed nickel loaded nano rod-shaped cobalt molybdate. The diameter of the nano rod is 60-80 nanometers, and the length is 200-300 nanometers.
Electrochemical performance test of the foam nickel supported nano rod-shaped cobalt molybdate prepared in this example: the experimental battery is assembled by using the foam nickel-loaded nano rodlike cobalt molybdate prepared in the embodiment as a raw material, and the assembling method is the same as that of the experimental battery
Example 1, the results are shown in table 1.
Table 1 example 2 electrochemical performance of nickel foam supported nano-rod cobalt molybdate as negative electrode material
Figure BDA0001533848780000071
As is clear from Table 1, the voltage was controlled at 500mA · g at 0.01-3V-1After 100 cycles, the capacity was still 776mAh g-1The reversible specific capacity of (a).
While the capacity-cycle curves measured at different current densities of 0.01 to 3V, it can be seen that the current density was 2000mA · g-1The foam nickel supported nano-rod-shaped cobalt molybdate shows 496 mAh.g at high current density-1When the current density is reduced to 100mA g-1The reversible specific capacity reaches 1450 mAh.g-1And excellent rate performance is shown.
Example 3
This example prepares the foamed nickel supported nanorod cobalt molybdate by a hydrothermal method.
The preparation method comprises the following steps:
(1) cleaning of foamed nickel: taking small pieces (1 cm) with aperture of about 250um2) The foamed nickel is sequentially put into 5ml of ethanol, 5ml of deionized water, 5ml of 1mol/L hydrochloric acid, 5ml of acetone, 5ml of ethanol and 5ml of deionized water, the ultrasonic cleaning time in each cleaning solution is 10min, and the ultrasonic power is 3 KW;
(2) preparation of reaction solution: respectively weighing 0.1694g of sodium molybdate dihydrate (0.7mmol) and 0.2037g of cobalt nitrate hexahydrate (0.7mmol) and dissolving in 35ml of deionized water, stirring and dissolving, then dropwise adding the sodium molybdate solution into the cobalt nitrate solution, stirring while dropwise adding, and continuing for 10min to obtain a uniformly mixed reaction solution;
(3) a hydrothermal treatment step: transferring the reaction liquid into a 100ml sealed reaction kettle, placing a piece of cleaned foamed nickel obtained in the step (1), and performing hydrothermal treatment by using electric heating at the temperature of 180 ℃ for 12 hours to obtain a hydrothermal product;
(4) and (3) treating the hydrothermal product: and naturally cooling the obtained hydrothermal product to room temperature, alternately cleaning the hydrothermal product with water and ethanol for six times, and drying the hydrothermal product in a constant-temperature drying oven at the temperature of 80 ℃ for 12 hours to obtain the target product, namely the foamed nickel loaded nano rod-shaped cobalt molybdate. The diameter of the nano rod is 60-80 nanometers, and the length is 200-300 nanometers.
Electrochemical performance test of the foam nickel supported nano rod-shaped cobalt molybdate prepared in this example: the experimental battery is assembled by using the foam nickel-loaded nano rodlike cobalt molybdate prepared in the embodiment as a raw material, and the assembling method is the same as that of the experimental battery
Example 1, see table 2 for results.
Table 2 example 3 electrochemical performance of nickel foam supported nano-rod cobalt molybdate as negative electrode material
Figure BDA0001533848780000081
Figure BDA0001533848780000091
As is clear from Table 2, the voltage was controlled at 500mA · g at 0.01-3V-1After 100 cycles, the capacity is still maintained at 739mAh g-1The reversible specific capacity of (a).
While the capacity-cycle curves measured at different current densities of 0.01 to 3V, it can be seen that the current density was 2000mA · g-1The foam nickel supported nano-rod-shaped cobalt molybdate shows 483mAh g at high current density-1When the current density is reduced to 100mA g-1The reversible specific capacity reaches 1369 mAh.g-1And excellent rate performance is shown.
Example 4
This example prepares the foamed nickel supported nanorod cobalt molybdate by a hydrothermal method.
The preparation method comprises the following steps:
(1) cleaning of foamed nickel: taking small pieces (1 cm) with aperture of about 250um2) The foamed nickel is sequentially put into 5ml of ethanol, 5ml of deionized water, 5ml of 1mol/L hydrochloric acid, 5ml of acetone, 5ml of ethanol and 5ml of deionized water, and the ultrasonic waves in the washing solutionsThe cleaning time is 10 min;
(2) preparation of reaction solution: respectively weighing 0.2033g of sodium molybdate dihydrate (0.84mmol) and 0.2037g of cobalt nitrate hexahydrate (0.7mmol) which are respectively dissolved in 35ml of deionized water, stirring and dissolving, then dropwise adding the sodium molybdate solution into the cobalt nitrate solution, and stirring for 10min while dropwise adding to obtain a uniformly mixed reaction solution;
(3) a hydrothermal treatment step: transferring the reaction liquid into a 100ml sealed reaction kettle, placing a piece of cleaned foamed nickel obtained in the step (1), and performing hydrothermal treatment by using electric heating at the temperature of 180 ℃ for 8 hours to obtain a hydrothermal product;
(4) and (3) treating the hydrothermal product: and naturally cooling the obtained hydrothermal product to room temperature, alternately cleaning the hydrothermal product with water and ethanol for six times, and drying the hydrothermal product in a constant-temperature drying oven at the temperature of 80 ℃ for 12 hours to obtain the target product, namely the foamed nickel loaded nano rod-shaped cobalt molybdate. The diameter of the nano rod is 60-80 nanometers, and the length is 200-300 nanometers.
Electrochemical performance test of the foam nickel-supported nano rod-shaped cobalt molybdate prepared in this example: an experimental battery was assembled by using the nickel foam supported nano-rod cobalt molybdate prepared in this example as a raw material, the assembling method was the same as in example 1, and the results are shown in table 3.
Table 3 example 4 electrochemical performance of nickel foam supported nano-rod cobalt molybdate as negative electrode material
Figure BDA0001533848780000101
As is clear from the table, the voltage was controlled at 500mA · g at 0.01 to 3V-1At a current density of 747mAh g after 100 cycles-1The reversible specific capacity of (a).
While the capacity-cycle curves measured at different current densities of 0.01 to 3V, it can be seen that the current density was 2000mA · g-1The foamed nickel supported nano-rod-shaped cobalt molybdate shows 488 mAh.g at high current density of (2)-1When the current density is reduced to 100mA g-1The reversible specific capacity reaches 1387 mAh.g-1Exhibit an excellent magnificationRate capability.
Example 5
This example prepares the foamed nickel supported nanorod cobalt molybdate by a hydrothermal method.
The preparation method comprises the following steps:
(1) cleaning of foamed nickel: taking small pieces (1 cm) with aperture of about 250um2) The foamed nickel is sequentially put into 5ml of ethanol, 5ml of deionized water, 5ml of 1mol/L hydrochloric acid, 5ml of acetone, 5ml of ethanol and 5ml of deionized water, and the ultrasonic cleaning time in each cleaning solution is 10 min;
(2) preparation of reaction solution: respectively weighing 0.2033g of sodium molybdate dihydrate (0.84mmol) and 0.2037g of cobalt nitrate hexahydrate (0.7mmol) and dissolving in 35ml of deionized water, stirring and dissolving, then dropwise adding the sodium molybdate solution into the cobalt nitrate solution, and stirring for 10min while dropwise adding to obtain a uniformly mixed reaction solution;
(3) a hydrothermal treatment step: transferring the reaction liquid into a 100ml sealed reaction kettle, placing a piece of cleaned foamed nickel obtained in the step (1), and performing hydrothermal treatment by using electric heating at the temperature of 180 ℃ for 12 hours to obtain a hydrothermal product;
(4) and (3) treating the hydrothermal product: and naturally cooling the obtained hydrothermal product to room temperature, alternately cleaning the hydrothermal product with water and ethanol for six times, and drying the hydrothermal product in a constant-temperature drying oven at the temperature of 80 ℃ for 12 hours to obtain the target product, namely the foamed nickel loaded nano rod-shaped cobalt molybdate. The diameter of the nano rod is 60-80 nanometers, and the length is 200-300 nanometers.
Electrochemical performance test of the foam nickel supported nano rod-shaped cobalt molybdate prepared in this example: the experimental battery is assembled by using the foam nickel-loaded nano rodlike cobalt molybdate prepared in the embodiment as a raw material, and the assembling method is the same as that of the experimental battery
Example 1, see table 4 for results.
Table 4 example 5 electrochemical performance of nickel foam supported nano-rod cobalt molybdate as negative electrode material
Figure BDA0001533848780000111
As can be seen from the table, in the range of 0.01 to 3V,at 500mA · g-1After 100 cycles, the capacity is still kept at 709mAh g-1The reversible specific capacity of (a).
While the capacity-cycle curves measured at different current densities of 0.01 to 3V, it can be seen that the current density was 2000mA · g-1The foam nickel supported nano-rod-shaped cobalt molybdate shows 445 mAh.g at high current density-1When the current density is reduced to 100mA g-1The reversible specific capacity reaches 1223 mAh.g-1And excellent rate performance is shown.
Example 6
This example prepares the foamed nickel supported nanorod cobalt molybdate by a hydrothermal method.
The preparation method comprises the following steps:
(1) cleaning of foamed nickel: taking small pieces (1 cm) with aperture of about 250um2) The foamed nickel is sequentially put into 5ml of ethanol, 5ml of deionized water, 5ml of 1mol/L hydrochloric acid, 5ml of acetone, 5ml of ethanol and 5ml of deionized water, and the ultrasonic cleaning time in each cleaning solution is 10 min;
(2) preparation of reaction solution: respectively weighing 0.2033g of sodium molybdate dihydrate (0.84mmol) and 0.2037g of cobalt nitrate hexahydrate (0.7mmol) and dissolving in 35ml of deionized water, stirring and dissolving, then dropwise adding the sodium molybdate solution into the cobalt nitrate solution, and stirring for 10min while dropwise adding to obtain a uniformly mixed reaction solution;
(3) a hydrothermal treatment step: transferring the reaction liquid into a 100ml sealed reaction kettle, placing a piece of cleaned foamed nickel obtained in the step (1), and performing hydrothermal treatment by using electric heating at the temperature of 180 ℃ for 8 hours to obtain a hydrothermal product;
(4) and (3) treating the hydrothermal product: and naturally cooling the obtained hydrothermal product to room temperature, alternately cleaning the hydrothermal product with water and ethanol for six times, and drying the hydrothermal product in a constant-temperature drying oven at the temperature of 120 ℃ for 12 hours to obtain the target product, namely the foamed nickel loaded nano rod-shaped cobalt molybdate. The diameter of the nano rod is 60-80 nanometers, and the length is 200-300 nanometers.
Electrochemical performance test of the foam nickel-supported nano rod-shaped cobalt molybdate prepared in this example: an experimental battery was assembled by using the nickel foam supported nano-rod cobalt molybdate prepared in this example as a raw material, the assembling method was the same as in example 1, and the results are shown in table 5.
Table 5 example 6 electrochemical performance of nickel foam supported nano-rod cobalt molybdate as negative electrode material
Figure BDA0001533848780000121
As can be seen from the graph, the voltage is 500mA · g at 0.01 to 3V-1After 100 cycles, the capacity is still maintained at 716mAh g-1The reversible specific capacity of (a).
While the capacity-cycle curves measured at different current densities of 0.01 to 3V, it can be seen that the current density was 2000mA · g-1The foam nickel supported nano-rod-shaped cobalt molybdate shows 453mAh g at a high current density-1When the current density is reduced to 100mA g-1The reversible specific capacity reaches 1305 mAh.g-1And excellent rate performance is shown.
Example 7
This example prepares the foamed nickel supported nanorod cobalt molybdate by a hydrothermal method.
The preparation method comprises the following steps:
(1) cleaning of foamed nickel: taking small pieces (1 cm) with aperture of about 250um2) The foamed nickel is sequentially put into 5ml of ethanol, 5ml of deionized water, 5ml of 1mol/L hydrochloric acid, 5ml of acetone, 5ml of ethanol and 5ml of deionized water, and the ultrasonic cleaning time in each cleaning solution is 10 min;
(2) preparation of reaction solution: respectively weighing 0.27104g of sodium molybdate dihydrate (1.12mmol) and 0.2037g of cobalt nitrate hexahydrate (0.7mmol) and dissolving in 35ml of deionized water, stirring and dissolving, then dropwise adding the sodium molybdate solution into the cobalt nitrate solution, and stirring for 10min while dropwise adding to obtain a uniformly mixed reaction solution;
(3) a hydrothermal treatment step: transferring the reaction liquid into a 100ml sealed reaction kettle, placing a piece of cleaned foamed nickel obtained in the step (1), and performing hydrothermal treatment by using electric heating at 160 ℃ for 12 hours to obtain a hydrothermal product;
(4) and (3) treating the hydrothermal product: and naturally cooling the obtained hydrothermal product to room temperature, sequentially washing with water and ethanol for three times, and drying in a constant-temperature drying oven at the temperature of 80 ℃ for 12 hours to obtain the target product, namely the foamed nickel loaded nano rod-shaped cobalt molybdate. The diameter of the nano rod is 60-80 nanometers, and the length is 200-300 nanometers.
Electrochemical performance test of the foam nickel supported nano rod-shaped cobalt molybdate prepared in this example: the experimental battery is assembled by using the foam nickel-loaded nano rodlike cobalt molybdate prepared in the embodiment as a raw material, and the assembling method is the same as that of the experimental battery
Example 1, see table 6 for results.
Table 6 example 7 electrochemical performance of nickel foam supported nano-rod cobalt molybdate as negative electrode material
Figure BDA0001533848780000131
At 0.01-3V, at 500mA · g-1After 100 cycles, the capacity is still maintained at 702mAh g-1The reversible specific capacity of (a).
While the capacity-cycle curves measured at different current densities of 0.01 to 3V, it can be seen that the current density was 2000mA · g-1The foam nickel supported nano-rod-shaped cobalt molybdate shows 442 mAh.g at high current density-1When the current density is reduced to 100mA g-1The reversible specific capacity reaches 1211mAh g-1And excellent rate performance is shown.
Examples 8 to 11
Examples 8 to 11 except that the hydrothermal reaction temperature and time were different from those of example 1, the preparation process parameters were the same as those of example 1, the electrochemical performance test method was the same as that of example 1, and the hydrothermal synthesis conditions and test results of these four examples are shown in table 7.
Table 7 examples 8-11 electrochemical performance of nickel foam supported nano-rod cobalt molybdate as negative electrode material
Figure BDA0001533848780000141
Examples 12 to 15
Examples 12-15 the same procedure as in example 1 was repeated except that the reaction products were dried at different temperatures and times in the same manner as in example 1, and the electrochemical properties were measured in the same manner as in example 1, and the drying temperatures and times and the results of the test were shown in Table 8 for the reaction products of these four examples.
Table 8 examples 12-15 electrochemical performance of nickel foam supported nano-rod cobalt molybdate as anode material
Figure BDA0001533848780000142
Figure BDA0001533848780000151
Example 16
The cleaning method of the foamed nickel in this example is different from that in example 1, the other processes are the same as in example 1, and the cleaning method of the foamed nickel in this example is as follows: taking foamed nickel with the aperture of about 250um and a small piece (1cm2), and sequentially putting the foamed nickel into 5ml of ethanol, 5ml of deionized water, 5ml of 1mol/L hydrochloric acid and 5ml of deionized water, wherein the ultrasonic cleaning time in each cleaning solution is 10 min. The electrochemical performance test method is also the same as the example, and the test results are shown in Table 9.
Table 9 example 16 electrochemical performance of nickel foam supported nano-rod cobalt molybdate as negative electrode material
Figure BDA0001533848780000152
Example 17
This example is shown with the following exception: the process was the same as in example 1 except that the sodium molybdate solution was added dropwise to the cobalt nitrate solution while stirring, and the stirring time was 3 min. The electrochemical performance test method is also the same as the example, and the test results are shown in Table 10.
Table 10 example 17 electrochemical performance of nickel foam supported nano-rod cobalt molybdate as negative electrode material
Figure BDA0001533848780000153

Claims (3)

1. A preparation method of foam nickel-supported nano rodlike cobalt molybdate is characterized in that the foam nickel-supported nano rodlike cobalt molybdate is used as a negative electrode material of a lithium ion battery, and the preparation method is any one of the following methods:
the method comprises the following steps:
(1) cleaning of foamed nickel: taking the pore diameter of 250 μm, 1cm2The small piece of foamed nickel is sequentially put into 5mL of ethanol, 5mL of deionized water, 5mL of 1mol/L hydrochloric acid, 5mL of acetone, 5mL of ethanol and 5mL of deionized water, the ultrasonic cleaning time in each cleaning solution is 10min, and the ultrasonic power is 3 KW;
(2) preparation of reaction solution: respectively weighing 0.1694g of sodium molybdate dihydrate and 0.2037g of cobalt nitrate hexahydrate, dissolving in 35mL of deionized water, and stirring to dissolve to obtain a sodium molybdate solution and a cobalt nitrate solution; then dropwise adding the sodium molybdate solution into the cobalt nitrate solution, stirring while dropwise adding, and continuing for 10min to obtain a uniformly mixed reaction solution;
(3) a hydrothermal treatment step: transferring the reaction solution into a 100mL sealed reaction kettle, placing the cleaned small piece of foamed nickel in the step (1), and performing hydrothermal treatment by using electric heating at 180 ℃ for 8 hours to obtain a hydrothermal product;
(4) and (3) treating the hydrothermal product: naturally cooling the obtained hydrothermal product to room temperature, alternately cleaning with water and ethanol for six times, and drying in a constant-temperature drying oven at 80 ℃ for 12 hours to obtain the foam nickel-loaded nano rod-shaped cobalt molybdate;
the second method comprises the following steps:
(1) cleaning of foamed nickel: taking the pore diameter of 250 μm, 1cm2The small piece of foamed nickel is sequentially put into 5mL of ethanol, 5mL of deionized water, 5mL of 1mol/L hydrochloric acid, 5mL of acetone, 5mL of ethanol and 5mL of deionized water, and the ultrasonic cleaning time in each cleaning solution is equalIs 10 min;
(2) preparation of reaction solution: respectively weighing 0.1694g of sodium molybdate dihydrate and 0.2037g of cobalt nitrate hexahydrate, dissolving in 35mL of deionized water, stirring and dissolving, dropwise adding the sodium molybdate solution into the cobalt nitrate solution while stirring, and continuing for 10min to obtain a uniformly mixed reaction solution;
(3) a hydrothermal treatment step: transferring the reaction liquid into a 100mL sealed reaction kettle, placing the cleaned small piece of foamed nickel in the step (1), and performing hydrothermal treatment by using electric heating at 160 ℃ for 12 hours to obtain a hydrothermal product;
(4) and (3) treating the hydrothermal product: naturally cooling the obtained hydrothermal product to room temperature, alternately cleaning with water and ethanol for six times in total, and drying in a constant-temperature drying oven at 80 ℃ for 12 hours to obtain foam nickel-loaded nano rod-shaped cobalt molybdate;
the third method comprises the following steps:
(1) cleaning of foamed nickel: taking the pore diameter of 250 μm, 1cm2The small piece of foamed nickel is sequentially put into 5mL of ethanol, 5mL of deionized water, 5mL of 1mol/L hydrochloric acid, 5mL of acetone, 5mL of ethanol and 5mL of deionized water, the ultrasonic cleaning time in each cleaning solution is 10min, and the ultrasonic power is 3 KW;
(2) preparation of reaction solution: respectively weighing 0.1694g of sodium molybdate dihydrate and 0.2037g of cobalt nitrate hexahydrate, dissolving in 35mL of deionized water, stirring and dissolving, dropwise adding the sodium molybdate solution into the cobalt nitrate solution while stirring, and continuing for 10min to obtain a uniformly mixed reaction solution;
(3) a hydrothermal treatment step: transferring the reaction liquid into a 100mL sealed reaction kettle, placing a piece of cleaned foamed nickel obtained in the step (1), and performing hydrothermal treatment by using electric heating at 180 ℃ for 12 hours to obtain a hydrothermal product;
(4) and (3) treating the hydrothermal product: naturally cooling the obtained hydrothermal product to room temperature, alternately cleaning the hydrothermal product with water and ethanol for six times, and drying the hydrothermal product in a constant-temperature drying oven at the temperature of 80 ℃ for 12 hours to obtain the foam nickel-loaded nano rod-shaped cobalt molybdate;
the method four comprises the following steps:
(1) cleaning of foamed nickel:taking the pore diameter of 250 μm, 1cm2The small piece of foamed nickel is sequentially put into 5mL of ethanol, 5mL of deionized water, 5mL of 1mol/L hydrochloric acid, 5mL of acetone, 5mL of ethanol and 5mL of deionized water, and the ultrasonic cleaning time in each cleaning solution is 10 min;
(2) preparation of reaction solution: respectively weighing 0.2033g of sodium molybdate dihydrate and 0.2037g of cobalt nitrate hexahydrate, dissolving in 35mL of deionized water, stirring and dissolving, dropwise adding the sodium molybdate solution into the cobalt nitrate solution, and stirring while dropwise adding for 10min to obtain a uniformly mixed reaction solution;
(3) a hydrothermal treatment step: transferring the reaction liquid into a 100mL sealed reaction kettle, placing a piece of cleaned foamed nickel obtained in the step (1), and performing hydrothermal treatment by using electric heating at 180 ℃ for 8 hours to obtain a hydrothermal product;
(4) and (3) treating the hydrothermal product: naturally cooling the obtained hydrothermal product to room temperature, alternately cleaning the hydrothermal product with water and ethanol for six times, and drying the hydrothermal product in a constant-temperature drying oven at the temperature of 80 ℃ for 12 hours to obtain the foam nickel-loaded nano rod-shaped cobalt molybdate;
the method five comprises the following steps:
(1) cleaning of foamed nickel: taking the pore diameter of 250 μm, 1cm2The small piece of foamed nickel is sequentially put into 5mL of ethanol, 5mL of deionized water, 5mL of 1mol/L hydrochloric acid, 5mL of acetone, 5mL of ethanol and 5mL of deionized water, and the ultrasonic cleaning time in each cleaning solution is 10 min;
(2) preparation of reaction solution: respectively weighing 0.2033g of sodium molybdate dihydrate and 0.2037g of cobalt nitrate hexahydrate, dissolving in 35mL of deionized water, stirring and dissolving, dropwise adding the sodium molybdate solution into the cobalt nitrate solution, and stirring while dropwise adding for 10min to obtain a uniformly mixed reaction solution;
(3) a hydrothermal treatment step: transferring the reaction liquid into a 100mL sealed reaction kettle, placing a piece of cleaned foamed nickel obtained in the step (1), and performing hydrothermal treatment by using electric heating at 180 ℃ for 8 hours to obtain a hydrothermal product;
(4) and (3) treating the hydrothermal product: and naturally cooling the obtained hydrothermal product to room temperature, alternately cleaning the hydrothermal product with water and ethanol for six times, and drying the hydrothermal product in a constant-temperature drying oven at the temperature of 120 ℃ for 12 hours to obtain the foam nickel-loaded nano rod-shaped cobalt molybdate.
2. The foamed nickel-supported nano-rod-shaped cobalt molybdate prepared by the method of claim 1, wherein the nano-rod-shaped cobalt molybdate with uniform morphology uniformly covers the surface of the foamed nickel, and the size of the nano-rod-shaped cobalt molybdate supported on the foamed nickel is as follows: the diameter of the nano rod is 60-80 nanometers, and the length is 200-300 nanometers.
3. The use of the nickel foam supported nano rod-shaped cobalt molybdate according to claim 2 as a negative electrode material in a lithium ion battery.
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