CN117457876A - Nickel ion doped modified lithium molybdate nano material, preparation method thereof, negative plate and battery - Google Patents

Nickel ion doped modified lithium molybdate nano material, preparation method thereof, negative plate and battery Download PDF

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CN117457876A
CN117457876A CN202311562691.XA CN202311562691A CN117457876A CN 117457876 A CN117457876 A CN 117457876A CN 202311562691 A CN202311562691 A CN 202311562691A CN 117457876 A CN117457876 A CN 117457876A
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nickel
lithium
molybdate
source
lithium molybdate
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宋忠诚
蔡玉婷
孙丽侠
郁超
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Jiangsu University of Technology
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Jiangsu University of Technology
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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
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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

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Abstract

The embodiment of the application relates to a nickel ion doped modified lithium molybdate nano material and a preparation method thereof, a negative plate and a battery, and belongs to the technical field of lithium ion battery negative electrode materials. The embodiment of the application aims to solve the technical problems of rapid specific capacity decay and poor cycle performance caused by serious structural degradation and slow dynamics related to large volume change of a metal molybdate material due to Jahn-Teller distortion in the prior art. The nickel ion doped modified lithium molybdate nano material disclosed by the embodiment of the application has the chemical molecular formula: li (Li) 2 Mo 1‑x Ni x O 4 Wherein x is more than or equal to 0.03 and less than or equal to 0.1. According to the material provided by the embodiment of the application, the Jahn-Teller distortion is dealt with by doping transition metal nickel to construct a nanoscale lithium molybdate material, the phenomenon of rapid attenuation of specific capacity caused by poor circulation performance is reduced, and the electrochemical performance of lithium molybdate is improved.

Description

Nickel ion doped modified lithium molybdate nano material, preparation method thereof, negative plate and battery
Technical Field
The embodiment of the application belongs to the technical field of lithium ion battery negative electrode materials, and particularly relates to a nickel ion doped modified lithium molybdate nano material, a preparation method thereof, a negative electrode plate and a battery.
Background
Lithium Ion Batteries (LIBs) have important applications in mobile electronics and electric vehicles due to their high electromotive force and high energy density. However, the commercially used graphite anode material showed 372mAhg -1 Low theoretical capacity and low voltage plateau (relative to Li/Li) + About 0.1V) results in poor safety. Accordingly, various studies have been made to find a substitute for graphite anode materials having a high theoretical capacity, safety voltage and good cycle stability. The transition metal oxide has the advantages of better electrochemical performance, low cost, environmental friendliness, high natural abundance, good safety, strong corrosion resistance and the like compared with single oxide, is expected to meet the requirements of future energy storages, and attracts great attention in supercapacitor application.
The metal molybdate has low cost and higher theoretical capacity, and the molybdenum element is in Mo in the electrochemical reaction process 6+ /Mo 4+ Is considered a promising lithium battery material, but these high capacity materials suffer from severe structural degradation, unstable Solid Electrolyte Interface (SEI), and slow kinetics associated with large volume changes during lithiation/delithiation.
Disclosure of Invention
In view of this, the embodiment of the application provides a nickel ion doped modified lithium molybdate nano material, a preparation method thereof, a negative plate and a battery, so as to solve the technical problems of rapid specific capacity attenuation and poor cycle performance caused by serious structural degradation and slow dynamics related to large volume change of a metal molybdate material due to Jahn-Teller distortion.
An embodiment of the present application provides a modified lithium molybdate nanomaterial doped with nickel ions, where the chemical formula of the modified lithium molybdate nanomaterial is: li (Li) 2 Mo 1-x Ni x O 4 Wherein x is more than or equal to 0.03 and less than or equal to 0.1.
In some embodiments, which may include the embodiments described above, x has a value of 0.03, 0.05, 0.07, 0.1.
The second aspect of the embodiment of the application also provides a preparation method of the nickel ion doped modified lithium molybdate nano material, which comprises the following steps:
dissolving a molybdenum source, a lithium source, a nickel source and a certain amount of complexing agent in a proper amount of deionized water, and uniformly stirring to obtain a mixed solution; heating and stirring the mixed solution, and performing sol-gel treatment to obtain precursor gel; and heating and drying the precursor gel, and calcining to obtain the nickel ion doped modified lithium molybdate nano material.
In some embodiments, which may include the above embodiments, the lithium source, nickel source, molybdenum source are used in a molar ratio of Li: ni: mo of 2:x (1-x).
In some embodiments, which may include the embodiments described above, the calcination temperature is 450-600 ℃ and the calcination time is 8-12 hours.
In some embodiments, which may include the above embodiments, the nickel source is one or more of nickel nitrate, nickel sulfate, nickel hydroxide, nickel oxide; or (b)
The complexing agent is oxalic acid.
In some embodiments, which may include the above embodiments, the lithium source is one or more of lithium acetate, lithium hydroxide, lithium molybdate, lithium carbonate.
In some embodiments, which may include the above embodiments, the molybdenum source is one or more of molybdenum trioxide, ammonium molybdate, sodium molybdate, molybdenum chloride.
The third aspect of the embodiment of the application also provides a negative plate, which contains the nanomaterial or the nanomaterial prepared by the method.
The fourth aspect of the embodiment of the application also provides a battery, which comprises the negative electrode plate, a battery shell, a positive electrode plate, a separation membrane and electrolyte.
Compared with the prior art, the embodiment of the application has the following beneficial effects:
1. the preparation method of the embodiment of the application is simpler, reduces energy consumption and saves economic cost. The nickel-doped lithium molybdate material prepared by the method can meet the requirements of the market on the emerging energy driving technology;
2. the nickel-doped lithium molybdate material provided by the embodiment of the application has the initial discharge capacity of up to 759.2mAh/g under a small current (100 mA/g), has a higher theoretical capacity, is a promising lithium ion battery anode active material, and is more hopeful to replace graphene; the xerogel obtained can be directly calcined in air atmosphere, so that the preparation process is simple, the energy consumption is low, the energy is greatly saved, and the practical value and the economic value are more remarkable;
3. according to the embodiment of the application, the nano-grade nickel-doped lithium molybdate material is prepared synthetically by a sol-gel method, the contact surface is enlarged by small size, and the ion diffusion distance between the material and the electrolyte is shortened. The size of the material determines that the basic electricity is changed substantially to a great extent, has rich electrochemical active sites, reduces the resistance of ion and electron transfer, thereby improving the conductivity and the rate of oxidation-reduction reaction, and has stronger practical value and economic benefit. The preparation method of the embodiment of the application has the advantages of simple flow, easy realization, low cost, high repeatability, reduced energy consumption and high raw material utilization rate, and can prepare the nickel-doped lithium molybdate anode material with excellent crystallinity and electrochemical performance and high purity.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are some embodiments of the present application, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is Li produced in example 2 of the present application 2 Ni 0.05 Mo 0.95 O 4 X-ray diffraction analysis spectrogram of the material;
FIG. 2 is Li produced in example 2 of the present application 2 Ni 0.05 Mo 0.95 O 4 Foolproof refining of the material;
FIG. 3 is Li produced in example 2 of the present application 2 Ni 0.05 Mo 0.95 O 4 SEM images of the material;
FIG. 4 is a graph showing the performance of the battery prepared in example 2 of the present application at a current density of 100mA/g, 200mA/g, 300mA/g, 500mA/g, 1000mA/g, 100mA/g for 60 cycles;
FIG. 5 is a graph showing the performance of the battery prepared in example 2 of the present application at a current density of 100mA/g for 60 cycles;
FIG. 6 is a graph showing that the battery prepared in example 2 of the present application was at 0.0001mV.s -1 Cyclic voltammograms for the first two cycles at the scan rate of (a);
FIG. 7 is a battery obtained in example 2 of the present application and Li obtained in comparative example 1 2 MoO 4 A comparison graph of the material battery with 60 circles of circulation at current densities of 100mA/g, 200mA/g, 300mA/g, 500mA/g, 1000mA/g and 100 mA/g.
Detailed Description
For the purposes of making the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art based on the embodiments herein without making any inventive effort, are intended to be within the scope of the present application.
In order to solve the technical problems of rapid specific capacity attenuation and poor cycle performance caused by serious structural degradation and slow dynamics related to large volume change of a metal molybdate material due to Jahn-Teller distortion, the embodiment of the application synthesizes the nano-scale nickel-doped lithium molybdate material by a sol-gel method, enlarges the contact surface by small size, and shortens the ion diffusion distance between the material and electrolyte. The size of the material determines to a large extent that the basic electrical substantial change has rich electrochemically active sites, reducing the resistance to ion and electron transfer, thereby increasing conductivity and the rate of redox reactions. The preparation method of the embodiment of the application has the advantages of simple flow, easy realization, low cost, high repeatability, reduced energy consumption and high raw material utilization rate, and can prepare the nickel-doped lithium molybdate anode material with excellent crystallinity and electrochemical performance and high purity.
The experimental methods in the following examples, for which specific conditions are not noted, are generally determined according to national standards; if the corresponding national standard does not exist, the method is carried out according to the general international standard or standard requirements known in the art. Unless otherwise indicated, all parts are parts by weight and all percentages are percentages by weight.
Unless otherwise indicated, all starting materials in the examples of the present application were purchased commercially.
Example 1
The preparation method of the nickel doped lithium molybdate nano material comprises the following steps:
1.7072g of ammonium molybdate, 2.04g of lithium acetate, 0.0789g of nickel nitrate and 0.2g of oxalic acid are dissolved in 40ml of deionized water, and stirred for 1.5h until the materials are uniformly mixed to obtain a mixed solution; stirring and heating the mixed solution until the solvent is evaporated to dryness, wherein the outlet temperature is 80 ℃, and obtaining precursor gel; then the obtained precursor gel is placed in a blast drying oven for drying, the temperature is 80 ℃, and the time is 14 hours; grinding the obtained sample, sintering in a muffle furnace at 500 ℃ in air atmosphere for 10 hours, setting the heating rate to 5 ℃/min, and cooling to obtain a nickel-doped lithium molybdate material, abbreviated as Li 2 Ni 0.03 Mo 0.97 O 4 Material (denoted LMO 0.03-500).
Example 2
The preparation method of the nickel doped lithium molybdate nano material comprises the following steps:
1.672g of ammonium molybdate, 2.04g of lithium acetate, 0.13214g of nickel nitrate and 0.2g of oxalic acid are dissolved in 40ml of deionized water, and stirred for 1.5h until the materials are uniformly mixed to obtain a mixed solution; stirring and heating the mixed solution until the solvent is evaporated to dryness, wherein the outlet temperature is 80 ℃, and obtaining precursor gel; then the obtained precursor gel is placed in a blast drying oven for drying, the temperature is 80 ℃, and the time is 14 hours; grinding the obtained sample, sintering in a muffle furnace at 500 ℃ in air atmosphere for 10 hours, setting the heating rate to 5 ℃/min, and cooling to obtain a nickel-doped lithium molybdate material, abbreviated as Li 2 Ni 0.05 Mo 0.95 O 4 Material (denoted LMO 0.05-500).
Li prepared in this example was measured by X-ray powder diffractometer 2 Ni 0.05 Mo 0.95 O 4 The material (marked as LMO 0.05-500) is subjected to X-ray diffraction analysis, the spectrogram is shown in figure 1, and the diffraction peak is clearly visible in the spectrogram as can be seen from figure 1.
Li prepared in this example was prepared using Foolproof software 2 Ni 0.05 Mo 0.95 O 4 The composite material (LMO 0.05-500) is refined, the spectrogram is shown in figure 2, and the obtained refined result accords with the experimental result as can be seen from figure 2.
Li of this example was examined by a field emission scanning electron microscope 2 Ni 0.05 Mo 0.95 O 4 The morphology of the material (LMO 0.05-500) is observed, the SEM image is shown in FIG. 3, and the material is coated on Li as can be seen from FIG. 3 2 Ni 0.05 Mo 0.95 O 4 The surface of the particulate material; li (Li) 2 Ni 0.05 Mo 0.95 O 4 (LMO 0.05-500) the whole material has irregular sphere shape with particle diameter of about 5 μm.
Example 3
The preparation method of the nickel doped lithium molybdate nano material comprises the following steps:
1.6368g of ammonium molybdate, 2.04g of lithium acetate, 0.1853g of nickel nitrate and 0.2g of oxalic acid are dissolved in 40ml of deionized water, and stirred for 1.5h until the materials are uniformly mixed to obtain a mixed solution; stirring the mixed solutionHeating to evaporate the solvent to dryness, wherein the outlet temperature is 80 ℃, so as to obtain precursor gel; then the obtained precursor gel is placed in a blast drying oven for drying, the temperature is 80 ℃, and the time is 14 hours; grinding the obtained sample, sintering in a muffle furnace at 500 ℃ in air atmosphere for 10 hours, setting the heating rate to 5 ℃/min, and cooling to obtain a nickel-doped lithium molybdate material, abbreviated as Li 2 Ni 0.07 Mo 0.93 O 4 Material (denoted LMO 0.07-500).
Example 4
The preparation method of the nickel doped lithium molybdate nano material comprises the following steps:
dissolving 1.584g of ammonium molybdate, 2.04g of lithium acetate, 0.2643g of nickel nitrate and 0.2g of oxalic acid in 40ml of deionized water, and stirring for 1.5h until the materials are uniformly mixed to obtain a mixed solution; stirring and heating the mixed solution until the solvent is evaporated to dryness, wherein the outlet temperature is 80 ℃, and obtaining precursor gel; then the obtained precursor gel is placed in a blast drying oven for drying, the temperature is 80 ℃, and the time is 14 hours; grinding the obtained sample, sintering in a muffle furnace at 500 ℃ in air atmosphere for 10 hours, setting the heating rate to 5 ℃/min, and cooling to obtain a nickel-doped lithium molybdate material, abbreviated as Li 2 Ni 0.1 Mo 0.9 O 4 Material (denoted LMO 0.1-500).
Example 5
The preparation method of the nickel doped lithium molybdate nano material comprises the following steps:
1.672g of ammonium molybdate, 2.04g of lithium acetate, 0.13214g of nickel nitrate and 0.2g of oxalic acid are dissolved in 40ml of deionized water, and stirred for 1.5h until the materials are uniformly mixed to obtain a mixed solution; stirring and heating the mixed solution until the solvent is evaporated to dryness, wherein the outlet temperature is 80 ℃, and obtaining precursor gel; then the obtained precursor gel is placed in a blast drying oven for drying, the temperature is 80 ℃, and the time is 14 hours; grinding the obtained sample, sintering in a muffle furnace with air atmosphere at 450 ℃ for 10 hours, setting the heating rate to 5 ℃/min, and cooling to obtain a nickel-doped lithium molybdate material abbreviated as Li 2 Ni 0.05 Mo 0.95 O 4 Material (denoted LMO 0.05-450).
Example 6
The preparation method of the nickel doped lithium molybdate nano material comprises the following steps:
1.672g of ammonium molybdate, 2.04g of lithium acetate, 0.13214g of nickel nitrate and 0.2g of oxalic acid are dissolved in 40ml of deionized water, and stirred for 1.5h until the materials are uniformly mixed to obtain a mixed solution; stirring and heating the mixed solution until the solvent is evaporated to dryness, wherein the outlet temperature is 80 ℃, and obtaining precursor gel; then the obtained precursor gel is placed in a blast drying oven for drying, the temperature is 80 ℃, and the time is 14 hours; grinding the obtained sample, sintering in a muffle furnace in an air atmosphere at 550 ℃ for 10 hours, setting the heating rate to 5 ℃/min, and cooling to obtain a nickel-doped lithium molybdate material, abbreviated as Li 2 Ni 0.05 Mo 0.95 O 4 Material (denoted LMO 0.05-550).
Example 7
The preparation method of the nickel doped lithium molybdate nano material comprises the following steps:
1.672g of ammonium molybdate, 2.04g of lithium acetate, 0.13214g of nickel nitrate and 0.2g of oxalic acid are dissolved in 40ml of deionized water, and stirred for 1.5h until the materials are uniformly mixed to obtain a mixed solution; stirring and heating the mixed solution until the solvent is evaporated to dryness, wherein the outlet temperature is 80 ℃, and obtaining precursor gel; then the obtained precursor gel is placed in a blast drying oven for drying, the temperature is 80 ℃, and the time is 14 hours; grinding the obtained sample, sintering in a muffle furnace at 600 ℃ in an air atmosphere for 10 hours, setting the heating rate to 5 ℃/min, and cooling to obtain a nickel-doped lithium molybdate material, abbreviated as Li 2 Ni 0.05 Mo 0.95 O 4 Material (denoted LMO 0.05-600).
Example 8
The preparation method of the nickel doped lithium molybdate nano material comprises the following steps:
1.672g of ammonium molybdate, 2.04g of lithium acetate, 0.13214g of nickel nitrate and 0.2g of oxalic acid are dissolved in 40ml of deionized water, and stirred for 1.5h until the materials are uniformly mixed to obtain a mixed solution; stirring and heating the mixed solution until the solvent is evaporated to dryness, wherein the outlet temperature is 80 ℃, and obtaining precursor gel; then the obtained precursor gel is placed in a blast drying oven for drying, the temperature is 80 ℃, and the time is 14 hours; grinding the obtained sampleSintering in a muffle furnace at 500 ℃ in air atmosphere for 9 hours, setting the heating rate to be 5 ℃/min, and cooling to obtain a nickel-doped lithium molybdate material, abbreviated as Li 2 Ni 0.05 Mo 0.95 O 4 Material (denoted LMO 0.05-500).
Example 9
The preparation method of the nickel doped lithium molybdate nano material comprises the following steps:
1.672g of ammonium molybdate, 2.04g of lithium acetate, 0.13214g of nickel nitrate and 0.2g of oxalic acid are dissolved in 40ml of deionized water, and stirred for 1.5h until the materials are uniformly mixed to obtain a mixed solution; stirring and heating the mixed solution until the solvent is evaporated to dryness, wherein the outlet temperature is 80 ℃, and obtaining precursor gel; then the obtained precursor gel is placed in a blast drying oven for drying, the temperature is 80 ℃, and the time is 14 hours; grinding the obtained sample, sintering in a muffle furnace at 500 ℃ in air atmosphere for 11h, setting the heating rate to 5 ℃/min, and cooling to obtain a nickel-doped lithium molybdate material abbreviated as Li 2 Ni 0.05 Mo 0.95 O 4 Material (denoted LMO 0.05-500).
Comparative example 1
Dissolving 1.76g of ammonium molybdate, 2.04g of lithium acetate and 0.2g of oxalic acid in 40ml of deionized water, mixing and stirring for 1.5h until the mixture is uniform, and obtaining a mixed solution; stirring and heating the mixed solution until the solvent is evaporated to dryness, wherein the outlet temperature is 80 ℃, and obtaining precursor gel; then the obtained precursor gel is placed in a blast drying oven for drying, the temperature is 80 ℃, and the time is 14 hours; grinding the obtained sample, sintering in a muffle furnace at 500 ℃ in air atmosphere for 10 hours, setting the heating rate to 5 ℃/min, and cooling to obtain a lithium molybdate material, abbreviated as Li 2 MoO 4 Material (denoted LMO-500).
Application example 1
Li obtained in example 2 2 Ni 0.05 Mo 0.95 O 4 The (LMO 0.05-500) material is used as an electrode material in a lithium ion battery, the lithium ion battery is used as a negative electrode material, and then the lithium ion battery is assembled into a button cell, and the specific steps are as follows:
(1) Preparing a negative electrode: according to mass ratio (active substance: conductive)Super P binder polyvinylidene fluoride=8:1:1) Li of example 2 2 Ni 0.05 Mo 0.95 O 4 Grinding (LMO 0.05-500) materials according to mass in a mortar, mixing uniformly, adding a proper amount of N-methyl pyrrolidone as a dispersing agent, continuously grinding until the mixture is uniformly dispersed, uniformly coating the mixed slurry on a copper foil to prepare a negative electrode plate, and vacuum drying at 80 ℃ for 10 hours to obtain the negative electrode plate.
(2) Assembling a button cell: a 2016-type button cell is manufactured in a glove box under inert protective atmosphere by taking a metal lithium sheet as a counter electrode, a diaphragm adopts a cellgard 2250 diaphragm, and electrolyte adopts LiPF with the concentration of 1M 6 EC: DEC (volume ratio 1:1).
Li produced in comparative example 1 was obtained by the same method as described above 2 MoO 4 The materials are assembled into button cells.
As can be seen from FIG. 4, li obtained in example 2 was used 2 Ni 0.05 Mo 0.95 O 4 (LMO 0.05-500) the composite material is assembled into a half cell (taking a lithium sheet as a counter electrode), and after the half cell is cycled for 60 circles under the current density of 100mA/g, the specific capacity is about 432.6 mAh/g; the charge and discharge stability is good, and the lithium ion battery is very stable.
As can be seen from FIG. 5, li obtained in example 2 was used 2 Ni 0.05 Mo 0.95 O 4 The composite material (LMO 0.05-500) is assembled into a half battery (lithium sheet is taken as a counter electrode), and the specific capacities are about 759.2mAh/g, 677.6mAh/g, 591.8mAh/g, 465.9mAh/g, 310.2mAh/g and 542.8mAh/g respectively under different charge and discharge current densities of 100mA/g, 200mA/g, 300mA/g, 500mA/g, 1000mA/g and 100 mA/g; the charge and discharge stability is good, and the lithium ion battery is very stable. The electrochemical performance is better, the constant-current multiplying power performance of the battery is better, and the battery has longer cycle life and higher coulombic efficiency.
As can be seen from FIG. 6, li obtained in example 2 was used 2 Ni 0.05 Mo 0.95 O 4 (denoted as LMO 0.05-500) assembled into half-cells (lithium sheets as counter electrodes) at 0.1mV.s -1 Cyclic voltammetric properties of the first second cycle at a scan rate of (2) it can be seen that each sample was at 0.2VAnd about 0.65V, and 0.4V, 1.2V, 1.7V and 2.3V, and several oxidation peaks appear, the voltammetric curve circulation is more stable, which shows that the electrochemical performance of the battery is better and the cycle life is longer.
As can be seen from FIG. 7, in example 2 of the present application, li is obtained by in-situ doping of nickel element 2 Ni 0.05 Mo 0.95 O 4 Material, li compared with comparative example 1 2 MoO 4 The specific capacity of the material is obviously improved under the charge-discharge current density of 100mA/g, 200mA/g, 300mA/g, 500mA/g, 1000mA/g and 100 mA/g. We can conclude that doping Ni can improve conductivity, reduce the occurrence of severe capacity fade phenomenon caused by structural collapse of lithium molybdate during charge/discharge cycles, and exhibit excellent electrochemical, longer cycle stability and higher coulombic efficiency as electrode materials.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present application.

Claims (10)

1. The nickel ion doped modified lithium molybdate nano material is characterized by comprising the following chemical formula: li (Li) 2 Mo 1-x Ni x O 4 Wherein x is more than or equal to 0.03 and less than or equal to 0.1.
2. The nickel ion doped modified lithium molybdate nanomaterial of claim 1, wherein x has a value of 0.03, 0.05, 0.07, 0.1.
3. A method for preparing the modified lithium molybdate nanomaterial of claim 1 or 2, characterized by comprising the steps of:
dissolving a molybdenum source, a lithium source, a nickel source and a certain amount of complexing agent in a proper amount of deionized water, and uniformly stirring to obtain a mixed solution; heating and stirring the mixed solution, and performing sol-gel treatment to obtain precursor gel; and heating and drying the precursor gel, and calcining to obtain the nickel ion doped modified lithium molybdate nano material.
4. The method according to claim 3, wherein the lithium source, the nickel source and the molybdenum source are used in a molar ratio of Li to Ni to Mo of 2:x (1-x).
5. A method according to claim 3, wherein the calcination is carried out at a temperature of 450-600 ℃ for a calcination time of 8-12 hours.
6. A method according to claim 3, wherein the nickel source is one or more of nickel nitrate, nickel sulphate, nickel hydroxide, nickel oxide; or (b)
The complexing agent is oxalic acid.
7. The method according to claim 3, wherein the lithium source is one or more of lithium acetate, lithium hydroxide, lithium molybdate, and lithium carbonate.
8. A method according to claim 3, wherein the molybdenum source is one or more of molybdenum trioxide, ammonium molybdate, sodium molybdate, molybdenum chloride.
9. A negative electrode sheet, characterized in that the negative electrode sheet contains the nanomaterial of claim 1 or 2 or the nanomaterial produced by the method of any one of claims 3 to 8.
10. A battery comprising the negative electrode sheet of claim 9, further comprising a battery case, a positive electrode sheet, a separator, and an electrolyte.
CN202311562691.XA 2023-11-22 2023-11-22 Nickel ion doped modified lithium molybdate nano material, preparation method thereof, negative plate and battery Pending CN117457876A (en)

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