CN111509188A - Anode material, anode, lithium ion battery and preparation method - Google Patents

Anode material, anode, lithium ion battery and preparation method Download PDF

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CN111509188A
CN111509188A CN202010361628.XA CN202010361628A CN111509188A CN 111509188 A CN111509188 A CN 111509188A CN 202010361628 A CN202010361628 A CN 202010361628A CN 111509188 A CN111509188 A CN 111509188A
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anode material
salt
anode
soluble
specific capacity
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赵桃林
纪日新
孟瑜
申建钢
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Shijiazhuang Tiedao University
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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
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention particularly discloses an anode material, an anode, a lithium ion battery and a preparation method. The preparation method of the anode material comprises the steps of taking cheap and easily-obtained biomass raw material gelatin as a carbon precursor, taking soluble ferric salt and + 2-valent soluble transition metal salt as a spinel precursor, and preparing MFe with a novel foam structure through low-temperature drying, expansion, pore-forming and high-temperature calcination processes2O4a/C composite anode material. MFe prepared according to the invention2O4the/C composite electrode material has excellent cycling stability and high-rate discharge performance, and the first discharge specific capacity can reach 1555.6mAh/g and the first charge specific capacity can reach 1058.4mAh/g under the rate of 0.2C; under the condition of 0.2C, after 100 cycles of charge and discharge, the discharge specific capacity is kept to 925mAh/g, and the charge specific capacity is kept to 903.4 mAh/g.

Description

Anode material, anode, lithium ion battery and preparation method
Technical Field
The invention relates to the technical field of electrochemical materials, in particular to an anode material, an anode, a lithium ion battery and a preparation method.
Background
With the continuous development of electronic intelligent devices and electric automobiles, the demand of lithium ion batteries (L IBs) is increasing, and the lithium ion batteries are widely applied as energy storage power sources of portable electronic devices and electric automobiles due to the outstanding advantages of high energy density, long cycle life, good rate performance and the like-1) And the development requirement of high energy density of the lithium ion battery cannot be met. In recent years, researchers have made great efforts to find a material that can replace graphite as an anode material. Transition metal oxides are considered to be good electrode materials for replacing graphite due to their high theoretical specific capacity. Mixed transition metal oxides often exhibit higher electrochemical performance than simple transition metal oxides due to their complex chemical composition and synergy. Spinel ferrites (MFO, denoted MFe) in binary transition metal oxides2O4M ═ Mn, Ni, Cu, Zn, or Co) is a promising mixed transition metal oxide material.
As a typical mixed transition metal oxide, MnFe2O4Due to the higher theoretical specific capacity (926mAh g)-1) The advantages of low cost and environmental friendliness, etc., have attracted the interest of many researchers. However, MnFe2O4As anode materials there are still some disadvantages: if the electronic conductivity is poor, the diffusion coefficient of lithium ions is low, and the volume is changed rapidly in the circulation process, the MnFe is greatly hindered2O4The material is applied to the field of lithium ion batteries as an anode material. Therefore, the development of the lithium ion battery electrode material with high electronic conductivity and good cycle performance has very important significance for the development of the lithium ion battery.
Disclosure of Invention
The invention provides an anode material, an anode, a lithium ion battery and a preparation method thereof, aiming at the problems of low capacity and poor cycle performance of a carbon anode material in the conventional lithium ion battery.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a preparation method of an anode material comprises the following steps:
dissolving gelatin in water to obtain a gelatin solution; dissolving soluble ferric salt and + 2-valent soluble transition metal salt in water to obtain a mixed salt solution;
dropwise adding the mixed salt solution into the gelatin solution under the stirring condition, and stirring at 60-80 ℃ for 4-8h to obtain gel;
and step three, drying the gel at 80-120 ℃ for 12-24h, and then calcining at 500-800 ℃ for 2-8h in an inert atmosphere to obtain the anode material.
Compared with the prior art, the preparation method of the anode material provided by the invention is characterized in that the biomass material gelatin, the soluble ferric salt and the + 2-valent soluble transition metal salt are used as precursors, and the MFe with the novel foam structure is prepared through the processes of low-temperature drying, expansion, pore-forming and high-temperature calcination2O4the/C composite anode material (M is transition metal) provides a new idea for the synthesis of the electrode material of the lithium ion battery.
In the low-temperature drying stage, the gelatin performs self-expansion to perform preliminary pore forming, so that a large amount of nano-scale pores are generated in the subsequent calcination; then calcining at 500-800 ℃ for 2-8h, further carbonizing the gelatin to form a porous foam substrate after the gelatin is carbonized, which is beneficial to uniformly dispersing and embedding the soluble ferric salt and the soluble manganese salt into the porous structure of the carbon substrate, and growing the MFe in situ in the porous structure of the substrate2O4Nanocrystalline grains with increased carbon base and MFe2O4The bonding force of the nano-crystalline grains. At the same time, due to the porous structure to MFe2O4The limit effect in the growth process of the nano crystal grains effectively inhibits MFe2O4Size of nanoparticles to give MFe of 5-50nm2O4Nanoparticles, increase the specific surface area of electrode materialFurthermore, MFe can be limited due to the presence of the porous carbon material during multiple charging and discharging2O4The growth and agglomeration of the nano particles slow down the volume expansion of the inner layer oxide in the reaction process, and avoid the rapid volume change in the circulation process. In addition, the inner layer MFe is formed by the bonding of the carbon material2O4The electron transfer between the nano-particles provides a good electron transport channel, and L i of the electrode material is improved+Diffusion rate and electron conductivity.
Through the carbon material, inner layer MFe2O4Due to the synergistic effect among the nano particles, the prepared composite electrode material has excellent cycling stability and high-rate discharge performance, the first discharge specific capacity can reach 1555.6mAh/g at the rate of 0.2C (200mA/g), the first charge specific capacity can reach 1058.4mAh/g, and the first coulombic efficiency can reach 68%; under the condition of 0.2C (200mA/g), after 100 cycles of charge and discharge, the specific discharge capacity is kept to 925mAh/g, the specific charge capacity is kept to 903.4mAh/g, the charge capacity retention rate is 85.34% after 100 cycles of charge and discharge, and the charge and discharge capacity is almost not attenuated from the 10 th cycle, so that the high-stability cycle is shown.
The inert gas in the present invention is an inert gas which is conventional in the art, such as argon, nitrogen, and the like.
Preferably, in the first step, the mass concentration of the gelatin solution is 5-15 wt%.
Preferably, in the first step, the +2 soluble transition metal salt is a soluble manganese salt or a soluble zinc salt.
Preferred + 2-valent soluble transition metal salts can form MnFe during calcination2O4/C or ZnFe2O4the/C anode material is beneficial to improving the capacity of the electrode material.
Preferably, in the first step, the molar ratio of iron ions in the soluble iron salt to metal ions in the +2 valent soluble transition metal salt is 1.8-2.2: 1.
More preferably, in step one, the soluble iron salt is Fe3+With metal ions in + 2-valent soluble transition metal saltsIn a molar ratio of 2: 1.
Preferably, in the first step, the concentration of iron ions in the soluble iron salt in the mixed salt solution is 0.1-0.5 mol/L, and the concentration of metal ions in the + 2-valent soluble transition metal salt is 0.05-0.25 mol/L.
Preferably, in the second step, the volume ratio of the mixed salt solution to the gelatin solution is 4: 1.5-3.
Preferably, in the second step, the dropping speed of the mixed salt solution is 1-2m L/min.
The preferable concentration of the gelatin solution, the concentration of the mixed salt solution, the proportion of the two and the dropping speed are favorable for uniformly mixing the mixed salt solution and the gelatin solution, and further favorable for MFe2O4The nano particles are uniformly dispersed in the carbon material, so that the in-situ growth of MFe is avoided2O4The agglomeration problem occurs during the process of nano particles, so that the prepared material has excellent cycle stability and rate capability.
The stirring speed in the second step is not limited in any way, and the stirring speed known to those skilled in the art is adopted for stirring to achieve the purpose of uniform mixing, optionally, in the second step, the stirring speed is 1500-.
Preferably, in the third step, the calcination at 500-800 ℃ adopts a temperature programming mode, and the temperature raising rate is 5-10 ℃/min.
More preferably, in the third step, the calcining temperature is 700 ℃ and the heating rate is 8 ℃/min.
Preferred rate of temperature rise, to facilitate MFe2O4The nanoparticles are uniformly dispersed in the porous structure of the carbon material, and the MFe is made2O4The close combination between the nano particles and the carbon material effectively prevents the volume change in the de-intercalation process and prevents the MFe2O4The agglomeration, pulverization and shedding of the nano particles further improve the cycling stability and rate capability of the prepared electrode material.
The invention also provides an anode material prepared by the preparation method of any one of the anode materials.
The invention also provides an anode comprising the anode material.
The invention also provides a lithium ion battery which comprises the anode.
The anode material prepared by the invention has rich nano-and micro-structure porous structures, has excellent lithium ion transmission channels, can effectively relieve volume expansion, and has excellent cycling stability and higher capacity. The anode material is applied to the lithium ion battery, so that the lithium ion battery with stable structure and excellent rate capability and cycle performance can be obtained.
Drawings
FIG. 1 shows MnFe prepared in example 1 of the present invention2O4XRD pattern of the/C composite anode material;
FIG. 2 shows MnFe prepared in example 1 of the present invention2O4N of/C composite anode material2Adsorption-desorption isotherms;
FIG. 3 shows MnFe prepared in example 1 of the present invention2O4The pore size distribution curve of the/C composite anode material;
FIG. 4 shows MnFe prepared in example 1 of the present invention2O4SEM images of the/C composite anode material under different magnifications;
FIG. 5 shows MnFe prepared in example 1 of the present invention2O4TEM images of the/C composite anode material at different magnifications;
FIG. 6 shows MnFe prepared by example 1 of the present invention2O4A cycle performance diagram of a battery composed of the/C composite anode material;
FIG. 7 shows MnFe prepared by example 1 of the present invention2O4Comparing the charge-discharge curves at 1 week, 2 week, 50 week and 100 week of the battery assembled by the/C composite anode material;
FIG. 8 shows MnFe prepared by example 1 of the present invention2O4A rate performance diagram of a battery assembled by the/C composite anode material;
FIG. 9 shows ZnFe prepared in example 4 of the present invention2O4SEM images of the/C composite anode material under different magnifications;
FIG. 10 is ZnFe prepared by example 4 of the invention2O4A cycle performance diagram of a battery assembled by the/C composite anode material;
FIG. 11 is ZnFe prepared by example 4 of the invention2O4Comparative charge-discharge curves of 1 week, 2 week, 10 week, 40 week and 100 week of the battery assembled by the/C composite anode material.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In order to better illustrate the invention, the following examples are given by way of further illustration.
Example 1
A preparation method of an anode material comprises the following steps:
step one, adding gelatin into deionized water at the temperature of 60 ℃ under the condition of continuous stirring, and stirring to dissolve the gelatin to obtain a gelatin solution with the mass fraction of 10%;
step two, weighing Fe (NO) according to the molar ratio of 2:13)3·9H2O and Mn (NO)3)2Adding the mixed solution into deionized water for dissolving to obtain a mixed salt solution, wherein the concentration of ferric nitrate is 0.3 mol/L, and the concentration of manganese nitrate is 0.15 mol/L;
step three, under the condition of intense stirring, dripping 40m L mixed salt solution into 25m L gelatin solution at the speed of 1.5m L/min, then continuously stirring for 6h at the temperature of 70 ℃ to obtain gel, and drying the gel for 15h at the temperature of 100 ℃ to obtain a foamy solid precursor;
step four, heating the foamed solid precursor to 700 ℃ in a tube furnace at the heating rate of 8 ℃/min under the protection of argon gas, calcining for 5h, and cooling to room temperature to obtain MnFe2O4a/C composite anode material.
FIG. 1 shows the MnFe2O4XRD pattern of/C composite anode material, comparisonKnown MnFe2O4The XRD diffraction pattern shows that the cubic spinel type MnFe is successfully prepared by the method2O4。
FIG. 2 shows the MnFe2O4N of/C composite anode material2The adsorption-desorption isotherm, FIG. 3 is the corresponding pore size distribution curve, and it can be seen from the graph that the temperature is measured at the relative pressure (P/P)0) The MnFe prepared by the invention is 0.4-1.02O4the/C anode material exhibited typical type IV behavior and a significant hysteresis loop, which illustrates the MnFe prepared in this example2O4the/C anode material contains a large amount of mesopores, and the pore diameter is mainly distributed at about 5 nm. MnFe according to the Brunauer-Emmett-Teller (BET) method2O4The surface area of the/C sample was 60.0735m2·g-1。
FIG. 4 shows MnFe prepared in this example2O4SEM images of the/C composite anode material under different magnifications, and the magnifications of (a) - (d) are increased in sequence. As can be seen from the figure, the material prepared by the embodiment has a foam porous structure, the pore diameter is 100-500nm, and MnFe2O4The particles may be uniformly dispersed and embedded in the porous carbon matrix.
FIG. 5 shows MnFe prepared in this example2O4TEM images of the/C composite anode material at different magnifications, the magnifications (a) - (b) being successively increased. As can be seen from the figure, MnFe prepared in this example2O4The particles can be uniformly dispersed and embedded in a porous carbon matrix, MnFe2O4The size of the nanoparticles is 5-50 nm.
And (3) electrochemical performance testing:
to test MnFe prepared in this example2O4The performance of the/C composite anode material is prepared into an electrode and assembled into a battery.
The preparation method of the electrode comprises the following steps:
the prepared MnFe2O4Respectively weighing the/C composite anode material, the conductive agent (acetylene black) and the binder (sodium carboxymethyl cellulose) according to the mass ratio of 8:1:1, and putting the materials into an agate mortar for grindingGrinding and mixing uniformly, adding a proper amount of water, and grinding to obtain uniform slurry. Coating the obtained mixed slurry on a copper foil by using a scraper, drying the copper foil in a vacuum drying oven at 60 ℃ to fully volatilize the solvent, and finally coating MnFe by using a slicer2O4And cutting the copper foil of the/C composite anode material into a circular sheet with the diameter of 11mm to obtain the electrode plate.
Assembling the battery:
the electrode plate prepared by the method is used as a working electrode, a metal lithium plate is used as a counter battery, and the solute adopted by the electrolyte is L iPF6The concentration is 1 mol/L, the solvent is a mixed solvent of Ethylene Carbonate (EC) and dimethyl carbonate (DMC) in a volume ratio of 1:1, a diaphragm is Celgard 2400, the CR2025 button cell is assembled in a glove box in an argon atmosphere, then a special hydraulic edge-buckling machine is used for compacting the cell, and the cell is tested after standing for 12 hours.
The L and battery test system is selected to test the charge and discharge performance of the assembled battery, the voltage interval of charge and discharge is 0.005-3.0V, and the test multiplying power of the battery is 0.1C (100mA/g), 0.2C, 0.5C, 1C, 2C and 5C, so as to test the specific capacity, the cycle performance and the multiplying power performance of the battery.
FIG. 6 is a graph of the cycling performance of the above cell at 0.2C (current density of 200mA/g) rate for 100 cycles. Fig. 7 is a graph comparing charge and discharge curves of the battery at 1 st, 2 nd, 50 th and 100 th weeks, wherein the curves represent the 1 st, 2 nd, 50 th and 100 th weeks in order of the arrow direction according to the positions indicated by the arrows. As can be seen from the figure, MnFe is used2O4Under the multiplying power of 0.2C, the first specific discharge capacity and the first specific charge capacity of the electrode made of the/C composite anode material are 1555.6mAh/g and 1058.4mAh/g respectively, and the first coulombic efficiency is 68%. The discharge specific capacity and the charge specific capacity can still be kept at 925mAh/g and 903.4mAh/g after 100-week circulation, the charge capacity retention rate is 85.4% after 100-week circulation, and the material is almost free from attenuation from the 10 th week, so that the material shows good circulation stability.
FIG. 8 is a graph of rate performance of the above batteries at 0.1C (100mA/g), 0.2C, 0.5C, 1C, 2C, and 5C. As can be seen from the figure, the material prepared by the embodiment has good rate performance, the capacity is kept at about 1100mAh/g at the rate of 0.1C, the capacity is kept at about 680mAh/g at the rate of 1C, and the capacity is kept at about 410mAh/g at the rate of 2C. The material has the capability of bearing high current charge and discharge, and when the material returns to 0.1C again, the specific capacity can still reach about 935 mAh/g.
Example 2
A preparation method of an anode material comprises the following steps:
step one, adding gelatin into deionized water at the temperature of 90 ℃ under the condition of continuous stirring, and stirring to dissolve the gelatin to obtain a gelatin solution with the mass fraction of 5%;
step two, weighing Fe (NO) according to the molar ratio of 1.8:13)3·9H2O and Mn (NO)3)2Adding the mixed solution into deionized water for dissolving to obtain a mixed salt solution, wherein the concentration of ferric nitrate is 0.1 mol/L, and the concentration of manganese nitrate is 0.05 mol/L;
step three, under the condition of intense stirring, dripping 40m L mixed salt solution into 30m L gelatin solution at the speed of 2m L/min, then continuously stirring for 8h at the temperature of 60 ℃ to obtain gel, and drying the gel for 24h at the temperature of 80 ℃ to obtain a foamy solid precursor;
step four, heating the foamed solid precursor to 500 ℃ in a tubular furnace at a heating rate of 5 ℃/min and calcining for 8h in an argon protective atmosphere, and cooling to room temperature to obtain MnFe2O4a/C composite anode material.
Example 3
A preparation method of an anode material comprises the following steps:
step one, adding gelatin into deionized water at the temperature of 80 ℃ under the condition of continuous stirring, and stirring to dissolve the gelatin to obtain a gelatin solution with the mass fraction of 15%;
step two, weighing Fe (NO) according to the molar ratio of 2.2:13)3·9H2O and Mn (NO)3)2Adding the mixed solution into deionized water for dissolving to obtain a mixed salt solution, wherein the concentration of ferric nitrate is 0.5 mol/L, and the concentration of manganese nitrate is 0.25 mol/L;
step three, under the condition of intense stirring, dripping 40m L mixed salt solution into 15m L gelatin solution at the speed of 1m L/min, then continuously stirring for 4h at the temperature of 80 ℃ to obtain gel, and drying the gel for 12h at the temperature of 120 ℃ to obtain a foamy solid precursor;
step four, heating the foamed solid precursor to 800 ℃ in a tube furnace at a heating rate of 10 ℃/min and calcining for 2h in an argon protective atmosphere, and cooling to room temperature to obtain MnFe2O4a/C composite anode material.
Example 4
A preparation method of an anode material comprises the following steps:
step one, adding gelatin into deionized water at the temperature of 70 ℃ under the condition of continuous stirring, and stirring to dissolve the gelatin to obtain a gelatin solution with the mass fraction of 12%;
step two, weighing Fe (NO) according to the molar ratio of 2:13)3·9H2O and Zn (NO)3)2Adding the mixed solution into deionized water for dissolving to obtain a mixed salt solution, wherein the concentration of ferric nitrate is 0.4 mol/L, and the concentration of zinc nitrate is 0.2 mol/L;
step three, under the condition of intense stirring, dripping 40m L mixed salt solution into 25m L gelatin solution at the speed of 1.5m L/min, then continuously stirring for 6h at the temperature of 70 ℃ to obtain gel, and drying the gel for 15h at the temperature of 100 ℃ to obtain a foamy solid precursor;
step four, heating the foamy solid precursor to 500 ℃ in a tubular furnace at the heating rate of 8 ℃/min and calcining for 6h in the protective atmosphere of argon, and cooling to room temperature to obtain ZnFe2O4a/C composite anode material.
FIG. 9 shows ZnFe prepared in this example2O4SEM images of the/C composite anode material under different magnifications, and the magnifications of (a) - (b) are increased in sequence. As can be seen from the figure, the material prepared by the embodiment has a foam porous structure, and ZnFe2O4The particles may be uniformly dispersed and embedded in the porous carbon matrix.
ZnFe prepared in this example was mixed in accordance with the procedure of example 12O4After the/C composite anode material and the lithium sheet are assembled into the button cell, electrochemistry is carried outAnd (5) testing the performance.
FIG. 10 is a graph of the cycling performance of the above cell at 0.2C (current density of 200mA/g) rate for 100 cycles. Fig. 11 is a graph comparing charge and discharge curves at 1 st, 2 nd, 10 th, 40 th and 100 th weeks of the above-described battery, and the curves represent the 1 st, 2 nd, 10 th, 40 th and 100 th weeks in order of arrow direction according to the position indicated by the arrow, in which the curves at the 10 th and 40 th weeks during charging overlap and the curves at the 2 nd, 10 th and 40 th weeks during discharging overlap. Under the multiplying power of 0.2C (200mA/g), the first discharge specific capacity and the first charge specific capacity are 1220mAh/g and 910mAh/g, and the first coulombic efficiency is 75 percent; after the circulation for 100 weeks, the discharge specific capacity and the charge specific capacity can still be kept at 814mAh/g and 808mAh/g, and the charge capacity retention rate is 89%.
Comparative example 1
This comparative example provides a method of preparing an anode material, which is the same as example 1 except that gelatin in example 1 was replaced with gum arabic.
The anode materials prepared in this comparative example were assembled into a battery according to the method of example 1 to perform electrochemical performance tests. Under the multiplying power of 0.2C (200mA/g), the first discharge specific capacity and the first charge specific capacity are 1240.8mAh/g and 707.3mAh/g, and the first coulombic efficiency is 57%; after the circulation for 100 weeks, the discharge specific capacity and the charge specific capacity can still be kept at 535.7mAh/g and 516.3mAh/g, and the charge capacity retention rate is 73%.
Comparative example 2
This comparative example provides a method for preparing an anode material, which is the same as that of example 1 except that the calcination temperature in the fourth step of example 1 was replaced with 400 ℃ for 10 hours, and the temperature increase rate was 8 ℃/min.
The anode materials prepared in this comparative example were assembled into a battery according to the method of example 1 to perform electrochemical performance tests. Under the multiplying power of 0.2C (200mA/g), the first discharge specific capacity and the first charge specific capacity are 1190mAh/g and 654.4mAh/g, and the first coulombic efficiency is 55 percent; after the circulation for 100 weeks, the discharge specific capacity and the charge specific capacity can still be maintained at 516.8mAh/g and 495.4mAh/g, and the charge capacity retention rate is 75.7%.
Comparative example 3
This comparative example provides a method for preparing an anode material, which is the same as that of example 1 except that the temperature increase rate in step four of example 1 was replaced with 15 c/min.
The anode materials prepared in this comparative example were assembled into a battery according to the method of example 1 to perform electrochemical performance tests. Under the multiplying power of 0.2C (200mA/g), the first discharge specific capacity and the first charge specific capacity are 1350.5mAh/g and 810.3mAh/g, and the first coulombic efficiency is 60 percent; after the circulation for 100 weeks, the discharge specific capacity and the charge specific capacity can still be kept at 654.4mAh/g and 636.1mAh/g, and the charge capacity retention rate is 78.5 percent
The composite anode materials prepared in the embodiments 2 to 3 of the invention can achieve the effect basically equivalent to that of the embodiment 1.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (10)

1. The preparation method of the anode material is characterized by comprising the following steps of:
dissolving gelatin in water to obtain a gelatin solution; dissolving soluble ferric salt and + 2-valent soluble transition metal salt in water to obtain a mixed salt solution;
dropwise adding the mixed salt solution into the gelatin solution under the stirring condition, and stirring at 60-80 ℃ for 4-8h to obtain gel;
and step three, drying the gel at 80-120 ℃ for 12-24h, and then calcining at 500-800 ℃ for 2-8h in an inert atmosphere to obtain the anode material.
2. The method for preparing an anode material according to claim 1, wherein in the first step, the mass concentration of the gelatin solution is 5-15 wt%; and/or
In the first step, the + 2-valent soluble transition metal salt is soluble manganese salt or soluble zinc salt.
3. The method of claim 1 or 2, wherein in step one, the molar ratio of iron ions in the soluble iron salt to metal ions in the +2 valent soluble transition metal salt is 1.8-2.2: 1.
4. The method of claim 3, wherein in the first step, the concentration of iron ions in the soluble iron salt in the mixed salt solution is 0.1-0.5 mol/L, and the concentration of metal ions in the + 2-valent soluble transition metal salt is 0.05-0.25 mol/L.
5. The method for preparing an anode material according to claim 3, wherein in the second step, the volume ratio of the mixed salt solution to the gelatin solution is 4: 1.5-3.
6. The method for preparing an anode material according to claim 1, wherein in the second step, the dropping speed of the mixed salt solution is 1 to 2m L/min.
7. The method for preparing anode material according to claim 1, wherein in the third step, calcination at 500-800 ℃ is performed by temperature programming at a rate of 5-10 ℃/min.
8. An anode material produced by the method for producing an anode material according to any one of claims 1 to 7.
9. An anode comprising the anode material of claim 8.
10. A lithium ion battery comprising the anode of claim 9.
CN202010361628.XA 2020-04-30 2020-04-30 Anode material, anode, lithium ion battery and preparation method Pending CN111509188A (en)

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