CN108987699B - High-stability high-capacity lithium ion battery cathode active material and preparation method thereof - Google Patents

High-stability high-capacity lithium ion battery cathode active material and preparation method thereof Download PDF

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CN108987699B
CN108987699B CN201810769588.5A CN201810769588A CN108987699B CN 108987699 B CN108987699 B CN 108987699B CN 201810769588 A CN201810769588 A CN 201810769588A CN 108987699 B CN108987699 B CN 108987699B
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CN108987699A (en
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曹立军
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Guangzhou Mingmei new energy Co., Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
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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
    • H01M4/58—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
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • 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
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
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    • H01M4/606—Polymers containing aromatic main chain polymers
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    • 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
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract

The invention belongs to the technical field of lithium ion batteries, and particularly relates to a high-stability high-capacity lithium ion battery cathode active material and a preparation method thereof, wherein the preparation method comprises the following steps: (1) dispersing soluble metal salt into an organic solvent, adding 1, 2-di (4-pyridyl) ethylene, and carrying out sealed reaction to obtain a precursor A; (2) dissolving aniline derivatives in an organic solvent, adding a precursor A, performing ultrasonic dispersion, and then dropwise adding an N-phenyl phenylenediamine solution to obtain an intermediate product B; (3) placing the intermediate product B in a tubular furnace, and introducing steam for reaction to obtain a product C; (4) uniformly mixing the product C and a sulfur source in water, and carrying out thermal reaction under a sealed condition to obtain a negative electrode active material; the invention disperses polyaniline in M2Sx(C12H10N2)nThe surface of the three-dimensional skeleton structure provides a buffer space for the volume expansion of the material in the charging and discharging process, inhibits the change of the active material structure in the charging and discharging process, and improves the capacity, the coulombic efficiency and the cycle stability of the battery.

Description

High-stability high-capacity lithium ion battery cathode active material and preparation method thereof
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a high-stability high-capacity lithium ion battery cathode active material and a preparation method thereof.
Background
Lithium ion batteries have become the most widely used secondary batteries in the world today due to their advantages of high energy density, long cycle life, no memory effect, etc. With the further research of lithium batteries, the development of battery materials with high capacity, high rate performance and long cycle life becomes the key point in the field.
At present, the negative electrode material actually used in lithium ion batteries is generally a carbon material, and the theoretical capacity of the carbon negative electrode material is (372mAh g)-1) Various metal composites, metal oxides and metal sulfides have been extensively studied to replace carbon anodes, which have failed to meet the future high capacity needs. Transition metal sulfides have higher specific capacitance and power density than metal oxides. For example, Wei et al synthesized NiS in one step2Hollow nanospheres of materials having not only organic dyesThe material has good adsorbability, can also be used as an electrode material of a super capacitor, and simultaneously has high specific capacitance and cycle stability (Dalton transistors, 2015,44, 17278-. Lin et al Co9S8The composite with the three-dimensional graphene is used as a positive electrode, the graphene gel is used as a negative electrode, and the high-performance asymmetric supercapacitor is obtained, the output voltage of the asymmetric supercapacitor is up to 1.8V, and the power density of the asymmetric supercapacitor is 910 W.K.g-1When the energy density reaches 31.6 W.h.K.g-1(chem.Eng.J.,2015,279, 241-Sur 249). Huang et al will layer MoS2And graphene are compounded to obtain a conductive cross-linked network structure, so that the transmission efficiency of electrons is improved, the diffusion of electrolyte is promoted, and the volume change of the electrode material in the charge-discharge process is also prevented, so that the obtained electrode material has stable cycle performance (InterJ. hydrogen Energy,2013,38, 14027-14034).
Although the metal sulfide has high specific capacitance, the cycle stability is poor.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a preparation method of a high-stability high-capacity lithium ion battery negative electrode active material.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a high-stability high-capacity lithium ion battery negative electrode active material comprises the following steps:
(1) uniformly mixing soluble metal salt in an organic solvent, adding 1, 2-bis (4-pyridyl) ethylene, uniformly mixing, and carrying out sealing reaction at 100-160 ℃ for 2-6 h to obtain a precursor A;
(2) dissolving an aniline derivative in an organic solvent to obtain a mixed solution, adding the precursor A into the mixed solution, performing ultrasonic dispersion for 5-10 min to obtain a mixed system, dropwise adding an N-phenyl phenylenediamine solution into the mixed system under the stirring condition, and reacting for 2-6 h to obtain an intermediate product B;
(3) placing the intermediate product B in a tubular furnace, and introducing steam for reaction to obtain a product C;
(4) and (3) uniformly mixing the product C with a sulfur source in water, and carrying out thermal reaction on the mixed system under a sealed condition to obtain the cathode active material.
The invention also provides the high-stability high-capacity lithium ion battery cathode active material prepared by the preparation method.
Compared with the prior art, the invention has the following technical effects:
in the present invention, polyaniline is dispersed in M2Sx(C12H10N2)nThe surface of the three-dimensional skeleton structure enlarges the specific surface area of the polyaniline, provides more surface active sites for the de-intercalation of lithium ions in the charging and discharging processes of the battery, reduces the steric hindrance, can provide a buffer space for the volume expansion of the material in the charging and discharging processes, effectively inhibits the change of the active material structure in the charging and discharging processes, improves the reversibility of electrochemical reaction, and thus improves the capacity, the coulomb efficiency and the cycle stability of the battery; on the other hand, polyaniline is coated on the surface of the metal sulfide, so that the oxidation of the metal sulfide can be effectively prevented.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
In order to make the technical means, the creation features, the achievement purposes and the effects of the invention easy to understand, the invention is further clarified with the specific embodiments.
The invention provides a preparation method of a high-stability high-capacity lithium ion battery cathode active material, which comprises the following steps:
(1) uniformly mixing soluble metal salt in an organic solvent, adding 1, 2-bis (4-pyridyl) ethylene, uniformly mixing, and carrying out sealing reaction at 100-160 ℃ for 2-6 h to obtain a precursor A;
(2) dissolving an aniline derivative in an organic solvent to obtain a mixed solution, adding the precursor A into the mixed solution, performing ultrasonic dispersion for 5-10 min to obtain a mixed system, dropwise adding an N-phenyl phenylenediamine solution into the mixed system under the stirring condition, and reacting for 2-6 h to obtain an intermediate product B;
(3) placing the intermediate product B in a tubular furnace, and introducing steam for reaction to obtain a product C;
(4) and (3) uniformly mixing the product C with a sulfur source in water, and carrying out thermal reaction on the mixed system under a sealed condition to obtain the cathode active material.
The invention firstly mixes the soluble metal salt and 1, 2-di (4-pyridyl) ethylene (C)12H10N2) By thermal reaction in an organic solvent, a metal and (C) can be formed12H10N2) Complex M (C) of12H10N2)n(ii) a Then, mixing M (C)12H10N2)nReaction with an aniline derivative at M (C)12H10N2)nGenerating conductive polymer polyaniline derivative on the surface, namely an intermediate product B, reacting the intermediate product B with water vapor in a tubular furnace, oxidizing metal atoms in the intermediate product B into metal oxide, namely an intermediate product C, then reacting the intermediate product C with a sulfur source, and reducing the metal oxide in the intermediate product C into metal sulfide to obtain M2Sx(C12H10N2)n/PPy。M2Sx(C12H10N2)nPPy has the advantages of metal sulfide and polyaniline, 1, 2-bis (4-pyridyl) ethylene is inlaid on the surface of the metal sulfide to form a three-dimensional framework structure, and the polyaniline is dispersed on the surface of the three-dimensional framework structure, so that on one hand, the specific surface area of the polyaniline is enlarged, more surface active sites are provided for de-intercalation of lithium ions in the charging and discharging processes of the battery, the steric hindrance is reduced, a buffer space can be provided for volume expansion of materials in the charging and discharging processes, the change of the active material structure in the charging and discharging processes is effectively inhibited, the reversibility of electrochemical reaction is improved, and the capacity, the coulomb efficiency and the cycling stability of the battery are improved; on the other hand, polyaniline is coated on the surface of the metal sulfide, so that the oxidation of the metal sulfide can be effectively prevented.
Further, according to the present invention, the soluble metal salt is selected from at least one of soluble zinc salt, soluble iron salt, soluble nickel salt and soluble cobalt salt. Specifically, the soluble zinc salt is one of zinc chloride, zinc sulfate, zinc nitrate and zinc acetate; the soluble ferric salt is one of ferric chloride, ferric sulfate and ferric nitrate; the soluble nickel salt is one of nickel chloride, nickel sulfate and nickel nitrate; the soluble cobalt salt is one of cobalt chloride and cobalt sulfate.
Further, the aniline derivative is at least one of 2-hydroxyaniline, 2-mercaptomethylaniline, 2-methoxyaniline, 2-chloroaniline, 2-ethoxyaniline or 2-methylaniline.
According to the invention, in the step (3), the temperature in the tube furnace is 120-150 ℃;
the pressure intensity in the tube furnace is 200-300 MPa.
According to the invention, in the step (4), the temperature of the thermal reaction is 100-160 ℃, and the time of the thermal reaction is 4-8 h.
In the present invention, the organic solvent is at least one selected from the group consisting of methanol, DMF, toluene, dichloromethane, tetrahydrofuran, ethyl acetate, acetone, N-dimethylformamide, N-methylpyrrolidone, N-dimethylacetamide, N-diethylformamide, petroleum ether, and dimethyl sulfoxide.
According to the present invention, the kind of the sulfur source is not particularly limited, and may be known to those skilled in the art, and preferably, the sulfur source is at least one selected from the group consisting of sodium sulfide, potassium sulfide, and thiourea.
The invention also provides a lithium ion battery prepared by adopting the prepared cathode active material, the lithium ion battery comprises an anode, a cathode, a diaphragm and electrolyte, and the cathode of the lithium ion battery comprises the cathode active material, a conductive agent and a binder.
The solvent in the electrolyte comprises ethylene carbonate, ethyl methyl carbonate and dimethyl carbonate; wherein the mass ratio of the ethylene carbonate, the ethyl methyl carbonate and the dimethyl carbonate is 1 (0.8-1.2) to 1-1.5.
The binder can be selected from polyvinyl alcohol, polytetrafluoroethylene, sodium carboxymethylcellulose, polyolefin binders, fluorinated rubber and the like, and preferably, the binder is PVDF.
The preparation method of the lithium ion battery cathode comprises the following steps: uniformly mixing the prepared negative electrode active material, the conductive agent and the binder in a vacuum mixer to obtain a negative electrode material;
uniformly mixing the negative electrode material in an organic solvent to obtain negative electrode slurry with the viscosity of 6300-7800 mPa & s;
and coating the negative electrode slurry on at least one surface of a negative electrode current collector, drying, rolling, slitting and tabletting to obtain the lithium ion battery negative electrode.
In the present invention, the positive electrode of the lithium ion battery includes a positive active material, which may be a material known to those skilled in the art, such as LiCoO, a conductive agent, and a binder2Lithium cobalt oxide, LiMn2O4Lithium manganese oxide, LiNiO, etc2Lithium nickel oxide, LiMPO4(M ═ Fe, Mn, Ni), and the like; the conductive agent is Super-P (purchased from Temi Gao company of Switzerland); the binder is HSV-900 (the binder is PVDF binder and is purchased from Arkema, France);
the preparation method of the positive electrode can adopt a conventional preparation method. Specifically, NMP is used as a solvent, a binder HSV-900 is dissolved, and then the positive active substance, the conductive agent Super-P and the solution of the binder are mixed and stirred to form uniform positive slurry; and uniformly coating the anode slurry on an aluminum foil, and drying to obtain the lithium ion battery anode.
In the invention, a polypropylene film is used as a diaphragm, the anode of the lithium ion battery and the cathode of the lithium ion battery are assembled into a battery core assembly, the battery core assembly is placed into a soft-package aluminum-plastic film battery shell, and the anode tab and the cathode tab are respectively welded with an aluminum-plastic film to obtain a battery semi-finished product, so that the insulation of the tabs and the battery shell is ensured in the process;
and injecting an electrolyte into the semi-finished product of the battery under the protection of a nitrogen atmosphere, sealing the battery, aging the battery for 48 hours at 40-50 ℃, charging to 4.0V at a current of 0.6A, secondarily aging for 48 hours at 40-50 ℃, and finally extracting gas generated in the battery under the protection of the nitrogen atmosphere and secondarily sealing the battery to obtain the lithium ion battery.
The advantages of the high stability and high capacity lithium ion battery provided by the present invention are further illustrated by the following specific examples.
Example 1
A high-stability high-capacity lithium ion battery comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the negative electrode comprises a negative electrode active material, a conductive agent and a binder,
the preparation method of the anode active material comprises the following steps:
(1) uniformly mixing zinc chloride in an organic solvent DMF, adding 1, 2-bis (4-pyridyl) ethylene, uniformly mixing, and sealing and reacting at 130 ℃ for 4 hours to obtain a precursor A;
(2) dissolving 2-hydroxyaniline in an organic solvent DMF to obtain a mixed solution, adding a precursor A into the mixed solution, performing ultrasonic dispersion for 8min to obtain a mixed system, dropwise adding an N-phenyl phenylenediamine solution into the mixed system under the stirring condition, and reacting for 4h to obtain an intermediate product B;
(3) placing the intermediate product B in a tube furnace, wherein the temperature in the tube furnace is 130 ℃; introducing steam into the tubular furnace to react under the pressure of 250Mpa to obtain a product C;
(4) and (3) uniformly mixing the product C with sodium sulfide in water, and carrying out thermal reaction on the mixed system under a sealed condition, wherein the temperature of the thermal reaction is 130 ℃, and the time of the thermal reaction is 5h, so as to obtain the cathode active material.
Uniformly mixing the prepared negative electrode active material, the conductive agent and the binder in a vacuum mixer to obtain a negative electrode material;
uniformly mixing the negative electrode material in DMF to obtain negative electrode slurry with the viscosity of 7000 mPas;
and coating the negative electrode slurry on at least one surface of a negative electrode current collector, drying, rolling, slitting and tabletting to obtain the lithium ion battery negative electrode.
Dissolving a binder HSV-900 by taking NMP as a solvent, mixing the positive active substance, the conductive agent Super-P and the solution of the binder, and stirring to form uniform positive slurry; and uniformly coating the anode slurry on an aluminum foil, and drying to obtain the lithium ion battery anode.
The positive pole and the negative pole of the lithium ion battery are assembled into a battery core assembly by taking a polypropylene film as a diaphragm, the battery core assembly is placed into a soft-package aluminum-plastic film battery shell, and the positive pole tab and the negative pole tab are respectively welded with an aluminum-plastic film to obtain a battery semi-finished product, so that the insulation of the tabs and the battery shell is ensured in the process;
preparing ethylene carbonate, methyl ethyl carbonate and dimethyl carbonate according to the mass ratio of 1:1.2:1 to obtain electrolyte;
and injecting an electrolyte into the semi-finished product of the battery under the protection of a nitrogen atmosphere, sealing the battery, aging the battery at 45 ℃ for 48h, charging the battery to 4.0V at a current of 0.6A, secondarily aging the battery at 45 ℃ for 48h, and finally extracting gas generated in the battery under the protection of the nitrogen atmosphere and secondarily sealing the battery to obtain the lithium ion battery A1.
Example 2
The lithium ion battery provided in this example is substantially the same as the lithium ion battery provided in example 1 in terms of the preparation method;
in contrast, the method for preparing the anode active material includes the steps of:
(1) uniformly mixing zinc chloride in an organic solvent DMF, adding 1, 2-bis (4-pyridyl) ethylene, uniformly mixing, and sealing and reacting at 130 ℃ for 4 hours to obtain a precursor A;
(2) dissolving 2-mercaptomethylaniline in an organic solvent DMF to obtain a mixed solution, adding a precursor A into the mixed solution, performing ultrasonic dispersion for 8min to obtain a mixed system, dropwise adding an N-phenyl phenylenediamine solution into the mixed system under the stirring condition, and reacting for 4h to obtain an intermediate product B;
(3) placing the intermediate product B in a tube furnace, wherein the temperature in the tube furnace is 130 ℃; introducing steam into the tubular furnace to react under the pressure of 250Mpa to obtain a product C;
(4) and (3) uniformly mixing the product C with sodium sulfide in water, and carrying out thermal reaction on the mixed system under a sealed condition, wherein the temperature of the thermal reaction is 130 ℃, and the time of the thermal reaction is 5h, so as to obtain the cathode active material.
The lithium ion battery prepared in this example was a 2.
Example 3
The lithium ion battery provided in this example is substantially the same as the lithium ion battery provided in example 1 in terms of the preparation method;
in contrast, the method for preparing the anode active material includes the steps of:
(1) uniformly mixing zinc chloride in an organic solvent DMF, adding 1, 2-bis (4-pyridyl) ethylene, uniformly mixing, and sealing and reacting at 130 ℃ for 4 hours to obtain a precursor A;
(2) dissolving 2-methoxyaniline in an organic solvent DMF to obtain a mixed solution, adding a precursor A into the mixed solution, performing ultrasonic dispersion for 8min to obtain a mixed system, dropwise adding an N-phenyl phenylenediamine solution into the mixed system under the stirring condition, and reacting for 4h to obtain an intermediate product B;
(3) placing the intermediate product B in a tube furnace, wherein the temperature in the tube furnace is 130 ℃; introducing steam into the tubular furnace to react under the pressure of 250Mpa to obtain a product C;
(4) and (3) uniformly mixing the product C with sodium sulfide in water, and carrying out thermal reaction on the mixed system under a sealed condition, wherein the temperature of the thermal reaction is 130 ℃, and the time of the thermal reaction is 5h, so as to obtain the cathode active material.
The lithium ion battery prepared in this example was a 3.
Example 4
The lithium ion battery provided in this example is substantially the same as the lithium ion battery provided in example 1 in terms of the preparation method;
in contrast, the method for preparing the anode active material includes the steps of:
(1) uniformly mixing zinc chloride in an organic solvent DMF, adding 1, 2-bis (4-pyridyl) ethylene, uniformly mixing, and sealing and reacting at 130 ℃ for 4 hours to obtain a precursor A;
(2) dissolving 2-chloroaniline in an organic solvent DMF to obtain a mixed solution, adding a precursor A into the mixed solution, performing ultrasonic dispersion for 8min to obtain a mixed system, dropwise adding an N-phenyl phenylenediamine solution into the mixed system under the stirring condition, and reacting for 4h to obtain an intermediate product B;
(3) placing the intermediate product B in a tube furnace, wherein the temperature in the tube furnace is 130 ℃; introducing steam into the tubular furnace to react under the pressure of 250Mpa to obtain a product C;
(4) and (3) uniformly mixing the product C with sodium sulfide in water, and carrying out thermal reaction on the mixed system under a sealed condition, wherein the temperature of the thermal reaction is 130 ℃, and the time of the thermal reaction is 5h, so as to obtain the cathode active material.
The lithium ion battery prepared in this example was a 4.
Example 5
The lithium ion battery provided in this example is substantially the same as the lithium ion battery provided in example 1 in terms of the preparation method;
in contrast, the method for preparing the anode active material includes the steps of:
(1) uniformly mixing zinc chloride in an organic solvent DMF, adding 1, 2-bis (4-pyridyl) ethylene, uniformly mixing, and sealing and reacting at 130 ℃ for 4 hours to obtain a precursor A;
(2) dissolving 2-ethoxyaniline in an organic solvent DMF to obtain a mixed solution, adding a precursor A into the mixed solution, performing ultrasonic dispersion for 8min to obtain a mixed system, dropwise adding an N-phenyl phenylenediamine solution into the mixed system under the stirring condition, and reacting for 4h to obtain an intermediate product B;
(3) placing the intermediate product B in a tube furnace, wherein the temperature in the tube furnace is 130 ℃; introducing steam into the tubular furnace to react under the pressure of 250Mpa to obtain a product C;
(4) and (3) uniformly mixing the product C with sodium sulfide in water, and carrying out thermal reaction on the mixed system under a sealed condition, wherein the temperature of the thermal reaction is 130 ℃, and the time of the thermal reaction is 5h, so as to obtain the cathode active material.
The lithium ion battery prepared in this example was a 5.
Example 6
The lithium ion battery provided in this example is substantially the same as the lithium ion battery provided in example 1 in terms of the preparation method;
in contrast, the method for preparing the anode active material includes the steps of:
(1) uniformly mixing zinc chloride in an organic solvent DMF, adding 1, 2-bis (4-pyridyl) ethylene, uniformly mixing, and sealing and reacting at 100 ℃ for 6 hours to obtain a precursor A;
(2) dissolving 2-hydroxyaniline in an organic solvent DMF to obtain a mixed solution, adding a precursor A into the mixed solution, performing ultrasonic dispersion for 5min to obtain a mixed system, dropwise adding an N-phenyl phenylenediamine solution into the mixed system under the stirring condition, and reacting for 2h to obtain an intermediate product B;
(3) placing the intermediate product B in a tube furnace, wherein the temperature in the tube furnace is 120 ℃; introducing water vapor to react under the pressure of 200Mpa in the tubular furnace to obtain a product C;
(4) and (3) uniformly mixing the product C with sodium sulfide in water, and carrying out thermal reaction on the mixed system under a sealed condition, wherein the temperature of the thermal reaction is 100 ℃, and the time of the thermal reaction is 8h, so as to obtain the cathode active material.
The lithium ion battery prepared in this example was a 6.
Example 7
The lithium ion battery provided in this example is substantially the same as the lithium ion battery provided in example 1 in terms of the preparation method;
in contrast, the method for preparing the anode active material includes the steps of:
(1) uniformly mixing zinc chloride in an organic solvent DMF, adding 1, 2-bis (4-pyridyl) ethylene, uniformly mixing, and sealing and reacting at 160 ℃ for 2 hours to obtain a precursor A;
(2) dissolving 2-hydroxyaniline in an organic solvent DMF to obtain a mixed solution, adding a precursor A into the mixed solution, performing ultrasonic dispersion for 10min to obtain a mixed system, dropwise adding an N-phenyl phenylenediamine solution into the mixed system under the stirring condition, and reacting for 6h to obtain an intermediate product B;
(3) placing the intermediate product B in a tube furnace, wherein the temperature in the tube furnace is 150 ℃; introducing steam into the tubular furnace to react under the pressure of 300Mpa to obtain a product C;
(4) and (3) uniformly mixing the product C with sodium sulfide in water, and carrying out thermal reaction on the mixed system under a sealed condition, wherein the temperature of the thermal reaction is 160 ℃, and the time of the thermal reaction is 4h, so as to obtain the cathode active material.
The lithium ion battery prepared in this example was a 7.
Comparative example 1
The lithium ion battery provided in this example is substantially the same as the lithium ion battery provided in example 1 in terms of the preparation method;
in contrast, the method for preparing the anode active material includes the steps of:
(1) uniformly mixing zinc chloride in an organic solvent DMF, adding 1, 2-bis (4-pyridyl) ethylene, uniformly mixing, and sealing and reacting at 130 ℃ for 4 hours to obtain a precursor A;
(2) dissolving 2-hydroxyaniline in an organic solvent DMF to obtain a mixed solution, adding a precursor A into the mixed solution, performing ultrasonic dispersion for 8min to obtain a mixed system, dropwise adding an N-phenyl phenylenediamine solution into the mixed system under the stirring condition, and reacting for 4h to obtain an intermediate product B;
(3) placing the intermediate product B in a tube furnace, wherein the temperature in the tube furnace is 130 ℃; introducing steam into the tubular furnace to react under the pressure of 250Mpa to obtain a product C;
(4) and carrying out thermal reaction on the product C under a sealed condition, wherein the temperature of the thermal reaction is 130 ℃, and the time of the thermal reaction is 5h, so as to obtain the cathode active material.
The lithium ion battery prepared in this example was D1.
The lithium ion battery prepared in the above embodiment was tested for relevant performance by the following method:
1. at 0.1mA/cm2The current density is subjected to constant-current charge and discharge experiments, the voltage range is limited to 0.001-2.0V, and the first charge and discharge specific capacity and the first discharge efficiency are tested. The calculation formula is as follows: first discharge efficiency is first charge capacity/first discharge capacity × 100%.
2. And (4) carrying out a battery cycle performance test of the material on a Luhua battery tester.
The results of the above tests are summarized in Table 1.
Table 1:
Figure BDA0001729910320000101
the foregoing shows and describes the general principles, essential features, and inventive features of this invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (8)

1. A preparation method of a high-stability high-capacity lithium ion battery cathode active material is characterized by comprising the following steps: the method comprises the following steps:
(1) uniformly mixing soluble metal salt in an organic solvent, adding 1, 2-di (4-pyridyl) ethylene, uniformly mixing, and carrying out sealing reaction at 100-160 ℃ for 2-6 h to obtain a complex precursor A, wherein the structural formula of the complex precursor A is M (C)12H10N2)nWherein M represents a metal;
(2) dissolving an aniline derivative in an organic solvent to obtain a mixed solution, adding a complex precursor A into the mixed solution, performing ultrasonic dispersion for 5-10 min to obtain a mixed system, dropwise adding an N-phenyl phenylenediamine solution into the mixed system under the stirring condition, and reacting for 2-6 h to obtain an intermediate product B, wherein the structural formula of the intermediate product B is M (C)12H10N2)n(ppy) wherein M represents a metal;
(3) placing the intermediate product B in a tubular furnace, introducing steam for reaction to obtain a product C, wherein the structural formula of the product C is M2Ox(C12H10N2)nThe formula is/PPy, wherein M represents metal, and the value of x is the chemical value of M;
(4) uniformly mixing the product C and a sulfur source in water, and carrying out thermal reaction on the mixed system under a sealed condition to obtain the cathode active material M2Sx(C12H10N2)nThe value of x is the combined value of M.
2. The method for preparing the negative active material of the high-stability high-capacity lithium ion battery according to claim 1, wherein the method comprises the following steps: the soluble metal salt is at least one selected from soluble zinc salt, soluble iron salt, soluble nickel salt and soluble cobalt salt.
3. The method for preparing the negative active material of the high-stability high-capacity lithium ion battery according to claim 1, wherein the method comprises the following steps: the aniline derivative is at least one of 2-hydroxyaniline, 2-mercaptomethylaniline, 2-methoxyaniline, 2-chloroaniline, 2-ethoxyaniline or 2-methylaniline.
4. The method for preparing the negative active material of the high-stability high-capacity lithium ion battery according to claim 1, wherein the method comprises the following steps: in the step (3), the temperature in the tube furnace is 120-150 ℃.
5. The method for preparing the negative active material of the high-stability high-capacity lithium ion battery according to claim 1, wherein the method comprises the following steps: in the step (4), the temperature of the thermal reaction is 100-160 ℃, and the time of the thermal reaction is 4-8 h.
6. The method for preparing the negative active material of the high-stability high-capacity lithium ion battery according to claim 1, wherein the method comprises the following steps: the organic solvent is at least one selected from methanol, toluene, dichloromethane, tetrahydrofuran, ethyl acetate, acetone, N-dimethylformamide, N-methylpyrrolidone, N-dimethylacetamide, N-diethylformamide, petroleum ether and dimethyl sulfoxide.
7. The method for preparing the negative active material of the high-stability high-capacity lithium ion battery according to claim 1, wherein the method comprises the following steps: the sulfur source is at least one selected from sodium sulfide, potassium sulfide and thiourea.
8. The high-stability high-capacity lithium ion battery negative electrode active material prepared by the preparation method of any one of claims 1 to 7.
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