CN108963244B - Preparation method of composite electrode material - Google Patents

Preparation method of composite electrode material Download PDF

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CN108963244B
CN108963244B CN201810831232.XA CN201810831232A CN108963244B CN 108963244 B CN108963244 B CN 108963244B CN 201810831232 A CN201810831232 A CN 201810831232A CN 108963244 B CN108963244 B CN 108963244B
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solution
black powder
electrode material
composite electrode
stirring
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CN108963244A (en
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刘玉华
徐勇霖
李智敏
曾芝
林海吟
徐丽琴
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Guangzhou 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • 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

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  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The invention provides a preparation method of a composite electrode material, which comprises the following steps of (1) mixing L i2Dissolving S and glucose in ethylene glycol, and stirring for 20-40min to obtain solution A; (2) adding C to the A solution4H6FeO4And C4H6CuO4H2O, stirring for 50-70min to obtain a solution B; (3) drying the solution B into black powder, and calcining; (4) washing the black powder burned in the step (3) with water and alcohol and drying; (5) and (4) dispersing the black powder obtained in the step (4) in an oleic acid ethanol solution, and utilizing a laser focusing beam to act on the black powder to obtain the composite electrode material. The material has stable charging and discharging structure, and the prepared electrode material has high purity, uniform electrochemical reaction and good cycling stability.

Description

Preparation method of composite electrode material
Technical Field
The invention relates to a preparation method of a composite electrode material.
Background
Lithium ion batteries have been used in various fields as the most advanced energy storage devices. The negative electrode material in the lithium ion battery is the key for determining the performance and the cost of the lithium ion battery, and along with the increase of energy requirements caused by scientific development, the requirements of high capacity, long-period stability and safety performance of the lithium ion battery become more and more urgent.
In a large number of anode materials, transition metal sulfides, e.g. Co9S8、FeS2、CoS2And NiS has high theoretical capacity, low cost, safety and small influence on environment. Furthermore, byTransition metal sulfides are considered as an alternative anode material battery for lithium ions in view of high conductivity, superior mechanical and thermal stability, and excellent redox reversibility. For the binary metal sulfide, due to the introduction of another metal ion, the connection between atoms is more enriched, so that the crystal structure is diversified, the binary metal sulfide has unique properties, the electrochemical performance is more excellent, and the binary metal sulfide must be a better cathode material of a lithium ion battery. CuFeS, a poorly performing semiconductor2(chalcopyrite) is ubiquitous and stable in nature, presents low fiber band gap and antiferromagnetic property, is a natural mineral with special golden gloss, and presents a tetragonal structure in which Fe and Cu ions are coordinated with sulfur in a tetrahedral lattice. Due to the unique structure, CuFeS2Has high conductivity and excellent electrochemical performance. How to avoid the oxidation of the metal nanoparticles and maintain their inherent properties stably for a long time is a key technology in the field of metal particle preparation, and is also the fundamental way to increase the application range.
Disclosure of Invention
The invention aims to provide a preparation method of a composite electrode material.
In order to achieve the purpose, the invention adopts the technical scheme that: a preparation method of a composite electrode material is characterized by comprising the following steps:
(1) l i2Dissolving S and glucose in ethylene glycol, and stirring for 20-40min to obtain solution A;
(2) adding C to the A solution4H6FeO4And C4H6CuO4·H2O, stirring for 50-70min to obtain a solution B;
(3) drying the solution B into black powder, and calcining;
(4) washing the calcined black powder in the step (3) with water and alcohol and drying;
(5) and (4) dispersing the black powder obtained in the step (4) in an oleic acid ethanol solution, and utilizing a laser focusing beam to act on the black powder to obtain the composite electrode material.
The prepared composite electrode material is CuFeS with a relatively complete carbon frame layer2QDs, and all have ordered carbons of graphitic structure.
Preferably, the wavelength of the laser is 1064 nm.
Preferably, the volume concentration of the oleic acid in the oleic acid ethanol solution is 0.5%.
Preferably, the laser focusing beam action is performed under an inert gas atmosphere.
Preferably, the inert gas is argon.
Preferably, the calcination procedure of step (3) is: calcining for 30min at 10 deg.C for 10 min-1Heating rate of (2) to 300 ℃.
Preferably, the L i2S、C4H6FeO4、C4H6CuO4·H2The mass ratio of the amounts of O and glucose was 4:2:2: 1.1.
Preferably, in the step (4), the black powder calcined in the step (3) is washed with water and alcohol in the step (4), and dried at 80 ℃ for 24 hours.
Preferably, the stirring in the step (1) is carried out for 30 min.
Preferably, the stirring in the step (2) is carried out for 60 min.
The invention also provides a composite electrode material prepared by any one of the preparation methods.
The invention has the beneficial effects that: the composite electrode material prepared by the method has a stable charge-discharge structure, uniform electrochemical reaction and good cycle stability. The composite electrode material prepared by the method has large-scale CuFeS2 Quantum Dots (QDs) on a carbon frame, is free from control of a pollution stage, has good phase purity, is stable in frequency and small in error when a battery is charged and discharged, and has few byproducts, so that the conductivity of the material can be improved, and the internal resistance of the assembled battery is minimum.
Drawings
FIG. 1a is a CV plot of a composite electrode material of example 1;
b is a discharge charge profile of the composite electrode material of example 1.
FIG. 2a is a graph of the cycling performance and coulombic efficiency of the composite electrode material of example 1;
b is a plot of the rate performance of the composite electrode material of example 1;
and c is a long-term cycling stability performance graph of the composite electrode material of example 1.
Detailed Description
The present invention will be described in detail with reference to examples, but is not limited thereto.
Example 1
A composite electrode material and a preparation method thereof comprise the following steps:
1.4 mmol L i2S and 200mg of glucose are dissolved in 20m L of ethylene glycol and stirred for 30 minutes;
2. 2mmol of C4H6FeO4And 2mmol of C4H6CuO4·H2Adding O into the solution obtained in the step 1, and magnetically stirring for 60 minutes;
3. drying the 10m L solution at 300 deg.C for 5min to obtain black powder;
4. placing the obtained black powder in a test tube furnace, and calcining in the furnace for 30min at 10 deg.C for 10 min-1Heating to 300 deg.C;
5. washing the black powder with deionized water and ethanol, centrifuging to obtain solid powder, and drying at 80 deg.C for 24 hr;
6. a parallel laser beam with the wavelength of 1064nm is focused by a lens and then acts on the solid target material in the ethanol oleic acid solution. The process is as follows:
(1) preparing an ethanol solution with the volume concentration of oleic acid being 0.5%;
(2) placing the ethanol oleic acid solution in a quartz beaker which does not absorb laser, placing the black powder obtained in the step (5) at the bottom of the beaker, wherein the liquid level is about 3 mm;
(3) focusing a focused beam of 1064nm nanosecond pulse laser on a target material in the solution and acting on the target material, and performing argon gas protection on the solution while the laser acts.
Materials without laser action are not subjected to high-temperature reaction, and the product is inevitably accompanied with other byproducts such as carbon nano tubes, fullerene, carbon black and the like besides carbon-coated metal particles due to the complexity of high-temperature reaction, so that the purity of the main product is low. After the laser action, other by-products contained in the material are removed, and the prepared electrode material has high purity, uniform electrochemical reaction and good cycle stability.
The CV curve of FIG. 1a shows, at a scan rate of 0.2mVs-1Anodic scans at 0.0050 to 3.0V showed four peaks, 2.10V (a), 1.45V (b), 1.08V (g) and 0.55V (h), respectively, while the first cathodic scan showed three peaks, 1.56V (d), 1.95V (e) and 2.40V (f), respectively. On the first and subsequent cycles, the product was found to have a consistent CV curve, showing a uniform electrochemical reaction and good cycle stability.
FIG. 1b is a cross-sectional view of the discharged charge showing that the current density is 50mA g-1The first cycle discharge capacity was 1540mA hg-1. During the first charge, three plateaus are seen, with a capacity of 1079mA hr g-1. The initial coulombic specific efficiency was 70.0%. The discharge charge profiles of the second and fifth cycles showed the same characteristics as the CV curve, with a reversible capacity of about 1050mA h g-1。
FIG. 2a shows that the charge-discharge density at current is 0.2mA g-1The initial first-cycle discharge capacity is 1174mA h g-1. The charge capacity of the first charging process was 900mA h g-1. Thus, the initial coulombic efficiency was 76.7%. After 250 cycles of the cycle, the discharge capacity and the charging capacity are 825.6mA h g and g respectively-1And 825.5mA hr g-1. The retention of this capacity can reach 91.7%, which indicates that there is little capacity degradation. Furthermore, in the next 249 cycles, the coulombic efficiency approaches 100%, except for the first cycle.
As shown in fig. 2 b. Reversible capacity 1150mA h g with different interest rates-1(0.05g-1)，1060mA h g-1(0.1g-1)，960mA h g-1(0.2g-1)，850mA h g-1(0.4Ag)-1)，700mA h g-1(0.8g-1)，450mA h g-1(1.6g-1)，250mA h g-1(3.2g-1) And 110mA h g-1(6.4g-1). When the current is reversed to 0.1g-1When the capacity is reversible, the capacity can be recovered to 900mA h g-1This is 90% of the reversible capacity. Even at 1.6A g-1Under the condition of (2), can also reach 450mA h g-1This still exceeds the theoretical capacity of graphite. Thus, the composite electrode exhibits a long cycle life at different current densities and superior rate performance.
FIG. 2c shows the stable cycling performance
CuFeS2 QDs @ c composite electrode at a g of 0.5-1Is taken as a basis. After 700 cycles, 92.5% of the capacity may be retained.
The CuFeS with a relatively complete carbon frame layer is prepared by adopting a laser method2The QDs material, the material preparation film not only can regenerate the components of the target material easily, but also can adopt the multi-target technology to realize the layered growth of the film, thereby providing convenience for further modification and improvement of the film electrode material. The method can improve the cycle characteristic and the thermal stability, and can also improve the average valence state of manganese ions, increase the specific surface area of a film material, reduce the interface impedance of the battery, and improve the diffusion characteristic and the mobility of lithium ions and electrons, thereby further improving the discharge voltage platform, the energy density, the reversible capacity and the large-current discharge capacity of the lithium ion battery. The method aims to solve the problem of reduction of electrochemical activity of the material caused by instability of a substrate, and has the advantages of high working voltage, long cycle life, high energy density and excellent rate capability.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims (7)

1. CuFeS with relatively complete carbon frame layer2The preparation method of the QDs composite electrode material is characterized by comprising the following steps:
(1) l i2Dissolving S and glucose in ethylene glycol, and stirring for 20-40min to obtain solution A;
(2) adding C to the A solution4H6FeO4And C4H6CuO4·H2O, stirring for 50-70min to obtain a solution B;
(3) drying the solution B into black powder, and calcining;
(4) washing the black powder calcined in the step (3) with water and alcohol, and drying;
(5) dispersing the black powder obtained in the step (4) in an oleic acid ethanol solution, and using a laser focusing beam to act on the black powder to obtain the composite electrode material, wherein the wavelength of the laser is 1064 nm;
the L i2S、C4H6FeO4、C4H6CuO4·H2The mass ratio of the O to the glucose is 4:2:2: 1.1;
the calcining procedure of the step (3) is as follows: calcining for 30min at 10 deg.C for 10 min-1Heating rate of (2) to 300 ℃.
2. The method according to claim 1, wherein the oleic acid ethanol solution has a concentration of 0.5% by volume of oleic acid.
3. The method of claim 1, wherein the laser focused beam is applied under an inert gas atmosphere.
4. The method of claim 3, wherein the inert gas is argon.
5. The method of claim 1, wherein in the step (4), the black powder calcined in the step (3) is washed with water and alcohol and dried at 80 ℃ for 24 hours.
6. The method according to claim 1, wherein the stirring is carried out for 30min in the step (1) and for 60min in the step (2).
7. A composite electrode material produced by the production method according to any one of claims 1 to 6.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103298736A (en) * 2010-12-28 2013-09-11 东北精机工业株式会社 Process for production of compound having chalcopyrite structure
CN103794788A (en) * 2014-02-21 2014-05-14 合肥国轩高科动力能源股份公司 Surface carbon coating method of lithium iron phosphate positive electrode material
CN104362343A (en) * 2014-11-21 2015-02-18 厦门大学 Preparation method and application of one-dimensional rod-like CuFeS2 compound
CN105154060A (en) * 2015-07-21 2015-12-16 东华大学 Preparation method for three-element copper-iron-sulfur (CuFeS2) fluorescent quantum dot with magnetic property by aqueous-phase synthesis

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103298736A (en) * 2010-12-28 2013-09-11 东北精机工业株式会社 Process for production of compound having chalcopyrite structure
CN103794788A (en) * 2014-02-21 2014-05-14 合肥国轩高科动力能源股份公司 Surface carbon coating method of lithium iron phosphate positive electrode material
CN104362343A (en) * 2014-11-21 2015-02-18 厦门大学 Preparation method and application of one-dimensional rod-like CuFeS2 compound
CN105154060A (en) * 2015-07-21 2015-12-16 东华大学 Preparation method for three-element copper-iron-sulfur (CuFeS2) fluorescent quantum dot with magnetic property by aqueous-phase synthesis

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
碳包覆对CuFeS2电化学性能的影响;沈洁 等;《电源技术》;20170420;第41卷(第4期);第527-529页 *

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