CN110474031B - Method for preparing copper-doped manganous-manganic oxide composite material by using polymeric complexing agent - Google Patents

Method for preparing copper-doped manganous-manganic oxide composite material by using polymeric complexing agent Download PDF

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CN110474031B
CN110474031B CN201910768832.0A CN201910768832A CN110474031B CN 110474031 B CN110474031 B CN 110474031B CN 201910768832 A CN201910768832 A CN 201910768832A CN 110474031 B CN110474031 B CN 110474031B
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copper
complexing agent
composite material
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metal complex
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CN110474031A (en
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刘伟良
高庆立
常金
李东帅
任慢慢
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Shandong Jiqing Technology Service Co ltd
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Qilu 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

The invention discloses a method for preparing a copper-doped manganous-manganic oxide composite material by using a polymer complexing agent. Firstly complexing manganese ions and a high-molecular complexing agent according to a certain proportion, then complexing copper ions and polyethyleneimine, and then mixing the two complexing systems to form a uniform precursor. And centrifuging to obtain wet gel of the binary metal complex, and drying for 10 hours to obtain binary metal complex powder. And finally, placing the powder in a muffle furnace, and roasting at the high temperature of 350-400 ℃ for 2~3 hours to obtain the copper-doped manganous-manganic oxide composite material. The invention has the advantages that the dispersibility and the compatibility of the copper element in the trimanganese tetroxide main body are better, and the obtained composite material has excellent conductive performance and electrochemical performance. In addition, the method has the advantages of simple preparation process, low production cost and wide application prospect.

Description

Method for preparing copper-doped manganous-manganic oxide composite material by using polymeric complexing agent
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a preparation method of a cathode material of a water-based zinc ion secondary battery.
Background
The global energy crisis and the rapid increase in environmental pollution are driving the opportunity for the rapid development of clean energy, and the demand for large energy storage devices is increasing. Rechargeable zinc ion batteries have many advantages and are receiving more and more attention, and particularly, the rechargeable zinc ion batteries can replace the traditional organic electrolyte with a water-based electrolyte, which is very important in aspects of reducing cost and environmental pollution. Most zinc ion batteries often employ manganese metal oxides as positive electrodes, for example, zhou Jiang topic group manganomanganic oxide as positive electrode material of aqueous zinc ion secondary batteries (Zhu, chuyu, et al, binder-free solid support @ Mn 3 O 4 nanoflower composite: a high-activity aqueous zinc-ion battery cathode with high-capacity and long-cycle-life. Journal of Materials Chemistry A2018, 6.20: 9677-9683), and the electrochemical material is found to have good electrochemical performance and is an electrode material with wide application prospect. In addition, xu Chengjun sets of subjects made intensive theoretical studies on this material (Hao, jianwu, et al. Electrochemically induced spin-layered phase tran)sition of Mn 3 O 4 in high performance neutral aqueous rechargeable zinc battery. Electrochimica Acta, 2018, 259: 170-178.). However, when the material is used as a positive electrode of a zinc ion battery, the problems of low battery capacity, low coulombic efficiency and the like exist, so that the modification of pure mangano-manganic oxide to improve the electrical property is imperative, and the research is started from the preparation aspect of a precursor, so that the material is an effective way for improving the electrochemical property of the material.
Disclosure of Invention
The invention aims to provide a simple method for preparing a high-performance anode material, which is mainly realized by doping metal atoms for modification. The macromolecular complexing agent is combined with manganese ions, so that the manganese ions can be uniformly distributed in the macromolecular complexing agent, and the dispersibility of the manganese ions in a solution system is improved; meanwhile, after a small amount of copper ions are complexed with polyethyleneimine, the two metal complexes are mixed to obtain a binary metal complex, and then the binary metal complex is sintered at high temperature to form the copper-doped manganous manganic oxide composite material. In addition, the high molecular complexing agent is converted into a carbon substance in the sintering process, and the electronic conductivity of the composite material can be effectively improved.
In order to realize the purpose of the invention, the following technical scheme is provided:
a method for preparing a copper-doped manganous-manganic oxide composite material by using a polymer complexing agent is characterized by comprising the following steps:
(1) Dispersing a high molecular complexing agent in a proper amount of deionized water, heating the mixture to 50-60 ℃ in an oil bath, and magnetically stirring the mixture for 1~2 hours until the high molecular complexing agent is swelled or dissolved;
(2) Dissolving a divalent manganese salt in a proper amount of deionized water, carrying out ultrasonic treatment until the divalent manganese salt is completely dissolved, then adding the divalent manganese salt into the suspension or solution obtained in the step (1), and continuously stirring for 4~5 hours to obtain a precursor containing a manganese metal complex;
(3) Dissolving a copper salt in a proper amount of deionized water, performing ultrasonic-assisted dissolution for 5 minutes, then adding a proper amount of polyethyleneimine with the molecular weight of 600, performing ultrasonic-assisted dispersion for 5 minutes, then dropwise adding the copper complex into the precursor in the step (2), performing magnetic stirring for 1~2 hours, finally separating the metal complex from water by using a centrifugal machine, and washing with water and ethanol once respectively to obtain a binary metal complex wet gel;
(4) Drying the wet gel obtained in the step (3) at 50 ℃ for 10 hours to obtain binary metal complex powder;
(5) And (3) roasting the metal complex powder obtained in the step (4) in an air atmosphere at the speed of 5 ℃/min to 350-400 ℃ for 2~3 hours to obtain the copper ion doped manganous-manganic oxide composite material.
Further, the polymer complexing agent in the step (1) is at least one of chitosan or polyvinyl alcohol.
Further, the divalent manganese salt in the step (2) is at least one of manganese chloride, manganese acetate or manganese nitrate.
Further, the copper salt in the step (3) is at least one of copper sulfate or copper chloride.
Further, the mass ratio of the copper salt, the divalent manganese salt and the polymer complexing agent is 1.
The invention is characterized in that: in the preparation process of the material, divalent manganese ions are combined with a macromolecular complexing agent through complexing action, copper ions are complexed with polyethyleneimine, and then the two metal complexes are mixed, so that the metal ions have better dispersibility in the binary metal complex. The complexation can reduce free metal ions in the system, and the stable coordination bond is formed between the complexing group and the metal ions, so that the stability of the metal ions is effectively improved. And then the coordination bond is destroyed by high-temperature sintering, and the copper-doped manganous-manganic oxide composite material is formed by sintering. The carbon substance generated in the sintering process can improve the electronic conductivity of the composite material; the preparation process is simple, short in flow, low in material cost, less in environmental pollution and the like.
The present invention will be further described with reference to specific examples, but the present invention is not limited to the above-described examples.
Example 1:
(1) Placing 0.217 g chitosan and 40 ml deionized water into a 100 ml three-neck flask, heating the oil bath to 50 ℃, and magnetically stirring for 1 hour to fully swell and even dissolve chitosan molecules;
(2) Dissolving 0.402 g manganese acetate in 10 ml deionized water, dissolving for 5 minutes under the assistance of ultrasonic waves, adding the solution into the suspension obtained in the step (1), and stirring for 4 hours to fully complex manganese ions and chitosan molecules to obtain a precursor containing a manganese metal complex;
(3) Dissolving 0.0514 g copper sulfate in 10 ml deionized water, carrying out ultrasonic-assisted dissolution for 5 minutes, then adding 1 ml polyethyleneimine, continuing ultrasonic-assisted dispersion for 5 minutes, dropwise adding the complex into the precursor in the step (2), carrying out magnetic stirring for 1 hour, separating the metal complex from water by using a centrifugal machine, and washing with water and ethanol once respectively to obtain a metal complex wet gel;
(4) Drying the wet gel obtained in the step (3) at 50 ℃ for 10 hours to obtain binary metal complex powder;
(5) And (5) roasting the sample obtained in the step (4) in an air atmosphere at the speed of 5 ℃/min to 400 ℃ for 2 hours to obtain the composite material.
Example 2:
(1) Placing 0.309 g chitosan and 50 ml deionized water in a 100 ml three-neck flask, raising the temperature to 50 ℃ by oil bath, and stirring for 1 hour by magnetic force to fully swell and even dissolve chitosan molecules;
(2) Dissolving 0.415 g manganese chloride in 10 ml deionized water, dissolving for 5 minutes under the assistance of ultrasonic waves, adding the solution into the suspension obtained in the step (1), and stirring for 4 hours to fully complex manganese ions and chitosan molecules to obtain a precursor containing a manganese metal complex;
(3) Dissolving 0.0504 g copper sulfate in 12 ml deionized water, carrying out ultrasonic-assisted dissolution for 5 minutes, then adding 1 ml polyethyleneimine, continuing ultrasonic-assisted dispersion for 5 minutes, dropwise adding the complex into the precursor in the step (2), carrying out magnetic stirring for 2 hours, separating the metal complex from water by using a centrifugal machine, and washing with water and ethanol once respectively to obtain a metal complex wet gel;
(4) Drying the wet gel obtained in the step (3) at 50 ℃ for 10 hours to obtain binary metal complex powder;
(5) And (4) roasting the sample obtained in the step (4) in an air atmosphere at the speed of 5 ℃/min to 400 ℃ for 3 hours to obtain the composite material.
Example 3:
(1) Placing 0.205 g polyvinyl alcohol and 40 ml deionized water into a 100 ml three-neck flask, heating the oil bath to 60 ℃, and magnetically stirring for 2 hours to fully swell and even dissolve chitosan molecules;
(2) Dissolving 0.413 g manganese acetate in 15 ml deionized water, dissolving for 5 minutes under the assistance of ultrasonic waves, adding the solution into the suspension obtained in the step (1), and stirring for 5 hours to fully complex manganese ions and chitosan molecules to obtain a precursor containing a manganese metal complex;
(3) Dissolving 0.0524 g copper chloride in 10 ml deionized water, carrying out ultrasonic-assisted dissolution for 5 minutes, then adding 1.5 ml polyethyleneimine, continuing ultrasonic-assisted dispersion for 5 minutes, dropwise adding the complex into the precursor in the step (2), carrying out magnetic stirring for 1 hour, separating the metal complex from water by using a centrifugal machine, and washing with water and ethanol once respectively to obtain a metal complex wet gel;
(4) Drying the wet gel obtained in the step (3) at 50 ℃ for 10 hours to obtain binary metal complex powder;
(5) And (4) roasting the sample obtained in the step (4) in an air atmosphere at the speed of 5 ℃/min to 350 ℃ for 3 hours to obtain the composite material.
Example 4:
(1) Placing 0.235 g chitosan and 50 ml deionized water in a 100 ml three-neck flask, raising the temperature to 60 ℃ in an oil bath, and magnetically stirring for 2 hours to fully swell and even dissolve chitosan molecules;
(2) Dissolving 0.403 g manganese nitrate in 15 ml deionized water, dissolving for 5 minutes under the assistance of ultrasonic waves, adding the solution into the suspension obtained in the step (1), and stirring for 5 hours to fully complex manganese ions and chitosan molecules to obtain a precursor containing a manganese metal complex;
(3) Dissolving 0.0532 g copper chloride in 12 ml deionized water, carrying out ultrasonic-assisted dissolution for 5 minutes, then adding 1 ml polyethyleneimine, continuing ultrasonic-assisted dispersion for 5 minutes, dropwise adding the complex into the precursor in the step (2), carrying out magnetic stirring for 2 hours, separating the metal complex from water by using a centrifuge, and washing with water and ethanol once respectively to obtain a metal complex wet gel;
(4) Drying the wet gel obtained in the step (3) at 50 ℃ for 10 hours to obtain binary metal complex powder;
(5) And (5) roasting the sample obtained in the step (4) in an air atmosphere at the speed of 5 ℃/min to 400 ℃ for 2 hours to obtain the composite material.

Claims (4)

1. A method for preparing a copper-doped manganous-manganic oxide composite material by using a polymer complexing agent is characterized by comprising the following steps:
(1) Dispersing chitosan or a mixture of chitosan and polyvinyl alcohol serving as a macromolecular complexing agent into a proper amount of deionized water, heating the mixture to 50-60 ℃ in an oil bath, and magnetically stirring the mixture for 1-2 hours until the macromolecular complexing agent is swelled or dissolved;
(2) Dissolving a divalent manganese salt in a proper amount of deionized water, carrying out ultrasonic treatment until the divalent manganese salt is completely dissolved, then adding the divalent manganese salt into the suspension or the solution obtained in the step (1), and continuously stirring for 4-5 hours to obtain a precursor containing a manganese metal complex;
(3) Dissolving a copper salt in a proper amount of deionized water, performing ultrasonic-assisted dissolution for 5 minutes, then adding a proper amount of polyethyleneimine with the molecular weight of 600, performing ultrasonic-assisted dispersion for 5 minutes, then dropwise adding the copper complex into the precursor in the step (2), performing magnetic stirring for 1-2 hours, finally separating the metal complex from water by using a centrifugal machine, and washing with water and ethanol once respectively to obtain a binary metal complex wet gel;
(4) Drying the wet gel obtained in the step (3) at 50 ℃ for 10 hours to obtain binary metal complex powder;
(5) And (4) roasting the metal complex powder obtained in the step (4) in an air atmosphere at the speed of 5 ℃/min to 350-400 ℃ for 2-3 hours to obtain the copper ion doped manganous-manganic oxide composite material.
2. The method for preparing the copper-doped manganous-manganic oxide composite material by using the polymeric complexing agent according to claim 1, wherein the mass ratio of the copper salt to the manganous salt to the polymeric complexing agent is 1.
3. The method for preparing copper-doped manganous-manganic oxide composite material by using polymeric complexing agent as claimed in claim 1, wherein the manganous salt is at least one of manganese chloride, manganese acetate or manganese nitrate.
4. The method of claim 1, wherein the copper salt is at least one of copper sulfate or copper chloride.
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