CN107134570B - Zinc ion battery active composite material and preparation method and application thereof - Google Patents

Zinc ion battery active composite material and preparation method and application thereof Download PDF

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CN107134570B
CN107134570B CN201710328366.5A CN201710328366A CN107134570B CN 107134570 B CN107134570 B CN 107134570B CN 201710328366 A CN201710328366 A CN 201710328366A CN 107134570 B CN107134570 B CN 107134570B
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zinc
composite material
ion battery
active composite
substance
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CN107134570A (en
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王丽平
邹剑
杨静怡
赵明娟
李晶泽
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University of Electronic Science and Technology of China
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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
    • H01M10/36—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
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • 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
    • 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 discloses a zinc ion battery active composite material and a preparation method and application thereof. The preparation method comprises the following steps: (1) placing terephthalic acid series acid or salt, zinc salt and a conductive additive into a container, mixing, and grinding for 0.5-2 hours to obtain a mixture; (2) adding deionized water into the mixture obtained in the step (1), performing ultrasonic dispersion, then centrifuging, removing the supernatant of the centrifugation, alternately washing the precipitate for 2-3 times by using N-methylpyrrolidone and deionized water respectively, and filtering; (3) and (3) adding deionized water into the substance obtained in the step (2), performing ultrasonic dispersion, performing ball milling for 4-5 h, and performing spray drying to obtain the active composite material of the zinc ion battery. The zinc ion battery active composite material prepared by the method has good crystallization property, can be naturally degraded in the environment, and is green and environment-friendly; the prepared battery is non-toxic, environment-friendly and low in cost.

Description

Zinc ion battery active composite material and preparation method and application thereof
Technical Field
The invention belongs to the field of material synthesis, and particularly relates to a zinc ion battery active composite material, and a preparation method and application thereof.
Background
The material is a material basis necessary for human production activities and life, and is closely related to human civilization and technical progress. With the continuous progress and development of society, people face the dual challenges of resource exhaustion and living environment deterioration. Therefore, various countries strive to promote and research new materials, promote low-carbon life concepts, and promote the human society to move towards an energy-saving and resource-recycling sustainable development mode. Clean energy sources such as solar energy, wind energy and the like which are vigorously popularized by governments of various countries are gradually applied to human life in a large scale, and hybrid electric vehicles or pure electric vehicles are also slowly replacing gasoline which is widely used at present to drive traditional vehicles. However, the large-scale development and utilization of these renewable resources require the construction of a complete electrical energy storage device to ensure the continuity and stability of the power supply. Among the energy storage systems, electrochemical energy storage cells are the most interesting energy storage devices due to their flexibility, high efficiency and no geographical restrictions.
For electrochemical energy storage devices, a great deal of research is currently focused on the field of rechargeable secondary batteries, and a great deal of commercial applications including nickel-hydrogen batteries, nickel-cadmium batteries, lead-acid batteries, lithium ion batteries, and the like are already available. However, these battery systems also have certain disadvantages, such as environmental pollution, low specific energy, and poor safety. There are a lot of research on solving these problems, including developing novel organic degradable electrode materials to overcome the pollution problem; the specific energy is improved by replacing lithium ions with metal lithium; exploring all-solid-state batteries to improve battery safety, and the like. The research on rechargeable batteries belongs to a research system for revitalizing glowing compared with the research on rechargeable batteries applied to primary batteries, and the zinc cathode has the advantages of no toxicity, low price, environmental friendliness, high energy density and the like, and has attracted more and more attention in recent years.
The current research on zinc secondary batteries mainly focuses on two aspects, one is the research on the electrolyte and the other is the research on the electrode material. The electrolyte of the current battery mostly adopts aqueous electrolyte, such as aqueous solution of zinc sulfate, the system is cheap and environment-friendly, for electrode materials, the current positive electrode materials applied to the zinc secondary battery are not many, and the main systems comprise zinc-manganese dioxide, zinc-air and a new zinc-Prussian blue system. Therefore, the development of a novel battery electrode material system is of great significance for accelerating the commercialization of the battery, and is also necessary.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a zinc ion battery active composite material, a preparation method and application thereof, and provides the zinc ion battery active composite material which is naturally degradable, environment-friendly, pollution-free and low in production cost and is applied to battery preparation.
A preparation method of a zinc ion battery active composite material comprises the following steps:
(1) placing terephthalic acid series acid or salt, zinc salt and a conductive additive into a container, mixing, and grinding for 0.5-2 hours to obtain a mixture; wherein, the molar ratio of the zinc salt to the substituent group in the terephthalic acid series acid or the salt is 1:2, the mass of the two products is 50-95% of the mass of the mixture, and the rest is the conductive additive;
(2) adding deionized water into the mixture obtained in the step (1), performing ultrasonic dispersion, centrifuging for 5-8 min at 9000-10000 r/min, removing supernatant, alternately washing precipitates for 2-3 times by using 40-50 mL of N-methylpyrrolidone and deionized water respectively, and filtering to obtain mixed particles of a substance A and a substance B; wherein the substance A is one or more of zinc terephthalate, zinc benzoate, zinc phthalate or zinc isophthalate; the substance B is a conductive additive;
(3) and (3) adding deionized water into the particles obtained in the step (2), performing ultrasonic dispersion, performing ball milling for 4-5 h under the condition of 400-450 r/min, and performing spray drying to obtain the active composite material for the zinc ion battery.
Further, in the step (1), the terephthalic acid series acid is one or more of benzoic acid, phthalic acid, isophthalic acid and terephthalic acid; the terephthalic acid series salt is lithium salt, sodium salt, potassium salt or calcium salt.
Further, the terephthalic acid series acid in the step (1) is terephthalic acid.
Further, the zinc salt in the step (1) is one or more of zinc sulfate, zinc acetate, zinc nitrate and zinc chloride.
Further, the conductive additive in the step (1) is one or more of carbon black, furnace black, graphite particles, acetylene black, Super P, Ketjen black, carbon nanotubes and graphene.
Further, the conductive additive in the step (1) is carbon nano-tubes.
Further, the shape of the active composite material of the zinc ion battery in the step (3) is one or more of a spherical shape, an ellipsoid shape and an irregular polyhedron; wherein the particle size of the substance A is 50-500 nm, and the substance A is uniformly distributed around the substance B or uniformly coated on the substance B.
The zinc ion battery active composite material prepared by the preparation method is adopted.
The application of the active composite material of the zinc ion battery in battery preparation.
The invention has the beneficial effects that:
1. the zinc-based terephthalic acid material is successfully synthesized by the method, and the prepared zinc terephthalate has good crystallinity.
2. The conductive additive is directly added in the preparation process, so that the uniform compounding of the conductive additive and the active substance can be realized, and the conductive additive is uniformly dispersed and distributed on the surface and around the zinc phthalate series material, thereby being beneficial to improving the conductive capability of the material.
3. The invention has low practical application cost and is environment-friendly, wherein the active material zinc terephthalate is micromolecular organic metal salt which can be naturally degraded in the environment and is green and environment-friendly; the counter electrode is metal zinc, the zinc element is relatively abundant in China, the mining and application cost is low, and the element is non-toxic and environment-friendly; for the battery assembling process, the process can be realized in the air, and is insensitive to air humidity, carbon dioxide content, oxygen content and the like, so that the production cost can be greatly reduced.
4. The zinc ion battery active composite material prepared by the invention has good crystallization performance, and when the zinc ion battery active composite material is applied to a zinc ion battery, the zinc ion battery active composite material is stable in electrolyte, the cycle performance is good, and the stable capacity can reach 96 mAh/g; the electrolyte adopts zinc sulfate aqueous solution, and has the characteristics of low price and environmental protection; the battery cathode material adopts metal zinc, and has the characteristics of no toxicity, environmental protection and low cost; the whole battery assembly can be completely realized in the air, the requirement on the production environment is low, and the cost can be greatly reduced.
Drawings
Fig. 1 is an X-ray diffraction (XRD) pattern of the zinc terephthalate/carbon nanotube composite prepared in example 1 of the present invention;
FIG. 2 is an SEM image of a zinc terephthalate/carbon nanotube composite prepared in example 1 of the present invention;
FIG. 3 is a charge-discharge curve obtained by testing a button cell assembled in accordance with example 1 of the present invention;
FIG. 4 is a graph of cycle performance data obtained from a test of a button cell assembled in accordance with example 1 of the present invention;
FIG. 5 is a charge-discharge curve obtained by testing a button cell assembled in accordance with embodiment 2 of the present invention;
FIG. 6 is a graph of cycle performance data obtained from a test of a button cell assembled in accordance with example 2 of the present invention;
FIG. 7 is a charge-discharge curve obtained by testing a button cell assembled in accordance with example 3 of the present invention;
FIG. 8 is a graph of cycle performance data obtained from a button cell assembled in accordance with example 3 of the present invention.
Detailed Description
The following description of the embodiments of the present invention is provided to facilitate the understanding of the present invention by those skilled in the art, but it should be understood that the present invention is not limited to the scope of the embodiments, and it will be apparent to those skilled in the art that various changes may be made without departing from the spirit and scope of the invention as defined and defined in the appended claims, and all matters produced by the invention using the inventive concept are protected.
Example 1
A preparation method of a zinc ion battery active composite material comprises the following steps:
(1) 1.66g of terephthalic acid C are weighed8H6O42.30g of zinc acetate Zn (Ac)2·2H2O and 1.15g of carbon nano tubes are added into a mortar and ground for 1 hour to obtain a mixture;
(2) adding 80mL of deionized water into the mixture, performing ultrasonic oscillation for 20min to fully disperse the deionized water, then centrifuging the mixture for 5min at 10000r/min by using a centrifuge, washing the mixture by using 40mL of N-methylpyrrolidone, performing ultrasonic oscillation to fully disperse the deionized water, separating the mixture by using the centrifuge, removing supernatant, alternately washing the precipitate by using 40mL of deionized water and N-methylpyrrolidone for 3 times, and filtering the precipitate to obtain particles with the particle size of 1-20 microns;
(3) adding 40mL of deionized water into the particles obtained in the step (2), performing ultrasonic oscillation to fully disperse the deionized water, adding the deionized water into a ball milling tank, performing ball milling for 4 hours at a rotating speed of 400r/min, and collecting the obtained product;
(4) and (4) adding 60mL of deionized water into the product obtained in the step (3), performing ultrasonic oscillation again to uniformly disperse the deionized water, performing secondary granulation on the product by using a spray drying method, and collecting the product to obtain the target product zinc terephthalate/carbon nano tube composite material with the particle size of 50-500 nm.
The application of the zinc terephthalate/carbon nano tube composite material in the preparation of the battery comprises the following specific processes:
mixing and grinding a zinc terephthalate/carbon nano tube composite material and PVDF (N-methylpyrrolidone as a solvent) according to a mass ratio of 9:1, coating the mixture on a copper foil to prepare an electrode slice, drying, cutting the electrode slice into a wafer with the diameter of 1mm, and using metal zinc as a counter electrode and 1mol/L ZnSO as electrolyte4And (3) assembling the water solution into a button cell CR2032 by adopting a glass fiber diaphragm, and testing the charge and discharge performance of the assembled cell, wherein the current density is 44mA/g (-0.2C).
Example 2
A preparation method of a zinc ion battery active composite material comprises the following steps:
(1) 2.44g of benzoic acid C are weighed out7H6O22.30g of zinc acetate Zn (Ac)2·2H2O and 1.15g of carbon nano tubes are added into a mortar and ground for 1 hour to obtain a mixture;
(2) adding 80mL of deionized water into the mixture, performing ultrasonic oscillation for 20min to fully disperse the deionized water, then centrifuging the mixture for 5min at 10000r/min by using a centrifuge, washing the mixture by using 40mL of N-methylpyrrolidone, performing ultrasonic oscillation to fully disperse the deionized water, separating the mixture by using the centrifuge, removing supernatant, alternately washing the precipitate by using 40mL of deionized water and N-methylpyrrolidone for 3 times, and filtering the precipitate to obtain particles with the particle size of 1-20 microns;
(3) adding 40mL of deionized water into the particles obtained in the step (2), performing ultrasonic oscillation to fully disperse the deionized water, adding the deionized water into a ball milling tank, performing ball milling for 4 hours at a rotating speed of 400r/min, and collecting the obtained product;
(4) and (4) adding 60mL of deionized water into the product obtained in the step (3), dispersing the deionized water uniformly by using ultrasonic again, performing secondary granulation on the product by adopting a spray drying method, and collecting the product to obtain the target product zinc benzoate/carbon nanotube composite material.
The application of the zinc benzoate/carbon nanotube composite material in the preparation of the battery comprises the following specific processes:
mixing and grinding the zinc benzoate/carbon nanotube composite material and PVDF (N-methylpyrrolidone as a solvent) according to a mass ratio of 9:1, then coating the mixture on copper foil to prepare an electrode sheet, drying the electrode sheet, cutting the electrode sheet into a wafer with the diameter of 1mm, and assembling the wafer into a button cell CR2032 by using a glass fiber diaphragm and taking metal zinc as a counter electrode and 1mol/L ZnSO4 aqueous solution as an electrolyte.
Example 3
A preparation method of a zinc ion battery active composite material comprises the following steps:
(1) 2.44g of benzoic acid C are weighed out7H6O22.30g of zinc acetate Zn (Ac)2·2H2Adding O and 1.15g of graphene into a mortar, and grinding for 1h to obtain a mixture;
(2) adding 80mL of deionized water into the mixture, performing ultrasonic oscillation for 20min to fully disperse the deionized water, then centrifuging the mixture for 5min at 10000r/min by using a centrifuge, washing the mixture by using 40mL of N-methylpyrrolidone, performing ultrasonic oscillation to fully disperse the deionized water, separating the mixture by using the centrifuge, removing supernatant, alternately washing the precipitate for 3 times by using 40mL of deionized water and N-methylpyrrolidone, and filtering the precipitate to obtain particles with the particle size of 1-20 microns;
(3) adding 40mL of deionized water into the particles obtained in the step (2), performing ultrasonic oscillation to fully disperse the deionized water, adding the deionized water into a ball milling tank, performing ball milling for 4 hours at a rotating speed of 400r/min, and collecting the obtained product;
(4) and (4) adding 60mL of deionized water into the product obtained in the step (3), dispersing the deionized water uniformly by using ultrasonic again, performing secondary granulation on the product by using a spray drying method, and collecting the product to obtain the target product zinc benzoate/graphene composite material.
The application of the zinc benzoate/graphene composite material in the preparation of the battery comprises the following specific processes:
mixing and grinding a zinc benzoate/graphene composite material and PVDF (N-methylpyrrolidone as a solvent) according to a mass ratio of 9:1, coating the mixture on a copper foil to prepare an electrode sheet, drying the electrode sheet, cutting the electrode sheet into a wafer with the diameter of 1mm, and using zinc metal as a counter electrode and 0.5mol/L ZnSO as an electrolyte4And (4) assembling the aqueous solution into a button cell CR2032 by adopting a glass fiber diaphragm.
Fig. 1 is an X-ray diffraction pattern of the zinc terephthalate/carbon nanotube composite prepared in example 1 of the present invention, and it can be seen from fig. 1 that the zinc-ion battery active composite has good crystallinity.
Fig. 2 is an SEM picture of the zinc terephthalate/carbon nanotube composite material prepared in example 1 of the present invention, and it can be seen from fig. 2 that a portion of the zinc terephthalate particles are distributed around the carbon nanotubes in an irregular spherical or ellipsoidal shape, and a portion of the zinc terephthalate particles are uniformly coated on the carbon nanotubes.
Fig. 3 is a typical charge-discharge curve of the zinc terephthalate/carbon nanotube composite material prepared in example 1 of the present invention, and the result shows that the charge plateau is about 1.0V and the discharge plateau is about 0.85V.
Fig. 4 is a graph of the cycling performance of the button cell assembled according to example 1 of the present invention, which shows that the initial activation process is increased, the capacity is increased gradually, the stable capacity is about 96mAh/g, and the cycling performance is good without capacity fading after 100 cycles.
Fig. 5 is a typical charge-discharge curve of the zinc benzoate/carbon nanotube composite material prepared in example 2 of the present invention, and the result shows that the charge plateau is about 0.95V and the discharge plateau is about 0.85V.
FIG. 6 is a graph of the cycling performance of the assembled coin cell of example 2 of the present invention, again with an initial activation process, increasing capacity, stabilizing capacity of about 84mAh/g, and no capacity fade for 100 cycles.
Fig. 7 is a typical charge-discharge curve of the zinc benzoate/graphene composite material prepared in example 3 of the present invention, and the result shows that the charge plateau is about 0.80V, and the discharge plateau is about 0.77V.
FIG. 8 is a graph of the cycling performance of a button cell assembled with the active material prepared in example 3 of the present invention, the capacity gradually increased in the first 15 weeks, and the final stable capacity was about 90mAh/g, and the cycling performance was good.

Claims (7)

1. The preparation method of the active composite material of the zinc ion battery is characterized by comprising the following steps:
(1) placing terephthalic acid, zinc salt and a conductive additive into a container, mixing, and grinding for 0.5-2 h to obtain a mixture; wherein, the molar ratio of the zinc salt to the substituent group in the terephthalic acid is 1:2, the mass of the two products is 50-95% of the total mass of the mixture, and the rest is the conductive additive;
(2) adding deionized water into the mixture obtained in the step (1), performing ultrasonic dispersion, centrifuging for 5-8 min at 9000-10000 r/min, removing supernatant, alternately washing precipitates for 2-3 times by using 40-50 mL of N-methylpyrrolidone and deionized water respectively, and filtering to obtain mixed particles of a substance A and a substance B; wherein the substance A is zinc terephthalate; the substance B is a conductive additive;
(3) and (3) adding deionized water into the particles obtained in the step (2), performing ultrasonic dispersion, performing ball milling for 4-5 h under the condition of 400-450 r/min, and performing spray drying to obtain the active composite material for the zinc ion battery.
2. The method for preparing the active composite material for the zinc-ion battery according to claim 1, wherein the zinc salt in the step (1) is one or more of zinc sulfate, zinc acetate, zinc nitrate and zinc chloride.
3. The method for preparing the active composite material of the zinc-ion battery according to claim 1, wherein the conductive additive in the step (1) is one or more of furnace black, graphite particles, acetylene black, Super P, Ketjen black, carbon nanotubes and graphene.
4. The method of claim 3, wherein the conductive additive in step (1) is carbon nanotubes.
5. The method for preparing the active composite material of the zinc ion battery according to claim 1, wherein the shape of the active composite material of the zinc ion battery in the step (3) is one or more of a sphere, an ellipsoid and an irregular polyhedron; wherein the particle size of the substance A is 50-500 nm, and the substance A is uniformly distributed around the substance B or uniformly coated on the substance B.
6. The active composite material of the zinc ion battery prepared by the preparation method of any one of claims 1 to 5.
7. Use of the zinc ion battery active composite material of claim 6 in battery preparation.
CN201710328366.5A 2017-05-11 2017-05-11 Zinc ion battery active composite material and preparation method and application thereof Active CN107134570B (en)

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CN108258244B (en) * 2018-01-25 2022-10-21 电子科技大学 Novel lithium ion/potassium ion battery negative electrode material and preparation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Organic Potassium Terephthalate (K2C8H4O4) with Stable Lattice Structure Exhibits Excellent Cyclic and Rate Capability in Li-ion Batteries;Qijiu Deng等;《Electrochimica Acta》;20161114;第222卷;第1086-1093页 *
Zinc terephthalates ZnC8H4O4 as anodes for lithium ion batteries;Liping Wang等;《Electrochimica Acta》;20170318;第235卷;第304-310页 *
微波固相法合成邻苯二甲酸锌、铜配合物;张艳等;《精细化工》;20111024;第28卷(第11期);第1059-1062页 *

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