CN114864920B - V for water-based zinc ion battery 2 O 3 Positive electrode material @ C and preparation method thereof - Google Patents

V for water-based zinc ion battery 2 O 3 Positive electrode material @ C and preparation method thereof Download PDF

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CN114864920B
CN114864920B CN202210592287.6A CN202210592287A CN114864920B CN 114864920 B CN114864920 B CN 114864920B CN 202210592287 A CN202210592287 A CN 202210592287A CN 114864920 B CN114864920 B CN 114864920B
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positive electrode
electrode material
ion battery
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heating
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CN114864920A (en
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姚卫棠
陈祥杰
孔清泉
安旭光
吴小强
张靖
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Chengdu 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
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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 V for a water system zinc ion battery 2 O 3 The preparation method takes ammonium metavanadate and dopamine hydrochloride as raw materials, and V is prepared by a simple one-step hydrothermal method and a calcination process 2 O 3 @ C positive electrode material. The V is 2 O 3 The @ C positive electrode material can improve a range of electrochemical properties, particularly capacity and cycling stability, of aqueous zinc ion batteries.

Description

V for water-based zinc ion battery 2 O 3 Positive electrode material @ C and preparation method thereof
Technical Field
The invention belongs to the technical field of positive electrode materials of water-based zinc ion batteries, and particularly relates to a V for a water-based zinc ion battery 2 O 3 An @ C positive electrode material and a preparation method thereof.
Background
Along with the industrial development and technological progress, the development of society is more and more separated from energy sources such as petroleum, natural gas and the like. As countries around the world enter modernization, environmental and energy problems are pushed up the tuyere tip. The search for and development of sustainable energy is a trend that is essential today. In this regard, the use of an electrochemical energy storage system may enable cost-effective charge storage, enabling long-term operation, thereby mitigating utilization of non-renewable resources. Currently, lithium ion batteries are considered as the leading technology for energy storage applications due to their high quality energy density and good recyclability, and have been widely used in cell phones, notebook computers, and new energy automobiles as energy storage devices for high-precision devices. However, because of uneven global abundance distribution and shortage of lithium cobalt resources, there is a need for more intelligent management of global reserves associated with electrochemical large energy storage. Therefore, there is a need to explore alternative electrochemical systems for other energy storage applications.
Various battery systems such as sodium ion battery, potassium ion battery, magnesium ion battery, zinc ion battery and aluminum ion battery have been widely studied. Among these new secondary batteries, aqueous zinc ion batteries composed of a zinc metal negative electrode, a mild neutral electrolyte, and a host positive electrode containing a zinc ion guest are receiving increasing attention. Zinc abundance in crust is 79ppm, fourth in world metal yield, and therefore zinc market price is lower. Zinc metal anodes have good electrical conductivity, high volumetric energy density, high theoretical capacity and relatively low redox potential, which is more suitable for aqueous solutions. In addition, multivalent zinc ions can transfer two electrons, with more energy storage than monovalent batteries. Meanwhile, the ionic radius of the zinc ion isLess than sodium ion->Near lithium ion->In a word, zinc has the advantages of low cost, low toxicity, abundant resources, easy recycling, environmental friendliness and the like.
In recent years, the report amount of the positive electrode of the water-based zinc ion battery is continuously and rapidly increased, and the reported positive electrode mainly comprises the following four types: a manganese (Mn) -based positive electrode, a vanadium (V) -based positive electrode, prussian blue analogues, and organics. However, in the preliminary stage, researchers have focused mainly on manganese-based anodes, and vanadium-based anodes have not been widely studied as positive electrode materials for aqueous zinc-ion batteries until the last two years. In V form 2 O 5 The typical vanadium-based material has a layered structure similar to graphene, and intercalation and deintercalation of ions occurs during charge and discharge, and a new phase is formed with the participation of water. The vanadium-based material has V during charge and discharge 4+ 、V 3+ The change of the equivalent multivalent state shows good electrochemical performance. However, vanadium-based materials also have some unavoidable drawbacks, in that their structure slowly collapses during cycling, resulting in a constant capacity decay. And, the conductivity of the vanadium-based material is low compared with other materials. Therefore, more researches are needed to be put into the modification aiming at the defects of the vanadium-based material, so that the positive electrode of the water-based zinc ion battery is more efficient.
Disclosure of Invention
The invention aims to provide V for a water-based zinc ion battery 2 O 3 The @ C positive electrode material and the preparation method thereof can improve a series of electrochemical performances, especially capacity and cycle stability, of the water-based zinc ion battery.
To achieve the above object, the present invention provides a V for an aqueous zinc ion battery 2 O 3 The preparation method of the @ C positive electrode material comprises the following steps:
(1)V 2 O 5 is synthesized by (a)
Adjusting the pH value of an ethanol solution of ammonium metavanadate, then carrying out heating reaction to obtain a precursor, and calcining the precursor to obtain V 2 O 5 A nanoparticle; will V 2 O 5 The nano particles are dissolved in deionized water to prepare V 2 O 5 Is an aqueous solution of (a);
(2)V 2 O 3 synthesis of @ C
At V 2 O 5 Sequentially adding Tris-HCl buffer solution and dopamine hydrochloride into the aqueous solution of (1) and then heating and stirring to obtain a precursor, calcining the precursor in an inert gas atmosphere to obtain V 2 O 3 The @ C positive electrode material is V 2 O 3 @ C nanoparticles.
Further, the concentration of ammonium metavanadate in the ethanol solution of ammonium metavanadate is 0.02-0.04mmol/mL, and the ethanol solution of ammonium metavanadate is prepared by dissolving ammonium metavanadate in absolute ethanol, heating to 55-65 ℃ and stirring for 5-7 h.
Further, the pH is adjusted to 3.0-4.0.
Further, the heating temperature in the step (1) is 190-210 ℃, and the heating time is 20-25h.
Preferably, the heating temperature in step (1) is 200 ℃ and the heating time is 24 hours.
Further, the calcination temperature in the step (1) is 450-550 ℃, and the calcination time is 1.5-2.5h.
Preferably, the calcination temperature in step (1) is 500℃and the calcination time is 2.0h.
Further, V 2 O 5 V in the aqueous solution of (2) 2 O 5 The concentration of (2) is 0.1-0.2g/mL; v (V) 2 O 5 The mass volume ratio of the nano particles, the Tris-HCl buffer solution and the dopamine hydrochloride is 0.1g:1mL:0.5g.
Further, the heating temperature in the step (2) is 55-65 ℃, and the heating time is 20-25h; the calcination temperature is 650-750 ℃ and the calcination time is 1.5-2.5h.
Preferably, the heating temperature in the step (2) is 60 ℃, and the heating time is 24 hours; the calcination temperature was 700℃and the calcination time was 2.0h.
The invention also provides a V for the water system zinc ion battery 2 O 3 The @ C positive electrode material adopts the V for the water-based zinc ion battery 2 O 3 The @ C positive electrode material is prepared by a preparation method.
In summary, the invention has the following advantages:
1、V 2 O 3 the @ C has a special core-shell structure, can accommodate the intercalation of a large amount of zinc ions, and can lead the zinc ions to be in a precursor V 2 O 5 Further increases the discharge capacity thereof on the basis of (a).
2. The calcined material has a hard carbon shell, and thus can maintain the capacity without decay during continuous charge and discharge.
3. Coating of carbon shell compensates for V 2 O 5 The disadvantage of insufficient conductivity is that the material is kept at V 2 O 5 The graphene-like structure and the multivalent state change can better receive ions.
Drawings
FIG. 1 is V 2 O 3 X-ray diffraction pattern (XRD) of the @ C sample;
FIG. 2 is V 2 O 3 Scanning electron microscope image (SEM) of @ C sample;
FIG. 3 is V 2 O 3 Transmission electron microscope image (TEM) of the @ C sample;
FIG. 4 shows a cell at a scan rate of 2 mV.s -1 Cyclic Voltammogram (CV) at time;
FIG. 5 shows a battery at 0.5 A.g -1 Cycling stability diagram at current density;
FIG. 6 shows a battery at 10 A.g -1 Long cycle diagram at current density.
Detailed Description
The principles and features of the present invention are described below in connection with the following examples, which are set forth to illustrate, but are not to be construed as limiting the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
This example provides a V for a water-based zinc ion battery 2 O 3 The preparation method of the @ C positive electrode material comprises the following steps:
(1)V 2 O 5 is synthesized by (a)
2mmol of NH 4 VO 3 Dissolving in 50mL of absolute ethanol, stirring with a magnetic stirrer at 60deg.C for 6 hr until NH 4 VO 3 Completely dissolving, and then adding 2mL of dilute nitric acid for adjusting the pH value to 3.0;
transferring the orange-yellow solution into a 100mL stainless steel lined high-pressure reaction kettle, and reacting for 24 hours at 200 ℃;
after the reaction kettle is cooled to room temperature, respectively cleaning the sample for three times by using ethanol and deionized water until the sample is cleaned, so as to obtain a vanadium oxide precursor;
then calcining the precursor for 2 hours at 500 ℃ in air atmosphere to obtain golden yellow V 2 O 5 And (3) nanoparticles.
(2)V 2 O 3 Synthesis of @ C
0.1g of synthesized V 2 O 5 Added to 100mL deionized water, followed by 1mL Tris-HCl (0.05 mol/L,25 ℃) buffer, and 0.5g C was slowly added during stirring 8 H 12 ClNO 2 (dopamine hydrochloride) and stirring was continued for 24 hours at 60 ℃ and repeatedly rinsed with absolute ethanol and deionized water. The obtained precursor is transferred into a tube furnace and calcined for 2 hours at 700 ℃ in Ar atmosphere to obtain V 2 O 3 @ C nanoparticles.
Example 2
This example provides a V for a water-based zinc ion battery 2 O 3 The preparation method of the @ C positive electrode material comprises the following steps:
(1)V 2 O 5 is synthesized by (a)
1.5mmol of NH 4 VO 3 Dissolving in 50mL of absolute ethanol, stirring with a magnetic stirrer at 65deg.C for 6 hr until NH 4 VO 3 Completely dissolving, and then adding 2mL of dilute nitric acid for adjusting the pH value to 3.5;
transferring the orange-yellow solution into a 100mL stainless steel lined high-pressure reaction kettle, and reacting at 210 ℃ for 24 hours;
after the reaction kettle is cooled to room temperature, respectively cleaning the sample for three times by using ethanol and deionized water until the sample is cleaned, so as to obtain a vanadium oxide precursor;
then calcining the precursor for 2 hours at 550 ℃ in air atmosphere to obtain golden yellow V 2 O 5 And (3) nanoparticles.
(2)V 2 O 3 Synthesis of @ C
0.1g of synthesized V 2 O 5 Added to 100mL deionized water, followed by 1mL Tris-HCl buffer, 0.5g C was slowly added during stirring 8 H 12 ClNO 2 The stirring process was continued for 24 hours at 55 ℃ and repeatedly rinsed with absolute ethanol and deionized water. The obtained precursor is transferred into a tube furnace and calcined for 2.5 hours at 650 ℃ in Ar atmosphere to obtain V 2 O 3 @ C nanoparticles.
Example 3
This example provides a V for a water-based zinc ion battery 2 O 3 The preparation method of the @ C positive electrode material comprises the following steps:
(1)V 2 O 5 is synthesized by (a)
2mmol of NH 4 VO 3 Dissolving in 50mL of absolute ethanol, stirring with a magnetic stirrer at 60deg.C for 6 hr until NH 4 VO 3 Completely dissolving, and then adding 2mL of dilute nitric acid for adjusting the pH value to 4.0;
transferring the orange-yellow solution into a 100mL stainless steel lined high-pressure reaction kettle, and reacting for 24 hours at 190 ℃;
after the reaction kettle is cooled to room temperature, respectively cleaning the sample for three times by using ethanol and deionized water until the sample is cleaned, so as to obtain a vanadium oxide precursor;
then calcining the precursor for 2.5 hours at 450 ℃ in air atmosphere to obtain golden yellow V 2 O 5 And (3) nanoparticles.
(2)V 2 O 3 Synthesis of @ C
0.1g of synthesized V 2 O 5 Added to 100mL deionized water, followed by 1mL Tris-HCl buffer, 0.5g C was slowly added during stirring 8 H 12 ClNO 2 The stirring process was continued for 24 hours at 60 ℃ and repeatedly washed with absolute ethanol and deionized water. The obtained precursor is transferred into a tube furnace and calcined for 1.5 hours at 750 ℃ under Ar atmosphere to obtain V 2 O 3 @ C nanoparticles.
Test examples
A. Assembled battery
V prepared in example 1 2 O 3 The @ C nanoparticle is used for preparing a water-based zinc ion battery anode material and comprises the following steps of:
s1, V prepared 2 O 3 Mixing @ C with Super P and PVDF in a mass ratio of 70:20:10 (total 0.1g, wherein Super P and PVDF act as conductive agent and binder, respectively) in an agate mortar and grinding for 30 minutes;
s2, adding an organic solvent NMP after grinding uniformly, grinding for half an hour again to form slurry, and coating the uniformly mixed slurry on a titanium foil with the thickness of 0.02 mu m (the titanium foil is used as a current collector);
s3, transferring the coated pole piece into a vacuum oven, drying for 12 hours at 60 ℃, taking out the complete pole piece after drying, and cutting the complete pole piece into small wafers with the same diameter by using a handheld sheet punching device with the diameter of 14mm to serve as the positive pole piece of the button cell.
S4, assembling the water-based zinc ion battery in an indoor normal environment:
the raw materials for assembling the battery comprise zinc sheets (used as a negative electrode), 3M concentration zinc trifluoromethane sulfonate electrolyte (Zn (CF) 3 SO 3 ) 2 ) Glass fiber diaphragm, positive plate, spring piece, gasket and positive and negative shell.
The assembled battery adopts a flip-chip method, namely, a negative electrode shell, a zinc sheet, electrolyte, a glass fiber diaphragm, electrolyte, a positive electrode sheet, a gasket, a spring piece and a negative electrode shell are respectively arranged from bottom to top. And after the assembly is completed, the battery is pressed by a tablet press, and the complete button battery is obtained.
After 12 hours of rest, it can be started to perform test analysis.
B. Inspection and results
Structural characterization and performance analysis: the device designed by the test of the invention comprises an X-ray diffractometer, a scanning electron microscope, a transmission electron microscope, a Chen Hua electrochemical workstation and a Xinwei battery test system.
Structural characterization included XRD, SEM, TEM, performance characterization included Cyclic Voltammograms (CVs), cyclic curves, and long cycle performance.
As can be seen from fig. 1-3, V 2 O 3 The @ C material is successfully synthesized, and the microstructure is a core-shell structure coated by a nano spherical carbon shell, so that the structure is favorable for embedding and releasing ions during charge and discharge.
Fig. 4 is a CV curve that reflects the redox potential of a battery and the voltage interval, from which the voltage interval at the time of constant current charge-discharge test can be determined. In addition, the degree of overlap of the CV curves can also determine the stability of the structure.
FIG. 5 is a flow chart of 0.5A g- 1 Lower cycle performance diagram, V due to its special structure 2 O 3 The capacity at C is higher than most vanadium oxides and has a specific commercial V 2 O 5 And V 2 O 3 Better cycle stability.
Fig. 6 shows a cell at 10A g -1 The long cycle still maintains most of the capacity after 4000 cycles, which shows the ultra-strong current and electrochemical impact resistance of the material.
While specific embodiments of the invention have been described in detail, it should not be construed as limiting the scope of the patent. Various modifications and variations which may be made by those skilled in the art without the creative effort are within the scope of the patent described in the claims.

Claims (5)

1. V for water-based zinc ion battery 2 O 3 The preparation method of the @ C positive electrode material is characterized by comprising the following steps of:
(1)V 2 O 5 is synthesized by (a)
Adjusting the pH value of an ethanol solution of ammonium metavanadate, then carrying out heating reaction to obtain a precursor, and calcining the precursor to obtain V 2 O 5 A nanoparticle; will V 2 O 5 Dissolving the nano particles in deionized water to obtain V 2 O 5 Is an aqueous solution of (a); the concentration of ammonium metavanadate in the ethanol solution of ammonium metavanadate is 0.02-0.04mmol/mL, and the ethanol solution of ammonium metavanadate is prepared by dissolving ammonium metavanadate in absolute ethanol, heating to 55-65 ℃ and stirring for 5-7 h; the pH value is regulated to 3.0-4.0; the heating temperature is 190-210 ℃, and the heating time is 20-25h; the calcining temperature is 450-550 ℃, and the calcining time is 1.5-2.5h;
(2)V 2 O 3 synthesis of @ C
At V 2 O 5 Sequentially adding Tris-HCl buffer solution and dopamine hydrochloride into the aqueous solution of (1) and then heating and stirring to obtain a precursor, and placing the precursor in an inert gas atmosphereAfter middle calcination, V is prepared 2 O 3 @ C positive electrode material.
2. V for aqueous zinc-ion battery according to claim 1 2 O 3 The preparation method of the @ C positive electrode material is characterized in that 2 O 5 V in the aqueous solution of (2) 2 O 5 The concentration of (2) is 0.1-0.2g/mL; the V is 2 O 5 The mass volume ratio of the nano particles, the Tris-HCl buffer solution and the dopamine hydrochloride is 0.1g:1mL:0.5g.
3. V for aqueous zinc-ion battery according to claim 1 2 O 3 The preparation method of the @ C positive electrode material is characterized in that the heating temperature in the step (2) is 55-65 ℃ and the heating time is 20-25h; the calcination temperature is 650-750 ℃ and the calcination time is 1.5-2.5h.
4. A V for an aqueous zinc-ion battery according to claim 3 2 O 3 The preparation method of the @ C positive electrode material is characterized in that the heating temperature in the step (2) is 60 ℃, and the heating time is 24 hours; the calcination temperature is 700 ℃, and the calcination time is 2 hours.
5. V for water-based zinc ion battery 2 O 3 A positive electrode material comprising V for aqueous zinc-ion batteries according to any one of claims 1 to 4 2 O 3 The @ C positive electrode material is prepared by a preparation method.
CN202210592287.6A 2022-05-27 2022-05-27 V for water-based zinc ion battery 2 O 3 Positive electrode material @ C and preparation method thereof Active CN114864920B (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102602997A (en) * 2012-03-01 2012-07-25 长沙学院 Method for preparing indium vanadate nano particles

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102602997A (en) * 2012-03-01 2012-07-25 长沙学院 Method for preparing indium vanadate nano particles

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"A multi-shelled V2O3/C composite with an overall coupled carbon scaffold enabling ultrafast and stable lithium/sodium storage";Yutong Li等;《J. Mater. Chem. A》;第第7卷卷(第第33期期);第19234-19240页 *
"Scalable synthesis of novel V2O3/carbon composite as advanced cathode material for aqueous zinc-ion batteries";Xiaodong Liu等;《Ceramics International》;第第48卷卷(第第11期期);第15594-15602页 *

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