CN113921796A - Phytic acid-vanadium pentoxide composite material, preparation method thereof, electrode and battery - Google Patents
Phytic acid-vanadium pentoxide composite material, preparation method thereof, electrode and battery Download PDFInfo
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- CN113921796A CN113921796A CN202111183889.8A CN202111183889A CN113921796A CN 113921796 A CN113921796 A CN 113921796A CN 202111183889 A CN202111183889 A CN 202111183889A CN 113921796 A CN113921796 A CN 113921796A
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
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- 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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- 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
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Abstract
The invention belongs to the technical field of composite materials, and particularly relates to a phytic acid-vanadium pentoxide composite material, a preparation method thereof, an electrode and a battery. The composite material is a lamellar material, and the phytic acid is coated on the outer surface of vanadium pentoxide and is intercalated between adjacent layers of the vanadium pentoxide. The composite material can effectively overcome/improve the problems of poor specific capacity and cycle performance caused by difficult zinc ion de-intercalation and poor structural stability in the recycling process when the existing vanadium pentoxide is used as the anode material of the water-based zinc ion battery.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a phytic acid-vanadium pentoxide composite material, a preparation method thereof, an electrode and a battery.
Background
Advanced rechargeable batteries are of great significance to large-scale energy storage grids and portable electronic devices in daily life. Nowadays, Lithium Ion Batteries (LIBs) are indispensable energy storage devices in our daily life, and dominate portable electronic devices. However, organic electrolytes, which are inefficient, costly, less safe and flammable, remain a challenge for large-scale applications due to insufficient lithium abundance. In contrast, rechargeable aqueous batteries have higher safety, lower loss, and higher ionic conductivity than non-aqueous electrolytes, as well as environmental friendliness. These advantages make the system suitable for large-scale applications of stored energy. Among them, the water system zinc ion rechargeable battery is a hot spot of current research due to excellent performance of the Zn negative electrode, abundant raw materials, low cost, chemical stability in water, high theoretical capacity, and low oxidation-reduction potential.
The gravimetric energy and power density as well as the cost of ZIBs are largely dependent on the cathode material. The stability and integrity of the positive electrode structure is of crucial importance for the cycling stability of the entire battery system. Designing and developing a positive electrode material having a large storage capacity, a high discharge potential, and a stable and rapidly deintercalable crystal structure has been a great challenge in the development of high-performance ZIBs. Heretofore, manganese-based compounds, vanadium-based materials, prussian blue and the like, and organic redox active compounds have been more suitable as positive electrode materials for zinc ion batteries. Wherein V2O5As a typical material among vanadium-based materials, it has been widely studied due to its controllable layered structure and vanadium having a plurality of redox states. V2O5The positive electrode generally has a high specific capacity, but it has poor cycle performance in an aqueous electrolyte due to structural instability and chemical dissolution. Theoretically, V2O5Is much larger than the radius of the zinc ion, but the zinc ion is usually present in the form of hydrated zinc ion, and thus the V of the zinc ion is at2O5Interlayer deintercalation becomes difficult, which may result in a decrease in charge and discharge speed. And after a repeated de-intercalation process, V2O5The layer structure begins to collapse, which results in a severe drop in battery capacity.
To enhance the reaction kinetics, it is generally at V2O5Intercalation of water molecules, metal cations such as Li between layers+、Na+、K+、Ca2 +、Mg2+、Al3+Thereby achieving the purposes of increasing the interlayer spacing and improving the stability of the structure. But in Zn2+The repeated de-intercalation process inevitably causes the structural collapse of the main material. Besides cations, conjugated conductive polymers can be used as intercalation materials, such as polyaniline and polypyrrole, so as to enhance the performance of the layered positive electrode material. At present, although the application of vanadium base in water-based zinc ion is gradually developed, the specific capacity of the vanadium base as a water-based zinc ion positive electrode material needs to be improved and the synthetic method needs to be simplified in the prior art.
Disclosure of Invention
The invention aims to provide a phytic acid-vanadium pentoxide composite material which can effectively solve/improve the problems of poor specific capacity and cycle performance caused by difficult zinc ion de-intercalation and poor structural stability in the recycling process when the existing vanadium pentoxide is used as a cathode material of a water-based zinc ion battery.
In order to achieve the above purpose, the invention provides the following technical scheme: the phytic acid-vanadium pentoxide composite material is a sheet material, and the phytic acid is coated on the outer surface of vanadium pentoxide and is intercalated between adjacent layers of the vanadium pentoxide.
Preferably, the interlayer spacing between two adjacent layers of vanadium pentoxide in the composite material is 1.0-1.5 nm.
Preferably, the composite material is in a cuboid shape, the width of the composite material is 0.8-1.1 μm, the length of the composite material is 1-2 μm, and the average thickness of the composite material is 0.6 μm.
Preferably, the thickness of the phytic acid coated on the outer surface of the vanadium pentoxide is 5-30 nm.
Preferably, the molar ratio of vanadium pentoxide to phytic acid in the composite material is 0.2-0.3.
Preferably, the phytic acid is cross-linked with vanadium-oxygen bonds of vanadium pentoxide.
The invention also provides a preparation method of the phytic acid-vanadium pentoxide composite material, which adopts the following technical scheme:
the method comprises the following steps:
step (1): mixing phytic acid, vanadium pentoxide, hydrogen peroxide and water, and stirring to obtain a mixed solution;
step (2): carrying out hydrothermal reaction on the mixed solution obtained in the step (1);
and (3): after the hydrothermal reaction is finished, centrifuging, washing and drying to obtain the phytic acid-vanadium pentoxide composite material;
preferably, the molar ratio of the vanadium pentoxide to the phytic acid in the step (1) is 0.02-0.3.
Preferably, the temperature of the hydrothermal reaction in the step (2) is 120-200 ℃, and the reaction time is 10-48 h.
Preferably, the washing in the step (3) is ultrasonic washing; the drying is vacuum drying;
preferably, the conditions of the centrifugation are: the centrifugation speed is 6000 to 10000r/min, and the centrifugation lasts for 3 to 8 min;
preferably, the power of the ultrasound during the ultrasonic washing is 80-120W, the frequency is 20-30 kHz, and the time is 10-15 min; the washed solvent is deionized water or ethanol;
still preferably, the vacuum drying conditions are: the negative pressure is 0.06-0.08 MPa, the temperature is 50-100 ℃, and the drying time is 8-20 h.
Preferably, the step (1) comprises:
a. stirring and mixing a hydrogen peroxide solution and deionized water according to a volume ratio of 0.1-0.5 to obtain a hydrogen peroxide solution, wherein the mass fraction of hydrogen peroxide in the hydrogen peroxide solution is 25-35%;
b. adding vanadium pentoxide into an aqueous hydrogen peroxide solution, and stirring to obtain a mixed solution of the vanadium pentoxide and the hydrogen peroxide;
c. mixing and stirring phytic acid and deionized water according to the volume ratio of 0.001-0.1 to obtain a phytic acid aqueous solution;
d. dripping a phytic acid aqueous solution into a mixed solution of vanadium pentoxide and hydrogen peroxide, and stirring to obtain the mixed solution in the step (1);
preferably, the stirring temperature in the step a, the step b, the step c or the step d is independently selected from 15-30 ℃, and the stirring time in the step a is 10-20 min; the stirring time of the steps b and d is independently selected from 5-20 min; and c, stirring for 1-10 min.
The invention also provides an electrode, which adopts the following technical scheme: the raw material or the effective component of the electrode comprises the phytic acid-vanadium pentoxide composite material.
The invention also provides a battery, which adopts the following technical scheme: the battery comprises the phytic acid-vanadium pentoxide composite material or the electrode;
preferably, the battery is an aqueous zinc ion battery.
Has the advantages that:
1. in the phytic acid-vanadium pentoxide composite material, the phytic acid intercalation is carried out on the vanadium pentoxide, so that an ion transmission channel can be further widened, and the phytic acid is coated outside a vanadium pentoxide layer, so that when the composite material is used for a water system zinc ion battery anode material, the structural stability of the phytic acid-vanadium pentoxide composite material can be improved, the cycle performance of the anode material is effectively improved, and the performance of the water system zinc ion battery is greatly improved.
2. When the phytic acid-vanadium pentoxide composite material is used as a positive electrode material of a water-based zinc ion battery, the rate conversion performance is good, the current density is recovered to 0.1A/g from 5A/g, the same rate capacity change of the phytic acid-vanadium pentoxide composite material is small, and the structural stability of the phytic acid-vanadium pentoxide composite material is good.
3. When the molar ratio of the phytic acid to the vanadium pentoxide adopted for preparing the phytic acid-vanadium pentoxide composite material is 0.06-0.12, the prepared phytic acid-vanadium pentoxide composite material is used as a positive electrode material of a water-based zinc ion battery, so that the phytic acid-vanadium pentoxide composite material can be further activated in the circulation process of the water-based zinc ion battery, and the specific discharge capacity is improved.
When the molar ratio of the phytic acid to the vanadium pentoxide adopted for preparing the phytic acid-vanadium pentoxide composite material is 0.12, the prepared phytic acid-vanadium pentoxide composite material is used as a positive electrode material of a water-system zinc ion battery, and the specific capacity of the water-system zinc ion battery can be 363.38mA h g from the initial discharge specific capacity under the current density of 0.1A/g in the circulation process-1After 200 cycles, 401.69mA h g are achieved-1(ii) a The specific capacity can reach 406mA h g at the current density of 0.1A/g-1The phytic acid-vanadium pentoxide composite material has excellent electrochemical performance; under the current density of 5A/g, the circulating capacity after 5000 cycles is 184mA h g-1173mA h g with respect to the initial capacity-1Still lifting; under the current density of 5A/g, the capacity retention rate reaches 97.3 percent after 6000 cycles; the phytic acid-vanadium pentoxide composite material has good structural stability.
4. The preparation method of the phytic acid-vanadium pentoxide composite material adopts vanadium pentoxide and phytic acid as raw materials, and the sources are wide; the synthesis is carried out by adopting a one-step hydrothermal method, the preparation efficiency is high, the hydrothermal reaction time is short, and the energy can be effectively saved; and the solvent in the reaction system is water, which meets the requirement of green chemistry.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. Wherein:
FIG. 1 is a schematic diagram of a synthetic process and a principle of one embodiment of the phytic acid-vanadium pentoxide composite material according to the invention;
FIGS. 2a to d respectively correspond to scanning electron microscope images of the phytic acid-vanadium pentoxide composite material prepared in embodiments 1 to 4 of the present invention;
FIG. 3 is a transmission electron microscope image and a high-resolution transmission electron microscope image of the phytic acid-vanadium pentoxide composite material according to embodiment 3 of the present invention;
FIG. 4 is an XPS chart of the phytic acid-vanadium pentoxide composite material according to example 3 of the present invention;
FIG. 5 is a cycle curve at a current density of 0.1A/g when the phytic acid-vanadium pentoxide composite material of example 1 of the invention is used as a positive electrode material of a water-based zinc ion battery;
FIG. 6 is a cycle curve at a current density of 0.1A/g when the phytic acid-vanadium pentoxide composite material of embodiment 2 of the invention is used as a positive electrode material of a water-based zinc ion battery;
FIG. 7 is a cycle curve at a current density of 0.1A/g when the phytic acid-vanadium pentoxide composite material of embodiment 3 of the invention is used as a positive electrode material of a water-based zinc ion battery;
FIG. 8 is a cycle curve at a current density of 0.1A/g when the phytic acid-vanadium pentoxide composite material of embodiment 4 of the invention is used as a positive electrode material of a water-based zinc ion battery;
fig. 9 is a graph of rate performance at current densities of 0.1, 0.3, 0.5, 1, 3, 5A/g when the phytic acid-vanadium pentoxide composite material of example 1 of the invention is used as a positive electrode material of a water-based zinc ion battery;
fig. 10 is a graph of rate performance at current densities of 0.1, 0.3, 0.5, 1, 3, 5A/g when the phytic acid-vanadium pentoxide composite material of embodiment 2 of the invention is used as a positive electrode material of a water-based zinc ion battery;
fig. 11 is a graph of rate performance at current densities of 0.1, 0.3, 0.5, 1, 3, 5A/g when the phytic acid-vanadium pentoxide composite material of embodiment 3 of the invention is used as a positive electrode material of a water-based zinc ion battery;
fig. 12 is a graph of rate performance at current densities of 0.1, 0.3, 0.5, 1, 3, 5A/g when the phytic acid-vanadium pentoxide composite material of embodiment 4 of the invention is used as a positive electrode material of a water-based zinc ion battery;
FIG. 13 is a long cycle performance graph of 6000 cycles at 5A/g when the phytic acid-vanadium pentoxide composite material of example 1 of the invention is used as a positive electrode material of a water-based zinc ion battery;
FIG. 14 is a long cycle performance graph of 5000 cycles at 5A/g when the phytic acid-vanadium pentoxide composite material of example 2 of the invention is used as a positive electrode material of a water-based zinc ion battery;
FIG. 15 is a long cycle performance graph of 5000 cycles at 5A/g when the phytic acid-vanadium pentoxide composite material of embodiment 3 of the invention is used as a positive electrode material of a water-based zinc ion battery;
fig. 16 is a long cycle performance graph of 5000 cycles at 5A/g when the phytic acid-vanadium pentoxide composite material of embodiment 4 of the invention is used as a positive electrode material of a water-based zinc ion battery.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated. Unless otherwise indicated, reagents and materials used in the present invention are commercially available. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict. In order to make the technical solutions of the present invention better understood, the present invention is further described in detail below with reference to the accompanying drawings.
V2O5(vanadium pentoxide) is widely studied as a typical material in vanadium-based materials due to its controllable layered structure and the fact that vanadium has multiple redox states. V2O5When used as a positive electrode material, the lithium ion secondary battery generally has a high specific capacity, but the lithium ion secondary battery has poor cycle performance in an aqueous electrolyte due to structural instability and chemical dissolution. Theoretically, V2O5Is much larger than the radius of the zinc ion, but the zinc ion is usually present in the form of hydrated zinc ion, and thus the V of the zinc ion is at2O5Interlayer deintercalation becomes difficult, which may result in a decrease in charge and discharge speed. And after a repeated de-intercalation process, V2O5The layer structure begins to collapseThese can result in a severe drop in battery capacity.
Aiming at the existing problems, the invention provides a phytic acid-vanadium pentoxide composite material which can effectively overcome/improve the problems of poor specific capacity and cycle performance caused by difficult zinc ion de-intercalation and poor structure stability in the recycling process when the existing vanadium pentoxide is used as the anode material of a water system zinc ion battery.
The phytic acid-vanadium pentoxide composite material is a sheet material, and the phytic acid is coated on the outer surface of vanadium pentoxide and is intercalated between adjacent layers of the vanadium pentoxide.
In the phytic acid-vanadium pentoxide composite material, the phytic acid is not only intercalated into V2O5Between layers and also covered with V2O5The surface of the particles; the phytic acid can be inserted into the reactor to make V2O5The interlayer spacing is increased, so that an ion transmission channel is further widened, and the zinc ions are conveniently de-intercalated; phytic acid is in V2O5The external coating of the layer enables the structural integrity and stability to be maintained in the repeated zinc ion de-intercalation process, and further the electrochemical performance of the anode material can be improved when the phytic acid-vanadium pentoxide composite material is used for the anode material.
In a preferred embodiment of the invention, the interlayer spacing of vanadium pentoxide in the composite material is 1.0-1.5 nm (e.g. 1.0nm, 1.1nm, 1.2nm, 1.3nm, 1.4nm or 1.5 nm).
In a preferred embodiment of the present invention, the composite material is in a rectangular parallelepiped shape, the width of the composite material is 0.8 to 1.1 μm (e.g., 0.8 μm, 0.9 μm, 1.0 μm, or 1.1 μm), the length is 1 to 2 μm (e.g., 1 μm, 1.1 μm, 1.2 μm, 1.3 μm, 1.4 μm, 1.5 μm, 1.6 μm, 1.7 μm, 1.8 μm, 1.9 μm, or 2 μm), and the average thickness is 0.6 μm.
In a preferred embodiment of the present invention, the phytic acid coated on the outer surface of the vanadium pentoxide has a thickness of 5 to 30nm (e.g., 5nm, 7nm, 9nm, 11nm, 13nm, 15nm, 18nm, 21nm, 23nm, 25nm, 28nm, or 30 nm).
In a preferred embodiment of the present invention, the molar ratio of vanadium pentoxide to phytic acid in the composite material is 0.2-0.3 (e.g., 0.2, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29 or 0.3).
In a preferred embodiment of the invention, the phytic acid is in crosslinking connection with vanadium oxygen bonds of vanadium pentoxide (the contact part of the phytic acid and the vanadium pentoxide).
The invention also provides a preparation method of the phytic acid-vanadium pentoxide composite material, which comprises the following steps:
step (1): mixing phytic acid, vanadium pentoxide, hydrogen peroxide and water, and stirring to obtain a mixed solution;
step (2): carrying out hydrothermal reaction on the mixed solution obtained in the step (1);
and (3): and after the hydrothermal reaction is finished, centrifuging, washing and drying to obtain the phytic acid-vanadium pentoxide composite material.
In a preferred embodiment of the invention, the molar ratio of vanadium pentoxide to phytic acid in the step (1) is 0.02-0.3, namely the molar ratio of the adopted vanadium pentoxide raw material to the phytic acid raw material when preparing the composite material of the invention; for example, the molar ratio of vanadium pentoxide to phytic acid may be 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.10, 0.12, 0.14, 0.16, 0.18, 0.19, 0.20, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29 or 0.3.
In a preferred embodiment of the present invention, the molar ratio of vanadium pentoxide to phytic acid in step (1) is 0.03-0.24 (e.g., 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.10, 0.12, 0.14, 0.16, 0.18, 0.19, 0.20, 0.21, 0.22, 0.23 or 0.24).
In a preferred embodiment of the present invention, the molar ratio of vanadium pentoxide to phytic acid in step (1) is 0.06-0.12 (e.g. 0.06, 0.07, 0.08, 0.10 or 0.12).
In a preferred embodiment of the present invention, the temperature of the hydrothermal reaction in step (2) is 120-200 ℃ (e.g., 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃ or 200 ℃), and the reaction time is 10-48 h (e.g., 10h, 15h, 20h, 25h, 30h, 35h, 40h, 41h, 42h or 48 h). Wherein, the hydrothermal reaction can be carried out in a high-temperature high-pressure reaction kettle.
In a preferred embodiment of the invention, the temperature of the hydrothermal reaction in the step (2) is 150-180 ℃ (e.g. 155 ℃, 158 ℃, 162 ℃, 165 ℃, 168 ℃, 172 ℃, 175 ℃, 178 ℃ or 180 ℃), and the reaction time is 10-14 h (e.g. 10h, 10.4h, 10.8h, 11.2h, 11.5h, 11.8h, 12.1h, 12.5h, 12.8h, 13.2h, 13.5h, 13.8h or 14 h).
In a preferred embodiment of the present invention, the washing in the step (3) is ultrasonic washing; the drying is vacuum drying.
In the preferred embodiment of the invention, the centrifugation speed is 6000 to 10000r/min (such as 6000r/min, 6500r/min, 7000r/min, 7500r/min, 8000r/min, 9000r/min, 9500r/min or 10000r/min), and the centrifugation lasts 3 to 8min (such as 3min, 4min, 5min, 6min, 7min or 8 min);
in a preferred embodiment of the present invention, the centrifugation conditions are: the centrifugation speed is 8000r/min, and the centrifugation lasts for 5 min.
In a preferred embodiment of the present invention, the power of the ultrasound during the ultrasonic washing is 80-120W (e.g. 80W, 85W, 90W, 95W, 100W, 105W, 110W, 115W or 120W), and the frequency is 20-30 kHz (e.g. 20kHz, 21kHz, 22kHz, 23kHz, 24kHz, 25kHz, 26kHz, 27kHz, 28kHz, 29kHz or 30 kHz).
In a preferred embodiment of the invention, the power of the ultrasound during the ultrasonic washing is 100W, the frequency is 25kHz, and the time is 10-15 min (for example, 10min, 11min, 12min, 13min, 14min or 15 min); the solvent for washing is deionized water or ethanol.
In a preferred embodiment of the present invention, the vacuum drying conditions are as follows: the negative pressure is 0.06-0.08 MPa, the temperature is 50-100 ℃ (for example, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃), and the drying time is 8-20 h (for example, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h or 20 h).
In a preferred embodiment of the present invention, the vacuum drying conditions are as follows: the temperature is 60-100 deg.C (such as 60 deg.C, 70 deg.C, 80 deg.C, 90 deg.C or 100 deg.C), and the drying time is 10-16 h (such as 10h, 11h, 12h, 13h, 14h, 15h or 16 h).
In a preferred embodiment of the present invention, the step (1) comprises: a. stirring and mixing a hydrogen peroxide solution and deionized water according to a volume ratio of 0.1-0.5 (such as 0.1, 0.2, 0.3, 0.4 or 0.5) to obtain an aqueous hydrogen peroxide solution, wherein the mass fraction of hydrogen peroxide in the hydrogen peroxide solution is 25-35% (such as 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34% or 35%);
b. adding vanadium pentoxide into an aqueous hydrogen peroxide solution, and stirring to obtain a mixed solution of the vanadium pentoxide and the hydrogen peroxide;
c. mixing and stirring phytic acid and deionized water according to the volume ratio of 0.001-0.1 (such as 0.001, 0.003, 0.006, 0.008, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09 or 0.1) to obtain a phytic acid aqueous solution;
d. and (2) dropwise adding a phytic acid aqueous solution into the mixed solution of vanadium pentoxide and hydrogen peroxide, and stirring to obtain the mixed solution in the step (1).
In a preferred embodiment of the present invention, the stirring temperature in the steps a, b, c or d is independently selected from 15 to 30 ℃ (e.g., 15 ℃, 16 ℃, 18 ℃, 19 ℃, 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃ or 30 ℃), and the stirring time in the step a is 10 to 20min (e.g., 10min, 11min, 13min, 15min, 17min, 18min, 19min or 20 min); the stirring time of the steps b and d is independently selected from 5-20 min (such as 5min, 7min, 9min, 11min, 13min, 15min, 17min, 18min, 19min or 20 min); the stirring time in the step c is 1-10 min (for example, 1min, 2min, 3min, 4min, 5min, 6min, 7min, 8min, 9min or 10 min).
In a preferred embodiment of the present invention, the stirring temperature in the step a, b, c or d is independently selected from 20 to 25 ℃ (e.g., 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃ or 25 ℃).
In a preferred embodiment of the present invention, the stirring time in step a is 10 min.
In a preferred embodiment of the present invention, the stirring time in step b is 10-15 min (e.g., 10min, 11min, 12min, 13min, 14min or 15 min).
In a preferred embodiment of the present invention, the stirring time in step c is 1-5 min (e.g., 1min, 2min, 3min, 4min or 5 min).
In a preferred embodiment of the present invention, the stirring time in step d is 5-15 min (e.g., 5min, 6min, 7min, 8min, 9min, 10min, 11min, 12min, 13min, 14min or 15 min).
In a preferred embodiment of the present invention, the volume ratio of the phytic acid to the deionized water in step c is 0.001-0.05 (e.g., 0.001, 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.02, 0.03, 0.04, or 0.05).
The invention also provides an electrode, and the raw material/effective component of the electrode comprises the phytic acid-vanadium pentoxide composite material. For example, the phytic acid-vanadium pentoxide composite material can be used as a positive electrode material of an aqueous zinc ion battery, and can also be used as an electrode of a lithium ion battery and a solid-state battery.
The invention also provides a battery, which comprises the phytic acid-vanadium pentoxide composite material or the electrode. For example, the battery may be a lithium ion battery, a solid state battery, or the like.
In a preferred embodiment of the present invention, the battery is an aqueous zinc ion battery.
The phytic acid-vanadium pentoxide composite material, the preparation method thereof, the electrode and the battery of the present invention are explained in detail by specific examples below.
In the following examples: vanadium pentoxide was purchased from Shanghai mountain shop chemical Co., Ltd; the hydrogen peroxide solution is 35% by mass; phytic acid was purchased from Shanghai Chamaecyparis pisifera Biotech Co.
Example 1
The phytic acid-vanadium pentoxide composite material comprises raw materials of phytic acid and vanadium pentoxide; as shown in fig. 1, in the composite material, phytic acid is coated on the surface of vanadium pentoxide and intercalated between adjacent layers of vanadium pentoxide (the interlayer spacing of vanadium pentoxide is increased), and is crosslinked with vanadium oxygen bonds (the structure of vanadium pentoxide is stabilized).
The phytic acid-vanadium pentoxide composite material of the embodiment is a block lamellar material coated and intercalated by an organic matter, the width is 0.8-1.1 μm, the length is 1-2 μm, the average thickness is 0.6 μm, and the surface of the nanosheet is smooth and tidy (as shown in fig. 2 a). In the embodiment, the phytic acid is less in incorporation amount (details are shown in the preparation method of the phytic acid-vanadium pentoxide composite material), so that the phytic acid is less in coating.
The preparation method of the phytic acid-vanadium pentoxide composite material comprises the following steps:
(1) stirring and dissolving vanadium pentoxide in a mixed solution consisting of a hydrogen peroxide solution and deionized water, and marking as a solution A; wherein the volume ratio of the hydrogen peroxide solution to the deionized water is 0.3, and the mass fraction of the hydrogen peroxide in the hydrogen peroxide solution is 35 percent; stirring at 25 deg.C for 15 min; the concentration of vanadium pentoxide in the resulting solution A was 0.034 g/mL.
(2) Dissolving phytic acid in deionized water, stirring to obtain a phytic acid aqueous solution, and recording as a solution B; wherein the volume ratio of the phytic acid to the deionized water is 0.006, the stirring temperature is 25 ℃, and the stirring time is 5 min.
(3) And then dropwise adding the solution B into the solution A (the molar ratio of the addition amount of vanadium pentoxide to the addition amount of phytic acid is 0.03), and stirring at the stirring temperature of 25 ℃ for 10 min.
(4) And transferring the mixed solution to a high-temperature high-pressure reaction kettle for hydrothermal reaction, controlling the reaction temperature to be 160 ℃, and controlling the reaction time to be 12 hours.
(5) The phytic acid-vanadium pentoxide composite material (marked as PHVO-0.125) is obtained after collection, centrifugation, washing and vacuum drying. Wherein the washing solvent is deionized water or ethanol (under ultrasonic condition, ultrasonic power is 100W, frequency is 25kHz, and time is 10 min); the centrifugation conditions were: centrifuging at 8000r/min for 5 min; the vacuum drying time is 12h, the drying temperature is 80 ℃, and the negative pressure is 0.06 MPa.
An electrode: the phytic acid-vanadium pentoxide composite material (prepared as described above) of this example was used as the positive electrode material of an aqueous zinc ion battery.
A battery: an aqueous zinc ion battery was prepared using the electrode of this example. The method specifically comprises the following steps: the phytic acid-vanadium pentoxide composite material prepared by the preparation method is used as a positive electrode material of a water-system zinc ion battery; using 1.8M zinc trifluoromethanesulfonate solution as electrolyte; GF/D glass fiber is used as a diaphragm; zinc foil is used as a negative electrode; and assembling to form the full cell.
Testing the performance of the battery: the cycle performance chart of the composite material of the embodiment at the current density of 0.1A/g is shown in FIG. 5; as can be seen from FIG. 5, when the phytic acid-vanadium pentoxide composite material is used as the anode of a water-based zinc ion battery, the initial discharge specific capacity can reach 312.43mAh/g, and the capacity retention rate can reach 83% after 100 cycles.
In addition, the composite material of the embodiment also has better rate capability. As shown in fig. 9, even if the current density is restored from 5A/g to 0.1A/g, the same rate capacity of the composite material has a small change, which indicates that the composite material has a good rate conversion performance, thereby indicating that the phytic acid-vanadium pentoxide composite material of the embodiment has good structural stability.
FIG. 13 is a graph showing the cycle performance of the composite material of this example after 6000 cycles at a current density of 5A/g. As is clear from fig. 13, the composite material still has good stability under high-power charge and discharge conditions, and the capacity retention rate after 6000 cycles is 64%.
Example 2
The preparation method of the phytic acid-vanadium pentoxide composite material comprises the following steps:
(1) stirring and dissolving vanadium pentoxide in a mixed solution consisting of a hydrogen peroxide solution and deionized water, and marking as a solution A; wherein the volume ratio of the hydrogen peroxide solution to the deionized water is 0.25, and the mass fraction of the hydrogen peroxide in the hydrogen peroxide solution is 35 percent; stirring at 25 deg.C for 15 min; the concentration of vanadium pentoxide in the resulting solution A was 0.034 g/mL.
(2) Dissolving phytic acid in deionized water, stirring to obtain a phytic acid aqueous solution, and recording as a solution B; wherein the volume ratio of the phytic acid to the deionized water is 0.012, the stirring temperature is 25 ℃, and the stirring time is 5 min.
(3) And then dropwise adding the solution B into the solution A (the molar ratio of the addition amount of vanadium pentoxide to the addition amount of phytic acid is 0.06), and stirring at the temperature of 25 ℃ for 10 min.
(4) And transferring the mixed solution to a high-temperature high-pressure reaction kettle for hydrothermal reaction, controlling the reaction temperature to be 160 ℃, and controlling the reaction time to be 12 hours.
(5) The phytic acid-vanadium pentoxide composite material (marked as PHVO-0.25) is obtained after collection, washing, centrifugation and vacuum drying. Wherein the washing solvent is deionized water or ethanol (under ultrasonic condition, ultrasonic power is 100W, frequency is 25kHz, and time is 20 min); the centrifugation conditions were: centrifuging at 8000r/min for 5 min; the vacuum drying time is 12h, the drying temperature is 80 ℃, and the negative pressure is 0.08 MPa.
The phytic acid-vanadium pentoxide composite material of the embodiment is prepared according to the preparation method, the synthetic schematic diagram is shown in fig. 1, and the principle is the same as that of embodiment 1. Fig. 2b is a scanning electron microscope image of the phytic acid-vanadium pentoxide composite material prepared in this embodiment, the morphology of the phytic acid-vanadium pentoxide composite material in this embodiment is the same as that in embodiment 1, and the phytic acid-vanadium pentoxide composite material is a block lamellar material coated and intercalated by an organic substance (the width of the block lamellar material is 0.8-1.1 μm, the length is 1-2 μm, and the average thickness is 0.6 μm), but the surface of the nanosheet has obvious phytic acid coating compared with that in embodiment 1.
An electrode: the phytic acid-vanadium pentoxide composite material (prepared as described above) of this example was used as the positive electrode material of an aqueous zinc ion battery.
A battery: the same as example 1 was repeated except that the positive electrode material used was the phytic acid-vanadium pentoxide composite material prepared in this example (example 2).
Testing the performance of the battery: the cycle performance diagram of the composite material of the embodiment under the current density of 0.1A/g is shown in fig. 6, and as can be seen from fig. 6, when the phytic acid-vanadium pentoxide composite material is used as the anode material of the water-based zinc ion battery, the initial discharge specific capacity can reach 301.62mAh/g, the capacity after 200 cycles is 343.36mAh/g, and the capacity is improved, which is related to the activation of the anode material.
In addition, the composite material of the embodiment also has better rate capability. As shown in fig. 10, in the graph of the rate performance under the current densities of 0.1, 0.3, 0.5, 1, 3 and 5A/g, the current density is recovered from 5A/g to 0.1A/g, and the change of the same rate capacity of the composite material is small, which indicates that the composite material has a good rate conversion performance, thereby indicating that the phytic acid-vanadium pentoxide composite material of the embodiment has good structural stability.
FIG. 14 is a graph showing the cycle performance of the composite material of this example after 5000 cycles at a current density of 5A/g. As can be clearly seen from fig. 14, the composite material still has good stability under high-power charge and discharge conditions, and the capacity is still improved after 5000 cycles, which indicates that the composite material has good structural stability.
Example 3
The preparation method of the phytic acid-vanadium pentoxide composite material comprises the following steps:
(1) stirring and dissolving vanadium pentoxide in a mixed solution consisting of a hydrogen peroxide solution and deionized water, and marking as a solution A; wherein the volume ratio of the hydrogen peroxide solution to the deionized water is 0.26, and the mass fraction of the hydrogen peroxide in the hydrogen peroxide solution is 35 percent; stirring at 25 deg.C for 15 min; the concentration of vanadium pentoxide in the resulting solution A was 0.034 g/mL.
(2) Dissolving phytic acid in deionized water, stirring to obtain a phytic acid aqueous solution, and recording as a solution B; wherein the volume ratio of the phytic acid to the deionized water is 0.025, the stirring temperature is 25 ℃, and the stirring time is 5 min.
(3) And then dropwise adding the solution B into the solution A (the molar ratio of the addition amount of vanadium pentoxide to the addition amount of phytic acid is 0.12), and stirring at the stirring temperature of 25 ℃ for 10 min.
(4) And transferring the mixed solution to a high-temperature high-pressure reaction kettle for hydrothermal reaction, controlling the reaction temperature to be 160 ℃, and controlling the reaction time to be 12 hours.
(5) The phytic acid-vanadium pentoxide composite material (marked as PHVO-0.5) is obtained after collection, washing, centrifugation and vacuum drying. Wherein the washing solvent is deionized water or ethanol (under ultrasonic condition, ultrasonic power is 100W, frequency is 25kHz, and time is 15 min); the centrifugation conditions were: centrifuging at 8000r/min for 5 min; the vacuum drying time is 12h, the drying temperature is 80 ℃, and the negative pressure is 0.07 MPa.
The phytic acid-vanadium pentoxide composite material of the embodiment is prepared according to the preparation method, the synthetic schematic diagram is shown in fig. 1, and the principle is the same as that of embodiment 1. Fig. 2c is a scanning electron microscope image of the phytic acid-vanadium pentoxide composite material prepared in this embodiment, the morphology of the phytic acid-vanadium pentoxide composite material in this embodiment is the same as that in embodiments 1 and 2, and the phytic acid-vanadium pentoxide composite material is a block-shaped lamellar material coated and intercalated with organic substances (the width of the block-shaped lamellar material is 0.8-1.1 μm, the length of the block-shaped lamellar material is 1-2 μm, and the average thickness of the block-shaped lamellar material is 0.6 μm). The transmission diagram of fig. 3 shows that the surface of the vanadium pentoxide nanosheet has a thin phytic acid coating layer, further demonstrating the coating of phytic acid. The high-resolution transmission electron microscope image can test that the distance between vanadium pentoxide layers is increased to
(1.35nm), a significant increase in interlayer spacing can increase the zinc ion diffusion rate. It can be known from the XPS chart (fig. 4) of the phytic acid-vanadium pentoxide composite material of this embodiment that the valence state of vanadium has changed, which is inferred to be caused by the cross-linking of the phytic acid contacting with vanadium pentoxide and the vanadium-oxygen bond of vanadium pentoxide, so that the structural stress of the phytic acid-vanadium pentoxide composite material of the present invention is increased, and the structural integrity and stability are maintained during the repeated zinc ion deintercalation process.
An electrode: the phytic acid-vanadium pentoxide composite material of this example (prepared as described above in this example) was used as the positive electrode material of an aqueous zinc ion battery.
A battery: the same as example 1 was repeated except that the positive electrode material used was the phytic acid-vanadium pentoxide composite material prepared in this example (example 3).
Testing the performance of the battery: fig. 7 shows a cycle performance diagram of the composite material of the embodiment at a current density of 0.1A/g, and it can be seen from fig. 7 that when the phytic acid-vanadium pentoxide composite material is used as a positive electrode material of an aqueous zinc ion battery, the initial discharge specific capacity can reach 368.38mAh/g, the capacity after 200 cycles is 401.69mAh/g, and the capacity is improved, which is related to the activation of the positive electrode material. The capacity can reach 406mAh/g at most, which shows that the composite material of the embodiment has excellent electrochemical performance.
In addition, the composite material of the embodiment also has better rate capability. As shown in fig. 11, in the rate performance diagram at current densities of 0.1, 0.3, 0.5, 1, 3, and 5A/g, the corresponding capacities are 379, 324, 296, 259, 169, and 115mAh/g, respectively, the current density is restored from 5A/g to 0.1A/g, the same rate capacity of the composite material changes very little, which indicates that the composite material has a good rate conversion performance, thereby indicating that the phytic acid-vanadium pentoxide composite material of the present embodiment has a good structural stability.
FIG. 15 is a graph of the cycle performance of the composite material of this example at 5A/g current density for 6000 cycles. As is clear from fig. 15, the composite material still has good stability under high-power charge and discharge conditions, the initial capacity is 173mAh/g, the capacity after 5000 cycles is 184mAh/g, and the capacity is still improved, which indicates that the composite material of the present embodiment has good structural stability. The capacity retention rate after 6000 cycles is 97.3%, which shows that the phytic acid-vanadium pentoxide composite material of the embodiment has good structural stability.
Example 4
The preparation method of the phytic acid-vanadium pentoxide composite material comprises the following steps:
(1) stirring and dissolving vanadium pentoxide in a mixed solution consisting of a hydrogen peroxide solution and deionized water, and marking as a solution A; wherein the volume ratio of the hydrogen peroxide solution to the deionized water is 0.25, and the mass fraction of the hydrogen peroxide in the hydrogen peroxide solution is 35 percent; stirring at 25 deg.C for 15 min; the concentration of vanadium pentoxide in the resulting solution A was 0.034 g/mL.
(2) Dissolving phytic acid in deionized water, stirring to obtain a phytic acid aqueous solution, and recording as a solution B; wherein the volume ratio of the phytic acid to the deionized water is 0.05, the stirring temperature is 25 ℃, and the stirring time is 5 min.
(3) And then dropwise adding the solution B into the solution A (the molar ratio of the addition amount of vanadium pentoxide to the addition amount of phytic acid is 0.24), and stirring at the stirring temperature of 25 ℃ for 10 min.
(4) And transferring the mixed solution to a high-temperature high-pressure reaction kettle for hydrothermal reaction, controlling the reaction temperature to be 160 ℃, and controlling the reaction time to be 12 hours.
(5) The phytic acid-vanadium pentoxide composite material (marked as PHVO-1) is obtained by collection, washing, centrifugation and vacuum drying. Wherein the washing solvent is deionized water or ethanol (under ultrasonic condition, ultrasonic power is 100W, frequency is 25kHz, and time is 15 min); the centrifugation conditions were: centrifuging at 8000r/min for 5 min; the vacuum drying time is 12h, the drying temperature is 80 ℃, and the negative pressure is 0.06 MPa.
The phytic acid-vanadium pentoxide composite material of the embodiment is prepared according to the preparation method, the synthetic schematic diagram is shown in fig. 1, and the principle is the same as that of embodiment 1. Fig. 2d is a scanning electron microscope image of the phytic acid-vanadium pentoxide composite material prepared in this embodiment, the morphology of the phytic acid-vanadium pentoxide composite material in this embodiment is the same as that in embodiments 1-3, and the phytic acid-vanadium pentoxide composite material is a block-shaped lamellar material coated and intercalated with organic substances (the width of the block-shaped lamellar material is 0.8-1.1 μm, the length of the block-shaped lamellar material is 1-2 μm, and the average thickness of the block-shaped lamellar material is 0.6 μm).
An electrode: the phytic acid-vanadium pentoxide composite material of this example (prepared as described above in this example) was used as the positive electrode material of an aqueous zinc ion battery.
A battery: the same as example 1 was repeated except that the positive electrode material used was the phytic acid-vanadium pentoxide composite material prepared in this example (example 4).
Testing the performance of the battery: the cycle performance diagram of the composite material of the embodiment under the current density of 0.1A/g is shown in FIG. 8, and it can be seen from FIG. 8 that when the phytic acid-vanadium pentoxide composite material is used as the anode material of the water-based zinc ion battery, the initial discharge specific capacity can reach 319.41mAh/g, the capacity after 200 cycles is 287.96mAh/g, and the capacity retention rate is 90.28%.
In addition, the composite material of the embodiment also has better rate capability. As shown in fig. 12, the same-rate capacity of the positive electrode material of this embodiment has a small change, which indicates that the composite material has a good rate conversion performance, thereby indicating that the structural stability of the phytic acid-vanadium pentoxide composite material of this embodiment is good.
FIG. 16 is a graph showing the cycle performance of the composite material of this example after 5000 cycles at a current density of 5A/g. As can be clearly seen from fig. 16, the composite material still has good stability under high-power charge and discharge conditions, the initial capacity is 141mAh/g, the capacity after 5000 cycles is 131mAh/g, and the capacity retention rate is 92.91%, indicating that the composite material of the present embodiment has good structural stability.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The phytic acid-vanadium pentoxide composite material is characterized in that the composite material is a sheet material, and the phytic acid is coated on the outer surface of vanadium pentoxide and is intercalated between adjacent layers of the vanadium pentoxide.
2. The phytic acid-vanadium pentoxide composite material according to claim 1, wherein the interlayer spacing between two adjacent layers of vanadium pentoxide in the composite material is 1.0 to 1.5 nm;
preferably, the composite material is in a cuboid shape, the width of the composite material is 0.8-1.1 μm, the length of the composite material is 1-2 μm, and the average thickness of the composite material is 0.6 μm.
3. The phytic acid-vanadium pentoxide composite material according to claim 1, wherein the phytic acid coated on the outer surface of the vanadium pentoxide has a thickness of 5 to 30 nm.
4. The phytic acid-vanadium pentoxide composite material according to claim 1, wherein the molar ratio of vanadium pentoxide to phytic acid in the composite material is 0.2 to 0.3;
preferably, the phytic acid is cross-linked with vanadium-oxygen bonds of vanadium pentoxide.
5. The method for preparing the phytic acid-vanadium pentoxide composite material according to any one of claims 1 to 4, wherein the preparation method comprises the following steps:
step (1): mixing phytic acid, vanadium pentoxide, hydrogen peroxide and water, and stirring to obtain a mixed solution;
step (2): carrying out hydrothermal reaction on the mixed solution obtained in the step (1);
and (3): after the hydrothermal reaction is finished, centrifuging, washing and drying to obtain the phytic acid-vanadium pentoxide composite material;
preferably, the molar ratio of the vanadium pentoxide to the phytic acid in the step (1) is 0.02-0.3.
6. The preparation method of the phytic acid-vanadium pentoxide composite material as claimed in claim 5, wherein the temperature of hydrothermal reaction in the step (2) is 120-200 ℃, and the reaction time is 10-48 h.
7. The method for preparing the phytic acid-vanadium pentoxide composite material according to claim 5, wherein the washing in the step (3) is ultrasonic washing; the drying is vacuum drying;
preferably, the conditions of the centrifugation are: the centrifugation speed is 6000 to 10000r/min, and the centrifugation lasts for 3 to 8 min;
preferably, the power of the ultrasound during the ultrasonic washing is 80-120W, the frequency is 20-30 kHz, and the time is 10-15 min; the washed solvent is deionized water or ethanol;
still preferably, the vacuum drying conditions are: the negative pressure is 0.06-0.08 MPa, the temperature is 50-100 ℃, and the drying time is 8-20 h.
8. The method for preparing the phytic acid-vanadium pentoxide composite material according to any one of claims 5 to 7, wherein the step (1) comprises:
a. stirring and mixing a hydrogen peroxide solution and deionized water according to a volume ratio of 0.1-0.5 to obtain a hydrogen peroxide solution, wherein the mass fraction of hydrogen peroxide in the hydrogen peroxide solution is 25-35%;
b. adding vanadium pentoxide into an aqueous hydrogen peroxide solution, and stirring to obtain a mixed solution of the vanadium pentoxide and the hydrogen peroxide;
c. mixing and stirring phytic acid and deionized water according to the volume ratio of 0.001-0.1 to obtain a phytic acid aqueous solution;
d. dripping a phytic acid aqueous solution into a mixed solution of vanadium pentoxide and hydrogen peroxide, and stirring to obtain the mixed solution in the step (1);
preferably, the stirring temperature in the step a, the step b, the step c or the step d is independently selected from 15-30 ℃, and the stirring time in the step a is 10-20 min; the stirring time of the steps b and d is independently selected from 5-20 min; and c, stirring for 1-10 min.
9. An electrode, characterized in that the raw material or active ingredient of the electrode comprises the phytic acid-vanadium pentoxide composite material according to any one of claims 1 to 4.
10. A battery comprising the phytic acid-vanadium pentoxide composite material according to any one of claims 1 to 4 or the electrode according to claim 9;
preferably, the battery is an aqueous zinc ion battery.
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