CN111916709B - Preparation method of electrode material for water system zinc ion hybrid energy storage device - Google Patents

Preparation method of electrode material for water system zinc ion hybrid energy storage device Download PDF

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CN111916709B
CN111916709B CN202010811356.9A CN202010811356A CN111916709B CN 111916709 B CN111916709 B CN 111916709B CN 202010811356 A CN202010811356 A CN 202010811356A CN 111916709 B CN111916709 B CN 111916709B
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expanded graphite
electrode
zinc
energy storage
storage device
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赵睿
朱伟伟
高小洪
薛卫东
孔坤伦
张子栋
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University of Electronic Science and Technology of China
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • C01B32/182—Graphene
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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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
    • 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
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    • H01M4/625—Carbon or graphite
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to the field of electrode material preparation, and discloses a preparation method of an electrode material for a water system zinc ion hybrid energy storage device. The method mainly aims at solving the defect of poor cycle life of the traditional Prussian blue material and the problem of traditional zinc metal dendrites. The main scheme is that a graphite sheet is used as a substrate raw material, the surface of the graphite is modified by an electrochemical micro-processing method to enable the graphite to have oxygen-containing functional groups, surface active sites are improved, then a Prussian blue nanoparticle compound is electrodeposited on the graphite sheet by an electrochemical deposition technology to be directly used as a positive electrode material of a water system zinc ion energy storage device, a zinc nanosheet is deposited on the graphite sheet by the electrodeposition technology to be directly used as a negative electrode, the electrochemical performance of the water system zinc ion energy storage device is excellent, the cycle life of the water system zinc ion energy storage device exceeds that of all electrode materials of the same type reported so far, and the water system zinc ion energy storage device is expected to become a novel electrode material of the next generation water system zinc ion energy storage device.

Description

Preparation method of electrode material for water system zinc ion hybrid energy storage device
Technical Field
The invention relates to the field of electrode material preparation, and particularly provides a preparation method of an electrode material of a high-performance long-life water-based secondary battery.
Background
With the continuous aggravation of energy crisis and environmental pollution, a series of ecological problems caused by the constant aggravation of the energy crisis and the environmental pollution are urgently solved. Therefore, the development of clean recyclable renewable energy is urgent. To ensure the continuous supply of future clean energy and the continuous development of a large number of mobile electronic devices, lithium ion batteries are considered as one of the important milestones in the field of energy storage. However, the development of lithium ion batteries is limited by various problems encountered in the development process, such as poor cycle stability, low safety and expensive cost. Instead of lithium ion batteries, aqueous zinc ion batteries are considered a good choice.
In the search for various cathode materials suitable for zinc ion batteries, prussian blue and its analogues (PBA) have become potential materials with excellent cycle life and rate performance. PBA has non-toxic properties, low cost and simple synthetic methods have attracted the interest of numerous researchers. PBA have been investigated as cathode materials for batteries, which are based on monovalent ions (Li)+，Na+And K+) The battery of (2) showed good results. They have also been used for Mg2+，Al3+And Ca2+Plasma multi-ion batteries. However, the high potential of the respective anode materials makes the voltage of these monovalent and multivalent ion batteries mostly below 1.5V. On the other hand, the lower electrode potential of zinc makes PBA applicable to zinc ion batteries. Zhang et al reported for the first time that zinc ferrite based on hexacyanoferrate (Zn)3[Fe(CN)6]2ZnHCF) as a cathode, the operating voltage of which reached 1.7V, but the capacity retention rate after 100 cycles was 76%, and the cycle stability thereof was not satisfactory. Lu et al reported coating of ZnHCF with MnO by in situ co-precipitation2Preparing ZnHCF/MnO2The nano cubic electrode is used as the cathode of the water system zinc ion battery and is made of 0.5M ZnSO4The aqueous solution is used as electrolyte and has a concentration of 500mAg-1The capacity retention ratio after 1000 charge-discharge cycles at a high current density of (2) was 77%. Jea et al studied an aqueous zinc ion battery using CuHCF as a cathode, comprising 1M ZnSO4For electrolytes, at 20mA g-1The capacity drops to 77% after only 20 cycles at current density of (2). Liu et al, using FeHCF as the cathode, studied their application in zinc ion batteries, except that they used a bio-ionic liquid-waterElectrolyte as electrolyte, at 0.1mA cm-2The capacity after 50 cycles of charge and discharge at the current density of (a) is close to 99%. Yang et al proposed that low spin Fe in FeHCF could be efficiently activated by high voltage scanning, which created an ultra-long cycle life of Zn-FeHCF hybrid ion battery, and in this study, they achieved a capacity retention of 82% after 5000 cycles and 73% after 10000 ultra-long cycles. The above studies show that none of the cycle lives of the PBA type electrode materials exceed 80-2400 cycles, which results are unsatisfactory. On the other hand, in the continuous charge-discharge cycle process of the traditional zinc metal anode, along with desorption and adsorption of zinc ions, dendritic crystals are easily formed on the surface of the electrode, and the dendritic crystals can puncture the diaphragm, so that the connection of the positive electrode and the negative electrode can cause short circuit, and the safety and the service life of the battery are seriously influenced. Therefore, the invention provides an electrode material with high performance, safety and long service life. In addition, cuprammonia dubia, heyafei et al prepared graphene oxide by Hummers method in the patent of "a preparation method of an asymmetric supercapacitor based on prussian blue/reduced graphene film", prepared prussian blue by coprecipitation method, and then prepared a composite material as an electrode material of the asymmetric supercapacitor. Chenrenjie, Xiegan, Wufeng et al in the patent of Prussian blue analogue positive electrode material of sodium ion battery and preparation method thereof, the cycle stability of Prussian blue material doped with Na, Ni and Co as the positive electrode material of sodium ion battery is still not ideal enough. The prussian blue/graphene composite electrode described in 'a preparation method of a novel high-performance composite nanomaterial modified electrode' by luxiafeng, royal et al is prepared by a wet chemical method, and the method has complex steps, low speed and low efficiency. The Prussian blue/expanded graphite electrode prepared by the electrochemical method provided by the invention has the advantages of high speed, simple steps, high efficiency and the like.
Disclosure of Invention
The invention aims to solve the defects of poor cycle life of the traditional Prussian blue material and the problem of traditional zinc metal dendrites.
The invention adopts the following technical scheme for solving the technical problems:
a preparation method of an electrode material for a water system zinc ion hybrid energy storage device is characterized in that a graphite sheet is used as a substrate raw material, expanded graphite is prepared by an electrochemical micro-processing method, then the expanded graphite is used as a substrate, and a Prussian blue/expanded graphite composite material and a zinc/expanded graphite composite material are directly prepared by an electrochemical deposition method and are respectively used as the anode and the cathode of the water system zinc ion hybrid energy storage device.
In the technical scheme, the method for preparing the expanded graphite comprises the following steps: cutting graphite into graphite sheets with the width of 2-3 cm and the length of 6-8 cm for later use; dissolving ammonium persulfate in deionized water to prepare 0.001-1M/L ammonium persulfate solution as electrolyte, taking a graphite sheet as a positive electrode and a platinum foil as a negative electrode, and keeping the constant voltage of 8-12V for 3-8 minutes on an electrochemical workstation to obtain an expanded graphite sheet subjected to electrochemical micro-treatment; then washing the expanded graphite sheet with deionized water and ethanol for 3-5 times; cutting the expanded graphite into the size of 0.1-2 cm, the width of 5-8 cm and the length of the graphite; and finally drying for later use.
In the technical scheme, the method for preparing the Prussian blue/expanded graphite electrode comprises the following steps: directly electrodepositing prussian blue under an electrochemical workstation three-electrode system by taking expanded graphite prepared by an electrochemical micro-processing method as a working electrode, an Ag/AgCl reference electrode, a platinum foil as a counter electrode and a mixed aqueous solution of potassium ferricyanide, ferric trichloride and hydrochloric acid as an electrolyte, then cleaning the prussian blue/expanded graphite electrode, and finally drying.
In the technical scheme, the method for preparing the zinc/expanded graphite electrode comprises the steps of taking expanded graphite prepared by an electrochemical micro-processing method as a working electrode, taking an Ag/AgCl reference electrode, taking a platinum foil as a counter electrode, taking a zinc sulfate and sodium sulfate mixed aqueous solution as an electrolyte, directly electrodepositing a zinc nanosheet under a three-electrode system of an electrochemical workstation, cleaning the zinc/expanded graphite electrode, and finally drying.
In the technical scheme, the specific preparation method of the mixed aqueous solution of potassium ferricyanide, ferric trichloride and hydrochloric acid comprises the following steps: weighing 0.1-1M potassium ferricyanide, 0.1-1M ferric trichloride and 80-240 mu L hydrochloric acid by weight, dissolving in 80-120mL deionized water, and stirring with a glass rod for 3-5 minutes.
In the technical scheme, the specific method for directly electrodepositing the Prussian blue under the electrochemical workstation three-electrode system comprises the following steps: adopting CV scanning method, potential window is (0.2-0.4) - (0.7-0.9) V, scanning rate is (45-55) mV/s, and scanning cycle number is 45-55 cycles.
In the technical scheme, the prussian blue/expanded graphite cleaning method comprises the following specific steps: washing with ethanol for 20-30 s, then washing with deionized water for 30-50 s, repeating for 3-5 times until impurities on the surface of the material are cleaned;
in the technical scheme, the drying temperature of the Prussian blue/expanded graphite is 50-90 ℃ and the drying time is 8-16 hours.
In the technical scheme, the specific preparation method of the zinc sulfate and sodium sulfate mixed aqueous solution comprises the following steps: weighing 0.1-2M zinc sulfate and 0.1-2M sodium sulfate by weight, dissolving in 80-120mL deionized water, and stirring with a glass rod for 3-5 minutes.
In the technical scheme, the specific method for directly electrodepositing the zinc nanosheets under the three-electrode system of the electrochemical workstation comprises the following steps: the constant current density was-60 mAcm-2 to-20 mAcm-2 for 600-2400 s.
In the technical scheme, the zinc/expanded graphite cleaning method comprises the following specific steps: washing with ethanol for 20-30 s, then washing with deionized water for 30-50 s, repeating for 3-5 times until impurities on the surface of the material are cleaned;
in the technical scheme, the drying temperature of the zinc/expanded graphite is 50-90 ℃ and the drying time is 8-16 hours.
Based on the above explanation, compared with the prior art, the invention has the beneficial effects that:
(1) the prussian blue/expanded graphite overcomes the defect of poor cycle life of the traditional prussian blue materials, and exceeds all the current electrode materials of the same type;
(2) the zinc/expanded graphite solves the problem of traditional zinc metal dendrites, and brings great help to the safety of the battery.
(3) According to the invention, a plurality of layers of graphite on the surface of the graphite are peeled and tilted by an electrochemical method to form the surface with the graphene structure, and the peeling is not realized at the lower part of the graphite. The expanded graphite of the invention has similar overall shape with the graphite before stripping, still is a block material, and has better mechanical property compared with the existing expanded graphite which is powder or stock solution block.
(4) The organic combination of the Prussian blue and the expanded graphite is realized by an electrochemical method, and the mechanism of the Prussian blue formation is as follows: the action of the current being such that Fe is bound to the cyano carbon atom3+Is reduced to Fe2+Formation of Fe (CN)6 -4Ions and free Fe in solution3+Combined to finally form Fe4[Fe(CN)6]3Nanoparticles. The prussian blue/expanded graphite prepared by the process of the present invention achieves surprising cycle life during electrochemical charging and discharging.
Drawings
Fig. 1 a SEM image of the prussian blue/expanded graphite composite;
FIG. 2 is an SEM image of a zinc/expanded graphite composite material;
FIG. 3 Prussian blue/expanded graphite composite XPS spectra;
fig. 4 is a charge-discharge cycle chart of prussian blue/expanded graphite zinc sulfate/expanded graphite.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments. Various alterations and modifications based on other technical knowledge and conventional means in the field are included in the invention without departing from the spirit of the invention.
The technical scheme of the first aspect of the invention is that the Prussian blue/expanded graphite composite cathode material is used for a water system zinc ion battery and capacitor hybrid energy storage device, the Prussian blue/graphene electrode material is a composite structure formed by Prussian blue nano particles and expanded graphite sheets, and the thickness of the composite structure is 500 +/-10 mu m.
The prussian blue disclosed by the invention is one of traditional dyes, has a special crystal structure and higher stability, has great research interest in the field of chemical energy storage, not only achieves good performances in the field of monovalent ions, but also has better performances in the field of multivalent ion energy storage, but by the research results reported at present, the cycle life of prussian blue materials cannot meet the requirements of more and more electronic products at present. The applicant creatively discovers that the organic combination of the prussian blue nano-particles and the expanded graphite through an electrochemical method can show a surprising cycle life in an aqueous zinc ion energy storage system, and more oxygen reduction sites on the surface of the expanded graphite provide more combination sites for the prussian blue nano-particles, so that the loading capacity of the prussian blue nano-particles is greatly enhanced. And in the reversible embedding/removing process of zinc ions, the Prussian blue nano particles continuously grow into a perfect cubic structure, and the cubic structure has fewer defects, so that the storage capacity of ions is greatly improved. With the continuous progress of circulation, the structure is continuously optimized, so that the Prussian blue/expanded graphite electrode has extremely high cycle life and capacity storage, which exceed that of all the current cathode materials of the same type.
The technical scheme of the second aspect of the invention is a preparation method of the Prussian blue/expanded graphite electrode for the water-based zinc-ion battery capacitor hybrid energy storage device. The method is characterized in that potassium ferricyanide, ferric trichloride, hydrochloric acid, ammonium sulfate and graphite flakes are taken, prussian blue nano-particles are deposited on the expanded graphite flakes by an electrochemical method, and rapid and compact deposition of prussian blue nano-ions on the expanded graphite can be realized.
Preferably, the specific preparation method for synthesizing the prussian blue/expanded graphite electrode by the electrochemical method comprises the following steps: firstly, dissolving ammonium persulfate in deionized water to obtain an ammonium persulfate aqueous solution as an electrolyte, taking a graphite sheet as a working electrode and a platinum foil as a counter electrode, carrying out micro-treatment on the graphite sheet under a double-electrode system of an electrochemical workstation to prepare expanded graphite, and then cleaning and drying. And secondly, dissolving potassium ferricyanide, ferric trichloride and hydrochloric acid in deionized water to obtain a mixed solution as an electrolyte, taking the prepared expanded graphite as a working electrode, an Ag/AgCl electrode as a reference electrode and a platinum foil as a counter electrode, electrodepositing prussian blue under a three-electrode system of an electrochemical workstation, and cleaning and drying to obtain the prussian blue/expanded graphite electrode.
Preferably, the aqueous ammonium persulfate solution is prepared from ammonium persulfate and deionized water in the ratio of (20-30) to 100 by weight.
Preferably, the parameters of the electrochemical workstation two-electrode system are: the voltage is 8-12V, and the time is 3-7 minutes.
Preferably, the mixed solution of potassium ferricyanide, ferric trichloride, hydrochloric acid and deionized water is prepared from potassium ferricyanide, ferric trichloride, hydrochloric acid and deionized water in the proportion of (1-2) to (0.5-1) to (0.03-0.07) to 100 by weight.
Preferably, the parameters of the electrochemical workstation three-electrode system are: the sweep rate is (45-55) mV/s, the voltage window is (0.2-0.4) - (0.7-0.9) V, and the number of turns is (45-55).
The technical scheme of the third aspect of the invention is that the zinc/expanded graphite composite anode material is used for a water system zinc ion battery and capacitor hybrid energy storage device, the zinc/graphene electrode material is a composite structure formed by zinc nanosheets and expanded graphite sheets, and the thickness of the composite structure is 500 +/-20 microns. The traditional zinc anode can generate crystal branches on the surface along with the continuous stripping/deposition of zinc in the charging and discharging circulation process, which brings adverse effect to the battery safety, and the problem of the crystal branches can be solved by depositing zinc nano sheets on the surface of a graphite sheet by an electrochemical method.
The zinc nano sheet/expanded graphite electrode is a modification of the traditional zinc anode. The zinc metal anode is used as the anode of the traditional zinc ion battery due to higher theoretical capacity, but the surface structure of the zinc metal is changed due to the stripping/deposition of zinc in the charging and discharging process, so that crystal branches are generated, and the appearance of the crystal branches can puncture a diaphragm, so that the safety and the service life of the battery are greatly influenced. The applicant finds that the occurrence of zinc crystal branches can be effectively avoided by electrochemically depositing the zinc nanosheets, so that the safety and the cycle life of the battery are improved. On the other hand, the plurality of functional groups on the surface of the expanded graphite provide more active sites for zinc and are good carriers for zinc deposition.
The technical scheme of the fourth aspect provided by the invention is a preparation method of a zinc/expanded graphite composite anode material for a water-based zinc-ion battery capacitor hybrid energy storage device. Zinc sulfate, sodium sulfate and graphite flakes are taken, and zinc nanosheets are deposited on the expanded graphite flakes by an electrochemical method, so that the problem of zinc dendrite branches can be solved.
Preferably, the specific preparation method for synthesizing the zinc/expanded graphite electrode by the electrochemical method comprises the following steps: taking zinc sulfate and sodium sulfate to dissolve in deionized water to obtain a mixed solution as an electrolyte, taking the prepared expanded graphite as a working electrode, taking an Ag/AgCl electrode as a reference electrode and a platinum foil as a counter electrode, electrodepositing zinc nanosheets under a three-electrode system of an electrochemical workstation, and cleaning and drying to obtain the zinc/expanded graphite electrode.
Preferably, the mixed solution of zinc sulfate, sodium sulfate and deionized water is prepared from zinc sulfate, sodium sulfate and deionized water in the ratio of (25-30) to (12-16) to 100 by weight.
Preferably, the parameters of the electrochemical workstation three-electrode system are: constant current of (-60 mAcm)-2)-(-20mAcm-2). Preparing substrate expanded graphite: the expanded graphite is prepared by taking common commercial graphite and ammonium persulfate as raw materials, and the specific preparation route is as follows: 2-3g of Ammonium Persulfate (APS) was dissolved in 100mL of deionized water, and the resulting mixed solution was used as an electrolyte, and graphite sheets were cut into 2.5X 7 cm long strips. The graphite sheet is used as a working electrode, the Ag/AgCl reference electrode and the platinum foil is used as a counter electrode, the voltage is kept constant at 10V for 5 minutes, then the processed expanded graphite is cut into strips of 1 multiplied by 6 cm, and the strips are washed and dried by deionized water.
Preparation of zinc/expanded graphite anode: self-made expanded graphite is used as a working electrode, 1M zinc sulfate and 1M sodium sulfate aqueous solution are used as electrolyte, an Ag/AgCl reference electrode and a platinum foil are used as counter electrodes, and the constant current is-50 mAcm-2Keeping the time for 1800s, and using deionized water and water after the deposition is finishedRepeatedly cleaning with ethanol, and oven drying at 50-90 deg.C overnight.
In fig. 3, the peak of 01S corresponds to the oxygen-containing functional groups of the expanded graphite substrate, providing more active sites; while the peaks for C1S, N1S, Fe 2P correspond to prussian blue, demonstrating the successful polymerization of prussian blue on expanded graphite.
The charge-discharge cycling profile shown in fig. 4 is as described in example 5, with 50 cycles of deposition leading to the highest capacity contribution and cycling stability. The reason for this is that the thickness of the deposited prussian blue is moderate at 50 cycles, making the electrochemical behavior more efficient, which provides the highest capacity; in the process of charging and discharging, the defects of the Prussian blue gradually become less, and the capacity continuously rises, which is also the reason that the capacity continuously rises after 12000 charging and discharging cycles.
Example 1:
the self-made expanded graphite is used as a working electrode, a mixed solution of 0-1M potassium ferricyanide, 0-1M ferric trichloride and 80-240 mu L hydrochloric acid is used as an electrolyte, an Ag/AgCl reference electrode and a platinum foil are used as a counter electrode, the sweeping speed is 45-55mV/s, the number of turns is 10 turns, and the voltage window is (0.1-0.5) - (0.6-1) V. After deposition is finished, the mixture is repeatedly washed clean by deionized water and ethanol and then dried overnight at 50-90 ℃.
The obtained Prussian blue/expanded graphite is directly used as a cathode, a 1-3M/L zinc sulfate aqueous solution is used as an electrolyte, the obtained zinc/expanded graphite is directly used as an anode, and after the water system battery is assembled, the current density is 0.1mA cm-2Has a reversible capacity of 0.1mAh cm-2。
Example 2:
the self-made expanded graphite is used as a working electrode, a mixed solution of 0-1M potassium ferricyanide, 0-1M ferric trichloride and 80-240 mu L hydrochloric acid is used as an electrolyte, an Ag/AgCl reference electrode and a platinum foil are used as a counter electrode, the sweeping speed is 50mV/s, the number of turns is 20 turns, and the voltage window is (0.1-0.5) - (0.6-1) V. After deposition is finished, the mixture is repeatedly washed clean by deionized water and ethanol and then dried overnight at 50-90 ℃.
The prepared Prussian blue/expanded graphite is directly used as a cathode, and a 1-3M/L zinc sulfate aqueous solution is used for electrolysisThe prepared zinc/expanded graphite is directly used as an anode, and after the zinc/expanded graphite is assembled into an aqueous battery, the reversible capacity of the zinc/expanded graphite is 0.12mAh cm under the condition that the current density is 0.1mA cm & lt-2 & gt-2。
Example 3:
the self-made expanded graphite is used as a working electrode, a mixed solution of 0-1M potassium ferricyanide, 0-1M ferric trichloride and 80-240 mu L hydrochloric acid is used as an electrolyte, an Ag/AgCl reference electrode and a platinum foil are used as a counter electrode, the sweeping speed is 50mV/s, the number of turns is 30 turns, and the voltage window is (0.1-0.5) - (0.6-1) V. After deposition is finished, the mixture is repeatedly washed clean by deionized water and ethanol and then dried overnight at 50-90 ℃.
The obtained Prussian blue/expanded graphite is directly used as a cathode, a 1-3M/L zinc sulfate aqueous solution is used as an electrolyte, the obtained zinc/expanded graphite is directly used as an anode, and after the water system battery is assembled, the current density is 0.1mA cm-2Has a reversible capacity of 0.13mAh cm-2。
Example 4:
the self-made expanded graphite is used as a working electrode, a mixed solution of 0-1M potassium ferricyanide, 0-1M ferric trichloride and 80-240 mu L hydrochloric acid is used as an electrolyte, an Ag/AgCl reference electrode and a platinum foil are used as a counter electrode, the sweeping speed is 50mV/s, the number of turns is 40 turns, and the voltage window is (0.1-0.5) - (0.6-1) V. After deposition is finished, the mixture is repeatedly washed clean by deionized water and ethanol and then dried overnight at 50-90 ℃.
The obtained Prussian blue/expanded graphite is directly used as a cathode, a 1-3M/L zinc sulfate aqueous solution is used as an electrolyte, the obtained zinc/expanded graphite is directly used as an anode, and after the water system battery is assembled, the current density is 0.1mA cm-2Has a reversible capacity of 0.13mAh cm-2。
Example 5:
the self-made expanded graphite is used as a working electrode, a mixed solution of 0-1M potassium ferricyanide, 0-1M ferric trichloride and 80-240 mu L hydrochloric acid is used as an electrolyte, an Ag/AgCl reference electrode and a platinum foil are used as a counter electrode, the sweeping speed is 50mV/s, the number of turns is 50 turns, and the voltage window is (0.1-0.5) - (0.6-1) V. After deposition is finished, the mixture is repeatedly washed clean by deionized water and ethanol and then dried overnight at 50-90 ℃.
The obtained Prussian blue/expanded graphite is directly used as a cathode, a 1-3M/L zinc sulfate aqueous solution is used as an electrolyte, the obtained zinc/expanded graphite is directly used as an anode, and after the water system battery is assembled, the current density is 0.1mA cm-2Has a reversible capacity of 0.2mAh cm-2The current density after 12000 cycles of the cell was 0.1mA cm by testing the cell on a blue test system-2The capacity retention rate exceeds 120%.
Example 6:
the self-made expanded graphite is used as a working electrode, a mixed solution of 0-1M potassium ferricyanide, 0-1M ferric trichloride and 80-240 mu L hydrochloric acid is used as an electrolyte, an Ag/AgCl reference electrode and a platinum foil are used as a counter electrode, the sweeping speed is 50mV/s, the number of turns is 60 turns, and the voltage window is (0.1-0.5) - (0.6-1) V. After deposition is finished, the mixture is repeatedly washed clean by deionized water and ethanol and then dried overnight at 50-90 ℃.
The obtained Prussian blue/expanded graphite is directly used as a cathode, a 1-3M/L zinc sulfate aqueous solution is used as an electrolyte, the obtained zinc/expanded graphite is directly used as an anode, and after the water system battery is assembled, the current density is 0.1mA cm-2Has a reversible capacity of 0.15mAh cm-2。
Example 7:
the self-made expanded graphite is used as a working electrode, a mixed solution of 0-1M potassium ferricyanide, 0-1M ferric trichloride and 80-240 mu L hydrochloric acid is used as an electrolyte, an Ag/AgCl reference electrode and a platinum foil are used as a counter electrode, the sweeping speed is 50mV/s, the number of turns is 80 turns, and the voltage window is (0.1-0.5) - (0.6-1) V. After deposition is finished, the mixture is repeatedly washed clean by deionized water and ethanol and then dried overnight at 50-90 ℃.
The obtained Prussian blue/expanded graphite is directly used as a cathode, a 1-3M/L zinc sulfate aqueous solution is used as an electrolyte, the obtained zinc/expanded graphite is directly used as an anode, and after the water system battery is assembled, the current density is 0.1mA cm-2Has a reversible capacity of 0.15mAh cm-2。
The above are only specific embodiments of the present invention, and it should be noted that the above embodiments should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention, and these modifications and variations should also be considered as within the scope of the invention.

Claims (6)

1. A preparation method of an electrode material for a water system zinc ion hybrid energy storage device is characterized in that a graphite sheet is used as a substrate raw material, expanded graphite is prepared by an electrochemical micro-processing method, then the expanded graphite is used as a substrate, and a Prussian blue/expanded graphite composite material and a zinc/expanded graphite composite material are directly prepared by an electrochemical deposition method and are respectively used as the anode and the cathode of the water system zinc ion hybrid energy storage device;
the method for preparing the expanded graphite comprises the following steps: cutting graphite into graphite sheets with the width of 2-3 cm and the length of 6-8 cm for later use; dissolving ammonium persulfate in deionized water to prepare 0.001-1M/L ammonium persulfate solution as electrolyte, taking a graphite sheet as a positive electrode and a platinum foil as a negative electrode, and keeping the constant voltage of 8-12V for 3-8 minutes on an electrochemical workstation to obtain an expanded graphite sheet subjected to electrochemical micro-treatment; then washing the expanded graphite sheet with deionized water and ethanol for 3-5 times; cutting the expanded graphite into the size of 0.1-2 cm, the width of 5-8 cm and the length of the graphite; finally, drying for later use;
the method for preparing the Prussian blue/expanded graphite electrode comprises the following steps: directly electrodepositing prussian blue under an electrochemical workstation three-electrode system by taking expanded graphite prepared by an electrochemical micro-processing method as a working electrode, an Ag/AgCl reference electrode, a platinum foil as a counter electrode and a mixed aqueous solution of potassium ferricyanide, ferric trichloride and hydrochloric acid as an electrolyte, then cleaning the prussian blue/expanded graphite electrode and finally drying;
the method for preparing the zinc/expanded graphite electrode comprises the following steps: taking expanded graphite prepared by an electrochemical micro-processing method as a working electrode, an Ag/AgCl reference electrode, a platinum foil as a counter electrode, taking a zinc sulfate and sodium sulfate mixed aqueous solution as an electrolyte, directly electrodepositing a zinc nanosheet under a three-electrode system of an electrochemical workstation, cleaning the zinc/expanded graphite electrode, and finally drying;
the specific preparation method of the mixed aqueous solution of potassium ferricyanide, ferric trichloride and hydrochloric acid comprises the following steps: weighing 0-1M potassium ferricyanide, 0-1M ferric trichloride and 80-240 mu L hydrochloric acid by weight, dissolving in 80-120mL deionized water, and stirring with a glass rod for 3-5 minutes.
2. The preparation method of the electrode material for the aqueous zinc ion hybrid energy storage device according to claim 1, wherein the specific method for directly electrodepositing prussian blue under the electrochemical workstation three-electrode system is as follows: adopting CV scanning method, potential window is (0.2-0.4) - (0.7-0.9) V, scanning rate is (45-55) mV/s, and scanning cycle number is 45-55 cycles.
3. The preparation method of the electrode material for the aqueous zinc ion hybrid energy storage device according to claim 1, wherein the prussian blue/expanded graphite cleaning comprises the following specific steps: washing with ethanol for 20-30 s, then washing with deionized water for 30-50 s, repeating for 3-5 times until impurities on the surface of the material are cleaned; the drying temperature of the Prussian blue/expanded graphite is 50-90 ℃, and the drying time is 8-16 hours.
4. The preparation method of the electrode material for the aqueous zinc ion hybrid energy storage device according to claim 1, wherein the specific preparation method of the zinc sulfate and sodium sulfate mixed aqueous solution comprises the following steps: weighing 0-2M of zinc sulfate and 0-2M of sodium sulfate by weight, dissolving in 80-120mL of deionized water, and stirring for 3-5 minutes by using a glass rod.
5. The preparation method of the electrode material for the aqueous zinc ion hybrid energy storage device according to claim 1, wherein the specific method for directly electrodepositing the zinc nanosheets under the electrochemical workstation three-electrode system is as follows: the constant current density is-60 mA. cm-2To-20 mA. cm-2The time is 600 times 2400 s.
6. The preparation method of the electrode material for the aqueous zinc ion hybrid energy storage device according to claim 1, wherein the zinc/expanded graphite cleaning comprises the following specific steps: washing with ethanol for 20-30 s, then washing with deionized water for 30-50 s, repeating for 3-5 times until impurities on the surface of the material are cleaned; the drying temperature of the zinc/expanded graphite is 50-90 ℃ and the drying time is 8-16 hours.
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