CN116190550A

CN116190550A - Preparation and application of ferrite anode for water-based zinc ion battery

Info

Publication number: CN116190550A
Application number: CN202211705844.7A
Authority: CN
Inventors: 陈人杰; 胡正强
Original assignee: Beijing Institute of Technology BIT
Current assignee: Beijing Institute of Technology BIT
Priority date: 2022-12-29
Filing date: 2022-12-29
Publication date: 2023-05-30

Abstract

The invention relates to the field of water-based zinc ion batteries, in particular to a method for a ferrite positive electrode of a zinc ion battery, wherein the ferrite is prepared by performing oxidation reduction on ferric iron to realize reversible storage of zinc ions, and metal cations coordinated with the ferrite can be zinc, cobalt, nickel, copper and the like; the anode can not cause problems of metal dissolution, environmental pollution and the like. The preparation method involves calcining in an air atmosphere in combination with low temperature hydrothermal. The ferrite is used as the positive electrode material of the zinc ion battery, can effectively improve the cycling stability of the zinc ion battery, and has very broad application prospect in the aspect of large-scale green energy storage.

Description

Preparation and application of ferrite anode for water-based zinc ion battery

Technical Field

The invention relates to the technical field of water-based zinc ion batteries, in particular to a ferrite positive electrode for a water-based zinc ion battery, and a preparation method and application thereof.

Background

Compared with a lithium battery using inflammable and toxic organic electrolyte, the water-based zinc ion battery is expected to replace the existing energy storage technology by virtue of the advantages of safety, greenness, low cost, simple preparation process and the like of battery materials, and is widely studied. At present, a main challenge faced by zinc ion batteries is to explore a positive electrode material which can reversibly store zinc ions under the condition of keeping a structure stable and has high capacity.

However, the current positive electrode materials of the water-based zinc ion battery are limited, and mainly concentrate on manganese-based compounds and vanadium-based compounds. The manganese-based anode has rich resources and low cost, but manganese element is extremely easy to dissolve, has poor stability and short cycle life, and prevents further application; the vanadium-based positive electrode has very high capacity, but the material has serious environmental pollution, is not green and environment-friendly, and does not accord with the concept of sustainable development, so the invention provides the ferrite positive electrode which can reversibly store zinc ions by utilizing the redox capability of iron, and meanwhile, the positive electrode can not have the problems of metal dissolution, environmental pollution and the like.

Disclosure of Invention

The invention aims to provide a ferrite positive electrode material of a water-based zinc ion battery and application thereof, aiming at solving the problems of manganese metal dissolution, vanadium metal environmental pollution and the like of the positive electrode material of the water-based zinc ion battery at the present stage.

Specifically, the inventive arrangements of the present disclosure are as follows:

(1) A mixed solution of a weak reducing agent and a salt containing cation a will be prepared and an iron salt will be added to the solution to form a mixed system.

(2) And (3) placing the solution obtained in the step (1) into a reaction kettle, heating at 120-180 ℃ for 8-12h, cooling to room temperature, and centrifugally cleaning.

(3) And (3) placing the precursor obtained in the step (2) in a muffle furnace, and heating at 150-240 ℃ for 8-12h to obtain the ferrite.

Preferably, in step (1), the weak reducing agent may be at least one of citric acid, oxalic acid, ascorbic acid, formaldehyde. The solvent is at least one of glycerol, ethanol and isopropanol.

Preferably, in the step (1), the salt of the cation A may be any one of cobalt, nickel, zinc and copper, and the concentration is 2-3mol/L.

Preferably, in step (1), the iron salt may be any one of ferric nitrate or ferric chloride. The molar ratio to the cation a salt is about 1:2-1:2.8

Preferably, in the step (2), the solvothermal temperature is 150 ℃ and the incubation time is 10 hours;

preferably, in step (3), the calcination temperature is 200℃and the incubation time is 8 hours.

And mixing the obtained ferrite, PTFE and carbon black according to a mass ratio of 8:1:1, coating the aqueous zinc ion battery on titanium foil to prepare a positive electrode, and assembling the aqueous zinc ion battery.

The electrolyte of the common zinc ion battery electrolyte can be one or more of zinc sulfate, zinc chloride or zinc triflate.

The negative electrode of the zinc ion battery adopted by the invention is metallic zinc.

The invention provides a water-based zinc ion battery based on a ferrite positive electrode, wherein the zinc storage active center of the ferrite positive electrode is ferric iron, and the zinc ions can be stored through oxidation reduction of iron, so that the corresponding specific capacity is realized. The metal cations A involved may be various. Meanwhile, the green pollution-free anode can not relate to the dissolution problem, and is beneficial to improving the stability of the zinc ion battery. The invention has the advantages of expanding the selectivity of the water-based zinc ion battery, having the specific capacity exceeding 150mAh/g and being expected to become the electrode material with the next generation of long circulation, environmental protection and sustainable development.

Drawings

In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required to be used in the description of the embodiments or the prior art will be briefly described below, and it will be obvious to those skilled in the art that other drawings can be obtained from these drawings without inventive effort.

FIG. 1 is a cyclic voltammogram provided using example 1 of the present application;

fig. 2 is a cycle life chart of a zinc ion full cell provided in example 1 of the present application.

Detailed Description

In order to better understand the technical solutions in the present application, the following description will clearly and completely describe the technical solutions in the embodiments of the present application with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art based on the embodiments herein without making any inventive effort, shall fall within the scope of the present application.

Example 1

0.3g of zinc acetate is dissolved in 20mL of glycerin and 75mL of isopropanol, then 1.1g of ferric nitrate nonahydrate is added to form a mixed solution, the solution is placed in a 100mL reaction kettle, after hydrothermal reaction is carried out for 12h at 180 ℃, the precursor is obtained by centrifugation, the solution is placed in an oven for drying for 12h at 80 ℃, and the precursor is placed in a muffle furnace for calcining for 2h at 400 ℃ to obtain zinc ferrite.

The mass ratio of the zinc ferrite, the PTFE and the conductive carbon black is 8:1:1, then coating the mixture on a Ti net, drying the mixture for 12 hours at the temperature of 80 ℃ in vacuum to prepare an anode, and taking 2M zinc sulfate as electrolyte and zinc foil as a cathode to assemble a battery for electrochemical performance test.

Fig. 1 shows a cyclic voltammogram of a full cell, a pair of distinct redox peaks can be observed, and the second and third CV curves substantially coincide, demonstrating the stability of the zinc ferrite positive electrode.

The example also conducted a charge-discharge cycle test, and the positive electrode still had a specific capacity of 105mAh/g after 500 cycles at a current density of 100 mA/g.

It should be noted that in this document, relational terms such as "first" and "second" and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.

The foregoing is only a specific embodiment of the invention to enable those skilled in the art to understand or practice the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

The same or similar parts between the various embodiments in this specification are referred to each other. In particular, for the terminal embodiment, since it is substantially similar to the method embodiment, the description is relatively simple, and reference should be made to the description in the method embodiment for relevant points.

The above-described embodiments of the present application are not intended to limit the scope of the present application.

Claims

1. The preparation method of the ferrite positive electrode is characterized by comprising the following steps of:

(1) Mixing a weak reducing agent and a salt containing cation A to prepare a mixed solution, and adding ferric salt into the mixed solution to form a mixed system;

(2) Placing the solution obtained in the step (1) into a reaction kettle, heating at 120-180 ℃ for 8-12h, cooling to room temperature, and centrifugally cleaning;

(3) Placing the precursor obtained in the step (2) in a muffle furnace, and heating at 150-240 ℃ for 8-12h to obtain ferrite;

(4) Mixing the obtained ferrite anode powder with a conductive agent and a binder, adding isopropanol, coating on a current collector, and vacuum drying to obtain the electrode plate.

2. The method according to claim 1, wherein in the step (1), the weak reducing agent is at least one of citric acid, oxalic acid, ascorbic acid, formaldehyde; the solvent is at least one of glycerol, ethanol and isopropanol.

3. The preparation method according to claim 1, wherein in the step (1), the salt of the cation A is any one of cobalt, nickel, zinc and copper, and the concentration is 2-3mol/L.

4. The method of claim 1, wherein in step (1), the iron salt is any one of ferric nitrate or ferric chloride; the molar ratio to the cation a salt is about 1:2-1:2.8.

5. the method according to claim 1, wherein in the step (2), the solvothermal temperature is 150℃and the incubation time is 10 hours.

6. The method according to claim 1, wherein in the step (3), the calcination temperature is 200 ℃ and the holding time is 8 hours.

7. The method according to claim 1, wherein in the step (4), the mass ratio of the active material, the binder and the conductive agent is 8:1:1, the current collector can be titanium mesh, carbon cloth or titanium foil.

8. A ferrite positive electrode material, characterized in that it is produced by the method for producing a ferrite positive electrode material according to any one of claims 1 to 7.

9. Use of a ferrite positive electrode according to any of claims 1-8 in an aqueous zinc ion battery or a zinc ion electrochemical energy storage device.