CN111640933A - Manganese dioxide/carbon nanotube foam material, zinc-manganese battery, and preparation methods and applications thereof - Google Patents
Manganese dioxide/carbon nanotube foam material, zinc-manganese battery, and preparation methods and applications thereof Download PDFInfo
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Abstract
The invention discloses a manganese dioxide/carbon nano tube foam material, a zinc-manganese battery, and preparation methods and applications thereof. The preparation method of the manganese dioxide/carbon nano tube foam material comprises the following steps: soaking the carbon nano tube foam with a potassium permanganate solution, and carrying out etching treatment at the temperature of 80-95 ℃ for 1-3h to obtain the manganese dioxide/carbon nano tube foam material. The invention adopts low-concentration potassium permanganate solution to etch carbon nanotube foam, solves the problem that the carbon nanotube foam is not hydrophilic, and simultaneously, the loaded manganese dioxide not only can provide the capacity contribution of single electron reaction, but also provides the capacity contribution for realizing double electron reactionAn active site; the anode material of the water-based zinc-manganese battery prepared by the invention can store electrolyte automatically, and can stably realize single electron (Mn) in a neutral or weakly acidic system 3+ /Mn 4+ ) And two electrons (Mn) 2+ /Mn 4+ ) The reaction coexists, and meanwhile, the water-based zinc-manganese battery prepared by the method is higher in cycle stability.
Description
Technical Field
The invention belongs to the technical field of electrochemical energy storage, and particularly relates to a manganese dioxide/carbon nanotube foam material, a zinc-manganese battery, and preparation methods and applications thereof.
Background
Substances, energy and information are fundamental elements constituting natural society. With the coming of the information-based society, novel portable devices such as mobile phones and computers and new energy vehicles are becoming an indispensable part of daily life, however, the existing secondary batteries (lithium ion batteries, lead-acid batteries and the like) applied in large scale have the problems of low energy density, poor safety, high cost and environment, so that the development of novel energy storage devices which are environment-friendly, low in price and high in capacity density has important significance. Among them, zinc-manganese secondary batteries (manganese dioxide is a positive electrode, zinc is a negative electrode, and an aqueous solution is an electrolyte) have been the direction of intense research due to their advantages of high safety, low cost, and environmental friendliness. However, most of the existing research is limited to Mn 3+ /Mn 4+ (one-electron reaction, theoretical capacity 308mA · h/g), the prevailing mechanism is that zinc ions and hydrogen ions are constantly deintercalated in manganese dioxide crystal lattice (lattice expansion and contraction), thereby affecting the cycling stability. Mn-based materials developed in recent two years 2+ /Mn 4+ The cycle stability and the capacity performance of the novel zinc-manganese battery (with double electron reaction and theoretical capacity of 616mA · h/g) are obviously superior to those of a single electron process, but the current research proves that the complete double electron reaction has higher requirements on hydrogen ions, is generally an acid electrolyte, is easy to corrode a metal cathode, is not very friendly to the environment and human body, and limits the application range of the novel zinc-manganese battery.
Current electrode designs are mainly divided into three major categories: 1. conventional electrode preparation represented by coating method: uniformly coating an active material powder, carbon black and a conductive polymer on a thin metal sheet, and connecting an electrode (mixed slurry) and a current collector (flat metal plate) by drying; 2. metal frame filling method: the metal foam is used for replacing the thin metal sheet, and the mixed slurry is filled in the foam metal to realize better contact. Both of these methods have the following problems: 1. the active substance is prepared into powder and mixed, the aggregation size of the common particles is more than 100 microns, the specific surface area is low, and the electrochemical active sites are limited; 2. the mixed slurry is simply adsorbed on the surface of the current collector by drying, and the bonding strength can be sharply reduced along with the cycle period; 3. the dispersants used are typically PVDF and carbon black, which present a risk of fire explosion when the battery is subjected to extreme conditions. 3. In recent years, self-supporting electrodes represented by carbon cloth and carbon nanotube films have been developed, in which active materials are directly bonded to current collectors by deposition or other chemical methods, and thus binders and conductive agents are not required, but the carbon cloth and carbon nanotube films cannot store electrolytes themselves, and thus, battery devices are required to have high requirements for achieving two-electron reactions.
The existing electrode design of the water system zinc-manganese battery has the following defects: 1. the traditional coating method electrode has no conductive frame, and can not realize double-electron reaction; 2. the metal frame electrode has the advantages of low specific surface area, low double-electron reaction efficiency, serious hydrogen evolution phenomenon and overlarge dead weight, and influences the energy density of the battery; 3. the conventional self-supporting electrodes such as carbon cloth and carbon nanotube film cannot store electrolyte by themselves, and the battery device is required to be excessively high in order to realize the two-electron reaction.
Disclosure of Invention
The invention mainly aims to provide a manganese dioxide/carbon nano tube foam material (MnO) 2 /CNT foam), zinc-manganese battery, its preparation method and application, in order to overcome the deficiency of the prior art.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of a manganese dioxide/carbon nano tube foam material, which comprises the following steps:
providing a carbon nanotube foam;
soaking the carbon nano tube foam with a potassium permanganate solution, and carrying out etching treatment at the temperature of 80-95 ℃ for 1-3h to obtain MnO 2 a/CNT foam.
The embodiment of the invention also provides MnO prepared by the method 2 /CNT foam, said MnO 2 the/CNT foam material comprises carbon nano tube foam and manganese dioxide loaded on the surface and/or inside of the carbon nano tube foam, and MnO 2 the/CNT foam has a micro-channel structure.
The embodiment of the invention also provides the MnO 2 Use of/CNT foam as electrode in the field of zinc manganese batteries.
The embodiment of the invention also provides an electrode for a zinc-manganese battery, which comprises the manganese dioxide/carbon nano tube foam material.
The embodiment of the invention also provides a water-based zinc-manganese battery, which comprises a first film, a positive electrode, a diaphragm, a negative electrode and a second film which are sequentially arranged along a set direction, wherein the positive electrode is the electrode for the zinc-manganese battery, the electrode for the zinc-manganese battery is loaded with electrolyte, and the electrolyte is neutral or weakly acidic.
The embodiment of the invention also provides a preparation method of the water-based zinc-manganese battery, which comprises the following steps:
providing a zinc sheet as a negative electrode;
providing the electrode for the zinc-manganese battery as a positive electrode;
soaking the electrode for the zinc-manganese battery in electrolyte to prepare an electrode for the zinc-manganese battery loaded with the electrolyte;
and packaging the first film, the electrode for the zinc-manganese battery loaded with the electrolyte, the diaphragm, the negative electrode and the second film along a set direction to form the aqueous zinc-manganese battery.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention adopts the low-concentration potassium permanganate solution to etch the carbon nanotube foam, solves the problem that the carbon nanotube foam is not hydrophilic in one step, and simultaneously loads a layer of manganese dioxide, thereby not only providing the capacity contribution of single electron reaction, but also providing active sites for realizing double electron reaction, and simultaneously the etching method is mild and has little damage to the carbon tube structure;
(2) The invention is based on MnO 2 The water-based zinc-manganese battery prepared from the CNT foam material solves the problem that the structure of the traditional zinc-manganese battery can not adapt to Mn 2+ /Mn 4+ Under the condition of reaction, the micro-channel structure with rich carbon nano tube foam can not only accumulate equal volume of electrolyte but also has rich ion channels, the double-electron reaction has higher requirement on the electrolyte amount, the electrolyte is generally stored in a special device, and MnO is directly used in the invention 2 the/CNT foam electrode stores electrolyte, the device is simple, and the ion directional migration efficiency is higher;
(3) The invention can realize the design of a thick electrode by combining a large three-dimensional interconnected conductive network, manganese ions in the electrolyte can be freely deposited on the surface of the carbon nano tube, the length-diameter ratio of the carbon nano tube is high, the specific surface area is far higher than that of common current collectors such as carbon cloth, metal frames and the like, and the dual-electron reaction of manganese dioxide can be realized easily;
(4) The invention is based on MnO 2 The aqueous zinc-manganese dioxide battery prepared by the/CNT foam material can store electrolyte with the same volume and can stably realize single electron (Mn) in a neutral or weakly acidic system 3+ /Mn 4+ ) And two electrons (Mn) 2+ /Mn 4+ ) The reaction coexists, so as to solve the problem of insufficient hydrogen ions in the neutral electrolyte; the water-based zinc-manganese battery with coexisting single-electron and double-electron reactions in a neutral system is realized due to the cross-linked carbon nanotube network system and the capability of self-storing electrolyte.
(5) The invention is based on MnO 2 The cycling stability of the aqueous zinc-manganese battery prepared by the CNT foam material is higher, and the battery is at 10mA/cm 2 13000 turns of long cycle is realized under the current density, and the capacity is not attenuated relative to the initial state.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the description below are only some embodiments described in the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 shows MnO in one embodiment of the present invention 2 Schematic preparation of/CNT foams;
FIG. 2 is a MnO based scheme in an embodiment of the present invention 2 Schematic structure of water-based zinc-manganese battery of/CNT foam material;
FIGS. 3a-3d are carbon nanotube foams and MnO in example 1 of the present invention 2 Scanning electron microscope images and hydrophilicity images of/CNT foam electrodes;
FIG. 4 shows preparation of MnO in example 1 of the present invention 2 Cyclic compression plot of/CNT foam electrode;
FIG. 5 is an impedance diagram of pure carbon nanotube foam, carbon nanotube film, carbon cloth, and nickel foam in example 1 of the present invention;
FIG. 6 is a CV diagram of an aqueous Zn-Mn battery of example 1 of the present invention at various sweep rates;
FIG. 7 is a rate performance graph of an aqueous zinc-manganese battery according to example 1 of the present invention;
FIG. 8 is a graph of the voltage capacity of an aqueous zinc-manganese battery of example 1 of the invention at different current densities;
FIG. 9 shows the results of the experiment of the present invention at 10mA/cm for the aqueous Zn-Mn battery in example 1 2 Long cycle graph below.
Detailed Description
In view of the defects of the prior art, the inventor of the present invention has long studied and largely practiced to provide the technical solution of the present invention, and in recent years, the inventor has developed a self-supporting electrode represented by carbon cloth and carbon nanotube film,the invention is based on manganese dioxide/carbon nanotubes (MnO) because the active material is directly bound to the current collector by deposition or other chemical methods, without the need for binders and conductive agents, inspired by the structural design of self-supporting electrodes 2 the/CNT) foam material realizes single-double electron mixed reaction in a neutral electrolyte system to obtain the zinc-manganese ion battery with high energy density and long stable cycle. The zinc-manganese battery can realize high current (10 mA/cm) 2 ) Stable charging and discharging. At this current density, the ratio of contribution of the two-electron and one-electron reactions to the battery capacity is close to one-to-one, while the battery has almost no attenuation after 13000 cycles from the initial value.
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The technical solution, its implementation and principles, etc. will be further explained as follows.
It is to be noted that the definitions of the terms mentioned in the description of the present invention are known to those skilled in the art. For example, some of the terms are defined as follows:
1. manganese dioxide/carbon nanotube foam: mnO (MnO) 2 /CNT foam
2. Single electron reaction: mn (Mn) 3+ /Mn 4+
3. Two-electron reaction: mn 2+ /Mn 4+
4. Cyclic voltammetry: CV of
5. Floating catalytic chemical vapor deposition: FCCVD;
one aspect of the embodiments of the present invention provides a method for preparing a manganese dioxide/carbon nanotube foam material (as shown in fig. 1), which includes:
providing a carbon nanotube foam;
and infiltrating the carbon nano tube foam with a potassium permanganate solution, and carrying out etching treatment at the temperature of 80-95 ℃ for 1-3h to obtain the manganese dioxide/carbon nano tube foam material.
Further, the concentration of the potassium permanganate solution is 0.01-0.1wt%.
Further, the preparation method comprises the following steps: and preparing the carbon nano tube foam at least by adopting a CVD method.
In another aspect of embodiments of the invention, there is also provided MnO prepared by the foregoing method 2 The manganese dioxide/carbon nano tube foam material comprises carbon nano tube foam and manganese dioxide loaded on the surface and/or the inside of the carbon nano tube foam, and the manganese dioxide/carbon nano tube foam material has a micro-channel structure.
Further, the manganese dioxide is loaded on the surface of the carbon nanotube bundle of the carbon nanotube foam. Furthermore, the loading amount of the manganese dioxide on the carbon nano tube foam is 30-50wt%.
Further, the density of the manganese dioxide/carbon nano tube foam material is 5-10mg/cm 3 The porosity is 85-95%, and the specific surface area is 60-100m 2 /g。
Another aspect of the embodiments of the present invention further provides a use of the aforementioned manganese dioxide/carbon nanotube foam material as an electrode in the field of zinc-manganese batteries; preferably a zinc-manganese secondary battery.
In another aspect of the embodiments of the present invention, an electrode for a zinc-manganese battery is further provided, which includes the aforementioned manganese dioxide/carbon nanotube foam material.
In another aspect of the embodiment of the present invention, there is provided an aqueous zinc-manganese dioxide battery, which includes a first thin film, a positive electrode, a separator, a negative electrode, and a second thin film sequentially arranged along a set direction, where the positive electrode is the aforementioned electrode for a zinc-manganese dioxide battery, and the electrode for a zinc-manganese dioxide battery is loaded with an electrolyte, and the electrolyte is neutral or weakly acidic.
Further, the water-based zinc-manganese battery is at 10mA/cm 2 At a current density, the capacity was about 0.22 mA.h/cm 2 And after 13000 cycles long there is no capacity fade with respect to the initial state.
In some more specific embodiments, the negative electrode includes a zinc sheet, and is not limited thereto.
Further, the first film includes any one of a PET film, a polyethylene film, and a polypropylene film, and is not limited thereto.
Further, the second film includes any one of a PET film, a polyethylene film, and a polypropylene film, and is not limited thereto.
Further, the separator includes a glass fiber separator, and is not limited thereto.
Further, the electrolyte is a salt solution containing zinc ions and manganese ions.
Further, the molar ratio of the zinc ions to the manganese ions is 1.
In some more specific embodiments, the volume ratio of the electrolyte to the electrode for a zinc-manganese battery is 1.
Another aspect of the embodiments of the present invention also provides a preparation method of the foregoing aqueous zinc-manganese dioxide battery, including:
providing a zinc sheet as a negative electrode;
providing the electrode for the zinc-manganese battery as a positive electrode;
soaking the electrode for the zinc-manganese battery in electrolyte to prepare an electrode for the zinc-manganese battery loaded with the electrolyte;
and packaging the first film, the electrode for the zinc-manganese battery loaded with the electrolyte, the diaphragm, the negative electrode and the second film along a set direction to form the water-based zinc-manganese battery.
In some more specific test protocols, the method for preparing the aqueous zinc-manganese battery comprises the following steps: (1) Providing carbon nanotube foam, and cutting into square blocks with the size of 1 × 0.3cm for later use by laser;
(2) Preparing a low-concentration (mass ratio of 0.05%) potassium permanganate solution;
(3) Completely soaking the carbon nano tube foam into 1ml of potassium permanganate solution, keeping the temperature at 90 ℃ for 6 hours, and taking out the carbon nano tube foam to find that the solution is clarified from mauve color to obtain MnO 2 a/CNT foam electrode;
(4) MnO as described above 2 Putting the/CNT foam between two glass sheets, pressing out redundant etching liquid, and completely soaking the surplus etching liquid into 2mol/L zinc sulfate and 0.0mol/L manganese sulfate electrolyte for later use;
(5) Assembling the battery: mnO to be completely infiltrated with electrolyte 2 the/CNT foam electrode is taken out and assembled according to the structure shown in figure 2 to prepare the water-based zinc-manganese battery.
The technical solutions of the present invention are further described in detail below with reference to several preferred embodiments and the accompanying drawings, which are implemented on the premise of the technical solutions of the present invention, and the detailed embodiments and the specific operation procedures are given, but the scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples below were obtained from conventional biochemicals unless otherwise specified.
Example 1
(1) Providing carbon nanotube foam, and cutting into blocks with the size of 1 × 0.3cm for later use;
(2) Completely soaking the pretreated carbon nano tube foam into 1ml of potassium permanganate (0.05 wt%) solution, keeping the temperature at 95 ℃ for 2h, taking out, and finding that the solution turns from purplish red to be clear to obtain MnO 2 a/CNT foam electrode;
(4) MnO as described above 2 Putting the/CNT foam between two glass sheets, pressing out the redundant etching liquid, and completely soaking the etching liquid into 2mol/L zinc sulfate and 0.02mol/L manganese sulfate electrolyte for later use;
(5) Assembling the battery: mnO to be completely soaked in electrolyte 2 Taking out the/CNT foam electrode, and then putting the first PET film, the zinc sheet, the glass fiber diaphragm and the MnO loaded with the electrolyte 2 the/CNT foam electrode and the second PET film are assembled according to the structure shown in figure 2 to prepare the water-based zinc-manganese battery.
And (3) performance characterization:
FIGS. 3a and 3b are SEM and water repellency test charts of the carbon nanotube foam in example 1; FIGS. 3c and 3d are those of example 1MnO 2 SEM and hydrophilicity effect test chart of/CNT foam electrode; the method solves the problem that the carbon nano tube foam is not hydrophilic by adopting the low-concentration potassium permanganate solution to etch the carbon nano tube foam, and simultaneously provides a layer of manganese dioxide, thereby not only providing the capacity contribution of single electron reaction, but also providing active sites for realizing the following double electron reaction.
FIG. 4 shows preparation of MnO in example 1 2 Cyclic compression of the/CNT foam electrode, mnO can be seen 2 the/CNT foam electrode still maintains excellent mechanical properties;
FIG. 5 is an impedance plot of pure carbon nanotube foam, as well as carbon nanotube films, carbon cloth, and nickel foam in example 1; it can be seen that the carbon nanotube foam is easier for manganese dioxide to realize double electron reaction;
FIG. 6 is a CV plot for the aqueous Zn-Mn battery of example 1 at various sweep rates; as can be seen from the figure, peaks 1 and 4 are typical single electron reaction processes, and peaks 2 and 3 are characteristic peaks of a two electron process.
FIG. 7 is a rate expression graph of the aqueous zinc-manganese battery of example 1; it can be seen that at 10mA/cm 2 The capacity can still be kept at 0.202 mA.h/cm under the high-current charging and discharging capacity 2 ；
FIG. 8 is a graph of the voltage capacity of the aqueous zinc-manganese cell of example 1 at different current densities; as can be seen from the figure, mnO is compared with the conventional zinc-manganese battery 2 the/CNT foam battery has two discharge platforms, wherein 2.0V-1.6V belongs to double-electron reaction, and 1.4V-1.1V belongs to single-electron reaction;
FIG. 9 shows the results of the experiment at 10mA/cm for the aqueous Zn-Mn battery of example 1 2 Lower long cycle plot, from which it can be seen that the aqueous zinc manganese cell is at 10mA/cm 2 13000-turn long cycle is realized under the current density, and the capacity is not attenuated relative to the initial state.
Example 2
(1) Providing carbon nanotube foam, and cutting into blocks with the size of 1 × 0.3cm for later use;
(2) Will be provided withThe pretreated carbon nano tube foam is completely immersed into 1ml of potassium permanganate (0.01 wt%) solution, and is taken out after heat preservation at 95 ℃ for 1h, so that the solution is clarified from mauve to obtain MnO 2 a/CNT foam electrode;
(4) MnO as described above 2 Putting the/CNT foam between two glass sheets, pressing out the redundant etching liquid, and completely soaking the etching liquid into 2mol/L zinc sulfate and 0.05mol/L manganese sulfate electrolyte for later use;
(5) Assembling the battery: mnO to be completely soaked in electrolyte 2 Taking out the/CNT foam electrode, and then putting the first polyethylene film, the zinc sheet, the glass fiber diaphragm and the MnO loaded with the electrolyte 2 the/CNT foam electrode and the second polyethylene film are assembled according to the structure shown in figure 2 to prepare the water-based zinc-manganese battery.
Example 3
(1) Providing carbon nanotube foam, and cutting into 1 × 0.3cm square blocks for later use;
(2) Completely soaking the pretreated carbon nano tube foam into 1ml of potassium permanganate (0.05 wt%) solution, keeping the temperature at 85 ℃ for 2h, taking out, and finding that the solution turns from purplish red to be clear to obtain MnO 2 a/CNT foam electrode;
(4) MnO as described above 2 Putting the/CNT foam between two glass sheets, pressing out redundant etching liquid, and completely soaking the surplus etching liquid into 2mol/L zinc sulfate and 0.01mol/L manganese sulfate electrolyte for later use;
(5) Assembling the battery: mnO to be completely infiltrated with electrolyte 2 Taking out the/CNT foam electrode, and then putting the first polypropylene film, the zinc sheet, the glass fiber diaphragm and the MnO loaded with the electrolyte 2 the/CNT foam electrode and the second polypropylene film are assembled according to the structure shown in figure 2 to prepare the water-based zinc-manganese battery.
Example 4
(1) Providing carbon nanotube foam, and cutting into blocks with the size of 1 × 0.3cm for later use;
(2) Completely immersing the pretreated carbon nano tube foam into 1ml of potassium permanganate(0.1 wt%) of the solution, after incubation at 80 ℃ for 3h, the solution was removed and it was found that the solution became clear from a purple color to give MnO 2 a/CNT foam electrode;
(4) MnO as defined above 2 Putting the/CNT foam between two glass sheets, pressing out the redundant etching liquid, and completely soaking the redundant etching liquid into 2mol/L zinc sulfate and 0.005mol/L manganese sulfate electrolyte for later use;
(5) Assembling the battery: mnO to be completely soaked in electrolyte 2 Taking out the/CNT foam electrode, and then putting the first PET film, the zinc sheet, the glass fiber diaphragm and the MnO loaded with the electrolyte 2 the/CNT foam electrode and the second PET film are assembled according to the structure shown in figure 2 to prepare the water-based zinc-manganese battery.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and sections in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
Although the present invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (11)
1. A preparation method of manganese dioxide/carbon nanotube foam material is characterized by comprising the following steps:
providing a carbon nanotube foam;
and infiltrating the carbon nano tube foam with a potassium permanganate solution, and carrying out etching treatment at the temperature of 80-95 ℃ for 1-3h to obtain the manganese dioxide/carbon nano tube foam material.
2. The production method according to claim 1, characterized in that: the concentration of the potassium permanganate solution is 0.01-0.1wt%.
3. The method of claim 1, wherein: and preparing the carbon nano tube foam at least by adopting a CVD method.
4. A manganese dioxide/carbon nanotube foam material prepared by the method of any one of claims 1 to 3, comprising carbon nanotube foam and manganese dioxide supported on the surface and/or inside of the carbon nanotube foam, the manganese dioxide/carbon nanotube foam material having a microchannel structure; preferably, the manganese dioxide is loaded on the surface of the carbon nanotube bundle of the carbon nanotube foam;
preferably, the loading amount of the manganese dioxide on the carbon nanotube foam is 30-50wt%;
preferably, the density of the manganese dioxide/carbon nano tube foam material is 5-10mg/cm 3 The porosity is 85-95%, and the specific surface area is 60-100m 2 /g。
5. Use of the manganese dioxide/carbon nanotube foam material of claim 4 as an electrode in the field of zinc-manganese batteries; preferably a zinc-manganese secondary battery.
6. An electrode for a zinc-manganese battery, characterized by comprising the manganese dioxide/carbon nanotube foam material according to claim 4.
7. An aqueous zinc-manganese dioxide battery, characterized by comprising a first thin film, a positive electrode, a separator, a negative electrode and a second thin film which are sequentially arranged along a set direction, wherein the positive electrode is the electrode for the zinc-manganese dioxide battery as claimed in claim 6, the electrode for the zinc-manganese dioxide battery is loaded with an electrolyte, and the electrolyte is neutral or weakly acidic.
8. The aqueous zinc-manganese dioxide cell of claim 7, characterized in that: the negative electrode comprises a zinc sheet;
and/or the first film comprises any one of a PET film, a polyethylene film and a polypropylene film;
and/or the second film comprises any one of a PET film, a polyethylene film and a polypropylene film;
and/or the membrane comprises a fiberglass membrane;
and/or the electrolyte is a salt solution containing zinc ions and manganese ions; preferably, the molar ratio of the zinc ions to the manganese ions is 1.
9. The aqueous zinc-manganese cell of claim 7, characterized in that: the volume ratio of the electrolyte to the electrode for the zinc-manganese battery is 1.
10. The aqueous zinc-manganese cell of claim 7, characterized in that: the water-based zinc-manganese battery is at 10mA/cm 2 At a current density, the capacity is about 0.22 mA.h/cm 2 And after 13000 cycles long there is no capacity fade with respect to the initial state.
11. The method of manufacturing an aqueous zinc-manganese battery of any one of claims 7 to 10, characterized in that it comprises:
providing a zinc sheet as a negative electrode;
providing the electrode for a zinc-manganese battery according to claim 6 as a positive electrode;
soaking the electrode for the zinc-manganese battery in electrolyte to prepare an electrode for the zinc-manganese battery loaded with the electrolyte;
and packaging the first film, the electrode for the zinc-manganese battery loaded with the electrolyte, the diaphragm, the negative electrode and the second film along a set direction to form the water-based zinc-manganese battery.
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| CN112421022A (en) * | 2020-11-19 | 2021-02-26 | 北京大学深圳研究生院 | Self-supporting electrode, preparation method thereof and zinc ion battery |
| CN113054194A (en) * | 2021-03-15 | 2021-06-29 | 浙江大学 | Nitrogen-carbon nanotube material, preparation method thereof and application thereof in preparation of flexible zinc-manganese battery |
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