CN107611378A - Nitrogen-containing composite material for zinc-based battery and preparation method thereof - Google Patents
Nitrogen-containing composite material for zinc-based battery and preparation method thereof Download PDFInfo
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- CN107611378A CN107611378A CN201710731104.3A CN201710731104A CN107611378A CN 107611378 A CN107611378 A CN 107611378A CN 201710731104 A CN201710731104 A CN 201710731104A CN 107611378 A CN107611378 A CN 107611378A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a nitrogenous composite material for a zinc-based battery, which is formed by compounding a nitrogenous carbon material and zinc and/or zinc oxide, wherein the mass of the zinc and/or the zinc oxide accounts for 60-95% of the composite material; the composite material has one or more of a three-dimensional structure, a hierarchical pore structure and a coating structure; the size of the zinc oxide is 50 nm-200 microns. The invention also provides a preparation method of the nitrogen-containing composite material for the zinc-based battery. The invention adopts zinc-based compound and precursor with low price as raw materials, and prepares the nitrogenous composite material by a simple heat treatment method; when the obtained nitrogen-containing composite material for the zinc-based battery is used as a negative electrode material of the zinc-nickel battery, a good discharge platform is formed at about 1.6V; the obtained nitrogenous composite material for the zinc-based battery has specific capacity of more than 400mAh/g when used as a negative electrode material of the zinc-nickel battery, and has good cycle performance when used as the negative electrode material of the zinc-nickel battery.
Description
Technical Field
The invention belongs to the field of secondary batteries, and particularly relates to an electrode material of a zinc-based battery. And a method for preparing the same.
Background
With the increasing energy demand and environmental protection, the current power battery market includes lead-acid batteries, nickel-cadmium batteries, nickel-hydrogen batteries and lithium ion batteries, but these battery systems all have some problems, which restrict the further development of these batteries. Lead-acid batteries and cadmium-nickel batteries are secondary batteries which are widely used for a long time and occupy the main market of power batteries, but the energy density of the two batteries is lower, and the commercial batteries can only reach 30-50 Wh kg -1 And is not suitable for being used in occasions requiring a large amount of stored energy and moving. Lead-acid batteries and nickel-cadmium batteries contain heavy metal elements which cause serious environmental pollution, and the production and waste treatment of the lead-acid batteries and the nickel-cadmium batteries have serious influence on the environment, for example, the European Union has forced the battery production enterprises to bear the waste treatment of the batteries, the lead-acid batteries and the nickel-cadmium batteries cannot realize sustainable development, and the prospect is limited. The LiCoO is used for the technical problems of large increase of nickel price and poor consistency of battery packs of the hydrogen-nickel batteries 2 The commercial lithium ion battery as the anode material has higher cost and poorer safety, and the fuel battery is difficult to become the mainstream product of the power battery in the near future due to the technical maturity and the cost. At present, research and development of novel high-performance green secondary power batteries become a major problem to be solved urgently.
The zinc-nickel battery consists of a zinc electrode and a nickel electrode, has the excellent performances of high capacity of a zinc cathode in the zinc-silver battery and long service life of a nickel anode in the cadmium-nickel battery, and is a high-performance green secondary power battery. The performance characteristics of the zinc-nickel secondary battery comprise: the battery has the advantages of high working voltage (higher than nickel-hydrogen batteries and nickel-cadmium batteries), high energy density (generally 2 times of lead-acid batteries and 1.5 times of nickel-cadmium batteries), high power density (second only to lithium ion batteries), wide working temperature (-20-50 ℃), no memory effect, no pollution to the environment in the production and use processes of the battery, and the battery is known as a real green battery, rich zinc storage capacity and low price. The zinc-nickel battery becomes a continuous lead-acid battery, a cadmium-nickel battery, a hydrogen-nickel battery and a lithium ion battery, and is a novel high-performance green power battery which is low in price and practical.
Hitherto, the composition of the negative electrode material for zinc-nickel batteries has been greatly developed, for example, oxides for increasing hydrogen evolution overpotential, mainly bismuth oxide, indium oxide, tin oxide, etc., are added. Although the above methods have been practically applied to a certain extent or a certain scale, they have the disadvantages of low specific capacity (400 mAh/g), short cycle life (< 200 times), and in particular, the generation of dendrites. Therefore, research in this field is focused on research, development and preparation techniques of novel anode materials with high energy, high power, long life and low cost.
In recent years, nitrogen-containing composite materials have been studied for use as negative electrode materials of zinc-nickel batteries, and hydrogen gas is easily generated during cycling of zinc-nickel batteries to cause contact separation of active materials, which ultimately leads to rapid degradation of battery performance and excessive consumption of electrolyte, especially during high-rate charge and discharge and overcharge. In the nitrogen-containing composite material, the nitrogen-containing carbon material has a plurality of active sites, is very stable in the charging and discharging process and enables current to be distributed uniformly. However, the current cycle performance and limited preparation method of the zinc-nickel battery still limit the practical application of the zinc-nickel battery.
Disclosure of Invention
The invention aims to solve the technical problems that the negative electrode of the zinc-based battery in the prior art is easy to generate hydrogen evolution and has poor cyclicity during charging and discharging, and provides a nitrogen-containing composite material which has high capacity, high rate capability and excellent cyclicity and can be used as the negative electrode of the zinc-based battery.
Another purpose of the invention is to provide a preparation method of the nitrogen-containing composite material.
A third object of the invention is to propose a battery comprising a composite material containing nitrogen.
The technical scheme for realizing the purpose of the invention is as follows:
a nitrogenous composite material for a zinc-based battery is formed by compounding a nitrogenous carbon material and zinc and/or zinc oxide, wherein the mass of the zinc and/or the zinc oxide accounts for 60-95% of the composite material; the composite material has one or more of a three-dimensional structure, a hierarchical pore structure and a coating structure; the size of the zinc oxide is 50 nm-200 microns.
Further, the nitrogen-containing carbon material is C 3 N 4 Or nitrogen-doped graphene.
The preparation method of the nitrogen-containing composite material for the zinc-based battery comprises the following steps:
(1) Dispersing a zinc-based compound and a precursor in water and/or an organic solvent, and then drying at the temperature of 50-200 ℃; the drying treatment is freeze drying or supercritical drying; wherein the feeding mass ratio of the zinc-based compound to the precursor is 0.5-50;
(2) And (2) carrying out heat treatment on the precursor mixture obtained in the step (1) at the temperature of 500-1000 ℃ for 0.5-10 hours in one or more of air, nitrogen, argon and ammonia.
In the step (1), the zinc-based compound is one or more selected from zinc oxide, zinc chloride, zinc nitrate, zinc sulfate, zinc carbonate and zinc acetate.
In the step (1), the precursor is one or more of urea, cyanamide, dicyandiamide, melamine, pyrrole, polypyrrole, aniline, polyaniline, glucose, sucrose, graphene oxide and the like.
In the step (1), the organic solvent is one or more of ethanol, N-dimethylformamide, ethylene glycol, dichloromethane, isopropanol and methyl pyrrolidone; the mass ratio of the zinc-based compound to water or organic solvent is 10:2 to 10.
Preferably, the precursor mixture in step (2) is heat treated at a temperature of 500 ℃ to 700 ℃.
The battery containing the nitrogen-containing composite material is one of a zinc-nickel battery, a zinc-air battery, a zinc-manganese battery and a zinc-silver battery; the nitrogen-containing composite material is the negative electrode of the battery.
The invention has the beneficial effects that:
the nitrogen-containing composite material for the zinc-based battery has an ordered porous structure, excellent performance and good cycle stability, is a very ideal zinc-based battery negative electrode material, and can be widely applied to the fields of various portable electronic devices, electric automobiles, aerospace and the like; in addition, the compound can be prepared from low-price raw materials by a process with high repeatability, simple process and less time consumption, and is suitable for industrial production.
Compared with the prior art, the invention has the following specific advantages:
(1) The invention adopts zinc-based compound and precursor with low price as raw materials; (2) Preparing the nitrogen-containing composite material by using a simple heat treatment method; (3) When the obtained nitrogen-containing composite material for the zinc-based battery is used as a negative electrode material of the zinc-nickel battery, a good discharge platform is formed at about 1.6V; (4) The specific capacity of the obtained nitrogenous composite material for the zinc-based battery is more than 400mAh/g when the nitrogenous composite material is used as a negative electrode material of a zinc-nickel battery; (5) The obtained nitrogen-containing composite material for the zinc-based battery has good cycle performance (higher than 340mAh/g after 500 times of repeated charge and discharge) when being used as a negative electrode material of the zinc-nickel battery.
Drawings
FIG. 1 is a Scanning Electron Micrograph (SEM) of the nitrogen-containing composite material for a zinc-based battery in example 1, which shows that ZnO has a particle morphology and is loaded at C 3 N 4 C, removing;
FIG. 2 is a structural characterization result of the nitrogen-containing composite for a zinc-based battery of example 1, in which X-rays confirm that C is obtained 3 N 4 ZnO in ZnO is hexagonal wurtzite crystalline phase (JCPDS 65-3411);
fig. 3 is a graph showing the results of the spectral characterization of the nitrogen-doped graphene used in example 5, and X-ray electron spectroscopy (XPS) confirmed that the nitrogen-doped graphene treated with ammonia gas has different nitrogen doping amounts at different temperatures;
fig. 4 is an electrochemical performance result of the nitrogen-containing composite material for a zinc-based battery according to the present invention: constant current discharge curve at 1C for the electrode made of the composite of example 1;
FIG. 5 shows the electrochemical performance results of the nitrogen-containing composite material for zinc-based battery according to the invention: constant current cycling performance curve at 1C for electrodes made from the composite of example 1.
Detailed Description
The following specific embodiments are illustrative of the invention and should not be construed as limiting the invention.
In the examples, the technical means used are those conventional in the art unless otherwise specified.
In the embodiment, the following steps are adopted to prepare the cathode working electrode of the zinc-nickel sub-battery:
(1) Mixing the nitrogen-containing composite material, the adhesive, PTFE and acetylene black in a proportion of 60 percent, wherein the proportion is as follows: 10:10, mixing uniformly, preparing into paste with water, and uniformly coating on a brass net;
(2) Drying in a vacuum oven at 80 ℃ for 12 hours;
(3) The brass mesh coated with the nitrogen-containing composite material is cut into wafers to make the working electrodes.
The electrochemical performance of the electrode material was tested as follows:
(1) The simulated cell used a button CR2032 type system, in which the counter electrode was a nickel hydroxide positive electrode.
(2) The reversible capacity and the cycle performance of the electrode material are tested and analyzed by adopting a constant current charge-discharge experiment. The charging and discharging system is as follows: voltage range: 1.2-2.0V; the number of cycles is generally from 1 to 500.
Example 1:
a nitrogen-containing composite material for a zinc-based battery, which is prepared by the steps of:
(1) Mixing 100g of zinc nitrate and 10g of urea (the mass ratio of the zinc nitrate to the urea is 10: 1), dispersing the mixture into 50g of water, placing the mixture into a beaker, and stirring the mixture for about 24 hours at room temperature;
(2) Drying the system in the step (1) in an oven at 60 ℃;
(3) Carbonizing at 550 deg.C (carbonizing in air with muffle furnace), separating and drying to obtain the final product.
The morphology and the like of the obtained nitrogen-containing composite material for the zinc-based battery are characterized, and the results are shown in figure 1.ZnO has the morphology of particles and is loaded in C 3 N 4 The above. The mass of zinc oxide is about 65% of the composite material according to the chemical equation of the added reactants.
The structure of the nitrogen-containing composite material for the zinc-based battery is characterized, and the result is shown in figure 2, which shows that ZnO in the obtained C3N4-ZnO is a hexagonal wurtzite crystal phase (JCPDS 65-3411).
The zinc-based battery is made into a working electrode by using the nitrogen-containing composite material according to the method provided by the invention, and corresponding electrical property tests are carried out, and the results are shown in table 1, figure 4 and figure 5: the stable specific capacity is 500mAh/g during 1C charging and discharging; when the charge and discharge are carried out at the multiplying power, the capacity can be kept more than 80% of the initial capacity after 500 times of repeated charge and discharge.
Example 2
This example provides a nitrogen-containing composite material for a zinc-based battery, which is prepared substantially as in example 1, except that the raw materials of zinc nitrate and urea are fed in a mass ratio of 40. The nitrogenous composite material for the zinc-based battery is made into a working electrode according to the method provided by the invention and corresponding electrical property tests are carried out, and the results are as follows: the stable specific capacity is 420mAh/g during 1C charging and discharging; when the charge and discharge are carried out at the multiplying power, the capacity can be kept more than 70% of the initial capacity after 500 times of repeated charge and discharge.
Example 3
The nitrogen-containing composite material for the zinc-based battery is prepared basically in the same way as in example 1, except that the mass ratio of the raw materials of zinc nitrate and urea is 1 (100 g of zinc nitrate and 100g of urea are dispersed in 50g of water; the two salts are very easy to dissolve in water, and the subsequent drying operation can be carried out, so that the water consumption is slightly larger).
The nitrogenous composite material for the zinc-based battery is made into a working electrode according to the method provided by the invention and corresponding electrical property tests are carried out, and the results are as follows: the stable specific capacity is 350mAh/g when charging and discharging are carried out at 1C; when the charge and discharge are carried out at the multiplying power, the capacity can be kept more than 65% of the initial capacity after 500 times of repeated charge and discharge.
Example 4
This example provides a nitrogen-containing composite material for zinc-based batteries prepared substantially as in example 1, except that the starting material urea was replaced with melamine. The nitrogenous composite material for the zinc-based battery is made into a working electrode according to the method provided by the invention, and corresponding electrical property tests are carried out, wherein the results are as follows: the stable specific capacity is 470mAh/g during 1C charging and discharging; when the charge and discharge are carried out at the multiplying power, the capacity can be kept more than 80% of the initial capacity after 500 times of repeated charge and discharge.
Example 5
The preparation method of the nitrogen-doped graphite system comprises the steps of reacting graphene oxide with ammonia gas at 600 ℃ for 4 hours, wherein the energy spectrum result is shown in figure 3, and pyridine represents different valence bond structures MG of nitrogen atoms in figure 3 represents modified graphene.
This example provides a nitrogen-containing composite material for zinc-based batteries, which is prepared substantially in the same manner as in example 1, except that urea, which is a raw material, is replaced with nitrogen-doped graphene (in which the amount of nitrogen doping is about 3%). The nitrogenous composite material for the zinc-based battery is made into a working electrode according to the method provided by the invention, and corresponding electrical property tests are carried out, wherein the results are as follows: the stable specific capacity is 510mAh/g when charging and discharging at 1C; when the charge and discharge are carried out at the multiplying power, the capacity can be kept more than 85% of the initial capacity after 500 times of repeated charge and discharge.
Table 1: examples 1-4 cycling performance of the cells
Aiming at the defects of easy hydrogen evolution and poor cycle performance in the charging and discharging processes of the zinc-nickel battery, the invention finally obtains the cathode material for the zinc-nickel battery with high capacity, high rate performance and excellent cycle performance by controlling the preparation method and the preparation conditions. The method has very important significance for promoting the development of high-power zinc-nickel batteries, solving the problem of energy shortage and the like.
The above embodiments are only intended to illustrate specific embodiments of the present invention, and are not intended to limit the scope of the present invention, and those skilled in the art may make various modifications and changes based on the prior art, and various modifications and improvements made to the technical solution of the present invention by those skilled in the art without departing from the spirit of the present invention are intended to be included within the scope of the present invention defined by the claims.
Claims (8)
1. The nitrogenous composite material for the zinc-based battery is characterized by being formed by compounding a nitrogenous carbon material and zinc and/or zinc oxide, wherein the mass of the zinc and/or zinc oxide accounts for 60-95% of the composite material; the composite material has one or more of a three-dimensional structure, a hierarchical pore structure and a coating structure; the size of the zinc oxide is 50 nm-200 microns.
2. The nitrogen-containing composite material for zinc-based batteries according to claim 1, wherein the nitrogen-containing carbon material is C 3 N 4 Or nitrogen-doped graphene.
3. The method for preparing a nitrogen-containing composite material for a zinc-based battery according to claim 1 or 2, comprising the steps of:
(1) Dispersing a zinc-based compound and a precursor in water and/or an organic solvent, and then drying at the temperature of 50-200 ℃; the drying treatment is freeze drying or supercritical drying; wherein the feeding mass ratio of the zinc-based compound to the precursor is 0.5-50;
(2) And (2) carrying out heat treatment on the precursor mixture obtained in the step (1) at the temperature of 500-1000 ℃ for 0.5-10 hours in one or more of air, nitrogen, argon and ammonia.
4. The method according to claim 3, wherein in the step (1), the zinc-based compound is one or more selected from zinc oxide, zinc chloride, zinc nitrate, zinc sulfate, zinc carbonate, and zinc acetate.
5. The method according to claim 3, wherein in step (1), the precursor is one or more of urea, cyanamide, dicyanamide, melamine, pyrrole, polypyrrole, aniline, polyaniline, glucose, sucrose, graphene oxide, and the like.
6. The preparation method according to claim 3, wherein in the step (1), the organic solvent is one or more of ethanol, N-dimethylformamide, ethylene glycol, dichloromethane, isopropanol, and methyl pyrrolidone; the mass ratio of the zinc-based compound to water or organic solvent is 10:2 to 10.
7. The method according to any one of claims 3 to 6, wherein the precursor mixture in the step (2) is heat-treated at a temperature of 500 ℃ to 700 ℃.
8. A battery containing the nitrogen-containing composite material according to claim 1 or 2, wherein the battery is one of a zinc-nickel battery, a zinc-air battery, a zinc-manganese battery, and a zinc-silver battery; the nitrogen-containing composite material is the negative electrode of the battery.
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| CN112436144A (en) * | 2020-11-06 | 2021-03-02 | 风帆有限责任公司 | Preparation method of positive lead paste and positive plate of lead-acid storage battery |
| CN113964306A (en) * | 2021-10-22 | 2022-01-21 | 安徽建筑大学 | In g-C3N4Lead-carbon battery cathode material with hydrogen evolution inhibitor as carbon source and cathode |
| CN113991069A (en) * | 2021-10-22 | 2022-01-28 | 安徽艾克瑞德科技有限公司 | In g-C3N4Preparation process of lead-carbon battery cathode with/ZnO as carbon source |
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Cited By (5)
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