CN108199032B - Preparation of carbon-coated nano hollow bismuth simple substance and application of alkaline battery - Google Patents
Preparation of carbon-coated nano hollow bismuth simple substance and application of alkaline battery Download PDFInfo
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/24—Alkaline accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to preparation of a carbon-coated nano hollow bismuth simple substance and application research of an alkaline battery thereof, belonging to the technical field of alkaline batteries. The nano metal bismuth has good conductivity and electrochemical characteristics, but has poor structural stability in an electrolyte environment. In order to improve the stability and the circulation efficiency of the carbon microreactor, an effective method for limiting nano hollow bismuth in the carbon microreactor is provided, and the method specifically comprises the following steps: firstly, synthesizing hollow bismuth ammonium fluoride (NH) by a room temperature liquid phase method4Bi3F10) A precursor; then, utilizing dopamine molecule polymerization to realize carbon coating of the precursor at room temperature; and finally, carrying out low-temperature carbonization treatment on the obtained product to obtain the carbon-coated nano hollow bismuth simple substance. When applied to alkaline batteries, the composite can exhibit superior rate performance and cycle durability. The related preparation process is very simple, large-scale production is easy to realize, the structural property of the product is stable, and the method has practical prospect and commercial value.
Description
Technical Field
The invention belongs to the technical field of alkaline batteries, and particularly relates to a preparation method and application of an alkaline battery cathode material.
Background
As the problems of exhaustion of fossil energy and deterioration of the environment become more serious, development and utilization of green energy (including wind energy, tidal energy, solar energy, etc.) become more important. Although these energy sources can be converted into electric energy and have sustainability, their utilization is often limited by external factors such as time, place, weather, etc. To facilitate the daily living needs, it is currently the most effective strategy to develop a battery system to collect the converted electrical energy. In recent years, lithium batteries have dominated the field of rechargeable energy storage. However, the current lithium battery has a plurality of serious problems, including battery explosion, waste battery pollution and safety recovery, besides the shortage of mineral resources such as lithium, the root of the problems is related to the high toxicity and flammability of the organic electrolyte. Thus, the development of safe high-performance batteries is an important trend in development today.
Compared with a lithium battery, the electrolyte of the alkaline battery is a common aqueous solution, is cheap and has low toxicity. Currently, many types of chargeable and dischargeable alkaline battery systems (including nickel-hydrogen, nickel-iron, nickel-bismuth, etc.) have been proposed. It is worth emphasizing that the novel bismuth-based alkaline battery is receiving general attention from the global scientific research community, for example, the liujin ping subject group of the university of wuhan theory of engineering recently has grown bismuth oxide nano-film directly on the titanium metal electrode, and uses it in the field of alkaline battery energy storage. Unfortunately, almost all of the developed bismuth-based negative electrode materials are poorly conductive oxides or hydroxides, which directly affect the rapid charge-discharge characteristics of the battery. Compared with the bismuth-based oxide/hydroxide, the bismuth simple substance has more excellent conductivity and electrochemical reaction activity, and the theoretical specific capacity is far higher than that of other bismuth-based oxides/hydroxides. However, the simple bismuth is easily corroded and oxidized in the electrolyte environment, and the chemical structure stability is poor, which becomes a fatal problem for further application and development of the material.
In order to improve the stability of the bismuth-based alkaline battery and realize the function of quick charge and discharge points, an effective synthesis method for limiting nano hollow bismuth in a carbon micro-reactor is provided, and the method specifically comprises the following steps: firstly, synthesizing nano hollow bismuth ammonium fluoride (NH) by a room temperature liquid phase method4Bi3F10) A precursor; then, coating the precursor by utilizing dopamine molecule polymerization at room temperature; and finally, carrying out low-temperature carbonization treatment on the obtained product to obtain the carbon-coated nano hollow bismuth simple substance. On one hand, the hollow metal bismuth nano-configuration provides a larger specific surface area, so that the electrode can be fully contacted with the electrolyte, and the electrochemical reaction rate of the system is accelerated; on the other hand, the hollow nano metal bismuth and the carbon shell layer form a better synergistic effect. The internal metal bismuth has excellent conductivity and electrochemical activity, and the external carbon layer enhances the chemical structure stability of the bismuth core and effectively inhibits the fragmentation and agglomeration of active substances. It is worth emphasizing that the preparation method and conditions are very simple, large-scale production is easy to realize, the structural property of the product is stable, and the method has practical prospect and commercial value.
Disclosure of Invention
In view of this, the object of the invention is: (1) providing a preparation method of carbon-coated metal nano hollow bismuth; (2) a cobalt/nickel-bismuth high power density chargeable and dischargeable alkaline full cell is provided.
In order to achieve the purpose, the invention provides the following technical scheme:
1. the preparation of the carbon-coated nano hollow bismuth simple substance and the application of the alkaline battery thereof comprise the following steps:
(1) material synthesis: bismuth salt and fluorine salt are used as raw materials and are reacted in a reaction solvent, and a room temperature liquid phase method and low temperature carbonization treatment are adopted to obtain the carbon-coated nano hollow bismuth composite negative electrode material;
(2) preparing an electrode slice: adding a negative electrode material, a conductive agent and an adhesive into a solvent, stirring at room temperature to prepare black viscous slurry, coating the slurry on a current collector electrode, and drying to obtain a carbon-coated nano hollow bismuth simple substance electrode;
(3) electrode activation and performance detection: activating the electrode of the carbon-coated nano hollow bismuth simple substance prepared in the step (2) by using a cyclic voltammetry scanning method; after activation is finished, constant current charging and discharging with different multiplying powers and cycle performance detection are carried out on the electrode slice;
(4) assembling and testing the full battery: coating carbon with CoNi3O4The nano array film positive plate is used as a positive electrode, the activated carbon-coated metal nano hollow bismuth simple substance electrode in the step (3) is used as a negative electrode, 6mol/L sodium hydroxide solution is used as electrolyte, cellulose filter paper is used as a diaphragm material, the positive electrode, the diaphragm and the negative electrode are stacked in sequence, and the electrolyte is injected and then is encapsulated in a transparent polyethylene film in a thermoplastic manner, so that the alkaline cobalt/nickel-bismuth full cell is assembled; and then the performance test is carried out on the full battery.
Further, the bismuth salt in the step (1) is bismuth nitrate pentahydrate, the fluorine salt is ammonium fluoride, and the reaction solvent is ethylene glycol.
Further, the conductive agent in the step (2) is carbon black; the adhesive in the step (2) is polyvinylidene fluoride (PVdF); the solvent in the step (2) is N-methyl pyrrolidone; the current collector electrode in the step (2) is foamed nickel.
Further, the mass ratio of the negative electrode material, the conductive agent and the adhesive in the step (2) is 8:1: 1.
further, the drying treatment in the step (2) is 120oAnd C, standing for 10 hours under the baking condition.
Further, the electrode activation in the step (3) comprises the steps of: and (3) immersing the carbon-coated nano hollow bismuth simple substance electrode prepared in the step (2) into 6mol/L sodium hydroxide solution, taking Ag/AgCl as a reference electrode, taking a platinum wire electrode as a counter electrode, and carrying out 100-loop 200-loop cyclic voltammetry scanning process on the electrode at the rate of 50 mV/s on an electrochemical workstation.
Further, the carbon-coated CoNi in the step (4)3O4The preparation method of the nano-array film positive plate comprises the following steps: 0.7 g of Ni (NO)3)2·6H2O、0.4 g Co(NO3)2·6H2O、0.2 g NH4F and 0.75 g CO (NH)2)2Ultrasonically dispersing in 50 mL of distilled water; then, the mixture was transferred into a 100 mL inner vessel of a reaction vessel, a stainless steel plate (size: 40X 25X 0.5 mm) was dipped in the solution, the reaction vessel was sealed, and the temperature was increased to 120 ℃oC, reacting for 4 hours under the constant temperature condition; after the reaction kettle is cooled, taking out the stainless steel sheet, washing the stainless steel sheet with distilled water for three times, and soaking the stainless steel sheet in a solution containing 0.1 g of Dopamine (DA) molecules; after immersing at room temperature for 6 hours, the stainless steel sheet was taken out and the surface thereof was rinsed with distilled water, and then the sample was placed in a quartz tube furnace 600 in an argon atmosphereoC was heated for 1 hour.
Further, the mass ratio of the negative electrode plate to the positive electrode plate in the full battery test in the step (4) is 7: 10.
2. the invention has the beneficial effects that: the invention discloses an effective and low-cost preparation method of novel carbon-coated metal nano hollow bismuth and application of the novel carbon-coated metal nano hollow bismuth to an alkaline battery. When applied to alkaline batteries, the composite can exhibit superior rate performance and cycle durability. The related preparation process is very simple, large-scale production is easy to realize, the structural property of the product is stable, and the method has practical prospect and commercial value.
Drawings
In order to make the object, technical scheme and beneficial effect of the invention more clear, the invention provides the following drawings for explanation:
FIG. 1 is a scanning electron micrograph (a) and an X-ray diffraction (XRD) spectrum (b) of a negative electrode material used in example 1;
FIG. 2 is a graph of discharge curves for different current densities for the negative electrode material used in example 2;
FIG. 3 is a specific capacity graph (a) and a cycle life graph (b) of the negative electrode material used in example 2 at different current densities;
FIG. 4 is a graph of discharge curves for different current densities for the full cell of example 2;
fig. 5 is a specific capacity graph (a) and a cycle life graph (b) of the full cell of example 2 at different current densities.
Detailed Description
Preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
Example 1 Synthesis of carbon-coated Metal Nano hollow bismuth Anode Material
(1) Bismuth ammonium fluoride (NH)4Bi3F10) Synthesis of a precursor: 0.2 g of Bi (NO) is taken3)3·6H2O and 0.6 g NH4F was placed in 25 mL ethylene glycol centrifuge tubes for vortex dissolution. Mixing the two solutions, standing at room temperature for 12 hr, filtering, washing at 60 deg.CoDrying the sample for 8 hours under the condition of C to obtain NH4Bi3F10A precursor material.
(2) Synthesizing a carbon-coated metal nano hollow bismuth cathode material: take 0.4 g NH4Bi3F10Adding into solution containing 0.1 g dopamine molecule, stirring at room temperature for 6 hr, centrifuging, washing with anhydrous ethanol for several times, and adding into 60oDrying the sample for 8 hours under the condition of C to obtain gray NH4Bi3F10@ PDA nanopowder. Then, 400 deg.C under argon atmosphereoAnd C, carbonizing at low temperature for 30 minutes to obtain the carbon-coated metal nano hollow bismuth material. Example results can be seen in figure 1.
FIG. 1 (a) shows the microstructure of the resulting product, with the surface sample in the form of hollow nanospheres having an average size of about 70 nm. Fig. 1 (b) shows the phase analysis result of X-ray diffraction (XRD) of the product, from which it can be seen that the diffraction peak of the prepared sample is consistent with the peak of the standard card, indicating that the sample prepared by this method is a metallic bismuth material.
Example 2 method for manufacturing and testing alkaline full cell using carbon-coated metal nano hollow bismuth as negative electrode
(1) Manufacturing a negative pole piece: mixing the negative electrode material, the conductive agent and the binder according to the mass ratio of 8:1:1, adding a proper amount of N-methyl pyrrolidone solvent, and stirring for 12 hours to obtain black viscous slurry. Uniformly coating the slurry on a foamed nickel current collector electrode by using a scraper, and coating the slurry on the foamed nickel current collector electrode by using a scraper 120oAnd C, vacuum drying for 12 hours to obtain the negative pole piece.
(2) Activating and testing an electrode plate: and (3) using the electrode slice prepared in the step (2) as a working electrode, respectively using Ag/AgCl and a platinum wire as a reference electrode and a counter electrode, using 6mol/L sodium hydroxide solution as an electrolyte, and circularly scanning the electrode prepared in the step (2) on an electrochemical workstation at a scanning speed of 50 mV/s for 100-fold 200 circles. And after the activation is finished, carrying out cyclic volt-ampere test and constant current charge and discharge test at different rates on the electrode slice. The results of the examples are shown in FIGS. 2 and 3.
(3) Assembling and testing the full battery: coating carbon with CoNi3O4The nano-array film positive plate is used as a working battery, the carbon-coated metal nano hollow bismuth is used as a negative electrode, 6mol/L sodium hydroxide solution is used as electrolyte, and cellulose filter paper is used as a diaphragm material. And stacking the positive electrode, the diaphragm and the negative electrode in sequence, injecting electrolyte, and then packaging the electrolyte in a transparent polyethylene film in a thermoplastic manner, thereby completing the assembly of the full cell. After the full battery is activated by cyclic volt-ampere for several circles, cyclic volt-ampere tests and constant-current charge and discharge tests with different rates are carried out on an electrochemical workstation. The results of the examples are shown in FIGS. 4 and 5.
Fig. 2 is a constant current discharge curve of the prepared carbon-coated metal nano hollow bismuth cathode material under different current densities. It can be seen that when the discharge current density is changed from 1A/g to 32A/g, the charge-discharge platform of the battery is not greatly changed, indicating the excellent electrochemical dynamic characteristics of the material system.
Fig. 3 (a) is a graph of specific capacity of the electrode at different current densities. Under the discharge current density of 1A/g, the specific capacity of the electrode is up to 110 mAh/g; namely, when the current density reaches 32A/g, the capacity can still be maintained at 83 mAh/g, and the excellent rate capability of the carbon-coated metal nano hollow bismuth is proved. Fig. 3 (b) is a cycle life diagram of the electrode, after 10000 cycles of charge and discharge under the current density of 0.5A/g, the specific capacity of the electrode is almost not greatly attenuated, the capacity retention rate can reach 96%, and the excellent cycle performance of the carbon-coated metal nano hollow bismuth is fully verified.
Fig. 4 is a constant current discharge curve of the prepared cobalt/nickel-bismuth full cell under different current densities. It can be seen that the main discharge plateau of the full cell is 0.9V at 0.5A/g discharge current density; the main discharge plateau of the full cell can be maintained around 0.8V even when the current density is increased by more than 30 times (to 16A/g).
Fig. 5 (a) shows the calculated specific capacity of the battery according to fig. 4, and the charge/discharge specific capacities of the material are respectively 80, 72, 63, 57, 48 and 36.5 mAh/g at current densities of 0.5, 1, 2, 4, 8 and 16A/g, and the rate capability of the cobalt/nickel-bismuth full battery is reflected. FIG. 5 (b) is a graph showing that the full cell is at 0.5A/g/The capacity retention rate of the full battery can still reach 88% after 2000 times of charge-discharge cycle tests on a cycle life diagram under the current density, and the larger practical application potential of the full battery is fully reflected.
Claims (8)
1. The preparation method of the alkaline battery containing the carbon-coated nano hollow bismuth composite anode material is characterized by comprising the following steps of: (1) material synthesis: bismuth salt and fluorine salt are used as raw materials and are reacted in a reaction solvent, and a room temperature liquid phase method and low temperature carbonization treatment are adopted to obtain the carbon-coated nano hollow bismuth composite negative electrode material; (2) preparing an electrode slice: adding a negative electrode material, a conductive agent and an adhesive into a solvent, stirring at room temperature to obtain black viscous slurry, and coating the black viscous slurry on a current collectorPerforming electrode treatment, and drying to obtain a carbon-coated nano hollow bismuth simple substance electrode slice; (3) electrode activation and performance detection: activating the carbon-coated nano hollow bismuth elemental electrode prepared in the step (2) by using a cyclic voltammetry scanning method; after activation is finished, constant current charging and discharging with different multiplying powers and cycle performance detection are carried out on the electrode slice; (4) assembling and testing the full battery: coating carbon with CoNi3O4The nano-array film positive plate is used as a positive electrode, the activated carbon-coated metal nano hollow bismuth simple substance electrode in the step (3) is used as a negative electrode, 6mol/L sodium hydroxide solution is used as electrolyte, and cellulose filter paper is used as a diaphragm material; and stacking the positive electrode, the diaphragm and the negative electrode in sequence, injecting electrolyte, then encapsulating the electrolyte in a transparent polyethylene film in a thermoplastic manner, namely completing the assembly of the alkaline cobalt/nickel-bismuth full battery, and then carrying out performance detection on the full battery.
2. The preparation method of the alkaline battery containing the carbon-coated nano hollow bismuth composite anode material as claimed in claim 1, wherein the bismuth salt in the step (1) is bismuth nitrate pentahydrate, the fluorine salt is ammonium fluoride, and the reaction solvent is ethylene glycol.
3. The preparation method of the alkaline battery containing the carbon-coated nano hollow bismuth composite anode material as claimed in claim 1, wherein the conductive agent in the step (2) is carbon black; the adhesive in the step (2) is polyvinylidene fluoride (PVdF); the solvent in the step (2) is N-methyl pyrrolidone; the current collector electrode in the step (2) is foamed nickel.
4. The preparation method of the alkaline battery containing the carbon-coated nano hollow bismuth composite anode material as claimed in claim 1, wherein the mass ratio of the anode material, the conductive agent and the binder in the step (2) is 8:1: 1.
5. the preparation method of the alkaline battery containing the carbon-coated nano hollow bismuth composite anode material according to claim 1, characterized by comprising the following steps(2) Middle drying treatment at 120oAnd C, standing for 10 hours under the baking condition.
6. The preparation method of the alkaline battery containing the carbon-coated nano hollow bismuth composite anode material as claimed in claim 1, wherein the activation of the electrode sheet in the step (3) comprises the following steps: and (3) immersing the electrode slice of the carbon-coated nano hollow bismuth simple substance prepared in the step (2) into 6mol/L sodium hydroxide solution, taking Ag/AgCl as a reference electrode, taking a platinum wire electrode as a counter electrode, and carrying out 100-loop 200-loop cyclic voltammetry scanning process on the electrode slice at the rate of 50 mV/s on an electrochemical workstation.
7. The preparation method of the alkaline battery containing the carbon-coated nano hollow bismuth composite anode material as claimed in claim 1, wherein the carbon-coated CoNi in the step (4)3O4The preparation method of the nano-array film positive plate comprises the following steps: 0.7 g of Ni (NO)3)2·6H2O、0.4 g Co(NO3)2·6H2O、0.2 g NH4F and 0.75 g CO (NH)2)2Ultrasonically dispersing in 50 mL of distilled water; then, the mixture was transferred to a 100 mL reactor liner, a stainless steel sheet 40X 25X 0.5 mm in size was dipped in the solution, the reactor was sealed and the contents were heated to 120 deg.CoC, reacting for 4 hours under the constant temperature condition; after the reaction kettle is cooled, taking out the stainless steel sheet, washing the stainless steel sheet with distilled water for three times, and soaking the stainless steel sheet in a solution containing 0.1 g of Dopamine (DA) molecules; after immersing at room temperature for 6 hours, the stainless steel sheet was taken out and the surface thereof was rinsed with distilled water, and then the sample was placed in a quartz tube furnace 600 in an argon atmosphereoC was heated for 1 hour.
8. The preparation method of the alkaline battery containing the carbon-coated nano hollow bismuth composite anode material according to claim 1, wherein the mass ratio of the anode plate to the cathode plate in the full battery test in the step (4) is 7: 10.
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| CN111769272A (en) * | 2020-07-28 | 2020-10-13 | 广西师范大学 | Bi @ C hollow nanosphere composite material and preparation method and application thereof |
| CN113161530A (en) * | 2021-03-10 | 2021-07-23 | 广州大学 | Bismuth-based nano material and preparation method and application thereof |
| CN113823785B (en) * | 2021-09-18 | 2023-05-05 | 山东省科学院新材料研究所 | Hollow mesoporous carbon shell coated metal nanosphere and super-assembly preparation method and application thereof |
| CN114023953A (en) * | 2021-11-03 | 2022-02-08 | 惠州亿纬锂能股份有限公司 | Modified lithium iron manganese phosphate cathode material and preparation method and application thereof |
| CN114171807A (en) * | 2021-12-13 | 2022-03-11 | 西南大学 | Low temperature resistant river system nickel-iron battery |
| CN114335484A (en) * | 2022-01-05 | 2022-04-12 | 徐州博磊达新能源科技有限公司 | Negative electrode composite material for alkali metal ion battery, preparation method of negative electrode composite material and alkali metal ion battery |
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| CN103754837A (en) * | 2013-12-17 | 2014-04-30 | 武汉工程大学 | Method for preparation of bismuth-containing nano-hollow ball by using porous bismuth oxide as template |
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