CN118099405A - Composite hydrogen storage alloy, preparation method thereof, negative electrode plate and nickel-hydrogen battery - Google Patents
Composite hydrogen storage alloy, preparation method thereof, negative electrode plate and nickel-hydrogen battery Download PDFInfo
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The application relates to a composite hydrogen storage alloy and a preparation method thereof, a negative electrode plate and a nickel-hydrogen battery. According to the scheme provided by the application, the polydopamine coating coated on the surface of the hydrogen storage alloy and the nitrogen doped carbon mesoporous coating coated hydrogen storage alloy with the hydrophobic property is obtained by annealing the coated polydopamine coating, so that the effect of isolating the hydrogen storage alloy from the electrolyte can be achieved, the contact between the hydrogen storage alloy and the electrolyte is reduced, the side reaction between the hydrogen storage alloy and the electrolyte is inhibited, the corrosion of the hydrogen storage alloy is slowed down, the electrochemical cycling stability of the hydrogen storage alloy is improved, and the cycling performance of the nickel-hydrogen battery is improved.
Description
Technical Field
The application relates to the technical field of nickel-hydrogen batteries, in particular to a composite hydrogen storage alloy and a preparation method thereof, a negative electrode plate and a nickel-hydrogen battery.
Background
The nickel-hydrogen battery is widely applied to the fields of mobile communication, instruments, detection equipment, electric automobiles, emergency power supplies and the like due to the characteristics of large capacity, large-current discharge, no memory effect and the like. The hydrogen storage alloy is used as the cathode material of the nickel-hydrogen battery and is a key material for battery preparation.
Superlattice hydrogen storage alloys are one of the most potential candidates for the current negative electrode materials of nickel-hydrogen batteries, however, their crystal structure is destroyed, oxidized, corroded during the battery cycle, and their cycle life is severely reduced.
In the related art, the superlattice hydrogen storage alloy is generally modified by adopting an element substitution method, but each element has the optimal content, the content of each element is difficult to accurately grasp, when the content exceeds the range, the electrochemical performance of the battery is easily deteriorated, and the cost of substitutable rare earth elements and the like is high. In addition, another effective improvement approach of superlattice hydrogen storage alloy is to carry out surface treatment, such as acid/alkali treatment, fluorination treatment, nickel and other metals or compounds for surface plating treatment, however, the surface treatment process is complex and difficult to control, the capacity loss of the hydrogen storage alloy is also larger, and the cycle performance of the nickel-hydrogen battery is deteriorated.
Disclosure of Invention
In order to solve or partially solve the problems in the related art, the application provides a composite hydrogen storage alloy and a preparation method thereof, a negative electrode plate and a nickel-hydrogen battery, which can slow down alloy corrosion, improve electrochemical cycling stability of the hydrogen storage alloy and improve cycling performance of the nickel-hydrogen battery.
The first aspect of the application provides a composite hydrogen storage alloy, which comprises a hydrogen storage alloy and a nitrogen-doped carbon mesoporous coating coated on the surface of the hydrogen storage alloy, wherein the nitrogen-doped carbon mesoporous coating is obtained by annealing a polydopamine coating coated on the surface of the hydrogen storage alloy.
In some embodiments of the application, the nitrogen-doped carbon mesoporous coating has a thickness of from 100nm to 1000nm; the particle diameter of the hydrogen storage alloy is 37-45 mu m.
The second aspect of the present application provides a method for producing a composite hydrogen storage alloy, comprising the steps of:
adding hydrogen storage alloy powder into a dopamine solution, mixing for a preset period of time, and separating to obtain the hydrogen storage alloy coated with the polydopamine coating;
And (3) annealing the hydrogen storage alloy coated with the polydopamine coating in a protective atmosphere environment, and cooling to obtain the composite hydrogen storage alloy coated with the nitrogen-doped carbon mesoporous coating.
In some embodiments of the application, the solute concentration of the dopamine solution is between 0.2g/L and 0.6g/L, and the solvent of the dopamine solution comprises a weakly alkaline buffer solution.
In some preferred embodiments of the application, the pH of the dopamine solution is in the range of 8 to 9.5.
In some embodiments of the application, the mass ratio of the solute to the hydrogen storage alloy is 1 (10-150).
In some embodiments of the application, the solute is dopamine hydrochloride.
In some embodiments of the application, the solvent comprises sodium tetraborate buffer and absolute ethanol.
In some embodiments of the application, the hydrogen storage alloy powder is mixed with the dopamine solution at 55 ℃ to 80 ℃.
In some embodiments of the application, the hydrogen storage alloy powder is mixed with the dopamine solution via stirring.
In some preferred embodiments of the application, the stirring speed is 15rpm to 120rpm.
In some embodiments of the application, the annealing temperature is 700 ℃ to 1500 ℃ and the annealing time is 1.5h to 15h.
In some preferred embodiments of the application, the annealing temperature is 700 ℃ to 900 ℃ and the annealing time is 9h to 13h.
The third aspect of the application provides a negative electrode plate comprising nickel carbonyl powder, and the composite hydrogen storage alloy according to the first aspect of the application or the composite hydrogen storage alloy prepared by the preparation method according to the second aspect of the application.
In some embodiments of the application, the mass ratio of the nickel carbonyl powder to the composite hydrogen storage alloy is 3:1.
The fourth aspect of the application provides a nickel-metal hydride battery comprising the negative electrode plate according to the third aspect of the application.
The technical scheme provided by the application can comprise the following beneficial effects:
1. The polydopamine coating coated on the surface of the hydrogen storage alloy can form a hydrophobic nitrogen-doped carbon mesoporous coating on the surface of the hydrogen storage alloy after annealing treatment, thereby playing a role in isolating the hydrogen storage alloy from the electrolyte, reducing the contact between the hydrogen storage alloy and the electrolyte, further slowing down the corrosion of the hydrogen storage alloy, inhibiting the side reaction between the hydrogen storage alloy and the electrolyte, improving the electrochemical cycling stability of the hydrogen storage alloy and improving the cycling performance of the nickel-hydrogen battery.
2. The coating and annealing processes are simple and efficient, the cost is low, and the emission of pollutants and toxic substances polluting the environment can be reduced, thereby being beneficial to industrial application.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the application as claimed.
Drawings
The foregoing and other objects, features and advantages of the application will be apparent from the following more particular descriptions of exemplary embodiments of the application as illustrated in the accompanying drawings wherein like reference numbers generally represent like parts throughout the exemplary embodiments of the application.
FIG. 1 is a graph of electrochemical cycling testing of a nitrogen-doped carbon-coated front and rear hydrogen storage alloy;
FIG. 2 is a graph of Tafel corrosion polarization testing of hydrogen storage alloys before and after nitrogen-doped carbon cladding;
FIG. 3 is a graph of cyclic voltammetry testing of hydrogen storage alloys before and after nitrogen-doped carbon cladding.
Detailed Description
In order that the invention may be readily understood, the invention will be described in detail. Before the present invention is described in detail, it is to be understood that this invention is not limited to particular embodiments described. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in this specification and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It should also be understood that the term "and/or" as used herein refers to and encompasses any or all possible combinations of one or more of the associated listed items.
Where a range of values is provided, it is understood that each intervening value, between the upper and lower limit of that range and any other stated or intervening value in that stated range, is encompassed within the application. The upper and lower limits of these smaller ranges may independently be included in the smaller ranges, and are also encompassed within the application, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the application. In the description of the present application, the meaning of "plurality of" means two or more, unless specifically defined otherwise.
Unless defined otherwise, all terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. Although any methods and materials equivalent to those described herein can also be used in the practice or testing of the present invention, the preferred methods and materials are now described.
In the related art, the superlattice hydrogen storage alloy is generally modified by adopting an element substitution method, but each element has the optimal content, the content of each element is difficult to accurately grasp, when the content exceeds the range, the electrochemical performance of the battery is easily deteriorated, and the cost of substitutable rare earth elements and the like is high. In addition, another effective improvement approach of superlattice hydrogen storage alloy is to carry out surface treatment, such as acid/alkali treatment, fluorination treatment or surface plating treatment by adopting metal or compound such as nickel, however, the surface treatment process is complex and difficult to control, the capacity loss of the hydrogen storage alloy is also larger, and the cycle performance of the nickel-hydrogen battery is deteriorated.
Wherein, the acid/alkali treatment of the hydrogen storage alloy can dissolve part of surface elements, so that the catalytic activity of the hydrogen storage alloy is improved; meanwhile, a nickel-rich layer is formed on the surface of the alloy, so that the potential of a discharge platform of the alloy and the conductivity of the alloy are improved, and the activation energy, the discharge performance and the like of the battery are improved. The metal oxide on the surface of the alloy can be dissolved by the fluorination treatment, so that a nickel-rich layer is formed, and the catalytic activity of the battery is improved. The above treatment method can cause great loss of the capacity of the hydrogen storage alloy.
The electroplating treatment can form a copper coating or a nickel coating on the surface of the alloy to prevent the hydrogen storage alloy from oxidation, pulverization and the like in the charge-discharge cycle process and improve the durability of the alloy, however, the electroplating treatment has the defects of complex process, the need of using some expensive and toxic reagents, difficult control of the plating amount and the like.
In view of the above problems, the embodiment of the application provides a composite hydrogen storage alloy, which plays a role of isolating alloy powder and electrolyte through a hydrophobic nitrogen-doped carbon mesoporous coating coated on the surface of the hydrogen storage alloy, and reduces contact between the hydrogen storage alloy and the electrolyte, thereby slowing down corrosion of the hydrogen storage alloy, inhibiting side reaction between the hydrogen storage alloy and the electrolyte, improving electrochemical cycling stability of the hydrogen storage alloy, and improving cycling performance of a nickel-hydrogen battery.
The composite hydrogen storage alloy comprises a hydrogen storage alloy and a nitrogen-doped carbon mesoporous coating coated on the surface of the hydrogen storage alloy, wherein the nitrogen-doped carbon mesoporous coating is obtained by annealing a polydopamine coating coated on the surface of the hydrogen storage alloy.
In the embodiment of the application, a layer of polydopamine coating is coated on the surface of the hydrogen storage alloy, wherein dopamine is an n-dihydroxyphenyl compound, consists of a benzene ring and an amino group, can be combined with the surface of the hydrogen storage alloy through covalent and non-covalent bonds, and can be attached to the surface of the hydrogen storage alloy through a self-polymerization process to form a layer of compact and uniform polydopamine coating on the surface of the hydrogen storage alloy; the polydopamine coating is annealed to form a layer of nitrogen-doped carbon mesoporous coating with strong hydrophobic property, which is coated on the surface of the hydrogen storage alloy, so that side reaction between the hydrogen storage alloy and electrolyte can be avoided, corrosion of the hydrogen storage alloy is slowed down, the cycling stability of an electrode material is improved, and the cycling performance of the nickel-hydrogen battery is further improved.
In some embodiments, the nitrogen-doped carbon mesoporous coating has a thickness of from 100nm to 1000nm; further, the thickness of the polydopamine coating is 100 nm-1000 nm. In the embodiment of the application, the polydopamine coating coated on the surface of the hydrogen storage alloy is a nano-scale thin coating, and the nitrogen-doped carbon mesoporous coating on the surface of the hydrogen storage alloy is also a nano-scale thin coating after annealing treatment, so that good corrosion resistance can be achieved, the charge transfer capacity of an electrode can not be influenced, and the nickel-hydrogen battery has good charge and discharge efficiency.
In addition, in the embodiment of the application, the mesoporous of the nitrogen-doped carbon mesoporous coating coated on the surface of the hydrogen storage alloy is also in a nano level, and the pore diameter is between 2 and 50nm, so that the specific surface area of the surface of the composite hydrogen storage alloy is obviously increased, hydrogen is favorably captured to the surface of the composite hydrogen storage alloy, and the hydrogen is tightly distributed on the surface of the composite hydrogen storage alloy against intermolecular repulsive force, thereby the hydrogen storage alloy has higher gas storage density; the nitrogen-doped carbon mesoporous coating obtained after the polydopamine coating is annealed has excellent hydrophobic performance, better adsorption and fixation performance for hydrogen, and can effectively increase the gas storage capacity of the electrode and improve the ion storage performance of the electrode.
In some embodiments, the hydrogen storage alloy has a particle size of 37 μm to 45 μm. In addition, the nitrogen-doped carbon mesoporous coating coated on the surface of the hydrogen storage alloy is in a nano level, so that the thin coating coated on the surface of the hydrogen storage alloy can not cause obvious change of the particle size of the hydrogen storage alloy, the particle size of the coated hydrogen storage alloy powder is not increased by more than 5%, and the degradation of the battery performance of the coating which is too thin or too thick is avoided.
The compound hydrogen storage alloy provided by the embodiment of the application adopts dopamine to self-polymerize to form a polydopamine coating, and the polydopamine coating is annealed to form the nitrogen-doped carbon mesoporous coating with strong hydrophobic property, and the specific preparation method is as follows.
The preparation method of the composite hydrogen storage alloy comprises the following steps:
adding hydrogen storage alloy powder into a dopamine solution, mixing for a preset period of time, and separating to obtain the hydrogen storage alloy coated with the polydopamine coating;
And (3) annealing the hydrogen storage alloy coated with the polydopamine coating in a protective atmosphere environment, and cooling to obtain the composite hydrogen storage alloy coated with the nitrogen-doped carbon mesoporous coating.
In some embodiments, the solute concentration of the dopamine solution is between 0.2g/L and 0.6g/L, such as 0.2g/L, 0.3g/L, 0.4g/L, 0.5g/L, 0.6g/L, etc.; preferably 0.5g/L.
In some embodiments, the solvent of the dopamine solution comprises a weakly basic buffer. The dopamine solution prepared by adopting the weak alkaline buffer solution is weak alkaline, and solute in the dopamine solution can grow polydopamine on the surface of the hydrogen storage alloy powder to form a polydopamine coating under the weak alkaline condition, so that the polydopamine coating can effectively isolate the active substances of the electrolyte and the hydrogen storage alloy powder, slow down the corrosion of the hydrogen storage alloy and improve the cycling stability of the hydrogen storage alloy.
In some preferred embodiments, the pH of the dopamine solution is greater than 7; preferably 8 to 9.5, for example, ph=8, ph=8.5, ph=9, ph=9.5, and the like. Too low or too high a pH of the dopamine solution may cause self-polymerization of dopamine to be unreactive or difficult to react, which is unfavorable for formation of the coating layer.
In some embodiments, the mass ratio of solute to hydrogen storage alloy is 1 (10-150); preferably 1 (30-50). The solute in the dopamine solution is too small, a uniform and compact polydopamine thin coating layer is difficult to form on the surface of the hydrogen storage alloy powder, too much solute in the dopamine solution can cause the formation of an excessively thick polydopamine coating layer on the surface of the hydrogen storage alloy powder, the thickness of the nitrogen doped carbon mesoporous coating on the surface of the formed composite hydrogen storage alloy is difficult to control, and the particle size change of the composite hydrogen storage alloy is also difficult to control, so that the ion migration rate of an electrode is influenced.
According to the embodiment of the application, the conditions of pH of the dopamine solution, solute concentration of the dopamine solution, mass ratio of the solute to the hydrogen storage alloy powder and the like are optimized, so that the dopamine can generate a thin, uniform and compact polydopamine coating on the surface of the hydrogen storage alloy powder through self-polymerization reaction.
In some embodiments, the solute in the dopamine solution is dopamine hydrochloride.
In some embodiments, the solvent in the dopamine solution comprises a sodium tetraborate buffer and absolute ethanol, specifically comprising a sodium tetraborate pH standard buffer at ph=9.18 and absolute ethanol. Further, the sodium tetraborate buffer solution and absolute ethyl alcohol are mixed according to the volume ratio of 4:6 to prepare the solvent.
In some embodiments, the hydrogen storage alloy powder may be selected from one of the RE-Mg-Ni, RE-Y-Ni-based superlattice hydrogen storage alloys, where RE may be selected from one or more of La, ce, sm, pr. The chemical equation of the hydrogen absorbing alloy powder may be La0.7Y0.1Mg0.2Ni3.3Al0.2、La0.7Sm0.1Mg0.2Ni3.2Co0.6, for example.
According to the embodiment of the application, the alkaline solvent is prepared by the sodium tetraborate buffer solution and the absolute ethyl alcohol, so that after the dopamine hydrochloride is dissolved in the alkaline solvent, polydopamine can be formed through a simple self-polymerization process in a weak alkaline environment, and a compact and uniform polydopamine coating layer is formed by adhering polydopamine to the surface of the hydrogen storage alloy; the polydopamine coating is used as a nitrogenous carbon precursor, and can form a nitrogen-doped carbon mesoporous coating with hydrophobic characteristics in the annealing treatment process. Therefore, by matching the weakly alkaline solvent, the pH and solute concentration of the dopamine solution, the mass ratio of the solute in the dopamine solution to the hydrogen storage alloy powder and the like, the formation condition of the polydopamine coating and the bonding relationship between the polydopamine coating and the hydrogen storage alloy powder are optimized, and the bonding performance of the polydopamine coating and the hydrogen storage alloy powder is improved, so that the polydopamine coating which is difficult to pulverize, break and has good structural stability is obtained; and the thickness, the density and the uniformity of the polydopamine coating on the surface of the hydrogen storage alloy can be optimized, so that the coating has the advantages of improving the corrosion resistance of the hydrogen storage alloy, simultaneously keeping the good charge transfer capacity of an alloy electrode and improving the charge and discharge efficiency of a battery. Too high pH is unfavorable for self-polymerization reaction of dopamine, too high or too low mass ratio of dopamine to hydrogen storage alloy powder can lead to too thick or too thin polydopamine coating, and too slow or too fast growth speed of polydopamine coating, which is unfavorable for forming polydopamine coating with proper density, uniformity and thickness, and is unfavorable for improving corrosion resistance of hydrogen storage alloy.
In some embodiments, the hydrogen storage alloy powder is mixed with the dopamine solution at room temperature; preferably, the hydrogen storage alloy is mixed with the dopamine solution at a temperature of 55-80 ℃.
The mixing of the hydrogen storage alloy powder and the dopamine solution at 55-80 ℃ can be that the dopamine solution is heated and warmed, and then the hydrogen storage alloy powder is added after the temperature is constant; the hydrogen storage alloy powder may be added to the dopamine solution, and then heated to a proper mixing temperature to perform self-polymerization reaction.
In some embodiments, the hydrogen storage alloy powder is immersed in a dopamine solution to cause self-polymerization of the dopamine.
In some preferred embodiments, the hydrogen storage alloy powder is mixed with the dopamine solution via agitation; preferably, the stirring speed is 1rpm to 120rpm; further preferably 15rpm to 120rpm; more preferably 90 to 120rpm.
In some embodiments, the hydrogen storage alloy powder is mixed with the dopamine solution for 3 to 48 hours, preferably 6 to 24 hours; further preferably 12 to 18 hours; for example 3h, 6h, 12h, 36h, 48h, etc.
For example, the following protocol may be used to mix the hydrogen storage alloy powder with the dopamine solution:
① At room temperature, directly adding hydrogen storage alloy powder into 0.5g/L dopamine hydrochloride-sodium tetraborate-absolute ethyl alcohol solvent, soaking for 12 hours, and separating to obtain the hydrogen storage alloy coated with the polydopamine coating. Under the condition of room temperature, dopamine gradually adheres to the surface of the hydrogen storage alloy and slowly generates a polydopamine coating through self-polymerization reaction.
② Soaking the hydrogen storage alloy powder in 0.5g/L dopamine hydrochloride-sodium tetraborate-absolute ethyl alcohol solution, heating to 80 ℃, magnetically stirring (the rotating speed is 120 rpm) for 12 hours, and separating to obtain the hydrogen storage alloy coated with the polydopamine coating. Firstly adding hydrogen storage alloy powder into a dopamine solution, then heating to a proper mixing temperature, and enabling dopamine to slowly adhere to the surface of the hydrogen storage alloy in the heating process and undergo self-polymerization reaction to generate a polydopamine coating. Through heating and stirring treatment, the formation of the polydopamine coating can be accelerated, so that the coating process is more complete, and the thickness of the polydopamine coating formed on the surface of the hydrogen storage alloy meets the required requirements.
③ And (3) soaking the hydrogen storage alloy powder in 0.6g/L dopamine hydrochloride-sodium tetraborate-absolute ethyl alcohol solvent, heating to 80 ℃, and magnetically stirring (the rotating speed is 120 rpm) for 48 hours to obtain the hydrogen storage alloy coated with the polydopamine coating. By adopting the scheme of increasing the concentration of dopamine hydrochloride and prolonging the reaction time of the hydrogen storage alloy powder and the dopamine solution, the dopamine begins to slowly adhere to the surface of the hydrogen storage alloy in the heating process and undergoes self-polymerization reaction to generate a polydopamine coating, and the dopamine solution with higher concentration can be completely coated on the surface of the hydrogen storage alloy powder in longer reaction time, so that a polydopamine thin coating with better thickness is formed on the surface of the hydrogen storage alloy powder, and the corrosion resistance of the hydrogen storage alloy can be further improved. However, too much dopamine solute also increases the thickness of the coating layer coated on the surface of the hydrogen storage alloy powder, deteriorating the ion transport rate of the electrode.
④ And uniformly mixing 0.5g of dopamine hydrochloride solute and 1L of sodium tetraborate-absolute ethyl alcohol solvent by magnetic stirring (the rotating speed is 120 rpm), heating to 70 ℃, adding 10g of hydrogen storage alloy powder after the temperature is constant, continuously stirring for 3 hours, and separating to obtain the hydrogen storage alloy coated with the polydopamine coating. The dopamine solution is heated and warmed up, the hydrogen storage alloy powder is added after the temperature is constant, stirring is continued, the dopamine can be quickly attached to the surface of the hydrogen storage alloy powder after being warmed up and stirred under alkaline conditions, and self-polymerization reaction is quickly carried out to generate the polydopamine coating. Through heating and stirring treatment, the growth speed of the polydopamine coating is accelerated, the coating process can be more complete, the coating time of the polydopamine coating can be saved, the manufacturing time of the composite hydrogen storage alloy is saved, and the cost is saved.
According to the preparation method of the compound hydrogen storage alloy, provided by the embodiment of the application, the growth speed of the polydopamine coating and the thickness of the polydopamine coating are optimized by adjusting the process parameters of the polydopamine coating formed by self-polymerizing dopamine on the surface of the hydrogen storage alloy, the polymerization speed of dopamine can be accelerated by heating, and in the temperature range, the growth speed of the polydopamine coating and the thickness growth speed of the polydopamine coating are accelerated; the magnetic stirring can accelerate the coating speed of the polydopamine coating, and the growth speed of the polydopamine coating is accelerated within the stirring speed range. Therefore, by controlling the growth speed of the dopamine coating, the embodiment of the application can coat a thin coating with good compactness, good uniformity and proper thickness on the surface of the hydrogen storage alloy powder, avoid uneven polydopamine coating or uncoated polydopamine coating on the surface of the hydrogen storage alloy powder caused by the factors of deposition, uneven self-polymerization reaction and the like of the hydrogen storage alloy powder, and prepare the hydrogen storage alloy with good coating effect, thereby improving the integral corrosion resistance of the hydrogen storage alloy powder.
In some embodiments, the protective atmosphere may be argon, helium, or the like.
In some embodiments, the annealing temperature is 700 ℃ to 1500 ℃ and the annealing time is 1.5h to 15h; preferably 700-900 deg.c and annealing time of 9-13 hr.
The annealing treatment may be performed, for example, by the following scheme:
① Annealing the hydrogen storage alloy coated with the polydopamine coating in a vacuum annealing furnace filled with argon, preserving heat at 700 ℃ for 13h, and cooling along with the furnace to obtain the composite hydrogen storage alloy coated with the nitrogen-doped carbon mesoporous coating. The hydrogen storage alloy coated with the polydopamine coating is annealed in a vacuum environment, and after the heat preservation is carried out for 13 hours at 700 ℃, the polydopamine coating on the surface of the hydrogen storage alloy is pyrolyzed to form a nano-scale nitrogen-doped carbon mesoporous coating, so that the surface of the hydrogen storage alloy has a large specific surface area and rich pores, the surface of the hydrogen storage alloy has hydrophobic performance, the corrosion resistance of the hydrogen storage alloy powder can be enhanced, and the hydrogen storage alloy has stronger hydrogen storage performance. And the annealing treatment carried out under the temperature and time conditions can change the phase composition of the alloy, so that the alloy has stronger activation performance and the discharge performance of the hydrogen storage alloy can be improved.
② And (3) annealing the hydrogen storage alloy coated with the polydopamine coating in a vacuum annealing furnace filled with argon, preserving heat for 13h at 900 ℃, and cooling along with the furnace to obtain the composite hydrogen storage alloy coated with the nitrogen-doped carbon mesoporous coating. Compared with the scheme ①, the pyrolysis reaction of the polydopamine coating on the surface of the hydrogen storage alloy can be faster and more complete by increasing the annealing temperature, so that the hydrophobicity of the nitrogen-doped carbon mesoporous coating on the surface of the hydrogen storage alloy is further enhanced, and the corrosion resistance, the hydrogen storage performance and the discharge performance of the hydrogen storage alloy are further improved.
③ Annealing the hydrogen storage alloy coated with the polydopamine coating in a vacuum annealing furnace filled with argon, preserving heat for 7 hours at 1100 ℃, and cooling along with the furnace to obtain the composite hydrogen storage alloy coated with the nitrogen-doped carbon mesoporous coating. Compared with the schemes ① and ②, the scheme of further improving the annealing temperature can further accelerate the pyrolysis reaction of the polydopamine coating on the surface of the hydrogen storage alloy, so that the hydrophobic performance of the nitrogen-doped carbon mesoporous coating on the surface of the hydrogen storage alloy is further enhanced, but too high annealing temperature can also lead to the reduction of the nitrogen doping amount and the composition of alloy phases, so as to influence the discharge performance, the cycle performance and the like of the alloy; therefore, the annealing temperature is increased, and the annealing time is reduced at the same time.
According to the compound hydrogen storage alloy disclosed by the embodiment of the application, the polydopamine coating coated on the surface of the compound hydrogen storage alloy is used as a nitrogenous carbon precursor, and is subjected to annealing treatment for a certain time under a certain temperature condition, so that the polydopamine coating on the surface of the alloy is heated to form a carbon skeleton, and is crushed and reconstructed into a mesoporous structure at a high temperature due to spherical distribution, so that the nitrogen-doped carbon mesoporous coating with superhydrophobic performance is formed. The higher the temperature and the longer the annealing time are during the annealing treatment, the more serious the polydopamine spherical structure is broken, and the larger the pore diameter of the formed mesoporous structure is; however, at the same time, nano-scale substances on the surface of the alloy are easy to agglomerate due to surface energy, and the mesoporous aperture is reduced. Therefore, the annealing temperature and the annealing time are controlled within the ranges, the formed nitrogen-doped carbon mesoporous coating is suitable in thickness, suitable in mesoporous aperture and good in mesoporous uniformity, so that contact between the alloy and alkaline electrolyte can be effectively reduced, alloy corrosion is further slowed down, electrochemical cycling stability of the alloy is improved, and cycling performance of the nickel-hydrogen battery is further improved. In addition, the embodiment of the application can control the annealing temperature and the annealing time to meet the conditions by adjusting the relation between the annealing temperature and the annealing time, so that the nitrogen-doped carbon mesoporous coating with superhydrophobic performance can be obtained, the composition of an alloy phase can be changed, the alloy arrangement is enabled to have better regularity, the segregation of alloy components is inhibited, and the component non-uniformity of the alloy is improved; meanwhile, the alloy grains are refined, the activation performance of the alloy is improved, the maximum discharge capacity and the high-rate discharge performance of the hydrogen storage alloy are improved, the electrochemical performance of the alloy is improved as a whole, and the electrochemical performance of the nickel-hydrogen battery is further improved.
The composite hydrogen storage alloy or the composite hydrogen storage alloy prepared by the preparation method can be used for preparing the negative electrode plate of the nickel-metal hydride battery.
The negative electrode plate comprises carbonyl carbon powder and the composite hydrogen storage alloy or the composite hydrogen storage alloy prepared by the preparation method.
In some embodiments, the mass ratio of nickel carbonyl powder to the composite hydrogen storage alloy is 3:1.
The embodiment of the application also provides a nickel-metal hydride battery which comprises the negative electrode plate.
The nickel-hydrogen battery also comprises a positive electrode plate, a diaphragm and electrolyte.
The positive electrode sheet may be, for example, a positive electrode sheet containing Ni (OH) 2/NiOOH active particles. The separator is used for separating the positive electrode plate and the negative electrode plate, and can be, for example, polypropylene separator. The battery cell is formed by winding a positive pole piece, a negative pole piece and a diaphragm into a metal shell.
The electrolyte may be one or two or more of aqueous solutions containing sodium hydroxide, potassium hydroxide, lithium hydroxide, etc., for example, 6mol/L KOH electrolyte is used. And placing the battery core into electrolyte to manufacture the sealed battery.
In order that the application may be more readily understood, the application will be further described in detail with reference to the following examples, which are given by way of illustration only and are not limiting in scope of application. The starting materials or components used in the present application may be prepared by commercial or conventional methods unless specifically indicated.
Examples
(1) Preparation of composite hydrogen storage alloy
The hydrogen storage alloy adopts a commercial superlattice hydrogen storage alloy.
The sodium tetraborate pH standard buffer with the pH value of 9.18 and absolute ethyl alcohol are mixed according to the volume ratio of 4:6 to prepare 1L solvent, and then 0.5g dopamine hydrochloride solute is added to obtain a dopamine solution with the concentration of 0.5g/L dopamine. And uniformly mixing solutes through magnetic stirring, heating to 70 ℃, adding 10g of hydrogen storage alloy powder after the temperature is constant, and magnetically stirring for 3 hours to obtain the polydopamine coated superlattice hydrogen storage alloy. And then placing the polydopamine coated hydrogen storage alloy into a vacuum annealing furnace filled with argon, preserving heat for 13h at 900 ℃, and cooling along with the furnace to obtain the superlattice hydrogen storage alloy coated by the nitrogen-doped carbon mesoporous coating.
(2) Preparation of negative electrode plate
Taking 0.1g of superlattice hydrogen storage alloy coated by the nitrogen-doped carbon mesoporous coating and 0.3g of nickel carbonyl powder, placing the superlattice hydrogen storage alloy and the 0.1g of nickel carbonyl powder into a flat weighing bottle, and stirring until the mixture is uniform to obtain a mixed sample; placing the mixed sample in a die, and pressing the mixed sample into a circular electrode plate with the size of 10mm by using a tablet press; coating the electrode plate sample by using foam nickel, compacting the coated electrode plate sample by using an electric welding machine, and welding the electrode plate sample with one end of a nickel strip to obtain the negative electrode plate of the nickel-hydrogen battery.
Comparative example
The difference from the examples is that the hydrogen storage alloy used is a commercial superlattice hydrogen storage alloy without the nitrogen-doped carbon mesoporous coating.
The electrochemical cycle performance test and the electrical analysis test are carried out on the cathode pole pieces of the embodiment and the comparative example through a three-electrode system, and the test results are shown in figures 1 to 3; wherein the positive electrode is a sintered Ni (OH) 2/NiOOH electrode, and the reference electrode is an Hg/HgO electrode.
Analysis of test results
FIG. 1 is a graph of electrochemical cycling testing of a nitrogen-doped carbon-coated front and back hydrogen storage alloy.
Referring to FIG. 1, the capacity of the composite hydrogen storage alloy (example) with the nitrogen-doped carbon mesoporous coating is still maintained above 350mAh/g after 100 charge-discharge cycles, and the electrode capacity is not attenuated; the uncoated original hydrogen storage alloy (comparative example) has the capacity continuously attenuated after reaching the maximum capacity, and the capacity is obviously attenuated to below 350mAh/g after being cycled for 100 times, so that compared with the uncoated original hydrogen storage alloy, the composite hydrogen storage alloy coated by the nitrogen-doped carbon mesoporous coating has obviously and effectively improved cycling stability, and further improves the cycling performance of the nickel-hydrogen battery.
FIG. 2 is a graph of Tafel corrosion polarization testing of hydrogen storage alloys before and after nitrogen-doped carbon cladding.
In combination with the illustration of fig. 2, the polarization curve of the uncoated original alloy (comparative example) is significantly more shifted to the left than the alloy with the nitrogen-doped carbon mesoporous coating (example), indicating that the composite hydrogen storage alloy coated with the nitrogen-doped carbon mesoporous coating according to the present application has significantly more positive corrosion voltage and better intrinsic corrosion resistance than the uncoated original hydrogen storage alloy. Compared with the original uncoated hydrogen storage alloy, the composite hydrogen storage alloy with the nitrogen-doped carbon mesoporous coating has the advantages that the intrinsic corrosion resistance is effectively improved, the cycle life of the alloy can be effectively improved, the cycle performance of a nickel-hydrogen battery is further improved, and the cycle life of the nickel-hydrogen battery is prolonged.
FIG. 3 is a graph of cyclic voltammetry testing of hydrogen storage alloys before and after nitrogen-doped carbon cladding.
Referring to fig. 3, the redox peaks of the composite hydrogen storage alloy (example) with the nitrogen-doped carbon mesoporous coating are closer to those of the original alloy (comparative example) without cladding, which shows that the alloy with the nitrogen-doped carbon mesoporous coating has better cycle reversibility, the cycle life of the alloy is improved, and the cycle life of the nickel-hydrogen battery is improved.
It should be noted that the above-described embodiments are only for explaining the present application and do not constitute any limitation of the present application. The application has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the application as defined in the appended claims, and the application may be modified without departing from the scope and spirit of the application. Although the application is described herein with reference to particular means, materials and embodiments, the application is not intended to be limited to the particulars disclosed herein, as the application extends to all other means and applications having the same function.
Claims (10)
1. The compound hydrogen storage alloy is characterized by comprising a hydrogen storage alloy and a nitrogen-doped carbon mesoporous coating coated on the surface of the hydrogen storage alloy, wherein the nitrogen-doped carbon mesoporous coating is obtained by annealing a polydopamine coating coated on the surface of the hydrogen storage alloy.
2. The composite hydrogen occluding alloy of claim 1, wherein:
the thickness of the nitrogen-doped carbon mesoporous coating is 100 nm-1000 nm;
The particle diameter of the hydrogen storage alloy is 37-45 mu m.
3. The preparation method of the composite hydrogen storage alloy is characterized by comprising the following steps:
adding hydrogen storage alloy powder into a dopamine solution, mixing for a preset period of time, and separating to obtain the hydrogen storage alloy coated with the polydopamine coating;
And (3) annealing the hydrogen storage alloy coated with the polydopamine coating in a protective atmosphere environment, and cooling to obtain the composite hydrogen storage alloy coated with the nitrogen-doped carbon mesoporous coating.
4. A method of preparation according to claim 3, characterized in that:
the solute concentration of the dopamine solution is 0.2 g/L-0.6 g/L, and the solvent of the dopamine solution comprises a weak alkaline buffer solution; preferably, the pH of the dopamine solution is 8-9.5;
and/or the mass ratio of the solute to the hydrogen storage alloy is 1 (10-150).
5. The method of manufacturing according to claim 4, wherein:
The solute is dopamine hydrochloride;
And/or the solvent comprises sodium tetraborate buffer and absolute ethanol.
6. A method of preparation according to claim 3, characterized in that:
the hydrogen storage alloy powder is mixed with the dopamine solution at 55-80 ℃;
And/or, the hydrogen storage alloy powder and the dopamine solution are stirred and mixed; preferably, the stirring speed is 15rpm to 120rpm.
7. A method of preparation according to claim 3, characterized in that:
the annealing temperature is 700-1500 ℃ and the annealing time is 1.5-15 h;
Preferably, the annealing temperature is 700-900 ℃ and the annealing time is 9-13 h.
8. A negative electrode sheet comprising nickel carbonyl powder and the composite hydrogen storage alloy according to claim 1 or 2 or comprising the composite hydrogen storage alloy produced by the production method according to any one of claims 3 to 7.
9. The negative electrode tab of claim 8, wherein: the mass ratio of the carbonyl nickel powder to the composite hydrogen storage alloy is 3:1.
10. A nickel-metal hydride battery comprising the negative electrode sheet of claim 8 or 9.
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