CN117208844A - AB 5 Hydrogen storage alloy, preparation method thereof, nickel-hydrogen alloy electrode and nickel-hydrogen battery - Google Patents
AB 5 Hydrogen storage alloy, preparation method thereof, nickel-hydrogen alloy electrode and nickel-hydrogen battery Download PDFInfo
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Classifications
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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 application relates to an AB 5 Hydrogen storage alloy, preparation method thereof, nickel-hydrogen alloy electrode and nickel-hydrogen battery. The AB is provided with 5 The A site of the hydrogen storage alloy contains La, ce, sm, zr, Y element, the B site contains Ni, co, mn, al, cu element, and the surface of the hydrogen storage alloy has needle-shaped Y (OH) 3 The coating layer, the stoichiometric ratio B/A of the hydrogen storage alloy is not less than 5.35 and not more than 5.55. The scheme provided by the application can improve AB 5 The dynamic performance and thermodynamic performance of the hydrogen absorbing and releasing process of the hydrogen storage alloy are accelerated, the hydrogen absorbing and releasing speed of the hydrogen storage alloy under the low temperature condition is accelerated, the pulverization tendency of the hydrogen storage alloy in the hydrogen absorbing and releasing process is reduced, the cycle life of the hydrogen storage alloy can be prolonged, and meanwhile, the product cost is effectively reduced.
Description
Technical Field
The application relates to the technical field of nickel-metal hydride batteries, in particular to an AB 5 Hydrogen storage alloy, preparation method thereof, nickel-hydrogen alloy electrode and nickel-hydrogen battery.
Background
The nickel-hydrogen battery is a high-performance battery which takes nickel hydride as a positive electrode material, hydrogen storage alloy as a negative electrode material and releases electric energy through chemical reaction between the positive electrode and the negative electrode. Because the energy density is high, the service life is long, the environmental protection performance is good and the like, the method is more and more widely applied to the fields of consumer electronics, electric automobiles and the like.
The use temperature of the conventional nickel-hydrogen battery is generally between 0 ℃ and 50 ℃. When the temperature is lower than 0 ℃, the discharge efficiency of the nickel-hydrogen battery is gradually reduced; when the temperature is only minus 40 ℃, the discharge efficiency of the nickel-hydrogen battery is lower than 50%; when the temperature is higher than 50 ℃, the nickel-metal hydride battery has low charging efficiency, high self-discharge rate and short cycle life. The battery in the field of vehicle-mounted and outdoor application power supplies at least meets the working conditions of storage at the temperature of minus 40 ℃ to 85 ℃ and at the same time has extremely strong safety and service life of 5 to 10 years, but the conventional nickel-hydrogen battery is difficult to meet the requirements at the same time.
Therefore, there is a need to design a nickel-metal hydride battery with good discharge performance and cycle life under a specific temperature environment.
Disclosure of Invention
To solve or partially solve the problems in the related art, the application provides an AB 5 The hydrogen storage alloy and the preparation method thereof, the nickel-hydrogen alloy electrode and the nickel-hydrogen battery have good reaction dynamics and thermodynamic properties at low temperature and long cycle life, and can meet the requirements of wide-temperature environment application, the cycle life of the hydrogen storage alloy, the price of the hydrogen storage alloy and the like.
The first aspect of the application provides an AB 5 A site of the hydrogen storage alloy contains La, ce, sm, zr, Y elements, a B site contains Ni, co, mn, al, cu elements, and the surface of the hydrogen storage alloy is provided with needle-shaped Y (OH) 3 And a coating layer, wherein the stoichiometric ratio B/A of the hydrogen storage alloy is not less than 5.35 and not more than 5.55.
In some embodiments of the application, the hydrogen storage alloy has a nickel-rich layer; preferably, the nickel-rich layer is positioned below the surface of the hydrogen storage alloy, and the nickel-rich layer is in contact with the Y (OH) 3 The coating layers are arranged at intervals.
In some embodiments of the application, the hydrogen storage alloy has a specific surface area of 3m or more 2 The magnetic susceptibility is more than or equal to 1.5emu/g.
In some embodiments of the application, the hydrogen storage alloy has the formula: la (La) a Ce b Sm c Zr d Y (1-a-b-c-d) Ni x Co y Mn z Al u Cu v ；0.22≤a≤0.54、0.27≤b≤0.42、0.10≤c≤0.17、0.01≤d≤0.02、4.76≤x≤4.94、0.06≤y≤0.13、0.15≤z≤0.20、0.15≤u≤0.30、0.05≤v≤0.15，3.35≤x+y+z+u+v≤5.55。
In some embodiments of the application, 1-a-b-c-d is greater than or equal to 0.08 in the hydrogen storage alloy; preferably 0.08.ltoreq.1-a-b-c-d.ltoreq.0.15.
In a second aspect the application provides an AB as described in the first aspect of the application 5 A method for producing a hydrogen occluding alloy comprising:
s1, acquiring a target raw material according to the stoichiometric number of each element in the general formula;
s2, heating and smelting the raw materials in a protective atmosphere environment to form molten liquid, and then adopting a rapid hardening process to prepare a hydrogen storage alloy sheet;
s3, carrying out vacuum heat treatment on the hydrogen storage alloy sheet, cooling and crushing into alloy powder;
s4, performing surface treatment on the alloy powder, cleaning and drying to obtain AB 5 Hydrogen storage alloy powder.
In some embodiments of the present application, the step S4 is to heat and stir the alloy powder with an alkaline solution; preferably, the alkaline solution is selected from at least one of sodium hydroxide solution, potassium hydroxide solution or lithium hydroxide solution; the concentration of the alkaline solution is 0.1 mol/L-12 mol/L; preferably 1mol/L to 10mol/L; the heating temperature in the step S4 is 30-80 ℃; preferably 50 to 70 ℃; the stirring time in the step S4 is 5-120 min; preferably 10min to 60min.
In some embodiments of the application, the alloy powder has a particle size of 40 μm or less.
A third aspect of the application provides a nickel-hydrogen alloy electrode comprising an AB as described in the first aspect of the application 5 Hydrogen storage alloys or AB according to the second aspect of the application 5 AB prepared by preparation method of hydrogen storage alloy 5 Hydrogen storage alloy.
A fourth aspect of the application provides a nickel-metal hydride battery comprising a nickel-metal hydride electrode according to the third aspect of the application.
The technical scheme provided by the application can comprise the following beneficial effects: by pairing AB 5 The composition of hydrogen storage alloy elements in the hydrogen storage alloy is regulated and controlled, and all elements in the hydrogen storage alloy are cooperated, so that AB can be effectively improved 5 The dynamic performance and thermodynamic performance of the hydrogen absorbing and releasing process of the hydrogen storage alloy are accelerated, the hydrogen absorbing and releasing speed of the hydrogen storage alloy under the low temperature condition is accelerated, the pulverization tendency of the hydrogen storage alloy in the hydrogen absorbing and releasing process is reduced, and the cycle life of the hydrogen storage alloy can be prolonged.
Further, needle-like Y (OH) formed by the surface of the hydrogen occluding alloy 3 The coating layer can further improve the specific surface area of the hydrogen storage alloy, so that the dynamic performance and the thermodynamic performance of the hydrogen storage alloy in the hydrogen absorption and desorption process are improved, and the low-temperature performance of the hydrogen storage alloy is improved; at the same time, the metering ratio in the hydrogen storage alloy is 5.35-5.55, and the design of the stoichiometric ratio is adopted to ensure that the hydrogen storage alloy can form a dispersed second phase and needle-like Y (OH) on the surface of the second phase 3 The cladding layers cooperate to catalyze the hydrogen absorption and desorption processes of the hydrogen storage alloy, further improve the hydrogen absorption and desorption rate of the hydrogen storage alloy at low temperature, improve the corrosion resistance of the hydrogen storage alloy, prolong the cycle life of the hydrogen storage alloy and enable AB 5 The nickel-hydrogen battery prepared from the hydrogen storage alloy can be applied in a wide-temperature environment, has good low-temperature performance and good cycle life, can effectively reduce the product cost, and is favorable for the application and popularization of the hydrogen storage alloy and the nickel-hydrogen battery.
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 an AB as shown in example 1 of the present application 5 A scanning electron microscope back-scattered image of the hydrogen storage alloy;
FIG. 2 is an AB of example 1 of the present application 5 Scanning electron microscope secondary electron image of hydrogen storage alloy.
Detailed Description
In order that the application may be readily understood, the application will be described in detail. Before the present application is described in detail, it is to be understood that this application 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.
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.
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 application pertains. Although any methods and materials equivalent to those described herein can also be used in the practice or testing of the present application, the preferred methods and materials are now described.
The use temperature of the conventional nickel-hydrogen battery is generally between 0 ℃ and 50 ℃. When the temperature is lower than 0 ℃, the discharge efficiency of the nickel-hydrogen battery is gradually reduced; when the temperature is only minus 40 ℃, the discharge efficiency of the nickel-hydrogen battery is lower than 50%; when the temperature is higher than 50 ℃, the nickel-metal hydride battery has low charging efficiency, high self-discharge rate and short cycle life. In the field of vehicle-mounted and outdoor application power sources, the battery needs to at least meet the working conditions of storage at the temperature of minus 40 ℃ to 85 ℃ and at the same time has extremely strong safety and service life of 5 to 10 years, but the conventional nickel-hydrogen battery is difficult to meet the requirements at the same time.
The first aspect of the application provides an AB 5 The hydrogen storage alloy contains La, ce, sm, zr, Y elements in the A site and Ni, co, mn, al, cu elements in the B site, and has needle-like Y (OH) on the surface 3 The coating layer, the stoichiometric ratio B/A of the hydrogen storage alloy is not less than 5.35 and not more than 5.55.
In order to meet the requirements of vehicle-mounted and outdoor application power supply related products on the working capacity of batteries in a special temperature environment, the A end of the hydrogen storage alloy is La-Ce-Sm-Zr-Y, the B end of the hydrogen storage alloy is Ni-Mn-Al-Co-Cu, and the element La-Ce-Sm-Zr-Y at the A end of the hydrogen storage alloy is easy to react with hydrogen to form stable hydride and emit a large amount of heat; the element Ni-Mn-Al-Co-Cu at the B end of the hydrogen storage alloy has small affinity with hydrogen, is not easy to form hydride, and is endothermic when dissolved in the hydrogen storage alloy. According to the application, the interaction of the element at the end A and the element at the end B in the hydrogen storage alloy can improve the dynamics performance of the hydrogen absorption and desorption process of the hydrogen storage alloy, so that the hydrogen absorption and desorption process of the hydrogen storage alloy can be realized rapidly at a lower temperature, the hydrogen absorption and desorption platform of the hydrogen storage alloy can be improved, the higher the hydrogen absorption and desorption platform of the hydrogen storage alloy is, the more excellent the thermodynamic performance of the hydrogen storage alloy is under the low-temperature condition, and the low-temperature performance of the hydrogen storage alloy is improved as a whole.
AB provided by the application 5 The interaction and influence among elements in the hydrogen storage alloy can also inhibit oxidation and pulverization of the hydrogen storage alloy in the hydrogen absorption and desorption process, improve the high-temperature corrosion resistance of the hydrogen storage alloy, prolong the cycle life of the hydrogen storage alloy, and ensure that the hydrogen storage alloy, a nickel-hydrogen electrode containing the hydrogen storage alloy and a nickel-hydrogen battery can be applied in a wide-temperature environment and simultaneously have the cycle life.
The application also regulates and controls the stoichiometric ratio of the hydrogen storage alloy to ensure that the stoichiometric ratio of the hydrogen storage alloy is not lower than 5.35 and not higher than 5.55. The composition proportion design of the stoichiometric ratio is adopted, and the dispersed second phase is formed in the hydrogen storage alloy by matching with the composition of each element of the hydrogen storage alloy, so that the corrosion resistance of the hydrogen storage alloy is improved, the pulverization tendency of the hydrogen storage alloy in the hydrogen absorption and desorption process is reduced, and the cycle life of the hydrogen storage alloy is prolonged; meanwhile, the catalyst can play a role in the hydrogen absorption and desorption process of the hydrogen storage alloy, so that the hydrogen absorption and desorption rate of the hydrogen storage alloy at low temperature is accelerated, and the low-temperature performance of the hydrogen storage alloy is further improved.
Meanwhile, needle-like Y (OH) 3 The coating layer can effectively improve the specific surface area of the hydrogen storage alloy, thereby improving the dynamic performance of the hydrogen absorption and desorption process of the hydrogen storage alloy, leading the hydrogen storage alloy to rapidly realize the hydrogen absorption and desorption process of the hydrogen storage alloy at a lower temperature,further improving the low temperature performance of the hydrogen storage alloy.
In the existing hydrogen storage alloy, the alloy with better low-temperature performance is mainly A 2 B 7 Hydrogen storage alloys, but such alloys are generally cheaper than AB 5 The main reasons for the high hydrogen storage alloy are: (1) The alloy contains neodymium metal, the neodymium metal is expensive, and the neodymium metal accounts for 20-30% of the total mass of the alloy; (2) The magnesium element must be added into the alloy, the melting point of the magnesium element is low, the saturated vapor pressure is large, the magnesium element is extremely volatile in the alloy smelting process, the content of the magnesium element in the alloy is difficult to accurately control, and meanwhile, the magnesium powder formed by the volatilized magnesium element is accumulated on the furnace wall of a smelting furnace, so that the explosion of the magnesium powder is easy to be initiated, the safety is low, and therefore, A is a 2 B 7 The hydrogen storage alloy is expensive to process. With the existing A 2 B 7 Compared with the hydrogen storage alloy, the hydrogen storage alloy does not contain neodymium element and magnesium element, greatly reduces the processing cost of the hydrogen storage alloy, improves the safety of the hydrogen storage alloy in the production process, and simultaneously can reach the low-temperature performance and the cycle life of A 2 B 7 Hydrogen storage alloys are at the same level.
In some embodiments, the hydrogen storage alloy has a nickel-rich layer. The nickel-rich layer has the same catalytic effect on hydrogen absorption and desorption of the hydrogen storage alloy, and the nickel-rich layer and the dispersed second phase are formed in the hydrogen storage alloy at the same time, so that the low-temperature performance of the hydrogen storage alloy can be further improved by the cooperation of the nickel-rich layer and the dispersed second phase.
In some embodiments, the nickel-rich layer is located below the surface of the hydrogen storage alloy, and the nickel-rich layer is in contact with Y (OH) 3 The coating layers are arranged at intervals. The nickel-rich layer of the application is formed at a position below a few micrometers on the surface of the hydrogen storage alloy and is matched with Y (OH) 3 The coating layers are arranged at intervals, so that the high-temperature corrosion resistance of the nickel-rich layer can be improved, and the cycle life of the hydrogen storage alloy can be prolonged.
In some embodiments, the nickel-rich layer may have a thickness of 1nm to 800nm; preferably 10nm to 500nm; more preferably 50nm to 300nm.
In some embodiments, the specific surface area of the hydrogen storage alloy is greater than or equal to 3m 2 The magnetic susceptibility is more than or equal to 1.5emu/g. The application is formed by the surface of Y (OH) 3 Effective increase of coating layerThe specific surface area of the hydrogen storage alloy is increased, and the magnetization intensity of the hydrogen storage alloy can be effectively improved through a nickel-rich layer formed under the surface of the hydrogen storage alloy with a few micrometers; when the specific surface area and magnetic susceptibility of the hydrogen storage alloy meet the conditions, the hydrogen storage alloy has high hydrogen absorption and desorption rate, good corrosion resistance and good cycle life.
In some embodiments, the hydrogen storage alloy has the formula: la (La) a Ce b Sm c Zr d Y (1-a-b-c-d) Ni x Co y Mn z Al u Cu v The method comprises the steps of carrying out a first treatment on the surface of the The numerical range is that a is more than or equal to 0.22 and less than or equal to 0.54, b is more than or equal to 0.27 and less than or equal to 0.42, c is more than or equal to 0.10 and less than or equal to 0.17, d is more than or equal to 0.01 and less than or equal to 0.02, x is more than or equal to 4.76 and less than or equal to 4.94, y is more than or equal to 0.06 and less than or equal to 0.13, z is more than or equal to 0.15 and less than or equal to 0.20, u is more than or equal to 0.15 and less than or equal to 0.30, and v is more than or equal to 0.05 and less than or equal to 0.15; and x+y+z+u+v is not less than 5.35 and not more than 5.55.
In the application, the stoichiometric number of the A end of the hydrogen storage alloy consisting of La-Ce-Sm-Zr-Y is 1, and the stoichiometric number of the B end of the hydrogen storage alloy consisting of Ni-Mn-Al-Co-Cu is 5.35-5.55. Thus the AB provided by the application 5 The stoichiometric number of the end B of the hydrogen storage alloy is not lower than 5.35 and not higher than 5.55 than that of the end A, namely the hydrogen storage alloy is designed in a stoichiometric ratio mode; on the basis of the proportioning design meeting the stoichiometric ratio, the stoichiometric number of each element in the hydrogen storage alloy is limited in the range, so that the synergistic effect among the elements can be further exerted, and the low-temperature performance and the cycle life of the hydrogen storage alloy are improved. Meanwhile, based on the stoichiometric ratio of each element in the hydrogen storage alloy, the addition amount of each element in the hydrogen storage alloy can be limited, so that the hydrogen storage alloy has good performance, and meanwhile, the cost of the hydrogen storage alloy can be effectively controlled, so that the hydrogen storage alloy can simultaneously take low-temperature performance, cycle life, cost price and the like into consideration, and the application and popularization of the hydrogen storage alloy are facilitated.
In the present application, the La element ratio is 0.22.ltoreq.a.ltoreq.0.54, and for example, 0.22, 0.25, 0.30, 0.35, 0.38, 0.39, 0.40, 0.45, 0.50 or 0.54 may be used, but the present application is not limited to the values mentioned, and other values not mentioned in the range are equally applicable. The La element in the hydrogen storage alloy can be combined with other elements to improve the hydrogen absorption amount of the hydrogen storage alloy, and can be combined with Sm and other elements to adjust the balance pressure of the hydrogen storage alloy after absorbing and releasing hydrogen.
The element Ce ratio of 0.27.ltoreq.b.ltoreq.0.42 in the present application may be, for example, 0.27, 0.30, 0.32, 0.35, 0.40 or 0.42, etc., but is not limited to the values mentioned, and other values not mentioned in the range are equally applicable. The Ce element is added into the hydrogen storage alloy, so that the hydrogen absorption and desorption platform of the hydrogen storage alloy can be improved under the combined action of the Ce element and other elements, the addition amount of the Ce element can be increased, the hydrogen absorption and desorption platform of the hydrogen storage alloy can be further improved, and the thermodynamic performance of the hydrogen storage alloy at low temperature can be further improved.
In the present application, the element Sm ratio is 0.10.ltoreq.c.ltoreq.0.17, and may be, for example, 0.10, 0.11, 0.14, 0.15, or 0.17, etc., but not limited to the values mentioned, and other values not mentioned in the range are applicable as well. The addition of a small amount of Sm element and other elements in the hydrogen storage alloy can reduce the pulverization tendency of the hydrogen storage alloy in the hydrogen absorption and desorption process and prolong the cycle life of the hydrogen storage alloy; and can be combined with La and other elements to adjust the balance pressure of the hydrogen storage alloy after hydrogen absorption and desorption.
In the present application, the ratio of Zr element is 0.01.ltoreq.d.ltoreq.0.02, and may be, for example, 0.01 or 0.02, etc., but not limited to the values mentioned, other values not mentioned in the range are applicable as well. Zr element in the hydrogen storage alloy can be combined with other elements to improve the hydrogen absorption amount of the hydrogen storage alloy.
By controlling the stoichiometric number of the element La, ce, sm, zr at the A end of the hydrogen storage alloy, the range of the stoichiometric number of the element Y in the hydrogen storage alloy can be limited, and the mass percent of each element in the hydrogen storage alloy is controlled, for example, the added element Y in the hydrogen storage alloy is not less than 1.5 percent of the mass percent of the hydrogen storage alloy, so that the interaction and influence among the elements in the hydrogen storage alloy are caused, and the low-temperature performance and the high-temperature performance of the hydrogen storage alloy are improved.
In the present application, the Ni element ratio is 4.76.ltoreq.x.ltoreq.4.94, and may be, for example, 4.76, 4.77, 4.80, 4.82, 4.85, 4.90 or 4.94, etc., but not limited to the values mentioned, and other values not mentioned in the range are applicable. The Ni element in the hydrogen storage alloy is used as a matrix material of the hydrogen storage alloy, and can interact with other elements to change the crystal structure of the hydrogen storage alloy, so that the hydrogen absorption and desorption performance of the hydrogen storage alloy is improved, and the hydrogen absorption and desorption amount and the hydrogen absorption and desorption rate of the hydrogen storage alloy are improved.
In the present application, the Co element ratio is 0.06.ltoreq.y.ltoreq.0.13, and may be, for example, 0.06, 0.08, 0.10, 0.12 or 0.13, etc., but not limited to the values mentioned, other values not mentioned in the range are applicable as well. The Co element addition amount in the hydrogen storage alloy is not more than 2% of the total mass of the hydrogen storage alloy, so that the purpose of effectively controlling the cost of the hydrogen storage alloy can be achieved, the influence of the Co element on the discharge rate can be reduced, and the good low-temperature discharge performance of the hydrogen storage alloy is ensured.
In the present application, the ratio of Mn element is 0.15.ltoreq.z.ltoreq.0.20, and may be, for example, 0.15, 0.17, 0.18, 0.20 or the like, but not limited to the values mentioned, and other values not mentioned in the range are applicable as well. Mn element is added into the hydrogen storage alloy, so that the Mn element can act together with other elements to adjust the hydrogen absorption amount of the hydrogen storage alloy and the hydrogen absorption and desorption platform of the hydrogen storage alloy.
The Al element ratio in the present application is 0.15.ltoreq.u.ltoreq.0.30, and may be, for example, 0.15, 0.20, 0.23, 0.25, 0.28, or 0.30, etc., but not limited to the values mentioned, and other values not mentioned in the range are equally applicable. The Al element added in the hydrogen storage alloy can be combined with other elements to improve the discharge performance of the hydrogen storage alloy, and can replace part of Ni element in the hydrogen storage alloy, so that the cost of the hydrogen storage alloy is reduced; and a stable oxide film can be formed on the surface of the hydrogen storage alloy to prevent the hydrogen storage alloy from being oxidized and corroded under the high temperature condition, so that the high temperature performance of the hydrogen storage alloy is improved.
The Cu element ratio in the present application is 0.05.ltoreq.v.ltoreq.0.15, and may be, for example, 0.05, 0.08, 0.10, 0.12, or 0.15, etc., but not limited to the values mentioned, and other values not mentioned in the range are applicable as well. The addition of a small amount of Cu element in the hydrogen storage alloy can improve the dynamic performance of the hydrogen storage alloy at low temperature under the combined action of other elements, improve the hydrogen absorption and desorption rate of the hydrogen storage alloy, and simultaneously strengthen the cycle life of the hydrogen storage alloy.
In some embodiments, 1-a-b-c-d is greater than or equal to 0.08 in the hydrogen storage alloy; preferably 0.08.ltoreq.1-a-b-c-d.ltoreq.0.15, i.e. the element Y may be, for example, 0.08, 0.10, 0.11, 0.12 or 0.15, etc., but is not limited to the values mentioned, other values not mentioned in this range being equally applicable. By limiting the addition amount of the key element Y in the hydrogen storage alloy, the Y can fully co-act with other elements in the hydrogen storage alloy, so that the low-temperature performance of the hydrogen storage alloy is improved.
In some embodiments, the hydrogen storage alloy may be:
La 0.38 Ce 0.42 Sm 0.11 Zr 0.01 Y 0.08 Ni 4.94 Co 0.06 Mn 0.15 Al 0.15 Cu 0.05 ；
La 0.39 Ce 0.35 Sm 0.14 Zr 0.01 Y 0.11 Ni 4.85 Co 0.10 Mn 0.17 Al 0.23 Cu 0.10 ；
La 0.40 Ce 0.27 Sm 0.17 Zr 0.01 Y 0.15 Ni 4.77 Co 0.13 Mn 0.20 Al 0.30 Cu 0.15 。
the application also provides an AB 5 A method for producing a hydrogen occluding alloy comprising:
s1, acquiring a target raw material according to the stoichiometric amount of each element in the general formula;
s2, heating and smelting raw materials in a protective atmosphere environment to form molten liquid, and then adopting a rapid hardening process to prepare a hydrogen storage alloy sheet;
s3, carrying out vacuum heat treatment on the hydrogen storage alloy sheet, cooling and crushing into alloy powder;
s4, performing surface treatment on the alloy powder, cleaning and drying to obtain AB 5 Hydrogen storage alloy powder.
In some embodiments, in step S1, the AB is determined first 5 The chemical formula of the structural formula of the hydrogen storage alloy calculates the mass percentage of each element, and the mass percentage of each element is proportioned.
In some embodiments, in step S2, the protective atmosphere may be an inert atmosphere, for example, may be helium, argon, or the like, so as to avoid oxidation of the elements of the hydrogen storage alloy.
In some embodiments, the heating temperature of step S2 is 1000 ℃ to 1600 ℃.
In some embodiments, the heat treatment temperature of step S3 is between 1000 ℃ and 1200 ℃.
In some embodiments, in step S4, the alloy powder is subjected to a heat-stirring treatment with an alkaline solution. The surface of the hydrogen storage alloy treated by the alkaline solution can form needle-shaped Y (OH) with larger specific surface area 3 The dynamic performance of the hydrogen absorption and desorption process of the hydrogen storage alloy can be improved, so that the hydrogen absorption and desorption process of the hydrogen storage alloy can be rapidly realized at a lower temperature, and the low-temperature performance of the hydrogen storage alloy is improved; at the same time, a nano-grade nickel-rich layer is formed below the surface of the hydrogen storage alloy after surface treatment, and the nickel-rich layer has the same catalysis effect on the hydrogen storage alloy and is similar to needle-shaped Y (OH) 3 The cladding layer and the dispersed second phase cooperate to improve the low temperature performance of the hydrogen storage alloy.
In some embodiments, the alkaline solution in step 4 may be selected from one or more of alkaline aqueous solutions such as sodium hydroxide solution, potassium hydroxide solution, lithium hydroxide solution, etc., to provide both a surface treatment and a reduced likelihood of introducing other elements on the surface of the hydrogen storage alloy that may affect the low temperature and high temperature properties of the hydrogen storage alloy.
In some embodiments, the concentration of the alkaline solution in step S4 is 0.1mol/L to 12mol/L, preferably 1mol/L to 10mol/L. For example, the amount may be 0.1mol/L, 0.5mol/L, 1mol/L, 5mol/L, 8mol/L, 10mol/L, 12mol/L, etc., but the present application is not limited to the values mentioned, and other values not mentioned in the range are equally applicable; the heating temperature in step S4 is 30℃to 80℃and preferably 50℃to 70℃and may be, for example, 30℃40℃50℃60℃70℃or 80℃but is not limited to the values mentioned, and other values not mentioned in the above range are equally applicable; the stirring time in step S4 is 5 to 120 minutes, preferably 10 to 60 minutes, and may be, for example, 5 minutes, 10 minutes, 20 minutes, 30 minutes, 50 minutes, 60 minutes, 80 minutes, 90 minutes or 120 minutes, etc., but not limited to the values mentioned, and other values not mentioned in the range are applicable.
Preparation of AB by the preparation procedure of the application 5 When the hydrogen storage alloy is used, the hydrogen storage alloy can form a dispersed second phase, so that the corrosion resistance of the hydrogen storage alloy is improved, and the cycle life of the hydrogen storage alloy is prolonged; but also can lead each element in the hydrogen storage alloy to interact with other elements to improve the hydrogen absorption amount and the hydrogen absorption and desorption rate of the hydrogen storage alloy and improve the low-temperature performance of the hydrogen storage alloy; can also form needle-like Y (OH) with larger specific surface area on the surface of the hydrogen storage alloy 3 The cladding layer and the nano-scale nickel-rich layer are formed below the surface of the hydrogen storage alloy, so that the catalytic effect on the hydrogen absorption and desorption process of the hydrogen storage alloy is achieved cooperatively, and the low-temperature performance of the hydrogen storage alloy is improved.
In some embodiments, the alloy powder produced in step 3 has a particle size of 40 μm or less; further, the particle diameter thereof is not less than 10 μm and not more than 40 μm. By controlling the grain size of the alloy powder, the hydrogen storage alloy powder not only has higher specific surface area and increases the activity of the hydrogen storage alloy, but also can ensure that the hydrogen storage alloy has good corrosion resistance and prolongs the cycle life of the hydrogen storage alloy.
In some embodiments, the hydrogen storage alloys of the present application have a 0.2C discharge capacity of 300+ -20 mAh/g under half cell test conditions; the discharge efficiency of 0.2C at the temperature of minus 40 ℃ is more than or equal to 85 percent; the cycle life of 1C is more than or equal to 500 weeks at normal temperature, and the pressure of a hydrogen releasing platform is not higher than 0.25MPa and not lower than 0.10MPa (45 ℃).
The term "normal temperature" in the present application generally refers to a temperature (25.+ -. 2) DEG C, unless otherwise specified; 1 c=300 mAh/g.
The application also provides a nickel-hydrogen alloy electrode, which comprises the AB 5 Hydrogen storage alloys or alloys derived from AB as described above 5 AB prepared by preparation method of hydrogen storage alloy 5 Hydrogen storage alloy.
The application also provides a nickel-hydrogen battery which comprises the nickel-hydrogen alloy electrode.
The nickel-metal hydride battery comprises a negative electrode plate, wherein the negative electrode plate comprises a negative electrode core body and negative electrode slurry. Wherein the cathode core body is distributed with through holesFor example, a punched metal sheet or a sintered substrate obtained by die-forming a metal powder and then sintering the metal powder may be used for forming the sheet-like metal member of the hole. The negative electrode slurry contains, as a negative electrode active material, AB capable of occluding and releasing hydrogen 5 Particles of hydrogen storage alloy, binder, thickener and other additives.
The binder serves to bond the hydrogen storage alloy particles and the conductive agent to each other and to the negative electrode core, and may be selected from, for example, styrene-butadiene rubber, hydrophilic polymers, hydrophobic polymers, and the like.
The thickener imparts tackiness to the negative electrode mixture, facilitating the formation of the negative electrode, and the binder may be selected from, for example, carboxymethyl cellulose.
Other additives may be added as needed to improve the negative electrode characteristics, and sodium polyacrylate may be selected, for example.
The negative electrode active material of the present application may contain a conductive agent as needed, and the conductive agent may be selected from, for example, graphite such as natural graphite (e.g., flake graphite), artificial graphite, and expanded graphite; carbon blacks such as acetylene black, ketjen black, channel black, furnace black, lamp black and pyrolytic carbon black; conductive fibers such as carbon fibers and metal fibers; metal powders such as copper.
In some embodiments, the amounts of each component added in the negative electrode slurry of the present application may be:
hydrogen storage alloy: additive: carboxymethyl cellulose: 48% styrene-butadiene rubber solution: pure water = 100: (0.3-1.0): (0.15-0.3): (1.0-1.5): (3-7).
In some embodiments, the method for preparing the negative electrode sheet includes: mixing hydrogen storage alloy, a binder, a thickener, an additive and water to prepare negative electrode slurry; and coating the obtained negative electrode slurry on a negative electrode core body, and drying, rolling and cutting to obtain the battery negative electrode plate.
The nickel-hydrogen battery also comprises a positive plate, wherein the positive plate comprises a positive plate core body and positive slurry. The positive electrode core is composed of a conductive substrate having a porous structure, and may be selected from, for example, a mesh-like, sponge-like or fibrous metal body after nickel plating, and foamed nickel. The positive electrode mix contains positive electrode active material particles, a conductive agent, a binder, a thickener, and other additives.
The positive electrode active particles are nickel hydroxide particles or nickel hydroxide particles, and among these nickel hydroxide particles, at least one of zinc, magnesium, and cobalt is preferably solid-dissolved. The conductive agent may be selected from cobalt oxide (CoO) or cobalt water oxide (Co (OH), for example 2 ) One or more than two of cobalt compounds. The binder serves to bind the positive electrode active material particles, the conductive agent, and the positive electrode additive to the positive electrode core, and may be selected from carboxymethyl cellulose, methyl cellulose dispersion, hydroxypropyl cellulose dispersion, and the like. The thickener imparts tackiness to the positive electrode and facilitates the formation of the positive electrode, and may be selected from carboxymethyl cellulose, for example. Other additives for improving the positive electrode characteristics may be selected according to actual needs, and for example, yttrium oxide, zinc oxide, or the like may be used.
In some embodiments, the positive electrode slurry of the present application may include the following components:
nickel hydroxide: additive: conductive agent: carboxymethyl cellulose: polytetrafluoroethylene dispersion: pure water = 100: (0.4-2.0): (0.3-1.8): (0.13-0.21): (0.3-0.5): (20-28).
In some embodiments, the method for preparing the positive electrode sheet includes: mixing positive electrode active particles, a conductive agent, a binder, a thickening agent, an additive and water to prepare positive electrode slurry; and filling the obtained positive electrode slurry into a positive electrode core body, and drying, rolling and cutting to obtain the battery positive electrode plate.
The nickel-hydrogen battery also comprises a diaphragm, wherein the diaphragm is used for separating the positive plate from the negative plate. The positive plate, the negative plate and the diaphragm are wound into a steel shell to form the electrode assembly. The separator may be, for example, a polypropylene separator.
The nickel-hydrogen battery of the application also comprises electrolyte, and the electrolyte can be one or more than two of aqueous solutions containing sodium hydroxide, potassium hydroxide, lithium hydroxide and the like. The electrode assembly is placed in an electrolyte to make a 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.
5 Example 1 preparation of AB-type Hydrogen storage alloy
1. The alloy design component is La 0.38 Ce 0.42 Sm 0.11 Zr 0.01 Y 0.08 Ni 4.94 Co 0.06 Mn 0.15 Al 0.15 Cu 0.05 Converting each element into weight percentage ratio according to the chemical structural formula;
2. placing the proportioned raw materials into a vacuum induction smelting furnace, vacuumizing, filling inert gas for protection, and carrying out induction heating to 1300+/-300 ℃; forming alloy melt after melting the raw materials, refining for 8-10 min, and preparing a hydrogen storage alloy sheet from the molten alloy melt by adopting a melt spinning process under vacuum;
3. carrying out vacuum heat treatment on the hydrogen storage alloy sheet, wherein the heat treatment temperature is 1100+/-100 ℃, preserving the heat for 8-9 hours, cooling along with a furnace, and crushing into alloy powder with the particle size less than 40 mu m;
4. adding the crushed alloy powder into an alkaline solution, heating and stirring for 30+/-10 minutes, wherein the concentration of alkali liquor is 5+/-0.5 mol/L, and the heating temperature is 50+/-5 ℃; after the stirring is finished, the pure water is used for preparing AB 5 Cleaning the hydrogen storage alloy powder until the PH value of the cleaning liquid is 7-9, and cleaning the AB 5 Vacuum packaging and storing the dried hydrogen storage alloy powder to obtain AB 5 Hydrogen storage alloy.
Example 2
The alloy design component is La 0.39 Ce 0.35 Sm 0.14 Zr 0.01 Y 0.11 Ni 4.85 Co 0.10 Mn 0.17 Al 0.23 Cu 0.10 In addition to the hydrogen storage alloy composition design parameters different from those of example 1, the composition of the hydrogen storage alloy composition was as followsThe same as in example 1.
Example 3
The alloy design component is La 0.40 Ce 0.27 Sm 0.17 Zr 0.01 Y 0.15 Ni 4.77 Co 0.13 Mn 0.20 Al 0.30 Cu 0.15 The same as in example 1 was conducted except that the hydrogen occluding alloy component design parameters were different from those of example 1.
Comparative example
Adopts a commercial A 2 B 7 The low-temperature hydrogen storage alloy comprises the following alloy components in percentage by weight:
Nd 0.7 Y 0.20 Mg 0.10 Ni 3.40 Al 0.17 。
the price comparisons of examples 1-3 with the comparative examples are shown in Table 1.
TABLE 1
| Alloy | Price (%) |
| Comparative example | 100％ |
| Example 1 | 48％ |
| Example 2 | 47.5％ |
| Example 3 | 49.15 |
Examples 1-3 and comparative examples electrochemical Performance test and hydrogen absorption and desorption plateau test
1. And (3) hydrogen absorption and desorption platform test: the test results are shown in Table 5 using Sievets type automatic equipment.
2. Electrochemical performance test: AB to be prepared 5 The hydrogen storage alloy adopts three electrodes (working electrode: hydrogen storage alloy electrode; counter electrode: sintered nickel hydroxide electrode; reference electrode: hg/HgO electrode), and the electrode is manufactured and tested in a constant temperature water bath at (25+ -0.5) deg.C.
(1) The electrode manufacturing method comprises the following steps: weigh 0.1g AB 5 The hydrogen storage alloy and 0.2g of carbonyl nickel powder are evenly mixed and cold-pressed into electrode plates.
(2) Activation of electrode sheet, electrodes corresponding to examples and comparative examples were each activated to the maximum discharge capacity C max The activation schedule is shown in Table 2.
TABLE 2
(3) The activated electrodes were subjected to-40 ℃ discharge testing, the testing schedule is shown in table 3, and the testing results are shown in table 5.
TABLE 3 Table 3
(4) And (3) after the treatment of the steps (2) and (3), obtaining the battery after formation, and performing charge and discharge cyclic test according to a cyclic test method, wherein the test system is shown in table 4, and the test result is shown in table 5.
TABLE 4 Table 4
The results of the electrochemical performance test and the hydrogen absorption and desorption plateau test of examples 1 to 3 and comparative examples are shown in Table 5.
TABLE 5
| Discharge efficiency at-40 ℃ of 0.2C | 1C cycle life | Hydrogen releasing platform pressure (MPa, 45 ℃ C.) | |
| Comparative example | 82.1％ | 450 weeks | 0.05 |
| Example 1 | 87.0％ | 521 weeks of | 0.20 |
| Example 2 | 87.1％ | 524 weeks | 0.16 |
| Example 3 | 86.8％ | 513 weeks | 0.11 |
(6) AB corresponding to example 1 5 Surface polishing is carried out on the hydrogen storage alloy powder, and a scanning electron microscope is shotMirror back-scattered image (see fig. 1). As can be seen from fig. 1, a darker, diffuse second phase appears in the hydrogen storage alloy phase.
(7) AB corresponding to example 1 5 The hydrogen occluding alloy powder was photographed as a secondary electron image of a scanning electron microscope (see fig. 2). As can be seen from FIG. 2, the surface of the hydrogen occluding alloy is formed into needle-like shape, and the needle-like shape is subjected to EDS elemental analysis to find that the main component thereof is Y (OH) 3 。
The test results according to tables 2 and 5 show that:
AB of the application 5 The 0.2C discharge efficiency of the hydrogen storage alloy reaches more than 86% under the condition of low temperature (-40 ℃), the normal temperature 1C cycle life is more than 510 weeks, and the hydrogen discharge platform pressure (45 ℃) is more than 0.1; by using the existing A 2 B 7 The 0.2C discharge efficiency of the hydrogen storage alloy reaches 82.1% under the condition of low temperature (-40 ℃), the normal temperature 1C cycle life is 450 weeks, and the hydrogen discharge platform pressure (45 ℃) is 0.05. It can be seen that AB using the present application 5 Hydrogen storage alloy with low temperature performance and cycle life reaching or exceeding A 2 B 7 The performance of the hydrogen storage alloy, but the price is only A 2 B 7 Half of the hydrogen storage alloy is beneficial to industrialized application.
To further verify the AB provided by the application 5 The application relates to application of a hydrogen storage alloy as a low-temperature long-service-life nickel-hydrogen battery.
Wherein, the positive electrode slurry is prepared by adopting a positive electrode wet slurry formula shown in table 6:
TABLE 6
| Nickel hydroxide/g | Additive/g | Conductive agent/g | Carboxymethyl cellulose/g | 60% polytetrafluoroethylene dispersion/g | Pure water/g |
| 100 | 1.0 | 1.0 | 0.18 | 0.3 | 25 |
The negative electrode wet slurry formulation shown in table 7 was used to prepare a negative electrode slurry:
TABLE 7
| Hydrogen storage alloy/g | Additive/g | Carboxymethyl cellulose/g | 48% styrene butadiene rubber solution/g | Pure water/g |
| 100 | 0.3 | 0.2 | 1.2 | 5 |
Preparing positive electrode slurry by adopting the formula in Table 6, and preparing the positive electrode slurry into a positive electrode plate; preparing a negative electrode slurry by adopting the formula in Table 7, and preparing a negative electrode plate, wherein the hydrogen storage alloy adopts the hydrogen storage alloys of examples 1-3 and comparative examples; the positive plate, the negative plate and the polypropylene diaphragm are wound into a steel shell, and electrolyte is injected to make the sealed battery.
The nickel-metal hydride batteries obtained in examples 1 to 3 and comparative example were subjected to a chemical conversion treatment in the chemical conversion manner shown in table 8:
TABLE 8
| Formation mode | Is formed into one | Formation into two | Formation into three |
| Charging method | 100mA charge for 10h | 100mA charge for 14h | 100mA charge for 16h |
| Discharge of electric power | 200mA discharge to 1.0V | 200mA discharge to 1.0V | 200mA discharge to 1.0V |
The nickel-metal hydride batteries after the formation were subjected to low-temperature discharge test as shown in table 9:
TABLE 9
The nickel-metal hydride battery after the formation was subjected to a charge-discharge cycle test as shown in table 10:
table 10
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The results of the low temperature discharge test and the charge-discharge cycle test of examples 1 to 3 and comparative examples are shown in Table 11.
TABLE 11
| Discharge efficiency at-40 ℃ of 0.2C | Cycle life | |
| Comparative example | 80.1％ | 800 weeks |
| Example 1 | 84.2％ | 970 weeks |
| Example 2 | 83.5％ | 910 weeks of |
| Example 3 | 84.7％ | 936 weeks of |
The test results according to table 11 show that:
AB using the application 5 The nickel-hydrogen battery prepared by the hydrogen storage alloy has the 0.2C discharge efficiency of more than 83% under the low-temperature (-40 ℃) condition, and the normal-temperature 1C cycle life of more than 910 weeks; by using the existing A 2 B 7 The nickel-hydrogen battery prepared by the hydrogen storage alloy has the 0.2C discharge efficiency reaching 80.1% under the condition of low temperature (-40 ℃), and the normal temperature 1C cycle life of 800 weeks. It can be seen that the low temperature performance and cycle life of the wide temperature range nickel-metal hydride battery of the application can reach or even exceed A 2 B 7 The performance of the hydrogen storage alloy is favorable for the application of the hydrogen storage alloy in a special temperature environment, and is particularly suitable for the related fields of outdoor power supplies, vehicle-mounted batteries and the like with severe requirements on the environment temperature; and its price is only A 2 B 7 The price of the wide-temperature nickel-hydrogen battery is effectively reduced by half of the hydrogen storage alloy, and the wide-temperature nickel-hydrogen battery is facilitated to be popularized and applied.
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. AB (Acrylonitrile butadiene styrene) 5 A hydrogen storage alloy is characterized in that A site of the hydrogen storage alloy contains La, ce, sm, zr, Y element and B site contains Ni, co and Mn, al and Cu elements, and the surface of the hydrogen storage alloy is provided with needle-shaped Y (OH) 3 And a coating layer, wherein the stoichiometric ratio B/A of the hydrogen storage alloy is not less than 5.35 and not more than 5.55.
2. AB according to claim 1 5 The hydrogen storage alloy is characterized in that: the hydrogen storage alloy is provided with a nickel-rich layer; preferably, the nickel-rich layer is positioned below the surface of the hydrogen storage alloy, and the nickel-rich layer is in contact with the Y (OH) 3 The coating layers are arranged at intervals.
3. AB according to claim 2 5 The hydrogen storage alloy is characterized in that: the specific surface area of the hydrogen storage alloy is more than or equal to 3m 2 The magnetic susceptibility is more than or equal to 1.5emu/g.
4. An AB according to any one of claims 1 to 3 5 The hydrogen storage alloy is characterized by having a general formula: la (La) a Ce b Sm c Zr d Y (1-a-b-c-d) Ni x Co y Mn z Al u Cu v ；0.22≤a≤0.54、0.27≤b≤0.42、0.10≤c≤0.17、0.01≤d≤0.02、4.76≤x≤4.94、0.06≤y≤0.13、0.15≤z≤0.20、0.15≤u≤0.30、0.05≤v≤0.15，3.35≤x+y+z+u+v≤5.55。
5. The AB of claim 4 5 The hydrogen storage alloy is characterized in that 1-a-b-c-d is more than or equal to 0.08; preferably 0.08.ltoreq.1-a-b-c-d.ltoreq.0.15.
6. An AB as claimed in any one of claims 1 to 5 5 A method for producing a hydrogen occluding alloy, comprising:
s1, preparing raw materials corresponding to elements required by preparation of the hydrogen storage alloy;
s2, heating and smelting the raw materials in a protective atmosphere environment to form molten liquid, and then adopting a rapid hardening process to prepare a hydrogen storage alloy sheet;
s3, carrying out vacuum heat treatment on the hydrogen storage alloy sheet, cooling and crushing into alloy powder;
s4, performing surface treatment on the alloy powder, cleaning and drying to obtain AB 5 Hydrogen storage alloy powder.
7. The AB of claim 6 5 The preparation method of the hydrogen storage alloy is characterized in that the step S4 adopts alkaline solution to heat and stir the alloy powder; preferably, the alkaline solution is selected from at least one of sodium hydroxide solution, potassium hydroxide solution or lithium hydroxide solution; the concentration of the alkaline solution is 0.1 mol/L-12 mol/L; preferably 1mol/L to 10mol/L; the heating temperature in the step S4 is 30-80 ℃; preferably 50 to 70 ℃; the stirring time in the step S4 is 5-120 min; preferably 10min to 60min.
8. AB according to claim 6 or 7 5 The preparation method of the hydrogen storage alloy is characterized by comprising the following steps: the grain diameter of the alloy powder is less than or equal to 40 mu m.
9. A nickel-metal hydride electrode comprising the AB of any one of claims 1 to 5 5 A hydrogen storage alloy or AB as claimed in any one of claims 6 to 8 5 AB prepared by preparation method of hydrogen storage alloy 5 Hydrogen storage alloy.
10. A nickel-metal hydride battery comprising the nickel-metal hydride electrode of claim 9.
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