CN113881872B - Low-cobalt high-rate AB5 type hydrogen storage alloy and preparation method thereof - Google Patents
Low-cobalt high-rate AB5 type hydrogen storage alloy and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a low-cobalt high-rate AB5 type hydrogen storage alloy and a preparation method thereof, wherein the low-cobalt high-rate AB5 type hydrogen storage alloy is CaCu5A single-phase structure of general formula La(1‑x‑y‑z)CexYyZrzNiaCobMncAldWherein x, y, z, a, b, c, d have the following numerical ranges: x is more than or equal to 0.2 and less than or equal to 0.4, y is more than or equal to 0.02 and less than or equal to 0.04, z is more than or equal to 0.02 and less than or equal to 0.04, a is more than or equal to 4.4 and less than or equal to 4.7, b is more than or equal to 0.1 and less than or equal to 0.3, c is more than or equal to 0.1 and less than or equal to 0.3, d is more than or equal to 0.2 and less than or equal to 0.4, and a + b + c + d is more than or equal to 5.0 and less than or equal to 5.3. The low-cobalt high-rate AB5 type hydrogen storage alloy can stably discharge at a large rate at a low temperature, has low raw material cost, and has excellent application prospect in the fields of power type nickel-metal hydride batteries, standby power supplies and the like.
Description
Technical Field
The invention relates to a hydrogen storage alloy, in particular to a low-cobalt high-rate AB5 type hydrogen storage alloy and a preparation method thereof.
Background
In recent years, the market of the field of backup power sources has expanded, and the market of vehicle backup power sources has become a new growth direction of nickel-metal hydride batteries. The application requires that the nickel-metal hydride battery has good low-temperature discharge performance, and the low-temperature discharge performance of the nickel-metal hydride battery depends on the alloy material of the battery cathode.
A common alloy material for the negative electrode of the battery is A2B7Superlattice rare earth hydrogen storage alloy and AB5Rare earth hydrogen storage alloy. It is composed ofIn A2B7The alloy is composed of elements such as lanthanum, samarium, praseodymium, neodymium, yttrium, magnesium, nickel, manganese, aluminum and the like, has a superlattice structure, has higher capacity and self-discharge performance than other types of alloys, and has excellent self-discharge performance to enable A to be in a state of being in a super-lattice structure2B7The alloy is better applied to batteries requiring low-temperature discharge, but is used in the field of vehicle-mounted standby power supplies, has the defect of short cycle life, and has difficulty in production technology in large-scale production.
AB5The hydrogen storage alloy is composed of rare earth elements such as lanthanum, cerium, praseodymium, neodymium and the like at the A end, and metal elements such as nickel, cobalt, manganese, aluminum and the like at the B end, and the material has stable performance, is an alloy mainly used as a cathode material of the existing nickel-hydrogen battery and accounts for more than 90 percent. But AB5The type hydrogen storage alloy generally contains expensive raw materials such as praseodymium, neodymium, cobalt and the like, so that the cost of alloy powder is high, and the fluctuation of the cobalt value also causes large fluctuation of the alloy price, thereby being not beneficial to the healthy development of the market. Taking Co as an example, the cobalt mass content of the rate-type hydrogen storage alloy is mostly above 5%, otherwise the problem of poor cycle life can be caused because of the low Co content. On the other hand, the cobalt is expensive, and the alloy cost is high due to the cobalt content exceeding 5%, so that the current production cost of the nickel-metal hydride battery tends to be high.
Some alloy materials introduce expensive rare earth elements such as Ta, Pr, Nd, Sm and the like, which can improve the electrochemical cycle life of the alloy and the service life of the nickel-metal hydride battery, but also cause the rise of the material cost, so that the advantages of the nickel-metal hydride battery compared with a lithium battery are weakened.
The kinetic performance of the AB5 type hydrogen storage alloy mainly relates to the rate discharge performance, low-temperature discharge performance and self-discharge performance of a battery, and the influence factors of the AB5 type hydrogen storage alloy include the composition components of the alloy, particularly the composition of B-end elements and the proportion of nickel and cobalt, the heat treatment process of the alloy and the like. The kinetic performance of the AB5 type hydrogen storage alloy can be obviously improved by improving the proportion of B-terminal elements and a proper heat treatment process.
In addition, the hydrogen absorption amount of the material is mainly related to the battery capacity of the battery, and the influence factors are the composition components of the alloy, mainly the composition of A-terminal elements, such as La/Ce ratio and the like. The hydrogen absorption amount of the material can also influence the heat treatment temperature of the alloy, and the higher the A-end element proportion is, the larger the La/Ce ratio is, the higher the hydrogen absorption amount of the material is; too high a heat treatment temperature of the alloy results in a reduction in the amount of hydrogen absorbed by the material.
It can be seen that there is a contradiction between improving the kinetic properties of the AB5 type hydrogen storage alloy and improving the hydrogen absorption of the material, and it is difficult to obtain the advantages of both.
Disclosure of Invention
The invention aims to overcome the contradiction between the performance and the cost of the existing nickel-hydrogen battery cathode alloy material in terms of cobalt content, and provides a low-cobalt high-rate AB5 type hydrogen storage alloy, which counteracts the adverse effect of the reduction of the Co content on the alloy cycle life by adjusting the ABx ratio and adding corrosion-resistant metals such as Y, Zr and the like, thereby obtaining better low-temperature cycle performance.
The inventors consider that the electrochemical activation performance and hydrogen atom transfer rate of the material are mainly related to the rate discharge performance of the battery, and the factors are whether the stoichiometric ratio is over stoichiometric ratio, whether the alloy components are uniform, the content of nickel element is in proportion, whether the alloy is subjected to surface treatment such as alkali treatment, and the like.
The invention adopts the stoichiometric ratio, improves the nickel content, and can obviously improve the multiplying power discharge performance of the material by adopting the surface treatment processes of preparing the alloy by a quenching and strip throwing method, adding alkali treatment in the stage of preparing the cathode of the battery and the like. Specifically, the low-cobalt high-rate AB5 type hydrogen storage alloy has a general formula of La(1-x-y-z)CexYyZrzNiaCobMncAldWherein x, y, z, a, b, c and d represent molar ratios, and the numerical ranges are as follows: x is more than or equal to 0.2 and less than or equal to 0.4, y is more than or equal to 0.02 and less than or equal to 0.04, z is more than or equal to 0.02 and less than or equal to 0.04, a is more than or equal to 4.4 and less than or equal to 4.7, b is more than or equal to 0.1 and less than or equal to 0.3, c is more than or equal to 0.1 and less than or equal to 0.3, d is more than or equal to 0.2 and less than or equal to 0.4, and a + b + c + d is more than or equal to 5.0 and less than or equal to 5.3.
From the general formula:
1) the B-end elements of the alloy are more than or equal to 5.0 and less than or equal to a + B + c + d and less than or equal to 5.3, the sum of the a ends consisting of La, Ce, Y and Zr is 1, and the formula shows that the B-end elements are in over-stoichiometric proportion.
2) The mass content of Co in the material is 1.5-3.5%, and the material belongs to a low-cobalt material.
3) The Ni content in the material is 60-65% by mass, so the nickel content is higher, and the nickel content in the AB5 type hydrogen storage alloy is 55% by mass.
4) The material does not contain expensive noble metals, and therefore the production cost is controlled.
Therefore, the invention further improves the hydrogen absorption and desorption dynamic performance of the annealed alloy by the composition proportion of the over-stoichiometric ratio and simultaneously increasing the heat treatment temperature of the alloy, thereby having the advantage of high multiplying power.
The alloy design idea of the invention is as follows: la, Ce, Ni, Co, Mn and Al are AB for the existing nickel-hydrogen battery5Common constituent elements of the hydrogen storage alloy material. The product reduces the alloy cost, reduces the composition content of Co element, and compensates the adverse effect of the reduction of the cobalt content on the cycle life of the alloy by adding Y, Zr and other trace elements. Specifically, the content range of the Ni is more than or equal to 4.4 and less than or equal to a and less than or equal to 4.7, if the content of the Ni is less than 4.3, the dynamic performance of the alloy is reduced, and the low-temperature discharge capacity is influenced, and if the content of the Ni is more than 4.7, the hydrogen absorption amount of the alloy is reduced, and the manufacturing cost is increased; the content range of Co is more than or equal to 0.1 and less than or equal to 0.3, if the content of Co is less than 0.1, the cycle life of the alloy is reduced, and if the content of Co is more than 0.3, the dynamic performance of the alloy is reduced; the content range of Mn is more than or equal to 0.1 and less than or equal to 0.3, if the content of Mn is more than 0.3, the cycle life and the equilibrium hydrogen pressure of the alloy are reduced, and if the content of Mn is less than 0.1, the hydrogen absorption amount of the alloy is reduced, and the equilibrium hydrogen pressure is too high. It can be seen that the relative contents of the three elements of Ni, Co and Mn in the material are closely related to the dynamic performance, low-temperature discharge capability, cycle life and equilibrium hydrogen pressure of the product.
The specific scheme is as follows:
a low-cobalt high-rate AB5 type hydrogen storage alloy is CaCu which is a low-cobalt high-rate AB5 type hydrogen storage alloy5A single-phase structure of general formula La(1-x-y-z)CexYyZrzNiaCobMncAldWherein x, y, z, a, b, c, d have the following numerical ranges: x is more than or equal to 0.2 and less than or equal to 0.4, y is more than or equal to 0.02 and less than or equal to 0.04, z is more than or equal to 0.02 and less than or equal to 0.04, a is more than or equal to 4.4 and less than or equal to 4.7, b is more than or equal to 0.1 and less than or equal to 0.3, c is more than or equal to 0.1 and less than or equal to 0.3, d is more than or equal to 0.2 and less than or equal to 0.4, and a + b + c + d is more than or equal to 5.0 and less than or equal to 5.3.
Furthermore, 0.6 is more than or equal to 1-x-y-z is more than or equal to 0.7, 4.45 is more than or equal to a is more than or equal to 4.66, and 0.1 is more than or equal to b is more than or equal to 0.15.
Further, the general formula of the low-cobalt high-rate AB5 type hydrogen storage alloy is as follows: la0.67Ce0.29Y0.024Zr0.024Ni4.5 5Co0.15Mn0.17Al0.29、La0.67Ce0.29Y0.024Zr0.024Ni4.6Co0.15Mn0.2Al0.29、La0.67Ce0.29Y0.024Zr0.024Ni4.6 3Co0.11Mn0.17Al0.29、La0.67Ce0.29Y0.024Zr0.024Ni4.48Co0.15Mn0.25Al0.29、La0.66Ce0.29Y0.025Zr0.024Ni4.66Co0.15Mn0.17Al0.29Or La0.67Ce0.29Y0.023Zr0.022Ni4.56Co0.15Mn0.17Al0.29。
Further, the equilibrium hydrogen pressure of the low-cobalt high-rate AB5 type hydrogen storage alloy is 0.29 +/-0.02 MPa at the temperature of 318K; when the pressure of hydrogen in the container is 0.3MPa, the hydrogen absorption quantity H/M is more than or equal to 0.22, and when the pressure is 1.0MPa, the hydrogen absorption quantity H/M is more than or equal to 0.86; the hysteresis lag of the low-cobalt high-multiplying-power AB5 type hydrogen storage alloy is less than or equal to 0.15, and the platform slope is less than or equal to 0.30.
The invention also provides a preparation method of the low-cobalt high-rate AB5 type hydrogen storage alloy, which comprises the following steps of proportioning the components according to the mass percentage of the general formula, placing the proportioned raw materials in a vacuum induction smelting furnace, vacuumizing, filling protective atmosphere, and then carrying out induction heating smelting at the heating temperature of 1400-1600 ℃; melting the raw materials to form a molten liquid, preserving heat for 1-5min, then casting on a water-cooled high-speed rotating roller, and obtaining an alloy sheet through quenching and melt spinning; the obtained alloy sheet is kept at the temperature of 900-1100 ℃ for 4-14 hours, and is made into alloy powder through air flow grinding after being cooled.
Further, the heating and smelting is to heat the raw materials to 1460-.
Further, an alloy sheet is obtained through quenching and strip throwing, and then the alloy sheet is subjected to heat preservation for 5-10 hours at the temperature of 920-1060 ℃, and the alloy sheet are combined to reduce the component segregation of the alloy, so that the alloy with more uniform composition is obtained, and the performance of the material is improved.
Further, the thickness of the alloy sheet is 0.1mm-0.3 mm;
optionally, the alloy powder has a particle size of 200 mesh or less, preferably 140 mesh or less.
The invention also protects a battery cathode which comprises the low-cobalt high-rate AB5 type hydrogen storage alloy.
The invention also protects a nickel-metal hydride battery which comprises a positive electrode and a negative electrode, wherein the 0.2C discharge capacity of the alloy is 305 +/-10 mAh/g, the 1C capacity of the nickel-metal hydride battery is 300 +/-10 mAh/g under the condition of half-battery test, and when the capacity loss of the alloy is 20%, the cycle life of the alloy is more than 300 weeks.
Has the advantages that:
the low-cobalt high-rate AB5 type hydrogen storage alloy has the advantages of low production raw material cost, good high-rate discharge cycle performance of the material, low-temperature discharge and potential application prospect in the fields of power type nickel-hydrogen batteries, standby power supplies and the like.
Drawings
In order to illustrate the technical solution of the present invention more clearly, the drawings will be briefly described below, and it is apparent that the drawings in the following description relate only to some embodiments of the present invention and are not intended to limit the present invention.
Fig. 1 is a PCT test chart of an alloy material according to an embodiment of the present invention.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are conventional products which are commercially available, and are not indicated by manufacturers. In the following examples, "%" means weight percent, unless otherwise specified.
Example 1
The alloy is designed to have the composition of La0.67Ce0.29Y0.024Zr0.024Ni4.55Co0.15Mn0.17Al0.29The prepared raw materials are placed in a vacuum induction melting furnace according to the weight percentage ratio converted by a chemical formula, argon is filled for protection after vacuum pumping, then induction heating melting is carried out, the actual complete melting temperature is 1450 ℃, heat preservation is carried out for 2min after complete melting, then the raw materials are cast on a water-cooled copper roller rotating at a high speed, and alloy sheets with the thickness of 0.2mm are obtained through quenching and strip throwing. And (3) preserving the heat of the alloy sheet for 8 hours at 1020 ℃, and cooling to prepare alloy powder with the granularity smaller than 140 meshes.
Testing PCT performance (decompression-composition-temperature characteristic curve), and measuring at 318K with a pressure component isothermal tester, wherein the equilibrium hydrogen pressure is 0.29 + -0.02 MPa, the hydrogen absorption H/M is not less than 0.22 when the pressure of hydrogen in a container is 0.3MPa, and the hydrogen absorption H/M is not less than 0.86 when the pressure is 1.0 MPa; the hysteresis of the alloy is less than or equal to 0.15, the plateau slope of the alloy is less than or equal to 0.30, and a specific PCT diagram is shown in figure 1.
As can be seen from FIG. 1, the equilibrium hydrogen pressure (0.29 +/-0.02 MPa) of the product is far higher than that (0.05MPa) of the conventional AB5 type alloy product, and for the AB5 type alloy, the equilibrium hydrogen pressure is reduced along with the reduction of the ambient temperature, so that the product still has a certain pressure magnitude and is discharged with a larger capacity in a low-temperature environment due to the higher hydrogen platform pressure. The H/M at 10atm is more than 0.85, and the 1C half-cell discharge capacity of the alloy under the hydrogen absorption index can reach more than 300 mAh/g.
Example 2
The alloy is designed to have the composition of La0.67Ce0.29Y0.024Zr0.024Ni4.6Co0.15Mn0.2Al0.29The same as example 1 except that the design composition is different from example 1.
Example 3
The alloy is designed to have the composition of La0.67Ce0.29Y0.024Zr0.024Ni4.63Co0.11Mn0.17Al0.29The same as example 1 except that the design composition is different from example 1.
Example 4
The alloy is designed to have the composition of La0.67Ce0.29Y0.024Zr0.024Ni4.48Co0.15Mn0.25Al0.29The same as example 1 except that the design composition is different from example 1.
Example 5
The alloy is designed to have the composition of La0.66Ce0.29Y0.025Zr0.024Ni4.66Co0.15Mn0.17Al0.29The same as example 1 except that the design composition is different from example 1.
Example 6
The alloy is designed to have the composition of La0.67Ce0.29Y0.023Zr0.022Ni4.56Co0.15Mn0.17Al0.29The same as example 1 except that the design composition is different from example 1.
Comparative example 1
The alloy is designed to have the composition of La0.67Ce0.29Y0.025Zr0.024Ni4.7Co0.15Mn0.22Al0.29The same as example 1 except that the design composition is different from example 1.
Comparative example 2
The alloy is designed to have the composition of La0.67Ce0.29Y0.024Zr0.024Ni4.63Co0.07Mn0.17Al0.29Except that the design composition is different from that of example 1Otherwise, the same procedure as in example 1 was repeated.
Comparative example 3
The alloy is designed to have the composition of La0.67Ce0.29Y0.024Zr0.024Ni4.41Co0.15Mn0.32Al0.29The same as example 1 except that the design composition is different from example 1.
Comparative example 4
The alloy is designed to have the composition of La0.66Ce0.29Y0.024Zr0.024Ni4.78Co0.15Mn0.32Al0.3The same as example 1 except that the design composition is different from example 1.
Comparative example 5
The alloy design composition is the same as that of example 1, the preparation method is different from that of example 1, and the main difference is that the alloy sheet is not subjected to heat treatment, and the specific steps are as follows: according to the weight percentage ratio converted by a chemical formula, the prepared raw materials are placed in a vacuum induction smelting furnace, argon is filled for protection after vacuum pumping, then induction heating smelting is carried out, the actual complete melting temperature is 1450 ℃, heat preservation is carried out for 2min after complete melting, then the raw materials are cast on a water-cooled copper roller rotating at a high speed, alloy sheets are obtained through quenching and strip throwing, and the alloy sheets are ground into alloy powder with the granularity of less than 140 meshes.
Electrochemical performance test
The prepared alloy powder is tested by an open nickel-metal hydride battery test method, and the open nickel-metal hydride battery is manufactured and tested by the following steps:
firstly, 0.2g of alloy powder and 0.8g of hydroxyl nickel powder are uniformly mixed, a wafer with the diameter of 10mm is pressed under the pressure of 20MPa and is used as a negative electrode, the wafer is re-weighed after burrs are removed, and the actual content of the hydrogen-storage alloy powder in the wafer is calculated according to the proportion of the alloy powder and the hydroxyl nickel powder. And spot welding a nickel strip on the negative electrode wafer, and adopting a sintered spherical nickel sheet with the same spot welding property as the positive electrode. And assembling the negative plate wrapped by the diaphragm and the two positive plates together in a sandwich clamping piece mode, fixing the negative plate and the two positive plates by using a PVC plate, and soaking the negative plate and the two positive plates into a KOH solution with the concentration of 6mol/L to form the open nickel-metal hydride battery.
The electrochemical capacity and the cycle performance of the open cell are tested on a Xinwei tester, the test temperature is constant at 25 ℃, and the specific test method is as follows:
1. and (3) activation: the cell was charged at 60mA/g for 450 minutes and left undisturbed for 5 minutes, and then discharged at 60mA/g to 1.0V and left undisturbed for 5 minutes. The above-mentioned charging and discharging process was repeated 5 times.
2. And (3) circulation: after the activation of the open cell was completed, the cell was charged at 300mA/g for 80 minutes, left to stand for 5 minutes, and then discharged at 300mA/g to 1.0V, left to stand for 5 minutes, and the above charge and discharge process was repeated. Wherein the maximum discharge capacity is the maximum discharge capacity of the battery 1C. The cycle number at which the discharge capacity decayed to 80% of the maximum discharge capacity was the cycle life of the battery.
The results of electrochemical performance tests are shown in table 1, and it can be seen from table 1 that: based on examples 1-2 and comparative example 1, it is understood that the increase in the stoichiometric ratio affects the decrease in the electrochemical discharge capacity of the alloy. The 1C discharge capacity of the examples 1-2 is more than 300mAh/g, the stoichiometric number of the comparative example 1 is 5.36 and more than 5.3, and the 1C discharge capacity is 289mAh/g and is obviously lower than that of the examples 1-2.
② based on the examples 1, 3 and comparative example 2, the reduction of Co content affects the reduction of the cycle life of the alloy, the cycle life of example 3 is 310 weeks, the cycle life of example 1 is 306 weeks, and the cycle life of comparative example 2 is only 288 weeks, which is obviously lower than that of examples 1 and 3. This is because the cobalt content of comparative example 2 is reduced.
Based on examples 1 and 4 and comparative example 3, the increase of Mn content can reduce the cycle life of the alloy, the cycle life of example 4 is 300 weeks, and the cycle life of comparative example 3 is only 261 weeks, which is much lower than that of examples 1 and 4, because the Mn content of comparative example 3 is greatly increased.
Based on examples 1 and 5 and comparative example 4, it can be seen that the increase in Ni content results in a decrease in alloy discharge capacity, with the 1C discharge capacity of example 5 being 303mAh/g and the 1C discharge capacity of comparative example 4 being 282mAh/g, which is lower than those of examples 1 and 5 due to the increase in Ni content.
Based on example 1 and comparative example 5, the invention adopts a quenching and strip casting process combined with heat treatment, compared with the conventional ingot casting process, the composition segregation of the alloy can be effectively reduced, the alloy with more uniform composition can be obtained, and the performance is more excellent.
TABLE 1 electrochemical capacity Performance and cycle life of examples and comparative examples
Note: in the table,% represents the mass content of each element
Low temperature discharge performance test
The tests were carried out using the samples prepared in example 1, as well as a high cobalt high rate alloy designed to have a composition of La and a conventional AB5 type alloy0.62Ce0.37Ni4.32Co0.45Mn0.10Al0.29The preparation method is the same as that of example 1; the conventional AB5 type alloy is designed to have a composition of La0.72Ce0.28Ni3.77Co0.73Mn0.42Al0.18The preparation method is the same as that of example 1.
Low-temperature discharge performance test mode: and (3) testing the sealed battery, fully charging the battery at normal temperature, standing the battery at minus 40 ℃ for 6 hours, discharging the battery to 1V at 0.5 ℃, and counting the discharge time (min), wherein the result is shown in table 2.
TABLE 2 Low-temperature discharge Performance test results Table
As can be seen from table 2, the low-temperature discharge capacity of example 1 is superior to that of the high-cobalt high-rate alloy, because the reduction of the cobalt content is favorable for the electrochemical activation of the alloy and the improvement of the low-temperature discharge capacity; the low-temperature discharge capacity of the alloy in the embodiment 1 is much higher than that of the alloy in the conventional AB5 type, because the B-terminal elements, particularly the nickel element, of the embodiment 1 are higher in content, and the equilibrium hydrogen pressure (0.3MPa) of the embodiment 1 is much higher than that of the alloy in the conventional AB5 type (0.05MPa), which shows that the rate capability of the alloy prepared in the embodiment 1 is better.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (11)
1. A low-cobalt high-rate AB5 type hydrogen storage alloy is characterized in that: the low-cobalt high-rate AB5 type hydrogen storage alloy is CaCu5A single-phase structure of general formula La(1-x-y-z)CexYyZrzNiaCobMncAldWherein x, y, z, a, b, c, d have the following numerical ranges: x is more than or equal to 0.2 and less than or equal to 0.4, y is more than or equal to 0.02 and less than or equal to 0.04, z is more than or equal to 0.02 and less than or equal to 0.04, a is more than or equal to 4.4 and less than or equal to 4.7, b is more than or equal to 0.1 and less than or equal to 0.15, c is more than or equal to 0.1 and less than or equal to 0.3, d is more than or equal to 0.2 and less than or equal to 0.4, and a + b + c + d is more than or equal to 5.0 and less than or equal to 5.3;
the preparation method of the low-cobalt high-magnification AB5 type hydrogen storage alloy comprises the following steps: proportioning according to the mass percentage of the components of the general formula, putting the proportioned raw materials into a vacuum induction smelting furnace, vacuumizing, filling protective atmosphere, and then carrying out induction heating smelting at the heating temperature of 1400-1600 ℃; melting the raw materials to form a molten liquid, preserving heat for 1-5min, then casting on a water-cooled high-speed rotating roller, and obtaining an alloy sheet through quenching and melt spinning; the obtained alloy sheet is kept at the temperature of 900-1100 ℃ for 4-14 hours, and is made into alloy powder through air flow grinding after being cooled.
2. The low-cobalt high-rate AB5 type hydrogen storage alloy according to claim 1, wherein: 0.6-1-x-y-z is less than or equal to 0.7, and 4.45-a is less than or equal to 4.66.
3. The low-cobalt high-rate AB 5-type hydrogen storage alloy according to claim 1 or 2, wherein: the equilibrium hydrogen pressure of the low-cobalt high-magnification AB5 type hydrogen storage alloy is 0.29 +/-0.02 MPa at the temperature of 318K; when the pressure of hydrogen in the container is 0.3MPa, the hydrogen absorption quantity H/M is more than or equal to 0.22, and when the pressure is 1.0MPa, the hydrogen absorption quantity H/M is more than or equal to 0.86; the hysteresis of the low-cobalt high-rate AB5 type hydrogen storage alloy is less than or equal to 0.15, and the platform slope is less than or equal to 0.30.
4. The method for preparing the low-cobalt high-rate AB5 type hydrogen storage alloy according to any one of claims 1-3, wherein the method comprises the following steps: proportioning according to the mass percentage of the components of the general formula, putting the prepared raw materials into a vacuum induction smelting furnace, vacuumizing, filling protective atmosphere, and then carrying out induction heating smelting at the heating temperature of 1400-1600 ℃; melting the raw materials to form a molten liquid, preserving heat for 1-5min, then casting on a water-cooled high-speed rotating roller, and obtaining an alloy sheet through quenching and melt spinning; the obtained alloy sheet is kept at the temperature of 900-1100 ℃ for 4-14 hours, and is made into alloy powder through air flow grinding after being cooled.
5. The method for preparing the low-cobalt high-rate AB5 type hydrogen storage alloy according to claim 4, wherein the method comprises the following steps: the heating smelting is to heat the raw materials to 1460-1580 ℃, melt the raw materials, and preserve heat for 1-5min at 1460-1580 ℃ after the raw materials are melted.
6. The method for preparing the low-cobalt high-rate AB5 type hydrogen storage alloy according to claim 4 or 5, wherein the method comprises the following steps: alloy flakes are obtained through quenching and strip throwing, and then the alloy flakes are subjected to heat preservation for 5-10 hours at the temperature of 920-1060 ℃, so that the composition segregation of the alloy is reduced, the alloy with more uniform composition is obtained, and the performance of the material is improved.
7. The method for preparing the low-cobalt high-rate AB5 type hydrogen storage alloy according to claim 4 or 5, wherein the method comprises the following steps: the thickness of the alloy sheet is 0.1mm-0.3 mm.
8. The method for preparing the low-cobalt high-rate AB5 type hydrogen storage alloy according to claim 7, wherein the method comprises the following steps: the grain size of the alloy powder is less than or equal to 200 meshes.
9. The method for preparing the low-cobalt high-rate AB5 type hydrogen storage alloy according to claim 8, wherein the method comprises the following steps: the particle size of the alloy powder is less than 140 meshes.
10. A battery negative electrode comprising a low-cobalt high-rate AB 5-type hydrogen storage alloy according to any one of claims 1-3.
11. A nickel-metal hydride battery comprising a positive electrode and a negative electrode of the battery of claim 10, wherein: under the condition of a half-cell test, the 0.2C discharge capacity of the alloy is 305 +/-10 mAh/g, the 1C capacity of the alloy is 300 +/-10 mAh/g, and when the capacity loss of the alloy is 20%, the cycle life of the alloy is more than 300 weeks.
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