CN110241350B - Copper-containing cobalt-boron hydrogen storage material and preparation method and application thereof - Google Patents
Copper-containing cobalt-boron hydrogen storage material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a copper-cobalt-boron-containing hydrogen storage material and a preparation method and application thereof, belonging to the technical field of hydrogen storage materials. The expression of the material is Co2B +3 wt% Cu, the copper element enters into the cobalt boron material in a doped form, is distributed on the surface of crystal grains, or is coated on Co2B alloy surface. The invention also provides a preparation method of the copper-containing cobalt-boron hydrogen storage material, copper is added by mechanical alloying and solution replacement coating methods respectively, the preparation process is simple, the safety is high, the operability is strong, and the copper-containing cobalt-boron hydrogen storage material effectively improves the cycle life and the discharge capacity of the battery.
Description
Technical Field
The invention belongs to the technical field of hydrogen storage materials, and particularly relates to a copper-cobalt-boron-containing hydrogen storage material as well as a preparation method and application thereof.
Background
The hydrogen storage alloy is used as a negative electrode material of the nickel-metal hydride battery, and the hydrogen storage performance of the hydrogen storage alloy plays an important role in the performance of the whole nickel-metal hydride battery. Therefore, the significance of improving the performance of the nickel-metal hydride battery by improving the hydrogen storage performance of the hydrogen storage alloy is significant.
As can be seen from the results of the current research, Co-based hydrogen storageThe discharge capacity of the alloy exceeds that of the current commercialized rare-earth hydrogen storage alloy AB5The theoretical discharge capacity of the alloy (372mAh/g, LaNi5H6) is much higher than that of Mg2 Ni-based (AB-type hydrogen storage alloy) hydrogen storage alloy. For example, songwei et al prepare a Co-B alloy having a clad structure by chemical reduction and heat treatment, and the initial Co-B alloy is decomposed into crystalline elemental Co and B having a clad structure by annealing. The initial discharge capacity of the alloy reaches 550mAh/g, and after 80 times of charge and discharge, the charge and discharge performance of the material reaches 400 mAh/g. Chung and the like respectively use a chemical reduction method and an electric arc melting method to prepare nanocrystalline superfine Co powder, the maximum discharge capacity of the sample is more than 410mAh/g, after 50 times of charge-discharge cycles, the discharge capacity is stabilized at about 350mAh/g, and good cycle stability is shown. Wang, etc. synthesizes the superfine amorphous Co-B alloy particles by a chemical reduction method. The reversible discharge capacity of the alloy exceeds 300mAh/g at the charge-discharge rate of 100mAh/g, and is almost the same as the capacity of the traditional hydrogen storage material. The reversible discharge capacity of the alloy is only reduced by 10 percent after 100 charge-discharge cycles at the charge-discharge rate of 300 mAh/g. Therefore, most of the cobalt-boron alloys have a large capacity hydrogen storage property.
Adding super entropy change elements such as magnesium, lithium, potassium, sodium, zinc and the like into the hydrogen storage material is an effective way for improving electrochemical performance including discharge capacity and rate discharge capacity of the hydrogen storage material, and the representative invention is as follows: chinese patent office No. 5/2 in 2012 entitled "AB4.7CN102437317A patent of super entropy change method of non-stoichiometric hydrogen storage material. The invention has the advantages that elements such as magnesium, lithium, potassium, sodium, zinc and the like added in the prior art are systematized and preliminarily theorized to reach the height of 'super entropy change'.
The Chinese patent office of 12/15/2010 discloses a patent of CN101914699A invention entitled "molten salt electrosynthesis method for adding magnesium, lithium, sodium and potassium into hydrogen storage material". The invention has the advantages that four elements with super entropy change of magnesium, lithium, sodium and potassium are safely and effectively added into the hydrogen storage material through the same molten salt electrolytic cell in an electroosmosis and electrolysis interaction mode; however, the disadvantages are: the addition method has relatively high requirements on technical proficiency and equipment necessary for molten salt electrosynthesis, and is slightly insufficient in the aspects of practicability such as simple process, small equipment investment and the like.
The simple substances of the elements such as magnesium, lithium, potassium, sodium and the like are usually strong in chemical activity, and besides the addition of the molten salt electrosynthesis method into the hydrogen storage material, another effective method is mechanical alloying. Table 1 shows that the hydrogen storage material is synthesized by adding simple substances or compounds of magnesium, lithium, potassium, sodium and the like, which are elements with super entropy change, into a high-energy ball milling tank through a mechanical alloying method, and representative patents disclosed in the chinese patent office are shown in table 1.
TABLE 1
The invention for synthesizing the hydrogen storage material by adding simple substances or compounds of magnesium, lithium, potassium, sodium and the like into the high-energy ball-milling tank and utilizing the mechanical alloying method has the common advantages of simple operation and strong practicability.
To sum up: coating copper on Co2The hydrogen storage material with super entropy change performance obtained by a cladding method and a mechanical alloying method on the surface of alloy microparticles and a manufacturing method thereof are not reported in patent publication and article.
Disclosure of Invention
The invention aims to provide a copper-containing cobalt boron hydrogen storage material, a preparation method and application thereof, wherein the copper-containing cobalt boron hydrogen storage material effectively improves the cycle life and the discharge capacity of a battery.
The invention firstly provides a copper-cobalt-boron-containing hydrogen storage material, the expression of which is Co2B +3 wt% Cu, the copper element enters into the cobalt boron material in a doped form, is distributed on the surface of crystal grains, or is coated on Co2B alloy surface.
The invention also provides a preparation method of the copper-cobalt-boron-containing hydrogen storage material, which comprises the following steps:
the method comprises the following steps: according to Co2B hydrogen storage material component expression formula is used for weighing Co metal powder and B powder, mixing and then putting into a tube furnace for annealing to obtain Co2B；
Step two: co obtained in the first step2B mechanical crushing to obtain Co2B hydrogen storage material powder;
step three: respectively weighing Cu powder and Co obtained in the second step2B, putting the hydrogen storage material powder into a ball milling tank for ball milling to obtain a copper-containing cobalt-boron hydrogen storage material; the Cu powder and Co2B, the weight percentage of the hydrogen storage material powder is 3 wt%: 97 wt%; or preparing CuSO4Solution of Co obtained in step two2B hydrogen storage material powder is poured into the mixture, after stirring, the precipitate is filtered out to obtain the copper-cobalt-boron-containing hydrogen storage material, and the CuSO4Mass of Cu relative to Co in solution 23 wt% of the mass of B.
Preferably, the first step is specifically: putting the mixed powder into a quartz boat, then putting the quartz boat into a tube furnace, sealing the quartz boat, and vacuumizing the tube furnace to 2 x 10-1MPa-1×10-1MPa, preferably 1X 10-1Introducing high-purity argon to 1.1 +/-0.1 atmospheric pressure under MPa, pumping and discharging for three times, then turning on a power supply, heating by using a resistance wire, raising the temperature at a heating speed of 5 ℃/min until the temperature reaches 800 ℃, preserving the temperature for 10 hours, and annealing to obtain Co2B hydrogen storage alloy.
Preferably, the Co of the second step2And B, the size of the hydrogen storage material powder is 200-400 meshes.
Preferably, the ball milling tank of the third step is a stainless steel ball milling tank.
Preferably, the diameter of the stainless steel ball milling tank in the third step is 4-15 mm.
Preferably, the vibration frequency of the ball milling tank in the third step is 200-1000 rpm.
Preferably, the weight ratio of the ball material in the third step is 10: 1, the ball milling time is 10-15 min.
Preferably, the stirring time in the third step is 1-2 min.
The invention also provides application of the copper-containing cobalt boron hydrogen storage alloy material as a negative electrode material in a battery.
The invention has the advantages of
(1) The invention provides a copper-containing cobalt-boron hydrogen storage alloy material, which is based on cobalt-boron hydrogen storage alloy, copper is added by mechanical alloying and solution replacement coating methods respectively, the preparation process is simple, the safety is high, the operability is strong, the ball milling process can be controlled by adjusting the ball milling time, the ball-material ratio and the ball quality of a ball mill, and Co is ensured2And successfully adding Cu into the B structure without damaging the B structure to form the copper-cobalt-boron-containing hydrogen storage alloy material.
(2) The copper element in the copper-containing cobalt-boron hydrogen storage material enters the cobalt-boron material in a doped form and is distributed on the surface of the crystal grain, so that the corrosion degree of the cobalt-boron material in an alkaline electrolyte solution is reduced, and the attachment point of a reversible reaction is increased, thereby improving the catalytic activity of the negative electrode of the battery and prolonging the cycle life of the battery.
(3) The copper element in the copper-cobalt-boron-containing hydrogen storage material can also be Cu in solution2+Substitution of Co2Co in B, thereby coating Co2On the surface of the B alloy, Cu in the processing mode is distributed more uniformly, the dispersibility is good, and meanwhile, the anti-corrosion effect is achieved. The experimental results show that: after 50 cycles, the capacity fading rate of the two copper-containing cobalt-boron hydrogen storage alloys is lower than that of the cobalt-boron hydrogen storage alloy;
drawings
FIG. 1 shows Co2B. XRD patterns of the copper-cobalt-boron-containing hydrogen storage alloy materials prepared in examples 1 and 2;
FIG. 2 is an ESD image of a copper-cobalt-boron-containing hydrogen storage alloy material prepared in example 1;
FIG. 3 is an ESD image of a copper-cobalt-boron-containing hydrogen storage alloy material prepared in example 2;
FIG. 4 shows Co2B. The relationship curve chart of the cycle number and the discharge capacity of the simulated battery taking the copper-cobalt-boron-containing hydrogen storage alloy material prepared in the examples 1 and 2 as the negative electrode active material.
Detailed Description
The invention firstly provides a copper-cobalt-boron-containing hydrogen storage material, the expression of which is Co2B +3 wt% Cu, the copper element being dopedThe form is entered into the cobalt boron material, distributed on the surface of crystal grains or coated on Co2B alloy surface.
Copper element in the copper-containing cobalt-boron hydrogen storage material can enter the cobalt-boron material in a doped form and is distributed on the surface of crystal grains, so that the corrosion degree of the cobalt-boron material in an alkaline electrolyte solution is reduced, and attachment points of reversible reaction are increased, thereby improving the catalytic activity of a battery cathode and prolonging the cycle life; in addition, the copper element can also be Cu in solution2+Substitution of Co2Co in B, thereby coating Co2On the surface of the B alloy, Cu in the processing mode is distributed more uniformly, the dispersibility is good, and meanwhile, the anti-corrosion effect is achieved.
The invention also provides a preparation method of the copper-cobalt-boron-containing hydrogen storage material, which comprises the following steps:
the method comprises the following steps: according to Co2B hydrogen storage material component expression formula is used for weighing Co metal powder and B powder, mixing and then putting into a tube furnace for annealing to obtain Co2B；
Step two: co obtained in the first step2B mechanical crushing to obtain Co2B hydrogen storage material powder;
step three: respectively weighing Cu powder and Co obtained in the second step2B, putting the hydrogen storage material powder into a ball milling tank for ball milling to obtain a copper-containing cobalt-boron hydrogen storage material; the Cu powder and Co2B, the weight percentage of the hydrogen storage material powder is 3 wt%: 97 wt%; or
Prepared CuSO4Solution of Co obtained in step two2B hydrogen storage material powder is poured into the mixture, after stirring, the precipitate is filtered out to obtain the copper-cobalt-boron-containing hydrogen storage material, and the CuSO4Mass of Cu relative to Co in solution 23 wt% of the mass of B.
The invention is firstly based on Co2B hydrogen storage material composition expression Co metal (purity 99.9%) and B powder (purity 99.9%) are weighed, mixed uniformly, and then placed in a tube furnace for annealing.
Annealing the small pieces in a tube furnace to prepare Co2The specific process of the hydrogen storage alloy B is as follows:putting the mixed powder into a quartz boat, then putting the quartz boat into a tube furnace, sealing the quartz boat, and vacuumizing the tube furnace to 2 x 10-1MPa-1×10-1MPa, preferably 1X 10-1Introducing high-purity argon to 1.1 +/-0.1 atmospheric pressure under MPa, pumping and discharging for three times, then turning on a power supply, heating by using a resistance wire, raising the temperature at a heating speed of 5 ℃/min until the temperature reaches 800 ℃, preserving the temperature for 10 hours, and annealing to obtain Co2B hydrogen storage alloy.
According to the invention, the Co obtained as described above is used2B, mechanically grinding the hydrogen storage alloy, wherein the grinding time is preferably 10min, and Co is formed2B hydrogen storage alloy material powder, then using sieve to make Co2B hydrogen occluding alloy powder is divided into different sizes, preferably Co2The size of the hydrogen storage alloy powder B is 200-400 meshes.
According to the invention, copper element is doped into the cobalt boron material, and the method specifically comprises the following steps: mixing the obtained Co2B, placing hydrogen storage alloy powder and pure copper powder into a ball milling tank for ball milling under the atmosphere of high-purity argon, wherein the preferred weight ratio of ball materials is 10: the method comprises the following steps of 1, preferably selecting ball milling time for 10-15min, preferably selecting a stainless steel ball milling tank as the ball milling tank, preferably selecting the diameter of the stainless steel ball milling tank to be 4-15 mm, preferably selecting the vibration frequency of the ball milling tank to be 200-1000 rpm, taking the ball milling tank down from a ball mill, opening the ball milling tank in a high-purity argon atmosphere glove box to obtain the copper-containing cobalt boron hydrogen storage material, sealing and storing in a dryer. The copper powder and Co2B the weight percentage of the hydrogen storage alloy powder is 3 wt%: 97 wt%.
Or coating Co with copper element2The surface of the B alloy specifically comprises the following components:
firstly, 200ml of CuSO is prepared4The solution is placed in a 500ml beaker with a volume of 300 and preferably 400 ml. Then the obtained Co is mixed2Slowly pouring hydrogen storage alloy powder B into the mixture, stirring the mixture for 1-2min by using a glass rod, filtering out precipitates in the mixture, washing the precipitates with distilled water and absolute alcohol for three times, finally placing the precipitates in a vacuum drying oven, setting the drying temperature to be 60-80 ℃, drying the precipitates for 10-12 h, and taking out the precipitates for later use. The CuSO4Copper and Co in solution2B the weight percentage of the hydrogen storage alloy powder is 3 wt%: 97 wt%.
The phase structure of the copper-cobalt-boron-containing hydrogen storage material obtained by the two methods is characterized by using an X-ray diffraction method (XRD), a Cu-K α target is adopted during testing, the continuous scanning speed is 5 degrees/min, and the scanning range is 10 degrees-80 degrees.
The electrochemical hydrogen storage performance test of the copper-containing cobalt boron hydrogen storage alloy obtained by the two methods adopts a DC-5 type battery tester, the test process is carried out in a simulated nickel-hydrogen experimental battery, and the battery manufacturing method specifically comprises the following steps: the copper-containing cobalt boron hydrogen storage alloy is used as an active substance in a negative electrode of a nickel-hydrogen experimental battery, the active substance and carbonyl nickel powder which is 5 times the weight of the active substance and is used as a current collector are uniformly mixed, a tablet press is used for cold static pressing to form a circular sheet with the diameter of 10mm to be used as the negative electrode of the battery, a tab of the negative electrode adopts a nickel wire with the diameter of 1mm and is connected with the negative electrode sheet in a pulse spot welding mode, and a positive electrode of the experimental battery adopts commercial sintered nickel hydroxide (Ni (OH)2NiOOH), the diaphragm between the anode and the cathode is a polypropylene diaphragm with good wettability and air permeability, and the electrolyte is KOH aqueous solution with the concentration of 6M.
The present invention will be described in further detail with reference to examples for further understanding of the present invention, but the present invention is not limited to these examples.
CuSO used in the examples4And the copper powder is commercially available, the purity is 99.9%, and the granularity of the copper powder is 200 meshes.
Example 1
The expression of the copper-containing cobalt boron hydrogen storage material is as follows: co2B +3 wt% Cu (doped), and the preparation method of the material is as follows:
(1) accurately weighing 9.16Co metal (purity 99.9%) and 0.84B nonmetal (purity 99.9%), mixing the weighed powders, placing the quartz boat with the uniformly mixed powders into the quartz tube of a tube furnace, sealing the quartz tube, and vacuumizing the tube furnace to 1 × 10-1Introducing protective gas high-purity argon to 1.1 +/-0.1 atmospheric pressure under MPa, pumping and discharging for three times, then starting a power supply, heating by using a resistance wire, raising the temperature to 800 ℃ at a heating speed of 5 ℃/min, preserving the temperature for 10 hours, and carrying outAnnealing to obtain Co2B hydrogen storage alloy.
(2) Annealing the Co obtained in the step (1)2Placing the B alloy into an agate grinding bowl, mechanically grinding for 10min, pouring the alloy powder in a grinder into a sieve for separating particles with different sizes, and Co2The size of the hydrogen storage alloy powder B is 200-400 meshes.
(3) Accurately weighing 10mg of Co obtained in the step (2)2B, putting hydrogen storage alloy powder and 0.3mg copper powder into a glove box filled with high-purity argon atmosphere, and ball-milling in a stainless steel ball-milling tank, wherein the diameter of a steel ball is 4mm, and the ball-material ratio is 10: 1, vibrating at a frequency of 200 r/min, ball milling for 10min, taking the ball milling tank off the ball mill, opening the ball milling tank in a glove box in a high-purity argon atmosphere to obtain the copper-cobalt-boron-containing hydrogen storage material, and sealing and storing in a dryer.
The XRD pattern of the hydrogen storage material containing copper, cobalt and boron obtained in example 1 is shown in figure 1, and a Cu-K α target is adopted during the test, the continuous scanning speed is 5 degrees/min, and the scanning range is 10 degrees to 80 degrees.
FIG. 2 is an ESD image of a copper-cobalt-boron-containing hydrogen storage alloy material prepared in example 1; FIG. 2 illustrates Co2The surface distribution of the B hydrogen storage alloy is relatively uniform.
Example 2
The expression of the copper-containing cobalt boron hydrogen storage material is as follows: co2B +3 wt% Cu (cladding), the preparation method of the material is as follows
(1) Accurately weighing 9.16Co metal (purity 99.9%) and 0.84B nonmetal (purity 99.9%), mixing the weighed powders, placing the quartz boat with the uniformly mixed powders into the quartz tube of a tube furnace, sealing the quartz tube, and vacuumizing the tube furnace to 1 × 10-1Introducing protective gas high-purity argon to 1.1 +/-0.1 atmospheric pressure under MPa, pumping and discharging for three times, then starting a power supply, heating by using a resistance wire, raising the temperature to 800 ℃ at a heating speed of 5 ℃/min, preserving the temperature for 10 hours, and annealing to obtain Co2B hydrogen storage alloy.
(2) Annealing the Co obtained in the step (1)2Placing the hydrogen storage alloy B into an agate grinding bowl, and mechanically grindingThe time is 10min, after the time is up, the alloy powder in the grinding mill is poured into a sieve for separating particles with different sizes, Co2The size of the hydrogen storage alloy powder B is 200-400 meshes.
(3) Accurately weighing 10mg of Co obtained in the step (2)2B Hydrogen occluding alloy powder and 0.75mg CuSO4(purity: 99.9%), poured into distilled water, stirred until the powder is completely dissolved, and prepared into 200ml of CuSO4And (3) solution. Then mixing Co2Slowly pouring hydrogen storage alloy powder into the mixture, stirring the mixture for 1min by using a glass rod, changing the original blue solution into a purple solution, filtering out the precipitate, washing ionic impurities on the surface of the precipitate by using distilled water and absolute ethyl alcohol, finally placing the precipitate in a vacuum drying oven, setting the drying temperature to be 60 ℃, drying the precipitate for 10h, sealing and placing the dried precipitate in a dryer for storage.
The XRD pattern of the hydrogen storage material containing copper, cobalt and boron obtained in example 2 is shown in figure 1, and a Cu-K α target is adopted during the test, the continuous scanning speed is 5 degrees/min, and the scanning range is 10 degrees to 80 degrees.
FIG. 3 is an ESD image of a copper-cobalt-boron-containing hydrogen storage alloy material prepared in example 2; FIG. 3 illustrates Co2The distribution of Cu on the surface of the hydrogen storage alloy B is uniform, and the distribution amount of Cu in unit area is more than that of Cu in the material obtained in example 2.
Example 3
The copper-containing cobalt boron hydrogen storage material obtained in the example 1-2 and the carbonyl nickel powder are uniformly mixed according to the weight ratio of 1: 5, 8MPa pressure is applied to the obtained powder mixture, the mixture is subjected to isostatic cool pressing to form a circular sheet with the diameter of 10mm and the thickness of 1.5mm to serve as a negative electrode, a tab of the negative electrode adopts a nickel wire with the diameter of 1mm and is connected with the negative electrode sheet in a pulse spot welding mode, and a positive electrode of a nickel-hydrogen experimental battery adopts commercial sintered nickel hydroxide (Ni (OH)2NiOOH), the diaphragm between the anode and the cathode is a polypropylene diaphragm with good wettability and air permeability, and the electrolyte is KOH aqueous solution with the concentration of 6M.
Will be mixed with Co2The performance test of the simulated battery using the alloy B and the hydrogen storage alloy containing copper, cobalt and boron obtained in the embodiment 1-2 as the negative electrode active material specifically comprises the following steps:
the lifting rate calculation formula is as follows: the capacity increase rate [ ("discharge capacity of the hydrogen storage alloy containing copper, cobalt and boron" - "discharge capacity of the blank cell for comparison" -/") of the blank cell for comparison" - "discharge capacity of the blank cell for comparison ] × 100%.
The attenuation rate calculation formula is as follows: the capacity fade rate is [ (maximum discharge capacity of the same battery-discharge capacity of the same battery at 50 th cycle)/maximum discharge capacity of the same battery ] × 100%.
FIG. 4 shows a graph of Co2Graph of relationship between cycle number and discharge capacity of simulated battery using alloy B and hydrogen storage alloy containing copper, cobalt and boron obtained in examples 1-2 as negative active material. In the figure, curve 1 represents Co2B, Curve 2 represents Co2B +3 wt% Cu (doped), curve 3 represents Co2B +3 wt% Cu (coating), as can be seen from the figure, the maximum discharge capacity can be achieved by the first electrochemical charge and discharge of the three batteries, and the capacity change of the copper-containing cobalt-boron hydrogen storage material is specifically shown in Table 2:
TABLE 2
Table 2 shows the expression of Co2The cycling stability performance data of the simulated batteries using the B alloy and the hydrogen storage alloy containing copper, cobalt and boron obtained in examples 1-2 as the negative active material are shown in Table 22Compared with the negative electrode of the B alloy, the simulated battery taking the two copper-cobalt-boron hydrogen storage alloys as the negative electrode active substances has excellent high-efficiency discharge performance, and the copper-cobalt-boron hydrogen storage alloy prepared by the coating method has better discharge performance than the alloy prepared by the other method.
Claims (9)
1. A hydrogen storage material containing copper, cobalt and boron is characterized in that the expression is Co2B +3 wt% Cu, the copper element enters into the cobalt boron material in a doped form, is distributed on the surface of crystal grains, or is coated on Co2B alloy surface;
the preparation method of the copper-cobalt-boron-containing hydrogen storage material is characterized by comprising the following steps of:
the method comprises the following steps: according to Co2B hydrogen storage material component expression formula is used for weighing Co metal powder and B powder, mixing and then putting into a tube furnace for annealing to obtain Co2B；
Step two: co obtained in the first step2B mechanical crushing to obtain Co2B hydrogen storage material powder;
step three: respectively weighing Cu powder and Co obtained in the second step2B, putting the hydrogen storage material powder into a ball milling tank for ball milling to obtain a copper-containing cobalt-boron hydrogen storage material; the Cu powder and Co2B, the weight percentage of the hydrogen storage material powder is 3 wt%: 97 wt%;
or preparing CuSO4Solution of Co obtained in step two2B hydrogen storage material powder is poured into the mixture, after stirring, the precipitate is filtered out to obtain the copper-cobalt-boron-containing hydrogen storage material, and the CuSO4Mass of Cu relative to Co in solution23 wt% of the mass of B.
2. The copper-cobalt-boron-containing hydrogen storage material of claim 1, wherein the first step is specifically: putting the mixed powder into a quartz boat, then putting the quartz boat into a tube furnace, sealing the quartz boat, and vacuumizing the tube furnace to 2 x 10- 1MPa-1×10-1Introducing high-purity argon to 1.1 +/-0.1 atmospheric pressure under MPa, pumping and discharging for three times, then turning on a power supply, heating by using a resistance wire, raising the temperature at a heating speed of 5 ℃/min until the temperature reaches 800 ℃, preserving the temperature for 10 hours, and annealing to obtain Co2B hydrogen storage alloy.
3. The copper-cobalt-boron-containing hydrogen storage material of claim 1, wherein the Co of step two2And B, the size of the hydrogen storage material powder is 200-400 meshes.
4. The hydrogen storage material containing copper, cobalt and boron as claimed in claim 1, wherein the ball milling pot of step three is a stainless steel ball milling pot.
5. The hydrogen storage material containing copper, cobalt and boron as claimed in claim 1, wherein the diameter of the stainless steel ball milling tank in step three is 4-15 mm.
6. The hydrogen storage material containing copper, cobalt and boron as claimed in claim 1, wherein the vibration frequency of the ball milling tank in the third step is 200-1000 rpm.
7. The hydrogen storage material containing copper, cobalt and boron as claimed in claim 1, wherein the weight ratio of the pellets in the third step is 10: 1, the ball milling time is 10-15 min.
8. The hydrogen storage material containing copper, cobalt and boron as claimed in claim 1, wherein the stirring time in step three is 1-2 min.
9. Use of a hydrogen storage alloy material containing copper, cobalt and boron according to claim 1 as a negative electrode material in a battery.
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| CN113097470A (en) * | 2021-03-29 | 2021-07-09 | 长春理工大学 | Nitrogen-sulfur-containing co-doped graphene cobalt-copper-silicon hydrogen storage composite material and preparation method thereof |
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