CN110950302A - Hydrogen storage alloy containing cobalt oxide and cobalt boron of carbon fiber micron tube and preparation method thereof - Google Patents
Hydrogen storage alloy containing cobalt oxide and cobalt boron of carbon fiber micron tube and preparation method thereof Download PDFInfo
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
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- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
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Abstract
The invention provides a cobalt oxide and cobalt boron hydrogen storage alloy containing carbon fiber micron tubes and a preparation method thereof, belonging to the field of hydrogen storage materials, wherein the expression of the hydrogen storage alloy is as follows: co2B+x wt％Co3O4+1 wt% of CFMTs, wherein x is more than or equal to 1 and less than or equal to 5. The invention also provides a preparation method of the cobalt oxide and cobalt boron hydrogen storage alloy containing the carbon fiber micron tube, which comprises the steps of mixing Co powder and B powder, and then putting the mixture into a tube furnace for annealing; weighing Co3O4Powder and Co2B, putting the hydrogen storage material powder into a ball milling tank for ball milling to obtain a hydrogen storage alloy material containing cobalt oxide and cobalt boron; then mixing the carbon fiber-containing micron tube with the obtained hydrogen storage alloy containing cobalt oxide and cobalt boronGrinding to obtain the cobalt oxide and cobalt boron hydrogen storage alloy material containing the carbon fiber micron tube. The experimental results show that: after 50 times of circulation, the capacity attenuation rate of the carbon fiber micron tube cobalt oxide and the cobalt boron hydrogen storage alloy is lower than that of the cobalt boron hydrogen storage alloy.
Description
Technical Field
The invention belongs to the technical field of hydrogen storage materials, and particularly relates to a preparation method of a cobalt oxide and cobalt boron hydrogen storage alloy material containing carbon fiber microtubes.
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 current research results, the discharge capacity of the Co-based hydrogen storage alloy exceeds that of the current commercial rare earth-based hydrogen storage alloy AB5Theoretical discharge capacity of type alloy (372mAh/g, LaNi)5H6) And the cycling stability is far higher than that of Mg2Ni-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 et al use chemical reduction and arc melting, respectivelyThe nanocrystalline superfine Co powder is prepared by a smelting method, the maximum discharge capacity of the sample is above 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 charging and discharging rate of 100mA/g, and is almost the same as the capacity of the traditional hydrogen storage material. The reversible discharge capacity of the alloy decays by only 10% after 100 charge-discharge cycles at a charge-discharge rate of 300 mA/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: the cobalt oxide and cobalt boron hydrogen storage alloy material of the carbon fiber-containing micron tube and the manufacturing method thereof are not disclosed in patent publications and article reports.
Disclosure of Invention
The invention aims to provide a cobalt oxide and cobalt boron hydrogen storage alloy material containing carbon fiber microtubes and a preparation method thereof.
The invention firstly provides a cobalt oxide and cobalt boron hydrogen storage alloy material containing carbon fiber micron tubes, and the expression is Co2B+x wt％Co3O4+1 wt% of CFMTs, wherein x is more than or equal to 1 and less than or equal to 5.
The invention also provides a preparation method of the cobalt oxide and cobalt boron hydrogen storage alloy material containing the carbon fiber micron tube, which comprises the following steps:
the method comprises the following steps: according to Co2B, weighing Co metal powder and B powder according to a hydrogen storage material component expression, mixing, and then putting into a tube furnace for annealing;
step two: co obtained in the first step2B mechanical crushing to obtain Co2B hydrogen storage material powder;
step three: separately weighing Co3O4Powder and Co obtained in step two2B, putting the hydrogen storage material powder into a ball milling tank for ball milling to obtain a hydrogen storage alloy material containing cobalt oxide and cobalt boron, wherein the ball material weight ratio is (10-15): 1, ball milling for 10-15 min;
step four: and (3) washing the absorbent cotton with distilled water, drying at 60-80 ℃ for 12-24h, calcining in air at 750-850 ℃ for 1-2h to obtain the carbon fiber-containing micron tube, and grinding the carbon fiber-containing micron tube and the hydrogen storage alloy containing cobalt oxide and cobalt boron obtained in the step three for 10-20 min to obtain the cobalt oxide and cobalt boron hydrogen storage alloy material containing the carbon fiber micron tube.
Preferably, the first step is specifically: mixing Co metal powder and B powder, placing the mixture into a quartz boat, then placing 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.
Preferably, said Co2And B, the size of the hydrogen storage material powder is 200-400 meshes.
Preferably, said Co3O4Powder and Co2The weight percentage of the hydrogen storage material powder B is (1-5 wt%): (99 wt% to 95 wt%).
Preferably, the ball milling tank is a stainless steel ball milling tank.
Preferably, the diameter of the stainless steel ball milling tank is 4-15 mm.
Preferably, the vibration frequency of the ball milling tank is 200-1000 r/min.
Preferably, the weight ratio of the ball material is 10: and 1, ball milling time is 10 min.
Preferably, the weight percentage of the carbon fiber micron tube and the hydrogen storage material containing cobalt oxide and cobalt boron is 1 wt%: 99 wt%.
The invention has the advantages of
(1) The invention relates to a cobalt oxide and cobalt boron hydrogen storage alloy material containing carbon fiber micron tubes, wherein Co in the material3O4And carbon fiber micron tubes are doped into the cobalt boron material and distributed on the surfaces of the crystal grains, and Co3O4Making cobalt boron alloyThe activation energy of the reaction with alkaline components in the electrolyte solution is reduced, so that the reaction is easier, the carbon fiber microtube can enhance the conductivity and the corrosion resistance of the alloy, and the catalytic activity and the discharge capacity of the battery cathode and the service life of the battery cathode are improved under the combined action of the two substances;
(2) the invention relates to a cobalt oxide and cobalt boron hydrogen storage alloy material containing carbon fiber micron tubes, which is prepared by mechanically alloying Co3O4The additive is added into the cobalt boron alloy, 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 speed, the ball-material ratio and the ball quality of the ball mill, and the Co alloy is ensured2The Co is successfully added on the premise that the B structure is not damaged3O4Added into the mixture to form the hydrogen storage alloy material containing cobalt oxide and cobalt boron.
Drawings
FIG. 1 shows Co2B, XRD patterns of the cobalt oxide and cobalt boron hydrogen storage alloy materials of the carbon fiber-containing micron tubes obtained in the embodiments 1-3;
FIG. 2 shows Co2B, scanning electron microscope images of the cobalt oxide and cobalt boron hydrogen storage alloy materials of the carbon fiber-containing micron tube obtained in the embodiment 1;
FIG. 3 is Co2B and the relationship curve graph of the cycle times and the discharge capacity of the simulated battery taking the cobalt oxide and cobalt boron hydrogen storage alloy material of the carbon fiber-containing micron tube obtained in the embodiment 1-3 as the negative active material.
Detailed Description
The invention firstly provides a cobalt oxide and cobalt boron hydrogen storage alloy material containing carbon fiber micron tubes, and the expression is Co2B+x wt％Co3O4+1 wt% of CFMTs, wherein x is more than or equal to 1 and less than or equal to 5.
The invention also provides a preparation method of the cobalt oxide and cobalt boron hydrogen storage alloy material containing the carbon fiber micron tube, which comprises the following steps:
the method comprises the following steps: according to Co2B, weighing Co metal powder and B powder according to a hydrogen storage material component expression, mixing, and then putting into a tube furnace for annealing;
step two: co obtained in the first step2B mechanical crushing to obtain Co2B hydrogen storage material powder;
step three: separately weighing Co3O4Powder and Co obtained in step two2B, putting the hydrogen storage material powder into a ball milling tank for ball milling to obtain a hydrogen storage material containing cobalt oxide, cobalt and boron, wherein the ball material weight ratio is (10-15): 1, ball milling for 10-15 min;
step four: and (3) washing the absorbent cotton with distilled water, drying at 60-80 ℃ for 12-24h, calcining in air at 750-850 ℃ for 1-2h to obtain the carbon fiber-containing micron tube, and grinding the carbon fiber-containing micron tube and the hydrogen storage alloy containing cobalt oxide and cobalt boron obtained in the step three for 10-20 min to obtain the cobalt oxide and cobalt boron hydrogen storage alloy material containing the carbon fiber micron tube.
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.
Mixing the obtained Co2B hydrogen storage alloy is mechanically ground to form Co2B storing hydrogen alloy powder, and sieving Co with sieves of different specifications2B hydrogen occluding alloy powder is divided into different sizes, preferably Co2The size of the hydrogen storage alloy powder B is 200-300 meshes.
According to the invention, the Co obtained as described above is used2B Hydrogen occluding alloy powder and Co3O4Putting the powder into a ball milling tank for ball milling under the atmosphere of high-purity argon, wherein the ball material weight ratio is (10-15): 1, preferably 10:1, ball milling time is 10-15 min, preferably 10min, the ball milling tank is preferably a stainless steel ball milling tank, the diameter of the stainless steel ball milling tank is preferably 4-15 mm, the vibration frequency of the ball milling tank is preferably 200-1000 rpm, the ball milling tank is taken down from a ball mill, and the ball milling tank is opened in a high-purity argon atmosphere glove box to obtain a hydrogen storage material containing cobalt oxide and cobalt boron; said Co3O4And Co2The weight percentage of the hydrogen storage alloy material powder is (1-5 wt%): (99 wt% -95 wt%);
and (3) washing the absorbent cotton with distilled water, drying at 60-80 ℃ for 12-24h, calcining in air at 750-850 ℃ for 1-2h to obtain the carbon fiber-containing micron tube, and grinding the carbon fiber-containing micron tube and the hydrogen storage alloy containing cobalt oxide and cobalt boron obtained in the step three for 10-20 min to obtain the cobalt oxide and cobalt boron hydrogen storage alloy material containing the carbon fiber micron tube. The weight percentage of the carbon fiber micron tube and the hydrogen storage material containing cobalt oxide and cobalt boron is preferably 1 wt%: 99 wt%.
The phase structure of the cobalt oxide and cobalt boron hydrogen storage alloy material of the carbon fiber-containing micron tube 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 to 80 degrees.
The invention relates to a method for testing the electrochemical hydrogen storage performance of cobalt oxide and cobalt boron hydrogen storage materials of carbon fiber-containing microtubes, which 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 cobalt oxide and cobalt boron hydrogen storage alloy material containing the carbon fiber micron tube is used as an active substance in the cathode of a nickel-hydrogen experimental battery, the active substance is uniformly mixed with carbonyl nickel powder which is 5 times of the weight of the carbonyl nickel powder and is used as a current collector, a tablet press is used for cold static pressing to form a circular sheet with the diameter of 10mm to be used as the cathode of the battery, a tab of the cathode adopts a nickel wire with the diameter of 1mm and is connected with a cathode sheet in a pulse spot welding mode, and the anode 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.
Co used in examples3O4Is commercially available and has a purity of 99.9%.
Example 1: the expression of the cobalt oxide and cobalt boron hydrogen storage material of the carbon fiber-containing micron tube is as follows: co2B+1wt％Co3O4+1 wt% CFMTs, the material was prepared as follows:
(1) accurately weighing 9.16g of Co metal (purity 99.9%) and 0.84g of B nonmetal (purity 99.9%), uniformly mixing the weighed powders, placing a quartz boat containing the uniformly mixed powders into a 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) Placing the annealed alloy powder obtained in the step (1) 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 after the time is up, and selecting Co2The size of the hydrogen storage alloy powder B is 200-300 meshes.
(3) Accurately weighing 9.9gCo obtained in the step (2)2B Hydrogen occluding alloy powder and 0.1g Co3O4And putting the mixture into a stainless steel ball-milling tank for ball milling in a glove box filled with high-purity argon atmosphere, 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 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 a hydrogen storage material containing cobalt oxide and cobalt boron, and sealing and storing in a dryer.
(4) And (2) washing absorbent cotton with distilled water, drying for 12h at 60 ℃, calcining for 1h at 800 ℃ in the air to obtain the carbon fiber-containing micron tube, accurately weighing 9.9g of hydrogen storage material containing cobalt oxide and cobalt boron and 0.1g of carbon fiber micron tube obtained in the step (3), and grinding for 10min in an agate mortar to obtain the cobalt oxide and cobalt boron hydrogen storage material containing the carbon fiber micron tube.
The XRD pattern of the carbon fiber-containing micron tube, cobalt oxide and cobalt boron hydrogen storage material 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.
Example 2: the expression of the cobalt oxide and cobalt boron hydrogen storage material of the carbon fiber-containing micron tube is as follows: co2B+3wt％Co3O4+ 1% by weight of CFMTs, the material being prepared as follows
Step (1) and steps (2) and (4) are the same as in example 1;
(3) accurately weighing 9.7g of Co obtained in the step (2)2B Hydrogen occluding alloy powder and 0.3g Co3O4And putting the mixture into a stainless steel ball-milling tank for ball milling in a glove box filled with high-purity argon atmosphere, 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 milling machine, opening the ball milling tank in a glove box in a high-purity argon atmosphere to obtain a hydrogen storage material containing cobalt oxide, cobalt oxide and boron, and sealing and storing in a dryer.
The XRD pattern of the cobalt oxide and cobalt boron hydrogen storage material of the second carbon fiber-containing micron tube 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.
Example 3: the expression of the cobalt oxide and cobalt boron hydrogen storage material of the carbon fiber-containing micron tube is as follows: co2B+5wt％Co3O4+ 1% by weight of CFMTs, the material being prepared as follows
Step (1) and steps (2) and (4) are the same as in example 1;
(3) accurately weighing 9.5g of Co obtained in the step (2)2B Hydrogen occluding alloy powder and 0.5g Co3O4And putting the mixture into a stainless steel ball-milling tank for ball milling in a glove box filled with high-purity argon atmosphere, wherein the diameter of a steel ball is 4mm, and the ball-material ratio is 10: 1, vibration frequency of 200 r/min, ball milling time of 10min, taking off the ball milling tank from the ball mill, and opening the ball milling tank in a glove box in high-purity argon atmosphere to obtain a ballHydrogen storage material containing cobalt oxide, cobalt and boron is sealed and stored in a drier.
The XRD pattern of the cobalt oxide and cobalt boron hydrogen storage material of the carbon fiber-containing micron tube obtained in example 3 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.
Example 4
The cobalt oxide and cobalt boron hydrogen storage materials of the carbon fiber-containing micron tube obtained in the examples 1-3 and the nickel carbonyl 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 as a negative electrode, a tab of the negative electrode adopts a nickel wire with the diameter of 1mm and is connected with a 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 B alloy and the simulated battery taking the cobalt oxide and cobalt boron hydrogen storage material of the carbon fiber-containing micron tube obtained in the embodiment 1-3 as the negative active material are subjected to performance test, and the performance test 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. 2 shows the surface topography of cobalt oxide and cobalt boron alloy (FIG. b) of carbon fiber-containing nanotubes (FIG. a) and carbon fiber-containing nanotubes obtained in example 1, respectively.
FIG. 3 shows a graph of Co2And a relation curve graph of cycle number and discharge capacity of a simulated battery using the B alloy and the cobalt oxide and cobalt boron hydrogen storage materials of the carbon fiber-containing micron tube obtained in the embodiments 1-3 as negative active materials. In the figure, curve 1 represents Co2B, Curve 2 represents Co2B+1wt％Co3O4+1 wt% CFMTs, curve 3 for Co2B+3wt％Co3O4+1 wt% CFMTs, curve 4 for Co2B+5wt％Co3O4+1 wt% CFMTs it can be seen from the figure that the maximum discharge capacity can be achieved with the first electrochemical charge and discharge of the four cells, and the capacity change of the carbon fiber microtube cobalt oxide cobalt boron hydrogen storage material is specifically shown in table 2:
TABLE 2
Table 2 shows the expression of Co2The cycle stability performance data of the simulated battery using the B alloy and the carbon fiber microtubes-containing cobalt oxide and cobalt boron hydrogen storage materials obtained in examples 1-3 as negative active materials are shown in Table 2, and the data are compared with the data obtained by using the alloy containing Co and cobalt boron as the negative active materials2Compared with the cathode of B alloy, the simulated battery taking the cobalt oxide and cobalt boron hydrogen storage material of the carbon fiber-containing micron tube as the cathode active material has excellent high-efficiency discharge performance, and when Co is used as the cathode active material3O4When the content of (b) is 1 wt%, the discharge performance is better than that of other batteries.
Claims (10)
1. The hydrogen storage alloy material containing carbon fiber micron tube and cobalt oxide and cobalt boron is characterized in that the expression is Co2B+xwt％Co3O4+1 wt% of CFMTs, wherein x is more than or equal to 1 and less than or equal to 5.
2. The method for preparing the cobalt oxide and cobalt boron hydrogen storage alloy material containing the carbon fiber micron tube as claimed in claim 1, which is characterized by comprising the following steps:
the method comprises the following steps: according to Co2B, weighing Co metal powder and B powder according to a hydrogen storage material component expression, mixing, and then putting into a tube furnace for annealing;
step two: co obtained in the first step2B mechanical crushing to obtain Co2B hydrogen storage material powder;
step three: separately weighing Co3O4Powder and Co obtained in step two2B storing hydrogenPutting the material powder into a ball milling tank for ball milling to obtain a hydrogen storage alloy material containing cobalt oxide and cobalt boron, wherein the weight ratio of the ball material is (10-15): 1, ball milling for 10-15 min;
step four: and (3) washing the absorbent cotton with distilled water, drying at 60-80 ℃ for 12-24h, calcining in air at 750-850 ℃ for 1-2h to obtain the carbon fiber-containing micron tube, and grinding the carbon fiber-containing micron tube and the hydrogen storage alloy containing cobalt oxide and cobalt boron obtained in the step three for 10-20 min to obtain the cobalt oxide and cobalt boron hydrogen storage alloy material containing the carbon fiber micron tube.
3. The method for preparing the cobalt oxide and cobalt boron hydrogen storage alloy material containing the carbon fiber micron tube according to the claim 2, wherein the first step is specifically as follows: mixing Co metal powder and B powder, placing the mixture into a quartz boat, then placing 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.
4. The method for preparing the cobalt oxide and cobalt boron hydrogen storage alloy material containing carbon fiber micron tubes as claimed in claim 2, wherein the Co is Co2And B, the size of the hydrogen storage material powder is 200-400 meshes.
5. The method for preparing the cobalt oxide and cobalt boron hydrogen storage alloy material containing carbon fiber micron tubes as claimed in claim 2, wherein the Co is Co3O4Powder and Co2The weight percentage of the hydrogen storage material powder B is (1-5 wt%): (99 wt% to 95 wt%).
6. The method for preparing the cobalt oxide and cobalt boron hydrogen storage alloy material containing the carbon fiber micro-tubes according to claim 2, wherein the ball milling tank is a stainless steel ball milling tank.
7. The method for preparing the cobalt oxide and cobalt boron hydrogen storage alloy material containing the carbon fiber microtubes as claimed in claim 2, wherein the diameter of the stainless steel ball milling tank is 4-15 mm.
8. The method for preparing the cobalt oxide and cobalt boron hydrogen storage alloy material containing the carbon fiber microtubes as claimed in claim 2, wherein the vibration frequency of the ball milling tank is 200-1000 rpm.
9. The method for preparing the cobalt oxide and cobalt boron hydrogen storage alloy material containing the carbon fiber micron tube as claimed in claim 2, wherein the weight ratio of the ball material is 10: and 1, ball milling time is 10 min.
10. The method for preparing the cobalt oxide and cobalt boron hydrogen storage alloy material containing the carbon fiber micro-tube according to claim 2, wherein the weight percentage of the carbon fiber micro-tube and the hydrogen storage alloy material containing cobalt oxide and cobalt boron is 1 wt%: 99 wt%.
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