CN113097470A - Nitrogen-sulfur-containing co-doped graphene cobalt-copper-silicon hydrogen storage composite material and preparation method thereof - Google Patents

Nitrogen-sulfur-containing co-doped graphene cobalt-copper-silicon hydrogen storage composite material and preparation method thereof Download PDF

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CN113097470A
CN113097470A CN202110329976.3A CN202110329976A CN113097470A CN 113097470 A CN113097470 A CN 113097470A CN 202110329976 A CN202110329976 A CN 202110329976A CN 113097470 A CN113097470 A CN 113097470A
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copper
hydrogen storage
sulfur
nitrogen
cobalt
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刘万强
范文浩
孙岩
刘大勇
赵建勋
刘恒
陈鹏
王清爽
王新伟
王芳
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Changchun University of Science and Technology
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    • 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
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10—Energy storage using batteries
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage

Abstract

The invention provides a cobalt-copper-silicon hydrogen storage composite material containing nitrogen and sulfur Co-doped graphene and a preparation method thereof, belonging to the field of hydrogen storage materials0.9Cu0.1The preparation method of the composite material comprises the steps of putting cobalt powder, copper powder and silicon powder into a ball milling tank according to a certain proportion, performing ball milling to obtain a cobalt-copper-silicon hydrogen storage alloy, preparing nitrogen-sulfur co-doped graphene by a hydrothermal method, grinding the nitrogen-sulfur co-doped graphene and the obtained cobalt-copper-silicon hydrogen storage alloy to obtain the nitrogen-sulfur co-doped graphene-containing cobalt-copper-silicon hydrogen storage composite material, wherein the x is more than or equal to 3 and less than or equal to 10, and the experimental result proves that: the discharge capacity of the nitrogen and sulfur co-doped graphene-containing cobalt-copper-silicon hydrogen storage composite material is higher than that of a cobalt-copper-silicon hydrogen storage alloy, and after 50 cycles, the capacity attenuation rate of the nitrogen and sulfur co-doped graphene-containing cobalt-copper-silicon hydrogen storage composite material is lower than that of the cobalt-copper-silicon hydrogen storage alloy.

Description

Nitrogen-sulfur-containing co-doped graphene cobalt-copper-silicon hydrogen storage composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of hydrogen storage materials, and particularly relates to a nitrogen and sulfur co-doped graphene cobalt-copper-silicon hydrogen storage composite material and a preparation method thereof.
Background
In order to improve the market competitiveness of the nickel-metal hydride battery and improve the cycle life and the discharge capacity of the nickel-metal hydride battery, the hydrogen storage alloy is used as a negative electrode material of the nickel-metal hydride battery, and the hydrogen storage alloy is a key factor for restricting the performance of the 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.
In recent years, cobalt-based alloys such as Co-B, Co-S, Co-Si, cobalt nanocomposites and the like have received extensive attention and intensive research. Zhang et al studied Co-Si alloys prepared by homogeneous mixing. When the mass ratio of Si to Co is 1: 4, the alloy electrode shows the best electrochemical hydrogen storage performance, CmaxMore than 400 mAh/g. Wang et al prepared C by chemical reductionThe discharge capacity of the chain Co-B nano material reaches 325 mAh/g. A series of novel Co-S-B materials are prepared by a simple chemical reduction method. Co75.4B17S7.6After 60 cycles at a current density of 513.6mAh/g, the discharge capacity remained at 100 mAh/g. The Co-S-B electrode also exhibited excellent cycling stability. In addition, by reducing NiCl2·6H2O and CoCl2·6H2Preparing the Co-Ni-B ternary alloy by using the O solution. The alloy shows excellent electrochemical performance in the temperature range of 243K-323K. Yuan et al investigated the effects of synthetic methods and component ratios on Co-Si particle structure and electrochemical performance. In addition, the maximum discharge capacity of the Co-S alloy is 350mAh/g, and the capacity retention rate after 100 cycles is 86%. Cao et al prepared ultrafine particles of Co-P with excellent electrochemical hydrogen storage capacity and long cycle life. He et al also describe the electrochemical properties of Co-Si alloys. The maximum discharge capacity of the alloy prepared by the arc method is 245 mAh/g. Therefore, most cobalt-based alloys have a large capacity hydrogen storage property.
Graphene has high conductivity and electrocatalysis capability, can improve high-rate discharge and electrochemical reaction rate, has a high specific surface area, can provide more active sites, can effectively improve the discharge capability and electrochemical performance of the hydrogen storage alloy by adding the graphene into the hydrogen storage material, and is disclosed in table 1 in representative patents disclosed by the Chinese patent office.
TABLE 1
Figure BDA0002995816230000011
Figure BDA0002995816230000021
To sum up: the cobalt-copper-silicon hydrogen storage alloy is synthesized by a mechanical alloying mode, the cobalt-copper-silicon hydrogen storage alloy is taken as a base, nitrogen and sulfur are added to codope graphene, and the obtained nitrogen and sulfur codope graphene-containing cobalt-copper-silicon hydrogen storage composite material and the manufacturing method thereof are not disclosed in patent publications and article reports.
Disclosure of Invention
The invention aims to provide a nitrogen and sulfur co-doped graphene-containing cobalt-copper-silicon hydrogen storage composite material and a preparation method thereof.
The invention firstly provides a nitrogen and sulfur co-doped graphene-containing cobalt-copper-silicon hydrogen storage composite material, which has the expression: co0.9Cu0.1Si+x wt％NSG，3≤x≤10。
The invention also provides a nitrogen and sulfur co-doped graphene-containing cobalt-copper-silicon hydrogen storage composite material and a preparation method thereof, wherein the preparation method comprises the following steps:
the method comprises the following steps: respectively weighing cobalt powder, copper powder and silicon powder according to stoichiometric ratio, putting the cobalt powder, the copper powder and the silicon powder into a ball milling tank under the atmosphere of high-purity argon, and sieving the powder after ball milling to obtain the cobalt-copper-silicon hydrogen storage alloy with the chemical formula of Co0.9Cu0.1Si；
Step two: ultrasonically dispersing 70mg of graphene oxide in 30mL of deionized water to obtain a graphene oxide suspension, then adding thiourea, ultrasonically treating for 1-2 h, transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining, reacting for 10-12 h at 160-180 ℃, performing a hydrothermal reaction, performing suction filtration, and drying in an oven to obtain nitrogen and sulfur co-doped graphene with a chemical formula of NSG;
step three: and grinding the nitrogen-sulfur co-doped graphene and the cobalt-copper-silicon hydrogen storage alloy for 5-10 min according to the proportion to obtain the nitrogen-sulfur co-doped graphene-containing cobalt-copper-silicon hydrogen storage composite material.
Preferably, the size of the cobalt-copper-silicon hydrogen storage alloy in the first step is 300 meshes after being sieved. The preferred powder size allows for more pure ball-milled cobalt copper silicon hydrogen storage alloys.
Preferably, the ball milling tank in the step one is a stainless steel ball milling tank, the vibration frequency is 300r/min, and the ball milling time is 6 h. The preferred stainless steel ball milling jar can reduce the loss of raw materials, and the preferred vibration frequency and ball milling time can make the hydrogen storage alloy ball milling more uniform.
Preferably, the mass ratio of the ball material in the step one is 8: 1, the diameter of the ball is 4-15 mm. The preferred ball-to-material ratio is that different sizes of stainless steel balls enable the hydrogen storage alloy to be ball milled more uniformly.
Preferably, the mass ratio of the thiourea to the graphene oxide in the second step is 20: 1. the preferred material ratio can make the purity of nitrogen sulphur codope graphite alkene better.
Preferably, the hydrothermal reaction temperature in the second step is 180 ℃ and the time is 12 h. The drying temperature is 60 ℃ and the time is 24 h. The preferred heating temperature and time enable the reaction to be more complete and the resulting product to be purer.
Preferably, the grinding time of the nitrogen and sulfur co-doped graphene and the cobalt-copper-silicon hydrogen storage alloy in the third step is 8min, and the preferable grinding time can not only successfully dope the nitrogen and sulfur co-doped graphene into the hydrogen storage alloy, but also can ensure that the structure of the hydrogen storage alloy is not damaged.
Preferably, the nitrogen and sulfur co-doped graphene and cobalt-copper-silicon hydrogen storage alloy in the third step has a weight percentage (3 wt% -10 wt%): (97 wt% to 90 wt%). The preferred material ratio can improve the performance of the hydrogen storage alloy better.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the cobalt-copper-silicon hydrogen storage composite material containing nitrogen-sulfur co-doped graphene, the nitrogen-sulfur co-doped graphene enters the cobalt-copper-silicon hydrogen storage alloy in a doping manner, so that the conductivity and corrosion resistance of the hydrogen storage alloy can be enhanced, and the catalytic activity, discharge capacity and service life of a battery cathode are improved under the combined action of the two substances;
(2) according to the nitrogen and sulfur co-doped graphene-containing cobalt-copper-silicon hydrogen storage composite material, the cobalt-copper-silicon hydrogen storage alloy is prepared by a mechanical alloying method, the ball milling process can be controlled by controlling the rotating speed, the ball material ratio and the size of balls, the nitrogen and sulfur co-doped graphene is prepared by a hydrothermal method, and the nitrogen and sulfur co-doped graphene is successfully added into the cobalt-copper-silicon hydrogen storage composite material by a grinding method on the premise of ensuring that the structure of the cobalt-copper-silicon hydrogen storage alloy is not damaged.
Drawings
FIG. 1 is an XRD (X-ray diffraction) diagram of a cobalt-copper-silicon hydrogen storage alloy and the nitrogen and sulfur-containing co-doped graphene obtained in examples 1 to 4;
fig. 2 is a scanning electron microscope image of a cobalt copper silicon hydrogen storage alloy (a), nitrogen and sulfur co-doped graphene (b), and a nitrogen and sulfur co-doped graphene-containing cobalt copper silicon hydrogen storage composite material (c) obtained in example 2;
fig. 3 is a graph showing the relationship between cycle number and discharge capacity of a simulated battery using a cobalt-copper-silicon hydrogen storage alloy and the nitrogen-and-sulfur-doped graphene-containing cobalt-copper-silicon hydrogen storage composite material obtained in examples 1 to 4 as a negative electrode active material.
Detailed Description
The invention firstly provides a nitrogen and sulfur co-doped graphene-containing cobalt-copper-silicon hydrogen storage composite material, which has the expression: co0.9Cu0.1Si+x wt％NSG，3≤x≤10。
The invention also provides a nitrogen and sulfur co-doped graphene-containing cobalt-copper-silicon hydrogen storage composite material and a preparation method thereof, and the preparation method comprises the following steps:
the method comprises the following steps: respectively weighing cobalt powder, copper powder and silicon powder according to stoichiometric ratio, putting the cobalt powder, the copper powder and the silicon powder into a ball milling tank under the atmosphere of high-purity argon, and sieving the powder after ball milling to obtain the cobalt-copper-silicon hydrogen storage alloy with the chemical formula of Co0.9Cu0.1Si；
Step two: ultrasonically dispersing 70mg of graphene oxide in 30mL of deionized water to obtain a graphene oxide suspension, then adding thiourea, ultrasonically treating for 1-2 h, transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining, reacting for 10-12 h at 160-180 ℃, performing a hydrothermal reaction, performing suction filtration, and drying in an oven to obtain nitrogen and sulfur co-doped graphene with a chemical formula of NSG;
step three: and grinding the nitrogen-sulfur co-doped graphene and the cobalt-copper-silicon hydrogen storage alloy for 5-10 min according to the proportion to obtain the nitrogen-sulfur co-doped graphene-containing cobalt-copper-silicon hydrogen storage composite material.
The phase structure of the nitrogen and sulfur co-doped graphene-containing cobalt-copper-silicon hydrogen storage composite material is characterized by an X-ray diffraction method (XRD), and a copper target (Cu-Ka,
Figure BDA0002995816230000031
) The tube current is 40mA, the tube voltage is 40kV, the scanning speed is 5-10 DEG/min, the scanning range 2 theta is 10-80 degrees, and the scanning step length is 0.02 degree.
The electrochemical hydrogen storage performance of the cobalt-copper-silicon hydrogen storage composite material containing nitrogen and sulfur co-doped graphene is tested on line by adopting a LAND battery side test system and a computer, and the test process is carried out in a simulation nickel-metal hydride experimental battery.
For further understanding of the present invention, the present invention will be described in further detail with reference to examples, of which example 2 is the most preferred example.
Example 1: an expression formula of the nitrogen and sulfur co-doped graphene cobalt-copper-silicon hydrogen storage composite material is as follows: co0.9Cu0.1Si +3 wt% NSG. The preparation method of the material comprises the following steps:
(1) accurately weighing 3.18g of cobalt powder, 0.38g of copper powder and 1.70g of silicon powder, and putting the cobalt powder, the 0.38g of copper powder and the 1.70g of silicon powder into a ball milling tank for ball milling in a high-purity argon atmosphere, wherein the weight ratio of ball materials is 8: 1, ball milling time is 6 hours, ball milling is stopped for half an hour every 1 hour, the vibration frequency of a ball milling tank is 300r/min, and alloy powder is ground and sieved by a mortar for 300 meshes.
(2) Dissolving 70mg of graphene oxide in 30ml of deionized water, and performing ultrasonic treatment for 1h to obtain a graphene oxide suspension, wherein the weight ratio of thiourea to graphene oxide is 20: 1.4g of thiourea is added according to the mass ratio of 1, ultrasonic treatment is carried out for 2 hours, the mixed solution is transferred into a reaction kettle with a polytetrafluoroethylene lining, heating is carried out for 12 hours at 180 ℃, black substances are obtained through suction filtration, and the black substances are placed into a 60 ℃ oven for 24 hours, so that the nitrogen and sulfur co-doped graphene can be obtained.
(3) Respectively weighing 0.2g of cobalt-copper-silicon hydrogen storage alloy powder and 0.006g of nitrogen-sulfur co-doped graphene powder, and grinding in an agate mortar for 8min to obtain the nitrogen-sulfur co-doped graphene-containing cobalt-copper-silicon hydrogen storage composite material.
Example 2: an expression formula of the nitrogen and sulfur co-doped graphene cobalt-copper-silicon hydrogen storage composite material is as follows: co0.9Cu0.1Si +5 wt% NSG. The preparation method of the material comprises the following steps:
the steps (1) and (2) are the same as in example 1;
(3) respectively weighing 0.2g of cobalt-copper-silicon hydrogen storage alloy powder and 0.01g of nitrogen-sulfur co-doped graphene powder, and grinding in an agate mortar for 8min to obtain the nitrogen-sulfur co-doped graphene-containing cobalt-copper-silicon hydrogen storage composite material.
Example 3: an expression formula of the nitrogen and sulfur co-doped graphene cobalt-copper-silicon hydrogen storage composite material is as follows: co0.9Cu0.1Si +7 wt% NSG. The preparation method of the material comprises the following steps:
the steps (1) and (2) are the same as in example 1;
(3) respectively weighing 0.2g of cobalt-copper-silicon hydrogen storage alloy powder and 0.014g of nitrogen-sulfur co-doped graphene powder, and grinding in an agate mortar for 8min to obtain the nitrogen-sulfur co-doped graphene-containing cobalt-copper-silicon hydrogen storage composite material.
Example 4: an expression formula of the nitrogen and sulfur co-doped graphene cobalt-copper-silicon hydrogen storage composite material is as follows: co0.9Cu0.1Si +10 wt% NSG. The preparation method of the material comprises the following steps:
the steps (1) and (2) are the same as in example 1;
(3) respectively weighing 0.2g of cobalt-copper-silicon hydrogen storage alloy powder and 0.02g of nitrogen-sulfur co-doped graphene powder, and grinding in an agate mortar for 8min to obtain the nitrogen-sulfur co-doped graphene-containing cobalt-copper-silicon hydrogen storage composite material.
Example 5
The nitrogen and sulfur co-doped graphene-containing cobalt-copper-silicon hydrogen storage composite material obtained in the embodiment 1-4 and carbonyl nickel powder are respectively and uniformly mixed according to the weight ratio of 1: 5, the mixture is poured into a mold after being uniformly ground in an agate crucible, the powder is pressed into a circular alloy electrode plate with the diameter of about 10mm by a manual powder pressing machine under the pressure of 8MPa, a nickel plate is spot-welded on the alloy plate by a spot welding machine to be used as a tab, the alloy electrode plate is clamped by two pieces of foamed nickel, the alloy electrode plate is compacted under the pressure of 20MPa, and the foamed nickel is sealed by the spot welding machine. The positive electrode adopts sintered NiOOH/Ni (OH)2The anode plate is cut into two rectangular anode plates with the capacity far larger than that of the cathode plate by a pair of scissors, and a nickel plate is connected with the two anode plates by a spot welding machine. The battery comprises a hydrogen storage alloy negative plate, NiOOH/Ni (OH)2A positive plate, an Hg/HgO reference electrode, a commercial polyethylene sulfonated diaphragm and 6mol/L KOH water-soluble electrolyteThe liquid and battery jar is a 80mL plastic bottle. And wrapping the alloy negative plate by using a diaphragm, fixing the alloy negative plate in the middle by using two positive plates with enough sizes, winding, binding and fixing the two positive plates by using a nickel wire, putting the two positive plates into a battery jar, injecting enough KOH electrolyte, and standing for a period of time.
The performance test of the simulated battery using the cobalt-copper-silicon hydrogen storage alloy and the nitrogen and sulfur co-doped graphene-containing cobalt-copper-silicon hydrogen storage composite material obtained in the embodiment 1-4 as the negative active material is specifically as follows:
the lifting rate calculation formula is as follows: the capacity increase rate [ ("discharge capacity of cobalt-containing copper-silicon hydrogen storage alloy" - "discharge capacity of blank cell for comparison" -/") discharge capacity of 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. 3 is a graph showing the relationship between cycle number and discharge capacity of a simulated battery using a cobalt-copper-silicon hydrogen storage alloy and the nitrogen-and-sulfur-doped graphene-containing cobalt-copper-silicon hydrogen storage composite material obtained in examples 1 to 4 as a negative electrode active material. In the figure, curve 1 represents Co0.9Cu0.1Si, Curve 2 represents Co0.9Cu0.1Si +3 wt% NSG, Curve 3 represents Co0.9Cu0.1Si +5 wt% NSG, Curve 4 represents Co0.9Cu0.1Si +7 wt% NSG, Curve 5 represents Co0.9Cu0.1From the figure, it can be seen that the maximum discharge capacity can be achieved by the first electrochemical charge and discharge of five batteries, and the capacity change of the cobalt-copper-silicon hydrogen storage composite material containing nitrogen and sulfur co-doped graphene is specifically shown in table 2:
TABLE 2
Figure BDA0002995816230000051
Table 2 shows cycle stability performance data of a simulated battery using a cobalt copper silicon hydrogen storage alloy and the nitrogen and sulfur co-doped graphene-containing cobalt copper silicon hydrogen storage composite material as a negative active material obtained in examples 1 to 4, and as can be seen from table 2, compared with a negative electrode containing a cobalt copper silicon hydrogen storage alloy, the simulated battery using the nitrogen and sulfur co-doped graphene-containing cobalt copper silicon hydrogen storage composite material as a negative active material has excellent high-efficiency discharge performance, and when the content of doped NSG is 5 wt%, the maximum discharge capacity of the simulated battery reaches 580.1mAh/g, the capacity increase rate is 38.4%, the capacity decay rate is 35.9%, and the discharge performance is better compared with other batteries.

Claims (10)

1. The cobalt-copper-silicon hydrogen storage composite material containing nitrogen and sulfur co-doped graphene is characterized by comprising the following expression: co0.9Cu0.1Si + x wt% of NSG, wherein x is more than or equal to 3 and less than or equal to 10.
2. The preparation method of the nitrogen and sulfur co-doped graphene-containing cobalt-copper-silicon hydrogen storage composite material according to claim 1, wherein the preparation method comprises the following steps:
the method comprises the following steps: respectively weighing cobalt powder, copper powder and silicon powder according to stoichiometric ratio, putting the cobalt powder, the copper powder and the silicon powder into a ball milling tank under the atmosphere of high-purity argon, and sieving the powder after ball milling to obtain the cobalt-copper-silicon hydrogen storage alloy with the chemical formula of Co0.9Cu0.1Si；
Step two: ultrasonically dispersing 70mg of graphene oxide in 30mL of deionized water to obtain a graphene oxide suspension, then adding thiourea, ultrasonically treating for 1-2 h, transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining, reacting for 10-12 h at 160-180 ℃, performing a hydrothermal reaction, performing suction filtration, and drying in an oven to obtain nitrogen and sulfur co-doped graphene with a chemical formula of NSG;
step three: and grinding the nitrogen-sulfur co-doped graphene and the cobalt-copper-silicon hydrogen storage alloy for 5-10 min according to the proportion to obtain the nitrogen-sulfur co-doped graphene-containing cobalt-copper-silicon hydrogen storage composite material.
3. The preparation method of the nitrogen and sulfur co-doped graphene-containing cobalt-copper-silicon hydrogen storage composite material according to claim 2, wherein the cobalt-copper-silicon hydrogen storage alloy obtained in the step one is sieved to have a size of 300 meshes.
4. The preparation method of the nitrogen and sulfur co-doped graphene-containing cobalt-copper-silicon hydrogen storage composite material according to claim 2, wherein the ball milling tank in the first step is a stainless steel ball milling tank, the vibration frequency of the ball milling tank is 300r/min, and the ball milling time is 6 hours.
5. The preparation method of the nitrogen and sulfur co-doped graphene cobalt copper silicon hydrogen storage composite material according to claim 2, wherein the mass ratio of the ball material in the step one is 8: 1, the diameter of the ball is 4-15 mm.
6. The preparation method of the nitrogen and sulfur co-doped graphene-containing cobalt-copper-silicon hydrogen storage composite material according to claim 2, wherein the mass ratio of thiourea to graphene oxide in the second step is 20: 1.
7. the preparation method of the nitrogen and sulfur co-doped graphene-containing cobalt-copper-silicon hydrogen storage composite material according to claim 2, wherein the hydrothermal reaction temperature in the second step is 180 ℃ and the time is 12 hours.
8. The preparation method of the nitrogen and sulfur co-doped graphene-containing cobalt-copper-silicon hydrogen storage composite material according to claim 2, wherein the drying temperature in the second step is 60 ℃ and the drying time is 24 hours.
9. The preparation method of the nitrogen and sulfur co-doped graphene-containing cobalt-copper-silicon hydrogen storage composite material according to claim 2, wherein the grinding time of the nitrogen and sulfur co-doped graphene and cobalt-copper-silicon hydrogen storage alloy in the step three is 8 min.
10. The preparation method of the nitrogen and sulfur co-doped graphene-containing cobalt-copper-silicon hydrogen storage composite material according to claim 2, wherein the nitrogen and sulfur co-doped graphene and cobalt-copper-silicon hydrogen storage alloy in the third step has a weight percentage of (3 wt% -10 wt%): (97 wt% to 90 wt%).
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