CN108987759A - The application of nickel, cobalt, sulphur, boron codope carbon material in zinc-air battery catalyst - Google Patents
The application of nickel, cobalt, sulphur, boron codope carbon material in zinc-air battery catalyst Download PDFInfo
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- CN108987759A CN108987759A CN201810711430.2A CN201810711430A CN108987759A CN 108987759 A CN108987759 A CN 108987759A CN 201810711430 A CN201810711430 A CN 201810711430A CN 108987759 A CN108987759 A CN 108987759A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
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Abstract
The invention discloses the application of nickel, cobalt, sulphur, boron codope carbon material in zinc-air battery catalyst, belong to zinc-air battery catalyst technical field.Technical solution of the present invention main points are as follows: by the alcoholic solution of the alcoholic solution of cobalt nitrate and 2-methylimidazole mix after in be stored at room temperature reaction synthesis polyhedron ZIF-67 presoma, then by ZIF-67 presoma and nickel source, heating water bath back flow reaction obtains hollow polyhedral nanocages product in alcoholic solvent, then obtained product and sulphur source and boron source are obtained target product by solvent thermal reaction.Catalyst of the invention introduces nickel, and the synergistic effect between different component is made to enhance the catalytic activity of composite material, and the introducing of hetero atom sulphur and boron effectively optimizes the electronic structure of material, improves electrocatalysis characteristic.Catalyst of the invention and preparation method thereof has broad application prospects on zinc-air battery catalyst.
Description
Technical field
The invention belongs to zinc-air battery catalyst technical fields, and in particular to nickel, cobalt, sulphur, boron codope carbon material exist
Application in zinc-air battery catalyst.
Background technique
Zinc-air battery belongs to one kind of metal-air battery, its invention has had the history of upper a century, the battery
It is aoxidized and is produced electricl energy in air by zinc.Because its capacity is big, energy is high, stable operating voltage, long service life, performance are steady
It is fixed, nontoxic, safe and reliable, without hidden peril of explosion, it is resourceful, low in cost many advantages, such as and be acknowledged as very excellent
Elegant energy storage material becomes next-generation most promising new energy battery.
Zinc-air battery is also known as zinc-oxygen battery, is that a kind of oxygen used in activated carbon adsorption air or pure oxygen are living as anode
Property substance, using zinc as cathode, using ammonium chloride or caustic solution as the primary battery of electrolyte, catalyst is to improve zinc-air electricity
The key components of pond efficiency for charge-discharge.MOFs has the characteristics that structure diversity, specific surface area are high, cellular structure is abundant,
Ideal persursor material, gas storage, gas absorption in separation, sensor, catalysis reaction etc. fields have it is important
Using.
Currently, double function that noble metal and alloy such as Pt, Pt-Au and Pt-Pd have been studied and have been developed as metal-air battery
Energy elctro-catalyst, however, since the finite availability of these noble metal-based catalysts and high cost limit it in metal-air
Long-term practical application in battery.Therefore, it develops efficient bifunctional electrocatalyst and then improves the efficiency for charge-discharge ten of battery
Divide necessity；In addition to this, it is very urgent come the cost for reducing zinc-air battery catalyst that noble metal alternative materials are found.
Summary of the invention
The technical problem to be solved by the present invention is to provide a kind of nickel, cobalt, sulphur, boron codope carbon materials in zinc-air battery
Application in catalyst, the nickel, cobalt, sulphur, boron codope carbon material effectively increase zinc-sky as zinc-air battery catalyst
The performance in pneumoelectric pond.
The present invention adopts the following technical scheme that nickel, cobalt, sulphur, boron codope carbon material are in zinc-to solve above-mentioned technical problem
Application in air cell catalyst, it is characterised in that: the nickel, cobalt, sulphur, boron codope carbon material are urged as zinc-air battery
Agent is used to be catalyzed ORR and the OER reaction of zinc-air battery, specific preparation process are as follows:
Step S1；Cobalt nitrate and 2-methylimidazole are dissolved in solvent respectively to being completely dissolved, then after two kinds of solution are mixed in
It is stored at room temperature reaction 18-48h and obtains polyhedron ZIF-67 presoma；
Step S2；By the obtained polyhedron ZIF-67 presoma of step S1 and nickel source compound, heating water bath extremely flows back in a solvent
Reaction 0.5-6h obtains the hollow polyhedral nanocages structured product of surface folding；
Step S3: in the hollow polyhedral nanocages structured product of the surface folding obtained to step S2 be added sulphur source compound and
Boron source compound, in a solvent ultrasonic disperse uniformly after heating water bath obtain the hollow polyhedral of functionalization to back flow reaction 1-6h
The zinc-air battery elctro-catalyst of nanometer basket structure, the average grain diameter of the catalyst are 500nm, shell thickness 20-50nm；
The solvent is methanol, ethyl alcohol, ethylene glycol, glycerine or isopropanol；The nickel source compound be nickel nitrate, nickel chloride,
Nickel sulfate or nickel hydroxide；The sulphur source compound is thioacetamide, vulcanized sodium or thiocarbamide；The boron source compound is boric acid
Sodium or boron oxide.
Further preferably, the mass ratio of nickel source compound described in step S2 and polyhedron ZIF-67 presoma is 1:1-4:
1, the introducing of the nickel source compound is for inducing polyhedron to form the microstructure of inner hollow and surface folding；Institute in step S3
The mass ratio for stating sulphur source compound and polyhedron ZIF-67 presoma is 1:1-4:1；Boron source compound described in step S3 and more
The mass ratio of face body ZIF-67 presoma is 1:1-6:1.
Compared with the prior art, the invention has the following beneficial effects:
1, the present invention has synthesized nickel, cobalt, phosphor codoping carbon material zinc-air electricity of a kind of hollow polyhedral nanocages microstructure
Pond catalyst, which does not need high-temperature calcination, simple and safe, green economy.
2, the hollow polyhedral nanocages material that the present invention synthesizes preferentially introduces metallic nickel, and the stronger coordination ability of nickel makes
Cobalt-based presoma forms the structure of inner hollow and surface folding, effectively expands specific surface area；Secondly doping heteroatom phosphate
With sulphur provide catalytic active site abundant, the optimizing regulation electronic structure of catalyst material is conducive to catalyst performance
It improves.
3, the hollow polyhedral nanocages material that the present invention synthesizes has inner hollow surface folding structure, this fine multiple
Miscellaneous structure feature assigns material high specific surface area, promotes the diffusion of active material and the electrification of accelerator activator material surface
Reaction is learned, the double-function catalyzing activity of catalyst is effectively increased.
Detailed description of the invention
Fig. 1 is the TEM figure that catalyst is made in embodiment 1；
Fig. 2 is the FESEM figure that catalyst is made in embodiment 3；
Fig. 3 is the FESEM figure that catalyst is made in comparative example 1；
Fig. 4 is the ORR polarization curve that catalyst is made in embodiment 1 and comparative example 1, comparative example 2, comparative example 3, comparative example 4；
Fig. 5 is the OER polarization curve that catalyst is made in embodiment 1 and comparative example 1, comparative example 2, comparative example 3, comparative example 4.
Specific embodiment
Above content of the invention is described in further details by the following examples, but this should not be interpreted as to this
The range for inventing above-mentioned theme is only limitted to embodiment below, and all technologies realized based on above content of the present invention belong to this hair
Bright range.
Embodiment 1
Step S1；249mg cobalt nitrate and 328mg 2-methylimidazole are dissolved in 25mL methanol respectively to being completely dissolved, then by nitre
Acidic cobalt solution, which is added in 2-methylimidazole solution, to be formed purple mixed liquor and stands reaction for 24 hours at room temperature, is centrifuged with methanol
Vacuum drying obtains purple powder sample i.e. ZIF-67 presoma afterwards for several times for washing；
Step S2；It disperses the obtained ZIF-67 presoma of 40mg step S1 and 80mg nickel nitrate in 25mL methanol, dispersion is equal
Heating water bath is to back flow reaction 0.5h after even, and with ethyl alcohol centrifuge washing, vacuum drying obtains light green solid powder afterwards for several times；
Step S3: 80mg thioacetamide and 160mg Boratex being added into the light green solid powder that step S2 is obtained,
In 25mL ethyl alcohol ultrasonic disperse uniformly after heating water bath to back flow reaction 1h, cooled to room temperature with ethyl alcohol centrifuge washing for several times
Vacuum drying obtains the zinc-air battery catalyst of the hollow polyhedral nanometer basket structure of the i.e. functionalization of black objects product afterwards,
The average grain diameter of the catalyst be 500nm, shell thickness 20-50nm, as shown in Figure 1.
Electro-chemical test uses three electrode body of Solartron 1287(Solartron Analytical, England) type
The half-cell of system carries out.To be coated with the glass-carbon electrode of catalyst as working electrode, to electrode and reference electrode be respectively carbon-point and
Ag/AgCl saturated calomel electrode, the electrolyte of ORR test are 0.1M KOH solution, and the electrolyte of OER test is that 1M KOH is molten
Liquid.The preparation process of catalyst pulp is as follows: taking 5mg catalyst to be dispersed in 0.5mL ethyl alcohol, adds proton exchange membrane
(Nafion), ultrasonic disperse about 30min takes 25 μ L mixed liquors to be coated in glassy carbon electrode surface, does at room temperature with microsyringe
Can be tested after dry, electric performance test result such as Fig. 4,5, it is shown.
Embodiment 2
Step S1；249mg cobalt nitrate and 328mg 2-methylimidazole are dissolved in 25mL methanol respectively to being completely dissolved, then by nitre
Acidic cobalt solution, which is added in 2-methylimidazole solution, to be formed purple mixed liquor and stands reaction 18h at room temperature, is centrifuged with methanol
Vacuum drying obtains purple powder sample i.e. ZIF-67 presoma afterwards for several times for washing；
Step S2；It disperses the obtained ZIF-67 presoma of 40mg step S1 and 40mg nickel chloride in 25m dehydrated alcohol, disperses
Heating water bath is to back flow reaction 3h after uniformly, and with ethyl alcohol centrifuge washing, vacuum drying obtains light green solid powder afterwards for several times；
Step S3: 40mg vulcanized sodium and 40mg Boratex are added into the light green solid powder that step S2 is obtained, in 25mL second
Uniformly for rear heating water bath to back flow reaction 0.5h, cooled to room temperature is true after for several times with ethyl alcohol centrifuge washing for ultrasonic disperse in alcohol
Sky is dried to obtain the zinc-air battery catalyst of the hollow polyhedral nanometer basket structure of the i.e. functionalization of black objects product.
Electro-chemical test uses three electrode body of Solartron 1287(Solartron Analytical, England) type
The half-cell of system carries out.To be coated with the glass-carbon electrode of catalyst as working electrode, to electrode and reference electrode be respectively carbon-point and
Ag/AgCl saturated calomel electrode, the electrolyte of ORR test are 0.1M KOH solution, and the electrolyte of OER test is that 1M KOH is molten
Liquid.The preparation process of catalyst pulp is as follows: taking 5mg catalyst to be dispersed in 0.5mL ethyl alcohol, adds proton exchange membrane
(Nafion), ultrasonic disperse about 30min takes 25 μ L mixed liquors to be coated in glassy carbon electrode surface, does at room temperature with microsyringe
Can be tested after dry, electric performance test result such as Fig. 4,5, it is shown.
Embodiment 3
Step S1；249mg cobalt nitrate and 328mg 2-methylimidazole are dissolved in 25mL methanol respectively to being completely dissolved, then by nitre
Acidic cobalt solution, which is added in 2-methylimidazole solution, to be formed purple mixed liquor and stands reaction 48h at room temperature, is centrifuged with methanol
Vacuum drying obtains purple powder sample i.e. ZIF-67 presoma afterwards for several times for washing；
Step S2；25m dehydrated alcohol is dispersed by the obtained ZIF-67 presoma of 40mg step S1 and 160mg nickel hydroxide nickel
In, heating water bath is to back flow reaction 6h after being uniformly dispersed, and with ethyl alcohol centrifuge washing, vacuum drying obtains light green solid afterwards for several times
Powder；
Step S3: 150mg thiocarbamide and 240mg boron oxide are added into the light green solid powder that step S2 is obtained, in 25mL second
In alcohol ultrasonic disperse uniformly after heating water bath to back flow reaction 3h, cooled to room temperature with ethyl alcohol centrifuge washing for several times after vacuum
It is dried to obtain the zinc-air battery catalyst of the hollow polyhedral nanometer basket structure of the i.e. functionalization of black objects product, such as Fig. 2 institute
Show.
Electro-chemical test uses three electrode body of Solartron 1287(Solartron Analytical, England) type
The half-cell of system carries out.To be coated with the glass-carbon electrode of catalyst as working electrode, to electrode and reference electrode be respectively carbon-point and
Ag/AgCl saturated calomel electrode, the electrolyte of ORR test are 0.1M KOH solution, and the electrolyte of OER test is that 1M KOH is molten
Liquid.The preparation process of catalyst pulp is as follows: taking 5mg catalyst to be dispersed in 0.5mL ethyl alcohol, adds proton exchange membrane
(Nafion), ultrasonic disperse about 30min takes 25 μ L mixed liquors to be coated in glassy carbon electrode surface, does at room temperature with microsyringe
Can be tested after dry, electric performance test result such as Fig. 4,5, it is shown.
Comparative example 1
Step S1；249mg cobalt nitrate and 328mg 2-methylimidazole are dissolved in 25mL methanol respectively to being completely dissolved, then by nitre
Acidic cobalt solution, which is added in 2-methylimidazole solution, to be formed purple mixed liquor and stands reaction for 24 hours at room temperature, is centrifuged with methanol
Vacuum drying obtains purple powder sample i.e. ZIF-67 presoma afterwards for several times for washing；
Step S2；It disperses the obtained ZIF-67 presoma of 40mg step S1 and 200mg magnesium nitrate in 25m dehydrated alcohol, point
Heating water bath is to back flow reaction 0.5h after dissipating uniformly, and with ethyl alcohol centrifuge washing, vacuum drying obtains solid powder afterwards for several times；
Step S3: 80mg thioacetamide and 160mg Boratex are added in the solid powder obtained to step S2, in 25mL ethyl alcohol
Uniformly rear heating water bath is to back flow reaction 1h for middle ultrasonic disperse, and rear vacuum is dry for several times with ethyl alcohol centrifuge washing for cooled to room temperature
It is dry to obtain that pattern is inhomogenous and the black objects catalyst of surface corrugationless, as shown in Figure 3.
Electro-chemical test uses three electrode body of Solartron 1287(Solartron Analytical, England) type
The half-cell of system carries out.To be coated with the glass-carbon electrode of catalyst as working electrode, to electrode and reference electrode be respectively carbon-point and
Ag/AgCl saturated calomel electrode, the electrolyte of ORR test are 0.1M KOH solution, and the electrolyte of OER test is that 1M KOH is molten
Liquid.The preparation process of catalyst pulp is as follows: taking 5mg catalyst to be dispersed in 0.5mL ethyl alcohol, adds proton exchange membrane
(Nafion), ultrasonic disperse about 30min takes 25 μ L mixed liquors to be coated in glassy carbon electrode surface, does at room temperature with microsyringe
It can be tested after dry, electric performance test result is as shown in Figure 4,5.
Comparative example 2
Step S1；249mg cobalt nitrate and 328mg 2-methylimidazole are dissolved in 25mL methanol respectively to being completely dissolved, then by nitre
Acidic cobalt solution, which is added in 2-methylimidazole solution, to be formed purple mixed liquor and stands reaction for 24 hours at room temperature, is centrifuged with methanol
Vacuum drying obtains purple powder sample i.e. ZIF-67 presoma afterwards for several times for washing；
Step S2；80mg thioacetamide and 160mg Boratex are added in the ZIF-67 presoma obtained to 40mg step S1,
In 25mL ethyl alcohol ultrasonic disperse uniformly after heating water bath to back flow reaction 1h, cooled to room temperature with ethyl alcohol centrifuge washing for several times
Vacuum drying obtains black objects catalyst afterwards.
Electro-chemical test uses three electrode body of Solartron 1287(Solartron Analytical, England) type
The half-cell of system carries out.To be coated with the glass-carbon electrode of catalyst as working electrode, to electrode and reference electrode be respectively carbon-point and
Ag/AgCl saturated calomel electrode, the electrolyte of ORR test are 0.1M KOH solution, and the electrolyte of OER test is that 1M KOH is molten
Liquid.The preparation process of catalyst pulp is as follows: taking 5mg catalyst to be dispersed in 0.5mL ethyl alcohol, adds proton exchange membrane
(Nafion), ultrasonic disperse about 30min takes 25 μ L mixed liquors to be coated in glassy carbon electrode surface, does at room temperature with microsyringe
It can be tested after dry, electric performance test result is as shown in Figure 4,5.
Comparative example 3
Step S1；249mg cobalt nitrate and 328mg 2-methylimidazole are dissolved in 25mL methanol respectively to being completely dissolved, then by nitre
Acidic cobalt solution, which is added in 2-methylimidazole solution, to be formed purple mixed liquor and stands reaction for 24 hours at room temperature, is centrifuged with methanol
Vacuum drying obtains purple powder sample i.e. ZIF-67 presoma afterwards for several times for washing；
Step S2；It disperses the obtained ZIF-67 presoma of 40mg step S1 and 200mg nickel nitrate in 25mL methanol, dispersion is equal
Heating water bath is to back flow reaction 0.5h after even, and with ethyl alcohol centrifuge washing, vacuum drying obtains light green solid powder afterwards for several times；
Step S3: 160mg Boratex, the ultrasonic disperse in 25mL ethyl alcohol are added into the light green solid powder that step S2 is obtained
Heating water bath is to back flow reaction 1h after uniformly, and vacuum drying obtains black to cooled to room temperature ethyl alcohol centrifuge washing afterwards for several times
Final catalyst.
Electro-chemical test uses three electrode body of Solartron 1287(Solartron Analytical, England) type
The half-cell of system carries out.To be coated with the glass-carbon electrode of catalyst as working electrode, to electrode and reference electrode be respectively carbon-point and
Ag/AgCl saturated calomel electrode, the electrolyte of ORR test are 0.1M KOH solution, and the electrolyte of OER test is that 1M KOH is molten
Liquid.The preparation process of catalyst pulp is as follows: taking 5mg catalyst to be dispersed in 0.5mL ethyl alcohol, adds proton exchange membrane
(Nafion), ultrasonic disperse about 30min takes 25 μ L mixed liquors to be coated in glassy carbon electrode surface, does at room temperature with microsyringe
It can be tested after dry, electric performance test result is as shown in Figure 4,5.
Comparative example 4
Step S1；249mg cobalt nitrate and 328mg 2-methylimidazole are dissolved in 25mL methanol respectively to being completely dissolved, then by nitre
Acidic cobalt solution, which is added in 2-methylimidazole solution, to be formed purple mixed liquor and stands reaction for 24 hours at room temperature, is centrifuged with methanol
Vacuum drying obtains purple powder sample i.e. ZIF-67 presoma afterwards for several times for washing；
Step S2；It disperses the obtained ZIF-67 presoma of 40mg step S1 and 200mg nickel nitrate in 25mL methanol, dispersion is equal
Heating water bath is to back flow reaction 0.5h after even, and with ethyl alcohol centrifuge washing, vacuum drying obtains light green solid powder afterwards for several times；
Step S3: 80mg thioacetamide being added into the light green solid powder that step S2 is obtained, ultrasonic in 25mL ethyl alcohol
Heating water bath is to back flow reaction 1h after being uniformly dispersed, and vacuum drying obtains cooled to room temperature ethyl alcohol centrifuge washing afterwards for several times
Black objects catalyst.
Electro-chemical test uses three electrode body of Solartron 1287(Solartron Analytical, England) type
The half-cell of system carries out.To be coated with the glass-carbon electrode of catalyst as working electrode, to electrode and reference electrode be respectively carbon-point and
Ag/AgCl saturated calomel electrode, the electrolyte of ORR test are 0.1M KOH solution, and the electrolyte of OER test is that 1M KOH is molten
Liquid.The preparation process of catalyst pulp is as follows: taking 5mg catalyst to be dispersed in 0.5mL ethyl alcohol, adds proton exchange membrane
(Nafion), ultrasonic disperse about 30min takes 25 μ L mixed liquors to be coated in glassy carbon electrode surface, does at room temperature with microsyringe
It can be tested after dry, electric performance test result is as shown in Figure 4,5.
Nickel obtained by the present invention, cobalt, sulphur, boron codope carbon material zinc-air battery catalyst all have ORR and OER
There is good catalytic activity, integrated embodiment 1 and comparative example 1-4, which can be seen that, introduces nickel since its strong coordination ability makes cobalt
Base presoma forms the structure of inner hollow and surface folding, and catalyst material is made to possess biggish specific surface area, is added certain
The magnesium of amount is while maintaining presoma shape characteristic to be basically unchanged, so that improving catalysis by synergistic effect between different component
The doping of the activity of agent, sulphur and boron enhances the electrical property of catalyst material, and the catalyst is made to be expected to become a kind of with wide
The zinc-air battery catalyst of application prospect.
Embodiment above describes basic principles and main features of the invention and advantage, the technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe originals of the invention
Reason, under the range for not departing from the principle of the invention, various changes and improvements may be made to the invention, these changes and improvements are each fallen within
In the scope of protection of the invention.
Claims (2)
1. the application of nickel, cobalt, sulphur, boron codope carbon material in zinc-air battery catalyst, it is characterised in that: the nickel, cobalt,
Sulphur, boron codope carbon material are used to be catalyzed ORR and the OER reaction of zinc-air battery, tool as zinc-air battery catalyst
Production procedure are as follows:
Step S1；Cobalt nitrate and 2-methylimidazole are dissolved in solvent respectively to being completely dissolved, then after two kinds of solution are mixed in
It is stored at room temperature reaction 18-48h and obtains polyhedron ZIF-67 presoma；
Step S2；By the obtained polyhedron ZIF-67 presoma of step S1 and nickel source compound, heating water bath extremely flows back in a solvent
Reaction 0.5-6h obtains the hollow polyhedral nanocages structured product of surface folding；
Step S3: in the hollow polyhedral nanocages structured product of the surface folding obtained to step S2 be added sulphur source compound and
Boron source compound, in a solvent ultrasonic disperse uniformly after heating water bath obtain the hollow polyhedral of functionalization to back flow reaction 1-6h
The zinc-air battery elctro-catalyst of nanometer basket structure, the average grain diameter of the catalyst are 500nm, shell thickness 20-50nm；
The solvent is methanol, ethyl alcohol, ethylene glycol, glycerine or isopropanol；The nickel source compound be nickel nitrate, nickel chloride,
Nickel sulfate or nickel hydroxide；The sulphur source compound is thioacetamide, vulcanized sodium or thiocarbamide；The boron source compound is boric acid
Sodium or boron oxide.
2. the application of nickel according to claim 1, cobalt, sulphur, boron codope carbon material in zinc-air battery catalyst,
It is characterized by: the mass ratio of nickel source compound described in step S2 and polyhedron ZIF-67 presoma is 1:1-4:1, the nickel source
The introducing of compound is for inducing polyhedron to form the microstructure of inner hollow and surface folding；Sulphur source described in step S3
The mass ratio for closing object and polyhedron ZIF-67 presoma is 1:1-4:1；Boron source compound described in step S3 and polyhedron ZIF-
The mass ratio of 67 presomas is 1:1-6:1.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109559902A (en) * | 2018-11-15 | 2019-04-02 | 江苏鑫美龙新能源科技有限公司 | Derivative cobalt nickel boron sulphide material of a kind of metal organic frame and the preparation method and application thereof |
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| CN110783549B (en) * | 2019-11-07 | 2022-05-31 | 吉林大学 | Polypyrrole-coated sulfur-doped cobalt-based carbon nanocage material, and preparation method and application thereof |
| CN111111721A (en) * | 2020-01-19 | 2020-05-08 | 西北师范大学 | Preparation and application of boron-doped carbon shell-coated CoNi nanoparticle composite material |
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| CN115125578B (en) * | 2022-08-01 | 2023-06-23 | 天津科技大学 | Preparation method of B-S co-doped nickel-cobalt-based electrolytic water oxygen evolution catalyst |
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Application publication date: 20181211 |