CN113013425B - Difunctional anion-doped MPS 3 Catalyst, preparation method and application thereof - Google Patents
Difunctional anion-doped MPS 3 Catalyst, preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a difunctional anion-doped MPS 3 The catalyst is mainly used for an alkaline medium oxygen precipitation reaction and an oxygen reduction reaction, and belongs to the technical field of zinc-air batteries. The invention firstly obtains a blocky catalyst precursor through solid-phase reaction, then strips the blocky catalyst precursor into a flake catalyst through an ultrasonic-assisted stripping method, and finally obtains two-dimensional flake anion-doped MPS 3 A catalyst. Since the doping element Se has a stronger metal than S, doping Se into MPS 3 The conductivity of the catalyst can be improved and the catalytic activity can be improved. Experiments prove that the introduction of the anion Se enables the prepared catalyst to have more active sites and higher conductivity compared with the undoped catalyst, thereby showing better catalytic activity and stability. The anion doping strategy provided by the invention provides an effective way for preparing the non-noble metal catalyst of the zinc air battery with high catalytic activity.
Description
Technical Field
The invention relates to a difunctional anion-doped MPS 3 The catalyst is mainly used for an alkaline medium oxygen precipitation reaction and an oxygen reduction reaction, and belongs to the technical field of zinc-air batteries.
Background
The zinc-air battery has higher theoretical specific energy density (1084 Wh kg) -1 ) Further, since the zinc-air battery has high safety by using an electrolyte whose aqueous system is not flammable and also has a rich zinc ore resource, it is a promising and attractive technology for the next-generation portable devices. In addition, the zinc-air battery has the advantages of low cost, low balance potential, mild discharge, long service life and good environmental protection, further effectively ensures the vigorous development of the zinc-air battery, and meets the huge energy market demand. However, the performance of zinc-air cells is still subject to slow Oxygen Evolution Reactions (OERs) at the air electrode and due to the lack of an effective bifunctional catalystInhibition of Oxygen Reduction Reaction (ORR). At present, catalysts used by zinc-air batteries are mainly noble metal catalysts such as Pt, but the catalysts are expensive and lack resources, so that the development and application of the catalysts are limited. Therefore, the search for alternative non-noble metal catalytic systems has become an important task for the research of zinc air cells.
In recent years, MPS 3 The catalyst has the advantages of rich source, various components, good catalytic activity and stability and the like, and has good application prospect in the field of catalysis. Compared with bulk materials, their two-dimensional plate catalysts have higher specific surface area and more effective edge structure, and are easily functionalized, thus being more favorable for catalyzing reactions. However, during the process of peeling the bulk material to obtain the lamellar catalyst, the nanosheets tend to be absorbed by many surfactants, causing contamination. Further, MPS 3 The crystal is a semiconductor, and the inherent low conductivity of the crystal causes the slow catalytic reaction speed and the relatively high Tafel slope, so that the catalytic efficiency is not high. In response to the above problems, there is a literature report on MPS 3 The number of active sites of the catalyst is improved or they are combined with conductive carbon groups to enhance their conductivity and thus their HER or OER electrocatalytic activity. However, MPS 3 Very few reports of catalysts in zinc-air batteries have been made, since the selective synthesis of multifunctional and highly active MPS 3 Catalysts still face significant challenges. Anion doping has been reported to alter the electronic structure and optimize hydrogen adsorption energy, e.g., researchers have prepared Se-doped MoS based on anion-doped transition metal disulfides 2 And WS 2(1-x) Se 2x Equal catalyst and obtain pure MoS 2 And WS 2 High catalytic activity, which indicates that anion doping is an effective way to increase the catalyst activity.
Disclosure of Invention
The invention aims to provide the difunctional anion-doped MPS with high catalytic activity, good stability and low cost 3 Catalyst to solve the MPS existing in the prior art 3 The problem that the electrocatalytic activity of the catalyst HER and OER is not high is to prepare the catalyst with high catalytic activityNon-noble metal catalysts for zinc air cells provide an effective approach.
Secondly, the present invention provides a bifunctional anion-doped MPS 3 A method for preparing the catalyst.
Thirdly, the invention provides a dual-function anion-doped MPS 3 The application of the catalyst in preparing zinc-air batteries.
Finally, the present invention provides a method for doping MPS using the above-mentioned bifunctional anion 3 A zinc-air cell with a catalyst.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
difunctional anion-doped MPS 3 A catalyst having the formula MPS 3-x Se x Wherein x is more than 0 and less than 2,M is selected from one or more of transition metals of iron (Fe), cobalt (Co), nickel (Ni), manganese (Mn) and chromium (Cr), P is phosphorus, S is sulfur, and Se is selenium.
As a preferred embodiment, the catalyst is in a lamellar (e.g. sheet-like) structure with a thickness of 1-10nm; preferably, the thickness is 1-5nm.
As a preferred embodiment, said catalyst MPS 3-x Se x In the formula, x is more than or equal to 0.1 and less than or equal to 1.5; preferably, 0.5. Ltoreq. X.ltoreq.1.5. More preferably, the catalyst is NiPS 2.9 Se 0.1 、NiPS 2.7 Se 0.3 、NiPS 2.5 Se 0.5 、FePS 1.5 Se 1.5 、CoPS 2 Se 1 、 MnPS 2 Se 1 、CrPS 2.5 Se 0.5 . Further preferably, the catalyst is NiPS 2.7 Se 0.3 。
Bifunctional anion-doped MPS of the present invention 3 The catalyst is mainly used in an alkaline medium oxygen precipitation reaction and an oxygen reduction reaction, and the doped catalyst has more active sites and higher conductivity compared with the undoped catalyst by introducing anions (Se), so that the catalyst shows better catalytic activity and stability and can be used for preparing a zinc-air battery.
As a preferred embodiment, the catalystReagent MPS 3-x Se x The preparation method comprises the following steps: mixing transition metal powder, phosphorus powder, sulfur powder and dopant powder (selenium powder), reacting at 600-900 ℃, and then washing to obtain a catalyst precursor; stripping the catalyst precursor into lamellar form to obtain the bifunctional anion-doped MPS 3 A catalyst.
In the preparation method, the molar ratio of the raw materials is as follows: transition metal powder: phosphorus powder: (sulfur powder + dopant powder) =1:1:3, wherein the proportion of the sulfur powder and the dopant powder is adjustable, and the total molar quantity of the sulfur powder and the dopant powder is 3. During preparation, the raw materials are put into a reaction vessel and vacuumized, then the reaction is carried out for 4 to 8 days at the temperature of 600 to 900 ℃, and after the reaction is finished, the reaction vessel is cooled and washed by carbon disulfide to obtain the catalyst precursor. Adding a stripping agent (such as absolute ethyl alcohol) into the catalyst precursor, stripping by adopting an ultrasonic-assisted mode, centrifuging at low rotation speed (2000-4000 rpm) and high rotation speed (8000-12000 rpm) in sequence after stripping, removing the un-stripped material and the stripping agent, and drying to obtain the lamellar bifunctional anion-doped MPS 3 A catalyst.
Difunctional anion-doped MPS 3 The preparation method of the catalyst comprises the following steps:
(1) Mixing transition metal powder, phosphorus powder, sulfur powder and dopant powder, reacting at 600-900 ℃, and then washing to obtain a catalyst precursor;
(2) Stripping the catalyst precursor into lamellar form to obtain the bifunctional anion-doped MPS 3 A catalyst.
In a preferred embodiment, in step (1), the molar ratio of each raw material is: transition metal powder: phosphorus powder: (sulfur powder + dopant powder) =1:1:3, wherein the proportion of the sulfur powder and the dopant powder is adjustable, and the total molar quantity of the sulfur powder and the dopant powder is 3.
As a preferred embodiment, in the step (1), the dopant powder is Se powder.
As a preferred embodiment, in the step (1), the reaction time is 4 to 8 days. Preferably, the reaction is carried out at 750 ℃ for 6 days.
As a preferred embodiment, in step (1), the reaction is carried out under vacuum. For example, transition metal powder, phosphorus powder, sulfur powder, and dopant powder are charged into a reaction vessel (e.g., a quartz ampoule), evacuated, and then placed in a muffle furnace for heating at a heating rate of 0.5-5 deg.C/min. Preferably, the heating rate is 1 deg.C/min.
As a preferred embodiment, in step (1), after the reaction is completed, the reaction mixture is naturally cooled to room temperature, and then the solid powder obtained by the reaction is washed with carbon disulfide to obtain a (black) bulk material, i.e., a catalyst precursor.
As a preferred embodiment, in step (2), a stripping agent is added into the catalyst precursor, and stripping is carried out in an ultrasonic-assisted manner, wherein the power of ultrasonic-assisted stripping is 100-150W, the frequency is 20-50kHz, and the time is 24-96 hours. Preferably, the stripping agent is absolute ethyl alcohol, the power of ultrasonic treatment is 100W, the frequency is 50kHz, and the time is 48 hours.
As a preferred embodiment, in step (2), after the catalyst precursor is stripped in an ultrasonic-assisted manner, the catalyst precursor is centrifuged at a first rotation speed to remove residual bulk material, and then centrifuged at a second rotation speed to separate and remove liquid, so as to obtain a wet solid powder. Preferably, the first rotation speed is 2000-4000rpm and the second rotation speed is 8000-12000rpm. Still further preferably, the first rotation speed is 3000rpm and the second rotation speed is 10000rpm. Thereafter, the moist solid powder was dispersed in water and freeze-dried to obtain a lamellar (or flake) catalyst.
As a preferred embodiment, the bifunctional anion-doped MPS 3 The preparation method of the catalyst comprises the following steps:
(1) Anion doped MPS 3 Preparation of the material: mixing transition metal powder, phosphorus powder, sulfur powder and dopant powder, reacting for 4-8 days at 600-900 ℃ under a vacuum condition, cooling, and washing with carbon disulfide to obtain a catalyst precursor;
(2) Two-dimensional plate anion doped MPS 3 Preparation of the catalyst: adding absolute ethyl alcohol into the catalyst precursor as a stripping agent, and stripping by adopting an ultrasonic-assisted modeSeparating, centrifuging to remove non-peeled material and peeling agent, and drying to obtain lamellar bifunctional anion doped MPS 3 A catalyst.
The invention firstly obtains a blocky catalyst precursor through solid-phase reaction, then strips the blocky catalyst precursor into a flake catalyst through an ultrasonic-assisted stripping method, and finally obtains two-dimensional flake anion-doped MPS 3 A catalyst.
Difunctional anion-doped MPS 3 The application of the catalyst in preparing zinc-air batteries. Preferably, in the preparation of solid-state zinc-air batteries.
A zinc-air battery comprising the above bifunctional anion-doped MPS 3 A catalyst.
In a preferred embodiment, the zinc-air battery is a solid-state battery, and an alkaline electrolyte is used. The solid zinc-air battery is assembled in a layer-by-layer overlapping manner. Specifically, a zinc foil and a carbon cloth covered with a catalyst were placed on both sides of the gel film, and then wrapped with an aluminum foil.
The invention has the beneficial effects that:
the invention provides a difunctional anion doped transition Metal Phosphorus Sulfur (MPS) 3 ) The catalyst is mainly used for alkaline medium oxygen precipitation reaction and oxygen reduction reaction, and can be used for (solid state) zinc-air batteries.
The improved object of the present invention is MPS 3 Catalyst, MPS 3 The crystal is a semiconductor, the inherent low conductivity of the crystal causes the speed of catalytic reaction to be slow, and the Tafel slope is relatively high, so that the catalytic efficiency is not high. Se has stronger metal than S, and Se atoms are doped into MPS 3 The conductivity of the compound in the framework of the compound can be improved, and the electrocatalytic activity is improved.
The invention provides a bifunctional anion-doped MPS 3 The preparation method of the catalyst comprises the steps of firstly obtaining a massive catalyst precursor through solid-phase reaction, then stripping the massive catalyst precursor into a flake catalyst through an ultrasonic-assisted stripping method, and finally obtaining the two-dimensional flake anion-doped MPS 3 A catalyst.
Experiments prove that the prepared catalyst has more active sites and higher conductivity compared with an undoped catalyst due to the introduction of the anion (Se), so that better catalytic activity and stability are shown. The anion doping strategy provided by the invention provides an effective way for preparing the non-noble metal catalyst of the zinc air battery with high catalytic activity.
Drawings
In order to more clearly illustrate the technical solution of the embodiment of the present invention, the drawings used in the experimental examples are briefly described below. It is to be understood that the following drawings illustrate only some experimental examples of the present invention and are not to be considered limiting of the scope of the claims. For a person skilled in the art, it is possible to derive other relevant figures from these figures without inventive effort.
FIG. 1 is a Se-doped MPS prepared in example 1 of the present invention 3 Catalyst (NiPS) 2.7 Se 0.3 ) AFM spectrum of (1);
FIG. 2 is Se-doped MPS prepared in example 1 of the present invention 3 Catalyst (NiPS) 2.7 Se 0.3 ) XPS full spectrum of (a);
FIG. 3 is Se-doped MPS prepared in example 1 of the present invention 3 Catalyst (NiPS) 2.7 Se 0.3 ) EDX test chart of (a);
FIG. 4 is Se-doped MPS prepared in example 1 of the present invention 3 Catalyst (NiPS) 2.7 Se 0.3 ) The TEM test chart of (1);
FIG. 5 is Se-doped MPS prepared in example 1 of the present invention 3 Catalyst NiPS 2.7 Se 0.3 、NiPS 3 And RuO 2 OER linear scan of catalyst in 1M KOH solution;
FIG. 6 is Se-doped MPS prepared in example 1 of the present invention 3 Catalyst NiPS 2.7 Se 0.3 、NiPS 3 And ORR linear scan of Pt/C catalyst in 0.1M KOH solution;
FIG. 7 is a diagram showing the constitution of a solid zinc-air battery and a catalyst NiPS 2.7 Se 0.3 And Pt/C charge-discharge polarization curve.
Detailed Description
In order to make the technical problems to be solved, the technical solutions to be adopted and the technical effects to be achieved by the present invention easier to understand, the technical solutions of the present invention will be clearly and completely described below with reference to specific embodiments. The specific conditions not noted in the examples were carried out according to conventional conditions or conditions recommended by the product manufacturer; the instruments and reagents used in the examples are not specified by manufacturers, and are conventional products commercially available.
Example 1
Bifunctional anion-doped MPS in this example 3 The structural formula of the catalyst is NiPS 2.7 Se 0.3 Thin sheet structure, thickness about 1.4nm.
Bifunctional anion-doped MPS in this example 3 The preparation method of the catalyst comprises the following steps:
(1) Bulk anion doped MPS 3 Preparation of the material: sealing nickel powder, phosphorus powder, sulfur powder and selenium powder into a quartz ampoule, wherein in 4, the weight ratio of nickel powder: phosphorus powder: the molar ratio of (sulfur powder + selenium powder) is 1:1:3, the molar ratio of the sulfur powder to the selenium powder is 2.7:0.3, vacuumizing, heating the mixture in a muffle furnace at the high temperature of 750 ℃ under vacuum conditions for 6 days at the heating rate of 1 ℃/min, and after the reaction is finished, naturally cooling the mixture to room temperature, and washing solid powder with carbon disulfide to obtain a black block material;
(2) Two-dimensional plate anion doped MPS 3 Preparation of the catalyst: placing 0.05g of the block material into a 500mL glass bottle, then adding 200mL of absolute ethyl alcohol, and carrying out ultrasonic treatment on the mixture for 48 hours at the ultrasonic power of 100W and the frequency of 50kHz; then, the mixed solution is sequentially centrifuged at a first rotating speed and a second rotating speed, the first rotating speed is set to 3000rpm to remove residual large samples, then the residual samples are centrifuged at the second rotating speed of 10000rpm, and after centrifugation, the wet solid powder is dispersed in water again and freeze-dried to obtain the flake NiPS 2.7 Se 0.3 A catalyst.
Example 2
The double function cathode in this embodimentIon-doped MPS 3 The structural formula of the catalyst is FePS 1.5 Se 1.5 Thin sheet structure, thickness 3nm.
Bifunctional anion-doped MPS in this example 3 The preparation method of the catalyst comprises the following steps:
(1) Bulk anion doped MPS 3 Preparation of the material: and (2) enclosing iron powder, phosphorus powder, sulfur powder and selenium powder in a quartz ampoule, wherein the weight ratio of the iron powder: phosphorus powder: the molar ratio of (sulfur powder + selenium powder) is 1:1:3, the molar ratio of the sulfur powder to the selenium powder is 1.5: 1.5, vacuumizing, heating the mixture in a muffle furnace at the high temperature of 750 ℃ under vacuum conditions for 6 days at the heating rate of 1 ℃/min, and after the reaction is finished, naturally cooling the mixture to room temperature, and washing solid powder with carbon disulfide to obtain a black block material;
(2) Two-dimensional plate anion doped MPS 3 Preparation of the catalyst: placing 0.05g of the block material into a 500mL glass bottle, then adding 200mL of absolute ethyl alcohol, and carrying out ultrasonic treatment on the mixture for 48 hours, wherein the ultrasonic power is 100W, and the frequency is 40kHz; then the mixed solution is centrifuged at a first rotating speed and a second rotating speed in sequence, the first rotating speed is set to be 2500rpm so as to remove residual large samples, then the residual samples are centrifuged at the second rotating speed of 12000rpm, and the moist solid powder is dispersed in water again after centrifugation and is frozen and dried, thus obtaining the flake FePS 1.5 Se 1.5 A catalyst.
Example 3
Bifunctional anion-doped MPS in this example 3 The structural formula of the catalyst is CoPS 2 Se 1 Thin plate structure, thickness of 2.6nm.
Bifunctional anion-doped MPS in this example 3 The preparation method of the catalyst comprises the following steps:
(1) Bulk anion doped MPS 3 Preparation of the material: and (2) sealing cobalt powder, phosphorus powder, sulfur powder and selenium powder into a quartz ampoule, wherein the weight ratio of cobalt powder: phosphorus powder: the molar ratio of (sulfur powder + selenium powder) is 1:1:3, the molar ratio of the sulfur powder to the selenium powder is 2: 1, vacuumizing, heating the mixture in a muffle furnace at the high temperature of 800 ℃ under vacuum condition for 5 days, addingThe thermal rate is 1 ℃/min, after the reaction is finished, the solid powder is washed by carbon disulfide after the reaction is naturally cooled to room temperature, and a black blocky material is obtained;
(2) Two-dimensional plate anion doped MPS 3 Preparation of the catalyst: placing 0.05g of the block material into a 500mL glass bottle, then adding 200mL of absolute ethyl alcohol, and carrying out ultrasonic treatment on the mixture for 36 hours, wherein the ultrasonic power is 105W, and the frequency is 50kHz; and then centrifuging the mixed solution at a first rotating speed and a second rotating speed in sequence, wherein the first rotating speed is set to 4000rpm to remove residual large samples, centrifuging the rest samples at the second rotating speed of 9000rpm, dispersing the wet solid powder in water again after centrifugation, and freeze-drying to obtain the flake CoPS 2 Se 1 A catalyst.
Example 4
Bifunctional anion-doped MPS in this example 3 The structural formula of the catalyst is MnPS 2 Se 1 Thin sheet structure, thickness 2.7nm.
Bifunctional anion-doped MPS in this example 3 The preparation method of the catalyst comprises the following steps:
(1) Bulk anion doped MPS 3 Preparation of the material: and (2) sealing manganese powder, phosphorus powder, sulfur powder and selenium powder into a quartz ampoule, wherein the weight ratio of manganese powder: phosphorus powder: the molar ratio of (sulfur powder + selenium powder) is 1:1:3, the molar ratio of the sulfur powder to the selenium powder is 2: 1, vacuumizing, heating the mixture in a muffle furnace at the high temperature of 600 ℃ under vacuum conditions for 8 days at the heating rate of 1.5 ℃/min, and after the reaction is finished, naturally cooling the mixture to room temperature, and washing solid powder with carbon disulfide to obtain a black block material;
(2) Two-dimensional plate anion doped MPS 3 Preparation of the catalyst: placing 0.05g of the block material into a 500mL glass bottle, then adding 200mL of absolute ethyl alcohol, and carrying out ultrasonic treatment on the mixture for 56 hours, wherein the ultrasonic power is 100W, and the frequency is 50kHz; the mixed solution was then centrifuged sequentially at a first speed set at 2500rpm to remove residual bulk sample and at a second speed of 11000rpm to remove the moist solid powderDispersing in water again and freeze drying to obtain flake MnPS 2 Se 1 A catalyst.
Example 5
Bifunctional anion-doped MPS in this example 3 The structural formula of the catalyst is CrPS 2.5 Se 0.5 Thin sheet structure, thickness 3.5nm.
Dual-function anion-doped MPS in this example 3 The preparation method of the catalyst comprises the following steps:
(1) Bulk anion doped MPS 3 Preparation of the material: sealing chromium powder, phosphorus powder, sulfur powder and selenium powder into a quartz ampoule, wherein the chromium powder: phosphorus powder: the molar ratio of (sulfur powder + selenium powder) is 1:1:3, the molar ratio of the sulfur powder to the selenium powder is 2.5: 0.5, vacuumizing, heating the mixture in a muffle furnace at the high temperature of 900 ℃ under vacuum conditions for 4 days at the heating rate of 0.5 ℃/min, and after the reaction is finished, naturally cooling the mixture to room temperature, and washing solid powder with carbon disulfide to obtain a black block material;
(2) Two-dimensional plate anion doped MPS 3 Preparation of the catalyst: placing 0.05g of the block material into a 500mL glass bottle, then adding 200mL of absolute ethyl alcohol, and carrying out ultrasonic treatment on the mixture for 72 hours, wherein the ultrasonic power is 105W, and the frequency is 50kHz; then centrifuging the mixed solution at a first rotation speed and a second rotation speed in sequence, wherein the first rotation speed is set to 3000rpm to remove residual large samples, centrifuging the rest samples at the second rotation speed of 10000rpm, dispersing the wet solid powder in water again after centrifugation, and freeze-drying to obtain the flaky CrPS 2.5 Se 0.5 A catalyst.
Comparative example 1
NiPS in this comparative example 3 The preparation method of the catalyst comprises the following steps:
(1) Block MPS 3 Preparation of the material: sealing nickel powder, phosphorus powder and sulfur powder in a quartz ampoule, wherein the weight ratio of nickel powder: phosphorus powder: the molar ratio of the sulfur powder is 1:1:3, vacuumizing, heating the mixture in a muffle furnace at the high temperature of 750 ℃ under vacuum condition for 6 days at the heating rate of 1 ℃/min, naturally cooling the mixture to room temperature after the reaction is finished,washing the solid powder with carbon disulfide to obtain a black blocky material;
(2) Two-dimensional sheet-like MPS 3 Preparation of the catalyst: placing 0.05g of the block material into a 500mL glass bottle, then adding 200mL of absolute ethyl alcohol, and carrying out ultrasonic treatment on the mixture for 48 hours at the ultrasonic power of 100W and the frequency of 50kHz; then, the mixed solution is sequentially centrifuged at a first rotating speed and a second rotating speed, the first rotating speed is set to 3000rpm to remove residual large samples, then the residual samples are centrifuged at the second rotating speed of 10000rpm, and after centrifugation, the wet solid powder is dispersed in water again and freeze-dried to obtain the flake NiPS 3 A catalyst.
Comparative example 2
RuO in this comparative example 2 And Pt/C catalyst from Aladdin reagent (Shanghai, china).
Examples of the experiments
In this example, two-dimensional flaky NiPS prepared in example 1 was subjected to AFM, XPS, EDX and TEM tests 2.7 Se 0.3 And (5) characterizing the catalyst.
AFM characterization
FIG. 1 shows a two-dimensional sheet NiPS prepared in example 1 of the present invention 2.7 Se 0.3 AFM full spectrum of catalyst. As can be seen from FIG. 1, niPS prepared by the method of the present invention 2.7 Se 0.3 The catalyst had a lamella thickness of about 1.4nm.
XPS characterization
FIG. 2 shows two-dimensional sheet NiPS prepared in example 1 of the present invention 2.7 Se 0.3 XPS survey of the catalyst. As can be seen from FIG. 2, nickel, phosphorus, sulfur, selenium were successfully detected, indicating that NiPS can be prepared by the method of the present invention 2.7 Se 0.3 A catalyst.
EDX test
FIG. 3 shows two-dimensional sheet NiPS prepared in example 4 of the present invention 2.7 Se 0.3 EDX test pattern of catalyst. As can be seen from FIG. 3, the four elements of nickel, phosphorus, sulfur and selenium exist in the catalyst prepared by the invention, and further proves that Se-doped NiPS is successfully prepared 3 A catalyst.
TEM test
FIG. 4 shows two-dimensional sheet NiPS prepared in example 1 of the present invention 2.7 Se 0.3 TEM test pattern of catalyst. As can be seen from fig. 4a, the catalyst prepared according to the present invention exhibits a single crystal structure characteristic. As can be seen from fig. 4b, the catalyst obtained after the peeling was in the form of a flake. The lattice spacing shown in FIG. 4c is 0.272nm, corresponding to NiPS 3 The (202) crystal plane of (c).
5. Se-doped MPS 3 Performance of catalyst in zinc-air cell
FIG. 5 is Se-doped NiPS prepared in example 1 of the present invention 3 Catalyst NiPS 2.7 Se 0.3 、NiPS 3 And RuO 2 OER linear scan in 1M KOH solution. As can be seen from FIG. 5, when the current density reached 10mA cm -2 In the invention, niPS is prepared 2.7 Se 0.3 The required overpotential of the catalyst is the lowest, which shows that the OER catalytic performance of the catalyst is better than that of NiPS 3 And RuO 2 Catalyst, the Se doping is shown to be an effective way to improve the activity of OER catalyst.
FIG. 6 shows NiPS, a catalyst prepared in example 1 of the present invention 2.7 Se 0.3 、NiPS 3 And ORR linear scan of Pt/C catalyst in 0.1M KOH solution. As can be seen in FIG. 6, niPS 2.7 Se 0.3 Possess a NiPS ratio 3 The more positive half-potential suggests that Se doping is an effective way to increase the activity of ORR catalysts.
FIG. 7 is a diagram showing the composition of a solid zinc-air cell and a catalyst NiPS 2.7 Se 0.3 And Pt/C charge-discharge polarization curve. As can be seen from fig. 7a, the solid zinc-air cell is assembled in a layer-by-layer stack with zinc foil and catalyst coated carbon disposed on both sides of the gel film. As can be seen in FIG. 7b, niPS 2.7 Se 0.3 The charging and discharging polarization curve shows lower voltage gap than that of Pt/C catalyst, which indicates that NiPS 2.7 Se 0.3 The bifunctional catalyst has excellent activity as a zinc-air battery.
Table 1 shows Se-doped MPS in examples 2-5 3 Catalyst OER, ORR and zinc-air cell sectionsAnd dividing performance parameters.
TABLE 1 Se-doped MPS in examples 2-5 3 Performance parameters of catalyst OER, ORR and zinc-air battery
In conclusion, the Se-doped NiPS prepared by the invention is obtained by comparing the catalyst with the undoped catalyst 3 The catalyst shows better OER, ORR and zinc-air battery catalytic activity, which provides a new idea for designing a zinc-air battery catalyst with high efficiency and low cost.
Although the preferred embodiments of the present invention have been described above with reference to the accompanying drawings, they are not intended to limit the scope of the present invention. Various modifications and changes may be made by those skilled in the art, and any modifications, equivalents, and improvements made within the spirit and principles of the present invention are intended to be included within the scope of the present invention.
Claims (1)
1.A zinc-air cell, characterized by: the zinc-air battery comprises a bifunctional anion-doped MPS 3 A catalyst; the battery is a solid-state battery and adopts alkaline electrolyte;
the zinc-air battery difunctional anion-doped MPS 3 The preparation method of the catalyst comprises the following steps:
bifunctional anion-doped MPS 3 The structural formula of the catalyst is CrPS 2.5 Se 0.5 Is in a thin sheet layer shape, and the thickness is 3.5nm;
(1) Bulk anion doped MPS 3 Preparation of the material: sealing chromium powder, phosphorus powder, sulfur powder and selenium powder into a quartz ampoule, wherein the weight ratio of chromium powder: phosphorus powder: the molar ratio of (sulfur powder + selenium powder) is 1:1:3, the molar ratio of the sulfur powder to the selenium powder is 2.5:0.5, vacuumizing, heating the mixture in a muffle furnace at the high temperature of 900 ℃ under vacuum conditions for 4 days at the heating rate of 0.5 ℃/min, and after the reaction is finished, naturally cooling the mixture to room temperature, and washing solid powder with carbon disulfide to obtain a black block material;
(2) Two-dimensional plate anion doped MPS 3 Preparation of the catalyst: placing 0.05g of the block material into a 500mL glass bottle, then adding 200mL of absolute ethyl alcohol, and carrying out ultrasonic treatment on the mixture for 72 hours, wherein the ultrasonic power is 105W, and the frequency is 50kHz; then centrifuging the mixed solution at a first rotation speed and a second rotation speed in sequence, wherein the first rotation speed is set to 3000rpm to remove residual large samples, centrifuging the rest samples at the second rotation speed of 10000rpm, dispersing the wet solid powder in water again after centrifugation, and freeze-drying to obtain the flaky CrPS 2.5 Se 0.5 A catalyst.
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| US20170044679A1 (en) * | 2015-08-11 | 2017-02-16 | Wisconsin Alumni Research Foundation | High performance earth-abundant electrocatalysts for hydrogen evolution reaction and other reactions |
| CN105879891B (en) * | 2016-04-20 | 2018-04-03 | 燕山大学 | A kind of preparation method of nickel phosphorus/molybdenum disulfide liberation of hydrogen composite |
| CN110359059B (en) * | 2018-04-11 | 2021-05-28 | 中国科学院金属研究所 | NiPS for electrocatalytic oxygen production3Graphene composite catalyst and preparation method thereof |
| CN110589787A (en) * | 2019-10-22 | 2019-12-20 | 中国人民解放军国防科技大学 | Nickel-phosphorus-sulfur two-dimensional material and synthesis and application thereof |
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| CN106976911A (en) * | 2016-01-19 | 2017-07-25 | 同济大学 | A kind of few layer MoS2The preparation method of nanometer sheet |
| CN109225182A (en) * | 2018-09-04 | 2019-01-18 | 合肥工业大学 | A kind of ultra-thin silicon nanosheet photocatalyst and the preparation method and application thereof |
| CN109231272A (en) * | 2018-12-03 | 2019-01-18 | 清华-伯克利深圳学院筹备办公室 | A kind of stripping means of molybdenum disulfide and its molybdenum disulfide and purposes of preparation |
| CN111807335A (en) * | 2020-07-08 | 2020-10-23 | 陕西科技大学 | Microwave-assisted method for preparing boron nitride nanosheets |
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