阅读说明：本技术 一种磷化镍/泡沫镍电化学功能析氢材料的制备方法 (A kind of preparation method of nickel phosphide/nickel foam electrochemical function liberation of hydrogen material ) 是由 宋来洲 杨淑琴 霍思月 *** 牛倩倩 于 2019-09-16 设计创作，主要内容包括：本发明公开了一种磷化镍/泡沫镍电化学功能析氢材料的制备方法,涉及氢能源应用技术领域,包括泡沫镍集流体的预处理,配制化学镀镍磷镀液,在泡沫镍片表面载负化学镀镍磷镀层,制备氢氧化镍/含有镍磷镀层的泡沫镍前驱体以及磷化镍/泡沫镍自支撑电极的制备。本发明所制得的磷化镍/泡沫镍自支撑电极电化学催化析氢性能优异,性质高效稳定,应用范围广,所需物料来源广泛,制备过程便捷,对pH值条件要求宽泛,制备过程绿色无污染,技术实施过程简洁易操作,成本低,易于产业化推广。(The invention discloses a kind of nickel phosphide/nickel foam electrochemical function liberation of hydrogen material preparation methods, it is related to hydrogen energy source applied technical field, pretreatment including foamed nickel current collector, prepare chemical nickel phosphorus plating plating solution, Electroless Ni-P Coating is loaded on foam nickel sheet surface, prepares nickel hydroxide/nickel foam presoma containing nickel-phosphorus coating and the preparation of nickel phosphide/nickel foam self-supporting electrode.Nickel phosphide obtained by the present invention/nickel foam self-supporting electrode electro Chemical catalytic hydrogen evolution is had excellent performance, property efficient stable, have a wide range of application, required material is from a wealth of sources, and preparation process is convenient, requires pH value condition wide in range, preparation process green non-pollution, technology implementation process is succinctly easy to operate, at low cost, is easy to industrialization promotion.)

1. a kind of nickel phosphide/nickel foam electrochemical function liberation of hydrogen material preparation method, it is characterised in that: the following steps are included:

(1) pretreatment of foamed nickel current collector: nickel foam is cut into specified size, and carries out pre-treatment；Pre-treatment is obtained Foam nickel sheet be immersed in stannous chloride solution, sufficiently react and be immersed in palladium chloride solution after cleaning up, it is sufficiently anti- Should after clean and dry；

(2) prepare chemical nickel phosphorus plating plating solution: with certain proportion by nickel sulfate, citric acid, succinic acid, sodium acetate, ammonium acid fluoride according to Secondary to be added in the container for filling distilled water, heating stirring is allowed to be completely dissolved；Sodium hypophosphite is added into solution, heating is stirred It mixes and makes it dissolve, ammonium hydroxide is added dropwise into solution after solution is cooled to room temperature by solution ph and is adjusted to 4.6~5.0, then It stirs evenly, obtains chemical nickel plating phosphor bath；

(3) Electroless Ni-P Coating is loaded on foam nickel sheet surface: heating chemical nickel plating phosphor bath to certain temperature, by step (1) processed foam nickel sheet is immersed in chemical nickel plating phosphor bath in, keeps bath temperature, is controlled plating time, is sufficiently applied Foam nickel sheet cleaning, drying is taken out after plating；

(4) it prepares nickel hydroxide/nickel foam presoma containing nickel-phosphorus coating: hexamethylenetetramine and six is weighed with certain proportion Nitric hydrate nickel is placed in the beaker for filling deionized water, is stirred to dissolve, and solution is poured into polytetrafluoroethyllining lining, so Polytetrafluoroethyllining lining is put into reaction kettle afterwards, hydro-thermal reaction is carried out after heating and obtains nickel hydroxide/containing nickel-phosphorus coating Nickel foam presoma, and by its cleaning, drying；

(5) nickel phosphide/nickel foam self-supporting electrode preparation: by nickel hydroxide/nickel foam presoma containing nickel-phosphorus coating and Sodium hypophosphite powder is respectively put into two corundum porcelain boats, and two corundum porcelain boats are put into the tube furnace furnace for having nitrogen atmosphere In thorax, heating furnace simultaneously obtains nickel phosphide/nickel foam electrochemical function liberation of hydrogen material by phosphating reaction after keeping the temperature a period of time, A kind of specifically nickel phosphide/nickel foam self-supporting electrode.

2. a kind of nickel phosphide according to claim 1/nickel foam electrochemical function liberation of hydrogen material preparation method, feature Be: the pre-treatment step in step (1) includes that the foam nickel sheet after cutting is placed in the beaker for filling acetone, then will be burnt Cup, which is placed in ultrasonic cleaner, to be ultrasonically treated, and then by treated, foam nickel sheet is taken out from beaker, uses deionization Water cleans 5 times, is put into the beaker for fill hydrochloric acid and performs etching, and then places the beaker in ultrasonic cleaner and carries out at ultrasound Reason, foam nickel sheet is taken out, cleaned 5 times from beaker with deionized water later, after foam nickel sheet be placed in fill dehydrated alcohol Beaker in be ultrasonically treated, then by dehydrated alcohol, treated that foam nickel sheet is taken out from beaker, cleans 5 with deionized water Secondary juxtaposition is dried in a vacuum drying oven.

3. a kind of nickel phosphide according to claim 1/nickel foam electrochemical function liberation of hydrogen material preparation method, feature It is: foam nickel sheet is immersed in while density is in 10g/L stannous chloride solution in step (1) and passes through ultrasound at room temperature Washer is ultrasonically treated, and later takes out foam nickel sheet from stannous chloride solution, is cleaned 5 times with deionized water； It will be ultrasonically treated at room temperature in the palladium chloride solution of foam nickel sheet submergence 0.2g/L and by ultrasonic cleaning machine again, later Foam nickel sheet is taken out from palladium chloride solution, is cleaned 5 times with deionized water；Finally the foam nickel sheet of washes clean is set It dries in a vacuum drying oven.

4. a kind of nickel phosphide according to claim 1/nickel foam electrochemical function liberation of hydrogen material preparation method, feature Be: the mass ratio of nickel sulfate, sodium hypophosphite, citric acid, succinic acid, sodium acetate, ammonium acid fluoride in step (2) is 25 ~30:15~30:10~15:3~5:3~5:3~5.

5. a kind of nickel phosphide according to claim 1/nickel foam electrochemical function liberation of hydrogen material preparation method, feature Be: nickel sulfate, citric acid, succinic acid, sodium acetate, ammonium acid fluoride are added to the burning for filling distilled water in (2) by step first It in cup, and places the beaker on magnetic stirring apparatus, opens Stirring control handle and computer heating control switch, control solution temperature It is 40~50 DEG C, agitating solution is completely dissolved each reagent being added；Sodium hypophosphite is added in solution again, stirring makes it Dissolution closes the computer heating control switch of magnetic stirring apparatus, naturally cools to solution temperature after sodium hypophosphite is completely dissolved Room temperature.

6. a kind of nickel phosphide according to claim 1/nickel foam electrochemical function liberation of hydrogen material preparation method, feature It is: the beaker for filling chemical nickel plating phosphor bath is placed in the temperature constant magnetic stirring water bath for filling deionized water in step (3) In, foam nickel sheet is immersed in chemical nickel plating phosphor bath by heating chemical nickel-plated phosphor bath temperature to 80~85 DEG C, keeps plating solution Temperature is 80~85 DEG C, and control plating time is 40~60min；Nickel foam chemically is taken out in nickel plating phosphor bath after reaction completely Piece is cleaned 5 times with deionized water, after place it in vacuum oven and dry.

7. a kind of nickel phosphide according to claim 1/nickel foam electrochemical function liberation of hydrogen material preparation method, feature Be: the ratio between mole of hexamethylenetetramine and Nickelous nitrate hexahydrate is 1:1 in step (4).

8. a kind of nickel phosphide according to claim 1/nickel foam electrochemical function liberation of hydrogen material preparation method, feature Be: the ratio between mole of the amount of loading with and sodium hypophosphite of foam nickel sheet surface nickel phosphorus coating is 1:5, the load in step (3) Negative quantity, that is, foam nickel sheet is of poor quality before and after chemical plating.

9. a kind of nickel phosphide according to claim 1/nickel foam electrochemical function liberation of hydrogen material preparation method, feature It is: the corundum porcelain boat for holding sodium hypophosphite is placed on close to tube furnace nitrogen inlet side, heating furnace in step (5) To 300 DEG C and keep the temperature 2h.

10. a kind of nickel phosphide according to claim 1/nickel foam electrochemical function liberation of hydrogen material preparation method, special Sign is: after placing two corundum porcelain boats in tube furnace burner hearth center in step (5), opening nitrogen cylinder switching knob, makes Nitrogen slowly enters in tube furnace, and the intake of nitrogen is 10~30 mL/min；Diamond heating switch is opened simultaneously, makes furnace Bore temperature is increased to 300 DEG C by room temperature with the heating rate of 1~5 DEG C/min, and temperature is kept to make nickel hydroxide/contain nickel-phosphorus coating 2 h of nickel foam presoma phosphating reaction.

Technical field

The present invention relates to hydrogen energy source applied technical field, especially a kind of nickel phosphide/nickel foam electrochemical function liberation of hydrogen material The preparation method of material.

Background technique

The important measure that efficient renewable and clean energy resource is current response environment and energy problem is developed, efficiently can be again In raw energy resource system, the crucial energy storage means full of potentiality are exactly to convert electrical energy into the chemistry stored with fuel forms Can, most important and simplest step is exactly to decompose aquatic products hydrogen during this.With the industrial production hydrogen for relying on non-renewable energy Method is compared, and water electrolysis hydrogen producing is concerned because it has the characteristics that device is simple, production hydrogen purity is high, energy transformation ratio is high； Catalyst of the efficiency of aquatic products hydrogen dependent on cathode hydrogen evolution reaction and two half-reactions of anode oxygen uptake is decomposed, thus is used for electrochemistry The performance superiority and inferiority of cathode hydrogen evolution catalysts is the key that restrict hydrogen production by water decomposition efficiency.Currently, it is main industrially to decompose water Traditional platinum based catalyst is relied on, but in view of noble metals such as platinum bases because it is few, expensive without being able to satisfy in earth's crust reserves It is engineered the defect of application demand, so to researching and developing, from a wealth of sources, easy to use, catalytic hydrogen evolution performance efficiency is stable, inexpensive easy The non-precious metal catalyst obtained is very urgent.In addition, during producing hydrogen, different electrolysis units such as pem fuel electricity Pond, microbiological fuel cell etc. require difference, therefore, base metal based electrochemical cathode hydrogen evolution catalysis material to the pH of electrolytic cell Except have the characteristics that catalytic hydrogen evolution performance efficiency it is stable, it is cheap and easy to get in addition to, should also have the wide pH scope of application, this is that green produces hydrogen The core of behave.

In base metal base cathode catalysis material, nickel-phosphorus alloy and using nickel phosphide as the transition metal phosphide of representative by In cheap and easy to get and received significant attention as liberation of hydrogen material.Domestic and foreign scholars have carried out many researchs in this field, probe into phosphorus Change the preparation approach of nickel and evaluates the research emphasis that its water electrolysis is the field from Hydrogen Evolution Performance.Currently, the solution such as hydrothermal synthesis Phase reaction prepares nickel phosphide and mainly white phosphorus or tri-n-octyl phosphine is applied to make phosphorus source, but the range of reaction temperature is by a fixed limit System, and the toxicity of reaction process intermediate product is big.For this purpose, scholars improve above-mentioned operation, patent CN109650360A discloses a kind of method that phosphatization nano nickel particles are continuously prepared using micro passage reaction, and being will be organic Nickel presoma and organic phosphorus sources mixing, after being diluted using the more carbon organic matters of higher boiling as diluent, gained suspension is passed through Ultrasonic treatment is directly injected into reaction, products therefrom in micro passage reaction and obtains after precipitating, separation, washing and vacuum drying Phosphatization nano nickel particles.Though made phosphatization nano nickel particles have the characteristics that size is minimum, uniform in size, good dispersion, need With a variety of toxic chemical substances such as triphenylphosphine and 1- octadecylene, harm to the human body is big.Patent CN109267095A is referred to one The preparation method of kind new phosphide nickel catalytic material, synthesizes nitrogenous, phosphorus atoms metal organic frameworks with microlayer model method first Presoma, is then sintered heat treatment under 900~1100 DEG C of high temperature to it, is then prepared for nickel phosphide catalytic hydrogen evolution material, should Although method is not necessarily to additional phosphorus source, a variety of toxic chemical substances are used when precursor preparation, harm to the human body is big, and Need that high-temperature operation, energy consumption is high.Existing technological deficiency is prepared based on current nickel phosphide, seeks that a kind of material is from a wealth of sources, preparation Process is convenient, green non-pollution, the nickel phosphide system for being easy to industrialization promotion, Hydrogen Evolution Performance efficient stable and the width pH scope of application Standby technology is the important measure for promoting the dissociation hydrogen manufacturing of cathode water power.

Summary of the invention

The technical problem to be solved by the invention is to provide a kind of nickel phosphide/nickel foam electrochemical function liberation of hydrogen material systems The electrochemical catalysis Hydrogen Evolution Performance of Preparation Method, obtained product is excellent, and property efficient stable has a wide range of application, required material From a wealth of sources, preparation process is convenient, requires wide in range, preparation process green non-pollution to pH value condition, technology implementation process is succinct It is easy to operate, it is at low cost, it is easy to industrialization promotion.

In order to solve the above technical problems, the technical scheme adopted by the invention is that:

A kind of preparation method of nickel phosphide/nickel foam electrochemical function liberation of hydrogen material, comprising the following steps:

(1) pretreatment of foamed nickel current collector: nickel foam is cut into specified size, and carries out pre-treatment；Pre-treatment is obtained Foam nickel sheet be immersed in stannous chloride solution, sufficiently react and be immersed in palladium chloride solution after cleaning up, it is sufficiently anti- Should after clean and dry；

(2) prepare chemical nickel phosphorus plating plating solution: with certain proportion by nickel sulfate, citric acid, succinic acid, sodium acetate, ammonium acid fluoride according to Secondary to be added in the container for filling distilled water, heating stirring is allowed to be completely dissolved；Sodium hypophosphite is added into solution, heating is stirred It mixes and makes it dissolve, ammonium hydroxide is added dropwise into solution after solution is cooled to room temperature solution ph is adjusted to 4.6~5.0, It is stirred for uniformly, obtaining chemical nickel plating phosphor bath；

(3) Electroless Ni-P Coating is loaded on foam nickel sheet surface: heating chemical nickel plating phosphor bath to certain temperature, by step (1) processed foam nickel sheet is immersed in chemical nickel plating phosphor bath in, keeps bath temperature, is controlled plating time, is sufficiently applied Foam nickel sheet cleaning, drying is taken out after plating；

(4) it prepares nickel hydroxide/nickel foam presoma containing nickel-phosphorus coating: hexamethylenetetramine and six is weighed with certain proportion Nitric hydrate nickel is placed in the beaker for filling deionized water, is stirred to dissolve, and solution is poured into polytetrafluoroethyllining lining, so Polytetrafluoroethyllining lining is put into reaction kettle afterwards, hydro-thermal reaction is carried out after heating and obtains nickel hydroxide/containing nickel-phosphorus coating Nickel foam presoma, and by its cleaning, drying；

(5) nickel phosphide/nickel foam self-supporting electrode preparation: by nickel hydroxide/nickel foam presoma containing nickel-phosphorus coating and Sodium hypophosphite powder is respectively put into two corundum porcelain boats, and two corundum porcelain boats are put into the tube furnace furnace for having nitrogen atmosphere In thorax, heating furnace simultaneously obtains nickel phosphide/nickel foam electrochemical function liberation of hydrogen material by phosphating reaction after keeping the temperature a period of time, A kind of specifically nickel phosphide/nickel foam self-supporting electrode.

Technical solution of the present invention further improvement lies in that: the pre-treatment step in step (1) includes the bubble after cutting Foam nickel sheet is placed in the beaker for filling acetone, is then placed the beaker in ultrasonic cleaner and is ultrasonically treated, then will place Foam nickel sheet after reason is taken out from beaker, is cleaned 5 times with deionized water, is put into the beaker for fill hydrochloric acid and performs etching, so After place the beaker in ultrasonic cleaner and be ultrasonically treated, foam nickel sheet is taken out from beaker later, uses deionized water Cleaning 5 times, after foam nickel sheet be placed in the beaker for fill dehydrated alcohol be ultrasonically treated, then treated by dehydrated alcohol Foam nickel sheet is taken out from beaker, cleans 5 juxtapositions with deionized water and dries in a vacuum drying oven.

Technical solution of the present invention further improvement lies in that: in step (1) by foam nickel sheet be immersed in density be 10g/L chlorine Pass through ultrasonic cleaning machine at room temperature while change in stannous solution and be ultrasonically treated, later by foam nickel sheet from stannous chloride It takes out in solution, is cleaned 5 times with deionized water；It again will be in the palladium chloride solution of foam nickel sheet submergence 0.2g/L and by super Sound washer is ultrasonically treated at room temperature, later takes out foam nickel sheet from palladium chloride solution, with deionized water by its Cleaning 5 times；The foam nickel sheet of washes clean is finally placed in a vacuum drying oven drying.

Technical solution of the present invention further improvement lies in that: nickel sulfate, sodium hypophosphite, citric acid, fourth in step (2) Diacid, sodium acetate, ammonium acid fluoride mass ratio be 25~30:15~30:10~15:3~5:3~5:3~5.

Technical solution of the present invention further improvement lies in that: first by nickel sulfate, citric acid, succinic acid, second in step (2) Sour sodium, ammonium acid fluoride are added in the beaker for filling distilled water, and are placed the beaker on magnetic stirring apparatus, Stirring control rotation Button simultaneously opens computer heating control switch, and control solution temperature is 40~50 DEG C, and agitating solution is completely dissolved each reagent being added；Again Sodium hypophosphite is added in solution, is stirred to dissolve, after sodium hypophosphite is completely dissolved, closes magnetic stirring apparatus Computer heating control switch, makes solution temperature cooled to room temperature.

Technical solution of the present invention further improvement lies in that: step sets the beaker for filling chemical nickel plating phosphor bath in (3) In the temperature constant magnetic stirring water bath for filling deionized water, heating chemical nickel-plated phosphor bath temperature is to 80~85 DEG C, by foam Nickel sheet is immersed in chemical nickel plating phosphor bath, and keeping bath temperature is 80~85 DEG C, and control plating time is 40~60min；It is complete Foam nickel sheet is chemically taken out after full response in nickel plating phosphor bath, clean 5 times with deionized water, after place it in vacuum and do It is dried in dry case.

Technical solution of the present invention further improvement lies in that: hexamethylenetetramine and Nickelous nitrate hexahydrate in step (4) Mole the ratio between be 1:1.

Technical solution of the present invention further improvement lies in that:: the amount of loading with of foam nickel sheet surface nickel phosphorus coating in step (3) The ratio between mole with sodium hypophosphite is 1:5, and the amount of loading with i.e. foam nickel sheet is of poor quality before and after chemical plating.

Technical solution of the present invention further improvement lies in that: step puts the corundum porcelain boat for holding sodium hypophosphite in (5) Close to tube furnace nitrogen inlet side, heating furnace is to 300 DEG C and keeps the temperature 2h.

Technical solution of the present invention further improvement lies in that: in step (5) by two corundum porcelain boats in tube furnace burner hearth After centre places, nitrogen cylinder switching knob is opened, slowly enters nitrogen in tube furnace, the intake of nitrogen is 10~30 mL/ min；Diamond heating switch is opened simultaneously, and fire box temperature is made to be increased to 300 DEG C by room temperature with the heating rate of 1~5 DEG C/min, Temperature is kept to make nickel hydroxide/2 h of nickel foam presoma phosphating reaction containing nickel-phosphorus coating.

By adopting the above-described technical solution, the technological progress achieved by the present invention is:

Nickel phosphide obtained by the present invention/nickel foam self-supporting electrode electro Chemical catalytic hydrogen evolution is had excellent performance, property efficient stable, Have a wide range of application, there is efficient catalytic to produce hydrogen efficiency in acid, alkaline medium, in electrochemical catalysis hydrogen manufacturing, hydrodesulfurization, choosing Selecting property adds hydrogen and other hydrogen-involved reaction fields to have broad application prospects.The present invention relates to material source needed for technique is wide General, raw material is cheap and easy to get, and preparation process is convenient, wide in range to pH value condition requirement, and preparation process green non-pollution, technology was implemented Journey is succinctly easy to operate, is conducive to large-scale industrial production application.

The corundum porcelain boat for holding sodium hypophosphite is placed on close to tube furnace nitrogen inlet side, to ensure ortho phosphorous acid The phosphine gas that sodium decomposes can make its phosphatization with the nickel hydroxide/nickel foam presoma containing nickel-phosphorus coating comes into full contact with, Improve reaction efficiency.

Without the adhesive effect of binder, nickel phosphide liberation of hydrogen catalyst loads with secured, change on nickel foam supporter Stablize.

Detailed description of the invention

Fig. 1 is the scanning electron microscope diagram of untreated nickel foam；

Fig. 2 is the partial enlarged view of Fig. 1；

Fig. 3 is to load with the scanning electron microscope diagram of the foam nickel sheet of Electroless Ni-P Coating on surface；

Fig. 4 is the partial enlarged view of Fig. 3；

Fig. 5 is the X-ray diffraction spectrogram of nickel phosphide/nickel foam self-supporting electrode and nickel foam；

Fig. 6 is that the linear scan of the nickel phosphide/nickel foam self-supporting electrode, nickel foam, commercial glass-carbon electrode in acid medium lies prostrate Peace method curve；

Fig. 7 is that the linear scan of the nickel phosphide/nickel foam self-supporting electrode, nickel foam, commercial glass-carbon electrode in alkaline medium lies prostrate Peace method curve.

Specific embodiment

Technical solution of the present invention and working principle are done further specifically below with reference to schematic diagram and specific embodiment It is bright.Part relevant to the technical solution of the claims in the present invention is illustrated only in attached drawing of the invention, and not all, the present invention Specific embodiment be also only through the optimal embodiment in part technical solution of the present invention be illustrated, not realize Whole specific technical solutions of the object of the invention, embodiment part cannot function as the range of the claims in the present invention protection.Below The present invention is described in further details in conjunction with the embodiments: