阅读说明：本技术 一种纳米级Fe9Ni9S16基电催化剂的制备方法 (A kind of nanoscale Fe9Ni9S16The preparation method of base elctro-catalyst ) 是由 刘岗 张露露 杨勇强 成会明 于 2018-05-25 设计创作，主要内容包括：本发明涉及材料制备与电催化、电池储能领域,具体为一种纳米级Fe_9Ni_9S_(16)基电催化剂的制备方法,目的为发展新型、廉价、稳定、高效的电催化和电池储能用电极材料,并解决现有该材料制备方法工序复杂、高温、高耗能、大粒径等不利于大规模应用的问题。本发明通过将铁盐、镍盐、有机硫源和导电载体混合后,在惰性气体中适当温度下反应的方法,制备出纳米级的纯相硫镍铁矿相Fe-Ni-S固溶体Fe_9Ni_9S_(16)。本发明中所得到的材料制备方法简单、温度温和、能耗小、成本低,适用于大规模制备,在电催化和电池储能等领域具有广阔的应用前景。(The present invention relates to material preparations and electro-catalysis, battery energy storage field, specially a kind of nanoscale Fe 9 Ni 9 S 16 The preparation method of base elctro-catalyst, purpose is Development of Novel, cheap, stable, efficient electro-catalysis and battery energy storage electrode material, and solves the problems, such as the existing material preparation method complex procedures, high temperature, highly energy-consuming, big partial size etc. and be unfavorable for large-scale application.After the present invention is by mixing molysite, nickel salt, organic sulphur source and conductive carrier, the method reacted under proper temperature in inert gas prepares nanoscale pure phase pentlandite phase Fe-Ni-S solid solution Fe 9 Ni 9 S 16 .Obtained material preparation method is simple in the present invention, temperature is mild, energy consumption is small, at low cost, is suitable for large scale preparation, has broad application prospects in the fields such as electro-catalysis and battery energy storage.)

1. a kind of nanoscale Fe₉Ni₉S₁₆The preparation method of base elctro-catalyst, which is characterized in that select iron content, nickeliferous presoma With organic sulphur source as starting material, after it is sufficiently mixed with conductive carrier, heating reaction is carried out in non-oxidizing atmosphere, Obtain the nanoscale pure phase pentlandite phase Fe-Ni-S solid solution Fe of conductive carrier load₉Ni₉S₁₆Elctro-catalyst.

2. nanoscale Fe described in accordance with the claim 1₉Ni₉S₁₆The preparation method of base elctro-catalyst, which is characterized in that selected Iron content and nickeliferous presoma are as follows: the salt being made of the cation of Fe and Ni and the anion of inorganic acid or organic acid, it is former The mass ratio of the material of iron atom and nickle atom is between 1:1~1:3 in material.

3. nanoscale Fe according to claim 2₉Ni₉S₁₆The preparation method of base elctro-catalyst, which is characterized in that inorganic acid For hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or hydrofluoric acid, organic acid is acetic acid or lactic acid, and salt is frerrous chloride, ferric sesquichloride, nitric acid Nickel or nickel acetate.

4. nanoscale Fe described in accordance with the claim 1₉Ni₉S₁₆The preparation method of base elctro-catalyst, which is characterized in that selected Organic sulphur source be thiocarbamide, thiourea derivative, thiocyanic acid or thiocyanic acid derivative, the amount of the substance of thiocarbamide is iron, nickel in raw material 5 times or more of the amount sum of atom species.

5. nanoscale Fe according to claim 4₉Ni₉S₁₆The preparation method of base elctro-catalyst, which is characterized in that thiocarbamide spreads out Biology is benzene thiocarbamide, and thiocyanic acid derivative is trithiocyanuric acid or rhodanate.

6. nanoscale Fe described in accordance with the claim 1₉Ni₉S₁₆The preparation method of base elctro-catalyst, which is characterized in that by iron content, The method that nickeliferous presoma, organic sulphur source are mixed with conductive carrier are as follows: be stirred after direct solid abrasive, dissolution- It is stirred-is freeze-dried after evaporation or dissolution.

7. according to nanoscale Fe described in claim 1 or 6₉Ni₉S₁₆The preparation method of base elctro-catalyst, which is characterized in that conductive Carrier is commercialization carbon black XC-72R, is commercialized carbon pipe or commercialization graphene, conductive carrier and Fe₉Ni₉S₁₆Mass ratio Between 10:1~1:10.

8. nanoscale Fe described in accordance with the claim 1₉Ni₉S₁₆The preparation method of base elctro-catalyst, which is characterized in that when reaction Required non-oxidizing atmosphere is N₂, Ar, He or vacuum.

9. according to nanoscale Fe described in claim 1 or 8₉Ni₉S₁₆The preparation method of base elctro-catalyst, which is characterized in that reaction For temperature between 200 to 1200 DEG C, the reaction time is 10min between for 24 hours.

10. nanoscale Fe described in accordance with the claim 1₉Ni₉S₁₆The preparation method of base elctro-catalyst, which is characterized in that nanoscale Fe₉Ni₉S₁₆The size range of base elctro-catalyst is 5~500nm.

Technical field

The present invention relates to material preparations and electro-catalysis, battery energy storage field, specially a kind of nanoscale Fe₉Ni₉S₁₆Base electricity The preparation method of catalyst.

Background technique

The reaction of electrochemical decomposition aquatic products oxygen is electrolysis water, solar energy cracking water installations and chargeable metal-air battery etc. Important half-reaction in green, high efficient energy sources conversion and energy storage technology.The multistep reaction process that up to four electronics participate in produce Oxygen reaction faces higher thermodynamics potential barrier, needs higher overpotential that could generate electric current required for Clean Fuel Production close Spend (10mA/cm²)。RuO₂、IrO₂Although equal noble metals base, which produces oxygen elctro-catalyst, higher activity, but the lower earth's crust stores up Amount and the higher market price limit its more massive application.Efficiently, stablize, the exploitation of cheap electrolysis aquatic products VPO catalysts Development and research important in inhibiting to the related industries such as clean energy resource and energy storage and basic research field.Period 4 mistake Cross the electricity of the hydroxide of metal (such as: Mn, Fe, Co, Ni), phosphide, chalcogenide and other nonmetallic elctro-catalysts Catalysis produces oxygen performance and is also therefore widely studied.In recent years studies have shown that on the basis of Ni-based electrocatalysis material, Fe and Ni two Kind atomic ordered couples to obtain more effectively in the electronic structure of production oxygen, and develops (such as: FeNi₃N, FeNiP etc.) it is single-phase solid Solution [document 1:BoZhang, Chunhui Xiao, Sanmu Xie, Jin Liang, Xu Chen, Yuhai Tang, Iron- Nickel Nitride Nanostructures in Situ Grown on Surface-Redox Etching Nickel Foam:Efficient and Ultrasustainable Electrocatalysts for Overall Water Splitting, Chem.Mater.2016,28,6934-6941. document 2:Manman Qian, Shengsheng Cui, Daochuan Jiang,Lei Zhang,Pingwu Du,Highly Effcient and Stable Water-Oxidation Electrocatalysis with a Very Low Overpotential using FeNiP Substitutional Solid-SolutionNanoplateArrays, Adv.Mater.2017,1704075], it shows excellent electro-catalysis and produces oxygen Performance.For nickel sulfide (such as: Ni₃S₂), itself there is preferable electro-catalysis to produce oxygen performance, and adulterate the Ni after Fe₃S₂ [document 3:NingyanCheng, QianLiu, AbdullahM.Asiri, WeiXing, Xuping Sun, A Fe-doped Ni₃S₂particle film as a high-efficiency robust oxygen evolution electrode with Very high currentdensity, J.Mater.Chem.A, 2015,3,23207-23212] performance significantly improves.However, Since Fe is foreign atom wherein, there are the uncertainties of structure and component, and therefore bring unstability becomes fatal Short slab [document 4:Cheng-Zong Yuan, Zhong-Ti Sun, Yi-Fan Jiang, Zheng-KunYang, Nan Jiang, Zhi-Wei Zhao,UmairYaqub Qazi,Wen-Hua Zhang,An-Wu Xu,One-Step In Situ Growth of Iron–Nickel Sulfde Nanosheets on FeNi Alloy Foils:High-Performance and Self-Supported Electrodes for Water Oxidation, small 2017,13,1604161], and at present still No pure phase Fe-Ni-S base electro-catalysis produces the controllable method for preparing of VPO catalysts.On the other hand, Konkena etc. [document 5: Bharathi Konkena1,Kai junge Puring,Ilya Sinev,Stefan Piontek,Oleksiy Khavryuchenko,Johannes P.Du¨rholt,Rochus Schmid,Harun Tu¨ysu¨z,Martin Muhler, Wolfgang Schuhmann&Ulf-PeterApfel,Pentlanditerocks as sustainable andstable Efficient electrocatalysts forhydrogen generatio, Nat.Commun.7:12269] in 2016 It was found that the Fe in natural pentlandite_4.5Ni_4.5S₈There is very high electro-catalysis to produce hydrogen activity, is directly using natural crystal system Overpotential can be down to 280mV when standby electrode is for producing hydrogen reaction；[the document 6:Stefan such as Stefan of same seminar Piontek,Corina Andronescu,Aleksandr Zaichenko,Bharathi Konkena,Kaijunge Puring,Bernd Marler,Hendrik Antoni,Ilya Sinev,Martin Muhler,Doreen Mollenhauer,Beatriz Roldan Cuenya,Wolfgang Schuhmann,Ulf-Peter Apfel, Influence ofthe Fe:Ni Ratio and Reaction Temperature on the Efficiency of (Fe_xNi_1-x)₉S₈Electrocatalysts Applied in the HydrogenEvolutionReaction, ACSCatal.2018,8,987-996] the further pyroreaction of 1100 DEG C of report, using simple substance Fe, simple substance Ni and simple substance S are Raw material, the Fe prepared by corresponding atom ratio_4.5Ni_4.5S₈Also there is excellent electro-catalysis H2-producing capacity.However, either In natural crystal or pyroreaction prepared by Fe_4.5Ni_4.5S₈, the influence such as biggish particle size limitation specific surface area An important factor for electrocatalytic reaction, harsh acquisition pattern limit the further research to the material, and the electro-catalysis of the material produces Oxygen activity is not seen in always report yet.In summary factor, the preparation method of the Fe-Ni-S single phase solid solution of nanoscale and its The research that electro-catalysis produces oxygen performance is the project currently needed.

Summary of the invention

The purpose of the present invention is to provide a kind of high activities, high-stability nano grade Fe₉Ni₉S₁₆The preparation of base elctro-catalyst Method for Development of Novel, cheap, stable, efficient electro-catalysis and battery energy storage electrode material, and solves the existing material The problem of preparation method complex procedures, high temperature, highly energy-consuming, big partial size etc. are unfavorable for large-scale application.

The technical scheme is that

A kind of nanoscale Fe₉Ni₉S₁₆The preparation method of base elctro-catalyst selects iron content, nickeliferous presoma and organic sulfur Source is as starting material, after it is sufficiently mixed with conductive carrier, carries out heating reaction in non-oxidizing atmosphere to get to leading The nanoscale pure phase pentlandite phase Fe-Ni-S solid solution Fe of charge carrier load₉Ni₉S₁₆Elctro-catalyst.

The nanoscale Fe₉Ni₉S₁₆The preparation method of base elctro-catalyst, selected iron content and nickeliferous presoma Are as follows: the salt being made of the cation of Fe and Ni and the anion of inorganic acid or organic acid, iron atom and nickle atom in raw material The mass ratio of the material is between 1:1~1:3.

3, nanoscale Fe according to claim 2₉Ni₉S₁₆The preparation method of base elctro-catalyst, which is characterized in that nothing Machine acid be hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or hydrofluoric acid, organic acid be acetic acid or lactic acid, salt be frerrous chloride, ferric sesquichloride, Nickel nitrate or nickel acetate.

The nanoscale Fe₉Ni₉S₁₆The preparation method of base elctro-catalyst, selected organic sulphur source are thiocarbamide, thiocarbamide Derivative, thiocyanic acid or thiocyanic acid derivative, in raw material the amount of the substance of thiocarbamide be 5 times of the amount sum of iron, nickle atom substance with On.

The nanoscale Fe₉Ni₉S₁₆The preparation method of base elctro-catalyst, thiourea derivative are benzene thiocarbamide, and thiocyanic acid spreads out Biology is trithiocyanuric acid or rhodanate.

The nanoscale Fe₉Ni₉S₁₆The preparation method of base elctro-catalyst, by iron content, nickeliferous presoma, organic sulphur source The method mixed with conductive carrier are as follows: be stirred-evaporate or be stirred after dissolving after direct solid abrasive, dissolution- Freeze-drying.

The nanoscale Fe₉Ni₉S₁₆The preparation method of base elctro-catalyst, conductive carrier be commercialization carbon black XC-72R, It is commercialized carbon pipe or commercialization graphene, conductive carrier and Fe₉Ni₉S₁₆Mass ratio between 10:1~1:10.

The nanoscale Fe₉Ni₉S₁₆The preparation method of base elctro-catalyst, when reaction, required non-oxidizing atmosphere was N₂、 Ar, He or vacuum.

The nanoscale Fe₉Ni₉S₁₆The preparation method of base elctro-catalyst, reaction temperature is between 200 to 1200 DEG C, instead It is 10min between seasonable between for 24 hours.

The nanoscale Fe₉Ni₉S₁₆The preparation method of base elctro-catalyst, nanoscale Fe₉Ni₉S₁₆The ruler of base elctro-catalyst Very little range is 5~500nm.

Design philosophy of the invention is as follows:

Based on industrialization large-scale application and high electrocatalytic decomposition water activity to the group preparation process of material and physical property It is required that using raw material that is cheap, being easy to get, by easy method obtain small size, easily dispersion, compatible different matrix, by cheap The elctro-catalyst of element composition is design philosophy of the invention.

The invention has the advantages and beneficial effects that:

1, presoma used in the present invention is Fe salt, Ni salt and simple organic sulphur source (such as: thiocarbamide), low in cost, acquisition side Formula multiplicity, is conducive to the cost of material that product is greatly lowered.

2, the method applied in the present invention is in 200~900 DEG C of inert gas, and reaction condition is more mild, consumes energy It is low, simple process, easy to operate, compared to the preparation cost that existing method can significantly reduce product.

3, resulting product of the present invention be single phase solid solution, not doped is single-phase, thus have higher structure with The stability of performance, it is possible to realize that more stable electro-catalysis produces oxygen performance.

4, resulting product of the present invention is higher compared to specific surface area has been reported having a size of Nano grade, is conducive to micro- The depth analysis for seeing information, is more advantageous to applied to other field, such as: as electrode material of lithium battery.

Detailed description of the invention

Fig. 1: with FeCl₃·6H₂O、NiCl₂·6H₂O, thiocarbamide is presoma, using carbon nanotube as carrier, by mixing, After freeze-drying, 1h, prepared Fe are reacted in the 50sccmAr air-flow at 600 DEG C₉Ni₉S₁₆XRD spectrum.(a) for according to upper State the Fe of condition preparation₉Ni₉S₁₆, (b) for above-mentioned raw materials and carrier 20sccm of the mixture at 600 DEG C H₂It is anti-in S air-flow The XRD of 1h products therefrom is answered to compose.Wherein, abscissa is 2 θ of the angle of diffraction, and unit is angle (degree)；Ordinate is diffraction peak intensity It spends (a.u.).

Fig. 2: with FeCl₃·6H₂O、NiCl₂·6H₂O, thiocarbamide is presoma, with (a, b) carbon nanotube and (c, d) business Change the Fe of conductive additive XC-72R preparation₉Ni₉S₁₆Pattern and HRTEM image under the tem.

Fig. 3: with FeCl₃·6H₂O、NiCl₂·6H₂O, thiocarbamide is presoma, and with (a) carbon nanotube, (b) XC-72R is carried Body compares its electro-catalysis and produces oxygen performance curve.

Fig. 4: with FeCl₃·6H₂O、NiCl₂·6H₂O, thiocarbamide is presoma, using XC-72R as carrier, by mixing, freezing After dry, 1h is reacted in the 50sccmAr air-flow at 600 DEG C, in 1M (molar concentration) KOH solution, utilizes rotating disk electrode (r.d.e) Device tests Fe using galvanostatic method₉Ni₉S₁₆The stability curve [email protected]XC-72R elctro-catalyst.During the test, OER electric current Constant is 10mA/cm².Wherein, abscissa Time is the time (s)；Ordinate Overpotential is overpotential (V).

Specific embodiment

In the specific implementation process, after the present invention is by mixing molysite, nickel salt, organic sulphur source and conductive carrier, lazy The method reacted under proper temperature in property gas, prepares nanoscale pure phase pentlandite phase Fe-Ni-S solid solution Fe₉Ni₉S₁₆, the specific steps are as follows:

(1) 50mg thiocarbamide is weighed, is dissolved in 10mL deionized water, 13mgFeCl is added₃·6H₂O, 12mg NiCl₂· 6H₂O continues stirring to dissolve completely；

(2) 1mL ethyl alcohol is added in the above solution, 25mg conductive carrier is then added, continues to stir, realizes conductive carrier It is fully dispersed；

(3) after above-mentioned mixed system stirring 12h, chilling is carried out to solution using liquid nitrogen, and be freeze-dried, will be lyophilized Mixed raw material be fully ground in the agate mortar, milling time be 30min or more；

(4) raw material-carrier mixture after taking above-mentioned grinding, is put into burning boat, is placed in the tube furnace for being connected with 50sccmAr, Setting temperature program is 10 degree and rises to 600 DEG C per minute, keeps the temperature 1h, after heat preservation, cools to room temperature with the furnace, closes argon gas, Taking out sample can be obtained the Fe being supported on conductive carrier₉Ni₉S₁₆。

In the following, being further elaborated on by embodiment and attached drawing to the present invention.