CN108155391A - A kind of efficient nickel-base catalyst for promoting sodium borohydride direct oxidation - Google Patents

A kind of efficient nickel-base catalyst for promoting sodium borohydride direct oxidation Download PDF

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Publication number
CN108155391A
CN108155391A CN201711042926.7A CN201711042926A CN108155391A CN 108155391 A CN108155391 A CN 108155391A CN 201711042926 A CN201711042926 A CN 201711042926A CN 108155391 A CN108155391 A CN 108155391A
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electrode
catalyst
nickel
solution
direct oxidation
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Inventor
余丹梅
熊欣
徐川岚
胡兵兵
刘丽君
刘渝萍
陈昌国
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Chongqing University
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Chongqing University
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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
    • H01M4/90—Selection of catalytic material
    • 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
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Inert Electrodes (AREA)

Abstract

A kind of efficient nickel-base catalyst for promoting sodium borohydride direct oxidation, it is characterized in that the catalyst is prepared by following methods：(1) under normal pressure, 20~30 DEG C of ranges prepare 0.2mol/dm3Nickel sulfate electric depositing solution.Prepare chemical plating solution (25g/L NiSO4·6H2O, 30g/L NaH2PO2·H2O, 30g/L NaAc, 18g/L lactic acid)；(2) three-electrode system：With 2cm2Smooth Ni pieces for working electrode, carbon-point is to electrode, and saturated calomel electrode is reference, and nickel sulfate is electric depositing solution；(3) Ni is deposited in nickel sheet using potentiostatic method and a kind of nickel-base catalyst is made, sedimentation potential 1.0V, time 100s.Electro-deposition and chemical plating changed dramatically the configuration of surface of Ni catalyst, greatly increase its specific surface area, and active site increases, and enhances BH4 ‑Direct oxidation performance；The charge transfer resistance of electrode reaction is also reduced simultaneously, significantly improves the discharging efficiency of fuel.

Description

A kind of efficient nickel-base catalyst for promoting sodium borohydride direct oxidation
Technical field
The invention belongs to electrochemical applications fields, and in particular to electro-deposition and electroless plating method preparation catalysis sodium borohydride are direct The nickel-base catalyst of oxidation, and sodium borohydride is the negative electrode active material of direct sodium borohydride fuel cell, the i.e. fuel of battery.
Background technology
Direct sodium borohydride fuel cell (DBFC) has open-circuit voltage height, and specific capacity is big and energy conversion rate is high, transport The a series of advantage such as facilitate.But just it also there are problems that from the point of view of current progress：①BH4 -In electrochemical oxidation When the hydrolysis liberation of hydrogen supervened, fuel availability is caused to decline, the raising of anode open circuit potential；2. when battery works, BH4 -'s " penetrating " phenomenon declines waste of fuel, cathode performance.The high noble metal of hydrogen overpotential is selected as catalyst, to a certain degree Upper inhibition BH4 -Hydrolyze liberation of hydrogen；" penetrating " phenomenon can be solved, but theirs is expensive, improves DBFC using amberplex Production cost, limit its and large-scale produce.Precious metal catalyst superior performance, when making the anode catalyst of DBFC with Au, 1mol BH4 -6.9mol electronics can be generated, Pd, which makees anode, can generate 6mol, and Pt, which makees anode, can generate 5-5.5mol.Although Ni 4mol electronics can only be generated, but compared with noble metal, there is price absolute predominance.So seeking function admirable prepares simple cost Low anode catalyst is a problem to be solved.
Invention content
The purpose of the invention is to overcome above-mentioned a series of deficiency.
A kind of efficient Raney nickel for promoting sodium borohydride direct oxidation according to the present invention, utilizes electro-deposition and chemistry Plating method prepares plating Raney nickel, and preparation method is as follows：
(1) under normal pressure, temperature is in 20~30 DEG C of ranges, preparation 0.2mol/dm3Nickel sulfate NiSO4Solution 100mL, (2) three-electrode system is assembled：By 1 × 2cm2Smooth Ni pieces be placed in above-mentioned solution as working electrode, using carbon-point as to electricity Pole, saturated calomel electrode electrode are reference electrode；(3) when temperature is 25 DEG C using chronoamperometry, sedimentation potential for- 1.0V deposits to Ni in the above-mentioned nickel sheet polished smooth, sedimentation time 100s, and (4) are molten in the chemical plating that temperature is 25 DEG C 5min is put in leaching in liquid, and prepared by Raney nickel completes.
The nickel-base catalyst that catalysis direct sodium borohydride fuel cell is prepared with electro-deposition and electroless plating method of the present invention, two The mode of kind deposition Ni changes the configuration of surface of Ni base catalyst, dramatically increases specific surface area, active site is significantly Increase, so as to enhanceDirect oxidation performance；Meanwhile the charge transfer resistance that Ni also reduces electrode reaction is deposited, Significantly improve the discharging efficiency of fuel.
Description of the drawings
The SEM figures of Fig. 1 Ni catalyst；
Fig. 2, the SEM figures of plating Ni catalyst before 3 electric discharges；
The SEM figures of plating Ni catalyst after the test of Fig. 4 constant current discharges；
Fig. 5 plates the XRD diagram of Ni catalyst；
Fig. 6 Ni catalystsThe cyclic voltammetry curve of oxidation；
Fig. 7 deposits Ni catalystsThe cyclic voltammetry curve of oxidation；
Fig. 8 chemical platings 5min plates Ni catalystsThe cyclic voltammetry curve of oxidation；
Fig. 9 chemical platings 10min plates Ni catalystsThe cyclic voltammetry curve of oxidation；
Figure 10 Ni catalyst and plating Ni catalyst take-off potentials compare figure；
Figure 11 Ni catalystsThe discharge curve of oxidation；
Figure 12 plates Ni catalystsThe discharge curve of oxidation；
Under Figure 13 Ni and plating Ni catalyst actionsThe ac impedance spectroscopy of direct oxidation.
Specific embodiment
The method of the present invention is further described below in conjunction with the accompanying drawings and embodiments：
Embodiment 1：
Under normal pressure, room temperature prepares 0.2mol/dm between 20~30 DEG C3NiSO4Solution, with dilute H2SO4Adjust pH Value as electric depositing solution, prepares chemical plating solution 2.8 or so, forms and is：Reducing agent NiSO4·6H2O is 25g/L, oxidation Agent NaH2PO2·H2O is 30g/L, and buffer NaAc is 30g/L, and complexant lactic acid is 18mg/L.By 1 × 2cm2It polishes smooth Ni pieces are placed in as working electrode in electric depositing solution, and using carbon-point as to electrode, saturated calomel electrode is reference electrode, water-bath temperature It is 25 DEG C to spend, and is deposited using chronoamperometry, and sedimentation potential is -1.0V, sedimentation time 100s, cleans, dries.Then in temperature It spends leaching in the chemical plating solution for 25 DEG C and puts 5min, nickel plating catalyst preparation is completed.
Electron scanning figure (SEM) such as Fig. 1 of Ni catalyst and plating Ni catalyst prepared by the present embodiment, shown in 2,3, Ni The surface of piece catalyst is smooth plane, and plating Ni catalyst surfaces has one layer of loose nickel layer, and such structure, which changes, urges The configuration of surface of agent, dramatically increases specific surface area, and active site increases significantly, and catalyst is corrosion-resistant in lye Property also accordingly enhance, by long-time discharge after, plate Ni catalyst SEM as shown in figure 4, plating Raney nickel be all corroded React into block-like Ni (OH)2, lose catalytic activity.The X ray diffracting spectrum (XRD) of Ni catalyst is plated as shown in figure 5, scheming In spectrum, occur very strong diffraction maximum when 2 θ are respectively 44.5,51.78 and 76.4, be corresponding in turn to (111), (200), (220) Crystal face, the position of crystal face and the standard card PDF#70-0908 ten of W metal divide identical, it was demonstrated that passes through electro-deposition and chemical plating Process, it is all same metal simple-substance " nickel " to plate ingredient in Ni catalyst.
Embodiment 2
Under normal pressure, room temperature prepares 0.2mol/dm between 20~30 DEG C3NiSO4Solution 100mL adjusts pH value and exists 2.8 or so, as electric depositing solution, chemical plating solution is prepared, forms and is：Reducing agent NiSO4·6H2O is 25g/L, oxidant NaH2PO2·H2O is 30g/L, and buffer NaAc is 30g/L, and complexant lactic acid is 18mg/L.By 1 × 2cm2The Ni polished smooth Piece is placed in as working electrode in electric depositing solution, and using carbon-point as to electrode, saturated calomel electrode is reference electrode, bath temperature It is 25 DEG C, is deposited using chronoamperometry, sedimentation potential is -1.0V, sedimentation time 100s, cleans, dries.It is 25 in temperature DEG C chemical plating solution in be soaked respectively and set to 0 min, 5min, 10min.The nickel plating catalyst preparation of different chemical plating durations is completed.Claim Take suitable NaBH4, and it is dissolved in 2mol/dm3NaOH solution in, 0.27mol/dm is made3NaBH4Solution, mixing are equal Direct NaBH is used as after even4The electrolyte of fuel cell.Respectively with 1 × 2cm2Ni catalyst and plating Ni catalyst be work electricity Pole, mercury/mercuric oxide electrode are reference electrode, and carbon-point is to electrode, is tested for the property using cyclic voltammetry.
Fig. 6 be under Ni catalyst actions,Direct oxidation peak current be 6.5mA, current potential is in -0.7V or so.Figure 7,8,9 be respectively chemical plating be 0min, the direct cyclic voltammogram of plating Ni catalysts of 5min, 10min, as shown in the figure, Their direct oxidation peak current is respectively 113mA, 141mA, 91mA.It follows that it is obtained during a length of 5min in chemical plating Plating Raney nickel catalytic effect it is best, and plate Ni catalystsThe peak current of direct oxidation is Ni catalyst 20 times.Electro-deposition and electroless plating method increase the surface area of the Ni base catalyst of script, it is made to be catalyzed specific surface increase, so as to The active site of matrix is increased, improves its catalysisThe activity of oxidation.
Embodiment 3：
Under normal pressure, room temperature prepares 0.2mol/dm between 20~30 DEG C3NiSO4Solution is adjusted as electric depositing solution PH value is saved 2.8 or so.Chemical plating solution is prepared, forms and is：Reducing agent NiSO4·6H2O is 25g/L, oxidant NaH2PO2· H2O is 30g/L, and buffer NaAc is 30g/L, and complexant lactic acid is 18mg/L.By 1 × 2cm2The Ni pieces polished smooth are as work It is placed in electric depositing solution as electrode, using carbon-point as to electrode, saturated calomel electrode is reference electrode, and bath temperature is 25 DEG C, It is deposited using chronoamperometry, sedimentation potential is -1.0V, sedimentation time 100s, is cleaned, in the change that temperature is 25 DEG C after drying It learns leaching in plating liquor and puts 5min, nickel plating catalyst preparation is completed.Weigh suitable NaBH4, and it is dissolved in 2mol/dm3's In NaOH solution, 0.27mol/dm is made3NaBH4Solution, after mixing as direct NaBH4The electrolyte of fuel cell.Point Not with 1 × 2cm2Ni catalyst and plating Ni catalyst be working electrode, mercury/mercuric oxide electrode is reference electrode, and stick is to electricity Pole carries out constant current discharge performance (CP).
As shown in Figure 10, it is 10mA/cm in current density2, electrolyte 0.27mol/dm3NaBH4+2mol/dm3NaOH, Ni catalyst and plating Ni catalystsThe initial discharge potential diagram of oxidation.As seen from the figure, Ni catalystsDirectly The initial discharge current potential for connecing oxidation is ENi=-0.79V, and plate Ni catalystsThe initial discharge current potential of direct oxidation EPlate Ni=-0.83V, the latter's current potential reduce 40mV.Figure 11,12 be respectively that Ni bases catalyst is put with the constant current for plating Ni catalyst Electric curve, as shown in the figure, a length of 1500s (about 0.42h) during the electric discharge of Ni catalyst, by formula Q=It=nZF and η=t '/t, It is 4% that discharging efficiency, which is calculated, and the electric discharge duration for plating Raney nickel is about 86h, and discharging efficiency is about 83%, discharging efficiency Increase about 21 times.Under the preparation process of electro-deposition and chemical plating, discharging efficiency increases substantially.
Embodiment 4：
Under normal pressure, room temperature prepares 0.2mol/dm between 20~30 DEG C3NiSO4Solution, with dilute H2SO4Adjust pH Value as electric depositing solution, prepares chemical plating solution 2.8 or so, consisting of：Reducing agent NiSO4·6H2O is 25g/L, oxygen Agent NaH2PO2·H2O is 30g/L, and buffer NaAc is 30g/L, and complexant lactic acid is 18mg/L.Now by 1 × 2cm2Polishing light Sliding Ni pieces are placed in as working electrode in electric depositing solution, and using carbon-point as to electrode, saturated calomel electrode is reference electrode, water Bath temperature is 25 DEG C, is deposited using chronoamperometry, and sedimentation potential is -1.0V, sedimentation time 100s, cleans, dries.In temperature It spends leaching in the chemical plating solution for 25 DEG C and puts 5min, nickel plating catalyst preparation is completed.Weigh suitable NaBH4, and dissolved In 2mol/dm3NaOH solution in, 0.27mol/dm is made3NaBH4Solution, after mixing as direct NaBH4Fuel electricity The electrolyte in pond.Respectively with 1 × 2cm2Ni catalyst and plating Ni catalyst be working electrode, mercury/mercuric oxide electrode is reference Electrode, carbon-point are to electrode, carry out ac impedance spectroscopy (EIS) and test.
Figure 13 is Ni catalyst and plating Ni catalyst pairThe ac impedance spectroscopy of direct oxidation.Semi arch reflection in figure The impedance of electrochemical reaction process, the diameter of semi arch represent the impedance magnitude of electrochemical reaction, and diameter is bigger to represent its correspondence The faradic currents impedance value of generation is bigger, and electrode reaction is more difficult to carry out；The intersection point of semi arch and real axis is solution resistance, is reflected The ohmic internal resistance of diaphragm, electrolyte and electrode.Ni catalyst is plated compared with Ni catalyst, either the diameter of semi arch, also It is the intersection point of semi arch and real axis, the value for depositing Ni catalyst is all smaller than Ni catalyst.The resistance value for plating Ni catalyst is left for 20 Ω The right side, and the resistance value of Ni catalyst, in 80 Ω or so, the latter is the former 4 times.Electrode reaction resistance becomes smaller at this time, reaction rate Soon, electrode reaction is easier to carry out, and solution resistance becomes smaller, and so as to enhance the charge transfer of electrode reaction, significantly improves plating Ni CatalystThe ability of direct oxidation.

Claims (1)

1. a kind of efficient nickel-base catalyst for promoting sodium borohydride direct oxidation, it is characterized in that the catalyst is by following methods system It is standby：
(1) under normal pressure, temperature is in 20~30 DEG C of ranges, preparation 0.2mol/dm3Nickel sulfate NiSO4Solution；Adjust pH value of solution Value is 2.8 or so, as electric depositing solution.Chemical plating solution is prepared, forms and is：Reducing agent NiSO4·6H2O is 25g/L, oxidation Agent NaH2PO2·H2O is 30g/L, and buffer NaAc is 30g/L, and complexant lactic acid is 18g/L；
(2) three-electrode system is assembled：By 1 × 2cm2Smooth Ni pieces be placed in electric depositing solution as working electrode, made with carbon-point For to electrode, saturated calomel electrode is reference electrode；
(3) it is first deposited using chronoamperometry.Sedimentation potential is -1.0V, sedimentation time 100s, cleans, dries.Exist again 5min is put in leaching in the chemical plating solution that temperature is 25 DEG C, and prepared by Raney nickel completes.
CN201711042926.7A 2017-10-20 2017-10-20 A kind of efficient nickel-base catalyst for promoting sodium borohydride direct oxidation Pending CN108155391A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109994744A (en) * 2019-01-31 2019-07-09 重庆大学 A kind of nickel cobalt binary catalyst promoting sodium borohydride direct oxidation
CN110504457A (en) * 2019-08-21 2019-11-26 中国华能集团清洁能源技术研究院有限公司 A kind of nickel base electrode antiseptic property optimization method
CN110649274A (en) * 2019-09-25 2020-01-03 重庆大学 Porous microsphere nickel-based catalyst for enhancing direct oxidation of borohydride

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CN1364114A (en) * 2000-03-03 2002-08-14 三井金属鉱业株式会社 Carrier foil-pasted metal foil and production method thereof
CN1818141A (en) * 2006-03-31 2006-08-16 北京航空航天大学 Method for coating Ni-P layer in same liquid by chemically plating and electrobath
CN105070926A (en) * 2015-07-13 2015-11-18 重庆大学 Nickel-based catalyst for improving performance of direct borohydride fuel cell

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CN1364114A (en) * 2000-03-03 2002-08-14 三井金属鉱业株式会社 Carrier foil-pasted metal foil and production method thereof
CN1818141A (en) * 2006-03-31 2006-08-16 北京航空航天大学 Method for coating Ni-P layer in same liquid by chemically plating and electrobath
CN105070926A (en) * 2015-07-13 2015-11-18 重庆大学 Nickel-based catalyst for improving performance of direct borohydride fuel cell

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109994744A (en) * 2019-01-31 2019-07-09 重庆大学 A kind of nickel cobalt binary catalyst promoting sodium borohydride direct oxidation
CN109994744B (en) * 2019-01-31 2021-09-07 重庆大学 Nickel-cobalt binary catalyst for promoting direct oxidation of sodium borohydride
CN110504457A (en) * 2019-08-21 2019-11-26 中国华能集团清洁能源技术研究院有限公司 A kind of nickel base electrode antiseptic property optimization method
CN110649274A (en) * 2019-09-25 2020-01-03 重庆大学 Porous microsphere nickel-based catalyst for enhancing direct oxidation of borohydride

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Application publication date: 20180612