CN105070926B - A kind of nickel-base catalyst for improving Direct sodium borohydride fuel cell performance - Google Patents

A kind of nickel-base catalyst for improving Direct sodium borohydride fuel cell performance Download PDF

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Publication number
CN105070926B
CN105070926B CN201510413148.2A CN201510413148A CN105070926B CN 105070926 B CN105070926 B CN 105070926B CN 201510413148 A CN201510413148 A CN 201510413148A CN 105070926 B CN105070926 B CN 105070926B
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catalyst
electrode
nickel
base catalyst
pieces
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CN105070926A (en
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余丹梅
邓维林
陈昌国
李黎
程浩
万慧
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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
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • 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
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/8853—Electrodeposition
    • 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Inert Electrodes (AREA)

Abstract

A kind of nickel-base catalyst for improving Direct sodium borohydride fuel cell performance, it is characterized in that the catalyst is prepared by following straightforward procedure：(1) at ambient pressure, temperature is in 293.15~313.15K scopes, configuration 0.2mol/dm3Nickel sulfate (NiSO4) solution；(2) three-electrode system is assembled：By 2cm2Smooth Ni pieces (making working electrode) be placed in above-mentioned solution, using Ni pieces as to electrode, silver/silver chloride electrode is reference electrode；(3) Ni is deposited in metal nickel sheet using constant potential (0.8V) method and a kind of nickel-base catalyst is made.Because deposition Ni changes the configuration of surface of catalyst, dramatically increase specific surface area, active site increases significantly, so as to enhance BH4 ‑Direct oxidation performance；Meanwhile the charge transfer resistance that Ni also reduces electrode reaction is deposited, significantly improve the discharging efficiency of fuel.

Description

A kind of nickel-base catalyst for improving Direct sodium borohydride fuel cell performance
Technical field
The invention belongs to electrochemical applications field, and in particular to a kind of raising the Ni-based of Direct sodium borohydride fuel cell performance is urged Agent.
Background technology
Currently in order to improve the noble metal catalyst such as Direct sodium borohydride fuel cell performance, generally use Pt, Ag, Pd and Au. Because the metals such as the expensive therefore cheap Ni of these metallic catalysts are urged used also as the anode of boron hydrogen fuel cell Agent.However, when making anode catalyst with Ni in the prior art, because Ni easily corrodes in alkaline environment, cause electrode anti- The charge transfer resistance answered is big, BH4 -Direct oxidation performance it is not high, fuel discharge efficiency is low.
The content of the invention
The purpose of the present invention is exactly in order to overcome the above-mentioned deficiencies of the prior art, there is provided one kind improves direct boron hydrogen fuel electricity The nickel-base catalyst of pond performance, it is desirable to improve BH4 -Direct oxidation performance, strengthen Ni catalyst corrosion resistance, reduce electrode The charge transfer resistance of reaction, improve the discharging efficiency of fuel.
The nickel-base catalyst of a kind of improvement Direct sodium borohydride fuel cell performance involved in the present invention, it is characterized in that the catalysis Agent is prepared by following straightforward procedure：(1) at ambient pressure, temperature is in 293.15~313.15K scopes, configuration 0.2mol/dm3Sulphur Sour nickel (NiSO4) solution；(2) three-electrode system is assembled：By 2cm2Smooth Ni pieces (making working electrode) be placed in above-mentioned solution, Using Ni pieces as to electrode, silver/silver chloride electrode is reference electrode；(3) Ni is deposited to by metallic nickel using constant potential (- 0.8V) method A kind of nickel-base catalyst is made on piece.
The nickel-base catalyst of a kind of improvement Direct sodium borohydride fuel cell performance of the present invention, because deposition Ni changes catalysis The configuration of surface of agent, dramatically increases specific surface area, and active site increases significantly, so as to enhance BH4 -Direct oxidation Performance；Meanwhile the charge transfer resistance that Ni also reduces electrode reaction is deposited, significantly improve the discharging efficiency of fuel.
Brief description of the drawings
The SEM figures of Fig. 1 Ni catalyst；
The SEM figures of Fig. 2 deposition Ni catalyst；
The lower BH of Fig. 3 different catalysts effect4 -The cyclic voltammetry curve of direct oxidation；
BH under deposition Ni catalyst actions prepared by Fig. 4 differences sedimentation time4 -The volt-ampere curve of direct oxidation；
The catalytic capability of deposition Ni catalyst prepared by Fig. 5 differences sedimentation time compares figure；
BH under Fig. 6 Ni catalyst actions4 -The multiple cyclic voltammetry curve of direct oxidation；
1 is the period 1；2 be second round；3 be the period 3
BH under Fig. 7 deposition Ni catalyst actions4 -The multiple cyclic voltammetry curve of direct oxidation；
1 is the period 1；2 be second round；3 be the period 3
The lower BH of Fig. 8 different catalysts effect4 -The ac impedance spectroscopy of direct oxidation；
The lower BH of Fig. 9 different catalysts effect4 -Discharge curve (discharge time 1000s)；
The lower BH of Figure 10 different catalysts effect4 -Discharge curve
Embodiment
The method of the present invention is further described below with reference to the accompanying drawings and examples：
Embodiment 1：
At ambient pressure, temperature is in 293.15~313.15K scopes, configuration 0.2mol/dm3NiSO4Solution.By 2cm2's Smooth Ni pieces (making working electrode) are placed in above-mentioned solution, using Ni pieces to be reference electrode to electrode, silver/silver chloride electrode, are adopted Ni is deposited in metal nickel sheet with constant potential (- 0.8V) method a kind of nickel-base catalyst is made.Weigh appropriate sodium borohydride (NaBH4), and it is dissolved in 2mol/dm3Sodium hydroxide (NaOH) solution in, 0.27mol/dm is made3NaBH4Solution, mix Direct NaBH is used as after closing uniformly4The electrolyte of fuel cell.Respectively with 2cm2Ni catalyst and deposition Ni catalyst be work Electrode, mercury/mercuric oxide electrode are reference electrode, and graphite rod is auxiliary electrode, and performance survey is carried out using linear sweep voltametry (LSV) Examination.
The electron scanning figure (SEM) of Ni catalyst and deposition Ni catalyst prepared by the present embodiment is as shown in Figure 1 and Figure 2. From figure 1 it appears that the surface of Ni catalyst is smooth plane；In Fig. 2 deposit Ni catalyst be by small block Ni not Smooth Ni pieces surface is evenly dispersed in form.Such structural change configuration of surface of catalyst, shows specific surface area Increase is write, active site increases significantly, so as to enhance BH4 -Direct oxidation performance.
Fig. 3 gives different catalysts effect lower BH4 -The cyclic voltammetry curve of direct oxidation.By with blank assay (nothing NaBH4) contrast, it can be seen that Ni catalyst and deposition Ni catalyst to BH4 -Direct oxidation have catalytic action.Urged in Ni Under agent effect, BH4 -Direct oxidation peak current be 11.5mA/cm2, and in the case where depositing Ni catalyst actions, BH4 -Direct oxygen Change peak current to significantly increase, reach 58mA/cm2.The BH in the case where depositing Ni catalyst actions4 -Direct oxidation peak current be that Ni is urged 5 times under agent effect.Illustrate that depositing Ni catalyst significantly enhances BH4 -Direct oxidation performance.
Fig. 4 gives BH under deposition Ni catalyst actions prepared by different sedimentation times4 -The volt-ampere curve of direct oxidation. As can be seen that being continuously increased with sedimentation time, BH in LSV (Fig. 4)4 -Direct oxidation peak current present first increases and then decreases Trend, BH4 -Direct oxidation peak current there is maximum (116mA), be BH under Ni catalyst actions4 -Oxidation peak current It is worth 5 times of (23mA).Fig. 5 compares the catalytic capability of deposition Ni catalyst prepared by different sedimentation times.Can from Fig. 5 Go out, when sedimentation time is 100s, BH4 -Oxidation peak current value it is maximum, the catalytic capability of catalyst is most strong.
Embodiment 2：
At ambient pressure, temperature is in 293.15~313.15K scopes, configuration 0.2mol/dm3NiSO4Solution.By 2cm2's Smooth Ni pieces (making working electrode) are placed in above-mentioned solution, using Ni pieces to be reference electrode to electrode, silver/silver chloride electrode, are adopted Ni is deposited in metal nickel sheet with constant potential (- 0.8V) method a kind of nickel-base catalyst is made.Weigh appropriate NaBH4, and will It is dissolved in 2mol/dm3NaOH solution in, 0.27mol/dm is made3NaBH4Solution, direct NaBH is used as after well mixed4 The electrolyte of fuel cell.Respectively with 2cm2Ni catalyst and deposition Ni catalyst be working electrode, mercury/mercuric oxide electrode is Reference electrode, graphite rod are auxiliary electrode, and performance test is carried out using cyclic voltammetry.
Fig. 6 is BH under Ni catalyst actions4 -The multiple cyclic voltammetry curve of direct oxidation.As can be seen that in Ni catalyst Under effect, BH4 -During the second round cyclic voltammetry scan of direct oxidation, BH4 -Direct oxidation peak very little, by the 3rd week Oxidation peak disappears substantially during the phase.Because in alkaline medium, Ni surfaces form one layer of fine and close Ni (OH)2It is covered in Ni Catalyst surface, Ni catalyst is corroded, lose catalytic activity.It is right in the case where depositing Ni catalyst actions under the same terms BH4 -Direct oxidation has carried out multiple cyclic voltammetry scan, as shown in Figure 7.As can be seen that compared with Ni catalyst, in deposition Ni Under catalyst action, BH4 -During the period 1 cyclic voltammetry scan of direct oxidation, oxidation peak current significantly increases.In second week In phase scanning, oxidation peak current is still very high, is 4 times under Ni catalyst actions.And during to the period 3, oxidation peak current Value can also reach BH under Ni catalyst actions4 -In the peak point current of period 1.Illustrate in alkaline NaBH4In solution, deposition Ni is urged The corrosion resistance of agent is much stronger than common Ni catalyst.
Embodiment 3：
At ambient pressure, temperature is in 293.15~313.15K scopes, configuration 0.2mol/dm3NiSO4Solution.By 2cm2's Smooth Ni pieces (making working electrode) are placed in above-mentioned solution, using Ni pieces to be reference electrode to electrode, silver/silver chloride electrode, are adopted Ni is deposited in metal nickel sheet with constant potential (- 0.8V) method a kind of nickel-base catalyst is made.Weigh appropriate NaBH4, and will It is dissolved in 2mol/dm3NaOH solution in, 0.27mol/dm is made3NaBH4Solution, direct NaBH is used as after well mixed4 The electrolyte of fuel cell.Respectively with 2cm2Ni catalyst and deposition Ni catalyst be working electrode, mercury/mercuric oxide electrode is Reference electrode, graphite rod are auxiliary electrode, carry out ac impedance spectroscopy performance test.
Fig. 8 is the lower BH of different catalysts effect4 -The ac impedance spectroscopy of direct oxidation.It can be seen that BH4 -It is straight Connect electrochemical impedance spectroscopy of the oxidation under Ni catalyst and deposition Ni catalyst actions and significant difference be present.Compare Fig. 8 and find height The diameter of the electrochemical impedance in frequency area is：Deposit Ni catalyst ＜ Ni catalyst.The diameter of semi arch represents electrode reaction Electrochemical impedance size.It is smaller to deposit the arc diameter of Ni catalyst, only the half of Ni catalyst, illustrate to urge in deposition Ni The lower BH of agent effect4 -Direct oxidation reaction be more prone to, the energy barrier that electrochemical reaction need to overcome is small, anti-so as to enhance electrode The charge transfer answered, significantly improves BH4 -Oxidation susceptibility.
Embodiment 4：
At ambient pressure, temperature is in 293.15~313.15K scopes, configuration 0.2mol/dm3NiSO4Solution.By 2cm2's Smooth Ni pieces (making working electrode) are placed in above-mentioned solution, using Ni pieces to be reference electrode to electrode, silver/silver chloride electrode, are adopted Ni is deposited in metal nickel sheet with constant potential (- 0.8V) method a kind of nickel-base catalyst is made.Weigh appropriate NaBH4, and will It is dissolved in 2mol/dm3NaOH solution in, 0.27mol/dm is made3NaBH4Solution, direct NaBH is used as after well mixed4 The electrolyte of fuel cell.Respectively with 2cm2Ni catalyst and deposition Ni catalyst be working electrode, mercury/mercuric oxide electrode is Reference electrode, graphite rod are auxiliary electrode, carry out constant current discharge performance test.
It in current density is 10mA/cm that Fig. 9, which is,2Under, with 0.27mol/dm3NaBH4For electrolyte solution, different catalysts The lower BH of effect4 -Discharge curve (discharge time 1000s).It can be seen that under Pt catalyst actions, BH4 -Directly The initial discharge current potential E of oxidationPt=-0.54V；Under the same conditions, BH under Ni catalyst actions4 -The initial of direct oxidation is put Electric potential is ENi=-0.80V, than reducing 0.26V under Pt catalyst action；Under the same terms, deposit under Ni catalyst actions BH4 -The initial discharge current potential E of direct oxidationDeposit Ni=-0.88V, than reducing 0.34V under Pt catalyst action.According to formula：P =IE (P is power, and I is discharge current, and E is current potential), because discharge current I is identical, PNi∶PPt≈ENi∶EPt=1.5； PDeposit Ni∶PPt≈EDeposit Ni∶EPt=1.6.From the foregoing, it will be observed that in the case where depositing Ni catalyst actions, BH4 -Initial discharge current potential it is most negative, The operating voltage highest of battery, power are maximum.
It in current density is 10mA/cm that Figure 10, which is,2Under, with 0.27mol/dm3NaBH4For electrolyte solution, different catalysts The lower BH of effect4 -Discharge curve.It can be seen that the BH in the case where depositing Ni catalyst actions4 -Discharge potential it is more negative, electricity Cell voltage is higher, and power is also bigger.The BH under Ni catalyst actions4 -Discharge time be 1.4 × 103S, in deposition Ni catalyst The lower BH of effect4 -Discharge time be 7.2 × 104s.By formula Q=It=nZF and η=t '/t, the BH under Ni catalyst actions4 - Discharging efficiency be 4%, the BH in the case where depositing Ni catalyst actions4 -Discharging efficiency be 23%, discharging efficiency improve close to 6 times.

Claims (1)

  1. A kind of 1. nickel-base catalyst for improving Direct sodium borohydride fuel cell performance, it is characterized in that the catalyst is by following methods system It is standby：
    (1) at ambient pressure, temperature is in 293.15~313.15K scopes, preparation 0.2mol/dm3Nickel sulfate NiSO4Solution；
    (2) three-electrode system is assembled：By 2cm2Smooth Ni pieces be placed in as working electrode in above-mentioned solution, using Ni pieces as to electricity Pole, silver/silver chlorate are reference electrode；
    (3) Ni is deposited on the smooth Ni pieces using potentiostatic method and a kind of nickel-base catalyst is made；Wherein described in preparation Used sedimentation potential is -0.8V during nickel-base catalyst.
CN201510413148.2A 2015-07-13 2015-07-13 A kind of nickel-base catalyst for improving Direct sodium borohydride fuel cell performance Expired - Fee Related CN105070926B (en)

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CN105826576A (en) * 2016-05-31 2016-08-03 重庆大学 Additive for improving nickel anode catalyst performance of direct borohydride fuel cell
CN106287529A (en) * 2016-07-27 2017-01-04 杨炳 A kind of LED light device based on solar energy
CN108155391A (en) * 2017-10-20 2018-06-12 重庆大学 A kind of efficient nickel-base catalyst for promoting sodium borohydride direct oxidation
CN108736023B (en) * 2018-05-18 2021-04-23 重庆大学 Preparation of nickel-based catalyst additive for efficiently catalyzing direct oxidation of borohydride

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4115628A (en) * 1975-01-10 1978-09-19 Agence Nationale De Valorisation De La Recherche (Anvar) Electrode comprising a nickel based catalyst for electrochemical generators
CN101914783A (en) * 2010-08-13 2010-12-15 上海交通大学 Electrochemical deposition-based method for preparing electro-catalysis ammonia oxide electrode
CN102244276A (en) * 2011-05-24 2011-11-16 重庆大学 Ni-Cu binary catalyst for improving performance of direct borohydride fuel cell

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4115628A (en) * 1975-01-10 1978-09-19 Agence Nationale De Valorisation De La Recherche (Anvar) Electrode comprising a nickel based catalyst for electrochemical generators
CN101914783A (en) * 2010-08-13 2010-12-15 上海交通大学 Electrochemical deposition-based method for preparing electro-catalysis ammonia oxide electrode
CN102244276A (en) * 2011-05-24 2011-11-16 重庆大学 Ni-Cu binary catalyst for improving performance of direct borohydride fuel cell

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