CN104084207A - Preparation method of Ni-loaded hollow carbon microsphere NaBH4 electro-oxidation catalyst - Google Patents

Preparation method of Ni-loaded hollow carbon microsphere NaBH4 electro-oxidation catalyst Download PDF

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CN104084207A
CN104084207A CN201410317178.9A CN201410317178A CN104084207A CN 104084207 A CN104084207 A CN 104084207A CN 201410317178 A CN201410317178 A CN 201410317178A CN 104084207 A CN104084207 A CN 104084207A
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electro
nabh
preparation
oxidizing
exchange resin
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CN104084207B (en
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王贵领
王滨
曲军
张硕
曹殿学
蔡庄
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Harbin Engineering University
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Harbin Engineering University
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    • 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

Abstract

The invention provides a preparation method of a Ni-loaded hollow carbon microsphere NaBH4 electro-oxidation catalyst. The method comprises the steps of (1) mixing styrene and divinylbenzene with deionized water, introducing N2 into the mixed solution, feeding CC14, and maintaining the temperature of 60 DEG C; after that, feeding K2S2O8 and NaCl, stirring, gradually heating up to 70 DEG C, and carrying out reaction for 10-12 hours to obtain an emulsion; cleaning by alcohol and centrifuging; carrying out vacuum drying for 8-10 hours at the temperature of 50 DEG C to obtain polystyrene microspheres; (2) putting the obtained polystyrene microspheres into dichloromethane, swelling for 30 minutes, feeding concentrated sulfuric acid, and carrying out reaction for 2-4 hours at the temperature of 80-90 DEG C; adjusting the pH value to be 10-12, and drying for 5-6 hours at the temperature of 50 DEG C to obtain sodium polystyrenesulfonate cation exchange resin microspheres; (3) soaking the obtained sodium polystyrenesulfonate cation exchange resin microspheres into NiCl solution for 8-10 hours, then taking out the product, and drying for 4-5 hours at the temperature of 50 DEG C to obtain Ni-loaded cation exchange resin microspheres; and (4) calcining the Ni-loaded cation exchange resin microspheres for 5-6 hours under the nitrogen atmosphere at the temperature of 650-750 DEG C to obtain the Ni-loaded hollow carbon microsphere catalyst. After the method is adopted, the electro-oxidation performance and the utilization rate of the NaBH4 can be greatly improved.

Description

Carry Ni Carbon Hollow microballoon NaBH 4the preparation method of electro-oxidizing-catalyzing agent
Technical field
The present invention relates to a kind of NaBH 4the preparation method of electro-oxidizing-catalyzing agent.
Background technology
Direct borohydride fuel cell is a kind of novel direct liquid fuel battery using boron hydride as anode fuel.High (the NaBH of boron hydride hydrogen content 4, 11wt.%), oxidation kinetics speed is fast, and energy density is high, and (specific energy is 9300Whkg -1, 2850WhL -1); Specific capacity reaches 5668Ahkg -1; Boron hydride is nonflammable, toxicity is low, and boron hydride is solid in addition, is convenient to store transport; The most important thing is not produce CO in boron hydride electro-oxidation process, therefore do not have catalyst poisoning phenomenon.Above-mentioned outstanding advantages makes direct borohydride fuel cell promise to be the compact power of space power system of new generation, underwater power source and high-energy high power density.
The complete electroxidation of sodium borohydride can provide 8 electronics in theory, referring to (1) formula:
BH 4 -+8OH -→BO 2 -+4H 2O+8e - (1)
NaBH 4electro-oxidizing-catalyzing agent is mainly divided into two large classes, and a class is the noble metals such as Pt, Pd, Au, Ir, another kind of for being hydrogen bearing alloy.But two class catalyst are all easy to occur NaBH 4hydrolysis, referring to (2) formula:
NaBH 4+2H 2O→4H 2+NaBO 2 (2)
(2) hydrogen that formula hydrolysis discharges also can continue to occur oxidation reaction at electrode surface:
H 2+2OH -→2H 2O+2e - (3)
Therefore, the electrode potential of real process Anodic is the mixed potential between formula (1) and (3); If the hydrogen that (2) formula hydrolysis discharges is too much, have little time to occur the electro-oxidation reaction of (3) formula, hydrogen just discharges and makes boron hydride oxidation not exclusively with the situation of hydrogen, and the electron number of release is less than 8, difficulty when produced simultaneously hydrogen can strengthen battery design.Can consult Wang Guiling, Lan Jian, Cao Dianxue etc., directly NaBH 4-H 2o 2the progress of fuel cell, Journal of Chemical Industry and Engineering, 2008,159 (4): 805-813, and Dongming Zhang, Kui Cheng, Nannan Shi, Fen Guo, Guiling Wang, Dianxue Cao.Nickel particles supported on multi-walled carbon nanotubes modified sponge for sodium borohydride electrooxidation.Electrochemistry Communications, 2013,35:128 – 130.
Summary of the invention
The object of the present invention is to provide one can greatly improve NaBH 4electroxidation performance and utilization rate carry Ni Carbon Hollow microballoon NaBH 4the preparation method of electro-oxidizing-catalyzing agent.
The object of the present invention is achieved like this:
(1) styrene, divinylbenzene are mixed with deionized water, pass into N 2, add pore-foaming agent CCl 4, keeping temperature is 60 DEG C; Then add K 2s 2o 8and NaCl, stir and be warmed up to gradually 70 DEG C, reaction 10-12h obtains emulsion; By emulsion breaking and put into cryostat,, clean and centrifugal with ethanol, 50 DEG C of vacuum drying 8-10h, obtain polystyrene microsphere;
(2) polystyrene microsphere is put in to swelling 30min in carrene, then adds the concentrated sulfuric acid, at 80 DEG C-90 DEG C, react 2-4h, adjust pH to 10～12, dry 5-6h obtains sodium polystyrene sulfonate cation exchange resin microballoon at 50 DEG C;
(3) sodium polystyrene sulfonate cation exchange resin microballoon immerses NiCl 28-10h in solution, then takes out dry 4-5h at 50 DEG C and obtains carrying Ni cationic ion-exchange resin microballoon;
(4) will carry Ni cationic ion-exchange resin microballoon, under nitrogen atmosphere, 650-750 DEG C of calcining 5-6h, obtains carrying Ni Carbon Hollow microspherical catalyst.
The present invention can also comprise:
1, the mass ratio of styrene, divinylbenzene and deionized water is 1:0.05:19, N 2the time that passes into be 20-30min, styrene and CCl 4weight ratio=1:0.1, styrene and K 2s 2o 8weight ratio=1:0.04:0.01 with NaCl.
2, the temperature of cryostat, is-5 DEG C.
3, the weight ratio=1:2 of polystyrene microsphere and carrene, the weight ratio=1:5 of polystyrene microsphere and 98% the concentrated sulfuric acid.
4, NiCl 2the concentration of solution is 0.01-0.05mol/L.
The present invention proposes a kind of year Ni hollow cationic ion-exchange resin microballoon catalyzing N aBH with carbonization 4the method of electroxidation performance.Cationic ion-exchange resin microballoon adds pore-foaming agent in the time of polymerisation, can form the skeleton of mandruka columnar structure, and there are a large amount of permanent micropores inside.Can be by Ni ion implantation resin inside by cation exchange, after anaerobic high temperature cabonization, the stephanoporate framework of cationic ion-exchange resin is preserved, and makes and carries Ni Carbon Hollow microspherical catalyst.Carry Ni Carbon Hollow microsphere surface long-pending very large, the carbon microspheres ball wall of hollow has a lot of holes, can be BH 4 -and OH -passage is provided, the electro-oxidation reaction of (1) formula occurs after Ni catalysis.Ni transplants behind carbon microspheres inside, make Ni with can not with BH 4 -directly contact, can suppress (2) formula NaBH 4the generation of hydrolysis, has reduced the generation of hydrogen.On the other hand, because carbon microspheres can also adsorb H 2such nonionic material, the H that the hydrolysis of (2) formula produces 2can be closed in the carbon microspheres of hollow, continue to occur electro-oxidation reaction by (3) formula, not discharge and overflow with the situation of hydrogen, greatly improve NaBH 4electroxidation performance and utilization rate.
Carry Ni Carbon Hollow microballoon, not only increased the electrocatalysis characteristic of Ni to boron hydride, reduced again the effusion of hydrogen, improved NaBH 4utilization rate.Essence of the present invention is on the basis of direct borohydride fuel cell anode catalyst, transplant and carry Carbon Hollow microballoon by Ni catalyst, strengthen the electrochemical oxidation activity of catalyst to boron hydride, improved the discharge performance of boron hydride anode, suppressed the effusion of hydrogen.
The invention has the advantages that to adopt that to carry a Ni Carbon Hollow microballoon be catalyst, first Ni transplants behind carbon microspheres inside, make Ni can not with BH 4 -directly contact, can suppress NaBH 4the generation of hydrolysis, has reduced the generation of hydrogen.Secondly, the carbon microspheres ball wall of hollow has a lot of holes, can be BH 4 -and OH -passage is provided, after Ni catalysis, BH occurs 4 -electro-oxidation reaction.The 3rd, the hole in carbon microspheres ball wall, is similar to effect capillaceous, can be BH on the one hand 4 -and OH -provide passage, the H that hydrolysis can also be produced on the other hand 2can be closed in the carbon microspheres of hollow, continue electro-oxidation reaction occurs, and do not discharge effusion.Greatly improve NaBH 4electroxidation performance and utilization rate.
Detailed description of the invention
For example the present invention is described in more detail below.
(1) styrene (St), divinylbenzene and deionized water are put into 250ml four-hole bottle according to the ratio of 1:0.05:19 (wherein styrene is got 5g).To the N that passes into low flow velocity in system 2stream 20-30min, adds pore-foaming agent CCl 4(St:CCl 4=1:0.1), keeping temperature is 60 DEG C; Then add K 2s 2o 8and NaCl (St:K 2s 2o 8: NaCl=1:0.04:0.01), stir and be warmed up to gradually 70 DEG C, reaction 10-12h; By the emulsion breaking of gained and put into cryostat, (5 DEG C), repeatedly clean and centrifugal with ethanol, be placed in 8-10h in 50 DEG C of vacuum drying chambers and can obtain polystyrene microsphere (Pst).
(2) polystyrene microsphere (Pst) is put in to swelling (Pst:CH in carrene 2cl 2=1:2) 30min, then add 98% the concentrated sulfuric acid (Pst:H 2sO 4=1:5) first at 80 DEG C-90 DEG C, react 2-4h, pH is transferred to 10～12 with 5%NaOH solution, product is put in and in vacuum drying chamber, is dried 5-6h at 50 DEG C and can obtains sodium polystyrene sulfonate cation exchange resin microballoon.
(3) cationic ion-exchange resin is immersed to the NiCl containing 0.01-0.05mol/L 28-10h in solution, then takes out the resin of implanting Ni, puts into vacuum drying chamber dry 4-5h at 50 DEG C and must carry Ni cationic ion-exchange resin microballoon.
(4) will carry Ni cationic ion-exchange resin microballoon and put into tube furnace, under nitrogen atmosphere, at 650-750 DEG C of calcining 5-6h, can obtain carrying Ni Carbon Hollow microspherical catalyst.
Effect of the present invention is by verifying for example as follows.
Example 1
Adopting general year Ni active carbon is catalyst.Taking carbon-point as to electrode, taking Ag/AgCl as reference electrode, to carry Ni active carbon as working electrode, at the NaOH of 2M and the NaBH of 0.10M 4solution in, under the voltage of-0.7V vs.Ag/AgCl, timing current density reaches 15mA/cm 2, NaBH 4in electro-oxidation process, there are a large amount of bubbles to overflow.
Example 2
Adopting and carrying Ni carbon microspheres is catalyst, does not add pore-foaming agent CCl while preparing polystyrene microsphere 4.Taking carbon-point as to electrode, taking Ag/AgCl as reference electrode, to carry Ni carbon microspheres as working electrode, at the NaOH of 2M and the NaBH of 0.10M 4solution in, under the voltage of-0.7V vs.Ag/AgCl, timing current density reaches 46mA/cm 2, NaBH 4in electro-oxidation process, there is a small amount of bubble to overflow.
Example 3
Adopting and carrying Ni Carbon Hollow microballoon is catalyst, adds pore-foaming agent CCl while preparing polystyrene microsphere 4.Taking carbon-point as to electrode, taking Ag/AgCl as reference electrode, to carry Ni carbon microspheres as working electrode, at the NaOH of 2M and the NaBH of 0.10M 4solution in, under the voltage of-0.7V vs.Ag/AgCl, timing current density reaches 82mA/cm 2, NaBH 4in electro-oxidation process, having no bubble overflows.

Claims (9)

1. one kind carries Ni Carbon Hollow microballoon NaBH 4the preparation method of electro-oxidizing-catalyzing agent, is characterized in that:
(1) styrene, divinylbenzene are mixed with deionized water, pass into N 2, add pore-foaming agent CCl 4, keeping temperature is 60 DEG C; Then add K 2s 2o 8and NaCl, stir and be warmed up to gradually 70 DEG C, reaction 10-12h obtains emulsion; By emulsion breaking and put into cryostat,, clean and centrifugal with ethanol, 50 DEG C of vacuum drying 8-10h, obtain polystyrene microsphere;
(2) polystyrene microsphere is put in to swelling 30min in carrene, then adds the concentrated sulfuric acid, at 80 DEG C-90 DEG C, react 2-4h, adjust pH to 10～12, dry 5-6h obtains sodium polystyrene sulfonate cation exchange resin microballoon at 50 DEG C;
(3) sodium polystyrene sulfonate cation exchange resin microballoon immerses NiCl 28-10h in solution, then takes out dry 4-5h at 50 DEG C and obtains carrying Ni cationic ion-exchange resin microballoon;
(4) will carry Ni cationic ion-exchange resin microballoon, under nitrogen atmosphere, 650-750 DEG C of calcining 5-6h, obtains carrying Ni Carbon Hollow microspherical catalyst.
2. according to claim 1 year Ni Carbon Hollow microballoon NaBH 4the preparation method of electro-oxidizing-catalyzing agent, is characterized in that: the mass ratio of styrene, divinylbenzene and deionized water is 1:0.05:19, N 2the time that passes into be 20-30min, styrene and CCl 4weight ratio=1:0.1, styrene and K 2s 2o 8weight ratio=1:0.04:0.01 with NaCl.
3. according to claim 1 and 2 year Ni Carbon Hollow microballoon NaBH 4the preparation method of electro-oxidizing-catalyzing agent, is characterized in that: the temperature of cryostat, is-5 DEG C.
4. according to claim 1 and 2 year Ni Carbon Hollow microballoon NaBH 4the preparation method of electro-oxidizing-catalyzing agent, is characterized in that: the weight ratio=1:2 of polystyrene microsphere and carrene, the weight ratio=1:5 of polystyrene microsphere and 98% the concentrated sulfuric acid.
5. according to claim 3 year Ni Carbon Hollow microballoon NaBH 4the preparation method of electro-oxidizing-catalyzing agent, is characterized in that: the weight ratio=1:2 of polystyrene microsphere and carrene, the weight ratio=1:5 of polystyrene microsphere and 98% the concentrated sulfuric acid.
6. according to claim 1 and 2 year Ni Carbon Hollow microballoon NaBH 4the preparation method of electro-oxidizing-catalyzing agent, is characterized in that: NiCl 2the concentration of solution is 0.01-0.05mol/L.
7. according to claim 3 year Ni Carbon Hollow microballoon NaBH 4the preparation method of electro-oxidizing-catalyzing agent, is characterized in that: NiCl 2the concentration of solution is 0.01-0.05mol/L.
8. according to claim 4 year Ni Carbon Hollow microballoon NaBH 4the preparation method of electro-oxidizing-catalyzing agent, is characterized in that: NiCl 2the concentration of solution is 0.01-0.05mol/L.
9. according to claim 5 year Ni Carbon Hollow microballoon NaBH 4the preparation method of electro-oxidizing-catalyzing agent, is characterized in that: NiCl 2the concentration of solution is 0.01-0.05mol/L.
CN201410317178.9A 2014-07-04 2014-07-04 Carry Ni Carbon Hollow microballoon NaBH 4the preparation method of electro-oxidizing-catalyzing agent Active CN104084207B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107774326A (en) * 2016-08-27 2018-03-09 中国石油化工股份有限公司 Fluid bed electrolytic catalyst and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101404331A (en) * 2008-11-14 2009-04-08 哈尔滨工业大学 Catalyst used for proton exchanging film fuel battery and method for producing the same
CN101485982A (en) * 2009-02-17 2009-07-22 中国人民解放军63971部队 Anodic electrocatalyst for direct borohydride fuel cell and preparation method thereof
CN101944620A (en) * 2010-08-02 2011-01-12 北京交通大学 Fuel cell catalyst taking multi-element compound as carrier and preparation method thereof
US20130273460A1 (en) * 2010-09-17 2013-10-17 Industry-University Cooperation Foundation Sogang University Spherical, porous carbon structure and a production method therefor

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101404331A (en) * 2008-11-14 2009-04-08 哈尔滨工业大学 Catalyst used for proton exchanging film fuel battery and method for producing the same
CN101485982A (en) * 2009-02-17 2009-07-22 中国人民解放军63971部队 Anodic electrocatalyst for direct borohydride fuel cell and preparation method thereof
CN101944620A (en) * 2010-08-02 2011-01-12 北京交通大学 Fuel cell catalyst taking multi-element compound as carrier and preparation method thereof
US20130273460A1 (en) * 2010-09-17 2013-10-17 Industry-University Cooperation Foundation Sogang University Spherical, porous carbon structure and a production method therefor

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107774326A (en) * 2016-08-27 2018-03-09 中国石油化工股份有限公司 Fluid bed electrolytic catalyst and preparation method thereof
CN107774326B (en) * 2016-08-27 2020-09-08 中国石油化工股份有限公司 Fluidized bed electrolytic catalyst

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