CN106159285A - The preparation method of a kind of ordered ultrathin Catalytic Layer and Catalytic Layer and application - Google Patents

The preparation method of a kind of ordered ultrathin Catalytic Layer and Catalytic Layer and application Download PDF

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CN106159285A
CN106159285A CN201510197922.0A CN201510197922A CN106159285A CN 106159285 A CN106159285 A CN 106159285A CN 201510197922 A CN201510197922 A CN 201510197922A CN 106159285 A CN106159285 A CN 106159285A
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carbon paper
array
preparation
catalytic layer
tio
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CN106159285B (en
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俞红梅
蒋尚峰
张洪杰
邵志刚
衣宝廉
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Dalian Institute of Chemical Physics of CAS
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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
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/8867—Vapour deposition
    • 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
    • H01M4/8867—Vapour deposition
    • H01M4/8871—Sputtering
    • 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
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • 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
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
    • 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 present invention relates to the preparation method of a proton exchanging film fuel battery ordered ultrathin electrode, comprise preparation and the structure of ultra-thin Catalytic Layer of orderly electrode structure.Carbon paper impregnates the TiO that anneals to obtain2By Hydrothermal Growth TiO after crystal seed2Nanometer rods, and through NH3Etching preparation TiN oldered array, catalyst-loaded on array, build ordered ultrathin Catalytic Layer, without proton conductor (such as Nafion).Constructed ordered ultrathin Catalytic Layer can be used for Proton Exchange Membrane Fuel Cells and other fuel cell and electrochemical device.

Description

The preparation method of a kind of ordered ultrathin Catalytic Layer and Catalytic Layer and application
Technical field
The invention belongs to fuel cell field and other electrochemical devices, relate generally to PEM combustion A kind of preparation method and applications of material battery ordered ultrathin Catalytic Layer.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFC) is that one is expected to take the lead in realizing business-like fuel electricity Pond, it is high that it has energy conversion efficiency, and power density is high, environmental friendliness, and room temperature quickly startup etc. is excellent Point.But cost, life-span, performance are to limit the big reason of Proton Exchange Membrane Fuel Cells business-like three. For Proton Exchange Membrane Fuel Cells, its cost high most for from membrane electrode assembly (MEA) In the cost of catalyst.The current approach solving problem is to start with from catalyst itself, uses The modes such as alloy, nucleocapsid or Pt monolayer reduce the content of noble metal in catalyst, or find non-noble gold Metal catalyst substitutes Pt base catalyst；Another approach is to build orderly catalyst layer structure, increases by three The area of boundary, improves Pt utilization rate.
At present in Proton Exchange Membrane Fuel Cells (PEMFC), the Catalytic Layer orderly for 3D of structure Structure, the NSTF electrode most practical value prepared with 3M company.Additionally, article ChemSusChem, 2013,6 (4), use the orderly TiO that hydrogen processes in 6592Nano-tube array as orderly supporter, On carrier the most catalyst-loaded, build orderly nano-array electrode, apply to proton exchange Single pond of membrane cell shows preferable catalyst stability and higher single pond performance.Article Journal of Power Sources, 2015 (276), 80-88 uses the TiO being grown on carbon paper2-C has Sequence nano-array, as orderly carrier, after supporting upper Pt nano-particle by magnetron sputtering, applies to matter The negative electrode of proton exchange film fuel cell, shows good activity and stability.Article Adv.Energy Mater.2011,1,1205-1214 uses the carbon nano pipe array of conduction, supports ultralow on array Pt load amount (cathode side 35 μ g/cm2), show and be better than commercialization 0.4mg/cm2Single pond performance of load amount, Stability is not surveyed.
The carrier TiN that electric conductivity is high and physical property is stable, as catalyst carrier, is employed for different necks In territory, show good performance.Article Nano Lett.2012,12,5376-5381 will be at carbon fiber TiN nano wire is directly prepared on surface, applies to show in electrochemical capacitance energy storage device good stablizing Property and energy-storage property.Article ChemSusChem 2012,5,1712-1715 has prepared at titanium plate surface Sequence TiN nano-tube array, by Pt catalyst loading on this orderly carrier, is applied to Li-Air battery In, show good battery performance.Article J.Mater.Chem.A, 2014,2,13966-13975 Using the TiN (unordered) of hollow and porous as catalyst carrier, support Pt catalyst, be situated between in acidity Matter shows good stability and ORR performance.Visible, that good conductivity, stability are high TiN The carrier of different-shape all relates in different field, but prepared by the TiN nanometer stick array being ordered into It is grown on carbon paper, as orderly catalyst carrier, uses the most in a fuel cell.
Summary of the invention
Present invention aim at providing preparation method and the catalysis of a kind of fuel cell ordered ultrathin Catalytic Layer Layer and application.
The present invention describes the preparation method and applications of a kind of ordered ultrathin Catalytic Layer.Including orderly battle array The preparation of array structure and the structure of ordered catalyst layer, first prepare TiN ordered nano rod battle array on carbon paper Row, then catalyst loading is obtained on oldered array ordered ultrathin Catalytic Layer.
Preparation method is as follows: the precursor solution the annealing that first impregnate Ti on carbon paper obtain TiO2Crystal seed, And obtain TiO by hydro-thermal method2Array, then through NH3Etching obtain orderly TiN array, On this array catalyst-loaded, be formed with the combination electrode of sequence structure, construct orderly ultra-thin catalysis Layer.
Specifically comprise the steps of；
1) compound concentration is the precursor water solution of titanium of 0.05M-0.2M, by carbon paper acetone: second Alcohol: after the volume ratio of water is the mixed solution cleaning of 1:1:1, be immersed in the precursor water solution of above-mentioned titanium Surface, impregnates 10-30min so that the precursor water solution of the single-side impregnated titanium of carbon paper, or by before titanium Drive liquid solution to be prepared as colloidal sol and be spin-coated on carbon paper with spin coating instrument again, air is heated to 300-400 DEG C Annealing 10-20min, obtains with TiO2The carbon paper of crystal seed；Or by magnetron sputtering (PVD) or former Sublayer deposition is directly by TiO2Seed particles is supported on carbon paper, obtains with TiO2The carbon paper of crystal seed； Described magnetron sputtering (PVD) i.e. uses TiO2Target (under an ar atmosphere) or use high-purity Ti target is (at O2Under the conditions of lower 50 DEG C-300 DEG C of/Ar mixed atmosphere, sputtering power 200-300W, very Reciprocal of duty cycle 0.4-1.0Pa), by magnetron sputtering (PVD) directly by TiO2Seed particles is supported on carbon paper, Obtain with TiO2The carbon paper of crystal seed；Described ald (ALD) will the organic metal salt of Ti, Being deposited on carbon paper surface by the way of pulsed deposition, temperature controls at 200 DEG C-300 DEG C, H2O makees Reacting gas, obtains with TiO2The carbon paper of crystal seed；
2) add the hydrochloric acid that isopyknic mass fraction is 37%-38% in deionized water to stir After, add the precursor solution of titanium, the two volume ratio is 36:1, stirs, by step 1) system Standby with TiO2The carbon paper of crystal seed is put in above-mentioned solution, 150 DEG C-200 DEG C reaction 5h-25h, Obtain with TiO2The carbon paper of array；
3) by step 2) obtain with TiO2The carbon paper of array is put in 500-550 DEG C of roasting in Muffle furnace Burn 1h-2h, be passed through 50-150ml/cm2Under conditions of ammonia, 800 DEG C-1000 DEG C roasting 1-6h, To the carbon paper with TiN array；
4) in step 3) prepare the orderly carbon paper with TiN array TiN array one side surface load Carried catalyst.
Above-mentioned steps 4) described in catalyst loading mode use electro-deposition, electronation, thermal decomposition, Any one or more than two kinds in evaporation, magnetron sputtering or ald；The catalyst supported For Pt metal, Pd, Au, Ru, Nb, Ta, Ir, Ag, Fe, Co, Ni, Mn, Cr or Ti In any one, or any one in any two or the alloy of more than three kinds in above-mentioned metal Or more than two kinds, it is possible to increase intermetallic alloy degree by annealing.
Described in above-mentioned steps (1), the presoma of titanium is titanyl sulfate, isopropyl titanate, butyl titanate.
The present invention uses TiN nanometer stick array to be grown directly upon on carbon paper as orderly carrier, and will urge Agent supports on array, forms orderly electrode structure (microporous layers and Catalytic Layer one), and will system Standby application of electrode is in Proton Exchange Membrane Fuel Cells.
Ordered ultrathin Catalytic Layer prepared by the preparation method provided according to the present invention can be used for preparing fuel electricity The male or female of pond membrane electrode.
The present invention is the Catalytic Layer of directly preparation on carbon paper, does not use conventional microporous layer, is expected to reduce A part of cost.The most orderly catalyst layer structure can reduce resistance to mass tranfer, adds phase reaction Area, improves the utilization rate of Pt.Additionally, the conducting path that the Catalytic Layer of ordered ultrathin makes proton subtracts Short, in the case of not using proton conductor (Nafion etc.) in cathode catalysis layer, battery can Normal operation.
Accompanying drawing explanation
Fig. 1 is the flow chart of the TiN array of preparation in the embodiment of the present invention 1.
Fig. 2 is the FESEM figure of the PtPdCo-TiN of preparation in the embodiment of the present invention 1.
Fig. 3 is to prepare the orderly electrode of PtPdCo-TiN (doing anode) in the embodiment of the present invention 1, at proton I-V curve in exchange film fuel battery.Cell operating conditions is: battery temperature: 65 DEG C；RH: H2/O2=100%/100%；H2Flow: 50mLmin-1；O2Flow: 200mLmin-1。
Fig. 4 is the FESEM figure preparing Pt-TiN in the embodiment of the present invention 2.
Fig. 5 is the TEM figure preparing PtPdCu-TiN in the embodiment of the present invention 3.
Fig. 6 is the preparation orderly electrode of PtNi-TiN in the embodiment of the present invention 4, at pem fuel I-V curve in battery.Cell operating conditions is: battery temperature: 65 DEG C；RH: H2/O2=100%/100%；H2Flow: 50mLmin-1；O2Flow: 150mLmin-1。
Detailed description of the invention
The present invention will be further described for following instance
Embodiment 1
Single-side impregnated in 0.05M-0.2M TiCl in carbon paper substrate4Aqueous solution surface, in 350 DEG C of air Annealing obtains TiO2Crystal seed.
By obtain with TiO2The carbon paper of crystal seed is immersed in the quality of 1.1mL butyl titanate, 37mL Mark is in the concentrated hydrochloric acid of 38%, the deionized water mixed liquor of 37mL, hydro-thermal 150 DEG C reaction 10h.
The TiO that will obtain2Array NH3Perform etching, NH3Flow is 60mL/cm2, temperature 850 DEG C, response time 4h, obtain TiN array.
TiN array surface by magnetron sputtering (under an ar atmosphere under the conditions of 20 DEG C, sputtering power 200W, vacuum 1.0Pa, sputtering time Pt:12min, Pd:7min, Co:15min) support PtPdCo Alloy catalyst (atomic ratio Pt:Pd:Co=1:0.96:0.090, wherein Pt:66.95 μ g/cm2,Pd:35.115 μg/cm2,Co:1.83μg/cm2), obtain orderly ultra-thin Catalytic Layer.
Fig. 1 is the flow chart of preparation process, and Fig. 2 is the FESEM figure of PtPdCo-TiN array.
Using prepared electrode as the anode in single pond, negative electrode is business-like GDE, is applied to proton In exchange film fuel battery.Battery temperature: 65 DEG C, PH2=PO2=0.05MPa, gas flow: H2=50 sccm,O2=200sccm, humidification degree: H2/O2=100%/100%, Nafion212 film.
Fig. 3 show prepared ordered ultrathin Catalytic Layer I-V in Proton Exchange Membrane Fuel Cells Performance curve.
Embodiment 2
The TiN nanometer stick array of Example 1 preparation.
Application electro-deposition techniques (here be impulse electrodeposition technology) supports in TiN array surface Pt catalyst, reaction solution is: 0.2mM H2PtCl6, supporting electrolyte is 1mol HCl, 150mL. Pulse electrodeposition parameter: jp=-40mA/cm2, Ton=0.3ms, Toff=0.7ms, burst length 5min.
Fig. 4 is the FESEM figure of Pt-TiN nanometer stick array.
Embodiment 3
The TiN nanometer stick array of Example 1 preparation
On TiN nanometer stick array magnetron sputtering (sputtering time Pt:10min, Pd:5min, Cu:5min, Sputter other conditions and embodiment 1 with) support PtPdCu alloy catalyst (atomic ratio Pt:Pd:Cu=1: 1.57:0.35, wherein Pt:45.375 μ g/cm2；Pd:15.775 μ g/cm2；Cu:5.245 μ g/cm2), Obtain ternary alloy three-partalloy (purpose of annealing is to increase alloying level) by annealing, had The ultra-thin Catalytic Layer of sequence.
Fig. 5 is the TEM figure of PtPdCu-TiN.
Embodiment 4
The TiN nanometer stick array of Example 1 preparation.
At this TiN nanometer stick array surface magnetic control sputtering sputtering time Pt:5min, Ni:15min, sputter it His condition is same with embodiment 1) PtNi catalyst (atomic ratio Pt:Ni=1:3.23, wherein Pt:21.575 μg/cm2, Ni:20.975 μ g/cm2), it is prepared as ordered ultrathin Catalytic Layer (PtNi-TiN).
This orderly application of electrode does the negative electrode of Proton Exchange Membrane Fuel Cells, and anode is Pt/C catalyst The CCM of spray.
Fig. 6 is the I_V that prepared orderly application of electrode is measured in Proton Exchange Membrane Fuel Cells Curve, cell operating conditions is: battery temperature: 65 DEG C；RH:H2/O2=100%/100%；H2 Flow: 50mLmin-1；O2Flow: 150mLmin-1。

Claims (7)

1. the preparation method of an ordered ultrathin Catalytic Layer, it is characterised in that: include orderly electrode structure Preparation and the structure of ultra-thin Catalytic Layer, preparation method is as follows: utilize TiN array to be formed on carbon paper Orderly electrode structure, and by catalyst loading on the surface of orderly carrier, form ultra-thin Catalytic Layer.
Preparation method the most according to claim 1, it is characterised in that: preparation method is as follows: The precursor solution the annealing that first impregnate Ti on carbon paper obtain TiO2Crystal seed, and obtained by hydro-thermal method TiO2Array, then through NH3Etching obtain orderly TiN array, supported catalyst on this array Agent, is formed with the combination electrode of sequence structure, constructs orderly ultra-thin Catalytic Layer.
Preparation method the most according to claim 1 and 2, it is characterised in that: specifically comprise following Step；
1) compound concentration is the precursor water solution of titanium of 0.05M-0.2M, by carbon paper acetone: second Alcohol: after the volume ratio of water is the mixed solution cleaning of 1:1:1, be immersed in the precursor water solution of above-mentioned titanium Surface, impregnates 10-30min so that the precursor water solution of the single-side impregnated titanium of carbon paper, or by before titanium Drive liquid solution to be prepared as colloidal sol and be spin-coated on carbon paper with spin coating instrument again, air is heated to 300-400 DEG C Annealing 10-20min, obtains with TiO2The carbon paper of crystal seed；Or by magnetron sputtering (PVD) or former Sublayer deposition is directly by TiO2Seed particles is supported on carbon paper, obtains with TiO2The carbon paper of crystal seed；
2) add the hydrochloric acid that isopyknic mass fraction is 37%-38% in deionized water to stir After, add the precursor solution of titanium, the two volume ratio is 36:1, stirs, by step 1) system Standby with TiO2The carbon paper of crystal seed is put in above-mentioned solution, 150 DEG C-200 DEG C reaction 5h-25h, Obtain with TiO2The carbon paper of array；
3) by step 2) obtain with TiO2The carbon paper of array is put in 500-550 DEG C of roasting in Muffle furnace Burn 1h-2h, be passed through 50-150ml/cm2Under conditions of ammonia, 800 DEG C-1000 DEG C roasting 1-6h, To the carbon paper with TiN array；
4) in step 3) prepare the orderly carbon paper with TiN array TiN array one side surface load Carried catalyst.
4. according to the preparation method described in claim 3, it is characterised in that: step 4) described catalysis Agent loading mode use electro-deposition, electronation, thermally decompose, be deposited with, magnetron sputtering or atomic layer deposition Any one or more than two kinds in Ji；The catalyst supported be Pt metal, Pd, Au, Ru, Nb, Any one in Ta, Ir, Ag, Fe, Co, Ni, Mn, Cr or Ti, or in above-mentioned metal Any one or more than two kinds in any two or the alloy of more than three kinds.
5. method as claimed in claim 3, it is characterised in that: the forerunner of titanium described in step (1) Body is titanyl sulfate, isopropyl titanate, butyl titanate.
6. the ordered ultrathin Catalytic Layer prepared according to the arbitrary described preparation method of claim 1-6.
7. the ordered ultrathin Catalytic Layer described in a claim 7 is preparing the sun of fuel cell membrane electrode Application in pole or negative electrode.
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CN106758146A (en) * 2017-03-21 2017-05-31 梁厚栋 A kind of ultra-thin-wall alveolate texture titanium dioxide nano material and preparation method thereof
CN106760268A (en) * 2017-02-17 2017-05-31 深圳汇通智能化科技有限公司 A kind of building roof system of effective utilization luminous energy
CN108232243A (en) * 2016-12-10 2018-06-29 中国科学院大连化学物理研究所 The activation method of one proton exchanging film fuel battery
CN108448126A (en) * 2018-02-09 2018-08-24 中南大学 A kind of PtAuTi nanowire catalytics material and preparation method thereof and application as fuel-cell catalyst
CN108675261A (en) * 2018-06-01 2018-10-19 徐州医科大学 The carbon fiber SERS base materials and its preparation method and application of gold-nano-piece modification
CN108677209A (en) * 2018-05-28 2018-10-19 中国科学院广州能源研究所 A kind of orderly membrane electrode and preparation method thereof for solid polymer water electrolyzer
CN108760857A (en) * 2018-06-01 2018-11-06 徐州医科大学 A kind of titanium dioxide nanofiber enzyme electrode of decorated by nano-gold and its preparation method and application
CN108771980A (en) * 2018-06-01 2018-11-09 徐州医科大学 One kind can self-cleaning titanium dioxide nanofiber membrane material and its preparation method and application
CN108878168A (en) * 2018-07-02 2018-11-23 北京工业大学 The modified electrode material in surface and the processing method modified to electrode material surface
CN109921047A (en) * 2017-12-13 2019-06-21 中国科学院大连化学物理研究所 One proton exchanging film fuel battery ordered catalyst layer and its preparation and application
CN110165228A (en) * 2019-05-23 2019-08-23 北京科技大学 From hydrophobic integrated ordered catalyst layer-diffusion layer electrode structure and preparation method
CN112382767A (en) * 2020-10-26 2021-02-19 江苏大学 Fuel cell electrode in-situ preparation method based on double-layer ordered structure microporous layer
CN113224362A (en) * 2021-03-26 2021-08-06 中国科学院宁波材料技术与工程研究所 H taking mesoporous titanium chromium nitrogen as carrier material to load Pt nano particles2S gas sensor and preparation method thereof

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CN106758146A (en) * 2017-03-21 2017-05-31 梁厚栋 A kind of ultra-thin-wall alveolate texture titanium dioxide nano material and preparation method thereof
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CN108760857A (en) * 2018-06-01 2018-11-06 徐州医科大学 A kind of titanium dioxide nanofiber enzyme electrode of decorated by nano-gold and its preparation method and application
CN108675261A (en) * 2018-06-01 2018-10-19 徐州医科大学 The carbon fiber SERS base materials and its preparation method and application of gold-nano-piece modification
CN108878168A (en) * 2018-07-02 2018-11-23 北京工业大学 The modified electrode material in surface and the processing method modified to electrode material surface
CN110165228A (en) * 2019-05-23 2019-08-23 北京科技大学 From hydrophobic integrated ordered catalyst layer-diffusion layer electrode structure and preparation method
CN110165228B (en) * 2019-05-23 2021-05-18 北京科技大学 Self-hydrophobic integrated ordered catalyst layer-diffusion layer electrode structure and preparation method thereof
CN112382767A (en) * 2020-10-26 2021-02-19 江苏大学 Fuel cell electrode in-situ preparation method based on double-layer ordered structure microporous layer
CN112382767B (en) * 2020-10-26 2021-10-12 江苏大学 Fuel cell electrode in-situ preparation method based on double-layer ordered structure microporous layer
CN113224362A (en) * 2021-03-26 2021-08-06 中国科学院宁波材料技术与工程研究所 H taking mesoporous titanium chromium nitrogen as carrier material to load Pt nano particles2S gas sensor and preparation method thereof
CN113224362B (en) * 2021-03-26 2022-05-27 中国科学院宁波材料技术与工程研究所 H taking mesoporous titanium chromium nitrogen as carrier material to load Pt nano particles2S gas sensor and preparation method thereof

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