CN110075886A - Ni-based-carbon composite electrocatalyst and preparation method thereof - Google Patents
Ni-based-carbon composite electrocatalyst and preparation method thereof Download PDFInfo
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- CN110075886A CN110075886A CN201910467789.4A CN201910467789A CN110075886A CN 110075886 A CN110075886 A CN 110075886A CN 201910467789 A CN201910467789 A CN 201910467789A CN 110075886 A CN110075886 A CN 110075886A
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- 239000002131 composite material Substances 0.000 title claims abstract description 75
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 75
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 104
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 28
- 239000002105 nanoparticle Substances 0.000 claims abstract description 25
- 239000000126 substance Substances 0.000 claims abstract description 21
- 239000011258 core-shell material Substances 0.000 claims abstract description 20
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 claims abstract description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 8
- 239000004917 carbon fiber Substances 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims description 21
- 229920001046 Nanocellulose Polymers 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 16
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 11
- 150000002815 nickel Chemical class 0.000 claims description 11
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 10
- 239000012498 ultrapure water Substances 0.000 claims description 10
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 9
- 229920002678 cellulose Polymers 0.000 claims description 8
- 239000001913 cellulose Substances 0.000 claims description 8
- 238000004108 freeze drying Methods 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 238000003837 high-temperature calcination Methods 0.000 claims description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 5
- 238000007710 freezing Methods 0.000 claims description 5
- 230000008014 freezing Effects 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 230000002045 lasting effect Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 239000012018 catalyst precursor Substances 0.000 claims 2
- 239000011248 coating agent Substances 0.000 abstract description 15
- 238000000576 coating method Methods 0.000 abstract description 15
- 239000003054 catalyst Substances 0.000 description 21
- 239000010410 layer Substances 0.000 description 21
- 239000000243 solution Substances 0.000 description 15
- 230000003197 catalytic effect Effects 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000010792 warming Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000004502 linear sweep voltammetry Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 6
- 238000007605 air drying Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 229910021397 glassy carbon Inorganic materials 0.000 description 5
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000013112 stability test Methods 0.000 description 5
- VUZNLSBZRVZGIK-UHFFFAOYSA-N 2,2,6,6-Tetramethyl-1-piperidinol Chemical class CC1(C)CCCC(C)(C)N1O VUZNLSBZRVZGIK-UHFFFAOYSA-N 0.000 description 4
- 238000003763 carbonization Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000002035 prolonged effect Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910001567 cementite Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- KSOKAHYVTMZFBJ-UHFFFAOYSA-N iron;methane Chemical compound C.[Fe].[Fe].[Fe] KSOKAHYVTMZFBJ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
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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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical Kinetics & Catalysis (AREA)
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- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of Ni-based-carbon composite electrocatalysts, the porous carbon conductive network that the composite electrocatalyst is constituted using carbon fiber is skeleton, load has the reactive nanoparticles of core-shell structure on the skeleton, the core-shell structure includes core and two layers of shell for being wrapped in core surface, the reactive nanoparticles are using nickel simple substance as core, to be wrapped in the nickel phosphide on nickel simple substance surface as first layer shell, to be wrapped in the carbon of phosphatization nickel surface as second layer shell.The present invention correspondingly provides a kind of preparation method of above-mentioned Ni-based-carbon composite electrocatalyst.After there is composite electrocatalyst of the invention porous carbon conductive network and carbon coating core-shell structure, the two to combine, make composite electrocatalyst of the invention that there is excellent OER electrocatalysis characteristic and stability.
Description
Technical field
The invention belongs to electrochemical fields more particularly to a kind of electrochemical catalyst and preparation method thereof.
Background technique
The most severe two large problems of the world today, facing mankind are exactly environmental degradation and energy crisis.In severe ring
Under border situation and growing energy demand, people increasingly value the research of the new energy of high-efficiency environment friendly.Hydrogen Energy is a kind of
Cleaning and the sustainable regenerated energy, have many advantages, such as high-energy density, zero-emission and rich reserves.Aqueous electrochemical is decomposed into
Hydrogen, oxygen are considered as a kind of method of promising large scale preparation hydrogen.
However, the sluggish dynamics performance of OER is considered as realizing that water divides entirely due to being related to four electronic transfer process
The rate-limiting step of solution.Worse, since content is rare on the earth, at high price and cyclical stability is general, business OER is urged
Agent (RuO2、IrO2) application receive very big limitation.Therefore, there is an urgent need to prepare highly efficient durable, low-cost OER
Catalyst.
Currently, the nano material based on transition metal is considered as promising catalyst, because their cost is opposite
It is lower, intrinsic activity is high, abundance is high, structure and form of diverse.Therefore, a large amount of to make great efforts to be put into design based on transition metal
High activity OER catalyst.For example, the team of king synthesizes the cementite elctro-catalyst of carbon-coating cladding and is carried on excellent
It is 10mAcm in current density on the carbon nano-fiber of electric conductivity-2When overpotential be only 284mV, show excellent OER
Catalytic activity, but above method preparation process is complicated, needs to prepare presoma by electrostatic spinning, product yield is low.It is existing to grind
Although achieving greater advance in studying carefully, still the preparation process of most of transition metal base elctro-catalysts is complicated and expensive, urge
Change inefficient.Therefore, development and production simple process, highly efficient durable, low-cost OER catalyst are of great significance.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the shortcomings of to mention in background above technology and defect, one kind is provided
Simple process, low in cost, high catalytic efficiency Ni-based-carbon composite electrocatalyst and preparation method thereof.To solve above-mentioned technology
Problem, technical solution proposed by the present invention are as follows:
A kind of Ni-based-carbon composite electrocatalyst, the porous carbon conductive mesh that the composite electrocatalyst is constituted with carbon fiber
Network is skeleton, and load has the reactive nanoparticles of core-shell structure on the skeleton, and the core-shell structure includes core and is wrapped in core
Two layers of shell on surface, the reactive nanoparticles are using nickel simple substance as core, to be wrapped in the nickel phosphide on nickel simple substance surface as first layer
Shell, to be wrapped in the carbon of phosphatization nickel surface as second layer shell.
In above-mentioned composite electrocatalyst, it is preferred that the granular size of the composite electrocatalyst is 20~80nm, specific surface
Product is 80~300m2/ g, pore size are 2~50nm, and the load factor of reactive nanoparticles is 0.5~10%.
As a general technical idea, the present invention also provides a kind of preparation method of Ni-based-carbon composite electrocatalyst, packets
Include following steps:
(1) nano cellulose sol, dicyandiamide, nickel salt solution are uniformly mixed, it is lasting to stir；
(2) progress of mixture obtained in step (1) freeze-drying process is obtained into freeze-drying product；
(3) it is multiple that Ni-based-carbon is obtained by the freeze-drying product high-temperature calcination under nitrogen atmosphere in step (2), after cooling
Close elctro-catalyst presoma；
(4) Ni-based obtained in step (3)-carbon composite electrocatalyst presoma is mixed with sodium hypophosphite, grinding, mixing
After uniformly under nitrogen atmosphere low temperature calcination, it is cooling after washing, drying to obtain it is Ni-based-carbon composite electrocatalyst.
In above-mentioned preparation method, the dosage by controlling hypophosphites can guarantee to form the active nano of two layers of clad
Particle.
In above-mentioned preparation method, it is preferred that the nickel salt is at least one of nickel nitrate, nickel chloride.
In above-mentioned preparation method, it is preferred that the quality of nano-cellulose and dicyandiamide in the nano cellulose sol
Be 1:(10~50 than control), the molar ratio control of nano-cellulose and nickel salt in the nano cellulose sol for (1~
20): 1.Active material itself electric conductivity that nickel salt generates is very poor, and nickel salt dosage excessively will lead to the electric conductivity of entire catalyst
Difference, thus poor catalytic activity, nickel salt dosage lacks corresponding reactive nanoparticles, and also just corresponding reduction, active catalytic center are reduced,
Catalytic activity reduces.
In above-mentioned preparation method, it is preferred that in the step (4), control Ni-based-carbon composite electrocatalyst presoma and time
The mass ratio of sodium phosphate is 1:(5~20).The dosage of sodium hypophosphite has a great impact to the catalytic performance of composite electrocatalyst,
Dosage by controlling hypophosphites can guarantee to form the reactive nanoparticles of two layers of clad, and control intermediate nickel phosphide
Thickness guarantees the presence of nickel simple substance core, can increase electric conductivity, to can enhance catalysis phenomenon, make the comprehensive of composite electrocatalyst
It is more excellent to close performance.
In above-mentioned preparation method, it is furthermore preferred that mole of nano-cellulose and nickel salt in control nano cellulose sol
It is (5~6) than control: 1, and the mass ratio for controlling Ni-based-carbon composite electrocatalyst presoma and sodium hypophosphite is 1:(9-10).
Pass through the restriction of above-mentioned two condition, it is ensured that compound electric of the present invention urges the structure of agent optimal, obtained composite electrocatalyst
Comprehensive electrochemical more preferably.
In above-mentioned preparation method, it is preferred that freeze-drying process is first in freeze drier with -50~-10 DEG C of freezings 7
~15h, then in 10~60 DEG C of 5~8h of vacuum drying.
In above-mentioned preparation method, it is preferred that controlling heating rate when the high-temperature calcination is 2~5 DEG C/min, calcination temperature
It is 700~1000 DEG C, calcination time is 1~4h.
In above-mentioned preparation method, it is preferred that controlling heating rate when the low temperature calcination is 1~4 DEG C/min, calcination temperature
It is 200~500 DEG C, calcination time is 1~4h.
In above-mentioned preparation method, it is preferred that the washing is first uses ultrapure water centrifuge washing at least 3 times, then with anhydrous second
Alcohol centrifuge washing at least 1 time.
In above-mentioned preparation method, main includes two steps, i.e. carbonization and phosphatization, and nickel ion is reduced to metal in carbonisation
Simple substance, parkerizing process nickel simple substance and sodium dihydric hypophosphite reaction then generate Ni2P, and form nucleocapsid package structure.Specifically
, the decomposition product of dicyandiamide is reduced nickel salt when high-temperature calcination, initially generates the nickel simple substance wrapped up by carbon-coating, then secondary phosphorus
Hydrochlorate generates gas PH in low temperature calcination3, PH3Carbon-coating is permeated, is reacted with internal part of nickel simple substance and generates nickel phosphide.It is above-mentioned
In carbonization and parkerizing process, by controlling the usage amount of phosphorus source, by controlling temperature, the time of high-temperature calcination and low temperature calcination,
The composite electrocatalyst with excellent OER electrocatalysis characteristic and stability can be prepared.
Ni-based-carbon composite electrocatalyst in the present invention has distinct porous carbon conductive network and carbon coating nucleocapsid
Structure (Ni@Ni2P/C).Above structure has the advantage that porous carbon conductive network 1) of the invention has high specific surface
Long-pending and porosity, and mesoporous accounting is bigger, unique porous network structure are conducive to the transmission of ion, and the nanofiber being carbonized
Element has high conductivity, conducive to the transmission of electronics in reaction process.2) chain carrier of carbon package is carried on carbonization nanometer
On the network frame that cellulose is constructed, the specific surface area and electric conductivity of composite electrocatalyst are substantially increased.3) porous network frame
The frame frame firm as one is conducive to the stabilization of composite electrocatalyst.4) preparation method of the invention can guarantee carbon coating
Nucleocapsid is double-coating structure, and carbon coating core-shell structure outermost layer is carbon coating layer, phosphating metal can be prevented in reaction process
Middle reunion is corroded, and stability is higher；There is nickel phosphide clad, catalytic activity is higher in carbon coating core-shell structure.
Composite electrocatalyst Ni@Ni obtained in the present invention2P/C has excellent OER electrocatalysis characteristic and stability.
It after tested, is 10mAcm in current density-2When, minimum overpotential is 277mV, by the constant potential stability test of 20h,
Its current density is only lost 2.5%.
Compared with the prior art, the advantages of the present invention are as follows:
1, composite electrocatalyst of the invention has porous carbon conductive network and carbon coating core-shell structure, and the two combines
Afterwards, make composite electrocatalyst of the invention that there is excellent OER electrocatalysis characteristic and stability.
2, composite electrocatalyst of the invention, raw material are easy to get, low in cost, and preparation process is simple, can prepare in batches.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is the present invention
Some embodiments for those of ordinary skill in the art without creative efforts, can also basis
These attached drawings obtain other attached drawings.
Fig. 1 is that Ni-based-carbon compound electric in embodiment 1 urges the SEM of agent to scheme.
Fig. 2 is that Ni-based-carbon compound electric in Examples 1 to 3 urges agent oxygen that linear sweep voltammetry (LSV) test chart is precipitated.
Fig. 3 urges the constant potential stability test figure of agent for Ni-based-carbon compound electric in embodiment 1.
Specific embodiment
To facilitate the understanding of the present invention, the present invention is made below in conjunction with Figure of description and preferred embodiment more complete
Face meticulously describes, but the protection scope of the present invention is not limited to the following specific embodiments.
Unless otherwise defined, all technical terms used hereinafter and the normally understood meaning of those skilled in the art
It is identical.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention
Protection scope.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city
Field is commercially available or can be prepared by existing method.
Embodiment 1:
A kind of Ni-based-carbon composite electrocatalyst, the porous carbon conductive network which is constituted with carbon fiber
For skeleton, load has a reactive nanoparticles of core-shell structure on skeleton, and core-shell structure includes core and be wrapped in two layers of core surface
Shell, reactive nanoparticles are using nickel simple substance as core, to be wrapped in the nickel phosphide on nickel simple substance surface as first layer shell, to be wrapped in phosphatization
The carbon of nickel surface is second layer shell.
In above-mentioned composite electrocatalyst, the granular size of composite electrocatalyst is 20~80nm, specific surface area 260m2/
G, pore size are 10~30nm, and the load factor of reactive nanoparticles is 1.2%.
The preparation method of above-mentioned Ni-based-carbon composite electrocatalyst, comprising the following steps:
(1) 0.220gNiCl is weighed2·6H2O is dissolved in 5mL ultrapure water, is stirred to being completely dissolved, is obtained solution x；It weighs
20.0g dicyandiamide, for use；It weighs 98.0g and aoxidizes the matter being prepared using 2,2,6,6- tetramethyl piperidine oxides (TEMPO)
The nano cellulose sol (nano-cellulose 0.0054mol, similarly hereinafter) that score is 1% is measured, then while stirring toward Nanowire
It ties up and solution x is added in plain colloidal sol, added in about 5min, then dicyandiamide is added into nano cellulose sol, stirring 10min makes
It is uniformly dispersed；
(2) by reaction product obtained in step (1) in freeze drier with -50 DEG C of freezing 12h, then at 25 DEG C of vacuum
Drying is for 24 hours；
(3) under nitrogen atmosphere by desciccate obtained in step (2), 900 are warming up to the heating rate of 5 DEG C/min
DEG C calcining 2h, be then naturally cooling to room temperature, obtain Ni-based-carbon composite electrocatalyst presoma；
It (4) is in mass ratio 1:10 by Ni-based-carbon composite electrocatalyst presoma obtained in step (3) and sodium hypophosphite
It is mixed, after grinding sufficiently, under nitrogen atmosphere, 300 DEG C of calcining 2h is warming up to the heating rate of 2 DEG C/min, then certainly
So it is cooled to room temperature；Product after cooling is first used ultrapure water centrifuge washing 3 times again, then with dehydrated alcohol centrifuge washing 1 time, it is cold
Freeze the Ni Ni of drying to obtain the present embodiment2P/C composite electrocatalyst.
Composite electrocatalyst powder sample in the present embodiment is coated on black conductive glue, metal spraying processing is then carried out,
Reuse the FE-SEM of Hitachi, Ltd, the scanning of JSM-6330F type scanning electron microscope.As a result as shown in Figure 1, as shown in Figure 1, from receiving
The carbon nano-fiber of rice cellulose has successfully constructed 3D porous network structure.
By the composite electrocatalyst grind into powder in the present embodiment, it is configured to the dispersion liquid that concentration is 6mg/mL, coating 5
μ L carries out oxygen in 1.0M KOH solution after rotation glassy carbon electrode surface, air drying and linear sweep voltammetry test is precipitated,
Measure the catalytic performance of its oxygen evolution reaction.As a result as shown in Fig. 2, as shown in Figure 2, the Ni@Ni in the present embodiment2P/C is compound
Elctro-catalyst is 10mAcm in current density-2When, overpotential is only 277mV, is lower than business OER catalyst RuO2And IrO2。
Elctro-catalyst constant potential stability test figure in the present embodiment by prolonged stability as shown in figure 3, as seen from the figure, survey
After examination, the activity of catalyst is substantially without change.The above results show the Ni@Ni in the present embodiment2P/C composite electrocatalyst tool
There are excellent catalytic performance and stability.
Embodiment 2:
A kind of Ni-based-carbon composite electrocatalyst, the porous carbon conductive network which is constituted with carbon fiber
For skeleton, load has a reactive nanoparticles of core-shell structure on skeleton, and core-shell structure includes core and be wrapped in two layers of core surface
Shell, reactive nanoparticles are using nickel simple substance as core, to be wrapped in the nickel phosphide on nickel simple substance surface as first layer shell, to be wrapped in phosphatization
The carbon of nickel surface is second layer shell.
In above-mentioned composite electrocatalyst, the granular size of composite electrocatalyst is 10~30nm, specific surface area 220m2/
G, pore size are 10~30nm, and the load factor of reactive nanoparticles is 1.8%.
The preparation method of above-mentioned Ni-based-carbon composite electrocatalyst, comprising the following steps:
(1) 0.330gNiCl is weighed2·6H2O is dissolved in 5mL ultrapure water, is stirred to being completely dissolved, is obtained solution x；It weighs
20.0g dicyandiamide, for use；It weighs 98.0g and aoxidizes the matter being prepared using 2,2,6,6- tetramethyl piperidine oxides (TEMPO)
The nano cellulose sol that score is 1% is measured, solution x, about 5min is then added into nano cellulose sol while stirring
It inside adds, then dicyandiamide is added into nano cellulose sol, stirring 10min makes it be uniformly dispersed；
(2) by reaction product obtained in step (1) in freeze drier with -50 DEG C of freezing 12h, then at 25 DEG C of vacuum
Drying is for 24 hours；
(3) under nitrogen atmosphere by desciccate obtained in step (2), 800 are warming up to the heating rate of 5 DEG C/min
DEG C calcining 2h, be then naturally cooling to room temperature, obtain Ni-based-carbon composite electrocatalyst presoma；
It (4) is in mass ratio 1:15 by Ni-based-carbon composite electrocatalyst presoma obtained in step (3) and sodium hypophosphite
It is mixed, after grinding sufficiently, under nitrogen atmosphere, 300 DEG C of calcining 2h is warming up to the heating rate of 2 DEG C/min, then certainly
So it is cooled to room temperature；Product after cooling is first used ultrapure water centrifuge washing 3 times again, then with dehydrated alcohol centrifuge washing 1 time, it is cold
Freeze the Ni Ni of drying to obtain the present embodiment2P/C composite electrocatalyst.
By the composite electrocatalyst grind into powder in the present embodiment, it is configured to the dispersion liquid that concentration is 6mg/mL, coating 5
μ L carries out oxygen in 1.0M KOH solution after rotation glassy carbon electrode surface, air drying and linear sweep voltammetry test is precipitated,
Measure the catalytic performance of its oxygen evolution reaction.As a result as shown in Fig. 2, as shown in Figure 2, the Ni@Ni in the present embodiment2P/C is compound
Elctro-catalyst is 10mAcm in current density-2When, overpotential is only 294mV, is lower than business OER catalyst RuO2And IrO2。
After prolonged stability test, the activity of catalyst is substantially without change.
Embodiment 3:
A kind of Ni-based-carbon composite electrocatalyst, the porous carbon conductive network which is constituted with carbon fiber
For skeleton, load has a reactive nanoparticles of core-shell structure on skeleton, and core-shell structure includes core and be wrapped in two layers of core surface
Shell, reactive nanoparticles are using nickel simple substance as core, to be wrapped in the nickel phosphide on nickel simple substance surface as first layer shell, to be wrapped in phosphatization
The carbon of nickel surface is second layer shell.
In above-mentioned composite electrocatalyst, the granular size of composite electrocatalyst is 10~30nm, specific surface area 280m2/
G, pore size are 10~30nm, and the load factor of reactive nanoparticles is 0.9%.
The preparation method of above-mentioned Ni-based-carbon composite electrocatalyst, comprising the following steps:
(1) 0.165gNiCl is weighed2·6H2O is dissolved in 5mL ultrapure water, is stirred to being completely dissolved, is obtained solution x；It weighs
20.0g dicyandiamide, for use；It weighs 98.0g and aoxidizes the matter being prepared using 2,2,6,6- tetramethyl piperidine oxides (TEMPO)
The nano cellulose sol that score is 1% is measured, solution x, about 5min is then added into nano cellulose sol while stirring
It inside adds, then dicyandiamide is added into nano cellulose sol, stirring 10min makes it be uniformly dispersed；
(2) by reaction product obtained in step (1) in freeze drier with -50 DEG C of freezing 12h, then at 25 DEG C of vacuum
Drying is for 24 hours；
(3) under nitrogen atmosphere by desciccate obtained in step (2), 800 are warming up to the heating rate of 5 DEG C/min
DEG C calcining 1h, be then naturally cooling to room temperature, obtain Ni-based-carbon composite electrocatalyst presoma；
It (4) is in mass ratio 1:5 by Ni-based-carbon composite electrocatalyst presoma obtained in step (3) and sodium hypophosphite
It is mixed, after grinding sufficiently, under nitrogen atmosphere, 300 DEG C of calcining 2h is warming up to the heating rate of 2 DEG C/min, then certainly
So it is cooled to room temperature；Product after cooling is first used ultrapure water centrifuge washing 3 times again, then with dehydrated alcohol centrifuge washing 1 time, it is cold
Freeze the Ni Ni of drying to obtain the present embodiment2P/C composite electrocatalyst.
By the composite electrocatalyst grind into powder in the present embodiment, it is configured to the dispersion liquid that concentration is 6mg/mL, coating 5
μ L carries out oxygen in 1.0M KOH solution after rotation glassy carbon electrode surface, air drying and linear sweep voltammetry test is precipitated,
Measure the catalytic performance of its oxygen evolution reaction.As a result as shown in Fig. 2, as shown in Figure 2, the Ni@Ni in the present embodiment2P/C is compound
Elctro-catalyst is 10mAcm in current density-2When, overpotential 302mV is lower than business OER catalyst RuO2And IrO2.Through
After crossing prolonged stability test, the activity of catalyst is substantially without change.
Embodiment 4:
A kind of Ni-based-carbon composite electrocatalyst, the porous carbon conductive network which is constituted with carbon fiber
For skeleton, load has a reactive nanoparticles of core-shell structure on skeleton, and core-shell structure includes core and be wrapped in two layers of core surface
Shell, reactive nanoparticles are using nickel simple substance as core, to be wrapped in the nickel phosphide on nickel simple substance surface as first layer shell, to be wrapped in phosphatization
The carbon of nickel surface is second layer shell.
In above-mentioned composite electrocatalyst, the granular size of composite electrocatalyst is 20~80nm, specific surface area 260m2/
G, pore size are 10~30nm, and the load factor of reactive nanoparticles is 1.2%.
The preparation method of above-mentioned Ni-based-carbon composite electrocatalyst, comprising the following steps:
(1)~(3) are the same as (1) the step of embodiment 1~(3)；
It (4) is in mass ratio 1:8 by Ni-based-carbon composite electrocatalyst presoma obtained in step (3) and sodium hypophosphite
It is mixed, after grinding sufficiently, under nitrogen atmosphere, 300 DEG C of calcining 2h is warming up to the heating rate of 2 DEG C/min, then certainly
So it is cooled to room temperature；Product after cooling is first used ultrapure water centrifuge washing 3 times again, then with dehydrated alcohol centrifuge washing 1 time, it is cold
Freeze the Ni Ni of drying to obtain the present embodiment2P/C composite electrocatalyst.
By the composite electrocatalyst grind into powder in the present embodiment, it is configured to the dispersion liquid that concentration is 6mg/mL, coating 5
μ L carries out oxygen in 1.0M KOH solution after rotation glassy carbon electrode surface, air drying and linear sweep voltammetry test is precipitated,
The catalytic performance for measuring its oxygen evolution reaction, the Ni@Ni by testing, in the present embodiment2P/C composite electrocatalyst is close in electric current
Degree is 10mAcm-2When, overpotential 285mV is lower than business OER catalyst RuO2And IrO2.By prolonged stability
After test, the activity of catalyst is substantially without change.
Comparative example 1:
A kind of Ni-based-carbon composite electrocatalyst, the porous carbon conductive network which is constituted with carbon fiber
For skeleton, load has a reactive nanoparticles of core-shell structure on skeleton, and core-shell structure includes core and be wrapped in two layers of core surface
Shell, reactive nanoparticles are using nickel simple substance as core, to be wrapped in the nickel phosphide on nickel simple substance surface as first layer shell, to be wrapped in phosphatization
The carbon of nickel surface is second layer shell.
In above-mentioned composite electrocatalyst, the granular size of composite electrocatalyst is 10~30nm, specific surface area 320m2/
G, pore size are 10~30nm, and the load factor of reactive nanoparticles is 0.37%.
The preparation method of above-mentioned Ni-based-carbon composite electrocatalyst, comprising the following steps:
(1) 0.068gNi (NO is weighed3)2·6H2O is dissolved in 5mL ultrapure water, is stirred to being completely dissolved, is obtained solution x；Claim
20.0g dicyandiamide is taken, for use；Weigh what 98.0g was prepared using 2,2,6,6- tetramethyl piperidine oxides (TEMPO) oxidation
Then solution x is added, about in the nano cellulose sol that mass fraction is 1% into nano cellulose sol while stirring
It is added in 5min, then dicyandiamide is added into nano cellulose sol, stirring 10min makes it be uniformly dispersed；
(2)~(4) are the same as step (2)~(4) in embodiment 1；
By the composite electrocatalyst grind into powder in this comparative example, it is configured to the dispersion liquid that concentration is 6mg/mL, coating 5
μ L carries out oxygen in 1.0M KOH solution after rotation glassy carbon electrode surface, air drying and linear sweep voltammetry test is precipitated,
Measure the catalytic performance of its oxygen evolution reaction.Ni@Ni by testing, in this comparative example2P/C composite electrocatalyst is close in electric current
Degree is 10mAcm-2When, overpotential 326mV.
Claims (10)
1. a kind of Ni-based-carbon composite electrocatalyst, which is characterized in that the porous carbon that the composite electrocatalyst is constituted with carbon fiber
Matter conductive network is skeleton, and load has a reactive nanoparticles of core-shell structure on the skeleton, the core-shell structure include core with
It is wrapped in two layers of shell on core surface, the reactive nanoparticles are using nickel simple substance as core, to be wrapped in the nickel phosphide on nickel simple substance surface
For first layer shell, to be wrapped in the carbon of phosphatization nickel surface as second layer shell.
2. composite electrocatalyst according to claim 1, which is characterized in that the granular size of the composite electrocatalyst is
20~80nm, specific surface area are 80~300m2/ g, pore size are 2~50nm, the load factors of reactive nanoparticles is 0.5~
10%.
3. a kind of preparation method of Ni-based-carbon composite electrocatalyst, which comprises the following steps:
(1) nano cellulose sol, dicyandiamide, nickel salt solution are uniformly mixed, it is lasting to stir；
(2) progress of mixture obtained in step (1) freeze-drying process is obtained into freeze-drying product；
(3) by the freeze-drying product high-temperature calcination under nitrogen atmosphere in step (2), Ni-based-carbon compound electric is obtained after cooling
Catalyst precursor；
(4) Ni-based obtained in step (3)-carbon composite electrocatalyst presoma is mixed with sodium hypophosphite, grinding is uniformly mixed
The low temperature calcination under nitrogen atmosphere afterwards, it is cooling after washing, drying to obtain it is Ni-based-carbon composite electrocatalyst.
4. preparation method according to claim 3, which is characterized in that the nickel salt be nickel nitrate, in nickel chloride at least
It is a kind of.
5. preparation method according to claim 3, which is characterized in that the nano-cellulose in the nano cellulose sol
It is 1:(10~50 with the control of the mass ratio of dicyandiamide), mole of nano-cellulose and nickel salt in the nano cellulose sol
It is (1~20) than control: 1.
6. preparation method according to claim 3, which is characterized in that in the step (4), control Ni-based-carbon compound electric
The mass ratio of catalyst precursor and sodium hypophosphite is 1:(5~20).
7. the preparation method according to any one of claim 3~6, which is characterized in that freeze-drying process is first cold
With -50~-10 DEG C of 7~15h of freezing in lyophilizer, then in 10~60 DEG C of 5~40h of vacuum drying.
8. the preparation method according to any one of claim 3~6, which is characterized in that control and rise when the high-temperature calcination
Warm rate is 2~5 DEG C/min, and calcination temperature is 700~1000 DEG C, and calcination time is 1~4h.
9. the preparation method according to any one of claim 3~6, which is characterized in that control and rise when the low temperature calcination
Warm rate is 1~4 DEG C/min, and calcination temperature is 200~500 DEG C, and calcination time is 1~4h.
10. the preparation method according to any one of claim 3~6, which is characterized in that the washing is first to use ultrapure water
Centrifuge washing at least 3 times, then with dehydrated alcohol centrifuge washing at least 1 time.
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