CN103706389A - Preparation method of lithium air battery catalyst with double catalytic activities - Google Patents
Preparation method of lithium air battery catalyst with double catalytic activities Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title abstract description 9
- 229910052744 lithium Inorganic materials 0.000 title abstract description 9
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 45
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 9
- 238000011065 in-situ storage Methods 0.000 claims abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- 229910002804 graphite Inorganic materials 0.000 claims description 24
- 239000010439 graphite Substances 0.000 claims description 24
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- 239000012265 solid product Substances 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 238000010306 acid treatment Methods 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical group [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 230000014759 maintenance of location Effects 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 229910052746 lanthanum Chemical group 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical group [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Chemical group 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- 238000007599 discharging Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 7
- 238000006722 reduction reaction Methods 0.000 abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 2
- 230000001351 cycling effect Effects 0.000 abstract 2
- 238000013329 compounding Methods 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 230000033116 oxidation-reduction process Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 description 3
- 238000013459 approach Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- HPGPEWYJWRWDTP-UHFFFAOYSA-N lithium peroxide Chemical compound [Li+].[Li+].[O-][O-] HPGPEWYJWRWDTP-UHFFFAOYSA-N 0.000 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 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002498 deadly effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000005183 dynamical system Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- -1 manganese, lanthanide Chemical class 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
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Abstract
The invention provides a preparation method of a lithium air battery catalyst with double catalytic activities (oxidization reduction reaction catalytic property ORR and oxygen evolution reaction property OER). The catalyst is prepared by compounding phenylamine in-situ polymerized nitrogen-doped graphene and double-metal oxide. The activity of the catalytic oxidation reduction of the lithium air battery cathode catalyst mainly influences the reaction level and capacity of the discharging reaction of an lithium air battery, and the catalytic oxygen evolution activity influences the decomposition degree of a discharging product of the lithium air battery so as to determine the cycling property of the lithium air battery. The catalyst is applied to the lithium air battery, the electrochemical performance of the lithium air battery can be improved through the double-activity combined action, the discharging level is increased (the discharging overpotential is reduced), the capacity is increased, and the cycling performance is improved.
Description
Technical field
The invention belongs to field of chemical power source, relate to the preparation method that a class can be applicable to the lithium-air battery catalyst with two catalytic activitys of the nitrogen-doped graphene load bimetallic oxide in lithium-air battery.
Background technology
From the nineties in last century, lithium-air battery, due to features such as its high-energy-density, green non-pollution, low-temp reactions, is subject to domestic and international energy field experts and scholars' strong interest, has started the agitation of lithium-air battery research.Lithium-air battery normal temperature can react the high-temperature behavior that this feature makes lithium-air battery compare fuel cell and more have real world applications, has more to substitute lithium ion battery and become novel energy storage system and the possibility of dynamical system.
The microstructure of the lithium-air battery of organic electrolyte system has determined the deadly defect of lithium-air battery---discharging product lithium peroxide is not soluble in organic electrolyte.In discharge process, discharging product generates gradually and is deposited in the 3 D pore canal of air electrode, until stop up duct completely, electrolyte cannot be contacted with oxygen, and solid-liquid-gas three phase reaction interface disappears, and cell reaction stops.The charging process discharging product of lithium-air battery is decomposed gradually and is realized energy storage effect.But the reaction gesture of lithium peroxide decomposition reaction is high, react more difficult generation, often decompose not exclusively, limited stability and the cyclicity of battery.The application of catalyst is to realize lithium-air battery energy to make full use of the large key factor with real world applications type.
The performance of catalyst mainly comprises catalytic oxidation-reduction reaction ORR and catalysis oxygen evolution reaction OER.Current potential and the capacity of the exoelectrical reaction of ORR major effect lithium-air battery, thus and OER affects the cycle performance that lithium-air battery discharging product degree of decomposition has determined lithium-air battery.
Lithium-air battery cathod catalyst mainly comprises noble metal, the large class of transition metal oxide two.Precious metal catalyst effect is quite outstanding, but considers that cost of material is higher, be unfavorable for practical application, so the research emphasis of catalyst is transferred to transition metal oxide.By change the different crystal forms of transition metal oxide and pattern, material nano, with the catalytic performance of method the improves catalyst such as other materials is compound.
Summary of the invention
The object of the invention is to provide in order to improve the deficiencies in the prior art a kind of have two catalytic activitys the preparation method of lithium-air battery catalyst.
Technical scheme of the present invention is: a kind of have two catalytic activitys the preparation method of lithium-air battery catalyst, its concrete steps are as follows: (1) is 1:(1～3 by slaine A and slaine B by metallic element molar ratio) be dispersed to the hydrochloric acid solution of graphite oxide with aniline monomer, the slaine wherein adding and the mol ratio of aniline are that the mol ratio of two metallic elements and aniline is 1:(1.5～4), the mass ratio of aniline and graphite oxide is 1:(0.075～0.2); Under ice-water bath, add catalyst to cause aniline in-situ polymerization, react 24～48 hours; (2) successively add reducing agent ammoniacal liquor and hydrazine hydrate to carry out the reduction of graphite oxide again, reduction temperature is 110～150 ℃, and the recovery time is 20～24 hours; (3) by roasting under inert atmosphere after the separated oven dry of the solid product obtaining, sintering temperature is 850～950 ℃, temperature retention time 0.5～3 hour, and roasting programming rate is controlled at 2～5 ℃/min; (4) solid product is processed with acid solution, acid solution carries out after baking after processing and cleaning under inert atmosphere, and sintering temperature is 850～950 ℃, and temperature retention time 0.5～3 hour makes the catalyst of nitrogen-doped graphene load bimetallic oxide.
Described slaine A and slaine B are nitrate, carbonate, sulfate or the chloride of transition metal.
In two kinds of described slaines, metallic element is transition metal, preferably cobalt, iron, nickel, manganese, lanthanide element.More preferably the metallic element in slaine A is iron or nickel; Metallic element in slaine B is cobalt, manganese or lanthanum.
The mol ratio of the metallic element in slaine A and slaine B is 1:(2～3)
Preferably in the hydrochloric acid solution of described graphite oxide, the concentration of graphite oxide is 0.5～1mg/mL; The concentration of hydrochloric acid solution is 0.5～1M.
Preferably above-mentioned catalyst is hydrogen peroxide, potassium bichromate, ammonium persulfate, potassium hyperchlorate, does not preferably introduce other metallic elements, the easy ammonium persulfate of post processing.The addition of preferred catalyst is that the mol ratio of catalyst and aniline is 1:(4～10).
Preferably the mass ratio of described reducing agent ammoniacal liquor volume, hydrazine hydrate volume and graphite oxide is ammoniacal liquor (mL): hydrazine hydrate (mL): graphite oxide (g)=2～3:0.2～0.4:1.
In preferred steps (3) and (4), inert atmosphere is helium, argon gas or nitrogen.
The acid used of preferred acid solution-treated is 0.5～2M sulfuric acid solution; Acid treatment temperature is 60～80 ℃, 8～10 hours processing times.
Beneficial effect:
There is by aniline, slaine and graphite oxide the catalyst that nitrogen-doped graphene load bimetallic oxide is prepared in the reduction of aniline in-situ polymerization, graphite oxide, slaine recombination reaction in the present invention, preparation cost lower step by step.The high ORR performance of the comprehensive nitrogenize Graphene of the catalyst OER performance high with bimetallic oxide of preparation, obtains the catalyst of pair catalytics.Discharge platform, charge/discharge capacity, cyclicity that uses the lithium-air battery of catalyst of the present invention etc. all obtains larger raising.
Accompanying drawing explanation
Fig. 1 is the catalyst of the embodiment of the present invention 1 preparation linear polarization curve under different rotating speeds;
Fig. 2 is catalyst and the linear polarization curve comparison of PANI-rGO under 1600 rotating speeds of the embodiment of the present invention 1, embodiment 2 preparations;
Fig. 3 is the embodiment of the present invention 1, embodiment 2 catalyst of preparation and the contrast of the OER performance curve of PANI-rGO;
Fig. 4 is the first charge-discharge curve of lithium-air battery that uses the catalyst of embodiment 1 preparation;
Fig. 5 is the restriction ratio capacity 300mAh/g, the cycle performance curve that 500mAh/g discharges and recharges of lithium-air battery that uses the catalyst of embodiment 1 preparation.；
Fig. 6 is the SEM figure of the catalyst of the embodiment of the present invention 1 preparation;
Fig. 7 is the TEM figure of the catalyst of the embodiment of the present invention 1 preparation;
Fig. 8 is the catalyst of the embodiment of the present invention 2 preparation linear polarization curve under different rotating speeds;
Fig. 9 is the cycle performance curve that uses the restriction ratio capacity 500mAh/g of lithium-air battery of the catalyst of embodiment 2 preparations to discharge and recharge.
The specific embodiment
The battery performance test of the preparation of the lithium-air battery catalyst of two catalytic activitys, catalytic performance and assembling lithium-air battery.
Embodiment 1:
By 1mL(10.95mmol) aniline monomer is dispersed in the hydrochloric acid solution (concentration of hydrochloric acid 0.5M) of the graphite oxide of 100mL1mg/mL, add again 1mol iron chloride, 2mol cobalt nitrate, routine ammonium persulfate in molar ratio under ice-water bath: aniline=1:4 adds ammonium persulfate, reacts 24 hours.At 110 ℃, add reducing agent 200 μ L ammoniacal liquor and 40 μ L hydrazine hydrates, the continuous reduction of carrying out graphite oxide for 24 hours.After drying the separated oven dry of solid product, in argon gas atmosphere, with 5 ℃/min, be warming up to 850 ℃ of roastings 2 hours, with 80 ℃ of 0.5M sulfuric acid solutions, process 8 hours, with roasting 30 minutes at 850 ℃ under argon gas atmosphere again after washed with de-ionized water, the final catalyst obtaining, is designated as PANI-Fe
1-Co
2-rGO.
Catalyst and deionized water and 5w%Nafion solution are made into catalyst ink, pipette 20 μ L catalyst inks on glass-carbon electrode, after air-dry, glass carbon working electrode and platinized platinum are formed to three-electrode system to electrode, Ag/AgCl reference electrode, 0.1M potassium hydroxide solution, with 5mV/s sweep speed, be rotated disk electrode test.
By the catalyst making and Ketjen black, binding agent (PVDF) in mass ratio 30:60:10 mixes, and is coated in nickel foam, and the electrode slice that is cut into required diameter is placed on vacuum drying chamber dries more than 12 hours.With lithium plate electrode, electrolyte 1mol/l LiClO
4pC/DME1:1 (W/W), in the glove box of argon shield, is assembled into lithium-air battery, the performance of test battery on high accuracy battery tester, and current density is 100mA/g, carries out the circularity test of complete charge-discharge test and limit capacity.
Fig. 1 is catalyst P ANI-Fe under different rotating speeds
1-Co
2the linear polarization curve of-rGO, calculates PANI-Fe according to Fig. 1 through Koutecky-Levich equation
1-Co
2it is 4.29 that the electronics of the ORR reaction of-rGO shifts number, corresponding with lithium-air battery exoelectrical reaction 4 electron reactions.As shown in Figure 2,3, PANI-Fe
1-Co
2-rGO increases with respect to ORR performance and the OER performance of the nitrogenize Graphene (PANI-rGO) of the not composite metal oxide of in kind preparing, and especially OER performance improves larger.
As shown in Figure 4, Figure 5, use the PANI-Fe of embodiment 1 preparation
1-Co
2the lithium-air battery of-rGO catalyst, discharge platform approaches 2.8V, specific discharge capacity 4772mAh/g, and there is good cycle performance, restriction ratio capacity 300mAh/g circulates 50 discharge cut-off voltage declines not quite, still, more than 2.7V, 30 discharge cut-off voltage of restriction ratio capacity 500mAh/g circulation are still in 2.6V left and right.
As shown in Figure 6,7, use the catalyst P ANI-Fe of embodiment 1 preparation
1-Co
2-rGO has good Graphene stratiform structure, nano level iron cobalt/cobalt oxide particle is scattered in Graphene stratiform structure.
Embodiment 2:
Changing iron chloride and cobalt nitrate addition is 1mol iron chloride, 3mol cobalt nitrate, with 1mL(10.95mmol) aniline adds in the hydrochloric acid solution (concentration of hydrochloric acid 0.5M) of the graphite oxide of 100mL1mg/mL, routine ammonium persulfate in molar ratio under ice-water bath: aniline=1:4 adds ammonium persulfate, react 24 hours, with 200 μ L ammoniacal liquor and 40 μ L hydrazine hydrates, at 110 ℃, reduce graphite oxide 20 hours.Under argon gas atmosphere, with 3 ℃/min, be warming up at 900 ℃ and be incubated 2 hours, then use 80 ℃ of acid treatments of 2M sulfuric acid solution roasting 30 minutes at 900 ℃ under argon gas atmosphere again after 10 hours, the catalyst of preparation is designated as PANI-Fe
1-Co
3-rGO.Catalyst activity test is as consistent in embodiment 1 with battery performance test process.
As shown in Figure 8, catalyst P ANI-Fe
1-Co
3the ORR better performances of-rGO, Koutecky-Levich equation calculates PANI-Fe as calculated
1-Co
3it is 3.40 to approach with lithium-air battery exoelectrical reaction 4 electron reactions that the electronics of the ORR reaction of-rGO shifts number.As shown in Figure 2,3, PANI-Fe
1-Co
3-rGO is as the PANI-Fe of embodiment 1 preparation
1-Co
2-rGO is identical, and ORR, OER performance all increase.
As shown in Figure 9, the catalyst P ANI-Fe of embodiment 1 preparation
1-Co
325 discharge cut-off voltage of battery limitation capacity 500mAh/g circulation of-rGO are still in 2.5V left and right.
Embodiment 3:
By 1mol nickel nitrate, 2mol lanthanum nitrate and 0.5mL(5.48mmol) aniline adds in the hydrochloric acid solution (concentration of hydrochloric acid 0.5M) of the graphite oxide of 100mL1mg/mL, routine ammonium persulfate in molar ratio under ice-water bath: aniline=1:10 adds ammonium persulfate, react 24 hours, at 130 ℃, add continuous 20 hours reduction graphite oxides of 200 μ L ammoniacal liquor and 20 μ L hydrazine hydrates.Under helium atmosphere, with 2 ℃/min of programming rates, be warming up at 950 ℃ and be incubated 30 minutes, then use 60 ℃ of acid treatments of 0.5M sulfuric acid solution roasting 3 hours at 950 ℃ under helium atmosphere again after 10 hours, the catalyst of preparation is designated as PANI-La
2-Ni
1-rGO, has good ORR, OER performance and has good chemical property, the head of the about 2.85V pressure of discharging, good cyclicity.
Embodiment 4:
1mol manganese sulfate, 1mol nickel nitrate and 0.5mL(5.48mmol) aniline monomer is dispersed in the hydrochloric acid solution (concentration of hydrochloric acid 1M) of the graphite oxide of 100mL0.5mg/mL, routine ammonium persulfate in molar ratio under ice-water bath: aniline=1:8 adds ammonium persulfate, reacts 48 hours.Maintain 150 ℃, add reducing agent 150 μ L ammoniacal liquor and 10 μ L hydrazine hydrates, the continuous reduction of carrying out graphite oxide for 24 hours.After drying the separated oven dry of solid product, at nitrogen atmosphere, with 5 ℃/min, be warming up to 950 ℃ of roastings 3 hours, with 80 ℃ of 1M sulfuric acid solutions, process 8 hours, after baking 30 minutes at 950 ℃ under nitrogen atmosphere, the final catalyst obtaining, is designated as PANI-Mn-Ni-rGO.There is good ORR, OER performance and the new energy of electrochemistry.
Claims (10)
- One kind have two catalytic activitys the preparation method of lithium-air battery catalyst, its concrete steps are as follows: (1) is 1:(1～3 by slaine A and slaine B by metallic element molar ratio) be dispersed to the hydrochloric acid solution of graphite oxide with aniline monomer, the slaine wherein adding and the mol ratio of aniline are that the mol ratio of two metallic elements and aniline is 1:(1.5～4), the mass ratio of aniline and graphite oxide is 1:(0.075～0.2); Under ice-water bath, add catalyst to cause aniline in-situ polymerization, react 24～48 hours; (2) successively add reducing agent ammoniacal liquor and hydrazine hydrate to carry out the reduction of graphite oxide again, reduction temperature is 110～150 ℃, and the recovery time is 20～24 hours; (3) by roasting under inert atmosphere after the separated oven dry of the solid product obtaining, sintering temperature is 850～950 ℃, temperature retention time 0.5～3 hour, and roasting programming rate is controlled at 2～5 ℃/min; (4) solid product is processed with acid solution, acid solution carries out after baking after processing and cleaning under inert atmosphere, and sintering temperature is 850～950 ℃, and temperature retention time 0.5～3 hour makes the catalyst of nitrogen-doped graphene load bimetallic oxide.
- 2. preparation method according to claim 1, is characterized in that nitrate, carbonate, sulfate or chloride that described slaine A and slaine B are transition metal.
- 3. preparation method according to claim 1, is characterized in that the metallic element in slaine A is iron or nickel; Metallic element in slaine B is cobalt, manganese or lanthanum.
- 4. preparation method according to claim 1, is characterized in that described slaine A and the mol ratio of the metallic element in slaine B are 1:(2～3).
- 5. preparation method according to claim 1, is characterized in that the concentration of graphite oxide in the hydrochloric acid solution of described graphite oxide is 0.5～1mg/mL; The concentration of hydrochloric acid solution is 0.5～1M.
- 6. preparation method according to claim 1, is characterized in that described catalyst is hydrogen peroxide, potassium bichromate, ammonium persulfate, potassium hyperchlorate.
- 7. preparation method according to claim 1, is characterized in that the described catalyst adding and the mol ratio of aniline are 1:(4～10).
- 8. preparation method according to claim 1, is characterized in that the mass ratio of described reducing agent ammoniacal liquor volume, hydrazine hydrate volume and graphite oxide is ammoniacal liquor (mL): hydrazine hydrate (mL): graphite oxide (g)=2～3:0.2～0.4:1.
- 9. preparation method according to claim 1, is characterized in that in step (3) and (4), inert atmosphere is helium, argon gas or nitrogen.
- 10. preparation method according to claim 1, is characterized in that it is 0.5～2M sulfuric acid solution that acid solution is processed acid used; Acid treatment temperature is 60～80 ℃, 8～10 hours processing times.
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| CN111952607A (en) * | 2020-07-16 | 2020-11-17 | 广东邦普循环科技有限公司 | Oxygen reduction catalyst prepared from waste graphite and preparation method thereof |
| CN111952607B (en) * | 2020-07-16 | 2022-07-15 | 广东邦普循环科技有限公司 | Oxygen reduction catalyst prepared from waste graphite and preparation method thereof |
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