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Scientific Reports Volume 6, Article Number: 24314 (2016) Cite this article
A low-cost non-precious metal composite material g-C3N4-LaNiO3 (CNL) was synthesized as a dual-function electrocatalyst for the air electrode of lithium oxygen (Li-O2) batteries. The composition strategy changes the electronic structure of LaNiO3 and g-C3N4, ensuring a high Ni3/Ni2 ratio and more hydroxyl groups adsorbed on the surface of CNL, which can promote oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). For ORR and OER, the activity of the composite catalyst is higher than that of the individual components g-C3N4 and LaNiO3. In non-aqueous Li-O2 batteries, CNL shows higher capacity, lower overpotential and better cycle stability than XC-72 carbon and LaNiO3 catalysts. Our results indicate that CNL composite material is a promising cathode catalyst for Li-O2 batteries.
Li-O2 battery is a promising energy storage solution because its theoretical specific energy is 5200 Wh kg-1 (including O2), which is much higher than the most advanced lithium-ion batteries1,2,3. A typical non-aqueous Li-O2 battery consists of a lithium metal as the anode, electrolyte and a porous air electrode as the cathode. During the discharge reaction, the cathode undergoes an oxygen reduction reaction to generate lithium peroxide (Li2O2)4. During the charging process, the reverse reaction of the oxygen evolution reaction occurs, decomposing Li2O2 into oxygen and lithium ions5 again. The use of high-efficiency catalysts to promote the ORR/OER process is essential. So far, many metals, metal oxides, carbon-containing materials and redox media have been reported as cathode catalysts in Li-O2 batteries 6,7,8,9,10. Noble metal and noble metal oxide nanoparticles are usually highly efficient catalysts, but the high cost of noble metals limits their large-scale applications11,12.
Graphite carbon nitride (g-C3N4) polymer with a planar phase similar to graphite. However, unlike graphite, g-C3N4 has three-fold coordination (graphite-like) and two-fold coordination (pyridine-like) nitrogen atoms, and each carbon atom is bonded to three nitrogen atoms, including pyridine nitrogen and graphitic nitrogen Part 13. g-C3N4 is an attractive catalytic material because of its high chemical stability, low-cost preparation, and structural and composition specificity14. So far, it has been applied in many fields, such as photochemical decomposition of water, fuel cell and metal-free heterogeneous catalysis of various organic reactions 15,16,17,18,19,20. In particular, g-C3N4 contains a so-called "nitrogen tank" with six nitrogen lone pairs of electrons, which enables the material to modify the electronic structure of the molecule and become an ideal site for metal inclusions 21, 22. However, poor electrical conductivity and relatively low ORR catalytic activity limit the electrocatalytic application of g-C3N423. These problems can be solved by composting g-C3N4 with other materials with better conductivity. For example, g-C3N4 combined with non-noble metals such as Co-g-C3N424, Fe-g-C3N425 and Ni-Co3O4-C3N426 are used as effective catalysts for fuel cells and Li-O2 batteries. The composite shows promising ORR and OER activity and tolerance comparable to commercial Pt/C.
Perovskite oxide (ABO3) is widely used as a catalyst for fuel cells and metal-O2 batteries due to its unique structure, excellent oxygen mobility and low cost. LaNiO3 has the inherent activity of ORR and OER in perovskite-type oxides, because Ni3 at the B site in the perovskite structure has a single-electron-filled eg orbital, so it provides a favorable bond for the M (B site)-O bond Can ORR and OER28. In addition, by replacing part of Ni ions with Mg or Fe ions to increase the Ni3 /Ni2 ratio, the catalytic activity of LaNiO3 can be easily improved. g-C3N4 has a large number of removable electrons between the layer and the cavity, and there are some pyridine nitrogens around 29. Therefore, it has a strong ability to complex with abundant metal ions and then adjust its conjugated structure. Therefore, combining g-C3N4 with LaNiO3 can theoretically improve the electron transfer and catalytic activity of CNL composites. However, as far as we know, g-C3N4 has never been compounded with LaNiO3 to explore the enhancement of the catalytic activity of ORR and OER.
In this work, we synthesized a composite catalyst g-C3N4-LaNiO3 (CNL), and proved that compared with the single component g-C3N4 or LaNiO3 in alkaline electrolyte, CNL significantly improved the resistance to OER and ORR The electrocatalytic activity. In addition, CNL exhibits higher round-trip efficiency and cycle stability in Li-O2 batteries. These results indicate that CNL is a promising dual-functional catalyst for oxygen oxidation/precipitation reaction.
Figure 1 depicts the synthesis process of CNL catalyst and the molecular structure of CNL catalyst catalytic sites. Figure 2 shows the XRD patterns of pure g-C3N4, LaNiO3 and mixed catalyst CNL with different weight percentages of g-C3N4. It can be seen that pure g-C3N4 has two different peaks. The strong peak at 27.39° corresponds to the (002) peak at an in-plane distance of 0.326 nm (JCPDS 87-1526) and is attributed to the long-range in-plane stacking of aromatic units. Due to the interlayer stacking, the intensity of the other peak at 13.08° is much weaker, which can be classified as (100) diffraction peak 20, which corresponds to a distance of 0.686 nm and belongs to the tri-s-triazine unit. After LaNiO3 is compounded with g-C3N4, the CNL hybrid shows a coexisting phase of g-C3N4 and LaNiO3, although the characteristic peaks of g-C3N4 are not obvious for 5 wt.% and 10 wt.% CNL hybrids.
Schematic diagram of CNL composite synthesis process.
(a) g-C3N4, (b) LaNiO3, (c) 5 wt.% CNL, (d) 10 wt.% CNL, (e) 20 wt.% CNL, (f) 30 wt.% CNL mixed catalyst. The percentage by weight represents g-C3N4.
For further information on the material microstructure, Figure 3 shows the SEM images of g-C3N4, LaNiO3 and 10 wt.% CNL. Pure g-C3N4 shows an aggregated layered structure with a smooth surface. The agglomerate size is a few microns. LaNiO3 particles are hundreds of nanometers in size, which is more than an order of magnitude smaller than g-C3N4. For the 10 wt.% CNL image, LaNiO3 particles are deposited on the surface of g-C3N4.
Enlarged images of (a) g-C3N4, (b) LaNiO3, (c) 10 wt.% CNL, and (d) 10 wt.% CNL hybrid catalysts.
In this study, we used X-ray photoelectron spectroscopy to study the physical and chemical properties of the composite catalyst surface. Figure 4a shows the O 1s XP spectra of g-C3N4, LaNiO3 and CNL catalysts. The O 1s XP spectrum contains four different species. The two low binding energy peaks at 528.6 eV and 530.1 eV are attributed to O2− species in lattice oxygen, lanthanum oxide and nickel oxide. The peaks at 531.5 eV and 532.2 eV are derived from lanthanum and nickel hydroxide 32,33. With the increase of g-C3N4, the low binding energy peak becomes weaker, and the high binding energy peak becomes stronger, indicating that g-C3N4 composite LaNiO3 can promote the adsorption of hydroxyl groups on the composite catalyst surface and the covalent bonding Ni-O bond becomes stronger 34 . It has been proved that the rate of O22-/OH- replacement and OH- regeneration dominate the ORR kinetics, and the huge covalentness of the Ni-O bond can promote ORR kinetics. In addition, OER is the formation of OOH- by chemical adsorption or the oxidation of surface OH-. The rate determining step of OER on perovskite oxides is controlled by the concentration of hydroxide species involved in the formation of OO bonds in hydroperoxides. Therefore, the high lattice hydroxide concentration on the surface can promote the HOO− form, which has a positive effect on OER activity.
(a) O 1s XPS spectrum, (b) N 1s XPS spectrum and (c) LaNiO3 and x wt.% CNL (x = 5, 10, 20 and 30) Ni 2p3/2 XPS spectrum of the composite catalyst.
The N 1s XPS spectrum of g-C3N4 shown in Figure 4b can be fitted to three peaks at 398.8, 400.5, and 404.7 eV, corresponding to pyridine-like N, pyrrole-like N, and oxide N 35,36, respectively. After adding g-C3N4, a new peak appeared at 398.2 eV, which also corresponds to pyridine-like N. The reason why it is lower than 398.8 eV can be explained by the presence of chemical bonds in the g-C3N4-LaNiO3 heterojunction.
Ni 2p3/2 is deconvoluted into two peaks. The binding energy of 854.3 eV is due to Ni2 and 856 eV is due to Ni3, as shown in Figure 4c 31. The peak intensity of the low oxidation state (Ni2) decreases, and the peak intensity of the high oxidation state (Ni3) increases with the increase of g-C3N4 in the composite material. This indicates that LaNiO3 can be doped with nitrogen atoms to form LaNiO3-xNx by heat treatment, which promotes the formation of Ni3 on the surface of the composite catalyst. According to previous reports, the presence of Ni3 in LaNiO3 is beneficial to the ORR and OER activity of the material.
The typical polarization curve of ORR was studied in a 0.1 M KOH solution saturated with O2, as shown in Figure 5a. The ORR onset potential of 10 wt.% CNL is about -0.286 V, which is the most active among LaNiO3 (-0.304 V), 20 wt.% CNL (-0.319 V), and 30 wt.% CNL (-0.315 V), g -C3N4 (-0.315 V) and XC-72 (-0.314 V). And the half-wave potential of 10 wt.% CNL is -0.35 V, which is about 350 mV higher than the second highest value of 5 wt.% CNL. In addition, 10 wt.% CNL also exhibits the largest diffusion limiting current, with a limiting current of 4.36 mA cm-2, which is much higher than the 2.82 mA cm-2 of LaNiO3. In addition, for kinetic analysis, the Koutecky-Levich equation is also used to analyze the current-potential curve at different speeds:
(a) ORR polarization curve, (b) Koutecky-Levich diagram and (c) OER polarization of XC-72, g-C3N4, LaNiO3 and x wt.% CNL (x = 5, 10, 20 and 30) catalysts curve.
This equation has been widely used to analyze ORR reaction kinetics 38, 39, 40, where id is the current density of the tested disk, n is the number of electron transfer in ORR, k is Boltzmann's constant, F is Faraday's constant, and A Is the geometric area of the disk electrode, CO is the saturation concentration of oxygen in the 0.1 M KOH solution, DO is the diffusion coefficient of oxygen, ν is the kinematic viscosity of the 0.1 M KOH solution, and ω is the electrode rotation rate. There should be a linear relationship between id-1 and ω-1/2, the intercept is equal to ik-1 and n can be calculated from the slope.
Figure 5b shows the Koutecky-Levich plots of XC-72, g-C3N4, and CNL, which are based on the ORR polarization curve at -0.6 V at 2000, 1600, 1200, and 900 rpm. All curves show good linear characteristics, indicating the first-order kinetic characteristics of ORR. According to equations (3 and 4), the value of n can be calculated, as shown in Table 1. The n value of 10 wt.% CNL is about 3.86, indicating that ORR is a four-electron process. Compared with LaNiO3 catalyst, the synthesized 10 wt.% CNL material has better ORR activity and kinetics. The higher electrocatalytic activity is due to the high Ni3/Ni2 ratio in 10 wt.% CNL, which can promote oxygen adsorption/desorption, thereby promoting ORR activity in alkaline electrolytes. Therefore, in this work, the composite strategy has been shown to be very effective in improving the ORR catalytic activity of the components.
The catalytic activity of the synthesized CNL on OER was also measured by the RDE technique from 0.0 V to 1.2 V in a 0.1 M KOH solution saturated with O2, with a scan rate of 5 mV s-1 and a rotation speed of 1600 rpm. As shown in Figure 5c, the catalytic activity of all synthesized composite catalysts for OER is much better than that of XC-72 carbon and LaNiO3. The OER onset potential of LaNiO3 is 0.70 V, and the OER diffusion limiting current density at 1.2 V is 20.2 mA cm-2. In contrast, 10 wt.% CNL has a more negative initial potential of 0.63 V and a current density of 47.0 mA cm-2, which is significantly higher than that of LaNiO3 at 1.2 V.
This improved performance of 10 wt.% CNL is mainly due to the increased adsorption of hydroxyl groups on the surface of CNL composites. The hydroxyl group participates in the formation of HOO−, and the increase in the concentration of HOO− leads to high OER electrocatalytic activity. As for the electrocatalytic activity of g-C3N4, since the electronegativity of N is stronger than that of C, electrons will be transferred from C to adjacent N, and π conjugation returns electrons to adjacent Cp2 orbitals 41, 42. These donation and anti-donation processes not only help to adsorb O2- through the strong chemical bond between O and C, but also promote the desorption of O2 on adjacent C atoms, thereby increasing the activity of ORR and OER. The ORR and OER activities of 20 wt.% CNL and 30 wt.% CNL are lower than 10 wt.% CNL. The reason can be explained that the excessive non-conductivity in the composite material leads to the deterioration of the electronic conduction environment.
XRD is used to confirm the formation and decomposition of Li2O2 on the 10 wt.% CNL positive electrode during the charging and discharging process of non-aqueous Li-O2 batteries. Figure 6 shows the XRD pattern of the 10 wt.% CNL cathode under the original, first discharge and first charge conditions. After the first discharge, compared with the XRD spectrum of the original cathode, some diffraction peaks appeared at 34.7, 40.3, 58.3 and 70.5°, which can be attributed to the Li2O2 formed during the discharge. After the first charging process, the diffraction peak of Li2O2 disappeared, indicating that the Li2O2 formed during the first discharge was decomposed during the charging process. The evolution of this XRD pattern proves the rechargeability of this 10 wt.% CNL cathode.
The XRD pattern of the 10 wt.% CNL positive electrode of Li-O2 battery under (a) original, (b) first charge and (c) first discharge conditions (in order to prevent Li2O2 from decomposing under the influence of water in the air) , So put the cathode in a sealed bag for XRD test).
We further studied the catalytic activity of composite materials in non-aqueous Li-O2 batteries. The first discharge and charge curves of XC-72, LaNiO3, and 10 wt.% CNL in lithium-air batteries were compared at a current density of 50 mA g-1 (Figure 7a). In particular, the initial discharge capacity of 10 wt.% CNL is 5500 mAh g-1, which is higher than LaNiO3 (4600 mAh g-1) and XC-72 carbon (3600 mAh g-1). In addition, it can be clearly seen that the discharge voltage plateau of the 10 wt.% CNL catalyst is ~2.8 V, which is higher than that of LaNiO3 (~2.7 V) and XC-72 carbon (~2.7 V). The charging voltage plateau of 10 wt.% CNL is ~4.0 V, which is lower than LaNiO3 (~4.3 V) and XC-72 carbon (~4.4 V). The smaller overvoltage of CNL indicates that its catalytic activity is higher than that of LaNiO3 and XC-72. In addition, the 10 wt.% CNL catalyst exhibited 65 cycles between the voltage window of 2.6 V to 4.7 V, as shown in Figure 7b. The performance of LaNiO3 and XC-72 carbon catalysts are only 32 and 25 cycles, respectively. These results indicate that 10 wt.% CNL as an air electrode catalyst improves the capacity and cycle performance of Li-O2 batteries.
The electrochemical performance of lithium-air batteries.
(a) Using XC-72 carbon, LaNiO3 and 10 wt.% CNL as the air electrode, the first charge-discharge curve of a lithium-air battery at a current density of 50 mA g-1. (bd) The discharge and charge curves of the battery using 10 wt.% CNL, LaNiO3 and XC-72 carbon as the air electrode at a current density of 250 mA g-1.
In short, LaNiO3 and g-C3N4 composite material can be used as a dual-functional catalyst for oxygen reaction. Compared with LaNiO3 and g-C3N4 alone, the composite material provides the ORR and OER activity of the battery. The reason is that the CNL catalyst has a high Ni3/Ni2 ratio, which can promote the adsorption/desorption of oxygen in the alkaline electrolyte and more hydroxyl groups adsorbed on the surface. Promote the CNL formed by HOO−. LaNiO3 and g-C3N4 composite materials were used for the first time as a dual-function catalyst for lithium-air batteries. The composite material has enhanced specific capacity and cycle stability. The results show that CNL composites can become potential dual-functional catalysts for Li-O2 batteries, and this composite strategy is worthy of further study.
LaNiO3 nanoparticles (NPs) are synthesized by the sol-gel method. Dissolve 1.3 g La2O3 (Chinese National Medicines, reagent grade) in 10 mL HNO3 solution (65%≤HNO3≤68%) to obtain La(NO3)3·xH2O solution. Then dissolve 2.37 g Ni(NO3)2·6H2O (Chinese National Medicines, reagent grade) and La(NO3)3·xH2O in 100 ml of deionized water. Subsequently, a mixture of 6.75 g of citric acid (HOC(COOH)(CH2COOH)2 ≥ 99.5%) and 3.6 mL of ethylene glycol (HOCH2-CH2OH, 99.8%) was added dropwise to the metal nitrate under magnetic stirring at 80 °C . The molar ratio of total metal cations: citric acid: ethylene glycol is 1:2:4. The resulting solution was then stirred at 80°C to evaporate water, forming a viscous gel. The gel was heated at 400°C for 1 hour to obtain an amorphous citrate precursor. The precursor was ground and then calcined in an oxygen atmosphere at 750°C for 5 hours to obtain the final LaNiO3 powder.
The block g-C3N4 sheet is synthesized by pyrolysis. In short, 5 g of melamine is heated at 550 °C for 2 hours at a heating rate of 5 °C min-1. The resulting agglomerate was ground in a mortar for 1 hour, and then heated at 550°C for a further 2 hours. Then the prepared block g-C3N4 was obtained.
CNL was synthesized as follows: 0.04 g g-C3N4 was dispersed in 50 mL ethanol in a beaker, and sonicated for 30 minutes to completely disperse g-C3N4. Then 0.4 g of LaNiO3 NPs was added to the g-C3N4 suspension, and the mixture was further dispersed by ultrasonic treatment for 30 minutes, and then heated to reflux at 90°C for 6 hours under stirring. Then the alcohol was completely evaporated under stirring to obtain a precipitate. The precipitate was collected and heated at 550°C for 2 hours in a nitrogen atmosphere. Then the obtained compound was ground in the mortar for 1 hour to make the final 10wt.% CNL composite material (the weight percentage represents g-C3N4). Through this method, CNL catalysts with different mass ratios (5 wt.% CNL, 20 wt.% CNL and 30 wt.% CNL) were also prepared.
The crystal phase and purity of the prepared powder were determined by X-ray powder diffraction, Cu Kα radiation (λ = 0.154056 nm) from 10° to 90°. The structure of the sample was measured by a field emission scanning electron microscope (SEM) on a Hitachi SU8020 at an accelerating voltage of 3 kV. X-ray photoelectron spectroscopy (XPS) data was obtained on a Rigaku D/MAX2500V X-ray photoelectron spectrometer with Al Kα (1486.6 eV) excitation source.
The electrochemical characterization of the samples was performed on a rotating disk electrode (RDE, ATA-1B) with a three-electrode battery. The platinum electrode is used as the counter electrode. The saturated calomel electrode is used as a reference electrode. The glassy carbon electrode is used as the working electrode. A 0.1 M potassium hydroxide (KOH) solution is used as the electrolyte. For CV, ORR and OER studies, 1 mg of composite catalyst powder was mixed with 2.5 mg of XC-72 carbon to ensure sufficient electronic conductivity. Disperse the prepared catalyst and 30 μL of 5 wt.% Nafion solution in 1 mL of deionized water/isopropanol solution (the volume ratio of deionized water: isopropanol is 5:1), and ultrasonic treatment is uniform for 40 minutes. Of ink. The glassy carbon electrode (diameter 3 mm, area 0.071 cm2) was polished with 0.05 μm alumina slurry on a clean polishing cloth, rinsed and dried. Then we draw 2.8 μL of the suspension dropwise and load it on the glassy carbon, and the glassy carbon is slowly dried in an airtight container. The glassy carbon electrode loaded with the catalyst was immersed in a KOH electrolyte saturated with N2 to obtain a steady-state CV. Switch N2 to O2 and purge for another 30 minutes. After that, measure the ORR polarization curve from 0 V to -1.0 V. Then, switch O2 to N2 and purge for 30 minutes. Subsequently, the OER polarization curve was checked by a voltage sweep from 0.0 V to 1.2 V. Use Autolab electrochemical workstation to collect electrochemical data.
For Li-O2 battery research, the battery is manufactured in a glove box filled with pure argon. Use lithium foil as anode, 1 M LiCF3SO3 in tetraethylene glycol dimethyl ether (TEGDME) as electrolyte, glass fiber filter paper as separator, carbon paper-supported catalyst as cathode and two pieces of nickel foam (1 mm thick) as cathode set Electrical 43,44. The mass ratio of CNL catalyst prepared by mixing, XC-72 carbon, 5 wt.% polyvinylidene fluoride (PVDF) and solvent N-methyl-2-pyrrolidone (NMP) and CNL catalyst: XC-72 carbon: 5 The wt.% PVDF is 1:2:3. Use a brush to spread the uniform slurry on the carbon paper and vacuum dry at 80°C for 12 hours. Transfer the ready-made Li-O2 battery to a sealed bottle filled with pure oxygen and connect it to the multi-channel battery test system (LAND CT 2001A). The constant current discharge of the battery was studied in the potential range of 4.5-2.0 V. The performance of the first discharge cycle was performed at a current density of 50 mA g-1. The following cycle performance is performed at a current density of 250 mA g-1, and the capacity is limited to 500 mAh g-1. It should be noted that the current density and capacity are calculated based on the mass of the catalyst supported on the cathode.
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Zhang Dawei thanks the National Natural Science Foundation of China (51472070, 51272004, U1361110) and the Key Laboratory of Energy Conversion Materials of the Chinese Academy of Sciences (KF2014004). Jiang Lanshui thanked the Chinese government's "Thousand Talents Program" and the special funding support for the basic scientific research business fees of central universities.
School of Chemistry and Chemical Engineering, Hefei University of Technology, Hefei 230009
Yixin Wu, Taohuan Wang, Yidie Zhang, Sen Xin & Dawei Zhang
School of Chemistry and Chemical Engineering, Anhui University of Technology, Ma'anshan 243002
Key Laboratory of Energy Conversion Materials, Chinese Academy of Sciences, Hefei 230026
School of Materials Science and Engineering, Beihang University, Beijing 100191
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DZ conceived this project. YW designed the experiment. YW and TW conducted experiments, characterization and electrochemical performance tests. YW, YZ, XH, and SX analyzed the results. All authors discussed the results and wrote manuscripts. JS and DZ revised the manuscript.
The author declares that there are no competing economic interests.
This work has been licensed under the Creative Commons Attribution 4.0 International License Agreement. The images or other third-party materials in this article are included in the Creative Commons license of the article, unless otherwise stated in the credit line; if the material is not included under the Creative Commons license, the user will need permission from the license holder to copy The material. To view a copy of this license, please visit http://creativecommons.org/licenses/by/4.0/
Wu, Y., Wang, T., Zhang, Y., etc. The electrocatalytic performance of g-C3N4-LaNiO3 composite as a dual-function catalyst for lithium-oxygen batteries. Scientific Report 6, 24314 (2016). https://doi.org/10.1038/srep24314
DOI: https://doi.org/10.1038/srep24314
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