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Lead Oxide Enveloped in N-doped Graphene Oxide Composites for Enhanced High-rate Partial-state-of-charge Performance of Lead-acid Battery Huan Yang, Kai Qi, Lanqian Gong, Wanli Liu, Shahid Zaman, Xing Peng Guo, Yubing Qiu, and Bao Yu Xia ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/acssuschemeng.8b01357 • Publication Date (Web): 27 Jul 2018 Downloaded from http://pubs.acs.org on August 1, 2018

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ACS Sustainable Chemistry & Engineering

Lead Oxide Enveloped in N-doped Graphene Oxide Composites for Enhanced High-rate Partial-state-of-charge Performance of Lead-acid Battery Huan Yang,† Kai Qi,† Lanqian Gong,† Wanli Liu, ‡ Shahid Zaman, † Xingpeng Guo,† Yubing Qiu,*,† and Bao Yu Xia, *,†,§ †

Key laboratory of Material Chemistry for Energy Conversion and Storage (Ministry of Education), Hubei

Key Laboratory of Material Chemistry and Service Failure, School of Chemistry and Chemical Engineering, Wuhan National Laboratory for Optoelectronics, Huazhong University of Science and Technology (HUST), 1037 Luoyu Road, Wuhan 430074, PR China ‡

Hubei Provincial Engineering Consulting Corporation, Wuhan 430074, PR China

§

Shenzhen Institute of Huazhong University of Science and Technology, Shenzhen 518000, PR China.

KEYWORDS:

Lead-acid

battery;

Hydrogen

evolution;

High-rate

oxide/graphene oxide composite; Cycle life.

Corresponding Author *E-mail: [email protected] (Y. B. Qiu); [email protected] (B. Y. Xia). 1 ACS Paragon Plus Environment

partial-state-of-charge;

Lead

ACS Sustainable Chemistry & Engineering 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ABSTRACT: Lead oxide/graphene oxide composites are prepared by a pyrolysis method followed by ultrasound pickling treatment to improve the high-rate partial-state-of-charge (HRPSoC) performance of lead-acid battery for hybrid-electric vehicle. Employing this composite in the negative plate can effectively alleviate the aggregation of PbSO4 crystals and accelerate the redox processes of lead species, the plate specific capacitance and HRPSoC cycle life of lead-acid battery are thus significantly enhanced with the well inhibition of hydrogen evolution process. The fewer content of carboxyl groups on N-doped graphene oxide and the undissolved lead oxide nanoparticles are considered to contribute the enhanced cycle life performance. As a result, this lead oxide/graphene oxide composite holds potential application in the negative plate of lead-acid battery with high capacitance and long cycle life.

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INTRODUCTION

Lead-acid batteries still dominate the rechargeable batteries market, especially as the starting power sources in the automotive.1 However, the operation status of high-rate partial-state-of-charge (HRPSoC) will lead to the irreversible sulfation of active materials in the negative plates, and consequently result in the quick failure of lead-acid battery in electric vehicle.2, 3 Recently, conductive carbon materials with high surface area are introduced to impede the sulfation degree of negative plates and improve the HRPSoC cycle performance of lead-acid batteries.4,

5

However, carbon composites involved still suffer from serious

hydrogen evolution, which would quickly dry out the electrolyte and cause the dangerous battery system.6 To this end, various carbon materials are modified by the surface functional groups to alter their surface chemistry for the repressive hydrogen evolution process.7, 8 For example, activated carbon (AC) modified by alkaline surface functional groups can inhibit the hydrogen evolution reaction (HER), while this process can be promoted by acidic surface functional groups.9 Alternative strategies to inhibit hydrogen evolution of negative plates are employing carbon composites10, 11 or mixtures composed of metal oxides (ZnO, PbO etc.) with higher hydrogen evolution over-potentials (ηH).12 Meanwhile, sulfuric acid and lead oxide powder may react with the active surface of PbO/C composites, which can make the binding force between the composites and the negative active materials (NAM) enhanced during HRPSoC cycle.12

Previous work demonstrated the effective additives of PbO/carbon black (PbO/CB) can inhibit the hydrogen evolution process happened in the negative plates.13 However, the specific capacitance and HRPSoC cycle life of these negative electrodes containing PbO/CB are not significantly satisfied. Due to the unique two-dimensional characteristics, graphene oxide (GO) possesses highly accessible surface area, good electric conductivity and high-performance capacitance.14 GO additives are also introduced into the negative plates of lead-acid battery to significantly enhance the HRPSoC cycle life, but largely promote the hydrogen



evolution process because of abundant oxygen functional groups.15,

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Therefore, combining with the

appropriate surface chemistry treatment, the designed PbO/GO composites are expected to improve the capacitive performance of negative plates, while maintaining the advantages of PbO/carbon additives in enhancing HRPSoC cycling life, but still comprehensive investigations to be put forwarded.

In this work, PbO/GO composite is prepared by a pyrolysis approach followed by the ultrasound pickling treatment and employed as the additive for the negative plate of lead-acid battery. The resultant composite exhibits an increased specific capacitance and significantly enhanced HRPSoC cycle life, as well as the excellent inhibition of HER. Obviously, the fewer content of carboxyl groups on N-doped graphene oxide and undissolved lead oxide nanoparticles are considered to contribute the enhanced performance, as the PbO/GO composite can effectively inhibit the hydrogen evolution process, alleviate the growth of PbSO4 particles and accelerate the redox processes of lead species.

RESULTS AND DISCUSSION

Figure 1a shows the illustration scheme of preparation process. Firstly, the GO-Pb-alkali precursor is formed through the ultra-sonication of GO and Pb(NO3)2 in the ethyl alcohol solution containing ammonia. After the pyrolysis of Pb-GO-alkali precursor at 500 oC in N2 atmosphere, the final sample is obtained after a 15 min ultrasound pickling treatment in 5 M HCl solution and denoted as PbO-GO-N500-UP. Here, the introduction of ammonia is used for the precipitation of Pb(OH)2 and consequently realize the N-doping to anchor PbO during the annealing followed by pickling treatment. X-ray diffraction (XRD) pattern of PbO-GO-N500-UP composite demonstrates the similar diffraction peaks of PbO (Figure 1b),17 confirming that there are still the undissolved PbO phase in the composite even after the ultrasonication-pickling treatment. The scanning electron microscopy (SEM) image reveals that the typical morphology of pure GO and PbO crystals covered by GO layers or dispersed between them (Figure S1, Supporting Information, 4 ACS Paragon Plus Environment

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SI). Figure 1c reveals that PbO-GO-N500-UP composite contains many undissolved PbO particles with the size of ~ 500 nm, these particles are mostly encased in the GO layers. However, only GO layers are observed in PbO-GO-N500-SP (Figure S1c, SI). The further EDS analysis of PbO-GO-N500-UP (Figure S1d, SI) indicates that small PbO phase still exists in the composite (Figure S1d, SI). Transmission electron microscopy (TEM) image also confirms these PbO particles are uniformly enveloped in the fluffy graphene oxide layers (Figure 1d). This characteristic would be helpful to restrain the aggregation of PbO particles during the high-rate charge/discharge cycling process of lead-acid battery.

Figure 1. (a) Scheme of preparation process, (b) XRD pattern, (c) SEM and (d) TEM images of PbO-GO-N500-UP composite. Fourier transformed infrared (FT-IR) spectrum in Figure 2a shows that the peaks of GO at 1720.96, 1619.01 and 1382.10 cm-1 are respectively assigned to the C=O, C-C and C-O-H.18 While the peak of PbO-GO-N500-UP composite at 1720.96 cm-1 almost disappears, indicating that the electron-withdrawing 5 ACS Paragon Plus Environment


groups (oxygen-containing functional groups) are dissociated to aromatic rings due to the decomposition of carboxyl after pyrolysis at 500 oC.19 Moreover, a new peak at 1200 cm-1 is corresponding to C-N,20 suggesting nitrogen atoms are doped in the skeleton of GO. In addition, a blue shift of C-O-H deformation vibrations suggests that the interaction between PbO and GO would result in a more stable absorption between GO and PbO.21 The chemical composition of PbO/GO composites are further examined by X-ray photoelectron spectroscopy (XPS). The deconvoluted XPS spectra of Pb 4f shows that Pb in the PbO-GO-N500-UP additive is in the form of Pb-O bond (Figure 2b),10 which is consistent with the Pb (II) oxide in XRD results (Figure 1b). The O 1s XPS spectra can be deconvoluted into four components, Pb-O (~530.1 eV), -OH (~531.7 eV), C-O (~532.5 eV) and C=O (~534.8 eV) (Figure 2c, and Figure S2a, SI).22, 23

Generally, C=O represents the acidic surface functional groups on GO. Combined with the high resolution

O1s spectrum of GO and GO-N500-UP (Figure S2 SI), the acidic groups on GO decreases after different processing (Table S1, SI). The numerical order of the acidic surface functional groups content (CCOOH) is: GO > PbO-GO-N500-UP > GO-N500-UP. The high-resolution C1s spectrum can be deconvoluted into three bands (Figure 2d), corresponds to C-C (~284.6 eV), C-O (~286.7 eV), and C=O (~288.4 eV), respectively.24 The contents of C-O and C=O in PbO-GO-N500-UP composite are much smaller than those of GO, indicating that the pyrolysis-pickling processing can significantly reduce the amount of oxygen-containing functional groups on GO (Table S2, SI). Results from Boehm titration method further confirm obviously higher content CCOOH of GO than that of PbO-GO-N500-UP (Table S3, SI), which is consistent with the XPS results (Table S1, S2, SI). The decreased CCOOH of PbO-GO-N500-UP would be attributed to the pyrolysis decomposition of carboxyl surface functional groups during annealing treatment.25 Moreover, the distinct N signal at the binding energy of ~400 eV evidence the successful N-doping in both PbO-GO-N500-UP and GO-N500-UP by the pyrolysis of ammonia contained precursors (Figure S2d, SI).


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Figure 2. (a) FT-IR spectra for GO and PbO-GO-N500-UP composite. High-resolution XPS spectra of (b) Pb 4f, (c) O 1s and (d) C 1s for PbO-GO-N500-UP composite. All CV curves of the different negative plates show two pairs of redox peaks (Figure 3a). one (peak 1 and 2) is the redox process of Pb and PbSO4 (Pb↔PbSO4). Because the dimensions of individual PbSO4 crystals in the outer layer are in the order of 0.1-10 µm, which become impermeable to SO42- and HSO4- when they have reached a thickness of several µm, then the pores are practically closed, and it will occur the corrosion of Pb by dissociation of H2O underneath the PbSO4 layer, thus the anodic polarization at the potential around -0.5 V will generate PbO·PbSO4 layer, therefore, another (peak 3 and 4) is the redox reaction of Pb and PbO·PbSO4.26, 27 The peak currents of oxidation reaction (Pb→PbSO4) are much larger than those of reduction reaction, suggesting the inevitable accumulation of PbSO4 crystals. Compared with other negative plates, the negative plate with PbO-GO-N500-UP demonstrate the largest redox peak currents, indicating that PbO-GO-N500-UP have more power to accelerate the redox processes (Pb↔PbSO4). Furthermore, the 7 ACS Paragon Plus Environment


current density of the peaks 4 in GO and PbO-GO-N500-UP are both larger than the NAM plate, which may be related to the size of PbSO4 crystals in the outer layer of the negative plates, suggesting that the size of PbSO4 crystals in the outer layer of the NAM+GO and NAM+PbO-GO-N500-UP plates are smaller than that of the NAM plate. The specific capacitance of negative plates containing various additives (Cadditives) are calculated from the CVs. After the addition of these additives, all Cadditives of various negative plates are enhanced and the CNAM+PbO-GO-N500-UP is the largest (Table S4, SI), which could be attributed to the nature porous structure of additives (Table S5, SI). A high capacitance of the negative plate can share high rate discharge/charge currents,28 therefore, the negative plate containing PbO-GO-N500-UP and GO will have a relatively stronger buffer to prevent the irreversible transformation of PbSO4 crystals.

Figure 3. (a) CVs and (b) cathodic polarization curves of negative plates containing different additives: Blank (NAM), NAM+GO, NAM+PbO-GO-N500-UP. (c) Vdischarge change under HRPSoC conditions for the simulated test cells containing different additives at 2C rate in (d) the first cycle; (e) the half-cycle life; (f) the final full-life cycle.

The cathodic polarization curves are collected to investigate the hydrogen evolution of different negative plates (Figure 3b, Figure S5a, SI). Considering the working conditions of the negative plate under the HRPSoC cycle, for the quantitative HER comparison of different negative plates, H2 evolution potential 8 ACS Paragon Plus Environment

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(EH), the PbSO4 reduction current density (I) at potential EH ( I E ) and current density of H2 evolution at H

−1.4 V (IH,E = IH,

−1.4V

- I E ) are obtained (Table S4, SI). Compared with the characteristics of the H

polarization curves of blank (NAM), NAM+GO and NAM+PbO-GO-N500, before H2 evolution, the similar diffusion-limited

do

not

show

in

the

cathodic

polarisation

curves

of

NAM+GO-N500-UP,

NAM+PbO-GO-N500-UP and NAM+PbO-GO-N500-SP (Figure 3b, Figure S5a and S6a, SI), which suggests that the diffusion of Pb2+ ions or the dissolution of PbSO4 crystals may not completely control the reduction of PbSO4. Compared with the EH of initial NAM plate (EHNAM, -1.228 V), EHGO (-1.207 V) increases by 21 mV, while EHPbO-GO-N500-UP (-1.250 V) decreases by 22 mV. After the introduction of GO additive, the IH, −1.4V of initial NAM plate increase from 12.57 to 22.28 mA cm-2, while the IH, −1.4V of GO-N500-UP involved NAM plate is 13.02 mA cm-2. Thus, the surface function groups (CCOOH) of GO additives determine the hydrogen evolution of whole NAM negative plates. Furthermore, the EH (-1.32 V) of negative plate containing PbO-GO-N500-UP is more negative and the IH, −1.4V (3.4 mA cm-2) is much smaller. Obviously, GO with more functional groups (CCOOH) in the NAM accelerates the H2 evolution processes while PbO limits the HER process in the negative plate. We further investigate PbO content in various PbO/GO composites on the HER of the negative plates (Figure 3b and Figure S6a, SI). TGA analysis gives the ratio between GO and PbO in the additive before and after pickling process (Figure S7, SI), and the percentage content of PbO in PbO-GO-N500 and PbO-GO-N500-UP are respectively 79.89 % and 37.17 % (Table S6, SI). Combined with the elemental and TGA analysis (Table S1, Figure S7 and Table S6, SI), PbO content in various additives is following: PbO-GO-N500 > PbO-GO-N500-UP > PbO-GO-N500-SP, which is consistent with the numerical order of IH, −1.4V (Table S4, SI). The EH of the negative plate with PbO-GO-N500-UP is the smallest, indicating the composite processed with pyrolysis-ultrasound pickling method has an important effect on hydrogen inhibition. The electrochemical impedance spectra of different negative plates before cycling show the features of two processes (cathode is to produce H2 evolution and 9 ACS Paragon Plus Environment


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anode is to dissolve Pb) (Figure S8, SI). The negative plate with PbO-GO-N500-UP shows the smallest system impedance, suggesting that this additive can apparently promote the above two processes in the negative plate.

Figure 3c shows the typical potential response (Vdischarge) and cycle life (CLadditive) of the simulated cells under the HRPSoC conditions at 2C rate. Among them, the simulated test cell containing PbO-GO-N500-UP demonstrates the largest HRPSoC cycle life (17613 cycles) than those of the cells with other additives (Figure S5, S6, and Table S4, SI). These results suggest that a certain amount of PbO absorbed onto GO layers in the PbO/GO composite is beneficial to the HRPSoC cycle of negative plate. Obviously, small PbSO4 particles are helpful to reduce the polarization during charging/discharging process.13 The potential change in charge (∆Vcharge) and discharge (∆Vdischarge) cycles are defined to describe the polarization level of the different negative plates (Figure 3d, Figure S9, SI). At the first cycle, the ∆Vcharge (0.02 V) of the negative plate with PbO-GO-N500-UP is relatively smaller than those blank and GO added plates. At the half-cycle life, the ∆Vcharge of blank (982th cycle) and GO added plates (7614th cycle) are 0.69 V and 0.42 V, respectively, while the ∆Vcharge of PbO-GO-N500-UP (8806th cycle) are only 0.17 V (Figure 3e). Even at the final full-life cycle, the ∆Vcharge of PbO-GO-N500-UP (17613th cycle) are only 0.33 V, while the ∆Vcharge of blank (1964th cycle) and GO involved plates (15228th cycle) are 0.72 V and 0.52 V, respectively (Figure 3f). Due to the formation of large and low soluble PbSO4 crystals, the sharp charge potential increase during the charging period, suggesting that the cathodic process may occur diffusion control. Furthermore, the lower polarization degree of NAM+PbO-GO-N500-UP plate indicates a lower growth of PbSO4 crystals, and there exist stable absorption bands between them (Figure 2a), then the interfacial compatibility between GO and Pb aggregates can be improved, carbon floatation can be relieved during the preparation of negative paste,29 and the binding force between PbO-GO-N500-UP and NAM can be enhanced during the charging-discharging cycle.12 10 ACS Paragon Plus Environment

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Figure 4. Cross-sectional SEM images of the negative plates before (a-b) and after the HRPSoC cycle test (c-d): (a, c) Blank (NAM); (b, d) NAM+PbO-GO-N500-UP (After the first cycle-set, the negative plates were fully recharged).

According to all the above electrochemical results, the negative plate containing PbO-GO-N500-UP exhibits the best cycle life performance at high-rate charging/discharging process. It is mainly attributed to an excellent porous plate structure containing a certain amount of PbO enveloped in GO layers, which could alleviate the irreversible sulfation of negative plates (Figure 1c-d). To confirm the redox reversibility and solubility of PbSO4 crystals on the different negative plates, after the first cycle-set, the negative plates were fully recharged. The microstructure of various negative additives before and after HRPSoC cycling tests are analyzed in Figure 4 (Figures S10-11, SI). Obviously, the negative plate with PbO-GO-N500-UP shows more porous microstructure and smaller particles before cycling tests (Figure 4a-b). After the final cycle at 2C rate (1966 cycles), large PbSO4 crystals are closely stacking in the blank plate (Figure 4c), and the plate with GO shows the smaller PbSO4 crystals (Figure S11a-b, SI). While the plate containing 11 ACS Paragon Plus Environment


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PbO-GO-N500-UP generally maintains the smallest PbSO4 crystals and there has the small PbSO4 crystals in the GO layers (Figure 4d, Figure S10, S11c, SI). Moreover, the XRD and Raman spectra show the plate with PbO-GO-N500-UP has the largest Pb intensity (Figure S12a, SI) and the smallest PbSO4 intensity (Figure S12a-b, SI), suggesting the growth and aggregation of PbSO4 particles have been suppressed during the HRPSoC cycling test (17613 cycles) and thus this plate has the smallest sulfation level. It would be ascribed to a higher specific surface and larger pore volume with different porosity of GO and PbO-GO-N500-UP (Table S7, SI), which can provide sufficient surface and space for the H2SO4 storage and the nucleation and formation of small PbSO4 crystals. Meanwhile, the dissolution rate of smaller PbSO4 crystals is promoted (Figure S11, SI), and the reduction reaction of PbSO4 is thus accelerated (reversible PbSO4 crystals), as proved by the increased reduction currents (Figure 3a and Figure S5, S6, SI).30 Furthermore, the additives with large special capacity can increase the Cadditives of the negative plate, which can share high rate discharge/charge currents and have a relatively stronger buffer to prevent the irreversible transformation of PbSO4 crystals.

CONCLUSIONS

In this work, PbO/GO composites are prepared by a pyrolysis approach followed by an ultrasound-pickling treatment and used as the additives in negative plates for the improvement of HRPSoC cycle performance of lead-acid batteries. The negative plate containing PbO-GO-N500-UP demonstrates an excellent cycling-life performance (17614 cycles) at a high-rate charging/discharging. Electrochemical results suggest a certain amount of PbO absorbed onto GO layers in the PbO/GO composite is beneficial to the stable HRPSoC cycle of negative plate while the negative hydrogen evolution is well inhibited. This lead oxide/graphene oxide composite holds potential application in the negative plates of lead-acid batteries with high capacitance and long cycle life. More importantly, this work also provides the useful understandings in improving the


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cycle-life of lead-acid battery at high-rate charging/discharging together with a repressive hydrogen evolution. ASSOCIATED CONTENT

Supporting information. This Supporting Information is available free of charge on the internet. Experimental section; XRD spectrum; Raman spectrum; XPS spectrum; Cathodic polarization curves; HRPSoC cycle curves; and other electrochemical results (PDF)

AUTHOR INFORMATION

Corresponding Author *E-mail: [email protected] (Y. B. Qiu); [email protected] (B. Y. Xia).

Notes The authors declare no competing financial interest.

ACKNOWLEDGMENT This work is financial supported by National 1000 Young Talents Program of China. The Innovation Foundation of Shenzhen Government (JCYJ20160408173202143), the Fundamental Research Funds for the Central Universities (2018KFYXKJC044, 2018KFYYXJJ121, 2017KFXKJC002), the Joint Fund of Energy Storage of Qingdao (20160012) and the Innovation Research Funds of HUST (3004013109, 0118013089, 2017KFYXJJ164) are also acknowledged. We also acknowledge the support of Analytical and Testing Center of Huazhong University of Science and Technology for XRD, SEM, TEM, FT-IR and XPS measurements. REFERENCE (1) Lujano-Rojas, J. M.; Dufo-López, R.; Atencio-Guerra, J. L.; et al. Operating conditions of lead-acid 13 ACS Paragon Plus Environment


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batteries in the optimization of hybrid energy systems and microgrids. Appl Energy 2016, 179, 590-600, DOI 10.1016/j.apenergy.2016.07.018. (2) Lam, L.; Haigh, N.; Phyland, C.; et al. Failure mode of valve-regulated lead-acid batteries under high-rate partial-state-of-charge operation. J Power Sources 2004, 133, (1), 126-134, DOI 10.1016/j.jpowsour.2003.11.048. (3) Gandhi, K. S., Modeling of effect of double-layer capacitance and failure of lead-acid batteries in HRPSoC application. J Electrochem Soc 2017, 164, (11), E3092-E3101, DOI 10.1149/2.0101711jes. (4) Long, Q.; Ma, G.; Xu, Q.; et al. Improving the cycle life of lead-acid batteries using three-dimensional reduced graphene oxide under the high-rate partial-state-of-charge condition. J Power Sources 2017, 343, 188-196, DOI 10.1016/j.jpowsour.2017.01.056. (5) Banerjee, A.; Ziv, B.; Shilina, Y.; et al. Single-Wall Carbon Nanotube Doping in Lead-Acid Batteries: A New Horizon. ACS Appl Mater Interfaces 2017, 9, (4), 3634, DOI 10.1021/acsami.6b13377. (6) Zhang, W.; Lin, H.; Lu, H.; et al. On the electrochemical origin of the enhanced charge acceptance of the lead-carbon electrode. J Mater Chem A 2015, 3, (8), 4399-4404, DOI 10.1039/C4TA05891G. (7) Sánchez-Sánchez, A.; Suárez-García, F.; Martínez-Alonso, A.; et al. Evolution of the complex surface chemistry in mesoporous carbons obtained from polyaramide precursors. Appl. Surf. Sci 2014, 299, 19-28, DOI 10.1016/j.apsusc.2014.01.171. (8) Wang, F.; Hu, C.; Lian, J.; et al. Phosphorus-doped activated carbon as a promising additive for high performance lead carbon batteries. RSC Adv 2017, 7, (7), 4174-4178, DOI 10.1039/C6RA26093D. (9) Wang, L.; Zhang, H.; Cao, G.; et al. Effect of activated carbon surface functional groups on nano-lead electrodeposition and hydrogen evolution and its applications in lead-carbon batteries. Electrochim. Acta 2015, 186, 654-663, DOI 10.1016/j.electacta.2015.11.007. (10) Dhanabalan, K.; Sadhasivam, T.; Sang, C. K.; et al. Novel core–shell structure of a lead-activated carbon (Pb@AC) for advanced lead–acid battery systems. J Mater Sci Mater in Electron 2017, 28, (14), 10349-10356, DOI 10.1016/j.electacta.2015.11.007. (11) Xiang, J.; Hu, C.; Chen, L.; et al. Enhanced performance of Zn(II)-doped lead-acid batteries with electrochemical active carbon in negative mass. J Power Sources 2016, 328, 8-14, DOI 10.1016/j.jpowsour.2016.07.113. (12) Gao, Y. F.; Song, Y. L.; Ren, D. L.; et al. Preparation and Electrochemical Behavior in H2SO4 Electrolyte of Nano-Pb (PbO)/Activated Carbon. J Inorg Mater 2013, 12, 006, DOI 10.3724/SP.J.1077.2013.13165. (13) Yang, H.; Qiu, Y.; Guo, X., Lead oxide/carbon black composites prepared with a new pyrolysis-pickling method and their effects on the high-rate partial-state-of-charge performance of lead-acid batteries. Electrochim. Acta 2017, 235, 409-421, DOI 10.1016/j.electacta.2017.03.138. (14) Li, L.; Zhang, J.; Peng, Z.; et al. High-Performance Pseudocapacitive Microsupercapacitors from Laser-Induced Graphene. Adv Mater 2016, 28, 838-845, DOI 10.1002/adma.201503333. (15) Liu P.; Yan T.; Shi L.; et al. Graphene-based materials for capacitive deionization. J Mater Chem A 2017, 5, 13907-13943, DOI 10.1039/C7TA02653F. (16) Yang, H.; Qiu, Y.; Guo, X., Effects of PPy, GO and PPy/GO composites on the negative plate and on the high-rate partial-state-of-charge performance of lead-acid batteries. Electrochim. Acta 2016, 215, 346-356, DOI 10.1016/j.electacta.2016.08.115. (17) Cui, X. P.; Jiang, K. J.; Huang, J. H.; et al. Electrodeposition of PbO and its conversion to CH3NH3PbI3 for mesoscopic perovskite solar cells. Chem Commun 2015, 51, (8), 1457-1460, DOI 10.1039/C4CC08269A. (18) Chen, Y.; Wang, Y.; Zhang, H. B.; et al. Enhanced electromagnetic interference shielding efficiency of polystyrene/graphene composites with magnetic Fe3O4 nanoparticles. Carbon 2015, 82, 67-76, DOI 14 ACS Paragon Plus Environment

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10.1016/j.carbon.2014.10.031. (19) Nie, R.; Miao, M.; Du, W.; et al. Selective hydrogenation of C=C bond over N-doped reduced graphene oxides supported Pd catalyst. Appl Catal B: Environ 2016, 180, 607-613, DOI 10.1016/j.apcatb.2015.07.015. (20) Yu, C.; Fang, H.; Liu, Z.; et al. Chemically grafting graphene oxide to B,N co-doped graphene via ionic liquid and their superior performance for triiodide reduction. Nano Energy 2016, 25, 184-192, DOI 10.1016/j.nanoen.2016.04.039. (21) He, X.; Peng, X.; Zhu, Y.; et al. Producing hierarchical porous carbon monoliths from hydrometallurgical recycling of spent lead acid battery for application in lithium ion batteries. Green Chem 2015, 17, (9), 4637-4646, DOI 10.1039/C5GC01203A. (22) Rey, A.; Zazo, J.; Casas, J.; et al. Influence of the structural and surface characteristics of activated carbon on the catalytic decomposition of hydrogen peroxide. J. Appl Catal A: Gen 2011, 402, (1), 146-155, DOI 10.1016/j.apcata.2011.05.040. (23) Stavrinadis, A.; So, D.; Konstantatos, G.; et al. The role of surface passivation for efficient and photostable PbS quantum dot solar cells. Nat. Energy 2016, 1, (4), 16035, DOI 10.1038/NENERGY.2016.35. (24) Liu, S.; Tian, J.; Wang, L.; et al. A method for the production of reduced graphene oxide using benzylamine as a reducing and stabilizing agent and its subsequent decoration with Ag nanoparticles for enzymeless hydrogen peroxide detection. Carbon 2011, 49, (10), 3158-3164, DOI 10.1016/j.carbon.2011.03.036. (25) Liu, W. J.; Jiang, H.; Yu, H. Q., Development of Biochar-Based Functional Materials: Toward a Sustainable Platform Carbon Material. Chem Rev 2015, 115, (22), 12251, DOI 10.1021/acs.chemrev.5b00195. (26) Kumar, S. M.; Kiran, U. V.; Raju, A. K.; et al. Effect of boron–carbon–nitride as a negative additive for lead acid batteries operating under high-rate partial-state-of-charge conditions. RSC Adv 2016, 6, (79), 75122-75125, DOI 10.1039/C6RA13458K. (27) Liao, Y. S.; Chen, P. Y.; Sun, I. W., Electrochemical study and recovery of Pb using 1:2 choline chloride/urea deep eutectic solvent: A variety of Pb species PbSO4, PbO2, and PbO exhibits the analogous thermodynamic behavior. Electrochim. Acta 2016, 214, 265-275, DOI 10.1016/j.electacta.2016.08.053. (28) Tong, P.; Zhao, R.; Zhang, R.; et al. Characterization of lead (Ⅱ)-containing activated carbon and its excellent performance of extending lead-acid battery cycle life for high-rate partial-state-of-charge operation. J Power Sources 2015, 286, 91-102, DOI 10.1016/j.jpowsour.2015.03.150. (29) Hong, B.; Jiang, L.; Xue, H.; et al. Characterization of nano-lead-doped active carbon and its application in lead-acid battery. J Power Sources 2014, 270, 332-341, DOI 10.1016/j.jpowsour.2014.07.145. (30) Xiang, J.; Ding, P.; Zhang, H.; et al. Beneficial effects of activated carbon additives on the performance of negative lead-acid battery electrode for high-rate partial-state-of-charge operation. J Power Sources 2013, 241, 150-158, DOI 10.1016/j.jpowsour.2013.04.106.



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PbO Enveloped in N-doped Graphene composite is prepared to improve the high-rate partial-state-of-charge performance of lead-acid battery, while the hydrogen evolution is also well-inhibited.


Lead Oxide Enveloped in N-Doped Graphene ... - ACS Publications

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