High-rate Partial-state-of-charge Research Articles

Long-Life Lead-Carbon Batteries for Stationary Energy Storage Applications.

Owing to the mature technology, natural abundance of raw materials, high recycling efficiency, cost-effectiveness, and high safety of lead-acid batteries (LABs) have received much more attention from large to medium energy storage systems for many years. Lead carbon batteries (LCBs) offer exceptional performance at the high-rate partial state of charge (HRPSoC) and higher charge acceptance than LAB, making them promising for hybrid electric vehicles and stationary energy storage applications. Despite that, adding carbon to the negative active electrode considerably enhances the electrochemical performance. However, carbon brings some adverse effects, such as the severe hydrogen evolution reaction (HER) in the NAM due to the low overpotential of carbon material, promoting severe water loss in LCBs. From a practical application point of view, the irreversible sulfation of the negative active material (NAM) and extreme shedding and softening of the positive active material (PAM) are the main obstacles for next-generation LCBs. Recently, a lead-carbon composite additive delayed the parasitic hydrogen evolution and eliminated the sulfation problem, ensuring a long life of LCBs for practical aspects. This comprehensive review outlines a brief developmental historical background of LAB, its shifting towards LCB, the failure mode of LAB, and possible potential solutions to tackle the failure problems. The detailed LCB's development towards long life was discussed in light of the reported literature to guide the researcher to date progress. More emphasis was directed toward the new applications of LCBs for stationary energy storage applications. Finally, state-of-the-art progress and further research gaps were pointed out for future work in this exciting era.

Reduced graphene oxide coated with amorphous lead as positive additive for enhanced performance of lead–carbon batteries

Composites of reduced graphene oxide coated with amorphous lead (Pb/rGO) were prepared by electrostatic adsorption and hydrothermal methods, and used as positive additives for lead–carbon batteries to enhance discharge specific capacity and cycle life under high-rate partial-state-of-charge (HRPSoC) of batteries. Amorphous Pb inhibits the oxygen evolution reaction (OER) that occurs on the surface of reduced graphene oxide (rGO) and increases the specific capacitance of the positive active material (PAM). In addition, the presence of amorphous Pb enhances the affinity of rGO to PAM, which avoids the separation of additive and PAM during the cycling process. Pb/rGO additives can act as pore forming agents and significantly increase the specific surface area of PAM, which enables the electrolyte to fully react with PAM to inhibit the overgrowth of PbSO4 crystals. Thus, Pb/rGO additives help to improve the electrochemical performance of batteries. To be specific, when the Pb/rGO additive content is 0.7 wt%, battery showed the best discharge specific capacity (102 mAh/g) and cycle life (18,104 cycles), which is 117% and 104% higher than that of blank battery, respectively. And the rate capability is also improved compared to its counterpart. In short, the Pb/rGO composite material has potential application value in lead–carbon batteries.

Carbon thermal shock assisted activated carbon for lead carbon batteries: Uniform loading of lead nanoparticles and pore regulation

Activated carbon is currently recognized as one of the most promising additives for lead carbon batteries, but how to suppress intense hydrogen evolution and sulfation of lead carbon anode remains a challenge. Herein, we innovatively use programmable carbon thermal shock to achieve uniform dispersion and anchoring of lead nanoparticles on the surface of activated carbon, as well as selective removal of a portion of micropores. Owing to the synergistic mechanism of uniform dispersion of lead nanoparticles and pore regulation, the composites have extremely low hydrogen evolution rate, ultra-fast catalytic Pb2+ reduction rate, and can facilitate the growth of stable lead carbon interphase. The collaboration of multiple functions of composites increases the cycling life of simulated anode under high rate partial state of charge (HRPSoC) from 5449 cycles to 18,139 cycles, and the capacity retention rate under partial state of charge (PSoC) from 49 % to 82 % after 150 cycles. Furthermore, the as-fabricated lead carbon battery (12 V-12 Ah) exhibits an ultra-long cycle life of 32,107 cycles under HRPSoC and excellent rate discharge performance.

Bifunctional additive: Lead dioxide nanoparticle-doped graphene oxide composites for the preparation and performance study of positive electrodes in lead-carbon batteries

Lead-carbon batteries (LCBs) possess the dual functions of supercapacitors and lead-acid batteries (LABs), which can meet the demand for renewable energy and in mild hybrid electric vehicles (HEVs) for energy storage and short-term high-rate charging and discharging. With the cycle of high-rate partial state-of-charge (HRPSoC), irreversible sulfation of the positive electrode becomes increasingly prominent and serious, resulting in low discharge capacity and short cycle life. In this study, to reduce the sulfation of the positive plate and improve the battery capacity and cycle life, a lead dioxide nanoparticle-doped graphene oxide (nano-PbO2/GO) composite material with dual functions of conducting and nucleating was prepared by a hydrothermal method as a positive electrode additive. The results show that the addition of nano-PbO2/GO promotes the formation of a three-dimensional short rod-like structure of PbO2 nanoparticles in a dendritic arrangement, accelerates the generation of new phases and inhibits the growth of bulk PbSO4. Moreover, the positive plate with nano-PbO2/GO exhibits good electrochemical activity to maintain the stability and reversibility of the electrode redox reaction. Finally, the initial discharge specific capacity of the LCBs with nano-PbO2/GO is increased to 153.85 mAh/g, and the HRPSoC cycle life is up to 15658 cycles at a 2 C discharge rate. Overall, the dual functions of nano-PbO2/GO greatly alleviate battery sulfation and provide a reference for improving the performance of LCBs by modifying the electrode structure.

A novel three-dimensional hierarchical porous lead-carbon composite prepared from corn stover for high-performance lead-carbon batteries

In this work, a novel three-dimensional(3D) hierarchical porous lead-carbon composite (Nano-PbO@3DCSHPAC) derived from corn stover biomass was prepared by chemical deposition coupled with pyrolysis to alleviate the problems associated with the high occurrence of the hydrogen evolution reaction (HER) and irreversible sulfation of the negative electrode under a high-rate partial state of charge (HRPSoC). As an additive of negative electrode in lead-carbon battery. PbO, evenly distributed on the Nano-PbO@3DCSHPAC composite, effectively inhibits the HER, acting as a nucleus for the active substance Pb, refining the grains of sponge Pb, and maintaining the high electrochemical active area of the electrode. The Nano-PbO@3DCSHPAC composite with a high specific surface area and porosity possesses good ion channels, provides an ion reservoir, and effectively inhibits irreversible sulfation. As a result, the initial discharge capacity of the battery with Nano-PbO@3DCSHPAC (164 mAh·g-1) is greater than that of the blank battery (109 mAh·g-1). The cycling life of the Nano-PbO@3DCSHPAC battery (10120 cycles) is 9.4 times that of a blank battery (1073 cycles). Our work provides insights into how to regulate the specific surface area and porosity of lead-carbon additives and makes full use of biomass straw to provide new ideas for solving the environmental problems caused by straw incineration. It is the embodiment of the circular economy.

Monosodium glutamate as an effective electrolyte additive in lead acid battery

High-rate partial state of charge (HRPSoC) life and stability of lead-acid batteries are largely limited by the surface morphology of lead sulfate and the reactivity of anode plates. In this study, sodium glutamate (MSG) was introduced as an electrolyte additive for lead-acid battery to improve lead sulfate deposition process and lead sulfate crystal morphology at the interface between lead anode and sulfuric acid electrolyte, and the influence of MSG on battery performance were explored. By electrochemical tests and material characterization, it was proved that glutamic acid anion can promote the formation of uniform deposition of lead sulfate with a structure similar to stacked flakes, which make it easy to form active lead and restrain irreversible sulfate during the fast charging and discharging process.

Lead single atoms anchored on reduced graphene oxide as multifunctional additive for lead–carbon battery

The application of lead–carbon batteries (LCBs) in hybrid electric vehicles and large-scale energy storage was limited by gradual sulfation and parasitic hydrogen evolution reaction (HER) of negative plates. Here, Pb single atoms anchored on reduced graphene oxide (PbSAs@rGO) were prepared through electrostatic adsorption and thermal reduction method, and confirmed by two aberration-corrected transmission electron microscopy (TEM and STEM) and synchrotron-based X-ray absorption fine structure spectroscopy (XAFS). By anchoring PbSAs on rGO surfaces where HER is prone to occur, the HER rate was greatly reduced. Moreover, PbSAs could serve as seeds to induce three-dimensional growth of Pb branches, which endows the NAM containing PbSAs@rGO additives with a specific surface areas (SSA) about 2.3 times than that of control one. The increased SSA can help to delay the sulfation of negative plate. Meanwhile, PbSAs can help enhance the affinity of rGO towards negative active material (NAM), which enable electrochemical reduction reaction proceeds at a higher rate. Thanks to the coordination of various functions from multifunctional additives, service life of LCBs under high-rate partial-state-of-charge (HRPSoC) have been extend from 3529 to 16,097 cycles, and from 4692 to 22,606 cycles, in 50% state of charge (SoC) and 75% SoC, respectively.

Investigation of lead particles loading on the surface of activated carbon on the performance of lead carbon batteries and its potential mechanisms

Loading lead particles on the surface of activated carbon (AC) is an effective strategy to further improve the performance of lead carbon batteries (LCBs). However, the influence of lead particle size on the properties of AC is ignored. Herein, AC loaded with lead phosphate particles of different sizes by ultrasonic adsorption is prepared. The results show that large size lead phosphate particles are conducive to the formation of lead carbon connection interphase with tens of microns, so as to avoid the electronic path failure of AC caused by sulfation. Moreover, with the increase of lead phosphate particle size, the cycle life under high rate partial state of charge (HRPSoC) and the capacity retention rate after 150 deep cycles under 60 % state of charge (SoC) increase by 49.12 % and 47.2 % respectively.

N-doped reduced graphene oxide loading nano lead oxide as negative additive for enhanced properties of lead-carbon batteries

The use of carbon materials could significantly increase the cycle life of lead-acid batteries (LABs) by inhibiting the irreversible sulfation. However, it will exacerbate hydrogen evolution side reaction at the negative plates, which not only reduce coulombic efficiency, destroy the plate microstructure, but also accelerate moisture loss. Herein, a N-doped reduced graphene oxide/lead oxide nanoparticles(N-rGO/PbO) composite was synthesized by hydrothermal and calcination process. Comparative studies found that the strategy of loading with metal oxide nanoparticles, which with high hydrogen evolution overpotentials (ηH), and N-doped can retard the rate of hydrogen evolution reaction (HER) on composite materials. In addition, the resultant composite can help to promote the uniform distribution of graphene in negative active materials (NAM) and structural stability of the negative plate and enhance the combination between the additive and NAM. Thanks to the superiority of the prepared composite material additives, the high-rate partial-state-of-charge (HRPSoC) life of lead-carbon battery (LCB) containing the composite additive shown a prominent enhancement. Specifically, the simulated micro battery containing 0.50 wt% N-rGO/PbO additive showed the best cycle life (17390 cycles), compared to that with same content rGO additive (7742 cycles) and that without any carbon additive (2777 cycles). What’s more, by adding 0.50 wt% N-rGO/PbO additive, the initial discharge capacity of simulated micro battery could be enhanced from 145.6 to 162.6 mAh g−1 and the rate capability had also been improved. In summary, the N-rGO/PbO composite manifests great potential in lead-carbon batteries for improving HRPSoC cycle life and discharge capacity.

Hydrogen evolution reaction at lead/carbon porous electrodes studied by a novel electrochemical mass spectrometry set-up

Lead–acid batteries are robust, low-cost, and have a large power-to-weight ratio. Recently, small amounts of carbon-based materials with a high surface area have been included in the Pb electrode as additives to improve the high-rate partial state of charge. However, carbon-based materials also enhance the hydrogen evolution reaction during the charging process at the negative active material (NAM), which is undesirable and dangerous. Therefore, in the current communication, a promising differential electrochemical mass spectrometry (DEMS) set-up suitable for studying the hydrogen evolution reaction (HER) at technical NAM electrodes in lead–acid batteries (LABs) is reported for the first time.

PbO nanoparticles anchored on reduced graphene oxide for enhanced cycle life of lead-carbon battery

The composites of PbO nanoparticles anchored on reduced graphene oxide (PbO@rGO) are prepared by electrostatic interaction and ostwald ripening strategy to enhance cycle life of lead-carbon battery under high-rate partial-state-of-charge (HRPSoC). By occupying the hydrogen evolution reactive sites on the rGO surfaces, the PbO@rGO composite exhibits better inhibition for hydrogen evolution behavior than the rGO. Thus, introducing the composite additives to negative plates can effectively inhibit the hydrogen evolution reaction (HER) and alleviate the aggregation of PbSO4 crystals simultaneously, resulting in their HRPSoC cycle life show 2.6-fold enhancements compared with negative plates without any carbon additives (extend from 3501 to 12,885 cycles). The chemical bond between the rGO and PbO nanoparticles can not only help solve the "floating carbon" phenomenon, but also effectively avoid the separation of the additive and the negative active material (NAM) during the cycles. In addition, the PbO@rGO additives can act like a miniaturized stereo plate grid, which refines and expands the conductive network on the plate and provides deposition sites for Pb/PbSO4 redox couple. Outstanding performance of the batteries containing composite additives indicates that the composites have potential application value in the lead-carbon battery while providing a new idea for preparing lead-carbon composite.

Leaching of waste tin indium oxide glass components and its application as negative additive of lead-carbon cells

In2O3 plays an important role in inhibiting hydrogen evolution reaction of lead-carbon battery (LCB). In this study, high purity indium hydroxide obtained by leaching tin indium oxide (ITO) glass waste has been applied in lead-carbon cell. Compared with ordinary lead-carbon cell, hydrogen evolution reaction (HER) of lead-carbon cell with added ITO recovery (R-ITO) is effectively inhibited.Under high-rate partial state-of-charge (HRPSoC) operation, cells with 0.1%R-ITO and 0.3 % conductive carbon black (CB) showed the best cycle performance (17,632), which was 2.3 times than lead-carbon cell with 0.3 % CB (7746) and 11.9 times than conventional lead-acid cell without additive (1485). Under different current densities, the capacity of lead-carbon cell with waste ITO has been significantly improved, and has a high reversible capacity.

Inhibition of irreversible sulfation of lead-acid batteries by hierarchal porous carbon with in-situ grown carbon nanotube clusters

Hierarchical porous carbon with in-situ grown carbon nanotube clusters(HPC-CNTs) was synthesized by transition metal catalytic cracking and used as an additive to inhibit irreversible sulfation of negative electrode of lead-acid batteries. The synthesis method not only makes a stable connection point between HPC and CNTs, but also avoids the agglomeration of CNTs. The HPC-CNTs has rich pore structure, and the specific surface area and specific capacitance are as high as 1307 m2 g−1and 164.03F g−1 respectively. The specific capacity of the negative active material(NAM) with the addition of this material is up to 175.71 mAhg−1, which is 22.57% higher than that of the commercial NAM(143.36 mAhg−1). The cycle life of the battery under high-rate partial-state-of-charge(HRPSoC) exceeds that of commercial batteries by 154%, reaching 42,946 cycles. Finally, the action mechanism of the material in the negative electrode of lead acid battery is analyzed, which provides a new material for prolonging the life of lead-acid batteries.

The influence of the characteristics of rice husk-based activated carbon on the performance of lead-carbon batteries and its potential mechanisms

We explore the effects of rice husk-based activated carbon (RHAC) with different pore structure and functional groups on the performance of lead-carbon batteries (LCB) in high-rate partial state of charge (HRPSoC) and its potential mechanisms. The results show that the performance of negative electrode is mainly affected by the rate and efficiency of RHAC on electrocatalytic of lead deposition. Notably, the reaction of phosphoric acid with silica in rice husk can significantly increase the content of phosphorus functional groups, which can enhance the electrocatalytic rate by complexing lead ions and inhibit hydrogen evolution reaction (HER). Micropore is more prone to hydrogen evolution in the medium-to-high polarization region (-1.25V∼-1.5 V vs Hg/Hg2SO4) and hinder lead ion mass transfer, which leads to the general cycle performance of LCB containing high microporosity RHAC. In addition, RHAC only has a certain electric double layer capacitance (EDLC) contribution at the end of cycle, which is still on the premise that RHAC has high specific surface area (SSA) and mesoporosity.

Hierarchical porous carbon material regenerated from natural bamboo-leaf: How to improve the performance of lead-carbon batteries?

Lead-carbon battery is supposed as the promising candidate for lead-acid battery for energy storage application ascribed to the unique performance under the high-rate-partial-state-of-charge (HRPSoC). Herein, a bamboo-leaf hierarchical porous carbon material (BLHPC) is successfully generated as the lead-carbon batteries negative electrode additive. BLHPC manifests hierarchical and multidirectional porous structure with broad size distribution and large specific surface area (2595 m 2 g −1 ), which is attributed to the abundant hollow structure in bamboo-leaf and etching of biogenetic SiO 2 nanoparticles. In electrochemical characterization, BLHPC presents high specific capacitance (252 F g −1 at 0.5 A g −1 ) and remarkable rate capability (68.6% retention rate at 10 A g −1 ). Furthermore, cycle life of simulated battery with 0.5 wt% BLHPC (56700) is twice that of the same amount of commercial rice-husk carbon (RHC) material additive (23701) and 7.6 times for blank battery (7455). The battery performance enhancement owes to the high surface area and hierarchical porous structure of BLHPC to mitigate the sulfation and promote electrolyte permeation. • Bamboo-leaf hierarchical porous carbon material (BLHPC) is successfully generated. • BLHPC manifests large specific surface area and high specific capacitance. • Cycle life of simulated battery with 0.5 wt% BLHPC is significantly improved. • The structure of BLHPC mitigates sulfation and promotes electrolyte permeation.

Nitrogen-doped redox graphene as a negative electrode additive for lead-acid batteries

To suppress the sulfation of the negative electrode of lead-acid batteries, a graphene derivative (GO-EDA) was prepared by ethylenediamine (EDA) functionalized graphene oxide (GO), which was used as an effective additive for the negative electrode of lead-acid batteries. The effect of GO-EDA on the performance of lead-acid batteries was studied by electrochemical methods, simulated cell performance test, X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results show that when the negative active material (NAM) contains 0.5 wt.% GO-EDA additive (the N-0.5 cell), the initial discharge capacity of the cell at a rate of 0.05 C is 171.47 mAh g−1. Meanwhile, the high-rate partial state of charge (HRPSoC) cycle life of the N-0.5 cell under 1 C rate is 17,970 cycles, which is 280% higher than that of the blank control cell. In a word, GO-EDA has the potential to be applied to enhance the specific capacity and HRPSoC cycle-life of lead-acid batteries.

Boosting high-rate-partial-state-of-charge performance of lead-acid batteries by incorporating trace amount of sodium dodecyl sulfate modified multi-walled carbon nanotubes into negative active materials

In this work, trace amount of sodium dodecyl sulfate modified multi-walled carbon nanotubes acid-treated multi-walled carbon nanotubes (SDS-MWCNTs) is incorporated into the negative active materials (NAMs) of lead acid battery by simply blending the SDS-MWCNTs aqueous dispersion with the dry mixture of lead oxide powder, expanders and carbon black for lead paste preparation. As the sulfate groups on SDS can combine with Pb2+ ions to make PbSO4 to generate 3PbO·PbSO4·H2O (3BS), the cured NAMs incorporated with SDS-MWCNTs exhibit an improved 3BS percentage as well as an increased 3BS crystal size. The 3BS percentage reaches 22.47% in the cured NAMs with 100 ppm SDS-MWCNTs, more than 5.4% higher than that in the NAMs without SDS-MWCNTs. After formation, the NAMs containing SDS-MWCNTs presents a morphology of the interconnected Pb rods, which accelerates the kinetics for the electrochemical reactions between Pb and PbSO4 and thus retards PbSO4 accumulation. Simulated cells are assembled, and the cell constructed by the negative plate containing 100 ppm SDS-MWCNTs can achieve a high-rate partial-state-of-charge (HRPSoC) cycle-life of 45,692 cycles, more than 2.1 times as long as that of the cell assembled with the negative plate without SDS-MWCNTs. Our method is of great convenience and low-cost, it is supposed to have a great feasibility in lead-acid battery industry.

Rapid preparation of nano lead sulfate-lead carbon black composite by microwave method as a negative electrode additive for lead-carbon batteries

We first propose and successfully use a simple microwave method to prepare a new nano lead sulfate-lead carbon black (PbSO4@Pb/C) composite as the lead-carbon batteries negative electrode additives, aiming to extend high-rate partial-state-of-charge (HRPSoC) life of lead-carbon batteries. Carbon black as lead sulfate nucleation centers and nano scale lead sulfate as templates growth mode during discharge process may significantly inhibit irreversible sulfation processes of negative electrode. HRPSoC cycle life (24513) of battery with 3 wt% PbSO4@Pb/C composite is 8.5 times that of the same amount of original carbon material (2880) additives and 31.2 times for blank battery (785). Hydrogen evolution effect of carbon material is also restrained.

Effects of sulfonated graphene on lead sulfate negative electrode of Pb-C batteries

We have proved that chemically prepared micro-crystalline PbSO4 can be directly used as the electrode active material of lead acid batteries. Therefore, we would like to know how it works in start-stop SLI batteries working under high-rate partial-state-of-charge (HRPSoC), where PbSO4 microcrystals are very easy to grow up, thus degenerate the batteries. To increase the interaction between the conductive additive and PbSO4, a sulfonated graphene has been prepared by reacting reduced graphene oxide (rGO) with 4-benzenediazoniumsulfonate using H3PO2 as the reducing agent, and its conductive property has been studied. Results show that the battery performance can be promoted significantly with 1.0 wt.% of PbSO4 added: the initial discharge capacity is 123.3 mA•g−1 at a current density of 100 mA•g−1 and it can survive 1000 cycles of 100% DOD, and 12,126 HRPSoC micro cycles of 60-second charge and discharge at 200 mA•g−1 after it is discharged to 50% state of charge (SoC), while the one with 0.5% or 1.5% of sulfonated graphene can only last 3872 and 8122 cycles, respectively.

Perspective and advanced development of lead–carbon battery for inhibition of hydrogen evolution

With the global demands for green energy utilization in automobiles, various internal combustion engines have been starting to use energy storage devices. Electrochemical energy storage systems, especially ultra-battery (lead–carbon battery), will meet this demand. The lead–carbon battery is one of the advanced featured systems among lead–acid batteries. The key limitation of lead–carbon battery is the sulfation of negative plates under a partial state of charge, which reduces the charging capacity and cycle life. To solve this problem, carbon as a kind of suitable materials is proposed to incorporate into the negative plates of the active materials for working under partial state of charge (PSOC) and high rate partial state of charge (HRPSOC) conditions. In this review, we discuss the properties of carbon materials and their function towards the inhibition of hydrogen evolution. Furthermore, the influence of grid composition, separator, and binder content on the electrochemical performance of the lead–carbon battery is also elaborately described. The main challenging issues of hydrogen evolution on lead–carbon batteries are discussed in different ways and perspective views to higher performance on future energy storage applications have also been presented.