Lead-acid Battery Electrodes Research Articles

Fabrication of PbSO4 negative electrode of lead-acid battery with high performance

This paper reports the preparation and electrochemical properties of the PbSO4 negative electrode with polyvinyl alcohol (PVA) and sodium polystyrene sulfonate (PSS) as the binders. The results show that the mixture of PVA and PSS added to the PbSO4 electrode can significantly improve the specific discharge capacity of the PbSO4 electrode, which reaches 110 mAh g−1 and survives 700 cycles at full charge and discharge at 100 mA g−1. The mixture of PVA and PSS can also replace the short fibers used in conventional cells, and shortens the activation time of the electrode.

Industrial Validation of Lead-plated Aluminum Negative Grid for Lead-acid Batteries

Aluminum metal grids as lightweight substitutes for lead grid are promising to achieve the overall weight reduction of lead-acid battery for increasing energy density without sacrificing charge/discharge and cyclic performance. In this paper, a dense lead layer with an average thickness of 40 μm is industrially electro-deposited onto aluminum grid with a pre-plated nickel interlayer as the negative electrode for lead-acid battery. The charge/discharge tests with such an grid as negative plates show that the false welding between the lead-plated aluminum grid and lead busbar is an important challenge due to the thin plated lead layer, which would be a potential long-term risk for the charge step and sulfation. From dissection of the failed battery, it is found that the dense lead layer is partially corroded by sulfuric acid and aluminum substrate is partially dissolved into the electrolyte. Sulfation at such a negative electrode brings about a dense and sticky layer composed of the mixed PbSO4 and Al2(SO4)3·18H2O, which is the main failure mode of the lead-acid battery. This industial validation demonstrates that lead-deposited aluminum grids are not feasible at negative electrodes of light-weight lead-acid batteries from the viewpoint of commmercial reliability.

The application of rice husk-based porous carbon in positive electrodes of lead acid batteries

Abstract The positive electrodes of lead-acid batteries are typical thick electrodes where the mass transfer is limited. Therefore, the improvement of the mass transfer inside positive electrode can effectively enhance battery performance. In this article, the rice husk-based porous carbon (RHPC), is applied as an additive in positive electrodes of lead acid batteries. The addition of RHPC can increase the content of 3BS(3PbO·PbSO4·H2O) with decreased crystallinity and particle size in cured electrode. Next, it improves the formation efficiency. The electric conductivity and electron transfer rate of positive electrode are also enhanced. Under 100% DoD discharge condition, the discharge capacity of RHPC electrode increased by 16% and 23% at 0.05C and 1C, compared to that of blank electrode, respectively. Besides, the RHPC experimental cell displays higher discharge specific capacity compared to the blank experimental cell in a long-term deeply charge/discharge process. The developed pore structure of RHPC is beneficial to the curing process, while the developed pore structure and gas production of RHPC make major contributions to the formation and the deeply charge/discharge process. With RHPC additive in PAM, the improvement of the mass transfer can effectively reduces the risk of the failure mode for the mass transfer limit in such a typical thick electrode. Moreover, the particle growth rate of PAM will be inhibited during long-term deeply charge/discharge, thus the addition of RHPC will be very beneficial to increase the cyclic life of the positive electrode.

Corrigendum to “Higher capacity utilization and rate performance of lead acid battery electrodes using graphene additives” [Journal of Energy Storage Volume 23, June, Pages (2019) 579–589/EST_730

Corrigendum to “Higher capacity utilization and rate performance of lead acid battery electrodes using graphene additives” [Journal of Energy Storage Volume 23, June, Pages (2019) 579–589/EST_730

Effects of nano-SiO2 doped PbO2 as the positive electrode on the performance of lead-carbon hybrid capacitor

The PbO2 electrodes of lead-acid batteries are normally applied as the positive electrodes in lead-carbon hybrid capacitors. However, the effective utilization rate of active materials in the electrodes is only about 12.5%, leading to a low energy density of lead-carbon hybrid capacitors. In this paper, a nano-SiO2 doped PbO2 electrode was prepared by the co-electrodeposition method. The energy density of the lead-carbon hybrid capacitor using a nano-SiO2/PbO2 electrode can reach 61 Wh kg−1 at 3 A g−1. The results show that the inert nano-SiO2 can establish electrolyte diffusion channels in the positive electrode, and thus improve the effective utilization rate of active materials. This work provides a new idea for the design and development of the positive materials for high-performance lead-carbon hybrid capacitors.

One-pot and high-yield preparation of ultrathin β-PbO nanowires and nanosheets for high-capacity positive electrodes in lead-acid batteries

To obtain high-capacity electrode materials and meanwhile actualize the reuse of scrap lead paste, a novel alkylamine-mediated thermolysis route is proposed herein for one-pot preparation of high-quality PbO nanomaterials, relying on the thermal decomposition of lead carboxylate in hot solvent in the presence of hexadecylamine (HDA). This synthetic route allows us to produce uniform PbO nanowires with a diameter of 7.1 nm and a length beyond 10 μm, and nanosheets and nanorings with a lateral size of ca. 310 nm on a gram scale, by simply tuning the alkylamine content or reaction time. In particular, we have employed various means to unveil the key role of HDA, i.e., precursor activation and surface passivation function, in the controlled preparation of such PbO nanomaterials. Impressively, when serving as the positive active materials for lead acid batteries (LABs), the anodes based on PbO nanowires displayed an excellent discharge performance: its discharge capacity and active material utilization ratios could reach 164.3 mA h/g and 68.5% respectively even at a discharge current density as high as 50 mA/g, which are superior to most of the previously-reported values. Such an excellent discharge performance was speculated to result from the synergization effect of the large ECSA, small charge transfer resistance and highly active exposed facets associated with the PbO nanowires.

In-situ AFM observations of the effect of addition of glass fibers and lignosulfonates on performance of the negative active mass of a lead-acid storage battery

Abstract Surface visualization of a negative lead-acid battery electrode during charging and discharging using atomic force microscopy was performed. To accommodate the fine resolution of AFM and its inability to follow rough surfaces of the negative active mass of a real battery electrode, a smooth lead metal electrode was used. The focus was on the role of expanders on growth and dissolution of lead sulfate crystals. In one series of experiments we studied the effect of glass fibers embedded by pressure in the lead surface. The other series of experiments involved also glass fibers, but with the surface treated by lignosulfonates. It was observed that lignosulfonates suppress formation of the passivation layer on the electrode. On the other hand they cause higher polarization resistance of the electrode and reduce charge acceptance during charging.

Long‐Life Lead‐Acid Battery for High‐Rate Partial‐State‐of‐Charge Operation Enabled by a Rice‐Husk‐Based Activated Carbon Negative Electrode Additive

AbstractLead sulfation severely shortens the cycling life of lead‐acid battery under high‐rate partial‐state‐of‐charge (HRPSoC) operation. Adding carbon materials into negative active mass has been demonstrated as an effective strategy to suppress the sulfation. In this paper, rice‐husk‐based activated carbon (RHAC) with high specific surface area and high pore volume exhibits excellent performances on enhancing the discharge capacity, the dynamic charge acceptance and especially the cycling life of negative electrode of lead acid battery. Results show that the HRPSoC cycling life of negative electrode with RHAC exceeds 5000 cycles which is 4.65 and 1.42 times that of blank negative electrode and negative electrode with commercial activated carbon, respectively. These outstanding performances are ascribed to the unique architectural properties of RHAC comparing with commercial activated carbon, such as three‐dimensional porous structure for acid storage, high mesopore volume for efficient ions transport and large external specific surface area for energetic Pb deposition.

Effects of additives on the morphology and stability of PbO2 films electrodeposited on nickel substrate for light weight lead-acid battery application

Abstract This work investigated the effects of NaF and sodium dodecyl sulfate (SDS) on the morphology and stability of electrodeposited PbO2 film. The PbO2 electrodeposition was conducted on the Ni-substrate by galvanostatic anodic deposition in acidic Pb(NO3)2 solution to be employed as a positive electrode in the lightweight lead-acid battery. The stability and electrochemical properties of the film were investigated by cyclic voltammetry in 4.7 mol L−1 H2SO4. Phase constituents and microstructures of the deposited PbO2 before and after cycling was characterized using atomic force microscope (AFM), scanning electron microscope (SEM), and X-ray diffraction spectroscopy. Experimental results show that current density and the concentration of Pb(NO3)2 and NaF positively affected the current efficiency for PbO2 deposition. A mixed-phase (ɑ-PbO2 and β-PbO2), relatively less stable (persist up to 80 cycles) and larger-grained deposit with low charge-discharge density was produced in the absence of SDS. The addition of a small amount of SDS in the electrolyte increased the proportion of β-PbO2 having compact and small-grained crystals resulting in the improvement of the stability (persist up to 300 cycles) and charge-discharge density of the PbO2 film in the battery environment. The density functional theory (DFT) calculation confirmed that the higher binding energy of H2O to the defected PbO2 sites caused by high cycling was mainly responsible for enormous oxygen evolution which eventually resulted in the failure of the positive electrode and water loss of the battery during operation.

In Situ EC-AFM Observation of BaSO4 and Glass Fibers Effect on Lead Electrode for Lead-Acid Battery

The aim of the work was in situ observation of the negative lead electrode surface in various modes of operation using AFM. A total of two measurement procedures were chosen, which mainly differed during the charging / discharging cycles. Lead plate was used as a negative electrode. Glass fibers and barium sulphate were built into its surface.

Determination of current homogeneity on the electrodes of lead-acid batteries through electrochemical impedance spectroscopy

This work explores a qualitative appraisal of lead acid battery electrodes by Electrochemical Impedance Spectroscopy. Lead acid cells behavior has been examined by gathering data of impedance modifications in distinct electrolyte volumes, from a full one to a battery filled at about 20% of the total volume of acid. Since the current between electrodes is inhomogeneous around the collector by varying the quantity of the electrolyte, we have associated numerical values of the elements in the battery equivalent circuit, to the homogeneity of the current in the electrodes. Theoretical considerations dealing with modeling, equivalent circuits and corresponding equations are provided. As a function of the electrolyte quantity, we investigated the dependence of the values for components of the Randle circuit. A particular attention has been devoted to constant phase element (CPE) peculiarities, as this parameter was found essential for a good quality fit over an extended range of batteries. The stability depending on current homogeneity at a certain battery state of charge was analysed in order to assess the effect of electrolyte volumes, and thereby to provide new quality requirements for improvement of lead-acid battery performance.

Low Defect Planar Graphene Exfoliation By Sonication in Polypropylene Carbonate and 5 Sec Microwaving

This is an exceptional process on low cost, low defect and high-quality graphene which is produced by sonication in PPC and microwaving for just 5sec. Low energy arc-discharging process expands electrolytic graphite rods into hierarchical-like 3D-graphene retaining the basal plane carbon crystalline order and chemical purity [1-2]. Sonication in Polypropylene Carbonate causes non-covalent PPC-π bonding at graphene basal plane, aligning the graphene sheets in directions that allows efficient transmission of cavitation pressures and exfoliation; while microwave treatment for 5s separates any layered graphene, utilizing thermally induced lattice vibrations without changes on surface properties. Produced graphene (XRD 2θ = 26 ⁰C) has low defect (0.05 < ID/IG < 0.2), retainment of chemical purity (0~2.5% O2 content), with optimized effective graphene sizes (ranging from 350nm to 35 um), for diverse applications, dispersibility in diverse solvent, conformability to flat semi-transparent surfaces; storable in concentrated slurry (>50 mg mL−1). Planar graphene is suitable as 2D electronic materials applications [3], composites [4] and energy materials applications [5-10]. Keywords: Arc Discharge, Sonication, Microwave, Exfoliation, Planar, XRD, HR-SEM, HR-TEM. O.J. Dada, " In-Situ Electrochemical Functionalization of Reduced Graphene Oxide: Positive Lead Acid Case. " ECS Trans., vol. 66, no. 14, pp. 19–30, Aug. 2015O.J. Dada, “ In-Situ Electrochemical Functionalization of Reduced Graphene Oxide: Positive Lead Acid Case.,” ECS ., MA2015-01 (870), April 2015.O.J. Dada and D. Villaroman, " Superior Electronic and Dielectric Properties of Corrugated ElectrochemicallyReduced Graphene over Graphene Oxide Papers " Journal of the Electrochemical Society, vol 166 no.2, pp D1-D16, 2019.O.J. Dada, " Functional Cathodic and Anodic Transition of Graphene Oxide Paper in Lead Acid Battery System and Its Electrochemistry ". Materials Today: Proceedings”, vol. 3, no. 8, 2688-2697, 2016.O.J. Dada, " Interconnected Graphene Networks as Novel NanoComposite for Optimizing Lead Acid Cathode ". IEEE NANO 2015- Int. Conf. Nanotechnology, Rome, 2015.O.J. Dada, " Higher Capacity Utilization and Rate Performance of Lead Acid Battery Electrodes Using Graphene Additives ”. Journal of Energy Storage, vol. 23, pp579-589, Jun. 2019.O.J. Dada, " Effect of the Size and Conductivity of Tailored Graphene Electro-Catalysts, Lead Acid Battery Cathode as a Case ". IEEE NANO 2015- Int. Conf. Nanotechnology, Rome, Italy, 2015.O.J. Dada, " Wrinkled Graphene Oxide Synthesis by Electrolytic Arc Discharge of Graphite Rods and Slightly Modified Hummer’s Process ". Available at SSRN 3368351, 2019.O.J. Dada, " Highly Ordered Commercial Graphene Manufactured from 3 Simple Steps ". Available at SSRN 3335369, 2019.O.J. Dada, " Low Defect Planar Graphene Exfoliation by Sonication in Polypropylene Carbonate and 5 sec Microwaving ". Available at SSRN 3386581, 2019.O.J. Dada, " Utilization of Hard Carbon as a Substitute for Graphite As Efficient Lithium Battery Anode Material ". Available at SSRN 3368403, 2019.O.J. Dada, “ High Performance Lithium Battery Anodes from Non-Water based Graphene ”. Available at SSRN 3368433, 2019.O.J. Dada, “ Free Standing Porous Graphene and Reduced Graphene Papers Manufactured from Sedimentation of Arc Discharge of Graphite Rods ”. Available at SSRN 3481786, 2019.O.J. Dada, " Corrigendum to “Higher capacity utilization and rate performance of lead acid battery electrodes using graphene additives” . Journal of Energy Storage, vol. 23, pp579–589, Jun. 2019.

Higher capacity utilization and rate performance of lead acid battery electrodes using graphene additives

Abstract Graphene nano-sheets such as graphene oxide, chemically converted graphene and pristine graphene improve the capacity utilization of the positive active material of the lead acid battery. At 0.2C, graphene oxide in positive active material produces the best capacity (41% increase over the control), and improves the high-rate performance due to higher reactivity at the graphene/active material interface. The in-situ changes in the graphene structure and oxygen states support these, as well as higher adsorptive surface area, better graphene/lead dioxide interfacial reaction, and finer & highly utilized lead dioxide phases. The multi-scale physio-chemical mechanisms improving capacity and cycle life is thus: Electrolyte/ionic permeation improvements results from increase in pre-formation porosity, and higher interfacial reactivity at gel zone which enhances active material reversibility. Our ion transfer model reveals the optimized redox reaction in the electro-active zone of graphene enhanced active materials. This work shows the best enhancement in the capacity of lead-acid battery positive electrode till date.

Higher Capacity Utilization and Rate Performance of Lead Acid Battery Electrodes Using Graphene Additives

Graphene nano-sheets such as graphene oxide, chemically converted graphene and pristine graphene [1-8] improve the capacity utilization of the positive active material of the lead acid battery. At 0.2C, graphene oxide in positive active material produces the best capacity (41% increase over the control), and improves the high-rate performance due to the higher reactivity at the graphene/active material interface. The in-situ changes in the graphene structure and oxygen states [1-2] support these, as well as higher adsorptive surface area, better graphene/lead dioxide interfacial reaction, and finer & highly utilized lead dioxide phases. The multi-scale physio-chemical mechanisms improving capacity and cycle life is thus: Electrolyte/ionic permeation improvements results from increase in pre-formation porosity, and higher interfacial reactivity at gel zone which enhances active material reversibility. Our ion transfer model reveals the optimized redox reaction in the electro-active zone of graphene-enhanced active materials. This work shows the best enhancement in the capacity of lead-acid battery positive electrode till date.

Template electrodeposition and characterization of nanostructured Pb as a negative electrode for lead-acid battery

Despite Lead Acid Battery (LAB) is the oldest electrochemical energy storage system, diffusion in the emerging sectors of technological interest is inhibited by its drawbacks. The principal ones are low energy density and negative plate sulphating on high rate discharging. In this work, it is shown the possibility of overcoming such drawbacks by using nanostructured lead as a negative electrode. Lead nanowires (NWs) were fabricated by electrochemical deposition in template, which is an easy, cheap, and easily scalable process. Their morphology and crystal structure have been characterized by electron microscopy and X-ray diffraction, respectively. An electrochemical cell simulating LAB has been assembled with PbO2 as a counter electrode and an AGM separator, both from commercial battery. Cycling tests were conducted at 10C-rate, setting the cut-off voltage on discharging at 1.2 V. For comparison, also cycling tests at 1C-rate have been carried out, in otherwise identical conditions. At both C-rates, performances in terms of cycling efficiency and lifetime were found a lot better than those of current LABs. The high porosity formed under cycling at 10C-rate provides a reliable explanation of the results.

Effect of magnesium sulfate on the electrochemical behavior of lead electrodes for lead acid batteries

AbstractThe lead acid battery technology has undergone several modifications in the recent past, in particular, the electrode grid composition, oxide paste recipe with incorporation of foreign additives into the electrodes and similarly additives added in the electrolytes to improve electrical performance of the lead acid battery. In this paper, the electrochemical behavior of the lead electrodes with different weight/volume percentages (wt./v%) of MgSO4(0.0., 0.5., 1.0., 2.0., and 5.0) added into the electrolyte have been investigated with cyclic voltammetry (CV), linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS). The CV profile showed better redox behavior of the lead electrodes which was attributed to the increased active surface area of the electrode. Further studies of the gas evolution found a mixed trend and a considerable drop in the impedance as observed by LSV and EIS analysis as compared to the blank electrolyte solution. The influence of a modified electrolyte on the electrochemical activity of the lead electrodes is correlated and discussed.

Effect of polyvinyl alcohol/nano-carbon colloid on the electrochemical performance of negative plates of lead acid battery

Polyvinyl alcohol/nano-carbon colloid (PCC) was prepared through a simple physical mixture process. Both fully charge-discharge and insufficient charge tests were carried out to demonstrate the positive effects of PCC on the electrical storage capability of the negative electrode of lead acid battery. Cyclic voltammetry, steady polarization and electrochemical impedance spectroscopy were used to characterize the influences of PCC on the electrochemical behaviors of negative electrode in the lead acid battery. Experiment results demonstrate that PCC has positive effect on inhibiting PbSO4 growth and increasing the HER overpotential, thus the lead acid battery with PCC shows the enhanced charge acceptance and stable discharge capacities under insufficient charge test. This paper opens a new way for enhancing the performance of lead acid battery without changing the traditional structure and design of lead acid battery.

Operation of thin-plate positive lead-acid battery electrodes employing titanium current collectors

Abstract One of the root causes for the limited lifetime or the restricted high power performance of the lead-acid batteries is the corrosion of the positive current collectors. These barriers can be overcome using titanium as an attractive alternative of the lead and the lead alloy grids, due to a combination of excellent mechanical strength, corrosion resistance and great abundance. This article presents a new technological route to simultaneous decrease of the electrode thickness and weight, and a replacement of the classic grids with titanium substrates like tin dioxide coated foil or expanded mesh. The new electrodes are studied electrochemically and physically revealing that the reduction of the electrode thickness promotes the formation of positive electrodes composed of pure beta lead dioxide with high crystallinity. The latter induces an initial partial capacity loss, which can be avoided by lowering the depth of discharge, positive plate oversizing or changes in the paste mixing and curing processes.

Performance of recovered and reagent grade electrolyte in a soluble lead redox cell

Abstract This paper presents the performance of ‘recovered’ electrolyte for the soluble lead flow battery, made by recycling conventional lead-acid battery electrodes, and compares it to reagent grade electrolyte for the same system. The two electrolyte compositions were cycled in static and flow cells and their charge, energy, and voltage efficiencies compared. The average charge, energy, and voltage efficiencies of static cells using 1.0 mol·dm¯³ Pb²+ recovered electrolyte were 89%, 86%, and 96%, while cells using reagent grade electrolyte averaged 63%, 49%, and 78%, respectively. The average charge efficiency of flow cells with recovered electrolyte was consistently above 80% and within 10% of the average for cells with reagent grade electrolyte. The average energy and voltage efficiencies were 62% and 73%, respectively, diverting from averages for the reagent grade electrolyte cells by less than 15%. The highest average cycle life was for cells with recovered electrolyte at 187 cycles, while that of cells with reagent grade electrolyte peaked at 102. Trace elements in both electrolyte compositions were analysed and their presence in the recovered electrolyte appears to enhance performance of the soluble lead cells. The recovered electrolyte is an electrochemically viable substitute for the reagent grade electrolyte.

Examination of impact of lignosulfonates added to the negative active mass of a lead–acid battery electrode

Abstract We employed pasted negative electrodes of dimensions 55 × 20 × 7 mm placed between two pasted positive electrodes of the same dimensions separated with AGM separators of the type BG 260 EB 170 (1.7 mm in thickness). The negative paste was doped with 0.78 wt.% of milled CR2996 carbon (Maziva Týn Company, Czech Republic) and with different amounts of three types of organic lignosulfonates as expanders. The used expanders were commercial products Vanisperse A, Vanillex HW and Vanillex N (Borregaard LignoTech). After formation, the electrode packs were placed in custom cells with the usual H2SO4 electrolyte, designed to ensure application of defined pressure to the electrode system. Several conditioning cycles were performed, the excess electrolyte was then aspirated off and the cells were hermetically sealed. The initial capacity of the negative electrodes was around 3 Ah. The cells were then discharged to 50% of their capacity and subjected to partial-state of charge accelerated cycling by using symmetrical 25 s current pulses of 2.5 A followed by 3 s standing. The cells were cycled until their voltage dropped below 1.6 V. In each run, the cell voltage, the electrode potentials against a Cd electrode, and the applied pressure were measured after every 100 cycles. The performance of these electrodes was elevated by applying moderate compression of 4 N.cm−2. Higher pressures are not recommended. Cells with higher amount of the added organic expander well tolerate deep cycling, and were able to regenerate better during the conditioning cycles between PSoC runs and its capacities have increased. The low-lignosulfonate-containing cells showed during the PSoC charging good charge acceptance at the beginning of the experiment, but with progression of time (PSoC runs), there was the most significant increase in polarization resistances and gradual degradation of NAM. Medium lignosulfonate cells exhibited the best properties throughout the PSoC runs. During the PSoC charging there is a good charge acceptance, low maximum voltage and stable polarization resistance.