Capacitive carbon and electrochemical lead electrode systems at the negative plates of lead–acid batteries and elementary processes on cycling

Pavlov, D.; Nikolov, P.

doi:10.1016/j.jpowsour.2013.05.065

Cited by 119 publications

(80 citation statements)

References 20 publications

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“…As a result, the Pb 2+ formed during discharge of the battery in these small pores hydrolyzes, forming Pb(OH) 2 , which then transforms into α-PbO precipitate on the pore walls. 7 Under HRPSoC duty cycling, reactions between active material and electrolyte take place within pores. 35 Decreased pore volume and surface area is evidence of incomplete charge acceptance, reducing cell capacity.…”

Section: Resultsmentioning

confidence: 99%

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Understanding Function and Performance of Carbon Additives in Lead-Acid Batteries

Enos

Ferreira

Barkholtz

et al. 2017

J. Electrochem. Soc.

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While the low cost and strong safety record of lead-acid batteries make them an appealing option compared to lithium-ion technologies for stationary storage, they can be rapidly degraded by the extended periods of high rate, partial state-of-charge operation required in such applications. Degradation occurs primarily through a process called hard sulfation, where large PbSO 4 crystals are formed on the negative battery plates, hindering charge acceptance and reducing battery capacity. Various researchers have found that the addition of some forms of excess carbon to the negative active mass in lead-acid batteries can mitigate hard sulfation, but the mechanism through which this is accomplished is unclear. In this work, the effect of carbon composition and morphology was explored by characterizing four discrete types of carbon additives, then evaluating their effect when added to the negative electrodes within a traditional valve-regulated lead-acid battery design. The cycle life for the carbon modified cells was significantly larger than an unmodified control, with cells containing a mixture of graphitic carbon and carbon black yielding the greatest improvement. The carbons also impacted other electrochemical aspects of the battery (e.g., float current, capacity, etc.) as well as physical characteristics of the negative active mass, such as the specific surface area. Valve-regulated lead-acid (VRLA) batteries are a mature rechargeable energy storage technology. Low initial cost, well-established manufacturing base, proven safety record, and exceptional recycling efficiency make VRLA batteries a popular choice for emerging energy storage needs.1,2 VRLA batteries are employed in stationary storage applications such as: utility ancillary regulation services, wind farm energy smoothing, and solar photovoltaic energy smoothing.3 Stationary applications may require short duration, high-rate, and partial state-of-charge cycling (HRPSoC). 4 Under HRPSoC duty, conventional VRLA cells fail prematurely from irreversible PbSO 4 formation within the negative plates.5 Regular cycling to 100% state-of-charge (SoC) mitigates PbSO 4 crystal formation and growth. However, regularly cycling to 100% SoC is not viable for many stationary storage applications. Large PbSO 4 crystals are not easily reduced back to metallic lead during HRPSoC charging, reducing cycle life. Reduced cycle life of VRLA batteries increases the operating cost, thereby limiting their practicality for stationary applications.VRLA battery HRPSoC cycle life can be increased with carbon modification of the negative active material (NAM).6-10 Adding carbon to the negative plate inhibits PbSO 4 crystal formation and/or limits PbSO 4 crystal growth.11-13 The underlying mechanism responsible for reducing PbSO 4 formation/accumulation is dependent on the size of the PbSO 4 crystallites. Controlling PbSO 4 microstructure has been found to be difficult while maintaining low cost. Other methods exist to limit PbSO 4 crystal size; including utilization of a carbon honeyco...

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Section: Resultsmentioning

confidence: 99%

“…6,7,[9][10][11]13,[16][17][18][19][20][21][22][23][24][25] Researchers have hypothesized that carbon contributes in one or more different aspects of battery performance. Chemical reactivity and surface area are important if the material is electrochemically active.…”

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confidence: 99%

Understanding Function and Performance of Carbon Additives in Lead-Acid Batteries

Enos

Ferreira

Barkholtz

et al. 2017

J. Electrochem. Soc.

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“…Углеродные добавки в различных модификациях (аморфные или кристаллические [1][2][3][4], углеродные на-нотрубки [5,6] и др.) в составе отрицательных электрод-ных материалов (ОЭМ) за счет структурных особен-ностей и наличия поверхностно-функциональных групп повышают эксплуатационные характеристики свинцово-кислотных аккумуляторов (СКА).…”

Section: (поступило в редакцию 27 декабря 2016 г)unclassified

Влияние Поверхностно-Активных Связей Углеродных Структур На Разрядно-Зарядные Процессы Источника Тока

Кузьменко¹,

Гречушников²,

Харсеев³

2017

Журнал Технической Физики

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Проведено изучение влияния на разрядно-зарядные процессы источника тока поверхностно-активных связей углеродных структур, используемых в виде добавок в состав отрицательного электродного материала. Предложен механизм, основанный на выводах, вытекающих из молекулярно-кинетической теории Косселя-Странского, объясняющий рост кристаллов 3PbOPbSO 4 H 2 O при введении углеродных материалов. Установ-лено, что присутствие углеродных добавок в составе отрицательного электродного материала стартерных свинцово-кислотных батарей повышает емкость 20-h режима разряда -до 5%, длительность разряда током холодной прокрутки до конечного напряжения 6 V при отрицательных температурах −18 • C на 3−4.5% и при −30 • C на 9−13%. DOI: 10.21883/JTF.2017.09.44925.2151 Углеродные добавки в различных модификациях (аморфные или кристаллические [1-4], углеродные на-нотрубки [5,6] и др.) в составе отрицательных электрод-ных материалов (ОЭМ) за счет структурных особен-ностей и наличия поверхностно-функциональных групп повышают эксплуатационные характеристики свинцово-кислотных аккумуляторов (СКА). В частности, на рост и развитость поверхности базовых для СКА кристаллов сульфатов свинца существенное влияние оказывают ад-сорбционные процессы с участием солей и ингибитора, значение рН, рельеф поверхности.Натоящая работа посвящена анализу структурных и фазовых изменений в ОЭМ в зависимости от количе-ства аморфной углеродной добавки (УД) в виде широ-ко используемого углерода марки П803, получаемого термоокислительным разложением жидких углеводоро-дов, характеризуемого высокой развитостью поверхно-сти (удельная условная поверхность 14−18 m 2 /g), и установлению механизма влияния УД на электрические характеристики СКА.Испытываемые ОЭМ готовились с использованием высокоокисленного свинцового порошка (77−79% PbO) и водного раствора H 2 SO 4 (плотностью 1.4 g/cm 3 ), а также УД в виде технического углерода, BaSO 4 и органического расширителя на основе лигносульфоната.На всех стадиях приготовления ОЭМ и с разным содержанием УД проводился рентгенофазовый анализ (РФА) (GBC EMMA, 2θ, 0.02 • C, CuK α λ = 1.54 nm), изучались морфология поверхности ОЭМ на сканирую-щем растровом электронном микроскопе (СЭМ) (JEOL JSM-6610LV 3 nm, 30 kV) и колебательные возбуждения в диапазоне 500−1800 cm −1 на ИК Фурье-спектрометре (Nicolet iS50, 0.125 cm −1 с НПВО).Основными фазовыми составляющими ОЭМ были трехосновный сульфат свинца (3ВS)-3PbOPbSO 4 H 2 O и оксид свинца -α-PbO, что согласуется с данны-ми [1], содержание которых не изменялось для всех исследованных составов с содержанием УД (0.2, 0.4, 0.6, 0.8 и 1.0%). Морфология поверхности ОЭМ про-иллюстрирована СЭМ-изображениями (рис. 1), на ос-новании которых были выявлены изменения размеров кристаллических структур (рис. 2). Характерные раз-меры призматической слоистой структуры 3ВS как по длине L, так и по поперечному размеру D на микронном уровне изменялись явно нелинейно в зависимости от содержания УД L(C) и D(C). Так, при содержании УД от 0.2 до 0.6% L уменьшалась от 3 до 1.5 µm, тогда как поперечные размеры этих же кр...

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“…To achieve these new duties, some breakthrough improvements have been adapted to lead acid batteries. Newly developed carbon additives have been applied to negative electrodes to increase the cyclic ability and dynamic charge acceptance [5,6]. Electrode grids have been designed with computer aided optimization techniques to minimize voltage loss at high current rates without increasing the grid weight [7].…”

Section: Introductionmentioning

confidence: 99%

On the Compatibility of Electric Equivalent Circuit Models for Enhanced Flooded Lead Acid Batteries Based on Electrochemical Impedance Spectroscopy

Aksakal

Şişman

2018

Energies

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Electric equivalent circuit (EEC) models have been widely used to interpret the inner dynamics of all type of batteries. Added to this, they also have been used to estimate state of charge (SOC) and state of health (SOH) values in combination with different methods. Four EEC models are considered for enhanced flooded lead acid batteries (EFB) which are widely used in micro hybrid vehicles. In this study, impedance and phase prediction capabilities of models throughout a frequency spectrum from 1 mHz to 10 kHz are compared with those of experimental results to investigate their consistency with the data. The battery is charged, discharged, and aged according to appropriate standards which imitates a lifetime of a micro hybrid vehicle battery under high current partial cycling. Impedance tests are repeated between different charge and health states until the end of the battery's lifetime. It is seen that adding transmission line elements to mimic the high porous electrode electrolyte interface to a double parallel constant phase element resistance model (ZARC) can increase the model data representing capability by 100%. The mean average percentage error (MAPE) of the conventional model with respect to data is 3.2% while the same value of the transmission line added model found as 1.6%. The results can be helpful to represent an EFB in complex simulation environments, which are used in automobile industry.

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Capacitive carbon and electrochemical lead electrode systems at the negative plates of lead–acid batteries and elementary processes on cycling

Cited by 119 publications

References 20 publications

Understanding Function and Performance of Carbon Additives in Lead-Acid Batteries

Understanding Function and Performance of Carbon Additives in Lead-Acid Batteries

Влияние Поверхностно-Активных Связей Углеродных Структур На Разрядно-Зарядные Процессы Источника Тока

On the Compatibility of Electric Equivalent Circuit Models for Enhanced Flooded Lead Acid Batteries Based on Electrochemical Impedance Spectroscopy

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