Cd|KOH|NiOOH

Zn|NH4CI|MnO2

Li|LiClO4|MnO2

Pb|H2SO4|PbO2

H2|KOH|O2

Подходы к исследованию литиевого транспорта в интеркаляционных электродах на основе тонкопленочных структур и многофазных композитов

УДК 541.136

DOI:  https://doi.org/10.18500/1608-4039-2016-16-3-100-121

Представлены подходы к теоретическому описанию электрохимически стимулированных процессов переноса в твёрдых интеркаляционных соединениях лития; приведены результаты экспериментальной проверки разработанных подходов, найдены значения параметров ионного транспорта в тонкоплёночных и композитных электродах на основе ряда известных и зарекомендовавших себя литий -аккумулирующих соединений: LixC6, LixSn, LixWO3, LixTiO2, LiFePO4, Li3V2(PO4)3. Показан стадийный механизм литиевого транспорта в интеркаляционном электроде, который включает стадии переноса в объёме литий -аккумулирующего материала и на поверхности электрод | электролит. Это выражается в особенностях электроаналитических откликов интеркаляционного электрода в условиях различных электрохимических методов. Предложен оригинальный способ построения термодинамической зависимости потенциал–концентрация интеркаляционного электрода с приложением метода кулонометрического титрования: он основан на прогнозировании изменения электродного потенциала во времени путём экстраполяции начального участка транзиента потенциала на бесконечное время в координатах Et−0.5. Обсуждаются причины расхождения (гистерезиса) зависимостей E(c), измеренных таким способом при ступенчатом изменении состава (потенциала электрода) в анодном и катодном направлениях. Обоснована необходимость введения корректирующего параметра z в уравнение Рэндлса–Шевчика для учёта отличия активности ионов лития в твёрдом теле от их концентрации с целью корректного определения коэффициента диффузии из данных циклической вольтамперометрии с линейной развёрткой потенциала. Предложен способ определения параметра z из наклона экспериментальной зависимости E(c) в координатах Нернста E – ln c. Рассмотрены различные решения диффузионной задачи для анализа данных импульсных хроноамперо – и хронопотенциометрических методов в варианте прерывистого титрования с учётом различной геометрической и фазовой конфигурации диффузионного пространства в интеркаляционном электроде. Проанализированы зависимости коэффициента диффузии лития D от потенциала интеркаляционного электрода. Обсуждается применимость различных моделей – электрических эквивалентных схем (ЭС) для анализа данных метода спектроскопии электродного импеданса в приложении к интеркаляционному электроду. Предложен способ построения ЭС на основе анализа формы импедансного спектра и в предположении механизма литиевого транспорта в интеркаляционном электроде. Проанализированы зависимости найденных параметров ЭС от электродного потенциала. Проведено сравнение найденных кинетических параметров литиевого транспорта по данным различных методов. Показано различие в значениях кинетических параметров в зависимости от величины концентрационных возмущений в электроде.

Литература

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