Принцип работы и устройство литий-ионных конденсаторов

Литий-ионные суперконденсаторы (ЛИСК) являются гибридом двуслойного конденсатора (ДСК) и литий-ионного аккумулятора (ЛИА). Значения их удельных энергетических и мощностных характеристик находятся в пределах между значениями, свойственными литий-ионным аккумуляторам и суперконденсаторам. Такие системы демонстрируют повышенные мощностные, энергетические и ресурсные характеристики. Данный тип устройств в англоязычной литературе относят к ассиметричным двойнослойным электрохимическим конденсаторам (Asymmetric electrochemical double layer capacitors, AEDLC).

При изготовлении литий-ионного суперконденсатора обычно используют следующие пары активных материалов электродов (отрицательный электрод/положительный электрод):

  • Li4Ti5O12/углеродный материал с развитой поверхностью;
  • графит (неграфитизированный углерод)/углеродный материал с развитой поверхностью;
  • смесь Li4Ti5O12 и углерода с развитой поверхностью/смесь катодного материала литий-ионного аккумулятора (LiFePO4, LiMn2O4, LiNixCoyMn(1-x-y)O2 и другие литиевые соли или оксиды металлов с переменной валентностью) и углерода с развитой поверхностью.

В двух первых типах ЛИСК от ДСК взят положительный электрод (углеродный материал с развитой поверхностью), а от ЛИА — отрицательный (графит или нанотитанат Li4Ti5O12). Тип Li4Ti5O12/углеродный материал с развитой поверхностью исторически возник первым, однако на данный момент не имеет большого распространения. Третий тип появился совсем недавно и отличается тем, что в нем и анод, и катод включают композиционные материалы, как ЛИА, так и ДСК. При его функционировании как на аноде, так и на катоде параллельно протекают процессы, характерные для работы ЛИА и ДСК. На данный момент наиболее популярными считаются устройства, содержащие графит в составе отрицательного электрода и углеродный материал с развитой поверхностью в составе положительного электрода, то есть относящиеся ко второму типу ЛИСК.

Устройство литий-ионного конденсатора

ДСК имеет два одинаковых электрода, помещеннных в электролит и выполненных из углерода с развитой поверхностью, нанесенного на металлическую фольгу. Обычно электролит представляет собой соли, растворенные в органических растворителях. В процессе растворения образуются катионы (например, ТЕМА+ — триэтилметил аммоний) и анионы (к примеру, BF4–). При заряде ДСК катионы и анионы, входящие в состав электролита, локализуются на поверхности отрицательного и положительного электродов соответственно (рис. А). При разряде катионы и анионы переходят с поверхности электродов обратно в раствор электролита.

В ЛИА протекают другие электрохимические процессы. При заряде положительно заряженные ионы лития интеркалируют (встраиваются) в структуру графита и удаляются из катодного материала — деинтеркалируют (рис. В). При разряде ионы лития выходят из структуры графита и встраиваются обратно в структуру катодного материала. Электролит в данном случае выступает в качестве среды, обеспечивающей перенос ионов лития, то есть его функция отлична от электролита в ДСК, где он является источником катионов и анионов.

При заряде ЛИСК происходит локализация анионов (PF6–) на поверхности положительного электрода и внедрение катионов (Li+) лития в структуру активного материала отрицательного электрода (графит), (рис. Б). В данном случае электролит становится средой, обеспечивающей перенос ионов лития, и источником анионов для положительного электрода, совмещая две описанные выше функции. При разряде ЛИСК происходят обратные процессы. Емкость ДСК определяется емкостью каждого из электродов и вычисляется по формуле: 1/Сячейки = 1/С+1/С+.

В случае симметричного конденсатора С = С+ = С и Сячейки = С/2. Заряд накапливается на поверхности обоих электродов. Если на положительном электроде работает поверхность, то в отрицательном электроде можно добиться того, чтобы работал объем, — другими словами, происходило внедрение ионов лития в активный материал. Замена активного материала отрицательного электрода (углерода с развитой удельной поверхностью) на материалы, способные к обратимому внедрению лития, например, предварительно литированный графит, обладающий значительно большей емкостью, чем материал положительного электрода (С >> С+), приводит к повышению общей емкости ячейки в два раза. Тогда емкость ячейки — Сячейки = С+ — целиком определяется емкостью положительного электрода. У ДСК, имеющего симметричную конструкцию, заряд катода и анода при разряде изменяется одинаково. Максимальное напряжение устройства примерно равно 2,5 Вольт (рис. А). Напряжение полностью заряженного ЛИСК выше, чем у ДСК, и составляет 3,8–4 Вольта (рис. Б).

Устройство литий-ионного конденсатора

Увеличение напряжения устройства достигается ввиду использования в качестве анода литированного графита, потенциал которого близок к потенциалу металлического лития. При разряде потенциал катода снижается, а потенциал анода несколько увеличивается из-за деинтеркаляции лития. Для обеспечения длительного ресурса напряжение на ячейке не должно уменьшаться ниже или повышаться больше значений, указанных производителем. Таким образом, ЛИСК устойчиво работает в определенном диапазоне напряжений.

Компания VINATech предлагает литий-ионные суперконденсаторы Hy-Cap LIC (Lithium Ion Capacitor) под рабочее напряжение от 2.2 до 3.8 В с емкостями от 20 до 270 Фарад.

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