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Þ.Â. Ïîëèùóê, Í.Ä.

Êîøåëü

ÓÄÊ 541.136, 541.132.6, 621.352

Þ.Â. Ïîëèùóê, Í.Ä. Êîøåëü

ÏÐÎÒÎ×ÍÛÅ ÐÅÄÎÊÑ-ÀÊÊÓÌÓËßÒÎÐÛ Â ÑÈÑÒÅÌÀÕ ÐÅÇÅÐÂÈÐÎÂÀÍÈß


ÝÍÅÐÃÈÈ
ÃÂÓÇ «Óêðàèíñêèé ãîñóäàðñòâåííûé õèìèêî-òåõíîëîãè÷åñêèé óíèâåðñèòåò», ã. Äíåïðîïåòðîâñê

Ïðèâåäåí îáçîð íàó÷íûõ è òåõíè÷åñêèõ äîñòèæåíèé â îáëàñòè ñîçäàíèÿ ïðîòî÷-


íûõ ðåäîêñ-àêêóìóëÿòîðîâ (ÐÎÀ). Â ÐÎÀ ðåàãåíòû è ïðîäóêòû äâóõ ýëåêòðîäíûõ
ðåäîêñ-ñèñòåì â ðàñòâîðåííîì âèäå öèðêóëèðóþò ÷åðåç ýëåêòðîõèìè÷åñêèé ãåíå-
ðàòîð. Â óñëîâèÿõ ðàçäåëüíîãî õðàíåíèÿ ðåäîêñ-ñèñòåì êàòîäà è àíîäà áëîêèðóþò-
ñÿ ïðîöåññû ñàìîðàçðÿäà, íå äåãðàäèðóþò ðåàãåíòû â ðàñòâîðàõ. Ýíåðãèÿ è ìîù-
íîñòü ÐÎÀ íåçàâèñèìû äðóã îò äðóãà, òàê êàê çàïàñ ýíåðãèè çàâèñèò îò îáúåìà
ðàñòâîðîâ, à ìîùíîñòü çàâèñèò îò ïàðàìåòðîâ ãåíåðàòîðà. Öèðêóëÿöèÿ ðàñòâîðîâ
÷åðåç ãåíåðàòîð ñíèìàåò ïðîáëåìû îòâîäà òåïëà. ÐÎÀ ñ÷èòàëè ïåðñïåêòèâíûìè
äëÿ àêêóìóëèðóþùåé ïîäñèñòåìû íà òåïëîâûõ, âåòðîâûõ è ñîëíå÷íûõ ýëåêòðî-
ñòàíöèÿõ, ãäå ðåæèì íàãðóçêè èñïûòûâàåò çíà÷èòåëüíûå êîëåáàíèÿ âî âðåìåíè.
Ñ÷èòàëîñü âîçìîæíûì èõ ïðèìåíåíèå è â êà÷åñòâå ñèëîâûõ ýíåðãîóñòàíîâîê íà
òðàíñïîðòå. Ðàññìîòðåí ïðèíöèï ðàáîòû è ñõåìà óñòðîéñòâà ýëåêòðîõèìè÷åñêîãî
ãåíåðàòîðà.  íàñòîÿùåå âðåìÿ èç âñåõ âàðèàíòîâ íàèáîëåå óäà÷íîé îêàçàëàñü âà-
íàäèåâàÿ ðåäîêñ-ñèñòåìà. Äëÿ íåå îòìå÷åíî ïðàêòè÷åñêîå èñïîëüçîâàíèå â êà÷å-
ñòâå àêêóìóëèðóþùåé ñèñòåìû àâòîíîìíîé âåòðîâîé ýëåêòðîñòàíöèè â ðàéîíàõ,
ãäå îòñóòñòâóåò åäèíàÿ ñèñòåìà ðàñïðåäåëåíèÿ ýëåêòðè÷åñêîé ýíåðãèè. Îòìå÷åíû
ïðè÷èíû, êîòîðûå â çàìåòíîé ìåðå óõóäøàþò õàðàêòåðèñòèêè ðåäîêñ-àêêóìóëÿòî-
ðîâ. Ê íèì îòíîñÿòñÿ, â ïåðâóþ î÷åðåäü, íåèäåàëüíàÿ ñåëåêòèâíîñòü èîíîîáìåí-
íûõ ìåìáðàí è çàìåòíûé òðàíñìåìáðàííûé ýëåêòðîîñìîòè÷åñêèé ïåðåíîñ âîäû
ìåæäó ðàñòâîðàìè äâóõ ðåäîêñ-ñèñòåì.

© Þ.Â. Ïîëèùóê, Í.Ä. Êîøåëü, 2015

66 ISSN 0321-4095. Âîïðîñû õèìèè è õèìè÷åñêîé òåõíîëîãèè, 2015, Ò. 4 (102)


Ïðîòî÷íûå ðåäîêñ-àêêóìóëÿòîðû â ñèñòåìàõ ðåçåðâèðîâàíèÿ ýíåðãèè

Êëþ÷åâûå ñëîâà: ïðîòî÷íûé ðåäîêñ-àêêóìóëÿòîð, ðåçåðâèðîâàíèå ýíåðãèè, çàðÿ-


æåíèå, ðàçðÿæåíèå, óäåëüíàÿ ýíåðãèÿ, óäåëüíàÿ ìîùíîñòü, ìåìáðàíà.

Ââåäåíèå íåííûé öèêë. Òâåðäîôàçíûå àêòèâíûå âåùåñòâà,


Ñðåäè ìíîãèõ òèïîâ òåõíè÷åñêè îáðàòèìûõ âõîäÿùèå â ñîñòàâ ýëåêòðîäîâ ïðîìûøëåííûõ
ýëåêòðîõèìè÷åñêèõ èñòî÷íèêîâ òîêà îñîáîå ìå- áàòàðåé, â ïðîöåññå öèêëèðîâàíèÿ ïîäâåðæåíû
ñòî çàíèìàåò ãðóïïà ñèñòåì, èçâåñòíûõ ïîä îá- ìåõàíè÷åñêèì äåôîðìàöèÿì, ÷òî ñîêðàùàåò èõ
ùèì íàçâàíèåì ðåäîêñ-àêêóìóëÿòîðû (ÐÎÀ) èëè ñðîê ñëóæáû. Àêòèâíûå âåùåñòâà â ÐÎÀ íàõî-
ïðîòî÷íûå ðåäîêñ-àêêóìóëÿòîðû (Flow redox äÿòñÿ â ýëåêòðîëèòå â âèäå ðàñòâîðåííûõ ôîðì
battery) [1 – 6]. è íå äåãðàäèðóþò.
Ê ýòîìó êëàññó õèìè÷åñêèõ èñòî÷íèêî⠖ Ðàáîòà ïðîìûøëåííûõ àêêóìóëÿòîðíûõ
òîêà (ÕÈÒ) îòíîñÿòñÿ ñèñòåìû, â êîòîðûõ îêèñ- áàòàðåé â ðåæèìå áîëüøîé ìîùíîñòè ñîïðîâîæ-
ëåííàÿ è âîññòàíîâëåííàÿ ôîðìû äâóõ ðåàãåí- äàåòñÿ áîëüøèì âûäåëåíèåì òåïëà è òåðìè÷åñ-
òîâ, ó÷àñòâóþùèõ â ýëåêòðîõèìè÷åñêèõ ðåàêöèÿõ êèìè äåôîðìàöèÿìè ýëåêòðîäîâ, ÷òî ñîêðàùà-
íà ýëåêòðîäàõ (îêèñëèòåëü è âîññòàíîâèòåëü, åò èõ ñðîê ñëóæáû.  íåïðîòî÷íûõ èñòî÷íèêàõ
êàæäûé â äâóõ ôîðìàõ), íàõîäÿòñÿ â ðàñòâîðåí- ïðîáëåìà îòâîäà òåïëà ïðèíöèïèàëüíî îãðàíè-
íîì âèäå è õðàíÿòñÿ â îòäåëüíûõ åìêîñòÿõ. Ýòà ÷èâàåò ìàêñèìàëüíûé ãàáàðèòíûé ðàçìåð ÕÈÒ,
îñîáåííîñòü ïîçâîëÿåò êîíñòðóêòèâíî îòäåëèòü ïîñêîëüêó ïîòîê ãåíåðàöèÿ òåïëà ïðîïîðöèî-
ýëåêòðîõèìè÷åñêèé ýëåìåíò-ðåàêòîð îò çîíû íàëåí êóáó ãàáàðèòíîãî ðàçìåðà áàòàðåè (îáúå-
õðàíåíèÿ ðåàãåíòîâ (êàê è â òîïëèâíûõ ýëåìåí- ìó), à ïîòîê òåïëîîòâîäà – êâàäðàòó ãàáàðèòíî-
òàõ). Òàê êàê îáúåì ðåàãåíòîâ ìîæåò áûòü íåî- ãî ðàçìåðà (ãàáàðèòíîé ïëîùàäè áàòàðåè). Ïî-
ãðàíè÷åííûì, äîëÿ ìàññû ñàìîãî ðåàêòîðà ïî ýòîìó èñòî÷íèê òîêà íà áîëüøóþ ìîùíîñòü áåç
îòíîøåíèþ ê ìàññå ðåàãåíòîâ ñòàíîâèòñÿ î÷åíü ñïåöèàëüíîãî îõëàæäåíèÿ ìîæåò áûòü ñêîíñò-
ìàëîé. Ýòî è îáåñïå÷èâàåò ïðèíöèïèàëüíóþ ðóèðîâàí òîëüêî â âèäå áîëüøîãî ÷èñëà íåáîëü-
âîçìîæíîñòü ñîçäàíèÿ èñòî÷íèêîâ ñ âûñîêîé øèõ ýëåìåíòîâ.
óäåëüíîé ýíåðãèåé, êàê è ó òîïëèâíûõ ýëåìåí-  ÐÎÀ öèðêóëèðóþùèé ÷åðåç âíåøíèé òåï-
òîâ. ëîîáìåííèê ýëåêòðîëèò âûñòóïàåò â êà÷åñòâå
 îòëè÷èå îò òîïëèâíûõ ýëåìåíòîâ, ãäå îõëàæäàþùåé æèäêîñòè, ïîýòîìó ïðîáëåìà ñòà-
òîïëèâî è îêèñëèòåëü ðàñõîäóþòñÿ áåçâîçâðàò- áèëèçàöèè ðàáî÷åé òåìïåðàòóðû ëåãêî ðåøàåò-
íî, â ÐÎÀ – àêêóìóëÿòîðå çàïàñ õèìè÷åñêèõ ñÿ äëÿ áàòàðåé ëþáîé ìîùíîñòè.
âåùåñòâ ïîñòîÿííûé.  ðàçðÿäíîì ïðîöåññå ðå- – Êîíñòðóêòèâíî áàòàðåè ÐÎÀ ïðåäñòàâ-
àãåíòû ðàñõîäóþòñÿ (ïðåîáðàçóþòñÿ â ïðîäóê- ëÿþò ñîáîé ðàçáîðíûé áëîê ñ ëåãêî çàìåíÿåìû-
òû), à â çàðÿäíîì – âîññòàíàâëèâàþòñÿ. ìè ïðè íåîáõîäèìîñòè ýëåêòðîäàìè.  òàêîé
Ïðèíöèï ðàçäåëüíîãî õðàíåíèÿ îáîèõ ðåà- êîíñòðóêöèè ýëåêòðîäû óäîáíî âûïîëíÿòü áè-
ãåíòîâ ïîçâîëÿåò â çíà÷èòåëüíîé ìåðå (èíîãäà ïîëÿðíûìè, ò.å. îäíà ñòîðîíà êàæäîãî ýëåêòðî-
ïîëíîñòüþ) áëîêèðîâàòü ïðîöåññû ñàìîðàçðÿ- äà îäíîé ÿ÷åéêè ÿâëÿåòñÿ åå ïîëîæèòåëüíûì
äà, êîòîðûå ÷àùå âñåãî ïðîòåêàþò â ñàìîì ãå- ýëåêòðîäîì, à ïðîòèâîïîëîæíàÿ – îòðèöàòåëü-
íåðèðóþùåì áëîêå ïðè êîíòàêòå äâóõ ðåäîêñ- íûì ýëåêòðîäîì ñëåäóþùåé ÿ÷åéêè. Ýòî ïîçâî-
ñèñòåì ÷åðåç ðàçäåëÿþùèé èõ ñåïàðàòîð ìåæäó ëÿåò êîíñòðóèðîâàòü êîìïàêòíûå âûñîêîâîëüò-
ñîáîé è ñ ýëåêòðîäàìè. Ýòî äàåò ñóùåñòâåííûå íûå áàòàðåè áåç ñëîæíîé ñèñòåìû ìåæýëåêòðîä-
ïðåèìóùåñòâà ÐÎÀ ïðè èñïîëüçîâàíèè â ñèñòå- íûõ ñîåäèíåíèé.
ìàõ àêêóìóëèðîâàíèÿ ýíåðãèè, ðàññ÷èòàííûõ íà Áèïîëÿðíûé êîíñòðóêòèâíûé ïðèíöèï
áîëüøèå ýíåðãîåìêîñòè è äëèòåëüíûå öèêëû ïðàêòè÷åñêè íåâîçìîæíî èñïîëüçîâàòü äëÿ íå-
íàêîïëåíèÿ, õðàíåíèÿ è èñïîëüçîâàíèÿ ýíåð- ðàçáîðíûõ àêêóìóëÿòîðíûõ áàòàðåé ñ òâåðäîôàç-
ãèè. íûìè àêòèâíûìè âåùåñòâàìè, ïîñêîëüêó â ïðî-
Ê äîñòîèíñòâàì ÐÎÀ ñ äâóìÿ ðàñòâîðåí- öåññå öèêëèðîâàíèÿ èç-çà ïîñòåïåííîé äåãðà-
íûìè ðåàãåíòàìè ìîæíî îòíåñòè ñëåäóþùåå. äàöèè àêòèâíûõ âåùåñòâ íà ýëåêòðîäàõ óñêîðåí-
– Ýíåðãèÿ è ìîùíîñòü ÐÎÀ ÿâëÿþòñÿ íå- íî íàêàïëèâàþòñÿ ðàçëè÷èÿ â èõ åìêîñòè, ÷òî
çàâèñèìûìè äðóã îò äðóãà. Äëÿ ïðîòî÷íûõ ðå- ïðèâîäèò ê âûõîäó èç ñòðîÿ âñåé áàòàðåè.
äîêñ-àêêóìóëÿòîðîâ çàïàñ ýíåðãèè ïðîïîðöèî- – ÐÎÀ õàðàêòåðèçóþòñÿ áîëåå âûñîêîé îá-
íàëåí îáúåìó ðàñòâîðîâ, â òî âðåìÿ êàê ìîù- ðàòèìîñòüþ ïðè öèêëèðîâàíèè. Ýòî, íàðÿäó ñ
íîñòü çàâèñèò îò ðàçìåðà è êîëè÷åñòâà åäèíè÷- áîëåå ýôôåêòèâíûì òåðìîðåãóëèðîâàíèåì, ïî-
íûõ ÿ÷ååê. Ýòî îçíà÷àåò, ÷òî ÐÎÀ ìîæíî ìî- çâîëÿåò çàðÿæàòü ðåäîêñ-áàòàðåè òàêæå áûñòðî,
äåðíèçèðîâàòü äëÿ ïîëó÷åíèÿ áîëüøåé ýíåðãèè, êàê îíè ðàçðÿæàþòñÿ.
äîáàâèâ äîïîëíèòåëüíûå åìêîñòè ñ ýëåêòðîëè- – ÐÎÀ, ïî ñðàâíåíèþ ñ òðàäèöèîííûìè
òîì, à äëÿ óâåëè÷åíèÿ ìîùíîñòè – ïóòåì äî- ÕÈÒ, ìåíåå âîñïðèèì÷èâû ê ïåðåçàðÿäàì èëè
áàâëåíèÿ ÿ÷ååê. íåäîçàðÿäàì, ÷àñòè÷íîìó ðàçðÿäó, ÷òî óïðîùà-
– ÐÎÀ èìåþò îòíîñèòåëüíî äëèííûé æèç- åò èõ îáñëóæèâàíèå è ýêñïëóàòàöèþ.

ISSN 0321-4095. Âîïðîñû õèìèè è õèìè÷åñêîé òåõíîëîãèè, 2015, Ò. 4 (102) 67


Þ.Â. Ïîëèùóê, Í.Ä. Êîøåëü

– Ýëåêòðîëèòîì â ÐÎÀ, îáùèì äëÿ âñåõ êèõ è ýëåêòðîõèìè÷åñêèõ êîíäåíñàòîðîâ è äðó-


ÿ÷ååê, óïðàâëÿþò àâòîìàòè÷åñêè íà óðîâíå ñèñ- ãèõ âèäîâ ïðåîáðàçîâàòåëåé âèäîâ ýíåðãèè â
òåìû.  ïðîìûøëåííûõ æå áàòàðåÿõ êîíòðîëü ýëåêòðè÷åñòâî.
ñîñòîÿíèÿ ýëåêòðîëèòà (åãî óðîâåíü è êîíöåíò- Óñòðîéñòâî è ïðèíöèï ðàáîòû ðåäîêñ-àêêó-
ðàöèþ) íåîáõîäèìî ïðîâîäèòü èíäèâèäóàëüíî ìóëÿòîðà
äëÿ êàæäîé ÿ÷åéêè. Äëÿ áîëüøèõ áàòàðåé ýòî Íà ðèñóíêå ïîêàçàíà òèïè÷íàÿ ñèñòåìà
äîðîãîñòîÿùèé è òðóäîåìêèé ïðîöåññ. ÐÎÀ íà îñíîâå ðàñòâîðåííûõ ðåàãåíòîâ è ïðî-
Íåäîñòàòêè ÐÎÀ ñâÿçàíû ñ íåîáõîäèìîñ- äóêòîâ, ðàñòâîðåííûõ â ýëåêòðîëèòå. Â ðåæèìå
òüþ öèðêóëÿöèè ðàñòâîðîâ, ò.å. èñïîëüçîâàíèÿ ðàçðÿäà ðàñòâîðû àíîëèòà è êàòîëèòà ïðîõîäÿò
íàñîñîâ, ýëåêòðîëèòîïðîâîäîâ è ðåãóëèðóþùå- ÷åðåç ïîðèñòûå ýëåêòðîäû, ãåíåðèðóþùèå ýëåê-
ãî îáîðóäîâàíèÿ. Îòñþäà ñëåäóåò äîïîëíèòåëü- òðè÷åñêèé òîê, êîòîðûé ïðîõîäèò ÷åðåç âíå-
íîå óñëîæíåíèå è óäîðîæàíèå êîíñòðóêöèè, à øíþþ öåïü íàãðóçêè. Íîñèòåëè òîêà â ðàñòâî-
òàêæå ïîÿâëåíèå çàòðàò íà çàìåíó ðåãóëèðóþ- ðàõ òðàíñïîðòèðóþòñÿ ÷åðåç ñåïàðàòîð (îáû÷íî
ùèõ è êîíòðîëèðóþùèõ óçëîâ ïðîòî÷íîé ñèñ- èîíîîáìåííóþ ìåìáðàíó (ÈÎÌ)), êîòîðûé ñëó-
òåìû. ×àñòü âûðàáàòûâàåìîé ýëåêòðîýíåðãèè æèò äëÿ ðàçäåëåíèÿ ðàñòâîðîâ àíîëèòà è êàòî-
ðàñõîäóåòñÿ äëÿ öèðêóëÿöèè ðàñòâîðîâ. Ýòî ñíè- ëèòà. Ðåàêöèè â îáùåì âèäå ìîãóò áûòü çàïèñà-
æàåò ýíåðãîýôôåêòèâíîñòü ÐÎÀ, òåì ñèëüíåå, íû â òàêîì âèäå:
÷åì ìåíüøå óäåëüíàÿ ìîùíîñòü áàòàðåè îòðèöàòåëüíûé ýëåêòðîä
(êÂò/äì3), òàê êàê ÷åì ìåíüøå óäåëüíàÿ ìîù-
→ A(
íîñòü, òåì áîëüøå ðàçìåð áàòàðåè íà 1 êÂò (áîëü- n − x )+ , (1)
A n + + xe ⎯⎯⎯
çàðÿä

øåå ÷èñëî ýëåêòðîäîâ è èõ ãàáàðèòû), è òåì


A(
áîëüøå áóäåò ðàñõîä ýíåðãèè íà öèðêóëÿöèþ ðà- n − x )+ ðàçðÿä
⎯⎯⎯ → A n + + xe , (2)
ñòâîðîâ, ò.å. äîëÿ îò âûðàáîòàííîé ýíåðãèè.
×àñòü âûðàáîòàííîé ýíåðãèè òåðÿåòñÿ èç-çà âîç- ïîëîæèòåëüíûé ýëåêòðîä
íèêíîâåíèÿ íåèçáåæíûõ òîêîâ óòå÷êè, è ïîÿâ-
ëÿåòñÿ íåðàâíîìåðíîñòü ðàñïðåäåëåíèÿ òîêîâ ïî çàðÿä
Bm + + ye ⎯⎯⎯ → B( m + y )+
, (3)
ýëåìåíòàì. Ïðè ýòîì, ÷åì ýôôåêòèâíåå è ýêî-
B(
m + y )+ ðàçðÿä
íîìíåå öèðêóëÿöèîííàÿ ñèñòåìà, òåì áîëüøå ⎯⎯⎯ → Bm + + ye . (4)
òîêè óòå÷êè. È íàîáîðîò – óìåíüøåíèå òîêîâ
óòå÷êè êîíñòðóêòèâíûìè ñïîñîáàìè âåäåò ê âîç-
ðàñòàíèþ ïîòåðü ýíåðãèè íà öèðêóëÿöèþ.
Îáëàñòè ïðèìåíåíèÿ
Èçíà÷àëüíî ÐÎÀ ïðåäíàçíà÷àëñÿ äëÿ èñ-
ïîëüçîâàíèÿ â êà÷åñòâå àêêóìóëèðóþùåé ïîä-
ñèñòåìû â ñèñòåìàõ, ïðåîáðàçóþùèõ ýíåðãèþ
âîçîáíîâëÿåìûõ èñòî÷íèêîâ, ãäå ðåæèì íàãðóç-
êè èñïûòûâàåò çíà÷èòåëüíûå êîëåáàíèÿ âî âðå-
ìåíè. Ýòî ìîãóò áûòü è êðóïíûå ýëåêòðîñòàí-
öèè (äíåâíàÿ è íî÷íàÿ íàãðóçêà), è àâòîíîìíûå
ýíåðãîóñòàíîâêè, ðàáîòàþùèå íà âîçîáíîâëÿ-
åìûõ èñòî÷íèêàõ ýíåðãèè (âåòðîâîé è ñîëíå÷-
íîé), è ñèñòåìû àâàðèéíîãî ðåçåðâèðîâàíèÿ
ýíåðãèè íà ïðåäïðèÿòèÿõ. Èç-çà öèêëè÷íîñòè è
íåðàâíîìåðíîñòè ïîñòóïëåíèÿ è ðàñõîäîâàíèÿ
ýíåðãèè òàêèå ýíåðãîóñòàíîâêè ìîãóò ðàáîòàòü
ñ ïðèåìëåìûìè ýêñïëóàòàöèîííûìè õàðàêòåðè- Ðèñ. 1. Ïðèíöèïèàëüíàÿ ñõåìà îêèñëèòåëüíî-âîññòàíîâè-
ñòèêàìè è äîñòàòî÷íûì ÊÏÄ òîëüêî â êîìáè- òåëüíûõ ïðîöåññîâ, òðàíñïîðòà ýëåêòðîíîâ â öåïè,
íàöèè ñ àêêóìóëèðóþùåé ïîäñèñòåìîé. Ïî âå- ïåðåíîñà èîíîâ â ýëåêòðîëèòå è ÷åðåç ìåìáðàíó â ÐÎÀ â
ëè÷èíå óäåëüíîé ýíåðãèè è ìîùíîñòè, ÐÎÀ- ïðîöåññå ðàçðÿæåíèÿ. Ïðè çàðÿæåíèè íàïðàâëåíèÿ âñåõ
áàòàðåè çàíÿëè ñâîþ íèøó íàðàâíå ñ òðàäèöè- ïðîöåññîâ, óêàçàííûõ ñòðåëêàìè, ìåíÿþòñÿ íà îáðàòíûå
îííûìè áàòàðåÿìè. Ãåíåðèðóþùèé ìîäóëü (ðåàêòîð) ñîñòîèò èç
Âàæíîé õàðàêòåðèñòèêîé ïðè âûáîðå ïî- áàòàðåè îòäåëüíûõ ÿ÷ååê. Êàòîäíîå è àíîäíîå
òðåáèòåëåì áàòàðåè ñëóæèò âåëè÷èíà ñòîèìîñ- ïðîñòðàíñòâà êàæäîãî ýëåìåíòà, ÷åðåç êîòîðûå
òè ýíåðãèè, ïðèâåäåííîé íà åäèíèöó ìîùíîñòè öèðêóëèðóþò äâà ýëåêòðîëèòà, ðàçäåëåíû ñåïà-
èëè ýíåðãèè. Êàê ïîêàçûâàåò ïðàêòèêà, ñòî- ðàòîðîì. Îòäåëüíûå ýëåìåíòû â áëîêå ìîæíî
èìîñòü ãåíåðèðóåìîé ýíåðãèè â ðåäîêñ-àêêóìó- ðàñïîëàãàòü ïîñëåäîâàòåëüíî, ÷òîáû óâåëè÷èòü
ëÿòîðàõ íà ñåãîäíÿøíèé ìîìåíò âûøå, ÷åì ó îáùåå íàïðÿæåíèå áëîêà, èëè ïàðàëëåëüíî, ÷òî-
ïðîìûøëåííûõ èñòî÷íèêîâ òîêà, ýëåêòðè÷åñ- áû óâåëè÷èòü òîê. Áëîêè ìîãóò êîììóòèðîâàòü-

68 ISSN 0321-4095. Âîïðîñû õèìèè è õèìè÷åñêîé òåõíîëîãèè, 2015, Ò. 4 (102)


Ïðîòî÷íûå ðåäîêñ-àêêóìóëÿòîðû â ñèñòåìàõ ðåçåðâèðîâàíèÿ ýíåðãèè

ñÿ â ýëåêòðè÷åñêóþ öåïü ïîñëåäîâàòåëüíî èëè îñíîâå ïåðôòîðñóëüôîíîâîé êèñëîòû, Selemion


ïàðàëëåëüíî. è Flemion (Asahi Glass), k142 (Asahi Chemicals).
 ÐÎÀ ìîãóò èñïîëüçîâàòüñÿ äâà òèïà ñå-  ïîëóïðîìûøëåííûõ è ïðîìûøëåííûõ îáðàç-
ïàðàòîðîâ: öàõ ÐÎÀ ÷àùå èñïîëüçóþò Nafion èç-çà âûñîêîé
– ìèêðîïîðèñòûå ñåïàðàòîðû (òèïà ïðîòîííîé è íàòðèåâîé ïðîâîäèìîñòè è åå ïðî-
Daramic), êîòîðûå äîïóñêàþò íåêîòîðóþ ôèëü- âåðåííîé íàäåæíîñòüþ â äðóãèõ óñòðîéñòâàõ.
òðàöèþ æèäêîñòåé ìåæäó àíîäíûìè è êàòîäíû-  îáùåì ñëó÷àå ìåìáðàíà äîëæíà ñîâìå-
ìè êàìåðàìè ïðè íàëè÷èè ïåðåïàäà äàâëåíèÿ. ùàòü íèçêóþ ñòîèìîñòü ñ õîðîøåé èîííîé ïðî-
Èç-çà ìåõàíè÷åñêîãî ñìåøèâàíèÿ ðàñòâîðîâ è âîäèìîñòüþ è óñòîé÷èâîñòüþ â èñïîëüçóåìîì
äèôôóçèè ÷åðåç ñåïàðàòîð èñïîëüçîâàíèå ìèê- ýëåêòðîëèòå, íèçêîå ýëåêòðè÷åñêîå ñîïðîòèâëå-
ðîïîðèñòûõ ñåïàðàòîðîâ ïðèâîäèò ê äîïîëíè- íèå, áîëüøîé ñðîê ñëóæáû. Âûñîêèõ ìåõàíè-
òåëüíîé ïîòåðå ðåàãåíòîâ è ñíèæåíèþ êóëîíîâ- ÷åñêèõ ñâîéñòâ íå òðåáóåòñÿ [7–9].
ñêîãî ýôôåêòèâíîñòè. Èõ ïðèìåíåíèå äîïóñòè- Íåêîòîðûå ïðèìåðû ðåàëèçàöèè ðåäîêñ-àê-
ìî â òåõ ñëó÷àÿõ, êîãäà ýëåêòðîëèò â îáåèõ êà- êóìóëÿòîðîâ
ìåðàõ èìååò îäèíàêîâûé ñîñòàâ (íàïðèìåð, ùå- Ñèñòåìà Zn/Cl2 [10,11]
ëî÷ü èëè êèñëîòà â êèñëîðîäíî-âîäîðîäíûõ Ïðè êîìíàòíûõ òåìïåðàòóðàõ õëîð ÿâëÿåò-
ÐÎÀ, ãäå îáà ðåàãåíòà ãàçîôàçíûå è ìàëî ðà- ñÿ êîððîçèîííî àêòèâíûì è îïàñíûì êîìïî-
ñòâîðèìû â ýëåêòðîëèòå). íåíòîì. Íî ïðè òåìïåðàòóðå íèæå 90Ñ îáðàçóåò
– èîíîîáìåííûå ìåìáðàíû, êîòîðûå ÿâëÿ- òâåðäûé õëîðãèäðàò Cl2⋅6H2O, îáúåì êîòîðîãî
þòñÿ îäíèì èç íàèáîëåå âàæíûõ è äîðîãîñòîÿ- ñóùåñòâåííî ìåíüøå, ÷åì ó õëîðà. Ñóììàðíàÿ
ùèõ êîìïîíåíòîâ â ÐÎÀ. ðåàêöèÿ â ýëåìåíòå èìååò âèä:
Èîíîîáìåííûå ìåìáðàíû äåëÿòñÿ íà êà-
òèîíîîáìåííûå è àíèîíîîáìåííûå, â çàâèñè- Cl 2 ⋅6H 2 O+Zn→ZnCl 2 +6H 2 O±2e–. (5)
ìîñòè îò òèïà èîííûõ ôóíêöèîíàëüíûõ ãðóïï,
ïðèñîåäèíåííûõ ê ìàòðèöå ìåìáðàíû. Êàòèî- Íàïðÿæåíèå ðàçîìêíóòîé öåïè=2,1–2,2 Â.
íîîáìåííûå ñîäåðæàò îòðèöàòåëüíî çàðÿæåííûå Ìàòåðèàë õëîðíîãî ýëåêòðîäà – àêòèâèðî-
ãðóïïû, òàêèå êàê –SO3–, –COO–, –PO32–, – âàííûé ãðàôèò èëè òèòàí. Öèíêîâûé ýëåêòðîä
PO3H–, –C6H4O–. Îíè îáåñïå÷èâàþò ñâîáîäíîå ðàáîòàåò â ïîäêèñëåííîì ÍÑl ðàñòâîðå ZnCl2
ïðîõîæäåíèå êàòèîíîâ, íî íåïðîíèöàåìû äëÿ ïðè ðÍ 2–5. Äëÿ ñíèæåíèÿ äåíäðèòîîáðàçîâà-
àíèîíîâ. Àíèîíèòû ñîäåðæàò ôèêñèðîâàííûå íèÿ â ýëåêòðîëèò ââîäÿò NaCl èëè KCl. Ðàáî÷èå
ïîëîæèòåëüíûå ôóíêöèîíàëüíûå ãðóïïû, òàêèå ïëîòíîñòè òîêà íàõîäÿòñÿ â äèàïàçîíå 40–
êàê –NH3+, –NRH2+, –NR2H+, –NR3+, –SR2+ è 160 ìÀ/ñì2. Óäåëüíàÿ ýíåðãèÿ 70–150 Âò⋅÷àñ/êã,
îáåñïå÷èâàþò ñâîáîäíûé ïåðåíîñ òîëüêî àíèî- ÊÏÄ 55–65%, ðåñóðñ 500–1500 öèêëîâ.  ÑØÀ
íîâ. èñïûòûâàëè óñòàíîâêè äî 10 êÂò. Ñàìîðàçðÿä
Âûáîð òèïà ìåìáðàíû îïðåäåëÿåòñÿ òåì, áîëüøîé, äî 1%/÷.
êàêîé èîí – êàòèîí èëè àíèîí îáåñïå÷èâàåò Ñóùåñòâåííûì íåäîñòàòêîì äàííîé ñèñòå-
ïåðåíîñ çàðÿäà (òîêà) â îáîèõ íàïðàâëåíèÿõ ïðè ìû ÿâëÿåòñÿ, êðîìå îïàñíîñòè ðàáîòû ñ õëîðîì
çàðÿæåíèè è ðàçðÿæåíèè.  èäåàëüíûõ ìåìáðà- óçêèé òåìïåðàòóðíûé èíòåðâàë ðàáî÷èõ òåìïå-
íàõ ïåðåíîñ çàðÿäîâ (òîêà) äîëæåí îñóùåñòâ- ðàòóð +9…–100Ñ, òàê êàê ïðè t>+90C – õëîð
ëÿòüñÿ òîëüêî îäíèì èç âèäîâ èîíîâ. Îäíàêî ïåðåõîäèò â ãàç, à ïðè t<–100Ñ ýëåêòðîëèò çà-
÷åðåç ðåàëüíûå ÈÎÌ, êàê ïðàâèëî, íå îáëàäà- ìåðçàåò.
þùèå èäåàëüíîé ñåëåêòèâíîñòüþ, ìîãóò ïðîíè- Ñèñòåìà Zn/Br2 [4–6,12]
êàòü è äðóãèå èîíû òîãî æå èëè ïðîòèâîïîëîæ- Ýòî îäíà èç ïåðâûõ ñèñòåì ÐÎÀ, ðàçðàáîò-
íîãî çíàêà. Ýòî ñíèæàåò êóëîíîâñêóþ ýôôåê- êà êîòîðîé íà÷àëàñü ñ 1975 ã. Àíàëîã õëîð-öèí-
òèâíîñòü áàòàðåè è, ÷òî áîëåå ñóùåñòâåííî, êîâûõ àêêóìóëÿòîðîâ, êîòîðûå õîòÿ è èìåþò
âûçûâàåò íåîáõîäèìîñòü ïåðèîäè÷åñêîãî êîð- õîðîøèå òåõíè÷åñêèå õàðàêòåðèñòèêè, èç-çà
ðåêòèðîâàíèÿ ñîñòàâà ðàñòâîðîâ. îïàñíîñòè õëîðà ïåðñïåêòèâ íå èìåþò. Áðîì
Íà èîíîîáìåííûõ ìåìáðàíàõ, ÷èñëî ïåðå- áîëåå áåçîïàñåí â îáðàùåíèè, ïðè òåìïåðàòóðå
íîñà â êîòîðûõ äëÿ èîíîâ, ïåðåíîñÿùèõ çàðÿä, 15–300Ñ îí íàõîäèòñÿ â æèäêîì ñîñòîÿíèè. Íà
áëèçêî ê åäèíèöå, âîçíèêàåò ìàêñèìàëüíûé ïîëîæèòåëüíîì ýëåêòðîäå ïðîòåêàåò ðåàêöèÿ
äèôôóçèîííûé ïîòåíöèàë (ïîòåíöèàë Äîííà-
íà), ñíèæàþùèé ðàáî÷åå íàïðÿæåíèå êàæäîãî 3Br––2e– ↔Br3–, E0=+1,09 Â, (6)
ýëåìåíòà íà çàìåòíóþ âåëè÷èíó.
Èç àíèîíîîáìåííûõ ìåìáðàí àêòèâíî èñ- íà îòðèöàòåëüíîì:
ïîëüçóþò Selemion AMV (Asahi Glass).
Ïðåäëîæåí öåëûé ðÿä êàòèîíîîáìåííûõ Zn 2++2e– ↔Zn, E 0=–0,76 Â. (7)
ÈÎÌ, íàèáîëåå ðàñïðîñòðàíåííûìè èç êîòîðûõ
ÿâëÿþòñÿ Nafion (DuPont), Dow, ìåìáðàíû íà Òàêæå â îáúåìå ýëåêòðîëèòà âîçìîæíî ïðî-

ISSN 0321-4095. Âîïðîñû õèìèè è õèìè÷åñêîé òåõíîëîãèè, 2015, Ò. 4 (102) 69


Þ.Â. Ïîëèùóê, Í.Ä. Êîøåëü

òåêàíèå ïîáî÷íîãî ïðîöåññà: áèëüíîñòü, íèçêàÿ ñòîèìîñòü èçãîòîâëåíèÿ è


ýêñïëóàòàöèè, ïðîñòîòà ðàáîòû è îáñëóæèâàíèÿ.
Br 2 +Br – ↔Br 3 – . (8) Ïî ýòèì ïðèçíàêàì ñðåäè ÐÎÀ ìîæíî âûáðàòü
áîëåå ðàöèîíàëüíûå âàðèàíòû.
Îñîáåííîñòüþ ýòîé ñèñòåìû ÿâëÿåòñÿ áî- Äðóãàÿ îáëàñòü èñïîëüçîâàíèÿ áðîì-öèí-
ëåå âûñîêàÿ ñêîðîñòü ïðåâðàùåíèé íà ýëåêòðî- êîâûõ ÐÎÀ – äëÿ óñòðîéñòâ «ãàøåíèÿ» ïèêîâûõ
äå Zn/Zn2+ ïî ñðàâíåíèþ ñ ýëåêòðîäîì Br–/Br3–. íàãðóçîê. Îñíîâíûå äîñòîèíñòâà äàííîé ñèñòå-
Äëÿ êîìïåíñàöèè ýòîé ðàçíîñòè ñêîðîñòåé íå- ìû: îòíîñèòåëüíî íèçêàÿ ñòîèìîñòü, äîñòóïíîñòü
îáõîäèìî èñïîëüçîâàòü òîêîñúåìíèêè ñ âûñî- ýëåêòðîäíûõ ìàòåðèàëîâ, íèçêàÿ ïîëÿðèçàöèÿ
êîðàçâèòîé ïîâåðõíîñòüþ, êàê ïðàâèëî, èç ãðà- ýëåêòðîäîâ. Î÷åâèäíûìè íåäîñòàòêàìè ñèñòå-
ôèòà. Îäíàêî â ïðîöåññå äëèòåëüíîé ðàáîòû ìû ÿâëÿåòñÿ: âûñîêèé ñàìîðàçðÿä, îáðàçîâàíèå
ãðàôèò ñêëîíåí ê îêèñëåíèþ, ÷òî ïðèâîäèò ê äåíäðèòíîãî öèíêà (ïðè ïëîòíîñòÿõ òîêà âûøå
äåãðàäàöèè åìêîñòè áàòàðåè. Ýëåêòðîëèòîì ñëó- 15 ìÀ/ñì2), à ñëåäîâàòåëüíî, âîçìîæíîñòü êî-
æèò âîäíûé ðàñòâîð 1,0–7,7 Ì ZnBr2 ñ äîáàâêà- ðîòêîãî çàìûêàíèÿ, êîððîçèÿ öèíêà.
ìè õëîðèäà íàòðèÿ èëè êàëèÿ. Òàêæå â ðàñòâîð Òåì íå ìåíåå â 2009 ã ïî ïðîãðàììå ýíåð-
ââîäÿò ÷åòâåðòè÷íûå ñîåäèíåíèÿ àììîíèÿ äëÿ ãåòè÷åñêîãî âåäîìñòâà ÑØÀ íà ýòó ñèñòåìó äëÿ
ñíèæåíèÿ ïîòåðü áðîìà çà ñ÷åò èñïàðåíèÿ, â âåòðîýíåðãåòè÷åñêèõ óñòàíîâîê òîæå áûë âûäå-
êîòîðûõ ïîñëåäíèé ñâÿçûâàåòñÿ îðãàíè÷åñêèì ëåí îáúåì ðàáîò 6 ìëí $ (ñîçäàíèå ñòàíöèè ìîù-
ëèãàíäîì.  íåêîòîðûõ ñëó÷àÿõ äëÿ ñîçäàíèÿ íîñòüþ 500 êÂò, ñ ýíåðãîçàïàñîì 3000 êÂò⋅÷àñ, â
ðÍ=2–3 ââîäÿò ÍBr. Îáà ðàñòâîðà öèðêóëèðó- North Reading, MA; Syracuse, NY; Sacramento,
þò ÷åðåç âíåøíèå åìêîñòè. Rancho Cordova, CA ).
Äèàïàçîí ðàáî÷èõ ïëîòíîñòåé òîêà 20– Ñèñòåìà Br/S [4,6]
50 ìÀ/ñì2, íàïðÿæåíèå 1,6–1,8 Â, ðàáî÷àÿ òåì- Ïåðâîîòêðûâàòåëÿìè â ðàçðàáîòêå ýòîé
ïåðàòóðà –10…+500Ñ. Óäåëüíàÿ ýíåðãèÿ 40– ñèñòåìû ÿâëÿåòñÿ Regenesys Technologies Ltd. Íà
70 Âò⋅÷/êã. Ðåñóðñ 300–500 öèêëîâ. Ïðè íåâû- ñåãîäíÿøíèé ìîìåíò îíè ñêîíñòðóèðîâàëè âòî-
ñîêèõ ïëîòíîñòÿõ òîêà êîýôôèöèåíò èñïîëüçî- ðóþ ïèëîòíóþ áàòàðåþ äëÿ êðóïíîìàñøòàáíûõ
âàíèÿ ñîñòàâëÿåò 80% è ñíèæàåòñÿ äî 45–50% ýëåêòðè÷åñêèõ ñåòåé ýíåðãîåìêîñòüþ 120 MÂò⋅÷.
ïðè ïëîòíîñòÿõ òîêà îêîëî 100 ìÀ/ñì2.  2004 ã. ïîëó÷èëè ýêñêëþçèâíóþ ëèöåíçèþ íà
Ïîâûøåííûé èíòåðåñ ê ýòîé ñèñòåìå áûë èçãîòîâëåíèå Br/S àêêóìóëèðóþùåé ñèñòåìû.
ñâÿçàí ñ âîçìîæíîé ïåðñïåêòèâîé åå èñïîëüçî- Íà ïîëîæèòåëüíîì ýëåêòðîäå áðîìèä èîí
âàíèÿ äëÿ òÿãîâîé óñòàíîâêè ýëåêòðîìîáèëÿ ïåðåõîäèò â òðèáðîìèä èîí ïî ðåàêöèè (6).
(ïðàêòè÷åñêè åäèíñòâåííûé óäîâëåòâîðèòåëü- Íà îòðèöàòåëüíîì ýëåêòðîäå ñåðà, êîòîðàÿ
íûé âàðèàíò â êëàññå ÐÎÀ), ïîýòîìó óðîâåíü íàõîäèòñÿ â âèäå ðàñòâîðèìûõ ïîëèñóëüôèäîâ,
ðàçðàáîòêè áûë âåñüìà âûñîêèé, ìîùíûå áàòà- ïåðåõîäèò â ñóëüôèä-èîí
ðåè óñïåøíî èñïûòàíû íà ýëåêòðîìîáèëå è â
êðóïíîìàñøòàáíîé ýíåðãåòèêå íà ýëåêòðîñòàí- S42–+2e
–
↔2S2–, E0=–0,265 Â. (9)
öèÿõ. Âûñîêàÿ óäåëüíàÿ ýíåðãèÿ – 60–70 Âò÷/êã
è â 4–5 ðàç áîëåå íèçêàÿ ñòîèìîñòü àêêóìóëè- Àíîëèò – ðàñòâîð NaBr, êàòîëèò – ñìåñü
ðîâàíèÿ ýíåðãèè ïî ñðàâíåíèþ ñî ñâèíöîâûìè ïîëèñóëüôèäîâ íàòðèÿ. Òîêîñúåìíèê ñóëüôèä-
àêêóìóëÿòîðàìè äåëàëè ýòó ñèñòåìó âåñüìà ïðè- íîãî ýëåêòðîäà – ñóëüôèä íèêåëÿ, áðîìèäíîãî
âëåêàòåëüíîé äëÿ øèðîêîãî ïðèìåíåíèÿ. Îäíà- – ãðàôèò. Ýôôåêòèâíîñòü ðàáîòû ñîñòàâëÿåò
êî êîíêóðåíöèè ñ äðóãèìè ñèñòåìàìè áðîì-öèí- îêîëî 80%, ïðè ýòîì óäåëüíàÿ ýíåðãèÿ ñîñòàâ-
êîâàÿ ñèñòåìà ÐÎÀ òîæå ïîêà íå âûäåðæèâàåò. ëÿåò 20–30 Âò⋅÷/ë.
Äëÿ ýëåêòðîìîáèëÿ ñóùåñòâóåò ðÿä àëüòåð- Ê íåäîñòàòêàì ýòîé ñèñòåìû ìîæíî îòíåñ-
íàòèâíûõ âàðèàíòîâ, áîëåå ïðèåìëåìûõ ïî îò- òè íåîáõîäèìîñòü òóðáóëèçàöèè ýëåêòðîëèòà èëè
äåëüíûì õàðàêòåðèñòèêàì (òîïëèâíûå ýëåìåí- îáåñïå÷åíèå âûñîêîé ñêîðîñòè åãî ïðîêà÷êè,
òû, íèêåëü- âîäîðîäíûå, íàòðèé-ñåðíûå èëè ÷òîáû äîñòèãàòü âûñîêèõ õàðàêòåðèñòèê.
íèêåëü-õëîðèäíûå àêêóìóëÿòîðû è äð.). Òàê êàê Ñèñòåìà Zn/Ce [4,6,12–14]
â áðîì-öèíêîâîé ñèñòåìå íåîáõîäèìî àêòèâè- Èç âñåõ èçâåñòíûõ ÐÎÀ ñèñòåìà öèíê-öå-
ðîâàòü óãëåãðàôèòîâûå êàòîäû êàòàëèçàòîðàìè ðèé â ìåòàíñóëüôîíîâîì ýëåêòðîëèòå èìååò ñà-
íà îñíîâå áëàãîðîäíûõ ìåòàëëîâ, ìîæíî ïðåä- ìîå âûñîêîå çíà÷åíèå ÍÐÖ (2,4Â) è, ñëåäîâà-
ïîëàãàòü ñóùåñòâîâàíèå íåêîòîðîãî äðåéôà õà- òåëüíî, ñàìîå âûñîêîå çíà÷åíèå òåîðåòè÷åñêîé
ðàêòåðèñòèê âî âðåìåíè èç-çà ïàññèâàöèîííûõ óäåëüíîé ýíåðãèè. Îäíàêî ïðè òàêîì áîëüøîì
ÿâëåíèé, õàðàêòåðíûõ äëÿ êàòàëèòè÷åñêèõ ïðî- ÍÐÖ âîçíèêàþò ñåðüåçíûå ïðîáëåìû ñ êîððî-
öåññîâ. Â òî æå âðåìÿ äëÿ ñòàöèîíàðíûõ ýíåð- çèåé ìàòåðèàëîâ è ðàçëîæåíèåì âîäû.
ãîóñòàíîâîê â ýíåðãåòèêå âûñîêàÿ óäåëüíàÿ ýíåð- Ñèñòåìà ïðèíàäëåæèò ê ãèáðèäíîìó òèïó
ãèÿ íå ÿâëÿåòñÿ ñóùåñòâåííî âàæíûì äîñòîèí- – â çàðÿæåííîì ñîñòîÿíèè öèíê íàêàïëèâàåòñÿ
ñòâîì – çäåñü òðåáóåòñÿ äëèòåëüíûé ðåñóðñ, ñòà- â òâåðäîôàçíîé ôîðìå íà îòðèöàòåëüíîì ýëåêò-

70 ISSN 0321-4095. Âîïðîñû õèìèè è õèìè÷åñêîé òåõíîëîãèè, 2015, Ò. 4 (102)


Ïðîòî÷íûå ðåäîêñ-àêêóìóëÿòîðû â ñèñòåìàõ ðåçåðâèðîâàíèÿ ýíåðãèè

ðîäå, è êà÷åñòâåííî ïî ñâîèì õàðàêòåðèñòèêàì àêöèÿ:


àíàëîãè÷íà ñâèíöîâî-êèñëîòíûì ÐÎÀ ñ ìåòàí-
ñóëüôîíîâûì ýëåêòðîëèòîì. Cr3++e–↔Cr2+, E0=–0,407 Â. (15)
Íà îòðèöàòåëüíîì ýëåêòðîäå ïðîòåêàåò îñ-
íîâíàÿ ðåàêöèÿ: Íà ïîëîæèòåëüíîì:

Zn(CH3SO3)2+2H++2e– ↔Zn+2CH3SO3H, Fe3++e


e– ↔Fe2+, E0=0,771 Â. (16)
E0=–0,76 Â. (10)
Ýòà ñèñòåìà ÐÎÀ ðåàëèçóåòñÿ â ïðîñòåé-
Òàê êàê ðàâíîâåñíûé ïîòåíöèàë öèíêà íà- øåé êîíñòðóêöèè ñ äâóìÿ îòäåëüíûìè öèðêó-
ìíîãî îòðèöàòåëüíåå âîäîðîäíîãî, ïðè çàðÿäå ëÿöèîííûìè êîíòóðàìè (ïðîòîê ðàñòâîðîâ àê-
ïðîòåêàåò ïîáî÷íàÿ ðåàêöèÿ âûäåëåíèÿ âîäîðî- òèâíûõ âåùåñòâ â HCl – 7–12 ë/ìèí íà 1 êÂò
äà: ìîùíîñòè), ðàçäåëåííûìè â ìåæýëåêòðîäíûõ
ïðîñòðàíñòâàõ àíèîíîîáìåííûìè ìåìáðàíàìè.
2H++2e–→H2, E0=0 Â. (11) Ïðè íàïðÿæåíèè 0,9–1,2  äîñòèãàåòñÿ óäåëü-
íàÿ ìîùíîñòü äî 0,6 êÂò/ì2, ôàðàäååâñêèé ÊÏÄ
Íà ïîëîæèòåëüíîì ýëåêòðîäå ìîãóò èäòè äî 95%.
äâå ðåàêöèè, îñíîâíàÿ: Õîðîøèå êèíåòè÷åñêèå õàðàêòåðèñòèêè
äîñòèãàþòñÿ ïðè àêòèâàöèè êàòîäîâ çîëîòîì,
2Ce(CH3SO3)3+2CH3SO3H↔ õîòÿ, êàê ïîêàçàíî â [14], àêòèâàöèÿ íå îáÿçà-
↔2Ce(CH3SO3)4+2H++2e–, E0=+1,44  (12) òåëüíà è äàæå ïðèâîäèò ê íåêîòîðîìó óâåëè÷å-
íèþ âûõîäà ïî òîêó âîäîðîäà â çàðÿäíîì öèê-
è ïîáî÷íàÿ ðåàêöèÿ âûäåëåíèÿ êèñëîðîäà ïðè ëå. Ýêñïåðèìåíòàëüíûì ïóòåì óñòàíîâèëè, ÷òî
çàðÿäå: ñðîê ñëóæáû ÐÎÀ íà îñíîâå æåëåçîõðîìîâîé
ñèñòåìû ìîæåò ïðåâûøàòü 25–30 ëåò. Íåäîñòà-
H2O→1/2Î2+2H++2E, E0=1,23 Â. (13) òîê – íåîáõîäèìîñòü ïðèìåíåíèÿ àíèîíîîáìåí-
íûõ ìåìáðàí, êîòîðûå ñóùåñòâåííî óñòóïàþò
Ñóììàðíàÿ ðåàêöèÿ â áàòàðåå êàòèîíèòîâûì ïî âåëè÷èíå ñîïðîòèâëåíèÿ, òàê
êàê ïîäâèæíîñòü àíèîíîâ íàìíîãî ìåíüøå, ÷åì
2Ce(CH3SO3)3+Zn(CH3SO3)2↔ ïîäâèæíîñòü êàòèîíîâ.
↔Zn+Ce(CH3SO3)4, ÍÐÖ=2,4 Â. (14) Íåäîñòàòêîì äàííîé ñèñòåìû òàêæå ìîæ-
íî ñ÷èòàòü çàâèñèìîñòü ýôôåêòèâíîñòè öèêëè-
 êà÷åñòâå ðàñòâîðèòåëÿ äëÿ èîíîâ öèíêà ðîâàíèÿ îò ìàòåðèàëà èíåðòíîãî ýëåêòðîäà (îñî-
è öåðèÿ èñïîëüçóþò ìåòàíñóëüôîíîâóþ êèñëî- áåííî ñèëüíî âëèÿåò ñòåïåíü êðèñòàëëè÷íîñòè
òó, êîòîðàÿ ïî ýëåêòðîïðîâîäíîñòè ñîèçìåðèìà ãðàôèòà). Èçâåñòíî, ÷òî ãðàôèòîâûå ýëåêòðîäû
ñ ñîëÿíîé êèñëîòîé. Îáå ñîëè èìåþò â íåé õî- ñêëîííû ê èçìåíåíèþ ñòðóêòóðû â ïðîöåññå
ðîøóþ ðàñòâîðèìîñòü. Ýëåêòðîëèò ïðîêà÷èâà- äëèòåëüíîé ðàáîòû.
þò ÷åðåç îáå ýëåêòðîäíûå êàìåðû, ðàçäåëåííûå Ñèñòåìà Zn/ãåêñàöèàíîôåððàò (ôåððîöèà-
ìåìáðàíîé Nafion. íèä) [16,17]
Öèíê-öåðèåâàÿ ñèñòåìà õàðàêòåðèçóþòñÿ Ïðåäëîæåíà â 1978 ã â ßïîíèè è ÑØÀ.
äîñòàòî÷íî ñòàáèëüíîé ðàáîòîé, ïðîâåðåííîé äî Èññëåäîâàëàñü â ÄÕÒÈ â 1993–1996 ãã., ïîýòî-
60 öèêëîâ. Êîýôôèöèåíò èñïîëüçîâàíèÿ ñîñòàâ- ìó åå ïîòåíöèàëüíûå õàðàêòåðèñòèêè îïðåäåëå-
ëÿåò 60–80% ïðè 500Ñ, ïðè áîëåå íèçêèõ òåìïå- íû òî÷íî (áåç ðåêëàìíûõ ïàðàìåòðîâ). Ïðèíàä-
ðàòóðàõ íåñêîëüêî ìåíüøå – 30–40%. Åìêîñòü ëåæèò ê ãðóïïå ãèáðèäíûõ ÐÎÀ. Òàê êàê çäåñü
ïðè ðàçðÿäå â ëó÷øåì ñëó÷àå ñîñòàâëÿåò îäíî àêòèâíîå âåùåñòâî (öèíê) íàêàïëèâàåòñÿ
~1600 À⋅÷/ì2. Ê íåäîñòàòêàì ÐÎÀ Zn/Ce ñëåäó- íà ýëåêòðîäàõ, çàïàñ åìêîñòè è ýíåðãèè ïðîïîð-
åò îòíåñòè íåîáõîäèìîñòü èñïîëüçîâàòü ìåòàí- öèîíàëåí ãàáàðèòàì ñàìîãî ãåíåðèðóþùåãî òîê
ñóëüôîíîâóþ êèñëîòó âûñîêîé êîíöåíòðàöèè. óñòðîéñòâà. Ðàâíîâåñíîå íàïðÿæåíèå ÐÎÀ – 1,85
Ñ îäíîé ñòîðîíû, ýòî ñíèæàåò âåðîÿòíîñòü ïðî- Â, ÷òî áëèçêî ê íàïðÿæåíèþ ñâèíöîâîãî àêêó-
òåêàíèÿ ïîáî÷íûõ ïðîöåññîâ (çà ñ÷åò óìåíüøå- ìóëÿòîðà. Ðàçðÿäíûé ïðîöåññ íà ýëåêòðîäå
íèÿ êîëè÷åñòâà âîäû), à ñ äðóãîé – îáåñïå÷èâà- K3Fe(CN)6/K4Fe(CN)6 èìååò áîëüøóþ êîíñòàí-
åò áîëüøóþ ðàñòâîðèìîñòü öèíêà. òó ñêîðîñòè (îêîëî 0,01 ñì/ñ), ïîýòîìó ïðîòå-
Ñèñòåìà Fe/Cr [1,4,15] êàåò â äèôôóçèîííîì ðåæèìå áåç ïðèìåíåíèÿ
Çíà÷èòåëüíûå óñèëèÿ íàïðàâëåíû íà ðàç- êàòàëèçàòîðîâ. Îáû÷íî èñïîëüçóþò óãëåãðàôè-
ðàáîòêó ðåäîêñ-àêêóìóëÿòîðîâ ñèñòåìû Fe/Cr ñ òîâûå òêàíè, à ïðîöåññ âåäóò â íàñûùåííîì
äâóìÿ íåéòðàëüíûìè ýëåêòðîäàìè èç óãëåãðàôè- ðàñòâîðå ñ èçáûòêîì ñîëè â âèäå îñàäêà. Ýòî
òîâûõ ìàòåðèàëîâ. ñóùåñòâåííî óâåëè÷èâàåò óäåëüíóþ ýíåðãèþ
Íà îòðèöàòåëüíîì ýëåêòðîäå ïðîòåêàåò ðå- ñèñòåìû è äåëàåò åå íåçàâèñèìîé îò îáúåìà ñîá-

ISSN 0321-4095. Âîïðîñû õèìèè è õèìè÷åñêîé òåõíîëîãèè, 2015, Ò. 4 (102) 71


Þ.Â. Ïîëèùóê, Í.Ä. Êîøåëü

ñòâåííî ðàñòâîðà, êîòîðûé ïðè ýòîì âûïîëíÿåò äëÿ óâåëè÷åíèÿ ïîëÿðèçàöèè âûäåëåíèÿ âîäî-
òîëüêî òðàíñïîðòíûå ôóíêöèè è òðåáóåòñÿ â ðîäà è çàùèòû öèíêà îò êîððîçèè íàíåñåí ñëîé
îãðàíè÷åííîì êîëè÷åñòâå. Àíîäíûé ïðîöåññ ñâèíöà. Êàòîä – óãëåãðàôèòîâàÿ òêàíü. Àíîä-
ðàñòâîðåíèÿ öèíêà òàêæå ïðîòåêàåò äîñòàòî÷íî íûé è êàòîäíûé êîíòóðû ðàçäåëåíû êàòèîíî-
áûñòðî â ùåëî÷íîì ðàñòâîðå. îáìåííîé ìåìáðàíîé ÌÐÔ-26 (ÍÏÎ Ïëàñòïî-
 ýëåìåíòå ïðîòåêàþò ýëåêòðîäíûå ðåàê- ëèìåð, Ðîññèÿ). Äëÿ ñòàáèëèçàöèè ãèäðîäèíà-
öèè: ìè÷åñêîãî ðåæèìà è çàäåðæêè äåíäðèòîâ öèíêà
ïðè ðàçðÿäå â àíîäíîì ïðîñòðàíñòâå ðàñïîëî-
Zn+4ÎH––2e– ↔Zn(OH)2, E0=–1,216 B; (17) æåíà ãîôðèðîâàííàÿ è ïåðôîðèðîâàííàÿ ïëàñ-
òèíà (ñåïàðàòîð).
2K3Fe(CN)6+2e– +2K+↔2K4Fe(CN)6,  ïèêå ìîùíîñòè äîñòèãàåòñÿ ïëîòíîñòü
E0=+0,37 B. (18) òîêà 0,08–0,09 À/ñì2 è ïëîòíîñòü ìîùíîñòè
0,092 Âò/ñì2, èëè ïðè òîëùèíå ðàáî÷åé ÷àñòè
È ñóììàðíàÿ ðåàêöèÿ â áàòàðåå: ýëåìåíòà 3,6 ìì – 0,26 êÂò/ë .Ïðè ñðåäíåé ìàñ-
ñå ðàáî÷åãî ïðîñòðàíñòâà 3 ã/ñì3 óäåëüíàÿ ìîù-
Zn+2K3Fe(CN)6+4KOH↔ íîñòü ñîñòàâëÿåò îêîëî 90 Âò/êã.
↔Zn(OH) 2 +2K 4Fe(CN) 6±2e– . (19) Òåîðåòè÷åñêè òîê ïåðåíîñèòñÿ â áàòàðåå
òîëüêî èîíàìè Ê+, à â êîíòóðàõ ñ íàñûùåííû-
Çíà÷åíèå ñòàíäàðòíîé ÝÄÑ äëÿ ýòîé ðåàê- ìè ðàñòâîðàìè ãåêñàöèàíîôåððàòîâ Fe2+ è Fe3+
öèè ñîñòàâëÿåò 1,59 Â, îäíàêî ðåàëüíî íàïðÿ- äîëæíî ïðîèñõîäèòü òîëüêî ïðåâðàùåíèå îäíîé
æåíèå ðàçîìêíóòîé öåïè áóäåò íåñêîëüêî áîëü- ñîëè â äðóãóþ â òâåðäîé ôàçå, ïóòåì êðèñòàëëè-
øå: â çàðÿæåííîì ñîñòîÿíèè íàõîäèòñÿ â èí- çàöèè ïðîäóêòà è ðàñòâîðåíèÿ ðåàãåíòà â çàðÿä-
òåðâàëå 1,7–1,8 Â, â ðàçðÿæåííîì 1,5–1,6 Â. íî-ðàçðÿäíîì ïðîöåññå. Îäíàêî ïðè äëèòåëüíîé
Òåîðåòè÷åñêàÿ óäåëüíàÿ ýíåðãèÿ ýòîé ñèñ- ðàáîòå ÷åðåç ìåìáðàíó ïðîíèêàþò è èîíû Î͖
òåìû ñîãëàñíî ñóììàðíîé ðåàêöèè (19) ñîñòàâ- â çàìåòíîì êîëè÷åñòâå, ÷òî âûçûâàåò ïðîáëåìó
ëÿåò 92 Âò⋅÷/êã. Ýòî íåáîëüøàÿ âåëè÷èíà ïî ñðàâ- êîððåêòèðîâàíèÿ îáîèõ ðàñòâîðîâ. Âîçíèêàþò
íåíèþ ñ äðóãèìè ïåðñïåêòèâíûìè ñèñòåìàìè, òàêæå ïðîáëåìû íà öèíêîâîì ýëåêòðîäå, ñâÿ-
íî äëÿ ñòàöèîíàðíûõ ýíåðãåòè÷åñêèõ óñòàíîâîê çàííûå ñ êèíåòèêîé ðàñòâîðåíèÿ ïðîäóêòà ðàç-
ýòî íå åñòü ñóùåñòâåííûé íåäîñòàòîê. ðÿäà, öèðêóëèðóþùåãî â âèäå ñóñïåíçèè.
Ðåàëüíî ïî ëèòåðàòóðíûì äàííûì óäåëü- Âàíàäèåâàÿ ñèñòåìà [1–4,18–30]
íàÿ ýíåðãèÿ äîñòèãàåò çíà÷åíèé íà óðîâíå ñâèí- Ðàííèå ðàáîòû ïî âàíàäèåâûì ÐÎÀ (ÂÐÁ)
öîâûõ àêêóìóëÿòîðîâ, 20–30 Âò⋅÷/êã. Ðåàêöèÿ áûëè ïðåäïðèíÿòû ÍÀÑÀ â 1970-å ãîäû è ïîç-
âîññòàíîâëåíèÿ ãåêñàöèíîôåððàòà îáðàòèìà, æå «Ýëåêòðîòåõíè÷åñêîé ëàáîðàòîðèåé» (ETL)
ïðàêòè÷åñêè íà âñåõ ìàòåðèàëàõ ïðîòåêàåò â â ßïîíèè.
äèôôóçèîííîì ðåæèìå è íå òðåáóåò ïðèìåíå- Èíòåðåñíàÿ îñîáåííîñòü ýòèõ áàòàðåé çàê-
íèÿ êàòàëèçàòîðîâ. ëþ÷àåòñÿ â òîì, ÷òî íà îáîèõ ýëåêòðîäàõ (óãëå-
Àíîäíûé ïðîöåññ ïðîòåêàåò â íàñûùåííîì ãðàôèòîâûå ìàòåðèàëû) èñïîëüçóþòñÿ ñîëè âà-
öèíêàòîì ðàñòâîðå ùåëî÷è, ñ èçáûòêîì Zn(OH)2. íàäèÿ ðàçíîé âàëåíòíîñòè, ÷òî ñóùåñòâåííî
Îäíàêî ïðè çàðÿäå öèíê íàêàïëèâàåòñÿ íà ïî- óïðîùàåò òåõíîëîãè÷åñêèé öèêë è äåëàåò ñèñ-
âåðõíîñòè ýëåêòðîäà, ïîýòîìó ñóùåñòâóåò îãðà- òåìó áîëåå íàäåæíîé ïðè äëèòåëüíîé ýêñïëóà-
íè÷åíèå íà ïðåäåëüíûé çàïàñ ýíåðãîåìêîñòè, òàöèè. Íà îòðèöàòåëüíîì ýëåêòðîäå èäåò ðåàê-
èëè îòíîøåíèå ýíåðãèè ê ìîùíîñòè. Â [17] îïè- öèÿ:
ñàíà äëèòåëüíî öèêëèðîâàâøàÿñÿ áàòàðåÿ ñ
óäåëüíûì ýíåðãîçàïàñîì 0,25 À⋅÷/ñì3. Ïîëîæè- V2+↔V3++e–, E0=–0,255 Â. (20)
òåëüíûé ýëåêòðîä èç ãðàôèòîâîãî âîéëîêà êîí-
òàêòèðóåò ñ ìåòàëëè÷åñêîé ñåòêîé-òîêîñúåìíè- Íà ïîëîæèòåëüíîì:
êîì. Ýëåêòðîëèò – 2 í. ðàñòâîð NàÎÍ ñ äîáàâ-
êîé ãåêñàöèàíîôåððàòîâ.  1994 ã. íà êàôåäðå VÎ2++e–+2H+↔V2++H2Î, E0=1,000 Â. (21)
òåõíîëîãèè ýëåêòðîõèìè÷åñêèõ ïðîèçâîäñòâ
ÓÄÕÒÓ áûë èçãîòîâëåí ëàáîðàòîðíûé ìàêåò Ñóììàðíàÿ ðåàêöèÿ:
ðåäîêñ-àêêóìóëÿòîðà ñèñòåìû öèíê-ãåêñàöèàíî-
ôåððàò. ÐÎÀ ñîñòîÿë èç ðåàêòîðà 2×10 ñì (ïðî- VO2++2H++V2+↔V2++H2O+V3+, E0=1,255 Â. (22)
òîê âäîëü äëèííîé ñòîðîíû), äâóõ ðåçåðâóàðîâ
ñ êàòîëèòîì è àíîëèòîì, äâóõ ïåðèñòàëüòè÷åñ- Ñ 1984 ãîäà â Óíèâåðñèòåòå Íîâîãî Þæ-
êèõ íàñîñîâ, êîòîðûå îáåñïå÷èâàëè ïðîòîê ðà- íîãî Óýëüñà (UNSW) â Ñèäíåå, Àâñòðàëèÿ ðà-
ñòâîðîâ ñ ðåãóëèðîâàííîé ñêîðîñòüþ ÷åðåç äâà áîòû áûëè ñîñðåäîòî÷åíû íà ýëåêòðîëèòå è åãî
ýëåêòðîäíûõ êîíòóðà. Îòðèöàòåëüíûé ýëåêòðîä ñòàáèëüíîñòè ïðè âûñîêèõ êîíöåíòðàöèÿõ, à
–ñòàëüíàÿ êîëëåêòîðíàÿ ïëàñòèíà, íà êîòîðóþ òàêæå íà ïðîèçâîäñòâå ýëåêòðîëèòà èç äîñòóï-

72 ISSN 0321-4095. Âîïðîñû õèìèè è õèìè÷åñêîé òåõíîëîãèè, 2015, Ò. 4 (102)


Ïðîòî÷íûå ðåäîêñ-àêêóìóëÿòîðû â ñèñòåìàõ ðåçåðâèðîâàíèÿ ýíåðãèè

íîãî ñûðüÿ.  äîêàçàòåëüñòâî ïåðñïåêòèâíîñòè ìó, ÷åì òðàäèöèîííûå ñâèíöîâî-êèñëîòíûå.


äàííîé ñèñòåìû áûëè ïîñòðîåíû ïðîòîòèïû, Â 1998 êîìïàíèÿ HydroTasmania ïîñòðîè-
âêëþ÷àÿ áàòàðåè äëÿ õðàíåíèÿ ýëåêòðîýíåðãèè, ëà Huxley Wind Farm – óñòàíîâêó èç 3-õ âåòðÿ-
ïðîèçâåäåííîé íà ñîëíå÷íûõ ôîòîýëåêòðè÷åñ- íûõ òóðáèí äëÿ ñåëüñêîõîçÿéñòâåííîãî íàçíà-
êèõ ïàíåëÿõ (Òàèëàíä); ðåçåðâíûå ñèñòåìû äëÿ ÷åíèÿ ìîùíîñòüþ 250 êÂò, îáåñïå÷èâàþùàÿ 20%
ïîäâîäíûõ ëîäîê (àâñòðàëèéñêîãî ìèíèñòåðñòâà ýíåðãîïîòðåáëåíèÿ îñòðîâà King Island. Â ñåòÿõ
îáîðîíû), àêêóìóëÿòîð äëÿ ýëåêòðè÷åñêîãî ýíåðãîïåðåäà÷è âîçíèêàëè ñóòî÷íûå êîëåáàíèÿ,
ãîëüô-ìîáèëÿ; 450 êÂò–900 êÂò áàòàðåè äëÿ è äëÿ âûðàâíèâàíèÿ êîëåáàíèé íàãðóçêè â ñåòè
âûðàâíèâàíèÿ ïèêîâûõ íàãðóçîê (Kashima-Kita áûëè óñòàíîâëåíû âàíàäèåâûå ðåäîêñ-àêêóìó-
Electric Power Corporation, Japan). Â 1998 ãîäó, ëÿòîðû. Ïîçæå ýíåðãîóñòàíîâêà áûëà ðàñøèðå-
ïðàâà èíòåëëåêòóàëüíîé ñîáñòâåííîñòè íà òåõ- íà çà ñ÷åò äâóõ äîïîëíèòåëüíûõ âåòðÿíûõ òóð-
íîëîãèè áûëè ïðîäàíû Pinnacle VRB, Ltd (Ìåëü- áèí ïî 850 êÂò â ïàðå ñ ÂÐÁ íà 200 êÂò [24].
áóðí, Àâñòðàëèÿ). Sumitomo Electric Industries Íà îñíîâàíèè ðåçóëüòàòîâ, ïîëó÷åííûõ äëÿ
(Îñàêà, ßïîíèÿ) ïðèîáðåëà òåõíîëîãèþ è, â ñî- 1 êÂò ÂÐÁ, ñîñòîÿùåé èç 14 åäèíè÷íûõ ÿ÷ååê,
îòâåòñòâèè ñ ëèöåíçèåé îò Pinnacle, ïðîäîëæàåò ñêîíñòðóèðîâàíà ñòåêîâàÿ ñèñòåìà íà 10 êÂò
äàëüíåéøåå ðàçâèòèå òåõíîëîãèé ïóòåì ðàçðà- [25,26]. Àâòîðû [27] äëÿ 10 êÂò ñèñòåìû îòìå÷à-
áîòêè êîíñòðóêöèè áàòàðåè è âñïîìîãàòåëüíûõ þò, ÷òî ìàêñèìàëüíûé ÊÏÄ 82,4% íàáëþäàåòñÿ
ñèñòåì. ïðè ïëîòíîñòè òîêà 50 ìÀ/ñì2 äëÿ åäèíè÷íîé
Âàíàäèåâàÿ ñèñòåìà ê íàñòîÿùåìó âðåìå- ÿ÷åéêè è 82,35% äëÿ áàòàðåè íà 10 êÂò.
íè ïîëó÷èëà íàèáîëüøåå ðàçâèòèå è ïðåäñòàâ- Ñâèíöîâî-êèñëîòíûå ÐÎÀ ñ ðàñòâîðèìûìè
ëåíà ïðîìûøëåííûìè ïðîòîòèïàìè â ðàçëè÷- ðåàãåíòàìè [31–37]
íûõ ñòðàíàõ äëÿ ðàçëè÷íûõ îáëàñòåé ïðèìåíå- Õèìèçì ïðîöåññîâ â äàííîì òèïå ÐÎÀ îò-
íèÿ. Îáû÷íî äëÿ ðàçäåëåíèÿ ìåæýëåêòðîäíûõ ëè÷àåòñÿ îò òðàäèöèîííûõ ÑÊÀ ñ ñåðíîé êèñ-
ïðîñòðàíñòâ èñïîëüçóþò êàòèîíîîáìåííûå ìåì- ëîòîé, ïîñêîëüêó â ðàçðÿäíûõ ðåàêöèÿõ íà îáî-
áðàíû Nafion. Ïî÷òè âî âñåõ äðóãèõ ðåäîêñ-áà- èõ ýëåêòðîäàõ òâåðäîôàçíûå àêòèâíûå âåùåñòâà
òàðåÿõ èîííûé îáìåí ìåæäó ïîëóýëåìåíòàìè PbO2 è Pb îáðàçóþò îäèí ïðîäóêò, ïåðåõîäÿùèé
îñóùåñòâëÿåòñÿ ïóòåì ïåðåíîñà ïðîòîíîâ ÷åðåç â ðàñòâîð – ìåòàíñóëüôîíàò ñâèíöà. Ýòî ñåðü-
ÈÎÌ, íî ÷åðåç ðåàëüíûå ÈÎÌ ìîãóò õèìè÷åñ- åçíîå ïðåèìóùåñòâî ñèñòåìû, òàê êàê öèðêóëÿ-
êè ïåðåìåùàòüñÿ è äðóãèå êàòèîíû, ïóñòü è ìåä- öèííûé êîíòóð îäèí è ýëåêòðîäíûå ïðîñòðàí-
ëåííûìè òåìïàìè.  ñëó÷àå âàíàäèåâûõ áàòà- ñòâà íå íóæäàþòñÿ â ðàçäåëåíèè.
ðåé ýòî ÿâëåíèå íå êðèòè÷íî, ïîñêîëüêó îáà Ïðè çàðÿäå íà ïîëîæèòåëüíîì ýëåêòðîäå
ýëåêòðîëèòà ñîäåðæàò îäèíàêîâûå õèìè÷åñêèå ñâèíåö (²²) âîññòàíàâëèâàåòñÿ äî îêñèäà ñâèí-
êîìïîíåíòû. öà:
Èíòåðåñíûå ðåçóëüòàòû ïîêàçàíû â ðàáîòå
[21], ãäå ïðåäñòàâëåíû ðåçóëüòàòû èñïûòàíèÿ Pb2++2H2O↔PbO2+4H++2e–, E0=+1,6 Â. (23)
âàíàäèåâîãî àêêóìóëÿòîðà äëÿ ãîëüô-êàðà.
Ðåçóëüòàòû ñðàâíèâàëè ñ òðàäèöèîííûì Íà îòðèöàòåëüíîì ýëåêòðîäå ïðîòåêàåò ðå-
ñâèíöîâûì àêêóìóëÿòîðîì è ëèòèé-èîííîé áà- àêöèÿ:
òàðåé, ðàññ÷èòàííûõ íà îäèíàêîâóþ íàãðóçêó
ïðèìåíèòåëüíî ê ýëåêòðîìîáèëþ. Ñðåäíþþ Pb2++2e– ↔Pb, E0=–0,36 Â. (24)
óäåëüíóþ ìîùíîñòü îïðåäåëÿëè èñõîäÿ èç
22 Âò/ë (íà 1 ë ðåàãåíòîâ), ýíåðãîåìêîñòü ñî- Ñóììàðíàÿ ðåàêöèÿ â ýëåìåíòå:
ñòàâëÿëà 14,6 Âò÷/ë. ÊÏÄ îêîëî 65%, áåç ó÷åòà
ïîòåðü, ñâÿçàííûõ ñ öèðêóëÿöèåé. Àâòîðû ñ÷è- 2Pb 2+ +2H 2 O↔Pb+PbO 2 +4H + . (25)
òàþò, ÷òî ïîâûñèòü ïðîèçâîäèòåëüíîñòü ìîæíî
çà ñ÷åò óëó÷øåíèÿ ðàñòâîðèìîñòè âàíàäèÿ ñ èñ- Òî, ÷òî òâåðäîôàçíûå ðåàãåíòû â ðàçðÿäå
ïîëüçîâàíèåì ìîäèôèöèðîâàííûõ ýëåêòðîëèòîâ, ïîëíîñòüþ ðàñòâîðÿþòñÿ è ïðè çàðÿäå çàíîâî
óëó÷øåíèÿ è îïòèìèçàöèè êîíñòðóêöèè ÿ÷åé- âîññòàíàâëèâàþòñÿ íà ýëåêòðîäàõ, îáåñïå÷èâà-
êè. Íà ïðàêòèêå áûëà ïîëó÷åíà óäåëüíàÿ ìîù- åò ïîñòîÿíñòâî ñòðóêòóðû è ñâîéñòâ ðåàãåíòîâ
íîñòü 20–35 Âò/ë â çàâèñèìîñòè îò êîíöåíòðà- PbO2 è Pb â êàæäîì öèêëå.  êëàññè÷åñêèõ ÑÊÀ
öèè ýëåêòðîëèòà. Èç ðàñ÷åòà ïîëó÷åííîé ïëîò- îáà ðåàãåíòà â çàðÿäíî-ðàçðÿäíûõ öèêëàõ ïåðå-
íîñòè ýíåðãèè 25 Âò÷/ë, äëÿ îáåñïå÷åíèÿ 110 ÷ ñòðàèâàþòñÿ â òâåðäîôàçíîé ôîðìå, ïîñòåïåí-
ïðîáåãà ïðè 72 Â íà áàòàðåå íåîáõîäèìî ïðè- íî îñûïàÿñü è èçìåíÿÿ ñòðóêòóðíûå õàðàêòåðè-
ìåðíî 317 ë ýëåêòðîëèòà. Åñëè ïðîãíîçèðîâàòü ñòèêè, ÷òî ïðèâîäèò ê ñíèæåíèþ åìêîñòè. Ñâèí-
êîëè÷åñòâî ýëåêòðîëèòà äëÿ îïòèìèçèðîâàííûõ öîâî-êèñëîòíûé ÐÎÀ ïðèíàäëåæèò ê ãèáðèäíî-
áàòàðåé, åãî ïîòðåáóåòñÿ 424 ëèòðà è 400 êã ñî- ìó òèïó – íà îáîèõ ýëåêòðîäàõ íàêàïëèâàåòñÿ
îòâåòñòâåííî. Ýòî íàìíîãî áîëüøå, ÷åì ëèòèé- ïðè çàðÿäå òâåðäîôàçíûé ðåàãåíò, è ýòî ñòàâèò
èîííûé àêêóìóëÿòîð è íà 40% áîëüøå ïî îáúå- îãðàíè÷åíèå ïî ïðåäåëüíîé ýíåðãîåìêîñòè. Ê

ISSN 0321-4095. Âîïðîñû õèìèè è õèìè÷åñêîé òåõíîëîãèè, 2015, Ò. 4 (102) 73


Þ.Â. Ïîëèùóê, Í.Ä. Êîøåëü

ãðóïïå ÐÎÀ ñâèíöîâî-êèñëîòíóþ ñèñòåìó â ìå- Fe2+↔Fe3++e–, E0=+0,77 Â.


òàíñóëüôîíîâîì ýëåêòðîëèòå ìîæíî îòíåñòè
ïîòîìó, ÷òî ýëåêòðîëèò öèðêóëèðóåò ÷åðåç áà- Äîñòîèíñòâàìè äàííîé ñèñòåìû ÿâëÿþòñÿ:
òàðåþ, à ïðîöåññû ñàìîðàçðÿäà â ýëåìåíòàõ áëî- íèçêèå ðàáî÷èå òåìïåðàòóðû (200Ñ); èñïîëüçî-
êèðóþòñÿ èç-çà òîãî, ÷òî áîëüøàÿ ÷àñòü ýëåêò- âàíèå íåäîðîãèõ ìàòåðèàëîâ è êîíñòðóêöèé,
ðîëèòà íàõîäèòñÿ âíå áàòàðåè. îáðàçîâàíèå íà æåëåçíîì ýëåêòðîäå íåäåíäðèò-
Ïî ñðàâíåíèþ ñ äðóãèìè ÐÎÀ äàííàÿ ñèñ- íûõ îñàäêîâ è äëèòåëüíîå ñîõðàíåíèå ìîðôî-
òåìà èìååò ñåðüåçíîå ïðåèìóùåñòâî – èç-çà èñ- ëîãèè â ïðîöåññå öèêëèðîâàíèÿ. Ê íåäîñòàòêàì
ïîëüçîâàíèÿ îäíîãî ýëåêòðîëèòà â êîíòóðàõ îáî- ìîæíî îòíåñòè: íèçêîå çíà÷åíèå ðàáî÷åãî íà-
èõ ýëåêòðîäîâ, íåò íåîáõîäèìîñòè èñïîëüçîâàòü ïðÿæåíèÿ, íà óðîâíå 1,21 Â.
èîíîîáìåííóþ ìåìáðàíó, ÷òî ñóùåñòâåííî óäå- Ê ñîæàëåíèþ ìû íå íàøëè äîñòàòî÷íîãî
øåâëÿåò è óïðîùàåò êîíñòðóêöèþ. Ýòèì ñèñòå- êîëè÷åñòâà ïóáëèêàöèé ïî èññëåäîâàíèþ äàí-
ìà ÑÊÐÎÀ ïðèíöèïèàëüíî îòëè÷àåòñÿ îò àíà- íîãî òèïà ÐÎÀ. Ïèîíåðàìè â ðàçðàáîòêå æåëå-
ëîãè÷íûõ ãèáðèäíûõ. Îäíàêî, êàê è äðóãèå ãèá- çî-æåëåçíûõ ðåäîêñ-áàòàðåé (ÆÐÁ) ÿâëÿþòñÿ
ðèäíûå ýëåìåíòû ñ îäíèì òâåðäûì ýëåêòðîäîì, Õðóñê è Ñàâèíåë (Îãàéî, Diamond Shamrock
ñóùåñòâóåò ðèñê èçìåíåíèÿ ìîðôîëîãèè ýëåêò- Corporation.).
ðîäà ïðè öèêëèðîâàíèè (îáðàçîâàíèå äåíäðèò- Â [39] ïðèâåäåíû ðåçóëüòàòû èññëåäîâàíèÿ
íûõ îñàäêîâ ñ ïîñëåäóþùèì ðàçðûâîì ñåïàðà- íåáîëüøîé ñèììåòðè÷íîé îäíîýëåìåíòíîé
òîðà è ÊÇ). Äëÿ ïðåäîòâðàùåíèÿ äåíäðèòîîáðà- ÿ÷åéêè, â êîòîðîé îáà ýëåêòðîäà îäíîòèïíûå, è
çîâàíèÿ ïðåäëîæåíî ââîäèòü C16H33(CH3)3N+ â ïóòåì ïðîïóñêàíèÿ òîêà ìîäåëèðîâàëèñü îäíî-
ñîñòàâ ýëåêòðîëèòà, îñíîâíûì êîìïîíåíòîâ êî- âðåìåííî çàðÿäíûé è ðàçðÿäíûé ïðîöåññû íà
òîðîãî ÿâëÿåòñÿ ìåòàíñóëüôîíîâàÿ êèñëîòà. ðåäîêñ-ýëåêòðîäàõ ÆÐÁ: Fe(II)®Fe(0) è
 ëèòåðàòóðå ïðåäñòàâëåíû ðåçóëüòàòû èñ- Fe(II)®Fe(III). Íà÷àëüíîå íàïðÿæåíèå òàêîé
ïûòàíèé ëàáîðàòîðíûõ ìàêåòîâ åäèíè÷íûõ ÿ÷ååê ýëåêòðîëèçíîé ÿ÷åéêè ðàâíî íóëþ, à íàïðÿæå-
è áàòàðåè èç íåñêîëüêèõ ÿ÷ååê ðàçìåðîì 10´10 íèå ïðåäñòàâëÿåò ñîáîé ñóììó ïîëÿðèçàöèé êà-
ñì êàæäàÿ. Ðåçóëüòàòû èñïûòàíèé âûÿâèëè åùå òîäíîãî è àíîäíîãî ïðîöåññîâ è ïàäåíèå íàïðÿ-
îäíó ñåðüåçíóþ ïðîáëåìó, êîòîðàÿ ïîêà íå äàåò æåíèÿ â ìåìáðàíå. Â çàðÿæåííîì ñîñòîÿíèè â
âîçìîæíîñòè ðåàëèçîâàòü äàííóþ ñèñòåìó â ïðî- ñèñòåìåFe(III)/Fe(0) ïðîöåññû èäóò â îáðàòíîì
ìûøëåííûõ ìàñøòàáàõ – ïëîõàÿ àäãåçèÿ PbO2 ê íàïðàâëåíèè.
ýëåêòðîäíîé îñíîâå, à, ñëåäîâàòåëüíî, îñûïà- Íåîáõîäèìîñòü ðàáîòû â ïîäêèñëåííîì
íèå àêòèâíîãî âåùåñòâà è çàãðÿçíåíèå åãî ÷àñ- ðàñòâîðå (äëÿ ïðåäîòâðàùåíèÿ îáðàçîâàíèÿ ìà-
òèöàìè ýëåêòðîëèòà. Íåñìîòðÿ íà ýòî, ïðè öèê- ëîðàñòâîðèìûõ ãèäðîêñèäîâ) ïðèâîäèò ê õèìè-
ëèðîâàíèè â òå÷åíèè 100 öèêëîâ êîýôôèöèåíò ÷åñêîé êîððîçèè åìêîñòåé äëÿ õðàíåíèÿ ýëåêò-
îòäà÷è ïî åìêîñòè ñíèæàëñÿ îò 100 äî 80%. ðîëèòà. Èññëåäîâàíèÿ ðåäîêñ-ýëåêòðîäà ñ ðàç-
Ñíèæåíèå åìêîñòè ñâÿçàíî ñ âîçìîæíîñòüþ èç- ëè÷íûìè óãëåãðàôèòîâûìè ìàòåðèàëàìè íå âû-
ìåíåíèÿ ñîîòíîøåíèÿ α- è β-ìîäèôèêàöèé PbO2 ÿâèëè ïðîòåêàíèÿ ïîáî÷íûõ ïðîöåññîâ (íàïðè-
(ïî àíàëîãèè ñ òðàäèöèîííûì ñâèíöîâûì àê- ìåð, âûäåëåíèÿ êèñëîðîäà èëè õëîð-ãàçà). Ýô-
êóìóëÿòîðîì). ôåêòèâíîñòü ðàáîòû ïîëîæèòåëüíîãî ðåäîêñ-
Çà ïîñëåäíèå 10 ëåò èññëåäîâàòåëüñêîé ýëåêòðîäà Fe(II)/Fe(III)ñîñòàâëÿëà áëèçêóþ ê
ãðóïïîé ó÷åíûõ C-Tech Innovation Ltd (Àíãëèÿ) 100% âåëè÷èíó.
ïðîâåäåí øèðîêèé ðÿä èññëåäîâàíèé ðàáîòû Äëèòåëüíîå öèêëèðîâàíèå ìàêåòà ÆÐÁ ïðè
ïîëîæèòåëüíîãî è îòðèöàòåëüíîãî ýëåêòðîäà; 600Ñ ïîêàçàëî ñòàáèëüíóþ ðàáîòó äî 60 öèêëîâ.
âëèÿíèÿ ñîñòàâà è êîíöåíòðàöèè êîìïîíåíòîâ Èññëåäîâàíèÿ ÆÐÁ ïðîâîäèëèñü â Îäåñ-
ýëåêòðîëèòà. Îäíàêî ïðîìûøëåííîãî âíåäðåíèÿ ñêîì íàöèîíàëüíîì ìîðñêîì óíèâåðñèòåòå [40],
äàííàÿ ðàçðàáîòêà íå íàøëà. îäíàêî ïî ìàòåðèàëàì ïóáëèêàöèè ïðåäñòàâëåí-
Æåëåçî-æåëåçíûé ÐÎÀ [38–40] íûå ðåçóëüòàòû íà ïîðÿäîê óñòóïàþò çàðóáåæ-
Ñèñòåìà îòíîñèòñÿ ê ãèáðèäíûì ÐÎÀ, â íûì. Ïî îöåíêàì àâòîðîâ, áàòàðåÿ èç 20 ýëå-
êîòîðûõ òîëüêî îäíî àêòèâíîå âåùåñòâî ðàñòâî- ìåíòîâ îáùåé ïëîùàäüþ 10000 ñì2 ñ íàïðÿæå-
ðåíî â ýëåêòðîëèòå – Fe(III), à âòîðîå Fe(0) – íèåì 20  ïðè ðàçðÿäå òîêîì 50 À (ïëîòíîñòü
íàêàïëèâàåòñÿ ïðè çàðÿäå íà îòðèöàòåëüíîì òîêà 0,1 À/ñì2) ìîãëà áû ãåíåðèðîâàòü ýíåðãî-
ýëåêòðîäå (îáðàçîâàíèå òâåðäîé ôàçû). åìêîñòü 3,3 êÂò÷/ì3.
Èññëåäîâàíèÿ äàííîé ñèñòåìû òàêæå ïðî-
Fe2++2e– ↔Fe, E0=–0,41 Â. (26) âîäèëèñü íà êàôåäðå òåõíè÷åñêîé ýëåêòðîõèìèè
ÄÂÍÇ ÓÄÕÒÓ.  êà÷åñòâå ýëåêòðîëèòà èñïîëü-
Íà ïîëîæèòåëüíîì èíåðòíîì óãëåãðàôèòî- çîâàëè ðàñòâîð FeCl 3⋅6H2O ñ äîáàâêîé NaCl.
âîì ýëåêòðîäå ïðîòåêàåò îáðàòèìàÿ ðåàêöèÿ, îáà Îñíîâíîé öåëüþ èññëåäîâàíèÿ áûëî èñïîëüçî-
ó÷àñòíèêà êîòîðîé íàõîäÿòñÿ â ðàñòâîðå: âàíèå ðàñòâîðîâ õëîðíîãî æåëåçà (ïðîäóêò òðàâ-
ëåíèÿ æåëåçà), êîòîðûå ÿâëÿþòñÿ ýêîëîãè÷åñêè

74 ISSN 0321-4095. Âîïðîñû õèìèè è õèìè÷åñêîé òåõíîëîãèè, 2015, Ò. 4 (102)


Ïðîòî÷íûå ðåäîêñ-àêêóìóëÿòîðû â ñèñòåìàõ ðåçåðâèðîâàíèÿ ýíåðãèè

îïàñíûìè è òðóäíî ïåðåðàáàòûâàþòñÿ.  êà÷å- íîãî òðàíñïîðòà è äëÿ ýëåêòðîñòàíöèé, äàæå


ñòâå óãëåðîäíûõ ìàòåðèàëîâ äëÿ ýëåêòðîäîâ áûëè äîâåäåííûå äî ñòàäèè ïîëíîìàñøòàáíûõ íàòóð-
èñïîëüçîâàíû: óãëåâîëîêíî, òåðìîðàñøèðåííûé íûõ èñïûòàíèé îáðàçöîâ ýíåðãîóñòàíîâîê, äàëü-
ãðàôèò, à òàêæå ñìåñè ãðàôèòà è íàíîóãðåðîäà. íåéøåãî ðàçâèòèÿ íå ïîëó÷èëè. Ãëàâíàÿ ïðè÷è-
 ðåçóëüòàòå èññëåäîâàíèé áûë óñòàíîâëåí íà çàêëþ÷àåòñÿ â òîì, ÷òî ïðè òåõíè÷åñêîé ðåà-
îïòèìàëüíûé äèàïàçîí êîíöåíòðàöèè õëîðíîãî ëèçàöèè ñèñòåì âîçíèêàþò ïðîáëåìû, ñâÿçàí-
æåëåçà, êîòîðûé ñîñòàâëÿåò 0,1–0,5 ã/ë. Ïðè íûå ñ âòîðè÷íûìè ÿâëåíèÿìè íà ýëåêòðîäàõ è â
ìåíüøèõ è áîëüøèõ êîíöåíòðàöèÿõ ðåçêî âîç- ýëåêòðîëèòàõ. Î íèõ â îò÷åòàõ è ïóáëèêàöèÿõ
ðàñòàåò ïîëÿðèçàöèÿ ýëåêòðîäà.  äèàïàçîíå òåì- ïèøóò, ÷òî â áóäóùåì èõ ìîæíî ðåøèòü – ýòî
ïåðàòóð 40–600Ñ ýôôåêòèâíîñòü ðàáîòû ÆÐÁ äåãðàäàöèÿ ýëåêòðîëèòîâ è ðåàãåíòîâ èç-çà äåé-
ñîñòàâèëà 50%. Îäíàêî íèçêèå ïëîòíîñòè òîêà ñòâèÿ ïîáî÷íûõ ïðîöåññîâ, êîððîçèÿ ýëåìåí-
è êîíöåíòðàöèè, íèçêàÿ óäåëüíàÿ ìîùíîñòü è òîâ êîíñòðóêöèè, ñëîæíîñòè ñèñòåìû ñèíõðîí-
íåîáõîäèìîñòü èñïîëüçîâàíèÿ äîðîãîñòîÿùèõ íîãî óïðàâëåíèÿ öèðêóëÿöèîííûìè ïîòîêàìè
èîíîîáìåííûõ ìåìáðàí ïîêàçûâàþò íåïðèìå- ðàñòâîðîâ è ðåæèìîì ðàáîòû ýíåðãîáëîêà è ò.ä.
íèìîñòü ÆÐÁ äëÿ äîñòèæåíèÿ ïîñòàâëåííîé Èñêëþ÷åíèå ñîñòàâëÿåò âàíàäèåâûé ÐÎÀ,
öåëè. êîòîðûé âûøåë íà óðîâåíü ïðîìûøëåííîãî èñ-
Âûâîäû ïîëüçîâàíèÿ, õîòÿ è âåñüìà îãðàíè÷åííûé. Èí-
Ñðàâíèâàÿ îïèñàííûå âûøå âàðèàíòû ÐÎÀ, òåðåñíî, ÷òî ïðèìåðû åãî ïðèìåíåíèÿ ïîêàçû-
ñëåäóåò ïîä÷åðêíóòü ðàíåå óïîìèíàâøååñÿ ðàç- âàåò íèøó, ãäå ýòà ñèñòåìà èìååò òåõíèêî-ýêî-
ëè÷èå ìåæäó «èñòèííûìè» (äâå ôîðìû êàæäîãî íîìè÷åñêèå ïðåèìóùåñòâà – ìàëîíàñåëåííûå
èç äâóõ ðåàãåíòîâ íàõîäÿòñÿ â ðàñòâîðå) è ãèá- ðàéîíû, â êîòîðûõ îòñóòñòâóåò ðàçâèòàÿ ñèñòå-
ðèäíûìè ÐÎÀ, èìåþùåå ïðèíöèïèàëüíûé õà- ìà ðàñïðåäåëåíèÿ ýëåêòðîýíåðãèè, íî èìåþòñÿ
ðàêòåð.  «èñòèííûõ» ÐÎÀ ìîùíîñòü (ðàçìåð çíà÷èòåëüíûå ðåñóðñû âîçîáíîâëÿåìûõ âèäîâ
ýíåðãîáëîêà) è ýíåðãîåìêîñòü (îáúåì ðàñòâîðîâ) ýíåðãèè – âåòðîâîé èëè ñîëíå÷íîé.
íå çàâèñÿò îäíî îò äðóãîãî, ÷òî ïîçâîëÿåò ñâî-
áîäíî ïðîåêòèðîâàòü àêêóìóëèðóþùóþ ñèñòå-
ìó íà ëþáîé ðåæèì íàãðóçêè. Â ãèáðèäíûõ ÐÎÀ, ÑÏÈÑÎÊ ËÈÒÅÐÀÒÓÐÛ
ãäå õîòÿ áû îäíî âåùåñòâî â îäíîé èç ôîðì íà-
êàïëèâàëîñü íà ýëåêòðîäå, ìîùíîñòü è ýíåðãî- 1. Nguyen T., Savinell R.F. Flow Batteries // The
åìêîñòü âçàèìîñâÿçàíû. Ïîýòîìó òàêàÿ ñèñòåìà Electrochemical Society Interface. – 2010. – Vol.10. – Ð.54-56.
ìîæåò áûòü èñïîëüçîâàíà â áîëåå óçêîé îáëàñòè 2. Development of a redox flow battery system. SEI technical
óñëîâèé. review / Tokuda N., Kanno T., Hara T., Shigematsu T., Tsutsui Y.,
 ýëåêòðîõèìè÷åñêîé ýíåðãåòèêå ñôîðìè- Ikeuchi A., Itou T., Kumamoto T. // 2000. – Vol.50. – Ð.88-94.
ðîâàëîñü äîâîëüíî óñòîé÷èâîå ðàñïðåäåëåíèå 3. Redox flow cells for energy conversion / Ponce de Le´on
ÕÈÒ íà îñíîâå ðàçëè÷íûõ ðåäîêñ-ñèñòåì ìåæ- C., Fr´ýas-Ferrer A., Gonz´alez-Garc´ýa J., Sz´anto D.A., Walsh
äó òðàäèöèîííûìè êëàññàìè ïîòðåáèòåëåé.  F.C. // J. Power Sources. – 2006. – Vol.160. – Ð.716-732.
ñàìîé îáùåé êëàññèôèêàöèè ýòî ñèñòåìû ðå- 4. Redox flow batteries: a review / Weber A.Z., Mench
çåðâèðîâàíèÿ ýíåðãèè áîëüøîé ìîùíîñòè è M.M., Meyers J.P., Ross Ph.N., Gostick J.T., Liu Q. // J.Appl.
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íàçíà÷åíèÿ, àâòîíîìíûå òðàíñïîðòíûå ñðåäñòâà 5. Jurgen O. Besenhard. Handbook of battery materials. –
(ñòàðòåðíûå àêêóìóëÿòîðû äëÿ äâèãàòåëåé íà Weinheirn; New York; Chichester; Brisbane; Singapore; Toronto:
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ñòêèìè òðåáîâàíèÿìè è îãðàíè÷åíèÿìè, êîòî- H., Parasuraman A., Winardi S., Lim T.M., Skyllas-Kazacos M.
ðûå ïðåäúÿâëÿþò ïîòðåáèòåëè. Äëÿ òîãî, ÷òîáû // Membranes. – 2012. – ¹ 2. – Ð.275-306.
íîâàÿ ñèñòåìà ñìîãëà êîíêóðèðîâàòü çà ìåñòî â 8. Chieng S.C., Kazacos M., Skyllas-Kazacos M. Preparation
îïðåäåëåííîì êëàññå, îíà äîëæíà èìåòü î÷åâèä- and Evaluation of Composite Membrane for Vanadium Redox
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êóìóëÿòîðû òàêèìè ïðåèìóùåñòâàìè îáëàäàþò Microporous Separator for Redox Flow Battery Applications //
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Þ.Â. Ïîëèùóê, Í.Ä. Êîøåëü

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Ïðîòî÷íûå ðåäîêñ-àêêóìóëÿòîðû â ñèñòåìàõ ðåçåðâèðîâàíèÿ ýíåðãèè

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