相關申請的交叉引用
本申請要(yao)求于2014年(nian)12月8日提交的申請號為62/088,856的美國臨時專利申請的優先權的權益,其整體通過引用并(bing)入本文。
本公開總(zong)體(ti)涉(she)及能量存(cun)儲(chu),并且更特別地,涉(she)及用于能量存(cun)儲(chu)的液流(liu)電池和相(xiang)關聯的電化學系統。
背景技術:
諸如電(dian)池、超(chao)級(ji)電(dian)容器等(deng)的(de)電(dian)化(hua)學(xue)能量(liang)存(cun)(cun)儲系統已經被廣泛地實施用(yong)于大(da)規模能量(liang)存(cun)(cun)儲應(ying)用(yong)。為此目的(de)已經采用(yong)包括(kuo)液(ye)(ye)流電(dian)池的(de)各種電(dian)池設計。與其(qi)(qi)它類型的(de)電(dian)化(hua)學(xue)能量(liang)存(cun)(cun)儲系統相(xiang)比(bi),由(you)于液(ye)(ye)流電(dian)池能夠通過其(qi)(qi)活(huo)性物(wu)(wu)質(zhi)(zhi)(zhi)的(de)設置將(jiang)功率密度(du)的(de)參(can)數和(he)能量(liang)密度(du)的(de)參(can)數彼(bi)此分離,所以液(ye)(ye)流電(dian)池可(ke)以是有利的(de),特別是對于大(da)規模應(ying)用(yong)。可(ke)選地,液(ye)(ye)流電(dian)池可(ke)以被認為將(jiang)電(dian)力輸出和(he)能量(liang)存(cun)(cun)儲彼(bi)此分離。如本文所使用(yong)的(de),術語“活(huo)性物(wu)(wu)質(zhi)(zhi)(zhi)”、“電(dian)活(huo)性物(wu)(wu)質(zhi)(zhi)(zhi)”、“氧化(hua)還原(yuan)活(huo)性物(wu)(wu)質(zhi)(zhi)(zhi)”或其(qi)(qi)相(xiang)關變(bian)型是指(zhi)在(zai)電(dian)化(hua)學(xue)電(dian)池的(de)操作期間經歷氧化(hua)狀態(tai)變(bian)化(hua)的(de)物(wu)(wu)質(zhi)(zhi)(zhi)。
液流(liu)電(dian)(dian)(dian)池通(tong)常包括在相(xiang)應(ying)的(de)(de)電(dian)(dian)(dian)解質溶(rong)液中的(de)(de)負極活(huo)性物(wu)質和正(zheng)極活(huo)性物(wu)質,其分(fen)別流(liu)經電(dian)(dian)(dian)化學(xue)電(dian)(dian)(dian)池中的(de)(de)膜或隔膜(separator)的(de)(de)相(xiang)對側。電(dian)(dian)(dian)池通(tong)過在電(dian)(dian)(dian)池內部發(fa)生(sheng)的(de)(de)活(huo)性物(wu)質的(de)(de)電(dian)(dian)(dian)化學(xue)反應(ying)被(bei)充電(dian)(dian)(dian)或放(fang)電(dian)(dian)(dian)。電(dian)(dian)(dian)化學(xue)反應(ying)導致(zhi)充電(dian)(dian)(dian)或放(fang)電(dian)(dian)(dian)期間活(huo)性物(wu)質的(de)(de)氧化或還原。
對(dui)于(yu)(yu)液(ye)流(liu)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)池和(he)利用(yong)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)解質(zhi)(zhi)(zhi)(zhi)溶(rong)(rong)液(ye)的(de)其(qi)它(ta)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)化(hua)學(xue)(xue)系統,荷(he)(he)(he)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)狀(zhuang)態是(shi)(shi)重要的(de)操(cao)作(zuo)參(can)數(shu)。術語“荷(he)(he)(he)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)狀(zhuang)態(soc)”是(shi)(shi)眾所周知(zhi)的(de)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)化(hua)學(xue)(xue)能量(liang)(liang)存儲術語,其(qi)在(zai)本(ben)文中指的(de)是(shi)(shi)在(zai)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)化(hua)學(xue)(xue)系統的(de)半電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)池內的(de)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)極(ji)處(chu)的(de)還原(yuan)(yuan)物(wu)(wu)質(zhi)(zhi)(zhi)(zhi)和(he)氧化(hua)物(wu)(wu)質(zhi)(zhi)(zhi)(zhi)的(de)相(xiang)對(dui)量(liang)(liang)。對(dui)于(yu)(yu)負極(ji)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)解質(zhi)(zhi)(zhi)(zhi)溶(rong)(rong)液(ye),通(tong)過還原(yuan)(yuan)物(wu)(wu)質(zhi)(zhi)(zhi)(zhi)的(de)濃(nong)度(du)(du)除以負極(ji)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)解質(zhi)(zhi)(zhi)(zhi)溶(rong)(rong)液(ye)中活(huo)性(xing)(xing)物(wu)(wu)質(zhi)(zhi)(zhi)(zhi)的(de)總濃(nong)度(du)(du)來定(ding)(ding)義(yi)荷(he)(he)(he)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)狀(zhuang)態。對(dui)于(yu)(yu)正極(ji)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)解質(zhi)(zhi)(zhi)(zhi)溶(rong)(rong)液(ye),通(tong)過氧化(hua)物(wu)(wu)質(zhi)(zhi)(zhi)(zhi)的(de)濃(nong)度(du)(du)除以正極(ji)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)解質(zhi)(zhi)(zhi)(zhi)溶(rong)(rong)液(ye)中活(huo)性(xing)(xing)物(wu)(wu)質(zhi)(zhi)(zhi)(zhi)的(de)總濃(nong)度(du)(du)來定(ding)(ding)義(yi)荷(he)(he)(he)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)狀(zhuang)態。例如,當存在(zai)等(deng)量(liang)(liang)的(de)氧化(hua)物(wu)(wu)質(zhi)(zhi)(zhi)(zhi)和(he)還原(yuan)(yuan)物(wu)(wu)質(zhi)(zhi)(zhi)(zhi)時(shi),電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)化(hua)學(xue)(xue)系統的(de)荷(he)(he)(he)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)狀(zhuang)態為50%。電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)化(hua)學(xue)(xue)系統中各個(ge)半電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)池的(de)荷(he)(he)(he)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)狀(zhuang)態值(zhi)不(bu)(bu)一定(ding)(ding)彼(bi)此相(xiang)等(deng),并且全(quan)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)池的(de)荷(he)(he)(he)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)狀(zhuang)態取決于(yu)(yu)各個(ge)半電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)池的(de)荷(he)(he)(he)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)狀(zhuang)態值(zhi)。除了其(qi)它(ta)原(yuan)(yuan)因之外(wai),寄生(sheng)反應(例如,h2析出、h2o氧化(hua)、碳腐蝕等(deng))可以發生(sheng)在(zai)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)化(hua)學(xue)(xue)系統的(de)一個(ge)或兩(liang)個(ge)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)極(ji)處(chu),導致兩(liang)個(ge)半電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)池之間不(bu)(bu)平衡的(de)荷(he)(he)(he)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)狀(zhuang)態。
通(tong)常期(qi)(qi)望的(de)是監測(ce)電(dian)化學系(xi)(xi)統中的(de)荷(he)(he)電(dian)狀(zhuang)(zhuang)態以便提供更(geng)可(ke)靠且高效(xiao)的(de)操作。不平(ping)衡的(de)荷(he)(he)電(dian)狀(zhuang)(zhuang)態在電(dian)化學系(xi)(xi)統的(de)操作期(qi)(qi)間(jian)(jian)可(ke)能產生若(ruo)干不利影響。例如,在液(ye)流(liu)電(dian)池(chi)的(de)電(dian)解質溶(rong)液(ye)之間(jian)(jian)的(de)不平(ping)衡的(de)荷(he)(he)電(dian)狀(zhuang)(zhuang)態可(ke)導致(zhi)在電(dian)極中的(de)一(yi)個處(chu)的(de)質傳限制,從(cong)而降低往返(fan)操作效(xiao)率。荷(he)(he)電(dian)狀(zhuang)(zhuang)態的(de)準確測(ce)量可(ke)以允許確定所需的(de)電(dian)池(chi)再平(ping)衡的(de)程(cheng)度,其將液(ye)流(liu)電(dian)池(chi)恢復到(dao)更(geng)佳操作狀(zhuang)(zhuang)態。
盡管(guan)存在了(le)解電(dian)(dian)化(hua)學系統中的(de)(de)(de)(de)荷電(dian)(dian)狀態(tai)(tai)的(de)(de)(de)(de)愿望,但是目前缺乏準(zhun)確(que)(que)測(ce)量荷電(dian)(dian)狀態(tai)(tai)的(de)(de)(de)(de)準(zhun)備(ready)技(ji)術(shu),特別是原位測(ce)量技(ji)術(shu)。原位測(ce)量可以是被期望的(de)(de)(de)(de),以阻止在離(li)線實驗室分析(xi)(例如,暴(bao)露于(yu)空氣和(he)不反映電(dian)(dian)化(hua)學系統的(de)(de)(de)(de)操作環(huan)境(jing)的(de)(de)(de)(de)其(qi)它(ta)類似反應條(tiao)件)期間有(you)時(shi)可能(neng)發生(sheng)的(de)(de)(de)(de)活(huo)性物質的(de)(de)(de)(de)氧化(hua)形式(shi)和(he)還(huan)原形式(shi)的(de)(de)(de)(de)比例的(de)(de)(de)(de)變化(hua)。用(yong)于(yu)荷電(dian)(dian)狀態(tai)(tai)的(de)(de)(de)(de)原位確(que)(que)定的(de)(de)(de)(de)一(yi)種(zhong)常規技(ji)術(shu)涉及氧化(hua)還(huan)原探針(orp)的(de)(de)(de)(de)使用(yong)。然而,探針輸出(chu)容易隨(sui)時(shi)間浮(fu)動,并且因此(ci)可能(neng)會(hui)損害(hai)荷電(dian)(dian)狀態(tai)(tai)測(ce)量的(de)(de)(de)(de)準(zhun)確(que)(que)性。
鑒于前述情況,在本(ben)領域中非常(chang)期望結合(he)荷電狀態的準(zhun)備確定的電化學系統及與其(qi)相關(guan)聯的方法。本(ben)公開滿足前述需要(yao)并且(qie)還提供相關(guan)優點。
技術實現要素:
在一(yi)(yi)些(xie)實施(shi)例中(zhong)(zhong),本公(gong)開提(ti)供(gong)電(dian)(dian)(dian)化(hua)(hua)學系統的(de)(de)狀(zhuang)態的(de)(de)確定(ding)方(fang)法。該方(fang)法可以包括:提(ti)供(gong)包含與第(di)(di)一(yi)(yi)電(dian)(dian)(dian)極接觸的(de)(de)第(di)(di)一(yi)(yi)電(dian)(dian)(dian)解(jie)質(zhi)(zhi)溶液的(de)(de)電(dian)(dian)(dian)化(hua)(hua)學系統,其(qi)中(zhong)(zhong)第(di)(di)一(yi)(yi)電(dian)(dian)(dian)解(jie)質(zhi)(zhi)溶液含有具有氧化(hua)(hua)形式和還(huan)原形式的(de)(de)第(di)(di)一(yi)(yi)配位化(hua)(hua)合(he)物;在電(dian)(dian)(dian)化(hua)(hua)學系統內的(de)(de)位置處(chu)(chu)將電(dian)(dian)(dian)磁(ci)輻(fu)射(she)(she)與第(di)(di)一(yi)(yi)電(dian)(dian)(dian)解(jie)質(zhi)(zhi)溶液相互作(zuo)用(yong),使得電(dian)(dian)(dian)磁(ci)輻(fu)射(she)(she)通過光(guang)(guang)學材料(liao)被(bei)傳(chuan)送(song),該光(guang)(guang)學材料(liao)被(bei)配置為在光(guang)(guang)學材料(liao)和第(di)(di)一(yi)(yi)電(dian)(dian)(dian)解(jie)質(zhi)(zhi)溶液之間(jian)的(de)(de)界面處(chu)(chu)呈現衰(shuai)減(jian)全反射(she)(she)率;在檢測器處(chu)(chu)接收已經經由光(guang)(guang)學材料(liao)內的(de)(de)一(yi)(yi)個或多個衰(shuai)減(jian)全反射(she)(she)與第(di)(di)一(yi)(yi)電(dian)(dian)(dian)解(jie)質(zhi)(zhi)溶液相互作(zuo)用(yong)的(de)(de)電(dian)(dian)(dian)磁(ci)輻(fu)射(she)(she);以及(ji)利用(yong)在檢測器處(chu)(chu)接收的(de)(de)電(dian)(dian)(dian)磁(ci)輻(fu)射(she)(she),測量(liang)第(di)(di)一(yi)(yi)配位化(hua)(hua)合(he)物的(de)(de)氧化(hua)(hua)形式或還(huan)原形式中(zhong)(zhong)的(de)(de)至少一(yi)(yi)個的(de)(de)吸光(guang)(guang)度。光(guang)(guang)學材料(liao)具有高于第(di)(di)一(yi)(yi)電(dian)(dian)(dian)解(jie)質(zhi)(zhi)溶液的(de)(de)折射(she)(she)率。
在(zai)(zai)(zai)其(qi)(qi)(qi)它各(ge)種(zhong)實(shi)施例中,本公開(kai)提供其(qi)(qi)(qi)中可以(yi)原位(wei)確定操作狀態的(de)(de)電(dian)(dian)化(hua)(hua)學(xue)系統。電(dian)(dian)化(hua)(hua)學(xue)系統可以(yi)包(bao)(bao)括:與第(di)一(yi)電(dian)(dian)極(ji)接(jie)觸(chu)的(de)(de)第(di)一(yi)電(dian)(dian)解質(zhi)(zhi)溶液,其(qi)(qi)(qi)中第(di)一(yi)電(dian)(dian)解質(zhi)(zhi)溶液包(bao)(bao)含具有(you)氧(yang)化(hua)(hua)形式和還原形式的(de)(de)第(di)一(yi)配(pei)(pei)位(wei)化(hua)(hua)合物;電(dian)(dian)磁輻射源;光(guang)學(xue)材料(liao)(liao),其(qi)(qi)(qi)在(zai)(zai)(zai)電(dian)(dian)磁輻射源與第(di)一(yi)電(dian)(dian)解質(zhi)(zhi)溶液之間(jian)(jian)建(jian)立光(guang)學(xue)連通;以(yi)及檢測器,其(qi)(qi)(qi)被配(pei)(pei)置(zhi)(zhi)為從光(guang)學(xue)材料(liao)(liao)接(jie)收已經(jing)經(jing)由在(zai)(zai)(zai)光(guang)學(xue)材料(liao)(liao)和第(di)一(yi)電(dian)(dian)解質(zhi)(zhi)溶液之間(jian)(jian)的(de)(de)界(jie)面(mian)處的(de)(de)一(yi)個或多個衰減全反射與第(di)一(yi)電(dian)(dian)解質(zhi)(zhi)溶液相互(hu)作用(yong)的(de)(de)電(dian)(dian)磁輻射。光(guang)學(xue)材料(liao)(liao)被配(pei)(pei)置(zhi)(zhi)為在(zai)(zai)(zai)光(guang)學(xue)材料(liao)(liao)和第(di)一(yi)電(dian)(dian)解質(zhi)(zhi)溶液之間(jian)(jian)的(de)(de)界(jie)面(mian)處呈現衰減全反射率(lv),其(qi)(qi)(qi)中光(guang)學(xue)材料(liao)(liao)具有(you)高于第(di)一(yi)電(dian)(dian)解質(zhi)(zhi)溶液的(de)(de)折射率(lv)。
前述(shu)內容(rong)已經(jing)相當廣泛地概述(shu)了(le)本(ben)公開(kai)的(de)特(te)征(zheng),以便能夠(gou)更好地理解下(xia)(xia)面的(de)具體實(shi)施方式。在下(xia)(xia)文中將描述(shu)本(ben)公開(kai)的(de)附加特(te)征(zheng)和(he)(he)優(you)點。這些和(he)(he)其它(ta)優(you)點及特(te)征(zheng)將從以下(xia)(xia)描述(shu)中變得更加顯而易(yi)見。
附圖說明
為了更全面地理(li)解本公開(kai)及其(qi)優點,現在參(can)照結合(he)描述本公開(kai)的具體(ti)實施例的附圖的以下描述,其(qi)中:
圖1示出包含結合被(bei)配置用于衰減全反(fan)射率的(de)光學(xue)材(cai)料(liao)的(de)探針(zhen)的(de)電解質溶液的(de)說(shuo)明性示意圖;
圖2描繪說明性液流電池(chi)的示意圖;以及(ji)
圖3示出在各種荷電狀態下通過atr光譜法測量的包含ti3+/4+(兒茶酚酶(mei))2(焦酸鹽)的電解質溶液的說明性uv-vis光譜。
具體實施方式
本公開部(bu)分(fen)地(di)涉(she)及一(yi)種諸(zhu)如(ru)液(ye)流電池(chi)(chi)(chi)的電化學系統,其中荷電狀(zhuang)態(tai)和其它(ta)電池(chi)(chi)(chi)參數(shu)可(ke)以被原位測量(liang)。本公開還部(bu)分(fen)地(di)涉(she)及一(yi)種在諸(zhu)如(ru)液(ye)流電池(chi)(chi)(chi)的電化學系統內原位測量(liang)荷電狀(zhuang)態(tai)和其它(ta)電池(chi)(chi)(chi)參數(shu)的方法。
通(tong)過結合附圖和(he)示(shi)例(li)參考以下描(miao)(miao)(miao)述可以更(geng)容(rong)易地(di)理解本公(gong)(gong)開(kai),所有附圖和(he)示(shi)例(li)形(xing)成(cheng)本公(gong)(gong)開(kai)的(de)(de)一(yi)(yi)部(bu)分。應當(dang)(dang)理解的(de)(de)是,本公(gong)(gong)開(kai)不(bu)限于本文中(zhong)描(miao)(miao)(miao)述和(he)/或(huo)示(shi)出的(de)(de)具體產品、方法、條件或(huo)參數。進一(yi)(yi)步地(di),本文使(shi)用(yong)的(de)(de)術(shu)語僅(jin)用(yong)于通(tong)過示(shi)例(li)的(de)(de)方式(shi)描(miao)(miao)(miao)述特(te)定實施例(li)的(de)(de)目(mu)的(de)(de)并且不(bu)旨在限制,除非另有說明。類似地(di),應當(dang)(dang)認識到的(de)(de)是,在本公(gong)(gong)開(kai)描(miao)(miao)(miao)述電池、液流電池或(huo)其(qi)它電化學能量存儲系(xi)統的(de)(de)地(di)方,也被理解為(wei)隱含地(di)描(miao)(miao)(miao)述電池、液流電池或(huo)其(qi)它電化學能量存儲系(xi)統的(de)(de)操作方法。
還應(ying)當理解的是(shi),為(wei)了(le)清楚起(qi)見,本(ben)公(gong)開(kai)的某些特(te)征可(ke)(ke)以(yi)在(zai)本(ben)文中被(bei)(bei)描述(shu)(shu)在(zai)單(dan)獨實施(shi)例(li)(li)(li)的上下文中,但(dan)是(shi)也(ye)(ye)可(ke)(ke)以(yi)彼此組(zu)合的形(xing)式被(bei)(bei)提供在(zai)單(dan)個(ge)實施(shi)例(li)(li)(li)中。即,除非(fei)明顯不兼容或(huo)被(bei)(bei)具體地(di)排除,否則每(mei)個(ge)單(dan)獨的實施(shi)例(li)(li)(li)被(bei)(bei)認為(wei)與任何其它實施(shi)例(li)(li)(li)可(ke)(ke)組(zu)合,并且該組(zu)合被(bei)(bei)認為(wei)代表另一個(ge)不同的實施(shi)例(li)(li)(li)。相反(fan),為(wei)了(le)簡明起(qi)見,在(zai)單(dan)個(ge)實施(shi)例(li)(li)(li)的上下文中描述(shu)(shu)的本(ben)公(gong)開(kai)的各種特(te)征也(ye)(ye)可(ke)(ke)以(yi)單(dan)獨地(di)或(huo)以(yi)任何子組(zu)合的形(xing)式來(lai)提供。最后,雖然特(te)定實施(shi)例(li)(li)(li)可(ke)(ke)以(yi)被(bei)(bei)描述(shu)(shu)為(wei)一系(xi)列(lie)步驟(zou)的部分或(huo)更一般結(jie)構(gou)的部分,但(dan)是(shi)每(mei)個(ge)步驟(zou)或(huo)子結(jie)構(gou)本(ben)身也(ye)(ye)可(ke)(ke)以(yi)被(bei)(bei)認為(wei)是(shi)獨立的實施(shi)例(li)(li)(li)。
除非另有說明,否則(ze)應當理解(jie)(jie)的(de)(de)是,列表(biao)中的(de)(de)每個(ge)單(dan)獨(du)元件和該(gai)列表(biao)中的(de)(de)單(dan)獨(du)元件的(de)(de)每個(ge)組合將(jiang)被(bei)解(jie)(jie)釋為(wei)不同(tong)的(de)(de)實施(shi)(shi)例。表(biao)示為(wei)“a、b或(huo)c”的(de)(de)一列實施(shi)(shi)例應被(bei)解(jie)(jie)釋為(wei)包(bao)括實施(shi)(shi)例“a”、“b”、“c”、“a或(huo)b”、“a或(huo)c”、“b或(huo)c”或(huo)“a、b或(huo)c”。
在本公開中,用語“一(yi)”、“一(yi)個”和“該”的(de)單數(shu)形式還包(bao)括相應(ying)的(de)復數(shu)參(can)(can)考(kao),并且對特定數(shu)值的(de)參(can)(can)考(kao)至少包(bao)括該特定值,除非上(shang)下文(wen)另有(you)明確說明。因此,例如(ru),對“一(yi)種物質”的(de)參(can)(can)考(kao)是對這種物質及其(qi)等同物中的(de)至少一(yi)個的(de)參(can)(can)考(kao)。
通常(chang),術(shu)語“大(da)約”的(de)(de)(de)(de)使用(yong)表(biao)(biao)示可(ke)(ke)以根(gen)據由公開的(de)(de)(de)(de)主題所(suo)(suo)獲(huo)得的(de)(de)(de)(de)期望特性(xing)而變(bian)化(hua)的(de)(de)(de)(de)近(jin)似值(zhi)(zhi)并且(qie)將基于(yu)(yu)功(gong)能(neng)以上下(xia)文(wen)相關方式來(lai)解釋。因此,本(ben)領域普通技術(shu)人員將能(neng)夠根(gen)據具(ju)體(ti)情(qing)(qing)況(kuang)(kuang)解釋變(bian)化(hua)的(de)(de)(de)(de)程度。在一(yi)些情(qing)(qing)況(kuang)(kuang)下(xia),當(dang)表(biao)(biao)達特定值(zhi)(zhi)時使用(yong)的(de)(de)(de)(de)重要數(shu)字的(de)(de)(de)(de)數(shu)量可(ke)(ke)能(neng)是用(yong)于(yu)(yu)確定由術(shu)語“大(da)約”允許(xu)的(de)(de)(de)(de)變(bian)化(hua)的(de)(de)(de)(de)代表(biao)(biao)性(xing)技術(shu)。在其它情(qing)(qing)況(kuang)(kuang)下(xia),可(ke)(ke)以使用(yong)一(yi)系列數(shu)值(zhi)(zhi)中的(de)(de)(de)(de)漸變(bian)來(lai)確定由術(shu)語“大(da)約”允許(xu)的(de)(de)(de)(de)變(bian)化(hua)的(de)(de)(de)(de)范圍(wei)(wei)。進一(yi)步地,本(ben)公開中的(de)(de)(de)(de)所(suo)(suo)有范圍(wei)(wei)都是包(bao)含性(xing)的(de)(de)(de)(de)和可(ke)(ke)組合(he)的(de)(de)(de)(de),并且(qie)對范圍(wei)(wei)中所(suo)(suo)述的(de)(de)(de)(de)值(zhi)(zhi)的(de)(de)(de)(de)參考包(bao)括該(gai)范圍(wei)(wei)內的(de)(de)(de)(de)每個值(zhi)(zhi)。
如(ru)以(yi)上所討(tao)論的,目前難(nan)以(yi)確定(ding)(ding)諸如(ru)液流電池的各種(zhong)電化學(xue)系統中的荷電狀態和(he)其它操作參數(shu),特別是以(yi)原位方式。氧(yang)化還原探針有時可以(yi)用于荷電狀態的原位確定(ding)(ding),但是它們往往容易隨時間(jian)浮(fu)動。
從操作(zuo)的(de)(de)(de)角度來看,在液流電池的(de)(de)(de)電解質(zhi)溶(rong)(rong)液中(zhong)具有易溶(rong)(rong)的(de)(de)(de)活(huo)性物質(zhi)以避(bi)免循環微粒的(de)(de)(de)沉(chen)積是非(fei)常(chang)(chang)可取(qu)的(de)(de)(de)。如本(ben)文所使用的(de)(de)(de),術(shu)語“溶(rong)(rong)液”指的(de)(de)(de)是被至少部分(fen)溶(rong)(rong)解,理想地是完全溶(rong)(rong)解的(de)(de)(de)狀(zhuang)態。由于(yu)電化學(xue)系統的(de)(de)(de)存(cun)(cun)儲(chu)容(rong)量(能量密度)通常(chang)(chang)取(qu)決于(yu)存(cun)(cun)在于(yu)電解質(zhi)溶(rong)(rong)液中(zhong)的(de)(de)(de)活(huo)性物質(zhi)的(de)(de)(de)量,因此(ci)非(fei)常(chang)(chang)期(qi)望高溶(rong)(rong)解度活(huo)性物質(zhi)以便產生高濃(nong)度溶(rong)(rong)液。
uv-vis光譜法是另一種技術,其有時可用于基于電解(jie)質(zhi)溶(rong)液(ye)中活性物質(zhi)的(de)(de)氧(yang)化形式和還原形式之間的(de)(de)電磁(ci)輻(fu)射(she)(she)吸收差異(yi)來(lai)確定荷電狀態。uv-vis測量(liang)通常(chang)在傳輸配(pei)置(zhi)中執行,其中電磁(ci)輻(fu)射(she)(she)的(de)(de)單色光束(shu)或寬帶光束(shu)通過樣品并且透射(she)(she)光的(de)(de)強度(du)(du)在檢測器處(chu)被測量(liang)。在傳輸條件(jian)下,比爾-朗伯特(beer-lambert)定律(等式1)可用于將濃(nong)度(du)(du)值和吸光度(du)(du)值相互關(guan)聯。
a=εcl(等式1)
其中a是測量的吸光度,ε是被分析物質的摩爾吸光系數常數,c是物質的濃度,以及l是傳輸電磁輻射的路徑長度。對于具有相對較小摩爾吸光系數常數(例如,小于約50m-1cm-1)的(de)(de)(de)(de)物質,近似約為(wei)1cm或更長(chang)的(de)(de)(de)(de)路(lu)徑長(chang)度(du)(du)可用(yong)于在(zai)(zai)電解質溶(rong)液中存在(zai)(zai)的(de)(de)(de)(de)典(dian)型濃度(du)(du)范(fan)(fan)圍(wei)(wei)(例(li)如,約0.5m至(zhi)約4m)下產生約0.05至(zhi)約2的(de)(de)(de)(de)范(fan)(fan)圍(wei)(wei)中的(de)(de)(de)(de)絕對吸光度(du)(du)值。對于具有較(jiao)小摩(mo)爾吸光系(xi)數(shu)常數(shu)的(de)(de)(de)(de)物質,較(jiao)長(chang)的(de)(de)(de)(de)路(lu)徑長(chang)度(du)(du)可以用(yong)于將絕對吸光度(du)(du)保持在(zai)(zai)該(gai)范(fan)(fan)圍(wei)(wei)內(nei)。在(zai)(zai)該(gai)范(fan)(fan)圍(wei)(wei)內(nei)的(de)(de)(de)(de)絕對吸光度(du)(du)值可以是相當(dang)理想的(de)(de)(de)(de)以避免降(jiang)低的(de)(de)(de)(de)在(zai)(zai)該(gai)范(fan)(fan)圍(wei)(wei)的(de)(de)(de)(de)低端處的(de)(de)(de)(de)信(xin)噪(zao)比和在(zai)(zai)該(gai)范(fan)(fan)圍(wei)(wei)的(de)(de)(de)(de)高端處的(de)(de)(de)(de)檢測(ce)器(qi)飽和度(du)(du)。
雖然低摩爾吸光系數常數可以通過增加傳輸路徑長度來解決,但是高摩爾吸光系數常數和/或高濃度可能更難以解決,特別是對于原位分析。具體地,在重大操作困難開始之前,傳輸路徑長度只能減少到目前為止。在長度低于約1mm,特別是長度低于約0.1mm的傳輸路徑長度下,會導致窄的流場,其甚至可以容易地被少量的循環微粒阻擋。因此,對于強烈吸收電磁輻射的活性物質,傳統的傳輸吸收光譜法對于荷電狀態的原位確定是完全不切實際的。在許多情況下,普通電解質溶液濃度的實際工作極限可以達到約100m-1cm-1或更大的摩爾(er)吸光系數(shu)常數(shu)。包括各種(zhong)金(jin)屬-配位體(ti)配位化合物(wu)的多個感興趣的活性(xing)物(wu)質可以顯(xian)示高于該(gai)閾(yu)值(zhi)(zhi)的摩爾(er)吸光系數(shu)常數(shu),有時(shi)在諸如卟(bu)啉的配位體(ti)的情況下(xia)顯(xian)著地高于該(gai)閾(yu)值(zhi)(zhi)。
本發明人(ren)認為衰減全反射率(atr)光(guang)(guang)(guang)(guang)(guang)(guang)譜(pu)(pu)(pu)法可(ke)(ke)(ke)以(yi)(yi)(yi)(yi)用(yong)(yong)于(yu)確定(ding)諸如液流電(dian)(dian)(dian)池(chi)(chi)的(de)(de)(de)(de)(de)電(dian)(dian)(dian)化(hua)學(xue)(xue)系統中(zhong)(zhong)的(de)(de)(de)(de)(de)荷(he)(he)(he)電(dian)(dian)(dian)狀態(tai),特別(bie)是在從實際的(de)(de)(de)(de)(de)角度(du)來看傳統的(de)(de)(de)(de)(de)透射光(guang)(guang)(guang)(guang)(guang)(guang)譜(pu)(pu)(pu)法是不合(he)適的(de)(de)(de)(de)(de)情況下(xia)(xia)。特別(bie)地(di)(di),在高吸收性(xing)(xing)電(dian)(dian)(dian)解質(zhi)溶液對傳統透射光(guang)(guang)(guang)(guang)(guang)(guang)譜(pu)(pu)(pu)法另(ling)(ling)外極度(du)地(di)(di)要求(qiu)小(xiao)路徑長度(du)的(de)(de)(de)(de)(de)情況下(xia)(xia),atr光(guang)(guang)(guang)(guang)(guang)(guang)譜(pu)(pu)(pu)法可(ke)(ke)(ke)以(yi)(yi)(yi)(yi)有效地(di)(di)使用(yong)(yong)。因此,如果在半(ban)電(dian)(dian)(dian)池(chi)(chi)中(zhong)(zhong)的(de)(de)(de)(de)(de)活(huo)性(xing)(xing)物質(zhi)的(de)(de)(de)(de)(de)氧(yang)化(hua)形(xing)式(shi)(shi)(shi)或(huo)(huo)還(huan)原形(xing)式(shi)(shi)(shi)的(de)(de)(de)(de)(de)至少一(yi)(yi)個(ge)(ge)的(de)(de)(de)(de)(de)吸光(guang)(guang)(guang)(guang)(guang)(guang)度(du)可(ke)(ke)(ke)以(yi)(yi)(yi)(yi)用(yong)(yong)電(dian)(dian)(dian)磁(ci)輻射的(de)(de)(de)(de)(de)選擇類型來量(liang)化(hua),則如下(xia)(xia)文(wen)所述(shu)(shu),吸光(guang)(guang)(guang)(guang)(guang)(guang)度(du)可(ke)(ke)(ke)以(yi)(yi)(yi)(yi)與荷(he)(he)(he)電(dian)(dian)(dian)狀態(tai)相關聯。例如,通過了(le)解氧(yang)化(hua)形(xing)式(shi)(shi)(shi)或(huo)(huo)還(huan)原形(xing)式(shi)(shi)(shi)中(zhong)(zhong)的(de)(de)(de)(de)(de)一(yi)(yi)個(ge)(ge)的(de)(de)(de)(de)(de)濃(nong)度(du),則可(ke)(ke)(ke)以(yi)(yi)(yi)(yi)基(ji)于(yu)活(huo)性(xing)(xing)物質(zhi)的(de)(de)(de)(de)(de)總(zong)濃(nong)度(du)來推斷另(ling)(ling)一(yi)(yi)個(ge)(ge)形(xing)式(shi)(shi)(shi)的(de)(de)(de)(de)(de)濃(nong)度(du)。理想地(di)(di),活(huo)性(xing)(xing)物質(zhi)的(de)(de)(de)(de)(de)氧(yang)化(hua)形(xing)式(shi)(shi)(shi)和還(huan)原形(xing)式(shi)(shi)(shi)兩者的(de)(de)(de)(de)(de)吸光(guang)(guang)(guang)(guang)(guang)(guang)度(du)通過atr光(guang)(guang)(guang)(guang)(guang)(guang)譜(pu)(pu)(pu)法來直接確定(ding),以(yi)(yi)(yi)(yi)提(ti)供(gong)更可(ke)(ke)(ke)靠的(de)(de)(de)(de)(de)測量(liang)。如果需要,每個(ge)(ge)半(ban)電(dian)(dian)(dian)池(chi)(chi)的(de)(de)(de)(de)(de)荷(he)(he)(he)電(dian)(dian)(dian)狀態(tai)可(ke)(ke)(ke)以(yi)(yi)(yi)(yi)通過atr光(guang)(guang)(guang)(guang)(guang)(guang)譜(pu)(pu)(pu)技術來獨立地(di)(di)確定(ding),以(yi)(yi)(yi)(yi)提(ti)供(gong)全電(dian)(dian)(dian)池(chi)(chi)的(de)(de)(de)(de)(de)操作狀態(tai)。例如,兩個(ge)(ge)半(ban)電(dian)(dian)(dian)池(chi)(chi)的(de)(de)(de)(de)(de)荷(he)(he)(he)電(dian)(dian)(dian)狀態(tai)值之間的(de)(de)(de)(de)(de)差異(yi)可(ke)(ke)(ke)以(yi)(yi)(yi)(yi)提(ti)供(gong)用(yong)(yong)于(yu)啟動液流電(dian)(dian)(dian)池(chi)(chi)的(de)(de)(de)(de)(de)再平(ping)衡或(huo)(huo)再調節的(de)(de)(de)(de)(de)度(du)量(liang)。應用(yong)(yong)于(yu)諸如液流電(dian)(dian)(dian)池(chi)(chi)的(de)(de)(de)(de)(de)電(dian)(dian)(dian)化(hua)學(xue)(xue)系統的(de)(de)(de)(de)(de)atr光(guang)(guang)(guang)(guang)(guang)(guang)譜(pu)(pu)(pu)法的(de)(de)(de)(de)(de)詳細(xi)描述(shu)(shu)在下(xia)(xia)文(wen)中(zhong)(zhong)闡述(shu)(shu)。有利地(di)(di),用(yong)(yong)于(yu)進行(xing)atr光(guang)(guang)(guang)(guang)(guang)(guang)譜(pu)(pu)(pu)測量(liang)的(de)(de)(de)(de)(de)機構可(ke)(ke)(ke)以(yi)(yi)(yi)(yi)容易地(di)(di)被結合(he)到各(ge)種電(dian)(dian)(dian)化(hua)學(xue)(xue)系統中(zhong)(zhong),以(yi)(yi)(yi)(yi)便進行(xing)包(bao)括(kuo)確定(ding)荷(he)(he)(he)電(dian)(dian)(dian)狀態(tai)的(de)(de)(de)(de)(de)各(ge)種操作分析。
本公(gong)開(kai)的(de)(de)電(dian)化(hua)(hua)學系(xi)(xi)(xi)統(tong)(tong)和方(fang)(fang)法由于其在(zai)(zai)電(dian)化(hua)(hua)學系(xi)(xi)(xi)統(tong)(tong)內(nei)(nei)的(de)(de)原(yuan)位(wei)可(ke)(ke)操作(zuo)性而可(ke)(ke)以(yi)是進(jin)一(yi)步有利的(de)(de)。因此,本公(gong)開(kai)的(de)(de)系(xi)(xi)(xi)統(tong)(tong)和方(fang)(fang)法減輕實(shi)驗室(shi)人員對潛在(zai)(zai)的(de)(de)反應性、腐(fu)蝕性和/或有毒物質(zhi)的(de)(de)采樣(yang)和處理的(de)(de)需要。因為采樣(yang)可(ke)(ke)以(yi)在(zai)(zai)任(ren)何(he)合(he)適(shi)的(de)(de)位(wei)置(zhi)處在(zai)(zai)電(dian)化(hua)(hua)學系(xi)(xi)(xi)統(tong)(tong)內(nei)(nei)原(yuan)位(wei)發生,所以(yi)在(zai)(zai)實(shi)際操作(zuo)條件下的(de)(de)電(dian)解(jie)質(zhi)溶(rong)液(ye)的(de)(de)狀態可(ke)(ke)以(yi)比在(zai)(zai)實(shi)驗室(shi)分析期間取樣(yang)和處理電(dian)解(jie)質(zhi)溶(rong)液(ye)時(shi)更(geng)準(zhun)確(que)地被測(ce)定。進(jin)一(yi)步地,與離線分析技術相比,關(guan)于電(dian)解(jie)質(zhi)溶(rong)液(ye)的(de)(de)狀態的(de)(de)更(geng)快速的(de)(de)反饋可(ke)(ke)以(yi)被確(que)定。在(zai)(zai)下面進(jin)一(yi)步詳細描述用(yong)于在(zai)(zai)電(dian)化(hua)(hua)學系(xi)(xi)(xi)統(tong)(tong)內(nei)(nei)進(jin)行atr光譜測(ce)量的(de)(de)合(he)適(shi)位(wei)置(zhi)。最(zui)后,用(yong)于執行atr光譜法和檢測(ce)系(xi)(xi)(xi)統(tong)(tong)的(de)(de)探(tan)針相對不易于浮(fu)動,從而使它們相對于傳統(tong)(tong)使用(yong)的(de)(de)orp測(ce)量是有利的(de)(de)。
在(zai)本文中描述結合用于對電(dian)化(hua)學(xue)系(xi)統的半電(dian)池的至少一個中的電(dian)解(jie)質(zhi)溶(rong)液(ye)執行(xing)atr光(guang)(guang)譜法(fa)的機構的電(dian)化(hua)學(xue)系(xi)統。通過對電(dian)解(jie)質(zhi)溶(rong)液(ye)執行(xing)atr光(guang)(guang)譜法(fa),可以確定電(dian)化(hua)學(xue)系(xi)統的各種操作參數,其包括電(dian)解(jie)質(zhi)溶(rong)液(ye)的荷電(dian)狀態。在(zai)說明性實施(shi)例中,電(dian)化(hua)學(xue)系(xi)統可以是液(ye)流電(dian)池。
在各種實施例(li)中,本公開的(de)電(dian)(dian)化(hua)學系(xi)統可以包(bao)括:第(di)(di)一(yi)(yi)電(dian)(dian)解(jie)質(zhi)(zhi)(zhi)溶(rong)液(ye)(ye),其與第(di)(di)一(yi)(yi)電(dian)(dian)極接(jie)(jie)觸;電(dian)(dian)磁輻(fu)射(she)(she)源(yuan);光(guang)學材(cai)料(liao),其在電(dian)(dian)磁輻(fu)射(she)(she)源(yuan)與第(di)(di)一(yi)(yi)電(dian)(dian)解(jie)質(zhi)(zhi)(zhi)溶(rong)液(ye)(ye)之間(jian)建立光(guang)學連通;以及檢測器,其被配置(zhi)(zhi)為從(cong)光(guang)學材(cai)料(liao)接(jie)(jie)收電(dian)(dian)磁輻(fu)射(she)(she),該光(guang)學材(cai)料(liao)已(yi)經經由在光(guang)學材(cai)料(liao)和(he)第(di)(di)一(yi)(yi)電(dian)(dian)解(jie)質(zhi)(zhi)(zhi)溶(rong)液(ye)(ye)之間(jian)的(de)界面(mian)處(chu)(chu)的(de)一(yi)(yi)個(ge)(ge)或(huo)多個(ge)(ge)衰減全反(fan)射(she)(she)率與第(di)(di)一(yi)(yi)電(dian)(dian)解(jie)質(zhi)(zhi)(zhi)溶(rong)液(ye)(ye)相(xiang)互作用(yong)。光(guang)學材(cai)料(liao)具有(you)高于(yu)第(di)(di)一(yi)(yi)電(dian)(dian)解(jie)質(zhi)(zhi)(zhi)溶(rong)液(ye)(ye)的(de)折射(she)(she)率,并(bing)且被配置(zhi)(zhi)為在光(guang)學材(cai)料(liao)和(he)第(di)(di)一(yi)(yi)電(dian)(dian)解(jie)質(zhi)(zhi)(zhi)溶(rong)液(ye)(ye)之間(jian)的(de)界面(mian)處(chu)(chu)呈現衰減全反(fan)射(she)(she)率。第(di)(di)一(yi)(yi)電(dian)(dian)解(jie)質(zhi)(zhi)(zhi)溶(rong)液(ye)(ye)含有(you)具有(you)氧(yang)化(hua)形式和(he)還原形式的(de)第(di)(di)一(yi)(yi)配位化(hua)合物。即,第(di)(di)一(yi)(yi)配位化(hua)合物用(yong)作第(di)(di)一(yi)(yi)電(dian)(dian)解(jie)質(zhi)(zhi)(zhi)溶(rong)液(ye)(ye)中的(de)活性物質(zhi)(zhi)(zhi)。
如(ru)(ru)本文中(zhong)(zhong)所使(shi)(shi)用的(de)(de)(de)(de)(de),術(shu)語“配(pei)(pei)(pei)(pei)位(wei)化(hua)(hua)合物(wu)”將(jiang)指的(de)(de)(de)(de)(de)是(shi)由一種或(huo)(huo)多(duo)種配(pei)(pei)(pei)(pei)位(wei)體(ti)(ti),特(te)別是(shi)由至少一種螯(ao)合配(pei)(pei)(pei)(pei)位(wei)體(ti)(ti)絡合的(de)(de)(de)(de)(de)金(jin)(jin)屬(shu)離子(zi)。如(ru)(ru)本文中(zhong)(zhong)所使(shi)(shi)用的(de)(de)(de)(de)(de),術(shu)語“螯(ao)合配(pei)(pei)(pei)(pei)位(wei)體(ti)(ti)”將(jiang)指的(de)(de)(de)(de)(de)是(shi)同時在(zai)(zai)兩個(ge)或(huo)(huo)更(geng)多(duo)個(ge)位(wei)置處(chu)鍵合金(jin)(jin)屬(shu)離子(zi)的(de)(de)(de)(de)(de)配(pei)(pei)(pei)(pei)位(wei)體(ti)(ti)。在(zai)(zai)一些實施例(li)中(zhong)(zhong),配(pei)(pei)(pei)(pei)位(wei)體(ti)(ti)可(ke)以(yi)是(shi)含有(you)(you)c原(yuan)(yuan)子(zi)、h原(yuan)(yuan)子(zi)、n原(yuan)(yuan)子(zi)和/或(huo)(huo)o原(yuan)(yuan)子(zi)的(de)(de)(de)(de)(de)有(you)(you)機化(hua)(hua)合物(wu)。在(zai)(zai)一些實施例(li)中(zhong)(zhong),配(pei)(pei)(pei)(pei)位(wei)化(hua)(hua)合物(wu)可(ke)以(yi)包(bao)括至少一種配(pei)(pei)(pei)(pei)位(wei)體(ti)(ti),其不是(shi)水、氫(qing)氧化(hua)(hua)物(wu)或(huo)(huo)鹵化(hua)(hua)物(wu)。將(jiang)在(zai)(zai)下(xia)(xia)面(mian)進一步詳細討論可(ke)以(yi)存在(zai)(zai)于(yu)本公開(kai)的(de)(de)(de)(de)(de)配(pei)(pei)(pei)(pei)位(wei)化(hua)(hua)合物(wu)中(zhong)(zhong)的(de)(de)(de)(de)(de)其它說(shuo)明性(xing)配(pei)(pei)(pei)(pei)位(wei)體(ti)(ti)。配(pei)(pei)(pei)(pei)位(wei)體(ti)(ti)的(de)(de)(de)(de)(de)化(hua)(hua)學(xue)性(xing)質(zhi)可(ke)以(yi)改(gai)(gai)變連接的(de)(de)(de)(de)(de)金(jin)(jin)屬(shu)離子(zi)的(de)(de)(de)(de)(de)氧化(hua)(hua)還原(yuan)(yuan)電位(wei),從而能夠在(zai)(zai)含有(you)(you)配(pei)(pei)(pei)(pei)位(wei)化(hua)(hua)合物(wu)的(de)(de)(de)(de)(de)電解(jie)質(zhi)溶液的(de)(de)(de)(de)(de)工作(zuo)特(te)性(xing)中(zhong)(zhong)實現一定程度(du)(du)的(de)(de)(de)(de)(de)修(xiu)整(zheng)。與(yu)非(fei)連接的(de)(de)(de)(de)(de)金(jin)(jin)屬(shu)離子(zi)相比(bi),配(pei)(pei)(pei)(pei)位(wei)化(hua)(hua)合物(wu)也可(ke)以(yi)具有(you)(you)改(gai)(gai)變的(de)(de)(de)(de)(de)溶解(jie)度(du)(du)分布(例(li)如(ru)(ru),在(zai)(zai)不同ph值(zhi)下(xia)(xia)的(de)(de)(de)(de)(de)溶解(jie)度(du)(du)和/或(huo)(huo)在(zai)(zai)有(you)(you)機溶劑中(zhong)(zhong)的(de)(de)(de)(de)(de)溶解(jie)度(du)(du))。
通常,根據本公開可以分(fen)析在(zai)任(ren)何類(lei)型的(de)電(dian)化學系統(tong)內的(de)電(dian)解質溶液(ye)。例如,說明性(xing)電(dian)化學系統(tong)可以包括傳統(tong)電(dian)池(chi)(chi)、液(ye)流(liu)電(dian)池(chi)(chi)、超級電(dian)容器、燃(ran)料電(dian)池(chi)(chi)等。在(zai)下文中(zhong)更詳細(xi)地描述(shu)用(yong)于說明性(xing)液(ye)流(liu)電(dian)池(chi)(chi)的(de)特定配置(zhi)(參見圖2)。雖然液(ye)流(liu)電(dian)池(chi)(chi)已(yi)經被描述(shu)為其中(zhong)atr光譜法可以用(yong)于進行(xing)電(dian)解質溶液(ye)分(fen)析的(de)特定的(de)電(dian)化學系統(tong),但是應當認識(shi)到(dao)的(de)是,可以類(lei)似地分(fen)析其它類(lei)型的(de)電(dian)化學系統(tong)中(zhong)的(de)電(dian)解質溶液(ye)。
應當進一(yi)步認(ren)(ren)識到的(de)(de)是,在本(ben)文中(zhong)(zhong)描述(shu)的(de)(de)某些(xie)部分僅被明(ming)確(que)地描述(shu)為涉及(ji)用于分析電(dian)化(hua)(hua)學(xue)系統(tong)(tong)的(de)(de)一(yi)個半電(dian)池的(de)(de)電(dian)解(jie)質(zhi)(zhi)(zhi)溶(rong)(rong)(rong)液(ye)(ye)(即(ji),含(han)有(you)(you)第(di)一(yi)配(pei)位化(hua)(hua)合物(wu)的(de)(de)第(di)一(yi)電(dian)解(jie)質(zhi)(zhi)(zhi)溶(rong)(rong)(rong)液(ye)(ye))的(de)(de)機(ji)構(gou)和方法。然而(er),應當認(ren)(ren)識到的(de)(de)是,如果(guo)需要,可(ke)(ke)以(yi)獨立于其它(ta)電(dian)解(jie)質(zhi)(zhi)(zhi)溶(rong)(rong)(rong)液(ye)(ye)來(lai)分析用于電(dian)化(hua)(hua)學(xue)系統(tong)(tong)的(de)(de)另(ling)一(yi)半電(dian)池的(de)(de)電(dian)解(jie)質(zhi)(zhi)(zhi)溶(rong)(rong)(rong)液(ye)(ye)(即(ji),含(han)有(you)(you)第(di)二(er)配(pei)位化(hua)(hua)合物(wu)的(de)(de)第(di)二(er)電(dian)解(jie)質(zhi)(zhi)(zhi)溶(rong)(rong)(rong)液(ye)(ye))。即(ji),如果(guo)需要,可(ke)(ke)以(yi)分析電(dian)化(hua)(hua)學(xue)系統(tong)(tong)的(de)(de)第(di)一(yi)電(dian)解(jie)質(zhi)(zhi)(zhi)溶(rong)(rong)(rong)液(ye)(ye)和第(di)二(er)電(dian)解(jie)質(zhi)(zhi)(zhi)溶(rong)(rong)(rong)液(ye)(ye)兩(liang)者(zhe),其中(zhong)(zhong)通過本(ben)文所述(shu)的(de)(de)atr光(guang)譜(pu)技術(shu)來(lai)分析第(di)一(yi)電(dian)解(jie)質(zhi)(zhi)(zhi)溶(rong)(rong)(rong)液(ye)(ye)和第(di)二(er)電(dian)解(jie)質(zhi)(zhi)(zhi)溶(rong)(rong)(rong)液(ye)(ye)中(zhong)(zhong)的(de)(de)至少一(yi)個。在一(yi)些(xie)實施例(li)中(zhong)(zhong),可(ke)(ke)以(yi)通過本(ben)文所述(shu)的(de)(de)atr光(guang)譜(pu)技術(shu)來(lai)分析第(di)一(yi)電(dian)解(jie)質(zhi)(zhi)(zhi)溶(rong)(rong)(rong)液(ye)(ye)和第(di)二(er)電(dian)解(jie)質(zhi)(zhi)(zhi)溶(rong)(rong)(rong)液(ye)(ye)兩(liang)者(zhe)。
圖(tu)1示出包(bao)(bao)含(han)探(tan)針(zhen)的(de)(de)(de)電(dian)解(jie)質(zhi)(zhi)溶(rong)液(ye)的(de)(de)(de)說明性示意(yi)圖(tu),其(qi)中(zhong)探(tan)針(zhen)含(han)有被配置用于衰(shuai)減(jian)全反射率的(de)(de)(de)光學材(cai)料(liao)。如(ru)圖(tu)1所示,電(dian)解(jie)質(zhi)(zhi)溶(rong)液(ye)1被包(bao)(bao)含(han)在(zai)殼(ke)體(ti)2中(zhong)。雖然在(zai)圖(tu)1中(zhong)殼(ke)體(ti)2被示出為(wei)敞開(kai)的(de)(de)(de)容器(qi),但是(shi)其(qi)也(ye)可以是(shi)關閉的(de)(de)(de)。探(tan)針(zhen)3包(bao)(bao)含(han)探(tan)針(zhen)主體(ti)4和光學材(cai)料(liao)5。探(tan)針(zhen)主體(ti)4和光學材(cai)料(liao)5與(yu)源和檢測(ce)器(qi)光學連通,使得電(dian)磁輻射6a可以與(yu)電(dian)解(jie)質(zhi)(zhi)溶(rong)液(ye)1相互作用,并(bing)且改變的(de)(de)(de)電(dian)磁輻射6b可以返回(hui)到(dao)檢測(ce)器(qi)。光學材(cai)料(liao)5是(shi)在(zai)其(qi)與(yu)電(dian)解(jie)質(zhi)(zhi)溶(rong)液(ye)1的(de)(de)(de)界面處可以呈現衰(shuai)減(jian)全反射率的(de)(de)(de)物質(zhi)(zhi)。下(xia)面更詳細地(di)討(tao)論用于選擇光學材(cai)料(liao)5的(de)(de)(de)考慮事項(xiang)。
如(ru)(ru)圖1所示,在(zai)電(dian)磁輻(fu)射(she)6b返回到(dao)檢測器以用(yong)于分析之前(qian),在(zai)光(guang)學材料5內發生(sheng)三個(ge)(ge)點的(de)(de)(de)(de)(de)內反射(she)(7a、7b和7c)。在(zai)每(mei)次(ci)內反射(she)處,漸(jian)逝(shi)波(bo)在(zai)被反射(she)到(dao)后續(xu)反射(she)點之前(qian),少(shao)量(liang)滲透到(dao)電(dian)解質(zhi)(zhi)溶液1中并且與活(huo)性物質(zhi)(zhi)的(de)(de)(de)(de)(de)還(huan)原形式和/或(huo)氧化形式進行光(guang)學相互作用(yong)。這導(dao)致用(yong)于光(guang)學相互作用(yong)的(de)(de)(de)(de)(de)非常短的(de)(de)(de)(de)(de)有(you)效(xiao)路(lu)徑(jing)長度(du)(例如(ru)(ru),約0.05微(wei)米至約2微(wei)米),其(qi)比傳(chuan)輸(shu)配置短得多。隨著(zhu)每(mei)個(ge)(ge)后續(xu)的(de)(de)(de)(de)(de)反射(she),有(you)效(xiao)路(lu)徑(jing)長度(du)增加(jia)。因此,可(ke)以改變內反射(she)的(de)(de)(de)(de)(de)數(shu)量(liang)以產生(sheng)足以提供良好的(de)(de)(de)(de)(de)檢測信噪比但不使(shi)檢測器飽和的(de)(de)(de)(de)(de)有(you)效(xiao)路(lu)徑(jing)長度(du)。例如(ru)(ru),可(ke)以基于電(dian)解質(zhi)(zhi)溶液2中的(de)(de)(de)(de)(de)活(huo)性物質(zhi)(zhi)的(de)(de)(de)(de)(de)摩爾吸光(guang)系數(shu)常數(shu)及其(qi)濃度(du)來選擇內反射(she)的(de)(de)(de)(de)(de)數(shu)量(liang)。光(guang)學材料5的(de)(de)(de)(de)(de)幾何(he)形狀可(ke)以提供寬范圍的(de)(de)(de)(de)(de)內反射(she),但是(shi)1個(ge)(ge)至約6個(ge)(ge)內反射(she)是(shi)常見的(de)(de)(de)(de)(de)。因此,圖1中描述的(de)(de)(de)(de)(de)三個(ge)(ge)反射(she)不應(ying)被視(shi)為(wei)限(xian)制。
如(ru)(ru)(ru)以(yi)(yi)(yi)上(shang)所(suo)示,能夠(gou)(gou)衰(shuai)(shuai)(shuai)減(jian)(jian)全反(fan)(fan)(fan)射(she)(she)(she)(she)率(lv)(lv)(即內反(fan)(fan)(fan)射(she)(she)(she)(she))的(de)(de)(de)(de)(de)光(guang)(guang)(guang)(guang)學(xue)材(cai)料(liao)與(yu)第(di)一電(dian)解質溶液(ye)(ye)(ye)接觸以(yi)(yi)(yi)確定第(di)一電(dian)解質溶液(ye)(ye)(ye)的(de)(de)(de)(de)(de)狀態,諸如(ru)(ru)(ru)第(di)一電(dian)解質溶液(ye)(ye)(ye)的(de)(de)(de)(de)(de)荷電(dian)狀態。假設滿足發(fa)(fa)生衰(shuai)(shuai)(shuai)減(jian)(jian)全反(fan)(fan)(fan)射(she)(she)(she)(she)率(lv)(lv)的(de)(de)(de)(de)(de)其(qi)它(ta)條(tiao)件,則為了發(fa)(fa)生內反(fan)(fan)(fan)射(she)(she)(she)(she),光(guang)(guang)(guang)(guang)學(xue)材(cai)料(liao)具(ju)有(you)高于第(di)一電(dian)解質溶液(ye)(ye)(ye)的(de)(de)(de)(de)(de)折射(she)(she)(she)(she)率(lv)(lv)。否則,穿過光(guang)(guang)(guang)(guang)學(xue)材(cai)料(liao)的(de)(de)(de)(de)(de)電(dian)磁輻(fu)射(she)(she)(she)(she)會逃逸到第(di)一電(dian)解質溶液(ye)(ye)(ye)中,并(bing)且(qie)不會發(fa)(fa)生呈漸逝波形式的(de)(de)(de)(de)(de)內反(fan)(fan)(fan)射(she)(she)(she)(she)。在(zai)更具(ju)體的(de)(de)(de)(de)(de)實施例(li)(li)中,能夠(gou)(gou)內反(fan)(fan)(fan)射(she)(she)(she)(she)的(de)(de)(de)(de)(de)光(guang)(guang)(guang)(guang)學(xue)材(cai)料(liao)可(ke)(ke)(ke)具(ju)有(you)大(da)于約(yue)1.3的(de)(de)(de)(de)(de)折射(she)(she)(she)(she)率(lv)(lv)。更典型地,光(guang)(guang)(guang)(guang)學(xue)材(cai)料(liao)可(ke)(ke)(ke)以(yi)(yi)(yi)具(ju)有(you)在(zai)約(yue)1.3和(he)(he)(he)約(yue)6之間(jian)變化(hua)的(de)(de)(de)(de)(de)折射(she)(she)(she)(she)率(lv)(lv),甚至更典型地在(zai)約(yue)1.5和(he)(he)(he)約(yue)2.5之間(jian)變化(hua)的(de)(de)(de)(de)(de)折射(she)(she)(she)(she)率(lv)(lv)。用(yong)(yong)于本(ben)公開的(de)(de)(de)(de)(de)各(ge)種實施例(li)(li)的(de)(de)(de)(de)(de)合(he)適的(de)(de)(de)(de)(de)光(guang)(guang)(guang)(guang)學(xue)材(cai)料(liao)(n=折射(she)(she)(she)(she)率(lv)(lv))可(ke)(ke)(ke)以(yi)(yi)(yi)包(bao)括,例(li)(li)如(ru)(ru)(ru),藍(lan)寶石(shi)(n=1.77)、鍺(n=4.05)、硅(n=3.48)、熔融二氧(yang)化(hua)硅(n=1.46)、石(shi)英(n=1.54)、立方氧(yang)化(hua)鋯(gao)(n=2.11)、硒化(hua)鋅(n≥2.4)、金剛(gang)石(shi)(n=2.41)及其(qi)任何組合(he)。這些光(guang)(guang)(guang)(guang)學(xue)材(cai)料(liao)和(he)(he)(he)具(ju)有(you)高折射(she)(she)(she)(she)率(lv)(lv)的(de)(de)(de)(de)(de)其(qi)它(ta)物(wu)質可(ke)(ke)(ke)以(yi)(yi)(yi)特(te)別適于促進水(shui)溶液(ye)(ye)(ye)的(de)(de)(de)(de)(de)衰(shuai)(shuai)(shuai)減(jian)(jian)全反(fan)(fan)(fan)射(she)(she)(she)(she)率(lv)(lv)測量。除了鍺和(he)(he)(he)硅之外,上(shang)述(shu)光(guang)(guang)(guang)(guang)學(xue)材(cai)料(liao)可(ke)(ke)(ke)以(yi)(yi)(yi)在(zai)電(dian)磁光(guang)(guang)(guang)(guang)譜的(de)(de)(de)(de)(de)紫外線區(qu)域(yu)和(he)(he)(he)可(ke)(ke)(ke)見光(guang)(guang)(guang)(guang)區(qu)域(yu)中特(te)別有(you)用(yong)(yong)。通常,光(guang)(guang)(guang)(guang)學(xue)材(cai)料(liao)為進入的(de)(de)(de)(de)(de)電(dian)磁輻(fu)射(she)(she)(she)(she)和(he)(he)(he)出去的(de)(de)(de)(de)(de)電(dian)磁輻(fu)射(she)(she)(she)(she)提(ti)供光(guang)(guang)(guang)(guang)學(xue)透(tou)明度。在(zai)各(ge)種實施例(li)(li)中,能夠(gou)(gou)衰(shuai)(shuai)(shuai)減(jian)(jian)全反(fan)(fan)(fan)射(she)(she)(she)(she)率(lv)(lv)的(de)(de)(de)(de)(de)光(guang)(guang)(guang)(guang)學(xue)材(cai)料(liao)可(ke)(ke)(ke)以(yi)(yi)(yi)是晶體材(cai)料(liao)。在(zai)各(ge)種實施例(li)(li)中,晶體材(cai)料(liao)可(ke)(ke)(ke)以(yi)(yi)(yi)是單晶的(de)(de)(de)(de)(de)或多晶的(de)(de)(de)(de)(de)。
在(zai)各種實(shi)施(shi)例(li)中(zhong)(zhong),光(guang)學(xue)材(cai)料(liao)可(ke)(ke)(ke)以(yi)(yi)是棱鏡形式,其可(ke)(ke)(ke)以(yi)(yi)在(zai)電(dian)磁輻射返回到檢測器之前促進在(zai)與第一(yi)電(dian)解質溶液(ye)的界面處的至少一(yi)個(ge)內反(fan)(fan)射。在(zai)更特(te)定的實(shi)施(shi)例(li)中(zhong)(zhong),光(guang)學(xue)材(cai)料(liao)可(ke)(ke)(ke)被配置為(wei)在(zai)與第一(yi)電(dian)解質溶液(ye)的界面處提(ti)(ti)供在(zai)1個(ge)和約6個(ge)之間的衰(shuai)減(jian)全(quan)反(fan)(fan)射率。在(zai)一(yi)些實(shi)施(shi)例(li)中(zhong)(zhong),光(guang)學(xue)材(cai)料(liao)可(ke)(ke)(ke)以(yi)(yi)是錐形幾何(he)形狀(zhuang),其可(ke)(ke)(ke)以(yi)(yi)提(ti)(ti)供2個(ge)衰(shuai)減(jian)全(quan)反(fan)(fan)射。配置為(wei)提(ti)(ti)供在(zai)該范圍內的數(shu)量的衰(shuai)減(jian)全(quan)反(fan)(fan)射的光(guang)學(xue)材(cai)料(liao)可(ke)(ke)(ke)以(yi)(yi)從若干商業來(lai)源獲得。
入(ru)(ru)射(she)電磁(ci)輻(fu)射(she)(即,從源接收的電磁(ci)輻(fu)射(she))的入(ru)(ru)射(she)角(jiao)也可以指示(shi)衰(shuai)減全(quan)反射(she)率(lv)(lv)是否發生在(zai)光學(xue)材料內。低于其會發生衰(shuai)減全(quan)反射(she)率(lv)(lv)的入(ru)(ru)射(she)角(jiao)被稱為“臨(lin)界角(jiao)”。本領域普通(tong)技術人(ren)員(yuan)將能夠(gou)確定入(ru)(ru)射(she)角(jiao)的范圍,在(zai)該范圍內能夠(gou)針對(dui)被配置為提供給(gei)定數量的內反射(she)的特定光學(xue)材料幾何形狀發生衰(shuai)減全(quan)反射(she)率(lv)(lv)。
如上所述,在(zai)光學材料內部內反(fan)射(she)的(de)(de)電(dian)(dian)(dian)(dian)磁(ci)輻射(she)可以建立漸逝波(bo)(bo),該漸逝波(bo)(bo)少(shao)量地滲透到(dao)第一電(dian)(dian)(dian)(dian)解(jie)質溶(rong)液(ye)(ye)中并且在(zai)一個點或(huo)多(duo)個點處(chu)(chu)與(yu)電(dian)(dian)(dian)(dian)解(jie)質溶(rong)液(ye)(ye)相互(hu)作(zuo)用(yong)。在(zai)一些實(shi)施(shi)例(li)中,漸逝波(bo)(bo)可以呈現(xian)在(zai)約0.05微(wei)米(mi)和約2微(wei)米(mi)之間的(de)(de)范圍內的(de)(de)滲透到(dao)第一電(dian)(dian)(dian)(dian)解(jie)質溶(rong)液(ye)(ye)中的(de)(de)深(shen)度。滲透深(shen)度代(dai)表每個反(fan)射(she)點處(chu)(chu)的(de)(de)有效路徑長度。實(shi)際的(de)(de)滲透深(shen)度將取決于(yu)許多(duo)因素,其包(bao)括(kuo)例(li)如入射(she)角、光學材料的(de)(de)折射(she)率(lv)、第一電(dian)(dian)(dian)(dian)解(jie)質溶(rong)液(ye)(ye)的(de)(de)折射(she)率(lv)和入射(she)的(de)(de)電(dian)(dian)(dian)(dian)磁(ci)輻射(she)的(de)(de)波(bo)(bo)長。
在各種實(shi)施例(li)(li)(li)中,第一電解質溶(rong)(rong)(rong)液(ye)可以(yi)是水(shui)(shui)(shui)(shui)(shui)(shui)(shui)溶(rong)(rong)(rong)液(ye)。如(ru)本文所使用的(de)(de),術語“水(shui)(shui)(shui)(shui)(shui)(shui)(shui)溶(rong)(rong)(rong)液(ye)”或(huo)(huo)(huo)(huo)“含水(shui)(shui)(shui)(shui)(shui)(shui)(shui)電解液(ye)”將指(zhi)的(de)(de)是其中水(shui)(shui)(shui)(shui)(shui)(shui)(shui)是主要成(cheng)分的(de)(de)任何溶(rong)(rong)(rong)液(ye),包括含有(you)(you)(you)水(shui)(shui)(shui)(shui)(shui)(shui)(shui)溶(rong)(rong)(rong)性有(you)(you)(you)機(ji)(ji)溶(rong)(rong)(rong)劑(ji)作為少(shao)(shao)(shao)(shao)數成(cheng)分的(de)(de)溶(rong)(rong)(rong)液(ye)。例(li)(li)(li)如(ru),可以(yi)存在于含水(shui)(shui)(shui)(shui)(shui)(shui)(shui)電解液(ye)中的(de)(de)說(shuo)明性水(shui)(shui)(shui)(shui)(shui)(shui)(shui)溶(rong)(rong)(rong)性有(you)(you)(you)機(ji)(ji)溶(rong)(rong)(rong)劑(ji)包括任選地在一種或(huo)(huo)(huo)(huo)多(duo)種表面(mian)活(huo)性劑(ji)的(de)(de)存在下的(de)(de)醇(chun)(chun)和(he)二醇(chun)(chun)。在更具體的(de)(de)實(shi)施例(li)(li)(li)中,水(shui)(shui)(shui)(shui)(shui)(shui)(shui)溶(rong)(rong)(rong)液(ye)可以(yi)含有(you)(you)(you)以(yi)重(zhong)(zhong)(zhong)量(liang)(liang)(liang)(liang)(liang)(liang)計(ji)至(zhi)(zhi)少(shao)(shao)(shao)(shao)約(yue)(yue)98%的(de)(de)水(shui)(shui)(shui)(shui)(shui)(shui)(shui)。在其它實(shi)施例(li)(li)(li)中,水(shui)(shui)(shui)(shui)(shui)(shui)(shui)溶(rong)(rong)(rong)液(ye)可以(yi)含有(you)(you)(you)以(yi)重(zhong)(zhong)(zhong)量(liang)(liang)(liang)(liang)(liang)(liang)計(ji)至(zhi)(zhi)少(shao)(shao)(shao)(shao)約(yue)(yue)40%的(de)(de)水(shui)(shui)(shui)(shui)(shui)(shui)(shui)、或(huo)(huo)(huo)(huo)以(yi)重(zhong)(zhong)(zhong)量(liang)(liang)(liang)(liang)(liang)(liang)計(ji)至(zhi)(zhi)少(shao)(shao)(shao)(shao)約(yue)(yue)45%的(de)(de)水(shui)(shui)(shui)(shui)(shui)(shui)(shui)、或(huo)(huo)(huo)(huo)以(yi)重(zhong)(zhong)(zhong)量(liang)(liang)(liang)(liang)(liang)(liang)計(ji)至(zhi)(zhi)少(shao)(shao)(shao)(shao)約(yue)(yue)50%的(de)(de)水(shui)(shui)(shui)(shui)(shui)(shui)(shui)、或(huo)(huo)(huo)(huo)以(yi)重(zhong)(zhong)(zhong)量(liang)(liang)(liang)(liang)(liang)(liang)計(ji)至(zhi)(zhi)少(shao)(shao)(shao)(shao)約(yue)(yue)55%的(de)(de)水(shui)(shui)(shui)(shui)(shui)(shui)(shui)、或(huo)(huo)(huo)(huo)以(yi)重(zhong)(zhong)(zhong)量(liang)(liang)(liang)(liang)(liang)(liang)計(ji)至(zhi)(zhi)少(shao)(shao)(shao)(shao)約(yue)(yue)60%的(de)(de)水(shui)(shui)(shui)(shui)(shui)(shui)(shui)、或(huo)(huo)(huo)(huo)以(yi)重(zhong)(zhong)(zhong)量(liang)(liang)(liang)(liang)(liang)(liang)計(ji)至(zhi)(zhi)少(shao)(shao)(shao)(shao)約(yue)(yue)65%的(de)(de)水(shui)(shui)(shui)(shui)(shui)(shui)(shui)、或(huo)(huo)(huo)(huo)以(yi)重(zhong)(zhong)(zhong)量(liang)(liang)(liang)(liang)(liang)(liang)計(ji)至(zhi)(zhi)少(shao)(shao)(shao)(shao)約(yue)(yue)70%的(de)(de)水(shui)(shui)(shui)(shui)(shui)(shui)(shui)、或(huo)(huo)(huo)(huo)以(yi)重(zhong)(zhong)(zhong)量(liang)(liang)(liang)(liang)(liang)(liang)計(ji)至(zhi)(zhi)少(shao)(shao)(shao)(shao)約(yue)(yue)75%的(de)(de)水(shui)(shui)(shui)(shui)(shui)(shui)(shui)、或(huo)(huo)(huo)(huo)以(yi)重(zhong)(zhong)(zhong)量(liang)(liang)(liang)(liang)(liang)(liang)計(ji)至(zhi)(zhi)少(shao)(shao)(shao)(shao)約(yue)(yue)80%的(de)(de)水(shui)(shui)(shui)(shui)(shui)(shui)(shui)、或(huo)(huo)(huo)(huo)以(yi)重(zhong)(zhong)(zhong)量(liang)(liang)(liang)(liang)(liang)(liang)計(ji)至(zhi)(zhi)少(shao)(shao)(shao)(shao)約(yue)(yue)85%的(de)(de)水(shui)(shui)(shui)(shui)(shui)(shui)(shui)、或(huo)(huo)(huo)(huo)以(yi)重(zhong)(zhong)(zhong)量(liang)(liang)(liang)(liang)(liang)(liang)計(ji)至(zhi)(zhi)少(shao)(shao)(shao)(shao)約(yue)(yue)90%的(de)(de)水(shui)(shui)(shui)(shui)(shui)(shui)(shui)、或(huo)(huo)(huo)(huo)以(yi)重(zhong)(zhong)(zhong)量(liang)(liang)(liang)(liang)(liang)(liang)計(ji)至(zhi)(zhi)少(shao)(shao)(shao)(shao)約(yue)(yue)95%的(de)(de)水(shui)(shui)(shui)(shui)(shui)(shui)(shui)。在一些實(shi)施例(li)(li)(li)中,水(shui)(shui)(shui)(shui)(shui)(shui)(shui)溶(rong)(rong)(rong)液(ye)可以(yi)不(bu)含有(you)(you)(you)水(shui)(shui)(shui)(shui)(shui)(shui)(shui)溶(rong)(rong)(rong)性有(you)(you)(you)機(ji)(ji)溶(rong)(rong)(rong)劑(ji),而是由水(shui)(shui)(shui)(shui)(shui)(shui)(shui)單(dan)獨作為溶(rong)(rong)(rong)劑(ji)。
在其它各種(zhong)實施例(li)中,第一電(dian)解(jie)質(zhi)溶液可以(yi)是非水性的(de)并且包括(kuo)有(you)機(ji)(ji)溶劑。通常,在電(dian)化學(xue)系統的(de)操(cao)作條件下電(dian)化學(xue)穩定的(de)任何有(you)機(ji)(ji)溶劑可用于溶解(jie)活性物質(zhi)。
在各種(zhong)(zhong)實施(shi)例中(zhong),存(cun)在于(yu)第(di)一電解質溶液中(zhong)的(de)(de)(de)第(di)一配(pei)(pei)(pei)位(wei)化合物可(ke)(ke)(ke)以(yi)包(bao)(bao)括(kuo)至(zhi)少一種(zhong)(zhong)過渡(du)金屬離子(zi)和至(zhi)少一種(zhong)(zhong)配(pei)(pei)(pei)位(wei)體(ti)。可(ke)(ke)(ke)以(yi)存(cun)在于(yu)配(pei)(pei)(pei)位(wei)化合物中(zhong)的(de)(de)(de)說明性配(pei)(pei)(pei)位(wei)體(ti)包(bao)(bao)括(kuo),例如(ru),取代或(huo)(huo)未取代的(de)(de)(de)兒茶酚酶、抗壞血酸(suan)(suan)(suan)(suan)(suan)鹽(yan)、檸檬酸(suan)(suan)(suan)(suan)(suan)鹽(yan)、乙(yi)醇(chun)酸(suan)(suan)(suan)(suan)(suan)、多(duo)元醇(chun)、葡糖酸(suan)(suan)(suan)(suan)(suan)鹽(yan)、羥(qian)基(ji)鏈(lian)烷(wan)酸(suan)(suan)(suan)(suan)(suan)酯鹽(yan)、乙(yi)酸(suan)(suan)(suan)(suan)(suan)鹽(yan)、甲(jia)酸(suan)(suan)(suan)(suan)(suan)鹽(yan)、苯甲(jia)酸(suan)(suan)(suan)(suan)(suan)鹽(yan)、蘋果酸(suan)(suan)(suan)(suan)(suan)鹽(yan)、馬來(lai)酸(suan)(suan)(suan)(suan)(suan)鹽(yan)、鄰(lin)苯二(er)(er)甲(jia)酸(suan)(suan)(suan)(suan)(suan)鹽(yan)、肌氨酸(suan)(suan)(suan)(suan)(suan)鹽(yan)、水(shui)楊酸(suan)(suan)(suan)(suan)(suan)鹽(yan)、草酸(suan)(suan)(suan)(suan)(suan)鹽(yan)、脲、聚胺(an)、氨基(ji)苯酚、乙(yi)酰丙(bing)酮(tong)以(yi)及乳酸(suan)(suan)(suan)(suan)(suan)。在化學上(shang)可(ke)(ke)(ke)行的(de)(de)(de)情況下(xia),應當認識(shi)到的(de)(de)(de)是,這(zhe)些配(pei)(pei)(pei)位(wei)體(ti)可(ke)(ke)(ke)以(yi)被從以(yi)下(xia)之中(zhong)選(xuan)擇(ze)的(de)(de)(de)至(zhi)少一個基(ji)團任意地取代:c1-6烷(wan)氧基(ji)、c1-6烷(wan)基(ji)、c1-6烯基(ji)、c1-6炔基(ji)、5-或(huo)(huo)6-元芳基(ji)或(huo)(huo)雜芳基(ji)、硼酸(suan)(suan)(suan)(suan)(suan)或(huo)(huo)其(qi)(qi)衍(yan)生物、羧酸(suan)(suan)(suan)(suan)(suan)或(huo)(huo)其(qi)(qi)衍(yan)生物、氰基(ji)、鹵化物、羥(qian)基(ji)、硝(xiao)基(ji)、磺酸(suan)(suan)(suan)(suan)(suan)酯、磺酸(suan)(suan)(suan)(suan)(suan)或(huo)(huo)其(qi)(qi)衍(yan)生物、膦酸(suan)(suan)(suan)(suan)(suan)酯、膦酸(suan)(suan)(suan)(suan)(suan)或(huo)(huo)其(qi)(qi)衍(yan)生物、或(huo)(huo)諸如(ru)聚乙(yi)二(er)(er)醇(chun)的(de)(de)(de)乙(yi)二(er)(er)醇(chun)。鏈(lian)烷(wan)酸(suan)(suan)(suan)(suan)(suan)酯鹽(yan)包(bao)(bao)括(kuo)這(zhe)些配(pei)(pei)(pei)位(wei)體(ti)的(de)(de)(de)任何(he)α、β和γ形式。聚胺(an)包(bao)(bao)括(kuo)但不限于(yu)乙(yi)二(er)(er)胺(an)、乙(yi)二(er)(er)胺(an)四(si)乙(yi)酸(suan)(suan)(suan)(suan)(suan)(edta)和二(er)(er)亞乙(yi)基(ji)三胺(an)五乙(yi)酸(suan)(suan)(suan)(suan)(suan)(dtpa)。
在(zai)一(yi)些或(huo)其它各(ge)種(zhong)實施例(li)(li)中,可(ke)(ke)存(cun)在(zai)于第(di)(di)(di)一(yi)電(dian)解(jie)質(zhi)(zhi)溶(rong)(rong)液的(de)(de)第(di)(di)(di)一(yi)配(pei)(pei)位(wei)化(hua)(hua)合物(wu)中的(de)(de)單(dan)齒配(pei)(pei)位(wei)體包(bao)括(kuo)(kuo),例(li)(li)如(ru),鹵(lu)化(hua)(hua)物(wu)、氰化(hua)(hua)物(wu)、羰基或(huo)一(yi)氧化(hua)(hua)碳、氮化(hua)(hua)物(wu)、含氧化(hua)(hua)合物(wu)(oxo)、羥基、水、硫化(hua)(hua)物(wu)、硫醇(chun)、吡(bi)啶(ding)、吡(bi)嗪等(deng)。可(ke)(ke)以(yi)存(cun)在(zai)于第(di)(di)(di)一(yi)電(dian)解(jie)質(zhi)(zhi)溶(rong)(rong)液的(de)(de)第(di)(di)(di)一(yi)配(pei)(pei)位(wei)化(hua)(hua)合物(wu)中的(de)(de)二齒配(pei)(pei)位(wei)體的(de)(de)其它示(shi)例(li)(li)包(bao)括(kuo)(kuo),例(li)(li)如(ru),二吡(bi)啶(ding)、聯(lian)吡(bi)嗪(bipyrazine)、乙二胺、二醇(chun)(包(bao)括(kuo)(kuo)乙二醇(chun))等(deng)。可(ke)(ke)以(yi)任選地存(cun)在(zai)于第(di)(di)(di)一(yi)電(dian)解(jie)質(zhi)(zhi)溶(rong)(rong)液的(de)(de)第(di)(di)(di)一(yi)配(pei)(pei)位(wei)化(hua)(hua)合物(wu)中的(de)(de)三(san)齒配(pei)(pei)位(wei)體的(de)(de)其它示(shi)例(li)(li)包(bao)括(kuo)(kuo),例(li)(li)如(ru),三(san)聯(lian)吡(bi)啶(ding)、二亞乙基三(san)胺、三(san)氮雜(za)環壬烷、三(san)(羥甲基)氨基甲烷等(deng)。其它可(ke)(ke)接受的(de)(de)配(pei)(pei)位(wei)體可(ke)(ke)包(bao)括(kuo)(kuo)醌(kun)、氫醌(kun)、紫精、吖啶(ding)酯、多環芳(fang)烴及(ji)其組(zu)合。
在(zai)更具體的(de)實施例中,存在(zai)于(yu)第一電(dian)解(jie)質溶液中的(de)第一配位化合物(wu)可以(yi)具有以(yi)下化學(xue)式
axm(l1)(l2)(l3),
其中m是過渡金屬,a是nh4+或四烷基銨(c1-c4烷基)、na+、k+或其(qi)任(ren)何組合,x是(shi)范圍(wei)在1和(he)6之間的(de)(de)(de)整數,并且l1、l2和(he)l3是(shi)可以獨立(li)地(di)選自上(shang)述列表的(de)(de)(de)配位體。在更(geng)具(ju)體的(de)(de)(de)實施(shi)例(li)中(zhong)(zhong),l1、l2和(he)l3中(zhong)(zhong)的(de)(de)(de)至(zhi)少一個可以是(shi)螯合配位體。在更(geng)具(ju)體的(de)(de)(de)實施(shi)例(li)中(zhong)(zhong),l1、l2和(he)l3中(zhong)(zhong)的(de)(de)(de)至(zhi)少一個可以是(shi)兒(er)茶(cha)酚酶或取代的(de)(de)(de)兒(er)茶(cha)酚酶配位體。
由于(yu)過(guo)(guo)渡(du)金(jin)(jin)屬(shu)(shu)(shu)的(de)可(ke)變氧(yang)化(hua)態,在(zai)(zai)液(ye)流電(dian)(dian)池的(de)各(ge)種(zhong)實(shi)施例中(zhong),其可(ke)以(yi)構成(cheng)正(zheng)極活(huo)性物質(zhi)和/或負極活(huo)性物質(zhi)。可(ke)用的(de)氧(yang)化(hua)態之間(jian)的(de)循環可(ke)導致(zhi)化(hua)學能轉化(hua)為(wei)電(dian)(dian)能。在(zai)(zai)這(zhe)方面,鑭(lan)系元素可(ke)以(yi)類似地使用。通常,任何過(guo)(guo)渡(du)金(jin)(jin)屬(shu)(shu)(shu)或鑭(lan)系金(jin)(jin)屬(shu)(shu)(shu)可(ke)以(yi)存在(zai)(zai)于(yu)第一電(dian)(dian)解(jie)質(zhi)溶液(ye)的(de)第一配(pei)位化(hua)合物中(zhong)。在(zai)(zai)一些實(shi)施例中(zhong),過(guo)(guo)渡(du)金(jin)(jin)屬(shu)(shu)(shu)可(ke)以(yi)從(cong)al、cr、ti和fe中(zhong)選擇。為(wei)了本公(gong)開(kai)的(de)目的(de),al將被考(kao)慮為(wei)過(guo)(guo)渡(du)金(jin)(jin)屬(shu)(shu)(shu)。在(zai)(zai)更具體(ti)的(de)實(shi)施例中(zhong),過(guo)(guo)渡(du)金(jin)(jin)屬(shu)(shu)(shu)可(ke)以(yi)是ti。可(ke)以(yi)存在(zai)(zai)于(yu)第一電(dian)(dian)解(jie)質(zhi)溶液(ye)的(de)第一配(pei)位化(hua)合物中(zhong)的(de)其它合適的(de)過(guo)(guo)渡(du)金(jin)(jin)屬(shu)(shu)(shu)和主族金(jin)(jin)屬(shu)(shu)(shu)包(bao)括,例如(ru),ca、ce、co、cu、mg、mn、mo、ni、pd、pt、ru、sr、sn、v、zn、zr及其任何組合。在(zai)(zai)各(ge)種(zhong)實(shi)施例中(zhong),當過(guo)(guo)渡(du)金(jin)(jin)屬(shu)(shu)(shu)處(chu)(chu)于(yu)其氧(yang)化(hua)形式(shi)和還(huan)原形式(shi)兩者時,第一配(pei)位化(hua)合物可(ke)以(yi)包(bao)括處(chu)(chu)于(yu)非(fei)零氧(yang)化(hua)態的(de)過(guo)(guo)渡(du)金(jin)(jin)屬(shu)(shu)(shu)。在(zai)(zai)這(zhe)方面,cr、fe、mn、ti和v可(ke)以(yi)是特別理想的(de)。
除了溶劑和作為活性物質的配位化合物之外,第一電解質溶液還可以包括一種或多種移動離子(mobileion)。在一些實施例中,移動離子可以包括質子、水合氫離子或氫氧化物。在其它各種實施例中,除質子、水合氫離子或氫氧化物以外的移動離子可以單獨存在或與質子、水合氫離子或氫氧化物組合存在。這樣的可選的移動離子可以包括,例如,堿金屬或堿土金屬陽離子(例如,li+、na+、k+、mg2+、ca2+和sr2+)以及鹵化物(例如,f-、cl-或br-)。其它移(yi)動離(li)子(zi)可以包括,例(li)如,銨和四烷基銨離(li)子(zi)、硫(liu)族(zu)化物、磷酸(suan)(suan)鹽、磷酸(suan)(suan)氫(qing)(qing)鹽、膦酸(suan)(suan)鹽、硝(xiao)酸(suan)(suan)鹽、硫(liu)酸(suan)(suan)鹽、亞硝(xiao)酸(suan)(suan)鹽、亞硫(liu)酸(suan)(suan)鹽、高(gao)氯酸(suan)(suan)鹽、四氟硼酸(suan)(suan)鹽、六氟磷酸(suan)(suan)鹽及其任何組(zu)合。在(zai)一(yi)些(xie)實(shi)施(shi)例(li)中(zhong),少(shao)于(yu)約(yue)(yue)50%的移(yi)動離(li)子(zi)可以構(gou)(gou)成(cheng)質子(zi)、水合氫(qing)(qing)離(li)子(zi)或氫(qing)(qing)氧化物。在(zai)其它各種實(shi)施(shi)例(li)中(zhong),少(shao)于(yu)約(yue)(yue)40%、少(shao)于(yu)約(yue)(yue)30%、少(shao)于(yu)約(yue)(yue)20%、少(shao)于(yu)約(yue)(yue)10%、少(shao)于(yu)約(yue)(yue)5%或少(shao)于(yu)約(yue)(yue)2%的移(yi)動離(li)子(zi)可以構(gou)(gou)成(cheng)質子(zi)、水合氫(qing)(qing)離(li)子(zi)或氫(qing)(qing)氧化物。
在進(jin)一步的(de)實施例(li)中,第一電解(jie)質溶液還可以包(bao)括一種(zhong)或(huo)多種(zhong)另外的(de)添加劑(ji),其(qi)諸如(ru)但不(bu)限于緩(huan)沖劑(ji)、支持電解(jie)質、粘度調節劑(ji)、潤(run)濕(shi)劑(ji)或(huo)其(qi)任何組(zu)合(he)。說明性緩(huan)沖劑(ji)可以包(bao)括但不(bu)限于磷(lin)酸鹽(yan)、硼酸鹽(yan)、碳(tan)酸鹽(yan)、硅酸鹽(yan)、三(羥甲基(ji))氨(an)基(ji)甲烷(tris)、4-(2-羥乙基(ji))-1-哌嗪乙磺酸(hepes)、哌嗪-n、n’-雙(乙磺酸)(pipes)或(huo)其(qi)任何組(zu)合(he)。合(he)適的(de)緩(huan)沖劑(ji)和其(qi)它(ta)(ta)另外的(de)添加劑(ji)的(de)其(qi)它(ta)(ta)示例(li)將是本領域普通技術人員熟悉(xi)的(de)。
在(zai)(zai)(zai)各種實施例(li)(li)中,第(di)(di)一(yi)電解質溶(rong)(rong)液中的第(di)(di)一(yi)配位(wei)化(hua)(hua)合(he)物(wu)的濃(nong)度(du)(du)可以(yi)在(zai)(zai)(zai)約(yue)(yue)0.1m和(he)(he)約(yue)(yue)3m之(zhi)(zhi)間(jian)(jian)變化(hua)(hua)。該濃(nong)度(du)(du)范圍表(biao)示第(di)(di)一(yi)配位(wei)化(hua)(hua)合(he)物(wu)的氧化(hua)(hua)形(xing)(xing)式和(he)(he)還(huan)原(yuan)形(xing)(xing)式的各自濃(nong)度(du)(du)的總和(he)(he)。在(zai)(zai)(zai)更具(ju)體的實施例(li)(li)中,第(di)(di)一(yi)配位(wei)化(hua)(hua)合(he)物(wu)的濃(nong)度(du)(du)可以(yi)在(zai)(zai)(zai)約(yue)(yue)0.5m和(he)(he)約(yue)(yue)3m之(zhi)(zhi)間(jian)(jian),或約(yue)(yue)1m和(he)(he)約(yue)(yue)3m之(zhi)(zhi)間(jian)(jian),或約(yue)(yue)1.5m和(he)(he)約(yue)(yue)3m之(zhi)(zhi)間(jian)(jian),或約(yue)(yue)1m和(he)(he)約(yue)(yue)2.5m之(zhi)(zhi)間(jian)(jian)變化(hua)(hua)。在(zai)(zai)(zai)其它更具(ju)體的實施例(li)(li)中,在(zai)(zai)(zai)電解質水溶(rong)(rong)液中,第(di)(di)一(yi)配位(wei)化(hua)(hua)合(he)物(wu)的濃(nong)度(du)(du)可以(yi)在(zai)(zai)(zai)約(yue)(yue)1m和(he)(he)約(yue)(yue)1.8m之(zhi)(zhi)間(jian)(jian)變化(hua)(hua)。
第(di)(di)一(yi)電解(jie)質溶(rong)液(ye)(ye)可(ke)呈(cheng)現在(zai)(zai)約(yue)(yue)(yue)(yue)(yue)1至約(yue)(yue)(yue)(yue)(yue)14范(fan)圍(wei)內的(de)任何ph。在(zai)(zai)更具體的(de)實施(shi)例中,第(di)(di)一(yi)電解(jie)質溶(rong)液(ye)(ye)可(ke)以(yi)含有(you)第(di)(di)一(yi)配(pei)(pei)位(wei)化合物并(bing)且(qie)具有(you)在(zai)(zai)約(yue)(yue)(yue)(yue)(yue)1和約(yue)(yue)(yue)(yue)(yue)13之間(jian)(jian)、或(huo)(huo)在(zai)(zai)約(yue)(yue)(yue)(yue)(yue)2和約(yue)(yue)(yue)(yue)(yue)12之間(jian)(jian)、或(huo)(huo)在(zai)(zai)約(yue)(yue)(yue)(yue)(yue)4和約(yue)(yue)(yue)(yue)(yue)10之間(jian)(jian)、或(huo)(huo)在(zai)(zai)約(yue)(yue)(yue)(yue)(yue)6和約(yue)(yue)(yue)(yue)(yue)8之間(jian)(jian)、或(huo)(huo)在(zai)(zai)約(yue)(yue)(yue)(yue)(yue)1和約(yue)(yue)(yue)(yue)(yue)7之間(jian)(jian)、或(huo)(huo)在(zai)(zai)約(yue)(yue)(yue)(yue)(yue)7和約(yue)(yue)(yue)(yue)(yue)13之間(jian)(jian)、或(huo)(huo)在(zai)(zai)約(yue)(yue)(yue)(yue)(yue)8和約(yue)(yue)(yue)(yue)(yue)13之間(jian)(jian)、或(huo)(huo)在(zai)(zai)約(yue)(yue)(yue)(yue)(yue)9和約(yue)(yue)(yue)(yue)(yue)14之間(jian)(jian)、或(huo)(huo)在(zai)(zai)約(yue)(yue)(yue)(yue)(yue)10和約(yue)(yue)(yue)(yue)(yue)13之間(jian)(jian)、或(huo)(huo)在(zai)(zai)約(yue)(yue)(yue)(yue)(yue)9和約(yue)(yue)(yue)(yue)(yue)12之間(jian)(jian)變(bian)化的(de)ph。可(ke)以(yi)基于第(di)(di)一(yi)配(pei)(pei)位(wei)化合物和/或(huo)(huo)其配(pei)(pei)位(wei)體在(zai)(zai)給(gei)定(ding)(ding)ph下的(de)穩定(ding)(ding)性和/或(huo)(huo)溶(rong)解(jie)度來選擇第(di)(di)一(yi)電解(jie)質溶(rong)液(ye)(ye)的(de)適當ph范(fan)圍(wei),并(bing)且(qie)可(ke)以(yi)由(you)本(ben)領(ling)域普通技術人員(yuan)來確定(ding)(ding)這種考慮。
如上所述,atr光譜法可以特別適用于分析含有呈現高摩爾吸光系數常數的配位化合物的電解質溶液。高摩爾吸光系數常數可以通過配位化合物的氧化形式、配位化合物的還原形式或兩者來呈現。在更具體的實施例中,第一電解質溶液中的第一配位化合物可具有至少約100m-1cm-1的摩爾吸光系數常數。在更具體的實施例中,第一電解質溶液中的第一配位化合物可以具有在約100m-1cm-1和約1,000,000m-1cm-1之間變化的摩爾吸光系數常數。在進一步的實施例中,第一電解質溶液中的第一配位化合物可以具有摩爾吸光系數常數,其具有以下較低值:約100m-1cm-1、500m-1cm-1、1000m-1cm-1、2500m-1cm-1、5000m-1cm-1、7500m-1cm-1、10,000m-1cm-1、25,000m-1cm-1、50,000m-1cm-1、75,000m-1cm-1、100,000m-1cm-1、250,000m-1cm-1或500,000m-1cm-1,并且其變化到以下較高值:約1,000,000m-1cm-1、500,000m-1cm-1、250,000m-1cm-1、100,000m-1cm-1、50,000m-1cm-1、25,000m-1cm-1、或10,000m-1cm-1。即(ji)使這里(li)沒有具體(ti)公(gong)開,但是摩爾(er)吸光系數常數可(ke)以進一步位于這些低端值和高端值之間的任何子(zi)范圍內。
如以上進一步指出的,配位化合物的濃度及其摩爾吸光系數常數兩者可以指示其被atr光譜法分析的適用性。在一些實施例中,濃度和摩爾吸光系數常數的乘積(即,算術乘積)可以為至少約100cm-1。在更具體的實施例中,濃度和摩爾吸光系數常數的乘積可在約100cm-1至約1,000,000cm-1之間變化。在進一步的實施例中,第一電解質溶液中的配位化合物的濃度和摩爾吸光系數常數的乘積可以具有以下較低值:約100cm-1、500cm-1、1000cm-1、2500cm-1、5000cm-1、7500cm-1或10,000cm-1,并且變化到以下較高值:約1,000,000cm-1、100,000cm-1、50,000cm-1、10,000cm-1、5000cm-1、1000cm-1或500cm-1。即使這里沒有具體公開(kai),但是(shi)濃(nong)度和摩爾吸光系數常數的乘積可以(yi)進一步位于這些低端值和高端值之(zhi)間的任(ren)何子范圍內。
在一(yi)(yi)(yi)些實施例中,與(yu)第(di)(di)一(yi)(yi)(yi)電(dian)(dian)解(jie)(jie)(jie)(jie)質溶液(ye)相互作(zuo)用的(de)電(dian)(dian)磁(ci)輻(fu)射可(ke)以(yi)包(bao)括約(yue)(yue)180nm和(he)(he)(he)約(yue)(yue)800nm之間(jian)的(de)范(fan)圍內(nei)(nei)(nei)(nei)的(de)一(yi)(yi)(yi)個(ge)(ge)(ge)(ge)(ge)(ge)(ge)或(huo)(huo)(huo)多個(ge)(ge)(ge)(ge)(ge)(ge)(ge)波(bo)(bo)長。即(ji),與(yu)第(di)(di)一(yi)(yi)(yi)電(dian)(dian)解(jie)(jie)(jie)(jie)質溶液(ye)相互作(zuo)用的(de)電(dian)(dian)磁(ci)輻(fu)射可(ke)以(yi)位于電(dian)(dian)磁(ci)光(guang)譜(pu)的(de)紫外光(guang)區(qu)(qu)域(yu)和(he)(he)(he)/或(huo)(huo)(huo)可(ke)見光(guang)區(qu)(qu)域(yu)內(nei)(nei)(nei)(nei)。第(di)(di)一(yi)(yi)(yi)電(dian)(dian)解(jie)(jie)(jie)(jie)質溶液(ye)內(nei)(nei)(nei)(nei)的(de)第(di)(di)一(yi)(yi)(yi)配(pei)位化合(he)物可(ke)以(yi)吸(xi)收在該范(fan)圍或(huo)(huo)(huo)適于分析(xi)(xi)的(de)其它范(fan)圍內(nei)(nei)(nei)(nei)的(de)一(yi)(yi)(yi)個(ge)(ge)(ge)(ge)(ge)(ge)(ge)或(huo)(huo)(huo)多個(ge)(ge)(ge)(ge)(ge)(ge)(ge)波(bo)(bo)長的(de)電(dian)(dian)磁(ci)輻(fu)射。在更具體的(de)實施例中,與(yu)第(di)(di)一(yi)(yi)(yi)電(dian)(dian)解(jie)(jie)(jie)(jie)質溶液(ye)相互作(zuo)用的(de)電(dian)(dian)磁(ci)輻(fu)射可(ke)以(yi)包(bao)括在以(yi)下范(fan)圍內(nei)(nei)(nei)(nei)的(de)一(yi)(yi)(yi)個(ge)(ge)(ge)(ge)(ge)(ge)(ge)或(huo)(huo)(huo)多個(ge)(ge)(ge)(ge)(ge)(ge)(ge)波(bo)(bo)長:在約(yue)(yue)180nm和(he)(he)(he)約(yue)(yue)300nm之間(jian)、或(huo)(huo)(huo)在約(yue)(yue)300nm和(he)(he)(he)約(yue)(yue)400nm之間(jian)、或(huo)(huo)(huo)在約(yue)(yue)400nm和(he)(he)(he)約(yue)(yue)500nm之間(jian)、或(huo)(huo)(huo)在約(yue)(yue)500nm和(he)(he)(he)約(yue)(yue)600nm之間(jian)、或(huo)(huo)(huo)在約(yue)(yue)600nm和(he)(he)(he)約(yue)(yue)700nm之間(jian)、或(huo)(huo)(huo)在約(yue)(yue)700nm和(he)(he)(he)約(yue)(yue)800nm之間(jian)。這些范(fan)圍的(de)任何子(zi)范(fan)圍或(huo)(huo)(huo)任何組(zu)合(he)也被認為在本文中明確公(gong)開。即(ji),在一(yi)(yi)(yi)個(ge)(ge)(ge)(ge)(ge)(ge)(ge)或(huo)(huo)(huo)多個(ge)(ge)(ge)(ge)(ge)(ge)(ge)波(bo)(bo)長處的(de)吸(xi)光(guang)度可(ke)以(yi)被單獨分析(xi)(xi)或(huo)(huo)(huo)作(zuo)為光(guang)譜(pu)的(de)一(yi)(yi)(yi)部分分析(xi)(xi)。而且,可(ke)以(yi)連續地或(huo)(huo)(huo)周(zhou)期性地監測(ce)、測(ce)量和(he)(he)(he)/或(huo)(huo)(huo)分析(xi)(xi)一(yi)(yi)(yi)個(ge)(ge)(ge)(ge)(ge)(ge)(ge)或(huo)(huo)(huo)多個(ge)(ge)(ge)(ge)(ge)(ge)(ge)波(bo)(bo)長,其包(bao)括通過電(dian)(dian)磁(ci)輻(fu)射源的(de)脈沖(chong)。
因此(ci),用于確定(ding)電(dian)(dian)解(jie)質溶(rong)(rong)(rong)液(ye)(ye)(ye)狀(zhuang)(zhuang)(zhuang)態(tai)(tai)的(de)(de)(de)(de)方(fang)法(fa)的(de)(de)(de)(de)各種實施例可(ke)以(yi)(yi)包括:通過atr光譜法(fa)測定(ding)電(dian)(dian)解(jie)質溶(rong)(rong)(rong)液(ye)(ye)(ye),并且確定(ding)作為電(dian)(dian)解(jie)質溶(rong)(rong)(rong)液(ye)(ye)(ye)中的(de)(de)(de)(de)活性物質的(de)(de)(de)(de)配位(wei)化(hua)(hua)(hua)合物的(de)(de)(de)(de)氧化(hua)(hua)(hua)形(xing)(xing)(xing)式(shi)或(huo)還原形(xing)(xing)(xing)式(shi)中的(de)(de)(de)(de)至少(shao)一(yi)種的(de)(de)(de)(de)濃(nong)度(du)(du)和/或(huo)吸(xi)光度(du)(du)。然(ran)后,如(ru)在下文中所討論的(de)(de)(de)(de),配位(wei)化(hua)(hua)(hua)合物的(de)(de)(de)(de)氧化(hua)(hua)(hua)形(xing)(xing)(xing)式(shi)和/或(huo)還原形(xing)(xing)(xing)式(shi)的(de)(de)(de)(de)吸(xi)光度(du)(du)和/或(huo)濃(nong)度(du)(du)可(ke)以(yi)(yi)被(bei)關聯至包含電(dian)(dian)解(jie)質溶(rong)(rong)(rong)液(ye)(ye)(ye)的(de)(de)(de)(de)半電(dian)(dian)池(chi)的(de)(de)(de)(de)荷(he)電(dian)(dian)狀(zhuang)(zhuang)(zhuang)態(tai)(tai),諸如(ru)液(ye)(ye)(ye)流電(dian)(dian)池(chi)的(de)(de)(de)(de)荷(he)電(dian)(dian)狀(zhuang)(zhuang)(zhuang)態(tai)(tai)。如(ru)果需要,可(ke)以(yi)(yi)類(lei)似的(de)(de)(de)(de)方(fang)式(shi)分析電(dian)(dian)化(hua)(hua)(hua)學系(xi)統(tong)的(de)(de)(de)(de)其它半電(dian)(dian)池(chi)內的(de)(de)(de)(de)電(dian)(dian)解(jie)質溶(rong)(rong)(rong)液(ye)(ye)(ye)的(de)(de)(de)(de)狀(zhuang)(zhuang)(zhuang)態(tai)(tai)。兩個(ge)半電(dian)(dian)池(chi)中的(de)(de)(de)(de)電(dian)(dian)解(jie)質溶(rong)(rong)(rong)液(ye)(ye)(ye)的(de)(de)(de)(de)分析可(ke)以(yi)(yi)彼此(ci)獨立地發生。
在(zai)(zai)更具(ju)體(ti)的(de)(de)(de)(de)實施(shi)例中(zhong),用于(yu)確(que)定電(dian)解(jie)(jie)質溶(rong)液(ye)(ye)(ye)的(de)(de)(de)(de)狀態的(de)(de)(de)(de)方法可(ke)以包括:提供包含(han)與第(di)(di)一(yi)(yi)(yi)電(dian)極接(jie)觸的(de)(de)(de)(de)第(di)(di)一(yi)(yi)(yi)電(dian)解(jie)(jie)質溶(rong)液(ye)(ye)(ye)的(de)(de)(de)(de)電(dian)化(hua)(hua)(hua)學(xue)(xue)(xue)系統;在(zai)(zai)電(dian)化(hua)(hua)(hua)學(xue)(xue)(xue)系統內(nei)的(de)(de)(de)(de)位(wei)置處(chu)將電(dian)磁(ci)(ci)輻射(she)(she)(she)與第(di)(di)一(yi)(yi)(yi)電(dian)解(jie)(jie)質溶(rong)液(ye)(ye)(ye)相(xiang)(xiang)互(hu)作(zuo)用,其中(zhong)電(dian)磁(ci)(ci)輻射(she)(she)(she)通過被(bei)配置為在(zai)(zai)光(guang)(guang)(guang)學(xue)(xue)(xue)材料(liao)和(he)第(di)(di)一(yi)(yi)(yi)電(dian)解(jie)(jie)質溶(rong)液(ye)(ye)(ye)之間的(de)(de)(de)(de)界面處(chu)呈現衰(shuai)(shuai)減(jian)全(quan)(quan)反(fan)(fan)射(she)(she)(she)率(lv)的(de)(de)(de)(de)光(guang)(guang)(guang)學(xue)(xue)(xue)材料(liao)被(bei)傳遞;在(zai)(zai)檢測(ce)(ce)器處(chu)接(jie)收已經經由光(guang)(guang)(guang)學(xue)(xue)(xue)材料(liao)內(nei)的(de)(de)(de)(de)一(yi)(yi)(yi)個(ge)或(huo)(huo)多個(ge)衰(shuai)(shuai)減(jian)全(quan)(quan)反(fan)(fan)射(she)(she)(she)與第(di)(di)一(yi)(yi)(yi)電(dian)解(jie)(jie)質溶(rong)液(ye)(ye)(ye)相(xiang)(xiang)互(hu)作(zuo)用的(de)(de)(de)(de)電(dian)磁(ci)(ci)輻射(she)(she)(she);以及利用在(zai)(zai)檢測(ce)(ce)器處(chu)接(jie)收的(de)(de)(de)(de)電(dian)磁(ci)(ci)輻射(she)(she)(she)測(ce)(ce)量(liang)第(di)(di)一(yi)(yi)(yi)電(dian)解(jie)(jie)質溶(rong)液(ye)(ye)(ye)中(zhong)的(de)(de)(de)(de)第(di)(di)一(yi)(yi)(yi)配位(wei)化(hua)(hua)(hua)合物的(de)(de)(de)(de)氧化(hua)(hua)(hua)形式(shi)或(huo)(huo)還原(yuan)形式(shi)中(zhong)的(de)(de)(de)(de)至少一(yi)(yi)(yi)個(ge)的(de)(de)(de)(de)吸光(guang)(guang)(guang)度(du)。為了促進(jin)(jin)衰(shuai)(shuai)減(jian)全(quan)(quan)反(fan)(fan)射(she)(she)(she)率(lv),光(guang)(guang)(guang)學(xue)(xue)(xue)材料(liao)具(ju)有(you)高(gao)于(yu)第(di)(di)一(yi)(yi)(yi)電(dian)解(jie)(jie)質溶(rong)液(ye)(ye)(ye)的(de)(de)(de)(de)折(zhe)射(she)(she)(she)率(lv)。進(jin)(jin)一(yi)(yi)(yi)步(bu)地,光(guang)(guang)(guang)學(xue)(xue)(xue)材料(liao)上的(de)(de)(de)(de)電(dian)磁(ci)(ci)輻射(she)(she)(she)的(de)(de)(de)(de)入(ru)射(she)(she)(she)角(jiao)可(ke)以促進(jin)(jin)衰(shuai)(shuai)減(jian)全(quan)(quan)反(fan)(fan)射(she)(she)(she)率(lv)。
在(zai)進(jin)一(yi)步(bu)的(de)實施例(li)中,本(ben)公開(kai)的(de)方法可以(yi)進(jin)一(yi)步(bu)包括:基(ji)于在(zai)檢測(ce)器處測(ce)量的(de)吸光度(du)來確(que)定第(di)一(yi)配位(wei)化合物的(de)氧化形式或還原形式中的(de)至少一(yi)個(ge)的(de)濃(nong)度(du)。在(zai)一(yi)些或其它實施例(li)中,本(ben)公開(kai)的(de)方法可以(yi)進(jin)一(yi)步(bu)包括:確(que)定電化學系統(tong)中的(de)第(di)一(yi)電解質溶液(ye)的(de)荷電狀態。
如(ru)上(shang)所述(shu),在(zai)(zai)一些實施例(li)中,電(dian)(dian)(dian)化學(xue)系統(tong)可(ke)(ke)以(yi)是液(ye)(ye)流(liu)電(dian)(dian)(dian)池。在(zai)(zai)下文中提(ti)供液(ye)(ye)流(liu)電(dian)(dian)(dian)池的(de)示例(li)性(xing)描述(shu),以(yi)及在(zai)(zai)其中可(ke)(ke)以(yi)發(fa)生第一電(dian)(dian)(dian)解質溶液(ye)(ye)的(de)分析的(de)液(ye)(ye)流(liu)電(dian)(dian)(dian)池中的(de)示例(li)性(xing)位置(zhi)(zhi)。其中可(ke)(ke)以(yi)發(fa)生分析的(de)位置(zhi)(zhi)通常可(ke)(ke)以(yi)擴展(zhan)到其它類型的(de)適用的(de)電(dian)(dian)(dian)化學(xue)系統(tong)。
在各種實(shi)施例中(zhong)(zhong),可(ke)以(yi)根據本(ben)公開確(que)定(ding)第(di)(di)(di)一(yi)(yi)(yi)電(dian)解(jie)質溶(rong)液(ye)中(zhong)(zhong)的(de)(de)(de)第(di)(di)(di)一(yi)(yi)(yi)配位(wei)化(hua)(hua)(hua)合物(wu)的(de)(de)(de)氧(yang)化(hua)(hua)(hua)形(xing)式(shi)(shi)(shi)或(huo)(huo)還(huan)原(yuan)(yuan)形(xing)式(shi)(shi)(shi)的(de)(de)(de)濃(nong)(nong)度(du)(du)。假設第(di)(di)(di)一(yi)(yi)(yi)配位(wei)化(hua)(hua)(hua)合物(wu)的(de)(de)(de)氧(yang)化(hua)(hua)(hua)形(xing)式(shi)(shi)(shi)加上還(huan)原(yuan)(yuan)形(xing)式(shi)(shi)(shi)的(de)(de)(de)總(zong)濃(nong)(nong)度(du)(du)保持恒(heng)定(ding),則可(ke)以(yi)基(ji)于(yu)一(yi)(yi)(yi)個形(xing)式(shi)(shi)(shi)的(de)(de)(de)濃(nong)(nong)度(du)(du)來推斷另一(yi)(yi)(yi)個形(xing)式(shi)(shi)(shi)的(de)(de)(de)濃(nong)(nong)度(du)(du)。即,如果(guo)在完全充電(dian)的(de)(de)(de)第(di)(di)(di)一(yi)(yi)(yi)電(dian)解(jie)質溶(rong)液(ye)中(zhong)(zhong)的(de)(de)(de)第(di)(di)(di)一(yi)(yi)(yi)配位(wei)化(hua)(hua)(hua)合物(wu)的(de)(de)(de)氧(yang)化(hua)(hua)(hua)(或(huo)(huo)還(huan)原(yuan)(yuan))形(xing)式(shi)(shi)(shi)的(de)(de)(de)初(chu)始濃(nong)(nong)度(du)(du)是已知的(de)(de)(de),則可(ke)以(yi)通過(guo)從初(chu)始濃(nong)(nong)度(du)(du)中(zhong)(zhong)減去測量的(de)(de)(de)濃(nong)(nong)度(du)(du)來確(que)定(ding)氧(yang)化(hua)(hua)(hua)形(xing)式(shi)(shi)(shi)或(huo)(huo)還(huan)原(yuan)(yuan)形(xing)式(shi)(shi)(shi)的(de)(de)(de)濃(nong)(nong)度(du)(du)。在其它(ta)各種實(shi)施例中(zhong)(zhong),可(ke)以(yi)在確(que)定(ding)第(di)(di)(di)一(yi)(yi)(yi)電(dian)解(jie)質溶(rong)液(ye)的(de)(de)(de)荷電(dian)狀態(tai)的(de)(de)(de)過(guo)程(cheng)中(zhong)(zhong)通過(guo)本(ben)公開的(de)(de)(de)技術(shu)直接地確(que)定(ding)第(di)(di)(di)一(yi)(yi)(yi)配位(wei)化(hua)(hua)(hua)合物(wu)的(de)(de)(de)氧(yang)化(hua)(hua)(hua)形(xing)式(shi)(shi)(shi)和還(huan)原(yuan)(yuan)形(xing)式(shi)(shi)(shi)的(de)(de)(de)濃(nong)(nong)度(du)(du)。
當測量(liang)第(di)一電解質(zhi)溶(rong)液中的(de)(de)第(di)一配位化合物的(de)(de)氧化形式和/或還原形式的(de)(de)吸(xi)(xi)光度時(shi),可(ke)以(yi)單(dan)個(ge)波長(chang)或以(yi)一個(ge)以(yi)上波長(chang)測量(liang)吸(xi)(xi)光度。當以(yi)多(duo)個(ge)波長(chang)發(fa)生分析時(shi),可(ke)以(yi)獲得或不(bu)獲得光譜。
在更特定的(de)(de)(de)實施例中(zhong),分析(xi)第一(yi)(yi)配位(wei)(wei)化合(he)物(wu)(wu)(wu)的(de)(de)(de)氧化形(xing)(xing)式(shi)(shi)和/或(huo)還原形(xing)(xing)式(shi)(shi)的(de)(de)(de)波(bo)(bo)長的(de)(de)(de)至少(shao)一(yi)(yi)個可以(yi)(yi)(yi)對(dui)(dui)應于(yu)相(xiang)應吸(xi)(xi)收光(guang)(guang)譜中(zhong)的(de)(de)(de)局(ju)(ju)部(bu)最(zui)大(da)值。在更特定的(de)(de)(de)實施例中(zhong),波(bo)(bo)長的(de)(de)(de)至少(shao)一(yi)(yi)個可以(yi)(yi)(yi)是(shi)第一(yi)(yi)配位(wei)(wei)化合(he)物(wu)(wu)(wu)的(de)(de)(de)氧化形(xing)(xing)式(shi)(shi)或(huo)還原形(xing)(xing)式(shi)(shi)中(zhong)的(de)(de)(de)一(yi)(yi)個的(de)(de)(de)局(ju)(ju)部(bu)最(zui)大(da)值,以(yi)(yi)(yi)及(ji)可以(yi)(yi)(yi)是(shi)第一(yi)(yi)配位(wei)(wei)化合(he)物(wu)(wu)(wu)的(de)(de)(de)相(xiang)對(dui)(dui)形(xing)(xing)式(shi)(shi)的(de)(de)(de)零吸(xi)(xi)光(guang)(guang)度(du)(du)或(huo)接近零吸(xi)(xi)光(guang)(guang)度(du)(du)(即局(ju)(ju)部(bu)最(zui)小值)的(de)(de)(de)位(wei)(wei)置。如(ru)本(ben)領域(yu)普通技術人員將認識到的(de)(de)(de),可以(yi)(yi)(yi)期望在局(ju)(ju)部(bu)最(zui)大(da)值處(chu)的(de)(de)(de)吸(xi)(xi)光(guang)(guang)度(du)(du)測量,使得吸(xi)(xi)光(guang)(guang)度(du)(du)的(de)(de)(de)變化率(lv)最(zui)低,從而最(zui)小化由于(yu)光(guang)(guang)譜浮動而導(dao)致的(de)(de)(de)錯誤。理(li)想地,在對(dui)(dui)第一(yi)(yi)配位(wei)(wei)化合(he)物(wu)(wu)(wu)的(de)(de)(de)相(xiang)對(dui)(dui)形(xing)(xing)式(shi)(shi)進行分析(xi)的(de)(de)(de)波(bo)(bo)長處(chu),第一(yi)(yi)配位(wei)(wei)化合(he)物(wu)(wu)(wu)的(de)(de)(de)相(xiang)對(dui)(dui)形(xing)(xing)式(shi)(shi)基(ji)本(ben)顯示零或(huo)最(zui)小的(de)(de)(de)吸(xi)(xi)光(guang)(guang)度(du)(du)。因此,在這樣的(de)(de)(de)實施例中(zhong),局(ju)(ju)部(bu)最(zui)大(da)值處(chu)的(de)(de)(de)吸(xi)(xi)光(guang)(guang)度(du)(du)基(ji)本(ben)上表示由正在被分析(xi)的(de)(de)(de)第一(yi)(yi)配位(wei)(wei)化合(he)物(wu)(wu)(wu)的(de)(de)(de)形(xing)(xing)式(shi)(shi)引起。
在(zai)(zai)進一(yi)(yi)步的(de)(de)(de)(de)(de)(de)實施例中(zhong)(zhong),可(ke)以(yi)(yi)在(zai)(zai)用于(yu)第(di)(di)一(yi)(yi)配(pei)位(wei)化(hua)(hua)合(he)(he)物(wu)(wu)的(de)(de)(de)(de)(de)(de)氧化(hua)(hua)形(xing)(xing)(xing)式(shi)(shi)或還原形(xing)(xing)(xing)式(shi)(shi)中(zhong)(zhong)的(de)(de)(de)(de)(de)(de)一(yi)(yi)個的(de)(de)(de)(de)(de)(de)第(di)(di)一(yi)(yi)波(bo)長(chang)(chang)處(chu)測(ce)(ce)量(liang)(liang)第(di)(di)一(yi)(yi)吸(xi)光(guang)度(du),并且可(ke)以(yi)(yi)在(zai)(zai)用于(yu)第(di)(di)一(yi)(yi)配(pei)位(wei)化(hua)(hua)合(he)(he)物(wu)(wu)的(de)(de)(de)(de)(de)(de)相對(dui)形(xing)(xing)(xing)式(shi)(shi)的(de)(de)(de)(de)(de)(de)第(di)(di)二波(bo)長(chang)(chang)處(chu)測(ce)(ce)量(liang)(liang)第(di)(di)二吸(xi)光(guang)度(du)。理想地,在(zai)(zai)第(di)(di)一(yi)(yi)波(bo)長(chang)(chang)處(chu)測(ce)(ce)量(liang)(liang)的(de)(de)(de)(de)(de)(de)第(di)(di)一(yi)(yi)配(pei)位(wei)化(hua)(hua)合(he)(he)物(wu)(wu)的(de)(de)(de)(de)(de)(de)形(xing)(xing)(xing)式(shi)(shi)在(zai)(zai)該(gai)波(bo)長(chang)(chang)處(chu)顯示吸(xi)收(shou)最(zui)大(da)值,并且第(di)(di)一(yi)(yi)配(pei)位(wei)化(hua)(hua)合(he)(he)物(wu)(wu)的(de)(de)(de)(de)(de)(de)相對(dui)形(xing)(xing)(xing)式(shi)(shi)在(zai)(zai)該(gai)波(bo)長(chang)(chang)處(chu)基(ji)本顯示零或最(zui)小(xiao)吸(xi)光(guang)度(du)。相應地,在(zai)(zai)第(di)(di)二波(bo)長(chang)(chang)處(chu)測(ce)(ce)量(liang)(liang)的(de)(de)(de)(de)(de)(de)第(di)(di)一(yi)(yi)配(pei)位(wei)化(hua)(hua)合(he)(he)物(wu)(wu)的(de)(de)(de)(de)(de)(de)相對(dui)形(xing)(xing)(xing)式(shi)(shi)可(ke)以(yi)(yi)在(zai)(zai)該(gai)波(bo)長(chang)(chang)處(chu)顯示吸(xi)收(shou)最(zui)大(da)值,并且在(zai)(zai)第(di)(di)一(yi)(yi)波(bo)長(chang)(chang)處(chu)測(ce)(ce)量(liang)(liang)的(de)(de)(de)(de)(de)(de)第(di)(di)一(yi)(yi)配(pei)位(wei)化(hua)(hua)合(he)(he)物(wu)(wu)的(de)(de)(de)(de)(de)(de)形(xing)(xing)(xing)式(shi)(shi)可(ke)以(yi)(yi)在(zai)(zai)第(di)(di)二波(bo)長(chang)(chang)處(chu)基(ji)本顯示零或最(zui)小(xiao)吸(xi)光(guang)度(du)。本領域普通技術人員可(ke)以(yi)(yi)確定適于(yu)第(di)(di)一(yi)(yi)配(pei)位(wei)化(hua)(hua)合(he)(he)物(wu)(wu)的(de)(de)(de)(de)(de)(de)每種(zhong)形(xing)(xing)(xing)式(shi)(shi)的(de)(de)(de)(de)(de)(de)分(fen)析的(de)(de)(de)(de)(de)(de)波(bo)長(chang)(chang)以(yi)(yi)及在(zai)(zai)每種(zhong)波(bo)長(chang)(chang)下可(ke)以(yi)(yi)耐(nai)受的(de)(de)(de)(de)(de)(de)相對(dui)形(xing)(xing)(xing)式(shi)(shi)的(de)(de)(de)(de)(de)(de)吸(xi)光(guang)度(du)的(de)(de)(de)(de)(de)(de)量(liang)(liang)。
在(zai)更具體(ti)的(de)(de)(de)(de)實(shi)施例中(zhong),可(ke)以在(zai)第(di)一(yi)(yi)局(ju)部(bu)最(zui)大(da)值處測量(liang)(liang)第(di)一(yi)(yi)配(pei)位(wei)化(hua)合物的(de)(de)(de)(de)氧(yang)化(hua)形式(shi)的(de)(de)(de)(de)吸(xi)(xi)光(guang)度,并且可(ke)以在(zai)第(di)二局(ju)部(bu)最(zui)大(da)值處測量(liang)(liang)第(di)一(yi)(yi)配(pei)位(wei)化(hua)合物的(de)(de)(de)(de)還(huan)原形式(shi)的(de)(de)(de)(de)吸(xi)(xi)光(guang)度。第(di)一(yi)(yi)配(pei)位(wei)化(hua)合物的(de)(de)(de)(de)氧(yang)化(hua)形式(shi)和還(huan)原形式(shi)的(de)(de)(de)(de)局(ju)部(bu)最(zui)大(da)值可(ke)以彼此不同(tong)。在(zai)一(yi)(yi)些實(shi)施例中(zhong),在(zai)氧(yang)化(hua)形式(shi)的(de)(de)(de)(de)局(ju)部(bu)最(zui)大(da)值處測量(liang)(liang)第(di)一(yi)(yi)配(pei)位(wei)化(hua)合物的(de)(de)(de)(de)氧(yang)化(hua)形式(shi)的(de)(de)(de)(de)吸(xi)(xi)光(guang)度,并且在(zai)還(huan)原形式(shi)的(de)(de)(de)(de)局(ju)部(bu)最(zui)大(da)值處測量(liang)(liang)第(di)一(yi)(yi)配(pei)位(wei)化(hua)合物的(de)(de)(de)(de)還(huan)原形式(shi)的(de)(de)(de)(de)吸(xi)(xi)光(guang)度。
在(zai)一(yi)些實施例(li)中,可(ke)以至少(shao)在(zai)由第(di)(di)一(yi)配(pei)位(wei)化(hua)合物的(de)(de)(de)(de)氧化(hua)形式和(he)還(huan)原形式呈(cheng)現(xian)的(de)(de)(de)(de)等吸(xi)(xi)(xi)(xi)(xi)(xi)(xi)光(guang)(guang)(guang)(guang)點(dian)處(chu)測量(liang)(liang)吸(xi)(xi)(xi)(xi)(xi)(xi)(xi)光(guang)(guang)(guang)(guang)度(du)(du)(du)。如本領域普(pu)通技(ji)術人員將(jiang)認識(shi)到的(de)(de)(de)(de),等吸(xi)(xi)(xi)(xi)(xi)(xi)(xi)光(guang)(guang)(guang)(guang)點(dian)是吸(xi)(xi)(xi)(xi)(xi)(xi)(xi)光(guang)(guang)(guang)(guang)度(du)(du)(du)圖中當兩(liang)(liang)種吸(xi)(xi)(xi)(xi)(xi)(xi)(xi)收材(cai)(cai)料的(de)(de)(de)(de)濃(nong)度(du)(du)(du)變(bian)化(hua)(例(li)如,作為化(hua)學反應的(de)(de)(de)(de)結果)時吸(xi)(xi)(xi)(xi)(xi)(xi)(xi)光(guang)(guang)(guang)(guang)度(du)(du)(du)不變(bian)的(de)(de)(de)(de)一(yi)個(ge)(ge)或多個(ge)(ge)波長。即,當一(yi)種材(cai)(cai)料的(de)(de)(de)(de)吸(xi)(xi)(xi)(xi)(xi)(xi)(xi)光(guang)(guang)(guang)(guang)度(du)(du)(du)下(xia)降(jiang)以形成第(di)(di)二種材(cai)(cai)料時,第(di)(di)二種材(cai)(cai)料的(de)(de)(de)(de)吸(xi)(xi)(xi)(xi)(xi)(xi)(xi)光(guang)(guang)(guang)(guang)度(du)(du)(du)增加相應的(de)(de)(de)(de)量(liang)(liang)以維持恒定的(de)(de)(de)(de)吸(xi)(xi)(xi)(xi)(xi)(xi)(xi)光(guang)(guang)(guang)(guang)度(du)(du)(du)。這暗示兩(liang)(liang)個(ge)(ge)摩(mo)爾(er)吸(xi)(xi)(xi)(xi)(xi)(xi)(xi)光(guang)(guang)(guang)(guang)系數(shu)常數(shu)彼此(ci)相對相似。因此(ci),在(zai)具有氧化(hua)形式和(he)還(huan)原形式兩(liang)(liang)者的(de)(de)(de)(de)配(pei)位(wei)化(hua)合物的(de)(de)(de)(de)情(qing)況下(xia),等吸(xi)(xi)(xi)(xi)(xi)(xi)(xi)光(guang)(guang)(guang)(guang)點(dian)處(chu)的(de)(de)(de)(de)吸(xi)(xi)(xi)(xi)(xi)(xi)(xi)光(guang)(guang)(guang)(guang)度(du)(du)(du)表(biao)示兩(liang)(liang)個(ge)(ge)配(pei)位(wei)化(hua)合物形式的(de)(de)(de)(de)總濃(nong)度(du)(du)(du)。因此(ci),可(ke)以通過將(jiang)等吸(xi)(xi)(xi)(xi)(xi)(xi)(xi)光(guang)(guang)(guang)(guang)點(dian)處(chu)的(de)(de)(de)(de)固定吸(xi)(xi)(xi)(xi)(xi)(xi)(xi)光(guang)(guang)(guang)(guang)度(du)(du)(du)與(yu)在(zai)該波長處(chu)最初測量(liang)(liang)的(de)(de)(de)(de)吸(xi)(xi)(xi)(xi)(xi)(xi)(xi)光(guang)(guang)(guang)(guang)度(du)(du)(du)進(jin)行比較來(lai)監(jian)測第(di)(di)一(yi)電解(jie)質(zhi)(zhi)(zhi)溶液中的(de)(de)(de)(de)第(di)(di)一(yi)配(pei)位(wei)化(hua)合物的(de)(de)(de)(de)總濃(nong)度(du)(du)(du)。等吸(xi)(xi)(xi)(xi)(xi)(xi)(xi)光(guang)(guang)(guang)(guang)點(dian)吸(xi)(xi)(xi)(xi)(xi)(xi)(xi)光(guang)(guang)(guang)(guang)度(du)(du)(du)的(de)(de)(de)(de)降(jiang)低可(ke)以指(zhi)示活性(xing)物質(zhi)(zhi)(zhi)已經從第(di)(di)一(yi)電解(jie)質(zhi)(zhi)(zhi)溶液中丟失,可(ke)能指(zhi)示需要采取校(xiao)正措施。
因此,在(zai)一(yi)些實施(shi)例中,本(ben)公開(kai)的方法可以(yi)(yi)包括:在(zai)第一(yi)波(bo)(bo)長處(chu)(chu)測量(liang)第一(yi)配位化合物的氧化形式(shi)或(huo)還(huan)(huan)原形式(shi)的吸(xi)光(guang)(guang)度(du),并(bing)且(qie)(qie)還(huan)(huan)在(zai)第二波(bo)(bo)長處(chu)(chu)測量(liang)等吸(xi)光(guang)(guang)點處(chu)(chu)的吸(xi)光(guang)(guang)度(du)。因此,在(zai)第一(yi)波(bo)(bo)長處(chu)(chu)測量(liang)的氧化形式(shi)或(huo)還(huan)(huan)原形式(shi)的吸(xi)光(guang)(guang)度(du)可以(yi)(yi)應用于確定荷電狀(zhuang)態(tai),并(bing)且(qie)(qie)第二波(bo)(bo)長處(chu)(chu)的吸(xi)光(guang)(guang)度(du)可以(yi)(yi)被關聯至(zhi)總濃度(du)。這些值可以(yi)(yi)被同(tong)時(shi)地或(huo)順序地測量(liang)。
一(yi)旦已經(jing)確定(ding)第(di)一(yi)配(pei)(pei)位化(hua)(hua)合(he)物的氧化(hua)(hua)形式和還(huan)原形式的濃(nong)度(du),則然后可以通(tong)過計算第(di)一(yi)配(pei)(pei)位化(hua)(hua)合(he)物的氧化(hua)(hua)形式與總濃(nong)度(du)的比例(li)(等式2)來(lai)確定(ding)第(di)一(yi)電解質溶液(ye)的荷電狀(zhuang)態
soc=100%xcox/(cred+cox)等(deng)式2
其中cox是第(di)一(yi)配(pei)(pei)位(wei)化(hua)合物的(de)(de)氧化(hua)形(xing)式(shi)的(de)(de)濃(nong)(nong)度(du)(du),cred是第(di)一(yi)配(pei)(pei)位(wei)化(hua)合物的(de)(de)還(huan)原(yuan)(yuan)形(xing)式(shi)的(de)(de)濃(nong)(nong)度(du)(du)。等式(shi)2假設第(di)一(yi)配(pei)(pei)位(wei)化(hua)合物的(de)(de)氧化(hua)形(xing)式(shi)是活性物質處(chu)于(yu)全(quan)荷電狀態。然而,如果第(di)一(yi)配(pei)(pei)位(wei)化(hua)合物的(de)(de)還(huan)原(yuan)(yuan)形(xing)式(shi)在(zai)(zai)充(chong)(chong)電時代替活性物質,則cred將在(zai)(zai)等式(shi)2的(de)(de)分子中代替cox。因此(ci),soc可(ke)以在(zai)(zai)0%(完全(quan)放電)和100%(完全(quan)充(chong)(chong)電)之間變化(hua)。如以上所討論的(de)(de),可(ke)以通過在(zai)(zai)適當波(bo)長處(chu)測量吸(xi)光(guang)度(du)(du)來(lai)確定第(di)一(yi)配(pei)(pei)位(wei)化(hua)合物的(de)(de)氧化(hua)形(xing)式(shi)和還(huan)原(yuan)(yuan)形(xing)式(shi)的(de)(de)濃(nong)(nong)度(du)(du)。如果需要,可(ke)以通過應用(yong)比爾-朗伯特定律(lv)、查找表(biao)或吸(xi)光(guang)度(du)(du)對濃(nong)(nong)度(du)(du)的(de)(de)校準圖來(lai)將測量的(de)(de)吸(xi)光(guang)度(du)(du)轉化(hua)為吸(xi)光(guang)度(du)(du)值。
在(zai)(zai)一(yi)(yi)些實施(shi)例中(zhong),假(jia)設第(di)一(yi)(yi)配位化(hua)(hua)合(he)(he)物的(de)(de)(de)氧(yang)化(hua)(hua)形式(shi)或還(huan)原形式(shi)在(zai)(zai)選擇的(de)(de)(de)波(bo)長(chang)處(chu)是(shi)透明的(de)(de)(de)(即,不吸(xi)收(shou)的(de)(de)(de)),則可以在(zai)(zai)單個(ge)波(bo)長(chang)處(chu)確定荷電狀(zhuang)態(tai)。因此,在(zai)(zai)選擇的(de)(de)(de)波(bo)長(chang)處(chu),測量的(de)(de)(de)吸(xi)光度僅(jin)由于第(di)一(yi)(yi)配位化(hua)(hua)合(he)(he)物的(de)(de)(de)形式(shi)中(zhong)的(de)(de)(de)僅(jin)一(yi)(yi)個(ge)引起(qi)。在(zai)(zai)其中(zhong)第(di)一(yi)(yi)配位化(hua)(hua)合(he)(he)物的(de)(de)(de)氧(yang)化(hua)(hua)形式(shi)是(shi)吸(xi)收(shou)的(de)(de)(de)并且第(di)一(yi)(yi)配位化(hua)(hua)合(he)(he)物的(de)(de)(de)還(huan)原形式(shi)是(shi)不吸(xi)收(shou)的(de)(de)(de)單個(ge)波(bo)長(chang)測量中(zhong),荷電狀(zhuang)態(tai)可以使用等式(shi)3來計算
soc=100%x(1-ameas/aox)(等式3)
其(qi)中(zhong)(zhong)ameas是(shi)(shi)(shi)在(zai)(zai)選擇(ze)的(de)(de)(de)(de)(de)(de)(de)(de)波長(chang)處測量的(de)(de)(de)(de)(de)(de)(de)(de)吸(xi)(xi)(xi)光度(du),并(bing)(bing)且aox是(shi)(shi)(shi)當僅第(di)(di)(di)(di)一(yi)(yi)(yi)(yi)配位(wei)(wei)化(hua)(hua)(hua)合(he)物(wu)(wu)的(de)(de)(de)(de)(de)(de)(de)(de)氧(yang)化(hua)(hua)(hua)形(xing)(xing)(xing)式(shi)(shi)(shi)存在(zai)(zai)于(yu)(yu)第(di)(di)(di)(di)一(yi)(yi)(yi)(yi)電(dian)(dian)解(jie)質(zhi)溶(rong)(rong)液(ye)中(zhong)(zhong)時測量的(de)(de)(de)(de)(de)(de)(de)(de)吸(xi)(xi)(xi)光度(du)。aox可以(yi)是(shi)(shi)(shi)先前測量的(de)(de)(de)(de)(de)(de)(de)(de)值,諸如當第(di)(di)(di)(di)一(yi)(yi)(yi)(yi)電(dian)(dian)解(jie)質(zhi)溶(rong)(rong)液(ye)首次(ci)配制(zhi)或(huo)電(dian)(dian)化(hua)(hua)(hua)學系統完全充電(dian)(dian)或(huo)完全放電(dian)(dian)時。再(zai)次(ci),等式(shi)(shi)(shi)3假定(ding)(ding)還(huan)(huan)(huan)原物(wu)(wu)質(zhi)是(shi)(shi)(shi)活(huo)性形(xing)(xing)(xing)式(shi)(shi)(shi)。對(dui)于(yu)(yu)其(qi)中(zhong)(zhong)氧(yang)化(hua)(hua)(hua)物(wu)(wu)質(zhi)為活(huo)性形(xing)(xing)(xing)式(shi)(shi)(shi)的(de)(de)(de)(de)(de)(de)(de)(de)相對(dui)電(dian)(dian)解(jie)質(zhi)溶(rong)(rong)液(ye)(即正(zheng)極電(dian)(dian)解(jie)質(zhi)溶(rong)(rong)液(ye)),可以(yi)通(tong)過表(biao)(biao)達(da)式(shi)(shi)(shi)soc=100%x(ameas/aox)來確(que)(que)定(ding)(ding)荷(he)(he)電(dian)(dian)狀態(tai)。在(zai)(zai)其(qi)中(zhong)(zhong)第(di)(di)(di)(di)一(yi)(yi)(yi)(yi)配位(wei)(wei)化(hua)(hua)(hua)合(he)物(wu)(wu)的(de)(de)(de)(de)(de)(de)(de)(de)還(huan)(huan)(huan)原形(xing)(xing)(xing)式(shi)(shi)(shi)是(shi)(shi)(shi)吸(xi)(xi)(xi)收(shou)的(de)(de)(de)(de)(de)(de)(de)(de)并(bing)(bing)且氧(yang)化(hua)(hua)(hua)形(xing)(xing)(xing)式(shi)(shi)(shi)是(shi)(shi)(shi)透明的(de)(de)(de)(de)(de)(de)(de)(de)情況(kuang)下,可以(yi)通(tong)過表(biao)(biao)達(da)式(shi)(shi)(shi)soc=100%x(ameas/ared)來確(que)(que)定(ding)(ding)荷(he)(he)電(dian)(dian)狀態(tai),其(qi)中(zhong)(zhong)ared是(shi)(shi)(shi)還(huan)(huan)(huan)原形(xing)(xing)(xing)式(shi)(shi)(shi)的(de)(de)(de)(de)(de)(de)(de)(de)吸(xi)(xi)(xi)光度(du)。而對(dui)于(yu)(yu)相對(dui)電(dian)(dian)解(jie)質(zhi)溶(rong)(rong)液(ye),用于(yu)(yu)確(que)(que)定(ding)(ding)荷(he)(he)電(dian)(dian)狀態(tai)的(de)(de)(de)(de)(de)(de)(de)(de)表(biao)(biao)達(da)式(shi)(shi)(shi)將是(shi)(shi)(shi)soc=100%x(1-ameas/ared)。在(zai)(zai)進一(yi)(yi)(yi)(yi)步(bu)的(de)(de)(de)(de)(de)(de)(de)(de)實施例中(zhong)(zhong),可以(yi)在(zai)(zai)其(qi)中(zhong)(zhong)要么第(di)(di)(di)(di)一(yi)(yi)(yi)(yi)配位(wei)(wei)化(hua)(hua)(hua)合(he)物(wu)(wu)的(de)(de)(de)(de)(de)(de)(de)(de)氧(yang)化(hua)(hua)(hua)形(xing)(xing)(xing)式(shi)(shi)(shi)是(shi)(shi)(shi)不(bu)吸(xi)(xi)(xi)收(shou)的(de)(de)(de)(de)(de)(de)(de)(de),要么第(di)(di)(di)(di)一(yi)(yi)(yi)(yi)配位(wei)(wei)化(hua)(hua)(hua)合(he)物(wu)(wu)的(de)(de)(de)(de)(de)(de)(de)(de)還(huan)(huan)(huan)原形(xing)(xing)(xing)式(shi)(shi)(shi)是(shi)(shi)(shi)不(bu)吸(xi)(xi)(xi)收(shou)的(de)(de)(de)(de)(de)(de)(de)(de)兩個(ge)不(bu)同的(de)(de)(de)(de)(de)(de)(de)(de)波長(chang)處進行荷(he)(he)電(dian)(dian)狀態(tai)的(de)(de)(de)(de)(de)(de)(de)(de)確(que)(que)定(ding)(ding),以(yi)便提(ti)供對(dui)荷(he)(he)電(dian)(dian)狀態(tai)的(de)(de)(de)(de)(de)(de)(de)(de)獨立評估。在(zai)(zai)進一(yi)(yi)(yi)(yi)步(bu)的(de)(de)(de)(de)(de)(de)(de)(de)實施例中(zhong)(zhong),荷(he)(he)電(dian)(dian)狀態(tai)的(de)(de)(de)(de)(de)(de)(de)(de)確(que)(que)定(ding)(ding)可以(yi)在(zai)(zai)第(di)(di)(di)(di)一(yi)(yi)(yi)(yi)波長(chang)處作(zuo)出(chu)(chu),其(qi)中(zhong)(zhong)第(di)(di)(di)(di)一(yi)(yi)(yi)(yi)配位(wei)(wei)化(hua)(hua)(hua)合(he)物(wu)(wu)的(de)(de)(de)(de)(de)(de)(de)(de)氧(yang)化(hua)(hua)(hua)形(xing)(xing)(xing)式(shi)(shi)(shi)是(shi)(shi)(shi)吸(xi)(xi)(xi)收(shou)的(de)(de)(de)(de)(de)(de)(de)(de)并(bing)(bing)且第(di)(di)(di)(di)一(yi)(yi)(yi)(yi)配位(wei)(wei)化(hua)(hua)(hua)合(he)物(wu)(wu)的(de)(de)(de)(de)(de)(de)(de)(de)還(huan)(huan)(huan)原形(xing)(xing)(xing)式(shi)(shi)(shi)是(shi)(shi)(shi)不(bu)吸(xi)(xi)(xi)收(shou)的(de)(de)(de)(de)(de)(de)(de)(de),并(bing)(bing)且荷(he)(he)電(dian)(dian)狀態(tai)的(de)(de)(de)(de)(de)(de)(de)(de)確(que)(que)定(ding)(ding)可以(yi)在(zai)(zai)第(di)(di)(di)(di)二波長(chang)處作(zuo)出(chu)(chu),其(qi)中(zhong)(zhong)第(di)(di)(di)(di)一(yi)(yi)(yi)(yi)配位(wei)(wei)化(hua)(hua)(hua)合(he)物(wu)(wu)的(de)(de)(de)(de)(de)(de)(de)(de)還(huan)(huan)(huan)原形(xing)(xing)(xing)式(shi)(shi)(shi)是(shi)(shi)(shi)吸(xi)(xi)(xi)收(shou)的(de)(de)(de)(de)(de)(de)(de)(de)并(bing)(bing)且第(di)(di)(di)(di)一(yi)(yi)(yi)(yi)配位(wei)(wei)化(hua)(hua)(hua)合(he)物(wu)(wu)的(de)(de)(de)(de)(de)(de)(de)(de)氧(yang)化(hua)(hua)(hua)形(xing)(xing)(xing)式(shi)(shi)(shi)是(shi)(shi)(shi)不(bu)吸(xi)(xi)(xi)收(shou)的(de)(de)(de)(de)(de)(de)(de)(de)。
在進一步的(de)實施(shi)例(li)中,吸(xi)收(shou)(shou)光(guang)譜的(de)斜(xie)率可(ke)以(yi)在給定(ding)波長處(chu)測(ce)量(liang)(liang)并且與荷(he)(he)電狀態(tai)關(guan)聯。隨著荷(he)(he)電狀態(tai)的(de)變(bian)化,吸(xi)收(shou)(shou)光(guang)譜的(de)斜(xie)率可(ke)以(yi)以(yi)相應的(de)方式改(gai)變(bian)。吸(xi)收(shou)(shou)光(guang)譜的(de)斜(xie)率可(ke)以(yi)例(li)如通(tong)過將(jiang)切(qie)線擬合到吸(xi)收(shou)(shou)光(guang)譜并測(ce)量(liang)(liang)切(qie)線的(de)斜(xie)率來確(que)定(ding)。然后可(ke)以(yi)將(jiang)測(ce)量(liang)(liang)的(de)斜(xie)率與實際的(de)荷(he)(he)電狀態(tai)相關(guan)聯(例(li)如,經由查找表或計(ji)算機數據(ju)庫)。
如(ru)以上(shang)所指(zhi)示(shi)的(de)(de),當測(ce)量全電池的(de)(de)狀(zhuang)態時,可(ke)以使(shi)用本(ben)公(gong)開的(de)(de)技(ji)(ji)術(shu)獨立(li)(li)地測(ce)定(ding)第(di)一(yi)電解(jie)質(zhi)(zhi)溶(rong)(rong)液(ye)(ye)(ye)(ye)和(he)第(di)二電解(jie)質(zhi)(zhi)溶(rong)(rong)液(ye)(ye)(ye)(ye)。如(ru)果確定(ding)電解(jie)質(zhi)(zhi)溶(rong)(rong)液(ye)(ye)(ye)(ye)的(de)(de)任(ren)意一(yi)個不(bu)是處于所期望(wang)的(de)(de)狀(zhuang)態,則(ze)(ze)可(ke)以調(diao)節電解(jie)質(zhi)(zhi)溶(rong)(rong)液(ye)(ye)(ye)(ye)的(de)(de)任(ren)意一(yi)個的(de)(de)狀(zhuang)態。例如(ru),如(ru)果第(di)一(yi)電解(jie)質(zhi)(zhi)溶(rong)(rong)液(ye)(ye)(ye)(ye)和(he)第(di)二電解(jie)質(zhi)(zhi)溶(rong)(rong)液(ye)(ye)(ye)(ye)失衡(heng),則(ze)(ze)可(ke)以調(diao)節電解(jie)質(zhi)(zhi)溶(rong)(rong)液(ye)(ye)(ye)(ye)中的(de)(de)一(yi)個或(huo)(huo)兩者(zhe)以恢復平衡(heng)。然(ran)而,應(ying)當認識到的(de)(de)是,可(ke)以調(diao)節電解(jie)質(zhi)(zhi)溶(rong)(rong)液(ye)(ye)(ye)(ye)中的(de)(de)一(yi)個或(huo)(huo)兩者(zhe),而不(bu)進行其它的(de)(de)獨立(li)(li)測(ce)定(ding)。例如(ru),可(ke)以對電解(jie)質(zhi)(zhi)溶(rong)(rong)液(ye)(ye)(ye)(ye)中的(de)(de)一(yi)個或(huo)(huo)兩者(zhe)設置一(yi)組預定(ding)義的(de)(de)條(tiao)(tiao)件,并且如(ru)果如(ru)本(ben)公(gong)開的(de)(de)技(ji)(ji)術(shu)確定(ding)的(de)(de)第(di)一(yi)電解(jie)質(zhi)(zhi)溶(rong)(rong)液(ye)(ye)(ye)(ye)進入(ru)超(chao)范圍的(de)(de)條(tiao)(tiao)件,則(ze)(ze)操作員或(huo)(huo)自動化軟件可(ke)以采取校正(zheng)措施來糾(jiu)正(zheng)該情況。
因此(ci),本(ben)公開的(de)(de)(de)方法可(ke)以(yi)包(bao)括基于其荷電(dian)狀態來調(diao)(diao)整(zheng)至少第(di)(di)一(yi)電(dian)解(jie)質(zhi)溶(rong)(rong)(rong)液(ye)(ye)(ye)(ye)。在進一(yi)步的(de)(de)(de)實(shi)施(shi)例中,調(diao)(diao)整(zheng)第(di)(di)一(yi)電(dian)解(jie)質(zhi)溶(rong)(rong)(rong)液(ye)(ye)(ye)(ye)可(ke)以(yi)包(bao)括再調(diao)(diao)節或(huo)再平衡第(di)(di)一(yi)電(dian)解(jie)質(zhi)溶(rong)(rong)(rong)液(ye)(ye)(ye)(ye)、稀釋第(di)(di)一(yi)電(dian)解(jie)質(zhi)溶(rong)(rong)(rong)液(ye)(ye)(ye)(ye)、向第(di)(di)一(yi)電(dian)解(jie)質(zhi)溶(rong)(rong)(rong)液(ye)(ye)(ye)(ye)中加(jia)入(ru)另(ling)外量的(de)(de)(de)第(di)(di)一(yi)配位化(hua)(hua)合物、增加(jia)通過電(dian)解(jie)質(zhi)溶(rong)(rong)(rong)液(ye)(ye)(ye)(ye)的(de)(de)(de)電(dian)流、減小通過電(dian)解(jie)質(zhi)溶(rong)(rong)(rong)液(ye)(ye)(ye)(ye)的(de)(de)(de)電(dian)流、或(huo)其任意組合中的(de)(de)(de)至少一(yi)個。用于再調(diao)(diao)節或(huo)再平衡電(dian)解(jie)質(zhi)溶(rong)(rong)(rong)液(ye)(ye)(ye)(ye)的(de)(de)(de)合適(shi)的(de)(de)(de)技(ji)術和設備對(dui)于本(ben)領(ling)域普通技(ji)術人(ren)員來說是(shi)熟悉的(de)(de)(de)。例如,再調(diao)(diao)節或(huo)再平衡電(dian)解(jie)質(zhi)溶(rong)(rong)(rong)液(ye)(ye)(ye)(ye)可(ke)以(yi)涉及存在于第(di)(di)一(yi)電(dian)解(jie)質(zhi)溶(rong)(rong)(rong)液(ye)(ye)(ye)(ye)中的(de)(de)(de)第(di)(di)一(yi)配位化(hua)(hua)合物的(de)(de)(de)化(hua)(hua)學氧化(hua)(hua)或(huo)還原或(huo)者電(dian)化(hua)(hua)學氧化(hua)(hua)或(huo)還原。
用于調整第一(yi)電解質(zhi)溶液(ye)的進一(yi)步(bu)的技術可以(yi)涉及:在液(ye)流電池的特定情況下改變第一(yi)電解質(zhi)溶液(ye)的流速;增(zeng)加或減小恒(heng)電流操(cao)(cao)作中的電流密度或恒(heng)電位操(cao)(cao)作中的電壓;和/或增(zeng)加或減小電力輸入或輸出。
如(ru)以(yi)上所討(tao)論的(de),在(zai)一些實施例(li)中,上述電(dian)化學系(xi)統可以(yi)構成液流電(dian)池(chi)。示例(li)性液流電(dian)池(chi)的(de)討(tao)論在(zai)下文(wen)中闡述,其包括(kuo)液流電(dian)池(chi)內(nei)的(de)位置(zhi),在(zai)該位置(zhi)處(chu)可以(yi)通過本文(wen)公開的(de)技術來(lai)測定電(dian)解質溶(rong)液以(yi)確定荷電(dian)狀態(tai)。
在(zai)(zai)各種實施例中(zhong),液(ye)(ye)流電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)池可以(yi)包(bao)括:第(di)(di)一(yi)(yi)室(shi)(shi),其(qi)(qi)包(bao)含與第(di)(di)一(yi)(yi)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)解(jie)(jie)(jie)質(zhi)(zhi)(zhi)(zhi)(zhi)溶(rong)(rong)(rong)(rong)(rong)液(ye)(ye)接(jie)(jie)觸的(de)(de)(de)(de)負極(ji)(ji)(ji);第(di)(di)二(er)室(shi)(shi),其(qi)(qi)包(bao)含與第(di)(di)二(er)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)解(jie)(jie)(jie)質(zhi)(zhi)(zhi)(zhi)(zhi)溶(rong)(rong)(rong)(rong)(rong)液(ye)(ye)接(jie)(jie)觸的(de)(de)(de)(de)正極(ji)(ji)(ji);以(yi)及(ji)(ji)隔膜(mo),其(qi)(qi)被設置(zhi)在(zai)(zai)第(di)(di)一(yi)(yi)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)解(jie)(jie)(jie)質(zhi)(zhi)(zhi)(zhi)(zhi)溶(rong)(rong)(rong)(rong)(rong)液(ye)(ye)和第(di)(di)二(er)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)解(jie)(jie)(jie)質(zhi)(zhi)(zhi)(zhi)(zhi)溶(rong)(rong)(rong)(rong)(rong)液(ye)(ye)之(zhi)間(jian)。電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)解(jie)(jie)(jie)質(zhi)(zhi)(zhi)(zhi)(zhi)室(shi)(shi)在(zai)(zai)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)池內提供分開(kai)的(de)(de)(de)(de)儲存(cun)(cun)器,第(di)(di)一(yi)(yi)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)解(jie)(jie)(jie)質(zhi)(zhi)(zhi)(zhi)(zhi)溶(rong)(rong)(rong)(rong)(rong)液(ye)(ye)和/或第(di)(di)二(er)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)解(jie)(jie)(jie)質(zhi)(zhi)(zhi)(zhi)(zhi)溶(rong)(rong)(rong)(rong)(rong)液(ye)(ye)通(tong)過(guo)分開(kai)的(de)(de)(de)(de)儲存(cun)(cun)器循(xun)(xun)環(huan),以(yi)便接(jie)(jie)觸各自(zi)的(de)(de)(de)(de)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)極(ji)(ji)(ji)和隔膜(mo)。每個室(shi)(shi)及(ji)(ji)其(qi)(qi)相關(guan)聯的(de)(de)(de)(de)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)極(ji)(ji)(ji)和電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)解(jie)(jie)(jie)質(zhi)(zhi)(zhi)(zhi)(zhi)溶(rong)(rong)(rong)(rong)(rong)液(ye)(ye)限定相應的(de)(de)(de)(de)半電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)池。隔膜(mo)提供若干功能,其(qi)(qi)包(bao)括,例如,(1)用作第(di)(di)一(yi)(yi)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)解(jie)(jie)(jie)質(zhi)(zhi)(zhi)(zhi)(zhi)溶(rong)(rong)(rong)(rong)(rong)液(ye)(ye)和第(di)(di)二(er)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)解(jie)(jie)(jie)質(zhi)(zhi)(zhi)(zhi)(zhi)溶(rong)(rong)(rong)(rong)(rong)液(ye)(ye)及(ji)(ji)其(qi)(qi)活性(xing)物(wu)(wu)質(zhi)(zhi)(zhi)(zhi)(zhi)混合的(de)(de)(de)(de)屏(ping)障,(2)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)絕緣(yuan)以(yi)減少或防(fang)止(zhi)正極(ji)(ji)(ji)和負極(ji)(ji)(ji)之(zhi)間(jian)的(de)(de)(de)(de)短路,以(yi)及(ji)(ji)(3)以(yi)促進正極(ji)(ji)(ji)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)解(jie)(jie)(jie)質(zhi)(zhi)(zhi)(zhi)(zhi)室(shi)(shi)和負極(ji)(ji)(ji)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)解(jie)(jie)(jie)質(zhi)(zhi)(zhi)(zhi)(zhi)室(shi)(shi)之(zhi)間(jian)的(de)(de)(de)(de)離子(zi)(zi)傳(chuan)輸(shu),從而(er)在(zai)(zai)充(chong)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)和放(fang)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)循(xun)(xun)環(huan)期(qi)間(jian)平(ping)衡電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)子(zi)(zi)傳(chuan)輸(shu)。負極(ji)(ji)(ji)和正極(ji)(ji)(ji)提供其(qi)(qi)中(zhong)在(zai)(zai)充(chong)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)和放(fang)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)循(xun)(xun)環(huan)期(qi)間(jian)可以(yi)發(fa)生(sheng)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)化學(xue)反應的(de)(de)(de)(de)表面。在(zai)(zai)充(chong)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)或放(fang)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)循(xun)(xun)環(huan)期(qi)間(jian),電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)解(jie)(jie)(jie)質(zhi)(zhi)(zhi)(zhi)(zhi)溶(rong)(rong)(rong)(rong)(rong)液(ye)(ye)可以(yi)從單獨的(de)(de)(de)(de)儲存(cun)(cun)罐被輸(shu)送通(tong)過(guo)相應的(de)(de)(de)(de)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)解(jie)(jie)(jie)質(zhi)(zhi)(zhi)(zhi)(zhi)室(shi)(shi)。在(zai)(zai)充(chong)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)循(xun)(xun)環(huan)中(zhong),電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)力可以(yi)被施加到電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)池,使得包(bao)含在(zai)(zai)第(di)(di)二(er)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)解(jie)(jie)(jie)質(zhi)(zhi)(zhi)(zhi)(zhi)溶(rong)(rong)(rong)(rong)(rong)液(ye)(ye)中(zhong)的(de)(de)(de)(de)活性(xing)物(wu)(wu)質(zhi)(zhi)(zhi)(zhi)(zhi)經(jing)歷一(yi)(yi)次(ci)或多次(ci)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)子(zi)(zi)氧化,并(bing)且第(di)(di)一(yi)(yi)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)解(jie)(jie)(jie)質(zhi)(zhi)(zhi)(zhi)(zhi)溶(rong)(rong)(rong)(rong)(rong)液(ye)(ye)中(zhong)的(de)(de)(de)(de)活性(xing)物(wu)(wu)質(zhi)(zhi)(zhi)(zhi)(zhi)經(jing)歷一(yi)(yi)次(ci)或多次(ci)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)子(zi)(zi)還原。類(lei)似(si)地,在(zai)(zai)放(fang)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)循(xun)(xun)環(huan)中(zhong),第(di)(di)二(er)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)解(jie)(jie)(jie)質(zhi)(zhi)(zhi)(zhi)(zhi)溶(rong)(rong)(rong)(rong)(rong)液(ye)(ye)中(zhong)的(de)(de)(de)(de)活性(xing)物(wu)(wu)質(zhi)(zhi)(zhi)(zhi)(zhi)被還原,并(bing)且第(di)(di)一(yi)(yi)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)解(jie)(jie)(jie)質(zhi)(zhi)(zhi)(zhi)(zhi)中(zhong)的(de)(de)(de)(de)活性(xing)物(wu)(wu)質(zhi)(zhi)(zhi)(zhi)(zhi)被氧化以(yi)生(sheng)成電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)力。
在更具體的實施例中,說明性液流電池可以包括:(a)第一電解質水溶液,其含有第一配位化合物;(b)第二電解質水溶液,其含有第二配位化合物;(c)隔膜,其被定位在所述第一電解質水溶液和所述第二電解質水溶液之間;以及(d)在第一電解質水溶液和第二電解質水溶液中的移動離子。如以下更詳細描述的,隔膜可以是離聚物膜,并且其可以具有小于100微米的厚度,并且具有與第一配位化合物和第二配位化合物的凈電荷的符號相同的符號的相關凈電荷。在一些各種實施例中,第一配位化合物和第二配位化合物中的一個可以是鐵氰化物[fe(cn)63-]和亞鐵氰化物[fe(cn)64-]的(de)氧(yang)(yang)化(hua)(hua)(hua)(hua)還原(yuan)對(dui)。在更具體的(de)實施例中(zhong)(zhong),鐵氰化(hua)(hua)(hua)(hua)物(wu)(wu)/亞鐵氰化(hua)(hua)(hua)(hua)物(wu)(wu)氧(yang)(yang)化(hua)(hua)(hua)(hua)還原(yuan)對(dui)可(ke)以用(yong)作第(di)一電解(jie)(jie)質溶液(ye)中(zhong)(zhong)的(de)第(di)一配位化(hua)(hua)(hua)(hua)合(he)(he)物(wu)(wu),并且第(di)二電解(jie)(jie)質溶液(ye)中(zhong)(zhong)的(de)第(di)二配位化(hua)(hua)(hua)(hua)合(he)(he)物(wu)(wu)可(ke)以是(shi)含有至少一個兒茶酚酶配位體的(de)配位化(hua)(hua)(hua)(hua)合(he)(he)物(wu)(wu)。
圖(tu)2描繪(hui)說明性液流(liu)電池的示意圖(tu)。不同(tong)于其中活性物質和其它(ta)組分容置(zhi)在(zai)單個組件中的典(dian)型(xing)的電池技術(例(li)如,鋰離子、鎳金屬氫化(hua)物、鉛(qian)酸等),液流(liu)電池通(tong)過電化(hua)學堆從儲(chu)(chu)存罐輸送(song)(例(li)如,經由泵送(song))氧化(hua)還(huan)原活性能(neng)量(liang)(liang)存儲(chu)(chu)材料。該設(she)計(ji)特征將電能(neng)存儲(chu)(chu)系統的電力與能(neng)量(liang)(liang)存儲(chu)(chu)容量(liang)(liang)分離,從而允許相當大的設(she)計(ji)靈活性和成本優(you)化(hua)。
如(ru)圖2所示(shi),液(ye)(ye)流電(dian)(dian)池(chi)系統11包括電(dian)(dian)化學(xue)電(dian)(dian)池(chi),其以分(fen)離電(dian)(dian)化學(xue)電(dian)(dian)池(chi)的(de)兩(liang)個電(dian)(dian)極10和(he)10’的(de)隔膜20(例如(ru),膜)為特征。電(dian)(dian)極10和(he)10’由諸如(ru)金屬、碳、石墨等的(de)適(shi)當(dang)的(de)導電(dian)(dian)材料形成。罐50包含在第一電(dian)(dian)解質溶液(ye)(ye)中的(de)第一活(huo)性物(wu)質30,該物(wu)質能夠(gou)在氧(yang)化狀(zhuang)態和(he)還原狀(zhuang)態之間循環。例如(ru),第一活(huo)性物(wu)質30可以是配位化合物(wu)。
泵60影響(xiang)第(di)(di)(di)一(yi)活(huo)(huo)(huo)性(xing)物質(zhi)30從罐(guan)50到(dao)電(dian)(dian)(dian)(dian)化(hua)(hua)學(xue)(xue)電(dian)(dian)(dian)(dian)池(chi)(chi)的(de)(de)輸(shu)送(song)。液流(liu)電(dian)(dian)(dian)(dian)池(chi)(chi)還(huan)(huan)適(shi)(shi)當地包括包含第(di)(di)(di)二(er)(er)活(huo)(huo)(huo)性(xing)物質(zhi)40的(de)(de)第(di)(di)(di)二(er)(er)罐(guan)50’。第(di)(di)(di)二(er)(er)活(huo)(huo)(huo)性(xing)物質(zhi)40可(ke)以(yi)與(yu)活(huo)(huo)(huo)性(xing)物質(zhi)30相同,也可(ke)以(yi)不同。例(li)如(ru),如(ru)上所(suo)述,第(di)(di)(di)二(er)(er)活(huo)(huo)(huo)性(xing)物質(zhi)40可(ke)以(yi)是鐵氰(qing)化(hua)(hua)物/亞(ya)鐵氰(qing)化(hua)(hua)物。第(di)(di)(di)二(er)(er)泵60’可(ke)以(yi)影響(xiang)第(di)(di)(di)二(er)(er)活(huo)(huo)(huo)性(xing)物質(zhi)40向電(dian)(dian)(dian)(dian)化(hua)(hua)學(xue)(xue)電(dian)(dian)(dian)(dian)池(chi)(chi)的(de)(de)輸(shu)送(song)。泵還(huan)(huan)可(ke)用(yong)于(yu)影響(xiang)活(huo)(huo)(huo)性(xing)物質(zhi)從電(dian)(dian)(dian)(dian)化(hua)(hua)學(xue)(xue)電(dian)(dian)(dian)(dian)池(chi)(chi)返回到(dao)罐(guan)50和50’的(de)(de)輸(shu)送(song)(圖(tu)2中未示出(chu))。例(li)如(ru),諸(zhu)如(ru)虹吸管(guan)的(de)(de)其(qi)(qi)它影響(xiang)流(liu)體輸(shu)送(song)的(de)(de)方法也可(ke)以(yi)適(shi)(shi)當地將第(di)(di)(di)一(yi)活(huo)(huo)(huo)性(xing)物質(zhi)30和第(di)(di)(di)二(er)(er)活(huo)(huo)(huo)性(xing)物質(zhi)40輸(shu)送(song)到(dao)電(dian)(dian)(dian)(dian)化(hua)(hua)學(xue)(xue)電(dian)(dian)(dian)(dian)池(chi)(chi)中以(yi)及從電(dian)(dian)(dian)(dian)化(hua)(hua)學(xue)(xue)電(dian)(dian)(dian)(dian)池(chi)(chi)輸(shu)送(song)出(chu)。圖(tu)2中還(huan)(huan)示出(chu)了電(dian)(dian)(dian)(dian)源或負載70,其(qi)(qi)完成(cheng)電(dian)(dian)(dian)(dian)化(hua)(hua)學(xue)(xue)電(dian)(dian)(dian)(dian)池(chi)(chi)的(de)(de)回路(lu)并(bing)且(qie)允許用(yong)戶在其(qi)(qi)操作期間收集或存儲(chu)電(dian)(dian)(dian)(dian)力。
應當理解的(de)(de)是,圖2描繪液(ye)(ye)流電(dian)池的(de)(de)具體的(de)(de)非限制性實(shi)施例(li)。因此,與本公開的(de)(de)精神一致的(de)(de)液(ye)(ye)流電(dian)池可(ke)以相對于(yu)圖2的(de)(de)配置在各個(ge)方(fang)面不同。作(zuo)為一個(ge)示例(li),液(ye)(ye)流電(dian)池系(xi)統可(ke)以包括一個(ge)或多(duo)個(ge)活性物質,其為固(gu)體、氣體和(he)/或溶解在液(ye)(ye)體中的(de)(de)氣體。活性物質可(ke)以儲存在罐中、儲存在通向大(da)氣中的(de)(de)容器中、或者僅僅排放到大(da)氣中。
在(zai)(zai)(zai)進一(yi)(yi)(yi)步討論液(ye)流(liu)電(dian)(dian)(dian)(dian)(dian)(dian)池(chi)(chi)(chi)的(de)(de)各(ge)種(zhong)部(bu)件(jian)之(zhi)前,應當(dang)注(zhu)意的(de)(de)是,用于進行atr光譜法的(de)(de)機(ji)構可(ke)(ke)以(yi)并入液(ye)流(liu)電(dian)(dian)(dian)(dian)(dian)(dian)池(chi)(chi)(chi)系統11內的(de)(de)任(ren)(ren)何點處(chu)。在(zai)(zai)(zai)一(yi)(yi)(yi)些實(shi)施(shi)例(li)(li)中,電(dian)(dian)(dian)(dian)(dian)(dian)磁輻(fu)射(she)可(ke)(ke)以(yi)與(yu)(yu)接(jie)近第(di)一(yi)(yi)(yi)電(dian)(dian)(dian)(dian)(dian)(dian)極的(de)(de)第(di)一(yi)(yi)(yi)電(dian)(dian)(dian)(dian)(dian)(dian)解(jie)質溶(rong)(rong)液(ye)相(xiang)互(hu)作用。為了本公(gong)開的(de)(de)目的(de)(de),短(duan)語“接(jie)近第(di)一(yi)(yi)(yi)電(dian)(dian)(dian)(dian)(dian)(dian)極”將(jiang)(jiang)指的(de)(de)是在(zai)(zai)(zai)隔(ge)膜20與(yu)(yu)電(dian)(dian)(dian)(dian)(dian)(dian)極10和(he)10’之(zhi)間限定(ding)的(de)(de)室(shi)內的(de)(de)任(ren)(ren)何位置(未在(zai)(zai)(zai)圖2中標(biao)記)。在(zai)(zai)(zai)其它各(ge)種(zhong)實(shi)施(shi)例(li)(li)中,電(dian)(dian)(dian)(dian)(dian)(dian)磁輻(fu)射(she)可(ke)(ke)以(yi)在(zai)(zai)(zai)限定(ding)液(ye)流(liu)電(dian)(dian)(dian)(dian)(dian)(dian)池(chi)(chi)(chi)的(de)(de)電(dian)(dian)(dian)(dian)(dian)(dian)池(chi)(chi)(chi)外(wai)部(bu)的(de)(de)任(ren)(ren)何點處(chu)與(yu)(yu)第(di)一(yi)(yi)(yi)電(dian)(dian)(dian)(dian)(dian)(dian)解(jie)質溶(rong)(rong)液(ye)相(xiang)互(hu)作用。為了本公(gong)開的(de)(de)目的(de)(de),短(duan)語“電(dian)(dian)(dian)(dian)(dian)(dian)池(chi)(chi)(chi)外(wai)部(bu)”將(jiang)(jiang)指的(de)(de)是不在(zai)(zai)(zai)電(dian)(dian)(dian)(dian)(dian)(dian)極10和(he)10’與(yu)(yu)隔(ge)膜20之(zhi)間限定(ding)的(de)(de)室(shi)內的(de)(de)任(ren)(ren)何點。在(zai)(zai)(zai)說明性實(shi)施(shi)例(li)(li)中,電(dian)(dian)(dian)(dian)(dian)(dian)磁輻(fu)射(she)可(ke)(ke)以(yi)在(zai)(zai)(zai)罐50或(huo)50’內,或(huo)在(zai)(zai)(zai)將(jiang)(jiang)第(di)一(yi)(yi)(yi)電(dian)(dian)(dian)(dian)(dian)(dian)解(jie)質溶(rong)(rong)液(ye)輸送到電(dian)(dian)(dian)(dian)(dian)(dian)池(chi)(chi)(chi)中和(he)從電(dian)(dian)(dian)(dian)(dian)(dian)池(chi)(chi)(chi)輸送出的(de)(de)線路內的(de)(de)任(ren)(ren)何點處(chu),與(yu)(yu)第(di)一(yi)(yi)(yi)電(dian)(dian)(dian)(dian)(dian)(dian)解(jie)質溶(rong)(rong)液(ye)相(xiang)互(hu)作用。
當結(jie)合(he)在(zai)液流電池或其(qi)它(ta)電化(hua)學(xue)(xue)系(xi)(xi)統內(nei)時,將(jiang)電磁輻射傳遞(di)到第一(yi)電解質溶液并且在(zai)其(qi)中提供一(yi)個或多個內(nei)反射的光學(xue)(xue)材(cai)料可以是任(ren)何合(he)適(shi)的形式。在(zai)一(yi)些(xie)實施例(li)中,光學(xue)(xue)材(cai)料可以構成探(tan)針的至少一(yi)部(bu)分,其(qi)被結(jie)合(he)在(zai)電化(hua)學(xue)(xue)系(xi)(xi)統內(nei)的給(gei)定(ding)位置(zhi)處。在(zai)一(yi)些(xie)或其(qi)它(ta)實施例(li)中,例(li)如,光學(xue)(xue)材(cai)料可以物理地(di)安(an)裝在(zai)電化(hua)學(xue)(xue)系(xi)(xi)統中,諸(zhu)如以流通池的形式。在(zai)其(qi)它(ta)實施例(li)中,光學(xue)(xue)材(cai)料可以臨時地(di)或“按需(xu)地(di)”結(jie)合(he)在(zai)電化(hua)學(xue)(xue)系(xi)(xi)統中,諸(zhu)如通過在(zai)合(he)適(shi)的位置(zhi)插入(ru)便(bian)攜式探(tan)頭。
在(zai)一些實(shi)施(shi)例中(zhong),電(dian)磁輻(fu)(fu)射(she)(she)可(ke)以(yi)通(tong)過諸(zhu)如光纖(xian)(xian)(xian)材(cai)(cai)料的(de)合適(shi)的(de)傳輸介(jie)質被(bei)(bei)傳送(song)到(dao)光學(xue)材(cai)(cai)料和/或(huo)從光學(xue)材(cai)(cai)料傳送(song)。即,電(dian)磁輻(fu)(fu)射(she)(she)源、光纖(xian)(xian)(xian)材(cai)(cai)料、被(bei)(bei)配置為衰減全反射(she)(she)率的(de)光學(xue)材(cai)(cai)料和檢(jian)測器(qi)可(ke)以(yi)彼此連續地(di)布置。在(zai)一些實(shi)施(shi)例中(zhong),第(di)一光纖(xian)(xian)(xian)通(tong)道可(ke)以(yi)將電(dian)磁輻(fu)(fu)射(she)(she)傳送(song)到(dao)光學(xue)材(cai)(cai)料,并(bing)且第(di)二光纖(xian)(xian)(xian)通(tong)道可(ke)以(yi)將經歷(li)衰減全反射(she)(she)率的(de)電(dian)磁輻(fu)(fu)射(she)(she)傳送(song)回到(dao)檢(jian)測器(qi)。
合(he)適(shi)的檢(jian)(jian)測(ce)器不被認(ren)為是(shi)特別限制的。在一些實(shi)施例中,合(he)適(shi)的檢(jian)(jian)測(ce)器可以(yi)是(shi)光電二極管陣列檢(jian)(jian)測(ce)器。
應當進一(yi)步理(li)解(jie)的是,根據本(ben)公開,當第一(yi)電(dian)(dian)(dian)(dian)解(jie)質(zhi)(zhi)溶液(ye)與電(dian)(dian)(dian)(dian)磁輻射相(xiang)(xiang)互(hu)作用(yong)(yong)時,第一(yi)電(dian)(dian)(dian)(dian)解(jie)質(zhi)(zhi)溶液(ye)可(ke)以(yi)是流動的或(huo)靜態的。類似地,在與電(dian)(dian)(dian)(dian)磁輻射相(xiang)(xiang)互(hu)作用(yong)(yong)期(qi)間,第一(yi)電(dian)(dian)(dian)(dian)解(jie)質(zhi)(zhi)溶液(ye)可(ke)以(yi)處于經(jing)歷充(chong)電(dian)(dian)(dian)(dian)或(huo)放電(dian)(dian)(dian)(dian)的狀態中,或(huo)者其可(ke)以(yi)處于靜態充(chong)電(dian)(dian)(dian)(dian)狀態或(huo)靜態放電(dian)(dian)(dian)(dian)狀態。
如本文所使用(yong)的(de),術語(yu)“隔(ge)(ge)(ge)膜(mo)(mo)”和“膜(mo)(mo)”將指的(de)是設(she)置(zhi)在電化學電池的(de)正極(ji)和負極(ji)之間(jian)的(de)離(li)子(zi)導電和電絕緣材料。在一(yi)些實(shi)(shi)施例(li)中,隔(ge)(ge)(ge)膜(mo)(mo)可以(yi)是多孔膜(mo)(mo),和/或在其它各種(zhong)實(shi)(shi)施例(li)中,隔(ge)(ge)(ge)膜(mo)(mo)可以(yi)是離(li)聚物(wu)膜(mo)(mo)。在一(yi)些實(shi)(shi)施例(li)中,隔(ge)(ge)(ge)膜(mo)(mo)可以(yi)由離(li)子(zi)導電聚合(he)物(wu)形成。
聚(ju)(ju)合(he)物(wu)(wu)(wu)膜可(ke)以(yi)是(shi)陰(yin)離(li)(li)(li)(li)(li)子(zi)導電(dian)(dian)電(dian)(dian)解質或陽離(li)(li)(li)(li)(li)子(zi)導電(dian)(dian)電(dian)(dian)解質。當描述為(wei)“離(li)(li)(li)(li)(li)聚(ju)(ju)物(wu)(wu)(wu)”時,該術(shu)語是(shi)指含(han)有電(dian)(dian)中(zhong)(zhong)性重(zhong)(zhong)復(fu)單(dan)(dan)元和(he)(he)電(dian)(dian)離(li)(li)(li)(li)(li)重(zhong)(zhong)復(fu)單(dan)(dan)元的聚(ju)(ju)合(he)物(wu)(wu)(wu)膜,其中(zhong)(zhong)電(dian)(dian)離(li)(li)(li)(li)(li)重(zhong)(zhong)復(fu)單(dan)(dan)元是(shi)側鏈(lian)并(bing)(bing)且(qie)共價(jia)鍵合(he)到聚(ju)(ju)合(he)物(wu)(wu)(wu)主鏈(lian)上。通常,電(dian)(dian)離(li)(li)(li)(li)(li)單(dan)(dan)元的分(fen)(fen)數可(ke)以(yi)從約(yue)(yue)(yue)(yue)1摩爾(er)(er)百(bai)分(fen)(fen)比至約(yue)(yue)(yue)(yue)90摩爾(er)(er)百(bai)分(fen)(fen)比變化。例(li)(li)如(ru),在(zai)一(yi)些(xie)實施(shi)例(li)(li)中(zhong)(zhong),電(dian)(dian)離(li)(li)(li)(li)(li)單(dan)(dan)元的含(han)量(liang)小于約(yue)(yue)(yue)(yue)15摩爾(er)(er)百(bai)分(fen)(fen)比;并(bing)(bing)且(qie)在(zai)其它(ta)實施(shi)例(li)(li)中(zhong)(zhong),離(li)(li)(li)(li)(li)子(zi)含(han)量(liang)較高,諸(zhu)如(ru)大于約(yue)(yue)(yue)(yue)80摩爾(er)(er)百(bai)分(fen)(fen)比。在(zai)另外的實施(shi)例(li)(li)中(zhong)(zhong),離(li)(li)(li)(li)(li)子(zi)含(han)量(liang)由中(zhong)(zhong)間范(fan)圍(wei)限定,例(li)(li)如(ru),在(zai)約(yue)(yue)(yue)(yue)15至約(yue)(yue)(yue)(yue)80摩爾(er)(er)百(bai)分(fen)(fen)比的范(fan)圍(wei)內。離(li)(li)(li)(li)(li)聚(ju)(ju)物(wu)(wu)(wu)中(zhong)(zhong)的電(dian)(dian)離(li)(li)(li)(li)(li)重(zhong)(zhong)復(fu)單(dan)(dan)元可(ke)包(bao)(bao)括諸(zhu)如(ru)磺酸(suan)鹽(yan)、羧(suo)酸(suan)鹽(yan)等(deng)的陰(yin)離(li)(li)(li)(li)(li)子(zi)官(guan)能團。這些(xie)官(guan)能團可(ke)以(yi)通過單(dan)(dan)-、雙-或更(geng)高化合(he)價(jia)的陽離(li)(li)(li)(li)(li)子(zi),諸(zhu)如(ru)堿(jian)金屬或堿(jian)土金屬來(lai)電(dian)(dian)荷平衡(heng)。離(li)(li)(li)(li)(li)聚(ju)(ju)物(wu)(wu)(wu)也可(ke)以(yi)包(bao)(bao)括含(han)有連接或嵌入的季(ji)銨、锍、磷腈(jing)鹽(yan)和(he)(he)胍鹽(yan)殘基或鹽(yan)的聚(ju)(ju)合(he)物(wu)(wu)(wu)組合(he)物(wu)(wu)(wu)。本領域普通技術(shu)人員將(jiang)熟悉適(shi)當的示例(li)(li)。
在一些實施例中,作為隔膜的聚合物可以包括高度氟化或全氟化的聚合物主鏈。在本公開中有用的某些聚合物可以包括四氟乙烯和一個或多個氟化的酸官能共聚單體的共聚物,其可作為nafiontm全氟化聚合物電解質從杜邦(dupont)商購獲得。其它有用的全氟化聚合物可以包括四氟乙烯和fso2-cf2cf2cf2cf2-o-cf=cf2、flemiontm和selemiontm的共聚物。
另外,還可以使用利(li)用磺(huang)酸基(ji)(ji)團(tuan)(或(huo)陽離(li)子交換的(de)磺(huang)酸鹽基(ji)(ji)團(tuan))改性(xing)的(de)基(ji)(ji)本上非氟(fu)化(hua)的(de)膜(mo)。這樣(yang)的(de)膜(mo)可以包(bao)括具有(you)基(ji)(ji)本上芳族主鏈的(de)那些,諸(zhu)如(ru)例(li)如(ru)聚苯乙烯、聚苯、聯苯砜(bpsh)或(huo)諸(zhu)如(ru)聚醚酮(tong)和聚醚砜的(de)熱塑性(xing)塑料。
電池(chi)隔膜式多孔(kong)膜,也可(ke)用(yong)作隔膜。因(yin)為它們不包含固有的(de)離子傳(chuan)導能力(li),所以(yi)這些(xie)膜通常利用(yong)添(tian)加劑浸漬以(yi)起作用(yong)。這些(xie)膜通常包含聚(ju)(ju)合(he)物(wu)和無機填料(liao)的(de)混合(he)物(wu)以(yi)及具有開孔(kong)孔(kong)隙度(du)。合(he)適的(de)聚(ju)(ju)合(he)物(wu)可(ke)以(yi)包括(kuo)例如(ru)高(gao)密度(du)聚(ju)(ju)乙烯、聚(ju)(ju)丙烯、聚(ju)(ju)偏二氟乙烯(pvdf)或(huo)聚(ju)(ju)四氟乙烯(ptfe)。合(he)適的(de)無機填料(liao)可(ke)以(yi)包括(kuo)碳化硅基體(ti)材料(liao)、二氧化鈦(tai)、二氧化硅、磷(lin)化鋅和二氧化鈰(shi)。
隔膜也可以由聚(ju)酯、聚(ju)醚酮、聚(ju)(氯乙烯(xi))、乙烯(xi)基聚(ju)合(he)物(wu)和取代的乙烯(xi)基聚(ju)合(he)物(wu)形成。這些可以單獨使用或與任何(he)先(xian)前描述的聚(ju)合(he)物(wu)組合(he)使用。
多(duo)孔(kong)隔膜是非導電(dian)(dian)(dian)(dian)膜,其允許電(dian)(dian)(dian)(dian)荷經由(you)填(tian)充有電(dian)(dian)(dian)(dian)解(jie)質(zhi)(zhi)的(de)(de)開放通(tong)道(dao)(dao)在(zai)兩個(ge)電(dian)(dian)(dian)(dian)極之間(jian)轉移。滲透性(xing)(xing)(xing)(xing)(xing)增加化學物質(zhi)(zhi)(例如活性(xing)(xing)(xing)(xing)(xing)物質(zhi)(zhi))通(tong)過(guo)隔膜從一個(ge)電(dian)(dian)(dian)(dian)極到另一個(ge)電(dian)(dian)(dian)(dian)極的(de)(de)可能性(xing)(xing)(xing)(xing)(xing),并且導致電(dian)(dian)(dian)(dian)池(chi)能量效率的(de)(de)交叉污染和/或降低。這種交叉污染的(de)(de)程(cheng)度可以(yi)取決于(yu)孔(kong)的(de)(de)尺寸(有效直徑(jing)和通(tong)道(dao)(dao)長度)和特(te)性(xing)(xing)(xing)(xing)(xing)(疏水(shui)性(xing)(xing)(xing)(xing)(xing)/親水(shui)性(xing)(xing)(xing)(xing)(xing))、電(dian)(dian)(dian)(dian)解(jie)質(zhi)(zhi)的(de)(de)性(xing)(xing)(xing)(xing)(xing)質(zhi)(zhi)以(yi)及孔(kong)與電(dian)(dian)(dian)(dian)解(jie)質(zhi)(zhi)之間(jian)的(de)(de)潤濕程(cheng)度等特(te)征。
多孔(kong)(kong)隔(ge)膜(mo)的(de)(de)(de)(de)(de)(de)孔(kong)(kong)尺寸分布(bu)通常(chang)足以基(ji)(ji)本上(shang)防止(zhi)兩種電解(jie)質(zhi)溶液之間(jian)的(de)(de)(de)(de)(de)(de)活性物(wu)(wu)(wu)質(zhi)的(de)(de)(de)(de)(de)(de)交(jiao)(jiao)叉(cha)。合(he)適(shi)的(de)(de)(de)(de)(de)(de)多孔(kong)(kong)膜(mo)的(de)(de)(de)(de)(de)(de)平(ping)(ping)均(jun)(jun)孔(kong)(kong)徑(jing)(jing)(jing)(jing)(jing)分布(bu)可(ke)(ke)以在(zai)(zai)約(yue)(yue)0.001nm和20微(wei)米之間(jian),更典(dian)型地在(zai)(zai)約(yue)(yue)0.001nm和100nm之間(jian)。多孔(kong)(kong)膜(mo)中(zhong)的(de)(de)(de)(de)(de)(de)孔(kong)(kong)的(de)(de)(de)(de)(de)(de)尺寸分布(bu)可(ke)(ke)以是大(da)(da)(da)量的(de)(de)(de)(de)(de)(de)。換言(yan)之,多孔(kong)(kong)膜(mo)可(ke)(ke)以包(bao)含具有(you)非(fei)常(chang)小(xiao)(xiao)直(zhi)徑(jing)(jing)(jing)(jing)(jing)(大(da)(da)(da)約(yue)(yue)小(xiao)(xiao)于(yu)(yu)1nm)的(de)(de)(de)(de)(de)(de)多個第(di)一(yi)(yi)孔(kong)(kong)和具有(you)非(fei)常(chang)大(da)(da)(da)直(zhi)徑(jing)(jing)(jing)(jing)(jing)(大(da)(da)(da)約(yue)(yue)大(da)(da)(da)于(yu)(yu)10微(wei)米)的(de)(de)(de)(de)(de)(de)多個第(di)二孔(kong)(kong)。較(jiao)大(da)(da)(da)的(de)(de)(de)(de)(de)(de)孔(kong)(kong)徑(jing)(jing)(jing)(jing)(jing)可(ke)(ke)導致較(jiao)高(gao)量的(de)(de)(de)(de)(de)(de)活性物(wu)(wu)(wu)質(zhi)交(jiao)(jiao)叉(cha)。多孔(kong)(kong)膜(mo)基(ji)(ji)本上(shang)防止(zhi)活性物(wu)(wu)(wu)質(zhi)交(jiao)(jiao)叉(cha)的(de)(de)(de)(de)(de)(de)能(neng)力可(ke)(ke)取決(jue)于(yu)(yu)平(ping)(ping)均(jun)(jun)孔(kong)(kong)徑(jing)(jing)(jing)(jing)(jing)與活性物(wu)(wu)(wu)質(zhi)之間(jian)尺寸上(shang)的(de)(de)(de)(de)(de)(de)相對(dui)差異(yi)。例(li)如(ru),當活性物(wu)(wu)(wu)質(zhi)是配(pei)位(wei)化(hua)(hua)(hua)合(he)物(wu)(wu)(wu)中(zhong)的(de)(de)(de)(de)(de)(de)金(jin)屬(shu)中(zhong)心時,配(pei)位(wei)化(hua)(hua)(hua)合(he)物(wu)(wu)(wu)的(de)(de)(de)(de)(de)(de)平(ping)(ping)均(jun)(jun)直(zhi)徑(jing)(jing)(jing)(jing)(jing)可(ke)(ke)大(da)(da)(da)于(yu)(yu)多孔(kong)(kong)膜(mo)的(de)(de)(de)(de)(de)(de)平(ping)(ping)均(jun)(jun)孔(kong)(kong)徑(jing)(jing)(jing)(jing)(jing)約(yue)(yue)50%。另一(yi)(yi)方面,如(ru)果多孔(kong)(kong)膜(mo)具有(you)基(ji)(ji)本均(jun)(jun)勻的(de)(de)(de)(de)(de)(de)孔(kong)(kong)徑(jing)(jing)(jing)(jing)(jing),則配(pei)位(wei)化(hua)(hua)(hua)合(he)物(wu)(wu)(wu)的(de)(de)(de)(de)(de)(de)平(ping)(ping)均(jun)(jun)直(zhi)徑(jing)(jing)(jing)(jing)(jing)可(ke)(ke)大(da)(da)(da)于(yu)(yu)多孔(kong)(kong)膜(mo)的(de)(de)(de)(de)(de)(de)平(ping)(ping)均(jun)(jun)孔(kong)(kong)徑(jing)(jing)(jing)(jing)(jing)約(yue)(yue)20%。同(tong)樣(yang)地,當配(pei)位(wei)化(hua)(hua)(hua)合(he)物(wu)(wu)(wu)進一(yi)(yi)步與至少(shao)一(yi)(yi)個水分子(zi)配(pei)位(wei)時,配(pei)位(wei)化(hua)(hua)(hua)合(he)物(wu)(wu)(wu)的(de)(de)(de)(de)(de)(de)平(ping)(ping)均(jun)(jun)直(zhi)徑(jing)(jing)(jing)(jing)(jing)被(bei)增(zeng)加。至少(shao)一(yi)(yi)個水分子(zi)的(de)(de)(de)(de)(de)(de)配(pei)位(wei)化(hua)(hua)(hua)合(he)物(wu)(wu)(wu)的(de)(de)(de)(de)(de)(de)直(zhi)徑(jing)(jing)(jing)(jing)(jing)通常(chang)被(bei)認為是流(liu)體(ti)(ti)動(dong)力學(xue)直(zhi)徑(jing)(jing)(jing)(jing)(jing)。在(zai)(zai)這樣(yang)的(de)(de)(de)(de)(de)(de)實施例(li)中(zhong),流(liu)體(ti)(ti)動(dong)力學(xue)直(zhi)徑(jing)(jing)(jing)(jing)(jing)通常(chang)大(da)(da)(da)于(yu)(yu)平(ping)(ping)均(jun)(jun)孔(kong)(kong)徑(jing)(jing)(jing)(jing)(jing)至少(shao)約(yue)(yue)35%。當平(ping)(ping)均(jun)(jun)孔(kong)(kong)徑(jing)(jing)(jing)(jing)(jing)基(ji)(ji)本均(jun)(jun)勻時,流(liu)體(ti)(ti)動(dong)力學(xue)半徑(jing)(jing)(jing)(jing)(jing)可(ke)(ke)以大(da)(da)(da)于(yu)(yu)平(ping)(ping)均(jun)(jun)孔(kong)(kong)徑(jing)(jing)(jing)(jing)(jing)約(yue)(yue)10%。
在一些(xie)實施(shi)例(li)中,隔膜還可(ke)以包括(kuo)用于更大穩(wen)定(ding)(ding)性的增強(qiang)材料(liao)。合(he)適的增強(qiang)材料(liao)可(ke)以包括(kuo)聚四氟乙烯、尼龍、棉(mian)、聚酯、結晶二氧(yang)化(hua)硅(gui)、結晶二氧(yang)化(hua)鈦(tai)(tai)、無定(ding)(ding)形二氧(yang)化(hua)硅(gui)、無定(ding)(ding)形二氧(yang)化(hua)鈦(tai)(tai)、橡(xiang)膠、石棉(mian)、木材或其(qi)任何(he)組合(he)。
本公開的液流電池內的隔膜可以具有以下膜厚度:小于約500微米、小于約300微米、小于約250微米、小于約200微米、小于約100微米、小于約75微米、小于約50微米、小于約30微米、小于約25微米、小于約20微米、小于約15微米、或小于約10微米。合適的隔膜可以包括如下隔膜:當隔膜具有100微米的厚度時,液流電池能夠以大于約85%的電流效率以100ma/cm2的電流密度來操作。在進一步的實施例中,當隔膜具有小于約50微米的厚度時,液流電池能夠以大于99.5%的電流效率來操作;當隔膜具有小于約25微米的厚度時,液流電池能夠以大于99%的電流效率來操作;并且當隔膜具有小于約10微米的厚度時,液流電池能夠以大于98%的電流效率來操作。相應地,合適的隔膜包括其中液流電池能夠以100ma/cm2的電(dian)(dian)流(liu)密(mi)度以(yi)大(da)于(yu)60%的電(dian)(dian)壓(ya)效率(lv)來(lai)操(cao)作(zuo)的那些(xie)隔(ge)膜。在進一步的實(shi)施例中(zhong),合適的隔(ge)膜可以(yi)包(bao)括(kuo)其(qi)中(zhong)液(ye)流(liu)電(dian)(dian)池能(neng)夠(gou)以(yi)大(da)于(yu)70%、大(da)于(yu)80%或甚(shen)至(zhi)大(da)于(yu)90%的電(dian)(dian)壓(ya)效率(lv)來(lai)操(cao)作(zuo)的那些(xie)隔(ge)膜。
第一活性物質和第二活性物質通過隔膜的擴散速率可以小于約1×10-5molcm-2day-1、小于約1×10-6molcm-2day-1、小于約1×10-2molcm-2day-1、小于約1×10-9molcm-2day-1、小于約1×10-11molcm-2day-1、小于約1×10-13molcm-2day-1、或小于約1×10-15molcm-2day-1。
液流(liu)(liu)(liu)(liu)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)池(chi)(chi)還(huan)可以包括與(yu)第(di)(di)(di)一(yi)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)極(ji)(ji)和(he)第(di)(di)(di)二電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)極(ji)(ji)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)連通(tong)(tong)的(de)(de)(de)(de)外部電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)路。該(gai)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)路可在(zai)操作(zuo)(zuo)期間(jian)對液流(liu)(liu)(liu)(liu)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)池(chi)(chi)充電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)和(he)放電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)。參(can)考第(di)(di)(di)一(yi)活(huo)(huo)(huo)(huo)性(xing)物(wu)(wu)(wu)(wu)質(zhi)(zhi)、第(di)(di)(di)二活(huo)(huo)(huo)(huo)性(xing)物(wu)(wu)(wu)(wu)質(zhi)(zhi)或其兩(liang)者(zhe)的(de)(de)(de)(de)凈(jing)(jing)離(li)(li)(li)子(zi)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)荷(he)的(de)(de)(de)(de)符號(hao)(hao)與(yu)在(zai)操作(zuo)(zuo)液流(liu)(liu)(liu)(liu)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)池(chi)(chi)的(de)(de)(de)(de)條(tiao)件下(xia)氧(yang)(yang)(yang)化(hua)(hua)還(huan)原(yuan)(yuan)活(huo)(huo)(huo)(huo)性(xing)物(wu)(wu)(wu)(wu)質(zhi)(zhi)的(de)(de)(de)(de)氧(yang)(yang)(yang)化(hua)(hua)形(xing)(xing)式(shi)(shi)(shi)和(he)還(huan)原(yuan)(yuan)形(xing)(xing)式(shi)(shi)(shi)兩(liang)者(zhe)中的(de)(de)(de)(de)凈(jing)(jing)離(li)(li)(li)子(zi)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)荷(he)的(de)(de)(de)(de)符號(hao)(hao)相(xiang)(xiang)關。液流(liu)(liu)(liu)(liu)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)池(chi)(chi)的(de)(de)(de)(de)進一(yi)步的(de)(de)(de)(de)示例(li)性(xing)實施例(li)提供(gong):(a)第(di)(di)(di)一(yi)活(huo)(huo)(huo)(huo)性(xing)物(wu)(wu)(wu)(wu)質(zhi)(zhi)具(ju)(ju)有(you)相(xiang)(xiang)關的(de)(de)(de)(de)凈(jing)(jing)正(zheng)(zheng)(zheng)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)荷(he)或凈(jing)(jing)負(fu)(fu)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)荷(he),并(bing)且(qie)能夠(gou)(gou)在(zai)系(xi)統的(de)(de)(de)(de)負(fu)(fu)操作(zuo)(zuo)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)位范圍內的(de)(de)(de)(de)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)位上(shang)提供(gong)氧(yang)(yang)(yang)化(hua)(hua)形(xing)(xing)式(shi)(shi)(shi)或還(huan)原(yuan)(yuan)形(xing)(xing)式(shi)(shi)(shi),使得所得到(dao)的(de)(de)(de)(de)第(di)(di)(di)一(yi)活(huo)(huo)(huo)(huo)性(xing)物(wu)(wu)(wu)(wu)質(zhi)(zhi)的(de)(de)(de)(de)氧(yang)(yang)(yang)化(hua)(hua)形(xing)(xing)式(shi)(shi)(shi)或還(huan)原(yuan)(yuan)形(xing)(xing)式(shi)(shi)(shi)具(ju)(ju)有(you)與(yu)第(di)(di)(di)一(yi)活(huo)(huo)(huo)(huo)性(xing)物(wu)(wu)(wu)(wu)質(zhi)(zhi)相(xiang)(xiang)同的(de)(de)(de)(de)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)荷(he)符號(hao)(hao)(正(zheng)(zheng)(zheng)號(hao)(hao)或負(fu)(fu)號(hao)(hao))并(bing)且(qie)離(li)(li)(li)聚(ju)物(wu)(wu)(wu)(wu)膜(mo)(mo)也具(ju)(ju)有(you)相(xiang)(xiang)同符號(hao)(hao)的(de)(de)(de)(de)凈(jing)(jing)離(li)(li)(li)子(zi)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)荷(he);以及(b)第(di)(di)(di)二活(huo)(huo)(huo)(huo)性(xing)物(wu)(wu)(wu)(wu)質(zhi)(zhi)具(ju)(ju)有(you)相(xiang)(xiang)關的(de)(de)(de)(de)凈(jing)(jing)正(zheng)(zheng)(zheng)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)荷(he)或凈(jing)(jing)負(fu)(fu)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)荷(he),并(bing)且(qie)能夠(gou)(gou)在(zai)系(xi)統的(de)(de)(de)(de)正(zheng)(zheng)(zheng)工作(zuo)(zuo)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)位范圍內的(de)(de)(de)(de)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)位上(shang)提供(gong)氧(yang)(yang)(yang)化(hua)(hua)形(xing)(xing)式(shi)(shi)(shi)或還(huan)原(yuan)(yuan)形(xing)(xing)式(shi)(shi)(shi),使得所得到(dao)的(de)(de)(de)(de)第(di)(di)(di)二活(huo)(huo)(huo)(huo)性(xing)物(wu)(wu)(wu)(wu)質(zhi)(zhi)的(de)(de)(de)(de)氧(yang)(yang)(yang)化(hua)(hua)形(xing)(xing)式(shi)(shi)(shi)或還(huan)原(yuan)(yuan)形(xing)(xing)式(shi)(shi)(shi)具(ju)(ju)有(you)與(yu)第(di)(di)(di)二活(huo)(huo)(huo)(huo)性(xing)物(wu)(wu)(wu)(wu)質(zhi)(zhi)相(xiang)(xiang)同的(de)(de)(de)(de)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)荷(he)符號(hao)(hao)(正(zheng)(zheng)(zheng)號(hao)(hao)或負(fu)(fu)號(hao)(hao))并(bing)且(qie)離(li)(li)(li)聚(ju)物(wu)(wu)(wu)(wu)膜(mo)(mo)也具(ju)(ju)有(you)相(xiang)(xiang)同符號(hao)(hao)的(de)(de)(de)(de)凈(jing)(jing)離(li)(li)(li)子(zi)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)荷(he);或(a)和(he)(b)兩(liang)者(zhe)。第(di)(di)(di)一(yi)活(huo)(huo)(huo)(huo)性(xing)物(wu)(wu)(wu)(wu)質(zhi)(zhi)和(he)/或第(di)(di)(di)二活(huo)(huo)(huo)(huo)性(xing)物(wu)(wu)(wu)(wu)質(zhi)(zhi)和(he)離(li)(li)(li)聚(ju)物(wu)(wu)(wu)(wu)膜(mo)(mo)的(de)(de)(de)(de)匹配(pei)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)荷(he)可以提供(gong)高選擇性(xing)。更具(ju)(ju)體地(di),由于(yu)(yu)(yu)第(di)(di)(di)一(yi)活(huo)(huo)(huo)(huo)性(xing)物(wu)(wu)(wu)(wu)質(zhi)(zhi)或第(di)(di)(di)二活(huo)(huo)(huo)(huo)性(xing)物(wu)(wu)(wu)(wu)質(zhi)(zhi),因此(ci)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)荷(he)匹配(pei)可以提供(gong)通(tong)(tong)過(guo)離(li)(li)(li)聚(ju)物(wu)(wu)(wu)(wu)膜(mo)(mo)的(de)(de)(de)(de)小(xiao)(xiao)于(yu)(yu)(yu)約(yue)3%、小(xiao)(xiao)于(yu)(yu)(yu)約(yue)2%、小(xiao)(xiao)于(yu)(yu)(yu)約(yue)1%、小(xiao)(xiao)于(yu)(yu)(yu)約(yue)0.5%、小(xiao)(xiao)于(yu)(yu)(yu)約(yue)0.2%或小(xiao)(xiao)于(yu)(yu)(yu)約(yue)0.1%的(de)(de)(de)(de)離(li)(li)(li)子(zi)摩(mo)爾通(tong)(tong)量(liang)(liang)。術語“離(li)(li)(li)子(zi)摩(mo)爾通(tong)(tong)量(liang)(liang)”是(shi)指(zhi)通(tong)(tong)過(guo)離(li)(li)(li)聚(ju)物(wu)(wu)(wu)(wu)膜(mo)(mo)、平(ping)衡與(yu)外部電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)力(li)/電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)子(zi)的(de)(de)(de)(de)流(liu)(liu)(liu)(liu)動相(xiang)(xiang)關的(de)(de)(de)(de)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)荷(he)的(de)(de)(de)(de)離(li)(li)(li)子(zi)的(de)(de)(de)(de)量(liang)(liang)。即,液流(liu)(liu)(liu)(liu)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)池(chi)(chi)能夠(gou)(gou)利用活(huo)(huo)(huo)(huo)性(xing)物(wu)(wu)(wu)(wu)質(zhi)(zhi)被(bei)離(li)(li)(li)聚(ju)物(wu)(wu)(wu)(wu)膜(mo)(mo)大量(liang)(liang)排斥來操作(zuo)(zuo)。
在一些情況下(xia),用(yong)戶可能期望(wang)提(ti)供(gong)高于(yu)單(dan)個(ge)(ge)(ge)電(dian)(dian)池(chi)(chi)(chi)單(dan)元可用(yong)的(de)(de)(de)充電(dian)(dian)電(dian)(dian)壓(ya)或放電(dian)(dian)電(dian)(dian)壓(ya)。在這(zhe)樣的(de)(de)(de)情況下(xia),多個(ge)(ge)(ge)電(dian)(dian)池(chi)(chi)(chi)單(dan)元可以串聯(lian)連(lian)接,使得每個(ge)(ge)(ge)電(dian)(dian)池(chi)(chi)(chi)的(de)(de)(de)電(dian)(dian)壓(ya)是相(xiang)加的(de)(de)(de)。這(zhe)形(xing)成雙極(ji)堆(dui)(dui)。導(dao)電(dian)(dian)而(er)無孔的(de)(de)(de)材料(例(li)如,雙極(ji)板(ban))可以用(yong)于(yu)連(lian)接雙極(ji)堆(dui)(dui)中的(de)(de)(de)相(xiang)鄰電(dian)(dian)池(chi)(chi)(chi)單(dan)元,該材料允許電(dian)(dian)子傳輸(shu)但是防止相(xiang)鄰電(dian)(dian)池(chi)(chi)(chi)之間的(de)(de)(de)流(liu)體(ti)或氣體(ti)輸(shu)送。單(dan)個(ge)(ge)(ge)電(dian)(dian)池(chi)(chi)(chi)的(de)(de)(de)正(zheng)極(ji)隔室(shi)和負(fu)極(ji)隔室(shi)可以經由在堆(dui)(dui)中的(de)(de)(de)公(gong)共正(zheng)極(ji)流(liu)體(ti)歧(qi)管(guan)和負(fu)極(ji)流(liu)體(ti)歧(qi)管(guan)流(liu)體(ti)連(lian)接。以該方式,單(dan)個(ge)(ge)(ge)電(dian)(dian)池(chi)(chi)(chi)可以被串聯(lian)堆(dui)(dui)疊以產生(sheng)適用(yong)于(yu)dc應(ying)用(yong)或轉換為ac應(ying)用(yong)的(de)(de)(de)電(dian)(dian)壓(ya)。
在另外(wai)的(de)實施例(li)中,電(dian)池(chi)、電(dian)池(chi)堆或(huo)(huo)電(dian)池(chi)組(zu)可(ke)(ke)以(yi)被(bei)結合(he)到更大的(de)能量存儲系(xi)統(tong)中,適當(dang)地(di)包(bao)(bao)括用(yong)于這些大單(dan)元(yuan)的(de)操(cao)作的(de)管道(dao)和(he)控制(zhi)裝(zhuang)置。適于這種系(xi)統(tong)的(de)管道(dao)、控制(zhi)裝(zhuang)置和(he)其它設(she)備是本領域已知的(de),并(bing)且可(ke)(ke)以(yi)例(li)如(ru)包(bao)(bao)括管道(dao)和(he)泵(beng),其與各(ge)個(ge)室流(liu)體(ti)連通以(yi)用(yong)于將電(dian)解質溶液移(yi)進和(he)移(yi)出各(ge)個(ge)室;以(yi)及儲存罐,其用(yong)于保持充電(dian)的(de)電(dian)解質和(he)放電(dian)的(de)電(dian)解質。本公開的(de)電(dian)池(chi)、電(dian)池(chi)堆和(he)電(dian)池(chi)組(zu)還可(ke)(ke)以(yi)包(bao)(bao)括操(cao)作管理系(xi)統(tong)。操(cao)作管理系(xi)統(tong)可(ke)(ke)以(yi)是諸如(ru)計算機或(huo)(huo)微(wei)處理器的(de)任何合(he)適的(de)控制(zhi)器裝(zhuang)置,并(bing)且可(ke)(ke)以(yi)包(bao)(bao)含設(she)置各(ge)種閥(fa)、泵(beng)、循環回路等的(de)任何的(de)操(cao)作的(de)邏輯(ji)電(dian)路。
在更具(ju)體的(de)(de)實施(shi)例中,液(ye)(ye)流(liu)(liu)(liu)電(dian)(dian)(dian)(dian)(dian)池系(xi)(xi)統(tong)(tong)(tong)可以(yi)包括:液(ye)(ye)流(liu)(liu)(liu)電(dian)(dian)(dian)(dian)(dian)池(包括電(dian)(dian)(dian)(dian)(dian)池單(dan)(dan)元(yuan)或電(dian)(dian)(dian)(dian)(dian)池堆);儲(chu)存罐和(he)(he)(he)管道(dao),其用(yong)(yong)于(yu)容納和(he)(he)(he)運輸(shu)電(dian)(dian)(dian)(dian)(dian)解質(zhi)(zhi)溶液(ye)(ye);控(kong)制(zhi)(zhi)(zhi)硬(ying)件和(he)(he)(he)控(kong)制(zhi)(zhi)(zhi)軟件(其可以(yi)包括安全系(xi)(xi)統(tong)(tong)(tong));以(yi)及電(dian)(dian)(dian)(dian)(dian)力(li)(li)調節(jie)單(dan)(dan)元(yuan)。液(ye)(ye)流(liu)(liu)(liu)電(dian)(dian)(dian)(dian)(dian)池單(dan)(dan)元(yuan)堆實現(xian)充電(dian)(dian)(dian)(dian)(dian)循環和(he)(he)(he)放電(dian)(dian)(dian)(dian)(dian)循環的(de)(de)轉(zhuan)(zhuan)換并(bing)且確定(ding)峰值電(dian)(dian)(dian)(dian)(dian)力(li)(li)。儲(chu)存罐包含正極(ji)(ji)活(huo)性(xing)物(wu)(wu)質(zhi)(zhi)和(he)(he)(he)負極(ji)(ji)活(huo)性(xing)物(wu)(wu)質(zhi)(zhi),罐容積確定(ding)存儲(chu)在系(xi)(xi)統(tong)(tong)(tong)中的(de)(de)能(neng)量(liang)的(de)(de)量(liang)。控(kong)制(zhi)(zhi)(zhi)軟件、硬(ying)件和(he)(he)(he)可選的(de)(de)安全系(xi)(xi)統(tong)(tong)(tong)適(shi)當(dang)地包括傳感器、緩解設備和(he)(he)(he)其它電(dian)(dian)(dian)(dian)(dian)子/硬(ying)件控(kong)制(zhi)(zhi)(zhi)和(he)(he)(he)保護措施(shi),以(yi)確保液(ye)(ye)流(liu)(liu)(liu)電(dian)(dian)(dian)(dian)(dian)池系(xi)(xi)統(tong)(tong)(tong)的(de)(de)安全、自主和(he)(he)(he)高效操作。電(dian)(dian)(dian)(dian)(dian)力(li)(li)調節(jie)單(dan)(dan)元(yuan)可以(yi)在能(neng)量(liang)存儲(chu)系(xi)(xi)統(tong)(tong)(tong)的(de)(de)前端處(chu)使(shi)用(yong)(yong),以(yi)將輸(shu)入電(dian)(dian)(dian)(dian)(dian)力(li)(li)和(he)(he)(he)輸(shu)出電(dian)(dian)(dian)(dian)(dian)力(li)(li)轉(zhuan)(zhuan)換成對(dui)于(yu)能(neng)量(liang)存儲(chu)系(xi)(xi)統(tong)(tong)(tong)或應用(yong)(yong)最佳的(de)(de)電(dian)(dian)(dian)(dian)(dian)壓(ya)和(he)(he)(he)電(dian)(dian)(dian)(dian)(dian)流(liu)(liu)(liu)。對(dui)于(yu)連(lian)接到(dao)電(dian)(dian)(dian)(dian)(dian)網的(de)(de)能(neng)量(liang)存儲(chu)系(xi)(xi)統(tong)(tong)(tong)的(de)(de)示例,在充電(dian)(dian)(dian)(dian)(dian)循環中,電(dian)(dian)(dian)(dian)(dian)力(li)(li)調節(jie)單(dan)(dan)元(yuan)可以(yi)在用(yong)(yong)于(yu)電(dian)(dian)(dian)(dian)(dian)池堆的(de)(de)適(shi)當(dang)的(de)(de)電(dian)(dian)(dian)(dian)(dian)壓(ya)和(he)(he)(he)電(dian)(dian)(dian)(dian)(dian)流(liu)(liu)(liu)下將輸(shu)入的(de)(de)ac電(dian)(dian)(dian)(dian)(dian)力(li)(li)轉(zhuan)(zhuan)換為dc電(dian)(dian)(dian)(dian)(dian)力(li)(li)。在放電(dian)(dian)(dian)(dian)(dian)循環中,堆產生dc電(dian)(dian)(dian)(dian)(dian)力(li)(li),并(bing)且電(dian)(dian)(dian)(dian)(dian)力(li)(li)調節(jie)單(dan)(dan)元(yuan)在用(yong)(yong)于(yu)電(dian)(dian)(dian)(dian)(dian)網應用(yong)(yong)的(de)(de)適(shi)當(dang)的(de)(de)電(dian)(dian)(dian)(dian)(dian)壓(ya)和(he)(he)(he)電(dian)(dian)(dian)(dian)(dian)流(liu)(liu)(liu)下將dc電(dian)(dian)(dian)(dian)(dian)力(li)(li)轉(zhuan)(zhuan)換為ac電(dian)(dian)(dian)(dian)(dian)力(li)(li)。
在(zai)本領域普通(tong)技(ji)術(shu)人員在(zai)上文(wen)中(zhong)沒(mei)有另外定義或理解的(de)情況下(xia),以下(xia)段落中(zhong)的(de)定義將適用于本公開。
如本文所使用(yong)的,術語“能(neng)量(liang)(liang)密(mi)(mi)度”將(jiang)指(zhi)的是(shi)可在活性物質(zhi)中每單(dan)位(wei)體積存儲的能(neng)量(liang)(liang)的量(liang)(liang)。能(neng)量(liang)(liang)密(mi)(mi)度指(zhi)的是(shi)能(neng)量(liang)(liang)儲存的理論能(neng)量(liang)(liang)密(mi)(mi)度并且(qie)可由等式4計算
能量密度=(26.8a-h/mol)xocvx[e–](等式4)
其中ocv是50%荷電狀態下的開路電位,(26.8a-h/mol)是法拉第常數,并且[e–]是在99%荷電狀態下儲存在活性物質中的電子的濃度。在活性物質主要是用于正極電解質和負極電解質兩者的原子物質或分子物質的情況下,[e–]可以通(tong)過(guo)等式5計算(suan)
[e–]=[活性物質(zhi)]xn/2(等式5)
其中[活性(xing)(xing)物質(zhi)(zhi)(zhi)(zhi)]是負極電解質(zhi)(zhi)(zhi)(zhi)或(huo)正(zheng)極電解質(zhi)(zhi)(zhi)(zhi)中活性(xing)(xing)物質(zhi)(zhi)(zhi)(zhi)的(de)摩爾濃度中的(de)較(jiao)低(di)者(zhe),并且n是每分子(zi)活性(xing)(xing)物質(zhi)(zhi)(zhi)(zhi)轉移的(de)電子(zi)數。相(xiang)關(guan)術語“電荷(he)密(mi)度”將指的(de)是每種電解質(zhi)(zhi)(zhi)(zhi)包含的(de)電荷(he)的(de)總(zong)量(liang)。對于給定的(de)電解質(zhi)(zhi)(zhi)(zhi),電荷(he)密(mi)度可以通(tong)過(guo)等式6計算
電荷密度=(26.8a-h/mol)x[活(huo)性物質]xn(等式6)
其中(zhong)[活性物質]和(he)n如上述所限定的(de)。
如本文所使用的,術語“電流密度”是指在電化學電池中通過的總電流除以電池的電極的幾何面積,并且通常以ma/cm2為單位。
如本文所使(shi)用的,術(shu)語“電(dian)(dian)(dian)流效(xiao)率(lv)”(ieff)可(ke)以(yi)描述為在(zai)電(dian)(dian)(dian)池放電(dian)(dian)(dian)時(shi)產(chan)生的總(zong)電(dian)(dian)(dian)荷(he)與充電(dian)(dian)(dian)期(qi)間通(tong)過的總(zong)電(dian)(dian)(dian)荷(he)的比率(lv)。電(dian)(dian)(dian)流效(xiao)率(lv)可(ke)以(yi)是液流電(dian)(dian)(dian)池的荷(he)電(dian)(dian)(dian)狀(zhuang)態的函數。在(zai)一些非限(xian)制性(xing)實施例中,可(ke)以(yi)在(zai)約35%至(zhi)約60%的荷(he)電(dian)(dian)(dian)狀(zhuang)態范圍上評估電(dian)(dian)(dian)流效(xiao)率(lv)。
如本文所(suo)使用的(de)(de)(de),術(shu)語“電壓(ya)效率(lv)(lv)”可(ke)以描述為(wei)在給(gei)定(ding)(ding)電流密(mi)度(du)下觀察到的(de)(de)(de)電極電位與該電極的(de)(de)(de)半(ban)電池(chi)電位的(de)(de)(de)比率(lv)(lv)(×100%)。電壓(ya)效率(lv)(lv)可(ke)以被描述用于(yu)電池(chi)充電步驟、放(fang)電步驟或“往返(fan)電壓(ya)效率(lv)(lv)”。給(gei)定(ding)(ding)電流密(mi)度(du)下的(de)(de)(de)往返(fan)電壓(ya)效率(lv)(lv)(veff,rt)可(ke)以使用等(deng)式7從放(fang)電時的(de)(de)(de)電池(chi)電壓(ya)(v放(fang)電)和充電時的(de)(de)(de)電壓(ya)(v充電)來計算(suan):
veff,rt=v放(fang)電/v充電×100%(等(deng)式7)
如(ru)(ru)本(ben)文(wen)所(suo)使用(yong)的(de)(de)(de),術語“負(fu)極(ji)(ji)”和(he)“正(zheng)極(ji)(ji)”是相(xiang)對于彼(bi)此(ci)限定的(de)(de)(de)電(dian)(dian)(dian)極(ji)(ji),使得(de)負(fu)極(ji)(ji)在(zai)(zai)(zai)充電(dian)(dian)(dian)循環和(he)放電(dian)(dian)(dian)循環兩者(zhe)中在(zai)(zai)(zai)比(bi)正(zheng)極(ji)(ji)更負(fu)的(de)(de)(de)電(dian)(dian)(dian)位(wei)處操(cao)(cao)(cao)(cao)作(zuo)(zuo),或(huo)(huo)(huo)(huo)者(zhe)被(bei)設計為(wei)(wei)或(huo)(huo)(huo)(huo)旨在(zai)(zai)(zai)比(bi)正(zheng)極(ji)(ji)更負(fu)的(de)(de)(de)電(dian)(dian)(dian)位(wei)下操(cao)(cao)(cao)(cao)作(zuo)(zuo)(并(bing)且反之(zhi)亦(yi)然(ran)),而(er)與(yu)其操(cao)(cao)(cao)(cao)作(zuo)(zuo)的(de)(de)(de)實際電(dian)(dian)(dian)位(wei)無關(guan)。負(fu)極(ji)(ji)在(zai)(zai)(zai)相(xiang)對于可(ke)(ke)逆(ni)氫電(dian)(dian)(dian)極(ji)(ji)的(de)(de)(de)負(fu)電(dian)(dian)(dian)位(wei)處可(ke)(ke)能實際地操(cao)(cao)(cao)(cao)作(zuo)(zuo)或(huo)(huo)(huo)(huo)被(bei)設計為(wei)(wei)或(huo)(huo)(huo)(huo)旨在(zai)(zai)(zai)操(cao)(cao)(cao)(cao)作(zuo)(zuo),或(huo)(huo)(huo)(huo)者(zhe)負(fu)極(ji)(ji)在(zai)(zai)(zai)相(xiang)對于可(ke)(ke)逆(ni)氫電(dian)(dian)(dian)極(ji)(ji)的(de)(de)(de)負(fu)電(dian)(dian)(dian)位(wei)處可(ke)(ke)能不實際地操(cao)(cao)(cao)(cao)作(zuo)(zuo)或(huo)(huo)(huo)(huo)被(bei)設計為(wei)(wei)或(huo)(huo)(huo)(huo)旨在(zai)(zai)(zai)操(cao)(cao)(cao)(cao)作(zuo)(zuo)。如(ru)(ru)本(ben)文(wen)所(suo)述(shu)的(de)(de)(de),負(fu)極(ji)(ji)與(yu)第一(yi)電(dian)(dian)(dian)解(jie)質溶液相(xiang)關(guan)聯(lian),并(bing)且正(zheng)極(ji)(ji)與(yu)第二電(dian)(dian)(dian)解(jie)質溶液相(xiang)關(guan)聯(lian)。與(yu)負(fu)極(ji)(ji)和(he)正(zheng)極(ji)(ji)相(xiang)關(guan)聯(lian)的(de)(de)(de)電(dian)(dian)(dian)解(jie)質溶液可(ke)(ke)以(yi)分別(bie)描述(shu)為(wei)(wei)負(fu)極(ji)(ji)電(dian)(dian)(dian)解(jie)質(negolyte)和(he)正(zheng)極(ji)(ji)電(dian)(dian)(dian)解(jie)質(posolyte)。
示例
圖3示出在各種荷電狀態下通過atr光譜法測量的包含ti3+/4+(兒茶酚酶)2(焦酸鹽)的電解質溶液的說明性uv-vis光譜。如通過透射uv-vis光譜法確定的,對于在380nm處的主吸收帶,該配位化合物具有約10,800m-1cm-1的(de)(de)摩(mo)爾吸(xi)光(guang)系數常數。在(zai)(zai)atr條件(jian)下,該吸(xi)收帶移(yi)動(dong)到約410nm。通過(guo)將具有藍(lan)寶石尖部的(de)(de)atr探針(zhen)浸入具有最初(chu)處(chu)于完(wan)全氧化(hua)(hua)狀(zhuang)態(tai)的(de)(de)配(pei)位(wei)(wei)化(hua)(hua)合物(wu)的(de)(de)電解質溶(rong)液中來(lai)獲得光(guang)譜(pu)。atr探針(zhen)連接到使(shi)用光(guang)纖(xian)的(de)(de)商用uv-vis分(fen)光(guang)光(guang)度計。然后(hou),配(pei)位(wei)(wei)化(hua)(hua)合物(wu)的(de)(de)氧化(hua)(hua)形(xing)式被(bei)逐(zhu)漸轉(zhuan)化(hua)(hua)為還(huan)原形(xing)式,并且(qie)(qie)uv-vis光(guang)譜(pu)在(zai)(zai)每個還(huan)原階段后(hou)被(bei)獲得。基于還(huan)原,初(chu)始uv-vis光(guang)譜(pu)顯著變化(hua)(hua),即,在(zai)(zai)λ1和λ3處(chu)產(chan)生(sheng)強度下降,并且(qie)(qie)在(zai)(zai)λ2處(chu)產(chan)生(sheng)向內生(sheng)長(ingrowth)的(de)(de)新的(de)(de)吸(xi)光(guang)度。光(guang)譜(pu)在(zai)(zai)標記為ip的(de)(de)位(wei)(wei)置處(chu)顯示等吸(xi)光(guang)點。
雖然已經參照(zhao)公開(kai)(kai)的(de)(de)(de)實施(shi)例描(miao)述本(ben)(ben)公開(kai)(kai),但是(shi)本(ben)(ben)領域技術(shu)人員將容(rong)易地理解(jie),這些(xie)僅(jin)僅(jin)是(shi)對本(ben)(ben)公開(kai)(kai)的(de)(de)(de)說明(ming)。應當理解(jie)的(de)(de)(de)是(shi),在(zai)不脫離本(ben)(ben)公開(kai)(kai)的(de)(de)(de)精神的(de)(de)(de)情況下可(ke)以(yi)進行各種(zhong)變型。本(ben)(ben)公開(kai)(kai)可(ke)以(yi)被修改為(wei)包(bao)括迄今為(wei)止未描(miao)述但與本(ben)(ben)公開(kai)(kai)的(de)(de)(de)精神和范圍相稱(cheng)的(de)(de)(de)任何數量的(de)(de)(de)變化(hua)、變型、替(ti)換(huan)或等(deng)效布置。另外,雖然已經描(miao)述本(ben)(ben)公開(kai)(kai)的(de)(de)(de)各種(zhong)實施(shi)例,但是(shi)應當理解(jie)的(de)(de)(de)是(shi),本(ben)(ben)公開(kai)(kai)的(de)(de)(de)方(fang)面可(ke)以(yi)僅(jin)包(bao)括描(miao)述的(de)(de)(de)實施(shi)例中的(de)(de)(de)一些(xie)。因此,本(ben)(ben)發明(ming)不被視為(wei)受前述描(miao)述的(de)(de)(de)限制。