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但是在光電化學(xué)循環(huán)伏安測試實際測試體系情況下,由于電解液存在一定的電阻 Ru,Ru 是參比電極到工作電極表面電雙層(double layer)一邊的溶液電阻。根據(jù)歐姆定律,這個 Ru 就會產(chǎn)生一定壓降,壓降的大小為 Vir= I*Ru。這樣就造成工作電極上的實際電壓和相對參比電極而施加的電壓有所不同。如圖二所示。

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產(chǎn)品介紹

    大多數(shù)情況下,我們認(rèn)為參比電極(RE)和工作電極(WE)之間施加的電壓就是在工作電極上施加的電壓。如圖一所示。

循環(huán)伏安

    但是在循環(huán)伏安實際測試體系情況下,由于電解液存在一定的電阻Ru,Ru是參比電極到工作電極表面電雙層(doublelayer)一邊的溶液電阻。根據(jù)歐姆定律,這個Ru就會產(chǎn)生一定壓降,壓降的大小為Vir=I*Ru。這樣就造成工作電極上的實際電壓和相對參比電極而施加的電壓有所不同。如圖二所示。  

循環(huán)伏安

    在大多數(shù)情況下此電壓降是不予考慮的。但是當(dāng)實驗時使用了低電導(dǎo)性的電解液,這個壓差比較大時,就需要考慮對此Vir降進(jìn)行補償。通??梢允褂梦㈦姌O,或者改變電解液的電導(dǎo)率來消除,也可以采用自動實時壓降補償?shù)募夹g(shù)進(jìn)行補償。

   補償電阻Ru的大小可以通過直流電流快速遮斷法或者采用EIS方法進(jìn)行測試。EIS要比直流電流快速折斷法更確定。電流快速折斷方法是早期沒有AC技術(shù)的時候出現(xiàn)的。自從有AC技術(shù)之后,EIS成為選擇的測試技術(shù)。使用EIS技術(shù)時,測試1K-100KHz頻率范圍內(nèi)的交流阻抗譜。在高頻區(qū),相位為零時的阻值就是要補償?shù)碾娊庖弘娮鑂u,如圖三所示。
 

循環(huán)伏安

    獲得補償?shù)淖柚抵螅梢允褂谜答伒姆椒ㄟM(jìn)行實時補償。通過不斷調(diào)節(jié)補償量(0%-100%)直到出現(xiàn)振蕩為止。例如Ru為100?,推薦補償值為70?到90?。如果是100?全值補償,有可能會出現(xiàn)自激震蕩現(xiàn)象。

   下面使用Zahner的Zennium系列電化學(xué)工作站做一些實際測試。測試時使用圖四所示的模擬元件電路。
 

循環(huán)伏安

    使用EIS測試技術(shù),頻率范圍設(shè)定為1Hz-100KHz,得到的EIS譜圖后再進(jìn)行擬合。擬合結(jié)

   果和實際電路*一樣(考慮元件誤差)。Ru=100?,Rp=1995?,電容為993.8nF.如圖五所示。
 

循環(huán)伏安

   當(dāng)進(jìn)行CV和I/E測試時,若果需要,點擊溶液補償Ohnicdrop測試,軟件可以自動采用上面描述的交流阻抗的測試方法快速獲得Ru的值(圖六),然后就可以進(jìn)行溶液阻抗補償?shù)难h(huán)伏安測試。測試過程中電化學(xué)工作站進(jìn)行實時電壓補償。補償前后的CV曲線如圖七和圖八所示。自動獲取溶液電阻Ru

循環(huán)伏安

   圖七,紅色為未補償?shù)牡腃V曲線藍(lán)色為IR補償后的CV曲線通過計算,兩者之間的電阻差為100?左右。這個正是電解液阻值Ru。此時說明IR的實時補償效果有效。

循環(huán)伏安

 

   圖八,改變不同的補償電阻值,就會得到不同的CV曲線。在掃描電壓一樣時,電流值會依次增加,用以補償設(shè)置的Ru。

循環(huán)伏安

    綜合以上循環(huán)伏安測試結(jié)果,Zahner電化學(xué)工作站采用自動EIS方法測試補償電阻之Ru,然后在CV或者I/E測試方法中進(jìn)行實時的自動補償。在實際體系測試時,可能由于體系的性質(zhì)不同,補償電阻的大小需要調(diào)整來實現(xiàn)補償效果。














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