超聲波輔助水解共沉澱法製備β-Ni(OH)2 應用於鎳基電池;Preparation of β-Ni(OH)2 electrode using ultrasonic-assisted hydrolysis co-precipitation method for rechargeable Ni-based batteries

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题名:	超聲波輔助水解共沉澱法製備β-Ni(OH)2 應用於鎳基電池;Preparation of β-Ni(OH)2 electrode using ultrasonic-assisted hydrolysis co-precipitation method for rechargeable Ni-based batteries
作者:	蔡盈榛;Tsai, Ying-Chen
贡献者:	化學工程與材料工程學系
关键词:	氫氧化鎳;摻雜元素;高比表面積;β-Ni(OH)2;co-precipitating method;nickel acetate
日期:	2020-08-18
上传时间:	2020-09-02 15:16:42 (UTC+8)
出版者:	國立中央大學
摘要:	本研究於超音波環境下以水解共沉澱法製備β-Ni(OH)¬2正極材料，探討不同前驅物、鹼性沉澱環境、摻雜元素對於材料性質及電化學分析的影響。研究分為三個部分，第一部分探討NiCH¬¬3¬COOH、NiNO¬3、NiSO¬¬4、NiCl¬¬¬2四種前驅物於不同沉澱環境下(pH 8-pH 12)製備氫氧化鎳的材料分析，由XRD證實高於pH 10環境下¬¬得到純相且發現結晶強度隨著環境越趨鹼性，結晶性越好，以NiCH3COOH前驅物製備時有最小晶粒；而BET比表面積結果顯示NiCH¬3¬COOH前驅物製備氫氧化鎳具有高比表面積131.54 m2/g、較大的中孔體積93.04 Å、孔洞分布均勻。第二部分為四種前驅物於pH 12環境下製備氫氧化鎳電極於6 M KOH (pH 14)電解液中進行電化學分析，當晶粒越小時充放電循環穩定性增加，由循環伏安法測得NiCH¬3¬COOH前驅物電化學可逆性較好且有最佳的充電效率；電解液可有效地進入電極內部，於高比表面積中進行反應，有效使電化學反應增加，於300 mA/g下充放電，其電容值達246 mAh/g；經抗腐蝕測試結果發現有最低腐蝕電流181.52 μA/cm2¬¬，於強鹼電解液具高抗腐蝕能力。第三部分沿用前兩部分最佳參數於pH 12環境下利用NiCH¬3¬COOH前驅物製備氫氧化鎳，並摻雜錳元素提升比表面積及電化學表現。隨著錳含量增加，XRD繞射峰(001)面的β-Ni(OH)¬2¬¬特徵峰值明顯增強並有位移趨勢；由循環伏安法證實0.05 Mn有最佳的充電性能及穩定的可逆性，添加過量錳含量雖然能夠抑制氧氣產生，提升充電效率，但氧化還原的可逆穩定性較差；循環充放電測試於0.05 Mn有最高電容值258 mAh/g，由BET結果顯示0.05 Mn摻雜比表面積高達158.8 m2/g，使電解液擴散活材面積上升，證實添加錳可以提升電化學面積，增加電容值；腐蝕測試大幅降低腐蝕電流值為24.84¬¬ μA/cm2¬¬，進行長時間充放電時，極片結構不容易損壞。由以上實驗結果說明於pH 12鹼性環境下以NiCH¬3¬COOH作為前驅物並摻雜0.05 Mn製備氫氧化鎳極片改質作為鋅鎳電池之正極，有效提高電化學效能，於儲能電池上的應用有相當大的發展。 ;β-Ni(OH)2 as positive electrode materials were prepared by using the ultrasonic hydrolysis co-precipitating method. Different precursors, alkaline precipitation environment, and doping element on the material properties and electrochemical characteristics were discussed. The materials prepared by nickel acetate, nickel nitrate, nickel sulfate, and nickel chloride under different pH values (pH 8 to pH 12) .The BET results show that nickel hydroxide prepared from nickel acetate precursor has a high specific surface area 131.54 m2/g, a large mesopore volume 93.04 Å, uniform pore distribution . The electrochemical properties of various nickel hydroxide electrode were investigated in 6 M KOH electrolyte. Nickel acetate precursor exhibited a good electrochemical reversibility and an excellent rechargeable efficiency; the electrolyte can effectively enter the interior of the electrode and react with high specific surface area, increasing electrochemical reaction, and capacitance value reaches 246 mAh/g at 300 mA/g; The corrosion test results showed that nickel acetate precursor electrode has the lowest corrosion current of 121.34 μA/cm2, which has high corrosion resistance in strong alkaline electrolyte. We then prepared nickel hydroxide under pH 12 using nickel acetate as precursor, and doped with manganese to increase the specific surface area thus improve the electrochemical performance. As the level of manganese content increases, the characteristic peak of β-Ni(OH)2 on the (001) surface of the XRD diffraction peak enhanced significantly and shifted to a high angle ; Cyclic voltammetry showed 0.05 Mn possessed the best rechargeable performance and stability . The specific capacitance reaches 258 mAh/g. BET results show the specific surface area is as high as 158.8 m2/g, which increases the electrochemical area, the corrosion test greatly reduces the corrosion current, meaning structure is not easy to damage when charging and discharging. Above experimental results show nickel acetate as the precursor and 0.05 Mn doped nickel hydroxide prepared at pH 12 is used as the positive electrode of the zinc-nickel battery, which effective improves the electrochemical performance and them applying to energy storage rechargeable battery.
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