合金的微結(jié)構(gòu)和電化學(xué)性能的影響
(浙江大學(xué)材料與化學(xué)工程學(xué)院, 杭州 310027)
摘 要: 研究了退火處理(1 173~1 273 K、 3 h)對(duì)無(wú)Co貯氫合金MlNi4.0Al0.3Si0.1Fe0.6的微結(jié)構(gòu)和電化學(xué)性能的影響。 XRD分析表明, 退火態(tài)合金仍為單相CaCu5型結(jié)構(gòu), 但合金相的成分和結(jié)構(gòu)的均勻性得到明顯改善。 金相觀察和能譜分析顯示: 鑄態(tài)合金為比較粗大的樹(shù)枝晶結(jié)構(gòu)并存在明顯的成分偏析; 經(jīng)1 173 K處理后的合金仍為樹(shù)枝晶, 且樹(shù)枝結(jié)構(gòu)更為明顯; 但經(jīng)1 223~1 273 K處理后合金的顯微組織轉(zhuǎn)變?yōu)榈容S晶; 退火處理使合金中元素的分布趨于均勻化。 電化學(xué)測(cè)試表明, 退火處理后合金的放電容量有所提高, 循環(huán)穩(wěn)定性得到顯著改善, 但高倍率放電性能略有降低。 研究發(fā)現(xiàn), 退火態(tài)合金電極的交換電流密度及氫在合金中的擴(kuò)散系數(shù)較鑄態(tài)合金的有所減小是導(dǎo)致其高倍率放電性能降低的主要原因。
關(guān)鍵字: 貯氫電極合金; 無(wú)鈷合金; 退火處理; 微觀結(jié)構(gòu); 電化學(xué)性能
WEI Fan-song, CHEN Li-xin
( College of Materials Science and Chemical Engineering,
Zhejiang University, Hangzhou 310027, China)
Abstract: The effects of annealing treatment (1 173-1 273 K, 3 h) on the microstructures and electrochemical performances of Co-free MlNi4.0Al0.3Si0.1Fe0.6 hydrogen storage alloys were investigated. XRD analyses indicate that both as-cast and annealed alloys consist of a CaCu5-type structure single phase, but the crystallizability and homogeneity of the annealed alloys are improved. The optical microscope and EDS analyses show that the as-cast alloy has a crassi dendrite structure with noticeable composition segregation, while the alloy annealed at 1 173 K has a more conspicuous dendrite structure and a more homogenous composition, and the microstructures of the alloys annealed at 1 223-1 273 K change to an equiaxed structure. The electrochemical tests indicate that the annealed alloys, as compared with as-cast alloy, show a higher discharge capacity, much better cycling stability and lower high-rate dischargeability. It is found that the decrease in both exchange current density and diffusion coefficient of hydrogen in alloy bulk is the main reason for the degraded high-rate dischargeability (HRD) of annealed alloys.
Key words: hydrogen storage electrode alloy; Co-free alloy; annealing treatment; microstructure; electrochemical property


