羟基磷酸铁铵的制备与表征
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摘要
采用硫酸亚铁和磷酸为原料,在尿素存在的条件下,水热合成得到高纯度的羟基磷酸铁铵。研究发现,反应温度不同得到的羟基磷酸铁铵的结晶度会有所不同,形貌差异较大。利用XRD、SEM、TG-DTA和红外分析等手段对制备的样品组成、结构、晶型和形貌做分析表征,分析了羟基磷酸铁铵在加热过程中的相变过程。结果表明,在静态羟基磷酸铁铵中,磷酸和铁具有固定的化学计量比,经高温煅烧后得到高纯度磷酸铁,可应用其制备锂离子电池正极材料磷酸铁锂的前驱体,且此法合成工艺简单,具有良好的工业应用潜质。
Spheniscidite of high-purity was synthesized in the presence of urea by hydrothermal method using ferrous sulfate and phosphoric acid as raw materials.Spheniscidites with different crystallinity and morphology were obtained by changing the reaction temperature,and the ferric phosphate was ultimate product after the calcination.The composition,structure,crystal shape and morphology of the synthesized spheniscidites were systematically characterized and analyzed by XRD,SEM,TG-DTA and infrared analysis.The phase transition process of spheniscidite during heating was analyzed.The results showed that phosphoric acid and iron had a fixed stoichiometric ratio in the static spheniscidite,and iron phosphate was obtained with high purity when synthesized spheniscidite was calcinated at high temperature,which could be used as a precursor of cathode material for lithium ion batteries and the method had simple synthesis process and good industrial application potential.
Spheniscidite of high-purity was synthesized in the presence of urea by hydrothermal method using ferrous sulfate and phosphoric acid as raw materials.Spheniscidites with different crystallinity and morphology were obtained by changing the reaction temperature,and the ferric phosphate was ultimate product after the calcination.The composition,structure,crystal shape and morphology of the synthesized spheniscidites were systematically characterized and analyzed by XRD,SEM,TG-DTA and infrared analysis.The phase transition process of spheniscidite during heating was analyzed.The results showed that phosphoric acid and iron had a fixed stoichiometric ratio in the static spheniscidite,and iron phosphate was obtained with high purity when synthesized spheniscidite was calcinated at high temperature,which could be used as a precursor of cathode material for lithium ion batteries and the method had simple synthesis process and good industrial application potential.
引文
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[3]Zhang W J.Structure and performance of LiFePO4cathode materials:A review[J].Journal of Power Sources,2011,196(6):2962-2970.
[4]Jugovic D,Uskokovic D.A review of recent developments in the synthesis procedures of lithium iron phosphate powders[J].Journal of Power Sources,2009,190(2):538-544.
[5]郑典模,陈骏驰,叶焕英,等.正交法优化沉淀法制备超细磷酸铁工艺[J].电源技术,2014,38(5):815-818.
[6]Son D,Kim E,Kim T G,et al.Nanoparticle iron-phosphate anode material for Li-ion battery[J].Applied Physics Letters,2004,85(24):5875-5877.
[7]Lin Y,Wu J B,Chen W P.Enhanced electrochemical performance of LiFePO4/C prepared by sol-gel synthesis with dry ball-milling[J].Ionics,2013,19(2):227-234.
[8]Wang Q,Deng S X,Wang H,et al.Hydrothermal synthesis of hierarchical LiFePO4microspheres for lithium ion battery[J].Cheminform,2013,553(14):69-74.
[9]Novikova S A,Yaroslavtsev A B.Cathode materials based on olivine lithium-ion batteries[J].Rev.Adv.Mater.Sci.,2017,49:129-139.
[10]易均辉.磷酸铁和磷酸铁锂的制备,表征及电化学性能的研究[D]:南宁:广西大学,2010.
[11]Calderón C A,Thomas J E,Lener G,et al.Electrochemical comparison of LiFePO4synthesized by a solid-state method using either microwave heating or a tube furnace[J].Journal of Applied Electrochemistry,2017,47(10):1179-1188.
[12]韩梦莹.电池级磷酸铁的制备工艺研究[D]:郑州:郑州大学,2014.
[13]Masquelier C,Reale P,Wurm C,et al.Hydrated iron phosphates FePO4·n H2O and Fe4(P2O7)3·n H2O as 3V positive electrodes in rechargeable lithium batteries[J].Journal of the Electrochemical Society,2002,149(8):A1037-A1044.
[14]赖桂棠,李大光,李军,等.共沉淀法制备球形磷酸亚铁铵[J].化工新型材料,2007,35(11):38-39,42.
[15]田晓珍,廖森,吴昆,等.水合磷酸铁铵的低热固相合成及其对乙酸丁酯的催化作用[J].广西科学,2008,15(2):166-169.
[16]Trobajo C,Espina A,Jaimez E,et al.Hydrothermal synthesis of iron(Ⅲ)phosphates in the presence of urea[J].Journal of the Chemical Society,Dalton Transactions,2000(5):787-790.
[17]Sugiura S,Nakamura T.Fuel cell including separator with outer ends placed inward of fluid passages formed in frame:US,9660276[P].2017-05-23.
[18]Choudhury A,Natarajan S.A synthetic iron phosphate mineral,spheniscidite,[NH4]+[Fe2(OH)(H2O)(PO4)2]·H2O,exhibiting reversible dehydration[J].Journal of Chemical Sciences,1999,111(5):627-637.
[19]Wu K P,Liu D W,Tang Y.Self-assembly of red-blood-cell-like(NH4)[Fe2(OH)(PO4)2]·2H2O architectures from 2D nanoplates by sonochemical method[J].Ultrasonics Sonochemistry,2018,40:832-836.
[20]Liu X B.,Liu G B.,Wang Y,et al.Influence of pH value on the properties of NH4Fe2(OH)-(PO4)2·2H2O precursor and LiFePO4/Ccomposite[J].Journal of Electronic Materials,2015,44(3):1008-1014.