B掺杂对(Al_(0.2)Zr_(0.8))_(4/3.8)Nb(PO_4)_3固体电解质性能的影响
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摘要
采用高温固相反应法对(Al_(0.2)Zr_(0.8))_(4/3.8)Nb(PO_4)_3的P位进行B掺杂,获得了固体电解质(Al_(0.2)Zr_(0.8))_((4+2x)/3.8)NbP_(3–x)B_xO_(12)(x=0～0.2)。利用X射线衍射、场发射扫描电子显微镜、电化学交流阻抗法、直流极化法等对样品的相组成、微观形貌和电性能进行表征。结果表明:不同比例B掺杂的固体电解质(Al_(0.2)Zr_(0.8))_((4+2x)/3.8)Nb P_(3–x)B_xO_(12)(x=0～0.2)均具有NASICON型三维结构,B掺杂并未影响固体电解质的物相结构;与(Al_(0.2)Zr_(0.8))_(4/3.8)Nb(PO_4)_3相比,B掺杂后的样品致密度增大,电导率提高。(Al_(0.2)Zr_(0.8))_(4.2/3.8)Nb P_(2.9)B_(0.1)O_(12)(x=0.1)具有最大的致密度和最高的电导率。在600℃时,样品电导率达到1.27×10~(–3 )S·cm~(–1),是未掺杂样品的2倍;直流极化法测试证实,样品为纯Al~(3+)传导,电子传导可忽略不计。
P site in(Al_(0.2)Zr_(0.8))_(4/3.8)Nb(PO_4)_(3 )was doped by boron ions via high-temperature solid-state reaction to form(Al_(0.2)Zr_(0.8))_((4+2x)/3.8)Nb P_(3–x)B_xO_(12)(x=0–0.2)solid electrolyte.The phase composition,microstructure and electrical properties of the samples were investigated by X-ray diffraction,field emission scanning electron microscopy,electrochemical impedance spectroscopy and direct current polarization method,respectively.The results show that the solid electrolyte(Al_(0.2)Zr_(0.8))_((4+2x)/3.8)Nb P_(3–x)B_xO_(12)(x=0–0.2)samples doped with different proportions of B have a three-dimensional NASICON structure,implying that B ion doping does not affect the phase structure of the solid electrolyte.Compared with(Al_(0.2)Zr_(0.8))_(4/3.8)Nb(PO_4)_3,all the B ion-doped samples are of higher bulk density and conductivity.Among all the samples,(Al_(0.2)Zr_(0.8))_(4.2/3.8)Nb P_(2.9)B_(0.1)O_(12)(x=0.1)has the maximum bulk density and the total conductivity of 1.27×10~(–3 )S·cm~(–1) at 600℃.Based on the result of the DC polarization test,Al~(3+)is the main conduction ion in the electrolyte and the electronic conduction is negligible.
P site in(Al_(0.2)Zr_(0.8))_(4/3.8)Nb(PO_4)_(3 )was doped by boron ions via high-temperature solid-state reaction to form(Al_(0.2)Zr_(0.8))_((4+2x)/3.8)Nb P_(3–x)B_xO_(12)(x=0–0.2)solid electrolyte.The phase composition,microstructure and electrical properties of the samples were investigated by X-ray diffraction,field emission scanning electron microscopy,electrochemical impedance spectroscopy and direct current polarization method,respectively.The results show that the solid electrolyte(Al_(0.2)Zr_(0.8))_((4+2x)/3.8)Nb P_(3–x)B_xO_(12)(x=0–0.2)samples doped with different proportions of B have a three-dimensional NASICON structure,implying that B ion doping does not affect the phase structure of the solid electrolyte.Compared with(Al_(0.2)Zr_(0.8))_(4/3.8)Nb(PO_4)_3,all the B ion-doped samples are of higher bulk density and conductivity.Among all the samples,(Al_(0.2)Zr_(0.8))_(4.2/3.8)Nb P_(2.9)B_(0.1)O_(12)(x=0.1)has the maximum bulk density and the total conductivity of 1.27×10~(–3 )S·cm~(–1) at 600℃.Based on the result of the DC polarization test,Al~(3+)is the main conduction ion in the electrolyte and the electronic conduction is negligible.
引文
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[26]ADAMU M,KALE G M.Novel Sol-Gel Synthesis of MgZr4P6O24composite solid electrolyte and newer insight into the Mg2+-ion conducting properties using impedance spectroscopy[J].J Phys Chem C,2016,120(32):17909-17915.
[27]ZHANG P,MATSUI M,TAKEDA Y,et al.Water-stable lithium ion conducting solid electrolyte of iron and aluminum doped nasicon-type Li Ti2(PO4)3[J].Solid State Ionics,2014,263:27-32.
[28]ZHANG P,WANG H,SI Q,et al.High lithium ion conductivity solid electrolyte of chromium and aluminum co-doped nasicon-type Li Ti2(PO4)3[J].Solid State Ionics,2015,272:101-106.
[29]WANG D,ZHONG G,LI Y,et al.Enhanced ionic conductivity of Li3.5Si0.5P0.5O4 with addition of lithium borate[J].Solid State Ionics,2015,283:109-114.
[2]刘佳,周会珠,朱靖,等.高价阳离子固体电解质的研究进展[J].功能材料,2012,43(B08):22-28.LIU Jia,ZHOU Huizhu,ZHU Jing,et al.J Funct Mater(in Chinese),2012,43(B08):22-28.
[3]ANANTHARAMULU N,RAO K K,RAMBABU G,et al.Awide-ranging review on nasicon type materials[J].J Mater Sci,2011,46(9):2821-2837.
[4]OHTOMO T,MIZUNO F,HAYASHI A,et al.Electrical and electrochemical properties of Li2S-P2S5-P2O5 glass-ceramic electrolytes[J].J Power Sources,2005,146(1-2):715-718.
[5]THANGADURAI V,SHUKLA A K,GOPALAKRISHNAN J.New lithium-ion conductors based on the nasicon structure[J].J Mater Chem,1999,9(3):739-741.
[6]XIE H,GOODENOUGH J B,LI Y.Li1.2Zr1.9Ca0.1(PO4)3,a room-temperature li-ion solid electrolyte[J].J Power Sources,2011,196(18):7760-7762.
[7]GOODENOUGH J B,HONG Y P,KAFALAS J A.Fast Na+-ion transport in skeleton structures[J].Mater Res Bull,1976,11(2):203-220.
[8]IMANAKA N,OKAZAKI Y,ADACHI G.Divalent magnesium ionic conduction in Mg1-2x(Zr1-x Nbx)4P6O24(x=0-0.4)solid solutions[J].Electrochem Solid State Lett,2000,3(7):327-329.
[9]TAMURA S,OKADA Y,IMANAKA N.Divalent Sr2+cation conducting solid electrolyte with nasicon-type structure[J].Electrochem,2014,82(10):830-832.
[10]IMANAKA N,OKAZAKI Y,ADACHI G Y.Divalent magnesium ionic conduction in the magnesium phosphate based composites[J].Chem Lett,1999(9):939-940.
[11]HASEGAWA Y,TAMURA S,IMANAKA N.Effect of low-melting oxide additives on the sinterability and ion conductivity of Al3+ion conducting solid electrolytes with the nasicon type structure[J].J New Mater Electrochem Syst,2005,8(3):203-207.
[12]IMANAKA N,HASEGAWA Y,YAMAGUCHI M,et al.Extraordinary high trivalent Al3+ion conduction in solids[J].Chem Mater,2002,14(11):4481-4483.
[13]HASEGAWA Y,IMANAKA N,ADACHI G Y.Cerium ion conducting solid electrolyte[J].J Solid State Chem,2003,171(1-2):387-390.
[14]TAMURA S,YAMAMOTO S,IMANAKA N.New type of trivalent gadolinium ion conducting solid electrolyte[J].J New Mater Electrochem,2008,11(1):1-4.
[15]KATAYAMA H,TAMURA S,IMANAKA N.New bismuth ion conducting solid electrolyte[J].Solid State Ionics,2011,192(1):134-136.
[16]HASEGAWA Y,TAMURA S,IMANAKA N,et al.New trivalent ion conducting solid electrolyte with the nasicon type structure[J].J Alloys Compd,2004,379(1-2):262-265.
[17]HASEGAWA Y,TAMURA S,IMANAKA N,et al.Trivalent praseodymium ion conducting solid electrolyte composite with nasicon type structure[J].J Alloys Compd,2004,375(1-2):212-216.
[18]刘佳.以(Al0.2Zr0.8)20/19Nb(PO4)3为固体电解质的电化学传感器的研究[D].唐山:河北联合大学,2013.LIU Jia.Study on electrochemical sensor of aluminum solid electrolyte(Al0.2Zr0.8)20/19Nb(PO4)3(in Chinese,dissertation).Tangshan:Hebei United University,2013.
[19]史明,戴磊,周会珠,等.NASICON型固体电解质(Al0.2Zr0.8)(4-x)/3.8Nb P3-x Mox O12的合成及其电化学性能研究[J].陶瓷学报,2017,38(3):342-345.SHI Ming,DAI Lei,ZHOU Huizhu,et al.J Ceram(in Chinese),2017,38(3):342-345.
[20]HASEGAWA Y,IMANAKA N.Effect of the lattice volume on the Al3+ion conduction in nasicon type solid electrolyte[J].Solid State Ionics,2005,176(31-34):2499-2503.
[21]IMANAKA N,OKAMOTO K,ADACHI G.A new type of chlorine gas sensor with the combination of Cl-anion and Al3+cation conducting solid electrolytes[J].Mater.Lett,2003,57(13-14):1966-1969.
[22]NAGAI T,TAMURA S,IMANAKA N.Solid electrolyte type ammonia gas sensor based on trivalent aluminum ion conducting solids[J].Sens Actuators B:Chem,2010,147(2):735-740.
[23]INABA Y,TAMURA S,IMANAKA N.New type of sulfur diozide gas sensor based on bivalent Al3+ion conducting solid electrolyte[J]Solid State Ionics,2008,179(27-32):1625-1627.
[24]TAMURA S,HASEGAWA I,IMANAKA N,et al.Carbon dioxide gas sensor based on trivalent cation and divalent oxide anion conducting solids with rare earth oxycarbonate based auxiliary electrode[J].Sensors and Actuators B:Chem,2005,108(1-2):359-363.
[25]华正伸,冯晓晶,王晓然,等.离子掺杂对Nasicon型化合物电化学性能的影响[J].硅酸盐学报,2017,45(6):756-764.HUA Zhengshen,FENG Xiaojing,WANG Xiaoran,et al.J Chin Ceram Soc,2017,45(6):756-764.
[26]ADAMU M,KALE G M.Novel Sol-Gel Synthesis of MgZr4P6O24composite solid electrolyte and newer insight into the Mg2+-ion conducting properties using impedance spectroscopy[J].J Phys Chem C,2016,120(32):17909-17915.
[27]ZHANG P,MATSUI M,TAKEDA Y,et al.Water-stable lithium ion conducting solid electrolyte of iron and aluminum doped nasicon-type Li Ti2(PO4)3[J].Solid State Ionics,2014,263:27-32.
[28]ZHANG P,WANG H,SI Q,et al.High lithium ion conductivity solid electrolyte of chromium and aluminum co-doped nasicon-type Li Ti2(PO4)3[J].Solid State Ionics,2015,272:101-106.
[29]WANG D,ZHONG G,LI Y,et al.Enhanced ionic conductivity of Li3.5Si0.5P0.5O4 with addition of lithium borate[J].Solid State Ionics,2015,283:109-114.