卢佳垚等：钙钛矿型锂离子固体电解质Li2x-Sr1-xTi-Nb,O3的性能 ·1031· 体电解质，XRD显示当y≤0.70时，材料为立方钙 [12]Chen C H,Xie S,Sperling E,et al.Stable lithium-ion conducting 钛矿型结构.离子电导率随着掺杂含量的增加 perovskite lithium-strontium-tantalum-zirconium-oxide system. 先增后减小，Lio.35Sro.475Tio.3Nbo.7O3总的离子电导 Solid State lonics,2004,167(3-4):263 [13]Kong Y Z,Li Y,Lu J Y,et al.Conductivity and electrochemical 率最高为3.62×10Scm,电子电导率为2.55× stability of perovskite-structured lithium-strontium-niobium- 109Scm,活化能仅为0.29eV.以Lio.35Sro.475Tio.3 hafnium-oxide solid Li-ion conductors.J Mater Sci:Mater Nbo.O3为固态隔膜的LiFePO,/Li半电池的首次 Electron,.2017,28(12):8621 放电容量为103.5mAhg,并能稳定运行100圈 [14]Huang B.Xu BY,Li YT,et al.Li-ion conduction and stability of 以上. perovskite LissSrnHfuTaO3.ACS Appl Mater Interfaces, 20168(23):14552 参考文献 [15]Kong YZ,Li Y.Li J W.et al.Li ion conduction of perovskite [1]Takada K.Progress and prospective of solid-state lithium batteries. Lio.375Sro4375Tio25Tao.75O3 and related compounds.Ceram Int, Acta Mater,2013,61(3):759 2018,44(4):3947 [2]Sun C W,Liu J,Gong Y D,et al.Recent advances in all-solid-state [16]Kong Y Z,Li Y,Lu J Y,et al.Effect of doping (Al,La,Sm)on the rechargeable lithium batteries.Nano Energy,2017,33:363 conductivity of Lio.375Sro.437sHfo.25Tao.7503 ceramics.Mater Res [3]Zheng F,Kotobuki M,Song S F,et al.Review on solid Epe,2017,4(9):095504 electrolytes for all-solid-state lithium-ion batteries.J Power [17]Lu J Y,Li Y.Conductivity and stability of LiasSr Source3,2018.389:198 LaZrTa superionic solid electrolytes.Electrochimica Acta, [4] Wang C H,Yang Y F,Liu X J,et.al.Suppression of lithium 2018,282:409 dendrite formation by using LAGP-PEO(LiTFSI)composite solid [18]Mo SS,Lu P H,Ding F,et al.High-temperature performance of electrolyte and lithium metal anode modified by PEO(LiTFSI)in all-solid-state battery assembled with 95(0.7LiS-0.3P2Ss)-5LiPO all-solid-state lithium batteries.ACS Appl Mater Inter,2017,9: glass electrolyte.Solid State lonics,2016,296:37 13694 [19]Cheng S,Smith D M,Li C Y.Anisotropic ion transport in a [5]Adnan S B R S,Salleh F M,Mohamed N S.Effect of interstitial poly(ethylene oxide)-LiClO solid state electrolyte templated by Li'ion and vacant site Lit ion on the properties of novel graphene oxide.Macromolecules,2015,48(13):4503 Liz.osZnAlo.osSio.90 and Li19sZno.9sCro.osSiOa ceramic [20]Lu DL,Ma JM,Wu JL,et al.Preparation and electrochemical electrolytes.Ceram Int,2016,42(15):17941 properties of LioS,LaTiO based solid-state ionic [6]Hallopeau L,Bregiroux D,Rousse G,et al.Microwave-assisted supercapacitor.Ceram Int,2019,45(2):2584 reactive sintering and lithium ion conductivity of [21]Sotomayor M E,Varez A.Bucheli W,et al.Structural Li.3Alo.3Ti1x(PO)solid electrolyte.J Power Sources,2018,378 characterisation and Li conductivity of LiSrLaTiO3( 48 x<0.5)perovskites.Ceram Int,2013,39(8):9619 [7]Kokal I,Ramanujachary K V,Notten P H L,et al.Sol-gel [22]Teranishi T,Kouchi A,Hayashi H,et al.Dependence of the synthesis and lithium ion conduction properties of garnet-type conductivity of polycrystalline Lio.33Ba,Lao.56.2/TiO3 on Ba LiBaLa Ta,O2.Mater Res Bull,2012,47(8):1932 loading.Solid State lonics,2014,263:33 [8]Belous A G.Lithium ion conductors based on the perovskite [23]Wei Q,Cui W,Long X,et al.A investigation on the surface state Laz-LisTiOJEur Ceram Soc,2001,21(10-11):1797 of Laj-M,CoO:(M-Ca,Sr)perovskite oxides by XPS.Chem Res [Chen CH,Amine K.Ionic conductivity,lithium insertion and Chin Uni,1990,11(11):1227 extraction of lanthanum lithium titanate.Solid State lonics,2001, (魏诠，崔巍，龙骧，等.La(1-x)MCoO,(M=Ca,Sr)表面状态的 144(1-2):51 XPS研究.高等学校化学学报，1990,11(11)：1227) [10]Mitsuishi K,Ohnishi T,Tanaka Y,et al.Nazca Lines by La [24]Yu K,Jin L,Li Y,et al.Structure and conductivity of perovskite ordering in LazLisrTiO;ion-conductive perovskite.App/Phys Lio3ssLao.3sSro.Tio.MooosO (M =Al,Co and In)ceramics. Lem,2012,101(7):073903 Ceram Int,,2019,45(18):23941 [11]Yu R,Du Q X,Zou B K,et al.Synthesis and characterization of [25]Ofoegbuna T,Darapaneni P,Sahu S,et al.Stabilizing the B-site perovskite-type (Li,Sr(Zr,Nb)O;quaternary solid electrolyte for oxidation state in ABO:perovskite nanoparticles.Nanoscale, all-solid-state batteries./Power Sources,2016,306:623 2019,11(30):14303体电解质，XRD 显示当 y≤0.70 时，材料为立方钙 钛矿型结构. 离子电导率随着掺杂含量的增加 先增后减小，Li0.35Sr0.475Ti0.3Nb0.7O3 总的离子电导 率最高 为 3.62×10−5 S·cm−1，电子电导率 为 2.55× 10−9 S·cm−1，活化能仅为 0.29 eV. 以 Li0.35Sr0.475Ti0.3 Nb0.7O3 为固态隔膜的 LiFePO4 /Li 半电池的首次 放电容量为 103.5 mA·h·g−1，并能稳定运行 100 圈 以上. 参    考    文    献 Takada K. Progress and prospective of solid-state lithium batteries. Acta Mater, 2013, 61（3）: 759 [1] Sun C W, Liu J, Gong Y D, et al. Recent advances in all-solid-state rechargeable lithium batteries. Nano Energy, 2017, 33: 363 [2] Zheng  F,  Kotobuki  M,  Song  S  F,  et  al.  Review  on  solid electrolytes  for  all-solid-state  lithium-ion  batteries. J Power Sources, 2018, 389: 198 [3] Wang  C  H,  Yang  Y  F,  Liu  X  J,  et.  al.  Suppression  of  lithium dendrite formation by using LAGP-PEO (LiTFSI) composite solid electrolyte and lithium metal anode modified by PEO (LiTFSI) in all-solid-state  lithium  batteries. ACS Appl Mater Inter,  2017,  9: 13694 [4] Adnan S B R S, Salleh F M, Mohamed N S. Effect of interstitial Li+ ion  and  vacant  site  Li+ ion  on  the  properties  of  novel Li2.05ZnAl0.05Si0.95O4 and  Li1.95Zn0.95Cr0.05SiO4 ceramic electrolytes. Ceram Int, 2016, 42（15）: 17941 [5] Hallopeau  L,  Bregiroux  D,  Rousse  G,  et  al.  Microwave-assisted reactive  sintering  and  lithium  ion  conductivity  of Li1.3Al0.3Ti1.7(PO4 )3 solid electrolyte. J Power Sources, 2018, 378: 48 [6] Kokal  I,  Ramanujachary  K  V,  Notten  P  H  L,  et  al.  Sol-gel synthesis  and  lithium  ion  conduction  properties  of  garnet-type Li6BaLa2Ta2O12. Mater Res Bull, 2012, 47（8）: 1932 [7] Belous  A  G.  Lithium  ion  conductors  based  on  the  perovskite La23−xLi3xTiO3 . J Eur Ceram Soc, 2001, 21（10-11）: 1797 [8] Chen  C  H,  Amine  K.  Ionic  conductivity,  lithium  insertion  and extraction of lanthanum lithium titanate. Solid State Ionics, 2001, 144（1-2）: 51 [9] Mitsuishi  K,  Ohnishi  T,  Tanaka  Y,  et  al.  Nazca  Lines  by  La ordering  in  La2/3–xLi3xTiO3 ion-conductive  perovskite. Appl Phys Lett, 2012, 101（7）: 073903 [10] Yu R, Du Q X, Zou B K, et al. Synthesis and characterization of perovskite-type (Li, Sr)(Zr, Nb)O3 quaternary solid electrolyte for all-solid-state batteries. J Power Sources, 2016, 306: 623 [11] Chen C H, Xie S, Sperling E, et al. Stable lithium-ion conducting perovskite  lithium-strontium-tantalum-zirconium-oxide  system. Solid State Ionics, 2004, 167（3-4）: 263 [12] Kong Y Z, Li Y, Lu J Y, et al. Conductivity and electrochemical stability  of  perovskite-structured  lithium-strontium-niobium￾hafnium-oxide  solid  Li-ion  conductors. J Mater Sci: Mater Electron, 2017, 28（12）: 8621 [13] Huang B, Xu B Y, Li Y T, et al. Li-ion conduction and stability of perovskite  Li3/8Sr7/16Hf1/4Ta3/4O3 . ACS Appl Mater Interfaces, 2016, 8（23）: 14552 [14] Kong  Y  Z,  Li  Y,  Li  J  W,  et  al.  Li  ion  conduction  of  perovskite Li0.375Sr0.4375Ti0.25Ta0.75O3 and  related  compounds. Ceram Int, 2018, 44（4）: 3947 [15] Kong Y Z, Li Y, Lu J Y, et al. Effect of doping (Al, La, Sm) on the conductivity  of  Li0.375Sr0.4375Hf0.25Ta0.75O3 ceramics. Mater Res Express, 2017, 4（9）: 095504 [16] Lu  J  Y,  Li  Y.  Conductivity  and  stability  of  Li3/8Sr7/16−3x/2 LaxZr1/4Ta3/4O3 superionic solid electrolytes. Electrochimica Acta, 2018, 282: 409 [17] Mo S S, Lu P H, Ding F, et al. High-temperature performance of all-solid-state battery assembled with 95(0.7Li2S-0.3P2S5 )-5Li3PO4 glass electrolyte. Solid State Ionics, 2016, 296: 37 [18] Cheng  S,  Smith  D  M,  Li  C  Y.  Anisotropic  ion  transport  in  a poly(ethylene  oxide)-LiClO4 solid  state  electrolyte  templated  by graphene oxide. Macromolecules, 2015, 48（13）: 4503 [19] Lu D L, Ma J M, Wu J L, et al. Preparation and electrochemical properties  of  Li0.33SrxLa0.56−2/3xTiO3 − based  solid-state  ionic supercapacitor. Ceram Int, 2019, 45（2）: 2584 [20] Sotomayor  M  E,  Várez  A,  Bucheli  W,  et  al.  Structural characterisation  and  Li  conductivity  of  Li1/2−xSr2xLa1/2−xTiO3 (0< x< 0.5) perovskites. Ceram Int, 2013, 39（8）: 9619 [21] Teranishi  T,  Kouchi  A,  Hayashi  H,  et  al.  Dependence  of  the conductivity  of  polycrystalline  Li0.33BaxLa0.56-2/3xTiO3 on  Ba loading. Solid State Ionics, 2014, 263: 33 [22] Wei Q, Cui W, Long X, et al. A investigation on the surface state of La1−xMx CoO3 (M-Ca, Sr) perovskite oxides by XPS. Chem Res Chin Univ, 1990, 11（11）: 1227 （魏诠, 崔巍, 龙骧, 等. La(1−x)MxCoO3 (M=Ca, Sr)表面状态的 XPS研究. 高等学校化学学报, 1990, 11（11）：1227） [23] Yu K, Jin L, Li Y, et al. Structure and conductivity of perovskite Li0.355La0.35Sr0.3Ti0.995M0.005O3 (M  =  Al,  Co  and  In)  ceramics. Ceram Int, 2019, 45（18）: 23941 [24] Ofoegbuna  T,  Darapaneni  P,  Sahu  S,  et  al.  Stabilizing  the  B-site oxidation  state  in  ABO3 perovskite  nanoparticles. Nanoscale, 2019, 11（30）: 14303 [25] 卢佳垚等： 钙钛矿型锂离子固体电解质 Li2x−ySr1−xTi1−yNbyO3 的性能 · 1031 ·