固态电解质锂镧锆氧（LLZO）的研究进展

姜鹏峰, 石元盛, 李康万, 韩百川, 颜立全, 孙洋, 卢侠

Recent progress on the Li7La3Zr2O12 （LLZO） solid electrolyte

Pengfeng JIANG, Yuansheng SHI, Kangwan LI, Baichuan HAN, Liquan YAN, Yang SUN, Xia LU

表2 LLZO的掺杂组分、烧结条件、总电导率、活化能及致密度

Table 2 Doping compositions, sintering conditions, total conductivity, activation energy and density of LLZO

组分 掺杂元素 烧结温度与保温时间及方法 室温总电导率/S·cm 活化能/eV 致密度/% 无掺杂 c-LLZO[8] 无 1230 oC，36 h 2.4×10-4 0.31 92 c-LLZO[34] 无 1200 oC，35 h 0.4×10-4 0.46 95 t-LLZO[46] 无 1000 oC，5 h 4.2×10-7 0.58 60 t-LLZO[70] 无 1050 oC，1 h，热压 2.3×10-5 0.46 95 Li位掺杂 Li6.4Al0.2La3Zr2O12 [71] Al 1230 oC，6 h 2.63×10-5 0.314 85 Li6.24Al0.24La3Zr2O11.98 [72] Al 1000 oC，1 h，热压，氩气气氛 4.0×10-4 0.26 98 Li6.28Al0.24La3Zr2O12 [73] Al 1000 oC，4 h，溶胶凝胶 4×10-4 0.41 Li6.10Ga0.30La3Zr2O12 [74] Ga 1100 oC，24 h 1.12×10-3 0.25 96.3 Li6.6Ge0.10La3Zr2O12 [75] Ge 1150 oC，6 h，溶胶凝胶 2.8×10-4 0.38 98 Li6.25Fe0.25La3Zr2O12 [76] Fe 1230 oC，6 h 1.38×10-3 0.28 La位掺杂 Li6.6La2.6Ce0.4Zr2O12 [77] Ce 1050 oC，1 h，热压，氩气气氛 1.44×10-5 0.48 96 1.7 % Sr-LLZO[78] Sr 1200 oC，24 h 5×10-4 0.31 94 Li7.2La2.8Ca0.2Zr2O12 [79] Ca 1200 oC，10 h 3.9×10-5 Li7La2.8Nd0.2Zr2O12 [79] Nd 1200 oC，10 h 3.3×10-5 Li7La2.75Y0.25Zr2O12 [80] Y 1200 oC，18 h 3.21×10-4 0.31 96 Zr位掺杂 Li6.5La3Zr1.5Ta0.5O12 [81] Ta 1100 oC，4 h 8.4×10-4 0.426 Li6.75La3Zr1.75Nb0.25O12 [82] Nb 1200 oC，36 h 8.0×10-4 0.31 89～92 Li6.6La3Zr1.6Sb0.4O12 [83] Sb 1100 oC，24 h 7.7×10-4 0.34 91 Li6.5La3Zr1.75Te0.25O12 [84] Te 1100 oC，15 h 1.02×10-3 0.38 Li7La3Zr1.7Ti0.3O12 [85] Ti 1180 oC，20 h 4.16×10-4 0.48 92.1 Li6.4La3Zr1.7W0.3O12 [86] W 1100 oC，36 h 7.89×10-4 0.45 Li6.6La3Zr1.8Mo0.2O12 [87] Mo 1100 oC，3 h溶胶凝胶 5.09×10-4 0.29 92.8 Li7.1La3Zr1.9Cr0.1O12 [88] Cr 1230 oC，6 h 5.2×10-4 0.39 Li7.2La3Zr1.8Gd0.2O12 [89] Gd 1220 oC，36 h 2.3×10-4 0.25 93～95 Li7La3Zr1.96Sc0.05O12 [90] Sc 1075 oC，12 h 1.65×10-4 0.327 93.8 Li6La3SnNbO12 [91] Sn、Nb 1130 oC，12 h 3.5×10-5 0.503 89.6 Li6La3SnTaO12 [91] Sn、Ta 1130 oC，12 h 4.2×10-5 0.498 88.9 Li位、Zr位共掺杂 Li6.15Al0.2La3Zr1.75Ta0.25O12 [92] Al、Ta 1000 oC，3～4 h共沉淀 3.7×10-4 0.30 98 Li6.15Ga0.2La3Zr1.75Ta0.25O12 [92] Ga、Ta 1000 oC，3～4 h共沉淀 4.1×10-4 0.27 98 Li6.65Ga0.15La3Zr1.90Sc0.10O12 [93] Ga、Sc 1200 oC，6 h，溶胶凝胶，氧气气氛 1.8×10-3 0.29 93 Li6.775Al0.05La3Zr1.925Sb0.075O12 [94] Al、Sb 1170 oC，6 h 4.10×10-4 0.32 96.7 Li6.45Ca0.05La2.95Ta0.6Zr1.4O12 [95] Ca、Ta 1125 oC，6 h 4.03×10-4 Li6.375Al0.075La3Zr1.8Mo0.2O12 [96] Al、Mo 1040 oC，3 h 4.41×10-4 0.30 96.4 Li6.8La2.95Ca0.05Zr1.75Nb0.25O12 [97] Ca、Nb 790 oC，40 h助烧剂添加 3.6×10-4 0.32 90 Al-Li6.5La3Zr1.75Te0.25O12 [98] Al、Te 1150 oC，36 h 4×10-4 0.46 82.4 Li6.75La2.8Ga0.2Zr1.75Nb0.25O12 [99] Ga、Nb 1050 oC，12 h 2.28×10-4 0.33 90～92 Li5.1Al0.1La3Zr1.3Nb0.2O10.3 [100] Al、Nb 1200 oC，2 h 5×10-4 0.3 96 1.5%Al2O3+Li7La3Zr1.7Ti0.3O12 [85] Al、Ti 1180 oC，20 h 4.16×10-4 0.48 92.1 Li位、La位共掺杂 Li6.5Ga0.2La2.9Sr0.1Zr2O12 [101] Ga、Sr 1100 oC，6 h 5.5×10-4 0.31 — Li6.50Ga0.3La2.80Rb0.20Zr2O12 [102] Ga、Rb 1100 oC，24 h 1.16×10-3 0.27 — La位、Zr位共掺杂 Li6.66La2.94Sr0.06Zr1.6Sb0.4O12 [103] Sr、Sb 1100 oC，12 h 8.83×10-4 0.26 95.1 Li6.6La2.75Y0.25Zr1.6Ta0.4O12 [104] Y、Ta 1200 oC，18 h 4.36×10-4 0.34 95