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以Pb(Zr 1–xTi x)O 3(PZT)为代表的铅基压电陶瓷因为具有良好的压电性能和机电耦合性能已被广泛应用于科技、工业、军事以及日常生活中. 但是, PZT基陶瓷中Pb的含量超过了60% (质量比), 在生产、使用及废弃处理过程中都会给人类生态环境造成严重损害. 因此, 发展无铅压电陶瓷已成为世界压电陶瓷研究的热点之一. 铌酸钾钠 (K 0.5Na 0.5)NbO 3(KNN)无铅压电陶瓷因为具有较为优异的压电性能以及较高的居里温度, 被认为是最可能取代铅基压电陶瓷的材料体系之一. 经过研究者们的努力工作, 改性后的KNN基无铅压电陶瓷压电性能已经接近或超过了某些铅基压电陶瓷的性能. 本文综合介绍了具有高压电活性的KNN基无铅压电陶瓷国内外的研究进展, 重点阐述了高性能铌酸钾钠基无铅压电陶瓷制备工艺及相关理论基础的研究进展, 并就今后铌酸钾钠基无铅压电陶瓷研究发展的方向及前景提出建议.Due to excellent piezoelectric properties and electromechanical coupling properties, lead-based piezoelectric ceramics represented by lead zirconate titanate Pb(Zr xTi 1–x)O 3(PZT) are widely used in science and technology, industry, military and daily life. However, the content of Pb in PZT-based ceramics exceeds 60% (mass ratio), which will cause serious damage to human ecological environment in the process of their production, use and waste treatment. Therefore, the development of lead-free piezoelectric ceramics has become one of the hot research spots. Potassium sodium niobate (K 0.5Na 0.5)NbO 3(KNN) lead-free piezoelectric ceramics are considered as one of the most promising material systems to substitute for lead-based piezoelectric ceramics because of their good piezoelectric properties and higher Curie temperature. Through many years of researches, the piezoelectric properties of modified KNN based lead-free piezoelectric ceramics have approached to or even exceeded those of some lead-based piezoelectric ceramics. Combining with our relevant work, we comprehensively review the research progress of high piezoelectric activity of KNN based lead-free piezoelectric ceramics, especially focus on the research progress of high-performance potassium sodium niobate lead-free piezoelectric ceramics, preparation technology and related theoretical mechanisms. The future research direction and prospect of KNN-based lead-free piezoelectric ceramics are also presented.
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Keywords:
- lead-free piezoelectric ceramics/
- potassium sodium niobate/
- origin/
- high piezoelectric property
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Material system d33/pC·N–1 kp TC/℃ KNN-BNZ-BG[24] 312 0.44 341 KNN-BZ-BNZ[25] 345 0.50 ～260 KNN-NS-BNKZH[26] 452 0.63 ～270 KNNS-BNCZ[27] 415 0.46 245 KNNTS-BNKZ[28] 400 0.46 240 KNN-BNZN[29] 318 ± 10 — 360 KNNS-BKZH[30] 451 0.52 258 KNNS-BLKZ[31] 385 — 245 KNNS-SZ-BNH[32] 470 ± 5 0.51 ± 0.02 244 KNNS-BS-BNZ[33] ～480 — ～225 KNNS-BNZ-BZ[34] 610 0.58 241 KNNS-BNKZ-Fe-AS[12] 650 — ～180 
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Material system d33/pC·N–1 kp TC/℃ KNNS-BNZSn[35] 465 0.51 240 KNNS-BZH[36] 410 — 255 KNNS-BNKZ[37] 490 0.46 227 KNNTS-BNKZ[38] 460 0.40 ～220 KNNS-BNH[39] 419 0.45 242 KNNS-BKZS[40] 430 — 243 KNNS-BNLCZ[41] 485 0.48 227 KNNS-BNKH[42] 525 — ～210 KNNS-BF-BNZ[43] 550 — 237 KNNS-CZ-BKHT-MnO2[44] 425 0.49 215 KNNS-BZ-BKH[45] 570 ± 10 — ～190 KNNS-BNZ-BF[46] 511 0.515 269 KNANS-BNZ[47] 440 0.50 250 下载:
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Material system d33or $ {d}_{33}^{*} $ Domain size KNNS-SZ-BAZ[52] 487 pC/N 30—65 nm,
65—160 nm,
30—45 nmKNNS-BZ-BNH[48] 600 pm/V 10—100 nm KNNS-BNKH[42] 525 pC/N 10—30 nm KNNS-BNKZ-Fe-AS[12] (650 ± 20) pC/N 2 nm KNNS-BNZ-BZ[34] 610 pC/N 50—70 nm KNNT-BNKZ-CZ[51] 482 pm/V 60 nm KNNS-BZ-BNZ[65] 300 pC/N 150 nm—1.0 μm KNNS-CZ-BKH[66] 550 pC/N 30—230 nm KNNS-BNH[67] 512 pC/N 100 nm KNNS-SZ-BNZ[68] 450 pC/N 50—200 nm KNLNTS[54] 455 pC/N 110—310 nm KNNS-BNZ-BF[46] 510 pC/N < 1 μm KNN-BNZ-MnO2-Sb2O3[69] 318 pC/N < 1 μm KNN-BI-BNZ[57] 317 pC/N ～200 nm KNNdNS-BNZ[70] 400 pC/N ～ 1 μm 下载:
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Material system d33/pC·N–1 TC/℃ KNN-BNH[71] 385 315 KNN-BNZ-LF[72] 345 314 KNN-BNZ-MnO2[73] 300 345 KNN-BNZ-BG[24] 312 341 KNN-BNZ-BA[74] 355 335 KNN-BAZ[75] 347 318 KNN-BNZ[76] 360 329 KNN-BKZ-BZ[77] 305 ～300 KNLNS-BS[78] 325 358 KNN-BNZS[79] 350 315 KNN-BS-BNKLZ[80] 366 335 KNN-BNT-BNZ[81] 318 326 KNN-BNZ-BI[57] 317 336 下载:
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d33/pC·N–1 d33variation/% $ {d}_{33}^{*} $/pm·V–1 $ {d}_{33}^{*} $ variation/% KNLNT-CZ[86] — — — almost unchanged @140 ℃ KNN-BNZ-LF[72] 345 — 420 8%@100 ℃ KNNT-BNKZ-SZ-MnO2[49] — — 400 10%@180 ℃ KNNT-BNKZ-CZ-MnO2[51] — — 482 10%@120 ℃ KNNS-BNZ-SZ[87] 390 — — 13%@180 ℃ KNN-BLT-BZ-MnO2[88] — — 470 8.5%@100 ℃, 21.2%@170 ℃ KNNS-BZ-BNZ[65] 300 10@100 ℃ — — KNNS-(BHo)NHf[89] — — ～386 almost unchanged @140 ℃ KNNT-BNZ-CZ[90] — — 502 10%@135 ℃ KNNS-BNKH[42] 525 — 460 10%@80 ℃ KNN-BZ-BNH-MnO2[91] 300 15@120 ℃ 540 ± 10 5%@100 ℃ KNN-BNH-BF-MnO2[92] 450 — — 28%@160 ℃ KNN-BNZ-MnO2-Sb2O3[69] 318 — — 9%@170 ℃ KNNS-BZH-BNZ[36] 410 — 441 2.5%@100 ℃, 16.1%@180 ℃ 注: 16.1%@180 ℃表示到180 ℃性能下降16.1%. 下载:
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Nb5+ Ta5+ Zr4+ Hf4+ Sn4+ Ti4+ Sb5+ Sb3+ Ga3+ 离子半径/Å 0.64 0.64 0.72 0.71 0.69 0.605 0.60 0.76 0.62 下载:
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K Nb OⅡ OⅠ KN ∂u3/∂η3 0.108 0.166 –0.092 –0.091 ∂u1/∂η5 0.115 0.210 –0.151 –0.024 K Na Nb OⅡ OI,1 OI,2 KNN ∂u3/∂η3 0.103 0.542 0.125 –0.158 –0.125 –0.135 ∂u1/∂η5 0.094 0.828 0.194 –0.235 –0.061 –0.309 下载:
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