화학공학소재연구정보센터
Journal of Industrial and Engineering Chemistry, Vol.89, 375-382, September, 2020
Hydrogen halide-free synthesis of organohalides for organometal trihalide perovskite solar cells
E-mail:,
We report an environmentally benign and economical approach for the large-scale production of methylammonium halides (MAX, X = I or Br) and formamidinium halides (FAX, X = I or Br) as core materials in perovskite solar cells (PSCs), which have emerged as the most promising sustainable energy source. In contrast to conventional processes that use highly toxic HI and HBr, ion exchange between sodium halide (NaX) and methlyammonium chloride (MACl) or formamidinium chloride (FACl) was found to be highly suitable for mass production. The average reaction yields of the ion-exchange process were comparable to that of the HX synthesis route: 98.8% for MAI, 98.7% for MABr, 98.0% for FAI, and 98.9% for FABr. The purity of the prepared samples was analyzed by various spectroscopic methods. Finally, a perovskite solar cell was fabricated with MAI prepared by ion-exchange reaction. The power conversion efficiency, which was measured to support the industrial feasibility of the method, was found to be similar to that of a device fabricated with commercial MAI.
  1. Wehrenfennig C, Eperon GE, Johnston MB, Snaith HJ, Herz LM, Adv. Mater., 26(10), 1584 (2014)
  2. Bi Y, Hutter EM, Fang Y, Dong Q, Huang J, Savenije TJ, J. Phys. Chem. Lett., 7, 923 (2016)
  3. Shi D, Adinolfi V, Comin R, Yuan MJ, Alarousu E, Buin A, Chen Y, Hoogland S, Rothenberger A, Katsiev K, Losovyj Y, Zhang X, Dowben PA, Mohammed OF, Sargent EH, Bakr OM, Science, 347(6221), 519 (2015)
  4. Stranks SD, Eperon GE, Grancini G, Menelaou C, Alcocer MJP, Leijtens T, Herz LM, Petrozza A, Snaith HJ, Science, 342(6156), 341 (2013)
  5. Kojima A, Teshima K, Shirai Y, Miyasaka T, J. Am. Chem. Soc., 131(17), 6050 (2009)
  6. Im JH, Lee CR, Lee JW, Park SW, Park NG, Nanoscale, 3, 4088 (2011)
  7. Kim HS, Lee CR, Im JH, Lee KB, Moehl T, Marchioro A, Moon SJ, Sci. Rep., 2, 591 (2012)
  8. Lee MM, Teuscher J, Miyasaka T, Murakami TN, Snaith HJ, Science, 338(6107), 643 (2012)
  9. Burschka J, Pellet N, Moon SJ, Humphry-Baker R, Gao P, Nazeeruddin MK, Gratzel M, Nature, 499(7458), 316 (2013)
  10. Liu MZ, Johnston MB, Snaith HJ, Nature, 501(7467), 395 (2013)
  11. Jeon NJ, Noh JH, Kim YC, Yang WS, Ryu S, Il Seol S, Nat. Mater., 13(9), 897 (2014)
  12. Zhou HP, Chen Q, Li G, Luo S, Song TB, Duan HS, Hong ZR, You JB, Liu YS, Yang Y, Science, 345(6196), 542 (2014)
  13. Ahn N, Son DY, Jang IH, Kang SM, Choi M, Park NG, J. Am. Chem. Soc., 137(27), 8696 (2015)
  14. Yang WS, Noh JH, Jeon NJ, Kim YC, Ryu S, Seo J, Seok SI, Science, 348(6240), 1234 (2015)
  15. Saliba M, Matsui T, Seo JY, Domanski K, Correa-Baena JP, et al>, Energy Environ. Sci., 9, 1989 (2016)
  16. Yang WS, Park BW, Jung EH, Jeon NJ, Kim YC, Lee DU, Shin SS, Seo J, Kim EK, Noh JH, Seok SI, Science, 356(6345), 1376 (2017)
  17. Shin SS, Yeom EJ, Yang WS, Hur S, Kim MG, Im J, Seo J, Noh JH, Seok SJ, Science, 356, 167 (2017)
  18. National Renewable Energy Laboratory, NREL Efficiency Chart.
  19. Shen L, Fang YJ, Wang D, Bai Y, Deng YH, Wang MM, Lu YF, Huang JS, Adv. Mater., 28(48), 10794 (2016)
  20. Zhao Y, Li C, Shen L, InfoMat, 1, 164 (2019)
  21. Li G, Wang H, Wang F, Li T, Xu M, Wang H, Wang Z, Zhan X, Hu W, Shen L, Light Sci. Appl., 9, 31 (2020)
  22. Li C, Lu J, Zhao Y, Sun L, Wang G, Ma Y, Zhang S, Zhou J, Shen L, Huang W, Small, 15, 190359 (2019)
  23. Pang S, Hu H, Zhang J, Lv S, Yu Y, Wei F, Qin T, Xu H, Liu Z, Cui G, Chem. Mater., 26, 1485 (2014)
  24. Koh TM, Fu K, Fang Y, Chen S, Sum TC, Mathews N, Mhaisalkar SG, Boix PP, Baikie T, J. Phys. Chem. C, 118, 16458 (2014)
  25. Eperon GE, Stranks SD, Menelaou C, Johnston MB, Herz LM, Snaith HJ, Energy Environ. Sci., 7, 982 (2014)
  26. Pellet N, Gao P, Gregori G, Yang TY, Nazeeruddin MK, Maier J, Gratzel M, Angew. Chem.-Int. Edit., 53, 3151 (2014)
  27. Yang M, Zhang T, Schulz P, Li Z, Li G, Kim DH, Guo N, Berry JJ, Zhu K, Zhao Y, Nat. Commun., 7, 12305 (2016)
  28. Jeon NJ, Noh JH, Yang WS, Kim YC, Ryu S, Seo J, Seok SI, Nature, 517(7535), 476 (2015)
  29. Aharon S, Cohen BE, Etgar L, J. Phys. Chem. C, 118, 17160 (2014)
  30. Lin Y, Shen L, Dai J, Deng Y, Wu Y, Bai Y, Zheng X, Wang J, Fang Y, Wei H, Ma W, Zeng XC, Zhan X, Huang J, Adv. Mater., 290, 160454 (2017)
  31. Department for environment, food and rural affairs, Guidelines for halogens and hydrogen halides in ambient air for protecting human health against acute irritancy effects.
  32. The United states Drug Enforcement Administration, List I chemicals.
  33. Jahandar M, Khan N, Jahankhan M, Song CE, Lee HK, Lee SK, Shin WS, Lee JC, Im SH, Moon SJ, J. Ind. Eng. Chem., 80, 265 (2019)
  34. Kim JY, Kwak GS, Choi YC, Kim DH, Han YS, J. Ind. Eng. Chem., 73, 175 (2019)
  35. Bai Y, Dong Q, Shao Y, Deng Y, Wang Q, Shen L, Wang D, Wei W, Huang J, Nat. Commun., 7, 12806 (2016)
  36. Lee JW, Seol DJ, Cho AN, Park NG, Adv. Mater., 26(29), 4991 (2014)
  37. Levchuk I, Osvet A, Tang X, Brandl M, Perea JD, Hoegl F, Matt GJ, Hock R, Batentschuk M, Brabec CJ, Nano Lett., 17, 2765 (2017)
  38. Etgar L, Gao P, Xue ZS, Peng Q, Chandiran AK, Liu B, Nazeeruddin MK, Gratzel M, J. Am. Chem. Soc., 134(42), 17396 (2012)
  39. Park IJ, Seo S, Park MA, Lee S, Kim DH, Zhu K, Shin H, Kim JY, ACS Appl. Mater. Interfaces, 9, 41898 (2017)
  40. Lee DG, Kim MC, Kim BJ, Kim DH, Lee SM, Choi M, Lee S, Jung HS, Appl. Surf. Sci., 477, 131 (2019)
  41. Kim BJ, Lee S, Jung HS, J. Mater. Chem. A, 6, 12215 (2018)
  42. Lide DR, CRC Handbook of Chemistry and Physics, 86th ed., CRC Press, Boca Raton, 2005.
  43. Nagabhushana GP, Shivaramaiah R, Navrotsky A, Proc. Natl. Acad. Sci., 113, 7717 (2016)
  44. Ivanov IL, Steparuk AS, Bolyachkina MS, Tsvetkov DS, Safronov AP, Zuev AY, J. Chem. Thermodyn., 116, 253 (2018)
  45. Ivanov IL, Mazurin MO, Tsvetkov DS, Malyshkin DA, Sereda VV, Zuev AY, Thermochim. Acta, 674, 58 (2019)
  46. Van Gompel WTM, Herckens R, Reekmans G, Ruttens B, D’Haen J, Adriaensens P, Lutsen L, Vanderzande D, J. Phys. Chem. C, 122, 4117 (2018)
  47. Gunther H, NMR Spectroscopy.An Introduction, John Wiley and Sons, New York, 1980.
  48. Macomber RS, A Complete Introduction to Modern NMR Spectroscopy, John Wiley and Sons, New York, 1998.
  49. Kim YC, Kim KH, Son DY, Jeong DN, Seo JY, Choi YS, Han IT, Lee SY, Park NG, Nature, 550(7674), 87 (2017)
  50. Yoon Y, Ha D, Park IJ, Haney PM, Lee S, Zhitenev NB, Nano Energy, 48, 543 (2018)
  51. Deng K, Liu Z, Xin Y, Li L, Adv. Mater. Interfaces, 5, 180049 (2018)
  52. Klug HP, Alexander LE, For Polycrystalline and Amorphous Materials, 2nd ed., Wiley Interscience, New York, 1974.
  53. Steele JH, Practical Applications of Quantitative Metallography, ASTM International, West Conshohocken, 1984.
  54. Zhao D, Chen C, Wang C, Junda MM, Song Z, Grice CR, Yu Y, et al., Nat. Energy, 3, 1093 (2018)
  55. Tavakoli MM, Saliba M, Yadav P, Holzhey P, Hagfeldt A, Zakeeruddin SM, Gratzel M, Adv. Eng. Mater., 9, 180264 (2019)
  56. Kim DH, Han GS, Seong WM, Lee JW, Kim BJ, Park NG, Hong KS, Lee S, Jung HS, ChemSusChem, 8, 2392 (2015)
  57. Kwon SL, Jin YU, Kim BJ, Han MH, Han GS, Shin S, Lee S, Jung HS, Appl. Surf. Sci., 416, 96 (2017)
  58. Herz LM, ACS Energy Lett., 2, 1539 (2017)
  59. Peng W, Aranda C, Bakr OM, Garcia-Belmonte G, Bisquert J, Guerrero A, ACS Energy Lett., 3, 1477 (2018)
  60. Lee JW, Kim HS, Park NG, Accounts Chem. Res., 49, 311 (2016)
  61. Chu Z, Yang M, Schulz P, Wu D, Ma X, Seifert E, Sun L, Li X, Zhu K, Lai K, Nat. Commun., 8, 2230 (2017)
  62. Ahn N, Kwak K, Jang MS, Yoon H, Lee BY, Lee JK, Pikhitsa PV, Byun J, Choi M, Nat. Commun., 7, 13422 (2016)