• 综述 •
顾婷婷, 顾坚, 张喻, 任华. 金属硼氢化物基固态储氢体系[J]. 化学进展, 2020, 32(5): 665-686.
Tingting Gu, Jian Gu, Yu Zhang, Hua Ren. Metal Borohydride-Based System for Solid-State Hydrogen Storage[J]. Progress in Chemistry, 2020, 32(5): 665-686.
氢气储存仍是制约氢经济推行的关键问题,开发一种高效、安全的储氢技术仍面临着巨大挑战。近年来,利用固态氢化物的化学吸附储氢技术由于可靠、结构紧密和高储氢容量的特点,被视为最有潜力的储氢手段之一。在众多固态氢化物储氢材料中,金属硼氢化物由于其极高的重量和体积储氢密度而备受关注。然而,金属硼氢化物热力学稳定,动力学缓慢,导致其吸/放氢温度高、速率慢、可逆性及循环稳定性差。本文从替代、复合、掺杂、纳米结构限域及相应的反应机理等角度总结了金属硼氢化物储氢材料的最新改性研究和应用,并提出了其中存在的问题和相应对策,同时指出了未来的研究方向。
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MM'(BH4) n | H2 content(wt%) | Synthesis method | Byproduct | Purity(%) | ref |
---|---|---|---|---|---|
LiK(BH4)2 | 10.6 | LiBH4: KBH4(d) | NA | 77.5R | 80 |
LiZr(BH4)5 | 11.7 | ZrCl4: LiBH4(d) | LiCl | 50.4C | 84 |
Li2Zr(BH4)6 | 12.5 | ZrCl4: LiBH4(d) | LiCl | 53.4C | 84 |
LiMn(BH4)3 | 11.3 | MnCl2: LiBH4(d) | LiCl | 55.6C | 85 |
LiSc(BH4)4 | 14.5 | ScCl3: LiBH4(d) | LiCl | 46.6C | 86 |
Na2Mn(BH4)2 | 6.1 | MnCl2: NaBH4(d) | NaCl | 42.0C | 87 |
LiZn2(BH4)5 | 9.5 | ZnCl2: LiBH4(d) | LiCl | 55.6C | 88 |
NaZn2(BH4)5 | 8.8 | ZnCl2: NaBH4(d) | NaCl | 49.4C | 88 |
NaZn(BH4)3 | 9.0 | ZnCl2: NaBH4(d) | NaCl | 53.2C | 88 |
Li-Mg-B-H | 15.8 | MgCl2: LiBH4(w+f) | NA | - | 89 |
Li-Ca-B-H | 13.1 | CaCl2: LiBH4(w+h) | LiCl | 51.9C | 90 |
LiMg(BH4)3 | 15.8 | LiBH4: Mg(BH4)2(d) | NA | - | 91 |
LiCa(BH4)3 | 13.1 | LiBH4: Ca(BH4)2(d) | NA | - | 92 |
LiY(BH4)4 | 10.3 | LiBH4: Y(BH4)3(d@200 ℃+q) | NA | 87R | 93 |
NaY(BH4)4 | 9.4 | NaBH4: Y(BH4)3(d@180 ℃+q) | NA | 69R | 93 |
System | Event temperature( ℃) | Behavior | ref |
---|---|---|---|
0.65LiBH4-0.35NaBH4 | 94 | o-LiBH4→h-LiBH4 | 164 |
220 | Melting | ||
>300 | H2 release | ||
0.725LiBH4-0.275KBH4 | 113 | o-LiBH4→h-LiBH4 | 165 |
105 | Melting | ||
>400 | H2 release | ||
0.55LiBH4-0.45Mg(BH4)2 | 112 | o-LiBH4→h-LiBH4 | 166 |
180 | H2 release | ||
250 | H2 release(frothing) | ||
0.68LiBH4-0.32Ca(BH4)2 | 110 | o-LiBH4→h-LiBH4 | 83 |
250 | Frothing/expansion | ||
>320 | H2 release(Bubbling) | ||
0.4NaBH4-0.6Mg(BH4)2 | 205 | Melting | 167 |
>240 | H2 release | ||
0.5LiBH4-0.5Mn(BH4)2 | 110 | o-LiBH4→h-LiBH4 | 168 |
150 | Melting | ||
>160 | H2& B2H6 release | ||
0.45LiBH4-0.1NaBH4-0.45KBH4 | 103 | Melting | 169 |
>400 | H2 release |
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