1.福州大学化工学院,福建 福州 310029
2.贵州工程应用技术学院化学工程学院,贵州 毕节 100084
王世栋 (1993—) ,男,博士,讲师,wsd18703536@163.com
李润之 (1998—) ,男,硕士,工程师,3212970292@qq.com
张宏伟(1989—) ,男,博士,副教授,zhanghw@fzu.edu.cn
袁珮 (1983—) ,女,博士,教授,yuanpei@fzu.edu.cn
收稿:2025-11-25,
修回:2025-01-13,
网络首发:2026-04-29,
移动端阅览
王世栋, 李润之, 张宏伟, 袁珮. HNBR基固态电解质的设计及其性能研究[J]. 化工学报,
WANG Shidong, LI Runzhi, ZHANG Hongwei, YUAN Pei. Design and performance study of HNBR-based solid-state electrolytes[J]. CIESC Journal,
王世栋, 李润之, 张宏伟, 袁珮. HNBR基固态电解质的设计及其性能研究[J]. 化工学报, DOI: 10.11949/0438-1157.20251314
WANG Shidong, LI Runzhi, ZHANG Hongwei, YUAN Pei. Design and performance study of HNBR-based solid-state electrolytes[J]. CIESC Journal, DOI: 10.11949/0438-1157.20251314
为开发兼具高离子电导率、宽电化学窗口和良好稳定性的固态电解质,本研究以氢化丁腈橡胶 (HNBR) 为基体,系统研究其在固态电解质中的应用潜力。首先通过非均相催化加氢技术,成功制备了一系列具有不同腈基含量、分子量以及加氢度的HNBR样品,并系统评估其结构对电化学性能的调控规律。结果表明,在腈基含量处于35 - 41 wt%、分子量在10 - 36万且加氢度为0 - 97%的范围内,具备高腈基、高分子量以及高加氢度的HN41-36W-97%/LiTFSI电解质展现出最优性能,其分解电压达到4.8V,Li⁺迁移数为0.48,均优于其他HNx-y-z/LiTFSI体系。随后引入3 wt%的聚氧化乙烯与20 wt%的Li
6.4
La
3
Zr
1.4
Ta
0.6
O
12
,构建了复合固态电解质。该复合体系显著改善了离子传导与界面稳定性,其室温离子电导率为1.3×10
-5
S/cm,电化学稳定窗口扩展至5.1 V,Li
+
迁移数增加至0.58。基于该复合电解质组装的全固态电池在65
o
C、0.5 C条件下,首次放电比容量达到126 mAh/g,200次循环后仍保持121 mAh/g,容量保持率高达96%。本研究为开发兼具高安全性、良好柔性及优异电化学性能的固态电解质提供了新的路径。
To develop solid-state electrolytes with high ionic conductivity
a wide electrochemical window
and good stability
this study systematically explores the potential of hydrogenated nitrile butadiene rubber (HNBR) as a matrix in such electrolytes. First
a series of HNBR samples with varying nitrile content
molecular weight
and degree of hydrogenation were successfully prepared using heterogeneous catalytic hydrogenation technology
and the regulatory effects of their structures on electrochemical performance were systematically evaluated. The results indicate that within the ranges of nitrile group content from 35 to 41 wt%
molecular weight from 100
000 to 360
000
and hydrogenation degree from 0 to 97%
the HN41-36W-97%/LiTFSI solid electrolyte
which has a high nitrile content
high hydrogenation degree
and high molecular weight
demonstrates the best overall performance. It has a decomposition voltage of 4.8 V
and a Li
+
transference number of 0.48
all of which are superior to those of other HNx-y-z/LiTFSI systems. Subsequently
a composite solid-state electrolyte was constructed by introducing 3 wt% polyethylene oxide and 20 wt% Li
6.4
La
3
Zr
1.4
Ta
0.6
O
12
. This composite system significantly improved ion transport and interfacial stability
increasing the room-temperature ionic conductivity to 1.3×10
-5
S/cm
widening the electrochemical stability window to 5.1 V
and raising the Li
+
transference number to 0.58. The all-solid-state battery assembled based on this composite electrolyte achieved an initial discharge specific capacity of 126 mAh/g at 65
o
C and 0.5 C
maintaining 121 mAh/g
after 200 cycles
with a capacity retention rate as high as 96%. This study provides a novel pathway for developing solid-state electrolytes that combine high safety
good flexibility
and excellent electrochemical performance.
Liu X P , Xiao Z , Peng H R , et al . Rational design of LLZO/polymer solid electrolytes for solid-state batteries [J ] . Chemistry – An Asian Journal , 2022 , 17 ( 24 ): e202200929 .
Chen H S , Cong T N , Yang W , et al . Progress in electrical energy storage system: a critical review [J ] . Progress in Natural Science , 2009 , 19 ( 3 ): 291 - 312 .
Jiang C , Wang K H , Zhang L W , et al . Enhanced regional electric potential difference of graphdiyne through asymmetric substitution strategy boosts Li + migration in composite polymer solid-state electrolyte [J ] . Nano-Micro Letters , 2025 , 17 ( 1 ): 267 .
Divya K C , Østergaard J . Battery energy storage technology for power systems: An overview [J ] . Electric Power Systems Research , 2009 , 79 ( 4 ): 511 - 520 .
Zhao H R , Wu Q W , Hu S J , et al . Review of energy storage system for wind power integration support [J ] . Applied Energy , 2015 , 137 : 545 - 553 .
Liang H M , Wang L , Wang A P , et al . Tailoring practically accessible polymer/inorganic composite electrolytes for all-solid-state lithium metal batteries: a review [J ] . Nano-Micro Letters , 2023 , 15 ( 1 ): 42 .
Yu F H , Mu Y B , Han M S , et al . Electrochemically stable and ultrathin polymer-based solid electrolytes for dendrite-free all-solid-state lithium-metal batteries [J ] . Materials Futures , 2025 , 4 ( 1 ): 015101 .
Liu Q , Geng Z , Han C P , et al . Challenges and perspectives of garnet solid electrolytes for all solid-state lithium batteries [J ] . Journal of Power Sources , 2018 , 389 : 120 - 134 .
Hu Y B , Feng T S , Xu L , et al . Probing the phase transition during the formation of lithium lanthanum zirconium oxide solid electrolyte [J ] . ACS Applied Materials & Interfaces , 2022 , 14 ( 37 ): 41978 - 41987 .
Moy A C , Manjón-Sanz A , Caracciolo T C , et al . Effects of Al concentration on the structure and conductivity of lithium lanthanum zirconium oxide [J ] . Journal of Materials Chemistry A , 2024 , 12 ( 41 ): 28193 - 28210 .
Zhang J X , Wang C H , Fu J M , et al . Reducing surface roughness to achieve Li 2 CO 3 -existent lithiophilic interface in garnet-type solid-state batteries [J ] . Advanced Functional Materials , 2025 , 35 ( 9 ): 2416229 .
Zou Z Y , Ma N , Wang A P , et al . Relationships between Na + distribution, concerted migration, and diffusion properties in rhombohedral NASICON [J ] . Advanced Energy Materials , 2020 , 10 ( 30 ): 2001486 .
Jung S I , Nasir M , Park H J . Calcination-driven enhancement of LAGP for high-performance solid-state lithium metal batteries [J ] . Journal of Materials Chemistry A , 2025 , 13 ( 6 ): 4624 - 4633 .
Lin L , Hatzell K B . Polymorphism control of fast-sintered NASICON-type LiZr 2 (PO 4 ) 3 [J ] . Journal of Materials Chemistry A , 2024 , 12 ( 43 ): 29932 - 29940 .
Knauth P . Inorganic solid Li ion conductors: an overview [J ] . Solid State Ionics , 2009 , 180 ( 14/15/16 ): 911 - 916 .
Fujimura K , Seko A , Koyama Y , et al . Accelerated materials design of lithium superionic conductors based on first-principles calculations and machine learning algorithms [J ] . Advanced Energy Materials , 2013 , 3 ( 8 ): 980 - 985 .
Mena M F , Vásquez F A , Florentin O , et al . Electrochemical performance enhancement of perovskite-type Li 0.3 La 0.57 TiO 3 ceramic electrolyte by controlling synthesis parameters [J ] . Journal of the European Ceramic Society , 2025 , 45 ( 3 ): 116972 .
Luo C R , Shen Y , Zhang S H , et al . Smoothing Li transport via weak Metal-O bonds for improved ionic mobility in lithium lanthanum titanium oxide [J ] . Materials Today Physics , 2025 , 53 : 101704 .
O V S , Murugan R . An enhanced interface between garnet solid electrolyte and lithium through multifunctional lithium titanate anode-additive for solid-state lithium batteries [J ] . Journal of Alloys and Compounds , 2023 , 939 : 168774 .
Song S D , Qin X H , Ruan Y L , et al . Enhanced performance of solid-state lithium-air batteries with continuous 3D garnet network added composite polymer electrolyte [J ] . Journal of Power Sources , 2020 , 461 : 228146 .
Pan J , Peng H L , Yan Y H , et al . Solid-state batteries designed with high ion conductive composite polymer electrolyte and silicon anode [J ] . Energy Storage Materials , 2021 , 43 : 165 - 171 .
Tran H K , Truong B T , Zhang B R , et al . Sandwich-structured composite polymer electrolyte based on PVDF-HFP/PPC/Al-doped LLZO for high-voltage solid-state lithium batteries [J ] . ACS Applied Energy Materials , 2023 , 6 ( 3 ): 1475 - 1487 .
Wang X , Huang S P , Peng Y T , et al . Research progress on the composite methods of composite electrolytes for solid-state lithium batteries [J ] . ChemSusChem , 2024 , 17 ( 14 ): e202301262 .
Ren Y Y , Danner T , Moy A , et al . Oxide-based solid-state batteries: a perspective on composite cathode architecture [J ] . Advanced Energy Materials , 2023 , 13 ( 1 ): 2201939 .
Lin X J , Xu S Y , Tong Y Q , et al . A self-healing polymerized-ionic-liquid-based polymer electrolyte enables a long lifespan and dendrite-free solid-state Li metal batteries at room temperature [J ] . Materials Horizons , 2023 , 10 ( 3 ): 859 - 868 .
Cheng B , Du P , Xiao J , et al . Improving the ionic conductivity and anode interface compatibility of LLZO/PVDF composite polymer electrolytes by compositional tuning [J ] . ACS Applied Materials & Interfaces , 2024 , 16 ( 24 ): 31648 - 31656 .
Wang S D , Yang Z X , Li R Z , et al . Engineering aerobic-stable oxygen vacancies-Ti 3+ defects of Pd/Mn-TiO 2 for boosting nitrile butadiene rubber hydrogenation [J ] . Chemical Engineering Journal , 2025 , 522 : 167591 .
Wang S D , Wang Y X , Wu X R , et al . Pore-size dependent catalytic activity of supported Pd catalysts for selective hydrogenation of nitrile butadiene rubber [J ] . Chemical Engineering Science , 2023 , 273 : 118629 .
Wang S D , Ge B Q , Yang Z X , et al . Construction of highly active Pd–Ti 3+ sites in defective Pd/TiO 2 catalysts for efficient hydrogenation of styrene–butadiene–styrene [J ] . ACS Catalysis , 2024 , 14 ( 3 ): 1432 - 1442 .
Barthel J , Deser R . FTIR study of ion solvation and ion-pair formation in alkaline and alkaline earth metal salt solutions in acetonitrile [J ] . Journal of Solution Chemistry , 1994 , 23 ( 10 ): 1133 - 1146 .
Barthel J , Buchner R , Wismeth E . FTIR spectroscopy of ion solvation of LiClO 4 and LiSCN in acetonitrile, benzonitrile, and propylene carbonate [J ] . Journal of Solution Chemistry , 2000 , 29 ( 10 ): 937 - 954 .
Seo D M , Boyle P D , Sommer R D , et al . Solvate structures and spectroscopic characterization of LiTFSI electrolytes [J ] . The Journal of Physical Chemistry B , 2014 , 118 ( 47 ): 13601 - 13608 .
Guo J Z , Chan C K . Lithium dendrite propagation in Ta-doped Li 7 La 3 Zr 2 O 12 (LLZTO): comparison of reactively sintered pyrochlore-to-garnet vs LLZTO by solid-state reaction and conventional sintering [J ] . ACS Applied Materials & Interfaces , 2024 , 16 ( 4 ): 4519 - 4529 .
Duan T , Cheng H W , Liu Y B , et al . A multifunctional Janus layer for LLZTO/PEO composite electrolyte with enhanced interfacial stability in solid-state lithium metal batteries [J ] . Energy Storage Materials , 2024 , 65 : 103091 .
Mu Y B , Yang L , Feng Y T , et al . Achieving superior critical current density and rate performance in solid-state lithium batteries via vertically aligned LATP arrays [J ] . Nano Energy , 2025 , 138 : 110885 .
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