薄水铝石改善聚氧化乙烯基固态电解质离子电导率的研究

doi:10.19964/j.issn.1006-4990.2024-0684

摘要/Abstract

摘要：

聚氧化乙烯（PEO）基聚合物电解质因具有溶解多种钠盐及易于加工的特性，在全固态钠离子电池领域展现广阔的应用前景；但PEO存在结晶度较高及链段运动性不足的缺陷，导致其在室温下的离子电导率较低。研究提出一种解决该问题的有效策略，在PEO和双（三氟甲基磺酰）亚胺钠（NaTFSI）的聚合物体系中加入丁二晴（SN）和薄水铝石（BM）制备出性能优异的复合固态电解质（PEO-NaTFSI-SN-BM），并通过X射线衍射（XRD）、傅里叶变换红外光谱（FT-IR）、X射线光电子能谱（XPS）和扫描电子显微镜（SEM）等技术手段分析SN和BM提高固态电解质离子电导率的作用机理。实验结果表明：在仅添加SN情况下，SN和EO物质的量比为1∶8时，可形成自支撑膜（PNS₈），并明显提高PEO-NaTFSI聚合物电解质的离子电导率，在30 ℃下由初始的2.27×10^-6 S/cm提高到4.51×10^-5 S/cm；进一步加入BM后，复合固态电解质的离子电导率增至6.99×10^-5 S/cm，同时显著增强电解质膜的机械性能。在加入BM情况下，继续增加SN和EO物质的量比至1∶4时，仍能形成自支撑膜（PNS₄B₁₀）。PNS₄B₁₀在30 ℃下的离子电导率高达1.43×10^-4 S/cm，较初始的PEO-NaTFSI聚合物电解质提升约60倍。BM的引入不仅促进固态电解质的离子传输，还增强其机械性能，提高SN添加量，从而进一步优化离子电导率。该复合固态电解质为室温下实现全固态钠离子电池的高离子电导率提供有效途径。

关键词: 薄水铝石, 聚氧化乙烯, 丁二腈, 离子电导率, 钠固态电解质

Abstract:

Poly（ethylene oxide）（PEO）-based polymer electrolytes exhibit broad application prospects in the field of all-solid-state sodium-ion batteries due to their ability to dissolve various sodium salts and ease of processing.However，PEO has the defects of high crystallinity and insufficient segmental mobility，resulting in low ionic conductivity at room temperature.This study proposed an effective strategy to address this issue.By incorporating succinonitrile（SN） and boehmite（BM） into the polymer system of PEO and sodium bis（trifluoromethanesulfonyl）imide（NaTFSI）.A composite solid electrolyte（PEO-NaTFSI-SN-BM） with excellent performance was successfully prepared.The mechanism of SN and BM improving the ionic conductivity of solid-state electrolyte was analyzed by using techniques including X-ray diffraction（XRD），Fourier transform infrared spectroscopy（FT-IR），X-ray photoelectron spectroscopy（XPS） and scanning electron microscopy（SEM）.The experimental results demonstrated that，when only SN was added and the molar ratio of SN to EO was 1∶8，a self-supporting membrane（PNS₈） could be formed，significantly increasing the ionic conductivity of the PEO-NaTFSI polymer electrolyte from the initial 2.27×10^-6 S/cm to 4.51×10^-5 S/cm at 30 ℃.Upon further incorporation of BM，the ionic conductivity of the composite solid electrolyte was increased to 6.99×10^-5 S/cm，while simultaneously enhancing the mechanical properties of the electrolyte membrane.In the presence of BM，when the molar ratio of SN to EO was further increased to 1∶4，a self-supporting membrane（PNS₄B₁₀） could still be formed.The ionic conductivity of PNS₄B₁₀ at 30 ℃ reached as high as 1.43×10^-4 S/cm，representing an approximately 60-fold improvement compared to the initial PEO-NaTFSI polymer electrolyte.The introduction of BM not only facilitated ion transport of the solid-state electrolyte，but also enhanced its mechanical properties，thereby enabling higher SN loading and further optimization of ionic conductivity.This composite solid electrolyte represented a promising approach for achieving high ionic conductivity in all-solid-state sodium metal batteries at room temperature.

Key words: boehmite, poly（ethylene oxide）, succinonitrile, ionic conductivity, sodium solid state electrolyte

中图分类号:

TQ133.1

田朋, 杨广龙, 牟晨曦, 陈君熠, 宁桂玲. 薄水铝石改善聚氧化乙烯基固态电解质离子电导率的研究[J]. 无机盐工业, 2025, 57(11): 43-51.

TIAN Peng, YANG Guanglong, MU Chenxi, CHEN Junyi, NING Guiling. Study on enhancement of ionic conductivity in poly（ethylene oxide）-based solid-state electrolytes by boehmite[J]. Inorganic Chemicals Industry, 2025, 57(11): 43-51.

图/表 5

图1

表1

图2

图3

图4

参考文献 40

[1]	SHI Kuangyi， GUAN Bin， ZHUANG Zhongqi，et al.Recent progress and prospects on sodium-ion battery and all-solid-state sodium battery：A promising choice of future batteries for energy storage［J］.Energy & Fuels，2024，38（11）：9280-9319.
[2]	YIN Hang， HAN Chengjun， LIU Qirong，et al.Recent advances and perspectives on the polymer electrolytes for sodium/potassium-ion batteries［J］.Small，2021，17（31）：2006627.
[3]	康乐，景茂祥，李东红，等.铝酸锂纳米棒改性固态电解质的制备及电化学性能研究［J］.无机盐工业，2023，55（8）：65-70.
	KANG Le， JING Maoxiang， LI Donghong，et al.Study on preparation and electrochemical performance of lithium aluminate nanorods modified solid electrolyte［J］.Inorganic Chemicals Industry，2023，55（8）：65-70.
[4]	WANG Sen， JIANG Yingjun， HU Xianluo.Ionogel-based membranes for safe lithium/sodium batteries［J］.Advanced Materials，2022，34（52）：2200945.
[5]	YANG Huiling， ZHANG Binwei， KONSTANTINOV K，et al.Progress and challenges for all-solid-state sodium batteries［J］.Advanced Energy and Sustainability Research，2021，2（2）：2000057.
[6]	晁广召.硅烷偶联剂修饰纳米Al₂O₃对全固态电池性能提高的研究［D］.哈尔滨：哈尔滨工业大学，2021.
	CHAO Guangzhao.Study on improving the performance of all-solid-state battery by modified nano-Al₂O₃ with silane coupling agent［D］.Harbin：Harbin Institute of Technology，2021.
[7]	YANG Ruilu， ZHANG Zheng， ZHANG Qi，et al.Flexible asymmetric organic-inorganic composite solid-state electrolyte based on PI membrane for ambient temperature solid-state lithium metal batteries［J］.Frontiers in Chemistry，2022，10：855800.
[8]	ZHANG Zhizhen， ZHANG Qiangqiang， REN Cheng，et al.A ceramic/polymer composite solid electrolyte for sodium batteries［J］.Journal of Materials Chemistry A，2016，4（41）：15823-15828.
[9]	许希军，林见烽，罗雄伟，等.NASICON型Na₁₊ _x Zr₂Si _x P_3- _x O₁₂固态电解质及其钠金属电池研究进展［J］.无机盐工业，2024，56（11）：1-14，38.
	XU Xijun， LIN Jianfeng， LUO Xiongwei，et al.Recent progress of NASICON-type Na₁₊ _x Zr₂Si _x P_3- _x O₁₂ solid electrolyte for sodium metal batteries［J］.Inorganic Chemicals Industry，2024，56（11）：1-14，38.
[10]	LI Zhiyong， LI Zhuo， FU Jialong，et al.Sodium-ion conducting polymer electrolytes［J］.Rare Metals，2023，42（1）：1-16.
[11]	刘丽露.钠离子固体电解质及固态钠电池研究［D］.北京：中国科学院大学（中国科学院物理研究所），2018.
	LIU Lilu.Studies on solid state sodium ion electrolytes and solid state sodium batteries［D］.Beijing：University of Chinese Academy of Sciences（Institute of Physics，Chinese Academy of Sciences），2018.
[12]	LI Zhuo， FU Jialong， ZHOU Xiaoyan，et al.Ionic conduction in polymer-based solid electrolytes［J］.Advanced Science，2023，10（10）：2201718.
[13]	马静媛，李妍，周晗洁，等.PEO基有机/无机复合固态电解质的研究进展［J］.无机盐工业，2025，57（3）：1-8.
	MA Jingyuan， LI Yan， ZHOU Hanjie，et al.Research progress of PEO based organic/inorganic composite solid electrolyte［J］.Inorganic Chemicals Industry，2025，57（3）：1-8.
[14]	HE Fei， HU Zhenglin， TANG Wenjing，et al.Vertically heterostructured solid electrolytes for lithium metal batteries［J］.Advanced Functional Materials，2022，32（25）：2201465.
[15]	PAN Kecheng， ZHANG Lan， QIAN Weiwei，et al.A flexible ceramic/polymer hybrid solid electrolyte for solid-state lithium metal batteries［J］.Advanced Materials，2020，32（17）：2000399.
[16]	ZHANG Jinfang， WANG Yuanyuan， XIA Qingbing，et al.Confining polymer electrolyte in MOF for safe and high-performance all-solid-state sodium metal batteries［J］.Angewandte Chemie International Edition，2024，63（16）：e202318822.
[17]	赵兰清，侯敏杰，张达，等.固态钠离子电池用PEO基聚合物固体电解质［J］.化学进展，2023，35（11）：1625-1637.
	ZHAO Lanqing， HOU Minjie， ZHANG Da，et al.Poly（ethylene oxide）-based solid polymer electrolytes for solid-state sodiumI on batteries［J］.Progress in Chemistry，2023，35（11）：1625-1637.
[18]	XU Shengjun， SUN Zhenhua， SUN Chengguo，et al.Homogeneous and fast ion conduction of PEO-based solid-state electrolyte at low temperature［J］.Advanced Functional Materials，2020，30（51）：2007172.
[19]	QIU Genrui， SHI Yapeng， HUANG Bolong.A highly ionic conductive succinonitrile-based composite solid electrolyte for lithi-um metal batteries［J］.Nano Research，2022，15（6）：5153-5160.
[20]	ZHANG Xueyan， FU Chuankai， CHENG Shichao，et al.Novel PEO-based composite electrolyte for low-temperature all-solid-state lithium metal batteries enabled by interfacial cation-assistance［J］.Energy Storage Materials，2023，56：121-131.
[21]	ZHOU Dong， HE Yanbing， LIU Ruliang，et al.In situ synthesis of a hierarchical all-solid-state electrolyte based on nitrile materials for high-performance lithium-ion batteries［J］.Advanced Energy Materials，2015，5（15）：1500353.
[22]	CHEN Fei， ZHA Wenping， YANG Dunjie，et al.All-solid-state lithium battery fitted with polymer electrolyte enhanced by solid plasticizer and conductive ceramic filler［J］.Journal of the Electrochemical Society，2018，165（14）：A3558.
[23]	GUO Shiyuan， SU Yuefeng， YAN Kang，et al.Robust and adhesive laminar solid electrolyte with homogenous and fast Li-ion conduction for high-performance all-solid-state lithium metal battery［J］.Advanced Science，2024，11（30）：2404307.
[24]	WEI Xiuqin， WANG Qiulin， SONG Zhenglin，et al.Effect of hydroxyls and particle size on the electrochemical performance of boehmite coated PE separators for lithium-ion batteries［J］.Solid State Ionics，2021，366-367：115652.
[25]	冯锟，朱勇，张凯强，等.勃姆石纳米片增强锂离子电池隔膜性能研究［J］.无机材料学报，2022，37（9）：1009-1016.
	FENG Kun， ZHU Yong， ZHANG Kaiqiang，et al.Boehmite nanosheets-coated separator with enhanced performance for lithi-um-ion batteries［J］.Journal of Inorganic Materials，2022，37（9）：1009-1016.
[26]	GAO Tingting， TIAN Peng， XU Qianjin，et al.Class of boehmite/polyacrylonitrile membranes with different thermal shutdown temperatures for high-performance lithium-ion batteries［J］.ACS Applied Materials & Interfaces，2023，15（1）：2112-2123.
[27]	ZHAO Weiran， TIAN Peng， GAO Tingting，et al.Different-grain-sized boehmite nanoparticles for stable all-solid-state lithium metal batteries［J］.Nanoscale，2024，16（23）：11163-11173.
[28]	ALSULAMI Q A.Structural，dielectric，and magnetic studies based on MWCNTs/NiFe₂O₄/ZnO nanoparticles dispersed in poly-mer PVA/PEO for electromagnetic applications［J］.Journal of Materials Science：Materials in Electronics，2021，32（3）：2906-2924.
[29]	BANDYOPADHYAY S， GUPTA A， SRIVASTAVA R，et al.Bio-inspired design of electrospun poly（acrylonitrile） and novel ionene based nanofibrous mats as highly flexible solid state polymer electrolyte for lithium batteries［J］.Chemical Engineering Journal，2022，440：135926.
[30]	SHENG Ouwei， JIN Chengbin， LUO Jianmin，et al.Mg₂B₂O₅ nanowire enabled multifunctional solid-state electrolytes with high ionic conductivity，excellent mechanical properties，and flame-retardant performance［J］.Nano Letters，2018，18（5）：3104-3112.
[31]	XU Hao， LIU Shuai， LI Zhiang，et al.Ti₃C₂T _x MXene enhanced PEO/SN-based solid electrolyte for high-performance Li metal battery［J］.Journal of Materials Science & Technology，2025，219：101-112.
[32]	WANG Han， SUN Yongjiang， LIU Qing，et al.An asymmetric bilayer polymer-ceramic solid electrolyte for high-performance sodium metal batteries［J］.Journal of Energy Chemistry，2022，74：18-25.
[33]	LI Bangxing， YI Xianlin， XIE Zhenjun，et al.A promising composite room temperature solid electrolyte via incorporating LLZTO into cross-linked ETPTA/PEO/SN matrix for all solid state lithi- um batteries［J］.Ionics，2024，30（4）：2007-2017.
[34]	FU Wenjing， WEI Cundi， ZUO Jing，et al.A facile temperature-controlled“green” method to prepare multi-kinds of high-quality alumina hydrates via a Ga-In-Sn-alloyed aluminum-water interface reaction［J］.ACS Omega，2022，7（23）：19775-19783.
[35]	LIU Lehao， MO Jinshan， LI Jingru，et al.Comprehensively-modified polymer electrolyte membranes with multifunctional PMIA for highly-stable all-solid-state lithium-ion batteries［J］.Journal of Energy Chemistry，2020，48：334-343.
[36]	SONG Jiechen， XU Yuxing， ZHOU Yuncheng，et al.Incorporating 2D γ-Al₂O₃ nanosheets into the flexible PEO-based solid electrolyte for lithium metal batteries［J］.Electrochimica Acta，2023，437：141504.
[37]	WANG Meihuang， TIAN Liying， CAO Yu，et al.Surface positive-charged modification of inorganic fillers to optimize lithium ion conductive pathways in composite polymer electrolytes for lithium-metal batteries［J］.Journal of Colloid and Interface Science，2023，630：634-644.
[38]	SU Yanxia， MU Zheshen， QIU Yuqian，et al.Embedding of laser generated TiO₂ in poly（ethylene oxide） with boosted Li⁺ conduction for solid-state lithium metal batteries［J］.ACS Applied Materials & Interfaces，2023，15（48）：55713-55722.
[39]	WANG Xiaoen， ZHU Haijin， GIRARD G A，et al.Preparation and characterization of gel polymer electrolytes using poly（ionic liquids） and high lithium salt concentration ionic liquids［J］.Journal of Materials Chemistry A，2017，5（45）：23844-23852.
[40]	SHEN Lin， DENG Shungui， JIANG Rongrong，et al.Flexible composite solid electrolyte with 80% Na_3.4Zr_1.9Zn_0.1Si_2.2P_0.8O₁₂ for solid-state sodium batteries［J］.Energy Storage Materials，2022，46：175-181.

序号	样品名	n（SN）∶ n（EO）	w（BM）/ %	离子电导率 σ/（S cm^-1）	脱膜难易程度
1	PEO-NaTFSI	0	0	2.27×10^-6	容易
2	PNS₂₄	1∶24	0	1.53×10^-5	容易
3	PNS₁₆	1∶16	0	1.63×10^-5	容易
4	PNS₁₂	1∶12	0	2.30 0×10^-5	容易
5	PNS₈	1∶8	0	4.51×10^-5	容易
6	PNS₇	1∶7	0		困难
7	PNS₄	1∶4	0		无法
8	PNB₁₀	0	10	3.11×10^-6	容易
9	PNS₈B₅	1∶8	5	6.36×10^-5	容易
10	PNS₈B₁₀	1∶8	10	6.99×10^-5	容易
11	PNS₈B₁₅	1∶8	15	6.57×10^-5	容易
12	PNS₈B₂₀	1∶8	20	6.15×10^-5	容易
13	PNS₈B₂₅	1∶8	25	6.02×10^-5	容易
14	PNS₈B₃₀	1∶8	30	5.19×10^-5	容易
15	PNS₇B₁₀	1∶7	10	7.77×10^-5	容易
16	PNS₆B₁₀	1∶6	10	8.99×10^-5	容易
17	PNS₅B₁₀	1∶5	10	1.11×10^-4	容易
18	PNS₄B₁₀	1∶4	10	1.43×10^-4	容易
19	PNS₃B₁₀	1∶3	10		困难

首页

全国无机盐信息中心

中国化工学会

无机酸碱盐专业委员会