Research progress of piezoelectric materials in solid-state metal secondary batteries

doi:10.11949/0438-1157.20250052

Abstract

Abstract:

Although the solid-state metal secondary battery has high energy density and good safety, there are still some problems such as low ionic conductivity of solid electrolyte, poor interface contact between electrode and solid electrolyte, and dendrite growth from the metal anode, which seriously hinder its application prospect in large-scale energy storage. Piezoelectric materials can realize the mutual conversion between mechanical energy and electrical energy, possessing the characteristics of generating internal electric field by polarization. They can be used to suppress the space charge layer, promote ion transport dynamics, and regulate the uniform deposition of metals in solid-state batteries. This paper first introduces the basic concepts, classifications and working principles of piezoelectric materials, and then reviews in detail the research status of piezoelectric materials in solid-state metal secondary batteries in recent years. Finally, the main problems and future development prospects of piezoelectric materials applied in solid-state batteries are summarized.

Key words: electrochemistry, electronic materials, piezoelectricity, ferroelectricity, solid state electrolyte, metal secondary batteries, polarization

摘要：

固态金属二次电池虽然具有较高的能量密度和良好的安全性，但是当前普遍存在固态电解质离子电导率低、电极与固态电解质界面接触性差和金属负极枝晶生长等问题，这严重阻碍了其在大规模储能中的应用前景。压电材料能够实现机械能和电能的相互转换，具有极化产生内电场的特性，在固态电池中可以用于抑制空间电荷层、促进离子输运动力学、调控金属均匀沉积等。首先介绍了压电材料的基本概念、分类和工作原理，然后详细评述了近年来压电材料在固态金属二次电池中的研究现状，最后对压电材料应用于固态电池中存在的主要问题和未来发展前景进行了总结和展望。

关键词: 电化学, 电子材料, 压电, 铁电, 固态电解质, 金属二次电池, 极化

CLC Number:

TM 91

Jiaxin LUO, Yan YUAN. Research progress of piezoelectric materials in solid-state metal secondary batteries[J]. CIESC Journal, 2025, 76(8): 3822-3833.

罗佳欣, 袁艳. 压电材料在固态金属二次电池中的研究进展[J]. 化工学报, 2025, 76(8): 3822-3833.

Figures/Tables 5

Fig.1 (a) The relationship between piezoelectric, thermoelectric and ferroelectric materials[3]; (b) Classification of piezoelectric materials[4]

Fig.2 (a) Schematic illustration of Li+ concentration distribution around the BTO modified LiPON/LNM interface; (b) Comparison of the rate performance between unmodified and BTO-modified Li/LiPON/LNM batteries[29]; (c) In-situ DPCSTEM observations of net-charge-density accumulation at the LCO/LPSCl and BTO-LCO/LPSCl interface with bias voltages of 1.0, 1.6, and 2.2 V. The color bar is defined as the relative magnitude of the positive/negative charge density[30]; (d) Schematic diagram of cell distortion of C(NH2)3ClO4 coating layer, where C(NH2)3ClO4 is stretched along a direction and compressed along b direction (left). The phase-field simulation verifies the dipole orientation in the ferroelectric coating layer and the generation of built-in electric field (middle and right)[33]; (e) Tensile stress distribution for NCM811 and NCM811-LTO particles at the maximum strain state[34]

Table 1 Research summary on dielectric composite electrolytes based on PVDF and its copolymers

复合电解质	介电填料	介电常数	活化能/eV	离子电导率/(S·cm^-1)	文献
β-PVDF/LiFSI	β-PVDF	10⁸	0.22	7.7×10^-4	[38]
PVDF/LiTFSI	PVDF	9	0.49	1.77×10^-5	[35]
p(VDF-TrFE-CTFE)/LiTFSI	P(VDF-TrFE-CTFE)	44	0.26	3.1×10^-4	[35]
PVDF-Si₃N₄	Si₃N₄	16.2	0.21	5.7×10^-4	[50]
PVDF/BTO-LLTO	BTO-LLTO	24	0.2	8.2×10^-4	[43]
PVDF/LiFSI/NaNbO₃	NaNbO₃	20	—	5.56×10^-4	[51]
PVDF/LiFSI/LiTaO₃	LiTaO₃	—	0.24	4.9×10^-4	[39]
PVDF-HFP/LiFSI/BaTi₂O₅	BaTi₂O₅	—	0.078	3.4 × 10^-4	[52]
PVDF/LiTFSI/BiFeO₃	BiFeO₃	—	0.249	1.39× 10^-4	[40]
PVDF-b-PTFE/LiTFSI/TiO₂/BaTiO₃	TiO₂/BaTiO₃	—	0.1997	7.82× 10^-4	[42]
PVDF/LiNbO₃	LiNbO₃	18	—	1.081×10^-3	[41]
PVDF/LiTFSI/Ga/Nb@LLZO/BTO	Ga/Nb@LLZO/BTO	10²	0.16	0.74×10^-3	[53]
PVDF/LiFSI/BTO-MoSe₂	BTO-MoSe₂	—	0.12	6.5 ×10^-4	[54]

Fig.3 (a) Schematic diagram of the dissociation of lithium salts by a FE polymer (e.g. PVDF) with a relatively low εr and an RFE polymer [e.g. p(VDF-TrFE)-based terpolymer] with a high εr[35]; (b) Procedures for the fabrication and crystal structure model of BIT NFs[44]

Fig.4 (a) Schematic illustration of Cu, Cu@α-PF and Cu@β-PF after cycles[57]; (b) Schematic diagram of lithium dendrites regulated by the ferroelectric effect of BTO[58]

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