Co2+离子掺杂含量对Li1.3+xAl0.3-xCoxTi1.7(PO4)3陶瓷导电和吸波性能的影响

陈丹; 周影影; 杨鑫; 曹楠楠; 章杰勇; 杨纪龙

doi:10.11868/j.issn.1005-5053.2021.000153

Co²⁺离子掺杂含量对Li_1.3+xAl_0.3-xCo_xTi_1.7(PO₄)₃陶瓷导电和吸波性能的影响

doi: 10.11868/j.issn.1005-5053.2021.000153

西安航空学院材料工程学院，西安 710077

基金项目: 陕西省自然科学基础研究计划项目（2021JQ-850）；西安航空学院校级科研基金（2020KY0213）；西安航空学院2021年省级大学生创新创业训练计划项目资助项目（S202111736030）

详细信息

通讯作者:
陈丹（1990—），女，博士，主要研究方向为吸波材料，E-mail：chendan900408@163.com

中图分类号: TB34
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- 文章访问数: 136
- HTML全文浏览量: 39
- PDF下载量: 56
- 被引次数: 0
出版历程
- 收稿日期: 2021-09-14
- 录用日期: 2022-08-16
- 修回日期: 2022-10-13
- 网络出版日期: 2022-10-11
- 刊出日期: 2022-12-02

Effects of Co²⁺ ion doping content on conductivities and microwave absorption properties of Li_1.3+xAl_0.3-xCo_xTi_1.7 (PO₄)₃ ceramics

School of Materials Engineering, Xi’an Aeronautical University, Xi’an 710077, China

摘要

摘要: 采用高温固相法制备Li_1.3+xAl_0.3-xCo_xTi_1.7(PO₄)₃（x=0、0.04、0.08、0.12）陶瓷，研究Co²⁺离子含量对其微观形貌、物相成分、导电性能、介电性能和吸波性能的影响规律。结果表明：Li_1.3+xAl_0.3-xCo_xTi_1.7(PO₄)₃陶瓷晶粒为立方状，相对密度均在90%以上，物相呈菱方LiTi₂(PO₄)₃相，无杂质产生。Li_1.34Al_0.26Co_0.04Ti_1.7(PO₄)₃陶瓷具有最高的离子电导率1.14×10⁻³ S·cm⁻¹，低价掺杂能够降低Li⁺离子与骨架离子间的束缚力，适量掺杂能够获得合适的Li⁺离子通道尺寸，从而使得Li⁺离子具有最小活化能0.29 eV，易产生热离子松弛极化，也就同时具有了最高的复介电常数，ε'为12.9~13.7，ε''为3.1~3.8；基于极化损耗和电导损耗的共同作用，Li_1.34Al_0.26Co_0.04Ti_1.7(PO₄)₃陶瓷具有较优的吸波性能，吸收带宽可覆盖整个X波段，最小反射率在9.67 GHz达到−17.3 dB，有望成为一种高温轻质吸波材料。
- 离子掺杂 /
- LATP陶瓷 /
- 介电性能 /
- 吸波性能
Abstract: Li_1.3+xAl_0.3-xCo_xTi_1.7(PO₄)₃ (x=0, 0.04, 0.08, 0.12) ceramics were prepared by high temperature solid-state method. The effects of Co²⁺ ion doping content on the morphology, phase, ion conductivity, dielectric property and microwave absorption property were studied. Results show that Li_1.3+xAl_0.3-xCo_xTi_1.7(PO₄)₃ ceramics had cubic grains with relative densities of 90%, and they are single rhombohedral LiTi₂(PO₄)₃ phase without any impurity. Li_1.34Al_0.26Co_0.04Ti_1.7(PO₄)₃ ceramic has the highest ionic conductivity of 1.14×10⁻³ S·cm⁻¹. A lower valent cation occupying the Ti(Al) site can reduce the coulombic repulsion between Li⁺ ions and skeleton ions, and appropriate doping content can obtain suitable size of Li⁺ ions channel. Then, Li⁺ ion has a minimum activation energy of 0.29 eV, which is easy to generate thermal ion relaxation polarization. Therefore, Li_1.34Al_0.26Co_0.04Ti_1.7(PO₄)₃ ceramic also has the highest complex permittivity, ε' is 12.9-13.7 and ε" is 3.1-3.8. In addition, due to the combined effect of polarization loss and conductance loss, it has the optimum microwave absorption property of an absorption bandwidth covering the whole X-band and a minimum reflection loss of −17.3 dB at 9.67 GHz, which is a potential candidate of high-temperature lightweight microwave absorption material.
- ion doping /
- LATP ceramics /
- dielectric property /
- microwave absorption property

HTML全文

图 1 Li_1.3+xAl_0.3-xCo_xTi_1.7(PO₄)₃陶瓷的微观断面形貌图　（a）x=0；（b）x=0.04；（c）x=0.08；（d）x=0.12

Figure 1. Cross-sections of Li_1.3+xAl_0.3-xCo_xTi_1.7(PO₄)₃ ceramics 　(a) x=0； (b) x=0.04； (c) x=0.08； (d) x=0.12

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图 2 Li_1.3+xAl_0.3-xCo_xTi_1.7(PO₄)₃陶瓷的XRD图

Figure 2. XRD patterns of Li_1.3+xAl_0.3-xCo_xTi_1.7(PO₄)₃ ceramics

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图 3 Li_1.3+xAl_0.3-xCo_xTi_1.7(PO₄)₃陶瓷的常温交流阻抗谱

Figure 3. Typical impedance spectra of Li_1.3+xAl_0.3-xCo_xTi_1.7(PO₄)₃ ceramics

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图 4 Li_1.3+xAl_0.3-xCo_xTi_1.7(PO₄)₃陶瓷的阿伦尼乌斯曲线

Figure 4. Arrhenius curves of Li_1.3+xAl_0.3-xCo_xTi_1.7(PO₄)₃ ceramics

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图 5 Li_1.3+xAl_0.3-xCo_xTi_1.7(PO₄)₃陶瓷的复介电常数　（a）实部；（b）虚部

Figure 5. Complex permittivity of Li_1.3+xAl_0.3-xCo_xTi_1.7(PO₄)₃ ceramics　 (a) real part；(b) imaginary part

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图 6 Li_1.3+xAl_0.3-xCo_xTi_1.7(PO₄)₃陶瓷的Cole-Cole图　（a）x=0；（b）x=0.04；（c）x=0.08；（d）x=0.12

Figure 6. Cole-Cole plots of Li_1.3+xAl_0.3-xCo_xTi_1.7(PO₄)₃ ceramics　 (a) x=0； (b) x=0.04； (c) x=0.08；(d) x=0.12

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图 7 Li_1.3+xAl_0.3-xCo_xTi_1.7(PO₄)₃陶瓷在2.2 mm厚度的计算反射率

Figure 7. Calculated reflection loss of Li_1.3+xAl_0.3-xCo_xTi_1.7(PO₄)₃ ceramics in 2.2 mm

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表 1 Li_1.3+xAl_0.3-xCo_xTi_1.7(PO₄)₃陶瓷的计算点阵常数

Table 1. Calculated lattice parameters of Li_1.3+xAl_0.3-xCo_xTi_1.7(PO₄)₃ ceramics

Sample	a /nm	c /nm	β /(º)	V /nm³
LATP	0.8504	2.0523	120.204	1.2827
Co0.04	0.8554	2.0673	120.096	1.3086
Co0.08	0.8604	2.0830	120.003	1.3354
Co0.12	0.8600	2.0829	120.009	1.3340

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表 2 Li_1.3+xAl_0.3-xCo_xTi_1.7(PO₄)₃陶瓷的电性能参数

Table 2. Electrical characteristics of Li_1.3+xAl_0.3-xCo_xTi_1.7(PO₄)₃ ceramics

Sample	R_g/Ω	σ_g/(S·cm⁻¹)	R_gb/Ω	σ_gb/(S·cm⁻¹)	R/Ω	σ/(S·cm⁻¹)	R_gb/R
LATP	176.87	9.00×10⁻⁴	594.58	2.68×10⁻⁴	771.45	2.06×10⁻⁴	0.77
Co0.04	47.94	3.44×10⁻³	96.65	1.70×10⁻³	144.59	1.14×10⁻³	0.67
Co0.08	89.74	1.78×10⁻³	752.68	2.13×10⁻⁴	842.42	1.90×10⁻⁴	0.89
Co0.12	212.5	7.54×10⁻⁴	1829.7	8.75×10⁻⁵	2042.2	7.84×10⁻⁵	0.90

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