γ-NaxCoO2粉体的聚丙烯酸钠凝胶法制备及其表征

doi:10.15541/jim20160474

无机材料学报 ›› 2017, Vol. 32 ›› Issue (6): 603-608.DOI: 10.15541/jim20160474

γ-Na_xCoO₂粉体的聚丙烯酸钠凝胶法制备及其表征

李晓玉¹, 张莉², 唐新峰³, 张清杰⁴

(武汉理工大学材料复合新技术国家重点实验室, 武汉 430070)

收稿日期:2016-08-17 修回日期:2016-10-08 出版日期:2017-06-20 网络出版日期:2017-05-27
作者简介:李晓玉(1990–), 女, 硕士研究生.
基金资助:
国家自然科学基金(51402229);教育部留学回国人员科研启动基金(2013-1792)

Preparation and Characterization of γ-Na_xCoO₂ by Sodium Polyacrylate Gel Method

LI Xiao-Yu¹, ZHANG Li², TANG Xin-Feng³, ZHANG Qing-Jie⁴

(State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China)

Received:2016-08-17 Revised:2016-10-08 Published:2017-06-20 Online:2017-05-27
About author:LI Xiao-Yu.
Supported by:
National Natural Science Foundation of China (51402229);Project Sponsored by the Scientific Research Foundation for the Returned Oversens Chinese Scholars, State Education Ministry (2013-1792)

摘要/Abstract

摘要：

本研究发展了一种用于制备氧化物热电材料γ-Na_xCoO₂粉体的化学合成方法——聚丙烯酸钠(PAAS)凝胶法。主要研究了PAAS/Co²⁺摩尔比、原料浓度和煅烧温度对产物相组成及微观形态的影响规律, 探讨了物相形成机制, 同时用该方法结合SPS制备了不同Na离子浓度的Na_xCoO₂多晶样品, 并对其热电性能进行了表征。结果表明, PAAS/Co²⁺摩尔比对产物相组成产生了显著影响, 随着PAAS/Co²⁺摩尔比的增加, 样品的相组成由Co₃O₄相向单相γ-Na_xCoO₂转变, 合适的PAAS/Co²⁺摩尔比为0.8~1.1。而反应原料浓度对产物相组成的影响存在一个临界值(0.025 mol/L), 大于临界值抑制单相形成, 小于临界值促进单相形成。煅烧温度的升高有助于γ-Na_xCoO₂单相的形成, 800℃煅烧得到γ-Na_xCoO₂单相, 晶粒形态呈片状, 平均厚度约200 nm, 片状方向的尺寸在1~4 μm之间。随着Na含量的增加, 样品的Seebeck系数增大, 电导率增加, 热导率降低, 最终导致ZT值大幅增加。

关键词: 聚丙烯酸钠凝胶法, γ-Na_xCoO₂, 热电材料

Abstract:

Chemical synthesis method of sodium polyacrylate (PAAS) gel method was used to prepare γ-Na_xCoO₂ powders. The effects of PAAS/Co²⁺molar ratio, concentration of raw materials and calcination temperatures on the phase composition and microstructure of product were studied. Na_xCoO₂ polycrystalline samples with different Na⁺ concentrations were synthesized by the above method, and the thermoelectric properties were characterized. The results showed that the PAAS/Co²⁺molar ratio greatly affected the phase composition. With the increase of PAAS/Co²⁺molar ratio, the phase composition of sample was transformed from Co₃O₄ to γ-Na_xCoO₂. The proper molar ratio of PAAS/Co²⁺ to obtain γ-Na_xCoO₂ single phase is 0.8. the phase composition of sample will change slightly with different concentrations of raw materials. γ-Na_xCoO₂ single phase was formed at low concentration of raw materials (below 0.025 mol/L), however, when the concentration exceeded 0.025 mol/L, the second phase was formed. The formation of γ-Na_xCoO₂ single phase was promoted with the increase of calcination temperature. The γ-Na_xCoO₂ powders calcined at 800℃ were plate-like particles with about 200 nm in thickness and about 1-4 μm in width along the plane direction. With the increase of Na content in samples, σ value and S value were increased while κ value was decreased, leading to a significant increase in ZT value.

Key words: sodium polyacrylate gel method, γ-Na_xCoO₂, thermoelectric materials

中图分类号:

TQ174

李晓玉, 张莉, 唐新峰, 张清杰. γ-Na_xCoO₂粉体的聚丙烯酸钠凝胶法制备及其表征[J]. 无机材料学报, 2017, 32(6): 603-608.

LI Xiao-Yu, ZHANG Li, TANG Xin-Feng, ZHANG Qing-Jie. Preparation and Characterization of γ-Na_xCoO₂ by Sodium Polyacrylate Gel Method[J]. Journal of Inorganic Materials, 2017, 32(6): 603-608.

图/表 8

图1 不同PAAS/Co2+摩尔比制备样品的XRD图谱(800℃)

Fig. 1 XRD patterns of samples prepared with different PAAS/ Co2+ molar ratios(a) 0.5; (b) 0.6; (c) 0.7; (d) 0.8; (e) 0.9; (f) 1.0; (g) 1.1

表1 Na含量的ICP-AES分析结果

Table 1 ICP-AES results of Na content

Nominal Na content, x	Actual Na content, x
0.8	0.784
0.9	0.878
1.0	0.977

图2 不同PAAS/Co2+摩尔比制备样品的SEM照片

Fig. 2 SEM images of samples prepared with different PAAS/ Co2+ molar ratios(a) 0.8; (b) 0.9; (c) 1.0; (d) 1.1

图3 不同原料浓度制备样品的XRD图谱(PAAS/ Co2+=0.8)

Fig. 3 XRD patterns of samples with different source concentrations(A) (a) 0.025 mol/L; (b) 0.020 mol/L; (c) 0.013 mol/L; (B) (a) 0.05 mol/L; (b) 0.033 mol/L; (c) 0.025 mol/L

图4 不同PAAS反应原料浓度制备样品的SEM照片

Fig. 4 SEM images of samples prepared with different PAAS source concentrations(a) 0.025mol/L; (b) 0.02mol/L; (c) 0.033mol/L

图5 前驱体及前驱体经不同温度煅烧得到样品的XRD图谱

Fig. 5 XRD patterns of samples calcined at different temperatures(a) Precusor; (b) 400℃; (c) 500℃; (d) 600℃; (e) 700℃; (f) 800℃

图6 前驱体经不同温度煅烧后产物的SEM照片

Fig. 6 SEM images of products calcined from precursor at different temperatures(a) 400℃; (b) 500℃; (c) 600℃; (d) 700℃; (e) 800℃

图7 不同PAAS/Co2+摩尔比样品的电热输运性能随温度的变化关系

Fig. 7 Temperature dependence of the electrothermal transport properties for samples with different PAAS/Co2+ mole ratios

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γ-Na_xCoO₂粉体的聚丙烯酸钠凝胶法制备及其表征

Preparation and Characterization of γ-Na_xCoO₂ by Sodium Polyacrylate Gel Method

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