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 CSTR: 32189.14.10.15541/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

参考文献 15

[1]	卢喜凤, 郜超军, 郭娟, 等. 钴基氧化物热电材料掺杂研究进展. 材料导报, 2015, 29(13): 40-43.
[2]	VENGUST D, JANCAR B, SESTAN A, et al.Chemical decomposition as a likely source of ambient and thermal instabilities of layered sodium cobaltate.Chemistry of Materials, 2013, 25(23): 4791-4797.
[3]	VONESHEN D J, REFSON K, BORISSENKO E, et al.Suppression of thermal conductivity by rattling modes in thermoelectric sodium cobaltate.Nature Materials, 2013, 12(11): 1028-1032.
[4]	TIAN Z, WANG X, LIU J, et al.Power factor enhancement induced by Bi and Mn co-substitution in NaxCoO2 thermoelectric materials.Journal of Alloys and Compounds, 2016, 661: 161-167.
[5]	ASSADI M H N, KATAYAMA-YOSHIDA H. Dopant incorporation site in sodium cobaltate’s host lattice: a critical factor for thermoelectric performance.Journal of Physics: Condensed Matter, 2015, 27(17): 175504-175512.
[6]	LEI Y, LI X, LIU L, et al.Synthesis and stoichiometry of different layered sodium cobalt oxides. Chemistry of Materials, 2014, 26(18): 5288-5296.
[7]	OKANERDAL M, KOYUNCU M, USLU I.High thermoelectric performance of unsintered NaCo2O4 nanocrystal.International Journal of Scientific & Technology Research, 2015, 4(4): 37-39.
[8]	TERASAKI I.Layered cobalt oxides: correlated electrons for thermoelectrics.Thermoelectric Nanomaterials, 2013, 182: 51-70.
[9]	KRASUTSKAYA N S, KLYNDYUK A I, EVSEEVA L E, et al.Synthesis and properties of NaxCoO2 (x= 0.55, 0.89) oxide thermoelectrics.Inorganic Materials, 2016, 52(4): 393-399.
[10]	PANCHAKARLA L S, LAJAUNIE L, RAMASUBRAMANIAM A, et al.Nanotubes from oxide-based misfit family: the case of calcium cobalt oxide. ACS Nano, 2016, 10(6): 6248-6256.
[11]	ERDAL M O, KOYUNCU M, USLU I.The effect of synthesis technique on thermoelectric properties of nanocrystalline NaCo2O4 ceramics.Journal of Nanoparticle Research, 2014, 16(11): 1-8.
[12]	PRSIC S, SAVIC S M, BRANKOVIC Z, et al.Mechanochemically assisted solid-state and citric acid complex syntheses of Cu-doped sodium cobaltite ceramics.Journal of Alloys and Compounds, 2015, 640: 480-487.
[13]	HIROSHI ITAHARA, KENJIRO FUJITA, JUN SUGIYAMA, et al.Highly textured NaxCoO2 ceramics fabricated by both template grain growth and reactive template grain growth methods using single-crystalline particles as template.Journal of the Ceramic Society of Japan, 2003, 111: 227-231.
[14]	WU Y, WANG J, YAER X, et al. Effects of preferred orientation and crystal size on thermoelectric properties of sodium cobalt oxide. Functional Materials Letters, 2016, 9(01): 1650010-1-6.
[15]	KOSHIBAE W, TSUTSUI K, MAEKAWA S. Thermopower in cobalt oxides.Phys. Rev. B, 2000(62): 6869-6872.

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

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 8

参考文献 15

相关文章 15

编辑推荐

Metrics

本文评价

[1]	程俊, 张家伟, 仇鹏飞, 陈立东, 史迅. P掺杂β-FeSi₂材料的制备与热电输运性能[J]. 无机材料学报, 2024, 39(8): 895-902.
[2]	陈浩, 樊文浩, 安德成, 陈少平. 能带优化和载流子调控改善SnTe的热电性能[J]. 无机材料学报, 2024, 39(3): 306-312.
[3]	田震, 蒋全伟, 李建波, 于砺锋, 康慧君, 王同敏. 热变形协同优化BiSbSe_1.50Te_1.50材料电热输运[J]. 无机材料学报, 2024, 39(12): 1316-1324.
[4]	张哲, 孙婷婷, 王连军, 江莞. 不同维度Ag₂Se构筑柔性热电薄膜的性能优化与器件集成研究[J]. 无机材料学报, 2024, 39(11): 1221-1227.
[5]	孟雨婷, 王雪梅, 章淑娴, 陈志炜, 裴艳中. Bi₂Te₃基热电材料的单带和双带传输特性转变[J]. 无机材料学报, 2024, 39(11): 1283-1291.
[6]	苏浩健, 周敏, 李来风. 多元素掺杂优化SnTe的热电性能[J]. 无机材料学报, 2024, 39(10): 1159-1166.
[7]	肖娅妮, 吕嘉南, 李振明, 刘铭扬, 刘伟, 任志刚, 刘弘景, 杨东旺, 鄢永高. Bi₂Te₃基热电材料的湿热稳定性研究[J]. 无机材料学报, 2023, 38(7): 800-806.
[8]	贺丹琪, 魏明旭, 刘蕤之, 汤志鑫, 翟鹏程, 赵文俞. 一步法制备重费米子YbAl₃热电材料及其性能提升[J]. 无机材料学报, 2023, 38(5): 577-582.
[9]	李建波, 田震, 蒋全伟, 于砺锋, 康慧君, 曹志强, 王同敏. 不同元素掺杂对CaTiO₃微观结构及热电性能的影响[J]. 无机材料学报, 2023, 38(12): 1396-1404.
[10]	王鹏将, 康慧君, 杨雄, 刘颖, 程成, 王同敏. 熵调控抑制ZrNiSn基half-Heusler热电材料的晶格热导率[J]. 无机材料学报, 2022, 37(7): 717-723.
[11]	程成, 李建波, 田震, 王鹏将, 康慧君, 王同敏. In₂O₃/InNbO₄复合材料的热电性能研究[J]. 无机材料学报, 2022, 37(7): 724-730.
[12]	娄许诺, 邓后权, 李爽, 张青堂, 熊文杰, 唐国栋. Ge掺杂MnTe材料的热电输运性能[J]. 无机材料学报, 2022, 37(2): 209-214.
[13]	金敏, 白旭东, 张如林, 周丽娜, 李荣斌. 区熔法制备金属硫化物Ag₂S及其热电性能研究[J]. 无机材料学报, 2022, 37(1): 101-106.
[14]	张岑岑, 王雪, 彭良明. 基于分步式双重调控n型(PbTe)_1-_x_-_y(PbS)_x(Sb₂Se₃)_y体系的热电传输特性[J]. 无机材料学报, 2021, 36(9): 936-942.
[15]	杨青雨, 仇鹏飞, 史迅, 陈立东. 熵工程在热电材料中的应用[J]. 无机材料学报, 2021, 36(4): 347-354.