直写成型电极锰氧化物粉末的合成与浆料调控

doi:10.11949/0438-1157.20221688

摘要/Abstract

摘要：

制备可适用于直写成型程序的、具有较高固相含量的浆料是提升直写成型产品质量的关键，但现有研究在浆料调控的普适规律方面仍有所欠缺。采用水热法合成了一系列尺寸可控的锰氧化物粉末，并将其用于直写成型电极，采用XRD、SEM、BET表征并分析了不同颗粒尺度对固相含量选取的规律，采用稳态流动测试了相关浆料的流变行为。结果表明，通过调节水热反应温度，锰氧化物颗粒直径呈梯度变化，1.06~1.64 μm颗粒的适配固相含量随颗粒比表面积的下降而上升，46.46~91.36 μm颗粒的适配固相含量随颗粒直径的上升而下降。采用该规律所配浆料进行直写成型，挤出流畅、体积收缩小、产品机械强度高。

关键词: 锰氧化物, 浆料, 流变学, 粉体, 3D打印电极

Abstract:

The key to improving the quality of direct writing molding products is to prepare a slurry with a high solid content that is suitable for the direct writing process, but the existing research is still lacking in the universal law of slurry regulation. In this work, a series of manganese oxide powders with controllable size were synthesized by hydrothermal method and used in direct writing electrode. The manganese oxide powder was characterized by XRD, SEM and BET, and the rules of solid content selection for different manganese oxide particle sizes were analyzed. The rheological behavior of the related slurries was tested by steady flow method. The results show that the diameter of manganese oxide particles changes in gradient by adjusting the hydrothermal reaction temperature. The suitable solid content of particles of 1.06—1.64 μm increases with the decrease of particle specific surface area, while that of particles of 46.46—91.36 μm decreases with the increase of particle diameter. The slurry prepared according to this rule could be direct ink writing, with smooth extrusion, small volume shrinkage and high mechanical strength.

Key words: manganese oxide, slurry, rheology, powder, 3D printing electrode

中图分类号:

TM 912

何汉兵, 刘真, 陈勇, 王小锋, 曾婧. 直写成型电极锰氧化物粉末的合成与浆料调控[J]. 化工学报, 2023, 74(5): 2239-2247.

Hanbing HE, Zhen LIU, Yong CHEN, Xiaofeng WANG, Jing ZENG. Synthesis and slurry control of manganese oxide powder for direct ink writing electrode[J]. CIESC Journal, 2023, 74(5): 2239-2247.

图/表 8

图1 不同水热反应温度下的锰氧化物XRD谱图

Fig.1 XRD patterns of manganese oxide at different hydrothermal reaction temperatures

图2 不同水热反应温度下的锰氧化物SEM图像

Fig.2 SEM images of manganese oxides at different hydrothermal reaction temperatures

表1 不同水热反应温度下锰氧化物颗粒的直径、比表面积、可打印区间

Table 1 Diameter， specific surface area and printable range of manganese oxide particles under different hydrothermal reaction temperatures

水热反应温度/℃	颗粒直径/μm	比表面积/ (m²·g^-1)	可打印区间（固相质量分数）/%
100	1.64	33.0418	20~25
110	1.52	30.7876	20~25
120	1.39	28.4776	25~30
130	1.24	24.1953	25~30
140	1.06	17.2011	25~35
150	46.46	9.7487	25~30
160	67.63	6.4359	30~35
170	87.32	2.6529	25~30
180	91.36	2.2817	25~30

图3 添加不同增稠剂（从左至右依次为PEG-600、PEG-1000、CMC、HEMC、PVDF）的浆料沉降性测试(a)；Mn100浆料在固相质量分数为15% (b)、20% (c)、25% (d)时预打印情况

Fig.3 Slurry sedimentation test with different thickeners: PEG-600，PEG-1000，CMC，HEMC，PVDF (from left to right) (a); Preprinting of Mn100 slurry at different solid mass fractions: 15% (b)； 20% (c)； 25% (d)

图4 不同粉体所配浆料的表观黏度与剪切速率的函数图像

Fig.4 Function image of apparent viscosity and shear rate of slurry prepared by different powders

图5 打印过程示意图：浆料中颗粒的几种分布方式[(a)~(c)]；以Mn100 28%浆料制备的DIW电极干燥前(d)、干燥后(e)的数字显微镜图像

Fig.5 Schematic diagram of the printing process: several distribution modes of particles in the slurry [(a)—(c)]; digital microscope image of direct writing formed electrode prepared with Mn100 28% slurry before drying (d) and after drying (e)

图6 不同粉体所配浆料的表观黏度与剪切速率的函数图像及各浆料初始表观黏度与固相含量之间的关系

Fig.6 Function image of apparent viscosity and shear rate of slurry prepared by different powders and relationship between initial apparent viscosity and solid content of each slurry

图7 传统涂布电极和DIW电极在50 mA·g-1下的循环性能

Fig.7 Cyclic performance of traditional coating electrode and DIW electrode at 50 mA·g-1

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