Synthesis and slurry control of manganese oxide powder for direct ink writing electrode

doi:10.11949/0438-1157.20221688

Abstract

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

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

CLC Number:

TM 912

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.

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.

Figures/Tables 8

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

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

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

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)

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

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)

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

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

References 32

1	Wei M, Zhang F, Wang W, et al. 3D direct writing fabrication of electrodes for electrochemical storage devices[J]. Journal of Power Sources, 2017, 354: 134-147.
2	Goodenough J B. Electrochemical energy storage in a sustainable modern society[J]. Energy & Environmental Science, 2014, 7(1): 14-18.
3	Whittingham M S. Lithium batteries and cathode materials[J]. Chemical Reviews, 2004, 104(10): 4271-4301.
4	Zhong C, Liu B, Ding J, et al. Decoupling electrolytes towards stable and high-energy rechargeable aqueous zinc-manganese dioxide batteries[J]. Nature Energy, 2020, 5(6): 440-449.
5	Ji J, Wan H Z, Zhang B, et al. Co^2+/3+/4+-regulated electron state of Mn-O for superb aqueous zinc-manganese oxide batteries[J]. Advanced Energy Materials, 2021, 11(6): 2003203.
6	Tagliaferri S, Panagiotopoulos A, Mattevi C. Direct ink writing of energy materials[J]. Materials Advances, 2021, 2(2): 540-563.
7	Wu K, Huang J H, Yi J, et al. Recent advances in polymer electrolytes for zinc ion batteries: mechanisms, properties, and perspectives[J]. Advanced Energy Materials, 2020, 10(12): 1903977.
8	Luo Z X, Zeng J, Liu Z, et al. Carbon-coated hydrated vanadium dioxide for high-performance aqueous zinc-ion batteries[J]. Journal of Alloys and Compounds, 2022, 906: 164388.
9	Wei T S, Ahn B Y, Grotto J, et al. 3D printing of customized Li-ion batteries with thick electrodes[J]. Advanced Materials, 2018, 30(16): 1703027.
10	Chang P, Mei H, Zhou S X, et al. 3D printed electrochemical energy storage devices[J]. Journal of Materials Chemistry A, 2019, 7(9): 4230-4258.
11	Amato D N, Amato D V, Sandoz M, et al. Programmable porous polymers via direct bubble writing with surfactant-free inks[J]. ACS Applied Materials & Interfaces, 2020, 12(37): 42048-42055.
12	Tian X C, Wang T, Ma H, et al. A universal strategy towards 3D printable nanomaterial inks for superior cellular high-loading battery electrodes[J]. Journal of Materials Chemistry A, 2021, 9(29): 16086-16092.
13	李文利, 周宏志, 刘卫卫, 等. 光固化3D打印陶瓷浆料及流变性研究进展[J]. 材料工程, 2022, 50(7): 40-50.
	Li W L, Zhou H Z, Liu W W, et al. Research progress in ceramic slurries and rheology viaphotopolymerization-based 3D printing[J]. Journal of Materials Engineering, 2022, 50(7): 40-50.
14	Bae C J, Ramachandran A, Halloran J W. Quantifying particle segregation in sequential layers fabricated by additive manufacturing[J]. Journal of the European Ceramic Society, 2018, 38(11): 4082-4088.
15	Bae C J, Halloran J W. Concentrated suspension-based additive manufacturing-viscosity, packing density, and segregation[J]. Journal of the European Ceramic Society, 2019, 39(14): 4299-4306.
16	Zakeri S, Vippola M, Levänen E. A comprehensive review of the photopolymerization of ceramic resins used in stereolithography[J]. Additive Manufacturing, 2020, 35: 101177.
17	Dou R, Tang W Z, Hu K X, et al. Ceramic paste for space stereolithography 3D printing technology in microgravity environment[J]. Journal of the European Ceramic Society, 2022, 42(9): 3968-3975.
18	Praveen S, Santhoshkumar P, Joe Y C, et al. 3D-printed architecture of Li-ion batteries and its applications to smart wearable electronic devices[J]. Applied Materials Today, 2020, 20: 100688.
19	Wang J W, Sun Q, Gao X J, et al. Toward high areal energy and power density electrode for Li-ion batteries via optimized 3D printing approach[J]. ACS Applied Materials & Interfaces, 2018, 10(46): 39794-39801.
20	Shen C L, Wang T, Xu X, et al. 3D printed cellular cathodes with hierarchical pores and high mass loading for Li-SeS₂ battery[J]. Electrochimica Acta, 2020, 349: 136331.
21	Janssen R, Scheppokat S, Claussen N. Tailor-made ceramic-based components—advantages by reactive processing and advanced shaping techniques[J]. Journal of the European Ceramic Society, 2008, 28(7): 1369-1379.
22	Zhang Y N, Liu Y P, Liu Z H, et al. MnO₂ cathode materials with the improved stability via nitrogen doping for aqueous zinc-ion batteries[J]. Journal of Energy Chemistry, 2022, 64: 23-32.
23	Cao X W, Xu Y T, Yang B, et al. In-situ Co-precipitated α-MnO₂@2-methylimidazole cathode material for high performance zinc ion batteries[J]. Journal of Alloys and Compounds, 2022, 896: 162785.
24	Wang X, Li Y D. Synthesis and formation mechanism of manganese dioxide nanowires/nanorods[J]. Chemistry, 2003, 9(1): 300-306.
25	左文婧, 屈银虎, 祁攀虎, 等. 3D打印锂离子电池正极的制备及性能[J]. 工程科学学报, 2020, 42(3): 358-364.
	Zuo W J, Qu Y H, Qi P H, et al. Preparation and performance of 3D-printed positive electrode for lithium-ion battery[J]. Chinese Journal of Engineering, 2020, 42(3): 358-364.
26	王一博, 赵九蓬. 3D打印柔性可穿戴锂离子电池[J]. 材料工程, 2018, 46(3): 13-21.
	Wang Y B, Zhao J P. 3D printing of flexible electrodes towards wearable lithium ion battery[J]. Journal of Materials Engineering, 2018, 46(3): 13-21.
27	Friedrich L, Begley M. Printing direction dependent microstructures in direct ink writing[J]. Additive Manufacturing, 2020, 34: 101192.
28	Sydney Gladman A, Matsumoto E A, Nuzzo R G, et al. Biomimetic 4D printing[J]. Nature Materials, 2016, 15(4): 413-418.
29	Kou T Y, Wang S W, Shi R P, et al. Water splitting: periodic porous 3D electrodes mitigate gas bubble traffic during alkaline water electrolysis at high current densities[J]. Advanced Energy Materials, 2020, 10(46): 2070189.
30	Bu X M, Mao Z Y, Bu Y, et al. Remarkable gas bubble transport driven by capillary pressure in 3D printing-enabled anisotropic structures for efficient hydrogen evolution electrocatalysts[J]. Applied Catalysis B: Environmental, 2023, 320: 121995.
31	Smith P T, Basu A, Saha A, et al. Chemical modification and printability of shear-thinning hydrogel inks for direct-write 3D printing[J]. Polymer, 2018, 152: 42-50.
32	Wilt J K, Gilmer D, Kim S, et al. Direct ink writing techniques for in situ gelation and solidification[J]. MRS Communications, 2021, 11(2): 106-121.

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