一步氧化法制备锰酸锂正极材料用电池级四氧化三锰

doi:10.11949/0438-1157.20240820

化工学报 ›› 2025, Vol. 76 ›› Issue (3): 1363-1374.DOI: 10.11949/0438-1157.20240820

• 材料化学工程与纳米技术 • 上一篇

一步氧化法制备锰酸锂正极材料用电池级四氧化三锰

马钟琛¹^,²^,³(), 魏子杰⁴, 朱明涛¹^,², 叶恒棣¹^,²(), 郭学益³(), 谭磊⁴()

^1.中冶长天国际工程有限责任公司，湖南长沙 410015
^2.湖南省先进储能材料技术创新中心，湖南长沙 410015
^3.中南大学冶金与环境学院，湖南长沙 410083
^4.长沙理工大学能源与动力工程学院，能源高效清洁利用湖南省高校重点实验室，湖南长沙 410114

收稿日期:2024-07-18 修回日期:2024-10-12 出版日期:2025-03-25 发布日期:2025-03-28
通讯作者: 叶恒棣,郭学益,谭磊
作者简介:马钟琛（1990—），男，博士，高级工程师，mahuancontact@sina.com
基金资助:
中冶集团“181计划”重大研发项目;国家自然科学基金项目(52204306)

Preparation of battery-grade manganese tetroxide for lithium manganate cathode material by one-step oxidation method

Zhongchen MA¹^,²^,³(), Zijie WEI⁴, Mingtao ZHU¹^,², Hengdi YE¹^,²(), Xueyi GUO³(), Lei TAN⁴()

^1.Zhongye Changtian International Engineering Co. , Ltd. , Changsha 410015, Hunan, China
^2.Hunan Center of Technology Innovation for Advanced Energy Storage Materials, Changsha 410015, Hunan, China
^3.School of Metallurge and Environment, Central South University, Changsha 410083, Hunan, China
^4.Key Laboratory of Efficient & Clean Energy Utilization, The Education Department of Hunan Province, School of Energy and Power Engineering, Changsha University of Science and Technology, Changsha 410114, Hunan, China

Received:2024-07-18 Revised:2024-10-12 Online:2025-03-25 Published:2025-03-28
Contact: Hengdi YE, Xueyi GUO, Lei TAN

摘要/Abstract

摘要：

通过一步氧化制备Mn₃O₄，研究反应过程中温度、转速、氨锰摩尔比以及氨水流速变化对Mn₃O₄结构、形貌、粒径的影响。结果表明，升高温度会加快反应速率，降低体系过饱和度，从而增加产物的粒径；随着转速增加，溶液高速流动带来的剪切力会使Mn₃O₄的粒径趋于减小且分布更为集中；氨锰摩尔比的提高会直接降低体系的过饱和度并优化晶体的生长，使Mn₃O₄的粒径增加，球形度更好。其中，在搅拌转速900 r/min、氨锰摩尔比为2.0、温度为70℃的条件下获得的Mn₃O₄粒径D₅₀为10.3 μm，振实密度高达2.65 g/cm³，比表面积仅为0.369 m²/g。在此基础上，通过反应前期调低氨水流速加快成核，在反应后期调高氨水流速从而促进颗粒生长的方式，将Mn₃O₄粒径D₅₀降至5.34 μm，同时保证了2.51 g/cm³的高振实密度和0.400 m²/g的低比表面积。将粒径为10 μm级和5 μm级的Mn₃O₄作为前体混合Li₂CO₃烧制成LiMn₂O₄正极材料，结果表明10 μm的样品拥有更好的循环性能，在1 C的倍率下首圈放电比容量达到121.3 mAh/g，循环200圈后容量保持率为92.8%；5 μm样品具有更好的倍率性能，在3 C、5 C、10 C倍率下的比容量分别为102.6、93.4、77.6 mAh/g。

关键词: 四氧化三锰, 一步氧化法, 锰酸锂, 电化学性能

Abstract:

Mn₃O₄ is prepared by one-step oxidation. The effects of temperature, rotation speed, ammonia-manganesemolar ratio and ammonia flow rate the structure, morphology and particle size of Mn₃O₄ are studied. The results show that the increase of temperature will accelerate the reaction rate, reduce the super saturation of the system, and increase the particle size of the product. As the rotation speed increases, the shear force caused by the high-speed flow of the solution will make the particle size of Mn₃O₄ tend to decrease and the distribution more concentrated. The increase of the molar ratio of ammonia to manganese will directly reduce the supersaturation of the system and optimize the growth of the crystal, so that the particle size of Mn₃O₄ increases and the sphericity is better. Among them, the Mn₃O₄ particle size D₅₀ obtained under the condition of the mixing speed of 900 r/min, molar ratio of ammonia to manganese is 2.0 and the temperature is 70℃, the D₅₀ is 10.3 μm, the vibration density is as high as 2.65 g/cm³, and the surface area is only 0.369 m²/g. Based on this condition, the process of further regulating the particle size is explored. The particle size D₅₀ of Mn₃O₄ is further reduced to 5.34 μm by reducing the flow rate of ammonia in the early stage of the reaction and increasing the flow rate of ammonia in the later stage of the reaction, while ensuring a high tap density of 2.51 g/cm³ and a low specific surface area of 0.40 m²/g. The LiMn₂O₄ cathode material is prepared by using Mn₃O₄ with particle size of 10 μm and 5 μm mixed with Li₂CO₃. The results show that the sample with 10 μm has better cyclic performance. The discharge specific capacity reaches 121.3 mAh/g at the rate of 1 C, and the capacity retention is 92.8% after 200 cycles. The 5 μm sample has better rate performance, and the specific capacities at 3 C, 5 C, and 10 C are 102.6, 93.4, and 77.6 mAh/g, respectively.

Key words: manganese tetroxide, one-step oxidation method, lithium manganate, electrochemical properties

中图分类号:

TF 123

马钟琛, 魏子杰, 朱明涛, 叶恒棣, 郭学益, 谭磊. 一步氧化法制备锰酸锂正极材料用电池级四氧化三锰[J]. 化工学报, 2025, 76(3): 1363-1374.

Zhongchen MA, Zijie WEI, Mingtao ZHU, Hengdi YE, Xueyi GUO, Lei TAN. Preparation of battery-grade manganese tetroxide for lithium manganate cathode material by one-step oxidation method[J]. CIESC Journal, 2025, 76(3): 1363-1374.

图/表 25

图1 Mn-H2O体系E-pH图（25℃、[Mn]=1 mol/L）[23]

Fig.1 E-pH diagram of Mn-H2O system (25℃, [Mn]=1 mol/L)[23]

图2 不同转速下样品的XRD谱图

Fig.2 XRD patterns of samples at different rotation speeds

图3 不同转速下样品的SEM图

Fig.3 SEM images of samples at different rotation speeds

表1 不同转速下样品的粒径数据

Table 1 Particle size data of samples at different rotational speeds

样品	D₁₀/μm	D₅₀/μm	D₉₀/μm
Mn₃O₄-500	8.46	14.5	25.8
Mn₃O₄-700	9.62	14.3	23.9
Mn₃O₄-900	9.14	13.1	18.4

图4 不同转速下的粒径分布

Fig.4 Particle size distribution at different speeds

图5 不同氨锰摩尔比的样品XRD谱图

Fig.5 XRD patterns of samples with different ammonia-manganese ratios

图6 不同氨锰摩尔比的样品SEM图

Fig.6 SEM images of samples with different ammonia-manganese ratios

图7 不同氨锰摩尔比的样品粒径分布

Fig.7 Particle size distribution of samples with different ammonia-manganese ratios

表2 不同氨锰摩尔比的样品粒径数据

Table 2 Particle size data of samples with different ammonia-manganese ratios

样品	D₁₀/μm	D₅₀/μm	D₉₀/μm
Mn₃O₄-1∶1	4.29	7.04	12.3
Mn₃O₄-2∶1	6.7	10.3	15.7
Mn₃O₄-2.5∶1	9.14	13.1	18.4
Mn₃O₄-3∶1	10.9	16.8	25.5

图8 不同温度下的样品XRD谱图

Fig.8 XRD patterns of samples at different temperatures

图9 不同温度下的样品SEM图

Fig.9 SEM images of samples at different temperatures

图10 不同温度的样品粒径分布

Fig.10 Particle size distribution of samples at different temperatures

表3 不同温度下的样品粒径数据

Table 3 Sample particle size data at different temperatures

样品	D₁₀/μm	D₅₀/μm	D₉₀/μm
Mn₃O₄-50	5.54	8.08	11.7
Mn₃O₄-60	4.94	8.66	14
Mn₃O₄-70	6.7	10.3	15.7
Mn₃O₄-80	6.95	11.4	17.4

图11 反应不同时间段的样品SEM图

Fig.11 SEM images of samples at different reaction time periods

图12 不同流速条件下样品的XRD谱图

Fig.12 XRD patterns of samples at different flow rates

表4 不同流速条件下的样品粒径数据

Table 4 Sample particle size data at different flow rates

样品	D₁₀/μm	D₅₀/μm	D₉₀/μm
Mn₃O₄-0.3/1.4	3.49	5.34	9.33
Mn₃O₄-0.5/1.3	3.01	6.34	10.40
Mn₃O₄-0.7/1.25	5.31	7.11	9.55

图13 不同流速条件下样品的SEM图

Fig.13 SEM images of samples at different flow rates

图14 不同流速条件下的样品粒径分布

Fig.14 Sample particle size distribution under different flow rates

表5 不同流速条件下样品的部分参数

Table 5 Some parameters of samples at different flow rates

样品	D₅₀/μm	振实密度/（g/cm³）	比表面积/（m²/g）	Mn含量/%	产率/%
Mn₃O₄-5	5.34	2.51	0.400	70.93	91.6
Mn₃O₄-10	10.3	2.65	0.369	70.82	90.0

图15 Mn3O4-5和Mn3O4-10的BET吸脱附曲线

Fig.15 BET adsorption-desorption curves of Mn3O4-5 and Mn3O4-10

图16 LiMn2O4-10和LiMn2O4-5的XRD谱图

Fig.16 XRD patterns of LiMn2O4-10 and LiMn2O4-5

图17 两种粒径等级的LiMn2O4的SEM图

Fig.17 SEM images of LiMn2O4 with two particle sizes

图18 LiMn2O4-5和LiMn2O4-10材料的电化学性能：（a） LiMn2O4的首圈充放电曲线；（b） LiMn2O4正极材料的倍率性能图；（c） Nyquist图；（d） Z’和ω-1/2关系示意图；（e） LiMn2O4正极材料的循环曲线

Fig.18 Electrochemical properties of LiMn2O4-5 and LiMn2O4-10: (a) Charge-discharge curves of LiMn2O4; (b) Rate performance curves of LiMn2O4 cathode materials; (c) Nyquist plot; (d) Schematic diagram of the relationship between Z' and ω-1/2; (e) Cycle curves of LiMn2O4 cathode material

表6 样品LiMn2O4-10和LiMn2O4-5与文献样品的电化学性能对比

Table 6 Comparison of the electrochemical properties of LiMn2O4-10 and LiMn2O4-5 samples with those in the literatures

样品	电压区间/V	1 C比容量/（mAh/g）	5 C比容量/（mAh/g）	10 C比容量/（mAh/g）	容量保持率/%
文献样品1^[29]	3~4.3	109.2	91.0	77.9	72.1(1 C, 100圈)
文献样品2^[23]	3~4.3	108.4	96.5	85.1	91.3(0.2 C, 100圈)
文献样品3^[30]	3~4.3	121.0	90.6	80.5	88.1(1 C, 100圈)
文献样品4^[31]	3~4.4	117.0	49.0	—	65.8(1 C, 100圈)
文献样品5^[32]	3.2~4.3	102.0	85.0	69.0	41.1(2 C, 200圈)
LiMn₂O₄-10	3~4.3	121.3	71.6	50.6	92.8(1 C, 200圈)
LiMn₂O₄-5	3~4.3	120.2	93.4	77.6	89.4(1 C, 200圈)

撤稿声明

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一步氧化法制备锰酸锂正极材料用电池级四氧化三锰

Preparation of battery-grade manganese tetroxide for lithium manganate cathode material by one-step oxidation method

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