Citation: HUANG Ying-Heng, TONG Zhang-Fa, WEI Teng-You, LI Bin. Reaction Kinetics of the Intermediate in Synthesis of LiCoPO₄ by Solid-State Reaction[J]. Acta Physico-Chimica Sinica, ;2011, 27(06): 1325-1334. doi: 10.3866/PKU.WHXB20110507 shu

Reaction Kinetics of the Intermediate in Synthesis of LiCoPO₄ by Solid-State Reaction

1.
1. School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004, P. R. China;
2. Department of Metallurgy Engineering, Guilin University of Technology at Nanning, Nanning 530001, P. R. China

Received Date: 25 November 2010
Available Online: 25 March 2011
Fund Project: 国家自然科学基金(20766001) (20766001) 广西青年科学基金(0728101) (0728101)广西教育厅科研项目(200505083)资助 (200505083)

A precursor NH₄CoPO₄ containing Li⁺ was synthesized using a low temperature solid-state reaction with ammonium dihydrogen phosphate, cobalt acetate, and lithium hydroxide. LiCoPO₄ powder was manufactured by high temperature baking. The products were characterized by Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD) and thermogravimetry-differential thermal analysis (TG-DTA). The results showed that the formation of the intermediates was effected by the baking atmosphere. NH₄CoPO₄ containing Li⁺ was dehydrated and deaminated in air at 210?500 °C and then the (CoHPO₄·LiCoPO₄·Co₂(OH)PO₄·Li₃PO₄) intermediate (acid-base community) was emerged during the reaction process. The intermediate formation reaction mechanism followed the interfacial reaction power-law with an apparent activation energy of 50.0 kJ·mol^-1. The kinetic function was found to be g(x)=(1-α)^-1. The intermediate was dehydrated to form LiCoPO₄ with an average apparent activation energy of 54.2 kJ·mol^-1. The formation of the intermediate was not affected by the process of crystallization or non- crystallization of the materials. High temperatures accelerated the decomposition reaction of the intermediate and then the formation of LiCoPO₄ crystals. A perfect crystal of LiCoPO₄ was obtained by the decomposition of the intermediate at temperatures higher than 550 °C.
- LiCoPO₄,
- Lithium orthophosphate,
- Intermediate,
- Solid state reaction,
- Reaction mechanism,
- Kinetics
1. [1]
  
  (1) Zheng, J. C.; Li, X. H.; Wang, Z. X.; Li, J. H.; Wu, L.; Li, L. J.; Guo, H. J. Acta Phys. -Chim. Sin. 2009, 25, 1916.
2. [2]
  [郑俊超, 李新海, 王志兴, 李金辉, 伍凌, 李灵均, 郭华军. 物理化学学报. 2009, 25, 1916.]
3. [3]
  (2) Wolfenstine, J.; Allen, J. J. Power Sources 2004, 136, 150.
4. [4]
  (3) Zhou, F.; Cococcioni, M.; Kang, K.; Ceder, G. Electrochem. Commun. 2004, 6, 1144.
5. [5]
  (4) Rissouli, K.; Benkhouja, K.; Ramos-Barrado, J. R.; Julien, C. Mater. Sci. Eng. B 2003, 98, 185.
6. [6]
  (5) Okada, S.; Ueno, M.; Uebou, Y.; Yamaki, J. I. J. Power Sources 2005, 146, 565.
7. [7]
  (6) ni, A.; Lezama, L.; Barberis, G. E.; Pizarro, J. L.; Arriortua, M. I.; Rojo, T. J. Magn. Magn. Mater. 1996, 164, 251.
8. [8]
  (7) Brown, P. J.; Frsyth, J. B.; Tasset, F. Solid-State Sci. 2005, 7, 682.
9. [9]
  (8) Santoro, R. P.; Segal, D. J.; Newnham, R. E. J. Phys. Chem. Solids 1966, 27, 119.
10. [10]
  (9) Van Aken, B. B.; Rivera, J. P.; Schmid, H.; Fiebig, M. F. Nature 2007, 449, 702.
11. [11]
  (10) Ehrenberg, H.; Bramnik, N. N.; Senyshyn, A.; Fuess, H. Solid State Sci. 2009, 11, 18.
12. [12]
  (11) Bramnik, N. N.; Bramnik, K. G.; Baehtz, C.; Ehrenberg, H. J. Power Sources 2005, 145, 74.
13. [13]
  (12) Wolfenstine, J.; Poese, B.; Allen, J. L. J. Power Sources 2004, 138, 281.
14. [14]
  (13) Wolfenstine, J.; Read, J.; Allen, J. L. J. Power Sources 2007, 163, 1070.
15. [15]
  (14) Wolfenstine, J.; Lee, U.; Poese, B.; Allen, J. L. J. Power Sources 2005, 144, 226.
16. [16]
  (15) Gri rova, V.; Roussev, D.; Deniard, P.; Jobic, S. J. Phys. Chem. Solids 2005, 66, 1598.
17. [17]
  (16) Deniard, P.; Dulac, A. M.; Roequefdte, X; Gri rova, V.; Lebacq, O.; Pasturel, A.; Jobic. S. J. Phys. Chem. Solids 2004, 65, 229.
18. [18]
  (17) Han, D. W.; Kang, Y. M.; Yin, R. Z.; Song, M. S.; Kwon, H. S. Electrochem. Commun. 2009, 11, 137.
19. [19]
  (18) Huang, Y. H; Tong, Z. F; Lan, J. J.; Chen, Y. Z. J. Yunnan University (Natural Science) 2010, 32, 314.
20. [20]
  [黄映恒, 童张法, 蓝建京, 陈义族. 云南大学学报: 自然科学版, 2010, 32, 314.]
21. [21]
  (19) Huang, Y. H; Tong, Z. F; Lan, J. J.; Chen, Y. Z. The Chinese Journal of Process Engineering 2010, 10, 179.
22. [22]
  [黄映恒, 童张法, 蓝建京, 陈义族. 过程工程学报, 2010, 10, 179.]
23. [23]
  (20) Huang, Y. H; Tong, Z. F; Liao, S; Lan, J. J.; Chen, Y. Z. Journal of Chemical Engineering of Chinese Universities 2010, 24, 967.
24. [24]
  [黄映恒, 童张法, 廖森, 蓝建京, 陈义族. 高校化学工程学报, 2010, 24, 967.]
25. [25]
  (21) Koleva, G. V. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 2005, 62, 1196.
26. [26]
  (22) Koleva, G. V. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2007, 66, 413.
27. [27]
  (23) Ruan, Y. L.; Tang, Z. Y. Acta Phys. -Chim. Sin. 2008, 24, 873.
28. [28]
  [阮艳莉, 唐致远. 物理化学学报, 2008, 24, 873.]
29. [29]
  (24) Conesa, J. A.; Marcilla, A.; Caballero, J. A.; Font, R. J. Anal. Appl. Pyrolysis 2001, 58-59, 617.
30. [30]
  (25) Ozawa, T. J. Therm. Anal. 1970, 2, 301.
31. [31]
  (26) Kissinger, H. E. J. Anal. Chem. 1957, 29, 1702.
32. [32]
  (27) Sestak, J.; Berggren, G. Thermochim. Acta 1971, 3, 1
1. [1]
  Ronghao Zhao , Yifan Liang , Mengyao Shi , Rongxiu Zhu , Dongju Zhang . Investigation into the Mechanism and Migratory Aptitude of Typical Pinacol Rearrangement Reactions: A Research-Oriented Computational Chemistry Experiment. University Chemistry, 2024, 39(4): 305-313. doi: 10.3866/PKU.DXHX202309101
2. [2]
  Wentao Lin , Wenfeng Wang , Yaofeng Yuan , Chunfa Xu . Concerted Nucleophilic Aromatic Substitution Reactions. University Chemistry, 2024, 39(6): 226-230. doi: 10.3866/PKU.DXHX202310095
3. [3]
  Ling Fan , Meili Pang , Yeyun Zhang , Yanmei Wang , Zhenfeng Shang . Quantum Chemistry Calculation Research on the Diels-Alder Reaction of Anthracene and Maleic Anhydride: Introduction to a Computational Chemistry Experiment. University Chemistry, 2024, 39(4): 133-139. doi: 10.3866/PKU.DXHX202309024
4. [4]
  Yeyun Zhang , Ling Fan , Yanmei Wang , Zhenfeng Shang . Development and Application of Kinetic Reaction Flasks in Physical Chemistry Experimental Teaching. University Chemistry, 2024, 39(4): 100-106. doi: 10.3866/PKU.DXHX202308044
5. [5]
  Qian Huang , Zhaowei Li , Jianing Zhao , Ao Yu . Quantum Chemical Calculations Reveal the Details Below the Experimental Phenomenon. University Chemistry, 2024, 39(3): 395-400. doi: 10.3866/PKU.DXHX202309018
6. [6]
  Yong Wang , Yingying Zhao , Boshun Wan . Analysis of Organic Questions in the 37th Chinese Chemistry Olympiad (Preliminary). University Chemistry, 2024, 39(11): 406-416. doi: 10.12461/PKU.DXHX202403009
7. [7]
  Yiying Yang , Dongju Zhang . Elucidating the Concepts of Thermodynamic Control and Kinetic Control in Chemical Reactions through Theoretical Chemistry Calculations: A Computational Chemistry Experiment on the Diels-Alder Reaction. University Chemistry, 2024, 39(3): 327-335. doi: 10.3866/PKU.DXHX202309074
8. [8]
  Xuzhen Wang , Xinkui Wang , Dongxu Tian , Wei Liu . Enhancing the Comprehensive Quality and Innovation Abilities of Graduate Students through a “Student-Centered, Dual Integration and Dual Drive” Teaching Model: A Case Study in the Course of Chemical Reaction Kinetics. University Chemistry, 2024, 39(6): 160-165. doi: 10.3866/PKU.DXHX202401074
9. [9]
  Dexin Tan , Limin Liang , Baoyi Lv , Huiwen Guan , Haicheng Chen , Yanli Wang . Exploring Reverse Teaching Practices in Physical Chemistry Experiment Courses: A Case Study on Chemical Reaction Kinetics. University Chemistry, 2024, 39(11): 79-86. doi: 10.12461/PKU.DXHX202403048
10. [10]
  Heng Zhang . Determination of All Rate Constants in the Enzyme Catalyzed Reactions Based on Michaelis-Menten Mechanism. University Chemistry, 2024, 39(4): 395-400. doi: 10.3866/PKU.DXHX202310047
11. [11]
  Guoqiang Chen , Zixuan Zheng , Wei Zhong , Guohong Wang , Xinhe Wu . 熔融中间体运输导向合成富氨基g-C₃N₄纳米片用于高效光催化产H₂O₂. Acta Physico-Chimica Sinica, 2024, 40(11): 2406021-. doi: 10.3866/PKU.WHXB202406021
12. [12]
  Yingchun ZHANG , Yiwei SHI , Ruijie YANG , Xin WANG , Zhiguo SONG , Min WANG . Dual ligands manganese complexes based on benzene sulfonic acid and 2, 2′-bipyridine: Structure and catalytic properties and mechanism in Mannich reaction. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1501-1510. doi: 10.11862/CJIC.20240078
13. [13]
  Tianlong Zhang , Rongling Zhang , Hongsheng Tang , Yan Li , Hua Li . Online Monitoring and Mechanistic Analysis of 3,5-diamino-1,2,4-triazole (DAT) Synthesis via Raman Spectroscopy: A Recommendation for a Comprehensive Instrumental Analysis Experiment. University Chemistry, 2024, 39(6): 303-311. doi: 10.3866/PKU.DXHX202312006
14. [14]
  Zhilian Liu , Wengui Wang , Hongxiao Yang , Yu Cui , Shoufeng Wang . Ideological and Political Education Design for the Synthesis of Irinotecan Drug Intermediate 7-Ethyl Camptothecin. University Chemistry, 2024, 39(2): 89-93. doi: 10.3866/PKU.DXHX202306012
15. [15]
  Renxiao Liang , Zhe Zhong , Zhangling Jin , Lijuan Shi , Yixia Jia . A Palladium/Chiral Phosphoric Acid Relay Catalysis for the One-Pot Three-Step Synthesis of Chiral Tetrahydroquinoline. University Chemistry, 2024, 39(5): 209-217. doi: 10.3866/PKU.DXHX202311024
16. [16]
  Ruming Yuan , Pingping Wu , Laiying Zhang , Xiaoming Xu , Gang Fu . Patriotic Devotion, Upholding Integrity and Innovation, Wholeheartedly Nurturing the New: The Ideological and Political Design of the Experiment on Determining the Thermodynamic Functions of Chemical Reactions by Electromotive Force Method. University Chemistry, 2024, 39(4): 125-132. doi: 10.3866/PKU.DXHX202311057
17. [17]
  Yuting Zhang , Zhiqian Wang . Methods and Case Studies for In-Depth Learning of the Aldol Reaction Based on Its Reversible Nature. University Chemistry, 2024, 39(7): 377-380. doi: 10.3866/PKU.DXHX202311037
18. [18]
  Ruitong Zhang , Zhiqiang Zeng , Xiaoguang Zhang . Improvement of Ethyl Acetate Saponification Reaction and Iodine Clock Reaction Experiments. University Chemistry, 2024, 39(8): 197-203. doi: 10.3866/PKU.DXHX202312004
19. [19]
  Yuan Chun , Lijun Yang , Jinyue Yang , Wei Gao . Ideological and Political Design of BZ Oscillatory Reaction Experiment. University Chemistry, 2024, 39(2): 72-76. doi: 10.3866/PKU.DXHX202308072
20. [20]
  Shiyan Cheng , Yonghong Ruan , Lei Gong , Yumei Lin . Research Advances in Friedel-Crafts Alkylation Reaction. University Chemistry, 2024, 39(10): 408-415. doi: 10.12461/PKU.DXHX202403024

Get Citation

PDF

XML

Metrics

PDF Downloads(1097)
Abstract views(2789)
HTML views(16)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Reaction Kinetics of the Intermediate in Synthesis of LiCoPO4 by Solid-State Reaction

Metrics

通讯作者: 陈斌, bchen63@163.com

Reaction Kinetics of the Intermediate in Synthesis of LiCoPO₄ by Solid-State Reaction