Citation: CHEN Lai, CHEN Shi, HU Dao-Zhong, SU Yue-Feng, LI Wei-Kang, WANG Zhao, BAO Li-Ying, WU Feng. Crystal Structure and Electrochemical Performance of Lithium-Rich Cathode Materials xLi₂MnO₃·(1-x)LiNi_0.5Mn_0.5O₂ (x=0.1-0.8)[J]. Acta Physico-Chimica Sinica, ;2014, 30(3): 467-475. doi: 10.3866/PKU.WHXB201312252 shu

Crystal Structure and Electrochemical Performance of Lithium-Rich Cathode Materials xLi₂MnO₃·(1-x)LiNi_0.5Mn_0.5O₂ (x=0.1-0.8)

CHEN Lai ¹ ,
CHEN Shi ^1,2 ,
HU Dao-Zhong ³ ,
SU Yue-Feng ^1,2, ,
LI Wei-Kang ¹ ,
WANG Zhao ¹ ,
BAO Li-Ying ^1,2 ,
WU Feng ^1,2

1.
1 Beijing Key Laboratory of Environmental Science and Engineering, School of Chemical Engineering and the Environment, Beijing Institute of Technology, Beijing 100081, P. R. China;
2 National Development Center of Hi-Tech Green Materials, Beijing 100081, P. R. China;
3 China North Vehicle Research Institute, Beijing 100072, P. R. China

Received Date: 24 October 2013
Available Online: 25 December 2013
Fund Project: 国家重点基础研究发展规划项目(973) (2009CB220100)，国家自然科学基金(51102018，21103011)，国家高技术研究发展计划项目(863)(2011AA11A235，SQ2010AA1123116001) (973) (2009CB220100)，国家自然科学基金(51102018，21103011)，国家高技术研究发展计划项目(863)(2011AA11A235，SQ2010AA1123116001)北京理工大学重大项目培育专项计划项目(2013CX01003)资助 (2013CX01003)

A series of lithium-rich cathode materials, xLi₂MnO₃·(1-x)LiNi_0.5Mn_0.5O₂ (x=0.1-0.8), were successfully synthesized by a sol-gel method. X-ray diffraction, scanning electron microscopy, and electrochemical tests were used to investigate the crystal structure, morphology, and electrochemical performance of the as-synthesized materials, respectively. The results showed that the materials with higher Li₂MnO₃ content had higher initial discharge capacity but poorer cycle stability, while the materials with lower Li₂MnO₃ content showed lower discharge capacity but better cycle stability, and the spinel impurity phase was also found. Based on the data, the optimal electrochemical properties were obtained when x=0.5 in xLi₂MnO₃·(1-x)LiNi_0.5Mn_0.5O₂. Moreover, the electrochemical properties were also worthy of attention when x=0.4, 0.6.
- Lithium-ion battery,
- Cathode,
- Li₂MnO₃,
- Crystal structure,
- Electrochemical performance
1. [1]
  
  (1) Choi, N. S.; Chen, Z. H.; Freunberger, S. A.; Ji, X. L.; Sun, Y. K.; Amine, K.; Yushin, G.; Nazar, L. F.; Cho, J.; Bruce, P. G. Angew. Chem. Int. Edit. 2012, 51 (40), 9994. doi: 10.1002/anie.201201429
2. [2]
  (2) Li, H.;Wang, Z. X.; Chen, L. Q.; Huang, X. J. Adv. Mater. 2009, 21 (45), 4593. doi: 10.1002/adma.v21:45
3. [3]
  (3) Jeong, G. J.; Kim, Y. U.; Kim, H. S.; Kim, Y. J.; Sohn, H. J. Energ Environ. Sci. 2011, 4 (6), 1986. doi: 10.1039/c0ee00831a
4. [4]
  (4) He, P.; Yu, H. J.; De, L.; Zhou, H. S. J. Mater. Chem. 2012, 22 (9), 3680. doi: 10.1039/c2jm14305d
5. [5]
  (5) Whittingham, M. S. Chem. Soc. Rev. 2004, 104 (10), 4271.
6. [6]
  (6) Aricò, A. S.; Bruce, P.; Scrosati, B.; Tarascon, J. M.; Schalkwijk,W. V. Nat. Mater. 2005, 4 (5), 366. doi: 10.1038/nmat1368
7. [7]
  (7) Nagaura, T.; Tozawa, K. Prog. Batteries Solar Cells 1990, 9, 209.
8. [8]
  (8) Song, H. K.; Lee, K. T.; Kim, M. G.; Nazar, L. F.; Cho, J. Adv. Funct. Mater. 2010, 20 (22), 3818. doi: 10.1002/adfm.201000231
9. [9]
  (9) Armand, M.; Tarascon, J. M. Nature 2008, 451 (7179), 652. doi: 10.1038/451652a
10. [10]
  (10) odenough, J. B.; Kim, Y. J. Power Sources 2011, 196 (16), 6688. doi: 10.1016/j.jpowsour.2010.11.074
11. [11]
  (11) Wu, F.; Li, N.; Su, Y. F.; Shou, H. F.; Bao, L. Y.; Yang,W.; Zhang, L. J.; An, R.; Chen, S. Adv. Mater. 2013, 25 (27), 3722. doi: 10.1002/adma.v25.27
12. [12]
  (12) Du, K.; Hu, G. R. Chin. Sci. Bull. 2012, 57 (10), 794. [杜柯, 胡国荣. 科学通报, 2012, 57 (10), 794.] doi: 10.1360/972011-610
13. [13]
  (13) Ritchie, A. G. J. Power Sources 2001, 96 (1), 1. doi: 10.1016/S0378-7753(00)00673-X
14. [14]
  (14) Fergus, J.W. J. Power Sources 2010, 195 (4), 939. doi: 10.1016/j.jpowsour.2009.08.089
15. [15]
  (15) Wu, F.; Li, N.; Su, Y.; F.; Lu, H. Q.; Zhang, L. J.; An, R.;Wang, Z.; Bao, L.Y.; Chen, S. J. Mater. Chem. 2012, 22 (4), 1489. doi: 10.1039/c1jm14459f
16. [16]
  (16) Lu, Z. H.; MacNeil, D. D.; Dahn, J. R. Electrochem. Solid St. 2001, 4 (11), A191.
17. [17]
  (17) Lu, Z. H.; Beaulieu, L. Y.; Donaberger, R. A.; Thomas, C. L.; Dahn, J. R. J. Electrochem. Soc. 2002, 149 (6), A778.
18. [18]
  (18) Thackeray, M. M.; Kang, S. H.; Johnson, C. S.; Vaughey, J, T.; Benedek, R. B.; Hackney, S. A. J. Mater. Chem. 2007, 17 (30), 3112. doi: 10.1039/b702425h
19. [19]
  (19) Armstrong, A. R.; Holzapfel, M.; Novák, P.; Johnson, C. S.; Kang, S. H.; Thackeray, M. M.; Bruce, P. G. J. Am. Chem. Soc. 2006, 128 (26), 8694. doi: 10.1021/ja062027+
20. [20]
  (20) Wang, D. P.; Belharouak, I.; Zhou, G.W.; Amine, K. Adv. Funct. Mater. 2013, 23 (8), 1070. doi: 10.1002/adfm.v23.8
21. [21]
  (21) Chen, Z.; Ren, Y.; Lee, E.; Johnson, C.; Qin, Y.; Amine, K. Adv. Energy Mater. 2013, 3 (6), 729. doi: 10.1002/aenm.201201059
22. [22]
  (22) Park, Y. J.; Hong, Y. S.;Wu, X. L.; Kim, M. G.; Ryu, K. S.; Chang, S.H. J. Electrochem. Soc. 2004, 151 (5), A720.
23. [23]
  (23) Meng, Y. S.; Ceder, G.; Grey, C. P.; Yoon,W. S.; Jiang, M.; Bréger, J.; Horn, Y. S. Chem. Mater. 2005, 17 (9), 2386. doi: 10.1021/cm047779m
24. [24]
  (24) Bréger, J.; Jiang, M.; Dupré, N.; Meng, Y. S.; Horn, Y. S.; Ceder, G.; Grey, C. P. J. Solid State Chem. 2005, 178 (9), 2575. doi: 10.1016/j.jssc.2005.05.027
25. [25]
  (25) Kim, J. S.; Johnson, C. S.; Vaughey, J. T.; Thackeray, M. M. Chem. Mater. 2004, 16 (10), 1996. doi: 10.1021/cm0306461
26. [26]
  (26) Armstrong, A. R.; Bruce, P. G. Electrochem. Solid. St. 2004, 7 (1), A1.
27. [27]
  (27) Park, M. S.; Lee, J.W.; Choi,W.; Im, D.; Doo, S. G.; Park, K. S. J. Mater. Chem. 2010, 20 (34), 7208. doi: 10.1039/c0jm00617c
28. [28]
  (28) Weill, F.; Tran, N.; Martin, N.; Croguennec, L.; Delmas, C. Electrochem. Solid. St. 2007, 10 (8), A194.
29. [29]
  (29) Lu, Z.; Dahn, J. R. J. Electrochem. Soc. 2002, 149 (7), A815.
30. [30]
  (30) Park, Y. J.; Hong, Y. S.;Wu, X.; Ryu, K. S.; Chang, S. H. J. Power Sources 2004, 129 (2), 288. doi: 10.1016/j.jpowsour.2003.11.024
31. [31]
  (31) Hong, Y. S.; Park, Y. J.; Ryu, K. S.; Chang, S. H.; Kim, M. G. J. Mater. Chem. 2004, 14 (9), 1424. doi: 10.1039/b311888f
32. [32]
  (32) Jain, G.; Yang, J. S.; Balasubramanian, M.; Xu, J. J. Chem. Mater. 2005, 17 (15), 3850. doi: 10.1021/cm0503329
33. [33]
  (33) Thackeray, M. M.; Kang, S. H.; Johnson, C. S.; Vauqhey, J. T.; Benedek, R.; Hackney, S. A. J. Mater. Chem. 2007, 17 (30), 3112. doi: 10.1039/b702425h
34. [34]
  (34) Bareno, J.; Lei, C. H.;Wen, J. G.; Kang, S. H.; Petrov, I.; Abraham, D. P. Adv. Mater. 2010, 22 (10), 1122. doi: 10.1002/adma.200904247
35. [35]
  (35) Koyama, Y.; Tanaka, I.; Nagao, M.; Kanno, R. J. Power Sources 2009, 189 (1), 798. doi: 10.1016/j.jpowsour.2008.07.073
36. [36]
  (36) Bréger, J.; Meng, Y. S.; Hinuma, Y.; Kumar, S. D.; Kang, K.; Horn, Y. S.; Ceder, G.; Grey, C. P. Chem. Mater. 2006, 18 (20), 4768. doi: 10.1021/cm060886r
37. [37]
  (37) Johnson, C. S.; Li, N.; Lefief, C.; Vaughey, J. T.; Thackeray, M. M. Chem. Mater. 2008, 20 (19), 6095. doi: 10.1021/cm801245r
38. [38]
  (38) Thackeray, M. M.; Johnson, C. S.; Vaughey, J. T.; Li, N.; Hackney, S. A. J. Mater. Chem. 2005, 15 (23), 2257. doi: 10.1039/b417616m
39. [39]
  (39) Belharouak, I.; Koenig, G. M., Jr.; Ma, J.W.;Wang, D. P.; Amine, K. Electrochem. Commun. 2011, 13 (3), 232. doi: 10.1016/j.elecom.2010.12.021
40. [40]
  (40) Myung, S. T.; Kumagai, N.; Komaba, S.; Chung, H. T. Solid State Ionics 2001, 139 (1), 47.
41. [41]
  (41) Kim, Y.; Hyun, S. K.; Martin, S.W. Electrochim. Acta 2006, 52 (3), 1316. doi: 10.1016/j.electacta.2006.07.033
42. [42]
  (42) Morales, J.; Perez-Vicente, C.; Tirado, J. L. Mater. Res. Bull. 1990, 25 (5), 623. doi: 10.1016/0025-5408(90)90028-Z
43. [43]
  (43) Delmas, C.; Peres, J. P.; Rougier, A.; Demourgues, A.;Weill, F.; Chadwick, A.; Broussely, M.; Perton, F.; Biensan, P.;Willmann, P. J. Power Sources 1997, 68 (1), 120. doi: 10.1016/S0378-7753(97)02664-5
44. [44]
  (44) Kim, J. M.; Chung, H. T. Electrochim. Acta 2004, 49 (21), 3573. doi: 10.1016/j.electacta.2004.03.025
45. [45]
  (45) Fey, G. T. K.; Shiu, R. F.; Subramanian, V.; Chen, J. G.; Chen, C. L. J. Power Sources 2002, 103 (2), 265. doi: 10.1016/S0378-7753(01)00859-X
46. [46]
  (46) Kim, J. H.; Park, C.W.; Sun, Y. K. Solid State Ionics 2003, 164 (1), 43.
47. [47]
  (47) Yu, L.; Qiu,W.; Lian, F.; Huang, J.; Kang, X. L. J. Alloy. Compd. 2009, 471 (1), 317
48. [48]
  (48) Rossouw, M. H.; Liles, D. C.; Thackeray, M. M. J. Solid State Chem. 1993, 104 (2), 464. doi: 10.1006/jssc.1993.1182
49. [49]
  (49) Robertson, A. D.; Bruce, P. G. Chem. Commun. 2002, 2790.
50. [50]
  (50) Tran, N.; Croguennec, L.; Ménétrier, M.;Weill, F.; Biensan, P.; Jordy, C.; Delmas, C. Chem. Mater. 2008, 20 (15), 4815. doi: 10.1021/cm070435m
51. [51]
  (51) Jiang, M.; Key, B.; Meng, Y. S.; Grey, C. P. Chem. Mater. 2009, 21 (13), 2733. doi: 10.1021/cm900279u
52. [52]
  (52) Johnson, C. S.; Li, N.; Lefief, C.; Thackeray, M. M. Electrochem. Commun. 2007, 9 (4), 787. doi: 10.1016/j.elecom.2006.11.006
53. [53]
  (53) Kalyani, P.; Chitra, S.; Mohan, T.; pukumar, S. J. Power Sources 1999, 80 (1), 103.
54. [54]
  (54) Robertson, A. D.; Bruce, P. G. Chem. Mater. 2003, 15 (10), 1984. doi: 10.1021/cm030047u
55. [55]
  (55) Toshimi, T.; Hiroshi, H.; Etsuo, A. K. J. Solid State Chem. 1995, 115 (2), 420. doi: 10.1006/jssc.1995.1154
56. [56]
  (56) Belharouak, I.; Koenig, G. M., Jr.; Ma, J.W.;Wang, D. P.; Amine, K. Electrochem. Commun. 2011, 13 (3), 232. doi: 10.1016/j.elecom.2010.12.021
57. [57]
  (57) Ammundsen, B.; Paulsen, J. Adv. Mater. 2001, 13 (12-13), 943. doi: 10.1002/1521-4095(200107)13:12/13<943::AIDADMA943> 3.0.CO;2-J
58. [58]
  (58) Johnson, C. S.; Korte, S. D.; Vaughey, J. T.; Thackeray, M. M.; Bofinger, T. E.; Hom, Y. S.; Hackney, S. A. J. Power Sources 1999, 81, 491.
59. [59]
  (59) Wang, Z.;Wu, F.; Su, Y. F.; Bao, L. Y.; Chen, L.; Li, N.; Chen, S. Acta Phys. -Chim. Sin. 2012, 28 (4), 823. [王昭, 吴锋, 苏岳锋, 包丽颖, 陈来, 李宁, 陈实. 物理化学学报, 2012, 28 (4), 823.] doi: 10.3866/PKU.WHXB201202102
1. [1]
  Yuyao Wang , Zhitao Cao , Zeyu Du , Xinxin Cao , Shuquan Liang . Research Progress of Iron-based Polyanionic Cathode Materials for Sodium-Ion Batteries. Acta Physico-Chimica Sinica, 2025, 41(4): 100035-. doi: 10.3866/PKU.WHXB202406014
2. [2]
  Qingtang ZHANG , Xiaoyu WU , Zheng WANG , Xiaomei WANG . Performance of nano Li₂FeSiO₄/C cathode material co-doped by potassium and chlorine ions. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1689-1696. doi: 10.11862/CJIC.20240115
3. [3]
  Pengyang FAN , Shan FAN , Qinjin DAI , Xiaoying ZHENG , Wei DONG , Mengxue WANG , Xiaoxiao HUANG , Yong ZHANG . Preparation and performance of rich 1T-MoS₂ nanosheets for high-performance aqueous zinc ion battery cathode materials. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 675-682. doi: 10.11862/CJIC.20240339
4. [4]
  Jianbao Mei , Bei Li , Shu Zhang , Dongdong Xiao , Pu Hu , Geng Zhang . Enhanced Performance of Ternary NASICON-Type Na_3.5-xMn_0.5V_1.5-xZr_x(PO₄)₃/C Cathodes for Sodium-Ion Batteries. Acta Physico-Chimica Sinica, 2024, 40(12): 2407023-. doi: 10.3866/PKU.WHXB202407023
5. [5]
  Yuanchao LI , Weifeng HUANG , Pengchao LIANG , Zifang ZHAO , Baoyan XING , Dongliang YAN , Li YANG , Songlin WANG . Effect of heterogeneous dual carbon sources on electrochemical properties of LiMn_0.8Fe_0.2PO₄/C composites. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 751-760. doi: 10.11862/CJIC.20230252
6. [6]
  Qi Li , Pingan Li , Zetong Liu , Jiahui Zhang , Hao Zhang , Weilai Yu , Xianluo Hu . Fabricating Micro/Nanostructured Separators and Electrode Materials by Coaxial Electrospinning for Lithium-Ion Batteries: From Fundamentals to Applications. Acta Physico-Chimica Sinica, 2024, 40(10): 2311030-. doi: 10.3866/PKU.WHXB202311030
7. [7]
  Xinpeng LIU , Liuyang ZHAO , Hongyi LI , Yatu CHEN , Aimin WU , Aikui LI , Hao HUANG . Ga₂O₃ coated modification and electrochemical performance of Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ cathode material. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1105-1113. doi: 10.11862/CJIC.20230488
8. [8]
  Xiangyu CAO , Jiaying ZHANG , Yun FENG , Linkun SHEN , Xiuling ZHANG , Juanzhi YAN . Synthesis and electrochemical properties of bimetallic-doped porous carbon cathode material. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 509-520. doi: 10.11862/CJIC.20240270
9. [9]
  Yan Liu , Yuexiang Zhu , Luhua Lai . Introduction to Blended and Small-Class Teaching in Structural Chemistry: Exploring the Structure and Properties of Crystals. University Chemistry, 2024, 39(3): 1-4. doi: 10.3866/PKU.DXHX202306084
10. [10]
  Haitang WANG , Yanni LING , Xiaqing MA , Yuxin CHEN , Rui ZHANG , Keyi WANG , Ying ZHANG , Wenmin WANG . Construction, crystal structures, and biological activities of two Ln^Ⅲ₃ complexes. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1474-1482. doi: 10.11862/CJIC.20240188
11. [11]
  Yuting ZHANG , Zunyi LIU , Ning LI , Dongqiang ZHANG , Shiling ZHAO , Yu ZHAO . Nickel vanadate anode material with high specific surface area through improved co-precipitation method: Preparation and electrochemical properties. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2163-2174. doi: 10.11862/CJIC.20240204
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]
  Siyu Zhang , Kunhong Gu , Bing'an Lu , Junwei Han , Jiang Zhou . Hydrometallurgical Processes on Recycling of Spent Lithium-lon Battery Cathode: Advances and Applications in Sustainable Technologies. Acta Physico-Chimica Sinica, 2024, 40(10): 2309028-. doi: 10.3866/PKU.WHXB202309028
14. [14]
  Zhuo Wang , Xue Bai , Kexin Zhang , Hongzhi Wang , Jiabao Dong , Yuan Gao , Bin Zhao . MOF模板法合成氮掺杂碳材料用于增强电化学钠离子储存和去除. Acta Physico-Chimica Sinica, 2025, 41(3): 2405002-. doi: 10.3866/PKU.WHXB202405002
15. [15]
  Xiaoling LUO , Pintian ZOU , Xiaoyan WANG , Zheng LIU , Xiangfei KONG , Qun TANG , Sheng WANG . Synthesis, crystal structures, and properties of lanthanide metal-organic frameworks based on 2, 5-dibromoterephthalic acid ligand. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1143-1150. doi: 10.11862/CJIC.20230271
16. [16]
  Xin MA , Ya SUN , Na SUN , Qian KANG , Jiajia ZHANG , Ruitao ZHU , Xiaoli GAO . A Tb₂ complex based on polydentate Schiff base: Crystal structure, fluorescence properties, and biological activity. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1347-1356. doi: 10.11862/CJIC.20230357
17. [17]
  Xiaoning TANG , Shu XIA , Jie LEI , Xingfu YANG , Qiuyang LUO , Junnan LIU , An XUE . Fluorine-doped MnO₂ with oxygen vacancy for stabilizing Zn-ion batteries. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1671-1678. doi: 10.11862/CJIC.20240149
18. [18]
  Jiahong ZHENG , Jiajun SHEN , Xin BAI . Preparation and electrochemical properties of nickel foam loaded NiMoO₄/NiMoS₄ composites. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 581-590. doi: 10.11862/CJIC.20230253
19. [19]
  Weina Wang , Fengyi Liu , Wenliang Wang . “Extracting Commonality, Delving into Typicals, Deriving Individuality”: Constructing a Knowledge Graph of Crystal Structures. University Chemistry, 2024, 39(3): 36-42. doi: 10.3866/PKU.DXHX202308029
20. [20]
  Junqiao Zhuo , Xinchen Huang , Qi Wang . Symbol Representation of the Packing-Filling Model of the Crystal Structure and Its Application. University Chemistry, 2024, 39(3): 70-77. doi: 10.3866/PKU.DXHX202311100

Get Citation

PDF

XML

Metrics

PDF Downloads(761)
Abstract views(859)
HTML views(13)

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

Crystal Structure and Electrochemical Performance of Lithium-Rich Cathode Materials xLi2MnO3·(1-x)LiNi0.5Mn0.5O2 (x=0.1-0.8)

Metrics

通讯作者: 陈斌, bchen63@163.com

Crystal Structure and Electrochemical Performance of Lithium-Rich Cathode Materials xLi₂MnO₃·(1-x)LiNi_0.5Mn_0.5O₂ (x=0.1-0.8)