Sodium Storage Performance of Mixed-phase Sodium Titanate Tuned by Carbon Dots

doi:10.7503/cjcu20240356

Abstract

Abstract:

Na₂Ti₃O₇ and Na₂Ti₆O₁₃ are two typical titanate-based sodium-storage materials， featuring the high theoretical capacity and favorable structure stability， respectively. Regulating the ratio of them in the composite material is the key to strengthen its electrochemical characteristics. Herein， based on the high specific surface area and abundant surface functional groups of carbon dots（CDs）， sodium titanate precursors containing CDs were in situ prepared by one-step hydrothermal method. After the thermal conversion of the precursors， a composite material（NNTO/C） of Na₂Ti₃O₇ and Na₂Ti₆O₁₃ was obtained， containing conductive carbon derived from CDs. The introduction of conductive carbon not only adjusts the composition ratio of the mixed phases， but also provides a small charge transfer impedance（R_ct， 7.48 Ω） and a big specific surface area（100.8 m²/g）. As a result， NNTO/C composites exhibit better sodium storage behavior while playing the synergistic interaction of mixed phases. When employed as the anode， after 200 cycles at 0.05 A/g， NNTO/C still maintains a specific capacity of 143.8 mA‧h/g. After 400 cycles at 1.00 A/g， the specific capacity remains as high as 108 mA‧h/g. This study suggests an innovative thinking for designing two-phase structures of electrode materials and the greater use of CDs in electrochemical energy storage.

Key words: Na₂Ti₃O₇, Na₂Ti₆O₁₃, Mixed-phases, Carbon dots, Sodium storage behavior

CLC Number:

O614

TrendMD:

LI Dan, HU Honghui, HOU Hongshuai, ZHANG Sheng, LIU Lijie, JING Mingjun, WU Tianjing. Sodium Storage Performance of Mixed-phase Sodium Titanate Tuned by Carbon Dots[J]. Chem. J. Chinese Universities, 2025, 46(6): 20240356.

Figures/Tables 7

Fig.1 SEM images of NNTO(A) and NNTO/C(B), TEM(C) and HRTEM images(D) of NNTO/C

Fig.2 XRD patterns of NNTO and NNTO/C composites(A), Rietveld refinement(B), Raman analysis(C) and TGA profiles(D) of NNTO/C sample

Fig.3 N2 adsorption⁃desorption isotherms and pore size distributions(insets) of NNTO/C(A) and NNTO(B)

Fig.4 XPS survey(A) and high resolution spectra for Ti2p (B), O1s (C) and C1s (D) of NNTO/C

Fig.5 CV plots of NNTO/C at 0.1 mV/s(A), cycling performances of NNTO/C and NNTO at 0.05 A/g(B), rate capabilities of NNTO/C and NNTO(C), charge⁃discharge curves of NNTO/C(D), cycling properties of NNTO/C at 1.00 A/g(E)

Fig.6 CV plots at various sweep speeds(A), capacitive and diffusive contributions at 0.2 mV/s(B), diffusion and pseudo⁃capacitive contributions at various scan rates of NNTO/C(C)

Fig.7 Nyquist plots(A), GITT profiles(B) and Na+ diffusion coefficient(C) of NNTO/C and NNTO

References 35

1	Zhu Z. X.， Jiang T. L.， Ali M.， Meng Y. H.， Jin Y.， Cui Y.， Chen W.， Chem. Rev.， 2022， 122（22）， 16610—16751
2	Wu N. T.， Zhao Z. B.， Hua R.， Wang X. T.， Zhang Y. M.， Li J.， Liu G. L.， Guo D. L.， Sun G.， Liu X. M.， Zhang J. W.， Adv. Energy Mater.， 2024， 2400371
3	Zhu Y. R.， Zhong W. P.， Chen W. H.， Hu Z. L.， Xie Y. J.， Deng W. T.， Hou H. S.， Zou G. Q.， Ji X. B.， Nano Energy， 2024， 125， 109524
4	Zhu Z. X.， Zhang X.， Wang M. M.， Chen W.， Chem. J. Chinese Universities， 2021， 42（5）， 1610—1618
	朱正新，张翔，王明明，陈维. 高等学校化学学报， 2021， 42（5）， 1610—1618
5	Zhang J. Y.， Yan Y. L.， Wang X.， Cui Y. Y.， Zhang Z. F.， Wang S.， Xie Z. K.， Yan P. F.， Chen W. H.， Nat. Commun.， 2023， 14（1）， 3701
6	Jiang Y. M.， Zhang Z.， Liao H. Y.， Zheng Y. F.， Fu X. T.， Lu J. N.， Cheng S. Y.， Gao Y. H.， ACS Nano， 2024， 18（11）， 7796—7824
7	Wang J. L.， Hu J. Y.， Kang F. Y.， Zhai D. Y.， Energy Environ. Sci.， 2024， 17（9）， 3202—3209
8	Dong S. Y.， Lv N.， Wu Y. L.， Zhang Y. Z.， Zhu G. Y.， Dong X. C.， Nano Today， 2022， 42， 101349
9	Dong J.， Jiang Y. L.， Wang R. X.， Wei Q. L.， An Q. Y.， Zhang X. X.， J. Energy Chem.， 2024， 88， 446—460
10	Lai Q. S.， Mu J. J.， Liu Z. M.， Zhao L. K.， Gao X. W.， Yang D. R.， Chen H.， Luo W. B.， Batteries & Supercaps， 2023， 6（4）， e202200549
11	Wu C. J.， Hua W. B.， Zhang Z.， Zhong B. H.， Yang Z. G.， Feng G. L.， Xiang W.， Wu Z. G.， Guo X. D.， Adv. Sci.， 2018， 5（9）， 1800519
12	Cao K. Z.， Jiao L. F.， Pang W. K.， Liu H. Q.， Zhou T. F.， Guo Z. P.， Wang Y. J.， Yuan H. T.， Small， 2016， 12（22）， 2991—2997
13	Que L. F.， Yu F. D.， Zheng L. L.， Wang Z. B.， Gu D. M.， Nano Energy， 2018， 45， 337—345
14	Zhao R.， Liu C.， Zhu Y. R.， Zou G. Q.， Hou H. S.， Ji X. B.， Adv. Funct. Mater.， 2024， 231664
15	Mei J.， Wang T. T.， Qi D. C.， Liu J. J.， Liao T.， Yamauchi Y. K.， Sun Z. Q.， ACS Nano， 2021， 15（8）， 13604—13615
16	Cech O.， Vanýsek P.， Chladil L.， Castkova K.， ECS Transactions， 2016， 74（1）， 331—337
17	Chandel S.， Lee S.， Lee S.， Kim S. J.， Singh S. P.， Kim J.， Rai A. K.， J. Electroanal. Chem.， 2020， 877， 114747
18	Hwang J.， Setiadi Cahyadi H.， Chang W.Y.， Kim J.， J. Supercrit. Fluid， 2019， 148， 116—129
19	Mintz K. J.， Bartoli M.， Rovere M.， Zhou Y. Q.， Hettiarachchi S. D.， Paudyal S.， Chen J. Y.， Domena J. B.， Liyanage P. Y.， Sampson R.， Khadka D.， Pandey R. R.， Huang S. X.， Chusuei C. C.， Tagliaferro A.， Leblanc R. M.， Carbon， 2021， 173， 433—447
20	Zhai Y. P.， Zhang B. W.， Shi R.， Zhang S. Y.， Liu Y. A.， Wang B. Y.， Zhang K.， Waterhouse G. I. N.， Zhang T. R.， Lu S. Y.， Adv. Energy Mater.， 2021， 12（6）， 2103426
21	El⁃Azazy M.， Osman A. I.， Nasr M.， Ibrahim Y.， Al⁃Hashimi N.， Al⁃Saad K.， Al⁃Ghouti M. A.， Shibl M. F.， Al⁃Muhtaseb A. A. H.， Rooney D. W.， El⁃Shafie A. S.， Coord. Chem. Rev.， 2024， 517， 215976
22	Song H. Q.， Wu M.， Tang Z. Y.， Tse J. S.， Yang B.， Lu S. Y.， Angew. Chem. Int. Ed.， 2021， 60（13）， 7234—7244
23	Yun X. R.， Li J. Y.， Chen X. H.， Chen H.， Xiao L.， Xiang K. X.， Chen W. H.， Liao H. Y.， Zhu Y. R.， ACS Appl. Mater. Interfaces， 2019， 11（40）， 36970—36984
24	Jin Y. L.， Wang Y. L.， Ren P. G.， Zhang B. F.， Zhao Z. R.， Hou X.， Ren F.， Chen Z. Y.， Guo Z. Z.， Yang H. J.， Li X. F.， J. Energy Storage， 2024， 85， 111118
25	Lee H. R.， Kim Y. S.， Lee S. Y.， Son U. H.， Lee S.， Joh H. I.， Appl. Surf. Sci.， 2024， 664， 160228
26	Liu Z.， Zhang S.， Qiu Z. P.， Huangfu C.， Wang L.， Wei T.， Fan Z. J.， Small， 2020， 16（38）， 2003557
27	Wu M. H.， Gao Y. P.， Hu Y.， Zhao B.， Zhang H. J.， Chin. Chem. Lett.， 2020， 31（3）， 897—902
28	Liu F.， Xu S. H.， Gong W. B.， Zhao K. T.， Wang Z. M.， Luo J.， Li C. S.， Xue P.， Wang C. L.， Wei L.， Li Q. W.， Zhang Q. C.， ACS Nano， 2023， 17， 18494—18506
29	Li L.， Li Y. T.， Ye Y.， Guo R. T.， Wang A. N.， Zou G. Q.， Hou H. S.， Ji X. B.， ACS Nano， 2021， 15， 6872—6885
30	Zhong W.， Tao M. L.， Tang W. W.， Gao W.， Yang T. T.， Zhang Y. Q.， Zhan R. M.， Bao S. J.， Xu M. W.， Chem. Eng. J.， 2019， 378， 122209
31	Yin J.， Qi L.， Wang H. Y.， ACS Appl. Mater. Interfaces， 2012， 4， 2762—2768
32	Li P. X.， Guo X.， Zang R.， Wang S. J.， Zuo Y. Q.， Man Z. M.， Li P.， Liu S. S.， Wang G. X.， Chem. Eng. J.， 2021， 418， 129501
33	Wang N.， Xu X.， Liao T.， Du Y.， Bai Z. C.， Dou S. X.， Adv. Mater.， 2018， 30（49）， 1804157
34	Pradeep A.， Kumar B. S.， Verma V.， Kobi S.， Nandakumar T.， Mukhopadhyay A.， Carbon， 2023， 201， 1—11
35	Shan H.， Qin J.， Ding Y. C.， Sari H. M. K.， Song X. X.， Liu W.， Hao Y. C.， Wang J. J.， Xie C.， Zhang J. J.， Li X. F.， Adv. Mater.， 2021， 33（37）， 2102471

[1]	LIU Jinkun, RAN Zhun, LIU Qingqing, LIU Yingliang, ZHUANG Jianle, HU Chaofan. Preparation of Carbon Dot-based Multicolor Room-temperature Phosphorescent Materials via Precursor Structure Regulation Strategies [J]. Chem. J. Chinese Universities, 2025, 46(6): 20240412.
[2]	PANG E, TANG Yuanyu, ZHAO Shaojing, CHENG Qiang, WANG Chen, CHEN Jianmin, LAN Minhuan. Hypoxia Activated Chemotherapy Drug AQ4N and Carbon Dots Self-assembly for Chemotherapy Combined with Sonodynamic Therapy of Tumors [J]. Chem. J. Chinese Universities, 2025, 46(6): 20240489.
[3]	PAN Zhuohan, AI Lin, LU Siyu. Research Progress on the Mechanism， Synthesis and Application of Solid-state Luminescent Carbon Dots [J]. Chem. J. Chinese Universities, 2025, 46(6): 20250081.
[4]	GUO Dan, HUANG Genghong, BAI Huijie, WANG Yaling, CAO Guangqun, LIU Bin, HU Shengliang. Preparation and Applications of CO₂-Derived Red-emissive Carbon Dots with a High Quantum Yield [J]. Chem. J. Chinese Universities, 2025, 46(6): 20250091.
[5]	XUE Xiaokuang, LI Jian, LIANG Huanyi, WANG Yiying, GE Jiechao. Red-emissive Mitochondria-targeting Iron-doped Carbon Dots for Tumor Therapy via Peroxidase-mimicking Activity-induced Ferroptosis [J]. Chem. J. Chinese Universities, 2025, 46(6): 20250094.
[6]	LIU Yupeng, YANG Junxiang, HAO Yiming, QU Songnan. Recent Advances in Carbon Dots with Near-infrared Absorption/Emission [J]. Chem. J. Chinese Universities, 2025, 46(6): 20240070.
[7]	LI Fengshi, JIANG Kai, TONG Xinyuan, WU Yongjian, LIN Hengwei. Regulating Trap Density and Energy Levels Through Boron Doping to Achieve Duration-tunable Afterglow from Carbon Dots for Dynamic Information Encryption [J]. Chem. J. Chinese Universities, 2025, 46(6): 20240545.
[8]	WANG Changying, ZHANG Dawei, CHEN Guanji, ZHANG Zhenwei, XIAO Weihong, WANG Bin, CHEN Qidan, YANG Bai. Preparation of Carbon Dots Fluorescent Marker and Its Application in Highly Selective NO₂^‒ Detection [J]. Chem. J. Chinese Universities, 2025, 46(6): 20240519.
[9]	LIU Yize, LI Pengfei, SUN Zaicheng. Correlation Between the Photoluminescene Mechanism and Structure of Carbon Dots [J]. Chem. J. Chinese Universities, 2025, 46(6): 20250103.
[10]	YANG Chunyuan, CHEN Hao, ZHANG Pan, LI Fucheng, YUAN Weixiong, GUO Jiazhuang, WANG Caifeng, CHEN Su. Synthesis， Fluorescence Mechanism and Patterning of Green-emissive Carbon Dots [J]. Chem. J. Chinese Universities, 2025, 46(6): 20250093.
[11]	CHEN Qidan, CHEN Guanji, YOU Shanmei, ZANG Xinyao, YANG Bai. Preparation of Broad-spectrum UV Protection Carbon Dots for the Application of Sunscreen Absorber [J]. Chem. J. Chinese Universities, 2025, 46(6): 20240313.
[12]	LIU Yingqi, WANG Yemei, JIANG Kai, ZHENG Fenfen, ZHU Junjie. Colorimetric and Fluorescence Determination of Glucose Based on Cell-derived Fluorescent Carbon Dots [J]. Chem. J. Chinese Universities, 2025, 46(6): 20240386.
[13]	HAO Yongliang, LI Jian, WANG Zehua, GE Jiechao. Active Shrinkage Hydrogel Based on Red Emissive Carbon Dots Photosensitizers for Bacterial Infected Wound Healing [J]. Chem. J. Chinese Universities, 2025, 46(6): 20240409.
[14]	WANG Xin, WANG Yu, MU Fumao, YAN Lingpeng, WANG Zhenguo, YANG Yongzhen. Applications and Prospects of Carbon Dots in Interface Engineering of Organic Solar Cells [J]. Chem. J. Chinese Universities, 2025, 46(6): 20240416.
[15]	NI Jiawen, HUANG Zunhui, SONG Tianbing, MA Qianli, HE Tianle, ZHANG Xirong, XIONG Huanming. Ordered Lithium Deposition on Lithium Metal Anode Controlled by Boron-doped Carbon Dots from Solid-state Synthesis [J]. Chem. J. Chinese Universities, 2025, 46(6): 20240185.