高比容量Li2ZnTi3O8@C⁃N负极材料储锂性能研究

doi:10.3969/j.issn.1006-396X.2022.03.001

摘要/Abstract

摘要：

以盐酸多巴胺为N、C源，高温固相法合成N掺杂C包覆Li₂ZnTi₃O₈@C?N负极材料。在合成过程中发现，部分Ti⁴⁺被还原为Ti³⁺，达到了包覆和掺杂共同改性的目的。该方法有利于提高离子扩散系数和降低电荷转移电阻。在电流密度为0.5、1.0、1.5、2.0、2.5、3.0 A/g时，Li₂ZnTi₃O₈@C?N?2的放电比容量分别超过240.0、220.0、210.0、200.0、190.0、180.0 mA $?$ h/g。还研究了N掺杂C包覆Li₂ZnTi₃O₈复合材料的低温电化学性能。结果表明，0 ℃时该样品的放电比容量远高于未改性的Li₂ZnTi₃O₈负极材料；电流密度为0.2 A/g时的首次放电比容量为262.5 mA $?$ h/g，循环300次后放电比容量为241.7 mA $?$ h/g；在电流密度为1.0 A/g、循环300次后放电比容量依然有147.4 mA $?$ h/g。

关键词: 锂离子电池, 钛酸锌锂, 负极材料, 碳包覆, 自掺杂

Abstract:

Li₂ZnTi₃O₈ anodes coated with N?doped carbon from dopamine hydrochloride were synthesized via a high?temperature solid?state method.Some Ti⁴⁺ ions were reduced to Ti³⁺ ions during synthesis,which enabled the co?modification of coating and doping.The modification method can enhance the ion diffusion coefficients and reduce the charge?transfer resistance.In the rate performance tests at 0.5,1.0,1.5,2.0,2.5,3.0 A/g,the specific capacities of N?doped carbon?coated Li₂ZnTi₃O₈(Li₂ZnTi₃O₈@C?N?2) are over 240.0，220.0，210.0，200.0，190.0，180.0 mA $?$ h/g,respectively.In addition,the electrochemical performance of this material at a low temperature was also studied.The results show that the Li₂ZnTi₃O₈@C?N?2 sample has much higher discharge specific capacities than those of unmodified Li₂ZnTi₃O₈ anode material at 0 ℃.The initial discharge specific capacity is 262.5 mA $?$ h/g at 0.2 A/g,and the discharge specific capacity of 241.7 mA $?$ h/g is still obtained after 300 cycles.Even at 1.0 A/g,the discharge specific capacity is kept at 147.4 mA $?$ h/g after 300 cycles.

Key words: Lithium?ion batteries, Li₂ZnTi₃O₈, Anode materials, Carbon coating, Self?doping

中图分类号:

TQ152

沈紫烨, 王利娟. 高比容量Li₂ZnTi₃O₈@C⁃N负极材料储锂性能研究[J]. 石油化工高等学校学报, 2022, 35(3): 1-9.

Ziye Shen, Lijuan Wang. Li⁃Storage of Li₂ZnTi₃O₈@C⁃N Anode Materials with High Specific Capacities[J]. Journal of Petrochemical Universities, 2022, 35(3): 1-9.

图/表 14

图1 P?LZTO和LZTO@C?N系列样品的XRD图谱

Fig.1 XRD patterns of P?LZTO and LZTO@C?N samples

表1 P?LZTO和LZTO@C?N系列样品的晶胞参数

Table 1 Lattice parameters of P?LZTO and LZTO@C?N samples

样品名称	a/nm	V/nm³	空间群
P⁃LZTO	0.837 13	0.586 66	P4₃32
LZTO@C⁃N⁃1	0.836 89	0.586 15	P4₃32
LZTO@C⁃N⁃2	0.836 61	0.585 56	P4₃32
LZTO@C⁃N⁃3	0.836 35	0.585 01	P4₃32

图2 LZTO@C?N系列样品的TG图谱

Fig.2 TG curves of the LZTO@C?N samples

图3 LZTO@C?N系列样品的XPS图谱

Fig.3 XPS spectra of LZTO@C?N samples

图4 P?LZTO和LZTO@C?N系列样品的SEM和TEM图

Fig.4 SEM and TEM images of P?LZTO and LZTO@C?N samples

图5 P?LZTO和LZTO@C?N系列样品首次充放电曲线

Fig.5 Initial discharge?charge curves of P?LZTO and LZTO@C?N samples

图6 P?LZTO和LZTO@C?N系列样品的循环性能曲线

Fig.6 Cycling performance of P?LZTO and LZTO@C?N samples

表2 C包覆改性后的LZTO材料循环后的比容量

Table 2 Comparison of the specific capacities of carbon?coated LZTO materials

样品	电流密度/(A $⋅$ g^-1)	循环次数	比容量/(mA $⋅$ h $⋅$ g^-1)	来源
LZTO/C	0.5	50	203.2	[7]
LZTO/C⁃2	0.5	100	190.0	[8]
LZTO⁃M	0.5	100	187.2	[9]
LZTO@C⁃N⁃2	1.0	200	172.63	[12]
LZTO/C	1.0	100	165.2	[14]
LZTO@C⁃N⁃700	0.5	200	217.0	[27]
LZTO@C⁃N⁃2	0.5	50	242.89	本实验
LZTO@C⁃N⁃2	0.5	100	256.18	本实验
LZTO@C⁃N⁃2	0.5	200	237.06	本实验
LZTO@C⁃N⁃2	1.0	50	212.07	本实验
LZTO@C⁃N⁃2	1.0	100	209.81	本实验
LZTO@C⁃N⁃2	1.0	200	196.24	本实验

表2 C包覆改性后的LZTO材料循环后的比容量

Table 2 Comparison of the specific capacities of carbon?coated LZTO materials

样品	电流密度/(A $⋅$ g^-1)	循环次数	比容量/(mA $⋅$ h $⋅$ g^-1)	来源
LZTO/C	0.5	50	203.2	[7]
LZTO/C⁃2	0.5	100	190.0	[8]
LZTO⁃M	0.5	100	187.2	[9]
LZTO@C⁃N⁃2	1.0	200	172.63	[12]
LZTO/C	1.0	100	165.2	[14]
LZTO@C⁃N⁃700	0.5	200	217.0	[27]
LZTO@C⁃N⁃2	0.5	50	242.89	本实验
LZTO@C⁃N⁃2	0.5	100	256.18	本实验
LZTO@C⁃N⁃2	0.5	200	237.06	本实验
LZTO@C⁃N⁃2	1.0	50	212.07	本实验
LZTO@C⁃N⁃2	1.0	100	209.81	本实验
LZTO@C⁃N⁃2	1.0	200	196.24	本实验

图7 P?LZTO和LZTO@C?N样品的倍率性能曲线

Fig.7 Rate capability of P?LZTO and LZTO@C?N samples

表3 C包覆改性后LZTO材料的倍率性能对比

Table 3 Comparison of the rate capability for carbon?coated LZTO materials

样品	电流密度/(A $⋅$ g^-1)	循环次数	比容量/(mA $⋅$ h $⋅$ g^-1)	来源
LZTO/C	2.0	50	145.6	[6]
LZTO/C	0.5	20	229.0	[11]
LZTO/C	1.0	30	197.9	[11]
LZTO/C	2.0	40	169.8	[11]
LZTO/C	1.8	50	121.8	[14]
LZTO/C	1.0	45	206.4	[28]
LZTO/C	2.0	55	178.0	[28]
LZTO@ C⁃N⁃2	0.5	1~20	240	本实验
LZTO@ C⁃N⁃2	1.0	21~40	220	本实验
LZTO@ C⁃N⁃2	2.0	61~80	200	本实验

表3 C包覆改性后LZTO材料的倍率性能对比

Table 3 Comparison of the rate capability for carbon?coated LZTO materials

样品	电流密度/(A $⋅$ g^-1)	循环次数	比容量/(mA $⋅$ h $⋅$ g^-1)	来源
LZTO/C	2.0	50	145.6	[6]
LZTO/C	0.5	20	229.0	[11]
LZTO/C	1.0	30	197.9	[11]
LZTO/C	2.0	40	169.8	[11]
LZTO/C	1.8	50	121.8	[14]
LZTO/C	1.0	45	206.4	[28]
LZTO/C	2.0	55	178.0	[28]
LZTO@ C⁃N⁃2	0.5	1~20	240	本实验
LZTO@ C⁃N⁃2	1.0	21~40	220	本实验
LZTO@ C⁃N⁃2	2.0	61~80	200	本实验

图8 P?LZTO和LZTO@C?N?2样品的CV曲线

Fig.8 CV curves of P?LZTO and LZTO@C?N?2 samples

图9 P?LZTO和LZTO@C?N?2样品的EIS曲线及Zre与ω-1/2的关系图

Fig.9 Electrochemical impedance spectroscopies and relationship between Zre and ω-1/2 for P?LZTO and LZTO@C?N?2 samples

表4 P?LZTO和LZTO@C?N?2交流阻抗参数

Table 4 Electrochemical impedance parameters for P?LZTO and LZTO@C?N?2 electrodes

样品	R_E/Ω	R_ct/Ω	$D L i +$ /(cm² $⋅$ s^-1)
P⁃LZTO	1.834	82.03	4.50×10^-17
LZTO@C⁃N⁃2	2.223	66.83	1.67×10^-15

表4 P?LZTO和LZTO@C?N?2交流阻抗参数

Table 4 Electrochemical impedance parameters for P?LZTO and LZTO@C?N?2 electrodes

样品	R_E/Ω	R_ct/Ω	$D L i +$ /(cm² $⋅$ s^-1)
P⁃LZTO	1.834	82.03	4.50×10^-17
LZTO@C⁃N⁃2	2.223	66.83	1.67×10^-15

图10 P?LZTO和LZTO@C?N?2样品0 ℃性能曲线

Fig.10 Performance curves of P?LZTO and LZTO@C?N?2 samples at 0 ℃

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高比容量Li₂ZnTi₃O₈@C⁃N负极材料储锂性能研究

Li⁃Storage of Li₂ZnTi₃O₈@C⁃N Anode Materials with High Specific Capacities

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