Structural Engineering of Anode Materials for Low-Temperature Lithium-Ion Batteries: Mechanisms, Strategies, and Prospects

doi:10.1007/s40820-024-01363-y

Abstract

Abstract:

The severe degradation of electrochemical performance for lithium-ion batteries (LIBs) at low temperatures poses a significant challenge to their practical applications. Consequently, extensive efforts have been contributed to explore novel anode materials with high electronic conductivity and rapid Li⁺ diffusion kinetics for achieving favorable low-temperature performance of LIBs. Herein, we try to review the recent reports on the synthesis and characterizations of low-temperature anode materials. First, we summarize the underlying mechanisms responsible for the performance degradation of anode materials at subzero temperatures. Second, detailed discussions concerning the key pathways (boosting electronic conductivity, enhancing Li⁺ diffusion kinetics, and inhibiting lithium dendrite) for improving the low-temperature performance of anode materials are presented. Third, several commonly used low-temperature anode materials are briefly introduced. Fourth, recent progress in the engineering of these low-temperature anode materials is summarized in terms of structural design, morphology control, surface & interface modifications, and multiphase materials. Finally, the challenges that remain to be solved in the field of low-temperature anode materials are discussed. This review was organized to offer valuable insights and guidance for next-generation LIBs with excellent low-temperature electrochemical performance.

Key words: Low-temperature performance, Anode materials, Microstructural regulations, Surface modifications

Guan Wang, Guixin Wang, Linfeng Fei, Lina Zhao, Haitao Zhang. Structural Engineering of Anode Materials for Low-Temperature Lithium-Ion Batteries: Mechanisms, Strategies, and Prospects[J]. Nano-Micro Letters, 2024, 16(1): 150-.

Guan Wang, Guixin Wang, Linfeng Fei, Lina Zhao, Haitao Zhang. [J]. Nano-Micro Letters, 2024, 16(1): 150-.

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URL: https://www.qk.sjtu.edu.cn/nml/EN/10.1007/s40820-024-01363-y

https://www.qk.sjtu.edu.cn/nml/EN/Y2024/V16/I1/150

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Morphology regulation	Anode materials	Potential range/V	Mass loading/mg cm⁻²	Capacity/mAh g⁻¹	Current density/A g⁻¹	Test temperature/°C	Capacity retention ratio/vs. RT (%)	Electrolyte/volume ratio	References
0D	Carbon nanosphere	0.01-3.0	~ 12.4	160	0.1	− 35	20	1 M LiPF₆ in EC/DEC = 1:3	[75]
0D	Li₄Ti₅O₁₂	1.0-3.0	~ 2.1	83	0.13	− 30	51	1 M LiPF₆ in PC/DME = 1:1	[50]
0D	Li₄Ti₅O₁₂	1.1 − 2.5	~ 6.0	109	0.17	− 20	64	1 M LiPF₆ in EC/DMC = 1:1	[76]
0D	Rutile TiO₂	0.1-3.0	~ 2.0	77	0.07	− 40	24	1 M LiPF₆ in EC/DMC/DEC = 1:1:1	[77]
0D	Nanoscale Nb₂O₅	1.0-3.0	~ 1.0	121	0.01	− 75	64	5 M LiTFSI in EA/DCM = 1:4	[22]
0D	Nano SnO₂	0.01-3.0	-	423	0.2	− 30	50	1 M LiPF₆ in EC/PC/EMC = 1:1:2 with 5% FEC	[78]
0D	Ge particles	0.005−1.5	-	566	0.65	− 20	39	1.3 M LiPF₆ in EC/DEC = 3:7 with 10% FEC	[79]
1D	H₂Ti₂O₅ nanotubes	1.0 − 2.5	~ 3.0	100	0.34	− 25	50	1 M LiPF₆ in EC/DMC = 1:3	[80]
1D	Li_3.9Cr_0.3Ti_4.8O₁₂ nanofibers	1.0 − 2.5	~ 1.5	100	0.17	− 20	61	1 M LiPF₆ in EC/DEC = 1:1	[81]
1D	Ge nanowires	0.01-3.0	~ 0.06	255	1.5	− 50	22	1 M LiClO₄ in PC/DME = 7:3	[82]
2D	S/F carbon nanosheet	2.5-4.0	~ 3.0	63	0.1	− 10	46	1 M LiPF₆ in EC/DEC = 1:1 with 5% FEC	[83]
2D	MoS₂@graphene	0.01-3.0	-	720	0.1	− 20	66	1 M LiPF₆ in EC/EMC/DMC = 1:1:1	[84]
2D	PGN@CNT	0.01−1.5	~ 2.0	125	0.04	− 20 ℃	34	1 M LiPF₆ in EC/EMC/DMC = 1:1:1	[85]
2D	GeO_x@MXene	0.01−1.5	~ 1.0	334	0.24	− 40	28	1 M LiPF₆ in EC/DEC = 1:1 with 10% FEC and 2% VC	[86]
3D	graphitic tubular foam	0.005-3.0	-	136	0.04	− 20	16	1 M LiBF₄ in EC/EMC/DMC = 1:1:1	[87]
3D	Peony-like Co₃O₄	0.01-3.0	~ 0.9	1173	0.2	− 25	62	1 M LiPF₆ in EC/EMC/DMC = 1:1:1	[62]
3D	Coral-like Fe₇Se₈@C	0.01-3.0	-	462	1.0	− 25	53	1 M LiPF₆ in EC/DMC = 1:1	[88]
3D	Hollow Fe₂(MoO₄)₃	0.01-3.0	~ 5.0	281	1.0	− 20	29	1 M LiPF₆ in EC/DMC = 1:1 with 5% FEC	[89]

Morphology regulation	Anode materials	Potential range/V	Mass loading/mg cm⁻²	Capacity/mAh g⁻¹	Current density/A g⁻¹	Test temperature/°C	Capacity retention ratio/vs. RT (%)	Electrolyte/volume ratio	References
0D	Carbon nanosphere	0.01-3.0	~ 12.4	160	0.1	− 35	20	1 M LiPF₆ in EC/DEC = 1:3	[75]
0D	Li₄Ti₅O₁₂	1.0-3.0	~ 2.1	83	0.13	− 30	51	1 M LiPF₆ in PC/DME = 1:1	[50]
0D	Li₄Ti₅O₁₂	1.1 − 2.5	~ 6.0	109	0.17	− 20	64	1 M LiPF₆ in EC/DMC = 1:1	[76]
0D	Rutile TiO₂	0.1-3.0	~ 2.0	77	0.07	− 40	24	1 M LiPF₆ in EC/DMC/DEC = 1:1:1	[77]
0D	Nanoscale Nb₂O₅	1.0-3.0	~ 1.0	121	0.01	− 75	64	5 M LiTFSI in EA/DCM = 1:4	[22]
0D	Nano SnO₂	0.01-3.0	-	423	0.2	− 30	50	1 M LiPF₆ in EC/PC/EMC = 1:1:2 with 5% FEC	[78]
0D	Ge particles	0.005−1.5	-	566	0.65	− 20	39	1.3 M LiPF₆ in EC/DEC = 3:7 with 10% FEC	[79]
1D	H₂Ti₂O₅ nanotubes	1.0 − 2.5	~ 3.0	100	0.34	− 25	50	1 M LiPF₆ in EC/DMC = 1:3	[80]
1D	Li_3.9Cr_0.3Ti_4.8O₁₂ nanofibers	1.0 − 2.5	~ 1.5	100	0.17	− 20	61	1 M LiPF₆ in EC/DEC = 1:1	[81]
1D	Ge nanowires	0.01-3.0	~ 0.06	255	1.5	− 50	22	1 M LiClO₄ in PC/DME = 7:3	[82]
2D	S/F carbon nanosheet	2.5-4.0	~ 3.0	63	0.1	− 10	46	1 M LiPF₆ in EC/DEC = 1:1 with 5% FEC	[83]
2D	MoS₂@graphene	0.01-3.0	-	720	0.1	− 20	66	1 M LiPF₆ in EC/EMC/DMC = 1:1:1	[84]
2D	PGN@CNT	0.01−1.5	~ 2.0	125	0.04	− 20 ℃	34	1 M LiPF₆ in EC/EMC/DMC = 1:1:1	[85]
2D	GeO_x@MXene	0.01−1.5	~ 1.0	334	0.24	− 40	28	1 M LiPF₆ in EC/DEC = 1:1 with 10% FEC and 2% VC	[86]
3D	graphitic tubular foam	0.005-3.0	-	136	0.04	− 20	16	1 M LiBF₄ in EC/EMC/DMC = 1:1:1	[87]
3D	Peony-like Co₃O₄	0.01-3.0	~ 0.9	1173	0.2	− 25	62	1 M LiPF₆ in EC/EMC/DMC = 1:1:1	[62]
3D	Coral-like Fe₇Se₈@C	0.01-3.0	-	462	1.0	− 25	53	1 M LiPF₆ in EC/DMC = 1:1	[88]
3D	Hollow Fe₂(MoO₄)₃	0.01-3.0	~ 5.0	281	1.0	− 20	29	1 M LiPF₆ in EC/DMC = 1:1 with 5% FEC	[89]

Structural design	Anode materials	Potential range/V	Mass loading/mg cm⁻²	Capacity/mAh g⁻¹	Current density/A g⁻¹	Test temperature/°C	Capacity retention ratio/vs. RT	Electrolyte/volume ratio	References
Expanding interlayer spacing	Mesocarbon microbead	0.01−1.5	~ 3.0	100	0.08	− 40	-	-	[92]
Expanding interlayer spacing	MoS₂/carbon	0.01-3.0	~ 1.5	854	0.1	− 20	73%	1 M LiPF₆ in EC/DMC = 1:1	[63]
Expanding interlayer spacing	Ni₂Nb₃₄O₈₇	0.8-3.0	~ 1.1	207	0.04	− 10	61%	1 M LiPF₆ in EC/DMC/DEC = 1:1:1	[93]
Doping	Nb-doped Li₄Ti₅O₁₂/TiO₂	1.0 − 2.5	~ 1.5	128	0.34	− 20	86%	1 M LiPF₆ in EC/EMC/DMC = 1:1:1	[94]
Doping	Co-doped Zn₂SnO₄/graphene	0.01-3.0	~ 1.0	196	0.12	− 25	23%	1 M LiPF₆ in EC/EMC/DMC = 1:1:1	[95]
Doping	W-doped Li₄Ti₅O₁₂/TiO₂	1.0-3.0	~ 1.5	195	0.1	− 20	81%	1 M LiPF₆ in EC/EMC/DMC = 1:1:1	[96]
Doping	N-doped TiO₂/TiN/graphene	1.0-3.0	~ 1.5	211	0.1	− 20	65%	1 M LiPF₆ in EC/DMC = 1:1	[97]
Doping	La- and F-doped Li₄Ti₅O₁₂	0.5 − 2.5	-	100	0.17	− 20	57%	1 M LiPF₆ in EC/DEC = 1:1	[98]
Defects	Partially reduced TiNb₂₄O₆₂	1.0-3.0	~ 1.0	313	0.04	− 20	83%	1 M LiPF₆ in EC/DMC/DEC = 1:1:1	[99]
Defects	Dual-phase TiO₂	0.01-3.0	~ 1.0	120	0.34	− 25	48%	1 M LiPF₆ in EC/DEC = 1:1 with 5% FEC	[100]
Defects	Crumpled graphene	0.01 − 2.8	-	48	0.01	− 60	13%	1 M LiPF₆ in EC/EMC/MP = 2:6:2	[101]

Structural design	Anode materials	Potential range/V	Mass loading/mg cm⁻²	Capacity/mAh g⁻¹	Current density/A g⁻¹	Test temperature/°C	Capacity retention ratio/vs. RT	Electrolyte/volume ratio	References
Expanding interlayer spacing	Mesocarbon microbead	0.01−1.5	~ 3.0	100	0.08	− 40	-	-	[92]
Expanding interlayer spacing	MoS₂/carbon	0.01-3.0	~ 1.5	854	0.1	− 20	73%	1 M LiPF₆ in EC/DMC = 1:1	[63]
Expanding interlayer spacing	Ni₂Nb₃₄O₈₇	0.8-3.0	~ 1.1	207	0.04	− 10	61%	1 M LiPF₆ in EC/DMC/DEC = 1:1:1	[93]
Doping	Nb-doped Li₄Ti₅O₁₂/TiO₂	1.0 − 2.5	~ 1.5	128	0.34	− 20	86%	1 M LiPF₆ in EC/EMC/DMC = 1:1:1	[94]
Doping	Co-doped Zn₂SnO₄/graphene	0.01-3.0	~ 1.0	196	0.12	− 25	23%	1 M LiPF₆ in EC/EMC/DMC = 1:1:1	[95]
Doping	W-doped Li₄Ti₅O₁₂/TiO₂	1.0-3.0	~ 1.5	195	0.1	− 20	81%	1 M LiPF₆ in EC/EMC/DMC = 1:1:1	[96]
Doping	N-doped TiO₂/TiN/graphene	1.0-3.0	~ 1.5	211	0.1	− 20	65%	1 M LiPF₆ in EC/DMC = 1:1	[97]
Doping	La- and F-doped Li₄Ti₅O₁₂	0.5 − 2.5	-	100	0.17	− 20	57%	1 M LiPF₆ in EC/DEC = 1:1	[98]
Defects	Partially reduced TiNb₂₄O₆₂	1.0-3.0	~ 1.0	313	0.04	− 20	83%	1 M LiPF₆ in EC/DMC/DEC = 1:1:1	[99]
Defects	Dual-phase TiO₂	0.01-3.0	~ 1.0	120	0.34	− 25	48%	1 M LiPF₆ in EC/DEC = 1:1 with 5% FEC	[100]
Defects	Crumpled graphene	0.01 − 2.8	-	48	0.01	− 60	13%	1 M LiPF₆ in EC/EMC/MP = 2:6:2	[101]

Modification strategies	Anode materials	Potential range/V	Mass loading/mg cm⁻²	Capacity/mAh g⁻¹	Current density/A g⁻¹	Test temperature/°C	Capacity retention ratio/vs. RT (%)	Electrolyte/volume ratio	References
Surface coating	Carbon-coated natural graphite	0.005 − 2.5	~ 5	106	0.5	− 10	30	1 M LiPF₆ in EC/DEC = 3:7	[107]
Surface coating	Carbon-coated Li₄Ti₅O₁₂	1.0 − 2.5	-	150	0.17	− 20	71	1 M LiPF₆ in EC/DEC = 1:1	[108]
Surface coating	Carbon-coated modified graphite	0.001−1.5	~ 3	310	0.04	0	86	1 M LiPF₆ in EC/EMC = 1:1	[109]
Surface coating	Surface-fluorinated Li₄Ti₅O₁₂	1.0 − 2.5	~ 1.1	100	0.17	− 20	60	1 M LiPF₆ in EC/EMC = 3:7	[110]
Surface coating	Surface-fluorinated Li₄Ti₅O₁₂	1.0-3.0	-	65	0.17	− 20	42	1.2 M LiPF₆ in EC/EMC = 3:7	[111]
Surface coating	Sn-coated graphite	0.01−1.5	~ 2.5	152	0.08	− 30	41	1 M LiPF₆ in EC/DEC/DMC = 1:1:1	[112]
Interface modification	TiO₂(B)/ graphite	1.0-3.0	~ 1	106	2	− 30	53	1 M LiBF₄ in EC/PC/EMC = 1:2:7 with 1% FEC	[113]
Interface modification	SnO₂/LiF/graphite	0.01-3.0	~ 1	637	0.1	− 50	67	1 M LiPF₆ in EC/PC/EMC = 1:1:8 with 5% FEC	[114]
Interface modification	Sulfide-rich SiO/C	3.0-4.2	~ 2.6	135	0.02	− 20	73	1 M LiPF₆ in EC/DMC = 1:1	[115]
Interface modification	Ti₃C₂T_x MXene	0.01-3.0	-	213	0.2	− 10	47	1 M LiBF₄ in EC/DE/DMC = 1:1:1	[56]
Interface modification	Ti₃C₂T_x MXene	0.01-3.0	~ 2	226	0.1	− 20	56	1 M LiPF₆ in EC/DEC = 1:1	[116]

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