Application of Ag-based materials in high-performance lithium metal anode: A review

doi:10.1016/j.jmst.2022.06.015

Abstract

Abstract:

Li metal is a promising candidate for battery anodes due to its high theoretical specific capacity (3860 mAh g⁻¹) and low electrochemical potential (−3.04 V). Nevertheless, the challenges for Li metal include uncontrolled dendrites growth, unstable solid electrolyte interface, and infinite volume expansion during Li plating and stripping, which limit the further development of lithium metal anodes (LMAs). Introducing Ag-based materials in LMAs is regarded as one of the most effective solutions to solve the above-mentioned problems, which have received considerable attention because of their superior characteristics, such as high electrical conductivity, outstanding lithiophilicity, and excellent mechanical stability. Herein, we review the recent progress on the application of Ag-based materials in LMAs. Furthermore, the theoretical mechanism of Ag-based materials and their advantages in LMAs are emphasized. In addition, the relationship between their fabrication strategies, micro/nanostructures, and electrochemical performances is systematically discussed. Finally, the challenges and opportunities for the future research and application of Ag-based materials in lithium metal batteries are proposed based on the available academic knowledge.

Key words: Ag-based materials, Nucleation sites, Current collectors, Lithium metal anodes, Electrochemical performance

Zhongxiu Liu, Sihu Ha, Yong Liu, Fei Wang, Feng Tao, Binrui Xu, Renhong Yu, Guangxin Wang, Fengzhang Ren, Hongxia Li. Application of Ag-based materials in high-performance lithium metal anode: A review[J]. J. Mater. Sci. Technol., 2023, 133: 165-182.

Figures/Tables 14

Fig. 1. Timeline of various Ag-based materials for lithium metal anode. Images of Ag nanoparticles homogeneously anchored on the CNF substrate [47] (Reproduced with permission. copyright 2017, Wiley-VCH), Ag nanocrystals anchored on rGO sheets [48] (Reproduced with permission. Copyright 2018, Royal Society of Chemistry), fabrication process of Cu-Ag sample [49] (Reproduced with permission. Copyright 2019, American Chemical Society), synthesis process of Ag-doped lithium [50] (Reproduced with permission. Copyright 2020, Royal Society of Chemistry), and synthesis process of the Ag and stainless steel mesh composite [51] (Reproduced with permission. Copyright 2021, Wiley-VCH).

Fig. 2. (a) Li-Ag phase diagram [50] (Reproduced with permission. Copyright 2020, Royal Society of Chemistry). (b) Contact angle of bare lithium sample and Ag/Li electrode [53] (Reproduced with permission. Copyright 2019, Royal Society of Chemistry). (c) XRD spectra of different molar ratios of pristine lithium and Ag-doped lithium. (d) Structural characterizations of Ag-doped lithium. (e) DFT calculation of binding energies (Eb) for positioning pristine Li and Ag dopants on lithium surface. (f) XANES and (g) EXAFS patterns of Ag-doped Li anodes [50]. (Reproduced with permission Copyright 2020, Royal Society of Chemistry)

Fig. 3. (a) In-situ optical microscopy spectra for delithiation of AgLi anodes. (b) 3D profilometry image of lithium electrode [37] (Reproduced with permission. Copyright 2021, Wiley-VCH). Binding energies of Li atoms (c) with Ag atoms and (d) with Cu atoms [48] (Reproduced with permission. Copyright 2018, Royal Society of Chemistry).

Scheme 1. Advantages and applications of Ag-based materials in lithium metal anodes.

Table 1. Summary of synthetic methods and the battery performance of Li metal anodes enhanced by various Ag-based materials.

Material	Synthetic methods	Voltage hysteresis V^a (V)(C₁^c (mA cm^-2))	Lifespan T^b (h) [C₁^c (mA cm^-2), C₂^c (mAh cm^-2)]	Refs.
Li host modification
Ag-WDC	Dip coating method	30 (1)	450 (1, 1)	[42]
AgNP/CNFs	Joule heating method	25 (0.5)	500 (0.5,1)	[47]
AgNCs@GA	Hydrothermal method	18 (1)	100 (2, 1)	[48]
CF/Ag-Li	Electroplating method	60 (1)	320 (10, 10)	[54]
3D-AGBN	Blade coating method	60 (5)	120 (5, 1)	[57]
MS@AgNW	Hydrothermal method	19 (2)	1000 (2, 1)	[58]
MCNF/Ag-Li	Electrospinning method	26 (1)	600 (1, 1)	[67]
CC-Ag	Thermal evaporation	100 (0.2)	500 (1, 5)	[68]
CC/Ag/Li	Thermal evaporation	25 (1)	750 (1, 1)	[69]
Ag-NCNS	Heat treatment method	15 (0.5)	2000 (1, 1)	[70]
MXene/AgNW	Blade coating method	20 (20)	3000 (20, 10)	[71]
3D-Ag aerogel	Hydrothermal method	59 (0.5)	1589 (0.5, 2)	[72]
Ag@CMFs	Multistep templating	20 (5)	1000 (1, 1)	[73]
Ag₁₄@NC	Hydrothermal method	100 (1)	800 (1, 1)	[74]
AgNPs@GO	Spray coating method	32 (0.25)	1000 (0.25, 0.5)	[75]
GO-Ag	Infusion coating method	25 (1)	200 (3, 1)	[76]
Ag-rGO	Ray irradiation method	/	200 (1, 2)	[77]
Ag-NOCP	Electroplating method	50 (1)	1400 (1, 1)	[78]
PB-Ag	Dip coating method	70 (1)	400 (1, 1)	[79]
a-AZCH	Co-precipitation method	25 (0.5)	1500 (0.5, 0.5)	[80]
Ag/N-rGO	Blade-coating method	22 (2)	1500 (2, 1)	[81]
Modifying current collector
Ag/PVDF	Electrospinning method	100 (4)	1300 (4, 4)	[41]
Ag@HTO	Mirror reaction method	15 (1)	100 (1, 1)	[44]
CuAg-1.5	Electroless plating method	35 (1)	360 (1, 1)	[49]
Cu-Ag@Li	Spray coating method	18 (1)	900 (1, 1)	[59]
3D Cu@Ag	Galvanic displacement	42 (1)	210 (1, 1)	[60]
TNT-Ag	Cathodic reduction method	12 (1)	2500 (1, 2)	[61]
Ag@HKUST	Ethanol reduction method	9 (0.05)	300 (0.5, 1)	[62]
Cu@Ag foam	Electrodepositing method	15 (5)	3000 (5, 15)	[82]
Ag-Cu	Dip coating method	80 (1)	400 (1, 1)	[83]
Ag@Cu foam	Plating technique method	47 (0.5)	400 (2, 1)	[84]
3D Ni-Ag₂S	Cotton template method	40 (3)	267 (3, 1)	[85]
Li-ANCF	Dip coating method	24 (1,1)	800 (1, 1)	[86]
Ag@PDA-GO	Spin coating method	8.2 (1)	250 (0.5, 1)	[87]
Ag@Cu	Thermal evaporation	/	400 (0.5, 1)	[88]
Li/Ag@Cu	Dip coating method	6 (5)	1000 (1, 1)	[89]
Ag-Li₃N-Cu	Dip coating method	/	200 (0.5, 1)	[90]
Ag@NCHSs	A one-pot reduction method	/	400 (1, 1)	[91]
Ag@CF	Dip coating method	30 (1)	1600 (1, 1)	[92]
Decorating Li metal surface
Ag@Li	Evaporation method	38 (5)	250 (1, 1)	[32]
D-Ag@Li	Rolling method	16 (2)	1350 (1, 1)	[51]
Ag/Li	Drop coating method	70 (5)	1000 (5, 1)	[53]
Li-Ag-LiF	Drop coating method	50 (0.5)	1000 (0.5, 1)	[63]
Ag-Li	Dip coating method	85 (1)	900 (1, 1)	[64]
Other strategies
AgPF₆-LiNO₃	Electroless deposition	20 (0.5)	3000 (0.5, 0.5)	[31]
NP AgLi	Melting-rolling method	37(0.5)	800 (0.5, 0.5)	[37]
Ag@WSe₂	Cold press method	36 (0.1)	600 (0.1, 0.05)	[40]
Ag-doped Li	Melt impregnation method	130 (5)	600 (5, 10)	[50]
AgNWs@SiO₂	electrospinning method	55 (0.1)	500 (0.1, 1)	[65]
Ag-PCNFs-PP	Slurry-coating method	30 (0.5)	1500 (2, 2)	[66]
Li_92.5Cu₅Ag_2.5	Melting-rolling method	10 (0.5)	1200 (0.5, 0.5)	[93]

Table 1. Summary of synthetic methods and the battery performance of Li metal anodes enhanced by various Ag-based materials.

Material	Synthetic methods	Voltage hysteresis V^a (V)(C₁^c (mA cm^-2))	Lifespan T^b (h) [C₁^c (mA cm^-2), C₂^c (mAh cm^-2)]	Refs.
Li host modification
Ag-WDC	Dip coating method	30 (1)	450 (1, 1)	[42]
AgNP/CNFs	Joule heating method	25 (0.5)	500 (0.5,1)	[47]
AgNCs@GA	Hydrothermal method	18 (1)	100 (2, 1)	[48]
CF/Ag-Li	Electroplating method	60 (1)	320 (10, 10)	[54]
3D-AGBN	Blade coating method	60 (5)	120 (5, 1)	[57]
MS@AgNW	Hydrothermal method	19 (2)	1000 (2, 1)	[58]
MCNF/Ag-Li	Electrospinning method	26 (1)	600 (1, 1)	[67]
CC-Ag	Thermal evaporation	100 (0.2)	500 (1, 5)	[68]
CC/Ag/Li	Thermal evaporation	25 (1)	750 (1, 1)	[69]
Ag-NCNS	Heat treatment method	15 (0.5)	2000 (1, 1)	[70]
MXene/AgNW	Blade coating method	20 (20)	3000 (20, 10)	[71]
3D-Ag aerogel	Hydrothermal method	59 (0.5)	1589 (0.5, 2)	[72]
Ag@CMFs	Multistep templating	20 (5)	1000 (1, 1)	[73]
Ag₁₄@NC	Hydrothermal method	100 (1)	800 (1, 1)	[74]
AgNPs@GO	Spray coating method	32 (0.25)	1000 (0.25, 0.5)	[75]
GO-Ag	Infusion coating method	25 (1)	200 (3, 1)	[76]
Ag-rGO	Ray irradiation method	/	200 (1, 2)	[77]
Ag-NOCP	Electroplating method	50 (1)	1400 (1, 1)	[78]
PB-Ag	Dip coating method	70 (1)	400 (1, 1)	[79]
a-AZCH	Co-precipitation method	25 (0.5)	1500 (0.5, 0.5)	[80]
Ag/N-rGO	Blade-coating method	22 (2)	1500 (2, 1)	[81]
Modifying current collector
Ag/PVDF	Electrospinning method	100 (4)	1300 (4, 4)	[41]
Ag@HTO	Mirror reaction method	15 (1)	100 (1, 1)	[44]
CuAg-1.5	Electroless plating method	35 (1)	360 (1, 1)	[49]
Cu-Ag@Li	Spray coating method	18 (1)	900 (1, 1)	[59]
3D Cu@Ag	Galvanic displacement	42 (1)	210 (1, 1)	[60]
TNT-Ag	Cathodic reduction method	12 (1)	2500 (1, 2)	[61]
Ag@HKUST	Ethanol reduction method	9 (0.05)	300 (0.5, 1)	[62]
Cu@Ag foam	Electrodepositing method	15 (5)	3000 (5, 15)	[82]
Ag-Cu	Dip coating method	80 (1)	400 (1, 1)	[83]
Ag@Cu foam	Plating technique method	47 (0.5)	400 (2, 1)	[84]
3D Ni-Ag₂S	Cotton template method	40 (3)	267 (3, 1)	[85]
Li-ANCF	Dip coating method	24 (1,1)	800 (1, 1)	[86]
Ag@PDA-GO	Spin coating method	8.2 (1)	250 (0.5, 1)	[87]
Ag@Cu	Thermal evaporation	/	400 (0.5, 1)	[88]
Li/Ag@Cu	Dip coating method	6 (5)	1000 (1, 1)	[89]
Ag-Li₃N-Cu	Dip coating method	/	200 (0.5, 1)	[90]
Ag@NCHSs	A one-pot reduction method	/	400 (1, 1)	[91]
Ag@CF	Dip coating method	30 (1)	1600 (1, 1)	[92]
Decorating Li metal surface
Ag@Li	Evaporation method	38 (5)	250 (1, 1)	[32]
D-Ag@Li	Rolling method	16 (2)	1350 (1, 1)	[51]
Ag/Li	Drop coating method	70 (5)	1000 (5, 1)	[53]
Li-Ag-LiF	Drop coating method	50 (0.5)	1000 (0.5, 1)	[63]
Ag-Li	Dip coating method	85 (1)	900 (1, 1)	[64]
Other strategies
AgPF₆-LiNO₃	Electroless deposition	20 (0.5)	3000 (0.5, 0.5)	[31]
NP AgLi	Melting-rolling method	37(0.5)	800 (0.5, 0.5)	[37]
Ag@WSe₂	Cold press method	36 (0.1)	600 (0.1, 0.05)	[40]
Ag-doped Li	Melt impregnation method	130 (5)	600 (5, 10)	[50]
AgNWs@SiO₂	electrospinning method	55 (0.1)	500 (0.1, 1)	[65]
Ag-PCNFs-PP	Slurry-coating method	30 (0.5)	1500 (2, 2)	[66]
Li_92.5Cu₅Ag_2.5	Melting-rolling method	10 (0.5)	1200 (0.5, 0.5)	[93]

Fig. 4. (a) Schematic of the formation of CF/Ag-Li composite electrode; scanning electron microscopy (SEM) images and digital photographs of pristine CF, CF with Ag layer, CF/Ag with molten Li, and metallic Li fully infused in the CF framework. (b) Electrochemical performance of CF/Ag-Li/Li and Li/Li cells [54] (Reproduced with permission. Copyright 2018, Elsevier). (c) Schematics of Li nucleation and growth on Ag modified CNFs. SEM images of pristine AgNP/CNFs, Li nucleation and growth on AgNP/CNFs, and Li deposited on AgNP/CNFs after cycled. (d) Cycling performance of AgNP/CNFs Li anode [47] (Reproduced with permission. Copyright 2017, Wiley-VCH).

Fig. 5. (a) Schematic of the synthetic process and the optical images of AgNCs@GA. (b) Coulombic efficiency of AgNCs@GA-modified electrode [48] (Reproduced with permission. Copyright 2018, Royal Society of Chemistry). (c) Schematic of the fabrication process of the G-Ag aerogel. (d) SEM images of the G-Ag aerogel. (e) Electrochemical performance of the G-Ag aerogel [72] (Reproduced with permission. Copyright 2019, Wiley-VCH).

Fig. 6. (a) Fabrication process of the 3D MS@AgNWs host. (b) Schematic illustration of MS@AgNWs host with the Li-plating process. (c) Coulombic efficiency of MS@AgNWs and Cu foil electrodes. (d) Cycling stability of MS@AgNWs-Li anodes in symmetric cells [58] (Reproduced with permission. Copyright 2020, American Chemical Society).

Fig. 7. (a) Synthesis process for preparing the Ag modified Cu-collector. (b) SEM image of pure Cu and Ag modified collector. (c) Optical photographs before and after fabricating the Ag-modified Cu collector. (d) Coulombic efficiency of Li|Cu and Li|Cu-Ag cells [59] (Reproduced with permission. Copyright 2020, Wiley-VCH). (e) Schematic process of fabricating Ag@HKUST-1 and Li deposition. (f) Cycling performance of Ag@HKUST-1 modified Cu [62] (Reproduced with permission. Copyright 2019, American Chemical Society).

Fig. 8. (a) Schematic of the surface activation and lithium plating processes for the 3D-Cu@Ag electrode. (b) Schematic of the Li plating process. (c) SEM patterns of the 3D-Cu@Ag anode and optical photograph of the electrode after Li plating [60] (Reproduced with permission. Copyright 2019, Royal Society of Chemistry).

Fig. 9. (a) Fabrication process of 3D TNT-Ag scaffolds and Li deposition. (b) SEM images of TNT-Ag [61] (Reproduced with permission. Copyright 2020, Wiley-VCH). (c) Schematic illustration of the Ag modified anode. (d) Cross-sectional SEM images of lithium deposition. (e) Rate capability of ASSBs at 60? °C and (f) coulombic efficiency of the Ag-C|SSE|NMC pouch cell [107] (Reproduced with permission. Copyright 2020, Springer Nature).

Fig. 10. (a) Schematics of the Ag/Li composite anode fabrication process. (b) SEM of Ag/Li hybrid anode after 10 cycles. (c) Voltage profiles of symmetric cells [53] (Reproduced with permission. Copyright 2019, Royal Society of Chemistry). (d) Schematic of the preparation process of the d-Ag@Li anode. (e) SEM images of d-Ag@Li at plating status after 10 cycles and (f) long cyclic performance of d-Ag@Li composite anodes in symmetric cells [51] (Reproduced with permission. Copyright 2021, Wiley-VCH).

Fig. 11. (a) Surface optical photos of silver-doped lithium electrodes and (b) XRD/SEM results of Ag-doped lithium electrodes after exposed 90 days in the air. (c) Cycling performance of NMC 811 cells. (d) SEM images for Ag-doped Li electrodes after cycling. [50] (Reproduced with permission. Copyright 2020, Royal Society of Chemistry). (e) Illustration of the preparation process for nanoporous AgLi electrodes. (f) Electrochemical performance of NPAgLi anodes. (g) SEM of AgLi composite anode after lithium delithiation [37] (Reproduced with permission. Copyright 2021, Wiley-VCH).

Fig. 12. (a) Schematic of the Ag@WSe2-LLZO interface under cycling. (b) XPS spectra of Ag 3d for the Ag@WSe2-LLZO surface before and after cycling. (c) Cross-section SEM of the Li/Ag@WSe2-LLZO interface before and (d) after 600 cycles. (e) Cycling performance of Ag@WSe2-LLZO | LFP cell [40] (Reproduced with permission. Copyright 2020, Elsevier).

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