Acta Phys. -Chim. Sin. ›› 2022, Vol. 38 ›› Issue (6): 2103052.doi: 10.3866/PKU.WHXB202103052
Special Issue: Surface and Interface Engineering for Electrochemical Energy Storage and Conversion
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Research Progresses on Structural Optimization and Interfacial Modification of Silicon Monoxide Anode for Lithium-Ion Battery
Siying Zhu1, Huiyang Li1, Zhongli Hu1, Qiaobao Zhang2,*(
), Jinbao Zhao1, Li Zhang1,*()
- 1 College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian Province, China
2 College of Materials, Xiamen University, Xiamen 361005, Fujian Province, China
-
Received:2021-03-24Accepted:2021-04-25Published:2021-04-29 -
Contact:Qiaobao Zhang,Li Zhang E-mail:zhangqiaobao@xmu.edu.cn;zhangli81@xmu.edu.cn -
About author:Li Zhang, Email: zhangli81@xmu.edu.cn (L.Z.)
Qiaobao Zhang, Email: zhangqiaobao@xmu.edu.cn (Q.Z.)
-
Supported by:the National Natural Science Foundation of China(21875155);the National Natural Science Foundation of China(52072323)
Cite this article
Siying Zhu, Huiyang Li, Zhongli Hu, Qiaobao Zhang, Jinbao Zhao, Li Zhang. Research Progresses on Structural Optimization and Interfacial Modification of Silicon Monoxide Anode for Lithium-Ion Battery[J]. Acta Phys. -Chim. Sin. 2022, 38(6), 2103052. doi: 10.3866/PKU.WHXB202103052
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Fig 1
(a) Experimental/simulated ABED from SiO local structures and atomic models of amorphous Si, silicon suboxide and amorphous SiO2; (b) the model of amorphous SiO; (c) fractions of the five atomic coordinates existing in amorphous SiO: the Si–Si4 is from the Si clusters; the Si–O4 is from the SiO2 matrix; the Si–(Si3O), Si–(Si2O2), and Si–(SiO3) are from the Si/SiO2 interfaces 32. Adapted with permission from Ref. 32, Copyright 2016, Springer."
Fig 2
HRTEM images and SAED patterns of the SiO electrodes discharged to (a) 0.21 V, (b) 0.14 V, and (c) 0.0 V; (d) the schematic model of the SiO electrode reacting with Li 36. Adapted with permission from Ref. 36, Copyright 2011, Elsevier."
Fig 3
(a) Schematic Illustration of SiO Anode during repeated lithiation-delithiation cycles; (b) Li diffusivity and capacity values of different matrix components in SiO anode during lithiation; (c) crystal structures of Li15Si4, Li2Si2O5, Li6Si2O7, Li4SiO4, and Li2O, the yellow, blue, and red balls represent the Li, Si, and O atoms, respectively 37."
Fig 4
(a) Schematic illustration of the concept and preparation of m-SiO; (b) XRD patterns of SiO, d-SiO, and m-SiO; (c) SEM images of m3-SiO and m10-SiO; (d) bright field, high-resolution TEM images, and SAED patterns of SiO and d-SiO, bright field and dark field TEM images of m10-SiO; (e) voltage profiles of d-SiO, m3-SiO, and m10-SiO electrodes for the first cycle; (f) the comparisons of the cyclabilities for the SiO, m3-SiO and m10-SiO electrodes 39. Adapted with permission from Ref. 39, Copyright 2013, Elsevier."
Fig 5
(a, b) SEM, (c) TEM and (d) HRTEM images of the SiO@F-doped C composite obtained by annealing the mixture of SiO and PTFE with a mass ratio of 5:3 at 650 ℃; (e) charge-discharge profiles of the annealed SiO and (f) SiO@F-doped C obtained by annealing the mixture of SiO and PTFE with a mass ratio of 5:3 at 650 ℃ in the first three cycles at 100 mA·g-1; (g) cycling performance profiles of the annealed SiO and SiO@F-doped C obtained by annealing the mixture of SiO and PTFE with a mass ratio of 5:3 at 650 ℃ at 400 mA·g-1; (h) rate capability of the annealed SiO and SiO@F-doped C 44. Adapted with permission from Ref. 44, Copyright 2018, Elsevier."
Table 1
Electrochemical performances of SiO materials modified by downsizing."
| Sample | Initial discharge/charge specific capacity (mAh·g-1) | ICE (%) | Cycling performance (mAh·g-1) | Current density | Particle size | Year | Ref. |
| SiO/Graphite | 951.1/770.4 | 81 | 762.0 (50 cycles) | 0.1C | – | 2007 | 38 |
| SiO/C | 1050/800 | 76 | 710 (100 cycles) | – | 0.5–3 μm | 2007 | 40 |
| SiO/Graphite | 1556/693 | 44.5 | 688 (30 cycles) | – | 5–20 μm | 2008 | 41 |
| SiO/CNF | 2027/724 | 35.7 | 675 (200 cycles) | 0.1C | 0.1–1 μm | 2011 | 42 |
| SiO | 1779/1002 | 56.3 | 1000 (50 cycles) | 100 mA·g-1 | < 10 μm | 2013 | 39 |
| F-doped SiO@C | 1518/1050 | 70 | 975 (100 cycles) | 400 mA·g-1 | 2018 | 44 |
Fig 6
(a) SEM image of a coating layer of Ag on the surface of SiO via a galvanic displacement reaction; (b) SEM image of the etching of SiO particles in a chemical etchant of HF/H2O2; (c) SEM image of porous SiO obtained after the removal of the Ag catalyst in a strong nitric acid; (d) graphs of the chemical etching process at three different Ag deposition and chemical etching times; (e) schematic illustration of the synthetic route for preparing the porous SiO using Ag catalytic etching; (f, g) SEM image of porous SiO carbon-coated by a thermal decomposition of acetylene gas; (h) electrochemical performances of c-porous SiO anodes at 0.1C rate 47. Adapted with permission from Ref. 47, Copyright 2012, Elsevier."
Fig 7
(a) Characterization of the mp-SiO@N-doped C rods: SEM images (Ⅰ–Ⅲ), EDS hierarchical image (Ⅳ), and TEM images (V, VI), (b) cyclic voltammetry curves at 0.2 mV·s-1; (c) charge-discharge profiles in the first three cycles at 400 mA·g-1 of the mp-SiO@N-doped C rods; (d) cycling performance profiles of different samples at 400 mA·g-1 and (e) rate capability of the annealed SiO, SiO@N-doped C rods and mp-SiO@N-doped C rods 49. Adapted with permission from Ref. 49, Copyright 2017, Elsevier."
Table 2
Electrochemical performances of SiO materials modified with porous structure."
| Sample | Initial discharge/charge specific capacity/(mAh·g-1) | ICE (%） | Cycling performance (mAh·g-1） | Current density | Particle size | Pore size | Year | Ref. |
| p-SiO | 2250/1350 | 60 | – | 0.1C | – | – | 2012 | 46 |
| p-SiO@C | 1990/1520 | 76.4 | 1490 (50 cycles) | 0.1C | – | – | 2013 | 47 |
| p-SiO | 2653/1709 | 64.4 | 1242 (100 cycles) | 0.2C | < 20 μm | 75.2 nm | 2013 | 48 |
| mp-SiO@N-doped C | 1202/790 | 65.7 | 806 (250 cycles) | 400 mA·g-1 | < 400 nm | v | 2018 | 49 |
| p-SiO@C | – | 87 | 839.6 (110 cycles) | 500 mA·g-1 | ~60 μm | 6.67 nm | 2020 | 50 |
| p-SiO@C | ~1600/~1000 | 62 | 900 (200 cycles) | 1000 mA·g-1 | – | 2–15 nm | 2020 | 51 |
Fig 8
(a) Schematic illustration of preparation of SiO@C; (b) SEM images and TEM images of SiO@C-L (left), SiO@C-M (middle), and SiO@C-H (right); (c) top: Cycling performance at 0.1C and rate performance of SiO@C-L (green line), SiO@C-M (red line), SiO@C-H (blue line), and bare SiO (black line); bottom: long-term cycling performance of SiO@C-L 66. Adapted with permission from Ref. 66, Copyright 2018, Elsevier."
Fig 9
(a) Schematic chart of the fabrication for SiO/NPC; (b) schematic of nitrogen atoms and phosphorus atoms replacing carbon atoms; (c) cross-sectional SEM images of the fresh electrodes and the electrode after 200 cycles for SiO (left), SiO/NC (middle) and SiO/NPC (right); (d) electrochemical performance profiles of the SiO, H-SiO, SiO/NC and SiO/NPC 71. Adapted with permission from Ref. 71, Copyright 2020, Elsevier."
Fig 10
(a) Scheme of the synthetic process of the SiOx/C (SC) composite from bamboo charcoal; (b) TEM images (top), HRTEM image (middle left) of the SC composite, elemental mapping images of SC-3 (middle right) and SEM images of the SC-3 composite (bottom); (c) electrochemical performance profiles of different samples at a current density of 200 mA·g-1; (d) cycling performance of SC-3 at a current density of 1000 mA·g-1, inset: SEM images of the SC-3 electrode fabricated on copper foil before (Ⅰ, Ⅱ) and after (Ⅲ, Ⅳ) cycling for 300 cycles at a current density of 200 mA·g-1 74. Adapted with permission from Ref. 74, Copyright 2020, Elsevier."
Table 3
Electrochemical performances of carbon-coating SiO materials synthesized by wet chemical method."
| Sample | Carbon precursor | Synthesis method | Initial discharge/charge specific capacity (mAh·g-1) | ICE (%) | Cycling Performance (mAh·g-1) | Current density | Particle size | Coating thickness | Conductive property | Year | Ref. |
| NC-SiO | EMI-DCA ion liquid | High-temperature carbonization | 2024/1496 | 73.9 | 955 (100 cycles) | 1C | – | 20–30 nm | – | 2013 | 70 |
| SCG-5 | Aniline, Graphite | In situ polymerization, Annealing | 801/545 | 68 | 432 (500 cycles) | 0.8C | 1–10 μm | – | – | 2017 | 64 |
| SiO@C | Sodium dodecyl benzene sulfonate | Electrostatic force adsorption, Calcination | 2205/1142 | 51.8 | 1085 (100 cycles) | 0.1C | 6 μm | 7 nm | R = 329 Ω·sq-1 | 2018 | 66 |
| TC-SiO | Tetrabutyl titanate, Coal tar pitch | Calcination | 1741/1252 | 71.9 | 674.5 (100 cycles) | 0.14 A·g-1 | 5–10 μm | 4 nm | Rct = 31.3 Ω | 2018 | 65 |
| SiO/NC | Melamine, Citric acid | Magnetic stirring, Sinter | 1280/920 | 71 | 834 (150 cycles) | 1000 mA·g-1 | – | 15–20 nm | Rct = 64.28 Ω | 2019 | 68 |
| SiO/NPC | Melamine, Phosphoric acid, Gelatin | Magnetic stirring, Sinter | 1698/1223 | 72 | 847 (200 cycles) | 1000 mA·g-1 | – | 25–30 nm | Rct = 33 Ω | 2020 | 71 |
| SiO/C | Glucose | Ball-milling, Calcination | 1751/1259 | 71.9 | 850 (100 cycles) | 200 mA·g-1 | – | – | – | 2020 | 72 |
| SiO/C/G | Asphalt, Graphite | Ball-milling, Spray drying, Pyrolysis | 1509/963 | 63.8 | 950 (100 cycles) | 100 mA·g-1 | 15 μm | ~10 nm | – | 2020 | 73 |
| SC-3 | Bamboo charcoal | Ball-milling, Calcination, Aluminothermic reduction | 2308/1260 | 56.3 | 1100 (300 cycles) | 200 mA·g-1 | – | – | – | 2020 | 74 |
Fig 11
(a) SEM (top) and TEM (bottom) images of sample SiO/1D-C/α-C; (b) TEM images of samples S-600 and S-900; (c) related mechanism of pristine SiO and SiO/1D-C/α-C electrodes during cycling and SEM images of the surface morphology in pristine SiO, S-600, S-900 and SiO/1D-C/α-C electrodes after cycling tests; (d) schematic diagram of the carbon deposition mechanism via FBCVD; (e) initial charge/discharge profiles and (f) cycling performances of pristine SiO, S-600, S-900 and SiO/1D-C/α-C at 0.1 A·g-1 79. Adapted with permission from Ref. 79, Copyright 2020, Elsevier."
Fig 12
(a) Schematic diagram showing preparation process of the d-SiO/C@NCNBs; (b) microstructure and elemental composition of the d-SiO/C@NCNBs; (c) SEM images of the d-SiO/C@NCNBs sample; (d) cycle performances and rate performances of d-SiO/C and d-SiO/C@NCNBs 80. Adapted with permission from Ref. 80, Copyright 2020, Elsevier."
Fig 13
(a) Schematic illustration for synthesizing SiOx@NC; (b) HAADF-STEM images, EDS spectra and mappings of SiOx@NC; (c) electrochemical performances of different samples 83. Adapted with permission from Ref. 83, Copyright 2017, Royal Society of Chemistry."
Table 4
Electrochemical performances of carbon-coating SiO materials synthesized by dry chemical method."
| Sample | Carbon precursor | Synthesis method | Initial discharge/ charge specific capacity (mAh·g-1) | ICE(%) | Cycling performance (mAh·g-1) | Current density | Particle size | Coating thickness | Conductive property | Year | Ref. |
| d-SiO@vG | CH4 | CVD | – | – | 1600 (100 cycles) | – | – | – | R = 200 Ω·sq-1 | 2017 | 75 |
| SiO/CNT/C | C2H2, Asphalt | CVD | 1259/1083 | 86 | 821.7 (200 cycles) | 1 A·g-1 | 10–20 μm | – | Rct = 82.6 Ω | 2019 | 76 |
| SiO/C | CH4 | FTCVD | 1463/1200 | 82 | 501 (300 cycles) | 1.2 A·g-1 | 6–7 μm | 50 nm | Rct = 53.39 Ω | 2019 | 77 |
| SiO/Graphite/C | Graphite, CH4 | FTCVD | 930/800 | 86 | 799.1 (100 cycles) | 200 mA·g-1 | 12 μm | – | Rct = 14.55 Ω | 2019 | 78 |
| SiO/1D-C/α-C | C2H2 | FBCVD | 1445/1012 | 70 | 893.6 (120 cycles) | 0.1 A·g-1 | – | 100 nm | Rct = 170 Ω | 2020 | 79 |
| d-SiO/C @NCNB | C2H2, Hydroquinone, HCHO | CVD, Heat-treatment, Carbonization | 1375/1004 | 73 | 1043 (100 cycles) | 0.1C | 5–18 μm | – | – | 2020 | 80 |
| SiO/G/CNT | Graphite, CH4 | Ball-milling, CVD | 789/513 | 65 | 495 (100 cycles) | 230 mA·g-1 | 3 μm | – | Rct = 44.16 Ω | 2011 | 81 |
| Si/SiOx/C-3 | Graphite | Ball-milling | 882/649 | 73.6 | 726 (500 cycles) | 0.1 A·g-1 | – | – | – | 2017 | 82 |
| SiOx@NC | m-Phenylenediamine, Hexamethylenetetr amine, Pluronic F127 | Ball-milling, Grinding, Annealing | 1309/774 | 59.1 | 709 (100 cycles) | 200 mA·g-1 | 200–300 nm | 40 nm | – | 2020 | 83 |
Table 5
Comparison of wet and dry chemical carbon coating."
| Carbon precursor | Synthesis methods | Advantages | Disadvantages | |
| Wet chemical carbon coating | Organic solvents, ionic liquid | Stirring under heating, calcination | Abundant and cheap carbon sources; Simple and low-cost process; Various fabricating methods | The structure of carbon coat unlikely to be controlled due to the reactions in solvents; Consequent calcination after wet reaction increasing the whole cost; Toxic liquids produced from the reaction causing environmental pollution |
| Dry chemical carbon coating | C2H2, CH4, asphalt, graphite | CVD, ball-milling | Technology being mature and available for large-scale manufacturing; easy to control the reaction and manipulate the carbon-coating structure; forthright process and mild conditions for solid reactions | High-cost and severe danger due to gas reactions; Toxic gases produced from the reaction causing expensive disposal and environmental pollution |
Fig 14
(a) TEM images, dark-field STEM-HAADF image of Sn/SiO (1:2, w/w) powder and EDS mapping of O, Si, and Sn in the rectangular area; (b) ex situ XPS analysis of the phase evolution associated with Sn and Li2O during the charging process of the Sn/SiO electrode, high-resolution XPS spectra of Sn 3d and O 1s; (c) electrochemical performances of SiO and Sn/SiO anode materials; (d) the dQ/dV plots of the charging process; separated dealloying (< 0.9 V) and inverse conversion reaction (0.9–2.5 V) capacity as a function of lithiated capacity 92. Adapted with permission from Ref. 92, Copyright 2019, John Wiley and Sons."
Table 6
Electrochemical performances of metal-doped SiO materials."
| Sample | Initial discharge/charge specific capacity (mAh·g-1) | ICE (%) | Cycling performance (mAh·g-1) | Current density | Particle size | Year | Ref. |
| SiAl0.2O | 2225/1500 | 67.4 | 800 (100 cycles) | 200 mA·g-1 | – | 2010 | 86 |
| SiO/SnCoC | 1480/1030 | 69.6 | 900 (100 cycles) | C/3 | ~2.5 μm | 2012 | 88 |
| SiO/SnFeC | 1427/961 | 67 | 538 (100 cycles) | C/3 | ~9 μm | 2013 | 89 |
| SiO/ZrO2@C | 1737.3/1156.8 | 66.58 | 930 (100 cycles) | 80 mA·g-1 | 200–500 nm | 2017 | 90 |
| SiO/nano-Sn | 2066/1863.8 | 90.2 | 900 (100 cycles) | 200 mA·g-1 | – | 2018 | 92 |
Fig 15
(a) Schematic of the synthesis process of the SiO@TiO2 nanoparticles; (b) characterization of ST-3: TEM images (Ⅰ, Ⅱ), SEM image (Ⅲ) and the corresponding mapping images of elemental Si, Ti and O; (c) schematic of charge/discharge mechanism of the SiO@TiO2; (d) electrochemical performances of different samples; (e) SEM and TEM images of ST-3 electrode before (left) and after 200 cycles (right) 99. Adapted with permission from Ref. 99, Copyright 2019, Elsevier."
Table 7
Electrochemical performances of SiO materials modified by metal oxide coating."
| Sample | Initial discharge/charge specific capacity (mAh·g-1) | ICE (%) | Cycling performance (mAh·g-1) | Current density | Particle size | Coating thickness | Conductive property | Year | Ref. |
| SiO/TiO2 | 1757/1265 | 72 | – | – | 6 μm | – | Rct = 63.69 Ω | 2012 | 97 |
| SiO/ Fe2O3 | 2773/1893 | 68 | 1335 (50 cycles) | 160 mA·g-1 | – | – | – | 2013 | 93 |
| SiO/TiO2 | 1654/1292 | 78.1 | 730 (100 cycles) | 100 mA·g-1 | – | 50–150 nm | R = 12 Ω | 2019 | 98 |
| SiO/a-TiO2 | 1920/1524 | 79.4 | 901 (200 cycles) | 200 mA·g-1 | 160 nm | 20–30 nm | Rct = 391 Ω | 2019 | 99 |
Fig 16
(a) Schematic of the preparation of the SiO@C/TiO2 nanospheres via the sol-gel method; (b) SEM images of P-SiO, N-SiO, SiO@C and SiO@C/TiO2 composite; (c) electrochemical performances of different samples; (d) cross-section SEM image of N-SiO (left), SiO@C (middle), SiO@C/TiO2 (right) before (top) and after 100 cycles (bottom) 105. Adapted with permission from Ref. 105, Copyright 2020, Elsevier."
Table 8
Electrochemical performances of SiO materials modified by multiple coating."
| Sample | Initial discharge/charge specific capacity (mAh·g-1) | ICE (%) | Cycling performance (mAh·g-1) | Current density | Particle size | Coating thickness | Conductive property | Year | Ref. |
| SiO/Cu/EG | 2400/1177 | 49 | 836 (100 cycles) | 200 mA·g-1 | – | – | – | 2017 | 102 |
| bm-SiO/Ni/rGO | 1636.4/1021.7 | 62.4 | 720 (100 cycles) | 100 mA·g-1 | ~200 nm | ~5 nm | Rct = 72.4 Ω | 2018 | 103 |
| SiO@C/BaTiO3/CNT | 952/771 | 81 | 711.7 (100 cycles) | 0.1 A·g-1 | 8 μm | – | Rct =59.5 Ω | 2019 | 104 |
| SiO@C/TiO2 | 1590/1542 | 97 | 1565 (100 cycles) | 0.1 A·g-1 | 400 nm | 50 nm | – | 2020 | 105 |
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