Sieving carbons for sodium-ion batteries: Origin and progress
ZHANG Jun,1,2,3, LI Qi2,3, TAO Ying2,3, YANG Quanhong,1,2,3
1.Tianjin University-National University of Singapore Joint Institute in Fuzhou, Fuzhou 350207, Fujian, China
2.State Key Laboratory of Chemical Engineering, School of Chemical Engineering and Technology, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin University, Tianjin 300072, China
3.Haihe Laboratory of Sustainable Chemical Transformations, Tianjin 300192, China
Sodium-ion batteries (SIBs) are widely recognized as the best supplement to lithium-ion batteries in the field of large-scale energy storage applications. Hard carbons are the most practical anode materials for SIBs. However, the controversial sodium storage mechanism associated with the low-potential plateau and unknown structure-performance relationship of hard carbon anodes severely limits the commercialization of SIBs. This study summarizes the research progress and key challenges of different carbon anodes in SIBs and introduces the critical structural features of designing the ideal carbon anode. Then, inspired by our previous work on commercial carbon molecular sieves, we propose the ideal carbon model called "sieving carbons" The unique pore structure of sieving carbons, which we describe as a small pore mouth with a large pore stomach, and its impact on the sodium storage mechanism and properties are discussed in detail. Finally, the rational design principles for sieving carbon anodes with reversible and extensible low-voltage plateaus are discussed, as well as the opportunity and challenge of sieving carbons in promoting the commercialization of SIBs.
Fig. 1
(a) Typical X-ray diffraction patterns; (b) Schematic of representative microstructures; (c) Charge-discharge curves at second cycle in sodium half cell of graphite, soft carbon, hard carbon and reduced graphene oxide (rGO)[12]
Fig. 2
(a) Typical charge curves of hard carbon anodes carbonized at different temperatures[27]; (b) The relationship between the capacity from LPP and specific surface area obtained by N2 adsorption
Fig. 3
(a) Schematic of carbon molecular sieve for N2/O2 separation; (b) Charge-discharge curves at first cycle of graphite, activated carbon and carbon molecular sieve; (c) SAXS patterns of porous carbon (PC) and (d) sieving carbon (SC) anodes before and after (dashed line) five full cycles at a current density of 50 mA/g. Inset: the relative location of the SEI to the nanopores. The SEI is a green irregular shape with yellow solid circles (sodium ions) inside[26]
Fig. 4
Characterizing the sodium storage mechanism of SC (a) 23Na MAS ssNMR spectra of SC anodes at various states of charge in the first cycle. The spinning sideband is labeled with an asterisk (❋); (b) Operando Raman spectra of SC anodes during the first charge/discharge at a current density of 50 mA/g[26]
Fig. 5
Analysis of the local environment of stored sodium in SC using a smooth overlap of atomic positions kernel, as a structural similarity initially used for Gaussian approximation potential fitting. The most similar points are aggregated together with similar colors[26]
Fig. 6
Rational design principles for sieving carbon anodes. (a) Relationship between the pore diameter, quasi-metallic Na peak shift and sample pyrolysis temperature[27]; (b) Ex-situ23Na 55 kHz ssNMR spectra of SCs at 0.005 V for the 10th discharge at 50 mA/g (solid curves). The dashed curves are the corresponding ssNMR spectra of SCs at 0.005 V for the first discharge[26]; (c) Relationship among the plateau capacity (0.1-0 V), true density, and EtOH content; (d) Charge capacity from the low-potential plateau versus SSA obtained by SAXS and N2 adsorption for the SC anodes[26]
LU Y X, ZHAO C L, RONG X H, et al. Research progress of materials and devices for room-temperature Na-ion batteries[J]. Acta Physica Sinica, 2018, 67(12): doi: 10.7498/aps.67.20180847.
PAN H L, HU Y S, CHEN L Q. Room-temperature stationary sodium-ion batteries for large-scale electric energy storage[J]. Energy & Environmental Science, 2013, 6(8): doi: 10.1039/c3ee40847g.
RONG X H, LU Y X, QI X G, et al. Na-ion batteries: From fundamental research to engineering exploration[J]. Energy Storage Science and Technology, 2020, 9(2): 515-522.
JACHE B, ADELHELM P. Use of graphite as a highly reversible electrode with superior cycle life for sodium-ion batteries by making use of co-intercalation phenomena[J]. Angewandte Chemie International Edition, 2014, 53(38): 10169-10173.
LIU Y Y, MERINOV B V, GODDARD W A. Origin of low sodium capacity in graphite and generally weak substrate binding of Na and Mg among alkali and alkaline earth metals[J]. Proceedings of the National Academy of Sciences of the United States of America, 2016, 113(14): 3735-3739.
SAUREL D, ORAYECH B, XIAO B W, et al. From charge storage mechanism to performance: A roadmap toward high specific energy sodium-ion batteries through carbon anode optimization[J]. Advanced Energy Materials, 2018, 8(17): doi: 10.1002/aenm.201703268.
JIAN Z L, BOMMIER C, LUO L L, et al. Insights on the mechanism of Na-ion storage in soft carbon anode[J]. Chemistry of Materials, 2017, 29(5): 2314-2320.
LI Y M, HU Y S, QI X G, et al. Advanced sodium-ion batteries using superior low cost pyrolyzed anthracite anode: Towards practical applications[J]. Energy Storage Materials, 2016, 5: 191-197.
STEVENS D A, DAHN J R. High capacity anode materials for rechargeable sodium-ion batteries[J]. Journal of the Electrochemical Society, 2000, 147(4): doi: 10.1016/j.dld.2004.05.016.
YAMAMOTO H, MURATSUBAKI S, KUBOTA K, et al. Synthesizing higher-capacity hard-carbons from cellulose for Na- and K-ion batteries[J]. Journal of Materials Chemistry A, 2018, 6(35): 16844-16848.
LUO W, BOMMIER C, JIAN Z L, et al. Low-surface-area hard carbon anode for na-ion batteries via graphene oxide as a dehydration agent[J]. ACS Applied Materials & Interfaces, 2015, 7(4): 2626-2631.
LU Y X, ZHAO C L, QI X G, et al. Pre-oxidation-tuned microstructures of carbon anodes derived from pitch for enhancing Na storage performance[J]. Advanced Energy Materials, 2018, 8(27): doi: 10.1002/aenm.201800108.
ZHANG S W, LV W, LUO C, et al. Commercial carbon molecular sieves as a high performance anode for sodium-ion batteries[J]. Energy Storage Materials, 2016, 3: 18-23.
STEVENS D A, DAHN J R. The mechanisms of lithium and sodium insertion in carbon materials[J]. Journal of the Electrochemical Society, 2001, 148(8): doi: 10.1149/1.1379565.
QIU S, XIAO L F, SUSHKO M L, et al. Manipulating adsorption-insertion mechanisms in nanostructured carbon materials for high-efficiency sodium ion storage[J]. Advanced Energy Materials, 2017, 7(17): doi: 10.1002/aenm.201700403.
BOMMIER C, SURTA T W, DOLGOS M, et al. New mechanistic insights on Na-ion storage in nongraphitizable carbon[J]. Nano Letters, 2015, 15(9): 5888-5892.
STRATFORD J M, ALLAN P K, PECHER O, et al. Mechanistic insights into sodium storage in hard carbon anodes using local structure probes[J]. Chemical Communications (Cambridge, England), 2016, 52(84): 12430-12433.
MORIKAWA Y, NISHIMURA S I, HASHIMOTO R I, et al. Mechanism of sodium storage in hard carbon: An X-ray scattering analysis[J]. Advanced Energy Materials, 2020, 10(3): doi: 10.1002/aenm.201903176.
LI Q, LIU X S, TAO Y, et al. Sieving carbons promise practical anodes with extensible low-potential plateaus for sodium batteries[J]. National Science Review, 2022, doi: 10.1093/nsr/nwac084.
AU H, ALPTEKIN H, JENSEN A C S, et al. A revised mechanistic model for sodium insertion in hard carbons[J]. Energy & Environmental Science, 2020, 13(10): 3469-3479.
ZHANG B, GHIMBEU C M, LABERTY C, et al. Correlation between microstructure and Na storage behavior in hard carbon[J]. Advanced Energy Materials, 2016, 6(1): doi: 10.1002/aenm.201501588.
ZHENG Y H, LU Y X, QI X G, et al. Superior electrochemical performance of sodium-ion full-cell using poplar wood derived hard carbon anode[J]. Energy Storage Materials, 2019, 18: 269-279.
LI Y M, MU L Q, HU Y S, et al. Pitch-derived amorphous carbon as high performance anode for sodium-ion batteries[J]. Energy Storage Materials, 2016, 2: 139-145.
WANG Z H, FENG X, BAI Y, et al. Probing the energy storage mechanism of quasi-metallic Na in hard carbon for sodium-ion batteries[J]. Advanced Energy Materials, 2021, 11(11): doi: 10.1002/aenm.202003854.
MENG Q S, LU Y X, DING F X, et al. Tuning the closed pore structure of hard carbons with the highest Na storage capacity[J]. ACS Energy Letters, 2019, 4(11): 2608-2612.
... [12](a) Typical X-ray diffraction patterns; (b) Schematic of representative microstructures; (c) Charge-discharge curves at second cycle in sodium half cell of graphite, soft carbon, hard carbon and reduced graphene oxide (rGO)<sup>[<xref ref-type="bibr" rid="R12">12</xref>]</sup>Fig. 1
... 为什么闭孔对于低电位平台的产生如此关键?阐明这个问题是理解硬碳负极的构效关系并理性设计硬碳孔结构的重要前提.由于低电位平台一般低于0.1 V,在该平台出现前会形成负极和电解液间的固态电解质界面,界面性质可能会直接影响到平台的出现,这在锂离子电池石墨负极的相关研究中得到了普遍证实,即固态电解质界面主要形成于石墨层间的边缘.本课题组前期研究发现,在工业中用于分离氧气和氮气的碳分子筛(孔口尺寸介于0.3~0.5 nm)[图3(a)],直接作为钠离子电池负极时也出现了低电位平台,且首次库仑效率相比活性碳(孔口尺寸大于0.7 nm)实现了成倍的提升,未经任何处理即可达到70%以上[图3(b)],首效的变化也说明闭孔对于界面化学产生了巨大的影响[19].Zheng等[29]曾提出通过氮气吸脱附测得的比表面积并不能完全代表电化学活性比表面面积,而后者则与固态电解质界面的形成直接相关.通过对碳化杨木(不同温度)得到的硬碳样品进行分析,Li等[29]发现孔径分布也可能会对首效产生一定的影响.<strong>(a)</strong> 商业化碳分子筛的示意图;<strong>(b)</strong> 石墨、活性炭和碳分子筛的首圈充放电曲线;<strong>(c)</strong>典 型多孔碳在循环<strong>5</strong>圈后的小角<strong>X</strong>射线散射结果<strong>(</strong>示意图:固态电解质界面主要形成于孔内<strong>)</strong>;<strong>(d)</strong> 筛分型碳在循环<strong>5</strong>圈后的小角<strong>X</strong>射线散射结果<strong>(</strong>示意图:固态电解质界面主要形成于孔外<strong>)</strong><sup>[<xref ref-type="bibr" rid="R26">26</xref>]</sup>(a) Schematic of carbon molecular sieve for N<sub>2</sub>/O<sub>2</sub> separation; (b) Charge-discharge curves at first cycle of graphite, activated carbon and carbon molecular sieve; (c) SAXS patterns of porous carbon (PC) and (d) sieving carbon (SC) anodes before and after (dashed line) five full cycles at a current density of 50 mA/g. Inset: the relative location of the SEI to the nanopores. The SEI is a green irregular shape with yellow solid circles (sodium ions) inside<sup>[<xref ref-type="bibr" rid="R26">26</xref>]</sup>Fig. 3
... [26]<strong>Characterizing the sodium storage mechanism of SC (a) <sup>23</sup>Na MAS ssNMR spectra of SC anodes at various states of charge in the first cycle. The spinning sideband is labeled with an asterisk (</strong>❋<strong>); (b) Operando Raman spectra of SC anodes during the first charge/discharge at a current density of 50 mA/g<sup/></strong><sup>[<xref ref-type="bibr" rid="R26">26</xref>]</sup>Fig. 4
... [26]Analysis of the local environment of stored sodium in SC using a smooth overlap of atomic positions kernel, as a structural similarity initially used for Gaussian approximation potential fitting. The most similar points are aggregated together with similar colors<sup>[<xref ref-type="bibr" rid="R26">26</xref>]</sup>Fig. 5<strong>2.2</strong> 筛分型碳的理性设计原则
... [26];(c) 硬碳负极平台容量、真密度和乙醇含量间的关系;(d) 平台容量与氮气吸附和小角X射线散射测得的比表面积间的关系[26]<strong>Rational design principles for sieving carbon anodes. (a) Relationship between the pore diameter, quasi-metallic Na peak shift and sample pyrolysis temperature</strong><sup>[<xref ref-type="bibr" rid="R27">27</xref>]</sup><strong>; (b) <i>Ex-situ</i><sup>23</sup>Na 55 kHz ssNMR spectra of SCs at 0.005 V for the 10th discharge at 50 mA/g (solid curves). The dashed curves are the corresponding ssNMR spectra of SCs at 0.005 V for the first discharge</strong><sup>[<xref ref-type="bibr" rid="R26">26</xref>]</sup><strong>; (c) Relationship among the plateau capacity (0.1</strong>-<strong>0 V), true density, and EtOH content; (d) Charge capacity from the low-potential plateau versus SSA obtained by SAXS and N<sub>2</sub> adsorption for the SC anodes</strong><sup>[<xref ref-type="bibr" rid="R26">26</xref>]</sup>Fig. 6
... [26]<strong>Rational design principles for sieving carbon anodes. (a) Relationship between the pore diameter, quasi-metallic Na peak shift and sample pyrolysis temperature</strong><sup>[<xref ref-type="bibr" rid="R27">27</xref>]</sup><strong>; (b) <i>Ex-situ</i><sup>23</sup>Na 55 kHz ssNMR spectra of SCs at 0.005 V for the 10th discharge at 50 mA/g (solid curves). The dashed curves are the corresponding ssNMR spectra of SCs at 0.005 V for the first discharge</strong><sup>[<xref ref-type="bibr" rid="R26">26</xref>]</sup><strong>; (c) Relationship among the plateau capacity (0.1</strong>-<strong>0 V), true density, and EtOH content; (d) Charge capacity from the low-potential plateau versus SSA obtained by SAXS and N<sub>2</sub> adsorption for the SC anodes</strong><sup>[<xref ref-type="bibr" rid="R26">26</xref>]</sup>Fig. 6
... [26]; (c) Relationship among the plateau capacity (0.1-0 V), true density, and EtOH content; (d) Charge capacity from the low-potential plateau versus SSA obtained by SAXS and N2 adsorption for the SC anodes[26]Fig. 6
... [27];(b) 氮气吸脱附测得的比表面积与硬碳平台容量间的关系(代表性硬碳负极的结果总结)(a) Typical charge curves of hard carbon anodes carbonized at different temperatures<sup>[<xref ref-type="bibr" rid="R27">27</xref>]</sup>; (b) The relationship between the capacity from LPP and specific surface area obtained by N<sub>2</sub> adsorptionFig. 2
... [27];(b) 筛分型碳负极的准原位固体核磁(实线:循环10圈后,再放电到0.005 V;虚线:未经循环,直接放电到0.005 V)[26];(c) 硬碳负极平台容量、真密度和乙醇含量间的关系;(d) 平台容量与氮气吸附和小角X射线散射测得的比表面积间的关系[26]<strong>Rational design principles for sieving carbon anodes. (a) Relationship between the pore diameter, quasi-metallic Na peak shift and sample pyrolysis temperature</strong><sup>[<xref ref-type="bibr" rid="R27">27</xref>]</sup><strong>; (b) <i>Ex-situ</i><sup>23</sup>Na 55 kHz ssNMR spectra of SCs at 0.005 V for the 10th discharge at 50 mA/g (solid curves). The dashed curves are the corresponding ssNMR spectra of SCs at 0.005 V for the first discharge</strong><sup>[<xref ref-type="bibr" rid="R26">26</xref>]</sup><strong>; (c) Relationship among the plateau capacity (0.1</strong>-<strong>0 V), true density, and EtOH content; (d) Charge capacity from the low-potential plateau versus SSA obtained by SAXS and N<sub>2</sub> adsorption for the SC anodes</strong><sup>[<xref ref-type="bibr" rid="R26">26</xref>]</sup>Fig. 6
... [27]; (b) Ex-situ23Na 55 kHz ssNMR spectra of SCs at 0.005 V for the 10th discharge at 50 mA/g (solid curves). The dashed curves are the corresponding ssNMR spectra of SCs at 0.005 V for the first discharge[26]; (c) Relationship among the plateau capacity (0.1-0 V), true density, and EtOH content; (d) Charge capacity from the low-potential plateau versus SSA obtained by SAXS and N2 adsorption for the SC anodes[26]Fig. 6