Rethinking sodium-ion anodes as nucleation layers for anode-free batteries

Cohn, Adam P.; Metke, Thomas; Donohue, Jennifer; Muralidharan, Nitin; Share, Keith; Pint, Cary L.

doi:10.1039/c8ta05911j

Cited by 68 publications

(61 citation statements)

References 45 publications

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“…For planar Cu, it reaches 46.3, 193.7 mV at 0.5, 2.0 mA cm −2 , respectively (Figure S5a, Supporting Information). When the current density is increased to 4.0 mA cm −2 , dramatic voltage fluctuation originating from the amplified heterogeneity in ionic distribution can be observed . In contrast, the pure CNF and D‐HCF electrode exhibits low nucleation overpotentials of 17.2, 21.3, 34.3 mV (Figure S5b, Supporting Information) and 7.1, 9.7, 16.4 mV at 0.5, 2.0, and 4.0 mA cm −2 (Figure b), respectively, which indicates the effective ion regulation enabled by D‐HCF even under high rates.…”

Section: Resultsmentioning

confidence: 93%

“…When the current density is increased to 4.0 mA cm −2 , dramatic voltage fluctuation originating from the amplified heterogeneity in ionic Small 2019, 15,1902688 distribution can be observed. [54,55] In contrast, the pure CNF and D-HCF electrode exhibits low nucleation overpotentials of 17. (Figure 4b), respectively, which indicates the effective ion regulation enabled by D-HCF even under high rates.…”

Section: Resultsmentioning

confidence: 99%

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Boosting the Reversibility of Sodium Metal Anode via Heteroatom‐Doped Hollow Carbon Fibers

Zheng

Cao

et al. 2019

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Sodium (Na) metal anodes stand out with their remarkable capacity and natural abundance. However, the dendritic Na growth, infinite dimensional changes, and low Coulombic efficiency (CE) present key bottlenecks plaguing practical applications. Here, heteroatom‐doped (nitrogen, sulfur) hollow carbon fibers (D‐HCF) are rationally synthesized as a nucleation‐assisting host to enable a highly reversible Na metal. The “sodiophilic” functional groups introduced by the heteroatom‐doping and large surface area (≈1052 m2 g−1) synchronously contribute to a homogenous plating morphology with dissipated local current density. High “sodiophilicity” of the D‐HCF is confirmed by first‐principle calculations and experimental results, where strong adsorption energy of −3.52 eV with low Na+ nucleation overpotential of 3.2 mV at 0.2 mA cm−2 is realized. As such, highly reversible plating/stripping is achieved at 1.0 mA cm−2 with average CE approximating 99.52% over 600 cycles. The as‐assembled Na@D‐HCF symmetric cells exhibit a prolonged lifetime for 1000 h. A full‐cell paired with Na3V2(PO4)3 cathode further demonstrates stable electrochemical behavior for 200 cycles at 1 C along with excellent rate performance (102 mAh g−1 at 5 C). The results clearly show the effectiveness of the D‐HCF in manipulating Na+ deposition and thus the significance of nucleation control in realizing dendrite‐free metal anodes.

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Section: Resultsmentioning

confidence: 93%

Section: Resultsmentioning

confidence: 99%

Boosting the Reversibility of Sodium Metal Anode via Heteroatom‐Doped Hollow Carbon Fibers

Zheng

Cao

et al. 2019

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“…Cohn et al have also demonstrated anode‐free sodium batteries pairing a sodiated Na 3 V 2 (PO 4 ) 3 cathode with an aluminum current collector coated with various thin nucleation layers. [ 104 ] Among the different nongraphitic carbons and sodium‐alloying metals evaluated as nucleation layers, carbon black and bismuth showed the highest Coulombic efficiencies for sodium plating and stripping. With a 1 m NaPF 6 in diglyme electrolyte and carbon black as the nucleation layer, the authors demonstrated a remarkable capacity retention of 82.5% after 100 cycles (NIRR = 99.8%) at a reasonable 0.5 mA cm −2 current rate and a 1.26 mAh cm −2 sodium plating capacity.…”

Section: Anode‐free Sodium Batteriesmentioning

confidence: 99%

Anode‐Free Full Cells: A Pathway to High‐Energy Density Lithium‐Metal Batteries

Nanda

Gupta

Manthiram

2020

Advanced Energy Materials

333

294

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The development of high‐energy density batteries is critical to the decarbonization of the transportation and power generation sectors. For any given lithium‐containing cathode system, the anode‐free full cell configuration, which eliminates excess lithium and pairs the fully lithiated cathode with a bare current collector, can deliver the maximum possible energy density. The absence of free lithium metal during cell assembly confers significant practical advantages as well. It is also the ideal framework for developing a thorough understanding of lithium deposition in conjunction with various cathode systems. However, the poor efficiencies of lithium plating and stripping lead to rapid lithium inventory loss and poor cycle life. In the last few years, multiple studies have demonstrated the application of advanced electrolytes, modified current collectors, and optimized formation and cycling parameters to stabilize lithium deposition and improve cycle life (80% capacity retention) to 100 cycles and beyond. This review provides an overview of the various strategies toward sustaining lithium inventory in anode‐free full cells and summarizes the work undertaken in this nascent field. It is expected that further improvement upon these strategies and a combinatorial approach can enable cycle lives far in excess of what has been achieved so far.

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“…[4][5][6] To solve such problems of Na metal electrodes,e fforts have been proposed such as manipulating nanostructured scaffolds, [7][8][9][10][11][12] optimizing electrolyte, [13][14][15][16] and engineering artificial protection layers. [17][18][19] Unfortunately,t hese progresses are still difficult to meet the demands of practical applications of Na metal electrodes. [20] In general, inhomogeneous Na deposition is largely determined by uneven distribution of current density,N a + / electron transport kinetics,a nd sodiophilcity (nucleation barrier or local potential).…”

Section: Introductionmentioning

confidence: 99%

A 3D Hydroxylated MXene/Carbon Nanotubes Composite as a Scaffold for Dendrite‐Free Sodium‐Metal Electrodes

et al. 2020

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Sodium metal is a promising anode, but uneven Na deposition with a dendrite growth seriously impedes its application. Herein, a fibrous hydroxylated MXene/carbon nanotubes (h‐Ti3C2/CNTs) composite is designed as a scaffold for dendrite‐free Na metal electrodes. This composite displays fast Na+/electron transport kinetics and good thermal conductivity and mechanical properties. The h‐Ti3C2 contains abundant sodiophilic functional groups, which play a significant role in inducing homogeneous nucleation of Na. Meanwhile, CNTs provide high tensile strength and ease of film‐forming. As a result, h‐Ti3C2/CNTs exhibit a high average Coulombic efficiency of 99.2 % and no dendrite after 1000 cycles. The h‐Ti3C2/CNTs/Na based symmetric cells show a long lifespan over 4000 h at 1.0 mA cm−2 with a capacity of 1.0 mAh cm−2. Furthermore, Na‐O2 batteries with a h‐Ti3C2/CNTs/Na anode exhibit a low potential gap of 0.11 V after an initial 70 cycles.

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Rethinking sodium-ion anodes as nucleation layers for anode-free batteries

Abstract: The anode-free sodium battery with a nucleation layer is presented as a low-cost, high-performance option for stationary electric storage.

Cited by 68 publications

References 45 publications

Boosting the Reversibility of Sodium Metal Anode via Heteroatom‐Doped Hollow Carbon Fibers

Boosting the Reversibility of Sodium Metal Anode via Heteroatom‐Doped Hollow Carbon Fibers

Anode‐Free Full Cells: A Pathway to High‐Energy Density Lithium‐Metal Batteries

A 3D Hydroxylated MXene/Carbon Nanotubes Composite as a Scaffold for Dendrite‐Free Sodium‐Metal Electrodes

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