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Progress in Chemistry 2023, Vol. 35 Issue (3): 407-420 DOI: 10.7536/PC220902 Previous Articles   Next Articles

• Review •

Development of Na-Based Seawater Batteries: “Key Components and Challenges”

Niu Wenhui1,2,3, Zhang Da1,2,3(), Zhao Zhengang1,2,3, Yang Bin1,2,3, Liang Feng1,2,3()   

  1. 1. Key Laboratory for Nonferrous Vacuum Metallurgy of Yunnan Province, Kunming University of Science and Technology,Kunming 650093, China
    2. National Engineering Research Center of Vacuum Metallurgy, Kunming University of Science and Technology,Kunming 650093, China
    3. Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology,Kunming 650093, China
  • Received: Revised: Online: Published:
  • Contact: *e-mail: liangfeng@kust.edu.cn (Feng Liang); d912080781@163.com (Da Zhang)
  • Supported by:
    National Natural Science Foundation of China(12175089); National Natural Science Foundation of China(12205127); Key Research and Development Program of Yunnan Province(202103AF140006); Applied Basic Research Programs of Yunnan Provincial Science and Technology Department(202001AW070004)
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Na-based seawater batteries are expected to become a new-generation of energy storage device due to its advantages of environmental friendliness, high energy density, and abundant and easy availability of seawater. Its working principle is that the conversion between the chemical energy and the electrical energy is achieved through redox reaction when seawater is considered as the electrolyte. In this review, the electrochemical principle, and design and optimization strategy of battery structure of Na-based seawater batteries are summarized. The latest research progress of Na-based seawater batteries is reviewed. Finally, the challenges to overcome the performance improvement and commercialization of Na-based seawater batteries are discussed, and the future development directions of the batteries are forecasted. The review provides the theoretical guidance for the development of Na-based seawater batteries, and then promotes Na-based seawater batteries support for major national needs such as the deep-sea energy supply and extremely environmental-energy source.

Contents

1 Introduction

2 The introduction of Na-based seawater battery

2.1 The concept of Na-based seawater battery

2.2 The electrochemical principle of Na-based seawater battery

2.3 The characteristics of Na-based seawater battery

2.4 Battery design and optimization

3 Key components and challenges of Na-based seawater battery

3.1 Anode

3.2 Organic electrolyte

3.3 Solid electrolyte

3.4 Catalysts

4 Conclusion and prospect

Key words: Na-based seawater batteries, electrochemical principle, key components and challenges, design and optimization of battery structure
Fig. 1 Working diagram of Na-based seawater battery
Fig. 2 (a) Simulated Pourbaix diagram of seawater about thermodynamics. (b) Simulated Pourbaix diagram of seawater about kinetics[16]
Fig. 3 The physical map of (a) pouch cell[13], (b) coin cell, (c) rectangular cell, and (d) prismatic cell[51]
Fig. 4 (a) Time-lapse photographs of Na dendrite growth on the Cu current collector, the yellow circle shows the appearance of Na dendrite. (b) Schematic of the battery design and Na dendrite growth, top-view scanning electron microscope (SEM) images of (c) Cu and (d) Gr/Cu current collectors, the insets represent current collectors. (e) High resolution scanning tunneling microscope (STM) topography image of Gr/Cu current collector. (f) Time-lapse photographs of Na dendrite growth on the Gr/Cu current collector. the yellow circle shows the appearance of Na dendrite. (g) Chronopotentiometry plots of Gr/Cu (red line) and Cu (black line) current collectors. (h) Schematic diagram of charge-discharge of Na-base seawater battery with Cu and Gr/Cu current collectors[57]
Fig. 5 (a) Schematic diagram of charging and discharging process of Na-BP-DEGDME anode battery. (b) Cycle performance of Na-based seawater battery with Na-BP-DEGDME anode[59]. (c) Cycling performance and energy efficiency of battery with Na-BP-TEGDME anode at 0.01 mA·cm-2. (d) Galvanostatic cycling of battery with Na-BP-TEGDME anode at 0.01 mA·cm-2. (e) Power density of batteries with different catalysts and Na-BP-TEGDME anode[35]
Table 1 Comparison of electrochemical performance of Na-based seawater batteries with organic electrolyte
Anodic electrolyte Anode Applied current Discharge capacity
(mAh·g-1)		 Cyclic performance ref
1 M NaClO4 in EC/PC HC 0.05 mA·cm-2 115 30 63
1 M NaCF3SO3 in TEGDME HC 0.05 mA·cm-2 126 100 63
ILE-EC HC 0.3 mA·cm-2 290 600 46
1 M NaClO4 in EC/DMC (1∶1) with
1 vol% FEC		 PC 1.0 A·g-1 973 80 67
1 M NaClO4 in EC/DMC (1∶1) Sn-C 0.05 mA·cm-2 300 30 68
Fig. 6 (a) Charge-discharge curves and (b) Cycling performance of the seawater battery with 1 M NaCF3SO3 in TEGDME and 1 M NaClO4 in EC/PC electrolyte[63]. (c) Capacity retention of Na-based seawater battery with ILE-EC electrolyte[46]. (d) Cycling performance of Na-based seawater battery with ILE-EC and 1 M NaCF3SO3 in TEGDME electrolyte[56]
Fig. 7 (a) Crystal structures of the β-Al2O3,and β″-Al2O3 solid electrolytes[75]. (b) X ray diffraction (XRD) patterns of β″-Al2O3 solid electrolytes before and after cycling of Na-based seawater battery[43]. (c) Crystal structures and ion transport paths of NASICON (Na3Zr2Si2PO12) solid electrolytes[83]. (d) XRD patterns and SEM images of NASICON solid electrolytes before and after immersion in seawater[13]. (e) Ionic conductivity of NASICON solid electrolytes with immersion different time in solutions with different pH values. (f) Corrosion mechanism of NASICON solid electrolyte in acidic solutions with different pH values[86]
Table 2 Comparison of electrochemical performance of Na-based seawater batteries with different catalyst
Catalysts Anode Electrolyte Applied current Voltage
gap (V)		 Discharge capacity (mAh·g-1) Cyclic performance ref
CMO HC 1 M NaCF3SO3 in TEGDME 0.01 mA·cm-2 ~0.53 ~190 100 95
3D macroporous carbon sponge Na 1 M NaCF3SO3 in TEGDME 0.025 mA·cm-2 0.46 - 100 102
N,S-doped carbon nanospheres Na 1 M NaCF3SO3 in TEGDME 5 mA·g-1 0.56 - 100 103
Pine pollen carbon (PPC) PPC 1 M NaCF3SO3 in TEGDME 50 mA·g-1 ~195 100 93
Activated carbon cloth Na 1 M NaCF3SO3 in TEGDME 0.13 mA·cm-2 ~0.6 - 80 43
Co3V2O8 Na 1 M NaCF3SO3 in TEGDME 0.1 mA·cm-2 ~0.9 - 20 96
S-rGO-CNT-Co Na 1 M NaCF3SO3 in TEGDME 0.01 mA·cm-2 ~0.42 - 50 100
Porous carbon HC 1 M NaCF3SO3 in TEGDME 0.01 mA·cm-2 0.47 ~191 100 91
PPy+Co3O4@CF Na 1 M NaCF3SO3 in TEGDME 20 mA·g-1 ~0.95 - 150 101
Pyridinic-nitrogen-containing carbon Na/CC 1 M NaCF3SO3 in DME 0.25 mA·cm-2 0.84 - 20 104
Co-N/C Na 1 M NaCF3SO3 in TEGDME 0.1 mA 0.54 - 100 105
Fig. 8 (a) Charge-discharge curves of Na-based seawater half-battery with PC catalyst at 0.01 mA·cm-2. Inset is SEM image of PC[91]. (b) Cycling performance of Na-based seawater battery with PPC catalyst at 50 mA· g a n o d e - 1 [93]. (c) Charge-discharge curves of Na-based seawater half-battery with CMO catalyst at 0.01 mA·cm-2. Inset is SEM image of CMO[95]. (d) Cycling performance of Na-based seawater battery with Co3V2O8 catalyst at 0.1 mA·cm-2[96]. (e) Charge-discharge curves of Na-based seawater battery with S-rGO-CNT-Co catalyst at 0.01 mA·cm-2. Inset is SEM image of S-rGO-CNT-Co[100]. (f) Cycling performance of Na-based seawater battery with PPy+Co3O4@CF catalyst at 20 mA·g-1[101]
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