Cell degradation of a Na–NiCl2 (ZEBRA) battery

Li, Guosheng; Lu, Xiaochuan; Kim, Jin Y.; Lemmon, John P.; Sprenkle, Vincent

doi:10.1039/c3ta13644b

Cited by 74 publications

(90 citation statements)

References 18 publications

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“…[ 9,10 ] The button cell consisted of the stainless-steel battery housing (cathode and anode), α-alumina (99.5% purity) fi xture, and BASE (3 cm 2 active area) as reported in our previous publications. [ 9,10 ] The button cell consisted of the stainless-steel battery housing (cathode and anode), α-alumina (99.5% purity) fi xture, and BASE (3 cm 2 active area) as reported in our previous publications.…”

Section: Methodsmentioning

confidence: 99%

“…[ 9,10 ] The button cell consisted of the stainless-steel battery housing (cathode and anode), α-alumina (99.5% purity) fi xture, and BASE (3 cm 2 active area) as reported in our previous publications. [ 10 ] The cell assembly process was carried out in a nitrogen-purged glove box. [ 29 ] The thickness of the BASE disc after conversion and creep-fl attening was 500 µm.…”

Section: Methodsmentioning

confidence: 99%

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An Advanced Na–FeCl₂ ZEBRA Battery for Stationary Energy Storage Application

Kim

et al. 2015

Advanced Energy Materials

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development efforts are still required for reducing the cost and improving the cycle life needed before further penetration of ZEBRA batteries into the stationary energy-storage market.The important effort would be adopting a low-cost cathode chemistry that would replace the Ni cathode with low-cost cathode materials. Among various cathode chemistries that have been considered, [12][13][14][15] the Na-FeCl 2 redox couple could be a promising candidate for a lowcost ZEBRA battery. The overall reaction of Na-FeCl 2 redox couple and battery schematics are described in Figure 1 . [ 16,17 ] The theoretical specifi c capacity and energy density of the Na-FeCl 2 redox reaction are 310 mAh g −1 and 729 Wh kg −1 (without considering melts), which are quite comparable to the values from the Na-NiCl 2 redox couple. Na-FeCl 2 battery technologies have potential advantages over the current state-of-the-art Na-NiCl 2 ZEBRA battery technologies: (1) lower cathode material cost, where the price of Fe (LME price $0.48 kg −1 ) is much lower than Ni (LME price $14.5 kg −1 ) [ 18 ] and (2) more economical material choices (stainless steels could be used for cell components including cathode current collectors and cell cases). Based on the cost model of Na-NiCl 2 ZEBRA battery reported before, [ 19 ] it can easily be estimated that replacing Ni with Fe in Na-NiCl 2 battery could result up to 61% reduction in cell materials cost ($38 kWh −1 for Na-FeCl 2 ) shown in Figures S1 and S2 (Supporting Information). The real cost reduction from replacing Ni powder with Fe powders may not be as signifi cant as the LME price (additional costs for processes to obtain certain purity and particle size of metal powders); however, the advantages of utilizing earth abundance and low-cost Fe cathode in ZEBRA batteries are not diffi cult to foresee. Another effort is to operate a ZEBRA battery at an intermediate temperature (<200 °C), which could substantially lower capital, manufacturing, and maintenance costs by implementing a cost-effective, high-throughput manufacturing process such as compressive polymer seals rather than high-temperature batch processes such as glass sealing, thermal compression bonding, etc. Our recent studies on intermediate-temperature (IT) Na-NiCl 2 batteries reported that the lower operation temperature signifi cantly improves the cycle life by suppressing degradation mechanisms such as particle growth in the cathode materials of ZEBRA batteries. [ 20 ] Therefore, developing IT Na-FeCl 2 ZEBRA batteries is one of the most attractive approaches toward commercializing ZEBRA Sodium-metal chloride batteries, ZEBRA, are considered one of the most important electrochemical devices for stationary energy storage applications because of its advantages of good cycle life, safety, and reliability. However, sodium-nickel chloride (Na-NiCl 2 ) batteries, the most promising redox chemistry in ZEBRA batteries, still face great challenges for the practical application due to its inevitable feature of using Ni cathode (high materials cost). ...

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Section: Methodsmentioning

confidence: 99%

“…[ 9,10 ] The button cell consisted of the stainless-steel battery housing (cathode and anode), α-alumina (99.5% purity) fi xture, and BASE (3 cm 2 active area) as reported in our previous publications. [ 10 ] The cell assembly process was carried out in a nitrogen-purged glove box. [ 29 ] The thickness of the BASE disc after conversion and creep-fl attening was 500 µm.…”

Section: Methodsmentioning

confidence: 99%

An Advanced Na–FeCl₂ ZEBRA Battery for Stationary Energy Storage Application

Kim

et al. 2015

Advanced Energy Materials

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“…Intrinsically, the safer cathode chemistries in Na–MH batteries are achieved from using secondary electrolytes along with the inherent higher open‐circuit voltage, the lower operating temperature, and easier cell assembly at the discharge state . In fact, the sodium–nickel chloride (Na–NiCl 2 ) chemistry has been extensively investigated over the past few decades . The overall redox reaction of a Na–NiCl 2 battery can be described as follows

2 NaCl + Ni (normaldischarge normal normalstate) \leftrightarrow 2 Na + {NiCl}_{2} (normalcharge normal normalstate)

E_{0} = 2.58 V at 300 ° C

…”

Section: Introductionmentioning

confidence: 99%

“Ni‐Less” Cathodes for High Energy Density, Intermediate Temperature Na–NiCl₂ Batteries

Chang

Bonnett

et al. 2018

Adv Materials Inter

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a molten Na anode and β″-alumina solidstate electrolyte (BASE). Despite their similarities, sodium-sulfur (Na-S) and sodium-metal halide (Na-MH) batteries, which are the two main analogs of NBBs, are quite different in their chemistries and the cell operating conditions. Typically, a Na-S battery contains molten sulfur/ polysulfide cathodes that require an operating temperature range of 300 to 350 °C to retain the molten state of the electrode materials to facilitate the electrochemical reactions. [3] On the other hand, a conventional Na-MH battery (ZEBRA) contains metal halide based cathodes (e.g., NiCl 2 , FeCl 2 , etc.), a secondary electrolyte (NaAlCl 4 ), and operates at a temperature near 280 °C. [4,5] Intrinsically, the safer cathode chemistries in Na-MH batteries are achieved from using secondary electrolytes along with the inherent higher open-circuit voltage, the lower operating temperature, and easier cell assembly at the discharge state. [6] In fact, the sodium-nickel chloride (Na-NiCl 2 ) chemistry has been extensively investigated over the past few decades. [7][8][9][10][11] The overall redox reaction of a Na-NiCl 2 battery can be described as follows [7,12]

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“…The cell using reference NaAlCl 4 electrolyte (Cell C) also exhibited high coulombic efficiencies of 130% at 1 st cycle. In the previous report, 24) it has been noted that the NaAlCl 4 molten salt is designed to have excess amount of NaCl (the molar ratio of NaCl:AlCl 3 = 0.51:0.49) to prevent the formation of Lewis-acidic melts which increase the Ni solubility. 23) As a result, the high coulombic efficiency of the cell C using stoichiometric NaAlCl 4 at 1 st formation cycle could be attributable to the formation of Lewis-acidic melts.…”

Section: )mentioning

confidence: 99%

“…As a result, the modification of molten salt electrolytes with various additives may be advantageous to lower the NiCl 2 solubility and ultimately prevent over-discharge reactions. Since the Ni solubility is intensely related to Ni particle growth which causes rapid cell degradation of Zebra battery, 22,24) the long-term performance of the cells A, C, and D were compared at 12 mA/cm 2 (0.2C) in Fig. 5.…”

Section: )mentioning

confidence: 99%

Investigation of Al-Ni Alloys Deposition during Over-discharge Reaction of Na-NiCl₂Battery

Kim¹,

Jo²,

Park³

et al. 2016

Journal of the Korean Electrochemical Society

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:The over-discharging phenomena in sodium-nickel chloride batteries were investigated in relation to decomposition of molten salt electrolyte and consequent metal co-deposition. From XRD analysis, the material deposited on graphite cathode current collector was revealed to be by-product of molten salt electrolyte decomposition. In particular, the result showed that the Ni-Al alloys (Al Ni) were electrochemically deposited on graphite current collectors in line with over-discharging behaviors. It is assumed that the NiCl 2 solubility in molten salt electrolytes leads to the co-deposition of Ni-Al alloys by increasing metal deposition potential above 1.6 V (vs. Na/Na + ). The cell tests have revealed that the composition of molten salt electrolytes modified by various additives makes a decisive influence on the over-discharging behaviors of the cells. It was revealed that NaOCN addition to molten salt electrolytes was advantageous to suppress over-discharge reactions by modifying the characteristics of molten salt electrolytes. NaOCN addition into molten salt electrolytes seems to suppress Ni solubility by maintaining basic melts. The cell using modified molten salt electrolyte with NaOCN (Cell D) showed relatively less cell degradation compared with other cells for long cycles.

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Cell degradation of a Na–NiCl2 (ZEBRA) battery

Cited by 74 publications

References 18 publications

An Advanced Na–FeCl₂ ZEBRA Battery for Stationary Energy Storage Application

An Advanced Na–FeCl₂ ZEBRA Battery for Stationary Energy Storage Application

“Ni‐Less” Cathodes for High Energy Density, Intermediate Temperature Na–NiCl₂ Batteries

Investigation of Al-Ni Alloys Deposition during Over-discharge Reaction of Na-NiCl₂Battery

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Cell degradation of a Na–NiCl2 (ZEBRA) battery

Cited by 74 publications

References 18 publications

An Advanced Na–FeCl2 ZEBRA Battery for Stationary Energy Storage Application

An Advanced Na–FeCl2 ZEBRA Battery for Stationary Energy Storage Application

“Ni‐Less” Cathodes for High Energy Density, Intermediate Temperature Na–NiCl2 Batteries

Investigation of Al-Ni Alloys Deposition during Over-discharge Reaction of Na-NiCl2Battery

Contact Info

Product

Resources

About

An Advanced Na–FeCl₂ ZEBRA Battery for Stationary Energy Storage Application

An Advanced Na–FeCl₂ ZEBRA Battery for Stationary Energy Storage Application

“Ni‐Less” Cathodes for High Energy Density, Intermediate Temperature Na–NiCl₂ Batteries

Investigation of Al-Ni Alloys Deposition during Over-discharge Reaction of Na-NiCl₂Battery