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Metal nitrides as negative electrode materials for sodium-ion batteries

Metal nitrides as negative electrode materials for sodium-ion batteries
Metal nitrides as negative electrode materials for sodium-ion batteries
Sodium-ion batteries undergone a rapid development in recent years and have great potential to be a strong alternative to lithium-ion batteries for renewable energy storage. Taking inspiration from lithium-ion batteries, the electrode materials selection and charge storage mechanism in sodium-ion cells are developed. Metal nitrides have been reported to be suitable as negative electrode materials for lithium-ion batteries based on the conversion reaction mechanism.

In this work, the suitability of several metal nitrides, e.g. Ni3N, Cu3N or Sn3N4 as negative electrode materials for sodium-ion batteries was investigated. Metal nitrides were synthesized from ammonolysis of specific precursors at targeted temperatures.

As-synthesized metal nitrides were characterized by several techniques, such as PXD, TEM, or IR. Their electrochemical performance was evaluated in sodium half-cells and lithium half-cells via cyclic voltammetry or galvanostatic tests.

In sodium-ion half-cells, Ni3N was firstly studied as the negative electrode material and it exhibited a capacity of around 460 mA h g-1 at 0.5 C in the first reduction cycle and a reversible capacity of 134 mA h g-1 after 20 cycles, which was competitive to the most carbon based materials by then.

Cu3N showed 89 mA h g-1 observed in the 50th cycle at 0.1 C, which exhibited a better cycling stability than that of Ni3N in sodium-ion half-cells. Ex situ XRD showed the formation of metallic copper in the first cycle but the reflections of metallic copper did not vanish after re-oxidizing to 3 V, which indicates that the conversion reaction from Cu3N to Cu is not a completely reversible process.

Bulk tin nitride was synthesized from ammonolysis of polymeric amide-derived precursor which derived from the reaction of Sn(NEt2)4 with ammonia. After washing with 3M HCl, pure phase Sn3N4 was obtained. Samples obtained at 350 °C were observed to exhibit small particle size with the highest specific surface area among all samples.

The cell with alginate binder had a capacity of 175 mA h g-1 in the 2nd cycle and 155 mA h g-1 in the 50th cycle (89% capacity retention) at 200 mA g-1 while the one with CMC binder showed a capacity of 144 mA h g-1 in the 2nd cycle and 113 mA h g-1 in the 50th cycle (79% capacity retention) at the same current rate. The effect of FEC additives was also investigated in this work. With the help of FEC additives, Sn3N4 cells with alginate binder showed a capacity of 680 mA h g-1 in the first cycle at 50 mA g-1 in the sodium-ion cells with the FEC additive and approximately 47% of which (320 mA h g-1) was retained in the second cycle and the stable cycle performance around 85% capacity (compared with the second cycle) retention over 50 cycles. A significant capacity rise (~35%) against the cell without FEC additives was observed. The electrochemical behaviour of Sn3N4 is the best electrochemical performance of transition metal nitrides as negative electrode materials in Na-ion cells and it can be comparable with other negative electrode materials in sodium cells. Bulk tin nitride was firstly investigated as negative electrode materials in Li-ion batteries, with the aid of FEC additives, it showed a capacity of 370 mA h g-1 capacity over 50 cycles at 200 mA h g-1. The ex situ XRD measurements showed a hybrid charge mechanism combining conversion reaction with alloy/de-alloy process.

Screening the electrochemistry of other transition metal nitrides, e.g. chromium nitride, molybdenum nitride, or manganese nitride in battery applications was conducted. It is noted that molybdenum nitride and manganese nitride showed decent specific capacity and cycle stability in sodium cells. Manganese nitride showed a high specific capacity of 127 mA h g-1 at 50 mA g-1 over 50 cycles, which is comparable to other transition metal nitrides, e.g. nickel nitride and copper nitride. In lithium half-cells, it exhibited a 600 mA h g-1 reversible capacity at 200 mA g-1 and retained 340 mA h g-1 capacity in the 50th cycle.
Li, Xianji
af8b4164-d034-4ea3-8317-fa5dd676c1e2
Li, Xianji
af8b4164-d034-4ea3-8317-fa5dd676c1e2
Hector, Andrew
f19a8f31-b37f-4474-b32a-b7cf05b9f0e5

(2015) Metal nitrides as negative electrode materials for sodium-ion batteries. University of Southampton, Chemistry, Doctoral Thesis, 200pp.

Record type: Thesis (Doctoral)

Abstract

Sodium-ion batteries undergone a rapid development in recent years and have great potential to be a strong alternative to lithium-ion batteries for renewable energy storage. Taking inspiration from lithium-ion batteries, the electrode materials selection and charge storage mechanism in sodium-ion cells are developed. Metal nitrides have been reported to be suitable as negative electrode materials for lithium-ion batteries based on the conversion reaction mechanism.

In this work, the suitability of several metal nitrides, e.g. Ni3N, Cu3N or Sn3N4 as negative electrode materials for sodium-ion batteries was investigated. Metal nitrides were synthesized from ammonolysis of specific precursors at targeted temperatures.

As-synthesized metal nitrides were characterized by several techniques, such as PXD, TEM, or IR. Their electrochemical performance was evaluated in sodium half-cells and lithium half-cells via cyclic voltammetry or galvanostatic tests.

In sodium-ion half-cells, Ni3N was firstly studied as the negative electrode material and it exhibited a capacity of around 460 mA h g-1 at 0.5 C in the first reduction cycle and a reversible capacity of 134 mA h g-1 after 20 cycles, which was competitive to the most carbon based materials by then.

Cu3N showed 89 mA h g-1 observed in the 50th cycle at 0.1 C, which exhibited a better cycling stability than that of Ni3N in sodium-ion half-cells. Ex situ XRD showed the formation of metallic copper in the first cycle but the reflections of metallic copper did not vanish after re-oxidizing to 3 V, which indicates that the conversion reaction from Cu3N to Cu is not a completely reversible process.

Bulk tin nitride was synthesized from ammonolysis of polymeric amide-derived precursor which derived from the reaction of Sn(NEt2)4 with ammonia. After washing with 3M HCl, pure phase Sn3N4 was obtained. Samples obtained at 350 °C were observed to exhibit small particle size with the highest specific surface area among all samples.

The cell with alginate binder had a capacity of 175 mA h g-1 in the 2nd cycle and 155 mA h g-1 in the 50th cycle (89% capacity retention) at 200 mA g-1 while the one with CMC binder showed a capacity of 144 mA h g-1 in the 2nd cycle and 113 mA h g-1 in the 50th cycle (79% capacity retention) at the same current rate. The effect of FEC additives was also investigated in this work. With the help of FEC additives, Sn3N4 cells with alginate binder showed a capacity of 680 mA h g-1 in the first cycle at 50 mA g-1 in the sodium-ion cells with the FEC additive and approximately 47% of which (320 mA h g-1) was retained in the second cycle and the stable cycle performance around 85% capacity (compared with the second cycle) retention over 50 cycles. A significant capacity rise (~35%) against the cell without FEC additives was observed. The electrochemical behaviour of Sn3N4 is the best electrochemical performance of transition metal nitrides as negative electrode materials in Na-ion cells and it can be comparable with other negative electrode materials in sodium cells. Bulk tin nitride was firstly investigated as negative electrode materials in Li-ion batteries, with the aid of FEC additives, it showed a capacity of 370 mA h g-1 capacity over 50 cycles at 200 mA h g-1. The ex situ XRD measurements showed a hybrid charge mechanism combining conversion reaction with alloy/de-alloy process.

Screening the electrochemistry of other transition metal nitrides, e.g. chromium nitride, molybdenum nitride, or manganese nitride in battery applications was conducted. It is noted that molybdenum nitride and manganese nitride showed decent specific capacity and cycle stability in sodium cells. Manganese nitride showed a high specific capacity of 127 mA h g-1 at 50 mA g-1 over 50 cycles, which is comparable to other transition metal nitrides, e.g. nickel nitride and copper nitride. In lithium half-cells, it exhibited a 600 mA h g-1 reversible capacity at 200 mA g-1 and retained 340 mA h g-1 capacity in the 50th cycle.

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Published date: 19 February 2015
Organisations: University of Southampton, Chemistry

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Local EPrints ID: 374787
URI: http://eprints.soton.ac.uk/id/eprint/374787
PURE UUID: 613a6849-ae41-4210-96da-e412f12fd3a3
ORCID for Andrew Hector: ORCID iD orcid.org/0000-0002-9964-2163

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Date deposited: 11 May 2015 10:18
Last modified: 29 Jun 2018 04:01

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Author: Xianji Li
Thesis advisor: Andrew Hector ORCID iD

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