A new tilt and an old twist on the nickel arsenide structure-type: synthesis and characterisation of the quaternary transition-metal cyanamides A2MnSn2(NCN)6 (A = Li and Na)

Corkett, Alex J.; Dronskowski, Richard

doi:10.1039/c9dt03062j

Cited by 23 publications

(42 citation statements)

References 32 publications

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“…That being said, the vibrational character observed in CdNCN and MgNCN resembles the one of carbon dioxide, O=C=O, which also contains an inversion center [23,24] . In sharp contrast to that, neither CdNCN nor MgNCN give evidence for a ν s symmetric stretching vibration because such is IR‐forbidden for D ∞ h carbodiimides but not for cyanamides like PbNCN [16,25,26] . For the latter, this ν s vibration is observed around 1250 cm −1 , as also depicted in Figure 3, thereby highlighting the difference in chemical character and anionic shape.…”

Section: Resultsmentioning

confidence: 85%

Metathesis and Redetermination of the Crystal Structure of Cadmium Carbodiimide, CdNCN

Qiao

Mroz

Corkett

et al. 2021

Zeitschrift anorg allge chemie

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Cadmium carbodiimide, CdNCN, was synthesized by a solid‐state metathesis reaction between CdCl2 and Na2NCN in a 1 : 1 molar ratio at 500 °C, and its crystal structure was redetermined from Rietveld refinement of powder X‐ray data, aiming to clarify prior uncertainties as regards the carbodiimide vs. cyanamide shape. CdNCN adopts the centrosymmetric space group R3‾ m and is isostructural with MgNCN, the lattice parameters being a=3.536 Å and c=14.518 Å, the C−N double bond arriving at 1.23 Å. Both IR and Raman spectroscopy as well as DFT phonon calculations were carried out, and they corroborate the crystallographic result.

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Section: Resultsmentioning

confidence: 85%

Metathesis and Redetermination of the Crystal Structure of Cadmium Carbodiimide, CdNCN

Qiao

Mroz

Corkett

et al. 2021

Zeitschrift anorg allge chemie

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“…Their toxicity as well as redox potential-related problems in intercalating Na into pristine graphite have already been mentioned. 8,10,63,66,67,[87][88][89][90][91] 5a-c) arrive at Löwdin charges of about +0.7 e, which is somewhat smaller than the cationic Löwdin charge of +0.8 e in LiC6 and LiC12 (Fig. 2) but similar to those in the cathode materials (Fig.…”

Section: Dicyanamide Saltsmentioning

confidence: 75%

First-Principles Plane-Wave-Based Exploration of Cathode and Anode Materials for Li and Na-ion Batteries involving Complex Nitrogen-based Anions

Ertural

Stoffel

Müller

et al. 2021

Preprint

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We present a first-principles study based on plane-wave derived Löwdin population analysis and other local bonding descriptors to investigate cathode and anode materials for lithium and sodium ion batteries, with a special emphasis on complex nitrogen chemistry. By comparing the Löwdin charges of commonly used electrode materials to other phases such as salts of dicyanamide and nanoporous carbon-based compounds, new conclusions of an improved intercalation behavior of the latter are derived. In addition, we explore the stability of the dicyanamide salts upon Li and Na removal, some of them resulting in dimerized structures. In particular, having a look at the different kinds of bonds and the corresponding covalency indicators reveals insights into the bonding changes during dimerization. Considering the astonishing thermal stability of metal dicyanamide salts, which are solid at room temperature, their electrochemical activity as well as non toxicity of alkali metal-based compounds, these materials are potential alternatives to commercially available electrodes, particularly as they show some flexibility in exhibiting anodic and cathodic behavior and allow for transition metal-free cathode materials.

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“…An additional advantage over traditional graphite-based materials is that dicyanamide should provide an alternative to intercalate Na since this is impossible in pristine graphite, as alluded to already. 8,62,65,66,[86][87][88][89][90] 5a-c) arrive at Löwdin charges of about +0.7 e, which is somewhat smaller than the cationic Löwdin charge of +0.8 e in LiC6 and LiC12 (Fig. 2).…”

Section: Dicyanamide Saltsmentioning

confidence: 86%

First-Principles Plane-Wave-Based Exploration of Cathode and Anode Materials for Li and Na-ion Batteries

Ertural

Stoffel

Müller

et al. 2021

Preprint

Self Cite

View full text Add to dashboard Cite

We present a first-principles study based on plane-wave derived Löwdin population analysis and other local bonding descriptors to investigate cathode and anode materials for lithium and sodium ion batteries. By comparing the Löwdin charges of common graphite-based anode materials such as LiC6 and LiC12 to other phases such as salts of dicyanamide and nanoporous carbon-based compounds, new conclusions of an improved intercalation behavior of the latter are derived. In addition, we explore the stability of the dicyanamide salts concerning the removal of Li and Na atoms from the compounds with some of them resulting in dimerized structures. In particular, having a look at the different kinds of bonds and the corresponding covalency indicators reveals new insights into the change of the bonds during dimerization. Considering the generally high thermal stability of metal dicyanamide salts, which are solid at room temperature, their electrochemical activity as well as non-toxicity of alkali metal-based compounds, these materials are potential alternatives to commercially available electrodes, particularly for sodium ion batteries, to pristine graphite-based anode materials. This material is available free of charge via the Internet at http://pubs.acs.org.

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A new tilt and an old twist on the nickel arsenide structure-type: synthesis and characterisation of the quaternary transition-metal cyanamides A₂MnSn₂(NCN)₆ (A = Li and Na)

Abstract: Two quaternary transition-metal cyanamides with a novel crystal structure are stabilised through cyanamide tilts and octahedral twists.

Cited by 23 publications

References 32 publications

Metathesis and Redetermination of the Crystal Structure of Cadmium Carbodiimide, CdNCN

Metathesis and Redetermination of the Crystal Structure of Cadmium Carbodiimide, CdNCN

First-Principles Plane-Wave-Based Exploration of Cathode and Anode Materials for Li and Na-ion Batteries involving Complex Nitrogen-based Anions

First-Principles Plane-Wave-Based Exploration of Cathode and Anode Materials for Li and Na-ion Batteries

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