AN ELECTROCHEMICAL SYNTHESIS OF THE Li-CONTAINING PHASE BASED ON Cu5O2(PO4)2

V. Kordan, O. Zaremba, I. Oshchapovsky, P. Demchenko, V. Pavlyuk


DOI: http://dx.doi.org/10.30970/vch.6401.147

Abstract


The composition and electrochemical properties of the electrode material based on Cu5O2(PO4)2 (own structure type, space group P-1, Pearson’s code aP17) were studied by X-ray powder diffraction, scanning electron microscopy, energy dispersion and X-ray fluorescence spectroscopy. Electrochemical lithiation of the phase, which was used as cathode material, was carried out in the “Swagelok-cell”-type battery prototype. Sheet of Li-metal was used as anode material. The anode and cathode materials were separated to avoid contact between them. An electrolyte for batteries consisted of 1 M Li[PF6] solution and ethylene carbonate and dimethyl carbonate (1:1 vol. ratio). Morphology of the sample surfaces was studied using scanning electron microscope TESCAN Vega3 LMU. Quantitative composition of the powders (before and after lithiation) was studied using Oxford Instruments energy dispersive X-ray analyser (Aztec ONE system). X-ray fluorescent spectroscopy (spectrometer ElvaX Pro) was used for investigation of the integral composition of electrode before and after electrochemical processes and showed the Cu/P ratio equal 2.52 before lithiation and 2.47 after lithiation. The structural analysis of the Cu5O2(PO4)2 and LixCu5O2(PO4)2 phases was carried out by X-ray powder diffraction using STOE STADI P diffractrometer (CuKα1-radiation, λ = 1.54060 Å). The unit cell parameters increase because of the inclusion of lithium in the free channels of the structure: а = 5.20298(9)→5.20401(7) Å, b = 5.29851(9)→5.29991(8) Å, c = 7.60715(13)→7.60889(11) Å, α = 82.4944(10)→82.4931(8)°, β = 89.8368(11)→89.8309(8)°, γ = 68.2629(9)→68.2595(7)°, V = 192.897(6)→ 193.026(5) Å3. The polycrystalline Cu5O2(PO4)2 sample contains lamellar particles 0.2–0.4 μm thick and up to 5 μm in length. The surface of electrode adsorbs actively the components of electrolyte, resulting in the formation of block-like aggregates with 1–5 μm in size. The total composition of the electrode before and after electrochemical Li-intercalation is practically unchanged.

 

Keywords: electrochemical synthesis, X-ray powder diffraction, cathode material, Li-ion batteries.

 

 


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