Electroreduction of carbon dioxide

Vassiliev, Yu.B.; Bagotzky, V.S.; Хазова, О. А.; Mayorova, N. A.

doi:10.1016/0368-1874(85)80074-5

Cited by 70 publications

(34 citation statements)

References 16 publications

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“…tin coverage = 100%) and so does not use the kinetics on copper. The Tafel slopes of both reactions I and II were assumed as 0.118 V/decade at 298 K [15,16], with a charge transfer coefficient of 0.5, and corrected for temperature by:…”

Section: Extended Reactor (Cathode) Model [6]mentioning

confidence: 99%

Development of a continuous reactor for the electro-reduction of carbon dioxide to formate – Part 2: Scale-up

2007

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This paper reports experimental and modeling work for the laboratory scale-up of continuous ''trickle-bed'' reactors for the electro-reduction of CO 2 to potassium formate. Two reactors (A and B) were employed, with particulate tin 3D cathodes of superficial areas, respectively, 45 · 10 À4 (2-14 A) and 320 · 10 À4 m 2 (20-100 A). Experiments in Reactor A using granulated tin cathodes (99.9 wt% Sn) and a feed gas of 100% CO 2 showed slightly better performance than that of the tinned-copper mesh cathodes of our previous communications, while giving substantially improved temporal stability (200 vs. 20 min). The seven-fold scaled-up Reactor B used a feed gas of 100% CO 2 with the aqueous catholyte and anolyte, respectively [0.5 M KHCO 3 + 2 M KCl] and 2 M KOH, at inlet pressure from 350 to 600 kPa(abs) and outlet temperature 295 to 325 K. For a superficial current density of 0.6-3.1 kA m À2 Reactor B achieved corresponding formate current efficiencies of 91-63%, with the same range of reactor voltage as that in Reactor A (2.7-4.3 V), which reflects the success of the scale-up in this work. Up to 1 M formate was obtained in the catholyte product from a single pass in Reactor B, but when the catholyte feed was spiked with 2-3 M potassium formate there was a large drop in current efficiency due to formate cross-over through the Nafion 117 membrane. An extended reactor (cathode) model that used four fitted kinetic parameters and assumed zero formate cross-over was able to mirror the reactor performance with reasonable fidelity over a wide range of conditions (maximum error in formate CE = ±20%), including formate product concentrations up to 1 M.Keywords Carbon dioxide Á Continuous reactor Á Electro-reduction Á Formate Á 3D electrode Á Scale-up Á Tin granule cathode Nomenclature a 1 ,a 2 Tafel constant for reaction 1, 2 (V) b 1 ,b 2 Tafel slope for reaction 1, 2 (V decade À1 ) C Concentration of KCl (M) CECurrent efficiency (-) d p, average Average particle diameter (m) E a,1 , E a,2 Activation energies for reactions 1 and 2 (kJ kmol À1 ) E cell Full-cell operating voltage (absolute value) (V) E 1 , E 2 Electrode potential for reaction 1 and 2 (V(SHE)) E r,1 , E r,2 Reversible electrode potential for reaction 1 and 2 (V(SHE)) G Gas flow rate (mL STP min À1 ) H Height of 3D cathode (m)Exchange current densities for reactions 1 and 2 (kA m À2 ) j 1 ,j 2 Partial real current density for reaction 1, 2 (kA m À2 ) j 1L CO 2 mass transfer limited current density for reaction 1 (kA m À2 ) k 1 , k 2 Electrochemical rate constants for reactions 1 and 2 (m s À1 ) L Catholyte liquid flow rate (mL min À1 ) P cathode Cathode side pressure (kPa(abs))

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Section: Extended Reactor (Cathode) Model [6]mentioning

confidence: 99%

Development of a continuous reactor for the electro-reduction of carbon dioxide to formate – Part 2: Scale-up

2007

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“…In aprotic media, CO 2 is highly stable from at hermodynamic point of view,w ith as tandard electrode potential (E 0 )o fÀ1.90 Vv ersus the normalh ydrogen electrode( NHE) [7] for the one-electron reduction of CO 2 to the CO 2 À C radicala nion. In aprotic media, CO 2 is highly stable from at hermodynamic point of view,w ith as tandard electrode potential (E 0 )o fÀ1.90 Vv ersus the normalh ydrogen electrode( NHE) [7] for the one-electron reduction of CO 2 to the CO 2 À C radicala nion.…”

Section: Introductionmentioning

confidence: 99%

“…CO 2 conversion reaction mechanisms depend on the reaction mediaa nd (electro)catalysts used. In aprotic media, CO 2 is highly stable from at hermodynamic point of view,w ith as tandard electrode potential (E 0 )o fÀ1.90 Vv ersus the normalh ydrogen electrode( NHE) [7] for the one-electron reduction of CO 2 to the CO 2 À C radicala nion. In protic media, some CO 2 reduction routesa re thermodynamically easier through proton-coupled electron transfer pathways.…”

Section: Introductionmentioning

confidence: 99%

Electrochemical Reduction of CO₂ at Metal Electrodes in a Distillable Ionic Liquid

Chen

Guo

et al. 2016

ChemSusChem

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The electroreduction of CO2 in the distillable ionic liquid dimethylammonium dimethylcarbamate (dimcarb) has been investigated with 17 metal electrodes. Analysis of the electrolysis products reveals that aluminum, bismuth, lead, copper, nickel, palladium, platinum, iron, molybdenum, titanium and zirconium electroreduce the available protons in dimcarb to hydrogen rather than reducing CO2 . Conversely, indium, tin, zinc, silver and gold are able to catalyze the reduction of CO2 to predominantly carbon monoxide (CO) and to a lesser extent, formate ([HCOO](-) ). In all cases, the applied potential was found to have a minimal influence on the distribution of the reduction products. Overall, indium was found to be the best electrocatalyst for CO2 reduction in dimcarb, with faradaic efficiencies of approximately 45 % and 40 % for the generation of CO and [HCOO](-) , respectively, at a potential of -1.34 V versus Cc(+/0) (Cc(+) =cobaltocenium) employing a dimethylamine to CO2 ratio of less than 1.8:1.

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“…47 The reduction of CO 2 in aprotic solvents was extensively studied on a variety of metal electrodes and it was shown that the reaction depends strongly on the electrode material, the type of solvent, the water content, the temperature, and the CO 2 concentration. [51][52][53][54] After one-electron reduction, the proposed products are either (i) oxalate from the coupling of two CO 2…”

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confidence: 99%

The Effect of CO₂on Alkyl Carbonate Trans-Esterification during Formation of Graphite Electrodes in Li-Ion Batteries

Strehle

Solchenbach

Metzger

et al. 2017

J. Electrochem. Soc.

103

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Apart from the often-described formation of interphases between the electrodes and the electrolyte in Li-ion batteries, changes of the bulk electrolyte also occur during cycling. In this study, we use On-line Electrochemical Mass Spectrometry (OEMS) to measure the gas evolution associated with changes in the electrolyte during the initial cycles of graphite/lithium half-cells in an electrolyte composed of ethylene carbonate (EC), ethyl methyl carbonate (EMC), and the conducting salt LiPF 6 . The reduction of the electrolyte at the graphite surface within the first cycle is accompanied by the release of lithium alkoxides (LiOR), which initiate the conversion of the co-solvent EMC into the linear carbonates dimethyl carbonate (DMC) and diethyl carbonate (DEC). This trans-esterification can be suppressed by the use of additives such as vinylene carbonate (VC) and vinyl ethylene carbonate (VEC). Upon reduction, VC generates CO 2 , while VEC generates 1,3-butadiene. The beneficial impact of the additives arises from these gases, which scavenge the highly reactive LiOR species by forming non-reactive products. Furthermore, our results demonstrate the positive effect of CO 2 on the cell chemistry and the importance of adjusting the electrolyte volume and additive concentration with respect to the active material mass in Li-ion batteries. Li-ion batteries (LIBs) have been successfully used in electronic devices during the past 25 years. Recently, the expanding market of hybrid electric vehicles (HEVs), plug-in hybrid electric vehicles (PHEVs), and battery electric vehicles (BEVs) powered by LIBs has pushed the requirements on this technology even further.1-4 However, the application of LIBs particularly in PHEVs and BEVs is still hampered by their limited safety, thermal stability, and cycle life. Although the applied electrolyte solutions are prone to thermal decomposition, mixtures of cyclic and linear organic carbonate solvents in combination with the conducting salt LiPF 6 are widely used for LIBs. They represent an optimum between low viscosity, low vapor pressure, good salt solubility, and high conductivity. The electrolyte composition plays an important role in terms of cycle life. During the initial cycles, the electrolyte is reduced at the anode and forms a passivating layer, the so-called solid electrolyte interphase (SEI). The SEI prevents the further reduction of the bulk electrolyte by blocking the electron transport while allowing Li-ions to pass through. Its stability is thus critical for attaining long LIB cycle and storage life, 5,6 whereby electrolyte additives have been shown to substantially alter the composition of the SEI and to improve its effectiveness. 7Besides the formation of electrode interphases, also changes of the bulk electrolyte can occur during the cycling of a cell. These processes can be induced either by thermal reactions or by the dissolution and/or further reaction of reduced or oxidized electrolyte species from the anode or cathode, respectively. For example, the thermal decomposi...

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Electroreduction of carbon dioxide

Cited by 70 publications

References 16 publications

Development of a continuous reactor for the electro-reduction of carbon dioxide to formate – Part 2: Scale-up

Development of a continuous reactor for the electro-reduction of carbon dioxide to formate – Part 2: Scale-up

Electrochemical Reduction of CO₂ at Metal Electrodes in a Distillable Ionic Liquid

The Effect of CO₂on Alkyl Carbonate Trans-Esterification during Formation of Graphite Electrodes in Li-Ion Batteries

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Electroreduction of carbon dioxide

Cited by 70 publications

References 16 publications

Development of a continuous reactor for the electro-reduction of carbon dioxide to formate – Part 2: Scale-up

Development of a continuous reactor for the electro-reduction of carbon dioxide to formate – Part 2: Scale-up

Electrochemical Reduction of CO2 at Metal Electrodes in a Distillable Ionic Liquid

The Effect of CO2on Alkyl Carbonate Trans-Esterification during Formation of Graphite Electrodes in Li-Ion Batteries

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Electrochemical Reduction of CO₂ at Metal Electrodes in a Distillable Ionic Liquid

The Effect of CO₂on Alkyl Carbonate Trans-Esterification during Formation of Graphite Electrodes in Li-Ion Batteries