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Title: Direct Alcohol Fuel Cells: A Comparative Review of Acidic and Alkaline Systems

Journal Article · · Electrochemical Energy Reviews
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [4]; ORCiD logo [5]; ORCiD logo [6]; ORCiD logo [1]
  1. National Research Council (CNR), Florence (Italy)
  2. Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
  3. National Research Council (CNR), Messina (Italy)
  4. University of Palermo (Italy)
  5. National Research Council (CNR), Messina (Italy); Polytechnic Univ. of Turin (Italy)
  6. Univ. di Milano (Italy)

In the last 20 years, direct alcohol fuel cells (DAFCs) have been the subject of tremendous research efforts for the potential application as on-demand power sources. Two leading technologies respectively based on proton exchange membranes (PEMs) and anion exchange membranes (AEMs) have emerged: the first one operating in an acidic environment and conducting protons; the second one operating in alkaline electrolytes and conducting hydroxyl ions. In this review, we present an analysis of the state-of-the-art acidic and alkaline DAFCs fed with methanol and ethanol with the purpose to support a comparative analysis of acidic and alkaline systems, which is missing in the current literature. A special focus is placed on the effect of the reaction stoichiometry in acidic and alkaline systems. Particularly, we point out that, in alkaline systems, OH participates stoichiometrically to reactions, and that alcohol oxidation products are anions. This aspect must be considered when designing the fuel and when making an energy evaluation from a whole system perspective.

Research Organization:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Organization:
USDOE
Grant/Contract Number:
89233218CNA000001
OSTI ID:
1998120
Report Number(s):
LA-UR-22-25869
Journal Information:
Electrochemical Energy Reviews, Vol. 6, Issue 1; ISSN 2520-8489
Publisher:
Springer NatureCopyright Statement
Country of Publication:
United States
Language:
English

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Ternary Pt/Rh/SnO2 electrocatalysts for oxidizing ethanol to CO2 journal January 2009
Performance of an alkaline direct ethanol fuel cell with hydrogen peroxide as oxidant journal February 2014
Nanotechnology in Electrocatalysis for Energy book January 2013
Methanol crossover reduction by Nafion modification with palladium composite nanoparticles: Application to direct methanol fuel cells journal October 2010
Functionalized zeolite A–nafion composite membranes for direct methanol fuel cells journal July 2007
Product distributions and efficiencies for ethanol oxidation at PtNi octahedra journal October 2018
Direct Methanol Fuel Cells: From a Twentieth Century Electrochemist’s Dream to a Twenty-first Century Emerging Technology book January 2002
Direct electrochemical oxidation of alcohols with hydrogen evolution in continuous-flow reactor journal June 2019
Critical challenges in the system development of direct alcohol fuel cells as portable power supplies: An overview journal January 2019
Solvothermal Synthesis of Alloyed PtNi Colloidal Nanocrystal Clusters (CNCs) with Enhanced Catalytic Activity for Methanol Oxidation journal November 2017
Development of Poly(Vinyl Alcohol)-Based Polymers as Proton Exchange Membranes and Challenges in Fuel Cell Application: A Review journal July 2019
Pt-Rich core /Sn-Rich subsurface /Pt skin Nanocubes As Highly Active and Stable Electrocatalysts for the Ethanol Oxidation Reaction journal February 2018
Diphenylsilicate-incorporated Nafion® membranes for reduction of methanol crossover in direct methanol fuel cells journal October 2006
Effect of solvent and crystal size on the selectivity of ZSM-5/Nafion composite membranes fabricated by solution-casting method journal December 2006
Nafion/Sulfonated Montmorillonite Composite:  A New Concept Electrolyte Membrane for Direct Methanol Fuel Cells journal March 2005
Cell performance of direct methanol alkaline fuel cell (DMAFC) using anion exchange membranes prepared from PVA-Based block copolymer journal March 2020
Carbon-neutral sustainable energy technology: Direct ethanol fuel cells journal October 2015
Significantly enhanced performance of direct methanol fuel cells at elevated temperatures journal February 2020
Direct Alcohol Fuel Cells: Toward the Power Densities of Hydrogen-Fed Proton Exchange Membrane Fuel Cells journal December 2014
One-dimensional nanostructured electrocatalysts for polymer electrolyte membrane fuel cells—A review journal December 2016
Investigation of direct methanol fuel cells based on unsupported Pt–Ru anode catalysts with different chemical properties journal August 2000
Low-temperature oxidation of CO catalysed by Co3O4 nanorods journal April 2009
Alkaline-stable anion exchange membranes: A review of synthetic approaches journal January 2020
Metal foams as flow field and gas diffusion layer in direct methanol fuel cells journal February 2007
Simultaneous tuning of methanol crossover and ionic conductivity of sPEEK membrane electrolyte by incorporation of PSSA functionalized MWCNTs: A comparative study in DMFCs journal May 2014
Facile preparation of three-dimensional porous Pd–Au films and their electrocatalytic activity for methanol oxidation journal January 2016
Composite Nafion/Zirconium Phosphate Membranes for Direct Methanol Fuel Cell Operation at High Temperature journal January 2001
MEA for alkaline direct ethanol fuel cell with alkali doped PBI membrane and non-platinum electrodes journal March 2009
Fe–Mn bimetallic oxides-catalyzed oxygen reduction reaction in alkaline direct methanol fuel cells journal January 2018
Ag nanoparticles anchored Ag2WO4 nanorods: An efficient methanol tolerant and durable Pt free electro-catalyst toward oxygen reduction reaction journal April 2020
Surface-modified Nafion membranes with mesoporous SiO2 layers via a facile dip-coating approach for direct methanol fuel cells journal December 2008
Controllable Unzipping of Carbon Nanotubes as Advanced Pt Catalyst Supports for Oxygen Reduction journal July 2019
Novel organic–inorganic composite polymer-electrolyte membranes for DMFCs journal December 2009
Processing of Copper Based Foil Hardened with Zirconia by Non-Deformation Method journal May 2017
Porous Trimetallic PtRhCu Cubic Nanoboxes for Ethanol Electrooxidation journal June 2018
One-step efficiently coupling ultrafine Pt–Ni2P nanoparticles as robust catalysts for methanol and ethanol electro-oxidation in fuel cells reaction journal September 2019
Activated Graphite Supported Tunable Au–Pd Bimetallic Nanoparticle Composite Electrode for Methanol Oxidation journal October 2020
Palladium-Based Electrocatalysts for Alcohol Oxidation in Half Cells and in Direct Alcohol Fuel Cells journal September 2009
Performance of PdRu/C Anode Catalyst for Anion-Exchange Membrane Direct Ethanol Fuel Cell journal August 2013
Facet and dimensionality control of Pt nanostructures for efficient oxygen reduction and methanol oxidation electrocatalysts journal July 2016
Direct methanol alkaline fuel cell with catalysed metal mesh anodes journal April 2004
Performance and selectivity of PtxSn/C electro-catalysts for ethanol oxidation prepared by reduction with different formic acid concentrations journal May 2012
Microfluidic Synthesis and Characterization of FePtSn/C Catalysts with Enhanced Electro-Catalytic Performance for Direct Methanol Fuel Cells journal March 2017
A bi-functional cathode structure for alkaline-acid direct ethanol fuel cells journal October 2011
Graphene-nickel nitride hybrids supporting palladium nanoparticles for enhanced ethanol electrooxidation journal April 2021
Toward alkaline-stable anion exchange membranes in fuel cells: cycloaliphatic quaternary ammonium-based anion conductors journal June 2021
Pt-Bi on carbon aerogels as efficient electrocatalysts for ethanol oxidation reaction in alkaline medium journal March 2023
A simple model to assess the contribution of alloyed and non-alloyed platinum and tin to the ethanol oxidation reaction on Pt–Sn/C catalysts: Application to direct ethanol fuel cell performance journal September 2010
Anion exchange polyelectrolytes for membranes and ionomers journal February 2021
Replicating the Defect Structures on Ultrathin Rh Nanowires with Pt to Achieve Superior Electrocatalytic Activity toward Ethanol Oxidation journal November 2018
Regulating the Alloying Degree and Electronic Structure of Pt–Au Nanoparticles for High-Efficiency Direct C2+ Alcohol Fuel Cells journal May 2021
Performance of a passive direct ethanol fuel cell journal June 2014
Zeolite–Nafion composites as ion conducting membrane materials journal August 2003
Performance analysis of Fe–N–C catalyst for DMFC cathodes: Effect of water saturation in the cathodic catalyst layer journal December 2016
Characterization of transport properties in gas diffusion layers for proton exchange membrane fuel cells journal March 2007
Temperature‐Dependent Methanol Electro‐Oxidation on Well‐Characterized Pt‐Ru Alloys journal July 1994
Investigation of Supported Pd-Based Electrocatalysts for the Oxygen Reduction Reaction: Performance, Durability and Methanol Tolerance journal November 2015
PtRu Nanoparticles Deposited by the Sulfite Complex Method on Highly Porous Carbon Xerogels: Effect of the Thermal Treatment journal September 2013
The proton conductivity and mechanical properties of Nafion®/ ZrP nanocomposite membrane journal August 2019
Facile synthesis of composition-tunable PtRh nanosponges for methanol oxidation reaction journal March 2018
Liquid Water Transport in Gas Diffusion Layer of Polymer Electrolyte Fuel Cells journal January 2004
Methanol Oxidation at Platinum in Alkaline Media: A Study of the Effects of Hydroxide Concentration and of Mass Transport journal June 2021
Self-assembly of noble metal monolayers on transition metal carbide nanoparticle catalysts journal May 2016
Recent advances in direct methanol fuel cells at Los Alamos National Laboratory journal March 2000
Pt/CN-doped electrocatalysts: Superior electrocatalytic activity for methanol oxidation reaction and mechanistic insight into interfacial enhancement journal April 2017
Alkali doped polyvinyl alcohol/multi-walled carbon nano-tube electrolyte for direct methanol alkaline fuel cell journal July 2011
Mechanism study of the ethanol oxidation reaction on palladium in alkaline media journal March 2009
Transition metal-nitrogen co-doped carbide-derived carbon catalysts for oxygen reduction reaction in alkaline direct methanol fuel cell journal December 2017
Ruthenium–platinum core–shell nanocatalysts with substantially enhanced activity and durability towards methanol oxidation journal March 2016
Ethanol electrooxidation on PdIr/C electrocatalysts in alkaline media: electrochemical and fuel cell studies journal August 2014
Nafion based organic/inorganic composite membrane for air-breathing direct methanol fuel cells journal April 2007
Cost Analysis of Direct Methanol Fuel Cell Stacks for Mass Production journal November 2016
Influence of the acid–base characteristics of inorganic fillers on the high temperature performance of composite membranes in direct methanol fuel cells journal August 2003
Reconstructed PtFe Alloy Nanoparticles with Bulk-Surface Differential Structure for Methanol Oxidation journal September 2014
Synthesis of highly stable and methanol-tolerant electrocatalyst for oxygen reduction: Co supporting on N-doped-C hybridized TiO2 journal October 2015
Self-assembled flower-like MnO2 grown on Fe-containing urea-formaldehyde resins based carbon as catalyst for oxygen reduction reaction in alkaline direct methanol fuel cells journal December 2019
Activity, selectivity, and methanol tolerance of novel carbon-supported Pt and Pt3Me (Me = Ni, Co) cathode catalysts journal July 2007
Subnanometer PtRh Nanowire with Alleviated Poisoning Effect and Enhanced C–C Bond Cleavage for Ethanol Oxidation Electrocatalysis journal June 2019
Organic/inorganic composite membranes for application in DMFC journal September 2005
Reduction of alcohol permeation through Nafion® by polypyrrole journal December 2003
Ruthenium Crossover in Direct Methanol Fuel Cell with Pt-Ru Black Anode journal January 2004
Energy Savings in the Conversion of CO 2 to Fuels using an Electrolytic Device journal May 2014
Influence of ligands of palladium complexes on palladium/Nafion composite membranes for direct methanol fuel cells by supercritical CO2 impregnation method journal October 2014
New ETFE-based membrane for direct methanol fuel cell journal May 2005
Thermal Stability of Nafion® in Simulated Fuel Cell Environments journal January 1996
Analysis of the high-temperature methanol oxidation behaviour at carbon-supported Pt–Ru catalysts journal October 2003
Methanol permeability and proton conductivity of Nafion membranes modified electrochemically with polyaniline journal October 2008
Selective oxidation of ethanol to acetic acid in highly efficient polymer electrolyte membrane-direct ethanol fuel cells journal May 2009
Proton exchange membranes based on the short-side-chain perfluorinated ionomer for high temperature direct methanol fuel cells journal November 2006
Study of poly(vinyl alcohol)/titanium oxide composite polymer membranes and their application on alkaline direct alcohol fuel cell journal September 2008
Effects of electrolyte pH and composition on the ethanol electro-oxidation reaction journal September 2010
Development of a Direct Alcohol Alkaline Fuel Cell Stack journal June 2010
Impact of acid containing montmorillonite on the properties of Nafion® membranes journal November 2005
Where do poly(vinyl alcohol) based membranes stand in relation to Nafion® for direct methanol fuel cell applications? journal October 2012
Electrochemical conversion of alcohols for hydrogen production: a short overview journal January 2016
Hollow Pd/Te nanorods for the effective electrooxidation of methanol journal January 2021
Application of a non-noble Fe-N-C catalyst for oxygen reduction reaction in an alkaline direct ethanol fuel cell journal January 2018
Stabilization of the palladium electrocatalyst with alloyed gold for ethanol oxidation journal July 2010
Autocatalysis in the open circuit interaction of alcohol molecules with oxidized Pt surfaces journal January 2008
Low methanol permeable composite Nafion/silica/PWA membranes for low temperature direct methanol fuel cells journal May 2005
In-situ Quantification of Nanoparticles Oxidation: A Fixed Energy X-ray Absorption Approach journal July 2019
Cell performance of Pd–Sn catalyst in passive direct methanol alkaline fuel cell using anion exchange membrane journal April 2009
Organic silica/Nafion® composite membrane for direct methanol fuel cells journal October 2006
A review of quaternized polyvinyl alcohol as an alternative polymeric membrane in DMFCs and DEFCs journal March 2020
New Electrocatalysts for Electro-Oxidation of Methanol Prepared by Bönnemann´s Method journal January 2004
Rapid synthesis of a PtRu nano-sponge with different surface compositions and performance evaluation for methanol electrooxidation journal January 2015
Incorporation of heteropoly acid, tungstophosphoric acid within MCM-41 via impregnation and direct synthesis methods for the fabrication of composite membrane of DMFC journal November 2008
Nafion®/bio-functionalized montmorillonite nanohybrids as novel polyelectrolyte membranes for direct methanol fuel cells journal May 2009
Preparation of a PVA/HAP composite polymer membrane for a direct ethanol fuel cell (DEFC) journal April 2008
Facile Synthesis of Pt-Cu (Ni, Co)/GNs-CD and Their Enhanced Electro-Catalytic Activity for Methanol Oxidation journal January 2016
Pd and Pt–Ru anode electrocatalysts supported on multi-walled carbon nanotubes and their use in passive and active direct alcohol fuel cells with an anion-exchange membrane (alcohol=methanol, ethanol, glycerol) journal May 2009
Preparation of Nafion-sulfonated clay nanocomposite membrane for direct menthol fuel cells via a film coating process journal February 2007
Electro-Oxidation of Ethanol Using Pt 3 Sn Alloy Nanoparticles journal September 2018
PtCu catalyst for the electro-oxidation of ethanol in an alkaline direct alcohol fuel cell journal November 2017
Palladium-Based Nanocatalysts for Alcohol Electrooxidation in Alkaline Media book January 2013
Noble metal nanowires incorporated Nafion® membranes for reduction of methanol crossover in direct methanol fuel cells journal September 2010
Interfacial engineering of noble metals for electrocatalytic methanol and ethanol oxidation journal January 2020
Composite anode electrode based on iridium oxide promoter for direct methanol fuel cells journal May 2014
Hexapod PtRuCu Nanocrystalline Alloy for Highly Efficient and Stable Methanol Oxidation journal July 2018
Combining the core-shell construction with an alloying effect for high efficiency ethanol electrooxidation journal March 2021
A novel direct ethanol fuel cell with high power density journal August 2011
Insights on the extraordinary tolerance to alcohols of Fe-N-C cathode catalysts in highly performing direct alcohol fuel cells journal April 2017
Determination of energy efficiency for a direct methanol fuel cell stack by a fuel circulation method journal February 2004
Alkaline direct alcohol fuel cells using an anion exchange membrane journal October 2005
Improving Pd–N–C fuel cell electrocatalysts through fluorination-driven rearrangements of local coordination environment journal November 2021
Modifications on Promoting the Proton Conductivity of Polybenzimidazole-Based Polymer Electrolyte Membranes in Fuel Cells journal October 2021
Anode Catalysts for Direct Methanol Fuel Cells in Acidic Media: Do We Have Any Alternative for Pt or Pt–Ru? journal November 2014
Investigation of a direct methanol fuel cell based on a composite Nafion®-silica electrolyte for high temperature operation journal October 1999
Electrochemical oxidation of methanol on Pt/V2O5–C composite catalysts journal January 2009
PtAg bimetallic nanowires: Facile synthesis and their use as excellent electrocatalysts toward low-cost fuel cells journal March 2015
Zirconium phosphate/Nafion115 composite membrane for high-concentration DMFC journal July 2008
Commercial platinum group metal-free cathodic electrocatalysts for highly performed direct methanol fuel cell applications journal October 2019
Direct Electrodeposition of Tetrahexahedral Pd Nanocrystals with High-Index Facets and High Catalytic Activity for Ethanol Electrooxidation journal June 2010
Facile one-step room temperature synthesis of PdAg nanocatalysts supported on multi-walled carbon nanotubes towards electro-oxidation of methanol and ethanol journal April 2020
An in situ Fourier transform infrared spectroelectrochemical study on ethanol electrooxidation on Pd in alkaline solution journal March 2010
Carbon supported Ag and Ag–Co catalysts tolerant to methanol and ethanol for the oxygen reduction reaction in alkaline media journal November 2016