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Quinol/quinone equilibria are ubiquitous in nature and find multiple technological applications, most recently in electrical charge storage. Much research has been devoted to proton-coupled electron transfer (PCET) in such systems and to bidentate complexation of ortho-quinol (catechol) ligands with multivalent metal ions but rarely to the interplay of these two reactions. Here, we investigate the impact of a redox-inactive metal ion, as a complexing and charge-compensating agent, on redox processes of catechol in aqueous solutions, that is, in the presence of proton equilibria. We pay separate attention to their thermodynamics and kinetics, which can be regulated by the pH and buffer capacity. As the proton buffer concentration decreases, proton equilibria during catechol PCET are slower to establish, thus kinetically prioritizing the participation of the metal ion rather than the proton in the redox charge compensation. Making use of this kinetic interplay can be a general strategy to conceive organic battery cathodes for proton-free metal-ion aqueous batteries., Funding Agencies|Wallenberg Wood Science Center (WWSC); Knut and Alice Wallenberg Foundation [KAW 2019.0604, KAW 2021.0195]; Swedish Energy Agency [52023-1]; Vetenskapradet [2016-05990]

Zinc metal batteries (ZnBs) are poised as the next-generation energy storage solution, complementing lithium-ion batteries, thanks to their cost-effectiveness and safety advantages. These benefits originate from the abundance of zinc and its compatibility with non-flammable aqueous electrolytes. However, the inherent instability of zinc in aqueous environments, manifested through hydrogen evolution reactions (HER) and dendritic growth, has hindered commercialization due to poor cycling stability. Enter potassium polyacrylate (PAAK)-based water-in-polymer salt electrolyte (WiPSE), a novel variant of water-in-salt electrolytes (WiSE), designed to mitigate side reactions associated with water redox processes, thereby enhancing the cyclic stability of ZnBs. In this study, WiPSE was employed in ZnBs featuring lignin and carbon composites as cathode materials. Our research highlights the crucial function of acrylate groups from WiPSE in stabilizing the ionic flux on the surface of the Zn electrode. This stabilization promotes the parallel deposition of Zn along the (002) plane, resulting in a significant reduction in dendritic growth. Notably, our sustainable Zn-lignin battery showcases remarkable cyclic stability, retaining 80% of its initial capacity after 8000 cycles at a high current rate (1 A g-1) and maintaining over 75% capacity retention up to 2000 cycles at a low current rate (0.2 A g-1). This study showcases the practical application of WiPSE for the development of low-cost, dendrite-free, and scalable ZnBs. A dendrite-free and long-life cycle Zn-lignin battery was demonstrated using water-in-polymer salt electrolyte.

Ionic thermoelectric materials can generate large thermal voltages under temperature gradients while also being low-cost and environmentally friendly. Many electrolytes with large Seebeck coefficients are reported in recent years, however, the mechanism of the thermal voltage is remained elusive. In this work, three types of polyelectrolytes are studied with different cations and identified a significant contribution to their thermal voltage originating from a concentration gradient. This conclusion is based on studies of the loss and gain of water upon temperature changes, variations in conductivity with water content and temperature, and the voltages induced by changes in water content. The results are analyzed by the "hopping mode" dynamics of charge transport in electrolytes. The hydration of different cations influences the water concentration gradient, which affects the barrier height and ion-induced potential in the electrodes. This work shows that the hydro-voltage in ionic thermoelectric devices can be one order of magnitude larger than the contribution from thermodiffusion-induced potentials, and becomes the main contributor to energy harvesting when implemented into ionic thermoelectric supercapacitors. Together with the rationalized theoretical discussion, this work clarifies the mechanism of thermal voltages in electrolytes and provides a new path for the development of ionic thermoelectric materials. The thermal voltage of polyelectrolyte films largely depends on the water concentration gradient under a temperature difference, which can be optimized to promote the generated total voltage up to over 30 mV K-1.image, Funding Agencies|EU commission [101058284]; Swedish Research Council [VR 2018-04037]; AForsk Foundation [23-220]; Advanced Functional Materials Center at Linkoping University [2009-00971]

Herein, we have utilized agri-waste and amalgamating low Fe3+, to develop an economic iron oxide-carbon hybrid-based electrocatalyst for oxygen reduction reaction (ORR) with water as a main product following close to 4e- transfer process. The electrocatalytic activity is justified by electrochemical active surface area, synergetic effect, and density functional theory calculations. Herein, we have utilized agri-waste and amalgamating low Fe3+, to develop an economic iron oxide-carbon hybrid-based electrocatalyst for oxygen reduction reaction (ORR) with water as a main product following close to 4e- transfer process., Funding Agencies|Chhatrapati Shahu Maharaj Research Training and Human Development Institute [EMR/2017/003368, CSMNRF-2021, CSMNRF-2021/2021-22/896]; SERB New Delhi, India

“Water-in-polymer salt” electrolytes (WiPSEs) based on potassium polyacrylate (PAAK) belong to a new family of “water-in-salt” electrolytes that is envisioned as a potential solution for large-scale supercapacitors to balance the electric grid at short time scales. The WiPSEs display a broad electrochemical stability window up to 3 V, yet they are nonflammable and provide high ionic conductivity (100 mS/cm) as required in high-power devices. However, the transport of matter in PAAK-based WiPSEs has not been studied. In this work, we have extensively characterized PAAK by spectroscopic methods such as Raman spectroscopy and NMR diffusometry to determine the state of water and elucidate the mechanism of ionic transport as well as its interplay with water and polymer chain dynamics, which reveals that a significant proportion of the transport in WiPSEs is attributed to hydrated cations. The results are further supported by molecular dynamics (MD) simulations. Finally, the potential of WiPSEs based on PAAK is demonstrated in an activated carbon-based supercapacitor operating up to 2 V with reasonable self-discharge. This proof of concept shows promise for low-cost and large-scale supercapacitors., Funding Agencies|Swedish Energy Agency [P52023-1]; Knut and Alice Wallenberg Foundation [21-130]; Swedish Electricity Storage and Balancing Centre (SESBC); Swedish Energy Agency together with 5 academic and 26 non-academic partners; Ligna Energy; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University; Swedish Research Council; STandUP for Energy collaboration; [KAW 2020.0174]; [22-134]; [2009-00971]; [2020-05223]

Intrinsically stretchable energy storage devices are essential for the powering of imperceptible wearable electronics. Organic batteries based on plant-derived redox-active molecules can offer critical advantages from a safety, sustainability, and economic perspective, but such batteries are not yet available in soft and stretchable form factors. Here we report an intrinsically stretchable organic battery made of elastomeric composite electrodes formulated with alizarin, a natural dye derived from the plant Rubia tinctorum, whose two quinone motifs enable its uses in both positive and negative electrodes. The quaternary biocomposite electrodes possess excellent electron-ion conduction/coupling and superior stretchability (>300%) owing to self-organized hierarchical morphology. In a full-cell configuration, its energy density of 3.8 mW h cm−3 was preserved at 100% strain, and assembled modules on stretchy textiles and rubber gloves can power integrated LEDs during various deformations. This work paves the way for low-cost, eco-friendly, and deformable batteries for next generation wearable electronics., We thank Mohsen Mohammadi, Sangmin Park, and Dr Robert Brooke for assistance with illustrations, Meysam Karami Rad for LabVIEW programming and help with the circuit tests, and Laura Seufert for assistance with the module demonstration. This work was financially supported by the ÅForsk Foundation (19-428), the Swedish Government Strategic Research Area in Materials Science on Advanced Functional Materials at Linköping University (Faculty grant SFO-Mat-LiU no. 2009-00971), the Knut and Alice Wallenberg Foundation (POC “paper batteries” and “high voltage aqueous electrolyte”), and the Swedish Research Council (starting grant no. 2020-05218, no. 2019-04424 and no. 2016-06146). G. G. acknowledges financial support from the Swedish Research Council (no. 2018-03957) and the Swedish Energy Agency grant 51201-1. A. R. acknowledges Marie Skłodowska-Curie Actions Seal of Excellence Fellowship program from the Sweden's Innovation Agency (Vinnova grant no. 2021-01668). This work was partially supported by the Wallenberg Initiative Materials Science for Sustainability (WISE) funded by the Knut and Alice Wallenberg Foundation.

Zinc oxide (ZnO) is a thermally stable n-type semiconducting material. ZnO 2D nanosheets have mainly gained substantial attention due to their unique properties, such as direct bandgap and strong excitonic binding energy at room temperature. These are widely utilized in piezotronics, energy storage, photodetectors, light-emitting diodes, solar cells, gas sensors, and photocatalysis. Notably, the chemical properties and performances of ZnO nanosheets largely depend on the nano-structuring that can be regulated and controlled through modulating synthetic strategies. Two synthetic approaches, top-down and bottom-up, are mainly employed for preparing ZnO 2D nanomaterials. However, owing to better results in producing defect-free nanostructures, homogenous chemical composition, etc., the bottom-up approach is extensively used compared to the top-down method for preparing ZnO 2D nanosheets. This review presents a comprehensive study on designing and developing 2D ZnO nanomaterials, followed by accenting its potential applications. To begin with, various synthetic strategies and attributes of ZnO 2D nanosheets are discussed, followed by focusing on methodologies and reaction mechanisms. Then, their deliberation toward batteries, supercapacitors, electronics/optoelectronics, photocatalysis, sensing, and piezoelectronic platforms are further discussed. Finally, the challenges and future opportunities are featured based on its current development., Funding Agencies|SERB; SERB, New Delhi [EMR/2017/003368]

Zn-metal batteries (ZnBs) are safe and sustainable because of their operability in aqueous electrolytes, abundance of Zn, and recyclability. However, the thermodynamic instability of Zn metal in aqueous electrolytes is a major bottleneck for its commercialization. As such, Zn deposition (Zn2+ & RARR; Zn(s)) is continuously accompanied by the hydrogen evolution reaction (HER) (2H(+) & RARR; H-2) and dendritic growth that further accentuate the HER. Consequently, the local pH around the Zn electrode increases and promotes the formation of inactive and/or poorly conductive Zn passivation species (Zn + 2H(2)O & RARR; Zn(OH)(2) + H-2) on the Zn. This aggravates the consumption of Zn and electrolyte and degrades the performance of ZnB. To propel HER beyond its thermodynamic potential (0 V vs standard hydrogen electrode (SHE) at pH 0), the concept of water-in-salt-electrolyte (WISE) has been employed in ZnBs. Since the publication of the first article on WISE for ZnB in 2016, this research area has progressed continuously. Here, an overview and discussion on this promising research direction for accelerating the maturity of ZnBs is provided. The review briefly describes the current issues with conventional aqueous electrolyte in ZnBs, including a historic overview and basic understanding of WISE. Furthermore, the application scenarios of WISE in ZnBs are detailed, with the description of various key mechanisms (e.g., side reactions, Zn electrodeposition, anions or cations intercalation in metal oxide or graphite, and ion transport at low temperature)., Funding Agencies|Knut and Alice Wallenberg (KAW) foundation [KAW 2020.0174]; Wallenberg Initiative Materials Science for Sustainability WISE; Swedish Energy Agency (SESBC competence center) [P52023-1, 526701]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoeping University (Faculty Grant SFO-Mat-LiU ) [2009-00971]; Aforsk foundation [21-130, 22134]

Next-generation wearables will interface intimately with the human body either on-skin, implanted or woven into clothing. This requires electrical components that match the mechanical properties of biological tissues - stretchability (up to 60% strain) and softness (Youngs modulus of similar to 1 kPa to 1 MPa). As wearables become increasingly complex, the energy and mechanical requirements will increase, and an integrated power supply unit such as a soft and stretchable battery is needed to achieve autonomy and wireless operation. However, two key challenges remain for current stretchable battery technology: the mechanical performance (softness and stretchability) and its relation to the size and charge storage capacity (challenge I), and the sustainability and biocompatibility of the battery materials and its components (challenge II). Integrating all these factors into the battery design often leads to a trade-off between the various properties. This perspective will evaluate current strategies for achieving sustainable stretchable batteries and provide a discussion on possible avenues for future research. Stretchable battery technology still faces several challenges to progress the development of next-generation wearables. This perspective will evaluate current strategies and provide a discussion on possible avenues for future research., Funding Agencies|Swedish Governmental Agency for Innovation Systems, VINNOVA [2021-01668]; Knut and Alice Wallenberg Foundation; Linkoeping University; Wallenberg Wood Science Centre; Swedish Research Council [2020-05218]; Wallenberg Initiative Materials Science for Sustainability (WISE) - Knut and Alice Wallenberg Foundation

Zn-ion batteries are one of the hot candidates for low-cost and sustainable secondary batteries. The hydrogen evolution and dendritic growth upon zinc deposition are todays challenges for that technology. One of the new strategies to cope with these issues is to use "water-in-salt" electrolyte (WISE), that is, super concentrated aqueous electrolytes, to broaden its electrochemical stability window (ESW), suppressing hydrogen evolution reaction (HER), and perturbing the dendritic growth. Herein, this work proposes to use "water-in-polymer salt" electrolyte (WIPSE) concept to mitigate the challenges with Zn ion batteries and bring this technology toward one of the cheapest, greenest, and most sustainable electrodes: Lignin-carbon (L-C) electrode. Potassium polyacrylate (PAAK) as WISE bears out as better electrolyte for L-C electrodes in terms of self-discharge, cyclic stability, and specific capacity compared to conventional electrolyte based on chemically cousin molecule potassium acetate. Zinc bis(trifluoromethanesulfonyl) imide (Zn(TFSI)(2)) added into WIPSE shows deposition and dissolution of Zn in Zn//Zn symmetric cell suggesting that Zn2+ are moving into the polyanionic network. Furthermore, the added bis (trifluor omethanesul fonyl) imide (TFSI-) metal salts trigger a approximate to 40% enhancement of the capacity of L-C electrode. These results show a new promising direction toward the development of cost-effective and sustainable Zn-lignin batteries., Funding Agencies|Knut and Alice Wallenberg (KAW) foundation [KAW 2020.0174]; Swedish Research Council [2016-05990]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoeping University [2009-00971]; competence center FunMat-II - Swedish Agency for Innovation Systems (Vinnova) [2016-05156]; aforsk foundation [21-130]; KAW

Novel two-dimensional materials (2DMs) with balanced electrical conductivity and lithium (Li) storage capacity are desirable for next-generation rechargeable batteries as they may serve as high-performance anodes, improving output battery characteristics. Gaining an advanced understanding of the electrochemical behavior of lithium at the electrode surface and the changes in interior structure of 2DM-based electrodes caused by lithiation is a key component in the long-term process of the implementation of new electrodes into to a realistic device. Here, we showcase the advantages of bilayer-patched epitaxial graphene on 4H-SiC (0001) as a possible anode material in lithium-ion batteries. The presence of bilayer graphene patches is beneficial for the overall lithiation process because it results in enhanced quantum capacitance of the electrode and provides extra intercalation paths. By performing cyclic voltammetry and chronoamperometry measurements, we shed light on the redox behavior of lithium at the bilayer-patched epitaxial graphene electrode and find that the early-stage growth of lithium is governed by the instantaneous nucleation mechanism. The results also demonstrate the fast lithium-ion transport (similar to 4.7-5.6 x 10(-7) cm(2).s(-1)) to the bilayer-patched epitaxial graphene electrode. Raman measurements complemented by in-depth statistical analysis and density functional theory calculations enable us to comprehend the lithiation effect on the properties of bilayer-patched epitaxial graphene and ascribe the lithium intercalation-induced Raman G peak splitting to the disparity between graphene layers. The current results are helpful for further advancement of the design of graphene-based electrodes with targeted performance., Funding Agencies|VR [2018-04962]; SSF [SSF GMT14-0077, SSF RMA15-0024]; Angpanneforeningens Forskningsstiftelse [21-112]

In electrochemical energy storage devices (ESDs), organic electrolytes are typically used for wide operational potential window, yet they suffer with cost, environmental, flammability issues, and low ionic conductivity when compared with water-based electrolytes. Hence, for large-scale applications that require high power and safety, presently there is no true solution. Though water-based electrolytes have higher ionic conductivities, and are cost-effective and nonflammable, their high self-discharge rate with organic/carbon-based electrodes impedes their commercialization. It is found out that highly concentrated polymer electrolytes on the concept of "water-in-salt electrolyte" lead to extremely low leakage current within the electrochemical stability window (ESW) of water, thus solving the issue of self-discharge in organic/carbon-based ESDs. Herein, potassium polyacrylate (PAAK) is prepared as "water-in-polymer salt electrolyte" (WIPSE) and tested for one of most abundant wood-based biopolymer lignin and polyimide as positive and negative electrodes, respectively, in both half-cell and full-cell. The device shows an open-circuit voltage drops <0.45V in 100h setting a record for organic batteries using aqueous electrolyte. The high ionic conductivity (40-120mScm(-1)) nonflammability of PAAK with high ESW (3.1V) opens a new direction for truly safe, sustainable, and high power (6.8kWkg(-1)) organic ESD manufactured by printing technologies., Funding Agencies|Proof-of-Concept project "Paper Batteries" - Knut and Alice Wallenberg (KAW) foundation; "high-voltage aqueous electrolytes" - Knut and Alice Wallenberg (KAW) foundation; "Wood Wallenberg Science Center" - Knut and Alice Wallenberg (KAW) foundation; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [2009-00971]; Wallenberg Scholar grants from KAW

Lignin, the most abundant biopolymer on earth, has been explored as an electroactive material in battery applications. One essential feature for such lignin-based batteries to reach successful usage and implementation, e.g., large-scale stationary grid applications, is to have slow self-discharge characteristics on top of the essential safety and life-cycle properties. Water-in-polymer salt electrolytes (WIPSEs) have been demonstrated as an attractive route to solve this issue; however, little has been done to understand the fundamentals of actual self-discharge mechanisms. Herein, the impact of some critical chemical and physical parameters (pH, dissolved oxygen, viscosity, and cutoff potential) on self-discharge of batteries based on WIPSE and lignin has been investigated. The pH range is crucial as there is an interplay between long-term stability and high energy density. Indeed, lignin derivatives typically store relatively more charge in acidic media but later promote corrosion affecting device stability. A robust and high-performing organic battery, incorporating potassium polyacrylate as WIPSE, is demonstrated, which expresses good self-discharge behavior for a broad range of pH and with little impact on the atmosphere used for manufacturing. It is believed that the investigation will provide critical insights to the research community to promote the advancement of printed large-scale energy storage devices., Funding Agencies|Knut and Alice Wallenberg (KAW) foundation [KAW 2019.0344, KAW 2020.0174]; Swedish Research Council [2016-05990]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [2009-00971]; KAW

Internet-of-things which requires electronics, energy convertor and storage must be low-cost, recyclable and environmentally friendly. In the development of printed batteries, ideally all the components (electrode and electrolyte) must be printable to ensure low-cost manufacturing via printing technologies. Most of the printed batteries suffer with low power. One of the reasons is the poor ionic conductivity of the electrolyte due to the high viscosity needed for printing relatively thick layers. In the present work we have demonstrated a new class of electrolyte promising for printed organic batteries following the concept of water-in-polymer salt electrolytes (WIPSEs). These highly concentrated electrolytes of potassium polyacrylate are non-flammable, low cost and environmentally friendly. They possess high ionic conductivities (45-87 mS/cm) independent on the macroscopic viscosities varying from 7 to 33000 cP. The decoupling between ionic transport and macroscopic viscosity enables us to demonstrate organic batteries based on WIPSEs that can deliver a high and constant power (similar to 4.5 kW/kg; 7.1-11 mW/cm(2)) independent on the viscosity of the electrolytes. The tunability of the viscosity presents a prerequisite for printed technology manufacturing and compatibility with printed batteries., Funding Agencies|Proof-of-Concept project "Paper Batteries"; "Wallenberg Wood Science Center" - Knut and Alice Wallenberg (KAW) foundation; Swedish Research Council [201605990]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009-00971]; Wallenberg Scholar grants from KAW

Vanadium dioxide (VO2) received tremendous interest lately due to its unique structural, electronic, and optoelectronic properties. VO2 has been extensively used in electrochromic displays and memristors and its VO2 (B) polymorph is extensively utilized as electrode material in energy storage applications. More studies are focused on VO2 (B) nanostructures which displayed different energy storage behavior than the bulk VO2. The present review provides a systematic overview of the progress in VO2 nanostructures syntheses and its application in energy storage devices. Herein, a general introduction, discussion about crystal structure, and syntheses of a variety of nanostructures such as nanowires, nanorods, nanobelts, nanotubes, carambola shaped, etc. are summarized. The energy storage application of VO2 nanostructure and its composites are also described in detail and categorically, e.g. Li-ion battery, Na-ion battery, and supercapacitors. The current status and challenges associated with VO2 nanostructures are reported. Finally, light has been shed for the overall performance improvement of VO2 nanostructure as potential electrode material for future application., Funding Agencies|Jain University for Junior Research Fellowship; SERB, New DelhiDepartment of Science & Technology (India)Science Engineering Research Board (SERB), India [EMR/2017/003368]

The mass implementation of renewable energies is limited by the absence of efficient and affordable technology to store electrical energy. Thus, the development of new materials is needed to improve the performance of actual devices such as batteries or supercapacitors. Herein, the facile consecutive chemically oxidative polymerization of poly(1-amino-5-chloroanthraquinone) (PACA) and poly(3,4-ethylenedioxythiophene (PEDOT) resulting in a water dispersible material PACA-PEDOT is shown. The water-based slurry made of PACA-PEDOT nanoparticles can be processed as film coated in ambient atmosphere, a critical feature for scaling up the electrode manufacturing. The novel redox polymer electrode is a nanocomposite that withstands rapid charging (16 A g−1) and delivers high power (5000 W kg−1). At lower current density its storage capacity is high (198 mAh g−1) and displays improved cycling stability (60% after 5000 cycles). Its great electrochemical performance results from the combination of the redox reversibility of the quinone groups in PACA that allows a high amount of charge storage via Faradaic reactions and the high electronic conductivity of PEDOT to access to the redox-active sites. These promising results demonstrate the potential of PACA-PEDOT to make easily organic electrodes from a water-coating process, without toxic metals, and operating in non-flammable aqueous electrolyte for large scale pseudocapacitors.

The integration of epitaxial graphene on 4H-SiC with different metals may allow tunability of electronic and optical properties of graphene, enabling novel high-performance devices. Here we present a Raman spectroscopy study on epitaxial graphene decorated with electrodeposited Pb and Li adatoms and with magnetron sputtered 5 nm-thick Ag nano-island films. We find that the presence of metals on the epitaxial graphene surface generates defects and induces n-type doping, which is evidenced by the observation of the defect related Raman modes (namely D, D and D + G) and systematic red-shift of the main characteristic modes of graphene. In-depth statistical analysis of the Raman data before and after metal deposition complemented by density functional theory (DFT) calculations allowed to link the interaction strength between the three selected metals and graphene with the metal-induced changes in the vibrational/electronic properties of graphene. Large-area uniform electron doping of epitaxial graphene and surface-enhanced Raman scattering (SERS) effect are reached by room temperature deposition of Ag nano-island films. Very promising results have been obtained from graphene subjected to electrochemical intercalation by Li, which can serve as prerequisites of the construction of Li batteries. The strong interaction between Li or Pb with graphene implies the possibility to exploit the epitaxial graphene as an efficient material for energy storage or for heavy metal sensing, while predominant van der Waals interaction between Ag and graphene favors the formation of extremely thin silver coatings towards two-dimensional metal systems. The present results give better understanding of the nature of epitaxial graphene response to metal deposition and can be useful to design high-performance energy storage devices, optical sensors and heavy metal detection systems. (C) 2019 Elsevier Ltd. All rights reserved., Funding Agencies|VR grant [2018-04962, 302791]; SSF grants [SSF GMT14-0077, SSF RMA15-0024]; Angpanneforeningens Forskningsstiftelse [16-541]; Linkoping University ("LiU Career Contract") [Dnr-LiU-2015-01510]; Swedish research councilSwedish Research Council [VR-2015-04630]; Olle Engkvist foundation [SOEB 190-312]; Wenner-Gren foundations [UPD2018-0071]

The exploration for true electrocatalytic reactions at organic conducting polymer electrodes, including chemisorption of a reactant and desorption of a product, is receiving renewed interest due to the profound implications it could have on low-cost large area electrochemical energy technology. Here, we finalize the debate about the ability of an organic electrode, more specifically poly(3,4-ethylenedioxythiophene) (PEDOT), to be an electrocatalyst for hydrogen production. This paper proves and covers fundamental studies of the hydrogen evolution reaction (HER) on PEDOT films. Both theory based on DFT (Density Functional Theory) and experimental studies using electrochemical techniques and operando mass spectrometry suggest a Volmer-Heyrovsky mechanism for the actual HER on PEDOT. It is shown that PEDOT reaches an exchange current density comparable to that of metals (i.e. Cu, Ni, and Au) and in addition does not form passivating oxide layers or suffer from chemical corrosion in acidic media. Finally, an electrolyzer stack using the organic polymer electrode demonstrates HER performance in real applications., Funding Agencies|Goran Gustafssons Stiftelse [25034 300523]; Knut Alice Wallenberg Foundation (WWSC); Peter Wallenberg Foundation [PWS2016-0010]; VetenskapsradetSwedish Research Council; National Research Centre "Kurchatov Institute" [1808]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009-00971]