Carbon Electrocatalysts for High Performance Bromine and Iodine Redox Flow Battery Electrodes
Bibliographic record
Abstract
Redox flow battery (RFB) electrodes act as bi-functional electrocatalysts, improving the kinetics of the redox reactions of interest without being consumed in the reaction itself. This property of flow batteries allows them to be fully discharged without damaging the electrode, and also allows for the power and energy densities of RFBs to be uncoupled and designed separately. The power density is largely dependent on the activity of the electrocatalyst, whereas the energy density is determined by the solubility of the electroactive species in the external electrolyte tank. Due to the advantages of RFBs, they have been heavily studied and implemented for applications in large-scale energy storage and are often used in tandem with renewable energy sources. Zinc-bromine hybrid flow batteries have arguably become the most promising and common flow battery technology behind that of the all-vanadium RFB, but are held back by low power densities that result from the slower Br 2 /Br - half-cell kinetics compared to that of the Zn 2+ /Zn half-cell. Analogous zinc-iodine based flow batteries have recently become the subject of much scientific interest as well, as the electrolyte is less toxic and corrosive to common battery materials compared to bromine, and a high concentration of electroactive species can be achieved due to the formation of the triiodide ion (I 3 - ) (up to ~12 M). In addition, some scientific research has recently shifted towards flow batteries constructed from heteropolyhalides (such as I 2 Br - or Br 2 Cl - ) by combining different halogen-based electrolytes. Flow batteries constructed with Br 2 /Br - and I 2 /I - half-cells have been able to achieve some of the highest energy densities reported for aqueous flow batteries to date, but improvements still need to be made to the electrode materials. We investigated a variety of different carbon electrocatalysts for fabrication of low-cost and durable electrodes for the I 2 /I - , Br 2 /Br - , and heteropolyhalide redox couples in RFB technology. A variety of carbon blacks and phosphorus-doped graphitic carbons (PC x ) were drop-casted onto a glassy carbon electrode substrate and their electrocatalytic performance was assessed via a variety of techniques including cyclic voltammetry, rotating disc electrode studies, and electrochemical impedance spectroscopy. Phosphorus-doped graphitic carbon was synthesized via the reaction of phosphorus chloride and benzene in different volumes ratios to obtain samples with variable amounts of phosphorus content (PC, PC 3 , PC 5 , PC 8 ), characterized by X-ray diffraction analysis and 31 P NMR. The electrocatalytic activity of various carbon blacks had a strong dependence on their surface area and porosity. The electrocatalytic activity of the phosphorus-doped graphitic carbons exhibit a bell curve relationship with the degree of phosphorus-doping, where PC 5 and PC 3 exhibited higher electrocatalytic behaviour towards the halogen/halide redox reactions than PC and PC 8 . These observations can be explained by 31 PNMR indicating an increased amount of P-O bonds with increasing amounts of doping, with the oxygen containing functional group being catalytic. Excessive doping leads to faults in the lattice structure of the P-doped graphite. The surface area of the electrocatalyst material had the largest impact overall on the electrocatalytic performance of the electrode.
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How this classification was reachedexpand
Full frame distilled prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.
Codex and Gemma teacher scores by category
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.000 | 0.000 |
Machine scores (provisional)
The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.
Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.
score_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from itClassification
machine, unvalidatedMachine predicted; a candidate call from one teacher head, not a consensus.
How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".