Potassium Hybrid Supercapacitor Formation for Stable Cycling

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Solution Overview

Problem

Potassium hybrid supercapacitors face instability and reproducibility issues in cycling performance, particularly during the initial charge/discharge cycles, leading to rapid fluctuations in energy density, which is not adequately addressed by existing methods.

Innovation Solution

A process involving a negative electrode of graphite, a positive electrode of activated carbon, and a potassium salt-based electrolyte, with specific charging, maintaining, and discharging protocols, including a degassing step, to stabilize and enhance long-term cycling performance.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If conventional reference formation (5 charge/discharge cycles at Cx or 5Cy from 0.5 to 3.5 V) is used, then the supercapacitor can be activated, but cycling performance becomes unstable with drastic fluctuations in discharged capacity

Engineering Contradiction:
Improvecycling performance stabilityVSAvoidreproducibility of cycling performance
Core Design Contradiction:
ReliabilityVSManufacturing precision

Solution Approach 1:

The patent applies preliminary action by implementing a specific formation protocol before normal operation. This includes: (1) initial charging at constant current to 3.0-3.3V, (2) holding at constant voltage until leakage current reaches Cx/2000 to Cx/500, (3) discharging to 0-2V, and (4) repeating cycles at progressively higher rates. This preliminary conditioning establishes stable electrode-electrolyte interfaces and proper potassium intercalation patterns, preventing later performance fluctuations.

Inventive Principle:
Principle #10Preliminary action

Solution Approach 2:

The patent systematically changes operational parameters during formation to optimize performance. The protocol evolves through stages: initial slow charging/discharging, then progressively faster rates (Cx/10, Cx/5, 2Cx, 5Cx). Voltage cutoffs are precisely controlled (3.0-3.3V charge, 0-2V discharge). These parameter changes condition the electrodes properly while building tolerance to higher operating rates, resolving the contradiction between stability and reproducibility.

Inventive Principle:
Principle #35Parameter changes

2Use of energy by moving object

If high energy density is achieved through hybrid capacitor design, then power and energy density improve, but cycling stability deteriorates with rapid capacity fluctuations

Engineering Contradiction:
Improveenergy densityVSAvoidcycling stability
Core Design Contradiction:
Use of energy by moving objectVSReliability

Solution Approach 1:

The formation protocol performs preliminary action by pre-conditioning the hybrid capacitor before full operation. The multi-stage process including initial charging to 3.0-3.3V, holding until leakage current reaches Cx/2000-Cx/500, and controlled discharge establishes proper potassium ion pathways and electrode structures. This preliminary conditioning ensures that the high energy density design maintains cycling stability by preventing later capacity fluctuations.

Inventive Principle:
Principle #10Preliminary action

3Ease of manufacture

If simple and inexpensive formation method is used, then manufacturing cost decreases, but cycling performance stability is insufficient

Engineering Contradiction:
Improveformation process simplicityVSAvoidcycling performance stability
Core Design Contradiction:
Ease of manufactureVSReliability

Solution Approach 1:

The formation method applies self-service by using the supercapacitor's own electrochemical reactions to condition itself without external intervention. The protocol uses standard charging/discharging cycles with automatically determined endpoints (leakage current reaching Cx/2000 to Cx/500, voltage cutoffs at 3.0-3.3V/0-2V). This self-conditioning approach achieves stable cycling performance through inherent electrochemical processes rather than complex external treatments, maintaining both simplicity and reliability.

Inventive Principle:
Principle #25Self-service

Applied Scientific Principles

This section explains which scientific principles are used to turn an abstract innovation direction into a practical engineering solution.

Function Achieved in This Case

The method achieves reproducible and stable high-energy density performance, exceeding 12 Wh/kg, while being cost-effective and easy to implement, without the need for complex pre-potassiation steps, and effectively limits premature aging by managing leakage currents and gas elimination.

Implementation Method 1

Charge storage in a hybrid supercapacitor occurs at the negative electrode through a redox reaction

Methodology Applied
Scientific EffectRedox reaction: Redox Reactions

Implementation Method 2

charge storage at the positive electrode occurs through the formation of an electrochemical double layer

Methodology Applied
Scientific EffectElectrochemical double layer formation: Capacitance

Implementation Method 3

an electrolyte comprising at least one potassium salt

Methodology Applied
Scientific EffectIonic conduction: Conduction (electrical)

Data Source

PatentEP4148755B1Method for forming a potassium hybrid supercapacitor
Publication Date: 2024.07.03 COMMISSARIAT A LENERGIE ATOMIQUE ET AUX ENERGIES ALTERNATIVES
  • EP4148755B1 patent drawingFigure 1~2
  • EP4148755B1 patent drawingFigure 3~4

AI summary

Process for forming a potassium hybrid supercapacitor. Process for forming a potassium hybrid supercapacitor, comprising: a) supplying the potassium hybrid supercapacitor comprising: - a negative electrode comprising graphite, - a positive electrode comprising activated carbon, - an electrolyte comprising a potassium salt, b) a constant current charge of the supercapacitor at a rate between Cx/50 and Cx/2, up to a charge cut-off voltage between 3.0 V and 3.3 V, c) holding the supercapacitor at the charge cut-off voltage until the leakage current is between Cx/2000 and Cx/500, d) a constant current discharge of the supercapacitor at a rate between Cx/50 and Cx, up to a discharge cut-off voltage between 0 V and 2 V, the process further comprising degassing the supercapacitor after one of the steps b) to d).