Panel 4:

ELECTRICAL STORAGE

SUPERCAPACITORS

Daniella Pacheco Catalán

State of the art

• Which supercap technology offer the best compromise of economy, development

level, reliability?

• Are they commercially available or they are ad hoc developments?

• Are there environmental friendly materials that make the technology attractive from the

point of view of disposal and recycling?

• How the performance and health of supercaps are assessed?

http://www.mpoweruk.com/performance.htm .

Which supercap technology offer the best

compromise of economy, development

level, reliability?

Manufacter V C (F) ESR (mΩ) W h kg-1 W kg -1

Maxwell 2.7 2800 0.48 4.45 900

Apowercap 2.7 590 0.9 5 2618

Nesscap 2.7 1800 0.55 3.6 975

Nesscap 2.7 5085 0.24 4.3 958

Asahi Glass (PC) 2.7 1375 2.5 4.9 390

Panasonic (PC) 2.5 1200 1 2.3 514

LS Cable 2.8 3200 0.25 3.7 1400

BatScap 2.7 1680 0.2 4.2 2050

Power Sys (PC) 2.7 1350 1.5 4.9 650

• Organic electrolyte 2.7 V window• Limited specific energy

Table II. Comercial supercaps based on activated carbon

Supercapacitors

Types of Supercapacitors

Composite

hybrid

Asymmetric Type

battery

Polymer -Carbon composite materials

Wang, G., Zhang, L., & Zhang, J. (2012). Chemical Society Reviews, 41(2), 797-828.

Table 1 Specific capacitance of CPs-based composites

CPs-based composite Specific capacitance/F g- 1

Electrolyte Voltage window/V Current load or scan rate Reference

Ppy-20wt%MWNTs/ 320 (Type I I) 1.0 M H2SO

4 0–0.6 5 m V s

1 163

PANI-20 wt% MWNTs 670 (3-Electrode) 1.0 M H2SO

4 0.8–0.4 2 m V s

1

344 (Type II) 0–0.6

Ppy-20 wt% MWNTs 506 (3-Electrode) 1.0 M H2SO

4 0.6–0.2 5 m V s

1

PEDOT-Ppy (5: 1) 230 (3-Electrode) 1.0 M LiClO4 0.4–0.6 (vs. SCE) 2 m V s 1

168

Ppy-CNTs//PmeT-CNTs 87 (Type II) 1.0 M LiClO4 0–1.0 0.62 A g 1

169

PPy-65 wt% carbon 433 (3-Electrode) 6.0 M KOH 1.0–0(vs. Hg|HgO) 1 m V s 1

170

Ppy-graphene 165 (Type I) 1.0 M NaCl 0–1.0 1 A g 1

171

Ppy-MCNTs 427 (3-Electrode) 1.0 M Na2SO4 0.4–0.6 (vs. Ag|AgCl) 5 m V s 1

172

Ppy-29.22 wt% mica 197 (3-Electrode) 0.5 M Na2SO

4 0.2–0.8 (vs. SCE) 10 mA cm

2 173

Ppy-67.36 wt% mica 103 (3-Electrode)

Ppy-RuO2 302 (3-Electrode) 1.0 M H2SO4 0.2–0.7 (vs. Hg|HgO) 0.5 mA cm 2

174

Ppy-MnO2 602 (3-Electrode) 0.5 M Na2SO4 0.5–0.5 (vs. Ag|AgCl) 50 mV s 1

151

PANI-Ti 740 (3-Electrode) 0.5 M H2SO4 0.2–0.8 (vs. Ag|Ag) 3 A g 1

175

PANI-80wt% graphene 158 (3-Electrode) 2.0 M H2SO

4 0–0.8 (vs. AgCl|Ag) 0.1 A g

1 176

MPANI/CNTs 1030 (3-Electrode) 1.0 M H2SO4 0.2–0.7 (vs. SCE) 5.9 A g 1

164

PANI-Si 409 (3-Electrode) 0.5 M H2SO4 0–0.8 (vs. AgCl|Ag) 40 mA cm 2

177

PEDOT-MCNTs (70 : 30) 120 (Type II) 1.0 M H2SO

4 2 mV s

1 146

Note: PPy: polypyrrole; PANI: polyaniline; PEDOT: poly(3,4-ethylenedioxythiophene); PTh: poly(thiophene); PMeT: poly(3-methylthiophene);

PFPT: poly[3-(4-fluorophenyl)thiophene]; AN: acetonitrile; TEABF4: tetraethylammonium terafluoroborate; PC: propylene carbonate; 3-

electrode: standard 3-electrode cell; SCE: saturated calomel electrode; AC: activated carbon.

• Simulation results show that the system control

strategy and the power manager proposed in this

work are able to cover the typical load profile

requirements of a small house in Cancun, Mexico

under the tested weather conditions.

• Balanced power flow through different energy

sources and load demand.

Espinosa-Trujillo, M. J., Flota-Bañuelos, M., Pacheco-Catalán, D., Smit, M. A., & Verde-Gómez, Y. (2015). Journal of renewable and sustainable energy, 7(2), 023125.

Electronic availability to couple

supercap based systems with other

technologies

Opportunities of Mexico:

Use of agricultural waste for carbon based

electrode materials

Wei L; Yushin G, Nano Energy, 4, 552-565, 2012.

Carbon precursor Activation method SBET (m2 g-1)

Coconut shell KOH 1660

Eucalyptus wood KOH 2970

Bamboo KOH 1290

Cellulose KOH 2460

Potato starch KOH 2340

Banana fiber ZnCl2 1100

Corn grain KOH 3200

Sugar cane bagasse ZnCl2 1790

Sunflower seed shell KOH 2510

Coffee ground ZnCl2 1020

Wheat straw KOH 2316

Rice husk NaOH 1890

Rice husk KOH 1390

México• Agave residual • Sugar cane bagasse• Residual woody

biomass of biorefinery.• 76 MTon of fruits and

vegetables residuals

Mexico opportunities

• Dra. Ana Karina Cuentas Gallegos- IER

Synthesis of materials for supercapacitors. Environmental materials for supercapacitors

• Dra. Daniella Esperanza Pacheco Catalán- CICY

Synthesis of composites and hybrid materials for supercapacitors. Obtaining and synthesis of carbon materials (graphene family and carbon). Application of supercapacitors.

• Dr. Abraham Claudio Sánchez- CENIDET

Analysis and design of energy management in ultracapacitors connected in series; energy management for electric vehicles.

• Dr. Jorge Gabriel Vázquez Arenas- UAM Iztapalapa

Macroscopic continuous modeling of electrochemical systems; synthesis and characterization of materials for energy storage systems.

• Dr. Raúl Lucio Porto- UANL

Development of energy storage and conversion systems; Synthesis of nanomaterials

Scientific and technological challenges for

the improvement of the three supercap

technologies.

• Development level and TRL of voltage and current balancing systems in supercaps banks?

• How improve the per cell voltage?

• Investigation in the electrolyte field,

• Which novel materials offer promising characteristics for their use in electrodes.

• Is there a way to control the manufacture process in order to guaranty voltage distribution?

• Which components represent the higher scientific and technological challenges to improve current technology?

• What are the limitations? (Processes, design, bank integration, useful life, others?)

• Maximum voltage levels (per cell, per stack, total capacitance?)

Today

Future

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EmergentAdvanced

State of technology

• UPS.

• voltage stabilizers.

• frequency support.

• wind generators pitch control.

• high torque start of electric machines.

• intermittences smoothing.

Other applications

Types of electrolyte

Solids: conducting polymers (Nafion® membranes)

Liquid: Organics, acids, alkali, ionic liquids

Gel: Polymeric matrix with inorganic salts

Electrolytes

• Seek for low resistivity Electrolytes

• Non hazardous

• Look up for low densities to avoid pore clogging

Electrolyte Density Resistivity Cell

(g cm-3) (Ω-cm) Voltage

KOH 1.29 1.9 1

Sulfuric acid 1.2 1.35 1

Propylene carbonate 1.2 52 2.5-3

Acetonitrile 0.78 18 2.5-3

Ionic liquid 1.3 125(25°C) 4

Properties of various electrolytes.

Simon P, Burke A. Electrochem. Soc. Interface 2008;

CICY-UQROO-UADY

Obtaining by pyrolysis

Biorefinery

CICY-IER UNAM

Bagasse18 168 Ton/year

1L mezcal/ 6 kg de bagasse

Agave angustifolia

Samplea

Specific Capacitance

(F.g-1)

Ctrl600 2

KOH600 38

NaOH600 12

MixOH600 19

Ctrl700 7

KOH700 54

NaOH700 41

MixOH700 31

Ctrl800 9

KOH800 78

NaOH800 83

MixOH800 35a 50 mV/s

Supercapacitor market segmentation

• The supercapacitor market was segmented by Industry ARC in 5 sub markets:

1. By material: Electrode, Separator, Electrolyte .

2. By End-Product: Power and Energy products and transportation.

3. By Technology: Organic electrolyte or Aqueous electrolyte.

4. By Application: Transportation, Energy or Power managment.

5. By Region: North America, Europe, Asia-Pacific and ROW

http://industryarc.com/Report/212/Global-Supercapacitor-Market-analysis-report.html

Supercapacitor market estimation

• According to industryARC, The supercapacitor market is estimated to register a compound annual growth rat of around 35.4% for the period 2015-2020 and is projected to reach around $2 million USD by 2020.

• Consumer electronics and automotive segment will be the highest revenue generating segments during this period.

• North America is the leading region for supercapacitor in 2014 with 47% market revenue followed by Europe with 26% market revenue.