Emergence - Emergence

Scale-Up of [Ti8O12(H2O)24]Cl8, HCl, 7H2O] – Nano-OxTi

Toward the development of new business in the field of Organic Photovoltaic (OPV) and Hybrid Solar Cells, at low cost

With an efficiency ranging from 9.1% to 9.8%, research in the field of organic (OPV) and hybrid solar cells is continiously growing and is now approaching industrial development level. Basing production on standard printing technologies, opens prospects for mass production at low cost, which should lead to wide take-up of these technologies. OPV cells also have the advantages of lightness and flexibility that allow today to consider their use in applications such as portable and indoor use.

The Nano-OxTi project constitutes a critical preliminary step needed for industrial development of organic and hybrid solar cells

Industrial development of hybrid and OPV cells requires total control over all components of the production chain. This means integrating the preparation of materials, the formulation of colloidal solutions adapted to printing process, assembling devices and their encapsulation. The insertion of metal oxide semiconductors (TiOx/TiO2) between the organic active layer and the electrodes seems a promising approach since it results in a significant increase in lifetime and performance of OPV cells.The Nano-OxTi project is based on the CNRS patents «Titanium aquo-oxochloride and preparation method thereof« (FR2854623 issued on 07/07/2006; EP 04 742 604.4 under consideration; JP 4697808 issued on 25/01/2011; US 7858064 issued on 12.28.2011). The Nano-OxTi project is upstream and proposes to achieve a scale-up of the crystallisation of [Ti8O12(H2O)24]Cl8, HCl, 7H2O] involving industrial processes . The project aims to strengthen the proof of concept and facilitate the transfer to industrial partners. Within the project Nano-OxTi, the physicochemical parameters of different processes will be evaluated and optimized for industrial development. Production yields of crystals «Ti8O12« (xkg / day) and costs will be assessed as a function of the technologies implemented. For over 15 years we use for the synthesis, an industrial titanium precursor easily to handle: TiOCl2, xHCl, yH2O or «aqueous solution of TiCl4«. Under controlled relative humidity, the hydrolysis of TiOCl2, 1.4 HCl, 7H2O, allows quantitative preparation of pure Ti8O12 (H2O) 24] Cl8.HCl.7H2O crystals. Upon optimized conditions, 1kg TiOCl 2, 1.4 HCl, 7H2O (cost: 7 € / kg) should allow one to produce 600g of titania precursor at the laboratory scale. The method is reliable, inexpensive and reproducible. Industrial development requires to improve our skills in the field of «processing« to control and enhance the kinetics of crystal growth.

Compared to other commercialized titania precursors [Ti8O12 (H2O) 24] Cl8 • HCl • 7H2O crystals exhibit numerous advantages: i) chemical composition perfectly controlled and stable, ii) easy handling, iii) low hygroscopicity, iv) low cost, v) absence of organic solvent, vi) high solubility in polar solvents, vi) preparation of stable colloidal solutions ... Task 1: Scale- Up of «Ti8O12«. The aims are to develop and optimize processes for preparing «Ti8O12«. Two approaches are explored in parallel, i) the isothermal process using a generator allowing an accurate control over the relative humidity and ii) the non-isothermal using a Batch process based on the principle of freezing and lyophilizing. The common objective is to determine the optimal operating conditions (temperature and air speed, water quantity, time) for the hydrolysis of TiOCl2 , 1.4 HCl, 7H2O to prepare significant quantities of «Ti8O12« in a minimum of time. Both methods will be validated experimentally and supported by modeling.
Task 2: Exploring of the TiOCl2 - HCl - H2O system. This is to extend the previously study over the hydrolysis of TiOCl2, 1.4 HCl, 7H2O to isolate other compositions in the ternary TiOCl2 - HCl - H2O system with temperature ranging from -100 ° C to 50 ° C.
Task 3: Development . It will allow the transfer of the processes and materials implemented, from the laboratory to industrial partners.
Task 4: Coordination. It includes the organization of meetings on technical advancement (2 per year), with presentation of the work by partners and writing reports and project completion, as well as compliance with deliverables and milestones which will also be presented as intermediate and final reports.

Task 1: Milestones J1.1 :
The isothermal approach using CEM ( Evaporating Mixing Control ) system has been validated.
Process modeling :
- Acquisition static mechanisms of Ti8O12 crystal formation: 3 steps are identified
- Proposal of a representative model for kinetic and mass transfer reactions within the product and at the product - air interface . (Laminar flow reactor)
- Validation of the optimal operating conditions : 50 % < RH < 60 % : Ti8O12 crystals may be prepared in less than 24 hours ( L1.1 ) . For a given exchange surface, the mass of Ti8O12 produced equals 2kg/m2 for 36h
Prototype reactor laminar flow in progress
Task 2 : Exploring the phase diagram TiOCl2 - HCl - H2O
- Set of 3 equations reaction steps leading to Ti8O12
- Validation of Step 1 leading to the saturated solution of Ti8O12
- The stock solution (« TiOCl2 « ) has a HCl concentration higher than in a commercialized concentrated HCl ( 38 % HCl Kg / Kg ) and the species to be identified are Ti8O12 ( HCl.H2O ) and ( HCl.2H2O.
- Multiphysics modeling of different exchange processes : mass transfer and heat, consumption of HCl ...
Task 3: Development - Presentation of our activities in the framework of the Days Of Laboratories ( JDL ) organized by the competitiveness clusters ID4CAR and S2E2
- New collaboration agreement : PEPS Energy (2013-2015) (Lab Thermokinetics (LTN) UMR CNRS 6607 , Polytech -Nantes , Nantes Jean Rouxel Institute Materials UMR CNRS 6502 , IMN) TiO2 NP / microreactor , Optimization of the synthesis of sol -gel titanium oxide nanostructured for photochemical storage of solar energy : Intensification of mixing and monitoring in a microreactor .

i) The potential scale transfer for the synthesis process and the efficiency of OPV cells are currently being studied through the TANDORI, Innovative Organic Tandem cell, project (ANR 2012-2014 supported by the CEA- INES ) in partnership with PCAS for transfer synthetic [ Ti8O12 (H2O) 24] Cl8 , HCl, 7H2O crystals and ARMOR- Group for Roll-to-Roll process.
ii) The initial protocol for preparation of Ti8O12 crystals in isotherm (static) mode, was transferred and validated by PCAS.
iii) The use of Ti8O12 for the preparation of stable colloidal solutions containing monodisperse nanoparticles of n-type semiconductor (TiO2) was also validated by PCAS group. The process is based on IP patent: Brohan L., A. Karpinski , Richard Plouet M., S. Berson , S. Guillerez , Barret M., French CNRS -CEA , Ardège , Patent No. 11 58275 (16 September 2011) , PCT | EP2012 | 067 N WO 2013/ 050222 A1 (11 April 2013).

Publications: 1. Jouenne, V. ; Duvail, J.-L. ; Brohan, L. and Richard-Plouet, Electrophoretic deposition of TiO2 nanopillars from stable colloidal solution. M. MRS Spring meeting San Franscico Proceeding 2013
2. Karpinski A.; Berson S.; Terrisse H.; Mancini-Le Granvalet, M.; Guillerez, S,; Brohan, L.; Richard-Plouet, M., Anatase colloidal solutions suitable for inkjet printing: Enhancing lifetime of hybrid organic solar cells, SOLAR ENERGY MATERIALS AND SOLAR CELLS Volume: 116 Pages: 27-33 DOI: 10.1016/j.solmat.2013.04.006, Published: SEP 2013; Patents: 1. Formulation of colloidal solutions based on titanium oxide for coating and printing processes: improved performance and lifetime of organic photovoltaic cells PIN- PIN, Brohan L., Karpinski A., Richard-Plouet M., Berson S., Guillerez S., Barret M., French Patent CNRS, CEA, Ardège, N°11 58275, (issue October 18, 2013), PCT|EP2012|067 N°WO 2013/050222 A1 (issue April 11, 2013).

Research in the field of organic (OPV) and hybrid solar cells continues to grow and is now approaching industrial development stage. Basing production on standard printing techniques (roll-to-roll inkjet, silk screen ...) opens prospects for mass production and low cost, which should lead to wide take-up of these technologies. OPV cells also have the advantages of lightness and flexibility that allow today to consider their use in applications for which silicon is not necessarily suitable, such as portable and indoor use. OPV technology is now showing steadily increasing yields ranging from 9.1% to 9.8% for the best tandem cells. Industrial development of hybrid and OPV cells requires total control over all components of the production chain. This means integrating the preparation of materials, the formulation of colloidal solutions adapted to the printing process, assembling the devices and their encapsulation. The insertion of metal oxide semiconductors (TiOx/TiO2) between the organic active layer and the electrodes (ITO / TiOx / PCBM: P3HT/PEDOT: PSS / Metal) seems a promising approach since it results in a significant increase in lifetime and performance of OPV cells.
The Nano-OxTi project constitutes a critical preliminary step needed for industrial development of organic solar cells based on the three key axes of materials, processes and device architectures. It is based on the CNRS patents "Titanium aquo-oxochloride and preparation method thereof" (FR2854623 issued on 07/07/2006; EP 04 742 604.4 under consideration; JP 4697808 issued on 25/01/2011; US 7858064 issued on 12.28.2011). The Nano-OxTi project is upstream and proposes to achieve a scale-up of [Ti8O12(H2O)24]Cl8, HCl, 7H2O] involving industrial processes for their preparation methods. The project aims to strengthen the proof of concept and facilitate the transfer to industrial partners. Within the project Nano-OxTi, the physicochemical parameters of both processes will be evaluated and optimized for industrial development. Production yields of crystals "Ti8O12" (order of kg / day) and costs will be assessed as a function of the technologies implemented.
In order to reach this objectif, the Nano-OxTi project brings together the competence of physicists and chemists from IMN (Nantes) and LIMATB (Lorient) whereas FIST SA, manages the patent valorisation and registration.


Project coordinator

Monsieur Luc BROHAN (Institut des Matériaux Jean Rouxel) – luc.brohan@cnrs-imn.fr

The author of this summary is the project coordinator, who is responsible for the content of this summary. The ANR declines any responsibility as for its contents.

Partner

FIST France Innovation Scientifique et Transfert
LIMATB Laboratoire d'Ingénierie Des MATériaux de Bretagne
IMN Institut des Matériaux Jean Rouxel

Help of the ANR 228,792 euros
Beginning and duration of the scientific project: December 2012 - 24 Months

Useful links

Explorez notre base de projets financés

 

 

ANR makes available its datasets on funded projects, click here to find more.

Sign up for the latest news:
Subscribe to our newsletter