FR3016258A1 - HIGH-PERFORMANCE ELECTRICITY PHOTOVOLTAIC PRODUCTION SYSTEM WITH INTEGRATED STORAGE TO SUBSTRATE OR PANELBOARD (FIRST STORAGE) - Google Patents

Abstract

The invention proposes an innovative high-efficiency solution for the storage of intermittent energy of cells and solar systems on flexible and transferable films on support, integrable into the substrate of flexible cells or rigid solar panels preferably comprising a hybridization by additions of converters invisible and thermal radiation with a primary storage unit of electricity on board or at the cell using in particular the surface area of the cell housing the system for converting solar energy into electrical energy. Efficiently designed, it is segmentable or partitionable and offers easy divisional maintenance for large areas and significantly reduces the cost per watt for a given area while significantly increasing the efficiency of first-level solar cells. storage on board the solar cell by two possible ways of direct storage of the energy produced by the cell and its restitution after smoothing or storage of the latter or by the surplus energy not consumed or not injected into the network which greatly favors its use in homes with positive energy or self-consumption. The invention uses the atomic deposition technique for the construction of complex molecules and the molecular growth / deposition technique for 3D hybrid layer construction modeled by an innovative storage surface augmentation design and the efficiency of the system, as well as as hybridization options or piezoelectric components to capture the calories on the back side. The cell captures the sun's rays arriving on its surface. This absorbs visible light and the near infrared. Invisible radiation passes through the absorber layer and arrives at the high-power converter that emits additional light. The heat and calories are transformed by the piezonoyl layer. The photovoltaic cells may be of the organic and / or inorganic type in thin layers and / or ETA or in tandem, provided by grafts, printed or deposited. The storage is in gel-solid or solid state technology and uses Lithium-ion batteries based on nano Titanate offering a very long life and greater safety in the use of batteries built into the cell.

Description

ELECTRICITY STORAGE SYSTEM ON FILM, MODULAR AND TRANSFERABLE ON CARRIER, INTEGRABLE TO THE SUBSTRATE OF CELLS OR ONBOARD ON SOLAR PANELS (STORAGE FIRST).

FIELD OF THE INVENTION The present application proposes an innovative solution for increasing the active surface area of the battery, thus increasing its storage capacity of the energy received. The invention replaces the liquid electrolyte with a solid concept and makes the storage possible on transferable film, integrable with the substrate of the cells or on any solution of solar cells, roads, roads or solar panels. The battery thus produced uses the deposition of all the electrodes by the growth layer by layer of hybrid / inorganic / laminated polymer for Li-ion battery in a thin layer. The invention uses the pair ALD / MLD (atomic deposition of "ALD" and "molecular layer" layers of "MLD" layers) and growth layer by layer of hybrid / inorganic nano-laminated polymer for Li-ion batteries by atomic construction of Inorganic layers are thus transferable and feasible on hybrid organic-inorganic films grown according to molecular layer deposition (MLD) and atomic layer deposition (ALD). The invention proposes an innovative high-efficiency solution for the storage of intermittent energy of cells and solar systems on flexible and transferable films on support, integrable into the substrate of flexible cells or rigid solar panels preferably comprising a hybridization by additions of converters invisible and thermal radiation with a primary storage unit of electricity on board or at the cell using in particular the surface area of the cell housing the system for converting solar energy into electrical energy. Efficiently designed, it is customizable, segmentable or partitionable and provides easy divisional maintenance for large areas and significantly reduces the cost per watt for a given area while significantly increasing the efficiencies of solar cells providing a high surface area. first level of storage on board the solar cell by two possible ways of direct storage of the energy produced by the cell and its restitution after smoothing or storage of the latter or by the surplus energy not consumed or not injected on the network which greatly favors its use in homes with positive energy or self-consumption.

The storage is in gel-solid, polymers, glass or solid state technology and uses Lithium-ion batteries based on nano Titanate providing a very long life and greater safety in the use of batteries built into the cell . The photovoltaic cells can therefore be of the organic and / or inorganic type in thin layers and / or ETA (FIG. 5) and Organic Light Emitting Diode (OLED) organic electroluminescent junctions, made by grafts, printed or deposited. The system uses a variety of innovative techniques including (and without limitation): 1) Atomic Layer Deposition (ATL) atomic deposition for the atomic construction of complex molecules of quaternary compounds, 2) Molecular layer deposition growth (MLD) ), 3) Integration of thin-film storage battery with segment solar cell substrate over large areas, 4) Considerable increase in production line output capacity by implementing ALD half cycle and hybridization procedures MLD.

The invention covers methods for increasing the active surface area of the deposit and provides an efficient system with high throughput and continuous flow "roll to roll" continuous or batch (grouped and sequenced) and a quality control in real time, during production. Other innovative aspects of the present invention include: 1-A parallel processing of one or more coils of the flexible film, providing a considerable reduction in handling when capacitating the coils of the photovoltaic cells or film coils for the production of OLED screens during manufacturing processes. 2- Atomic construction of complex molecules. 3- Molecular construction of MLD layers a. Hybridization of the interface layers b. Modeling of nanotic textures c. Growth of inter-layer interfaces 4- Optimization of realization of tandem cells 5- Heat converter by the implementation of piezonano-elements 6- Storage of the energy integrated in the substrate (also called on board) of the cell The invention uses in particular the hybridization technique to increase very significantly the solar yields by: 7- ALD and sALD atomic deposition for the construction of the molecules according to a 3D engineering by: a. Increasing the gap band, or even doubling it, and addressing the case of quasiparticles, especially the so-called "vibration packets" of phonons. b. Increased Quantum Point 8- MLD to achieve: a. Organic and inorganic layers on the same substrate b. Growth of structures and complex textures of capture and trap photons c. Realization of interfaces between low-cost (low-cost) layers 9- Use of MLD in interface layer Piézonanofils (or Piézonanotubes) 10- Use of MLD nanotube interface layer liquid crystal 11- Storage integrated substrate a. Use of nano titanate to increase the lifetime with MLD in thin layer on solar cell substrate b. Use of electrolyte-semi gel printing for batteries integrated into substrates c. Using MLD in storage layer interface d. Use of ALD and MLD in Embodiment of the Electrodes This nanostructured molecular realization is made possible by the implementation of an innovative system of "Hybrid Nanostructured Solution" combining an ALD deposition technique with a Sol-gel deposition technique as described. in Figure 7. The stoichiometric control is then fully mastered while the disadvantage of the slowness of the ALD technique is considerably offset by the increase in area treated in the deposition cycles as shown in Figure 2. This application is an extension and a subsequent patent application with claiming the internal priority of a patent application number 14 01389 filed on, June 20, 2014, itself an extension and a subsequent patent application with claiming the internal priority of a first patent application number 14 00036 filed on, 09 January 2014, itself an extension and one of subsequent patent application with claim to the internal priority of a first patent application number 14 00035 filed on, 09 January 2014.

INTRODUCTION The first batteries go back to the battery of Alessandro Volta, in 1800, and its operation is the same regardless of the battery studied. A battery uses the energy of a chemical reaction to create a displacement of electrons, and thus an electric current. It can theoretically be used in two directions, charge and discharge, depending on whether it powers an electrical circuit or imposes a voltage on its terminals.

We can distinguish three parts of the electric battery having two electrodes: - Anode, where the chemical reaction of oxidation takes place. This one releases electrons. When discharging, the anode is the - terminal of the battery. - A cathode, where the chemical reduction reaction takes place. It captures electrons. When discharging, the cathode is the + terminal of the battery. - The electrolyte, a conductive substance, which contains ions and which connects the two electrodes. The overall balance of an electric cell is therefore a redox reaction, with each terminal an oxidizing / reducing pair.

Thus, its parameters depend entirely on the couples involved, the effectiveness of the different reactions, the speed of the movements of the various actors (ion diffusion, electrons), the control of the stability of the elements, and the control of the reactions. parallel.

A battery consists of a cell assembly, each cell being a pair of electrodes. There are mainly two types of cells, dry cells and wet cells. The dry cells are newer and allow a more flexible use (and in any direction) of the battery. The electrolyte is comparable to a conductive paste, and is therefore without liquid. There are several forms of pasta: polymers, gels, or in the form of glass. In general, the main (mass) measurements to be optimized are: - The nominal voltage, in Volts (V). - The energy density (gravimetric energy density) is measured in Watt hour (Wh / kg). It corresponds to the amount of energy that can be stored in the stack, per unit mass. Energy specificity is sometimes used when the measurement is volumetric. We have 1Wh = 3600 Joules. - The capacity (battery capacity) is often used as a measure, in Amperehour (Ah / kg). It corresponds to the charge of the battery, and thus also to the stored energy multiplies it by the nominal voltage (Ah x V = Wh). We have lAh = 3600 Coulombs. The nominal voltage varies little on the batteries studied (and is always of the order of the Volt), which allows to speak without distinction of the capacity or the energy density of the batteries. - The internal resistance, in Homs (mW). The summary of the batteries currently used in electric and hybrid vehicles is as follows: PRIOR STATE OF THE ART [00101] The recent development and new methods of making batteries. Most companies focus on lithium-ion technology, and try to optimize its efficiency and cost of production. The NiMH battery does not offer as favorable results, and only feeds the Toyota Prius in the market of electric vehicles. However, some research groups are considering alternative technologies to power electric cars, such as metal-air batteries.

"A. Guerfi et al. / Journal of Power Sources 195 (2010) 845-852", W. Porcher, B. Lestriez, S. Jouanneau, and D. Guyomard, Journal of the Electrochemical Society, 156 _3_ A133-A144 And the application patent "CEA Patent WO 2003/047021", JY Sanchez et al., Journal of Power Sources, 246 (2014) 299-304, show comparative analyzes of LiFePO4 and Li4Ti5012 (Association of Compounds of phosphate and LTO) during the cycle of charging and discharging at high temperature electrodes treated with different solvents and do not exhibit any battery solution with solid electrolyte and even less integrations on thin-film films by growing layer by layer in use ALD and / or MLD processes 'Vehicle Distance tt Fast Price Capacity time in town Battery Charge load Br.nv ".finished E 3 kWli 5000count 4 5h 50 24h (110V.12A) (AC' Propulsion) Cheyrolet 16 kWh Mn spinel 4h 40 Volt 10h (120V) 220 cells (hybrid) + 1AL engine (LG chem) Coda Sedani 34 kWh 90-120 Li-Fe-P 2h 40 611 (220V) 730 cells (40 miles) (Ltichen) Fisker Karma 22.6 kWh 50 mil Nanophosphate (A123 N. A 88 --- 2.0L engine , Ford Fucus EV '1 75 miles (Compact Power Tnc., LG c hem) NA 30 23 3 kWh' 6-Sh (230V) Mitsubishi 16 kWh. 80 miles N _A. N_ - & 50 i2sliEV 12-1311 (/ 10V) Nissan Leal 24 1: Wh. Mn-C N A. 33 Sh (220V) (own factory) Smart Fonwo 16.5 kWh 85 miles N a-Ni-Cl. zebra N ED Sh (110V) Tesla Mode] ..; 42 kWh 160 Miles 5000 cells 45 inM 57 5h (220V0 (Panasoic) _ 7, a,) n Tesla Roadster 56 kWh 220 miles 6000 cells N -A 110 5h (} 1.1211 r * 1 (Panasicon powe Thinking C ity 4.5 ( Enerdel) NA 20 2 kWh Sb (110V1 Toyota Plug-in Prius 3h (110V) (Panasonic) 100 min <35 Volvo Electric C30 24 kWh 90 miles (Enerl Er NA 25 8h (230V 16A) Atera 2nd p 20 kWh 1,00 mile; Nanophosphate (A123) 6 11 25 Ilh (e) Gross breakeven from 57,500 of the day before the end of this year, for its own, and S5C. 00 of the state of C aliforvie pote - electiique (r '') Indicated, paui the nizterz élecaique Similarly patents US20060210779 Weir, Richard Dean (Cedar Park, TX, US), Nelson, Carl Walter (Austin, TX, US ) and US 7466536 Weir, et al., teaches the use of "polyethylene terephthalate plastic and composition-modified barium titanate powders" for the production of the ultra-light storage unit with ultra-high electrical energy storage as much address the aspect power and integrability in thin layer of such a solution. Furthermore, the application patents US Pat. No. 8,765,213, US Pat. No. 8,691,443, US Pat. No. 8,715,614 and US Pat. No. 8,748,044, Nan, Cewen (Beijing, CN), Mei, Ao (Beijing, CN), Feng, Yuchuan (Beijing, CN), Yuanhua, Lin (Beijing, CN), Minamida, Yoshitaka (Susono, JP), Yokoishi, Shoji (Mishima, JP); "Li-La-Ti-0 composite solid electrolyte material containing silicon and synthesizing method" does not add any element on the increase in performance of the battery in terms of its charge capacity nor its integration in flat form layer film thin. In addition, the state of the prior art does not allow any realization by the molecular deposition of the "MLD" layers and growth layer by layer of hybrid / inorganic laminated nano polymer for the batteries in general and even less for the storage solutions. Li-ion base, LTO or LFP.

Lithium-ion Batteries: Operating Principles This technology first appeared in the 1970s, when it was developed by Mr. S. Whittinghal of Binghamton University, Exxon. Lithium ion batteries use the displacement of the Li + ion from one electrode to the other, through the electrolyte. At each electrode a reaction occurs, characterized by a balance half equation.

Conventional batteries have a carbon-based anode, LiC6 often in the form of graphite. The cathode is for example LiCoO2. During the discharge, the oxidation occurs at the + terminal, LiC6 = Li + + C6 + e-, which releases an electron and a Li + ion. The electron enters the external circuit and its displacement creates the current necessary for the operation of the engine, while the Li + ion passes through the electrolyte, typically lithium salt dissolved in a solvent. The Li + ion and the electron are then captured by the negative electrode through the reduction half-reaction Co02 + Li + + e- = LiCoO2. The total reaction is therefore: LiC6 + Co02 = C6 + LiCoO2. Figure 25 shows the charging and discharging of a Li ion battery. Each cycle deforms the electrodes through these different reactions. The reversibility of the reaction must also take into account these configuration changes, and in particular the formation of stable complexes. Thus, the Li + ion must be able to be inserted and released from both structures without changing the properties in the long term. The laws of Faraday (or Nernst equations) make it possible to calculate the voltage at the terminals of the battery (4V here) according to the different elements. This reaction is spontaneous (it has a negative standard free enthalpy): it is therefore necessary to supply energy to the battery to reverse it, and this is the principle of recharging. The work of researchers and specialized companies focuses on the optimization of these movements, and the stability of the various constituents. In particular, many research groups are interested in the side reactions that occur.

The choices for these three components (anode, cathode and electrolyte) are numerous, and allow a diversification of solutions made today. We can group by families: The researches are therefore generally concentrated on the following particular points (constituents of the battery): - Anode must withstand high oxidation / reduction rates for charging and discharging; must have a low electrochemical potential to withstand high voltages; must have slow Coulomb efficiency (to avoid side reactions); must have a large apparent surface to accelerate reactions; must be effectively in contact with the electrolyte to exchange ions, through a 'current collector' (copper sheet). In order to increase the electronic conduction, a layer of carbon is often added. - On the cathode: unlike the anode, the cathode must have a high electrochemical potential. The ceramics used, metal oxides, are subject to deformation during the insertion / extraction of Li + ions. These deformations can break the electrode. - On the electrolyte: it must have a very high ionic conductivity, and must be stable in contact with high potentials and low potentials. In addition, it is provided with a porous separator (a polymer) that prevents contact between the anode and the cathode. However, the electrolyte must overwhelm the whole.

It is therefore difficult to achieve volume production on large surfaces with current techniques (evaporation, co-evaporation, magnetron sputtering, etc.), as well as the repeatability of all these processes pose serious problems for the industry . [00157] Impact of the collector current on the high rate of efficiency of the electrode of a Li-ion battery. The basic principle for achieving a high power capacity of an electrode is by minimizing the overall resistance of the electrochemical system. For Li-ion batteries, the ionic and electron diffusion resistors associated with the resistance of the active material electrode have been a major concern in the past.

On the other hand, the resistance of the interface between the current collector and the active layer has received much less attention in the literature, probably because it has long been considered of less importance for Li-ion electrode materials of low power. However, the rapid progress in material synthesis technologies may in some cases have reduced the ionic and electronic resistance of the active ingredients, to the point that they become competitive for other sources of resistance. The importance of the electronic resistance to the active current layer / collector (AC / DC) interface is worthy of careful review. In this presentation, the effects of current collector, hence AC / CC interfacial resistance, on the performance of the two high-throughput active materials, including LiFePO4 cathode and Li4Ti5O12 anode, were investigated. In both cases, rather deep effects were observed. The charge / discharge capacity and stability of the cycle at high C-rate LiFePo4 (LFPO) electrodes using three types of current collectors, including Al smooth non-etched Al foil, anodizing etched aluminum foil, and the engraved aluminum foil coated with conformation C increased at 600 ° C to CH4, were studied. The use of the collector-coated current C not only remarkably increases the power capacity delivering, by 3-7 times on the basis of different comparison criteria, the LFPO electrode, but also greatly improves its high C cycle stability. -tals (5C). The improvement in speed is greater than that of a low temperature C-bound organic coating reported in the literature. The current collector effects on charge / discharge capacity and cycle stability of Li4Ti5012 (LTO) electrode under high C-rates (up to 20 C) were investigated by the application of five types of current collectors , including an aluminum foil, an engraved anodizing Al (E-A1), the same Al engraved with a conformal coating of C (CE-A1), a Cu (Cu) foil and the same Cu foil with a coating of C (C-Cu). The C coatings on the two metal current collectors are deposited by a chemical vapor deposition process using CH4 at 600 ° C. The capabilities of the LTO electrodes are in the range of Al <E-Al <Cu-Al-CE <C-Cu, exhibiting remarkable improvement in rate performance by the C-coating of both metals. Surface analyzes indicate that improvements in both cases can be attributed to the combination of two factors, including the removal of the native oxide layer and modification of the hydrophobicity of the surface, which improves the adhesion of the active layer, on the surface of the current collector. Both help reduce the resistance to the current collector / interface of the active layer. Molecular deposition growth of the layers (also called Molecular Layer Deposition or "MLD") 1. There has been a spectacular growth in the field of atomic layer deposition (ALD) over the last 10 years. Part of this ALD development has been driven by the needs of the semiconductor industry. Other developments have resulted from the application of ALDs for non-semiconductor arenas. Atomic layer control and conformality of the ALD film thickness have been found to be useful for a wide range of applications such as the fabrication of photonic bandgap materials and gaseous diffusion barriers. In addition to new technological developments, there has also been an expansion of film types that can be grown using ALD-inspired processes. The introduction of organic precursors using Molten Layer Deposition (MLD) has greatly extended the identity of the composition of the deposited film. MLD is distinguished from ALDs because a molecular fragment can be added during a sequential surface self-limiting reaction. Figure 4 schematically represents an ideal MLD growth sequence in "self-limiting reactions" using two homobifunctional reagents in a process having the sequence of chemistry spontaneously used for the growth of an organic polymer, thereby allowing mixing of the Organic precursors used for MLD with inorganic ALD precursors define novel organic-inorganic hybrid materials in a high efficiency solar hybrid cell subject of the present invention. 3. The original definition of MLD describes the sequence, the chemistry spontaneously used for the growth of an organic polymer. The first MLD system was based on condensation polymerization reactions and deposited a polyamide. More recently, the MLD of a variety of organic polymers has been demonstrated including polyamide, polyamide, polyurea, polyurethane, polythiourea and polythiolene. The organic precursors used for fully organic MLD can also be mixed with inorganic ALD precursors to define new hybrid organic-inorganic materials. The broad base game introduced by these hybrid materials has greatly expanded the possible materials that can be grown using ALD and MLD. The large amount of organic precursors available from organic chemistry leads to a wide variety of possibilities for organic-inorganic hybrid films using MLD. 4. Several hybrid organic-inorganic materials have recently been developed with MLD techniques. These systems have begun to define the wide range of materials that can be deposited using MLD. The ability to mix and match organic and inorganic precursors and their relative share in the film will lead to a wide range of film properties. In particular, the mechanical properties can be regulated by the control of the organic and the inorganic proportions. This brief report will first examine several MLD systems that have been demonstrated to illustrate the state's -of-the-art. Some new systems then be introduced to show the diversity of chemistries that can be used to develop various organic-inorganic hybrid films. Finally, speculations will be proposed in future prospects for the MLD of hybrid organic-inorganic materials. 5. Figure 5 illustrates the growth of Alucone (polymer film) in two stages using trimethylaluminum (TMA) and ethylene glycol (EG). TMA is exposed to a hydroxylated surface and produces a surface covered with A1CH3 species, thus allowing the mixing of the inorganic organic base of novel organic-inorganic hybrid materials in a high efficiency solar hybrid cell being subjected to the present invention. The state of the art has already demonstrated the interest of organic-inorganic hybridization of MLD film. One of the first organic-inorganic hybrid materials grown according to MLD was an "Alucone" based on the reaction between trimethylaluminum (TMA) and ethylene glycol (EG). 6. In general, a two-step MLD reaction between a metal alkyl, such as TMA, and a diol, as, for example, can be written as follows: a. Previous studies have shown that Alucone MLD using TMA and EG is very effective. Radiographic examinations (XRR) showed that the MLD growth rate is linear compared to the number of TMA / EG cycles. b. Furthermore, the growth rate MLD was temperature dependent and a decrease of 4.0 A per TMA / EG cycle at 85 ° C to 0.4 A per TMA / EG cycle at 175 ° C. Quartz (QCM) also revealed growth linearity in MLD as Alucone versus TMA and exposures for example. 7. The recent work in MLD motivated the inventor to consider the implementation of MLD process for the realization of organic-inorganic interface and hybrid layers in the construction of high-efficiency solar cells forming part of the present invention.

Other common problems of these methods proposed in the application patents dealing with the design of interlayer layers for the epitaxial growth of thin layers of semiconductors as well as the chemical treatments to improve the photovoltaic performance CIGS or method and system for selenization in the manufacture of CIGS / CIS solar cells dealing different due Sodium doping method and CIGS / CIS-based thin-film system with use of pigment and sodium species Bulk thin-film photovoltaic cell processing as cited in the patents US20090235983 Applied Quantum Technology, LLC; US20090235987 EPV Solar, Inc .; US20090293945 SAINT GOBAIN GLASS FRANCE; US20100087016 Global Solar Energy, Inc .; US20100087026 HELIANTHOS B.V: US20100087027 Stion Corporation .; US20100096007 SAINT-GOBAIN GLASS FRANCE; US20100101648 Sony Corporation .; US20100101649 SAINT-GOBAIN GLASS FRANCE; US20100212732 * Miasole; US20100224247 Applied Quantum Technology, LLC does not describe the band gap increase or even its doubling and process improvement by quantum dot augmentation and the use of the ALD or sALD and MLD processes subject of the present invention. [00107] Recovery of kinetic and thermal energy from solar radiation from photovoltaic cells using piezonanil and hybridization of solar cells. The state of the art identifies what is considered to be the top three categories of solar cells in terms of solar conversion efficiency and cost per unit area. Figure 8 shows the cost ratio per standard m2 identifying what are considered to be the top three categories of solar cells in terms of solar conversion efficiency and the cost per unit area in a high efficiency solar hybrid cell being the subject of the present invention. CIGS cells in thin PV layers are classified as type II solar cells. They are single junction solar cells and, as such, have a fundamental ultimate photon-to-electron conversion ratio limited to a maximum of about 33.7% by what is known as the Schockley-Queisser boundary (William Shockley and Hans J. Queisser, "Detailed Balance Limit of Efficiency of Pn Junction Solar Cells", Journal of Applied Physics, Volume 32 (March 1961), pp. 510-519, doi: 10.1063 / 1.1736034).

The "loss" of energy is mainly converted into lattic vibrations / phonons / heating. (Type III) advanced solar cell concepts seek to challenge the SchockleyQueisser limit by using tandem or multiple-junction approaches and other technologies such as hot support conversion and thermophotonics (through, for example, coupling with recovery approaches thermal energy, such as redox cells with liquid electrolyte). In general, however, such approaches are complex, bulky, difficult to manufacture and expensive. Thin film batteries integrated into the substrate (also called On-board Batteries); Between 1990 and 1995, mainly driven by Japanese manufacturers of portable equipment (camcorders, computers, nascent mobile telephony ...), two new electricity storage channels emerged, breaking with traditional technologies. The development of nickel-metal hydride accumulators at first, then the development of lithium batteries completely upset the original situation, and surprised most traditional manufacturers (Accumulators, batteries and batteries offer performance that is constantly improving). The evolution of these technologies, and essentially the latter, has also benefited in the mid-nineties from the sudden and considerable expansion of the mobile telephony market (+ 1% per month in 2000, 70 % of penetration rate in Europe in 2003 compared to a few percent in 1996).

Highly demanding high mass density of energy (D = dE / dm) J / kg under a small footprint. For example, the lithium battery market exceeded 4.5 billion euros in 2000 and the Japanese (Sony, Sanyo, Matsushita) and Korean (LG, Samsung) manufacturers share the lion's share (70%). a market now dominated more than 95% by Asian manufacturers (Japan, Korea and China), to the detriment of Europeans but also Americans, virtually absent from the main market that represents the power supply of portable equipment. Some European initiatives nevertheless see the light of day, which aims to develop specific sectors of lithium batteries, offering particular advantages over the lithium-ion sector currently developed in Japan and more generally in Asia. The work carried out at CEA / Grenoble is done in partnership with manufacturers such as SAFT, Batscap (Bolloré Group), Tadiran, and academics including LEPMI, ICMCB and IMN.

The current lithium-ion accumulators, based on a cobalt / graphite technology, are the ones with the best performances in terms of densities of mass and volume of energy, respectively 150 to 170 Wh / kg and more than 400 Wh / kg. (Figure 9a illustrates the principle of a charging and discharging cycle in a solid electrolyte battery). Charge: <H> + Li + + e - <HLi> <MLi> <M> + Li + + e Discharge: <HLi> <H> + Li '+ e- <M> + Li + + e- -> <MLi > In use, therefore during the discharge of the accumulator, the lithium released by charge / discharge the negative electrode (recipient intercalation material <H>) ionic form Li + migrates through the ionic conductive electrolyte and is interposed in the crystal lattice of the (Li +) solv (Li +) solv active material of the positive electrode (metal oxide type lithium insertion compound). The passage of each Li + ion in the internal circuit of the accumulator is exactly compensated by the passage of an electron in the external circuit, thereby generating an electric current. Other types of batteries are nano electrodes. Figure (9b) a thin layer illustration of the energy storage stage with Anode and Cathode on Flexible Thin Film Diffusion Interface (also called Thin Film), Composite and Flexible Batteries. Since 2007, 3D coating and process modeling developments including the following: ^ Nanoscale electrodes (eg capacitance, power, reliability) ^ Inorganic electrolyte Synthesis & characterization ^ Optimization of the interface of the state solid ^ Composite material synthesis and characterization Gave greater insight into the fundamentals of the diffusion interface of thin film (thin film) batteries and flexible. Generally, in micro lithium batteries, the capacity of the thin layers will be related to their mass (mass capacity expressed in mA.hg-1) or to their volume (volume capacity expressed in 1.4.Ahcm-2.μm-1) for the study of electrode materials and on their surface (surface capacity in [IA.h.cm-2] for the characterization of complete systems. The capacity of an electrochemical generator corresponds to the quantity of electricity supplied and its usual unit is A.h. It is given by the following relation: td Q = f 1 (t) dt 0 Where I (A) is the current flowing through the generator, t (h) is the time of the current flow and ta (h) the duration of the current discharge. From the previous equation, it is possible to calculate the number of moles of electrons x exchanged per form unit in the host material (often assimilated to the number of inserted Li + ions per mole of active material): x * F * m = 3600 * M Where m (g) is the mass of the active material, x is the number of electrons exchanged per mole of active material, F is the Faraday constant (9.64853399 C * mo1-1) and M (g * mo1-1) is the molar mass of the active material.

The energy of a lithium generator expressed in W * h is given by the following relation: td W = JU (t) I (t) dt 0 Where U (V) is the potential of the generator with respect to the potential of the torque Li / Li +. In the rest of the manuscript, the notation V / Li will be used. I (A) is the current flowing through the generator, t (h) is the time of the current flow and td (h) the duration of the discharge. Power is the ability of the generator to provide energy quickly.

It depends on the kinetics of the insertion reaction, hence the electronic conductivity and the mobility of the lithium ions in the structure. The average power during the discharge time, that is to say in the interval: [tdo, tdi] is defined as the energy supplied per unit of time and is expressed by the following relation: 1 td, P = U (t) I (t) dt (tdo - tai) ftdo Cycle life: from the point of view of applications, the cycle number life (cycling) of an electrochemical generator is an important quantity. . This is the number of discharge / charge cycles for which the capacity is greater than half of its initial value. This duration is related to the degree of reversibility of oxidation-reduction reactions. Recent developments have made it possible to consider other types of lithium titanate or lithium nanotitanate batteries. Figure (9c) is a schematic illustration of Lithium nano titanate micro batteries without solid electrolyte interface. For example, the Super Charge Ion Battery (SCiB) is a battery developed largely by Toshiba is close to "standard" lithium-ion batteries for portable computing devices (telephones, computers, etc.) with however advantages: - Lifetime: 10 years - Number of charge / discharge cycles: 6,000 (10 times more than for "standard" batteries) - Speed recharging: nine times faster than a lithium-ion battery (this is its main asset) - More security than lithium-ion batteries - Less difficulty to electronically control (load, support, ability to debit the current) But with a major disadvantage of Three times less capacity at equal weight than a lithium-ion battery. As an indication the History and characteristics of SCiB are: 2005: Toshiba publishes the principle of the SCiB, 2008: entry into service of a first production plant (150 000 units / month), 2009: Toshiba plans a new factory for 2011 (expected production: 500,000 units per month). Major technical features are: - Anode: Lithium-Titanium Oxide ^ Cathode: Negative electrode material ^ Thermal stability (little heating) ^ High flash point (little short circuit) [00109] State of the art of materials used in electric vehicle batteries To efficiently and properly use renewable energies, the use of various energy-generating devices (including solar cells) together with storage battery systems, and also electric or hybrid vehicles, are beginning to develop in the market. Batteries used in battery storage systems and in electric vehicles generally use lithium-ion batteries, but require further improvements. Other Japanese manufacturers such as Sekisui Chemical has developed a material that can triple the capacity of lithium ion batteries, allowing electric vehicles to have a range of around 600km. The company has also developed a new material to conduct electricity in the battery. It estimates that this new material can reduce the cost of producing batteries to about 30,000 yen (217 euros) per kilowatt hour, which would lower the total cost of electric vehicles and approach the cost of a gasoline car.

Normally solidification of the liquid electrolyte leads to drastic reduction of the lithium-ion conductivity. We considered the use of a lithium-ion high-conductivity gel electrolyte (about ten times compared to other products), printable on substrate R2R to achieve high productivity with a coating process instead of standard vacuum infusion process. By adding the advantage of this newly developed, high-capacity original material technology for the realization of negative electrode in this process, we can provide lithium-ion batteries of the type 'high-capacity, flexible, thin film and on a large surface. They make unprecedented savings in terms of space (one-third the size of previous products) and can be installed in any form whatsoever, giving rise to a large number of applications in automobiles, homes and various portable devices.

DESCRIPTION OF THE INVENTION Prior remarks on the integrated storage. Peak production peaks and troughs from wind and farm power or solar panels require energy storage systems to smooth out intermittent production and reduce the maximum rate of change for medium and large power plants. The high-energy battery solutions integrated in the substrate or embedded in the photovoltaic cell, allow to smooth, stabilize the power level and better distribute the energy obtained, while strengthening the production capacity. The invention makes renewable energies, a predictable component of the bouquet (also referred to as the energy MD) of network operators.The technology described in the present invention also provides the ideal combination of energy and power produced to compensate for dynamic behavior. The present invention proposes a solution to the storage problems of the prior art, in the face of a growing global energy requirement and in view of the production and storage costs of the solar energy still too large to compete with fossil or nuclear energy sources, the objective of the invention is to design a new product integrated solar cell substrate for energy storage for later consumption. storage process will be deposited by "thin-film" technology which will make it possible to make "flexible" batteries ", Of different sizes and shapes, which can be integrated on different substrates. This innovative technology is mainly intended to be more optimal and above all less expensive than the alternatives used until now. Invention brings real solution on the increase of the performances of the nanotitanate (nLTO) and LFP battery in terms of its charge capacity, its integration in thin film film as well as on low-cost capacity production processes during its production. by the molecular deposition of "MLD" layers and layered growth of nano laminated hybrid / inorganic polymer for integrable or embedded batteries and offers easy maintenance by division for large areas. In addition, the invention considerably reduces the cost per watt for a given surface while significantly increasing the efficiency of solar energy storage solutions offering a first level of storage on board the solar cell by two possible storage paths. . In general, the invention describes a system for storing solar energy composed of at least one anode, at least one cathode using lithium nanotitanate materials and a solid electrolyte on a substrate. can be integrated in the solar cell (or on the back of the solar cell substrate). Variations in the possible configurations are described as follows: positive electrode (cathode), a negative electrode (anode) and a separator interposed between said negative electrode, and said positive electrode in which a porous film containing nanotitanate of lithium alone, and having insulating properties, is formed on the surface of said positive electrode negative electrode (cathode), a negative electrode (anode) using lithium nanotitanate materials and a gelled or solvent-free polymer electrolyte. same as a system for storing solar energy composed of at least one anode, at least one cathode using lithium nanotitanate materials and an electrolyte whose production by the molecular deposition of the layers MLD "and growing layer by layer of hybrid / inorganic polymer laminated nano for batteries ensures the integration to the cell or the back of the support of the solar cell. The system remains transferable, juxtaposable, assemblable or embedded on a generator of different types of renewable energy "ie, solar, wind, marine" or on various substrates and can be implemented in sensor applications including autonomous embedded, able to communicate without wire in industrial conditions and temperatures -20 ° C to 100 ° C. Ideal for road applications, roads or solar motorways equipped with signaling with smart sensors, it offers means of transport and distribution of energy that can be cut and shaped. Assembled for a given configuration in pieces or segments it offers the ease of maintenance and repair by replacing the defective segments. By its definition, the implementation of thin film manufacturing technologies on substrate opens the way to a significant reduction in manufacturing costs per watt.

Currently, for photovoltaic applications, lead accumulators are the systems used for the most part because of their low cost (<150 E / kWh). However, their electrical performance and their degradation do not allow them to have an adequate life span for the associated solar panels (> 10 years). Recent improvements in lithium-ion technology have confirmed the interest of the technology for this application given the specific characteristics: high energy efficiency, longer life, lack of maintenance, reliability and predictability of behavior. However, the material cost of a Li-ion battery (about 80% of the cost of the battery) is assigned to 25% by the cost of cobalt and 25% to the costs of the security organs made necessary by the high reactivity to high temperature of this compound. It is then that the inventor decides to operate at a cost reduction of more than 30% that can be achieved through a new generation of lithium nanotitanate type accumulators. Finally, in order to meet the storage needs embedded in substrates, the inventor wishes to develop his own production process based on thin film technology applied to photovoltaic science. Faced with these technico-economic issues, the issues to be addressed today concern: on the one hand, the study and analysis of the different materials that can be used for its applications; and on the other hand, the identification, adaptation and control of appropriate deposit and production technologies based on the materials selected first. [00202] Degree of technological breakthrough; The use of an innovative nanomaterial for the storage of electricity. The first innovative feature of the project focuses on the use of lithium nanotitanate batteries. This technology, initiated by Toshiba during its first work on its Super Charge Ion Battery (SCiB), has, in comparison with that of li-ion batteries, convincing strengths: a lifetime of more than 20 years, 25,000 cycles charging / discharging (10 times more than "standard" batteries), a charging rate 9 times faster than a li-ion battery and greater security. The major disadvantage, however, is the capacity, equal weight, 3 times less important than a lithium-ion battery.

The technical characteristics of a li-nano-titanate battery (thermal stability, high flash point, short-circuit resistant internal structure) would make it possible to use stronger currents than for li-ion batteries without risk of explosion. Indeed, according to our preliminary studies, the li-nano-titanate technology is unique because it does not contain a solid electrolyte interface (SEI). The SEI is a "film" on the anode constituting an internal resistance limiting the power output and generating accumulated heat. Therefore, the absence of an IES would allow the battery to work effectively at extreme temperatures while reducing the risk of thermal "runaway" significantly. Thus, by replacing highly reactive graphite with nanostructured lithium titanate, as a negative electrode material, no significant interaction would occur with the electrolyte. The temperature range of the lithium nanotitanate battery would also be wider than that of other technologies: from -40 ° C to 100 ° C. This capability virtually eliminates the need for additional heating when the cell is used in low temperature environments and reduces or eliminates cooling requirements for high temperature operation. [00203] SODIUM case; A new generation of sodium batteries. In the particular case of the storage of a large quantity of electricity, the most widespread solution is that of sodium-sulfur batteries which offer very good performances: a high density, a high efficiency in the charge-discharge cycle and a long duration of life. The main disadvantages of this solution are its operating temperature (between 300 and 350 degrees) and the highly corrosive and flammable nature of sodium. We are focused on discovering and designing a new generation of sodium batteries with better performance. An important avenue in their research is to study the use of new materials that can replace graphite in the constitution of the negative electrode.

The main idea is to keep a structure in the form of layers similar to graphite, but replacing the carbon atoms by non-organic compounds, usually metal oxides. This academic collaboration just starting, the project is still in its infancy. The next step, before we can think of energy applications, is the synthesis of this type of nanostructures. This synthesis is still poorly controlled and the performance is very different from that obtained by their carbonated cousins. We have studied non-organic nanomaterials based on Titanate and sodium mixtures to replace graphite in the battery. Note that these materials improve the efficiency of the chemical reaction involving sodium, and thus make it possible in the medium term to obtain batteries with higher energy density, but also simpler to manufacture and maintain. [00204] Tests and calculations of materials; The expected capacity of the thin-film battery: 1) The initial parameters are: Electrode specific capacitance: 200mAh / g (This is typical of cathode LiMn2O4) Density of the cathode 4.5 g / cm3. Thin film thickness of 1 micrometer. 2) Calculations: Electrode Volume of 1 micron thin film and 1cm2 area = -4 cm3 Mass Electrode 0.450 mgr / cm2 Capacity 147mAh / g * 0.450 mg / cm2 = 0.066mAh / cm2 For a 6x6 inch cell total area = 232.6 cm2 Capacity per cell = 0.066mAh / cm2 * 232.6 cm2 = 15 mAh / cell. If we consider that the batteries should provide about 100 wh / kg, which means that the weight of the battery per square meter should be close to 2.5 kg (1st lens) and 5 kg (2 targets). This weight will be increased by the battery envelope and also by the electronic part (BMS, connections etc.). We will obtain respectively our targeted energies for the two 1st and 2nd samples, 250 Wh / m2 and 500 Wh / m2 (in theory, 200Wc / m2 = 200Wh / liter = 2Wh / Wc = 2mm thick) [00205] Tests and Characterizations of the materials The first technique is the limitation of the size of the films. In the case of sol-gel and spray technologies the optimal size for the test is 2x2 cm2, in order to implement the thin film parameter deposits in both methods. In a final step, it would be possible to magnify the films up to 4 inches in diameter, but a lot of homogeneity problem appears. In the case of sputtering, the situation is quite similar. At the beginning of our test, the maximum thickness that can be cultivated with quality is 1 micrometer. Subsequently, to grow anode (LTO) and cathode (LiCoO2 or Li-Mn-0 spinel) materials on metallized silicon was more easily achievable.

Achieving multilayer (LTO-ES-LiCoO2) thin films in average success, during the first six months was really very difficult and we could not compromise the project. Of course, the electrical and electrochemical characterization of the anode and cathode of the films on the half-cells was crucial. Our tests also show that for the substrate silicon is the most convenient for thin film compared to other or even molybdenum or stainless steels. We also encountered some oxidation problem during the annealing of the samples but we quickly resolved. At the start of this innovation program, there were no batteries or electrolytes adapted to the temperature range of the application. This means that we had to invent the electrolyte (liquid electrolyte and polymer separator) One solution (ceramic LTO) and a second solution with an LFP and an LTO / LFP battery. The operation of the charging and discharging system is as follows: Note: the memory effect of the batteries mainly concerns Ni-Cd batteries. On the other hand, studies relating to LTO-based batteries do not demonstrate memory effect. Regarding the depth of discharge (PDD or DOD), conditions the life of batteries and the 'fading' performance. The more we try to increase the capacity and the more the battery suffers. Another important point is the charging and discharging speed C / x. If one discharges on 10 hours one is with C / 10 and if one discharges with C / 0,1 that is to say with 10C one discharges in 6 mn. The same thing in recharge. 1) In the context of integration with a solar cell; Photovoltaic energy will pass through the batteries to be changed to alternating current before supplying electricity to the house, road or network. In this case we will have: a. Sun => PV => Batteries => microinverter => house (network), where the battery will store all PV energy for immediate use or for delayed restitution. 2) The photovoltaic energy will not totally pass through the batteries to be changed to alternating current before supplying electricity to the house, the road or the network. The battery will only store the surplus PV energy to restore it later (Only a part will charge the battery) So we will have in this case: a. Sun => PV => micro-inverter => house (network), where the battery will only store the excess PV energy to restore it later: In the first case, the battery buffering between PV and network. In this case, the battery should charge and discharge in rather slow regimes: at 40 C / 10 average. [00206] Tables of the materials tested Li Li4Ti5012 material LiVP04F Li (Si, Sn LiC6 Na NaxTi3 07 etc.) Tm vs 180> 1000 Not Not 98 110 ° C applicable applicabl Too low e Capacity mAh / g. Theo. Theo.35 0 Theo.175 Pract.160 Theo.156 Pract.131 Theo.790 (Sn) Theo.1.16 Pract. depend - 200 Pract. Theo.

Pract 800 2,000 (Si) Redox vs - 3.04 -1.5 -1.75 - 2.71 - 2.2 SHE (V) a Elec. YES NO NO YES YES No Available YES Available with Available C Rapid Binders No YES Inferior at LTO NO NO Charge Dendrite Dendrite Cycling NO. High - Vol. Only H.T Except Polymer Gold Glass changes Na / S 60% Current applicatio n US NO YES .pat Promising but still lab. level Not Not Not Mature 2002 <LTO [00207] An integrated thin-layer storage solution; The second innovative feature of the project is the implementation of a battery integrated in the substrate ("on-board batteries"), on or on the back, of the solar cell obtained thanks to the thin film technology. thin "are based on the use of extremely thin layers of a thickness of some microns and consist of depositing under vacuum on a substrate (glass, metal, plastic, etc.) a thin uniform layer composed of one and more often of several different materials. In contrast to the traditional silicon-based crystalline cells obtained by cutting a silicon ingot, thin-film technology has recently been used worldwide for the production of photovoltaic systems, thus enabling the production of photovoltaic products. high quality, made from controlled, timed and low cost techniques. On the other hand, we can also observe the use of this technology for the production of "micro-consumption" batteries. Thin-film semiconductor energy cells are a revolutionary energy storage solution for small devices such as smart cards, wireless sensor arrays, and many medical applications including assistive devices. hearing aids, automatic insulin pumps and portable medical monitoring systems. However, in the present state of our knowledge, no development has yet been carried out for large-scale productions, applied to photovoltaic storage and integrated with substrates such as CIGS cells designed by the inventor. The technical characteristics targeted would be multiple and would make it possible to enter the world race for the storage of solar energy. Physical flexibility would be one of the key advantages of thin-film battery technology because it would allow for flexible batteries of different sizes and shapes, and the thickness could be as thin as 200 microns which could satisfy other uses such as portable and ultra-compact products). In addition to being flexible and thin, this new generation of batteries would have charge times ranging from 60 seconds to 5 minutes, and charge retention times greater than 5 days (with 85% retention of the battery). initial charge).

The inventor aims to develop a system of mass production of these film-flexible batteries, which would make products for large varieties of use and application. Indeed, one of the advantages of the present invention is to propose a material that can triple the capacity of lithium-ion batteries, thus making it possible to increase the application potential of the products by considering, for example, a use for electric vehicles ( target autonomy close to 600km). The development of this type of film battery, large capacity while remaining thin and flexible, massively improve the freedom of design of many other end products, leading to the anticipation of their use for any other electrical device. [00208] Benchmarking of existing products is summarized in the following table: Technology Life (Years) / discharges Thickness Open Name. (Ecost / AT ° C - Lime # of (11) Capacitance h /> Charge Voltage (V) Current 3) TempC (I) Working mA / Cm2 range> 120 Present ni> 20> 25000 50 <T < TBD estimate, 0.4 / Wh Cymbet All SS> 5.000 150 4.0 <V <4.15 0.5 0.78> 90 Corp. (Tex. Inst.) GS Nanotech Lithium> 5> 5,000 10 3,7 400> 65 Power Altairnano LiTi power> 20> 20,000 App. 367 kWh 3.6 MW 1000E / Kwh> 95 Power / 4 MVA Toshiba LinTi> 20> 6,000 App. 12.8 to 36V 92Wh 1500E11 (h> 75 PHEV, & (9Ah) EV Thinenergy / All SS> 0> 5000 3.9 4.35 to> 70 IPS (Infinite 7.9 Power Solutions) ST Micro All SS: > 1,000 200 4,0 <V <4,15 0,775> 100 LiCoO 2 / LiPe Power Paper, Printing> 3> 1,000,500 1.5 0.1> 70 Blue Carbon> 2 NA: RFID <750,,> 95 Spark / Thin Zinc / smart Battery (Zn / Mn02) cards & ID Technologies badges Inc. Enfucell / Carbon> 1 Pharma & ID badges> 500 1,5 1,2> 75 Solicore Zinc / NA: RFID (Zn / Mn02) Excellatron Li / Air> 5> 2,000 <85> 105 SAFT Ni-Cd, Ni> 1> 500 to Prismatic / Jan-30> 145 to MH & Li- <1500 Coil <190 ion shape [00209] Test results are: - Storage capacity: 2kWh storage capacity for lkWc output power - Weight: 2.2Kg / m2 <target weight <4.1 kg / m2). - Charge (#): 25,000+ charge / discharge cycles with high security and low-temperature). - Technology: Solid state structure (ASSB), wide temperature range from -40C to 110 ° C, with peak temperature inside the panel near + 140 ° C in the Sahara). - Packaging: Substrate thickness & packaging between 0.90-to-1.5mm (200Whil or 2Wh / Wc) - Fast Charge Cycle: Charge time = 60 sec (Fast charging cycle 80% of charge in less than a minute) , max charging time <5mn). - Low self-discharge: Charge retention time: 5 days min with> 80% initial charge (self-discharge min 1-2% / day) - Charge Capacity: flexible TF 0.016 mm 0.1 mm: lmA / Cm2 - Integrated Battery Management: by ASIC & DSP (production and load management and supervision as well as ASIC functions on board) - Low Internal Resistance (8 - 10 milli ohms) [00210] Process and Roll-to-Roll Manufacturing Steps 1) The equipment of roller-to-roller (R2R) For R2R equipment. The steps are: a. Use a PET plastic film or polyimide: it should be metallized if you want to remove or connect a battery. While the negative graphite lithium-ion battery can not use a current collector on aluminum but requires copper, the negative LTO can use an Al current collector. Thus the support can be metallized by Al or can be made of aluminum foil. In this case, a dielectric must be inserted between the photovoltaic panel and the current collector of the battery. b. Start the negative layer deposition layer (LTO). The R2R treatment could be well suited to the electrolyte negative (LTO) layer deposition layer and positive. Expected spray thicknesses are 500 Wh / kg target. c. Another alternative is based on spin-coating by sol-gel but it does not always lead to homogeneous materials and therefore performance may vary. d. Another alternative is to print by inkjet (layer by layer) for the entire elements of the battery. e. An important option for electrodes is to create a dense or partially porous ceramic electrode of several hundred micrometers using Power Extrusion Sintering, and the alternative solution is to optimize a conventional LTO electrode in order to obtain sufficient stability. high temperature capacities (T> 110 ° C). Thus, the printing process is an effective alternative. We then have to stick the electrode on the chosen support. f. For Anode: i. Chemical vapor deposition (CVD) ii. High-energy mechanical milling (HEMM) iii. Extrusion Molding_Magnetron_Sputtering Our choice: the battery LTO / LFP - Elements of choice of the negative: - Robustness with cycling, tolerance vis-à-vis the electrolytes - No SEI (Interface of solid electrolyte) (- Fast recharge without risk of formations dendritic - LiC6: between 330 and 340 mAh / g, voltage at -0.3 V vs Li / Li + - But possibilities deposit of Li ° and dendrites if fast charge - SEI formed thanks to LiPF6, thermally unstable - Li metal: Li ° high capacity, OV vs Li / Li + - but only cycle with polymer electrolytes or solid glassy electrolytes - Negative Si-based: promising - But volumetric expansion, non-mature for thousands of cycles - Metallic alloys: strong volume expansion - LTO: robust, neither SEI nor dendrites, fast charging OK, electrolyte tolerance - But low practical capacity: 165 mAh / g and torque at -1.59 V vs Li / Li 'LTO / LFP - 1 "lens: - To demonstrate the validity of the innovative concept PV / batteries - To go quickly to the prototype - Given a demanding specification (T, cycles) - We chose the most robust couples - Despite its limited capacity and its high potential: - We chose LTO - We choose to couple it with LFP: capacity close to LTO, limited voltage - Once validated the concept and the prototype - Other positive ones could be envisaged: - To increase: - Energies specific and voluminal Materials of electrode: LTO - 2 possible approaches : - LTO called classic - Advantages: proven technology - Disadvantages: low density, low mechanical strength - LTO commercial (benchmark) - Formulation of LTO in the form of ink based on: - active material LiaTi5012, - electronic driver eg C black - binder eg PVdF or new binders: mechanical strength improvement - solid LTO: - Mixtures of LTO, LTTO (cond.ionic), Ag or C (cond.e-) - extrusion / extrusion processes sintering - before ages: high densities, strong Young moduli - Disadvantages: response of the material at a high rate of charge / discharge Regarding electrolytes: key element of the batteries of the present application (Figure 30a) - Operating temperatures - 20 ° C to + 110 ° C! Polymer electrolytes used are of the type: solvent-free polymer electrolytes. - Compatible with a temperature of 110 ° C - Incompatible with temperatures of - 20 ° C - Commercial liquid electrolytes: 1M LiPF6 - A good electrolyte <* Strong ionic dissociation and high mobility - The majority use ethylene carbonate: EC - Form with LiPF6 an SEI for cycling lithium graphite LiC6 - Strong dielectric constant E = 90 <r> promotes dissociation of ions - But solid up to 40 ° C, high viscosity beyond <=> decreases mobility of ions - Compromise < => associate EC with liquid and low viscosity solvents but low E - Dimethyl carbonate DMC, Eb = 90 ° C, Tf - 4 ° C - DEC diethyl carbonate, Eb = 126-128 ° C, Tf = - 43 ° C - Ethyl methyl carbonate EMC, Eb = 107, Tf = -14 ° C Note that to obtain good conductivities at -20 to + 110 ° C (Figure 30b) - Use of ionic liquids: - This solution has the following major disadvantages: - High cost, high viscosities - Electrochemical performances (reaction a electrodes) => unsatisfactory - High boiling solvent eg DMSO, PC, Sulfolane - propylene carbonate PC: E - 69 - Eb = 242 ° C, Tf = - 48,8 ° C - PC not used in Li-ion battery => exfoliates Li C6 - No incompatibilities neither with LTO nor with LFP - Disadvantages: viscosity at low temperature - Mixtures with DEC - To increase we will use complexing of Li + - Selected salt: LiTFSI (CF3S02) 2N-, Li + - LiPF6 unstable above 55-60 ° C. - stable LiTFSI up to more than 200 ° C. Macroporous separator or gelled polymer (FIG. 30C) - Regardless of the liquid electrolyte: - A polymer separator dense or porous must be used - to avoid a short circuit by direct contact. 40 - Macroporous separator: - Benchmark with Celgard® separators - Good mechanical properties - Quid at 110 ° C - High conductivity losses (factor 10) versus liquid electrolyte 45 - Compatibility with thin-film planar batteries - Gelled dense membrane liquid electrolyte: - Crosslinked solvent polymer film - A solution that has the following advantages: 50 - Excellent redox stability - Good complementarity with LiTFSI and PC - Aqueous process Reinforcement of the separators (Figure 30d) - In order to preserve the performance of the battery, it is advisable to: - Decrease the contribution of the electrolyte to the Internal Resistance - Film thinner because mechanical properties much stronger - Increase of the safety - Decrease the material cost because less salt and less solvent - Reinforcement with NanoCrystallineCellulose NCC: - Percole at - 5-6% by weight - Very high conservation modules: - No harmfulness Despite the Nano Dimension: LC 50 - NCC has recently been tested in batteries 5V ` 'LiC 6 / LNMO and has an energy saving of 30%.

In conclusion we can note that: - Main effort on the electrolyte: - Innovative and safe electrolytes - Secondary effort on solid LTO electrodes - Innovation in the synthesis and development - Calculations show: - with configurations series or series-parallel - The target can be reached: Specific energy of 500 Wh / m2 - A weight between 4 and 6 kg / m2 - A weight between 100 and 150g for a surface of 6X6 inches2 - A thickness of batteries between 4 and 8 mm - A voltage varying between 15 and 40 volts - according to the assemblies series or series-parallel [00212] Choice of materials: Conclusions of the development program of the Batteries subject of the present application is that: The choice of Li4Ti5012 in the application is motivated by the fact that the traditional materials Li-storage suffer from serious losses of capacity when charged and discharged at high rates, which is mainly attributable to high polarisat ion and slow diffusion of lithium ions and electrons in active materials. -Good structural stability, with an almost negligible volume change during Li + insertion and extraction processes, -No formation of dendrites Apartment operating voltage of about 1.5 V compared to lithium, which is higher than the reduction potential of most electrolyte solvents. Theoretical capacities of 175 mAh g-1, and the actual discharge capacity is> 160 mAgh -1. -Low electronic conductivity Li4Ti5012 poor flow capacity of the coarse due to its low lithium-ion conductivity We can increase the electronic conductivity in Li4Ti5012 by: - Synthesis of electronic conductive composites (carbon, metals, transition metal oxides - The substitution of a small amount of Li + or Ti4 + by metal ions supervises 50 (V5 +, Mn4 +, Fe3 +, Ni2 +, Cr3 + and Mg2 +). - Synthesis of nano-particles Li4Ti5012 Synthesis of electronically conductive composites - LTO-TMO (TMO = Metal Oxide Transition) -LTO-Fe203 -LTO-CuO o LTO-CuxO 5 -LTO-LLTO-LTO-TiO2 (C) - LTO- M (M = Ag and Cu) - LTO carbon and LTO-C composite [00112] The ALD process, sALD; Atomic layer deposition (ALD) is a technique for the chemical vapor deposition of ultrathin layers in the order of nm based on the self-termination of sequential gas-solid reactions. This is a variation of the Chemical Vapor Deposition (CVD) technique used in the semiconductor industry for the manufacture of thin films. In the general process, the substrate is exposed to one or more precursors that react together or decompose on the surface of the substrate to produce the desired deposit. Unlike CVD, the ALD technique benefits from the so-called surface saturation phenomenon. A uniform and homogeneous distribution of the reactive chemical elements forms on the surface of the substrate, thus ensuring a perfect control of the thickness (which generally depends on the number of reaction or deposit cycles). ALD is a cyclic and repetitive process based on the following principles: precursors are introduced alternately allowing sequential gas-solid reactions at the surface of the substrate. the continuity of the gas-solid reactions until the saturation of the surface of the substrate. From a time point of view, each reaction cycle can take from 0.5 seconds to a few seconds for a thickness film deposition between 0.1 and 3 A '. ALD cycles; Since the ALD process is a cyclic process, we will give the details of the time course of a cycle of this cycle: A and B being two precursors in this process TcycleALD = tA + tpurge tB + tpurge 35 Phase i: Introduction of the 1 "precursor A. It adsorbs by chemisorption to saturation = tA Phase ii: Purge by an inert gas to remove non adsorbed A molecules tpurge Phase iii: Introduction of 2nd precursor B, its reaction with A up to saturation = tB 40 Phase iv: The same as phase ii but for the precursor B tpurge A kinetic model for the diffusion of reagents: The time parameter plays a crucial role in the atomic deposition process. the speed with which the molecules of the precursors deliver their atoms into the film, even if a sufficient number of stoichiometric atoms enters the reactor chamber, for a time too short there would be a risk however, a long time would be a waste of the cycle time with possible thermal desorption of the adsorbed precursor. We must therefore find a compromise (tradoff) for these temporal parameters. A minimum time will therefore be necessary before these atoms are deposited on the entire surface of the substrate. It follows that a kinetic study at the atomic level is indispensable. The kinetic theory provides valuable information for this temporal optimization study: - Pulse time given by: t = S = SV2TrmkT where V2TrmkT (the density of atomic flux: their number crossing on both sides of the substrate per unit of time) P is the partial pressure of the precursors whose product over time provides a very useful measure of the surface area of the substrate exposed to the precursors: Pt = S tpurge - Purge time: C (t) = Coe Let tpurge = T ln C (tCo) with m: the mass, k: Boltzman constant let kT (the energy scale) = 23 * 10-3eV = 26 meV and P the partial pressure The ALD is used since about forty years for the manufacture of thin layers of inorganic materials with a thickness generally not exceeding a few tens of nanometers. The ALD layer growth process has the capability of producing extremely complex layers with uniform, high quality material deposition and unique ability among thin film deposition techniques.

Despite the many successful applications of material growth by ALD, many physicochemical processes that control growth are not yet sufficiently understood. In order to increase the understanding of ALD processes, multiple knowledge is needed not only at the level of existing ALD processes and their applications, but also those of the surface chemistry of ALD-specific processes. The purpose of this paper is to provide an overview of specific ALD processes by examining available experimental data on the surface chemistry of the methyl-aluminum / water sorting process. This process is generally known as a rather ideal process for ALD, and a lot of information is available on surface chemistry. This summary is also intended to provide insight into the current state of our need for ALD surface chemistry, typically process optimization. Knowing that the basic concepts related to surface chemistry of ALD are described from a generic point of view applicable to all ALD processes based on compound reagents, we seek to optimize our processes. Our application requires physicochemical skills of self-terminating reactions, kinetics of reaction, typical mechanisms chemisorption, factors causing saturation, reasons for growth of less than one monolayer per cycle, the effect of temperature , the number of cycles on the growth per cycle (GPC), and the growth mode (Figure 12a illustrates the principle of the ALD process) [00113] ALD-CIGS principle: The realization of the absorbing layer (engineering in 3D) Particularly recommends the use of smooth, dense and homogeneous CuInGa precursors which lead to a better crystalline quality of the absorbent layer compared to raw and more granular precursors. The crucial point in the formation of the absorbent layer is the first stage of selenization. This will be easier to control with smooth, dense and homogeneous precursors (Ternary alloyed). Principle of ALD-CIGS-R2R: Our modeling in terms of performance and QE2 photovoltaic cells based on CuInGaSe2 (prepared from 2 Quantum Efficiency: Quantum Efficiency precursors low cost) based on a mathematical model, the simulation and analysis of the transformation phases of thin multilayer films to better model the CIGS absorbing layer: The transition from CuInGa to CuInGaSe2 uses the Differential Scanning Calorimetry technique, and no (X-ray diffraction - XRD). Thin multilayer films of Cu-In, Cu-Ga, and Cu-In-Ga were analyzed to understand the phase transformations of the layers used for the production of Cu (In, Ga) Se2 (CIGS) photovoltaic solar cells. With the N 2 cooling technique, it is possible to have a precursor concentration gradient, for example a higher Ga content of precursor on the film surface, which can also contribute to higher yields. The technology of the present invention lies in engineering the structure of the CIGS cell with the control of the growth of the molecule during its formation. Uniformity and quality are factors considered very favorable for the purpose of the present invention for a highly efficient and economical solar cell. Figure 12b, illustrates the parameters to be taken into account in an ALD process 20 FF Form Factor (or A / R Aspect Ratio) FF = h: w Compliance (or compliance) or surface coverage = minimum thickness (b ) / maximum thickness (a) (the target value b / a is generally = b / a = 100%) [00115] Modeling and Numerical Simulation: Despite their simple appearance from an operational point of view, Photovoltaic modeling and design are difficult steps to overcome; this is due in large part to the multidisciplinary engineering of these systems requiring skills in several specialties, and in particular: - The physics of solids and semiconductors at the theoretical and technological level. - Design and analysis of electronic systems. The main difficulty concerns the components of the systems to be modeled because the partial derivative type equations which describe and govern their operation are non-linear in nature; it follows that the exact and analytical solution is not within the grasp of the modeling engineer. Therefore, the passage through numerical methods and in particular those of finite differences and / or finite elements is mandatory. Another aspect of these systems is related to the characteristics of solar cells which depend in particular on the intensity of solar radiation. The latter is a function of time. 40 The quality of a model is based on several criteria, especially the number of parameters introduced, but the most important is the ability to accurately reproduce the data resulting from measurements made by the Metrology team. From a computer point of view, a model can be likened to an Expert System. We use finite element methods or finite element analysis in this project, which are well adapted to complex geometries and are more flexible from this point of view. The approach of the engineer in Scientific Computation: Although all the engineers employ a certain methodology in the design of complex systems, which is common to them, the engineer in Scientific Computation differs from his counterparts by his versatility which gives him Ability to successfully conduct and carry out an industrial project that requires skills in various fields of applied sciences: mechanics, physics and analog and digital electronics. Modeling and mathematical processing: Any mathematical modeling of a phenomenon to be studied relies on a certain number of physical properties as well as the parameters that describe it. Since the phenomenon to be studied is a semiconductor structure, it is necessary to take into account its physical specificities such as:> the properties of the medium where the phenomenon occurs> the relative permittivity,> the electrical potential and> the concentration charges. The model can be described by the fish equation, in fact any spatial charge (in 3D) p (x, y, z) is accompanied by an electric field given by the law of fish: divE = V. E = p (x, y, z) E Where E is the dielectric constant of the semiconductor, the electric field itself being connected to the potential q by the equation: E = -grad ip = -V = -Ti (in tensor notation ) axi It follows that: = = E ° 2 * 1 axi The space charge p (x, y, z) is calculated taking into account all the charges existing at a point of the semiconductor, c ' that is, on the one hand mobile charges (electrons and holes) and on the other hand fixed charges that can be located on the ionized donors and acceptors. In the absence of ionized deep centers this space charge is given by: p = e (1 \ 1-dE-N p-n) at room temperature all donors and acceptors are ionized so that the space charge written in the following way: p = e (Nd-Na + p-n) 25 V (ErE0V 11J) = q (p -n Nd-Na) £ 0 = 4Tr * 10-7: the permittivity of the vacuum and Er The relative equilibrium of the dielectric The equations governing the behavior of the medium are as follows: = q (p - n Nd - Na) (ErE0) vJn = -c (G-Rn) pJp = + q (G - Rp) G and R generation rate and recombination Jn = q (ilenV 11J + D e '') n) Jp = q (pppV 11J - DpVp) Jn and Jp are the current densities respectively of the electrons and the holes De and Dp: the electron and hole diffusion constants respectively 35 The numerical resolution of the equation The study and the numerical resolution of the homogeneous fish / Laplace equation in 2D: a241 a2iij Alll = = aX2 ay2 By choosing an appropriate numerical scheme (Euler explicit for example) the discretized resolution 40 is translated by a system of matrix equations which is solved by the classical methods specific to the systems of linear equations.

We replace the second order partial derivatives by their discretized equivalents by carrying out Taylor's development: LXx and Ay being the discretization step given by: LH Lx = -m and Ay = -n L and H are respectively the length and the height of the rectangle used as the discretization domain (see Figure 12c illustrating the discretized rectangular domain). xi = - 1) Ax for i = 1, ..., m + 1 yi = - 114 for j = 1,, n + 1 -2111i, j + 114 + 1, j (AX) 2 -21Pij + tfri, j + 1 W, YY (AY) 2 We deduce the expression of 114, i 1-14-1, j + 114 + 1, j + [32 (114, j-1 + 11Ji, j + 1) tllij = 2 (1 + [32) ix = (37,) The iterative method and the criterion of convergence: tkii being a first approximation of the real solution of the Poisson / Laplace equation, in practice it is necessary to continue an iterative procedure in order to improve the quality of the solutions in terms of their convergence towards the real solution; this is the reason why we replace 114, i by: tl (ki) k indicates the current iteration, so we compute the iterative solution of the problem posed by: (k + 1) (32 (j (1j5) 1+ 'Vii5) +1) 2 (1 + 132) Convergence is reached after a sufficient number of iterations at each point of the considered discretized domain, the convergence criterion is given by: Sup 11, (k + 1) (k) ## EQU1 ## This relaxation procedure is called the relaxation method since the value in each solution domain node is slowly relaxed to the solution. One could further improve the speed of convergence by applying the so-called method of successive relaxation or SOR (Successive Over-Relaxation). It consists of assigning weights w and (1-w) respectively to the iteration at steps (k) and (k + 1), where w is called the relaxation parameter, which gives: (k + 1) i , j = (k) (1 - bij (i) tj 2 (1 + 02) f32 (ti j (k + 1) co) 1 The approach described above can be extended to 3D without major difficulty except that in this case the last case requires a discretization at 3 levels.

Numerical simulation of the model: We have developed in the previous part of the presentation the mathematical model defining the behavior of the physical phenomenon which describes the photovoltaic effect.

The Poisson / Laplace equation being discretized, it lends itself to numerical calculations and simulations; we will therefore perform numerical simulations on the model thus discretized. The computer coding of the problem will be done either in Matlab or in Scilab (its free version or Open Source) The computer program is provided in appendix, we present here the results of simulations of the numerical simulations. The results of numerical simulation by the relaxation method (k + i) = R2 (lep 1+ 441) 9 + 1) 1, J i 2 (1 + 02) Figure 12d illustrates "The contour of the function of potential y" Figure 12e illustrates "The surface of the function Potential y" The results of numerical simulation by the method of relaxation: = (1 co (k) + w [1, (k + 1) (22f ,,, (k + i ) \ 1 J 2 (1+ (32) Wi + 1,1 + P -1 mi, j + Figure (12f) is an illustration of the boundary conditions and (12g) an illustration of the pace and profile of the function electric potential y (x, y) by the relaxation and relaxation methods respectively in a high efficiency solar hybrid cell with storage integrated in the substrate that is the subject of the present invention [00117] Conclusion and comments on the simulations carried out: We proceeded to the numerical resolution of the homogeneous Poisson / Laplace equation: in this modeling approach, we opted for an explicit numerical scheme by discretizing the equation of departure. This digitization has led us to a resolution of the matrix systems whose accuracy and the convergence criterion are determined by the increase of the norm of the error vector while respecting a certain degree of tolerance given by the value of c. We then performed a simulation of this model with a maximum number of iterations of 1000. The quality of digital solution can be improved by adopting a resolution methodology based on that of relaxation. The latter gives a better speed of convergence towards the desired solution. The results of simulations show that for a value of (3 fixed at 2 (Ax = 1 and Dy = 0.5), the number of iterations decreases for a value of w E [1.5, 1.6]. The graphical figures illustrate the pace and the profile of the electric potential function y (x, y) by the relaxation and relaxation methods respectively Our approach allows us to go beyond the level of a simple diode in parallel with a current generator charging a capacitance (and then a battery) via a leakage resistor We continue in particular the following aspects: Other points to see: 1) Use a finite element approach 2) Solve the problem coupled with 5 fields 3) Examine the influence of the geometry of the cells with respect to load efficiency. In particular I think hexagonal shapes should be interesting but we can also see the influence of anisotropy, etc. [00118] The case of Cadmium; Decrease or even elimination of toxicity of photovoltaic solar cells. Cadmium sulphide (or Cds: Cadmium Sulfide) layer Cds 6-4 (Figure 6b) is not an ideal compound for the buffer layer in CIGS-based solar cells. The Cds is classified as toxic and its weak gap band causes the loss of current in the so-called blue zone because of a strong absorption of the buffer layer. The major challenge currently in the development of thin-film photovoltaic films, is to find other alternative compounds in the structure of solar cells based on CIGS. These compounds must meet a certain number of criteria for optimum performance in terms of electrical energy production, in particular these new chemical components must be: transparent for solar radiation, non-toxic with an optimum gap band. Recent research in this direction has led to a family of ZnO-based components. The following comparative table summarizes the properties of the latter according to different characteristics of the layer or the buffer zone of a solar cell. Buffer layer Vc0 (in mV) Jsc (in Acm-2) FF3 (in%) Efficiency (in%) Zni, Sx Oy 684 35.2 74.9 18.0 Zni, Mgx 0 668 35.7 75.7 18.1 ZnOi-x Sx 689 35.5 75.8 18.5 CdS 717 33.7 77.3 18.7 Table 1: Chemical components used for the buffer zone of a CIGS-based solar cell HYBRID High-Yield Cells This is to hybridize the cell to produce more than 30% SOLAR SUPER CELLS Energy Efficiency (Patent No. 08 04598, filed on, August 14, 2008 ROUSTAEI et al, and Patent No. 09 00921 filed on, March 02, 2009 - BOPI No. BOPI-2 932 010 and BOPI-2 932 002) are to be considered as being "inserted" in the present application in their entirety by referencing and as being part of this invention but attached separately in photocopy so as not to burden the application. Figures 13a, 13b and 13c show respectively; (13a) A schematic illustration of organic high layer modeling of a solar cell and (13b) a hybrid cell modeling illustration with CIGS absorbent layer and (13c) a flexible schematic illustration. Structure assembled in a high efficiency solar hybrid cell with integrated storage substrate that is the subject of the present invention. The scope of research on the innovative aspects of the invention is divided on the following points: 1) The interface of ALD and s-ALD (physico-chemical interdependencies): Conduct a study on particle kinetics at the level of ALD and s-ALD interfaces, in particular their physicochemical impact as a function of temperature and pressure parameters. Modeling of parameters related to the reaction chamber and reactants. 3 Form Factor 2) Definition of MSDS specifications: Determine the specifications and rules relating to the materials listed in the MSDS, particularly with regard to precursors CIGS and Mo. 3) Up & down- Converters (The influence of the use of up-and-down converters): Study of Erbium-type boost converters, for example, their properties and especially their use influences on the conductive and transparent layer (molybdenum). Means and possibilities of the implementation of Up & Down-Conversion mechanisms for high efficiency solar cells. 4) Absorbent layer CIGS and enhancement materials Efficiency 5) Quantifiable chemical influence of the use of elements like Na and K in the CIGS4 structure, as well as its physico-chemical modeling and quantification, with a yield greater than 20 %. 6) Study of the behavior of a given type of substrate at high temperature during the treatment process. The objective of this study is to determine if the efficiency can be increased to a level exceeding 21% by replacing a glass substrate with another type of flexible substrate such as stainless steel or kaptan. 7) Definition and confirmation of the modeling parameters during the different stages: a) Temperature, Pressure, Electromagnetic, Thermodynamics, Radiation, Electric Field, Thermal Conduction, Electromechanical, Material Reflectance, etc. b) change of treatment unit c) change of environment and equipment d) handling and transport e) short and long term storage 8) Contamination and risk parameters: Definition of the different steps (Inter equipment, materials, Processes , Transfer, Etc.) 9) MLD-ALD and MLD-sALD considerations: Organic-inorganic hybrid films grown according to Molecular Layer Deposition (MLD) and atomic layer deposition (ALD), realization of inter-layer interfaces, realization of solar layers Hybrids a) Transparent substrate hybrid films 10) Hybrid Organic / Inorganic and Tandem PV with efficiency> 26.8% i) Inorganic Tandem Cell: 6% ii) Upper Cell Organic b) Eg 1.7-2.0 eV c) Voc> 1 V -> 1.2V d) <$ 10 / m2 e) Printable 4 Details in "Advanced Online Publications" 45 f) Low process temperature i) Inorganic lower cell g) Si or CIGS h) Proven technology 0.6V i) Eg, =, 1.1 eV, VOC <0.7 V j) Ineffective in blue [00120] Intrinsic and extrinsic failure 15 k) Photochemical reactions. 1) Inadequate thermal expansion between the different layers. m) Disturbance of morphology at normal operating temperatures. n) Partial Packaging / Encapsulation Failure [00121] Energy Capture in Hybrid Cell / Quantum Dot / Valence Curve Mode: Energy Capture by Photovoltaic Cell is a global demand whose need in energy mix exceeds today 15 TW / year. The vast majority of this demand is satisfied by the consumption of fossil fuels in the form of oil (5.3 TW), coal (4.2 TW) and natural gas (3.5 TW). Currently, the solar provides only 0.004 TW and yet the earth receives more than 120,000 TW of sun power each day, which means that land power demands could be achieved by covering 0.125% of the Earth's surface with 25 cells. solar with a yield of only 10%. As the demand for energy grows more and more, it is imperative that new forms of low cost solar energy are available. To meet this demand and to reduce the high rate of energy and the high cost of vapor deposition, which is currently used in the production of solar cells, we have used its expertise in the synthesis of nano-crystals. or quantum dots (QD) to develop a range of novel copper, indium, gallium, and selenium (CIS, CIGS, and CGS) containing quantum dots of varying composition that can be used to manufacture low-cost solar cells with good Savings: 35> Advanced quantum dot PV research of the invention are being developed so that they are able to form printable inks in a variety of solvents, opening the way for low cost, a roll to the production of new solar cell technologies. The advanced PV-QD invention includes an exclusive organic "styling agent" or "ligand", which facilitates printing using a variety of printing techniques. organic is removed by heating to provide an inorganic photoactive layer of the desired phase 45. a) Figures 14a, 14b and 14c respectively represent (14a) The principle of photo generation in the valence band as a function of doping and (14b) the quantum dot curve of CuInSe2 PV-quantum dots (also called QDs), and (14c) spectral response 50 of quantum efficiency of the CIGS absorbent cell in a high efficiency solar hybrid cell forming the subject of the present invention. b) CIGS nanoparticles are available c) Manufacture of current thin-film solar cell technology involves expensive evaporation techniques, which hinder their adoption by the mass market. At the request of new and other solar technologies, we have developed a range of (copper indium gallium diselenides, copper indium diselenides) nano crystals or quantum dots (QD) CIGS for use in the next generation of thin layered solar cells which can be manufactured using conventional printing techniques. d) CIGS and PV-quantum dots are unique among nanomaterials developed for photovoltaic applications in that they are synthesized from the "ground", which provides materials with the desired elemental ratios or stoichiometry, which can be adjusted for meet needs. Our PV-quantum dots are highly crystalline, (5.0 nm) mono-dispersed particles, which absorb light at 800 nm and our PV-quantum dots are unique in that they are capped at an organic "capping agent" or "ligand". e) Because of the unique way in which PV-quantum dots of invention are synthesized, they can be printed on a substrate using a wide range of well-understood printing techniques, even in roll-to-roll processes. Once printed, the quantum PV boxes are heated to remove the organic styling agent, which destroys the quantum confinement associated with the quantum dots, and provides a p-type semiconductor film that has the desired crystal structure. The characteristic parameters of the high performance hybrid cell The most important parameter of a solar cell is its efficiency, expressed in% of incident solar energy flux. This efficiency can be expressed in terms of the following efficiency categories: i. Reflectance: the percentage (%) of the incident electromagnetic power. ii. Thermodynamics: the absolute maximum theoretically possible of conversion of solar radiation into electricity. This limit is determined by that of Carnot iii. Separation of charge carriers: it is subdivided into 2 main modes in a solar cell: - Drift: under the effect of the electric field created at the level of the thin absorbing layer. - Diffusion: due to thermal movements (agitations) of these particles. iv. Conduction: This is thermal conduction as one of the modes of heat transfer. Total efficiency is the product of these four categories of efficiency. Since direct measurement is directly difficult, in practice other parameters are used, these include: a) Quantum Efficiency (QE): which provides a measure of loss due to reflectance. These efficiency losses due to the reflectance affect the "External Quantum Yield" b) Open-circuit potential difference V. The losses due to the recombination of the carriers of the charges are measured by the EQ, V. and the factor of form (FF). c) Form Factor or FF Applications related to high performance hybrid cells The applications of solar cells are diverse and very varied. One of their uses is energy storage. The following figures illustrate some of its many applications.

These panels consist of bifacial (double-sided) solar cells that absorb light from two sides, therefore they are more efficient than their single-sided counterparts. The Theory of Underlying Physics The engineering of photovoltaic systems is based on the physical theory of solar cells. This theory describes the physical process of converting light into electric current when a semiconductor device is exposed to this light. Theoretical studies have a great interest in practical and industrial applications, since they give very useful information on the theoretical limits of efficiencies, as well as the various factors which are at the origin of losses of this efficiency. The solar frequency spectrum provides an approximation of the black body spectrum at a temperature of 5800k. The black body is the idealized physical model for a body that absorbs all incident electromagnetic radiation regardless of incident frequency and angle. At thermodynamic equilibrium, this black body emits radiation according to Planck's law, and consequently its spectrum is determined by its temperature only: wv (y, T) = n (v) i (y, T) hv (1) /, T) - hv average energy per mode (of vibration) ekT-1 Figure (8b) illustrates the Black body spectrum as a function of temperature The various curves correspond to the law of displacement of Wien, this one gives the distribution of thermal radiation. Thus the maximum wavelength of the emitted radiation energy varies inversely proportional with the temperature, so that there is the relation: IXmax * T = cte The other physical bodies emit the energy radiations which are function of their emissivities E which is a fraction of that of a black body for which e = 1. The solar radiation that reaches the earth has composed of photons whose energy is much higher than the gap band of the semiconductive absorbing layer. This large energy gap is at the origin of efficiency loss of the solar cells, since a large part of these solar (electromagnetic) radiations is converted into heat by the vibration of Lattice, also called Phonon or quantum of vibration energy. . A Lattice or Lattice is a physical model used in the field of condensed matter physics. In this context, atoms of a crystalline structure are formed.

In a crystalline solid, for a vibration mode of frequency y, the exchanges of energies are discretized and are carried out by energy packets quantified by hl /. Phonons can be described in the context of Quantum Mechanics, by the elementary vibratory motion in which a lattice of atoms or molecules vibrates uniformly in normal mode, that is to say according to a single frequency. Figure (8c) illustrates the structure of a lattice The challenge of efficiency As previously mentioned, the characteristic and principal parameter of a solar cell and in general of a photovoltaic system is its efficiency. This is a factor that gives the maximum capacity for converting incident solar or electromagnetic radiation into electrical current. The theory of solar cells, which has been outlined in the preceding parts of the paper, gives very useful indications of the technological limitations of this efficiency and the factors which give rise to it. In the following, we will recall these various factors of loss of efficiency: The Shockley-Queisser limit: calculated by William Shockley and Hans Queisser in 1961 at Shockley Semiconductor, this limit refers to the theoretical maximum threshold of efficiency. a solar cell using a pn junction at the absorbing layer. It is set at 33.7%. This is the most fundamental and important factor of efficiency loss in the field of solar energy production.

Figure (8d) shows the representative Shockley-Queisser boundary curve. The thermodynamic limit: this efficiency threshold, also called the Carnot limit, is set at 86%. It is due to the entropy of photons emitted by the sun's surface. ^ Quantum Efficiency: this is the rate of conversion of photons incident to the electric current. These various factors of loss of efficiency have led researchers to find ways of optimizing the yields of solar ones. The energy conversion process and the photo generation of the charge carriers When the photons of energy E = hv strike the semiconductor layer of a photovoltaic structure, the following three phenomena occur: a) the photons of low energies pass through this device b) They are reflected c) They are absorbed In the latter case, the electrons charge e = 1.6 * 10-19 C, are torn from their atoms and move inside of semiconductor material, leaving vacant an empty place or hole, it is said that photons create a pair of electron-hole. This transition of electrons from the valence band to that of conduction is explained by the fact that the solar radiation energy is greater than the gap band of the semiconductor layer, which is largely sufficient to excite the electrons. . Figure (14a) illustrates the principle of photo generation in the valence band as a function of doping. [00126] The solar spectrum, the black body and the consideration of quantum aspects: The solar frequency spectrum provides an approximation of the spectrum of the black body at a temperature of 5800K. The solar radiation that reaches the earth has composed of photons whose energy is much higher than the gap band of the semiconductive absorbing layer. This large energy gap is at the origin of efficiency loss of the solar cells, since a large part of these solar (electromagnetic) radiations is converted into heat by the vibration of Lattice, also called Phonon or quantum of vibration energy. . In a crystalline solid, for a mode of vibration of given frequency y, the exchanges of energies are discretized and are carried out by the energy packets quantity hv.

Example of QD is given in Figure 14b: The Quantum Point Curve of CuInSe2 PVquantum dots (also called QDs) [00127] Substrates; we noted that the substrate has a major importance in the realization of solar cells. In particular, Cu (In, Ga) Se2 (CIGS) solar cells on aluminum foils offer the advantage of being flexible, light and, because of the low cost substrate, which can be used for several applications, especially in buildings, where aluminum is already commonly used. There are reports of a-Si solar cells on aluminum foil, but the development of CIGS solar cells on Alu leaves have not been reported. We developed CIGS solar cells on Alu-foil coated samples. When using Alu as a substrate, CIGS layers of suitable structural and optoelectronic properties must be grown at low (<450 ° C) deposition temperatures, due to the difference in the thermo physical properties of the layers and substrates . We have grown layers of CIGS by evaporation of elemental Cu, In, Ga and Se at different substrate temperatures and studied the properties of these CIGS layers by different methods. The photovoltaic property of solar cells in small regions are characterized by IV and quantum efficiency measurements. A yield of 6.6% was achieved, which is the highest efficiency reported to date for CIGS solar cells on Alu foils. We also observed that some Alu from the sheet dissolves during Chemical Bath Deposition (CBD) of the CDS. The presence of Alu in the bath appears, in one case, to be beneficial for the electrical properties of CIGS solar cells. Thinner and more homogeneous CDS-layers are obtained. Elastic Recoil Detection Analysis (ADER) and SIIVIS measurements have shown incorporation of Alu into CdS (D. Brémaud, D. Rudmann, M. Kaelin, G. Bilger, H. Zogg, Tiwari AN, flexible and light Cu ( In, Ga) Se2 solar cells on aluminum sheets ", Proceedings of the 20th European Photovoltaic Solar Energy Conference, Barcelona, pp. 152-155, 2005.) Table 2 For example, the application presented here after CIGS Solar cell properties on SS substrates with or without ZnO scattering barriers Eff (%) Voc (V) Jsc (mA / cm2) FF (%) Without ZnO 6.63 0.46 28.68 0.51 With Zn0 (1mm) 9.94 0.51 31.76 0.61 With ZnO (2mm) 10.0 40.5 131.80 0.62 With ZnO (3mm) 10.0 40.5 031.16 0.64 The incorporation of Na can result in an improvement in the efficiency and reliability of CIGS solar cells. Cell performance is expected by incorporation of Potassium (K) and Sodium (Na) 45 [00128] Passivation CIGS thin film backing surface using nanoscale point contacts. World solar cell efficiency record for thin film and silicon (Si) solar cells are respectively 19.6% and 25.0%, where the best thin film technologies perform best are 50 based on the CIGS absorbent layers. It should be said that much of this gap in the world record in the cell between the Si and CIGS technology on the efficiency of the latter stems directly from their difference in complexity of the design of the cell. 40 In the silicon-based photovoltaic industry Si, a more advanced passivation of the transmitter and the back of the cell (called PERC) or the locally distributed pacified transmitter (called PERL) is used. and analog cells are introduced and put in place to achieve high yields with finer wafers. The best results are obtained by the use of - passivation layers on the front and back, - and locally - spot contacts scattered on the back.

The back of these Si Cell Advanced designs is enhanced by a combination of a sufficient back surface passivation series and local micron sized spot contacts.

FIG. 15 represents an illustration of the path traveled by the light in a rear passivation layer (rear dielectric passivation with SiO 2, Al 2 O 3 / SiN x and low-n) serving as an internal reflector in a high efficiency solar cell which is the subject of the present invention. invention. As described in section [00124], according to the underlying theory of physics. The solar spectrum, the black body and the taking into account of the quantum aspects leads us to look more closely at the solar frequency spectrum providing an approximation of the spectrum of the black body at a temperature of 5800K. The other physical bodies emit radiations of energy which are a function of their emissivities E which is a fraction of that of a black body for which e = 1. [00130] Principle of the sponge (Adsorption) Adsorption is the phenomenon by which a solid retains molecules on its surface. Storing hydrogen in solid form thus relies on the ability of certain materials to adsorb the hydrogen on themselves. Multiple variants are currently being developed to allow a means of storage of energy by hydrogen Only hydrides forming metal bonds thus act as a true "hydrogen sponge". Among them, magnesium hydride (formula MgH2) reduced in very fine powder is the most interesting to use because of its large storage capacity, but also and especially its speed of return to the need of gas. Magnesium hydride, which comes in the form of a white powder in tanks, is light in weight, stable, recyclable and has no impact on the planet. use. The reaction is exothermic which produces heat release on hydrogen adsorption. Conversely, the desorption, by which the gas is released, is endothermic, requiring external heat input to reach the 300 ° C required for the operation.

This is why we will privilege the use of hydrogen in a combustion engine whose operating heat will benefit the desorption. This method would make it possible to overcome the main disadvantages encountered during compression or liquefaction of the gas. But it will be necessary to wait a long time before seeing it generalize. Other techniques are still envisaged for storing hydrogen in solid form, requiring, again and again, relatively long research. Table 3 is a comparative table of H2 storage solutions Storage of hydrogen by state Advantages Disadvantages Compression Gas form The most used, Well controlled - The least expensive to date Pressure not large enough to store large volumes - Risk of explosion if too much pressure Liquefaction Liquid form Well controlled - Stores larger volumes Large mechanical constraints because of risks of leakage - High energy expended Adsorption Solid form More secure, Flexible storage capacity Under research - Complex and expensive Next to storage under solid form on other materials, it can also contain hydrogen by compression or in the liquid state. In a synthetic way, the advantages and the disadvantages of the storage of the hydrogen according to its state in Table 3. The inventor proposes to use the liberation of hydrogen by desorption in a system based on adsorption of hydrogen to pay the constant of time during current calls as described in the patent application ROUSTAEI et al, BOPI 2 931 844, DDB 08 03019, filed on, 02/06/2008, and integrated in the present application of patent application in its entirety by referencing. ADVANTAGES OF THE INVENTION The main remarkable advantages of the present invention are: 1) Provide an industrial solution to the storage of intermittent renewable energies by treating a maximum area with an optimized capacity architecture and a considerable improvement in energy yields, by simultaneous increase of treated surface and cost reduction of the final solution. 2) Decrease in cycle time and deposition time per treated area. 3) A large plurality of reel treatments by simultaneous deposition of several layers. 4) A major advantage of the present invention is its transfer or juxtaposition to a solar cell or panel of different technologies of the type mono or poly crystalline siliciums or thin film films on various substrates 5) Another advantage of the present invention is the smoothing or Another advantage of the present invention is its implementation in applications with a large energy storage in the context of solar farms. 7) Another advantage of the present invention is its implementation in particularly autonomous on-board sensor applications which communicate without a line under difficult industrial and climatic conditions. Another advantage of the present invention is its implementation in applications of Another advantage of the present invention is its implementation in applications of intelligent roads and solar highways. Another advantage of the present invention is its implementation in signaling applications with intelligent sensors. Another advantage of the present invention is its implementation in shapeable and cutable energy storage and transport routes 12) Another advantage of the present invention is that it is easier to maintain and repair by replacing the defective segments. Another advantage of the present invention is its implementation in applications of smart cities (smart city) 14) Another major advantage of the present invention is the simultaneous deposition of different materials and this by the individual parameterization of the arrival nozzles of the precursor and reactant gases (made possible by small gap / distances between the heads and the substrate). Another advantage of the present invention is the increase in energy efficiency of cells by the structuring of the molecule during construction by successive molecular organic and inorganic deposition. Another advantage of the present invention is the reduction in preparation time and / or pretreatment of the support or substrate. 17) One of the major economic advantages of the invention is the use of high availability materials and inexpensive. Another advantage of the present invention is just-in-flow production in the form of "rollers" with high output capacity with batch processes (sequentially programmed). Another advantage of the present invention is a reduction in handling of the substrate and coils. Another advantage of the present invention is to have a storage stage integrated in the support of the solar cell providing a possibility of producing electricity instantly to overcome the intermittent nature of the reaction related to the nanolytic electrolyzer. the passage of clouds or lack of sunshine or day / night serving as the storage buffer of electricity. 21) Another advantage of the present invention is the use of the entire surface of the solar cell for a storage of electricity integrated into the substrate providing autonomy in consumption of the energy produced by the cell itself at the request of One of the advantages of the present invention is that depending on the field of application, the solar cells can be made on flexible plastic films or on rigid glass substrates. The invention provides full printability of solar cells, and the removal of the use of indium tin oxide (ITO) as the electrode material. In the case of cells with flexible substrates, the inventors use transparent conductive films in place of the ITO. For those with glass substrates, they use a deposit of transparent electrodes based on metal microstructures and conductive buffer layers. In addition, the inventors are devoted to the study of solar cells and mini-modules semitransparent and highly efficient based on organic semiconductors. 23) Large capacity of the production tool for photovoltaic and / or organic thin film and / or ETA cells as well as organic light-emitting diode (OLED or generally thin film on substrate in the form of flexible films or rigid 24) Adaptability of the innovation to non-coil or flexible substrates (eg rigid substrates in the form of rectangular or square plates). Another advantage of the present invention is a plurality of parallel coil processing. Another advantage of the present invention is the possibility of hybridization of the processes on the same production line and at the same time (both) on a mobile substrate in motion. Another advantage of the present invention is the parallel processing of one or more coils of the flexible film, bringing about a considerable reduction in handling when capacitating the coils of photovoltaic cells or film coils for the production of OLED screens. during manufacturing processes. Another advantage of the present invention is the Atomic Construction of complex molecules as well as the hybrid cells of porous titanium oxide (TiOx) grafted with copper, indium and selenium (CIS) atoms, with a stoichiometry of materials and a spatial arrangement that only the present invention can achieve on a large scale. Another advantage of the present invention is the molecular construction of MLD layers a. Hybridization of the interface layers b. Modeling of nanotic textures c. Another advantage of the present invention is the optimization of realization of the tandem cells by making the interlayer layers in the form of a transparent film 31. Another advantage of the present invention is the use of the converters layers. Another advantage of the present invention is the use of heat transfer layers by the use of piezo-elements 33) Another advantage of the present invention is the storage of the energy integrated in the substrate (also called Another advantage of the present invention is, of course, the use of the hybridization technique to increase the solar yields very substantially by: a. ALD and sALD atomic deposition for the construction of molecules according to 3D engineering by: b. Increasing the gap band, or even doubling it, and addressing the case of quasiparticles, especially the so-called "vibration packets" of phonons. c. Another advantage of the present invention is of course the use of MLD to enable the realization of: a. Organic and inorganic layers on the same substrate b. Growth of structures and complex textures of capture and trap photons c. Realization of interfaces between low-cost layers (low-cost) d. [0009] Another advantage of the present invention is the use of MLD in the interface layer. Piezonanilils (Gold Piezonotubes) 37) Another advantage of the present invention is the use of MLD in the interface layer. Another advantage of the present invention is storage integrated in the substrate by: a. Use of nano titanate to increase the lifetime with MLD in thin layer on solar cell substrate b. Use of electrolyte-semi gel printing for batteries integrated into substrates c. Use of MLD in storage layer interface In general, the advantage of the present invention is to provide an industrial solution by treating a maximum area with a 3D volumetric architecture (for example spiral) and optimized in the times of treatment cycle, increasing the surfaces of the substrates to be treated in a particular spiral form, by arranging the heating sources as close to the substrates to be treated on the one hand, and by reducing the volumes of the gases in the reaction chambers, somewhere else. [00131] The advantageous approach of the design of the present invention This particular arrangement of treatment by the ALD technique or sALD (spatial half reaction) has the advantage of treating large areas in a reduced time. This performance is made possible by the very architecture of the device (shape / layout of the heating sources and arrival nozzles of precursor gases, reactants and their purge).

We summarize below the different steps implemented in the design and manufacturing process specific to the present invention: A) The target process: the development of a system (a set) of selenium-based solutions which contains precursors for the formation of CIGS with s-ALD in order to rapidly produce high performance / wide surface cells. The particularity and strength of the present invention lies in its s-ALD processes, thanks to this type of process the production of thin-film solar cells is optimized in particular in terms of efficiency and manufacturing time: i. 16% efficiency ii. A 20-minute duration for a complete manufacturing cycle, producing a maximum power density of 150Wc M-2 (in Wc I11-2: Watt-peak per square meter). B) A process summary: the deposition of an absorbent layer up to 100nm on a PETS film with excellent uniformity as well as a manufacturing speed of more than 100nm / min in the process R2R s-ALD6 invented and designed by the present invention. C) Production capacity in output: orders of magnitude: I. 500kW / day, with the results of the following validated tests: II. 600rpm7 and 100nm thick A / 203 in 60sec. D) Spatial separation in the process: The ALD concept of the present invention is based on the spatial separation of the half-reactions: the reactor is provided with separate zones which expose the precursors one by one on the substrate which is located under the reactor. a gas bearing device between these two zones eliminates the cross-diffusion of the gases, therefore the purge steps are necessary. The time scale for a half-reaction is of the order of 10 ms, this allows very high level deposits for a better quality of ALD films. Polyethylene terephthalate: Polyethylene terephthalate: Cio H8 04 6 Roll to Roll Spatial -ALD 7 Revolution or round-by-minute: 1/60 Hz E) Transitional kinetic interface: a project under the name: R2R sALDTF / CIGS is progressing with promising and satisfying results in the validation and validation process. F) the variation of the ALD buffer layer is contained by the ZnO buffer layer.

The various thicknesses of this component have been deposited by the ALD process on similar substrates like TCO / PS. G) By way of example, we can note some target absorbents: / CIGS 1000nm / CZTS 500nm / ZnO / CdSe 80 / 150nm / ZnO / TiO2 Summaries of some of the most common applications of the ALD process in which we have indicated the chemical components used: 1) Oxides: Al 2 O 3, TiO 2, SnO 2, ZnO, HfO 2 a. Anticorrosion layer (nano laminates) b. Diffusion barriers c. Gas sensors d. Integrated circuits e. Thin films: Optics 2) Metals: Cu, Ru, Ir, Pt a. Electric conductors b. metallization used in the integrated circuit industry c. Adhesion and nucleation layers 3) Nitrite of metals: TiN, NbN, AlTilV, TaN and TiAlN a. Diffusion barriers b. Superconductors c. Biomedical Materials [00133] Today's technological challenge in the field of renewable energies is to optimize the processes of the design and manufacture of photovoltaic modules in order to increase their efficiency.

The main technical advantages and manufacturing methodologies of the thin film photovoltaic films or TFPVs of the present invention are: the nano-ALD and CIGS breaking technology associated with the R2R process. The use of the atomic layer deposition technique ALD (Atomic Layer Deposition) is much more advantageous than other deposition techniques such as CVD. the realization of the absorbing layer by CIGS precursors. ^ engineering the structure of the CIGS cell with the control of the growth of the molecule during its formation. Uniformity and quality are factors considered very favorable by the inventor for a highly efficient and economical solar cell. One of the advantages of the present invention is its implementation on hybrid solar cells and bifaces. Indeed ; the converter (boost converter) manages to use infrared light when the sun's rays arrive on the cell. This absorbs visible light and the near infrared. The majority of the infrared component, however, is not absorbed and passes through the cell. On the back, this component arrives on the high-power converter (boost converter) - essentially a microcrystalline powder of sodium fluoride and integrated yttrium / embedded in a polymer. When the light arrives on this converter, it excites the erbium ions and places them in a state of higher energy. The return to lower energy levels is accompanied by light emission, which the solar cell is able to "see" and use. One of the advantages of the present invention is the creation of transparent flexible films for use in glazing, on decorated surfaces, vehicles, appliances, materials and various equipment and varied. To use such a converter (elevator) at high power, we had to optimize the solar cells. These are usually vaporized on the back side with metal so that the current can come out of the solar cells - so no light can pass through. In our case, part of the yttrium has been replaced by the optically active erbium element, which is ultimately responsible for the conversion. We also used a transparent substrate and coated the solar cells with metal grids on both sides, so that the infrared light passes through the solar cell. Yield enhancement by upconverters or Up Convertors. About solar cell (up-conversion) converter, we need to cite the example of materials that could be used for the scaling process. The best result obtained to date is a 20% improvement in quantum efficiency of a conversion process for lighting of 5 W / cm 2 at 50% of the intensity of the sun was confirmed by the inventor. This improvement of course implies that if the transmittance of the absorbing layer is sufficient for the upconverters of the light particles to react. It should be noted, however, that high-power step-up converters could theoretically allow about 30% of the sunlight they receive in electricity with a maximum potential of this part at 40%. Efficiency improvement by absorption of light (Plasmonic). This is the diffusion to metal nanoparticles at the front of the solar cell resulting in an increase in effective path length effective path of light). Figures 16a, 16b, 16c, 16d and 16e respectively; (16a) a schematic illustration of the improvement of light absorption (Plasmonic) and (16b) an illustration of the separation of semiconductor Ag particles by thin passivation layer (eg A1203) improves performance electric. a) Metallic nanoparticles embedded in semiconductors excitation of near-field transporters b) Corrugated semiconductor back surface / metal Increased length of effective light path more efficient c) Separation of semiconductor Ag particles by thin passivation layer (eg Al2 03) improves the electrical performance of the cell. [00137] Performance enhancement by biface cells. In addition, the light can thus be used from both sides; it is then referred to as a two-sided cell, which can be used in high-efficiency solar transparent films.The front and back of the solar cell have been equipped with special anti-reflective coatings which reduce light reflection and ensure that the cell absorbs as much light as possible, we have also optimized the antireflection layers of the back of the solar cell, which increases the efficiency of the modules and their energy production. has two double-sided techniques as shown in Figures 1a to 11c Figure 11d gives an example of additional efficiency compared to a single-sided cell - Cell efficiency vis-a-vis the sun 18.5%> Back-to-the-sun cell efficiency 5% Total Yield: 23.5% - Sun-Facing Cell Power 250W - Back-to-Sun Cell Power 50W ^ Total Cell Power: 300W The invention brings additional efficiency from conversions thermal radiation received by the cell by about 6% + [[00138] Efficiency improvement by anti-reflective layer / Plasmonic structures Theoretical efficiency absorption limit of light increase absorption of light: ^ Classic approaches Internal pyramids reflection layers increase in the absorption of light: o new concepts o plasmonic structures o diffractive optics o Full range use o Up-conversion Figure (16c) is an illustration of "self-organized opaline structures, hexagonal photon structures by deposition of ALD A1203 (surface passivation) Spin coating of spherical nanoparticles (SiO2).

Increased increasing light absorption by diffraction of back surfaces. Realization by opaline self-organized structures, hexagonal photonic structures by ALD Al2 03 deposition (surface passivation) Spin coating (spherical surface coating) of spherical nanoparticles (SiO2). Structure filled using ALD of TiO2 (SolGel variant).

Nanoparticles are therefore essential ingredients for making solar cells super efficient and low costs but they must not degrade the surface of the cell electrically [00139] Elevator solar cell converter device. Performance improvement by Up Conversion (UC). A nano-crystalline La203: Er3 + / Yb3 + fluorescent substance sample was synthesized by the combustion route of the solution using urea as a reducing agent. Thermal, structural and optical characterizations were conducted to explore several of its properties. By thermal analysis we conclude to the presence of moisture and phase hydroxide [La (OH) 3 and LaOH] of lanthanum in the sample as synthesized, which other modifications to the La 2 O 3 phase greater than 600 ° C. temperature. Up-conversion (UC) study shows intense emission bands in the UV, blue, green and red regions. This document also indicates the first observation of UC emission bands extending up to the UV region (240 nm) on excitation 976 nm wavelength. The heat treatment of the samples shows a change in the crystallite phase along with the growth of the crystallites and the UC luminescence intensities. The dependence of the input pump power indicates the involvement of up to four photons. As an example, we describe below the operation of an Er3 + / Yb3 + based elevator converter. The most efficient energy transfer process of CPU up converter (also called ETU or Energy Transfer Upconverter), after absorption of photons (GSA, ESA) UC luminescence due to spontaneous emission (SPE) generates multi-phonon relaxation (MPR).

Excerpted from F. Auzel, Chemicals Study 104, 139-73 (2004) KW Kramer, et al., Chemistry of Materials 16 (7), 1244-1251 (2004). Figure (16d) is an illustration of the short-circuit current density. Indeed ; The short-circuit current density is reported to be 1.79% at 1000W / m 2 (0.179 cm 2 / W) in Monochromatic Laser excitation with a Broadband excitation excitation of 0.77% at 1.063 W / m 2 ( 0.072 cm 2 / W), 2.2mA / cm 2 sun at 78%; Compared to the Solar Concentrator; the value is 13.3 mA / cm 2 under 207 suns. Efficiency increase of 0.19% and (16e) an illustration of simulated values of current densities in a high efficiency solar hybrid cell with storage integrated in the substrate. the subject of the present invention. Specifications for solar cell inverters 15 Double-sided solar cell with: High photon sub-band transmission High EQE of UC photons from the rear Upconverter provides a high absorbance as well as a large quantum yield upconversion (also called UCQY or quantum yield pconversion) over a wide absorption range. An Er 3 + boost converter improves the Shockley-Queisser limit by 30% to 40% * [* Extract from T. Trupke, et al., Sol. EnergyMater. Ground. Cells 30 © Fraunhofer ISE, SWGlunz, September 2013, 3327 (2006)]. [00140] Performance Improvement by Improvement of Diffraction Back Surfaces for More Light Absorption and Optimization Using Rigid Wave Coupled Rigid Analysis (RCWA1) 1 = Surface of Cell 30 10 = Thickness of Thickness cell [m] 100 = Simulated photo of current densities Figures 6d and 16e respectively represent; (16d) an illustration of the short-circuit current density at different light concentrations and (16e) an illustration of simulated values of current densities in a high efficiency solar hybrid cell with or without integrated storage on the substrate forming the object of the present invention. The legend of the values of the curves correspond respectively: 16-11 (Fig. 16e) is the reference curve AM1.5G (280-1200nm) 16-12 (Fig. 16e) is the reference curve ---- before: plane (not ARC) - rear-mirror 40 16-13 (Fig. 16e) is the reference curve ---- before: plane (DARC) - rear: mirror 16-14 (Fig. 16e) is the reference curve before : flat (not ARC) - rear: perfect 16-15 (Fig. 16e) is the diffuser front reference curve: plane (DARC) -back with a perfect diffuser 16-16 (Fig. 16e) is the reference curve * before: inverted pyramids with SARC - back: 45 mirror 16-17 (Fig. 16e) is the scholar reference curve: flat (DARC) - back: sphere grids [00141] One of the advantages of the present invention is its implementation the cells by molecular deposition of the layers (MLD). EG is one of many organic diols that can be used in conjunction with TMA for Alucone growth films. A diol difficulty is that they are homobifunctional precursors and can react twice with surface A1CH3 * species. These "double" reactions lead to a loss of surface reactive sites and could produce lower growth per cycle over MLD. The problem of double reactions can be minimized by using polyols to ensure that a hydroxyl group will be available for subsequent TMA exposure. This strategy will be discussed below for the MLD of Alucone based on TMA and glycerol. Alternatively, a heterobifunctional precursor, such as ethanolamine, HO-CH 2 -CH 2 -NH 2 (EA) can be used that shows the preferential reactivity between its hydroxyl group and the surface species of AlCH 3+. This preference leaves an amine (-NH 2) group available for subsequent surface reaction. Likewise, ring-opening reactions can be employed that will react and express a new functional group when the ring is open. The ring opening reaction also has the advantage of containing the functional group in a masked form. The hidden functionality results in higher vapor pressures and shorter purge times compared to precursors that have the same exposed functionality. A three-step MLD process A, B, and C (Figure 17a) that can be accomplished without the aid of homobifunctional precursors is based on: (1) TMA, a homomultifunctional mineral precursor, (2) ethanolamine (EA) , an organic reagent hetero and (3) maleic anhydride (MA) an organic reagent by ring opening (also called ring-opening). The surface reactions proposed during the ABC growth are: (A) S-COOH + Al (CH 3) 3 [17-1 (Fig 17a)] -> S-000-Al (CH 3) 2 + CH 4 17-2 (Fig. 17a)] (B) S-AlCH3 + HO (CH2) 2 -NH2 [17-3 (Fig. 17a)] S-Al-O (CH2) 2NH2 + CH4 [17-4 (FIG. Fig. 17a)] (C) S-NH 2 + C 4 H 2 O 3 (MA) [17-5 (Fig. 17a)] S-NH-C (O) CHCHCOOH * [17-6 (Fig. 17a)] The surface-creation mechanism is also illustrated in Figure 17a. In this reaction sequence ABC, TMA reacts with the carboxylic groups in the reaction yielded by the equation "S-000-Al (CH 3) 2 + CH 4" to form the A1CH 3+ species. Subsequently, the A1CH3 * species preferably react with the end of the EA reactive hydroxyl to form surface species Al-OCH2CH2NH2 * in reaction (B) given by the equation "S-A1-0 (CH2) 2NH2 * + CH4 ". MA then reacts with amine-terminated surface to reform carboxylic groups by a proposed ring-opening ring reaction (C) given by equation) S-NH-C (O) CHCHCOOH * The sequence of ABC three-step reaction is repeated by exposure to TMA, EA and MA to grow the MLD film to the desired thickness. 40 A series of studies characterized the MLD ABC process. FTIR difference spectra were consistent with the reaction mechanism shown in Figure 17a. The MLD linear growth ABC displayed as evidenced by the QCM measurements. However, large gains in mass of - 2500 ng / cm 2 by ABC cycle were observed at 90 ° C. This large gain in mass 45 may indicate the diffusion of a substantial amount of TMA into the ABC MLD film. After the TMA exposure, there was also a subsequent mass loss that was consistent with the diffusion of TMA on the MLD ABC film. The diffusion of the TMA in and out of the ABC film was measured experimentally and then adjusted using a digital model based on Fick's Law. The importance of TMA diffusion to and from the ABC film was verified by observing that the mass gain per cycle was dependent on the TMA purge time.

In addition to TMA, other inorganic ALD precursors can be paired with various organic precursors to define other classes of organic-inorganic hybrid materials. Thus, diethylzinc (DEZ) can react with diols to produce a "Zincone" film in MLD. Zincone MLD has been demonstrated using DEZ and EG. The growth and film characteristics of Zincone MLD were similar to Alucone MLD. The growth rates were linear observed for Zincone MLD function of the number of MLD cycles. However, the growth rates were lower than the higher growth temperatures and the EG precursor was observed to react almost exclusively twice at the highest growth temperatures. FIGS. 17a, 17b, 17c, 17d, 17e and 17f respectively represent; (17a) A schematic illustration of the growth of an MLD layer during ABC growth that can be accomplished without using homobifunctional precursors is based on: TMA, a precursor homomultifunctional mineral, ethanolamine (EA), a hetero and maleic anhydride organic reagent (MA) an organic ring opening reagent; and (17b) an illustration of MLD in two steps A and B for Glycerol-TMA and TMA-glycerol. The spectra are shifted for clarity in presentation and (17c) a difference illustration of the FTIR spectrum after TMA and GL exposure hang AB Alucone MLD at 150 ° C and (17d) an illustration of the four reaction sequence steps ABCD for a MLD layer growth process of an Alumina-siloxane film using trimethylaluminum (TMA), H2O, dimethylmethoxychlorosilane (DMMCS) and H2O and (17e) a schematic illustration of two-step reaction sequence for growth by MLD at AB plot of a Lewis film using trimethylaluminum (TMA) and triethylenediamine (TED) and (17f) an illustration of the density of A1203 and AB Alucone using TMA and EG from XRR analysis in a hybrid cell solar high efficiency with integrated storage substrate which is the subject of the present invention. One of the advantages of the present invention is a novel way of producing Organic-Inorganic hybrid film in MLD. A. Use of homotrifunctional precursors for the promotion of crosslinking. The MLD alucone AB system using TMA and EG displayed effective reactions. However, this MLD system has suffered double reactions because EG is a homobifunctional precursor. This MLD system also showed some contraction of the film on the first few days after this film was exposed to the air. In addition, tensile strain measurements of MLD films grown using TMA and EG with a thickness of 100 nm have a low critical tensile stress of 0.69%. This critical low voltage strain may result from the small amount of crosslinking in the MLD film. These problems with the TMA + EG MLD system has led to the recent exploration of the TMA + glycerol system. Glycerol provides an additional hydroxyl group for the reaction and must increase the crosslinking between the chains in the deposited film. The TMA reaction sequence and glycerol 45 (GL) project is shown in Figure 17b. In fact, Figure 17b depicting schematic two-stage growth MLD, AB alucone using trimethylaluminum (TMA) and glycerol (GL). Surface species studies using Fourier Transform (FTIR) difference spectra after TMA and GL exposures revealed that surface reactions are effective at 50 and proceed to completion. Figure 17c shows the difference of the FTIR spectra for Glycerol-TMA and TMA-glycerol. Spectra are moved for clarity in presentation. The added surface species appear as positive absorbance characteristics and the removed surface species appear as negative absorbance characteristics. The FTIR spectra show the "flipping" of OH stretching vibrations at higher frequencies with each TMA and GL exposure. This reversal between the positive absorbance for a reagent, then a negative absorbance mirror image for the second reagent is consistent with repetitive self-limiting reactions. There is also a reversal of the strong A1CH3 deformation mode at lower frequencies which is consistent with the addition and subtraction of the A1CH3 species surface. The TMA + GL reaction can also be characterized by QCM studies. The QCM analysis revealed a linear MLD growth with an average weight gain of 41.5 ng / cm 2 / cycle at 150 ° C. This weight gain of 41.5 ng / cm / cycle is equivalent to a growth rate of 2.5 A / cycle. Figure 17d displays the QCM results for two TMA + GL cycles at 150 ° C. The QCM shows that a gain in mass is observed during the TMA exposure. Likewise, a small mass loss is observed after the TMA exposure. This behavior suggests that some TMAs may be broadcast on the MLD movie after the TMA exposure. A similar mass gain is observed during the GL exposure. The light weight loss after the GL exposure may also indicate that some GL is diffusing out of the MLD film. The TMA + GL system also shows a growth rate that is much less temperature-dependent at the growth rate for TMA + EG17e. XRR analysis was used to study the film thickness after different numbers of MLD cycles at temperatures of 150, 170 and 190 ° C. These XRR results are shown in Figure 17f. The film thicknesses are similar for the three temperatures and are compatible with a growth rate of 2.0 to 2.3 A per cycle. The growth rate of 2.3 A per cycle at 150 ° C is in reasonable agreement with the QCM measurement of 2.5 A / cycle at 150 ° C under similar reaction conditions. This is more constant growth rates depending on the temperature compared to TMA + EG suggests that TMA diffusion may be a less important factor due to the greater crosslinking between the growing chains.

XRR analysis of the TMA + GL MLD films indicated that the film thickness was almost constant as a function of time after exposure to ambient temperature. MLD films grown using TMA + GL were not observed to contract as MLD films grown using TMA + EG Figure 17e. This stability of the top film may indicate that there is more crosslinking which increases the stability of the MLD film. Recent mechanical testing has also revealed that MLD films grown using TMA + GL have a higher tensile stress critical for cracking than MLD films grown using TMA + EG. (PDMS) is one of the most important organic-inorganic polymers and contains [-Si (CH3) 2 -O] n chains. The strength and flexibility of Si-0 bonds and bond angles give PDMS desirable thermal and mechanical properties. PDMS MLD would be extremely useful for the growth of flexible and compliant thin films. However, the first attempts at PDMS MLD revealed that the growth rate became negligible after about 15 MLD cycles. These attempts were made using the homobifunctional sequence of (dimethylamino) dimethylsilane and dichlorotetramethyldisiloxane or heterobifunctional or silane molecules such as dimethylmethoxychlorosilane (DMMCS). The lack of growth after about 15 MLD cycles was attributed to the desorption competition of cyclic siloxanes such as hexamethylcyclotrisiloxane (D3) or decamethylcyclopentasiloxane (D5) from the PDMS film. To avoid the desorption of cyclic siloxanes, a new approach was pursued where DMMCS and H2O were used with TMA in an ABCD process defined by MA / H2O / DMMCS / H2O. A schematic representation of this sequence of reactions is given in Figure 9 [31]. This sequence of reactions introduces the -Si (CH 3) 2 -binding group into the growing film. The addition of TMA adds -Al- O -units in the growing chain and prevents the ompeting desorption of cyclic siloxanes. The TMA can be introduced during each reaction cycle. The TMA may also be introduced less frequently to lengthen [-Si (CH3) 2 -O-] chains before inserting the-A1-0-subunit (see Figure 17d).

Early work explored the ABCD process to demonstrate the growth of siloxane alumina hybrid organic-inorganic films. MCQ experiments revealed that the MLD growth was linear with a mass gain of -21 ng / cm 2 / cycle at 200 ° C. Film growth at 200 ° C was also examined using XRR analysis. XRR measurements confirmed linear growth at 200 ° C with a growth rate of 0.9 A / cycle. Using the density of 2.3 g / cm3 for the MLD film of the alumina-siloxane, the weight gain of about 21 ng / cm / cycle yield of a growth rate of 0.9 A / cycle. FTIR analysis of surface reactions was also consistent with the mechanism reaction shown in Figure 17e. However, a low atomic concentration of silicon in the MLD Film measured by X-ray photoelectron spectroscopy indicates that the reaction of the chlorosilane with the hydroxylated surface was not very effective. The Outlook for MLD in making organic-inorganic hybrid films, the use of various organic and inorganic precursors offers an almost limitless set of combinations for the MLD of organic-inorganic hybrid films. Many of these combinations can be used to make films with specific functional properties. An example of a functional organic-inorganic hybrid film is a film developed using MLD TMA and triethylenediamine (TED).

TMA is a Lewis acid and TED is a Lewis base. Sequence exposure of TMA and TED can be used to develop an MLD film with unreacted A1CH3 species remaining in the film. A schematic representation of this sequence of reactions is given in Figure 17e. These A1CH3 species can react with H2O and serve as H2O getter. The H2O getters may be useful as interlayers in multilayer gas diffusion barrier films. Conductive organic-inorganic hybrid films may also be useful for screens and interlayers or buffer layers or flexible films.

ZnO ALD films are known to have a low resistivity of about 1 x 10-1 cm. ZnO ALD films are grown using diethylzinc (DEZ) and H2O. MLD organic-inorganic hybrid films can be grown using DEZ and EG as mentioned previously and are called "zincones".

Although the DEZ and EG based MLD Zincone film does not display any conductivity, recent results have shown that Zincone films based on DEZ and hydroquinone (HQ) displayed some conductivity when combined with ZnO ALD films. The scheme showing surface chemistry for Zincone MLD using DEZ and HQ is given in Figure 17g. While these MLD alloy conductive films exhibit sufficient toughness because of their organic constituents, they may be useful for flexible screens and may be candidates for replacing indium-tin oxide (1TO).

Figure 17g illustrates the two-step reaction sequence for MLD growth of AB Zincone using diethylzinc (DEZ) and hydroquinone (HQ). Organic-inorganic hybrid MLD films have a low density that approximates the low densities of organic polymers. In contrast, inorganic ALD films have a much higher density. Mixtures of organic-inorganic MLD hybrid layers with ALD layers can be used to obtain films with a density that ranges from the low density of the pure MLD film to the high density of the inorganic ALD film [36]. By way of example, the density of the A1203 ALD: AB Alucone MLD films are shown in Figure 17f. A1203 ALD was grown using TMA and H2O. AB Alucone MLD was grown using TMA and EG [13]. The density was varied by changing the relative number of ALD and MLD cycles during the growth of the alloy. Figure 17e shows the Density of Al203 and Alucone AB alloys using TMA and EG of XRR analysis. The alloys were prepared using different numbers of TMA / H20 and TMA / EG cycles. For example, the 3: 1 ratio sample was prepared using repetitive sequences of three cycles of TMA / H. Figure 17f indicates that the density may vary widely from the evolution of organic matter. [00143] One of the advantages of the present invention is a novel interlayer film or organic interlayer composition. Other properties that depend on the density will also change accordingly. For example, mechanical properties such as modulus and elastic stiffness must be tunable. The optical and electrical properties such as the refractive index and the dielectric constant should also vary depending on the composition of the alloy film. In general, films with a variety of tunable properties should be possible by modifying the ratio of the ALD and MLD cycles used to grow the alloy film. Most of the MLD comment systems in this chapter have been based on AB, ABC or ABCD Process using TMA. Other organometallic and organic precursors are also possible. As mentioned previously, zinc-based inorganic organic hybrid films are possible using DEZ. Other organic-inorganic hybrid systems based on zirconium and titanium are possible using Zr (Ot -Bu) 4 and TiCl 4, respectively. Many other organometallic precursors can also be used to define other MLD hybrid organic-inorganic polymers. For example, magnesium (Mg) and manganese (Mn) metal alkyls are available in Mg (PCIE) 2 and Mn (PCIE) 2. These alkylmetals are expected to react with diols or carboxylic acids to define new ones. MLD systems. The possibilities for the MLD of organic-inorganic hybrid films are virtually limitless considering all the metals in the periodic table and the organic compounds available from organic chemistry. The challenge for the next few years will be to determine the organic hybrid-inorganic films that can be grown easily and that may have useful properties. The tuneable or even adjustable mechanical, optical, dielectric, conductive and chemical properties of organic-inorganic hybrid films should be useful for a wide range of applications. [00144] One of the advantages of the present invention is its implementation on high yield flexible film production systems for inorganic / organic hybrid photovoltaic cells as well as PV tandem cells. For starters, the efficiency of the cell increases with the absorption rate of the constituent materials. Figure 18 is an illustration of the optimal response curve achieved by NREL in a high efficiency solar cell. Fourteen new results are presented in the current version of these tables. The first new result in Table I is an all-time record for solar conversion by a single junction photovoltaic device. An efficiency of 27.6% was measured at the National Renewable Energy Laboratory (NREL) for a 1 cm2 thin-film GaAs device manufactured by Alta Devices, Inc. Alta Devices is a Santa Clara-based "start-up" company seeking to develop low cost, 30% effective solar modules. The second new result in Table I is an improvement in efficiency to 19.6% for a single 1 cm 2 copper-indium-gallium cell junction (CIGS) manufactured by and measured with NREL. Modeling of the organic cells: Similarly, Figures 13a, 13b and 13c respectively represent; (13a) schematic illustration of organic high layer modeling of a solar cell and (13b) hybrid cell modeling illustration with CIGS absorbent layer and (13c) a flexible schematic illustration. Structure assembled in a high efficiency solar hybrid cell with integrated storage substrate that is the subject of the present invention. Another advantage of the present invention is its implementation on the integrated structure of the substrate (also called ON BOARD) piezonanofils. There are several forms of piezoelectric materials: monocrystalline: this is the natural form of piezoelectric materials. Used initially, they were used to develop piezoelectric ceramics. Ceramics: These are special ceramics whose grains are all oriented in a predefined direction so as to endow them with piezoelectric capacitance. Composites: These are grains of piezoelectric materials trapped in a non-piezoelectric resin (also called matrix). This form is mainly used in the field of acoustics. Thin layers: 0.5 to 5 micron thick, these thin layers of piezoelectric materials are used to feed MEMS (Micro Electronical Mecanical Systems) such as micro-valves, micromotors ... Piezoelectricity is generally used at different levels to produce free energy without pollution, and without major constraints. Figures 19a and 19b show respectively; (19a) the principle of operation of the piezonano elements (piezonanil / piezonotubes) of a cell and (19b) the structure of the layer on a multilayer substrate in a high efficiency solar hybrid cell subject of the present invention. The piezonanofile function is to recycle the heat of the surrounding systems with electrical current through its piezo component. The piezo material (PZT) is covered with a film of carbon nanotubes (CNF). In appearance, it looks like chewing gum, even over-cooked modeling clay, but it's actually a real revolution: it's a component that can recover and recycle the energy spent by electronic systems. Designed in part by the Long Que team, a researcher in electrical engineering from Louisiana Tech University (2010), State of Louisiana), the device consists of a lever made of piezoelectric material capable of converting a mechanical voltage 45 into electrical voltage ; PZT in Figure (19a) covered with a film of carbon nanotubes (CNF in the diagram). The heat absorption by the film forces the lever to twist cyclically ... and thus to emit current. Which is recovered by nickel electrodes and reinvested in the electronic device emitting heat. And so on ... What violate the principles of thermodynamics, which prohibit in practice the perpetual cycles. 50 Long That certainly does not pretend. But it offers at least something to limit energy consumption, thus extending the autonomy. Better: the piezo sensor can also capture and convert light. It extracts energy from the environment. It is an advantage of the present invention to consider a generation of electric current by capturing heat on the back of solar substrate to translate it into electric current. In addition, the inventor proposes to compensate for the loss of the efficiency of the photovoltaic cell caused by the heat of the solar radiation by the transformation of thermal radiation into electric current and even to increase the conversion efficiency (called efficiency of the cell) by the use of the piezonanil or piezonotube at the do (reverse side) of the solar cell substrate. Progress beyond the state of the art: ZnO exhibits one of the largest piezoelectric coefficients of any semiconductor and has the most thermoelectric-based of all transparent conductive oxides. This has led to recent work in which it is considered for use in kinetic energy recovery via piezogenerators and thermal energy recovery via thermoelectric effects.

Table 4 gives an estimate in 2001 of the power density generation potential of various energy collection and conversion techniques. H a rvesting .NlethoCl Power Density Cells Care 5m \ 1- cm- Pi ezoe1ectric; 30nW.: Cmj Vibration 1 1 (50 \ cm3 Thernioe ectuic .100V: cm Since this date, however, both piezoelectric and thermoelectric approaches have independently showed a considerable improvement of the potential for energy recovery by nano structuring.For piezo-generation, this is related to increasing the range of motion and elasticity plus the resonances presented by nanostructures, which can amplify the density of power of more harvest in order to magnitude xv For thermoelectric, this is related to a 50-fold reduction in thermal conductivity compared to the substrate.A growth experiment of ZnO nanowires and piezoelectric energy recovery allow to consider a new combined approach to kinetic and thermal energy harvesting coupled with CIGS solar cells Figure 19b illustrates a mic image Scanning electron roscope (SEM) showing two surfaces facing silicon wafers coated with vertically oriented self-forming arrays, ZnO nanowires grated by laser ablation.

The main advantages of the set of works have been developed with the following characteristics: 1) a ZnO based kinetic energy recovery of 5mW / cm3 2) a basic thermoelectric ZnO realization of 0.4. [00146] One of the advantages of the present invention is its implementation on the batteries integrated in the substrate (called on-board batteries) on or on the back of the substrate of the solar cell. For photovoltaic applications, lead accumulators are the systems used for the most part because of their low cost (<150 E / kWh), placing them 45 far ahead of other technologies (NiCd, NiMH and Li-ion). However, their electrical performance does not allow them to have the lifetime of the associated solar panels (> 10 years). The Miniature Energy Sources Laboratory (LSEM) proposes to use the new LiFePO4 / graphite technology whose short-term target cost is less than 300 E / kWh, with four advantages over lead technology: 1) duration higher life, 2) very low self-discharge, 3) 5 to 6 times lighter system and 4) no maintenance. The material cost of a Li-ion accumulator (approximately 80% of the cost of the battery) is assigned to 25% by the cost of cobalt and 25% by the safety devices made necessary in particular by the high reactivity at high temperature of the battery. this compound. It is a cost reduction of more than 30% that can be achieved in the new generations of accumulators thanks to the use of iron phosphate, partly because of its objective cost (1/3 of that of cobalt ), on the other hand the removal of safety devices because of its high chemical and electrochemical stability. The main lock on this family of compounds is the low electronic conductivity, making it difficult to use in battery. By optimizing its composition and the manufacturing process, CEA / Grenoble succeeded in stabilizing the performance of iron phosphate at room temperature (165 mAh / g at 23 ° C). In this sector "high capacity, low cost", a significant advance is the realization of LiNiO, 5Mn 1, 504 spinel type high voltage materials with stabilized performance over already more than 50 cycles and which will exceed 240 Wh / kg. But these materials still require R & D efforts to be integrated into commercial batteries capable of holding 500 cycles. Thin films and nanostructures of silicon as anodes in the context of lithium batteries (collaboration with T. Gacoin, PMC Solid Chemistry Group). Magnetic nanostructures and electrochemistry at the atomic scale: Influence of surface chemistry and electric field on the magnetic properties (anisotropy and domain wall propagation) of electro deposited layers. Local Atomic Order in Alloys: Continued studies of growth of surface alloys to correlate microstructure. Figures 20a, 20b, 20c and 20d show respectively; (20a) a schematic illustration of fields of application of the thin storage layers integrated in the solar cell substrate and (20b, 20c and 20d) a comparison of the conventional lithium ion solution with the nano titanate structures on a flexible substrate in a high efficiency solar hybrid cell which is the subject of the present invention. The different important aspects of thin-film batteries including Inorganic nanoscale electrodes, electrolyte and composite layers, require solid state interface optimization for increased capacity, power and reliability. The synthesis of composite materials and its characterization, the development of new 45 materials for battery electrode with emphasis on interface control and 3D engineering of thin electrolyte film have been other important aspects of the work of the present invention. In particular, the fundamental understanding of the diffusion interface of Thin Film Batteries composite and flexible. Development of 3D-compatible coating and process modeling 50 with materials for 3D micro-battery TF based on micro-processing techniques have been an important part of the research.

Another aspect of the present invention is the scaling of processes on metal sheets (roll-to-roll), the development of low-cost and abundant solutions and materials compatible with the production of hybrid solar cells [00148] One of the advantages of the present invention is the use of Nano-titanate lithium batteries. The Super Charge Ion Battery, or SCiB, is a battery developed largely by Toshiba. The SCiB is close to lithium-ion batteries "standard" portable computing tools (telephones, computers etc.) with however assets: ^ Lifespan: 10 yearsl ^ Number of cycles of charge / discharge: 6 000 (or 10 times more than for "standard" batteries) ^ Charging speed: nine times faster than a lithium-ion battery (its main asset) ^ More security than lithium-ion batteries ^ Less trouble controlling electronically (charge, support, ability to charge current) ^ But with one disadvantage: ^ Three times less capacity at equal weight than a lithium-ion battery 20 History of the birth of SCiB batteries can be summarized as follows: ^ 2005: Toshiba publishes SCiB principle ^ 2008: first production plant enters service (150,000 units / month) ^ 2009: Toshiba plans new plant for 2011 (expected production: 500,000 25 units per month) charac The most outstanding technical features of SCiB batteries are: ^ Anode: Lithium-Titanium Oxide ^ Cathode: Negative electrode material ^ Thermal stability (low heat) 30 ^ High flash point (few short circuits) ^ Short-circuit resistant internal structure Low risk of combustion / rupture ^ 10% loss of capacity obtained after 3000 cycles discharge / rapid charge. ^ Lifecycle> 6000 charges / discharges (life cycle = less than 20% capacity loss) ^ Very fast charging (90% achieved in 5-10 min) ^ Operating temperature range of -40 ° C to 60 ° C ° C ^ Voltage of a SCiB cell: 2,4 V ^ Density: 1,48 40 ^ Energy density: approx. 50 Wh / kg ^ Power density: approx. 3 kW / kg ^ Use of reduced pollutants ^ Fast charging Fast charging is not a direct characteristic of the battery. These are all elements 45 robustness (thermal stability, high flash point, internal structure resistant to short circuits) that allow to use stronger currents than for Lithium-ion batteries without risk of explosion. It can thus save up to 90% of the charging time compared to the latter. 50 In our studies: Lithium titanate technology is very unique because it does not contain solid electrolyte interface (SEI). The SEI is a "film" on the anode that is an internal resistance limiting the power output and generates heat accumulated in a standard lithium-ion battery. Therefore, the absence of an SEI allows the lithiumtitanate battery to work effectively at extreme temperatures and reduces the risk of thermal runaway significantly. In short, by removing the highly reactive graphite from the system design, and instead using lithium titanate nanostructured materials as the negative electrode material, no significant interaction takes place with the electrolyte. The temperature range of the Nano-titanate lithium battery is also wider than other technologies: -40 ° C to 55 ° C (-40 ° F to 131 ° F). This capability virtually eliminates the need for additional heating when the cell is used in low temperature environments and reduces or eliminates cooling requirements for high temperature operation. Conventional lithium-ion batteries can typically go through the charge / discharge cycle about 1000 times before they are considered more useful. In laboratory tests, storage systems and Altairnano, lithium titanate batteries have reached more than 25,000 charge-discharge cycles and - at rates up to 40 times greater than ordinary batteries, and still conserve up to at 80% of the initial load capacity. Figure 20c-1 illustrates a 3D Nano Lithium Titanate with more life cycle and without stress during charging and discharging Figure 20c-2 shows a standard Lithium-ion anode slowing the charge rate with the cathode due to its surface rounded carbon Figure 20c-3 shows a Nano Lithium-ion Titanate anode with more than 30 times exchange surface making a charge and discharge cycle faster. [00149] Other Advantages of Implementing New Material for Solar Cell Storage Batteries and / or Electric Vehicles. One of the advantages of the present invention is to propose a material that can triple the capacity of lithium ion batteries, thus enabling electric vehicles to have a range around 600km. The company has also developed a new material to drive electricity into the battery. Figures 21a and 21b show respectively; (21a) an illustration of solar cell with thin-film storage battery integrated into the solar cell substrate and (2 lb) an illustration of the steps of the nano-titanate multilayer solution on a flexible substrate 35 in a high efficiency solar hybrid cell making the subject of the present invention. (Note * 1: Gel-type electrolytes: electrolytes of a jelly-like substance.) Part of the results of this research and development (process technology) ) was carried out with the support of the Research Project on Advanced Technologies for the Application and Commercial Use of Lithium-Ion Batteries being managed by the New Energy and Industrial Technology Development Organization (NEDO). In the future, we will examine the mass production of these film-type lithium-ion batteries, the goal of rapidly producing products for a variety of uses, including electric vehicles. The achievements of this research will be announced at Eco-Products 2013 to be held at Tokyo Big Sight from December 12-14 this year. The research process of Sekisui Chemical, which aims to be a premier society contributing to the environment, has used its well-honed high-performance film as a tool to create an innovative environmental product. In particular, the company has focused its efforts on energy materials and devices, stimulating R & D on battery materials and lithium-ion battery production processes to find solutions to the current problems of weight, space, security and capacity. Since 2012, he has been involved in accelerating this research with the support of the Advanced Technology Research Project for the Application and Commercial Use of Lithium-Ion Batteries being managed by the New Energy and Industrial Technology Development Organization (NEDO). The company has made aggressive efforts in the development of high conductivity materials and processes allowing the manufacture of large / long battery cells that can only be achieved with the existing revolutionary lithium-ion processes. The Li-nano Titanate technology described in the present invention also provides the ideal combination of power and power produced to compensate for dynamic charge / discharge behavior at varying discharge levels.

One of the advantages of the present invention is a large scale integration of renewable energies (photovoltaics) on an optimized surface of the installation Lithium-ion batteries are a type of non-aqueous electrolyte of the rechargeable battery when the lithium-ion battery inside electrolytes provides electrical conductivity.

Standard models have lithium metal oxides at the positive electrode and a carbonaceous material such as graphite at the negative electrode, and typically use an electrolytic solution. Thanks to the electrolyte solution is a barrier to ensure the safety of the lithium ion battery, and many research institutes to solidify the electrolyte solution, but from the point of view of performance and productivity, the electrolyte solution remains the substance Standard. Sekisui Chemical, with a strong focus on the use of gel for electrolytes, has recently used new organic polymer electrolyte materials such as electrolyte gel type of high ionic conductivity (about ten times other Sekisui Chemical products) to obtain the prospect of continued high-speed production of battery cells (at ten times compared to other products of Sekisui Chemical) and improving safety by using a continuous coating process rather than a vacuum infusion process. In addition, it has developed high-capacity negative electrode silicon materials to make optimal use of this performance, achieving a high capacity (900Wh / L) battery cell. The development of high-capacity lithium-ion battery type film working practice while being flexible, thin long and covers a large area, has massively improved freedom in the design of the shape of the final products, leading to anticipation from their use in automobiles, homes, electrical appliances and so on while acquiring unprecedented lightness, improved design to be able to be installed in any form of shape * 3 save space ( one third of the size of the previous products). Note * 3: The values provided by these lithium-ion batteries in film form [1] Light weight As they weigh one third of the previous products, they are (Lightweight): able to reduce the input movement by touch of the battery power itself. [2] Space reduced (Space-slimming and their small size allow to be stored in a compact way for efficient use of space saving): saved. [3] Performance in Thanks to the strong freedom in product definition it design can be placed in what was otherwise space (Performance Design): unused, which makes even more use of space. Note * 4 on Film-type lithium-ion batteries: The supposed size of lithium-ion-type film batteries is currently 200cm, 30cm wide, and a thickness of 0.3-5mm (however, the size varies depending design capacity) [00150] Double sided (also called bifacial) and hybrid solar cells. At this point, to complete the solar cell process, the edge isolation must be done in order to avoid the short circuit between the transmitter and the back contact of the cell. In a mono-facial process this step can be carried out immediately after the emitter diffusion and, in this case, the wet chemical treatment is used. One of the most successful edge isolation processes is laser tracing. It is perfectly suited to online processing and the wafer remains intact, which is an important requirement for handling thin wafers. Other possible techniques for performing edge isolation are: wet chemical etching, plasma etching, saw cutting or sandpaper. A detailed report including most of the relevant techniques for isolating the edges is presented by Hauser et al. Here we presented the last step to make bifacial solar cells. The schematic structure is shown in Figure 11a, with respect to the standard mono-facial solar cell. Figures 22a, 22b and 22c show respectively; (22a) an illustration of a double-sided solar cell with its metallization (22b) and its response curve as well as the spectral responses of the cell (22c) in a high-efficiency solar hybrid cell forming the subject of the present invention. Figure 22a of the present invention shows a screen printed Al-back surface field (AlBSF) is widely used to passivate the back surface of silicon solar cells. In order to increase the cost-effectiveness of solar cells, there is a strong tendency to further reduce the wafer thickness down to at least 200 μm. Thus, the back surface recombination rate (Sb) begins to strongly influence the performance of the solar cells when approaches to the minority carrier diffusion length or exceeds the thickness of the apparatus. Al-BSF that can decrease Sb becomes much larger. Previously, most researchers used internal quantum cell quantum efficiency (IQE) at Al-BSF quality analysis. But this method is not able to characterize Al-BSF directly because of other factors. In FIG. 22a, the back-surface fields are formed using screen-type Al Cz P-silicon screen-type directly followed by strip-furnace sintering and we measure the lifetime of the minority carriers after firing. When these cells are based on a substrate instead of an n-type p-type substrate, the sequence process can be maintained, but in this case, the transmitter (front side) would be the diffused boron surface (p +) and the rear surface field 40 would be phosphorus (n +). Several changes in the processing steps were tested e.g., starting with phosphorus diffusion instead of boron scattering, texturing of the back face and the front side etching, among others. The best results were obtained with the method presented in this section. [00151] Results of the solar cell. Before presenting the results of solar cells obtained during this study, it is necessary to introduce the most important parameters that characterize the solar cell. Most relevant parameter are described below. As can be found in the literature on PV [PVE]: standardized tests allows the comparison of efficiency and other parameters of the cell manufactured by different companies and laboratories with different technologies. "10 The conditions of standard test (STC) are usually: - 1.5 air mass spectrum (AM1.5) for terrestrial cells and 0 air masses (AMO) for space cells - Intensity of 100 mW / cm2 (1 kW / m2, a lighting sun) - Cell temperature of 25 ° C (not 300 K) 15 - Four probe points to eliminate the effect of probe / cell contact resistance According to Wikipedia [ WIK: "The mass of air 1.5 (AM1.5G) spectrum corresponds to the illumination and spectrum of incident of sunlight in clear weather on a 37 ° inclined surface of sun facing with the sun at an angle of 41.81 ° above the horizon. The energy conversion efficiency of a solar cell "rl" is the percentage of incident light energy which actually ends up in electrical energy. This is calculated at the point of maximum power, Pm, divided by the radiation density of the input light (E, in W / m2) under DCP and the surface area of the solar cell (Ac in m2). 25 = Pm E - Ac The absolute maximum theoretically possible of the conversion efficiency of the sunlight is 93% because of the Carnot limit, given the temperature of the photons 30 emitted by the sun's surface [HEN Solar cell can operate over a wide range of voltages (V) and currents (I). By increasing the resistive load on a continuously irradiated cell from zero (short circuit) to a very high value (an open circuit), one can determine the maximum power point, to the point that maximizes V x I, c ' i.e., the load for which the cell can provide maximum electrical power (at this level of irradiation). The output power is zero in both the short-circuit and open-circuit modes. The maximum power point of a photovoltaic cell varies with incident illumination "[WIK] As explained by PV education [PVE:" IV curve of a solar cell is the superposition of the IV curve of the diode of the cell solar in the dark with the current 40 generated by the light. The effect of the light is to shift the IV curve down into the fourth quadrant where the power can be extracted from the diode (see Fig. 12). Enlightening a cell adds the normal "dark" currents in the diode so that the right of the diode becomes: 45 Figure12b illustrates the effect of light on current-voltage characteristics of a junction p- The two limiting parameters used to Characterize the efficiency of solar cells are short circuit current (Isc) which is the current at zero voltage, under ideal conditions proportional to sunlight is available) and open-circuit voltage (Voc) which is the maximum voltage zero current [S & Q]. This value increases logarithmically with an increase in sunlight.

For each point of curve IV, the product of the voltage and current represents the power output for the operating state. A solar cell can also be characterized by its maximum power point, when the product Vmpp x Je mpp is at its maximum value [WEN]. "Another term defining the overall behavior of a solar cell is the fill factor (FF), which is the ratio of the power available at the point of maximum power (Pm), divided by the circuit voltage. open (Voc) and short-circuit current (Isc): FF = H Voc Isc 11 - A - E = c Voc - Isc The fill factor is directly affected by the values of the series of the cell and shunt resistors " [WIK]. The increase of the shunt resistance (Rsh) and the decrease of the series resistance (Rs) of lead to a higher filling rate, thus resulting in greater efficiency, and bring the power output of the cell close to its theoretical maximum [NEL]. Another important method of characterizing the performance of solar cells is the spectral response. The spectral response is conceptually similar to quantum efficiency [PVE]. "Quantum Efficiency (QE) is the ratio of the number of charge carriers collected by the solar cell to the number of photons of a given energy shining on the solar cell, which leads to: SR = q - X QE h - c QE therefore deals with the response of a solar cell at different wavelengths in the spectrum of bright light on the cell.EQ is given as a function of each wavelength or energy. photons of a certain wavelength are absorbed and we collect the resulting minority carriers, the QE at this particular wavelength has a value of 1. The QE for photons with energy below the bandgap is zero Two types of quantum efficiency of a solar cell are often taken into consideration: External quantum efficiency (EQE) is the ratio between the number of charge carriers collected by the solar cell to the number of photons of a given energy that shine su r the solar cell from the outside (incident photons). Internal Quantum Yield (IQE) is the ratio of the number of charge carriers collected by the solar cell to the number of photons of a given energy that enter the solar cell from outside and are absorbed by the cell.

The WQI is always bigger than the European qualifying examination. A low IQE indicates that the active layer of the solar cell is not able to make good use of the photons. To measure the WQI, a first measure the EEQ of the solar device, measurements of its transmission and reflection, and combines these data to deduce the WQI "[WIK].

According to PV education [PVE: "the ideal spectral response is limited to long wavelengths by the semiconductor's inability to absorb photons with energies less than the bandwidth." This limit is the same as that encountered in However, in contrast to the square shape of EQ curves, the spectral response decreases at short wavelengths of photons.At these wavelengths, each photon has a high energy, and therefore the ratio of photons to power is reduced.All the energy above the band gap energy is not used by the solar cell and instead causes the heating of the cell. to make full use of the high-energy incident energy and the inability to absorb low light energies represents a significant loss of power in solar cells consisting of a single pn junction. [00151] Losses in solar cells: The losses in a solar cell will reduce its effectiveness. The main contributions are optical losses due to reflection, loss of recombination, resistive and thermal losses. "Optical losses primarily affect power from a solar cell by lowering the short-circuit current." Optical losses consist of light, which could have generated an electron-hole pair, but that does not work because the light is reflected from the front surface, or because it is not absorbed into the solar cell.For the most common semiconductor solar cells, the entire visible spectrum has enough energy to create electron-hole pairs and therefore all the visible light ideally be absorbed [PVE]. When the light is extinguished, the system must return to a state of equilibrium and the electron-hole pairs generated by the light must disappear. External energy, the electrons and the holes are walking until they meet and recombine.Fails or impurities inside or on the surface of the semiconductor promote recombin "Recombination can occur through several mechanisms: - radiative recombination: the inverse of absorption. Electrons in a state of high energy return to a lower energy state, with the output of light energy. - Auger recombination: an electron recombining with a hole gives the extra energy to another electron, which then relaxes to its original energy state, releasing phonons. This recombination is particularly effective in relatively heavily doped material, thus becoming the dominant process when the level of impurity greatly exceeds 1017 cm -3.

Recombination by traps (also called Shockley -Read -Hall recombination): can occur when impurities in the semiconductor or interface traps at the surface give rise to permissible energy levels in the forbidden energy band other. The electrons can thus recombine with the holes in a two-step process, first to relax at the level of the defect energy, then to the valence band. Solar cells usually have a parasitic series and the shunt resistance associated with them, both types acting to reduce the fill factor. The main factors of the series resistance (Rs) is the apparent resistance of the semiconductor material, the metallic contacts and interconnections, carrier transport through the diffuse upper layer, and the contact resistance between the metal contacts and the semiconductor . The shunt resistance (rsh) is due to the non-idealized PN junction and the impurities near the junction, which cause a partial short circuit of the junction, especially near the edges of the cell. " as quantum energy conversion devices, and are therefore subject to the "limit of thermodynamic efficiency". Photons with energy less than the forbidden band of the absorbing material can not generate an electron - hole pair, and so their energy is converted into a useful output and does not generate heat when absorbed. For photons of energy greater than the bandgap energy, only a fraction of the energy above the forbidden band can be converted into useful power. When a high energy photon is absorbed, excess energy above the forbidden band is converted into kinetic energy of the carrier assembly. The excess of kinetic energy is converted into heat by phonon interactions as the kinetic energy of the carriers slows the speed to equilibrium. Table 6 gives a summary of all these losses, including the parameters affected Table 6: Types of losses and the parameter affected The loss mechanism of the optical losses Isc with recombination Vc, the resistive losses Icc FF, thermal losses Vo,, FFI "Bars and fingers are the source of a variety of losses; these include shading losses, resistive losses and contact resistance losses [PVE. "The first results of IV on a batch of 50 solar cells [00152] Increased yield of solar cells by bifacialization At the beginning of this survey in 2008, we mainly worked on the optimization of the diffusion treatment step This step is the key to creating the rear surface fields (also called BSF), it can be done before or after the formation of the transmitter depending on the sequence of steps chosen .. Once a very small deviation in the homogeneity of boron scattering on platelet surfaces was obtained, the solar cells were made in a sequence similar to that presented by Kopecek, which was the starting point for several optimization steps and adjustments. The treated substrates were about 2 Ω-cm resistivity, 125 × 125 mm 2 p-capture Cz-Si of a thickness of about 200 μm. 10%, having a high degree of inhomogeneity in efficiency. Improving cell homogeneity on a defined lot was a primary goal. This goal was achieved after we gained some experience in processing techniques such as substrate cleaning, SiNx deposition, among others. These first results showed that mainly the rear face presents a great possibility for the overall improvement, in the short-circuit current. Jsc decreases mainly due to optical losses and recombination. These results indicate another optimization step: the passivation of the surface of + p. For the improvement of the front panel, we were mainly interested in optimizing the contact training. However, during this work most of the processing steps have been improved for the front and back side.

The order of the steps has been adjusted to obtain the best results in terms of solar cell results and production (time and consumption) results after sequence and optimization steps.

The maximum efficiencies obtained with this method are 17.3% for the front panel and 15% for rear side lighting under STC. The ratio of forward and backward efficiency is greater than 80% for all solar cells.

It is important to consider that for diffusions, a better passivation of the surfaces, and for the contacting of the metal, we suppose that the gains in efficiency should be at least 0.5% in absolute value. N-type substrates have also been included in this batch for processing for solar cells, using the same process. The best cell results were 15.1% for the front panel and 11.9% for the back panel. [00153] Increased cell efficiency by trapping light photons Recently, a team of researchers from the University of Illinois at Urbana-Champaign and the University of Central Florida at Orlando have been trying to implement systems of light. trapping of light with silicon solar cells of thickness 3 μm., The result obtained on the energy conversion efficiencies were more than z '190% compared to identical cells that do not have the characteristics The present invention provides new nano-textures in the form of micro-cellular networks that have the light-trapping characteristic of simple fabrication, which are lightweight, flexible, more efficient, and easy to mass-produce. Light trapping is a technique used to make the length of the optical path longer than the length (thickness) of the actual solar cell. The optical path is the path that light puts through the solar cell. By way of example, for a solar cell without a light trapping system, the length of an optical path is equal to the length of the device itself. In a solar cell with light trapping systems, the optical path length may be 40 times or more greater than the length of the device. The invention uses a light trapping system based on a very innovative technique. This is a light capture and blocking system based on a MLD layer growth or nano-imprint / deposition technique where a polymer deposit by MLD mechanically creates the model (nanoscale) at the cell. solar without the use of complex lithographic steps. This approach naturally leads to flexibility, making the design ideal for mass manufacturing. This study demonstrates that the light-trapping regime provides higher electrical efficiency in a flexible and lightweight module. Figure 23 shows a solar cell photon trap illustration for an increase in efficiency in a high efficiency solar hybrid cell subject of the present invention. [00154] Notes on Increase and Optimization of Cell Efficiency It should be noted that the most important elements in the increase and optimization of energy yields are: 1) The widening of the gap band (14-1 FIG. 14a) The expression of the gap band (in electronvolt): According to the law of quantum mechanics, the minimum energy required for the photon to cross the forbidden energy band = that of electromagnetic propagation of the associated wave hc E = mc2 = hv = - h = 6,62620 * 10-34 Js Planck constant c = 3 * 108ms-1 the speed of light Therefore: hc 1.24 Eg (ev) = hv = 2) the number of electrons created by the photogeneration process: N (x) = N (0) e-ax A being the absorption coefficient of the material used in m-1 3) the refractive index of the upper layers n 4) 1 thickness of the absorbent layer g It emerges that to have a better efficiency it takes a larger A (iim) possible so a study of the electromagnetic spectrum. An optimal choice of the absorption coefficient has to have more free electrons. It is therefore necessary to have a thorough and complete characterization of the various layers, in particular the CIGS layer. BRIEF DESCRIPTION OF THE FIGURES The set of FIGS. 1 to 24 show a schematic representation as well as various details of a system subject of the present invention. Figure 1 shows schematically the different layers of a double-sided hybrid solar cell subject of the present invention. Figure 2a shows schematically the different layers of a high efficiency hybrid solar cell with piezonotubes (or piezonoyl) converter being the subject of the present invention. Figure 2b shows schematically the different layers of a single high efficiency solar cell subject of the present invention. Figure 2c shows schematically the different layers of a high efficiency hybrid solar cell with storage battery integrated into the substrate of the cell subject of the present invention. Figures 3a and 3b schematize a high efficiency solar hybrid cell with antireflection layers and sun tracking subject of the present invention. Figures 3c and 3d show a high efficiency hybrid solar cell with storage batteries integrated in the cell substrate and antireflection and sun tracking layers subject of the present invention. Figure 4 schematically represents an ideal growth sequence by MLD in "self-limiting reactions" using two homobifunctional reactants in a process having the chemistry sequence spontaneously used for the growth of an organic polymer, thereby allowing mixing of the Organic precursors used for MLD with inorganic ALD precursors to define novel organic-inorganic hybrid materials in a high efficiency solar hybrid cell subject of the present invention. Figure 5 illustrates the growth of Alucone (polymer film) in two steps using trimethylaluminum (TMA) and ethylene glycol (EG). TMA is exposed to a hydroxylated surface and produces a surface covered with A1CH3 species, thus allowing the mixing of the inorganic organic base of novel organic-inorganic hybrid materials in a high efficiency solar hybrid cell being subjected to the present invention.

Figure 6a shows the graph of the energy absorbing bands (Abs / PL) as a function of the wavelength in a high efficiency solar hybrid cell forming the subject of the present invention.

FIG. 6b represents a model of the structure of a hybrid solar cell of the CIGS type, in a high efficiency solar hybrid cell which is the subject of the present invention. Figure 7a shows a schematic illustration of a possible configuration of bifacial solar cell with optical active layer in a high efficiency solar hybrid cell subject of the present invention. Figure 7b is a schematic illustration of a possible configuration of solar cell equipped with up converter layer (Up Converter) converting invisible radiation visible radiation of the light spectrum in a hybrid high efficiency solar cell subject of the present invention. Figures 7c and 7d represent respectively; (7c) the quantum efficiency extension curve (EQE) of a hybrid cell as a function of the wavelength and used and molecular materials of a cell and (7d) the structure of the entire light spectrum by wavelength division on a multilayer cell in a high efficiency solar hybrid cell forming the subject of the present invention. Figure (8a) shows the cost ratio per standard m2 identifying what is considered to be the top three categories of solar cells in terms of solar conversion efficiency and the cost per unit area in a high efficiency solar hybrid cell making the object of the present invention. Figure (8b): represents the Black Body Spectrum as a function of temperature in a high efficiency solar hybrid cell subject of the present invention.

Figure (8c) shows the structure of a lattice (ordered set), in a hybrid high efficiency solar cell subject of the present invention. Figure (8d) shows the Shockley-Queisser boundary representative curve, in a high efficiency solar hybrid cell subject of the present invention. Figures 9a, 9b and 9c show respectively; (9a) a schematic illustration of a charging and discharging cycle in a solid electrolyte battery and (9b) a thin-layer illustration of the energy storage stage with Anode and Cathode on flexible substrate of the thin film (Thin Film) interface, composite and flexible batteries. Coatings development (coating) and modeling of processes in 3D and (9c) a schematic illustration of Lithium nano titanate micro batteries without solid electrolyte interface (also called SEI or Solid Electrolyte Interface (SEI) in a high efficiency solar hybrid cell with integrated storage to the substrate subject of the present invention.

Figures 10a, 10b and 10c show respectively; (10a) a schematic illustration of a CIGS solar cell with an organic interface layer and (10b) an illustration of n-type CIGS and sulphide (n-sulphide) layers on a pn junction and (10c) a flexible schematic illustration. Coating development and modeling of 3D processes in a high efficiency solar hybrid cell with integrated storage on the substrate of the present invention.

Figures 11a, 11b, 11c and 1d represent respectively; (11a) A schematic illustration of a single-sided solar cell and (1 lb) a central layer illustration n covered front and back by p-type layer and n + and (11c) a diagrammatic illustration of a front and rear sintered junction by SnO2-type layer and (11d) a solar panel illustration in an upright frame-of-use environment in a high efficiency solar hybrid cell with built-in substrate storage the subject of the present invention. Figures 12a, 12b, 12c, 12d, 12e, 12f and 12g show respectively; (12a) a schematic illustration of a cyclic growth ALD and (12b) an illustration of layers in formation and (12c) an illustration of the discretized rectangular domain and (12d) an outline illustration of the function of Potential and (12e) a illustration of "the surface of the potential function yr" and (12f) an illustration of the boundary conditions and (12g) an illustration of the pace and profile of the electric potential function w (x, y) by the relaxation methods and relaxation respectively in a high efficiency solar hybrid cell with integrated storage to the substrate subject of the present invention. Figures 13a, 13b and 13c show respectively; (13a) A schematic illustration of organic high layer modeling of a solar cell and (13b) a hybrid cell modeling illustration with CIGS absorbent layer and (13c) a flexible schematic illustration. Structure assembled in a high efficiency solar hybrid cell with integrated storage substrate that is the subject of the present invention. Figures 14a, 14b and 14c respectively represent (14a) the principle of photo generation in the valence band as a function of doping and (14b) the quantum dot curve of CuInSe2 PV-quantum dots (also called QDs), and (14c) spectral response of quantum efficiency of the CIGS absorbent cell in a high efficiency solar hybrid cell subject of the present invention. FIG. 15 represents an illustration of the path traveled by the light in a rear passivation layer (rear dielectric passivation with SiO 2, Al 2 O 3 / SiN x and low-n) serving as an internal reflector in a high efficiency solar cell which is the subject of the present invention. invention. Figures 16a, 16b, 16c, 16d and 16e respectively; (16a) a schematic illustration of the improvement of light absorption (Plasmonic) and (16b) an illustration of the separation of semiconductor Ag particles by thin passivation layer (eg A1203) improves performance and (16c) an illustration of "self-organized opaline structures, hexagonal photonic structures by deposition of ALD A1203 (surface passivation) spin-coated surface coating of spherical nanoparticles (SiO2) and (16d) an illustration of the short-circuit current density and (16e) an illustration of simulated values of current densities in a solar hybrid high-efficiency cell with integrated storage on the substrate of the present invention.

Figures 17a, 17b, 17c 17d, 17e, 17f and 17g respectively represent; (17a) A schematic illustration of the growth of an MLD layer during ABC growth that can be accomplished without using homobifunctional precursors is based on: TMA, a homomultifunctional precursor mineral, ethanol amine (EA), a hetero and maleic anhydride organic reagent (MA) an organic reagent by ring opening and (17b) an illustration of the difference of the FTIR spectra for Glycerol - TMA and TMA - glycerol. The spectra are shifted for clarity in presentation and (17c) a difference illustration of the FTIR spectrum after TMA and GL exposure hang AB Alucone MLD at 150 ° C and (17d) an illustration of the four reaction sequence steps ABCD for a MLD layer growth process of an Alumina-siloxane film using trimethylaluminum (TMA), H2O, dimethylmethoxychlorosilane (DMMCS) and H2O and (17e) a schematic illustration of two-step reaction sequence for growth by MLD in AB reference of a Lewis film using trimethylaluminum (TMA) and triethylenediamine (TED) and (17f) an illustration of the density of A1203 and AB Alucone using TMA and EG from the analysis of XRR and (17g) is a two-step reaction sequence for MLD growth of AB Zincone using diethylzinc (DEZ) and hydroquinone (HQ) in a high efficiency solar hybrid cell with or without integrated storage on the substrate subject to the present invention. Figure 18 is an illustration of the optimal response curve achieved by NREL in a high efficiency solar cell.

Figures 19a and 19b show respectively; (19a) the principle of operation of the piezonano elements (piezonanil / piezonanotubes) of a cell and (19b) the structure of the layer on a multilayer substrate in a high efficiency solar hybrid cell subject of the present invention.

Figures 20a, 20b, 20c and 20d show respectively; (20a) a schematic illustration of application domains of the thin storage layers integrated in the solar cell substrate and (20b, 20c and 20d) a comparison of the conventional lithium ion solution with the nano titanate structures on a flexible substrate in a solar hybrid cell high efficiency subject of the present invention. Figures 21a and 21b show respectively; (21a) a solar cell illustration with thin film storage battery integrated into the solar cell substrate and (2 lb) an illustration of the steps of the multilayer nano titanate solution on a flexible substrate in a high efficiency solar hybrid cell making object of the present invention. Figures 22a, 22b and 22c show respectively; (22a) an illustration of a double-sided solar cell with its metallization (22b) and its response curve as well as the spectral responses of the cell (22c) in a high-efficiency solar hybrid cell forming the subject of the present invention. Figure 23 shows a solar cell photon trap illustration for an increase in efficiency in a high efficiency solar hybrid cell subject of the present invention.

Figures 24a and 24b respectively show (24a) a flexible solar cell illustration having its substrate integrated energy storage system and (24b) a flexible solar cell illustration having its energy storage system integrated into the substrate. the two-sided cell for an increase in efficiency in a high efficiency solar hybrid cell subject of the present invention. Figure 25 shows an illustration of charge and discharge cycle for a lithium-ion battery.

FIGS. 26a, 26b and 26c show the degradation of the discharge as a function of the number of cycles for a LTO-LMO (Transition Metal Oxide) type battery with LTO-LLTO for a composite conductor forming the subject of the present invention. FIGS. 27b represent the charge capacity as a function of the number of cycles for a LTO-Fe203 type LTO-LMO (Transition Metal Oxide) battery for a composite conductor forming the subject of the present invention. FIG. the LTO-LMO type LTO-LMO battery for a composite conductor of the present invention FIG. 29a represents the load capacity as a function of the number of cycles for a LTO-type LTO-LMO (Transition Metal Oxide) battery. LTO-TiO2 type LMO (C) for a composite conductor object of the present invention Figure 29b is an illustration of assemblies of electrodes for a bipolar battery by a type of construction Atomic ALD and the molecular deposition of the "MLD" and layer-by-layer nano-hybrid laminated / inorganic polymer layers laminated by divisible and shapeable segments for the integrable or embedded batteries forming the subject of the present invention. Figure 29c is an illustration of layer-by-layer electrodes by the molecular deposition of the "MLD" layers and growth layer by layer of hybrid / inorganic laminated nanoparticles for integrable or embedded batteries that are the subject of the present invention. Figure 30a is a liquid electrolyte formula based on ethylene carbonate (EC). Figure 30b is a high boiling solvent formula e.g. DMSO, PC, Sulfolane).

Figure 30c is an image of a macroporous separator very resistant. Figure 30d is an image illustrating the strengthening of macroporous separators. DETAILED DESCRIPTION OF THE INVENTION WITH FIGURES For a full understanding of the present invention, we will detail the set of figures describing the different points of the system. According to the invention, and as indicated through FIG. 2b, the base of the inorganic cell consists of a rigid or flexible substrate 2-1 (FIG. 2b or 2a) and a layer of molybdenum 2-2. (FIG. 2b or 2a), followed by an absorbent layer CIGS 2-3 (FIG. 2b or 2a) by ALD deposition in a device in the form of a spiral or batch roll with a layer Cds (sulphide cadmium) 2-4 (Fig.2b or 2a) and a conductive transparent window 2-5 (Fig.2b or 2a) followed according to the case of single cell CIGS by a metallization 2-5 (Fig.2b) or a planarization process (smoothing surfaces ) 2-7 (Fig.2a). The following table shows the performances obtained on a substrate of 50x30Cm format during a multi-stage realization during selenization with different doping of Na in the 9ng e F 'P EFF 12,43.3.4, o41, 12,1e 13,35 % 13.77, 13.06%, 11.33% 13.35%, 66.45%. 69.97A 66.48% 69.70% 67.6% 69.42% 67.53% 66.67% 70.95% Mea:: bed r Vare 646.43 633.38 666.95 643.72 880, 90 651.44 646.62 637.25 675.14 Ise 28.09 31.68 27.36 29.75 29.93 29.84 27.62 26.79 27.88 Cel D es 03'2: DEI 189 0.9C 0..88 0.68 0.67 Gell 0.311 0.31.3 C..31 3 31 0.31 0.31 0.31 C 3C substrate. The substrate may be reels to be treated beforehand and may be either stainless steel, plastic, aluminum, etc. For production CIGS / CZTS cells with a substrate in the form of a coil, beforehand a contact layer of molybdenum (Mo) 2-2 type (FIG. 2b) is generally deposited before being unrolled towards the entrance of the roll line. - to-roller (R2R). For a production of hybrid cells of the organic type, the flexible films may be coated with a transparent solid layer 2-8 (FIG. 2a) followed by an organic deposit 2-9 (FIG. 2a) of photoactive polymer in solvent solution. in the form of a thin layer on an active layer substrate of CIGS 2-3 (FIG. 2b or 2a) by thin-film processes in a liquid route (ultrasonic spray or rotogravure roll-to-roll) followed by deposition of the transparent electrode 2-10 (Fig. 2a), Note that this technique is well suited to complex and uniform processing and structure deposition (OLED, sealing barriers for OLED films and photovoltaic cells sensitive to moisture).

The piezonazole layer deposition device 2-11 (Figure 2a or 2c) is in this figure on the back of substrate 2-1 (Figure 2a, 2b or 2c) separated by a spacer layer 2-14 (Figure 2c). and finally followed by the thin-film battery 2-12 (Figure 2c). A protective encapsulant 213 (Fig. 2c) is generally used as a finish on the back of the cell. Figures 3a, 3b, 3c and 3d represent an exploded form of the cell with different hybridizations subject of the invention. Liquid crystals 3-1 (FIGS. 3a, 3b, 3c and 3d) are an important part of the increase in efficiency (see patent ROUSTAEI et al., 09 01503 of 27-03-09, P. 26-29). operation of the liquid crystal integrated in the solar cells). Another economic interest is that in this type of arrangement, cell efficiencies are considerably increased for a product that can be integrated into buildings and low-lift roofs. Indeed, the flexible film 3-2 (Fig. 3a, 3b, 3c and 3d), provided with its thermal conversion means in electrical current piezoanofils 3-3 (Fig. 3a, 3b, 3c and 3d), and its Hybrid or tandem organic layer 3-5 (Figs 3a and 3c) offers a conversion efficiency of solar radiation in excess of 30% with a weight <4kg / m2 in the form of a bankable product (a lifetime greater than 5 , 10 or 20 years depending on its resistance to mildew in an environment of -10 to + 60 ° C). The device further provides a storage area at most equal to the surface of the solar cells through the storage system (layer defined by 3-6 (Fig. 3c and 3d) on the back of the solar cell substrate 32 (Fig. 3a, 3b, 3c and 3d).

In another particular arrangement of the deposition system and in order to optimize the interconnection, or even the production of the various organic / inorganic layers, the molecular deposition of the layers (MLD) or the molecular growth of the layers is recommended by the present invention schematically. an ideal growth sequence by MLD in "self-limiting reactions" using two homobifunctional reagents 4-1 (Fig. 4) and 4-2 (Fig. 4) in a process with the sequence of chemistry spontaneously used for the growth of d an organic polymer on substrate / host layer 4-3 (FIG 4) thus allowing the mixture of organic precursors used for MLD with inorganic precursors ALD 4-4 (FIG 4) to define new organic-inorganic hybrid materials in a high efficiency solar hybrid cell which is the subject of the present invention. The layer of polymeric film 5-1 (Fig. 5) illustrates the growth of Alucone (polymer film) in two steps using trimethylaluminum (TMA) 5-2 (Fig. 5) and ethylene glycol (EG) 5- 3 (Fig. 5). TMA is exposed to a hydroxylated surface and produces a surface covered with A1CH3 species, thus allowing the mixing of the inorganic organic base of novel organic-inorganic hybrid materials in a high efficiency solar hybrid cell being subjected to the present invention.

As explained above, the principle of hybridization in the present invention consists in adding the QEQ quantum response efficiencies of the different materials to form a high efficiency solar cell. As illustrated by the diagram of the energy absorption bands of two organic materials 6-1 (Figure 6a) and the additional 6-2 (Figure 6a) inorganic results in a 6-3 response (Fig. 6a and 6b) in an average curve representing the spectral response diagram of the energy absorption bands (Abs / PL) as a function of the wavelength in a hybrid high efficiency solar cell subject of the present invention . FIG. 6b represents a modeling of the structure of a hybrid solar cell of the CIGS type, in a high efficiency solar hybrid cell which is the subject of the present invention. Note that the present invention replaces the Cds 6-4 layer (Figure 6b) with a family of ZnO-based components as described in section [00118]. In another particular arrangement, FIG. 7a is a schematic illustration of a possible bifacial solar cell configuration with an optical active layer 7-1 (FIG. 7a) in a solar hybrid cell 7-2 (FIG. object of the present invention. Figure 7b is a schematic illustration of a possible solar cell configuration equipped with Up Converter converting invisible radiation into visible radiation 7-3 (Fig. 7b) of the light spectrum into a high efficiency solar hybrid cell making the light object of the present invention. Figures 7c and 7d represent respectively; (7c) the quantum efficiency extension curve (EQE) of a hybrid cell as a function of the wavelength and used and molecular materials of a cell and (7d) the structure of the entire light spectrum by wavelength division on a multilayer cell in a high efficiency solar hybrid cell forming the subject of the present invention.

Figure (8a) shows the cost ratio per standard m2 identifying what is considered to be the top three categories of low cost solar cells -1 (Fig. 8a) in terms of solar conversion efficiency and cost per unit area in a high efficiency solar hybrid cell which is the subject of the present invention.

As described in section [00124], according to the underlying physics theory, the other physical bodies emit energy radiations which are a function of their emissivities E which is a fraction of that of a black body for which s = 1 . The various figures below explain the reasons for certain limitations in the poor yields of solar cells, namely: Figure (8b): represents the Blackbody Spectrum as a function of temperature in a high efficiency solar hybrid cell subject to the present invention. - Figure (8c) shows the structure of a lattice (ordered set) with free electrons 8-2 (Fig. 8c), on an ionic metal structure 8-3 (Fig. 8c) in a solar cell high efficiency solar cell object of the present invention. Figure 8d represents the representative Shockley-Queisser boundary curve 8-1 (Figure 8d) in a high efficiency solar hybrid cell subject of the present invention.

Another economic interest is that in this type of cell, the surface of the cell is useful for storing instantaneous / intermittent energy in a storage means close to the production site. The charging cycle 9-1 (Fig. 9a) and discharge 9-2 (Fig. 9a) in a solid electrolyte battery is performed on a thin layer substrate 9-3 (Fig. 9b) of the energy storage consisting of 9-4 cathode (Fig. 9b), electrolyte 9-5 (Fig. 9b), anode 9-6 (Fig. 9b) and the protective layer or encapsulation 9-7 (Fig. 9b) with the particularity Anode and Cathode on a flexible substrate of the thin film diffusion interface (Thin Film). 3D coating and process modeling development: 9-8 (Fig. 9b) and a schematic illustration of Lithium nano titanate micro-batteries without solid electrolyte interface 9-9 (Fig. 9c) (also called SEI or Solid Electrolyte Interface) (SEI) in a high efficiency hybrid solar cell with integrated storage on the substrate of the present invention The hybrid cell is remarkable for its organic interface layer 10-1 (Fig. 10a) and a CIGS absorbent layer 10 -2 (Fig. 10b) and sulphide layer (cadmium sulphide layer) 10-3 (Fig. 10a, 10b) of type n 10-4 (Fig. 10b) on a pn junction and (10c) a schematic illustration Flexible 10-5 coating development (Fig. 10c) and 3D process modeling in a high efficiency hybrid solar cell with integrated storage on the substrate of the present invention. solar cell, Figures (11a) is an illustrative schematic representation of a single-sided solar cell and (1 lb) a central layer illustration n covered at the front and rear by p-type layer and n + and (11c) a schematic illustration of a p-junction front and back cover by SnO2 layer and (11d) a solar panel illustration in an upright chassis environment in a high efficiency hybrid solar cell with built-in storage on the substrate being subjected to the present invention.

Moreover, the operation of sALD and ALD illustrated in FIGS. 12a, 12b, 12c, 12d, 12e, 12f and 12g respectively represent; (12a) a schematic illustration of a cyclic growth ALD and (12b) an illustration of layers in formation and (12c) an illustration of the discretized rectangular domain and (12d) an outline illustration of the function of Potential y and (12e) an illustration of "the surface of the function Potential y" and (12f) an illustration of the boundary conditions and (12g) an illustration of the pace and the profile of the electric potential function y (x, y) by the methods of relaxation and relaxation respectively in a high efficiency solar hybrid cell with integrated storage substrate that is the subject of the present invention. The principle is fully described in the patent application number 00828 filed on, 01 March 2010, Figures 13a, 13b and 13c respectively; (13a) a schematic illustration of a Figurel3-1 organic high layer modeling (Fig. 13a) of a solar cell and (13b) a hybrid cell modeling model with CIGS 13-5 absorbent layer (Fig. 13c) and 13 -2 (Fig. 13c) Thin film battery layer and 13-3 (Fig. 13c) The assembled structure encapsulant in a high efficiency solar hybrid cell with built-in storage on the substrate subject of the present invention.

Figures 14a, 14b and 14c respectively represent (14a) the principle of photo generation in the valence band as a function of doping and (14b) the quantum dot curve of CuInSe2 PV-quantum dots (also called QDs) and (14c) response spectral quantum efficiency of the CIGS absorbing cell alone 14-1 (Figure 14c) and 2-3 (Figure 2b) in a high efficiency solar hybrid cell subject of the present invention. Figure 15 shows an illustration of the path traveled by light in a rear passivation layer 15-1 (Figure 15) (rear dielectric passivation with SiO2 15-2 (Figure 15), Al2 03 / 15-3 (Figure 15). ) and SiNx 15-3 (Fig. 15) and low-n) serving as an internal photon reflector 15-4 (Fig. 15) in a high efficiency solar cell which is the subject of the present invention. A peculiarity of the present invention consists in the implementation of various simple and inexpensive techniques as described below for increasing the efficiency of the cell: a) the insertion of certain metal nanoparticles 16-1 (FIG 16a) embedded in the semiconductor / absorber layer 16-2 (Fig. 16a) causing an increase in the length of the effective light path 16-3 (Fig. 16a) b) Addition of some metallic 16-4 nanoparticles (Fig. excitation of near-field transporters 16-5 (Fig. 16a) c) Semiconductor rear surface ripple 16-6 (Fig. 16a) creating an increase in the length of the effective path 16-7 (Fig. ) Separation of the semiconductor Ag 16-8 particles (Figure 16b) by a thin passivation layer (for example Al2 03) improves the electrical performance of the cell e) Realization of surface coatings in hexagonal photonic structures 16- 9 (Fig. 16c) by dep. t ALD A1203 structures by self-organized-opaline 16-10 (Fig. 16c) (surface passivation) spin-coated surface coating of spherical nanoparticles (SiO2) For example, the simulated current density values in a high efficiency solar hybrid cell given below encourage Optimization of the cell according to the use of Rigorous Coupled Wave Analysis (also called Rigorous Coupled Wave Analysis or RCWA, of Lalann and Reticolo 2D) correspond respectively: 16-11 (Fig. 16e) is the reference curve AM1 .5G (280-1200nm) 16-12 (Fig. 16e) is the reference curve ---- before: plane (not ARC) - rear mirror 16-13 (Fig. 16e) is the reference curve - - front: flat (DARC) - rear: mirror 16-14 (Fig. 16e) is the front reference curve: flat (not ARC) - rear: perfect 16-15 (Fig. 16e) is the reference curve before Diffuser: plane (DARC) -back with a perfect diffuser 16-16 (Fig. 16e) is the reference curve * before: inverted p yramides with SARC - back: mirror 16-17 (Fig. 16th) is the scholar reference curve: plane (DARC) - back: sphere grids.

A major advantage of the present invention is that it allows for the first time a hybridization of organic and inorganic elements with the possibility of growing layers tunable to organic or inorganic materials. A three-step MLD process A, B, and C is shown in Figure (17a) that can be accomplished without using homobifunctional precursors based on: (1) TMA, a homomultifunctional mineral precursor, (2) ethanolamine ( EA), an organic reagent hetero and (3) maleic anhydride (MA) an organic reagent by ring opening (also called ring-opening). The surface reactions proposed during the ABC growth are: (A) S-COOH + Al (CH 3) 3 [17-1 (Fig 17a)] -> S-000-Al (CH 3) 2 + CH 4 17-2 (Fig. 17a)] (B) S-AlCH3 + HO (CH2) 2 -NH2 [17-3 (Fig. 17a)] -> S-Al-O (CH2) 2NH2 + CH4 [17-4 (Fig. 17a)] (C) S-NH2 + C4H203 (MA) [17-5 (Fig. 17a)] S-NH-C (O) CHCHCOOH * [17-6 (Fig. 17a)] The mechanism for creating surface is also illustrated in Figure 17a. In this reaction sequence ABC, TMA reacts with the carboxylic groups in the reaction given by the equation "S-000-Al (CH 3) 2 * + CH 4", to form the species A1CH3 *. Subsequently, the A1CH3 * species preferably react with the end of the EA reactive hydroxyl to form surface species Al-OCH2CH2NH2 * in reaction (B) given by the equation "S-A1-0 (CH2) 2NH2 * + CH4 ". MA then reacts with amine-terminated surface to reform carboxylic groups by a proposed ring-opening reaction (C) given by equation) S-NH-C (O) CHCHCOOH * The reaction sequence in three steps ABC is repeated by exposure to TMA, EA and MA to grow the MLD film to the desired thickness. Figure (17b) illustrates two-step MLD film growth A and B using TMA and glycerol (GL). MLD films in 2 steps TMA and EG are ideal for crosslinking applications. Figure (17c) an illustration of the difference of the FTIR spectrum after TMA and GL exposure hang Alucone AB MLD at 150 ° C showing addition 17-8 (Fig.17c) and subtraction 17-9 (Fig. 17c) of the surface Figure 17d shows a four-step reaction sequence illustration ABCD for a MLD layer growth process of an Alumina-siloxane film using trimethylaluminum (TMA), H2O, dimethylmethoxychlorosilane (DMMCS) and H2O Figure (17e) is a schematic illustration of a two-step reaction sequence for MLD growth at AB of a Lewis film using trimethylaluminum (TMA) and triethylenediamine (TED) Figure (17f) an illustration of density of A1203 and Alucone AB using TMA and EG from XRR analysis. We used different TMA / H20 and TMA / EG cycle numbers (for example the ratio of 3: 1 was used for samples with repetitive sequences of 3 cycles of TMA / H20 and a TMA / EG cycle). . Figure (17g) is a two-step reaction sequence A and B for MLD growth of AB Zincone using diethylzinc (DEZ) and hydroquinone (HQ) in a high efficiency solar hybrid cell with or without built-in storage. substrate subject of the present invention.

Figure 18 is an illustration of the optimal response curve achieved by NREL in a high efficiency solar cell.

Figures 19a and 19b show respectively; (19a) the principle of operation of the piezo nano elements (piezonoyl / piezonotubes) undergoing a 19-1 flexion (Fig.19a) following an exposure caused by a thermal radiation 19-2 (Fig.19a) of a solar cell generating a potential difference Vout (or electric current) 19-3 (Fig.19a) and (19b) the structure of the layer on a multilayer substrate in a high efficiency solar hybrid cell subject of the present invention. FIG. (20a) is a schematic illustration of fields of application of thin-film batteries 20-4 (FIG. 20a) for storage integrated in the solar cell substrate providing a gain in weight and in space on linked applications in the transport 20 -3 (Fig.20a), solar cells integrated in the 20-2 rack (Fig.20a) or portable devices of various and varied use 20-1 (Fig.20a), Figure (20b) compares a lithium battery classical ion 20-5 (Fig.20b) undergoing stresses 20-6 (Fig.20b) during charges and discharges in comparison with nano titanate structures 20-7 (Fig.20b) on a flexible substrate in a cell solar hybrid high efficiency subject of the present invention. Figure (20c) illustrates the structure of a 3D nano-titanate 20-8 (Fig.20c) and shows that a standard lithium anode 20-9 (Fig.20c) slows the charge rate due to its surface. Carbon rounds up whereas a battery with lithium nano-titanate 20-10 (Fig.20c) offers more than 30 times more surface with sharper angles bringing a greater number of charge and discharge. Figure (20d) is a comparison of the thin film construction of a conventional lithium-ion battery 20-11 (Fig.20d) with a construction with nano titanate structures 20-12 (Fig.20d) on a flexible substrate in a hybrid high efficiency solar cell which is the subject of the present invention. Figure; (21a) is an illustration of photovoltaic solar cell 21-1 (Fig. 21a) with a thin-film storage battery integrated in the flexible film 21-3 substrate 21-2 (Fig. 21a) (Fig. 21a). ) with the CIGS 21-4 absorbent layer (Fig. 21a) on the substrate face 21-2 (Fig. 21a) with the battery 21-5 (Fig. 21a) integrated on the back of the solar cell. And Figure (21b) is an illustration of the steps of the multilayer nano titanate solution on a flexible substrate in a high efficiency solar hybrid cell subject of the present invention. Figures 22a, 22b and 22c show respectively; (22a) a double-sided solar cell illustration with its front contact metallization 22-1 (Fig. 22a) and 22-2 (Fig. 22a) rear contacts in comparison to a single-sided cell 22-3 (Fig. 22a) and (22b).

The response curve as well as the spectral responses of cell 22-8 (Fig. 22c) show the responses for a bifacial cell SiO2 + SiNx 22-4 (Fig. 22c), bifacial without SiO2 22-7 (Fig. 22c) prolonged entrapment 22-6 (Fig. 22c) and back-to-back diffusion 22-4 (Fig. 22c) in a high efficiency solar hybrid cell of the present invention.

Fig. 23 shows a solar cell illustration with MLD 23-1 growth photonic trap (Fig. 23) on a substrate 23-2 (Fig. 23) for increased efficiency in a high efficiency solar hybrid cell of the present invention.

Figure (24a) is a double-sided flexible solar cell illustration with a 24-5 first face (Figure 24a) coated with the absorbent layer 24-6 (Figure 24a) and its integrated energy storage system on the back. 24-7 (Fig. 24a) and Fig. 24b is an illustration of a flexible solar cell with its energy storage system 24-5 (Fig. 24b) built into substrate 24-1 (Fig. 24b). ) of the two-sided cell 24-3 (Fig. 24b) for an increase in efficiency in a high efficiency solar hybrid cell subject of the present invention.

Figure 25 shows an illustration of charge and discharge cycle for a lithium-ion battery. FIGS. 26a, 26b and 26c show the degradation of the discharge as a function of the number of cycles for a LTO-LMO (Transition Metal Oxide) type battery with LTO-LLTO for a composite conductor forming the subject of the present invention. FIGS. 27b represent the charge capacity as a function of the number of cycles for a LTO-Fe203 type LTO-LMO (Transition Metal Oxide) battery for a composite conductor subject of the present invention. For the production of the electrolyte, the embodiment is given by Figure 28 which is a state synthesis model of the LTO-TiO2 type LTO-LMO battery for a composite conductor, including Ti-butoxide (Figure 28-1) in a mixture of materials (Figure 28-2). ) of citric acid and molten salt LiNO 3 (LiOH-H 2 O 2, Li 2 O 2, Figure 28-3) heated at 400 ° C for 3 h and then cooled to room temperature (state a) produces TiO 2 (Figure 28-10) , a salt in the initial state (Figure 28-12) and nanoparticu Li4Ti5012 (Figure 2813) and amorphous carbon (Figure 28-15) and molten solid salt (Figure 28-15) (state b). Nanocrystals grains Li4Ti5012 (Figure 28-20) and TiO2 nanocrystals grains (Figure 28-24) are covered with a thin layer of amorphous carbon (Figure 28-21) and interfacial boundary grains (Figure 28-22). ) embedded in a carbon envelope (Figure 28-23) Figure 29a shows the load capacity as a function of cycle number for a LTO-LMO type LTO-LTO type LTO-LMO (C) battery Figure 29b is an illustration of assemblies of the electrodes for a bipolar battery by an ALD atomic deposition type construction and the molecular deposition of the "MLD" and layer-by-layer growth layers of a composite conductor of the present invention. divisible and formable segmented nano-laminated hybrid / inorganic polymer for the integrable or embedded batteries of the present invention Figure 29c is a layer-by-layer illustration of the electrodes by the molecular deposition of the "MLD" and layer-by-layer growth layers of nano-laminated hybrid / inorganic polymer for the integrable or embedded batteries that are the subject of the present invention. Concerning electrolytes: key element of the batteries of the present application (FIG. ) - Operating temperatures - 20 ° C to + 110 ° C! Polymer electrolytes used are of the type: solvent-free polymer electrolytes. - Compatible with a temperature of 110 ° C - Incompatible with temperatures of - 20 ° C - Commercial liquid electrolytes: 1M LiPF6 - A good electrolyte "strong ionic dissociation and high mobility - The majority use ethylene carbonate: EC - Form with LiPF6 an SEI for cycling lithium graphite LiC6 - Strong dielectric constant E = 90 <z> promotes dissociation of ions - But solid up to 40 ° C, high viscosity beyond C * decreases mobility of ions - Compromise <=> combine EC with liquid solvents and low viscosity but low - dimethyl carbonate DMC, Eb = 90 ° C, Tf - 4 ° C - DEC diethyl carbonate, Eb = 126-128 ° C, Tf = - 43 ° C - Ethyl methyl carbonate EMC, Eb = 107, Tf = - 14 ° C Note that to obtain good conductivities at -20 to + 110 ° C (Figure 30b) - Use of ionic liquids: - This solution has the following major disadvantages: - High cost , high viscosities - Electrochemical performance (reaction to electrodes) => unsatisfactory - High boiling point solvent eg DMSO, PC, Sulfolane - propylene carbonate PC: E - 69 - Eb = 242 ° C, Tf = - 48,8 ° C - PC not used in Li-ion battery => exfoliates Li C6 - No incompatibilities neither with LTO nor with LFP - Disadvantages: viscosity at low temperature - Mixes with DEC - To increase 6 we will use complexing of Li + - Selected salt: LiTFSI (CF3S02) 2N -, Li + - LiPF6 unstable above 55-60 ° C - stable LiTFSI up to more than 200 ° C. Macroporous separator or gelled polymer (FIG. 30C) - Regardless of the liquid electrolyte: - A dense polymer separator or porous must be used - to avoid a short circuit by direct contact. 35 - Macroporous separator: - Benchmark with Celgard® separators - Good mechanical properties - Quid at 110 ° C - High conductivity losses (factor 10) versus liquid electrolyte 40 - Compatibility with thin-film planar batteries - Gelled dense membrane liquid electrolyte: - Crosslinked solvent polymer film - A solution which has the following advantages: 45 - Excellent redox stability - Good complementarity with LiTFSI and PC - Aqueous process Reinforcement of separators (Figure 30d) 50 - In order to preserve the performance of the battery, it is advisable to: - Decrease the contribution of the electrolyte to the Internal Resistance - Thinner film because mechanical properties much stronger - Increase of the safety - Decrease the material cost because less salt and less solvent - Reinforcement with NanoCrystallineCellulose NCC: - Percole at - 5-6% by weight - Very high conservation modules: - No harmful Despite the Nano dimension: LC 50: - NCC has recently been tested in 5V LiC6 / LNMO batteries and has a 30% energy gain.

This type of solar cells with or without substrate-integrated storage is invented and designed for continuous manufacturing on a high capacity production line and is well suited for deposits in a Roll-to-Roll process as described in the application. Patent 10,00828 filed March 1, 2010 and 09 01503 filed March 27, 2009 (27-03-09) and integrated in the present application in their entirety by referencing. It is important to note that the present invention is more clearly evidenced by the description of the particular methods and embodiments as described. Nevertheless, the object of the invention is not limited to these methods or to these embodiments described because other methods or other embodiments of the invention are possible and can easily be performed by extrapolation. In particular by manufacturers who manufacture inorganic or organic thin films, semiconductors and / or micro components with or without optical parts.

Claims (10)

CLAIMS1) A solar energy storage system consisting of at least one anode, at least one cathode using nanostructured lithium titanate materials (lithium titanate or nanotitanate) or titanate and sodium mixtures , in solid form and an electrolyte on a substrate that can be integrated into the solar cell (or on the back of the solar cell). 2) A solar energy storage system according to claim 1 wherein the electrolyte is solid without SEI (Solid Electrolyte Interface). 3) A solar energy storage system according to claim 1 wherein a separator interposed between said negative electrode, and said positive electrode wherein a porous film containing lithium nanotitanate alone, and having insulating properties, is formed. on the surface of said negative electrode integrable with the solar cell (or on the back of the solar cell substrate). 4) A solar energy storage system according to claim 1 wherein the electrolyte is gelled polymer or not on a transferable substrate, integrable to the cell or the back of the support of the solar cell. 5) A solar energy storage system according to claim 1 wherein the realization by the molecular deposition of the layers "MLD" and growth layer by layer hybrid polymer / inorganic laminate nano for batteries ensures the integration to the cell or the back of the solar cell support. 6) A solar, wind or marine energy generator comprising an energy storage system according to one of claims 1 to 5, transferable to the back of a solar panel or substrate, juxtaposable, assembled or embedded. 7) A solar, wind or marine energy generator comprising an energy storage system according to one of claims 1 to 5 for smoothing or storing energy. 8) Onboard autonomous sensors comprising an energy storage system according to one of claims 1 to 5, capable of wireless communication under industrial conditions and temperatures -20 ° C to 100 ° C. 9) A roadway comprising a storage system according to one of claims 1 to 5, with or without signaling with smart intelligent management sensors with display or signaling, comprising; at. a plurality of solar power generation devices on the ground; b. a plurality of solar energy storage devices on the ground; c. a plurality of LEDS devices for display or signaling on the ground; 10) An assembly of several systems according to one of claims 1 to 5, assembled for a given configuration by piece or by segment offering the ease of maintenance and repair by replacing the defective segments used in storage and transport applications. sharable and cutable energy.