ELECTRICALLY CONDUCTIVE ADHESIVE

Abstract

An electrically conductive adhesive composition, free of metals and metal salts, includes an adhesive polymer component selected from polyethylene-vinyl acetate, polyolefin elastomers, polyvinyl butyral, poly(acrylic acid), polyacrylates and poly(methyl methacrylate) from 5% to 40% by weight, an electrically conductive component including acetylene or carbon black nanoparticles, carbon nanotubes, and flakes or plates of graphene or graphene derivatives from 60% to 95% by weight, percentages by weight of the adhesive polymer component and electrically conductive component, the electrically conductive component consisting of acetylene or carbon black nanoparticles from 15% to 45% by weight, carbon nanotubes from 5% to 25% by weight, and flakes or plates of graphene or graphene derivatives from 35% to 70% by weight, percentages by weight of the electrically conductive component, and a solvent compatible with the adhesive polymer component from 50% to 90% by weight of the electrically conductive adhesive composition.

Claims

1. An electrically conductive adhesive composition, free of metals and metal salts, comprising: an adhesive polymer component selected from the group consisting of polyethylene-vinyl acetate, polyolefin elastomers, polyvinyl butyral, poly(acrylic acid), polyacrylates and poly(methyl methacrylate) in quantities ranging from 5% to 40% by weight, an electrically conductive component comprising acetylene or carbon black nanoparticles, carbon nanotubes and flakes or plates of graphene or graphene derivatives in quantities ranging from 60a to 95% by weight, percentages by weight being referred to 100 parts by weight of the adhesive polymer component and electrically conductive component, wherein said electrically conductive component consists of: acetylene or carbon black nanoparticles from 15% to 45% by weight, carbon nanotubes from 5% to 25% by weight, and flakes or plates of graphene or graphene derivatives from 35% to 70% by weight, the percentages by weight being referred to 100 parts by weight of said electrically conductive component, and a solvent compatible with the adhesive polymer component in quantities ranging from 50% to 90% by weight referred to 100 parts of the electrically conductive adhesive composition consisting of the adhesive polymer component, electrically conductive component and solvent.

2. The electrically conductive adhesive composition of claim 1, wherein said graphene derivatives are reduced graphene oxide.

3. The electrically conductive adhesive composition claim 1, wherein said electrically conductive component consists of: acetylene black nanoparticles from 35% to 45% by weight, carbon nanotubes from 10% to 20% by weight, and graphene flakes from 35% to 45% by weight, the percentages by weight being referred to 100 parts by weight of said electrically conductive component.

4. The electrically conductive adhesive composition of claim 1, comprising from 20% to 30% by weight of the adhesive polymer component and from 70% to 80% by weight of the electrically conductive component, the percentages by weight being referred to 100 parts by weight of the adhesive polymer component and electrically conductive component.

5. The electrically conductive adhesive composition of claim 1, in the form of a curable paste, wherein said solvent is selected from the group consisting of chlorobenzene, xylene, chloroform, acetic acid, cyclohexanone, butanol, dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, nitroethane, toluene, ethyl acetate, chlorobenzene, cyclohexanone, isopranol, ethanol, water and mixtures thereof.

6. The electrically conductive adhesive composition of claim 1, wherein the adhesive polymer component is selected from polyethylene-vinyl acetate and polyolefin elastomers and the solvent is selected from the group consisting of chlorobenzene, xylene, chloroform and mixtures thereof.

7. The electrically conductive adhesive composition of claim 1, wherein the adhesive polymer component is polyvinyl butyral and the solvent is selected from the group consisting of acetic acid, butanol, cyclohexanone, dimethylsulfoxide, dimethylformamide, N-methylpyrrolidone and mixtures thereof.

8. The electrically conductive adhesive composition of claim 1, wherein the adhesive polymer component is polymethyl methacrylate and the solvent is selected from the group consisting of ethyl acetate, nitroethane, toluene, chloroform, chlorobenzene, cyclohexanone and mixtures thereof.

9. The electrically conductive adhesive composition of claim 1, wherein the adhesive polymer component is poly(acrylic acid) and the solvent is selected from isopropyl alcohol, ethanol and mixtures thereof.

10. The electrically conductive adhesive composition of claim 1, wherein the solvent has a vapor pressure higher than 0.8 kPa.

11. A process for preparing an electrically conductive adhesive composition, free of metals and metal salts, comprising: an adhesive polymer component selected from the group consisting of polyethylene-vinyl acetate, polyolefin elastomers, polyvinyl butyral, poly(acrylic acid), polyacrylates and poly(methyl methacrylate) in quantities ranging from 5% to 40% by weight, an electrically conductive component comprising acetylene or carbon black nanoparticles, carbon nanotubes and flakes or plates of graphene or graphene derivatives in quantities ranging from 60% to 95% by weight, percentages by weight being referred to 100 parts by weight of the adhesive polymer component and electrically conductive component, wherein said electrically conductive component consists of: acetylene or carbon black nanoparticles from 15% to 45% by weight, carbon nanotubes from 5% to 25% by weight, and flakes or plates of graphene or graphene derivatives from 35% to 70% by weight, the percentages by weight being referred to 100 parts by weight of said electrically conductive component, and a solvent compatible with the adhesive polymer component in quantities ranging from 50% to 90% by weight referred to 100 parts of the electrically conductive adhesive composition consisting of the adhesive polymer component, electrically conductive component and solvent, the process comprising: melting said adhesive polymer component and dissolving or dispersing the adhesive polymer component in the solvent compatible with the adhesive polymer component, and mixing the electrically conductive component with the adhesive polymer component in said solvent at a temperature between 40° C. and 60° C. to obtain a paste.

12. A method for producing silicon-based heterojunction solar cells comprising a cooper (Cu) ribbon and a silver (Ag) busbar, said method comprising applying the electrically conductive adhesive composition of claim 1 for connecting said copper (Cu) ribbon to said silver (Ag) busbar at temperatures lower than 100° C.

13. A method for producing carbon-based back-electrodes in perovskite solar cells comprising a cooper (Cu) ribbon and a silver (Ag) busbar, wherein the electrically conductive adhesive composition of claim 1 is applied for connecting said copper (Cu) ribbon to said silver (Ag) busbar at a temperature lower than 100° C., including room temperature.

14. A method for producing a mechanical and electrical serial type connection of electrodes in batteries, supercapacitors or multi-component electronic systems, wherein the electrically conductive adhesive composition of claim 1 is applied to provide said mechanical and electrical serial type connection.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0020] In the accompanying drawings:

[0021] FIG. 1 illustrates images obtained with a scanning electron microscope of an adhesive composition according to the invention (C-EVA-ECA-4) with increasing magnification from panel a) to panel d);

[0022] FIG. 2 illustrates electrical resistance diagrams as a function of the tensile deformation for different adhesive compositions:

[0023] FIG. 2a, normalized resistance as a function of tensile deformation for adhesives C-EVA-ECA-4 and C-EVA-ECA-5 (according to the invention) compared with a commercial Ag-based composition (Henkel) and with comparative compositions and C-EVA-ECA-3;

[0024] FIG. 2b, normalized resistance as a function of tensile deformation for the C-EVA-ECA-3 (comparative) adhesive with the abscissa scale extended up to 335% tensile deformation (fracture point);

[0025] FIG. 3 illustrates the results of electrical resistance as a function of temperature for the adhesive compositions of FIG. 2;

[0026] FIG. 4 is a schematic representation of the layered structure of a HJT-Si solar cell;

[0027] FIG. 5 is a schematic representation of a ribbon/busbar connection in a HJT/Si solar cell;

[0028] FIG. 6 is a diagram illustrating the electrical contact resistance, as a function of the current applied for a sample of commercial silver-based adhesive (Henkel) and for the C-EVA-ECA-5 composition, according to the invention;

[0029] FIG. 7 is an image of the cross section of a PSC having a back-electrode based on the adhesive according to the invention, and

[0030] FIG. 8 is a photograph of the film deposited by doctor blading using the C-EVA-ECA-4 composition (on the left) compared with the material obtained in the comparative example 9 (on the right).

DETAILED DESCRIPTION OF THE INVENTION

[0031] A first aspect of the invention relates to a metal-free ECA composition, in the form of a curable paste or ink, comprising an adhesive polymer component and an electrically conductive carbon-based component, characterized by components having different topological morphologies, in accordance with the main claim.

[0032] In a preferred embodiment, the ECA composition is a paste which is processable at low temperature, lower than 100° C. including room temperature, where the term “processable” indicates the possibility of application by means of doctor blading or spin coating.

[0033] As the adhesive polymer component, a polymer may be used, which is known as a solar cell encapsulant. The polymer component can be selected from polyethylene-vinyl acetate (EVA), polyolefin elastomers (POEs), polyvinyl butyral (PVB), poly(acrylic acid) (PAA), (methyl methacrylate)(PMMA) and polyacrylates or commercial polyacrylate mixtures (e.g. Hydrolac 610L, polyacrylate water dispersion).

[0034] The polymer component is preferably an EVA copolymer, obtained by the copolymerization of ethylene with vinyl acetate, with a vinyl acetate content of 5 to 50% by weight, preferably 15 to 45% by weight. Commercial copolymers such as for example ELVAX® from DuPont, whose commercial grades have a vinyl acetate content generally of 9 to 40% by weight, can be used.

[0035] The POEs used within the scope of the invention comprise ethylene copolymers with various monomers such as propylene, butene, hexane and octene. In practice, ethylene-octene and ethylene-butene are commercial products that exhibit excellent elasticity, dielectric properties and easy processability. POEs can be combined with different polymers, including polyethylene, polypropylene and polyamide in order to modulate the material properties. Examples of commercial POEs comprise PHOTOCAP® 35521P HLT (STR), ENGAGE™ (Dow Chemical) and TAFMER™ (Mitsui Chemicals).

[0036] EVA and POE polymers can be specifically optimized with additives (for example metal peroxides) so as to adjust their melting point and/or their cross-linking temperature.

[0037] Adhesion of EVA and POE polymers to silicon and metal (including Ag and Cu) surfaces, mechanical elasticity and excellent mechanical and thermal fatigue resistance, are well known in the art and make these materials a technological standard as encapsulants in the PV field.

[0038] The carbon-based electro-conductive component is a mixture comprising at least 0D acetylene black (or carbon black)nanoparticles, 1D carbon nanotubes and 2D flakes or plates (platelets) of graphene or graphene derivatives. Graphene flakes are preferably obtained by means of the wet-jet milling exfoliation process in solvents described in WO2017089987 to the Applicant. Graphene derivatives comprise reduced graphene oxide.

[0039] The invention is based on the experimental acknowledgement that the use in the adhesive composition object of the invention of a mixture of the three above mentioned carbon-based fillers involves a substantial reduction in volumetric resistivity, reaching values which allow the use of the adhesive composition instead of conventional metal filler-based electrically conductive adhesive compositions.

[0040] According to the invention, the electro-conductive component comprises: [0041] acetylene black or carbon black particles from 15 to 45% by weight, preferably from 35 to 45% by weight, [0042] carbon nanotubes from 5 to 25% by weight, preferably from 10% to 20% by weight, [0043] flakes or plates of graphene or graphene derivatives from 35 to 70% by weight, preferably graphene flakes from 35 to 45% by weight, the above mentioned percentages being referred to 100 parts by weight of the conductive component.

[0044] The combination of carbon nanomaterials with different topological morphologies significantly increases electrical performance compared to the use of single carbon nanomaterials; thus, the electrical conductivity of the ECAs object of the invention can be adjusted by varying the weight ratio of the carbon nanomaterials.

[0045] Although the explanation of the mechanism is not binding for the scope of the invention, flakes of graphene/graphene derivatives are believed to provide excellent conductivity as far as flakes of graphene/graphene derivatives are concerned. Acetylene black nanoparticles fill the voids between the flakes of graphene/graphene derivatives that are electrically connected. Carbon nanotubes create highly conductive pathways that connect compact conductive domains formed by acetylene black nanoparticles and graphene flakes.

[0046] In the paste adhesive, the percentage by weight of the polymer component and of the conductive component as compared to the solid content can vary according to the final use of the ECAs, in accordance with the following data: [0047] polymer adhesive component 5-40% by weight, [0048] electrically conductive component 60-95% by weight.

[0049] Experimentally, the mechanical properties, such as tensile strength and elongation at break, improve as the percentage by weight of the adhesive component increases. However, an excess content of the adhesive component results in low electrical conductivity (conductivity <10 S m.sup.−1). The preferred content of adhesive component for the formulation of a paste with high electrical conductivity ranges from 20 to 30% by weight, more preferably 25% by weight. This value results in an excellent electrical connection of carbon nanomaterials.

[0050] With reference to mechanical properties, the specific mechanical properties of flakes of graphene/graphene derivatives and carbon nanotubes allow the ECA to be mechanically strengthened. In addition, the excellent thermal conductivity of graphene/graphene derivatives and carbon nanotubes allows effective heat dissipation, improving the reliability of ECAs in electrical and thermal durability tests. In particular, the synergistic combination of nanomaterials allows to obtain greater electrical performance (volumetric resistivity lower than 10.sup.−1 Ωcm) than that obtained with the individual carbon components (volumetric resistivity greater than 10 Ωcm for graphene- and acetylene black-based ECAs; volumetric resistivity >10.sup.−1 cm for single-walled carbon nanotubes). The compositions object of the invention thus allow to avoid the use of precious metals such as Ag and Au as conductive material, reducing the overall cost of the ECA.

[0051] Another aspect of the invention relates to the process for the preparation of the above described ECAs comprising the following steps: [0052] i) providing an adhesive component by melting, at a temperature preferably in the range from 120 to 180° C., a polymer selected from EVA, POE, PVB, PAA, PMMA, polyacrylates and dissolving or dispersing said polymer (or mixture of polymers) in a compatible solvent, preferably selected from chlorobenzene, chloroform, xylene, isopranol and their mixtures; [0053] ii) providing an electrically conductive component by mixing the powders of carbon nanomaterials comprising acetylene or carbon black nanoparticles, carbon nanotubes and flakes or plates of graphene or graphene derivatives, in the above mentioned proportions; [0054] iii) homogeneously mixing the adhesive and electrically conductive components by mechanical stirring at a temperature ranging from 40 to 60° C., to obtain a paste (slurry); [0055] iv) depositing the obtained paste, by means of process techniques in solution, optionally compatible with low temperatures (preferably <100° C., including room temperature), thus obtaining the ECA composition.

[0056] “Compatible solvent” herein means a solvent capable of dissolving or dispersing the polymer component, without causing aggregation phenomena.

[0057] In step i), the adhesive component is advantageously formulated in highly volatile organic solvents (i.e. having a high vapor pressure, preferably greater than about 0.8 kPa, and preferably with low process temperatures (<100° C., including room temperature (25° C.)), particularly chlorobenzene, xylene and isopranol, whose vapor pressures at 25° C. are: ˜1.6 kPa for chlorobenzene, 1.1 kPa for m-xylene, ˜0.88 for o-xylene, ˜1.16 kPa for p-xylene, 5.8 kPa for isopranol.

[0058] Further solvents that may be used within the scope of the invention are reported in the claims and in the following experimental section.

[0059] The solvents cited are also intended to include water solutions of such solvents, when compatible with the polymer component. Water can be used as a solvent or dispersant, or as a component of a solvent mixture, for example with polymer alcohols having sufficient water solubility. Such polymers mainly belong to the class of acrylates.

[0060] The amount of solvent in the paste adhesive generally is comprised between 50 and 90% by weight referred to 100 parts by weight of the ECA (solvent included).

[0061] Thanks to the use of highly volatile solvents in the preparation process, the herein described ECAs can be processed (i.e. deposited/applied) and cured at low temperature (<100° C.), including room temperature (25° C.). This avoids the high temperature treatment of pastes which is a pre-requisite for the applicability of traditional welding (welding temperature greater than 180° C. for Sn—Pb welding) and for commercially available ECA pastes (curing temperature typically >100° C.).

[0062] The ECAs object of the invention can be advantageously applied to thermally sensitive substrates including various plastic materials and semiconductors of solar cells.

[0063] It is also an object of the invention the use of the ECAs object of the invention for the connection of Cu ribbon, conventionally coated with Sn, to Ag busbars in HTJ-Si, whose ribbon application process is not compatible with traditional welding.

[0064] In these applications, mechanical adhesion and the quality of the electrical contact between the Ag busbar/ECA/Cu ribbon was assessed before and after mechanical, thermal and electrical stress, based on standard resistance tests reported in the IS/IEC 61730.2 and IEC 61215 standards.

[0065] The performance of the ECAs object of the invention for the process for applying the conductive ribbon in HJT-Si cells was comparable to that obtained by conventional Ag-filled ECAs. Another object of the invention is the use of the ECA pastes described herein for the production of carbon-based back-electrodes with a surface resistance of less than 200 Ωsq.sup.−1 for a thickness of less than 10 μm. The ECAs were deposited on PSC perovskite-based films using liquid-phase process techniques (e.g. spin-coating) at room temperature.

[0066] Multiple deposition cycles were effective for the production of back-electrodes with a surface resistance of less than 500 Ωsq.sup.−1, exceeding the values exhibited by TCO-based back-electrodes (used for example in HJT-Si or double-side PSC technologies).

Example 1: ECA with EVA Adhesive Component or Elastomer Polyolefines

[0067] In the tests that follow and in the following examples, the following materials were used for the conductive component: [0068] acetylene black nanoparticles (Sigma Aldrich), particle size: 24 nm, [0069] carbon nanotubes purchased from Cheap Tubes (single-walled carbon tubes, outer diameter: 1-4 nm, inner diameter: 0.8-1.6 nm, length: 5-30 μm); [0070] graphene flake powder isolated by drying a flake dispersion obtained by means of graphite wet-jet milling exfoliation in N-methyl-2-pyrrolidone in accordance with WO2017/089987; [0071] commercial graphene nanoplates purchased from Sigma Aldrich and reduced graphene oxide powders (Sigma Aldrich).

[0072] In example 1, the following polymers were used: [0073] EVA: commercial product ELVAX®, Du Pont (40% by weight of vinyl acetate) elastomer polyolefins: commercial product PHOTOCAP® 35521P HLT, STR.

[0074] In all the prepared samples, a percentage of 25% by weight of the adhesive component was used. The adhesive components were previously melted at 150° C. for EVA or 180° C. for polyolefin and dissolved in chlorobenzene or in a mixture of xylene isomers having the above mentioned vapor pressures; 6 mL of solvent were used for 1 g of solid polymer component

[0075] The exemplified ECA compositions have a content of polymer component of 25% by weight referred to 100 parts of polymer component and conductive component.

[0076] The ECAs were obtained by depositing the corresponding paste (slurry) by means of a doctor blade and subsequent drying of such pastes at 50° C. for 10 minutes. The thickness of the resulting ECAs is between 25 and 45 μm depending on the ECA formulation, measured by means of an optical profilometer.

[0077] Table 1 shows the percentages by weight of each carbon nanomaterial, the average volumetric resistivity and the error (standard deviation) for each ECA tested. The EVA- and POE-based ECAs are respectively called C-EVA-ECA-X and C-polyolefin-ECA-X, where X indicates different compositions of electro-conductive component and/or solvent.

[0078] The compositions indicated with an asterisk are shown by way of comparison.

TABLE-US-00001 TABLE 1 Composition of the electro-conductive component and volumetric resistivity for representative ECA samples (percentage by weight of the adhesive component = 25%). Reduced Average Acetylene Carbon Graphene Graphene graphene volumetric black nanotubes flakes nanoplates oxide resistivity Error ECA (% wt) (% wt) (% wt) (% wt) (% wt) Solvent (Ω cm) (Ω cm) *C-EVA- 100 0 0 0 0 Chlorobenzene 5.143 1.061 ECA-1 *C-EVA- 0 0 100 0 0 Chlorobenzene 8.525 12.838 ECA-2 *C-EVA- 20 0 80 0 0 Chlorobenzene 0.794 0.090 ECA-3 C-EVA- 42.5 15 42.5 0 0 Chlorobenzene 0.068 0.007 ECA-4 C-EVA- 42.5 15 42.5 0 0 Xylene 0.146 0.038 ECA-4B C-polyolefin- 42.5 15 42.5 0 0 Chlorobenzene 1.397 0.504 ECA-4 C-EVA- 17 15 68 0 0 Chlorobenzene 0.098 0.015 ECA-5 C-EVA- 17 15 68 0 0 Xylene 0.379 0.046 ECA-5B C-polyolefin- 17 15 68 0 0 Chlorobenzene 1.232 0.262 ECA-5 C-EVA- 42.5 15 0 42.5 0 Chlorobenzene 0.369 0.061 ECA-6 C-EVA- 17 15 0 68 0 Chlorobenzene 0.129 0.013 ECA-7 C-EVA- 42.5 15 0 0 42.5 Chlorobenzene 0.268 0.039 ECA-8 C-EVA- 17 15 0 0 68 Chlorobenzene 0.191 0.050 ECA-9 *comparative

[0079] The combination of acetylene black, carbon nanotubes and graphene flakes (produced by wet-jet milling) in the electro-conductive component, in the compositions according to the invention, is effective in reducing the volumetric resistivity to values lower than 10.sup.−1 Ωcm for the preferred compositions C-ECA-4 and C-ECA-5 which use EVA polymer and a chlorobenzene solvent as compared to the corresponding comparative compositions.

[0080] The volumetric resistivity of C-EVA-ECA-4 is comparable with that measured for commercially available Ag-based ECAs from Henkel (i.e. 0.055±0.007 Ωcm).

[0081] The polyolefin-based ECAs as the adhesive component show greater volumetric resistivity compared to EVA-based ones having the same composition of the electrically conductive component; however, the experimental tests have also shown for these compositions a reduction in resistivity compared to corresponding compositions having a single carbon-filler morphology or including two filler morphologies.

[0082] Perspectively, the optimization of the C-polyolefin-ECA composition can further reduce the volume resistivities obtained.

[0083] The experimental data confirm the use of chlorobenzene as the preferred solvent for the exemplified polymer components.

[0084] SEM analysis (FIG. 1) shows that the C-ECA-EVA-4 composition, which is the sample with the best electrical conductivity among those reported, consists of a lattice structure of graphene flakes filled with acetylene black nanoparticles. The conductive lattice structure is electrically connected by filling the voids among the highly conductive graphene flakes. Carbon nanotubes are not resolved due to their nanometric size. However, they are expected to provide electrical connections among multiple carbon nanomaterials. The EVA polymer acts as a bonding component to mechanically bond the entire film structure.

Example 2: Product Reliability

[0085] In order to test the reliability of the C-EVA-ECAs object of the invention, their electrical resistances were measured depending on the deformation applied. The results shown in FIG. 2 indicate that the C-EVA-ECA compositions have a behavior similar to that of commercially available Ag-based ECAs (Henkel), upon a tensile deformation of up to 20%. At tensile deformation values greater than 20%, the C-EVA-ECA compositions with greater percentage by weight of graphene (C-EVA-ECA-5) show an optimal retention of the initial electrical resistance, which is also greater than that obtained for Ag-based ECAs.

[0086] The reliability of C-EVA-ECAs was also tested by thermal stress. FIG. 3 illustrates the electrical resistances of the same compositions illustrated in FIG. 2 as a function of temperature. The temperature is varied from 20° C. (room temperature) to 250° C. For each resistance sampling point as a function of temperature, the temperature is kept constant for 5 minutes. The increase time between different temperatures tested is 5 minutes. After reaching 250° C., the temperature is allowed to cool down to room temperature. The results indicate that the C-EVA-ECA compositions maintain their initial electrical resistance up to a temperature of 120° C. Above this temperature, the electrical resistance decreases as the temperature increases. This effect should be deemed caused by the cross-linking of EVA at temperatures greater than 160° C. In fact, the changes in electrical resistance are then partially maintained when the samples are cooled to room temperature. The standard lamination temperature of PV modules (between 145 and 160° C.) improves the final electrical performance.

[0087] Overall, the C-EVA-ECA compositions show reliable electrical performance under mechanical and thermal stress which can also reach values greater than those of the practical operating condition of C-EVA-ECA in electrical devices, including solar cells.

Example 3: Validation of HJT-Si Solar Cells

[0088] The C-EVA-ECA-5 composition was validated as a composition suitable for the application process of metal ribbons to metal contact grids (ribbon tabbing) for the serial connection of HJT-Si solar cells. Tests were carried out with the use of C-EVA-ECA-5 due to its excellent mechanical and electrical properties (see examples 1-3). FIG. 4 shows the HJT-Si structure used for the tests. The table alongside the figure also shows the thicknesses of the layers of the HUT-Si structure.

[0089] The metal contact grids are deposited by silkscreen printing on the front and rear of the HJT-Si. Such grids consist of rectangular strips (busbars) perpendicular to “super-thin” grid fingers. Sn-coated Cu strips are used as ribbons. These ribbons are connected to the busbar by C-EVA-ECA-5. FIG. 5 illustrates a diagram of the ribbon/busbar connection by means of the aforementioned adhesive composition.

[0090] The quality of the electrical contact is assessed by measuring the electrical resistance between the non-contacting part of the busbar and the floating part of the ribbon (contact resistance). The busbar/ribbon contact area is 0.3 cm×1 cm. The contact resistance obtained using C-EVA-ECA-5 is 0.219Ω. This value is better than that obtained using commercially available Ag-based ECAs (0.295Ω). In order to determine the mechanical and electrical reliability of the contact, the same measurement is performed after encapsulation of the busbar/ribbon contact area with EVA. Following traditional encapsulation with EVA, the contact resistance obtained with C-EVA-ECA-5 is 0.293Ω. Again, this value is lower than that of the contact resistance measured using Ag-based ECAs (0.351Ω).

[0091] Busbar/ribbon contact resistance tests are carried out by measuring the contact resistance at different applied currents.

[0092] FIG. 6 illustrates the normalized contact resistances obtained using Ag-based ECAs and C-EVA-ECA-5 as a function of the applied current, starting from 0.01 A and increasing up to 1.5 A. The insert illustrates the results obtained after two hours at an applied current of 1.5 A, starting from such applied current and reducing the applied current to 0.01 A.

[0093] It should be noted that the maximum normalized applied current on the contact area is comparable or greater than those used for the hot-spot resistance test of solar cells reported in IEC 61730.2 (MQT 09) (minimum current tested 1.25 times greater than the short-circuit current of the entire solar cells). The purpose of this test is to determine the module's capability of withstanding hot-spot heating effects, i.e. melting of solder or encapsulation deterioration. This defect could be caused by defective cells, misaligned cells, shadowing or fouling. Since the absolute temperature and the relative performance losses are not criteria for this test, the most severe hot-spot conditions are used (corresponding to a minimum current 1.25 times greater than that of the short-circuit current of the entire solar cells), to ensure the reliability of the project. In fact, hot-spot heating takes place in a module when its operating current exceeds the reduced short-circuit current of a shaded or defective cell or groups of cells. When this condition occurs, the cell (or group of cells) affected thereby is forced with reverse polarization and must dissipate energy, causing overheating. If the energy dissipation is sufficiently high or sufficiently localized, the cell with reverse polarization can overheat, resulting, depending on the technology, in melting of solder, deterioration of the encapsulant of the front and/or back cover, breakage of the substrate superstrate and/or glass cover. Herein, ideal ECAs must show reliable mechanical and electrical contact by providing both thermal fatigue resistance and suitable heat dissipation. The results of FIG. 6 indicate that, similarly to the contact resistance obtained using Ag-based ECAs, the contact resistance obtained using C-EVA-ECA according to the invention has excellent holding as the applied current increases. After two hours, at an applied current of 1.5 A, the contact resistance obtained using Ag-based ECAs increases by about 20%, while the contact resistance obtained using C-EVA-ECA-5 is maintained. After reducing again the applied current to 0.01 A, both contact resistances show values similar to those measured at the beginning of the test.

[0094] The contact reliability in withstanding thermal variance, fatigue and other stresses caused by temperature changes is determined by measuring the contact resistance at representative temperatures. In more detail, the temperature is varied from 20° C. (room) to 100° C. After reaching 250° C., the temperature is allowed to drop to room temperature. The contact resistance is therefore measured at the temperature of −70° C. It should be noted that the upper and lower temperature limits are greater and lower than those used during the thermal cycling test (MQT 11) reported in IEC 61215, whose purpose is to determine the module's capability of withstanding thermal variance, fatigue and other stresses caused by repeated temperature changes. The contact resistance obtained using C-EVA-ECA drops from 0.293Ω to 0.257Ω. By cooling the contact to room temperature, the contact resistance is 0.2477Ω. After cooling the contact to −70° C., the electrical resistance decreases from 0.2477Ω to 0.1933Ω. After the contact returns to room temperature, the contact resistance increases to 0.2441Ω. This value is comparable to that measured at room temperature in the initial stage of the tests. Overall, resistance tests indicate that the C-EVA-ECA composition maintains its electrical performance under electrical or thermal stress.

Example 4: Validation of PSCs

[0095] The C-EVA-ECA-4 composition is deposited on active films of mesoscopic PSCs to provide cost-effective carbon-based back-electrodes obtained through a liquid-phase process at room temperature. According to previous reports (Najafi et al. in ACS Nano, 2018, 12(11), pages 10736-10754) architectures made from fluoride-doped tin oxide (FTO)/compact TiO.sub.2 (cTiO.sub.2)/mesoporous TiO.sub.2 (mTiO.sub.2)/CH.sub.3NH.sub.3PbI.sub.3/2,2′,7,7′-tetrakis(N,N-di-4-methoxyphenylamino)-9,9′-spirobifluorene (spiro-OMeTAD) are used as benchmarking PSCs not completed by Au-based back-electrodes. The TiO.sub.2 layers perform a selective extraction and transport function of the negative charge photo-generated by perovskite (in our case CH.sub.3NH.sub.3PbI.sub.3), and form the so-called electron transporting layer (ETL). The spiro-OMeTAD performs a selective extraction and transport function of the positive charge photo-generated by perovskite, and forms the so-called hole transporting layer (HTL). The concentration of the active materials (electrically conductive and adhesive components) of C-EVA-ECA-4 is adjusted to 111 mg m.sup.−1 in order to provide suitable viscosity for the spin-coating process.

[0096] The deposition of C-EVA-ECA-4 on CH.sub.3NH.sub.3PbI.sub.3/spiro-OMeTAD is carried out by deposition via dynamic spin-coating at room temperature with a two-stage protocol (stage 1: 1000 rpm, 3 min.; stage 2: 4000 rpm, 3 min.). As illustrated by the cross-sectional SEM image of FIG. 7, the deposition of C-EVA-ECA-4 does not significantly deteriorate the underlying layered structure. However, an interpenetration of C-EVA-ECA within the spiro-OMeTAD is to be expected, as the C-EVA-ECA solvent can dissolve the spiro-OMeTAD. Operationally, the efficiencies of C-EVA-ECA-based PSCs can be increased by subsequent deposition of spiro-OMeTAD over the C-EVA-ECA. In addition, mixtures of spiro-OMeTAD and C-EVA-ECA can be used to deposit an ECA with a dual HTL and electrode function. Finally, materials with the function of HTL alternative to the spiro-OMeTAD and not dissolvable in the C-EVA-ECA solvent can be used to avoid interpenetration of the C-EVA-ECA in the underlying structure of the solar cell. Alternatively, other ECAs object of the invention and discussed in example 7 can be used to avoid the use of solvents dissolving the materials with the HTL function.

[0097] No heat treatment is applied to the C-EVA-ECA-4-based PSC.

[0098] The resulting C-EVA-ECA-4-based back-electrodes have a surface resistance of 155±20 ΩSQ.sup.−1 for a thickness of less than 10 μm. Multiple deposition cycles are effective for the production of C-EVA-ECA-4-based back-electrodes with surface resistances of less than 50 Ωsq.sup.−1, exceeding the values often obtained by TCO-based back-electrodes used for example in HJT-Si or double-side PSC technologies.

Example 5: Validation of Batteries and Supercapacitors

[0099] The C-EVA-ECA-4 and C-EVA-ECA-5 compositions were used for the mechanical and electrical connection of electrodes in series of battery cells and supercapacitors, ensuring total reliability of the electrical contact of electrodes in series with electrical resistances lower than 0.1Ω on contact areas equal to or greater than 1 cm×1 cm and C-EVA-ECA thicknesses between 1 and 400 μm. The reliability of the mechanical and electrical contacts of electrodes in series is ensured by an even distribution of the compression forces acting on the electrodes themselves, deriving from the elastic properties of C-EVA-ECAs.

Example 6: ECAs with an EVA Adhesive Component with Different Vinyl Acetate Content

[0100] According to the procedure of example 1, ECA compositions were prepared using EVA polymers with different vinyl acetate content. In particular, the following EVA copolymers were used: [0101] EVA with 40% by weight vinyl acetate (Sigma Aldrich) called EVA-B; [0102] EVA with 25% by weight vinyl acetate (Sigma Aldrich) called EVA-C; [0103] EVA with 18% by weight vinyl acetate (Sigma Aldrich) called EVA-D; [0104] EVA with 12% by weight vinyl acetate (Sigma Aldrich) called EVA-E.

[0105] The main features of some of the ECAs thus prepared (composition of the electro-conductive component, solvent, volumetric resistivity) are reported in table 2 below.

TABLE-US-00002 TABLE 2 Composition of the electro-conductive component and volumetric resistivity for representative EVA-based ECA samples with different vinyl acetate content (percentage by weight of the adhesive component = 25%). Acetylene Carbon Graphene Volumetric black nanotubes flakes resistivity Error ECA (% wt) (% wt) (% wt) Solvent (Ω cm) (Ω cm) C-EVA- 42.5 15 42.5 Chlorobenzene 0.124 0.012 B-ECA C-EVA- 42.5 15 42.5 Chlorobenzene 0.144 0.017 C-ECA C-EVA- 42.5 15 42.5 Chlorobenzene 0.255 0.020 D-ECA

Example 7: ECAs with Different Polymer Components and Solvents

[0106] In addition to the polymers used in the tests of example 1, other polymers were used, reported as encapsulating materials, following the procedure described in example 1. Specifically, polyvinyl butyral (PVB), poly(acrylic acid) (PAA), poly(methyl methacrylate) (PMMA) and commercial acrylate mixtures (Hydrolac 610L, material supplied in the form of an aqueous dispersion) were used. Herein, other solvents were also used in addition to chlorobenzene and xylene, capable of properly dissolving or dispersing the polymers used.

[0107] In particular, the following solvents were used: [0108] for PVB, acetic acid and other solvents with lower volatility such as cyclohexanone, butanol, dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), dimethylsulfoxide (DMSO). For these tests, the ECAs produced by doctor-blade deposition were dried at 50° C. for 60 minutes; [0109] for PMMA, nitroethane, toluene, chloroform, ethyl acetate, chlorobenzene and cyclohexanone (solvent with less volatility); the ECAs produced by doctor-blade deposition were dried at 50° C. for 60 minutes; [0110] for PAA, isopropanol (IPA) and ethanol; [0111] for commercial acrylate mixtures, water.

[0112] Table 3 below shows the main features of the above mentioned ECAs, wherein the electrically conductive component composition corresponding to that of the C-EVA-ECA-4 (or C-EVA-ECA-4B or C-polyolefin-ECA-4) products was used.

TABLE-US-00003 TABLE 3 Composition of electrically conductive component and volumetric resistivity for ECAs using different adhesive polymer components and solvents in addition to chlorobenzene (percentage by weight of adhesive polymer component = 25%). Acetylene Carbon Graphene Volumetric black nanotubes flakes resistivity Error ECA (% wt) (% wt) (% wt) Solvent (Ω cm) (Ω cm) C-PVB- 42.5 15 42.5 Acetic acid 0.174 0.023 ECA-1 C-PVB- 42.5 15 42.5 Butanol 0.385 0.041 ECA-2 C-PVB- 42.5 15 42.5 Cyclohexanone 0.338 0.055 ECA-3 C-PVB- 42.5 15 42.5 DMSO 0.230 0.046 ECA-4 C-PVB- 42.5 15 42.5 DMF 0.091 0.009 ECA-5 C-PVB- 42.5 15 42.5 NMP 0.074 0.013 ECA-6 C-PMMA- 42.5 15 42.5 Ethyl acetate 0.132 0.031 ECA-1 C-PMMA- 42.5 15 42.5 Nitroethane 0.092 0.009 ECA-2 C-PMMA- 42.5 15 42.5 Toluene 0.253 0.032 ECA-3 C-PMMA- 42.5 15 42.5 Chloroform 0.201 0.030 ECA-4 C-PMMA- 42.5 15 42.5 Chlorobenzene 0.657 0.091 ECA-5 C-PMMA- 42.5 15 42.5 Cyclohexanone 0.429 0.065 6 C-PAA- 42.5 15 42.5 IPA 0.061 0.007 ECA-1 C-PAA- 42.5 15 42.5 Ethanol 0.015 0.004 ECA-2 C-acrylate 42.5 15 42.5 Water 0.045 0.009 mixture- ECA

Example 8: Adhesive Compositions with Different Solvents and Process Restrictions

[0113] Although the solvents used for the ECAs shown in example 1, table and for example 7, table 3, can generally be used for the formulation of the ECAs according to the procedures given in example 1, they can impose limitations in relation to the methods used for processing (i.e. depositing/applying) the ECAs. Depending on the properties of the solvents used, it is suggested that the resulting ECAs are processed at low temperature (<100° C.) with the techniques shown in table 4 below. Furthermore, other techniques such as gravure and flexographic printing can be used within the scope of the invention; the use of other deposition parameters, such as substrate temperature and paste temperature, other than those indicated in the notes relating to table 4 also falls within the scope of the invention.

TABLE-US-00004 TABLE 4 Preferred process methods for ECAs depending on the solvent Method of process (i.e., deposition/application)) Doctor Spin Spray Screen ECA's solvent blading.sup.a coating.sup.b coating.sup.c printing.sup.d,e Chlorobenzene yes yes yes yes Chloroform yes yes yes yes Toluene yes yes yes yes IPA yes yes yes yes Ethanol yes yes yes yes Water yes yes yes yes Acetic acid yes yes yes yes Ethyl acetate yes yes yes yes Nitroethane yes yes yes yes Xylene yes no no yes (mixture of isomers) NMP yes no no yes DMF yes no no yes DMSO yes no no yes Cyclohexanone yes no no yes Butanol yes no no yes .sup.asubstrate maintained at temperature <100° C. .sup.bpaste and substrate maintained at room temperature .sup.cas a function of the solid component content of the composition, the amount of solvent can be increased to values above 90% referred to 100 parts of ECA (solvent included) .sup.das a function of the materials of the ECA, the solvent and the concentration of the solid components, silkscreens are selected depending on material, mesh number and mesh tension .sup.esubstrate maintained at temperature <100° C.

Example 9 (Comparative)

[0114] By way of comparison, the formulation described in example 3 of CN 109320893 was reproduced.

[0115] The following table 5 shows the materials and the corresponding amounts used for the reproduction of such example.

TABLE-US-00005 TABLE 5 Composition of the product reported in example 3 of CN 108384103 Specifications (production and Material supply method) Amount (mg) graphene Wet-jet milling 180 exfoliation carbon nanotubes Cheap tubes 30 Carbon black Alfa Aesar 130 Epoxy resin Sigma Aldrich 250 Hydroxyl acrylic acid Vecom Srl 200 resin Curing agent (1) Sigma Aldrich 180 Aniline Sigma Aldrich 60 Silicon nanopowder Alfa Aesar 40 FeSO.sub.4•7H.sub.2O Sigma Aldrich 300 FeCl3•6H.sub.2O Sigma Aldrich 150 EVA (EVA-B) Sigma Aldrich 600 White oil Sigma Aldrich 60 Zirconium hydrogen Sigma Aldrich 10 phosphate Butyl acrylate emulsion Sigma Aldrich 80 NMP Sigma Aldrich 400 Polytetrafluoroethylene Sigma Aldrich 80 Polyvinylidene Sigma Aldrich 130 chloride emulsion Sodium dodecyl sulfate Sigma Aldrich 30 Auxiliary Sigma Aldrich 20 (1): curing agent: polyether amine

[0116] The material obtained is in a wet solid form formed by separate lumps, so that the material cannot be processed by the deposition methods previously described such as, in particular, by doctor blading, spin coating, spray coating and silkscreen printing. FIG. 8 shows a comparison of the film obtained by doctor-blade deposition of the C-EVA-ECA-4 product according to the invention (on the left) with the product obtained in this comparative example (on the right).

[0117] In order to measure the resistivity of the composite obtained, a lump of the material was pressed in the form of a film. The measured volumetric resistivity is 3.99 Ωcm which is about two orders of magnitude greater than that shown by the products according to the invention, using the same adhesive polymer component (EVA).