OA21286A - Electric power generator containing an active organic material. - Google Patents
Electric power generator containing an active organic material. Download PDFInfo
- Publication number
- OA21286A OA21286A OA1202300238 OA21286A OA 21286 A OA21286 A OA 21286A OA 1202300238 OA1202300238 OA 1202300238 OA 21286 A OA21286 A OA 21286A
- Authority
- OA
- OAPI
- Prior art keywords
- epg
- electric power
- power generator
- collecter
- oxygen
- Prior art date
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- 239000011368 organic material Substances 0.000 title claims abstract description 39
- 150000001875 compounds Chemical class 0.000 claims description 53
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 46
- 229910052760 oxygen Inorganic materials 0.000 claims description 46
- 239000001301 oxygen Substances 0.000 claims description 46
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 24
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 21
- 229920000620 organic polymer Polymers 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- 229910002804 graphite Inorganic materials 0.000 claims description 15
- 239000010439 graphite Substances 0.000 claims description 15
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 12
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 6
- 239000003575 carbonaceous material Substances 0.000 claims description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 6
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- 239000011888 foil Substances 0.000 claims description 6
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 6
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 6
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 6
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004065 semiconductor Substances 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 229910052682 stishovite Inorganic materials 0.000 claims description 4
- 229910052905 tridymite Inorganic materials 0.000 claims description 4
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 3
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910010293 ceramic material Inorganic materials 0.000 claims description 2
- 239000000571 coke Substances 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
- 150000001247 metal acetylides Chemical class 0.000 claims description 2
- 150000004767 nitrides Chemical class 0.000 claims description 2
- 235000021317 phosphate Nutrition 0.000 claims description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052596 spinel Inorganic materials 0.000 claims description 2
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- 150000003568 thioethers Chemical class 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims 2
- 239000004698 Polyethylene Substances 0.000 claims 1
- 229910006213 ZrOCl2 Inorganic materials 0.000 claims 1
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- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims 1
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 claims 1
- 230000004044 response Effects 0.000 description 12
- 239000011149 active material Substances 0.000 description 11
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 7
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- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920000609 methyl cellulose Polymers 0.000 description 4
- 239000001923 methylcellulose Substances 0.000 description 4
- 235000010981 methylcellulose Nutrition 0.000 description 4
- 239000000230 xanthan gum Substances 0.000 description 4
- 235000010493 xanthan gum Nutrition 0.000 description 4
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- 101001072903 Homo sapiens Phosphoglucomutase-2 Proteins 0.000 description 3
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- 101000583553 Homo sapiens Phosphoglucomutase-1 Proteins 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
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Abstract
The present invention relates to an electric power generator and a power generator module containing an active organic material.
Description
“ELECTRIC POWER GENERATOR CONTAINING AN ACTIVE ORGANIC
MATERIAL”
DESCRIPTION FIELD OF THE INVENTION
The présent invention relates to an electric power generator containing an active organic material.
STATE OF THE ART
It is widely known the use of thermoelectric power generators and thermionic power generators for the conversion of thermal energy directly into electrical energy.
The thermoelectric power generators are devices based on a thermoelectric effect, namely the Seebeck effect, involving interactions between the flow of heat and of electricity between solid bodies. Examples of such devices are disclosed in the patent EP 2521192 and in the patent application EP 2277209. In broad terms, thermoelectric power generators consist of three main components: thermoelectric material, thermoelectric modules and thermoelectric System that interface with a heat source.
Thermoelectric materials generate power directly from heat by converting température différences into electric voltage. In particular, these materials typically hâve both high electrical conductivity and low thermal conductivity. The low thermal conductivity ensures that when one side is made hot, the other side stays cold. This helps to generate 20 a large voltage while in a température gradient.
A thermoelectric module is a circuit containing thermoelectric materials which generate electricity from heat directly. A module consists of two dissimilar thermoelectric materials joining at their ends, namely a negatively charged semiconductor and a positively charged semiconductor. A direct electric current will flow in the circuit when 25 there is a température gradient between the two materials. Such gradient is provided by the thermoelectric System which typically comprise heat exchangers used on both sides on the module to supply respectively heating and cooling.
A thermionic power generators, also called thermionic power converters, convert heat directly into electricity. A thermionic power generator typically comprises two 30 électrodes arranged in a containment. One of these is raised to a sufficiently high température to become a thermionic électron emitter or “hot plate”. The other electrode is called collecter because it receives the emitted électrons. The collecter is operated at significantly lower température. The space between the électrodes can be vacuum or alternatively filled with a vapour gas at low pressure. The thermal energy may be supplied by Chemical, solar or nuclear sources.
Thermoelectric power generators as well as thermionic power generators hâve many drawbacks, among which the low conversion efficiency and the need of providing a température gradient. In addition, such generators, requires relatively constant thermal source.
Therefore, it is the primary object of the présent invention to provide an electric power 10 generator capable to convert part of the thermal energy in electric energy and allowing to overcome the drawbacks of the devices of the prior art.
In the International application WO 2018/029139, it is already described an active material capable to be applied on one electrode and to generate current when comprised between at least two électrodes, surprisingly without initial charging and dependently on 15 the température. Specifically, the material described in WO 2018/029139 comprises at least one oxygen-containing compound selected from the group consisting of MgO, ZnO, ZrOCh, ZrOz, S1O2, B12O3, AI2O3 and T1O2, at least one thickener additive selected from the group consisting of agar agar, xanthan gum, methyl cellulose, and arabic gum, and at least one plasticizer additive, wherein the particle size of the oxygen-containing 20 compound has a spécifie average diameter. The performances of such an active material were worse in the presence of températures above 80°C, and the température above 90°C induced the dégradation of the active material with lowering of the device performances and the decrease of stability of the final device.
In the International application WO 2019/122215, a further active material is then 25 proposed, capable to generate electric energy and having also high stability to température and thus providing an alternative and improvement compared to the prior art. Said further active material is an essentially dry State active material comprising at least one oxygen-containing compound selected from the group consisting of MgO, ZnO, ZrOCh, ZrO2, SiO2, Bi2O3, Fe3O4, AI2O3,TiO2, BeO, CaO, Ga2O3, In2O3, GeO2, SnO2 30 and PbO2, wherein the particle size of the oxygen- containing compound has an average diameter in the range from 10 nm to 40 μιτι and wherein a thickener additive selected from the group consisting of agar agar, xanthan gum, methyl cellulose, and arabic gum is absent.
The inventors found out that the performances of this essentially dry State active material worsened with the use over time, and that after long usage, a loss of device performances 5 in terms of recovery of the generated electric power due to ageing phenomena occurred.
A further object of the invention is therefore to provide an electric generator capable to stably provide electric energy even in conditions of prolonged use, without loss of performances in terms of recovery of the generated electric power. A still further object of the invention is therefore to provide an electric power generator capable to provide 10 electric energy at constant uniform température and/or with gradient of température between the two électrodes of the same electric power generator and even in conditions of prolonged use of the device itself.
SUMMARY OF THE INVENTION
The inventors surprisingly found out that a new electric power generator containing an 15 active organic material is capable to provide electric energy at constant uniform température and/or with gradient of température between at least one electrode and at least one current collecter of the same electric power generator without loss of performances in terms of recovery of the generated electric power even in conditions of prolonged use.
Therefore, the présent invention relates to an electric power generator (EPG) comprising: - at least one electrode,
- at least one current collecter, .
- at least one active organic material interposed between the at least one electrode and the at least one current collecter, and
- at least one oxygen-containing compound layer, wherein said at least one active organic material comprises at least one organic polymer obtainable by heating in a range of température of from 60 °C to 160 °C for a time from 1 hour to 3 hours a mixture comprising from 5 weight % to 70 weight % of polyvinyl alcohol and from 30 weight % to 95 weight % of at least one glycol selected from the 30 group consisting of ethylene glycol and propylene glycol with respect to the total weight of the at least one organic polymer, wherein the at least one oxygen-containing compound layer is in contact to said at least one active organic material and and wherein the at least one oxygen-containing compound layer is in contact of at least one current collecter.
The EPG according to the présent invention is indeed capable to provide electric energy at constant uniform température and/or with gradient of température between the at least one electrode and the at least one current collecter of the same electric power generator and even in conditions of prolonged use of same and, unexpectedly, the inventors found out that, thanks to said at least one active organic material, the recovery of the generated electric power of the EPG has been even increased, thus providing a further improvement compared to the EPGs of the prior art.
The présent invention also relates to a power generator module (PGM) comprising a plurality of EPG which can be connected in sériés or parallel without compromising the EPG characteristics (voltage and current).
The advantages of the power generator module (PGM) hâve been outlined above with respect to the EPG according to the invention and are not herewith repeated.
DESCRIPTION OF FIGURES
Further features and advantages of the invention will be more apparent in light of the detailed description of the active material and of the preferred embodiments of the electric power generator with the aid of enclosed drawings in which:
- Figure 1 shows the structure of a configuration of the electric power generator (EPG1) comprising the active organic material according to the présent invention;
- Figure 2 shows the structure of a further configuration of the electric power generator (EPG2) comprising the active organic material according to the présent invention;
- Figure 3 and 4 show examples of electrical circuits comprising a PGM having two
EPGs according to the présent invention, in parallel and in sériés respectively;
- Figure 5 shows the curve of response of the EPG, assembled according to Example 3 (EPG1) determined during the exposition test according to Example 5;
- Figure 6 shows the curve of response of stacks of EPG in sériés, assembled according to Example 4 (EPG2) determined during the exposition test according to Example 6;
- Figure 7 shows the curve of response of stacks of EPG in parallel, assembled according to Example 4 (EPG2) determined during the exposition test according to Example 7;
- Figure 8 shows the curve of response of EPG, assembled according to according to Example 4 (EPG2) determined during the exposition test according to Example 8;
- Figure 9 shows the curve of voltage and current response of EPG, assembled according t o Example 2 determined during the exposition test of example 9;
- Figure 10 shows the response of the EPG2 at different températures as tested in Example 10; and
- Figure 11 shows the electric power generator 2 of the invention (EPG2) with the 10 electrical contacts for connection.
DETAILED DESCRIPTION OF THE INVENTION
The présent invention relates to an electric power generator (EPG) comprising
- at least one electrode,
- at least one current collecter,
- at least one active organic material interposed between the at least one electrode and the at least one current collecter, and
- at least one oxygen-containing compound layer, wherein said at least one active organic material comprises at least one organic polymer obtainable by heating in a range of température of from 60 °C to 160 °C for a time from 20 1 hour to 3 hours a mixture comprising from 5 weight % to 70 weight % of polyvinyl alcohol and from 30 weight % to 95 weight % of at least one glycol selected from the group consisting of ethylene glycol and propylene glycol with respect to the total weight of the at least one organic polymer, and wherein the at least one oxygen-containing compound layer is in contact to said at least 25 one active organic material, and and wherein the at least one oxygen-containing compound layer is in contact of at least one current collecter.
In the présent invention when the following terms are used, it is intended:
- “in contact” means the formation of an interface with a real contact area among the two 30 materials more that 90% of the geometrical area, with preferred values equal to or higher than 95%;
- “at least one current collector” it is intended an essential element of the EPG of the invention which collects and modulâtes the charges;
- “primary current collector” is at least one current collector made of a métal material and/or of an organic/inorganic material which collects and modulâtes the charges; and 5 - “secondary current collector” is at least one current collector made of a métal material and/or of an organic material which collects and modulâtes the charges, and electrically interacts with the oxygen-containing compound layer.
Within the framework of the présent description and in the subséquent claims, except where otherwise indicated, ail the numerical entities expressing amounts, parameters, 10 percentages, and so forth, are to be understood as being preceded in ail instances by the term about. Also, ail ranges of numerical entities include ail the possible combinations of the maximum and minimum values and include ail the possible intermediate ranges, in addition to those specifically indicated herein below.
The EPG according to the présent invention is indeed capable to provide electric energy 15 at constant uniform température and/or with gradient of température between the at least one electrode and the at least one current collector of the same electric power generator and even in conditions of prolonged use of same and, unexpectedly, the inventors found out that, thanks to said at least one active organic material, the recovery of the generated electric power of the EPG has been even increased, thus providing a further improvement 20 compared to the EPGs of the prior art.
The présent invention may présent in one or more of the above aspects one or more of the characteristics disclosed hereinafter.
The EPG according to the invention comprises at least one active organic material comprising at least one organic polymer obtainable by heating in a range of température 25 of from 60 °C to 160 °C for a time from 1 hour to 3 hours a mixture comprising from 5 weight % to 70 weight % of polyvinyl alcohol and from 30 weight % to 95 weight % of at least one glycol selected from the group consisting of ethylene glycol and propylene glycol with respect to the total weight of the least one active organic polymer.
Preferably, the at least one active organic polymer is obtainable by heating said mixture 30 in a range of température of from 120 °C to 150 °C, more preferably a 140°C.
In a particularly advantageous embodiment, the invention can provide a second heating step from 120 °C to 150 °C, more preferably a 140°C.
Still more preferably the second step can provide the addition of a thickener, preferably glycerol.
Preferably, the at least one active organic polymer is obtainable by heating said mixture 5 for a time of from 1 hour to 2.5 hours, more preferably, the at least one active said organic polymer is obtainable by heating said mixture for a time of about 2 h, still more preferably in air or inert atmosphère.
The mixture according to the invention comprises from 5 weight % to 70 weight % of polyvinyl alcohol and from 30 weight % to 95 weight % of at least one glycol selected 10 from the group consisting of ethylene glycol and propylene glycol with respect to the total weight of the least one active organic polymer. Preferably, said mixture comprises from 8 weight % to 40 weight % of polyvinyl alcohol and from 60 weight % to 92 weight % of at least one glycol selected from the group consisting of ethylene glycol and propylene glycol with respect to the total weight of the least one active organic polymer.
In an advantageous and preferred embodiment, said polyvinyl alcohol has a density in the range from 1.19 to 1.31 g/cm3 at 20 °C. The density of the polyvinyl alcohol can be measured with the methods known to the skilled person on this purpose, for example by Pycnometry.
Preferably, said polyvinyl alcohol has a degree of hydrolysis in the range from 86 to 20 89%. The degree of hydrolysis of the polyvinyl alcohol may be determined according to any one of the methods known to the skilled person on this purpose, for example titration methods.
In a preferred embodiment of the invention, the at least one active organic material comprises at least one thickener additive, preferably selected from the group consisting 25 of agar agar, xanthan gum, methyl cellulose, glycerol and arabic gum.
In a further preferred embodiment of the invention, in the at least one active organic material a thickener additive is absent, more preferably a thickener additive selected from the group consisting of agar agar, xanthan gum, methyl cellulose, glycerol and arabic gum being absent from the at least one active organic material of the EPG according to 30 the invention.
The EPG according to the présent invention comprises at least one electrode and at least one carrent collecter.
Said at least one electrode and the at least one carrent collecter may be made of metals, alloys and/or carbon-based materials like graphite. When more the one electrode is présent, the further electrode can be made of the same material or different material.
Preferably, the thickness of the at least electrode and, independently, of the at least one carrent collecter is in the range from 0.1 to 3000 μιη, more preferably from 50 to 1000 μιη, still more preferably from 300 to 600 μπι.
In a preferred embodiment of the EPG according to the invention, the at least one electrode and the at least secondary carrent collecter are made of Cu and Al, respectively, 10 preferably in form of plates or foils substantially parallel. In case of flexible EPG both self-standing flexible materials and metallized polymers can be considered as électrodes and as carrent collectors. The shape of the at least one electrode or of the at least one carrent collecter is however not binding.
The at least one electrode, and independently, the at least one carrent collecter, are 15 preferably made of Cu or Al and can be more preferably subjected to cleaning and etching prior to be used in the electric power generator of the invention.
The EPG according to the invention, comprises at least one at least one oxygencontaining compound layer.
Preferably, said at least one oxygen-containing compound layer can be a passivated layer 20 of said at least one of the at least one current collecter, preferably a secondary current collecter, or a layer of at least one oxygen-containing compound selected from the group consisting of MgO, ZnO, ZrOCh, ZrO2, SiO2, Bi2O3, FesCL, Al2O3,TiO2, BeO, CaO, Ga2Ü3, In2O3, GeO2, SnO2 and PbO2.
In one embodiment the at least one oxygen-containing compound layer is a passivated 25 layer of the at least one current collecter, but it can also be a layer of at least one oxygencontaining compound deposited on the at least one current collecter. According to a further embodiment, the at least one oxygen-containing compound layer is both a passivated layer of one side of the at least one current collecter and a layer of at least one oxygen-containing compound deposited on the other side of the at least one current 30 collecter.
In an advantageous embodiment the at least one oxygen-containing compound layer can be formed in situ after having assembled the EPG when the at least one current collector is a secondary current collector. In this embodiment the secondary collector is aluminum. Preferably, said at least one oxygen-containing compound has particle average diameter in the range from 5 nm to 40 μιη, preferably in the range of 15 nm-10 μπι, more preferably 20 nm-5 μιη. In another advantageous and preferred aspect of the invention, the particles of oxygen-based compounds hâve an average diameter in the range from 10-200 nm, more preferably in the range of 15-100 nm, still more preferably 20-40 nm. The oxygen-containing compound can be anhydrous or can contain a certain amount of the water, as coordinated water molécules, deriving from the process for preparing it: the inventors deem that such coordinated water in the oxygen-containing compound can ameliorate the performances of the final devices obtained therefrom. The oxygencontaining compound can contain coordinated water in the range from 0.5% by weight to 7.5% by weight with respect to oxygen-containing compound preferably from 0.5% to 3.5%, more preferably from 0.5% to 1.5%.
The at least one oxygen-based compound can be placed as powder on said at least one electrode or on the at least one current collector and pressed against it using a machine press, thus obtaining the at least one oxygen-containing compound layer. Alternative techniques already known in the art can be used, for example sol-gel, inkjet printing and sputtering.
According to the invention the at least one oxygen-containing compound layer is in contact to said at least one active organic material. This means that there is the formation of an interface with a real contact area among the two materials more that 90% of the geometrical area, with preferred values equal to or higher than 95%.
According to the invention the at least one oxygen-containing compound layer is also in contact with the at least one current collector.
According to the invention the at least one oxygen-containing compound layer can be a passivated layer of said at least one current collector. The at least one current collector having a passivated layer can be one available on the market or prepared by passivation of the current collector by thermal or electrolytic oxidation.
The active organic material of the EPG of the invention is preferably deposited in contact with the at least one oxygen-containing compound layer with a thickness from 100 nm to 5 mm. On the other hand, the optimal thickness varies depending on applications, e.g. doctor blade equipment, spraying, etc.
In a preferred embodiment at least one electrode can be a secondary current collecter in contact with the at least oxygen-containing compound layer.
In a preferred embodiment the secondary current collecter is made of the same material of the at least one electrode. In a further preferred embodiment, the EPG comprises a secondary current collecter, preferably made of a material different from the material of the least one electrode.
Preferably, said secondary current collecter is made of a material selected from the group 10 consisting of: metals, porous carbon, and conductive oxides, sulphides, alloys with almost constant electric resistivity, manganèse oxide and its compounds, phosphates, and mixtures or composites thereof. According to the invention, the alloys with almost constant electric resistivity are for example constantan (55% copper and 45% nickel).
In a preferred embodiment the EPG comprises a further current collecter. In a more 15 preferred embodiment, this further collecter is a primary collecter.
In a still more preferred embodiment, the EPG comprises a primary current collecter, more preferably in contact to said secondary current collecter. Said secondary current collecter is characterized by the oxygen-containing layer on one or on the two sides of the collecter.
Preferably, said primary current collecter is made of a material selected from the group consisting of: pyrolytic graphite, carbon coke and/or carbon-based materials (e.g. graphene), boron, Silicon, germanium, silver and chemically stable semiconductors in their intrinsic and extrinsic State (e.g. gallium arsenide), ceramic materials as carbides and nitrides, perovskites, spinel compounds, PET (polyethylene terephthalate) and 25 mixtures or composites thereof.
Preferably, the electric power generator (EPG) according to the present invention may comprise at least one a porous layer. More preferably said at least one active organic polymer can be adsorbed on the at least one porous layer.
Preferably, said at least one porous layer is made of cellulose, cellulose composite 30 materials, porous carbonaceous materials, and composites with carbon matrix.
More preferably the cellulose material is sodium carboxy methylcellulose.
More preferably the porous carbonaceous material is powder active carbon.
In a preferred embodiment said the at least one porous layer comprises 85% water, 1% sodium carboxy methylcellulose and 14% powder active carbon.
Preferably, the electric power generator (EPG) according to the présent invention comprises at least one porous layer in contact to said at least one active organic material. Preferably, said porous layer has a surface area in the range from 100 to 600 m2/g. The surface area may be determined according to any one of the methods known to the skilled person on this purpose, for example Capillary Porosimetry or BET adsorption.
In a preferred embodiment schematically shown in Fig. 1, the EPG according to the invention (EPG 1) therefore includes:
- a current collecter (1), specifically a secondary current collecter;
- an oxygen-containing compound layer (2), as passivated layer in contact with the secondary current collecter,
- an active organic material (3) and
- an electrode (4).
In a further preferred embodiment schematically shown in Fig. 2, the EPG according to the invention includes:
- a primary current collecter (5),
- a current collecter (1), specifically a secondary current collecter;
- an oxygen-containing compound layer (2), as passivated layer in contact with the secondary current collecter,
- an active organic material (3),
- a porous layer (6),
- an electrode (4),
- a secondary current collecter (1) and
- a primary current collecter (5).
The présent invention also relates to a power generator module (PGM) comprising a plurality of EPGs which can be connected in sériés or parallel without compromising the EPG characteristics (voltage and current).
In a further aspect, the invention hence relates to a power generator module (PGM) comprising a plurality of EPG which can be connected in sériés or parallel. On this regards, Figure 3 shows a circuit comprising a PGM wherein the two EPGs are connected in parallel, while Figure 4 shows a circuit comprising a PGM having two EPGs connected in sériés. Both the circuits of Figures 3 and 4 comprise a load résistance Rl = 100 Ohm.
The voltage relative to the PGM can be monitored, for example, by connecting a 5 potentiostat/galvanostat parallel to the load résistance Rl.
Specifically and advantageously, the current measured by the electric power generator (EPG) of the invention is increased by a factor in the range from 1.5 to 4, increasing the température from 20 to 80°C.
The EPG of the invention was characterized by the electric point of view. First, the open 10 circuit voltage (OCV) was measured by means of a multimeter, the EPG device showed a voltage of 0.6 V in the configuration comprising aluminum oxide and graphite as électrodes.
With reference to Figures 3 and 4, a dedicated electrical circuit EC was selected, in order to characterize the EPG from the electrical point of view, measuring the voltage across 15 a résistance of 100 Ohm connected to the EPG and the current circulating through the résistance. The invention will now be illustrated by some not limitative examples of the active material and EPG of the invention.
Examples:
Example 1
Préparation of the active organic material grams of polyvinylalcohol (Zeus) and 76 grams of ethylene glycol (Sigma Aldrich) where fed to a glass reactor and then mixed to obtain a mixture. The mixture was heated up while stirring to 140 °C for a time of about 2h, specifically 1 hour and 55 minutes, thus obtaining a transparent and homogeneous melt of the active organic material. The 25 active organic material was then poured to form a film and cooled down to 25 °C.
Example 2
Préparation of the active organic material adsorbed on a porous layer
The active organic material was prepared, according to Example 1. The active organic material obtained was a transparent and homogeneous melt and was poured on a porous 30 layer made of a cellulose and then left to cool down to 25 °C.
Example 3
Préparation of the electric power generator 1 of the invention (EPG1)
The EPG1 device was assembled starting from an electrode (4) of graphite of size 15 mm x 35 mm and thickness of 1 mm on top it was deposited via doctor blade equipment the active organic material (3), prepared according to Example 1) with a thickness of 5 5 mm.
Afterwards, a secondary carrent collecter (1) made of aluminum and having a passivated layer (the at least one oxygen-containing compound layer (2)) was provided. This latter was a secondary current collecter with a passivated layer (2) onto the current collecter (15 mm x 35 mm): specifically, it had one face with the oxygen-containing compound 10 layer like an aluminium foil for commercial capacitor (0.36 - 0.80 pF/cm2)
The final EPG1 device, as represented in Figure 1 comprised:
- a current collecter (1) which is a secondary current collecter having an oxygencontaining compound layer (2) (anodic passivated layer);
- an active organic material (3) of Example 1; and 15 - an electrode (4).
Example 4
Préparation of the EPG 2 of the invention (EPG2)
The EPG2 device was assembled starting from a primary current collecter (5) made of pyrolytic graphite with dimensions of 15 mm x 50 mm and thickness of 1 mm. On top, 20 it was cladded in contact a secondary current collecter (1) in the form of graphite foil with dimensions of 15 mm x 35 mm and thickness of 100 μπι.
Afterwards, an electrode (4) made of carbon powder with dimensions of 15 mm x 35 mm and thickness 100 Qm and a porous layer (6) made of 85% water, 1% sodium carboxymethylcellulose, 14% powder active graphite dispersed at the surface with 25 dimensions of 15 mm x 35 mm and thickness 1 mm, were deposited on top of the secondary current collecter (1).
Subsequently, the active material (3) prepared according to Example 1 was deposited on the porous layer (6) with a thickness of 5 mm.
Then, a secondary current collecter (1) made of aluminum and having a passivated layer 30 (the at least one oxygen-containing compound layer (2)) was provided. This latter was a secondary current collecter with a passivated layer onto the current collecter (15 mm x mm): specifically, it had one face with oxygen-containing compound layer like an aluminium foil for commercial capacitor (0.36 - 0.80 pF/cm2)
Finally, a primary current collecter (5) made of pyrolytic graphite and having dimensions of 15 mm X 50 mm and thickness of 6 mm, was deposited on top of the secondary current 5 collecter (1), thus obtaining the final EPG2 device.
The EPG2 as represented in Figure 2 comprised:
- a primary current collecter (5) (15 mm x 50 mm): pyrolytic graphite (thickness 6 mm);
- a secondary current collecter having an oxygen-containing compound layer (2) 10 (anodic passivated layer);
- an active organic material (3) of Example 1;
- a porous layer (6): 85% water, 1% sodium carboxymethylcellulose, 14% powder active carbon;
- an electrode (4);
- a secondary current collecter (1) (15 mm x 35 mm): graphite foil (thickness: 100 pm); and
- a primary current collecter (5) (15 mm x 50 mm): pyrolytic graphite (thickness 1 mm).
Example 5:
Characterization of the EPG2 of the invention (EPG 2)
The EPG2 according to Example 4, was exposed to constant température of 25 °C and voltage across the two collectors connected for 2 minutes and disconnected for 2 minutes in parallel at 100 Ohm load, was measured for many cycles. Figure 5 shows the response of the EPG. When connected the EPG showed a decrease of voltage from 0.5-0.6 V to 25 about 0.1 V and a substantially total recovery of the initial value when disconnected.
This behavior consisting in reaching 0.1 V when connected and in recovering initial voltage when disconnected can be exploited for many cycles of connection/disconnection of the EPG to the load. This behavior demonstrates the capability of the EPG of the spontaneous charging recovery during the disconnected 30 phase.
Example 6
Characterization of a PGM1 of three stacks in sériés of five EPGs of the invention . Three stacks, each one of five EPG2, each one assembled according to Example 4, were connected in sériés, and exposed to constant température of 25 °C and the voltage across the two collectors at 100 Ohm load, was measured. Figure 6 shows the response of the
PGM1. When connected the PGM shows a decrease of voltage from 1.6-1.5 V to about 0.2 V and a stable current of about 2 mA. This set up demonstrates the possibility of connection of EPGs in sériés.
Example 7
Characterization a PGM2 of five EPGs of the invention in parallel
Five EPG2, each one assembled according to Example 4, were connected in parallel, and exposed to constant température of 25 °C and the voltage across the two collectors connected at 100 Ohm load, was measured. Figure 7 shows the response of the PGM2. When connected the PGM2 shows a decrease of voltage from 0.5-0.6 V to about 0.25 V and a stable current of about 2.7 mA. This set up demonstrates the possibility of connection of EPGs in parallel.
Example 8
Characterization of the EPG of the invention (EPG 2)
The EPG, assembled according to Example 4 was exposed to constant température of 25 °C and the voltage across the two collectors connected at 100 Ohm load, was measured.
The plot in Figure 8 shows the response of the EPG. When connected the EPG shows a decrease of voltage from 0.3-0.35 V to about 0.025 and a stable current of about 0.3 mA. Example 9
Characterization of the flexible EPG2 of the invention (EPG 2)
The EPG2 device was assembled starting from a primary current collecter (5) made of
PET polyethylene terephthalate polymeric foil with a silver conductive layer with dimensions of 660 cm2 and thickness of 80 □m. On top, it was deposited a secondary current collecter (1) in the form of graphite with dimensions of 660 cm2 and thickness of 10 Dm.
Afterwards, an electrode (4) made of carbon powder with dimensions of 660 cm2 and 30 thickness of 24 üm and a porous layer (6) made of 85% water, 1% sodium carboxymethylcellulose, 14% powder active graphite dispersed at the surface with dimensions of 660 cm2 and thickness of 24 Dm, were deposited on top of the secondary current collecter (1).
Subsequently, the active material (3) prepared according to Example 1 was deposited on the porous layer (6) with a thickness of 48 Dm with in between a commercial capacitor 5 paper.
Then, a secondary current collecter (1) made of aluminum and having a passivated layer (the at least one oxygen-containing compound layer (2)) was provided. This latter (commercial capacitor aluminum foil) was a secondary current collecter with a passivated layer onto the current collecter (660 cm2): specifically, it had one face with 10 oxygen-containing compound layer like an aluminium foil for commercial capacitor (0.36 - 0.80 pF/cm2).
Finally, a primary current collecter (5) made of pyrolytic graphite and having dimensions of 15 mm x 50 mm and thickness of 6 mm, was deposited on top of the secondary current collecter (1), thus obtaining the final EPG2 device.
The EPG was exposed to constant température of 25 °C and the voltage across the two collectors connected at 100 Ohm load, was measured. The plots in Figure 9 show the response of the EPG2. When connected the EPG2 showed a decrease of voltage from 0.60-0.65 V to about 0.375 and a stable current of about 7 mA.
Example 10
Characterization of the flexible EPG2 of the invention (EPG 2) at T = 40 °C and 50 C The EPG2 device of the Example 9 was tested at different températures with respect to room température. The plots in Figure 10 show the response of the EPG2. When connected the EPG2 showed a decrease of voltage from 0.60-0.65 V to about 0.375 and a current of about 5 mA; when température is increased, the values of the voltage and of 25 the current are increased, proportionally to the established température.
Example 11
Préparation of the electric power generator 2 of the invention (EPG2) with external electrical contacts
Figure 11 shows the electric power generator 2 of the invention (EPG2) with the 30 electrical contacts for connection. Said contacts were outside the active area of the device.
Claims (17)
1. An electric power generator (EPG) comprising:
- at least one electrode,
- at least one current collecter,
5 - at least one active organic material interposed between the at least one electrode and the least one current collecter, and
- at least one oxygen-containing compound layer, wherein said at least one active organic material comprises at least one organic polymer obtainable by heating in a range of température of from 60 °C to 160 °C for a time from 10 1 hour to 3 hours a mixture comprising from 5 weight % to 70 weight % of polyvinyl alcohol and from 30 weight % to 95 weight % of at least one glycol seleçted from the group consisting of ethylene glycol and propylene glycol with respect to the total weight of the at least one organic polymer, and wherein the at least one oxygen-containing compound layer is in contact to said at least 15 one active organic material and wherein the at least oxygen-containing compound layer is in contact with the at least one current collecter.
2. The electric power generator (EPG) according to claim 1, wherein the at least one organic polymer of the at least one active organic material is obtainable by a mixture 20 comprising from 8 weight % to 40 weight % of polyvinyl alcohol and from 60 weight % to 92 weight % of at least one glycol seleçted from the group consisting of ethylene glycol and propylene glycol with respect to the total weight of the least one active organic polymer.
3. The electric power generator (EPG) according to claim 1 or 2, wherein the at least one 25 oxygen-containing compound layer is a passivated layer of said at least one of said at least one current collecter.
4. The electric power generator (EPG) according to claim 1 or 2, wherein the at least one oxygen-containing compound layer is a layer of at least one oxygen-containing compound seleçted from the group consisting of MgO, ZnO, ZrOCl2, ZrO2, SiO2, Βί2Ο3, 30 Fe3O4, Al2O3)TiO2, BeO, CaO, Ga2O3, In2O3, GeO2, SnO2 and PbO2.
5. The electric power generator (EPG) according to claim 1 or 2, wherein the at least
1« one oxygen-containing compound layer is formed in situ after having assembled the EPG when the at least one current collecter is a secondary current collecter.
6. The electric power generator (EPG) according to anyone of claims 3-5, wherein said at least one oxygen-containing compound has particle average diameter in the range from 5 5 nm to 40 pm, preferably in the range of 15 nm-10 μιη, more preferably 20 nm-5 pm.
7. The electric power generator (EPG) according to anyone of claims 1-6, wherein said EPG comprises a further current collecter.
8. The electric power generator (EPG) according to anyone of claims 1-7, wherein the at least one current collecter is a secondary collecter made of a material selected from the 10 group consisting of: metals, porous carbon, and conductive oxides, sulphides, alloys with almost constant electric resistivity, manganèse oxide and its compounds, phosphates and mixtures or composites thereof.
9. The electric power generator (EPG) according to anyone of claims 1-8, wherein the EPG comprises a further current collecter, which is a primary current collecter.
15
10. The electric power generator (EPG) according to claim 9, wherein said primary current collecter is made of a material selected from the group consisting of: pyrolytic graphite, carbon coke and/or carbon-based materials, boron, Silicon, germanium, silver and chemically stable semiconductors in their intrinsic and extrinsic State, ceramic materials as carbides and nitrides, perovskites, spinel compounds and PET (polyethylene 20 terephthalate) and mixtures or composites thereof.
11. The electric power generator (EPG) according to claim 10, wherein said primary current collecter is made of PET polyethylene terephthalate polymeric foil with a silver conductive layer
12. The electric power generator (EPG) according to anyone of claims 1-11, wherein said 25 EPG comprises at least one porous layer.
13. The electric power generator (EPG) according to claim 12, wherein said at least one porous layer is made of cellulose, cellulose composite materials, porous carbonaceous materials, and composites with carbon matrix.
14. The electric power generator (EPG) according to claim 13, wherein the at least one 30 porous layer comprises 85% water, 1% sodium carboxy methyl cellulose and 14% powder active carbon.
'J Λ1
15. The electric power generator (EPG) according to anyone 1-14, wherein said at least one organic polymer is adsorbed on said at least one porous layer.
16. The electric power generator (EPG) according to anyone of daims 1-15, wherein said electric power generator (EPG) comprises at least one porous layer in contact to said at 5 least one active organic material.
17. A power generator module (PGM) characterized in that it comprises a plurality of electric power generators (EPGs) according to any one of the daims 1-16, wherein said generators are connected in parallel or in sériés.
Publications (1)
| Publication Number | Publication Date |
|---|---|
| OA21286A true OA21286A (en) | 2024-04-18 |
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