WO2013165268A1

WO2013165268A1 - Galvanic cell and battery on the basis of an electrically generating material

Info

Publication number: WO2013165268A1
Application number: PCT/RU2012/000350
Authority: WO
Inventors: Владимир Николаевич ПЛАТОНОВ; Александр Иванович ДРАЧЁВ
Original assignee: Platonov Vladimir Nikolaevich; Drachev Alexander Ivanovich
Priority date: 2012-05-03
Filing date: 2012-05-03
Publication date: 2013-11-07
Also published as: RU2596214C2; RU2014137656A

Abstract

The invention relates to the field of power engineering and the production of non-traditional sources for the generation of electrical energy and can be used for the autonomous provision of electrical energy both to separate equipment, mechanisms and machines and to large-scale residential and industrial facilities. The galvanic cell consists of two electrodes and an interelectrode layer, wherein the positive electrode is formed from zinc or nickel oxide, and the negative electrode is formed from aluminium, and the interelectrode layer used is an electrically generating material, which comprises carbon structures and is produced by the procedure of thermocatalytic decomposition of volatile hydrocarbons in a temperature range of 600-800°C on a catalyst on the basis of nickel nanoparticles or nickel-aluminium alloys or a mechanical mixture of nickel and aluminium nanoparticles, wherein the electrically generating material is capable of generating electrical energy when doped with deionized water molecules and in the event of chain splitting. The battery consists of two or more galvanic cells, as described above. The technical result consists in producing a galvanic cell and a battery which generate electrical energy over a long period of time and are capable of self-restoration of electrical parameters (emf, short-circuit current) without the use of known charging methods, such as, for example: oxidation of the electrode in an electrolyte, heating, charging from an electric grid, irradiation with light, exposure to electromagnetic fields, and exposure to radioactive radiation.

Description

GALVANIC ELEMENT AND BATTERY BASED ON ELECTRICITY MATERIAL

The invention relates to the field of energy and the production of non-traditional sources of electricity production and can be used to autonomously provide electricity to individual devices, mechanisms and machines, as well as large residential and industrial facilities.

Devices are known - solar cells and batteries based on them, which convert the energy of light quanta (photons) into electrical energy. The action of solar cells is based on the use of the phenomenon of the internal photoelectric effect. The first solar cells with a conversion factor of about 6% were developed by G. Pearson, C. Fuller and D. Chapin (USA) in 1953. based on inorganic semiconductors (e.g. Si, AsGa, CdS, etc.).

Currently, solar cells with conversion coefficients up to 20% are widely used in practice. They are made of single-crystal silicon of both the “p” and “p” type (p-Si and n-Si, respectively). Such elements are made of crystalline and / or amorphous silicon, consisting of three or more heterostructures. The open circuit voltage generated by one element is about 0.6 V at 25 ° C and does not depend on the size of the element. The current generated by the element depends on the intensity of the incident light and the area of the working surface of the element exposed to solar radiation. When the solar cell is heated, the voltage generated by it decreases, characterized by a negative temperature coefficient (T N) of about -0.002V / deg. On a bright sunny day, the elements heat up to 60-70 ° C, losing up to 0.1 V.

Thus, to increase the current, it is necessary to increase the area of the working surface of solar cells or assemble parallel connected individual elements into modules located in the same plane, and to increase the voltage, cells or modules must be assembled into a battery with a series connection between each other. The rated power of one module is about 100W / m ^" (10mW / cm ^~ ).

Solar panels and methods for their manufacture are known (European patent EP 2 061 089 dated 05/20/2009 and US 2009/0084433 dated 2.04.2009), in which, as a photovoltaic cell, it generates current after exposure to solar quanta radiation, heterostructures based on crystalline and / or amorphous silicon are used. In these patents, the photovoltaic cell is arranged in such a way that solar radiation passes through a semiconductor with a large band gap, transparent in the entire optical range, and a thin layer of doped silicon. Then, the radiation enters the conversion layer, which is an i- or p- or p-type silicon layer. In the conversion layer, there is a complete absorption of light quanta and the generation of electron-hole pairs. At the interfaces n ~ i (or n-n) and opposite ip (or n-p ⁺ ) boundaries, in the case of using silicon heterostructures nip (or n ⁺ -n ^~ p ⁺ ), the opposite charges are separated. In the case of using silicon pin (or p ⁺ -p-p ⁺ ) heterostructures, the separation of opposite charges occurs at the pi (or p ⁺ -p) interfaces and opposite in (or p-p ^' ) boundaries, as a result of which , under the influence of sunlight in the photovoltaic cell an emf (voltage) is generated.

The main drawback of the listed photovoltaic cells and solar panels based on them is the complete dependence on the intensity solar radiation and the inability to accumulate electricity in low light or complete absence thereof (for example, on cloudy days and at night). In addition, these elements and panels require the use of additional optically transparent moisture-proof protective layers of inorganic glass and / or polymers, which eliminate the destructive effect of water. An important point in the operation of solar cells is their temperature regime. When an element is heated by one degree above 25 ° C, it loses 0.002 V in the generated voltage, i.e. 0.4% per hail. On a bright sunny day, the elements are heated to 60-70 ° C, losing up to 0.1V in the emf. This is the reason for the decrease in the efficiency of solar cells, leading to a drop in the EMF and the power generated by the cell.

A device is known - an electrochemical cell and a battery operating on the basis of the conversion of chemical energy released in an electrolyte during the oxidation of an aluminum or lithium anode when interacting with hydrogen peroxide or oxygen and OH ions into electrical energy (US Pat. No. 6,573,008 In 1 dated 03.01.2003 and Germany DE 698 30 917 T2 dated 05.24.2006). The cathode has a cylindrical shape and consists of radially oriented carbon fibers fixed to a metal frame. The cathodes and anodes are immersed in a flowing electrolyte of a KOH or NaOH solution with a concentration of from 0.003M to 15M. To reduce the concentration of A1 (OH) ₃ as an oxidation product in the electrolyte and to maintain continuous operation of the device, the electrolyte is changed in the cell, which is provided by a circulation pump. The device uses a series and parallel connection of cathodes and anodes, depending on its required electrical parameters. Taking into account the consumption of reagents, the device is characterized by a specific energy output of 150Wh / kg at a certain load at the rate of 3, ZW / kg. An additional increase in energy density can be achieved. W

four

dashed by increasing the concentration in the electrolyte. Thus, an increase in the concentration of KOH to 12 M gives an increase in the energy density to about 250 Wh / kg in a balanced system. An electric cell is able to constantly work with a nominal load, provided that the electrolyte is replaced periodically every 1, 5 days and the aluminum anode after 100 hours.

The main disadvantage of the battery based on aluminum oxidation is that the formed particles A1 (OH) ₃ are deposited on the cathode and reduce the electrical parameters of the device. To reduce the concentration of A1 (OH) ₃ in the electrolyte and to maintain stable device parameters, a constant change of electrolyte in the battery is necessary.

The closest in technical essence and the achieved result to the claimed invention is a solar panel presented in EP 2 061 089 dated 05/20/2009, having a transparent glass substrate 1.4x 1 .1m and 4mm thick and many photos galvanic cells located on it. Each of the photovoltaic cells includes an optically transparent conductive layer, a photoelectric conversion layer, and a reverse electrode layer, which are formed on the substrate in this order. The photoelectric conversion layer has a flat structure either in the form of a thin silicon film consisting of p-, i-, and η-type layers, or it enters a more complex tandem system of a solar cell (cell) consisting of many layers of different flat structures. According to the prototype, the conversion layer consists of pin heterostructures made on the basis of amorphous silicon. The p-type layer deposited on an optically transparent conductive layer is boron-doped amorphous silicon carbide (SiC) 10–30 nm thick. The i-type layer contains amorphous silicon with a thickness of 250 - 350 nm. The η-type layer consists of phosphorus-doped microcrystalline silicon with a thickness of 30 - 50 nm. To improve the boundary properties between the p- and i-type layers, a buffer layer is formed. A metal film consisting of Ag (200–500 nm thick) and anticorrosive Ti (10–20 nm thick) layers deposited in such a way that the silver layer is internal is used as the reverse electrode layer. An intermediate ZnO layer doped with Ga with a thickness of 50-100 nm is used to reduce the contact resistance between the η layer and the return electrode layer and to improve light reflection.

The device described in the patent EP 2 061 089 has all the disadvantages listed above for solar cells and panels, and the method of its manufacture is multi-stage and has separate stages, which are complex CVD and / or laser deposition technologies for each layer individually in sequence defined by the design of the solar panel.

The objective of the invention is the creation of a galvanic cell and battery that produce electrical energy for a long time and capable of self-healing of electrical parameters (EMF, short circuit current) without using known charging methods, such as, for example, oxidation of an electrode in an electrolyte - those (for example, an aluminum anode in an alkaline medium in the presence of oxygen or hydrogen peroxide), heating, charging from the electric network, exposure to light (for example, solar energy), e electromagnetic fields, exposure to radioactive radiation (γ-rays, high-energy particles).

The problem is solved by synthesizing an electro-generating material containing carbon structures obtained by thermocatalytic decomposition of volatile hydrocarbons in the temperature range of 600 - 800 ° C on a catalyst based on nickel or nickel-aluminum alloy nanoparticles, or mechanical GMPRI u unuow ..! aluminum. The synthesized electro-generating material is capable of producing electricity when it is doped with molecules of deionized water, and placed between two dissimilar electrodes. When the electrodes are closed, an electric current arises in the circuit, the parameters of which gradually decrease over a long time (more than 2 days). However, the subsequent opening of the circuit leads to the restoration of the electrical parameters of the galvanic cells and the battery within a few minutes. In this case, the process of generating current into the external circuit proceeds without using known charging methods. X-ray diffraction analysis, electron microscopy, and X-ray microanalysis showed that the electric-generating material consists mainly of carbon nanoparticles with a size of 50 - 200 nm, having a graphite structure, containing less than 1 at.% Nanoparticles of nickel or nickel and aluminum in their volume .

The claimed devices (a galvanic cell and a battery based on two or more cells) differ from the above devices in that the current generation process proceeds: 1) without using known charging methods, for example, such as: irradiation with light, as in the case of tea solar panels; 2) without the use of alkaline electrolytes in which the oxidation of aluminum proceeds.

Thus, a fundamentally new technical result is achieved, namely, that the inventive devices (galvanic cell and battery) do not require the use of known charging methods to restore their electrical parameters, for example, such as chemical oxidation , heating, charging from the electric network, exposure to light (for example, solar energy), exposure to electromagnetic fields, exposure to radioactive radiation (γ-rays, high-energy particles). Figure 1 shows an electron micrograph (magnification x40000) of an electro-generating material synthesized by the thermocatalytic method at a temperature of 720 ° C in an atmosphere of argon and acetylene in the ratio argon / acetylene = 1/10 on a catalyst representing nickel powder.

Figure 2 presents an electron micrograph (magnification x40000) of an electrically generating material synthesized by the thermocatalytic method at a temperature of 720 ° C in an atmosphere of argon and acetylene in the ratio argon / acetylene = 1/10 on a catalyst representing a mechanical mixture of nickel nanopowders and aluminum in the ratio Ni / Al = 4 / \.

The invention can be illustrated by the following examples:

Example 1

The carbon material was synthesized by the thermocatalytic method at a temperature of 720 ° C in an atmosphere of inert (argon) and hydrocarbon gas (acetylene) in the ratio argon / acetylene = 1/10 on a catalyst containing Raney nickel particles (nickel-aluminum alloy).

A sample of the galvanic cell is prepared in the form of a tablet with a diameter of 10 mm, consisting of three layers: the first is an electrode of conductive zinc oxide ZnO (positive electrode), the second (interelectrode) is 20 ml of carbon material doped with 0.03 ml of deionized water, 3rd - aluminum electrode (negative electrode). Sample preparation was carried out by pressing a powder of carbon material between the electrodes. The prepared galvanic cell was stored in a desiccator at a humidity of 100% and was constantly in short circuit mode. The EMF of the element was measured immediately after its manufacture, after storage for a certain time in the short circuit mode and subsequent opening of the circuit and 10 minutes after the circuit was opened. After taking the EMF measurements, the element again shorted out.

The operation of the element is presented in the table. During 6 hours of operation of the element in the short circuit mode, the short circuit current gradually decreased from 1 mA to 0.23 mA, and the EMF from 0.25 V to 0.09 V. The subsequent opening of the circuit leads to the generation and restoration of the EMF to 0.27V and the short-circuit current to 0.96mA during Yumin.

Example 2

The carbon material and the sample of the power generating element were prepared according to Example 1, but a nickel electrode was used instead of the ZnO electrode.

The operation of the element is presented in the table. During the 6 hours of operation of the element in the short circuit mode, the short circuit current gradually decreased from 3.05 mA to 1.24 mA, and the EMF from 0.19 V to 0.07 V. The subsequent opening of the circuit leads to the generation and restoration of the EMF to 0.20 V and the short circuit current to ZmA during Yumin.

Example 3

The carbon material and the sample of the power generating element were prepared according to Example 1, and in addition to this, 50 wt.% Titanium oxide powder was added to the carbon material.

The operation of the element is presented in the table. Over the course of 6 hours of operation of the element in the short circuit mode, the short circuit current gradually decreased from 3.71 mA to 2, ZZmA, and the EMF from 0.61 V to 0.22 V. Subsequent opening of the circuit leads to the generation and restoration of EMF up to 0.6 V and short-circuit current up to 3.68 mA for Yumin. Example 4

The carbon material and the sample of the power generating element were prepared according to example 1, but the temperature of the synthesis of the carbon material was 620 ° C.

The operation of the element is presented in the table. During 6 hours of operation of the element in the short circuit mode, the short circuit current gradually decreased from 1.4 mA to 0.23 mA, and the EMF from 0.02 V to 0.01 V. The subsequent opening of the circuit leads to the generation and restoration of the EMF to 0, 02V and short circuit current - up to 1, 42mA during Yumin.

Example 5

The carbon material was synthesized according to Example 4, and a sample of the power generating element was prepared according to Example 1, and in addition to this, 50 wt.% Titanium oxide powder was added to the carbon material.

The operation of the element is presented in the table. During 6 hours of operation of the element in the short circuit mode, the short circuit current gradually decreased from 3.55mA to 2.22mA, and the EMF from 0.35V to 0.16V. Subsequent opening of the circuit leads to the generation and restoration of EMF up to 0.37V and short circuit current - up to 3.5mA during Yumin.

Example 6

The carbon material was synthesized by the thermocatalytic method at a temperature of 720 ° C in an atmosphere of inert (argon) and hydrocarbon gas (acetylene) in the ratio argon / acetylene = 1/10 on the catalyst, which is a mechanical mixture of nickel and aluminum nanopowders.

A sample of the cell is prepared in the form of a tablet according to Example 1. The operation of the cell is presented in the table. Over the course of 6 hours of operation of the cell in the short circuit mode, the short circuit current gradually decreased from 2.98 mA to 1, 73 mA. and ESN - Fri O? 3 R up to 0.1 IB. Subsequent opening of the circuit leads to the generation and restoration of the EMF to 0.23 V and the short circuit current to 2.96 mA for 10 minutes.

Example 7

The carbon material was synthesized according to Example 6, a sample of the power generating element was prepared according to Example 1. And in addition to this, 50 wt.% Of titanium oxide powder was added to the carbon material.

The operation of the element is presented in the table. Within 6 hours of operation of the element in the short circuit mode, the short circuit current gradually decreased from 1, 96mA to 1, 23mA, and the EMF from 0.25V to 0. 15V. Subsequent opening of the circuit leads to the generation and restoration of the EMF to 0.23 V and the short circuit current to 1, 96 mA for 10 minutes.

Example 8

The carbon material was synthesized according to example 6, a sample of the power generating element was prepared according to example 2.

The operation of the element is presented in the table. During 6 hours of operation of the cell in the short circuit mode, the short circuit current gradually decreased from 4.76mA to 2.25mA, and the EMF from 0.46V to 0.23V. Subsequent opening of the circuit leads to the generation and restoration of the EMF to 0.51 V and the short circuit current to 4.69 mA for 10 minutes.

Example 9

The carbon material was synthesized by the thermocatalytic method at a temperature of 720 ° C in an atmosphere of inert (argon) and hydrocarbon gas (acetylene) in the ratio argon / acetylene = 1/10 on the catalyst, which is nickel powder. A sample of the cell is prepared in the form of a tablet according to Example 2. The operation of the cell is presented in the table. Within 6 hours of operation of the element in the short circuit mode, the short-circuit current gradually decreased from 5.6 mA to 1, 77 mA, and the EMF from 0.21 V to 0.1 V. Subsequent opening of the circuit leads to the generation and restoration of the EMF to 0, 21V and short circuit current - up to 5.6mA for 10 minutes.

Example 10

The carbon material was synthesized by the thermocatalytic method at a temperature of 720 ° C in an inert atmosphere (argon) and hydrocarbon gas (acetylene) in the ratio argon / acetylene = 1/10 on a catalyst containing Raney nickel particles. Then, 50 wt.% Titanium oxide powder is added to the carbon material.

10 samples of a galvanic cell were prepared in the form of tablets with a diameter of 30 mm, consisting of three layers: the first was a nickel electrode, the second was 20 ml of carbon material doped with 0.04 ml of deionized water, and the third was an aluminum electrode.

On the basis of the fabricated samples of the galvanic cells, a battery was made in which all the samples were collected sequentially between each other in a stack. In the stack, the aluminum electrode of each subsequent element was in contact with the nickel electrode of the previous one.

Over the course of 6 hours of battery operation in short circuit mode, the short circuit current gradually decreased from 29mA to 1 6mA, and the EMF from 6, 1V to 2.2V. Subsequent opening of the circuit leads to the generation and restoration of EMF up to 6, 1 V and short-circuit current up to - 30 A during Yumin. Table. Short-circuit currents (1 _K ) and EMF (U) of samples of galvanic cells prepared according to examples 1-7, immediately after manufacturing, after long-term operation in the short-circuit mode (t _imi = 0) and after 10 min after open circuit (1 _ISM = 10min).

Claims

CLAIM

one . A galvanic cell consisting of two electrodes and an interelectrode layer, characterized in that the positive electrode is made of zinc oxide or nickel, the negative electrode is made of aluminum, and an electro-generating material containing carbon structures is used as the interelectrode layer obtained by thermocatalytic decomposition of volatile hydrocarbons in the temperature range of 600 - 800 ° C on a catalyst based on nickel nanoparticles or nickel-aluminum alloys or a mechanical mixture of nickel nanoparticles and aluminum, while the electricity generating material is doped with molecules of deionized water.

2. The galvanic cell according to claim 1, characterized in that the power generating material contains 50 wt.% Titanium oxide powder.

3. A battery consisting of two or more galvanic cells made according to claim 1 or claim 2.

SUBSTITUTE SHEET (RULE 26)