JP2014182870A - Silicon catalyst battery and manufacturing method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silicon catalyst battery and a manufacturing method thereof which can solve the following problems of lithium used in conventional lithium ion secondary batteries: the resource of lithium is unevenly distributed and lithium is in danger of causing a fire and corrosion; and it has been demanded to multiply an energy density.SOLUTION: A silicon catalyst battery is used as a secondary battery. The silicon catalyst battery comprises: a positive electrode including carbon capable of oxidizing and reducing oxygen in air; a negative electrode composed of a metal electrode; a layer of electrolyte; a separator interposed therebetween; and a current collecting electrode. The positive electrode has thereinside: carbon microparticles of graphite or the like; silicon microparticles; a positive electrode catalyst such as titanium or manganese dioxide; and an auxiliary material such as alginic acid or citric acid which serves as a stabilizer for the silicon microparticles. Outside the positive electrode, the silicon catalyst battery has the current collecting electrode having small holes for natural circulation of air, and a surface-processed film made of isoprene or the like through which water never permeates. The electrolyte includes: a metal chloride solution; and as an electrolytic solution, a metal ethoxide additive agent consisting of an ether-based solvent with a metal bromide added thereto.

Description

  The present invention relates to the structure and materials of a positive electrode, a negative electrode, and an electrolyte in a battery that employs an electrolyte between positive and negative electrodes.

  Recognizing a secondary battery with an energy density about three times that of current lithium-ion batteries as a “next-generation secondary battery”, a battery that has the potential to surpass it is called a “second-generation secondary battery / storage device” “Technology”. This includes metal-air secondary batteries, all-solid-state lithium secondary batteries, s-block metal secondary batteries, multivalent cation secondary batteries, and other “new-type / new-concept” secondary batteries and capacitors and other power storage devices. Is also considered to be included. Recently, with the widespread use of portable devices such as personal computers and mobile phones, and automobiles and smart grids, the demand for secondary batteries as power sources for such devices has increased rapidly, and typical examples of such secondary batteries. Is a lithium battery using lithium (Li) as a negative electrode and carbon fluoride or the like as a positive electrode. By interposing a non-aqueous electrolyte between the positive electrode and the negative electrode, it becomes possible to prevent the deposition of metallic lithium. For this reason, lithium batteries are widely used. However, lithium is rare and expensive, and when discarded, lithium flows out, which is not preferable in the environment.

  With the progress of electric vehicles, smart houses, robots, and various portable devices, it is strongly desired to increase the capacity of power storage devices, and the demand for innovative power sources is extremely increasing. The demand for high-capacity electricity storage devices is also high due to global warming problems associated with mass energy consumption and the leveling of natural energy, and expectations for the development of metal-air batteries are increasing. As a metal-air battery, a zinc-air battery has already been put into practical use. However, these air batteries are all primary batteries, and there are problems with repeated charge and discharge.

  Since air batteries use air as the positive electrode active material, in principle, they can function as a half-cell, and use an active material with a very high energy density, which is a metal, which may result in a light, high-capacity, and inexpensive battery. If a secondary battery can be realized, it is extremely promising as a post lithium ion secondary battery. Metal / air batteries have also been developed as secondary batteries, but have not yet been realized due to problems such as suppression of dendrite (metal tree) formation and reaction with water vapor and carbon dioxide in the air.

  In recent years, great progress has been made based on nanotechnology in the shape control of mesoporous materials and negative electrode metals, solidification of electrolytes, etc., and elemental technologies for making secondary batteries are being prepared. In the case of a lithium battery, 250 Wh / Kg is said to be the limit at present, but the current situation is that the negative electrode is made of silicon and 300 Wh / Kg is aimed. As shown in FIG. 2, magnesium has a strong reducing power, and in terms of the potential with respect to the standard hydrogen electrode reference, lithium has a voltage of about minus 3V, whereas magnesium has a voltage of about minus 2.37V. In addition, the cost is low and the toxicity is low. It should be noted that volume density is very important because the energy density per volume is twice that of lithium, and the battery has to decide how much oxidizer and reductant are packed in a closed space. Excellent in this respect. Furthermore, since the melting point of the magnesium metal is over 600 degrees Celsius, this is a very safe battery. Another advantage is that a safe battery design is possible compared to lithium having a melting point of about 160 degrees Celsius.

JP 2012-89266 A JP 2012-89328 A JP 2012-64314 A JP 2011-249175 A JP 2013-12491 A

  Patent Document 1 relates to a non-aqueous electrolyte air battery including a negative electrode, a positive electrode having an oxygen redox catalyst, and a non-aqueous electrolyte containing a fullerene derivative salt in order to increase a discharge voltage in the metal-air battery. Is. Non-aqueous electrolyte air battery of the present invention includes a positive electrode having an oxygen redox catalyst, a negative electrode having a negative electrode active material, and a non-aqueous electrolysis comprising a non-metal polyvalent cation salt interposed between the positive electrode and the negative electrode. And a liquid. In the nonaqueous electrolyte air battery, the nonaqueous electrolyte contains a nonmetallic polyvalent cation salt. In such a nonaqueous electrolyte air battery, the discharge voltage can be further increased. In an air battery, oxygen radicals are generated on the positive electrode during discharge. For example, when only a lithium ion is contained as a cation, the reaction between the generated oxygen radical and the lithium ion is considered to be a one-electron reaction. On the other hand, when a polyvalent cation is included as a cation, it is considered that the reaction between oxygen radicals and lithium ions includes not only a one-electron reaction but also a two-electron reaction or a four-electron reaction.

   Patent Document 2 discloses metal air including at least an air electrode, a negative electrode, and an electrolyte layer interposed between the air electrode and the negative electrode in order to collect dendrites deposited on the negative electrode in the metal-air battery. A sealed metal-air battery system comprising a battery, wherein a separator having a property of allowing the electrolyte solution in the electrolyte layer to permeate is further interposed between the air electrode and the electrolyte layer, and at least charging is started A metal-air battery system comprising: a pressing unit that moves the separator toward the negative electrode side from the air electrode side in the electrolyte layer and presses the separator against the negative electrode. is there. Dendrite is a term related to the field of metal engineering, particularly metal structure, crystal growth, and the like, and is a structure typically observed when a metal melt is solidified, and is also called a dendritic crystal.

Patent Document 3 is characterized in that non-aqueous organic molecules are used as carriers for transporting active oxygen species because active oxygen species move and move between electrolytes in a metal-air battery. Yes. A negative electrode layer having a negative electrode active material layer containing a negative electrode active material, a negative electrode having a negative electrode current collector for collecting the negative electrode layer, an air electrode layer containing an air electrode catalyst, and a collection of the air electrode layers Transport of any of the active oxygen species O ₂ −, O ₂ 2−, O−, and HO− between an air electrode having an air electrode current collector that conducts electricity, the negative electrode, and the air electrode. An air battery having an electrolyte carrier layer containing an electrolyte carrier, wherein the number of the electrolyte carrier layers is one or more, and the carrier is a non-aqueous organic molecule. I will provide a.

  Patent Document 4 uses a selective corrosion reaction of a primary crystal such as a cast material containing a magnesium primary crystal and a eutectic in order to provide an electrode material useful as a negative electrode for a magnesium battery in a metal-air battery, An electrode material having a porous magnesium alloy surface made of a network-like eutectic remaining at a grain boundary from the surface to a predetermined depth, and a method for producing the same. The magnesium alloy is made of magnesium and at least one metal selected from the group consisting of aluminum, zinc, manganese, silicon, rare earth elements, calcium, strontium, tin, germanium, lithium, zirconium, and beryllium. In the case of a lithium battery, 250 Wh / kg is said to be the limit at present, but the current situation is that the negative electrode is made of silicon and is aimed at 300 Wh / kg. Magnesium has a strong reducing power, and in terms of the potential with respect to the standard hydrogen electrode standard, lithium produces a voltage of about minus 3.37V, while magnesium produces a voltage of about minus 3.37V. In addition, the cost is low and the toxicity is low. It should be noted that the energy density per volume is twice that of lithium, and the battery has an advantage in how much the oxidizing agent and the reducing agent are packed in a closed space. You can say that. Furthermore, since the melting point of the magnesium metal is over 600 degrees Celsius, this is a very safe battery. Another advantage is that a safe battery design is possible compared to lithium having a melting point of about 160 degrees Celsius.

  Patent Document 5 provides a slurry for an electricity storage device electrode capable of producing an electrode for an electricity storage device that is excellent in binding property and powder fall-off property and also excellent in electrical characteristics. The slurry for an electricity storage device electrode according to the present invention contains polymer particles, active material particles, and water, and a ratio of an average particle size of the polymer particles to an average particle size of the active material particles is 20. 1 to 100, and the spinnability is in the range of 30 to 80%, and the active material particles contain a silicon-based active material.

  As will be described in detail below, the present invention differs from the above-mentioned prior art in its configuration, and exhibits a high performance without using lithium, is safe, and is advantageous in terms of cost. And a manufacturing method.

  The lithium used in the conventional lithium ion secondary battery is unevenly distributed, and there is a risk of fire and corrosion. Furthermore, there is an industrial demand to double the energy density. The present invention provides a battery module and a manufacturing method for solving these problems.

  Two having a positive electrode 2 containing carbon graphite 6 that oxidizes and reduces oxygen in the air, a negative electrode 10 made of a metal electrode, an electrolyte layer 7, a separator 8 interposed therebetween, and collector electrodes 1 and 11. In the secondary battery, the inside of the positive electrode composed of carbon fine particles 6 such as graphite and silicon (silicon) fine particles 4 is used as a positive electrode catalyst 5 such as titanium or manganese dioxide, and as a stabilizer for silicon fine particles such as alginic acid or citric acid. The secondary battery is constituted by the agent 3 and the positive electrode outside includes a collecting electrode 1 with small holes so that air naturally circulates, and an electrode and a surface treatment film 12 such as isoprene that does not transmit moisture.

  The lithium used in the lithium ion secondary battery is unevenly distributed, and there is a risk of fire and corrosion. Furthermore, there is an industrial demand to double the energy density. The present invention provides a battery module that solves these problems and a method of manufacturing the same. In an air battery having a positive electrode containing graphite, a negative electrode made of a metal electrode, an electrolyte layer, and a separator 7 interposed therebetween, the inside of the positive electrode is made of metal oxide such as manganese dioxide and silicon fine particles. The outer electrode is composed of an oxygen permeable film such as an isoprene thin film that does not transmit carbon dioxide and moisture in the air and a metal mesh such as titanium, and the inner surface of the negative electrode made of a metal such as aluminum or magnesium is uneven. It consists of a negative electrode surface treatment film with a large amount, and the electrolyte contains a metal chloride as a main component and an electrolyte additive such as siloxane. In order to assemble the secondary battery, after manufacturing the positive electrode and the negative electrode, the unit battery can be quickly assembled and manufactured by applying an electrolyte to each electrode and bonding them together. After unit cells are stacked in series, they can be joined by a method such as tightening with a pressurizable bolt to maintain airtightness and improve the energy density to about 1 Wh / g or more. The battery module that can withstand

FIG. 1 is a conceptual diagram showing a configuration of a silicon catalyst battery according to the present invention. Example 1 FIG. 2 is an explanatory diagram summarizing standard oxidation-reduction potential data of metal materials, open-circuit voltage and theoretical energy density of metal-air batteries. FIG. 3 is a conceptual diagram showing the configuration of the silicon catalyst battery module according to the present invention. FIG. 4 is a graph showing charge / discharge characteristics of the silicon catalyst battery according to the present invention. Example 1 FIG. 5 is a graph showing another configuration of the silicon catalyst battery according to the present invention. FIG. 6 is a conceptual diagram showing a configuration in which the silicon catalyst battery according to the present invention is applied as an alkaline secondary battery.

  FIG. 1 is a conceptual diagram showing an example of the configuration of a silicon catalyst battery according to the present invention. A positive electrode 2 containing carbon fine particles 6 such as graphite that oxidizes and reduces oxygen in the air, a negative electrode 10 made of a metal electrode, an electrolyte layer 7, a separator 8 interposed therebetween, and collector electrodes 1 and 11 In the secondary battery having the above structure, the inside of the positive electrode composed of carbon fine particles 6 such as graphite and silicon (silicon) fine particles 4 is composed of a positive electrode catalyst 5 such as titanium or manganese dioxide, and alginic acid or citric acid as a stabilizer for silicon fine particles. In addition to the auxiliary agent 3 such as acid, the outside of the positive electrode is composed of a collecting electrode 1 with a small hole so that air naturally circulates, and an electrode and a surface treatment film 12 such as isoprene that does not transmit moisture. An aqueous solution or organic solvent (such as acetonitrile or propylene carbonate) containing chlorides such as aluminum and magnesium as the main component, and 2 as an electrolyte. A silicon catalyst battery was prepared by adding a metal ethoxide additive containing metal bromide to an ether solvent such as MeTHF.

FIG. 2 is an explanatory diagram summarizing the standard oxidation-reduction potential data of the metal material, the open-circuit voltage of the metal-air battery, and the theoretical energy density.
The standard electrode potential is an electromotive force generated between a single substance and a solution when the ion is applied to a solution in which ions are present at 1 mol / L. In a magnesium air battery, the maximum output potential is -2.76 volts.
Here, the discharge reaction formula of an example of the battery according to the present invention is expressed as follows.
Positive electrode: O ₂ + H ₂ O + 4e− → 4OH− (E ₀ = 0.4V)
Negative electrode: 2Mg + 3OH− → 2Mg ₂ O + 4e− (E ₀ = −2.36 V)

  FIG. 3 is a conceptual diagram showing the configuration of the silicon catalyst battery module according to the present invention. In this example, two pairs of metal-air single cells were produced in an air battery having a positive electrode, a negative electrode made of a metal electrode, an electrolyte layer, and a separator interposed between them, After four cells are connected in parallel and the positive electrode 2 mesh for air supply is shared, a pair of cells are connected in series to form a metal-air assembled battery, and the air is naturally collected by the air inlet 13 and the air outlet 14. After circulation, the electrode leads 15 and 16 are connected, and then stored in the case 17.

  The inner surface of the negative electrode 10 made of magnesium shown in FIG. 1 is made of a negative electrode surface treatment film 12 with many irregularities, and the electrolyte 6 has a metal air containing a chloride such as magnesium as a main component and an electrolyte additive such as citric acid. A cell was created. A unit cell is formed by joining both electrodes, and the charging voltage is charged in the range of 2.1V to 2.7V for about 1 hour, and the discharging voltage is set to about 1 in the range of 2.1V to 1.6V. It was possible to discharge for hours. FIG. 4 shows a graph showing the charge / discharge characteristics of the silicon catalyst battery obtained in this example.

   In this embodiment, a positive electrode 2 containing carbon graphite 6 that oxidizes and reduces oxygen in the air, a negative electrode 10 made of a metal electrode, an electrolyte layer 7 and a separator 8 interposed therebetween, In the secondary battery having the collector electrodes 1 and 11, the inside of the positive electrode composed of carbon fine particles 6 such as graphite and silicon fine particles 4 is composed of a positive electrode catalyst 5 such as titanium or manganese dioxide, and alginic acid as a stabilizer for the silicon fine particles. Or, it is composed of an auxiliary agent 3 such as alginic acid or citric acid as a citric acid stabilizer, and a surface treatment film such as isoprene that does not transmit moisture to the collector electrode 1 with a small hole so that air naturally circulates outside the positive electrode The electrolyte 7 has an aqueous solution or organic solvent (acetonitrile or propylene carbonate) mainly composed of chlorides such as zinc, aluminum and magnesium. A silicon catalyst battery characterized by adding a metal ethoxide additive in which a metal bromide is added to an ether solvent such as 2-MeTHF as an electrolyte, and an electrolyte.

  Here, it is also effective to use tin for the electrode according to the present invention. Tin is made of iron plated with zinc, and zinc, aluminum, and zinc / aluminum plating are mainly used for steel plates. Steel sheets with a 91% zinc / 6% aluminum / 3% magnesium plating layer have better corrosion resistance than conventional hot dip galvanized steel sheets or hot dip galvanized 5% aluminum alloy plated steel sheets, and even in severe corrosive environments Chromate that improves corrosion resistance and appearance (decoration) by immersing steel in molten zinc and galvanizing by electroplating and then immersing it in a solution containing chromium. Processing can be substituted. Furthermore, since the plating layer is hard, it has excellent scratch resistance and can be applied to various processes. In this embodiment, when such a tin plate is used and charging is performed with a constant current source that provides a current density of 0.2 amperes, the charging voltage is charged within a range of 2.1 V to 2.7 V in about 30 minutes. It was possible to do.

  FIG. 5 is a graph showing another configuration of the silicon catalyst battery according to the present invention. The negative electrode 10 made of a metal such as magnesium shown in FIG. 1 was replaced with a graphite fine particle 6 to obtain an asymmetric capacitor. It has been found that with such a configuration, the silicon catalyst battery according to the present invention effectively functions as a so-called capacitor battery.

  In this embodiment, in an air battery having a positive electrode 2, a negative electrode 10 made of a metal electrode, an electrolyte layer, and a separator interposed between them, the inside of the positive electrode 2 is manganese dioxide and silicon. Positive electrode catalyst made of fine particles, the outer surface is composed of oxygen permeable membrane and titanium mesh, the inner surface of negative electrode 1 made of magnesium is made of negative electrode surface treatment film with many irregularities, and magnesium chloride is the main component in the electrolyte And a pair of metal-air cells characterized by containing an electrolyte additive. These two unit cells were juxtaposed in parallel to share the positive electrode mesh for air supply, and then configured as a magnesium-air assembled battery. As a result, one motor with a discharge current of 0.3 A could be operated for about 1 hour. It was also found that the energy density can be improved to about 0.5 Wh / g or more in the configuration of this example.

  FIG. 6 is a conceptual diagram showing a configuration in which the silicon catalyst battery according to the present invention is applied as an alkaline secondary battery. Graphite is added to the inside of the positive electrode of the alkaline primary battery, a catalyst 5 such as transition metal oxide titanium or manganese dioxide, a positive electrode catalyst made of silicon fine particles 4, and a stabilizer 3 of Si fine particles are mixed into the alkaline electrode. A secondary battery was obtained. It has been found that with this configuration, the function of the silicon catalyst battery according to the present invention can be dramatically improved even as an alkaline secondary battery.

  In this embodiment, the negative electrode 10 made of a metal such as magnesium shown in FIG. This asymmetric capacitor has the advantages of a secondary battery and a capacitor. The battery of this example can be charged with a constant current source that has a current density of 0.01 ampere, and can be charged / discharged at a charge voltage of 1V to 2.7V, with a capacitance of about 0. 0 1 Farad. As a result, one motor of 3A could be operated for about 1 hour. In addition, it was found that the energy density can be doubled to about 1 Wh / g or more in the configuration of this example.

  The lithium used in the lithium ion secondary battery is unevenly distributed, and there is a risk of fire and corrosion. Furthermore, there is an industrial demand to double the energy density. The present invention provides a battery module that solves these problems and a method of manufacturing the same. The catalyst battery using silicon according to the present invention can improve the energy density to about 1 Wh / g or more without using lithium, and can constitute a battery module that can withstand strong vibration and impact. The silicon catalyst battery of the present invention is a low-cost, high-safety, excellent-performance battery, particularly a secondary battery, and thus can be said to have great industrial applicability.

DESCRIPTION OF SYMBOLS 1 Positive electrode metal mesh 2 Positive electrode 3 Additive to silicon 4 Silicon fine particle 5 Adjunct 6 Graphite 7 Electrolyte 8 Separator 9 Negative electrode electrolyte 10 Negative electrode 11 Oxygen permeable membrane 12 Oxygen permeable membrane 13 Air inlet 14 Air outlet 15 Positive Lead wire 16 Negative lead wire 17 Case

Claims (14)

  A positive electrode 2 containing carbon fine particles 6 such as graphite that oxidizes and reduces oxygen in the air, a negative electrode 10 made of a metal electrode, an electrolyte layer 7, a separator 8 interposed therebetween, and a collector electrode 1, 11, the positive electrode is carbon fine particles 6 such as graphite, silicon fine particles 4, positive electrode catalyst 5 such as titanium or manganese dioxide, and an auxiliary agent such as alginic acid or citric acid as a stabilizer for the silicon fine particles. 3 is a silicon catalyst battery, and its manufacturing method.   A positive electrode 2 containing carbon fine particles 6 such as graphite that oxidizes and reduces oxygen in the air, a negative electrode 10 made of a metal electrode, an electrolyte layer 7, a separator 8 interposed therebetween, and a collector electrode 1, 11, the positive electrode is carbon fine particles 6 such as graphite, silicon fine particles 4, positive electrode catalyst 5 such as titanium or manganese dioxide, and an auxiliary agent such as alginic acid or citric acid as a stabilizer for the silicon fine particles. 3. The silicon according to claim 1, wherein the outside of the positive electrode comprises a collector electrode 1 with a small hole so that air naturally circulates, and an electrode and a surface treatment film 12 that does not transmit moisture. Catalyst battery and method for producing the same.   A positive electrode 2 containing carbon fine particles 6 such as graphite that oxidizes and reduces oxygen in the air, a negative electrode 10 made of a metal electrode, an electrolyte layer 7, a separator 8 interposed therebetween, and a collector electrode 1, 11, the positive electrode is carbon fine particles 6 such as graphite, silicon fine particles 4, positive electrode catalyst 5 such as titanium or manganese dioxide, and an auxiliary agent such as alginic acid or citric acid as a stabilizer for the silicon fine particles. 3. The silicon catalyst cell according to claim 1 or 2, wherein the electrolyte 7 is an aqueous solution or an organic solvent solution containing a metal chloride as a main component.   A positive electrode 2 containing carbon fine particles 6 such as graphite that oxidizes and reduces oxygen in the air, a negative electrode 10 made of a metal electrode, an electrolyte layer 7, a separator 8 interposed therebetween, and a collector electrode 1, 11, the positive electrode is carbon fine particles 6 such as graphite, silicon fine particles 4, positive electrode catalyst 5 such as titanium or manganese dioxide, and an auxiliary agent such as alginic acid or citric acid as a stabilizer for the silicon fine particles. 3 and using an aqueous solution or an organic solvent solution containing metal chloride as a main component for the electrolyte 7, and further adding a metal ethoxide additive containing metal bromide in an ether solvent such as 2-MeTHF as an electrolyte solution The silicon catalyst battery according to claim 3 and a method for manufacturing the same.   5. The silicon catalyst cell according to claim 1, wherein the average particle size of the silicon fine particles within the positive electrode is 0.5 to 50 μm.   6. The silicon catalyst cell according to claim 1, wherein the silicon fine particle stabilizer 3 is an auxiliary agent 3 such as alginic acid or citric acid.   7. The silicon catalyst cell according to claim 1, wherein the positive electrode contains a transition metal oxide, and a method for producing the same.   8. The silicon catalyst battery according to claim 1, wherein the outside of the positive electrode is composed of a metal mesh made of titanium or the like.   9. The silicon catalyst cell according to claim 1, wherein the inner surface of the negative electrode is made of a negative electrode surface treatment film having many irregularities by mechanical processing such as mechanical or chemical processing such as oxidation.   10. The silicon catalyst cell according to claim 1, wherein the electrolyte comprises a metal chloride as a main component.   11. The silicon catalyst cell according to claim 10, wherein the electrolyte comprises a metal chloride as a main component and an electrolyte additive such as citric acid, tartaric acid or malic acid.   The electrolyte 7 contains a metal chloride as a main component, contains an electrolyte additive 14 such as citric acid, tartaric acid or malic acid, and is further dissolved in a neutral solvent such as acetonitrile. Item 12. A silicon catalyst battery according to Item 11, and a method for producing the same.   A positive electrode 2 containing carbon fine particles 6 such as graphite that oxidizes and reduces oxygen in the air, a negative electrode 10 made of a metal electrode, an electrolyte layer 7, a separator 8 interposed therebetween, and a collector electrode 1, 11, the positive electrode is carbon fine particles 6 such as graphite, silicon fine particles 4, positive electrode catalyst 5 such as titanium or manganese dioxide, and an auxiliary agent such as alginic acid or citric acid as a stabilizer for the silicon fine particles. 3, and the negative electrode includes carbon fine particles such as graphite, and a silicon catalyst battery functioning as an asymmetric capacitor and a method for manufacturing the same.   A positive electrode 2 containing carbon fine particles 6 such as graphite that oxidizes and reduces oxygen in the air, a negative electrode 10 made of a metal electrode, an electrolyte layer 7, a separator 8 interposed therebetween, and a collector electrode 1, 11, the positive electrode is carbon fine particles 6 such as graphite, silicon fine particles 4, positive electrode catalyst 5 such as titanium or manganese dioxide, and an auxiliary agent such as alginic acid or citric acid as a stabilizer for the silicon fine particles. 3, a silicon catalyst battery and a method for manufacturing the same.