The present disclosure is related to an porous composite and a method of manufacturing same. In particular, the present disclosure is related to a porous metal matrix composite and a method for manufacturing same.
The storage of electric power is a key technique in electric power source management and in the usage of regenerating energy. The storage of electric power includes physical and chemical types. In consideration of the necessity of rapid electricity charging and discharging capability as well as high storage capacity, the electrochemical battery has become the first priority for the application of micro-grid energy storage.
In the field of electrochemical batteries, the well-developed hybrid lead-carbon battery, which is a combination of a conventional lead-acid battery and an asymmetrical super capacitor, provides a possible solution to implement an electric power storage device that is likely to achieve economic benefits. The super capacitor having a rapid charge and discharge capability and combined with the conventional lead-acid battery can inhibit the occurrence of a sulfurization reaction on the negative electrode (e.g. a lead plate electrode) of the battery during the high rate partial stage of charge (HRPSoC) process, which dramatically decreases the life time of the battery after each cycle of charging and discharging. The so-called sulfurization effect is that the solid metal lead (Pb(s)) on the negative electrode reacts with the sulfite ion (HSO4−(aq)) in the sulfuric acid solution during the oxidation process, and is converted into non-conductive solid sulfuric lead (PbSO4(s)). During the period in deep discharge or in the HRPSoC process, lead sulfate, which is non-conductive, easily forms and crystallizes. As the non-conductive lead sulfate grains gradually cover the surface of the lead electrode, the reverse reduction reaction cannot reduce all lead sulfate into metal lead due to poor conductivity. Thus, the energy storage efficiency of the battery is reduced and battery cycle life is also shortened.
Currently, a method to improve the issue of sulfurization of the negative electrode is to add a carbon material to the lead electrode to increase the effective electrical contact area between the lead sulfate and the conductive carbon material. This method can increase the cycle life of lead-acid batteries. However, without undergoing special high pressure (about 400 MPa) and high temperature (about 950° C.) treatment to form chemical bonds at the carbon-lead interface, the contact between the carbon materials and the lead electrode is only physically rather than chemically bonded, so the structure of the carbon modified electrode in the general process is quite loose. That is to say, the structural strength of the lead electrode decreases with the increase in the amount of carbon material added, so there is a certain limit to the addition ratio of the carbon material.
In addition, in the manufacture of such a hybrid type lead-carbon battery, a lead battery paste on a negative electrode of a conventional lead-acid battery is replaced partly or completely with a carbon material capacitor paste having a high specific area porosity. That is to say, the production of the hybrid lead-carbon battery can be completed through a highly industrialized conventional lead-acid battery manufacturing process, so it has the added benefit of low production costs. Moreover, the lead-acid battery itself has the properties of extremely high stability (or low maintenance cost) and high cyclic charge/discharge efficiency (above 75%). Therefore, this kind of hybrid lead-carbon battery can be used as an energy storage device of the micro grid class and for the lowest cost.
Although the combination of the conventional lead-acid battery and the asymmetric super capacitor can provide low-cost power storage, the high self-discharge rate and low cycle life of the battery at deep depth of discharge (DoD>50%) limit the wide application of the conventional hybrid type lead-carbon battery. The reason for the low cycle life at deep DoD is that two materials, i.e. a carbon material and a lead plate, present on the negative electrode plate are unable to bond to each other and cause the phenomena such as electrode interface corrosion and the like that easily occur on the lead-carbon interface. The reason for the high self-discharge rate is that porous carbon material with high surface area acts as an electrolyte super-capacitor storing charges and excess concentration of ions across the electric double layer. Those excess concentration of ions diffuse away and charges leak through the super-capacitor circuit when uncharged.
Therefore, a method that can effectively bond carbon material to lead material and form a porous structure of lead matrix with balanced super-capacitor effect is very important for the preparation of an electrode for the hybrid lead-carbon battery. In other words, it is a very important step on the way to achieving the goals of mass production and development of the porous hybrid lead-carbon battery with long cycle life at deep DoD.
In prior art, although the bonding problem between the lead and carbon materials can be solved by using coupling agents such as the precious metal, e.g. titanium, palladium, and platinum, or their oxides, these precious metal coupling agents are quite expensive and are still not beneficial to electrode production.
Therefore, the Applicant has disclosed a method for forming a lead-based porous substrate containing continuously interconnected lead-carbon interface layer to improve the problems of the prior art mentioned above. In addition, the Applicant has disclosed a porous metal matrix composite (MMC) having the lead-carbon interface layer and pores along the interface, and a method for producing the same.
In accordance with one aspect of the present disclosure, a method for producing a porous metal matrix composite (MMC) is provided. The method comprises the following steps: providing and stacking a first metal material and a layer including a plurality of spacing materials to form a stack; pressing the stack by applying a pressure; heating the stack under the pressure to melt a portion of the first metal material; cooling the stack to produce an MMC blank having a metal-spacing material interface; providing an electrolyte; and immersing the MMC blank into the electrolyte to form the porous MMC.
In accordance with another aspect of the present disclosure, a method for producing a porous metal matrix composite (MMC) is provided. The method comprises steps of providing a metal material; providing a spacing material forming an interconnected structure; embedding the spacing material in the metal material to form an interface between the metal material and the interconnected structure; and forming a first plurality of pores located at the interface.
In accordance with a further aspect of the present disclosure, a porous metal matrix composite (MMC) is provided. The porous MMC comprises a metal material; a spacing material forming an interconnected structure and embedded in the metal material to form an interface between the metal material and the interconnected structure; and a first plurality of pores located at the interface.
The above objectives and advantages of the present disclosure will become more readily apparent to those ordinarily skilled in the art after reviewing the following detailed descriptions and accompanying drawings, in which:
The present disclosure will now be described more specifically with reference to the following embodiments. It is to be noted that the following descriptions of embodiments of the present disclosure are presented herein for the purposes of illustration and description only; they are not intended to be exhaustive or to be limited to the precise form disclosed.
The present invention provides a feasible way to obtain a substrate having a chemically bonded lead-carbon interface. In addition, the present invention provides a feasible way to obtain a porous metal matrix composite having a lead-carbon interface.
One example of the porous metal matrix composite (MMC) is a porous lead plate having a carbon material embedded therein, or called a porous lead-carbon composite (LLC). A porous metal matrix composite having a lead-carbon interface made by the method according to the present invention can be applied to electrodes used in an acid battery including, but not limited to, a lead-acid battery. For example, the material for either one of the positive electrode (i.e. the cathode) and the negative electrode (i.e. the anode) can be a porous metal matrix composite.
According to an embodiment of the present invention, the candidate for the plurality of spacing materials can be one of a porous material and a nonporous material. The porous material is one selected from a group consisting of a microporous material, a mesoporous material, a macroporous material and a nonporous material. The microporous material is one selected from a group consisting of a microporous activated carbon material, a carbon fiber material, an activated carbon fiber material, a carbon black material, a graphene material, a graphene oxide material, a carbon nanotube material, a zeolite material, a metal organic framework material. The mesoporous material is one selected from a group consisting of a mesoporous activated carbon material and a zeolite material. The macroporous material is one selected from a group consisting of a fiber, a macroporous zeolite, a macroporous mesh, a macroporous resin, and a macroporous silica. The nonporous material is a chemically inert material. The chemically inert material is one selected from a group consisting of a stainless metal material, a metal oxide material, and a PTFE material.
In comparison with the non-woven fibers, the fibers in the woven fibers are interwoven so that the woven fibers are also inter-connected. It can be realized that, when using the woven fibers to make the porous lead-carbon material, the passages are more easily formed than that using the non-woven fibers.
As shown in
As shown in
As shown in
After the step S52 in
In another embodiment of the present invention, a second metal plate 41b can be provided, and in this case, the layer of the spacing materials 42 are sandwiched between the first metal plate 41a and the second metal plate 41b to form the stack 43, as shown in
As shown in
As shown in
If the pressing step S52 and the heating step S53 in
After the spacing materials 42 are pressed into the first metal material 41a and/or the second metal material 41b, a cooling step is performed and an MMC blank having a metal-spacing material interface, e.g. a lead carbon composite (LCC) blank having a lead-carbon interface in this case, is produced.
The MMC blank having the layer of plurality of spacing materials 42 embedded in the first metal material 41a and/or the second metal material 41b provides pores and the pathways for the electrolyte, such as sulfuric acid, to flow or penetrate into the MMC blank from its edges.
During the heating step S53 and cooling step S54 in
Expansion of Pores or Extension of Pathways in Porous Metal Matrix (MMC)
The MMC blank is then immersed into an electrolyte. The electrolyte can be one of H2O and an aqueous solution of an acid, a base, or a salt thereof. The acid is one selected from H2SO4, HNO3, HCl, HBr, HClO3, H2CO3 and CH3COOH, and the base is one selected from a group consisting of KOH and NH4OH. The base is one of KOH and NH4OH. A salt is a substance produced by the reaction of an acid with a base. A salt consists of the positive ion (cation) of a base and the negative ion (anion) of an acid. For example, the salt is, but is not limited to, one of NaCl, CaCl2, NH4Cl, CuSO4, KBr, CuCl2, NaCH3COO, CaCO3 and NaHCO3.
Initial Activation Stage
As shown in
First Discharging Stage
The MMC blank treated after the initial activation stage serves as an electrode, and a counter electrode is prepared. In a preferred embodiment according to the present invention, two MMC blanks (hereinafter called Blank A and Blank B) are immersed in an electrolyte, such as H2SO4, and serve as an anode and a cathode respectively. Similar to the operation of a lead acid battery, at the first discharging stage, a first voltage is applied to the anode and the cathode, Blank A serves as the anode, and Blank B serves as the cathode. The lead at the surface 91 or the lead at the inner surfaces 92a of Blank A is oxidized to form lead ions (Pb2+ ), and the lead ions react with sulfate ions dissociated from the sulfuric acid (H2SO4) to newly form additional grains 94b of PbSO4 at the surface or at the inner surfaces 92b that is further eroded from the inner surface 92a in the Blank A. It should be noted that, the size of the grains 94b newly formed at the first discharging stage is usually smaller than those of the grains 94a formed at the initial activation stage. It means that a lot of second pores/passages/pathways 95b are further formed between the grains 94b at the first discharging stage. The size of the second pores 95b is smaller than the pores 95a. In the meantime, the grains of the lead sulfate formed on the surfaces of the Blank B (not shown) serving as the cathode will dissociate into lead ions and sulfate ions, the lead ions dissociated from Blank B are reduced into lead to form at the surfaces or at the inner surfaces 92b in Blank B, and the sulfate ions are reduced to form sulfuric acid. The reduction-oxidation (redox) reaction occurs at the anode and the cathode results from an electro-chemical reaction during the first discharging process.
First Charging Stage
At the first charging stage, Blank B serves as the anode, and Blank A serves as the cathode now. A second voltage is applied to the anode and the cathode. The lead at the surface or at the inner surfaces of the pores in Blank B is oxidized to form lead ions, and the lead ions react with sulfate ions to form additional grains of lead sulfate at the surface or at the inner surfaces of Blank B. If the applied voltage is high enough, some gases such as hydrogen and/or oxygen are generated because of hydrolysis of water in the sulfuric acid solution. The generated gases are capable of expanding the spaces in the passages or pathways. In the meantime, Blank A serves as a cathode. As shown in
It is noted that, the reduction-oxidation (redox) reactions occurring at the first discharging stage and the first charging stage constitute one redox cycle. More redox cycles can be performed to obtain finer grains of the lead sulfate and finer grains of the reduced lead growing at Blanks A and B.
After experiencing the initiate stage, the first discharging stage, and a second discharging stage, some of the pores and passages (which form an erosion region) are formed at the positions (or the contact surfaces) that the lead material contacts the embedded plurality of the spacing materials. At the charging stage, the gasses (bubbles) of hydrogen and oxygen are formed to further erode the porous lead plate to form the erosion region.
If Blanks A and B are installed in a lead-acid battery, when the battery is operating in a vehicle, through continuing discharging and charging processes, the grains of the lead sulfate and the reduced lead will keep growing, and the size of each of the grains of the lead sulfate and the reduced lead will become smaller and smaller.
It should be also noted that, it is feasible to select any combination of the metal material and the electrolyte having the redox reaction similar to lead and sulfuric acid according to the present invention.
During the discharging stages, as shown in
Method for Forming an Electrode
A method for producing an electrode for a lead acid battery comprises the following steps: providing a metal material and a spacing material containing carbon; embedding the spacing material in the metal material to obtain a carbon-metal material; and immersing the carbon-metal material in a bath having an acid to form the electrode.
Method for Forming an Electrode for a Lead Acid Battery
An electrode for a lead acid battery comprise a metal material and a spacing material containing carbon and having an inter-connected structure with a surface. The spacing material is embedded in the metal material. The electrode further comprises a plurality of pores including a first pore and a second pore and disposed on at least a part of the surface. The electrode further comprises an additional plurality of pores disposed between the first pore and the second pore. The electrode further comprises a second layer of a plurality of carbon fibers embedded in the metal material, the first layers and the second layers of the plurality of carbon fibers have a same orientation or a different orientation. The inter-connected structure is one selected from a group consisting of 1-D, 2-D and 3-D structures.
Advantages of the Present Invention
The present invention discloses the porous metal matrix composite such as a porous lead-carbon composite having a high capacitance, a high coulomb efficiency, a high depth of discharge, and a long life-time resulting from the continuous formation of the passages for the grains of lead sulfate during the discharging and charging processes, and has the effect of a super capacitor.
The various embodiments according to the present invention described above and various changes or modifications thereof belong to the scopes of the method for forming a lead-carbon interface layer on a lead-based substrate, and the acid battery having the lead-carbon interface layer provided by the present invention. The advantages achieved by the method for forming a lead-carbon interface layer on a lead-based substrate, and the acid battery having the lead-carbon interface layer provided by the present invention include a significant improvement in the life time and the capacitance of the acid battery. In addition, because it is not necessary to use noble metal such as titanium, palladium and platinum, the cost of producing the lead-carbon interface layer is significantly lower than that of electrodes manufactured using prior techniques. Therefore, the present invention can surely be widely used in the practical applications of batteries.
While the present disclosure has been described in terms of what is presently considered to be the most practical and preferred embodiments, it is to be understood that the present disclosure need not be limited to the disclosed embodiments. On the contrary, it is intended to cover various modifications and similar arrangements included within the spirit and scope of the appended claims, which are to be accorded with the broadest interpretation so as to encompass all such modifications and similar structures.
The present disclosure claims the right of priority based on U.S. Patent Application Ser. No. 63/217,085, filed on Jun. 30, 2021, at the USPTO, the disclosure of which is incorporated herein in its entirety by reference.
Number | Date | Country | |
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63217085 | Jun 2021 | US |