Porous lead-carbon composite pole piece and manufacturing method thereof and lead-carbon composite battery

Abstract

The method for making a lead-carbon composite pole piece, a lead-carbon composite pole piece, and a lead-carbon composite battery disclosed in the present invention are to oxidize part of the lead material into lead oxide as an interface layer for combining the carbon material and the lead material in a low-temperature atmospheric environment, and then use a special exhaust method to connect the lead material and the carbon material; this lead oxide interface layer serves as a stable interface between the carbon material and the lead material, and at the same time, by controlling the pressure and temperature, a porous metal composite material is formed as a penetration path for gas and liquid in the back-end application. Therefore, the porous metal composite material formed by the lead-carbon connection can be used as a lead-carbon electrode piece, and can further be used as an electrode piece of a lead-carbon battery. The lead-carbon battery equipped with this lead-carbon composite pole piece has a coulomb efficiency of 100% in an unsaturated charge and discharge state with high efficiency charging and high efficiency discharging, and there is no heat energy loss.

Description

Technical Field

[0001] The present invention relates to a manufacturing method, and more particularly to a manufacturing method for a lead-carbon composite pole piece. The porous lead-carbon composite pole piece made by lead-carbon bonding can be further welded by wires to serve as an electrode piece of a lead-carbon composite battery. Background Art

[0002] Green energy has been a topic of widespread concern in recent years. Currently, in response to intermittent power generation types such as wind power generation and solar power generation, a distributed power storage system is used. The batteries used in this power storage system must meet two conditions: first, a higher energy density; second, a longer cycle charge and discharge life. With the development and expansion of green energy, the demand for energy storage with both high energy density and fast charge and discharge characteristics is expected to grow rapidly in the near future. However, as the preferred electrochemical battery for building green power microgrid energy storage, under the existing technical background, it generally has disadvantages such as easy electrode wear and short life.

[0003] In order to solve the above problems, storage components with lithium ion capacitors as the core are being actively developed. They use electrolytes containing lithium salts to charge and discharge through non-Faradaic reactions of anion adsorption and desorption in the positive electrode and lithium ion absorption and release in the negative electrode. In addition, the electrodes of lithium ion capacitors use oxides or carbon materials to increase their energy density, which can be 10 times higher than the non-Faradaic reaction using activated carbon, but there are currently no insurmountable issues in terms of battery life and charge and discharge efficiency. On the one hand, composite lead-carbon batteries have also attracted much attention because of their long life and are expected to reduce the cost loss caused by cyclic charge and discharge. However, the redox potential of carbon electrodes is much lower than that of lead plates, so the discharge voltage of lead-carbon batteries is mostly lower than 1.0V, which will lead to low energy storage efficiency.

[0004] The composite lead-acid battery developed by Axion in the United States is a lead-acid battery plus a supercapacitor. It uses the positive electrode placed on activated carbon to form a supercapacitor electrode. In order to avoid physical interface corrosion between the activated carbon material and lead, a corrosion-resistant conductive protective layer is used in this composite lead-acid battery to isolate the acid. However, the corrosion-resistant conductive protective layer has a high interface resistance with the electrode, which greatly affects the battery capacity. In addition, the cost of the corrosion-resistant conductive protective layer is high, making it difficult to fully amortize and reduce the cost.

[0005] The UltraBattery is improved by increasing the specific surface area of ​​carbon materials and stabilizing the lead-carbon bonding. Specifically, the ground carbon fibers are made into a honeycomb grid, carbonized under a nitrogen flow at a high temperature of 1000°C, and then electroplated with lead-tin to form a lead-carbon electrode skeleton. Then, a carbon fiber mixture is coated on the lead-tin-plated honeycomb grid, dried at 60°C for 48 hours, and then welded with pure lead wiring, and then carbonized to complete the lead-carbon negative electrode to increase the negative plate capacity and battery life. Although this method increases the specific surface area of ​​carbon materials and utilizes the good conductivity of carbon fibers after high-temperature carbonization to electroplate lead-tin to complete the lead-carbon bonding, such a production process is more complicated and costly.

[0006] In order to increase the specific surface area of ​​the electrode, templates are also used to electroplate long Pb and PbO2 nanowires to inhibit battery sulfidation under high-speed charge and discharge. PbO2 nanowires / PbO2 are used as the positive electrode and combined with commercial negative electrodes (containing activated carbon materials) to form a battery. The commercial negative electrode is replaced every 200 cycles to conduct HRPSoC charge and discharge tests. The test results show that the charge and discharge cycle life can reach 1400 times from 1C to high-power 10C, and the charge and discharge efficiency can reach 90%. However, this electrode is made by using sputtered gold film to catalyze the growth of nanowires and chloroform to wash away the polycarbonate template. It is expensive and has the risk of derivative pollution, making it difficult to mass produce. Summary of the invention

[0007] The electrode production of advanced lead-acid or composite lead-carbon batteries mainly involves applying lead paste to the lead grid, which is aged to achieve better adhesion and cohesion. Therefore, during the battery charging and discharging / oxidation-reduction process, it is easy to fall off due to volume changes, causing the electrode to be worn out as the battery is used more frequently. On the one hand, using composite lead-carbon batteries or lead-acid batteries to solve the service life or capacity problems has derivative problems such as low energy storage efficiency or high production costs that need to be solved.

[0008] Therefore, in order to solve the above-mentioned problems that the existing technology has not been able to overcome, the present invention provides a method for manufacturing a lead-carbon composite electrode, which comprises the following steps: providing a first lead material, a second lead material and a carbon material, wherein any main side surface of the first lead material is bonded to the carbon material, and any main side surface of the second lead material is bonded to the carbon material, so that the carbon material is located between the first lead material and the second lead material; at a first temperature, causing the air between the first lead material and the carbon material or between the second lead material and the carbon material to generate expansion pressure to discharge the air; and at the first temperature, applying external pressure to the first lead material, the second lead material and the carbon material and maintaining the temperature and pressure for 2 to 10 minutes to allow them to be composited, wherein the first temperature is 300 to 360°C, and the external pressure is 70 to 120 kg / m 2 .

[0009] In some embodiments, the manufacturing method further includes: placing a lead-carbon sandwich formed by the first lead material, the carbon material and the second lead material in a hot pressing mold, wherein the hot pressing mold includes: a punch, the punch having a plurality of punch exhaust holes and a punch ventilation groove, the punch exhaust holes are evenly dispersed along the inner side of the punch flange, and the punch ventilation groove is formed along the outer side of the flange; a die, the die having a plurality of die exhaust holes and a die ventilation groove, the die exhaust holes are evenly dispersed along the inner side of the die die edge corresponding to the punch exhaust holes, the die ventilation groove is a groove structure formed by an annular spiral arrangement along the inner side of the die edge toward the geometric center of the die, wherein, when the punch is engaged relative to the die, the punch exhaust groove is connected to the die exhaust groove for exhaust.

[0010] In some preferred embodiments, before providing the first lead material and the second lead material, a pre-treatment step is further included, and the steps include: continuously oxidizing the first lead material and the second lead material in an atmospheric environment at a second temperature, wherein the second temperature is 0 to 400°C.

[0011] In some preferred embodiments, before providing the carbon material, the carbon material is further cut into small pieces or drawn into threads; wherein the carbon material is carbon cloth, and the carbon material does not contain a carboxyl group (COOH).

[0012] Another object of the present invention is to provide a lead-carbon composite pole piece, which comprises: a first lead material; a second lead material; and a carbon material, wherein any main side surface of the first lead material is bonded to the carbon material, and any main side surface of the second lead material is bonded to the carbon material, so that the carbon material is located between the first lead material and the second lead material, and at a first temperature, the air between the first lead material and the carbon material or between the second lead material and the carbon material generates expansion pressure to discharge the air; and at the first temperature, external pressure is applied to the first lead material, the second lead material and the carbon material and the temperature and pressure are maintained for 2 to 10 minutes to make them composite, wherein the first temperature is 300 to 360°C, and the external pressure is 70 to 120 kg / m 2 .

[0013] In some preferred embodiments, before providing the first lead material and the second lead material, the first lead material and the second lead material are further pre-treated, and the pre-treatment includes: continuously oxidizing the first lead material and the second lead material in an atmospheric environment at a second temperature, wherein the second temperature is 0 to 400°C; wherein, before providing the carbon material, the carbon material is further cut into small pieces or drawn into threads; wherein the carbon material is carbon cloth, and the carbon material does not contain a carboxyl group (COOH).

[0014] In some preferred embodiments, the first lead material has a first welding point adjacent to the edge of the carbon material, and the second lead material has a second welding point corresponding to the first welding point adjacent to the edge of the carbon material, for welding to the electrode contacts of the lead-carbon battery.

[0015] Another object of the present invention is to provide an electrode sheet set, which comprises: a first lead-carbon composite electrode sheet, which is the lead-carbon composite electrode sheet as described above; a second lead-carbon composite electrode sheet, which is the lead-carbon composite electrode sheet as described above; and at least an absorbent glass fiber mat, the first lead-carbon composite electrode sheet is disposed on the absorbent glass fiber mat, and the second lead-carbon composite electrode sheet is disposed on the absorbent glass fiber mat relative to the first lead-carbon composite electrode sheet. Preferably, the electrode sheet set further comprises a lead plate, wherein the lead plate is a pure lead plate or a pure lead plate coated with lead paste.

[0016] Another object of the present invention is to provide a lead-carbon composite battery, which comprises: a positive electrode contact; a negative electrode contact; an electrolyte; at least a positive electrode sheet group, which is an electrode sheet group as described above, is arranged in the electrolyte and connected to the positive electrode contact by wire welding; and at least a negative electrode sheet group, which is an electrode sheet group as described above, is arranged in the electrolyte and connected to the negative electrode contact by wire welding.

[0017] The lead sheet electrode provided by the present invention is formed by integrating the nano-lead particles and pore structure formed by the unsaturated charge and discharge process with the lead plate, and has a strong bonding force. Therefore, the capacity of the battery increases with the increase of charge and discharge, and has a long service life. The simple process can achieve the effect of reducing costs. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 The present invention provides a flowchart of the steps of a method for manufacturing a lead-carbon composite pole piece.

[0019] Figure 2A It is a top view of a preferred embodiment of the hot pressing mold provided by the present invention.

[0020] Figure 2B It is a perspective view of the corresponding connection between the male mold and the female mold of the hot pressing mold provided by the present invention.

[0021] Figure 2C It is a side view of the male and female molds of the hot pressing mold provided by the present invention after being correspondingly joined and fixed.

[0022] Figure 3 It is a Fourier transform infrared spectrum used to illustrate the detection results of functional groups of carbon cloth produced by different manufacturers.

[0023] Figure 4A This is a 1000-fold SEM magnified image of the surface of the lead-carbon composite pole piece of the present invention after being corroded by nitric acid.

[0024] Figure 4B This is a 5000-fold SEM magnified image of the surface of the lead-carbon composite pole piece of the present invention after being corroded by nitric acid.

[0025] Figure 5 The present invention is a lead-carbon composite electrode after the cyclic voltammetry test, the surface of the electrochemical display amplification image.

[0026] Figure 6 It is a schematic diagram of the lead-carbon composite of the lead-carbon composite pole piece provided by the present invention.

[0027] Figure 7 It is a schematic diagram of the decomposition of the electrode sheet assembly provided by the present invention.

[0028] Fig. 8A It is the contact surface between the lead-carbon composite pole piece 11181 and the hot pressing mold punch.

[0029] Figure 8B It is the contact surface between the lead-carbon composite pole piece 11181 and the hot pressing mold cavity.

[0030] Fig.9A It is the contact surface between the lead-carbon composite pole piece 11182 and the hot pressing mold punch.

[0031] Fig. 9B It is the contact surface between the lead-carbon composite pole piece 11182 and the hot pressing mold cavity.

[0032] Fig. 10A It is the contact surface between the lead-carbon composite pole piece 11186 and the hot pressing mold punch.

[0033] Fig. 10B It is the contact surface between the lead-carbon composite pole piece 11186 and the hot pressing mold cavity.

[0034] Fig.11A It is the contact surface between the lead-carbon composite pole piece 11187 and the hot pressing mold punch.

[0035] Fig. 11B It is the contact surface between the lead-carbon composite pole piece 11187 and the hot pressing mold cavity.

[0036] Fig. 12A It is the contact surface between the lead-carbon composite pole piece 05241 and the hot pressing mold punch.

[0037] Fig. 12B It is the contact surface between the lead-carbon composite pole piece 05241 and the hot pressing mold cavity.

[0038] Fig.13A It is the contact surface between the lead-carbon composite pole piece 05242 and the hot pressing mold punch.

[0039] Fig. 13B It is the contact surface between the lead-carbon composite pole piece 05242 and the hot pressing mold cavity.

[0040] Fig.14AIt is the contact surface between the lead-carbon composite pole piece 10271 and the hot pressing mold punch.

[0041] Fig. 14B It is the contact surface between the lead-carbon composite pole piece 10271 and the hot pressing mold cavity.

[0042] Fig.15A It is the contact surface between the lead-carbon composite pole piece 10272 and the hot pressing mold punch.

[0043] Fig. 15B It is the contact surface between the lead-carbon composite pole piece 10272 and the hot pressing mold cavity.

[0044] Fig.16A It is the contact surface between the lead-carbon composite pole piece 12211 and the hot pressing mold punch.

[0045] Fig. 16B It is the contact surface between the lead-carbon composite pole piece 12211 and the hot pressing mold cavity.

[0046] Fig.17A It is the contact surface between the lead-carbon composite pole piece 12212 and the hot pressing mold punch.

[0047] Fig. 17B It is the contact surface between the lead-carbon composite pole piece 12212 and the hot pressing mold cavity.

[0048] Fig.18A It is the contact surface between the lead-carbon composite pole piece 12213 and the hot pressing mold punch.

[0049] Fig.18B It is the contact surface between the lead-carbon composite pole piece 12213 and the hot pressing mold cavity.

[0050] Fig.19A It is the contact surface between the lead-carbon composite pole piece 12214 and the hot pressing mold punch.

[0051] Fig.19B It is the contact surface between the lead-carbon composite pole piece 12214 and the hot pressing mold cavity.

[0052] Fig. 20A It is the contact surface between the lead-carbon composite pole piece 12231 and the hot pressing mold punch.

[0053] Fig. 20B It is the contact surface between the lead-carbon composite pole piece 12231 and the hot pressing mold cavity.

[0054] Fig.21A This is the charge and discharge capacity trend chart of LCFN28_2 cyclic charge and discharge.

[0055] Fig. 21B This is the Coulomb efficiency trend chart of LCFN28_2 cyclic charge and discharge.

[0056] Fig.22A It is a graph showing the cyclic voltammetry curve of the pure lead electrode of Experimental Example 5 from 1 to 500 times.

[0057] Fig. 22B It is a graph showing the cyclic voltammetric curves of the lead-carbon composite electrode of Experimental Example 5 from the 1st to the 500th time.

[0058] Fig. 22C It is a cyclic voltammetric analysis curve showing the 50th cycle of the lead-carbon composite electrode of Experimental Example 5.

[0059] Fig.22D It is a cyclic voltammetric analysis curve showing the 500th cycle of the lead-carbon composite electrode of Experimental Example 5. DETAILED DESCRIPTION

[0060] In order to provide a further understanding and recognition of the features and effects of the present invention, only preferred embodiments and accompanying drawings are described in detail as follows:

[0061] Please refer to Figure 1 One embodiment of the present invention provides a method for manufacturing a lead-carbon composite pole piece, which comprises:

[0062] Step 101: providing a first lead material, a second lead material and a carbon material, wherein any main side surface of the first lead material is bonded to the carbon material, and any main side surface of the second lead material is bonded to the carbon material, so that the carbon material is located between the first lead material and the second lead material;

[0063] Step 102: Apply external pressure to the first lead material, the second lead material and the carbon material at a first temperature and maintain the temperature and pressure for 2 to 10 minutes to compound them, wherein the first temperature is 300 to 360° C. and the external pressure is 70 to 120 kg / m 2 .

[0064] In some preferred embodiments, the method for manufacturing the lead-carbon composite electrode further comprises step 101': placing the lead-carbon sandwich formed by the first lead material, the carbon material and the second lead material in a hot pressing mold 2, wherein, see Figure 2A, is a top view of a preferred embodiment of the hot pressing mold 2, the hot pressing mold 2 includes: a punch 21, the punch 21 has a plurality of punch exhaust holes 211 and a punch ventilation groove, the punch exhaust holes 211 are evenly dispersed along the inner side of the flange of the punch 21, and the punch ventilation groove is formed along the outer side of the flange; a die 22, the die 22 has a plurality of die exhaust holes 221 and a die ventilation groove 222, the die exhaust holes 221 are evenly dispersed along the inner side of the die edge of the die 22 corresponding to the punch exhaust holes 211, the die ventilation groove 222 is a groove structure formed by annular spiral arrangement along the inner side of the die edge toward the geometric center of the die, wherein, when the punch 21 is engaged with the die 22, the punch exhaust holes 211 are connected with the die exhaust holes 221 for exhaust.

[0065] Specifically, the lead-carbon sandwich formed by the first lead material, the carbon material and the second lead material contains air between the interlayers under the action of the external pressure, which generates internal expansion pressure to make the air flow along the cavity vent groove 222 to the punch vent groove. Then, the air flows along the punch vent groove to the punch exhaust hole 211 and the cavity vent hole 221 and is discharged from the hot pressing mold 2. This design allows the internal expansion pressure to be applied to the hot pressing mold 2 while the external pressure is applied to the hot pressing mold 2, prompting the lead material to cover the carbon material to form the lead-carbon composite electrode; please refer to Figure 2B , is a perspective view of the corresponding engagement of the convex mold 21 and the concave mold 22 of the hot pressing mold 2. Preferably, the concave mold 22 further includes a concave mold overflow groove 223 and a positioning pin 224. The concave mold overflow groove 223 protrudes from the outer side of the concave edge of the concave mold 22 to form a groove structure. When the external pressure is applied to the lead-carbon sandwich, the positioning pin 224 fixes the lead-carbon sandwich to the bottom of the concave mold 22. Under the action of the hot pressing temperature, the lead material is in a semi-molten state. Under the corresponding action of the internal expansion pressure, the semi-molten lead material fixed at the bottom of the concave mold 22 overflows toward the concave edge of the concave mold 22 into the concave mold overflow groove 223. After the lead-carbon composite electrode is completed, the user can also easily remove the lead-carbon composite electrode through the lead sheet solidified in the concave mold overflow groove 223.

[0066] Please continue to refer to Figure 2A In order to cope with the excessive internal pressure of the mold caused by the external pressure and the internal expansion pressure, it is preferred that the punch 21 further includes a punch overflow groove 213, and the punch overflow groove 213 forms a groove structure along the outer side of the flange. When the external pressure is applied to the lead-carbon sandwich, under the interaction of the external pressure and the internal expansion pressure, the semi-molten lead material flows toward the outside of the flange to the punch overflow groove 213 to achieve the effect of pressure relief.

[0067] Please refer to Figures 2A to 2C ,in Figure 2CIt is a side view of the punch 21 and the die 22 of the hot pressing mold 2 after being correspondingly engaged and fixed. Preferably, the punch 21 further includes a plurality of punch locking holes 215, and the die 22 includes a plurality of die locking holes 225. The punch locking holes 215 are evenly dispersed along the outer side of the flange of the punch 21, and the die locking holes 225 correspond to the punch locking holes 215 and are evenly dispersed along the outer side of the concave edge of the die 22. When the punch 21 and the die 22 are correspondingly engaged, the punch locking holes 215 are connected with the die locking holes 225, and the hot pressing mold 2 is fixed with a plurality of fasteners 23, which are screws, bolts, nails, tacks, pins, rods or any other objects that can fasten two or more objects together.

[0068] Please continue to refer to Figures 2A to 2C Preferably, the punch 21 includes a punch socket 216, and the die 22 includes a die socket 226. The punch socket 216 is arranged on the outer edge side of the punch 21, and the die socket 226 is arranged on the outer edge side of the die 22. The punch socket 216 and the die socket 226 are used to insert a temperature sensor 24. The temperature sensor 24 allows the user to observe the temperature reached by the hot pressing mold 2 when pressing the lead-carbon composite pole piece. The temperature sensor 24 can be, for example, a thermistor, a thermocouple, a wire-type thermocouple or any other thermometer; more preferably, the die socket 226 is arranged on the outer edge side of the die 22 corresponding to the punch socket 216.

[0069] In some preferred embodiments, before providing the first lead material and the second lead material, a pre-treatment step is further included, wherein the steps include:

[0070] Step S1: continuously oxidizing the first lead material and the second lead material in an atmospheric environment at a second temperature, wherein the second temperature is 0-400°C.

[0071] Preferably, before providing the carbon material, the carbon material is cut into small pieces or drawn into threads.

[0072] Preferably, the carbon material is carbon cloth; in some preferred embodiments, the carbon cloth used has no carboxyl group (COOH), such as the fireproof fiber cloth (TCF) produced by Taiwan Carbon Technology Co., Ltd.; in some embodiments, carbon fiber cloths provided by different manufacturers are used respectively, such as the activated carbon fiber fabric (ECF) produced by Chemvi ron Carbon in the UK, and the general engineering reinforcement carbon fiber cloth (PCF) produced by Taiwan Plastic Industry Co., Ltd., China. The aforementioned activated carbon fiber fabric is a medical grade carbon cloth with the most complete functional groups including phenol Carboxyl (COOH), carbonyl (C=O), aromatic carbon (CC / C=C), hydroxyl (C-OH) and epoxy See also Figure 3 , is the Fourier transform infrared spectroscopy (FT IR) of the carbon cloth produced by the aforementioned manufacturers, wherein ECF is the activated carbon fiber fabric produced by Chemviron Carbon of the United Kingdom, TCF is the fireproof fiber cloth produced by Taiwan Carbon Technology Co., Ltd., and PCF is the general engineering reinforcement carbon fiber cloth produced by Formosa Plastics Corporation; in some embodiments, the carbon cloths are further subjected to oxidation treatment, such as chemical oxidation treatment (Cox), heat treatment (Aox) and plasma treatment (POX).

[0073] Please refer to Table 1, which illustrates the differences in the proportion of functional groups of carbon cloth produced by individual manufacturers after oxidation treatment. Among them, the fire-resistant fiber cloth TCF produced by Taiwan Carbon Technology Co., Ltd. has no carboxyl (COOH) modification after any of the aforementioned treatments (TCF, AoxTCF, PoxTCF).

[0074]

[0075] Table 1

[0076] The aforementioned step S1 is a processing step selected according to experimental conditions or environments; wherein, the oxidation of the lead material in the atmospheric environment generates partial lead oxide on the surface of the lead material, and the partial lead oxide can serve as an interface layer for combining the carbon material and the lead material when the external pressure is applied to the lead material in the aforementioned method for making the lead-carbon composite electrode, and enables the lead material of the composite lead-carbon electrode to tightly cover the carbon material; the principle behind this should be that, at the first temperature, the lead material is in a semi-molten state, and the external pressure applied to the hot pressing mold 2 reaches 70 to 120 kg / m 2 In addition to the pressure transmitted by the male mold 21 and the female mold 22, the expansion pressure generated by the extrusion of the air inside the hot pressing mold 2 also acts on the solid-liquid interface of the lead-carbon, forcing the semi-molten lead to penetrate the fiber structure of the carbon material. After natural cooling, the carbon fiber structure is gradually covered by the solidified lead while being immersed in the semi-molten lead. More specifically, lead oxide has the ability to wet carbon material. The principle is that the surface tension of lead oxide (132mN / m 2 ) is less than or close to the surface tension of the carbon material itself (100-200mJ / m 2), so the formed lead oxide interface layer can wet the carbon material, tightly combine the lead material and the carbon material together to form a lead-carbon interface with high electrochemical stability. This process makes the coating structure formed by the lead material more complete, and also makes the lead-carbon composite electrode more compact, which more effectively improves its capacitance. The present invention utilizes the combination of lead material and carbon material heterogeneous materials to form a porous metal composite material in the process of compounding, in which pores are reserved as a gas or liquid penetration path for the convenience of back-end application; this porous metal composite material is due to the design of the hot pressing mold 2. While exhausting gas to combine the lead and carbon, under the control of external pressure, internal expansion pressure and temperature, the lead and carbon materials are combined and fine pores are formed to form a porous metal composite material. The reserved pores can be used to allow gas and liquid to penetrate when used in the back-end, such as the penetration path of electrolytes, electrochemical reaction substances, etc.

[0077] Please refer to Figures 4A to 4B , is an electro-display magnified image showing the lead-carbon composite pole piece provided by the present invention after being corroded by nitric acid, through which the bonding of lead and carbon fibers is observed. In the lead-carbon composite pole piece after being corroded by 10% nitric acid, the exposed carbon fiber lead surface is covered with lead, and the carbon fibers in the pores of the lead plate are also covered with lead, indicating that the lead material and carbon material of the lead-carbon composite pole piece provided by the present invention are densely bonded.

[0078] See also Figure 5 , is an electro-display magnified image of the surface of the lead-carbon composite electrode provided by the present invention after the cyclic voltammetry test; Figure 5 It can be seen that after the cyclic voltage scan, lead sulfate blocks are generated on the lead material surface and the carbon fiber. From the comparison between Figure b) and Figure c), it can be seen that the surface of the carbon fiber is aggregated with nano-lead sulfate particles that are denser than the surface of the lead material. When the cyclic voltammetry test is carried out, the electrolyte enters the surface of the lead material and the pores of the lead-carbon composite electrode to produce an electrochemical reaction, causing nano-lead sulfate to be generated on the carbon fiber surface, and then attached to the lead material and the carbon fiber surface; this nano-lead sulfate structure continues to accumulate after multiple cycle tests, thereby increasing the capacitance of the lead-carbon composite electrode.

[0079] Please refer to Figure 6 , is a schematic diagram of the lead-carbon composite electrode 3 provided by the present invention, such as Figure 6As shown, the lead-carbon composite electrode 3 includes a first lead material 31, a second lead material 32 and a carbon material 33, any main side of the first lead material 31 is bonded to the carbon material 33, and any main side of the second lead material 32 is bonded to the carbon material, so that the carbon material 33 is located between the first lead material 31 and the second lead material 32 to form a lead-carbon sandwich, and at a first temperature, external pressure is applied to the first lead material 31, the second lead material 32 and the carbon material 33 and the temperature and pressure are maintained for 2 to 10 minutes to make them composite, the first temperature is 300 to 360°C, and the external pressure is 70 to 120 kg / m 2 .

[0080] In some preferred embodiments, before providing the first lead material 31 and the second lead material 32, the first lead material 31 and the second lead material 32 are further pre-treated, and the pre-treatment includes step S1: continuously oxidizing the first lead material 31 and the second lead material 32 in an atmospheric environment, wherein the second temperature is 0 to 400°C.

[0081] In some preferred embodiments, before providing the carbon material 33 , the carbon material 33 is further cut into small pieces or drawn into threads; preferably, the carbon material 33 is carbon cloth.

[0082] Preferably, the first lead material 31 has a first welding point 311 adjacent to the edge of the carbon material 33, and the second lead material 32 has a second welding point 321 corresponding to the first welding point 311 adjacent to the edge of the carbon material 33 for welding to the electrode contacts of the lead-carbon battery.

[0083] Another embodiment of the present invention is to provide an electrode sheet set 4, please refer to Figure 7 , is a schematic diagram of the electrode sheet group 4 provided by the present invention, such as Figure 7 As shown, the electrode sheet group 4 comprises: a first lead-carbon composite electrode sheet 41, which is the lead-carbon composite electrode sheet 3 as described above; a second lead-carbon composite electrode sheet 42, which is the lead-carbon composite electrode sheet 3 as described above; and at least an absorbent glass fiber mat 43, wherein the first lead-carbon composite electrode sheet 41 is disposed on the absorbent glass fiber mat 43, and the second lead-carbon composite electrode sheet 42 is disposed on the absorbent glass fiber mat 43 relative to the first lead-carbon composite electrode sheet 41. Preferably, the electrode sheet group 4 further comprises a lead plate, wherein the lead plate is a pure lead plate or a pure lead plate coated with lead paste.

[0084] Another embodiment of the present invention is to realize a lead-carbon composite battery, which includes: a positive electrode contact; a negative electrode contact; an electrolyte, preferably, the electrolyte is a 30-40% sulfuric acid solution; at least the positive electrode sheet group is the electrode sheet group 4 as described above, which is arranged in the electrolyte and connected to the positive electrode contact by wire welding; and at least the negative electrode sheet group is the electrode sheet group 4 as described above, which is arranged in the electrolyte and connected to the negative electrode contact by wire welding. In some embodiments, the coulomb efficiency of the lead-carbon composite battery is 100% under the unsaturated charge and discharge state of 2C charging and 10C discharging, and there is no heat energy loss, but it is not limited to this; preferably, the ratio of the number of lead-carbon composite pole pieces connected to the positive electrode contact to the number of lead-carbon composite pole pieces connected to the negative electrode contact is 1:1, 1:2, 1:3, 2:1, 2:2, 2:3, 3:1, 3:2 or 3:3, but it is not limited to this.

[0085] Several embodiments and experimental examples are listed below to further illustrate the technical features, applied technical means and expected effects of the present invention:

[0086] Embodiment 1:

[0087] Take the lead material, carbon cloth, paper, and carbon pad and weigh them. Then, put the lead material, carbon cloth, lead material, 2 pieces of paper, and 2 pieces of carbon pad in the concave groove of the hot press mold in sequence. In this embodiment, activated carbon fiber fabric (ECF) produced by Chemviron Carbon in the UK is used. Before being placed in the hot press mold, the ECF is first oxidized by chemical treatment to form CoxECF. Cover the convex mold of the hot press mold, then lock the hot press mold with screws and set a temperature sensing rod on the convex mold and the concave mold respectively. Place the aforementioned hot press mold in the hot press machine, pressurize until the convex mold and the concave mold are in contact with the heating plate of the hot press machine, and pressurize to 90kg / cm 2 . Heat to about 300℃ and tighten the screws once. When the die is heated to 320℃, continue to pressurize and maintain the temperature at 320℃. After 5 minutes, heat the entire set of hot pressing molds to 360℃ and terminate the heating process. After the hot pressing molds cool down naturally to 300℃, remove the hot pressing molds from the hot press. Remove the hot pressing molds and take out the lead-carbon composite pole piece.

[0088] like Fig. 8A As shown, it is the contact surface between the lead-carbon composite pole piece 11181 and the hot pressing mold convex mold; Figure 8B As shown, it is the contact surface between the lead-carbon composite pole piece 11181 and the hot pressing mold cavity.

[0089] like Fig.9A As shown, it is the contact surface between the lead-carbon composite pole piece 11182 and the hot pressing mold convex mold; Fig. 9B As shown, the contact surface between the lead-carbon composite pole piece 11182 and the hot pressing mold cavity is presented.

[0090] like Fig. 10A As shown, it is the contact surface between the lead-carbon composite pole piece 11186 and the hot pressing mold convex mold; Fig. 10B As shown, the contact surface between the lead-carbon composite pole piece 11186 and the hot pressing mold cavity is presented.

[0091] like Fig.11A As shown, it is the contact surface between the lead-carbon composite pole piece 11187 and the hot pressing die convex mold; Fig. 11B As shown, it is the contact surface between the lead-carbon composite pole piece 11187 and the hot pressing mold cavity.

[0092] The foregoing Fig. 8A , Fig.9A , Fig. 10A , Fig. 10A The black cracks on the surface of the lead-carbon composite pole piece presented are carbonized paper under high temperature. After the lead-carbon composite pole piece is removed from the hot pressing mold, it is cleaned with a copper brush.

[0093] Embodiment 2:

[0094] After weighing the lead material, carbon cloth, paper, and carbon pad, put the lead material, carbon cloth, lead material, 2 pieces of paper, and 2 pieces of carbon pad in the concave groove of the hot press mold in sequence; in this embodiment, the fireproof fiber cloth TCF produced by Taiwan Carbon Technology Co., Ltd. is used; cover the convex mold of the hot press mold, then lock the hot press mold with screws and set a temperature sensing rod on the convex mold and concave mold respectively. Place the aforementioned hot press mold in the hot press machine, pressurize until the convex mold and concave mold are in contact with the hot press machine heating plate, and pressurize to 90kg / cm 2 . Heat to about 300℃ and tighten the screws once. When the die is heated to 320℃, continue to pressurize and maintain the temperature at 320℃. After 20 minutes, heat the entire set of hot pressing molds to 360℃ and terminate the heating process. After the hot pressing molds cool down naturally to 300℃, remove the hot pressing molds from the hot press. Remove the hot pressing molds and take out the lead-carbon composite pole piece.

[0095] See also FIG. 12A to FIG. 13B , are the lead-carbon composite pole pieces prepared in this embodiment, and are numbered 05241 and 05242 respectively; after the hot pressing molds are removed from the lead-carbon composite pole pieces 05241 and 05242, the black cracks on the surface are removed with a copper brush, and the porous characteristics of the surface of the lead-carbon composite pole pieces can be clearly seen.

[0096] like Fig. 12A As shown, it is the contact surface between the lead-carbon composite pole piece 05241 and the hot pressing die convex mold; Fig. 12B As shown, the contact surface between the lead-carbon composite pole piece 05241 and the hot pressing mold cavity is presented.

[0097] like Fig.13AAs shown, it is the contact surface between the lead-carbon composite pole piece 05242 and the hot pressing die convex mold; Fig. 13B As shown, the contact surface between the lead-carbon composite pole piece 05242 and the hot pressing mold cavity is presented.

[0098] Embodiment 3:

[0099] Take the lead material, carbon cloth, paper, and carbon pad and weigh them. Then, put the lead material, carbon cloth, lead material, 2 pieces of paper, and 2 pieces of carbon pad in the concave groove of the hot press mold in sequence. In this embodiment, the fireproof fiber cloth TCF produced by Taiwan Carbon Technology Co., Ltd. is used. Cover the convex mold of the hot press mold, then screw the hot press mold with screws and set a temperature sensing rod on the convex mold and concave mold respectively. Place the aforementioned hot press mold in the hot press machine, pressurize until the convex mold and concave mold are in contact with the hot press machine heating plate, and pressurize to 60kg / cm 2 . Heat to about 300℃ and tighten the screws once. When the die is heated to 320℃, continue to pressurize and maintain the temperature at 320℃. After 20 minutes, keep the temperature and pressurize to 90kg / cm 2 , and start furnace cooling; after the hot pressing mold is naturally cooled to 300℃, remove the hot pressing mold from the hot press; remove the hot pressing mold and take out the lead-carbon composite pole piece. Then, perform a 600℃ heat treatment on the lead-carbon composite pole piece in the heat treatment furnace, release the pressure to break the vacuum state, put the hot-pressed lead-carbon composite pole piece in and tighten the screws, turn on the vacuum pump to reduce the pressure to -760mmHg, then open the nitrogen bottle to adjust the pressure to -500mmHg, and start heating after closing the nitrogen bottle, heating from 0 to 600℃ for 2 hours, and then take out the lead-carbon composite pole piece after keeping the temperature at 600℃ for 2 hours.

[0100] Please refer to FIG. 14A to FIG. 15B , are the lead-carbon composite pole pieces prepared in this embodiment, and their numbers are 10271 and 10272 respectively.

[0101] like Fig.14A As shown, it is the contact surface between the lead-carbon composite pole piece 10271 and the hot pressing mold convex mold; Fig. 14B As shown, the contact surface between the lead-carbon composite pole piece 10271 and the hot pressing mold cavity is presented.

[0102] like Fig.15A As shown, it is the contact surface between the lead-carbon composite pole piece 10272 and the hot pressing mold convex mold; Fig. 15B As shown, the contact surface between the lead-carbon composite pole piece 10272 and the hot pressing mold cavity is presented.

[0103] The foregoing Fig.14A , Fig.15A The black cracks on the surface of the lead-carbon composite pole piece presented are carbonized paper under high temperature. After the lead-carbon composite pole piece is removed from the hot pressing mold, it is cleaned with a copper brush.

[0104] Embodiment 4:

[0105] After weighing the lead material, oxidized carbon cloth, paper, and carbon pad, the lead material, carbon cloth, lead material, two pieces of paper, and two pieces of carbon pad are placed in the concave groove of the hot pressing mold in sequence; in this embodiment, the activated carbon fiber fabric ECF produced by Chemvi ron Carbon in the UK is used. After chemical oxidation to form CoxECF, the CoxECF has quite complete functional groups including phenol Carboxyl (COOH), carbonyl (C=O), aromatic carbon (CC / C=C), hydroxyl (C-OH) and epoxy Cover the convex mold of the hot press mold, then screw the hot press mold and set a temperature sensing rod on the convex mold and concave mold respectively. Place the above hot press mold in the hot press machine, pressurize until the convex mold and concave mold are in contact with the hot press machine heating plate, and pressurize to 90kg / cm 2 . Heat to about 300°C, and tighten the screws once again. When the die is heated to 320°C, continue to pressurize and maintain the temperature at 320°C. After 5 minutes, heat the entire set of hot pressing molds to 360°C and terminate the heating program. After the hot pressing molds are naturally cooled to 300°C, remove the hot pressing molds from the hot press; remove the hot pressing molds and take out the lead-carbon composite pole pieces. Next, perform a 600°C heat treatment on the aforementioned lead-carbon composite pole pieces in a heat treatment furnace, release the pressure to break the vacuum state, place the hot-pressed lead-carbon composite pole pieces in and tighten the screws, turn on the vacuum pump to reduce the pressure to -760 mmHg, then open the nitrogen bottle to adjust the pressure to -500 mmHg, and start heating after closing the nitrogen bottle. Heat from 0 to 600°C for 2 hours, and then keep the temperature at 600°C for 4 hours before taking out the lead-carbon composite pole pieces.

[0106] Please refer to FIG. 16A to FIG. 20B , are the lead-carbon composite pole pieces prepared in this embodiment, and their numbers are 12211, 12212, 12213, 12214, and 12231 respectively.

[0107] like Fig.16A As shown, it is the contact surface between the lead-carbon composite pole piece 12211 and the hot pressing mold convex mold; Fig. 16B As shown, the contact surface between the lead-carbon composite pole piece 12211 and the hot pressing mold cavity is presented.

[0108] like Fig.17A As shown, it is the contact surface between the lead-carbon composite pole piece 12212 and the hot pressing mold convex mold; Fig. 17B As shown, the contact surface between the lead-carbon composite pole piece 12212 and the hot pressing mold cavity is presented.

[0109] like Fig.18A As shown, it is the contact surface between the lead-carbon composite pole piece 12213 and the hot pressing mold convex mold; Fig.18BAs shown, the contact surface between the lead-carbon composite pole piece 12213 and the hot pressing mold cavity is presented.

[0110] like Fig.19A As shown, it is the contact surface between the lead-carbon composite pole piece 12214 and the hot pressing mold convex mold; Fig.19B As shown, the contact surface between the lead-carbon composite pole piece 12214 and the hot pressing mold cavity is presented.

[0111] like Fig. 20A As shown, it is the contact surface between the lead-carbon composite pole piece 12231 and the hot pressing mold convex mold; Fig. 20B As shown, the contact surface between the lead-carbon composite pole piece 12231 and the hot pressing mold cavity is presented.

[0112] The foregoing Fig.16A , Fig.17A , Fig.18A , Fig.19A , Fig. 20A The black cracks on the surface of the lead-carbon composite pole piece presented are carbonized paper under high temperature. After the lead-carbon composite pole piece is removed from the hot pressing mold, it is cleaned with a copper brush.

[0113] Embodiment 5:

[0114] The lead-carbon composite pole piece prepared according to Example 1 is used to form a carbon-lead battery LCFN4_N. The lead-carbon battery LCFN4_N has a positive electrode contact and a negative electrode contact, and 40 ml of sulfuric acid solution is added as an electrolyte. The positive electrode contact is connected to the positive electrode plate group by wire welding. The positive electrode plate group is set in the sulfuric acid solution and consists of pole pieces numbered LCFN4_N_positive 1, LCFN4_N_positive 2 and 3 absorbable glass fiber mats; the negative electrode contact is connected to the negative electrode plate group by wire welding. The negative electrode plate group is set in the sulfuric acid solution and consists of pole pieces numbered LCFN4_N_negative 1, LCFN4_N_negative 2, LCFN4_N_negative 3 and 2 absorbable glass fiber mats. Please refer to Table 2 for the sizes and The weights are as follows: LCFN4_N_positive 1 is 0.75mm high, 66.70mm long, 40.50mm wide, and weighs 11.31 grams; LCFN4_N_positive 2 is 0.80mm high, 67.20mm long, 40.50mm wide, and weighs 17.21 grams; LCFN4_N_negative 1 is 0.95mm high, 66.50mm long, 40.00mm wide, and weighs 16.66 grams; LCFN4_N_negative 2 is 0.80mm high, 66.85mm long, 40.70mm wide, and weighs 14.67 grams; LCFN4_N_negative 3 is 0.90mm high, 66.60mm long, 40.70mm wide, and weighs 16.89 grams.

[0115]

[0116] Table 2

[0117] Embodiment 6:

[0118] The lead-carbon composite pole piece prepared according to Example 4 is used to form a carbon-lead battery LCFN3_HP. The lead-carbon battery LCFN3_HP has a positive electrode contact and a negative electrode contact, and 40 ml of sulfuric acid solution is added as an electrolyte. The positive electrode contact is connected to the positive electrode plate group by wire welding. The positive electrode plate group is set in the sulfuric acid solution and consists of pole pieces numbered LCFN3_HP_positive 1, LCFN3_HP_positive 2, LCFN3_HP_positive 3 and 2 absorbable glass fiber mats; the negative electrode contact is connected to the negative electrode plate group by wire welding. The negative electrode plate group is set in the sulfuric acid solution and consists of pole pieces numbered LCFN3_HP_negative 1, LCFN3_HP_negative 2 and 3 absorbable glass fiber mats. Please refer to Table 3 for the dimensions of the aforementioned pole pieces. The dimensions and weights are as follows: LCFN3_HP_positive 1 are 0.95mm high, 66.50mm long, 40.00mm wide, and weigh 16.85 grams; the dimensions of LCFN3_HP_positive 2 are 0.80mm high, 66.00mm long, 39.00mm wide, and weigh 9.66 grams; the dimensions of LCFN3_HP_positive 3 are 1.70mm high, 66.70mm long, 40.50mm wide, and weigh 12.68 grams; the dimensions of LCFN3_HP_negative 1 are 0.75mm high, 66.70mm long, 40.50mm wide, and weigh 10.04 grams; the dimensions of LCFN3_HP_negative 2 are 1.70mm high, 66.70mm long, 40.50mm wide, and weigh 12.69 grams.

[0119]

[0120] Table 3

[0121] Embodiment 7:

[0122] The lead-carbon composite pole piece produced according to Example 3 is used to form a carbon-lead battery LCFN28_2. The lead-carbon battery LCFN28_2 has a positive electrode contact and a negative electrode contact, and 40 ml of sulfuric acid solution is added as an electrolyte. The positive electrode contact is connected to the positive electrode plate group by wire welding. The positive electrode plate group is set in the sulfuric acid solution and consists of pole pieces numbered LCFN28_2_positive 1, LCFN28_2_positive 2 and 3 absorbable glass fiber mats; the negative electrode contact is connected to the negative electrode plate group by wire welding. The negative electrode plate group is set in the sulfuric acid solution and consists of pole pieces numbered LCFN28_2_negative 1, LCFN28_2_negative 2, LCFN28_2_negative 3 and 2 absorbable glass fiber mats.

[0123] Please refer to Table 4. The dimensions and weights of the above-mentioned pole pieces are: LCFN28_2_positive 1 has a height of 1.00mm, a length of 66.00mm, a width of 39.00mm, and a weight of 19.1 grams; LCFN28_2_positive 2 has a height of 1.00mm, a length of 66.00mm, a width of 39.00mm, and a weight of 22.8 grams; LCFN28_2_negative 1 has a height of 1.00mm, a length of 66.00mm, a width of 39.00mm, and a weight of 15.3 grams; LCFN28_2_negative 2 has a height of 1.00mm, a length of 66.00mm, a width of 39.00mm, and a weight of 14.6 grams; LCFN28_2_negative 3 has a height of 1.00mm, a length of 66.00mm, a width of 39.00mm, and a weight of 12.7 grams.

[0124]

[0125]

[0126] Table 4

[0127] Experimental Example 1:

[0128] The unsaturated cycle charge and discharge test was performed on the lead-carbon battery LCFN4_N of Example 5 of the present invention and the lead-carbon battery LCFN3_HP of Example 6 in the constant current charge and discharge mode. The battery was charged at a maximum charge current rate of 2C for 420 seconds and then discharged at a current rate of 10C. The unsaturated cycle charge and discharge were performed three times, and the charge and discharge time and current were recorded to calculate the coulomb efficiency (charge capacity / discharge capacity, %). Please refer to Table 5. The battery capacity of the carbon-lead battery LCFN4_N is 0.3Ah. It is charged at a charging rate of 2C (0.6A) for 420 seconds to obtain a charging capacity of 0.070Ah. It is then discharged at a discharge efficiency of 10C (3A) for 84 seconds. The discharge capacity is calculated to be 0.070Ah. Based on this, its coulombic efficiency can be calculated to be 100%; the battery capacity of the carbon-lead battery LCFN3_HP is 0.15Ah. It is charged at a charging rate of 2C (0.3A) for 420 seconds to obtain a charging capacity of 0.035Ah. It is then discharged at a discharge efficiency of 10C (1.5A) for 86 seconds. The discharge capacity is calculated to be 0.035Ah. Based on this, its coulombic efficiency can be calculated to be 100%.

[0129]

[0130] Table 5

[0131] Experimental Example 2:

[0132] The lead-carbon battery LCFN4_N was subjected to saturated and unsaturated cyclic charge and discharge tests by constant current charge and discharge. The battery was charged at a constant current of 2C and then discharged at 10C. The cut-off voltage was 0.5V for cyclic charge and discharge tests. The test was continuous and data was recorded every 30 seconds. The charge and discharge time and current were recorded to calculate the coulomb efficiency (charge capacity / discharge capacity, %).

[0133] Please refer to Table 6, which records the charge and discharge records of the carbon-lead battery LCFN4_N of Example 5 of the present invention. The battery capacity of the carbon-lead battery LCFN4_N is 0.30Ah. Numbers 1 to 4 are charged for 1800 seconds to reach saturation charge, and their charging capacity is 0.3Ah, and they are discharged for about 150 seconds respectively, and their coulombic efficiency is about 40%; Numbers 5 to 8 are charged for 900 seconds but not to reach saturation charge, and are discharged for about 139 to 145 seconds respectively, and their coulombic efficiency is about 80%; Numbers 9 to 15 are charged for 420 seconds but not to reach saturation charge, and are discharged for 81 to 95 seconds respectively, and their coulombic efficiency is about 100%; Numbers 16 to 19 are charged for 240 to 268 seconds but not to reach saturation charge, and are discharged for 48 to 59 seconds respectively, and their coulombic efficiency is about 100%.

[0134]

[0135] Table 6

[0136] Experimental Example 3:

[0137] The lead-carbon battery LCFN3_HP was subjected to saturated and unsaturated cyclic charge and discharge tests by constant current charge and discharge. The battery was charged at a constant current of 2C and then discharged at 10C. The cut-off voltage was 0.5V for cyclic charge and discharge tests. The test was continuous and data was recorded every 30 seconds. The charge and discharge time and current were recorded to calculate the coulombic efficiency (charge capacity / discharge capacity, %). Please refer to Table 7, which records the charge and discharge records of the carbon-lead battery LCFN3_HP of Example 6. The battery capacity of the carbon-lead battery LCFN3_HP is 0.15Ah, and No. 1 is not charged; No. 2-4 are charged for 1800 seconds to reach saturation charge, and their charging capacity is 0.15Ah, and they are discharged for about 100 seconds respectively, and their coulombic efficiency is about 30%; No. 5-7 are charged for 900 seconds but not to reach saturation charge, and are discharged for about 100 seconds respectively, and their coulombic efficiency is about 60%; No. 8-14 are charged for 420 seconds but not to reach saturation charge, and are discharged for 86-100 seconds respectively, and their coulombic efficiency is about 100%.

[0138]

[0139] Table 7

[0140] Experimental Example 4

[0141] The lead-carbon battery LCFN28_2 of Example 7 was subjected to saturated and unsaturated cyclic charge and discharge tests by constant current charge and discharge. The battery was charged at a constant current of 2C and then discharged at 10C with a cut-off voltage of 0.5V for cyclic charge and discharge tests. The test was performed continuously, and data was recorded every 5 seconds. The charge and discharge time and current were recorded to calculate the coulombic efficiency (charge capacity / discharge capacity, %). Please refer to Table 8, which records the charge and discharge records of the carbon-lead battery LCFN28_2 of Example 7 of the present invention, wherein the battery capacity is 0.17Ah, wherein the 1st to 3rd cycles are charged for 900 seconds to reach saturation charge, and the charging capacity is 0.17Ah, and are discharged for about 118, 130, and 132 seconds, respectively, and the coulombic efficiency is about 59, 65, and 66%; the 4th to 8th cycles are charged for 420 seconds but not to reach saturation charge, and are discharged for about 111 to 96 seconds, respectively, and rest for 30 seconds after discharge before the next test, and the coulombic efficiency reaches 103 to 119%; the 9th to 21st cycles are charged for 240 seconds but not to reach saturation charge, and are discharged for 53 to 72 seconds, respectively, and rest for 30 seconds after discharge before the next test, and the coulombic efficiency is about 99 to 135%.

[0142] It can be seen from Experimental Examples 2 to 4 that the lead-carbon battery LCFN28_2 prepared in Example 7 of the present invention is compared with the LCFN4_N prepared in Example 5 and the lead-carbon battery LCFN3_HP prepared in Example 6. It can be clearly observed that according to the method for making the lead-carbon composite pole piece provided by the present invention, although the coulomb efficiency of LCFN4_N and LCFN3_HP reaches 100% coulomb efficiency after the 10th and 14th charge and discharge, respectively, the lead-carbon battery LCFN28_2 reaches 100% coulomb efficiency in a shorter cycle (the 4th charge and discharge), and achieves better than LCFN4_N and LCFN3_HP.

[0143]

[0144] Table 8

[0145] Coulombic efficiency; also see Fig.21A , is the charge and discharge capacity trend chart of LCFN28_2 cycle charge and discharge, and please refer to Fig. 21B , is the coulomb efficiency trend chart of LCFN28_2 cyclic charge and discharge. It can be seen that LCFN28_2 can reach a charge and discharge efficiency of more than 100% in a shorter time and withstand shorter charge and discharge cycles. After 240 seconds of charging, the discharge depth can be stably maintained at around 100% in the cyclic test.

[0146] Experimental Example 5

[0147] In this experimental example, the cyclic voltammetry analysis method is carried out using the lead-carbon composite electrode and the pure lead electrode of Example 2. The test area of ​​the lead-carbon composite electrode and the pure lead electrode is 1.0*1.0cm, the scanning voltage is -1.0V to 0V, and the scanning speed is 20mV / s; it should be noted that in the cyclic voltammetry test of this experimental example, the turning point of the redox reaction of the electrode is about -0.6V. In the cyclic voltammetry curve recording diagram, the area enclosed by the curves on both sides of -0.6V represents the current detected in the redox reaction; please refer to Fig.22A , is a graph showing the 1st to 500th cyclic voltammetry curve of pure lead electrode, Fig.22A It can be seen that in the cyclic voltammetry test of 1 to 500 times, the current required for the reduction reaction of the pure lead electrode is getting larger and larger during the cycle scanning process, and the current of the hydrolysis reaction to produce hydrogen also increases from -142mA to -660mA. Obviously, after multiple charges and discharges, the pure lead electrode absorbs a large amount of current during the reduction reaction to complete the reduction reaction of lead sulfate, resulting in a decrease in the charging efficiency of the pure lead electrode; please refer to Fig. 22B During the scanning process of the positive scanning potential (-1.0 to 0V), the lead-carbon composite electrode showed an obvious anodic peak, with the peak value reaching 111mA. However, during the scanning process of the negative scanning potential (0V to -1.0V), no cathodic peak appeared. In addition, during the negative scanning potential, the hydrolysis current generated by the reduction reaction was relatively small, with a peak value of about -82mA, indicating that the redox reaction of the lead-carbon composite electrode was a reversible reaction under the cyclic voltammetry test. It also indirectly explained that during the charge and discharge process, the nano-lead sulfate formed in the pores of the lead-carbon composite electrode not only accumulated and gradually thickened the lead-carbon composite electrode with the number of charge and discharge times, thereby increasing the capacitance of the lead-carbon composite electrode, but also the hydrolysis current of the reduction reaction was quite small, indicating that the carbon material in the lead-carbon composite electrode increased the conductivity of the electrode, and the input current was almost completely used for the chemical reaction of lead / lead sulfate, reducing the heat energy loss caused by hydrolysis.

[0148] Please see again Figures 22C to 22D , which respectively present the cyclic voltammetry analysis curves recorded for the 50th cycle and the 500th cycle; it can be seen from the above-mentioned record that the anode peak of the 50th cycle reaches 52mA; the anode peak of the 500th cycle is 111mA, and the curve area of ​​the oxidation reaction is obviously larger than that of the 50th cycle, indicating that after multiple charge and discharge, the electrochemical reaction of the lead-carbon composite electrode increases with the number of charge and discharge times.

[0149] In summary, the lead-carbon composite pole piece manufacturing method, lead-carbon composite pole piece, lead-carbon composite pole piece assembly and lead-carbon composite battery provided by the present invention can achieve the following technical effects, which are not easily achieved by the prior art:

[0150] 1. The method for making the lead-carbon composite electrode provided by the present invention, through a special exhaust design, performs the composite of the lead-carbon electrode under a relatively low temperature state. When the carbon material has very little or no carbon radical, in addition to achieving a dense lead-carbon composite effect, it more effectively increases the capacitance of the lead-carbon composite electrode and reduces the heat loss during charging and discharging. The energy of charging and discharging is fully used for the chemical reaction of lead / lead sulfate. Compared with pure lead electrode, the lead-carbon composite electrode sheet with high lead-carbon interface density, high charging capacity and high energy density is produced in this case. The production method is simple and meets the low-cost and high-efficiency battery production.

[0151] 2. The method for making the lead-carbon composite electrode provided by the present invention utilizes the oxygen radicals brought by the oxidation of the lead material in the low-temperature atmosphere as the source of oxygen radicals for the lead-carbon interface bonding. The carbon material used does not need to be further oxidized, such as carbon cloth without carboxyl groups (COOH). The lead-carbon composite interface achieved has high density, high charging capacity and high energy density, thereby further simplifying the process and improving battery production efficiency.

[0152] 3. The lead-carbon composite electrode provided by the present invention can promote the generation of nano-lead at the lead-carbon chemical interface under the action of unsaturated charge and discharge. With sufficient lead layer thickness, a 3D nanoporous structure can be naturally generated as the battery is used. It can be expected that its charging capacity will increase with the number of charge and discharge cycles, and as the number of charge and discharge cycles increases, its coulombic efficiency will be closer to 100%.

[0153] 4. The lead-carbon composite battery provided by the present invention can be expected to withstand more than 3,000 unsaturated cyclic charge and discharge cycles, with less heat loss and low electrode loss. The lead-carbon composite electrode can further generate a 3D nanopore structure after cyclic charge and discharge. As the number of cyclic charge and discharge cycles increases, its capacity increases, and its service life can be expected to be long. It is also suitable for green electricity, such as microgrid energy storage for intermittent power generation such as wind power, solar energy, and tidal power.

[0154] However, the above description is only an illustration of the preferred embodiment of the present invention. Those skilled in the art can make other improvements based on the above description, but these improvements still fall within the scope of protection defined by the claims of the present invention.

Claims

1. A method for manufacturing a porous lead-carbon composite electrode, characterized in that: It includes the following steps: A first lead material, a second lead material and a carbon material are provided, wherein any main side surface of the first lead material is bonded to the carbon material, and any main side surface of the second lead material is bonded to the carbon material, so that the carbon material is located between the first lead material and the second lead material, wherein the carbon material is a carbon cloth, and the carbon material does not contain a carboxyl group (COOH); The lead-carbon sandwich formed by the first lead material, the carbon material and the second lead material is placed in a hot pressing mold, wherein the hot pressing mold comprises: a punch, the punch having a plurality of punch exhaust holes and a punch ventilation groove, the punch exhaust holes are evenly dispersed and arranged along the inner side of the punch flange, and the punch ventilation groove is formed along the outer side of the flange; a die, the die having a plurality of die exhaust holes and a die ventilation groove, the die exhaust holes are evenly dispersed and arranged along the inner side of the die concave edge corresponding to the punch exhaust holes, the die ventilation groove is a groove structure formed by annularly spirally arranged along the inner side of the concave edge toward the geometric center of the die, wherein, when the punch is engaged with the die, the punch exhaust holes are connected with the die exhaust holes for exhaust; At a first temperature, causing the air between the first lead material and the carbon material or between the second lead material and the carbon material to generate expansion pressure to discharge the air; and At a first temperature, external pressure is applied to the first lead material, the second lead material and the carbon material and the temperature and pressure are maintained for 2 to 10 minutes to compound them, wherein the first temperature is 300 to 360° C. and the external pressure is 70 to 120 kg / m 2 .

2. The method for manufacturing a lead-carbon composite pole piece according to claim 1, characterized in that: Before providing the first lead material and the second lead material, a pre-treatment step is further included, and the steps include: continuously oxidizing the first lead material and the second lead material in an atmospheric environment at a second temperature, wherein the second temperature is 0~400℃.

3. The method for manufacturing a lead-carbon composite pole piece according to claim 1, characterized in that: The carbon material contains a carbonyl group (C=O) and a hydroxyl group (C-OH). Before providing the carbon material, the carbon material is further cut into small pieces or drawn into threads.

4. A lead-carbon composite pole piece, characterized in that: It is prepared by the method for preparing a lead-carbon composite pole piece according to any one of claims 1 to 3.

5. The lead-carbon composite pole piece according to claim 4, characterized in that: The carbon material contains a carbonyl group (C=O) and a hydroxyl group (C-OH). The first lead material has a first welding point adjacent to the edge of the carbon material, and the second lead material has a second welding point adjacent to the edge of the carbon material for welding to the electrode contacts of the lead-carbon battery.

6. An electrode sheet assembly, characterized in that Include: The first lead-carbon composite pole piece is the lead-carbon composite pole piece according to claim 4; The second lead-carbon composite pole piece is the lead-carbon composite pole piece according to claim 4; and At least an absorbable glass fiber pad, the first lead-carbon composite pole piece is arranged on the absorbable glass fiber pad, and the second lead-carbon composite pole piece is arranged on the absorbable glass fiber pad relative to the first lead-carbon composite pole piece.

7. The electrode sheet assembly according to claim 6, characterized in that: The electrode sheet group further comprises a lead plate, wherein the lead plate is a pure lead plate or a pure lead plate coated with lead paste.

8. A lead-carbon composite battery, characterized in that Include: Positive contact; Negative contact; Electrolyte; At least the positive electrode sheet group is the electrode sheet group according to claim 6 or 7, which is disposed in the electrolyte and connected to the positive electrode contact by wire welding; and At least the negative electrode sheet group is the electrode sheet group according to claim 6 or 7, which is disposed in the electrolyte and connected to the negative electrode contact by wire welding.

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