CN116111053A - Self-stirring water circulation rich liquid lead-carbon battery - Google Patents

Self-stirring water circulation rich liquid lead-carbon battery Download PDF

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CN116111053A
CN116111053A CN202111327510.6A CN202111327510A CN116111053A CN 116111053 A CN116111053 A CN 116111053A CN 202111327510 A CN202111327510 A CN 202111327510A CN 116111053 A CN116111053 A CN 116111053A
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carbon
lead
battery
carbon material
plate
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阎景旺
李先锋
席耀宁
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/06—Lead-acid accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/14—Electrodes for lead-acid accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/68—Selection of materials for use in lead-acid accumulators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention relates to the field of lead-carbon batteries, in particular to a self-stirring water circulation rich liquid lead-carbon battery, which comprises a flat electrode arranged in a closed battery box, wherein the flat electrode is vertical to the inner bottom surface of the battery box, a plate carbon material is arranged above the flat electrode in the battery box, and a flat grid with a through hole is used as a supporting framework for the flat electrode; filling carbon material in the lower part of a vertically placed grid, and filling negative electrode active substances on the grid above the carbon material to form a negative electrode; the positive electrode active material is filled on another grid to form a positive electrode.

Description

Self-stirring water circulation rich liquid lead-carbon battery
Technical Field
The invention relates to the field of lead-carbon batteries, in particular to a technique for eliminating acid layering of a rich liquid lead-carbon battery.
Background
Lead-acid batteries have the characteristics of low cost, high safety, good low-temperature performance and the like, and have been attracting attention for application in Hybrid Electric Vehicles (HEVs). However, HEVs require that lead-acid batteries operate in a high rate partial state of charge (HRPSoC), which can result in significant shortening of battery cycle life due to accelerated sulfation of the negative electrode. The addition of an appropriate carbon material to the anode active material to construct a lead-carbon battery (LCB) is one of the effective approaches to solve the anode sulfation problem.
The lead-carbon battery not only has the same safety, cheapness and stability as the traditional lead-acid battery, but also has longer cycle life and higher specific power as the super capacitor. Adding porous carbon material in the negative plate can prolong the cycle life under HRPSC. The carbon additives mainly play a role in providing a capacitance buffer, conductive network, thereby improving electrochemical kinetics. However, the introduction of the carbon additive also brings about problems such as an increase in hydrogen evolution rate during charging and a decrease in contact between the negative electrode active material sponge lead and the carbon material. In addition, the generated hydrogen bubbles separate the carbon particles from the electrode active material, resulting in a deterioration of the structural stability of the negative electrode plate. Because the lead element has higher hydrogen evolution overpotential, pb and the carbon material are compounded, and the hydrogen evolution reaction can be effectively inhibited. Pb/C composite materials have been reported as additives for lead-carbon batteries. Hao Zhang et al demonstrated that the functional groups on the carbon surface have an effect on the electrodeposition and hydrogen evolution of nano-lead. Tong et al studied the electrochemical properties of activated carbon materials containing divalent lead and its cycling performance in lead-carbon batteries under HRPSO conditions. Yang Gukuan et al indicate that nanostructured lead oxides formed by pyrolysis of lead citrate precursors can be used directly as additives for lead-carbon batteries.
Lead-carbon batteries can be classified into lean type and rich type according to the amount of electrolyte injected. The lean solution lead-carbon battery belongs to an energy type energy storage device, adopts an AGM separator, and is suitable for the fields of standby power supply, distributed energy storage and large-scale energy storage. The rich liquid lead-carbon battery belongs to a power type energy storage device, generally adopts a PE separator, and is suitable for automatic start-stop automobiles and hybrid electric vehicles. For the flooded lead-carbon battery, the acid stratification phenomenon is the same as that of the flooded lead-acid battery. If the problem of acid layering can be solved or the acid layering speed is slowed down, the cycle life of the lead-carbon battery can be further prolonged, and the market competitiveness of the lead-carbon battery is greatly improved. The use of a colloidal electrolyte in place of the dilute sulfuric acid solution can control acid stratification. However, the introduction of the colloidal electrolyte may reduce the utilization rate of the electrode active material, affect the performance of the battery capacity, and adversely affect the charge receiving ability and the high power discharge ability of the battery.
Disclosure of Invention
The technical problem to be solved by the invention (the purpose of the invention) is:
the self-stirring water circulation rich liquid lead-carbon battery comprises a flat plate electrode (comprising a positive electrode and a negative electrode) arranged in a closed battery box, wherein the flat plate electrode is arranged perpendicular to the inner bottom surface of the battery box, a plate carbon material is arranged above the flat plate electrode in the battery box, and the flat plate electrode takes a flat plate grid with a through hole as a supporting framework; filling carbon material in the lower part of a vertically placed grid, and filling negative electrode active substances on the grid above the carbon material to form a negative electrode; the positive electrode active material is filled on the other grid to form a positive electrode;
the carbon material of the filling is activated carbon and binder according to 50-95:50-5 (preferably 75-95:25-5, more preferably 85:15) by mass ratio.
The ratio of the area of the grid area filled with the carbon material to the total area of the grid in the negative electrode is (0.1-10): 50 preferably (0.2-4): 50, more preferably (0.5-2): 50.
the specific surface area of the carbon material is 200-3000m 2 Activated carbon or graphitized carbon material per gram, preferably 500-2000m 2 Material/g; the plate carbon material is carbon felt, graphite felt, carbon paper or carbon cloth.
The plate carbon material is a processed plate carbon material with oxyhydrogen compound function, the processing process is that,
1) Activation of the sheet carbon material: immersing a plate carbon material in a potassium hydroxide aqueous solution for 1-5 hours, wherein the mass ratio of the plate carbon material to the total mass ratio of the potassium hydroxide aqueous solution is 1: (10-1000) (preferably 1 (50-200)), the concentration of potassium hydroxide solution is 0.1mol/L-10mol/L (preferably 0.5-5 mol/L), the impregnated sheet carbon material is taken out and dried, the drying temperature is 40-120 ℃ (preferably 60-80 ℃), the drying time is 1-24 hours (preferably 8-16 hours), and the dried sheet carbon material is transferred into a sintering furnace in nitrogen atmosphere for activation, wherein the activation temperature is 700-1200 ℃, and the activation time is 1-10 hours (preferably 800-1000 ℃ and 4-6 hours);
2) Preparation of a plate carbon material with an oxyhydrogen compound function: immersing the activated plate carbon material in a chloroplatinic acid aqueous solution for 1-5 hours, wherein the mass ratio of the plate carbon material to the total mass of the aqueous solution is 1: (10-1000) (preferably 1 (50-200)), the concentration of the chloroplatinic acid solution is 0.1mol/L-10mol/L (preferably 0.5-5 mol/L), the impregnated sheet carbon material is taken out and dried, the drying temperature is 40-120 ℃ (preferably 60-80 ℃), the drying time is 1-24 hours (preferably 8-16 hours), the dried sheet carbon material is soaked in sodium borohydride solution for carrying out reduction reaction for 1-5 hours, wherein the total mass ratio of the mass of the activated sheet carbon material to the mass of the sodium borohydride solution is 1: (10-1000) (preferably 1 (50-200)), and the concentration of the sodium borohydride solution is 0.1mol/L to 10mol/L (0.5-5 mol/L).
The processed plate carbon material with oxyhydrogen function is placed on the top of the welded lead-carbon battery, and is prevented from contacting with the lugs of the electrodes, or insulation treatment is carried out outside the lugs, wherein the insulation treatment refers to that an insulation plastic sleeve is externally added to the part of the lugs higher than the plate carbon material or insulation glue is coated on the part of the lugs.
The thickness of the plate carbon material with the oxyhydrogen composite function is 0.01-10mm, preferably 0.5-2mm.
In order to ensure that the dosage of the catalyst is enough in the chemical process of generating water by hydrogen and oxygen combination, the mass ratio of chloroplatinic acid in the process of processing the plate carbon material to the carbon material filled in is 0.001-1000:1, preferably 50-500:1, the plate carbon material is carbon felt, carbon paper or carbon cloth.
The lead-carbon battery electrode negative electrode comprises the following materials in parts by weight: 500-800 parts of lead powder, 1-20 parts of carbon material, 6-10 parts of barium sulfate, and 0.1-0.5 part of polypropylene short fiber with the length of 0.1-5mm and the diameter of 100nm-5 mu m;
the lead-carbon battery electrode positive electrode comprises the following materials: 500-800 parts of lead powder, 6-10 parts of barium sulfate and 0.1-0.5 part of polypropylene short fiber with the length of 0.1-5mm and the diameter of 100nm-5 mu m.
The preparation process of the lead-carbon battery electrode comprises the following steps:
a, preparing a negative electrode: (1) According to the weight portions, 500 to 800 portions of lead powder, 1 to 20 portions of carbon material, 6 to 10 portions of barium sulfate and 0.1 to 0.5 portion of polypropylene short fiber with the length of 0.1 to 5mm and the diameter of 100nm to 5 mu m are stirred and premixed, 50 to 100 portions of water is added into the premixed powder while stirring, and the stirring is continued for 1 to 60 minutes to obtain the lead plaster; (2) Firstly, scraping the prepared carbon paste into a grid at the lowest part of a lead-carbon battery grid, then scraping the prepared lead paste onto other metal lead grids, and drying, solidifying and drying to obtain a lead-carbon battery negative electrode; the curing temperature is 30-50 ℃, the humidity is 70-95%, and the curing time is 10-30 hours; the drying temperature is 60-120 ℃ and the drying time is 10-30 hours.
B, preparation of a positive electrode: the positive electrode of the lead-acid battery is prepared according to the same process steps as the negative electrode preparation step (1) and the negative electrode preparation step (2), and the difference is that no carbon material is added in the positive electrode preparation process to prepare the lead plaster, and the lead plaster is only coated on the grid.
The lead-carbon battery is characterized in that a flat electrode is arranged in a sealed battery box, the electrode is perpendicular to the bottom of the battery box, sulfuric acid electrolyte is injected into the battery box, and the mass ratio of the sulfuric acid electrolyte to negative electrode lead plaster active substances is (60-200): 50, the mass concentration of the sulfuric acid electrolyte is 1.1-1.4g/ml, and the volume of the sulfuric acid electrolyte is as follows: the volume ratio of the battery box is (4-20): 35.
the invention has the beneficial effects that:
the invention provides a way for avoiding electrolyte layering of a flooded lead-carbon battery, which is provided with a self-stirring water circulation flooded lead-carbon battery, and specifically comprises the following steps: electrodes with low hydrogen evolution and oxygen evolution overpotential are arranged at the bottom ends of positive and negative polar plates of the lead-carbon battery, and the electrodes are used for electrolyzing a certain amount of water at the end of charging to generate hydrogen and oxygen. The hydrogen and the oxygen generate bubbles in the process of upward diffusion through the gaps between the polar plates and the separator, and play a role in stirring the electrolyte, so that the acid layering phenomenon is eliminated, the irreversible sulfation at the lower part of the cathode is inhibited, and the cycle life of the lead-carbon battery is prolonged. And preparing a composite carbon felt material with catalytic activity on the oxyhydrogen composite reaction at the upper part of the battery tank. The hydrogen and oxygen diffused out through the gaps between the polar plates and the baffle plates are subjected to chemical reaction under the action of the catalyst when passing through the carbon felt, so that water is generated, and water circulation is realized. By adopting the technical scheme provided by the invention, acid layering can be avoided, and the water consumption of the battery can be reduced, so that the cycle life of the lead-carbon battery is further prolonged on the basis of the original battery.
Detailed Description
The present invention is described in detail below with reference to examples.
Unless otherwise specified, the starting materials in the examples were purchased commercially and used without treatment; the instrument and equipment are recommended to use parameters by manufacturers.
In the examples, the cycle life of the lead-carbon battery was tested using a blue charge-discharge tester and a new-wire charge-discharge tester.
Example 1:
1. activation of carbon felt: 4 carbon felts (the total mass of the carbon felts is 1 g) with the length of 70mm, the width of 50mm and the thickness of 1mm are taken out, soaked carbon felts are taken out and dried in 100ml of 3mol/l potassium hydroxide aqueous solution for 1 hour, the drying temperature is 80 ℃, the drying time is 12 hours, and the dried carbon felts are transferred into a nitrogen atmosphere sintering furnace for activation, the activation temperature is 800 ℃, and the activation time is 5 hours.
2. Preparation of carbon felt with oxyhydrogen composite function: and immersing the activated carbon felt in 100ml of 3mol/l chloroplatinic acid aqueous solution for 1 hour, taking out the immersed carbon felt, drying at 80 ℃ for 12 hours, and immersing the dried carbon felt in 100ml of 3mol/l sodium borohydride solution for reduction reaction for 1 hour.
3. Preparing a lead-carbon battery cathode: the carbon material is transversely filled in the lowermost space of the grid, and the height is 1mm. The filling carbon material is prepared by mixing commercial activated carbon and a bonding agent PTFE according to a mass ratio of 85:15 (mass water content 10%) and the carbon material used is a carbon paste with a specific surface area of about 1300m 2 And (3) filling the carbon paste into the grid of the lowest grid when the lead paste is filled into the polar plate, wherein the filling mass is 1g, and the polar plate is used as the negative grid.
4. The lead-carbon battery is prepared by the following steps: A. preparation of the negative electrode: (1) Premixing 600g of lead powder, 9g of active carbon, 8.4g of barium sulfate and 0.3g of polypropylene short fiber with the length of 5mm and the diameter of 0.5-1.5 mu m by a high-speed stirrer, adding 84g of deionized water into the premixed powder while stirring, and continuously stirring for 10min to obtain lead plaster; (2) The lead plaster is coated on a metal lead grid, the size of the grid is 70mm long and 70mm wide (or high), 50mm thick and 2mm thick, the curing temperature is 40 ℃, the humidity is 80%, and the curing time is 20 hours; the drying temperature is 80 ℃ and the drying time is 24 hours; B. preparation of positive electrode: preparing a positive electrode of the lead-acid battery according to the same process steps as the negative electrode preparation step (1) and the step (2), wherein the difference is that no carbon material is added in the positive electrode preparation process to prepare lead plaster, and a grid is a conventional commercial grid, and only the lead plaster is coated on the grid; C. and (3) preparing a lead-carbon battery: three positive plates and two negative plates are sequentially and alternately arranged in parallel at intervals, and a commercial AGM membrane is adopted between the positive plates and the negative plates.
5. And placing the carbon felt with the oxyhydrogen composite function on the top of the welded lead-carbon battery, avoiding contact with the tab, and adhering insulating plastic to the part of the tab higher than the diaphragm. The width of the carbon felt with the oxyhydrogen composite function is 40mm and the length is 65mm. The thickness of the oxyhydrogen composite carbon felt is 0.01-10mm, preferably 0.5-2mm. And respectively welding the two negative plates in parallel and the three positive plates in parallel, wherein the total mass of the positive active material (the total mass of the lead plaster on the three positive plates after drying) of the lead-acid battery is 20.0g, the total mass of the positive active material refers to the total mass of the lead plaster contained in the three positive plates welded in parallel, the total mass of the negative active material (the total mass of the lead plaster on the two negative plates after drying) is 14.3g, and the total mass of the negative active material refers to the total mass of the lead plaster contained in the two negative plates welded in parallel. The positive and negative electrode grids adopt conventional lead grids, and the size is 70mm long and 50mm wide and 2mm thick; the positive and negative electrodes were placed in a tightly assembled battery case (electrodes perpendicular to the bottom of the case), wherein the case was 76mm long, 44mm wide and 100mm high, and 88g of sulfuric acid electrolyte having a density of 1.275g/ml was injected into the case;
the batteries were subjected to a cycle life test under the following conditions at 25 ℃): adopting 4.2A constant current discharge for 59 seconds, 18A discharge for 1 second, adopting 6.3A current for 2.3V voltage constant current constant voltage charge for 60 seconds, circulating the charge and discharge conditions 3600 times, then standing for 40 hours, restarting the circulation after 40 hours, and reducing the battery voltage to below 1.2V as the end condition of life test;
the initial voltage of the assembled internal mixed battery is 2.1824V in the normal-temperature full-charge state, and the internal mixed battery can run 18165 circles in the normal-temperature life test. Compared with the test result of the common lead-acid battery with the same lead element content under the same test condition (7198 circles), the normal-temperature cycle life of the internal mixed lead-acid carbon battery can reach 2.5 times of that of the conventional lead-acid battery.
Example 2:
lead carbon battery the procedure was the same as in example 1, except that the addition amount of the bottom activated carbon was reduced to 0.5g according to the requirements of example 1 without changing other conditions. The initial voltage of the assembled internal mixed battery is 2.1733V in the normal-temperature full-charge state, and the internal mixed battery can run for 17726 circles in the normal-temperature life test. Compared with the test result of the common lead-acid battery with the same lead element content under the same test condition (7198 circles), the normal-temperature cycle life of the internal mixed lead-acid carbon battery can reach 2.5 times of that of the conventional lead-acid battery.
Example 3:
lead-carbon battery the procedure is the same as in example 1, except that according to the requirements of example 1, no other conditions are changed, and a carbon felt with an oxyhydrogen composite function and a thickness of 2mm is placed on top of the battery to prepare the lead-carbon battery. The initial voltage of the assembled internal mixed battery in the normal temperature full-charge state is 2.1824V, and the internal mixed battery can run 18291 circles in the normal temperature life test. Compared with the test result of the common lead-acid battery with the same lead element content under the same test condition (7198 circles), the normal-temperature cycle life of the internal mixed lead-acid carbon battery can reach 2.5 times of that of the conventional lead-acid battery.
Example 4:
lead carbon battery the procedure was the same as in example 1, except that the bottom activated carbon was replaced with the same mass having a specific surface area of 1800m as required in example 1 without changing other conditions 2 And preparing the lead-carbon battery by using the active carbon material of/g. The initial voltage of the assembled internal mixed battery is 2.1925V in the normal-temperature full-charge state, and the internal mixed battery can run 18076 circles in the normal-temperature life test. Compared with the test result of the common lead-acid battery with the same lead element content under the same test condition (7198 circles), the normal-temperature cycle life of the internal mixed lead-carbon batteryThe life of the lead-acid battery can reach 2.5 times of that of the traditional lead-acid battery.
Example 5:
the procedure was as in example 1, except that the concentration of the chloroplatinic acid added was changed to 5mol/L as required in example 1 without changing other conditions. The initial voltage of the assembled internal mixed battery in the normal temperature full-charge state is 2.1723V, and the internal mixed battery can run 18132 circles in the normal temperature service life test. Compared with the test result of the common lead-acid battery with the same lead element content under the same test condition (7198 circles), the normal-temperature cycle life of the internal mixed lead-acid carbon battery can reach 2.5 times of that of the conventional lead-acid battery.
Example 6:
the procedure was as in example 1, except that the carbon felt used was changed to a 2mm thick carbon felt of the same mass, according to the requirements of example 1, without changing other conditions. The initial voltage of the assembled internal mixed battery in the normal temperature full-charge state is 2.1834V, and the internal mixed battery can run 18274 circles in the normal temperature life test. Compared with the test result of the common lead-acid battery with the same lead element content under the same test condition (7198 circles), the normal-temperature cycle life of the internal mixed lead-acid carbon battery can reach 2.5 times of that of the conventional lead-acid battery.
Example 7:
the procedure was as in example 1, except that the concentration of chloroplatinic acid solution used was changed to 9mol/L as required in example 1 without changing other conditions. The initial voltage of the assembled internal mixed battery is 2.1742V in the normal-temperature full-charge state, and the internal mixed battery can run 18372 circles in the normal-temperature life test. Compared with the test result of the common lead-acid battery with the same lead element content under the same test condition (7198 circles), the normal-temperature cycle life of the internal mixed lead-acid carbon battery can reach 2.5 times of that of the conventional lead-acid battery.
Example 8:
the procedure was as in example 1, except that the mass of the sulfuric acid electrolyte used was changed to 190g, as required in example 1, without changing other conditions. The initial voltage of the assembled internal mixed battery is 2.1742V in the normal-temperature full-charge state, and the internal mixed battery can run 18092 circles in the normal-temperature life test. Compared with the test result of the common lead-acid battery with the same lead element content under the same test condition (7198 circles), the normal-temperature cycle life of the internal mixed lead-acid carbon battery can reach 2.5 times of that of the conventional lead-acid battery.
Comparative example 1
The lead-carbon battery is the same as in example 1, except that according to the requirements of example 1, other conditions are not changed, and any carbon felt with an oxyhydrogen compound function is not added. The initial voltage of the assembled internal mixed battery in the normal temperature full-charge state is 2.1751V, and the battery can run for 5198 circles under the normal temperature condition.
Comparative example 2
Lead-carbon battery the procedure is the same as in example 1, except that according to the requirements of example 1, other conditions are not changed, the preparation of carbon felt with oxyhydrogen composite function is not carried out, and only carbon felt materials with the same quality and the same size and without any treatment are added to the surface of the negative electrode in the process of preparing the lead-acid battery. The initial voltage of the assembled internal mixed battery in the normal temperature full-charge state is 2.1832V, and the battery can run for 5425 circles under the normal temperature condition.
Comparative example 3
The procedure was as in example 1, except that the concentration of chloroplatinic acid solution was changed to 0.001mmol/L as required in example 1 without changing other conditions. Because no oxyhydrogen composite catalyst exists in the carbon felt, the hydrogen evolution condition of the battery is aggravated, the initial voltage of the assembled internal mixed battery is 2.1824V in the normal-temperature full-charge state, and the battery can run for 3996 times under the normal-temperature condition.
Comparative example 4
The procedure was as in example 1, except that the concentration of the sodium borohydride solution was changed to 0.001mmol/L as required in example 1 without changing other conditions. Due to the lack of reduction of sodium borohydride, no oxyhydrogen composite catalyst exists in the carbon felt, so that the hydrogen evolution condition of the battery is aggravated, the initial voltage of the assembled internal mixed battery is 2.1624V in the normal-temperature full-charge state, and the battery can run for 3678 circles under the normal-temperature condition.
Comparative example 5
The lead-carbon battery is the same as in example 1, except that according to the requirements of example 1, other conditions are not changed, and the carbon material below the negative electrode is not filled, i.e. a large amount of carbon material does not play a role of gas production disturbance below the electrode in the charging and discharging process of the battery. The initial voltage of the assembled internal mixed battery in the normal temperature full-charge state is 2.1356V, and the battery can run for 2421 circles under the normal temperature condition.
Comparative example 6
Lead carbon battery the procedure was the same as in example 1, except that the mass of sulfuric acid electrolyte added was changed to 40g according to the requirements of example 1 without changing other conditions. The initial voltage of the assembled internal mixed battery in the normal temperature full-charge state is 2.1734V, and the battery can run for 2654 circles under the normal temperature condition.
Comparative example 7
Lead carbon battery the procedure was the same as in example 1, except that the electrolyte was changed to 120g of sulfuric acid electrolyte having a mass density of 1.5g/ml, as required in example 1, without changing other conditions. The initial voltage of the assembled internal mixed battery in the normal temperature full-charge state is 2.1627V, and the battery can run for 1342 circles under the normal temperature condition.

Claims (10)

1. The utility model provides a from stirring hydrologic cycle rich liquid plumbous charcoal battery, is including arranging dull and stereotyped form electrode (including positive pole and negative pole) in airtight battery box in, and dull and stereotyped form electrode perpendicular to battery box inner bottom surface is placed, its characterized in that: a plate carbon material is arranged above a plate-shaped electrode in the battery box, and the plate-shaped electrode takes a plate grid with a through hole as a supporting framework; filling carbon material in the lower part of a vertically placed grid, and filling negative electrode active substances on the grid above the carbon material to form a negative electrode; the positive electrode active material is filled on the other grid to form a positive electrode;
the carbon material of the filling is activated carbon and binder according to 50-95:50-5 (preferably 75-95:25-5, more preferably 85:15) by mass ratio.
2. The lead-carbon battery of claim 1, wherein: the ratio of the area of the grid area filled with the carbon material to the total area of the grid in the negative electrode is (0.1-10): 50 preferably (0.2-4): 50, more preferably (0.5-2): 50.
3. a lead-carbon battery according to claim 1 or 2, characterized in that: the specific surface area of the carbon material is 200-3000m 2 Activated carbon or graphitized carbon material per gram, preferably 500-2000m 2 Material/g; the plate carbon material is carbon felt, graphite felt, carbon paper or carbon cloth.
4. The lead-carbon battery of claim 1, wherein:
the plate carbon material is a processed plate carbon material with oxyhydrogen compound function, the processing process is that,
1) Activation of the sheet carbon material: immersing a plate carbon material in a potassium hydroxide aqueous solution for 1-5 hours, wherein the mass ratio of the plate carbon material to the total mass ratio of the potassium hydroxide aqueous solution is 1: (10-1000) (preferably 1 (50-200)), the concentration of potassium hydroxide solution is 0.1mol/L-10mol/L (preferably 0.5-5 mol/L), the impregnated sheet carbon material is taken out and dried, the drying temperature is 40-120 ℃ (preferably 60-80 ℃), the drying time is 1-24 hours (preferably 8-16 hours), and the dried sheet carbon material is transferred into a sintering furnace in nitrogen atmosphere for activation, wherein the activation temperature is 700-1200 ℃, and the activation time is 1-10 hours (preferably 800-1000 ℃ and 4-6 hours);
2) Preparation of a plate carbon material with an oxyhydrogen compound function: immersing the activated plate carbon material in a chloroplatinic acid aqueous solution for 1-5 hours, wherein the mass ratio of the plate carbon material to the total mass of the aqueous solution is 1: (10-1000) (preferably 1 (50-200)), the concentration of the chloroplatinic acid solution is 0.1mol/L-10mol/L (preferably 0.5-5 mol/L), the impregnated sheet carbon material is taken out and dried, the drying temperature is 40-120 ℃ (preferably 60-80 ℃), the drying time is 1-24 hours (preferably 8-16 hours), the dried sheet carbon material is soaked in sodium borohydride solution for carrying out reduction reaction for 1-5 hours, wherein the total mass ratio of the mass of the activated sheet carbon material to the mass of the sodium borohydride solution is 1: (10-1000) (preferably 1 (50-200)), and the concentration of the sodium borohydride solution is 0.1mol/L to 10mol/L (0.5-5 mol/L).
5. The lead-carbon battery of claim 1, wherein:
the processed plate carbon material with oxyhydrogen function is placed on the top of the welded lead-carbon battery, and is prevented from contacting with the lugs of the electrodes, or insulation treatment is carried out outside the lugs, wherein the insulation treatment refers to that an insulation plastic sleeve is externally added to the part of the lugs higher than the plate carbon material or insulation glue is coated on the part of the lugs.
6. A lead-carbon battery according to claim 1 or 4, characterized in that: the thickness of the plate carbon material with the oxyhydrogen composite function is 0.01-10mm, preferably 0.5-2mm.
7. A lead-carbon battery according to claim 1 or 4, characterized in that: in order to ensure that the dosage of the catalyst is enough in the chemical process of hydrogen-oxygen composite to generate water, the mass ratio of chloroplatinic acid in the process of treating the plate carbon material to the carbon material filled in is 0.001-1000:1, preferably 50-500:1, the plate carbon material is carbon felt, carbon paper or carbon cloth.
8. The lead-carbon battery of claim 1, wherein:
the lead-carbon battery electrode negative electrode comprises the following materials in parts by weight: 500-800 parts of lead powder, 1-20 parts of carbon material, 6-10 parts of barium sulfate, and 0.1-0.5 part of polypropylene short fiber with the length of 0.1-5mm and the diameter of 100nm-5 mu m;
the lead-carbon battery electrode positive electrode comprises the following materials: 500-800 parts of lead powder, 6-10 parts of barium sulfate and 0.1-0.5 part of polypropylene short fiber with the length of 0.1-5mm and the diameter of 100nm-5 mu m.
9. The lead-carbon battery of claim 1, wherein:
the preparation process of the lead-carbon battery electrode comprises the following steps:
a, preparing a negative electrode: (1) According to the weight portions, 500 to 800 portions of lead powder, 1 to 20 portions of carbon material, 6 to 10 portions of barium sulfate and 0.1 to 0.5 portion of polypropylene short fiber with the length of 0.1 to 5mm and the diameter of 100nm to 5 mu m are stirred and premixed, 50 to 100 portions of water is added into the premixed powder while stirring, and the stirring is continued for 1 to 60 minutes to obtain the lead plaster; (2) Firstly, scraping the prepared carbon paste into a grid at the lowest part of a lead-carbon battery grid, then scraping the prepared lead paste onto other metal lead grids, and drying, solidifying and drying to obtain a lead-carbon battery negative electrode; the curing temperature is 30-50 ℃, the humidity is 70-95%, and the curing time is 10-30 hours; the drying temperature is 60-120 ℃ and the drying time is 10-30 hours;
b, preparation of a positive electrode: the positive electrode of the lead-acid battery is prepared according to the same process steps as the negative electrode preparation step (1) and the negative electrode preparation step (2), and the difference is that no carbon material is added in the positive electrode preparation process to prepare the lead plaster, and the lead plaster is only coated on the grid.
10. The lead-carbon battery of claim 1, wherein:
the lead-carbon battery is characterized in that a flat electrode is arranged in a sealed battery box, the electrode is perpendicular to the bottom of the battery box, sulfuric acid electrolyte is injected into the battery box, and the mass ratio of the sulfuric acid electrolyte to negative electrode lead plaster active substances is (60-200): 50, the mass concentration of the sulfuric acid electrolyte is 1.1-1.4g/ml, and the volume of the sulfuric acid electrolyte is as follows: the volume ratio of the battery box is (4-20): 35.
CN202111327510.6A 2021-11-10 2021-11-10 Self-stirring water circulation rich liquid lead-carbon battery Pending CN116111053A (en)

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