CN113036128B - Flexible carbon material layer and preparation method and application thereof - Google Patents

Flexible carbon material layer and preparation method and application thereof Download PDF

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CN113036128B
CN113036128B CN201911360364.XA CN201911360364A CN113036128B CN 113036128 B CN113036128 B CN 113036128B CN 201911360364 A CN201911360364 A CN 201911360364A CN 113036128 B CN113036128 B CN 113036128B
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carbon
battery
lead
material layer
carbon material
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CN113036128A (en
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阎景旺
李先锋
席耀宁
张洪章
张华民
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • 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
    • H01M10/12—Construction or manufacture
    • H01M10/125—Cells or batteries with wound or folded electrodes
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses a flexible carbon material layer and a preparation method and application thereof. According to the invention, the lead plaster and the flexible carbon material layer are made into an integrated electrode, and the flexible carbon material layer has the function of a current collector, so that the limitation that the conventional lead-carbon battery grid can only use lead alloy is broken through, and the quality and the internal resistance of a battery plate are reduced, thereby improving the power density and the energy density of the battery and improving the performance of the battery; meanwhile, the flexible carbon fiber layer limits the growth of lead sulfate grains in the battery, so that sulfation is reduced, the capacitance characteristic of carbon is fully exerted, and the service life of the battery is greatly prolonged.

Description

Flexible carbon material layer and preparation method and application thereof
Technical Field
The invention belongs to the technical field of energy storage batteries and start-stop batteries, and particularly relates to a flexible carbon material layer and a preparation method and application thereof.
Background
Lead-acid batteries play an important role in our daily lives. With the development of the technology, the 21 st century lead-acid battery is expected to be applied to brand new fields such as hybrid electric vehicles and renewable energy storage systems. In renewable energy storage systems, lead-acid batteries are used to collect intermittent electrical energy and provide a stable power output. Lead-acid batteries are always at partial state of charge due to the intermittency and instability of renewable energy sources. Through the use of the lead-acid battery for a long time, the problem of sulfation of the negative electrode of the lead-acid battery is gradually generated, the charge receiving capacity and the discharge capacity of the battery are greatly reduced, and the application of the lead-acid battery in a renewable energy storage system is greatly limited.
The lead-carbon battery is a capacitive lead-acid battery, is a novel battery evolved from the traditional lead-acid battery, and is characterized in that activated carbon is added into the negative electrode of the lead-acid battery, and a conductive network is formed by utilizing the high conductivity and capacitance characteristics of the activated carbon, so that the sulfation of the battery is reduced, and the service life of the lead-acid battery is obviously prolonged. The structure of the lead-carbon battery mainly comprises an internal mixing type lead-carbon battery and an internal parallel type lead-carbon battery, wherein the internal mixing type lead-carbon battery is formed by mixing activated carbon and lead paste to play the conductivity and the capacitance of the activated carbon, the internal parallel type lead-carbon battery is formed by connecting an activated carbon negative plate in parallel with the negative electrode of the lead-acid battery, and the impact of large-current charging and discharging is resisted by utilizing the capacitance of the activated carbon, so that the service life of the battery is prolonged.
The current collector of the traditional lead-acid battery mainly comprises lead alloy, and after the formation of the traditional lead-acid battery is finished, lead paste can be tightly combined with the current collector, so that the problem of overlarge contact resistance is naturally avoided. Once activated carbon is added into lead paste, the activated carbon and a current collector of a traditional lead-acid battery can generate larger contact resistance, and the excessive contact resistance can prevent carbon from playing a capacitance performance, even aggravate a battery sulfation process and shorten the service life of the battery.
Disclosure of Invention
In order to solve the technical problems, the invention provides a carbon material layer suitable for an internal mixing type lead-carbon battery, and particularly provides a flexible carbon material layer, a preparation method and application thereof.
In order to realize the purpose, the technical scheme adopted by the invention is as follows:
in one aspect of the present invention, a flexible carbon material layer is provided, and the flexible carbon material layer includes a graphitized carbon fiber layer having activation holes, and a hydrogen evolution inhibitor is loaded on a surface of the graphitized carbon fiber layer.
Optionally, the amount of the hydrogen evolution inhibitor is 1% to 50% of the total mass of the hydrogen evolution inhibitor and the graphitized carbon fiber layer.
Specifically, the dosage of the hydrogen evolution inhibitor is 1%, 5%, 10%, 20%, 35% and 50% of the total mass of the hydrogen evolution inhibitor and the graphitized carbon fiber layer.
Optionally, the hydrogen evolution inhibitor is a simple substance or a compound of a high hydrogen evolution overpotential element;
the high hydrogen evolution overpotential element comprises at least one of Zn, Bi, Cd, Pb, In and Sn;
the compound comprises at least one of nitrate, acetate and alkoxide.
Specifically, in the embodiment of the present invention, the carbon fiber layer is a carbon fiber felt, that is, a carbon felt.
In another aspect of the present invention, a method for preparing a flexible carbon material layer is provided, which at least comprises:
graphitizing the carbon fiber layer to obtain a graphitized carbon fiber layer;
carrying out pore-forming activation on the graphitized carbon fiber layer to obtain an activated graphitized carbon fiber layer;
and (3) soaking and mixing the activated graphitized carbon fiber layer in a solution of a hydrogen evolution inhibitor to obtain the flexible carbon material layer.
Optionally, a method for preparing a flexible carbon material layer at least includes:
graphitizing the carbon fiber layer under the catalytic action of a graphitizing catalyst to obtain a graphitized carbon fiber layer;
carrying out pore-forming activation on the graphitized carbon fiber layer by adopting alkali liquor to obtain an activated graphitized carbon fiber layer;
and dipping and mixing the activated graphitized carbon fiber layer in a solution of a hydrogen evolution inhibitor to obtain a dipped product, and drying and sintering the dipped product to obtain the flexible carbon material layer.
Alternatively, the graphitization catalyst is a metal compound;
the metal comprises at least one of iron, manganese, nickel, cobalt, tungsten, molybdenum and titanium;
the compound comprises at least one of nitrate, acetate and chloride.
Optionally, the sintering parameters of the impregnated product are: and preserving the heat for 2-5 hours at 200-900 ℃ under the atmosphere protection.
The lower limit of the sintering temperature is independently selected from 200 ℃, 300 ℃, 400 ℃, 500 ℃ and 800 ℃; the upper limit of the drying temperature is independently selected from the group consisting of 250 deg.C, 450 deg.C, 600 deg.C, 700 deg.C, and 900 deg.C.
The sintering time is independently selected from 2h, 2.5h, 3h, 4h and 5 h.
Optionally, the drying temperature is 80-120 ℃.
The lower limit of the drying temperature is independently selected from 80 deg.C, 90 deg.C, 95 deg.C, 100 deg.C, 110 deg.C; the upper limit of the drying temperature is independently selected from 90 deg.C, 100 deg.C, 110 deg.C, 115 deg.C, and 120 deg.C.
The drying time can be determined according to the dryness of the product, so as to remove free water in the product.
In a third aspect of the invention, an electrode is provided, which comprises at least one of any one of the flexible carbon material layers and the flexible carbon material layer prepared by any one of the methods;
and electrode lead paste is filled on the surface of the flexible carbon material layer.
Specifically, the electrode comprises a positive electrode and a negative electrode, the flexible carbon material layer is used as an electrode plate, and the positive electrode comprises the flexible carbon material layer and a positive active material filled on the surface of the flexible carbon material layer; the negative electrode includes a flexible carbon material layer and a negative active material filled on the surface thereof.
Optionally, the loading amount of the electrode lead paste is 1-99% of the total mass of the electrode.
In a fourth aspect of the invention, a lead-carbon battery is provided, comprising the above-mentioned electrode.
Alternatively, the electrode is wound and placed in a battery case filled with an electrolyte.
Specifically, the battery internal electrode is composed of a flexible carbon material layer filled with lead paste, and therefore the electrode also has flexibility. And stacking the positive electrode and the negative electrode layer by layer, then winding to form an electrode roll, and placing the electrode roll in a battery box filled with electrolyte to obtain the complete battery. In the battery, the flexible carbon material layer is not only an electrode but also a current collector, so that the electrode of the battery and the current collector are integrated, the internal resistance of a polar plate is reduced, the carbon material is favorable for playing the capacitance performance of the battery, the sulfation is reduced, the performance of the battery is greatly improved, and the service life of the battery is greatly prolonged.
The invention has the beneficial effects that:
1. the lead paste and the flexible carbon material layer are made into an integrated electrode, the flexible carbon material layer has the function of a current collector, the limitation that the conventional lead-carbon battery grid can only use lead alloy is broken through, and the quality and the internal resistance of a battery plate are reduced, so that the power density and the energy density of the battery are improved, and the performance of the battery is improved.
2. According to the invention, the carbon fiber layer is graphitized, so that the conductivity of the flexible carbon material layer is improved, and the battery performance is further improved.
3. According to the invention, the graphitized carbon fiber layer is activated to form pores, so that a high attachment area is provided for the hydrogen evolution inhibitor; meanwhile, the specific capacitance of the carbon fiber layer is improved, and the service life of the battery is further prolonged.
4. According to the invention, the flexible carbon material layer is used as an electrode grid, so that the growth of lead sulfate crystal grains is limited, the sulfation is reduced, the capacitance characteristic of carbon is fully exerted, and the service life of the battery is greatly prolonged.
Detailed Description
The present invention will be described in detail with reference to examples.
Unless otherwise specified, the raw materials in the examples were purchased commercially and used without treatment; the used instruments and equipment adopt the use parameters recommended by manufacturers.
In the examples, the graphitization of the carbon fiber layer was detected using an X-ray diffractometer.
In the examples, the normal temperature discharge capacity and cycle life of the battery were measured using a blue-ray charging and discharging instrument. The test conditions were: under the constant temperature environment of 25 ℃, discharging to 1.8V by adopting a constant current of 2.08A, charging to 2.4V by adopting a current of 0.52A, then charging the battery for 5 hours at a constant voltage under the condition of 2.4V, wherein the end condition of the life test is that the current discharge capacity of the battery is lower than 70 percent of the first cycle discharge capacity.
Example 1
1. Preparing a flexible carbon material layer:
firstly, carrying out catalytic activation on a carbon felt: taking 16 carbon felts with the length of 100mm, the width of 72mm and the thickness of 3mm, completely immersing the carbon felts in a cobalt nitrate solution with the concentration of 1M, stirring the carbon felts at a low speed for 1 hour, taking out the carbon felts, placing the carbon felts in an oven to dry the carbon felts for 12 hours at the temperature of 80 ℃, taking out the dried carbon felts, transferring the carbon felts to an atmosphere sintering furnace, sintering the carbon felts for 5 hours in a nitrogen environment at the temperature of 800 ℃, and naturally cooling the carbon felts to obtain the partially graphitized carbon felts. The partially graphitized carbon felt after cooling is repeatedly washed several times using ultrapure water.
And sampling the obtained partially graphitized carbon felt, and performing X-ray diffraction detection, wherein the result shows that the carbon felt fiber is partially graphitized.
And transferring the washed and dried partially graphitized carbon felt into a potassium hydroxide solution with the concentration of 3M for fully soaking, slowly stirring for 2 hours, then placing the partially graphitized carbon felt at the temperature of 80 ℃ for drying, transferring the dried partially graphitized carbon felt into an atmosphere sintering furnace, sintering in a nitrogen environment at the sintering temperature of 800 ℃, preserving heat for 5 hours, and naturally cooling. And transferring the cooled partially graphitized carbon felt into a 0.5M dilute nitric acid solution for soaking and repeatedly washing for a plurality of times, washing the washed partially graphitized carbon felt for a plurality of times by adopting ultrapure water until the pH value of the washing waste liquid reaches 7, and finally transferring the partially graphitized carbon felt into a blast drying box at the temperature of 80 ℃ for drying to obtain the activated graphitized carbon felt.
And soaking 80g of dried activated graphitized carbon felt in 5000ml of 84.7mmol/L zinc nitrate solution, slowly stirring, drying the product, transferring the dried product to an atmosphere sintering furnace, and preserving the heat at 200 ℃ for 3 hours in a nitrogen environment to obtain the flexible carbon material layer.
2. Preparing a coiled lead-carbon battery electrode:
the preparation method of the cathode comprises the following steps: (1) 100 parts of lead powder, 1.2 parts of additives (barium sulfate and 0.2 part of lignin) and 1.5 parts of commercial activated carbon are poured into a container of a paste mixer for dry mixing for 3 minutes, and all the components are fully and uniformly mixed to obtain a mixture; (2) weighing 15.5 parts of deionized water, and slowly adding the deionized water into the powderRapidly adding the mixture obtained in the step (1) into the mixture under slow stirring for 2 minutes, continuously stirring for 3 minutes, and then slowly adding the mixture with the density of 1.4g/cm3And 8.5 parts of sulfuric acid solution, wherein the whole acid adding time is controlled within 5 minutes, and the sulfuric acid solution is continuously stirred for 13 minutes after being completely added, so that the lead-carbon battery cathode lead paste is obtained. The temperature in the lead plaster and the container is not suitable to exceed 65 ℃ in the lead plaster mixing process, the plaster outlet temperature is not more than 40 ℃, and the apparent density of the lead plaster is controlled to be 3.6-4.4 g/cm3. (3) And (3) filling the lead-carbon battery negative electrode lead paste obtained in the step (2) into the flexible carbon material layer prepared in the step (1), wherein the length and the width of the coated area are 50mm and 72mm respectively, the mass of the filled lead paste is 14.3g, the rest part of the carbon felt is cut into battery tabs with the length of 50mm and the width of 20mm, the filled electrode is treated by acid spraying, then is put into a humidity-controllable high-low temperature box for curing and drying, is cured for 36h under the condition of 45 ℃ relative humidity of 95%, and then is dried for 9h at 85 ℃ to obtain the lead-carbon battery negative electrode.
The preparation method of the battery positive electrode is the same as that of the negative electrode, only commercial activated carbon is not added into the lead plaster, and the mass of the lead plaster filled and coated on the positive electrode is 20.0 g.
3. And (3) placing and winding the three positive plates and the four negative plates prepared in the step (2) at intervals. Placing the positive and negative electrodes into a tightly assembled battery case with a diameter of 40mm and a height of 100mm, and injecting 83g of a material with a density of 1.275g/cm into the battery case3The lead-carbon battery of 2V5.2Ah was assembled. And (3) after the assembled lead-carbon battery is formed, carrying out a normal-temperature discharge capacity test and a cycle life test. The cell was run for 47 cycles under test conditions. Compared with the test result of the coiled lead-acid battery prepared under the same condition, the service life of the battery can reach 2.04 times of that of the coiled lead-acid battery.
Example 2
1. Preparing a flexible carbon material layer:
firstly, carrying out catalytic activation on a carbon felt: taking 16 carbon felts with the length of 100mm, the width of 72mm and the thickness of 3mm, completely immersing the carbon felts in ferric nitrate solution with the concentration of 3M, stirring the carbon felts at a low speed for 1 hour, taking out the carbon felts, placing the carbon felts in an oven to dry the carbon felts for 12 hours at the temperature of 80 ℃, taking out the dried carbon felts, transferring the carbon felts to an atmosphere sintering furnace, sintering the carbon felts for 5 hours in a nitrogen environment at the temperature of 800 ℃, and naturally cooling the carbon felts to obtain the partially graphitized carbon felts. The partially graphitized carbon felt after cooling is repeatedly washed several times using ultrapure water.
And sampling the obtained partially graphitized carbon felt, and performing X-ray diffraction detection, wherein the result shows that the carbon felt fiber is partially graphitized.
And transferring the washed and dried partially graphitized carbon felt into a potassium hydroxide solution with the concentration of 3M for fully soaking, slowly stirring for 2 hours, then drying the partially graphitized carbon felt at the temperature of 80 ℃, transferring the dried partially graphitized carbon felt into an atmosphere sintering furnace, sintering in a nitrogen environment at the sintering temperature of 700 ℃, preserving heat for 5 hours, and naturally cooling. And transferring the cooled partially graphitized carbon felt into a 0.5M dilute nitric acid solution for soaking and repeatedly washing for a plurality of times, washing the washed partially graphitized carbon felt for a plurality of times by adopting ultrapure water until the pH value of the washing waste liquid reaches 7, and finally transferring the partially graphitized carbon felt into a blast drying box at the temperature of 80 ℃ for drying to obtain the activated graphitized carbon felt.
And soaking 80g of dried activated graphitized carbon felt in 5000ml of 40.5mmol/L bismuth nitrate solution, slowly stirring, drying the product, transferring the dried product into an atmosphere sintering furnace, and preserving heat for 5 hours at 400 ℃ in a nitrogen environment to obtain the flexible carbon material layer.
2. Preparing a coiled lead-carbon battery electrode:
The preparation method of the cathode comprises the following steps: (1) 100 parts of lead powder, 1.2 parts of additive (barium sulfate and 0.2 part of lignin) and 1.5 parts of commercial activated carbon are poured into a container of a paste mixer for dry mixing for 5 minutes, and all the components are fully and uniformly mixed to obtain a mixture; (2) weighing 15.5 parts of deionized water, quickly adding the deionized water into the mixture obtained in the step (1) for 3 minutes under the condition of slowly stirring the powder, continuously stirring the mixture for 6 minutes, and then slowly adding the deionized water into the mixture with the density of 1.4g/cm3And 8.5 parts of sulfuric acid solution, wherein the whole acid adding time is controlled within 10 minutes, and the stirring is continued for 20 minutes after the sulfuric acid solution is completely added, so that the lead-carbon battery negative electrode lead paste is obtained. The temperature in the lead plaster and the container is not suitable to exceed 65 ℃ and the temperature of the lead plaster discharged is not more than 40 ℃ in the lead plaster mixing process, and the apparent density of the lead plaster is controlled to be 3.6 to up to4.4g/cm3. (3) And (3) filling the lead-carbon battery cathode lead paste obtained in the step (2) into the flexible carbon material layer prepared in the step (1), wherein the area, the length and the width of the coating are respectively 50mm and 72mm, the mass of the filled lead paste is 14.3g, the rest part of the carbon felt is cut into a battery tab with the length of 50mm and the width of 20mm, the filled electrode is subjected to acid spraying treatment, then is put into a humidity-controllable high-low temperature box for curing and drying, is cured for 36 hours under the condition of relative humidity of 45 ℃ and 95%, and is dried for 9 hours at 85 ℃ to obtain the lead-carbon battery cathode.
The preparation method of the battery anode is the same as that of the battery cathode, only commercial activated carbon is not added into the lead plaster, and the mass of the lead plaster filled in the anode is 20.0 g.
3. And (3) placing and winding the three positive plates and the four negative plates prepared in the step (2) at intervals. Placing the positive and negative electrodes into a tightly assembled battery case with a diameter of 40mm and a height of 100mm, and injecting 83g of a material with a density of 1.275g/cm into the battery case3The lead-carbon battery of 2V5.2Ah was assembled. And (3) after the assembled lead-carbon battery is formed, testing the discharge capacity at normal temperature and the cycle life. The cell was run for 43 cycles under test conditions. Compared with the test result of the coiled lead-acid battery prepared under the same condition, the service life of the battery can reach 1.87 times of that of the coiled lead-acid battery.
Example 3
1. Preparing a flexible carbon material layer:
firstly, carrying out catalytic activation on a carbon felt: taking 16 carbon felts with the length of 100mm, the width of 72mm and the thickness of 3mm, completely immersing the carbon felts in a nickel nitrate solution with the concentration of 1M, stirring the carbon felts at a low speed for 1 hour, taking out the carbon felts, placing the carbon felts in an oven to dry the carbon felts for 12 hours at the temperature of 80 ℃, taking out the dried carbon felts, transferring the carbon felts to an atmosphere sintering furnace, sintering the carbon felts for 5 hours in a nitrogen environment at the temperature of 800 ℃, and naturally cooling the carbon felts to obtain the partially graphitized carbon felts. The partially graphitized carbon felt after cooling is repeatedly washed several times using ultrapure water.
And sampling the obtained partially graphitized carbon felt, and performing X-ray diffraction detection, wherein the result shows that the carbon felt fiber is partially graphitized.
And transferring the washed and dried partially graphitized carbon felt into a potassium hydroxide solution with the concentration of 3M to be fully soaked and slowly stirred for 2 hours, then placing the partially graphitized carbon felt into a condition of 80 ℃ to be dried, transferring the dried partially graphitized carbon felt into an atmosphere sintering furnace, sintering in a nitrogen environment at the sintering temperature of 900 ℃, preserving heat for 2 hours, and naturally cooling. And transferring the cooled partially graphitized carbon felt into a 0.5M dilute nitric acid solution for soaking and repeatedly washing for a plurality of times, washing the washed partially graphitized carbon felt for a plurality of times by adopting ultrapure water until the pH value of the washing waste liquid reaches 7, and finally transferring the partially graphitized carbon felt into a blast drying box at the temperature of 80 ℃ for drying to obtain the activated graphitized carbon felt.
And (3) soaking 80g of dried activated graphitized carbon felt in 5000ml of 67.7mmol/L cadmium nitrate solution, slowly stirring, drying the product, transferring the dried product to an atmosphere sintering furnace, and preserving the heat at 600 ℃ for 4 hours in a nitrogen environment to obtain the flexible carbon material layer.
2. Preparing a coiled lead-carbon battery electrode:
The preparation method of the negative electrode comprises the following steps: (1) 100 parts of lead powder, 1.2 parts of additives (barium sulfate and 0.2 part of lignin) and 1.5 parts of commercial activated carbon are poured into a container of a paste mixer for dry mixing for 4 minutes, and all the components are fully and uniformly mixed to obtain a mixture; (2) weighing 15.5 parts of deionized water, quickly adding the deionized water into the mixture obtained in the step (1) for 2 minutes under the condition of slowly stirring the powder, continuously stirring the mixture for 4 minutes, and then slowly adding the deionized water into the mixture with the density of 1.4g/cm3And 8.5 parts of sulfuric acid solution, wherein the whole acid adding time is controlled within 7 minutes, and the sulfuric acid solution is continuously stirred for 15 minutes after being completely added, so that the lead-carbon battery cathode lead paste is obtained. The temperature in the lead plaster and the container is not suitable to exceed 65 ℃ in the lead plaster mixing process, the plaster outlet temperature is not more than 40 ℃, and the apparent density of the lead plaster is controlled to be 3.6-4.4 g/cm3. (3) Filling the lead-carbon battery cathode lead plaster obtained in the step (2) into the flexible carbon material layer prepared in the step (1), wherein the length and the width of the coated area are 50mm and 72mm respectively, the mass of the filled lead plaster is 14.3g, the rest part of the carbon felt is cut into battery tabs with the length of 50mm and the width of 20mm, the filled electrodes are treated by acid spraying, then the battery tabs are put into a humidity-controllable high-low temperature box for curing and drying, the battery tabs are cured for 36h under the condition that the relative humidity is 95% at 45 ℃, and then the battery tabs are dried at 85 DEG C And 9h, obtaining the lead-carbon battery cathode.
The preparation method of the battery positive electrode is the same as that of the negative electrode, only commercial activated carbon is not added into the lead plaster, and the mass of the lead plaster filled and coated on the positive electrode is 20.0 g.
3. And (3) placing and winding the three positive plates and the four negative plates prepared in the step (2) at intervals. Placing the positive and negative electrodes into a tightly assembled battery case with a diameter of 40mm and a height of 100mm, and injecting 83g of a material with a density of 1.275g/cm into the battery case3The lead-carbon battery of 2V5.2Ah was assembled. And (3) after the assembled lead-carbon battery is formed, testing the discharge capacity at normal temperature and the cycle life. The cell was run for 39 cycles under test conditions. Compared with the test result of the coiled lead-acid battery prepared under the same condition, the service life of the battery can reach 1.70 times of that of the coiled lead-acid battery.
Example 4
1. Preparing a flexible carbon material layer:
firstly, carrying out catalytic activation on a carbon felt: taking 16 carbon felts with the length of 100mm, the width of 72mm and the thickness of 3mm, completely immersing the carbon felts in a manganese nitrate solution with the concentration of 1M, stirring the carbon felts at a low speed for 1 hour, taking out the carbon felts, placing the carbon felts in an oven to dry the carbon felts for 12 hours at the temperature of 80 ℃, taking out the dried carbon felts, transferring the carbon felts to an atmosphere sintering furnace, sintering the carbon felts for 5 hours in a nitrogen environment at the temperature of 800 ℃, and naturally cooling the carbon felts to obtain the partially graphitized carbon felts. The partially graphitized carbon felt after cooling is repeatedly washed several times using ultrapure water.
And sampling the obtained partially graphitized carbon felt, and performing X-ray diffraction detection, wherein the result shows that the carbon felt fiber is partially graphitized.
And transferring the washed and dried partially graphitized carbon felt into a potassium hydroxide solution with the concentration of 3M to be fully soaked and slowly stirred for 2 hours, then placing the partially graphitized carbon felt into a condition of 80 ℃ to be dried, transferring the dried partially graphitized carbon felt into an atmosphere sintering furnace, sintering in a nitrogen environment at the sintering temperature of 700 ℃, preserving heat for 3 hours and naturally cooling. And transferring the cooled partially graphitized carbon felt into a 0.5M dilute nitric acid solution for soaking and repeatedly washing for a plurality of times, washing the washed partially graphitized carbon felt for a plurality of times by adopting ultrapure water until the pH value of the washing waste liquid reaches 7, and finally transferring the partially graphitized activated partially graphitized carbon felt into a blast drying box for drying at the temperature of 80 ℃ to obtain the activated graphitized carbon felt.
And soaking 80g of dried activated graphitized carbon felt in 5000ml of 48.3mmol/L lead nitrate solution, slowly stirring, drying the product, transferring the dried product to an atmosphere sintering furnace, and preserving the heat at 800 ℃ for 2 hours in a nitrogen environment to obtain the flexible carbon material layer.
2. Preparing a coiled lead-carbon battery electrode:
the preparation method of the cathode comprises the following steps: (1) 100 parts of lead powder, 1.2 parts of additives (barium sulfate and 0.2 part of lignin) and 1.5 parts of commercial activated carbon are poured into a container of a paste mixer for dry mixing for 3 minutes, and all the components are fully and uniformly mixed to obtain a mixture; (2) weighing 15.5 parts of deionized water, quickly adding the deionized water into the mixture obtained in the step (1) for 3 minutes under the condition of slowly stirring the powder, continuously stirring the mixture for 5 minutes, and then slowly adding the deionized water into the mixture with the density of 1.4g/cm3And 8.5 parts of sulfuric acid solution, controlling the whole acid adding time within 9 minutes, and continuously stirring for 17 minutes after the sulfuric acid solution is completely added to obtain the lead-carbon battery cathode lead paste. The temperature in the lead plaster and the container is not suitable to exceed 65 ℃ in the lead plaster mixing process, the plaster outlet temperature is not more than 40 ℃, and the apparent density of the lead plaster is controlled to be 3.6-4.4 g/cm3. (3) And (3) filling the lead-carbon battery negative electrode lead paste obtained in the step (2) into the flexible carbon material layer prepared in the step (1), wherein the length and the width of the coated area are 50mm and 72mm respectively, the mass of the filled lead paste is 14.3g, the rest part of the carbon felt is cut into battery tabs with the length of 50mm and the width of 20mm, the filled electrode is treated by acid spraying, then is put into a humidity-controllable high-low temperature box for curing and drying, is cured for 36h under the condition of 45 ℃ relative humidity of 95%, and then is dried for 9h at 85 ℃ to obtain the lead-carbon battery negative electrode.
The preparation method of the battery positive electrode is the same as that of the negative electrode, only commercial activated carbon is not added into the lead plaster, and the mass of the lead plaster filled and coated on the positive electrode is 20.0 g.
3. And (3) placing and winding the three positive plates and the four negative plates prepared in the step (2) at intervals. Placing the positive and negative electrodes in a tightly assembled battery box with a diameter of 40mm and a height100mm, and 83g of a resin having a density of 1.275g/cm was injected into the battery case3The lead-carbon battery of 2V5.2Ah was assembled. And (3) after the assembled lead-carbon battery is formed, testing the discharge capacity at normal temperature and the cycle life. The cell was run for 45 cycles under test conditions. Compared with the test result of the coiled lead-acid battery prepared under the same condition, the service life of the battery can reach 1.96 times of that of the coiled lead-acid battery.
Comparative example 1
1. Preparing a flexible carbon material layer:
firstly, carrying out catalytic activation on a carbon felt: taking 16 carbon felts with the length of 100mm, the width of 72mm and the thickness of 3mm, completely immersing the carbon felts in a cobalt nitrate solution with the concentration of 1M, stirring the carbon felts at a low speed for 1 hour, taking out the carbon felts, placing the carbon felts in an oven to dry the carbon felts for 12 hours at the temperature of 80 ℃, taking out the dried carbon felts, transferring the carbon felts to an atmosphere sintering furnace, sintering the carbon felts for 5 hours in a nitrogen environment at the temperature of 800 ℃, and naturally cooling the carbon felts to obtain the partially graphitized carbon felts. The partially graphitized carbon felt after cooling is repeatedly washed several times using ultrapure water.
And sampling the obtained partially graphitized carbon felt, and performing X-ray diffraction detection, wherein the result shows that the carbon felt fiber is partially graphitized.
And transferring the washed and dried partially graphitized carbon felt into a potassium hydroxide solution with the concentration of 3M for fully soaking and slowly stirring for 2 hours, then drying the partially graphitized carbon felt at the temperature of 80 ℃, transferring the dried partially graphitized carbon felt into an atmosphere sintering furnace, sintering in a nitrogen environment at the sintering temperature of 800 ℃, preserving heat for 5 hours, and naturally cooling. And transferring the cooled partially graphitized carbon felt into a 0.5M dilute nitric acid solution for soaking and repeatedly washing for a plurality of times, washing the washed partially graphitized carbon felt for a plurality of times by adopting ultrapure water until the pH value of the washing waste liquid reaches 7, and finally transferring the partially graphitized activated partially graphitized carbon felt into a blast drying box for drying at the temperature of 80 ℃ to obtain the activated graphitized carbon felt.
And soaking 80g of dried activated graphitized carbon felt in 5000ml of 84.7mmol/L zinc nitrate solution, slowly stirring, drying the product, transferring the dried product to an atmosphere sintering furnace, and preserving the heat at 200 ℃ for 3 hours in a nitrogen environment to obtain the flexible carbon material layer.
2. The method comprises the following steps of:
the preparation method of the negative electrode comprises the following steps: (1) 100 parts of lead powder and additives (1.2 parts of barium sulfate and 0.2 part of lignin) are poured into a container of a paste mixer for dry mixing for 3 minutes, and all the components are fully and uniformly mixed to obtain a mixture; (2) weighing 15.5 parts of deionized water, quickly adding the deionized water into the mixture obtained in the step (1) for 2 minutes under the condition of slowly stirring the powder, continuously stirring the mixture for 3 minutes, and then slowly adding the deionized water into the mixture with the density of 1.4g/cm3And 8.5 parts of sulfuric acid solution, controlling the whole acid adding time within 5 minutes, and continuously stirring for 13 minutes after the sulfuric acid solution is completely added to obtain the lead-acid battery cathode lead paste. The temperature in the lead plaster and the container is not suitable to exceed 65 ℃ in the lead plaster mixing process, the plaster outlet temperature is not more than 40 ℃, and the apparent density of the lead plaster is controlled to be 3.6-4.4 g/cm3. (3) And (3) filling the lead-acid battery negative lead plaster obtained in the step (2) into the flexible carbon material layer prepared in the step (1), wherein the length and the width of the coated area are 50mm and 72mm respectively, the mass of the filled lead plaster is 14.3g, the rest part of the carbon felt is cut into battery tabs with the length of 50mm and the width of 20mm, the filled electrodes are treated by acid spraying, then are put into a humidity-controllable high-low temperature box for curing and drying, are cured for 36h under the condition of 45 ℃ relative humidity of 95%, and are dried for 9h at 85 ℃ to obtain the lead-acid battery negative electrode.
The preparation method of the battery anode is the same as that of the cathode, and the mass of an active substance lead paste filled in the anode is 20.0 g.
3. And (3) placing and winding the three positive plates and the four negative plates prepared in the step (2) at intervals. Placing the positive and negative electrodes into a tightly assembled battery case with a diameter of 40mm and a height of 100mm, and injecting 83g of a material with a density of 1.275g/cm into the battery case3The lead-acid battery of 2V5.2Ah is assembled. And after the formation of the assembled lead-acid battery is finished, testing the discharge capacity at normal temperature and the cycle life. The cell was run for 23 cycles under test conditions.
Comparative example 2
1. Preparing a low hydrogen evolution carbon felt:
taking 16 carbon felts with the length of 100mm, the width of 72mm and the thickness of 3mm, completely immersing the carbon felts in 5000ml of 1M bismuth nitrate solution, slowly stirring, drying the products, transferring the dried carbon felts into an atmosphere sintering furnace, and preserving the heat for 3 hours at 200 ℃ in a nitrogen environment to obtain the low hydrogen evolution carbon felt.
2. Preparing a coiled lead-carbon battery electrode:
the preparation method of the negative electrode comprises the following steps: (1) 100 parts of lead powder, 1.2 parts of additives (barium sulfate and 0.2 part of lignin) and 1.5 parts of commercial activated carbon are poured into a container of a paste mixer for dry mixing for 4 minutes, and all the components are fully and uniformly mixed to obtain a mixture; (2) weighing 15.5 parts of deionized water, quickly adding the deionized water into the mixture obtained in the step (1) for 2 minutes under the condition of slowly stirring the powder, continuously stirring the mixture for 4 minutes, and then slowly adding the deionized water into the mixture with the density of 1.4g/cm 3And 8.5 parts of sulfuric acid solution, wherein the whole acid adding time is controlled within 7 minutes, and the sulfuric acid solution is continuously stirred for 15 minutes after being completely added, so that the lead-carbon battery cathode lead paste is obtained. The temperature in the lead plaster and the container is not suitable to exceed 65 ℃ in the lead plaster mixing process, the plaster outlet temperature is not more than 40 ℃, and the apparent density of the lead plaster is controlled to be 3.6-4.4 g/cm3. (3) And (3) filling the lead-carbon battery negative electrode lead paste obtained in the step (2) into the low hydrogen evolution carbon felt prepared in the step (1), wherein the length and the width of the coated area are 50mm and 72mm respectively, the mass of the filled lead paste is 14.3g, the rest part of the carbon felt is cut into battery tabs with the length of 50mm and the width of 20mm, the filled electrode is treated by acid spraying, then is put into a humidity-controllable high-low temperature box for curing and drying, is cured for 36h under the condition of 45 ℃ relative humidity of 95%, and is dried for 9h at 85 ℃ to obtain the lead-carbon battery negative electrode.
The preparation method of the battery positive electrode is the same as that of the negative electrode, only commercial activated carbon is not added into the lead plaster, and the mass of the lead plaster filled and coated on the positive electrode is 20.0 g.
3. And (3) placing and winding the three positive plates and the four negative plates prepared in the step (2) at intervals. Placing the positive and negative electrodes into a tightly assembled battery case with a diameter of 40mm and a height of 100mm, and injecting 83g of a material with a density of 1.275g/cm into the battery case 3The lead-carbon battery of 2V5.2Ah was assembled. And (3) after the assembled lead-carbon battery is formed, carrying out a normal-temperature discharge capacity test and a cycle life test. In comparison with example 2, the elimination of carbon feltAfter the ink activation, the carbon material had reduced conductivity, specific capacitance, and reduced area of adhesion of the hydrogen evolution inhibitor, resulting in a reduction in charge acceptance and discharge capacity of the battery, which was operable for only 37 cycles under the test conditions.
Comparative example 3
1. Preparing a flexible carbon material layer:
firstly, carrying out catalytic activation on a carbon felt: taking 16 carbon felts with the length of 100mm, the width of 72mm and the thickness of 3mm, completely immersing the carbon felts in a nickel nitrate solution with the concentration of 1M, stirring the carbon felts at a low speed for 1 hour, taking out the carbon felts, placing the carbon felts in an oven to dry the carbon felts for 12 hours at the temperature of 80 ℃, taking out the dried carbon felts, transferring the carbon felts to an atmosphere sintering furnace, sintering the carbon felts for 5 hours in a nitrogen environment at the temperature of 800 ℃, and naturally cooling the carbon felts to obtain the partially graphitized carbon felts. The partially graphitized carbon felt after cooling is repeatedly washed several times using ultrapure water.
And sampling the obtained partially graphitized carbon felt, and performing X-ray diffraction detection, wherein the result shows that the carbon felt fiber is partially graphitized.
And transferring the washed and dried partially graphitized carbon felt into a potassium hydroxide solution with the concentration of 3M to be fully soaked and slowly stirred for 2 hours, then placing the partially graphitized carbon felt into a condition of 80 ℃ to be dried, transferring the dried partially graphitized carbon felt into an atmosphere sintering furnace, sintering in a nitrogen environment at the sintering temperature of 900 ℃, preserving heat for 2 hours, and naturally cooling. And transferring the cooled partially graphitized carbon felt into a 0.5M dilute nitric acid solution for soaking and repeatedly washing for a plurality of times, washing the washed partially graphitized carbon felt for a plurality of times by adopting ultrapure water until the pH value of the washing waste liquid reaches 7, and finally transferring the partially graphitized carbon felt into a blast drying box at the temperature of 80 ℃ for drying to obtain the activated graphitized carbon felt.
2. Preparing a coiled lead-carbon battery electrode:
the preparation method of the cathode comprises the following steps: (1) 100 parts of lead powder, 1.2 parts of additives (barium sulfate and 0.2 part of lignin) and 1.5 parts of commercial activated carbon are poured into a container of a paste mixer for dry mixing for 3 minutes, and all the components are fully and uniformly mixed to obtain a mixture; (2) weighing 15.5 parts of deionized water, and quickly adding the deionized water into the mixture obtained in the step (1) for 2 minutes under the condition of slowly stirring the powderTo this mixture, stirring was continued for 4 minutes, and then slowly added thereto a solution having a density of 1.4g/cm3And 8.5 parts of sulfuric acid solution, wherein the whole acid adding time is controlled within 7 minutes, and the sulfuric acid solution is continuously stirred for 15 minutes after being completely added, so that the lead-carbon battery cathode lead paste is obtained. The temperature in the lead plaster and the container is not suitable to exceed 65 ℃ in the lead plaster mixing process, the plaster outlet temperature is not more than 40 ℃, and the apparent density of the lead plaster is controlled to be 3.6-4.4 g/cm3. (3) And (3) filling the lead-carbon battery negative electrode lead paste obtained in the step (2) into the activated graphitized carbon felt prepared in the step (1), wherein the coated area, the length and the width are respectively 50mm and 72mm, the mass of the filled lead paste is 14.3g, the rest part of the carbon felt is cut into battery tabs with the length of 50mm and the width of 20mm, the filled electrode is treated by acid spraying, then is put into a humidity-controllable high-low temperature box for curing and drying, is cured for 36h under the condition of 45 ℃ relative humidity of 95%, and is dried for 9h at 85 ℃ to obtain the lead-carbon battery negative electrode.
The preparation method of the battery positive electrode is the same as that of the negative electrode, only commercial activated carbon is not added into the lead paste, and the mass of the lead paste filled in the positive electrode is 20.0 g.
3. And (3) placing and winding the three positive plates and the four negative plates prepared in the step (2) at intervals. Placing the positive and negative electrodes into a tightly assembled battery case with a diameter of 40mm and a height of 100mm, and injecting 83g of a material with a density of 1.275g/cm into the battery case3The lead-carbon battery of 2V5.2Ah was assembled. And (3) after the assembled lead-carbon battery is formed, testing the discharge capacity at normal temperature and the cycle life. Compared with example 3, the activated graphitized carbon felt is not loaded with a hydrogen evolution inhibitor, so that the hydrogen evolution of the battery charging process is serious, and the charging capacity is reduced, so that the battery can only run for 32 cycles under the test condition.
Comparative example 4
1. Preparing a flexible carbon material layer:
firstly, carrying out catalytic activation on a carbon felt: taking 16 carbon felts with the length of 100mm, the width of 72mm and the thickness of 3mm, completely immersing the carbon felts in a manganese nitrate solution with the concentration of 1M, stirring the carbon felts at a low speed for 1 hour, taking out the carbon felts, placing the carbon felts in an oven to dry the carbon felts for 12 hours at the temperature of 80 ℃, taking out the dried carbon felts, transferring the carbon felts to an atmosphere sintering furnace, sintering the carbon felts for 5 hours in a nitrogen environment at the temperature of 800 ℃, and naturally cooling the carbon felts to obtain the partially graphitized carbon felts. The partially graphitized carbon felt after cooling is repeatedly washed several times using ultrapure water.
And sampling the obtained partially graphitized carbon felt, and performing X-ray diffraction detection, wherein the result shows that the carbon felt fiber is partially graphitized.
And transferring the washed and dried partially graphitized carbon felt into a potassium hydroxide solution with the concentration of 3M to be fully soaked and slowly stirred for 2 hours, then placing the partially graphitized carbon felt into a condition of 80 ℃ to be dried, transferring the dried partially graphitized carbon felt into an atmosphere sintering furnace, sintering in a nitrogen environment at the sintering temperature of 700 ℃, preserving heat for 3 hours and naturally cooling. And transferring the cooled partially graphitized carbon felt into a 0.5M dilute nitric acid solution for soaking and repeatedly washing for a plurality of times, washing the washed partially graphitized carbon felt for a plurality of times by adopting ultrapure water until the pH value of the washing waste liquid reaches 7, and finally transferring the partially graphitized carbon felt into a blast drying box at the temperature of 80 ℃ for drying to obtain the activated graphitized carbon felt.
And (3) soaking 80g of dried activated graphitized carbon felt in 5000ml of 48.3mmol/L lead nitrate solution, slowly stirring, drying the product, transferring the dried carbon felt into an atmosphere sintering furnace, and preserving the temperature of the carbon felt for 2 hours at 800 ℃ in an argon environment to obtain the flexible carbon material layer.
2. Preparing a coiled lead-carbon battery electrode:
The preparation method of the pole comprises the following steps: (1) 100 parts of lead powder, 1.2 parts of additives (barium sulfate and 0.2 part of lignin) and 1.5 parts of commercial activated carbon are poured into a container of a paste mixer for dry mixing for 3 minutes, and all the components are fully and uniformly mixed to obtain a mixture; (2) weighing 15.5 parts of deionized water, quickly adding the deionized water into the mixture obtained in the step (1) for 3 minutes under the condition of slowly stirring the powder, continuously stirring the mixture for 5 minutes, and then slowly adding the deionized water into the mixture with the density of 1.4g/cm3And 8.5 parts of sulfuric acid solution, controlling the whole acid adding time within 9 minutes, and continuously stirring for 17 minutes after the sulfuric acid solution is completely added to obtain the lead-carbon battery cathode lead paste. The temperature in the lead plaster and the container is not suitable to exceed 65 ℃ in the lead plaster mixing process, the plaster outlet temperature is not more than 40 ℃, and the apparent density of the lead plaster is controlled to be 3.6-4.4 g/cm3. (3) Subjecting the product obtained in step (2)Filling lead paste of the negative electrode of the lead-carbon battery into the flexible carbon material layer prepared in the step 1, wherein the length and the width of the coated area are 50mm and 72mm respectively, the mass of the filled lead paste is 14.3g, the rest part of the carbon felt is cut into battery tabs with the length of 50mm and the width of 20mm, after acid spraying treatment is carried out on the filled electrodes, the filled electrodes are placed into a humidity-controllable high-low temperature box for curing and drying, the curing is carried out for 36h under the condition that the relative humidity is 95% at 45 ℃, and then the drying is carried out for 9h at 85 ℃ to obtain the negative electrode of the lead-carbon battery.
The preparation method of the battery anode is the same as that of the battery cathode, only commercial activated carbon is not added into the lead plaster, and the mass of the active substance filled in the anode is 20.0 g.
3. And (3) placing and winding the three positive plates and the four negative plates prepared in the step (2) at intervals. Placing the positive and negative electrodes into a tightly assembled battery case with a diameter of 40mm and a height of 100mm, and injecting 83g of a material with a density of 1.275g/cm into the battery case3The lead-carbon battery of 2V5.2Ah was assembled. And (3) after the assembled lead-carbon battery is formed, testing the discharge capacity at normal temperature and the cycle life. Compared with example 4, the cell can only run for 30 cycles under the test conditions, because the product is not sintered in a nitrogen environment after loading the hydrogen evolution inhibitor, so that the hydrogen evolution inhibitor cannot form a large number of coordination bonds with the carbon material, and the hydrogen evolution inhibitor has a partial dropping condition.
Comparing the discharge capacity at-10 ℃ of the batteries of the examples of the present invention and the comparative example, it is shown as follows:
Figure BDA0002337021730000161
from the above table, it can be seen that the charge-discharge cycle life of the coiled lead-carbon battery provided by the invention is far longer than that of the coiled lead-acid battery. Therefore, the graphitized carbon fiber layer with the activated holes is used as the electrode plate, so that the electrode and the current collector can be tightly combined, the contact resistance between the lead paste and the current collector is reduced, and the service life of the battery is prolonged.
According to the invention, the service life of the lead-carbon battery prepared from the flexible carbon material layer is prolonged by comparing the steps of eliminating graphitization and activation of the carbon material, and the service life of the battery can be prolonged by verifying graphitization and activation of the carbon material.
According to the invention, the service life of the lead-carbon battery prepared from the flexible carbon material layer is prolonged by comparing the service life of the lead-carbon battery before and after the load of the hydrogen evolution inhibitor is cancelled, the addition of the hydrogen evolution inhibitor is verified, the hydrogen evolution problem in the charging process of the battery can be relieved, the charging capacity of the battery is improved, and the discharging capacity and service life of the battery are further improved.
According to the invention, by comparing the discharge performance of the obtained lead-carbon battery before and after the flexible carbon material layer impregnated with the hydrogen evolution inhibitor is sintered, the fact that coordinate bonds can be formed between the hydrogen evolution inhibitor and the carbon material through sintering is verified, so that the hydrogen evolution problem in the carbon material charging process is solved, the charging capacity of the battery is improved, and the discharge capacity and the service life of the battery are further improved.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.

Claims (7)

1. A preparation method of a flexible carbon material layer for a lead-carbon battery is characterized in that,
the preparation method at least comprises the following steps:
graphitizing the carbon fiber layer under the catalytic action of a graphitizing catalyst to obtain a graphitized carbon fiber layer;
carrying out pore-forming activation on the graphitized carbon fiber layer by adopting alkali liquor to obtain an activated graphitized carbon fiber layer;
dipping and mixing the activated graphitized carbon fiber layer in a solution of a hydrogen evolution inhibitor to obtain a dipped product, and drying and sintering the dipped product to obtain a flexible carbon material layer;
the flexible carbon material layer comprises a graphitized carbon fiber layer with an activation hole, and a hydrogen evolution inhibitor is loaded on the surface of the graphitized carbon fiber layer;
the hydrogen evolution inhibitor is a compound of a high hydrogen evolution overpotential element;
the high hydrogen evolution overpotential element comprises at least one of Zn, Bi, Cd, Pb, In and Sn;
the compound comprises at least one of nitrate, acetate and alkoxide.
2. The method for preparing a flexible carbon material layer according to claim 1, wherein the amount of the hydrogen evolution inhibitor is 1-50% of the total mass of the hydrogen evolution inhibitor and the graphitized carbon fiber layer.
3. The method of manufacturing a flexible carbon material layer according to claim 1,
the graphitizing catalyst is a metal compound;
the metal comprises at least one of iron, manganese, nickel, cobalt, tungsten, molybdenum and titanium;
the compound comprises at least one of nitrate, acetate and chloride.
4. The method for producing a flexible carbon material layer as claimed in claim 1, wherein the sintering parameters of the impregnated product are: and preserving the heat for 2-5 hours at 200-900 ℃ under the protection of atmosphere.
5. An electrode comprising at least one of the flexible carbon material layers prepared according to the method of any one of claims 1 to 4;
and electrode lead paste is filled on the surface of the flexible carbon material layer.
6. A lead-carbon battery comprising the electrode of claim 5.
7. The lead-carbon battery according to claim 6, wherein the electrode is wound and placed in a battery case filled with an electrolyte.
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