CN117038965B - Lead-carbon energy storage battery with long cycle life - Google Patents

Lead-carbon energy storage battery with long cycle life Download PDF

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CN117038965B
CN117038965B CN202310986419.8A CN202310986419A CN117038965B CN 117038965 B CN117038965 B CN 117038965B CN 202310986419 A CN202310986419 A CN 202310986419A CN 117038965 B CN117038965 B CN 117038965B
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lead
carbon
energy storage
storage battery
cycle life
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CN117038965A (en
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何军华
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Hunan Kechuan Energy Development Co ltd
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Hunan Kechuan Energy Development Co ltd
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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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/56—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead
    • H01M4/57—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead of "grey lead", i.e. powders containing lead and lead oxide
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention relates to the technical field of energy storage, in particular to a lead-carbon energy storage battery with high cycle life, which comprises a negative plate, wherein the negative plate is prepared from a negative plate grid and lead plaster coated on the surface of the negative plate grid, the lead plaster comprises a carbon material, the carbon material is doped with hetero atoms, and the hetero atoms comprise transition metal hetero atoms and nonmetal hetero atoms.

Description

Lead-carbon energy storage battery with long cycle life
Technical Field
The invention relates to the technical field of energy storage, in particular to a lead-carbon energy storage battery with a long cycle life.
Background
The use of lead acid batteries in hybrid vehicles has attracted considerable attention because of its unique characteristics of low cost, high safety, and good low temperature performance. However, hybrid vehicles require that the lead-acid battery be operated at high rate partial charge conditions, which can lead to sulfidation of the negative electrode and failure of the battery. The lead-carbon battery has the advantages that proper carbon is added into the negative electrode, so that the vulcanization can be inhibited, and the cycle life can be prolonged. However, carbon accelerates hydrogen evolution reactions of lead carbon electrodes, and high rates of hydrogen evolution reactions lead to water loss of electrolyte and low energy efficiency of the battery, and more importantly, the generation of H 2 The separation of the carbon from the sponge lead is forced, thereby destroying the conductive network of the lead carbon electrode, resulting in a reduction in the cycle life of the lead carbon battery, which limits the performance of the lead carbon battery.
Disclosure of Invention
The invention aims to: aiming at the technical problems, the invention provides a lead-carbon energy storage battery with a long cycle life.
The technical scheme adopted is as follows:
a lead-carbon energy storage battery with high cycle life comprises a negative plate;
the negative plate is prepared from a negative grid and lead plaster coated on the surface of the negative grid;
the lead plaster comprises a carbon material, wherein the carbon material is doped with hetero atoms;
the heteroatoms include transition metal heteroatoms and nonmetallic heteroatoms.
Further, the transition metal heteroatom is any one or more of cobalt, nickel, copper and zinc, preferably zinc;
the nonmetallic heteroatom is boron and/or sulfur, preferably boron.
Further, the carbon material is any one or a combination of a plurality of active carbon, graphene, graphite, carbon nano tube and carbon aerogel.
Further, the lead plaster comprises the following components in parts by weight:
70-85 parts of lead powder, 3-7 parts of carbon material, 1-2 parts of barium sulfate, 0.05-0.15 part of lignosulfonate, 0.15-0.3 part of humic acid, 0.1-0.5 part of chopped fiber, 0.1-1 part of acetylene black, 5-10 parts of sulfuric acid, 1-3 parts of hydrogen evolution inhibitor and 10-20 parts of water.
Further, the lignosulfonate is any one or a combination of more of ammonium lignosulfonate, potassium lignosulfonate and sodium lignosulfonate.
Further, the chopped fibers are any one or a combination of more than one of polypropylene fibers, polyacrylonitrile fibers, polyacetylene fibers, polyaniline fibers, polypyrrole fibers and polyester fibers.
Further, the hydrogen evolution inhibitor is bisox, x=fluorine, chlorine, bromine or iodine.
Further, the hydrogen evolution inhibitor is BiOCl.
Further, the density of the sulfuric acid is 1.2-1.3g/cm 3 。
Further, the preparation method of the negative plate comprises the following steps:
mixing lead powder, carbon material, barium sulfate, lignosulfonate, humic acid, chopped fiber, acetylene black and hydrogen evolution inhibitor uniformly, adding sulfuric acid, continuously mixing uniformly, adding water, stirring for 10-20h to obtain lead paste, uniformly coating the lead paste on a negative grid, and heating the negative grid to 60-80 ℃ for curing for 24-48 h.
The invention has the beneficial effects that:
the invention provides a lead-carbon energy storage battery with long cycle life, the element doping the carbon material in the prior literature is N, P, no report of B doping is seen, and the inventor introduces B to dope the carbon material through an attempt, but the effect is achievedThe lead-carbon energy storage battery is not ideal, the effect of composite doping with other nonmetallic elements is still not ideal, but the transition metal element Zn is introduced while B is introduced, the performance of the lead-carbon energy storage battery is greatly improved, and the reason is probably that the Zn and the B are respectively used as anions and cations to have complementarity in valence, the co-doping changes the surface activity of the carbon material and the electron distribution around carbon atoms, thereby achieving the effect of inhibiting hydrogen evolution, and the Zn 2+ Electrode potential correction of Zn in carbon material 2+ The electrochemical reaction converted into Zn takes place preferentially to hydrogen evolution reaction, plays a role in inhibiting the hydrogen evolution reaction of the active carbon, and the BiOX belongs to a high hydrogen evolution overpotential bismuth-based material, has the effects of inhibiting hydrogen evolution of a negative electrode and prolonging the cycle life of a battery, and through tests, the prepared lead-carbon energy storage battery has a higher cycle life and can further widen the application scene of the lead-carbon energy storage battery.
Drawings
Fig. 1 is an SEM image of the negative electrode plate prepared in example 1 of the present invention.
Detailed Description
The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention. The technology not mentioned in the present invention refers to the prior art, and unless otherwise indicated, the following examples and comparative examples are parallel tests, employing the same processing steps and parameters.
Lead powder: 99.95%, microphone;
carbon material: self-making;
barium sulfate: battery grade, national drug group chemical reagent company;
sodium lignin sulfonate: 99%, hubei Wande chemical Co., ltd;
humic acid: 99%, shandong Jin Keli Power technologies Co., ltd;
chopped polypropylene fibers: 0.1-1 mu m, chinese boulder;
acetylene black: star Long Tai;
sulfuric acid: sigma;
BiOCl:99%, sienna ruixi organisms;
water: distilled water.
Example 1:
a lead-carbon energy storage battery with high cycle life comprises a negative plate;
the negative plate is prepared from a negative grid and lead plaster coated on the surface of the negative grid;
the lead plaster comprises:
80 parts of lead powder, 6 parts of carbon material, 1.4 parts of barium sulfate, 0.12 part of sodium lignin sulfonate, 0.2 part of humic acid, 0.3 part of chopped polypropylene fiber, 0.3 part of acetylene black, and 1.27g/cm of sulfuric acid 3 ) 6 parts of BiOCl2.5 parts and 14 parts of water.
The preparation method of the carbon material comprises the following steps:
adding 30mL of formaldehyde, 22g of resorcinol, 0.05g of sodium carbonate and 0.55g of zinc sulfate into 500mL of water, sealing, placing into a constant-temperature oil bath pot at 50 ℃ for reaction for 1d, regulating the temperature of the oil bath pot to 85 ℃, reacting for 4d, obtaining wet gel, placing the wet gel into an acetone solution of trifluoroacetic acid (the volume ratio of the trifluoroacetic acid to the acetone is 3:97), aging for 3d, soaking the wet gel with acetone for 3d, replacing fresh acetone every 24h, placing the wet gel into an oven at 50 ℃ for normal pressure for drying for 4d to obtain a precursor, heating the precursor to 900 ℃ under the atmosphere of argon/borane (the volume ratio of argon to borane is 1:1), keeping the temperature for 5h, naturally cooling to room temperature, grinding and sieving with a 200-mesh sieve to obtain the zinc/boron co-doped carbon aerogel.
The preparation method of the lead-carbon energy storage battery comprises the following steps:
mixing lead powder, carbon material, barium sulfate, sodium lignin sulfonate, humic acid, chopped polypropylene fiber, acetylene black and BiOCl for 30min, adding sulfuric acid, mixing for 25min, adding water, stirring for 12h to obtain lead paste, uniformly coating the lead paste on a negative electrode grid, heating the negative electrode grid to 80 ℃ for 36h to obtain a negative electrode plate, assembling the lead-carbon energy storage battery in a 3 positive-2 negative mode, wherein the positive electrode plate and the negative electrode plate are 50mm multiplied by 30mm multiplied by 4mm in size, and preparing the prepared negative electrodeBoard and PbO 2 The positive plate is connected with a lead, welded together and soaked in 1.27g/cm 3 The middle of the lead carbon energy storage battery is separated by an AGM separator with the thickness of 3mm in sulfuric acid, the prepared lead carbon energy storage battery is charged to 2.45V at the rate of 0.1C, the voltage is kept constant at 2.45V for 12h, the lead carbon energy storage battery is discharged to 50% of a state of charge (SoC) at the rate of 0.1C, the lead carbon energy storage battery is charged for 4h at the rate of 2C, the voltage of the battery is tested every 10min, when the discharge voltage of each battery is reduced to 1.7V, the cycle test is stopped, and the cycle number is 31225 times.
Example 2:
substantially the same as in example 1, except that the lead paste includes:
85 parts of lead powder, 7 parts of carbon material, 2 parts of barium sulfate, 0.15 part of sodium lignin sulfonate, 0.3 part of humic acid, 0.5 part of chopped polypropylene fiber, 1 part of acetylene black and 1.27g/cm of sulfuric acid 3 ) 10 parts of BiOCl, 3 parts of water and 20 parts of water.
The number of cycles was 31180 as tested.
Example 3:
substantially the same as in example 1, except that the lead paste includes:
75 parts of lead powder, 4 parts of carbon material, 1 part of barium sulfate, 0.05 part of sodium lignin sulfonate, 0.15 part of humic acid, 0.2 part of chopped polypropylene fiber, 0.1 part of acetylene black and 1.27g/cm of sulfuric acid 3 ) 6 parts of BiOCl1 part and 15 parts of water.
The number of cycles was 31164 as tested.
Comparative example 1:
substantially the same as in example 1, except that zinc sulfate was not added in the preparation of the carbon material.
The number of cycles was 17060 as tested.
Comparative example 2:
substantially the same as in example 1, except that the carbon material was prepared entirely under an argon atmosphere.
The number of cycles was 20992 as tested.
Comparative example 3:
substantially the same as in example 1, except that BiOCl was not added.
The number of cycles was 12840 as tested.
Comparative example 4:
substantially the same as in example 1, except that BiOCl was replaced with ZnO.
The number of cycles was 30152, as tested.
Performance test:
the negative electrode plates prepared in examples 1 to 3 and comparative examples 1 to 4 of the present invention were used as samples, and the cyclic voltammograms and the linear cyclic voltammograms of the samples were tested by an electrochemical analyzer (Shanghai morning glory CHI 604) and a three-electrode system, and the capacitance was calculated by the following formulas;
Cs＝A/(2s×△V×m)
wherein: s is the scanning speed, A is the rectangular area in the cyclic voltammogram, deltaV is the scanning voltage range, and m is the mass of the active substance;
the test results are shown in table 1 below:
table 1:
specific capacitance/(F/g)
Example 1 75.36
Example 2 72.44
Example 3 68.10
Comparative example 1 40.56
Comparative example 2 39.24
Comparative example 3 31.95
Comparative example 4 62.07
As can be seen from Table 1, the negative plate prepared by the method has high specific capacitance, and the high capacitance can share high-rate charge and discharge current, and has strong buffering to prevent PbSO 4 The irreversible conversion of the crystal prolongs the cycle life.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims (7)

1. The lead-carbon energy storage battery with high cycle life is characterized by comprising a negative plate;
the negative plate is prepared from a negative grid and lead plaster coated on the surface of the negative grid;
the lead plaster comprises the following components in parts by weight:
70-85 parts of lead powder, 3-7 parts of carbon material, 1-2 parts of barium sulfate, 0.05-0.15 part of lignosulfonate, 0.15-0.3 part of humic acid, 0.1-0.5 part of chopped fiber, 0.1-1 part of acetylene black, 5-10 parts of sulfuric acid, 1-3 parts of hydrogen evolution inhibitor and 10-20 parts of water;
the carbon material is doped with heteroatoms;
the heteroatoms include transition metal heteroatoms and nonmetallic heteroatoms;
the transition metal heteroatom is zinc;
the nonmetallic heteroatom is boron;
the hydrogen evolution inhibitor is bisox, x=fluorine, chlorine, bromine or iodine.
2. The high cycle life lead carbon energy storage battery of claim 1, wherein the carbon material is any one or a combination of more of activated carbon, graphene, graphite, carbon nanotubes, carbon aerogel.
3. The high cycle life lead carbon energy storage battery of claim 1, wherein the lignosulfonate is any one or a combination of more of ammonium lignosulfonate, potassium lignosulfonate, sodium lignosulfonate.
4. The high cycle life lead carbon energy storage battery of claim 1, wherein said chopped fibers are any one or a combination of polypropylene fibers, polyacrylonitrile fibers, polyacetylene fibers, polyaniline fibers, polypyrrole fibers, and polyester fibers.
5. The high cycle life lead carbon energy storage battery of claim 1, wherein said hydrogen evolution inhibitor is BiOCl.
6. The high cycle life lead carbon energy storage battery of claim 1, wherein said sulfuric acid has a density of 1.2 to 1.3g/cm 3 。
7. The high cycle life lead carbon energy storage battery of claim 1, wherein the negative plate is prepared by the following method:
mixing lead powder, carbon material, barium sulfate, lignosulfonate, humic acid, chopped fiber, acetylene black and hydrogen evolution inhibitor uniformly, adding sulfuric acid, continuously mixing uniformly, adding water, stirring for 10-20h to obtain lead paste, uniformly coating the lead paste on a negative grid, and heating the negative grid to 60-80 ℃ for curing for 24-48 h.
CN202310986419.8A 2023-08-07 2023-08-07 Lead-carbon energy storage battery with long cycle life Active CN117038965B (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103337624A (en) * 2013-06-28 2013-10-02 风帆股份有限公司 Lead-acid storage battery negative lead plaster capable of inhibiting hydrogen evolution and preparation method
CN105355860A (en) * 2015-11-05 2016-02-24 中国电力科学研究院 Lead carbon battery cathode
JP2016046118A (en) * 2014-08-22 2016-04-04 株式会社日本触媒 Electrode and battery constituted using the same
CN113948700A (en) * 2020-07-17 2022-01-18 中国科学院大连化学物理研究所 Monodisperse atomic cluster-activated carbon composite material and application thereof in lead-carbon battery

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103337624A (en) * 2013-06-28 2013-10-02 风帆股份有限公司 Lead-acid storage battery negative lead plaster capable of inhibiting hydrogen evolution and preparation method
JP2016046118A (en) * 2014-08-22 2016-04-04 株式会社日本触媒 Electrode and battery constituted using the same
CN105355860A (en) * 2015-11-05 2016-02-24 中国电力科学研究院 Lead carbon battery cathode
CN113948700A (en) * 2020-07-17 2022-01-18 中国科学院大连化学物理研究所 Monodisperse atomic cluster-activated carbon composite material and application thereof in lead-carbon battery

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