CN113540424A - Lead-acid storage battery negative electrode lead paste and preparation method thereof - Google Patents

Lead-acid storage battery negative electrode lead paste and preparation method thereof Download PDF

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CN113540424A
CN113540424A CN202110802840.XA CN202110802840A CN113540424A CN 113540424 A CN113540424 A CN 113540424A CN 202110802840 A CN202110802840 A CN 202110802840A CN 113540424 A CN113540424 A CN 113540424A
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CN113540424B (en
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代少振
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Chaowei Power Group 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
    • H01M4/362—Composites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
    • B60L50/00—Electric propulsion with power supplied within the vehicle
    • B60L50/50—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells
    • B60L50/60—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells using power supplied by batteries
    • B60L50/64—Constructional details of batteries specially adapted for electric vehicles
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • 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
    • 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
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

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Abstract

The invention relates to the field of negative electrode materials of lead-acid storage batteries, and discloses a negative electrode lead plaster of a lead-acid storage battery and a preparation method thereof. The negative electrode lead paste comprises the following raw materials in parts by weight: 1000 parts of lead powder, 8-12 parts of barium sulfate, 1-5 parts of humic acid, 1-5 parts of sodium lignosulfonate, 1-5 parts of mixed carbon, 1-5 parts of bismuth trioxide, 0.5-1.5 parts of conductive fiber, 130 parts of water and 80-90 parts of paste acid. The invention adopts specific negative electrode additive combination, and controls the dosage within a certain range, thereby improving the performance of the negative electrode. Compared with the commercial battery, the lead-acid storage battery prepared from the negative electrode lead paste has higher normal-temperature and low-temperature capacity, higher charging speed and longer cycle life.

Description

Lead-acid storage battery negative electrode lead paste and preparation method thereof
Technical Field
The invention relates to the field of negative electrode materials of lead-acid storage batteries, in particular to negative electrode lead plaster of a lead-acid storage battery and a preparation method thereof.
Background
Lead-acid batteries have been available for over a hundred years, and have been dominant in chemical power supplies due to a series of advantages of low price, high safety, long service life, good performance and the like. Along with the rapid development of the electric bicycle industry, higher technical requirements are provided for the lead-acid storage battery for the electric power-assisted vehicle. The technical indexes such as low-temperature performance, quick charging capacity, sulfation, hydrogen evolution water loss and the like are related to the negative electrode of the lead-acid storage battery, and the reasons influencing the negative electrode performance are mainly shrinkage of the specific surface area of the negative electrode, passivation of the negative electrode and poor charging and discharging performance at low temperature, and the service life of the battery is terminated due to sulfation or excessive hydrogen evolution water loss of the negative electrode.
In general, the negative electrode is improved by adding additives, which generally have the following functions: 1) adhesive: for increasing the mechanical strength of the active material or the plate; 2) conductive agent: for improving the conductivity of the active material; 3) nucleating agent: for acting as a discharge product PbSO4The crystal nucleus of (2) improves the crystal structure thereof; 4) swelling agent: for inhibiting shrinkage of the active substance; 5) antioxidant: for suppressing oxidation of the anode active material. The composition and proportion of the additive in the negative electrode can influence the performance of the lead-acid storage battery, and the influence is complicated and lacks obvious rules to be circulated, so that although the additives used in the negative electrode of the lead-acid storage battery are conventional in several types, the battery performance has obvious difference.
Disclosure of Invention
In order to solve the technical problems, the invention provides a lead-acid storage battery negative electrode lead plaster and a preparation method thereof. The invention adopts the additives with specific compositions and proportions, and can obtain the lead-acid storage battery cathode with higher performance, thereby improving the performance of the lead-acid storage battery.
The specific technical scheme of the invention is as follows:
the lead-acid storage battery negative electrode lead paste comprises the following raw materials in parts by weight: 1000 parts of lead powder, 8-12 parts of barium sulfate, 1-5 parts of humic acid, 1-5 parts of sodium lignosulfonate, 1-5 parts of mixed carbon, 1-5 parts of bismuth trioxide, 0.5-1.5 parts of conductive fiber, 130 parts of water and 80-90 parts of paste acid.
In the negative lead plaster formula of the invention, the functions of the additives are as follows:
barium sulfate: the lead sulfate is used as a nucleating agent and an expanding agent to prevent the passivation of the negative electrode;
sodium lignosulfonate, humic acid: as an expanding agent, the low-temperature, large-current and quick-charging performance of the battery is improved;
mixing carbon: active substances are adsorbed to form a conductive network, the conductivity of the negative electrode is enhanced, the phenomenon that lead sulfate cannot be completely converted into spongy metallic lead after overdischarge can be effectively avoided, and the recycling performance of the battery is improved;
bismuth oxide: the hydrogen evolution inhibitor is used for preventing hydrogen gas of the cathode from being precipitated and reducing water loss of the battery.
The invention adopts specific negative electrode additive combination, and controls the dosage within a certain range, thereby improving the performance of the negative electrode. Compared with the commercial battery, the lead-acid storage battery prepared from the negative electrode lead paste has higher normal-temperature and low-temperature capacity, higher charging speed and longer cycle life.
Preferably, the mixed carbon comprises acetylene black and also comprises one or more of activated carbon, graphene and carbon nanotubes; the specific surface area of the mixed carbon is 100-1500m2/g。
Preferably, the conductive fibers include polyester fibers and/or polyacrylonitrile fibers.
Preferably, the lead powder has an oxidation degree of 70-80% and an apparent density of 1.30-1.40g/cm3The particle size D50 is less than 2.8 μm.
Preferably, the water is pure water having an electrical conductivity of less than 2. mu.S/cm.
Preferably, the paste acid is dilute sulfuric acid; h2SO4The mass fraction in the paste acid is 45-51 wt%.
Further, the paste acid also contains an oxygen composite channel forming agent; the mass fraction of the oxygen composite channel forming agent in the paste acid is 0.5-1.5 wt%; the oxygen recombination channel former comprises polytetrafluoroethylene.
The polytetrafluoroethylene can form a cross-linked network in the negative lead plaster, and the polytetrafluoroethylene has strong hydrophobicity and poor wettability of electrolyte, so that the function of an oxygen composite channel can be exerted in the negative electrode, oxygen and hydrogen can be diffused along the polytetrafluoroethylene cross-linked network, the compounding of the oxygen and the hydrogen is promoted, the water loss phenomenon of the lead-acid storage battery is reduced, and the cycle life of the battery is prolonged.
The polytetrafluoroethylene has higher requirement on the dispersibility of the polytetrafluoroethylene in the lead-acid storage battery, and if the polytetrafluoroethylene is independently added into negative lead paste in the paste mixing process, due to the poor dispersibility of the polytetrafluoroethylene, the polytetrafluoroethylene is not favorable for forming a hydrophobic cross-linking network with higher cross-linking degree and uniform distribution, so that oxygen composite channels cannot be communicated with each other, and the effect of reducing the water loss of the battery is difficult to effectively exert. Therefore, in the invention, the polytetrafluoroethylene is added into the diachylon, and in the diachylon process, the polytetrafluoroethylene can enter between solid raw materials such as lead powder along with the diachylon, and is uniformly dispersed and crosslinked in the negative electrode to form an oxygen composite channel with relatively uniform distribution, thereby effectively reducing the water loss phenomenon of the lead-acid storage battery.
Further, the preparation method of the paste acid comprises the following steps: adding an oxygen composite channel forming agent emulsion into a sulfuric acid solution under stirring, wherein the mass ratio of the sulfuric acid solution to the oxygen composite channel forming agent emulsion is 20-30:1, and uniformly dispersing to obtain paste acid.
Further, the oxygen recombination channel former further comprises a tetrafluoroethylene-acrylic acid copolymer; the mass ratio of the polytetrafluoroethylene to the tetrafluoroethylene-acrylic acid copolymer is 3-4: 1.
Carboxyl in the molecular chain of the tetrafluoroethylene-acrylic acid copolymer can be complexed with lead powder, so that the bonding strength between the hydrophobic cross-linking network and the lead powder is further improved, the falling of a negative active substance in the battery circulation process is reduced, and the cycle life of the lead-acid storage battery is prolonged.
According to the invention, polytetrafluoroethylene and tetrafluoroethylene-acrylic acid copolymer are compounded, and the mass ratio of the polytetrafluoroethylene to the tetrafluoroethylene-acrylic acid copolymer is controlled within the range of 3-4:1, so that the bonding strength between a crosslinking network and lead powder is improved to reduce the falling-off of a negative electrode active substance under the condition of ensuring the hydrophobicity of the crosslinking network to reduce the water loss of the battery, and the cycle life of the battery is prolonged to a greater extent.
Further, the tetrafluoroethylene-acrylic acid copolymer is used for preparing the oxygen composite channel forming agent emulsion in the form of emulsion, and the preparation method of the tetrafluoroethylene-acrylic acid copolymer emulsion comprises the following steps:
(a) adding ammonium perfluorooctanoate, paraffin, ammonium persulfate and water into a reaction vessel, uniformly mixing, replacing air in the reaction vessel with inert gas, introducing tetrafluoroethylene, and carrying out a first polymerization reaction at 70-80 ℃ for 30-40 min;
(b) adding acrylic acid, wherein the mass volume ratio of the acrylic acid to the water in the step (1) is 1g:70-80mL, uniformly mixing, and continuing to perform a second polymerization reaction at 70-80 ℃ for 50-60min to obtain a tetrafluoroethylene-acrylic acid copolymer emulsion;
in the first polymerization reaction and the second polymerization reaction, the pressure in the reaction vessel is controlled to 1.0 to 1.5MPa by controlling the flow rate of tetrafluoroethylene.
In the tetrafluoroethylene-acrylic acid copolymer, too high carboxyl content can affect the hydrophobicity of a crosslinking network, further affect the effect of reducing water loss of the battery and cause the cycle life of the battery to be shorter; too low a carboxyl content may affect the bonding strength between the crosslinked network and the lead powder, resulting in increased shedding of the negative active material during the battery cycling process, and also resulting in a shorter cycle life. Therefore, the invention adds acrylic acid for copolymerization after the tetrafluoroethylene is prepolymerized for a certain time, and controls the polymerization time of two stages, the content of carboxyl in the tetrafluoroethylene-acrylic acid copolymer can be controlled within a certain range, and the lead-acid storage battery has longer cycle life.
A preparation method of negative pole lead paste comprises the following steps:
(1) adding lead powder accounting for 40-60wt% of the total mass of the lead powder into a paste mixing device, sequentially adding barium sulfate, sodium lignosulphonate, humic acid, bismuth trioxide, conductive fiber and mixed carbon, finally adding the rest lead powder, and uniformly stirring to obtain a mixture;
(2) and adding water into the mixture, adding paste acid, uniformly stirring, cooling, and discharging paste to obtain the lead-acid storage battery negative electrode lead paste.
A lead-acid battery includes a negative electrode made of the negative electrode lead paste.
An electric vehicle comprises the lead-acid storage battery.
Compared with the prior art, the invention has the following advantages:
(1) the lead-acid storage battery cathode and the lead-acid storage battery with higher performance can be obtained by adopting the additives with specific compositions and proportions;
(2) the polytetrafluoroethylene is added into the diachylon, so that the dispersibility of the polytetrafluoroethylene in the negative lead paste can be improved, a hydrophobic cross-linking network with higher cross-linking degree and uniform distribution is formed, an oxygen composite channel communicated with each other is formed, and the water loss phenomenon of the lead-acid storage battery is effectively reduced;
(3) the polytetrafluoroethylene and the tetrafluoroethylene-acrylic acid copolymer are compounded according to a certain proportion, so that the bonding strength between the crosslinking network and the lead powder can be improved to reduce the falling of the negative active material under the condition of ensuring the hydrophobicity of the crosslinking network to reduce the water loss of the battery, and the cycle life of the battery is greatly prolonged.
Detailed Description
The present invention will be further described with reference to the following examples.
General examples
The lead-acid storage battery negative electrode lead paste comprises the following raw materials in parts by weight: 1000 parts of lead powder, 8-12 parts of barium sulfate, 1-5 parts of humic acid, 1-5 parts of sodium lignosulfonate, 1-5 parts of mixed carbon, 1-5 parts of bismuth trioxide, 0.5-1.5 parts of conductive fiber, 115 parts of pure water, 130 parts of ion-doped sodium lignosulfonate and 80-90 parts of paste acid.
The mixed carbon comprises acetylene black and also comprises one or more of activated carbon, graphene and carbon nano tubes; the specific surface area of the mixed carbon is 100-1500m2/g。
The conductive fibers include polyester fibers and/or polyacrylonitrile fibers.
The oxidation degree of the lead powder is 70-80%, and the apparent density is 1.30-1.40g/cm3The particle size D50 is less than 2.8 μm.
The water is pure water with the conductivity less than 2 mu S/cm.
The paste acid is dilute sulfuric acid, wherein H2SO4The mass fraction of (B) is 45-51 wt%.
The preparation method of the negative electrode lead paste comprises the following steps:
(1) adding 600 parts of 400-doped lead powder into a paste mixing device, sequentially adding 8-12 parts of barium sulfate, 1-5 parts of sodium lignosulfonate, 1-5 parts of humic acid, 1-5 parts of bismuth trioxide, 0.5-1.5 parts of conductive fiber and 1-5 parts of mixed carbon, finally adding 500 parts of 400-doped lead powder, and uniformly stirring to obtain a mixture;
(2) adding 115-130 parts of pure water into the mixture, slowly adding 80-90 parts of diachylon acid, adding the diachylon acid for 12-20min, uniformly stirring, cooling to below 40 ℃, and discharging the diachylon to obtain the lead-acid storage battery cathode lead plaster.
Optionally, the paste acid also contains an oxygen composite channel forming agent; the mass fraction of the oxygen composite channel forming agent in the paste acid is 0.5-1.5 wt%; the oxygen recombination channel former comprises polytetrafluoroethylene. The preparation method of the paste acid comprises the following steps: adding an oxygen composite channel forming agent emulsion into a sulfuric acid solution under stirring, wherein the mass ratio of the sulfuric acid solution to the oxygen composite channel forming agent emulsion is 20-30:1, and uniformly dispersing to obtain paste acid.
Optionally, the oxygen recombination channel former further comprises a tetrafluoroethylene-acrylic acid copolymer; the mass ratio of the polytetrafluoroethylene to the tetrafluoroethylene-acrylic acid copolymer is 3-4: 1. The tetrafluoroethylene-acrylic acid copolymer is used for preparing an oxygen composite channel forming agent emulsion in an emulsion form, and the preparation method of the tetrafluoroethylene-acrylic acid copolymer emulsion comprises the following steps:
(a) adding ammonium perfluorooctanoate, paraffin, ammonium persulfate and water into a reaction vessel, uniformly mixing, replacing air in the reaction vessel with inert gas, introducing tetrafluoroethylene, and carrying out a first polymerization reaction at 70-80 ℃ for 30-40 min;
(b) adding acrylic acid, wherein the mass volume ratio of the acrylic acid to the water in the step (1) is 1g:70-80mL, uniformly mixing, and continuing to perform a second polymerization reaction at 70-80 ℃ for 50-60min to obtain a tetrafluoroethylene-acrylic acid copolymer emulsion;
in the first polymerization reaction and the second polymerization reaction, the pressure in the reaction vessel is controlled to 1.0 to 1.5MPa by controlling the flow rate of tetrafluoroethylene.
A lead-acid battery includes a negative electrode made of the negative electrode lead paste.
An electric vehicle comprises the lead-acid storage battery.
Example 1
The lead-acid storage battery negative electrode lead paste comprises the following raw materials in parts by weight: 1000 parts of lead powder, 10 parts of barium sulfate, 1 part of humic acid, 1 part of sodium lignosulphonate, 3 parts of mixed carbon (consisting of 2 parts of acetylene black and 1 part of graphene), 1 part of bismuth trioxide, 0.6 part of polyester fiber, 120 parts of pure water and 80 parts of paste acid.
The oxidation degree of the lead powder is 76%, and the apparent density is 1.33g/cm3The particle size is D50 ═ 2.6 μm; the specific surface area of the mixed carbon is 1000m2(ii)/g; the water is pure water with the conductivity of 1 mu S/cm; the paste acid is dilute sulfuric acid, wherein H2SO4Is 50.5 wt%.
The preparation method of the negative electrode lead paste comprises the following steps:
(1) adding 500 parts of lead powder into a paste mixer, sequentially adding 10 parts of barium sulfate, 1 part of sodium lignosulphonate, 1 part of humic acid, 1 part of bismuth trioxide, 0.6 part of polyester fiber and 3 parts of mixed carbon, finally adding 500 parts of lead powder, starting a motor, stirring and mixing for 5min, and obtaining a mixture after mixing;
(2) and within 3min after mixing, adding 120 parts of pure water into the mixture, slowly adding 80 parts of diachylon acid, adding the diachylon acid for 12min, uniformly stirring, cooling to below 40 ℃, and discharging to obtain the lead-acid storage battery cathode lead paste.
Example 2
The lead-acid storage battery negative electrode lead paste comprises the following raw materials in parts by weight: 1000 parts of lead powder, 12 parts of barium sulfate, 3 parts of humic acid, 2 parts of sodium lignosulphonate, 5 parts of mixed carbon (consisting of 3 parts of acetylene black and 2 parts of carbon nano tubes), 2 parts of bismuth trioxide, 0.9 part of polyacrylonitrile fiber, 124 parts of pure water and 84 parts of paste acid.
The oxidation degree of the lead powder is 76%, and the apparent density is 1.33g/cm3The particle size is D50 ═ 2.6 μm; the specific surface area of the mixed carbon is 1000m2(ii)/g; the water is pure water with the conductivity of 1 mu S/cm; the paste acid is dilute sulfuric acid, wherein H2SO4Is 50.5 wt%.
The preparation method of the negative electrode lead paste comprises the following steps:
(1) adding 500 parts of lead powder into a paste mixer, sequentially adding 12 parts of barium sulfate, 2 parts of sodium lignosulphonate, 3 parts of humic acid, 2 parts of bismuth trioxide, 0.9 part of polyacrylonitrile fiber and 3 parts of mixed carbon, finally adding 500 parts of lead powder, starting a motor, stirring and mixing for 10min, and obtaining a mixture after mixing;
(2) and within 3min after mixing, adding 124 parts of pure water into the mixture, slowly adding 84 parts of diachylon acid, adding the diachylon acid for 20min, uniformly stirring, cooling to below 40 ℃, and discharging to obtain the lead-acid storage battery cathode lead paste.
Example 3
This example differs from example 1 only in that the paste acid also contains an oxygen complex channel former; the mass fraction of the oxygen composite channel forming agent in the paste acid is 1 wt%; the oxygen composite channel forming agent is polytetrafluoroethylene.
The preparation method of the cream acid used in this example comprises the following steps:
(a) adding 5.83g of ammonium perfluorooctanoate, 1kg of paraffin, 0.17g of ammonium persulfate and 25L of water into a 50L polymerization reaction kettle, uniformly mixing, replacing air in a reaction container with inert gas, introducing tetrafluoroethylene, carrying out polymerization reaction at 75 ℃, wherein the reaction time is 1.5h, controlling the air pressure in the reaction container to be 1.0MPa by controlling the flow rate of the tetrafluoroethylene in the reaction process, and concentrating to obtain polytetrafluoroethylene emulsion with the solid content of 25 wt%, namely oxygen composite channel former emulsion;
(b) adding an oxygen composite channel forming agent emulsion into a 52.6 wt% sulfuric acid solution under stirring, wherein the mass ratio of the sulfuric acid solution to the oxygen composite channel forming agent emulsion is 24:1, and uniformly dispersing to obtain paste acid.
Example 4
This example differs from example 3 only in that the oxygen recombination channel former consists of polytetrafluoroethylene and tetrafluoroethylene-acrylic acid copolymer in a mass ratio of 3: 1.
The preparation method of the cream acid used in this example comprises the following steps:
(a) adding 5.83g of ammonium perfluorooctanoate, 1kg of paraffin, 0.17g of ammonium persulfate and 25L of water into a 50L polymerization reaction kettle, uniformly mixing, replacing air in the reaction container with inert gas, introducing tetrafluoroethylene, carrying out a first polymerization reaction at 75 ℃, wherein the reaction time is 35min, and in the reaction process, controlling the air pressure in the reaction container to be 1.0MPa by controlling the flow rate of the tetrafluoroethylene;
(b) adding 0.33g of acrylic acid, uniformly mixing, continuing to perform a second polymerization reaction at 75 ℃ for 55min, controlling the air pressure in a reaction container to be 1.0MPa by controlling the flow rate of tetrafluoroethylene in the reaction process, and concentrating to obtain a tetrafluoroethylene-acrylic acid copolymer emulsion with the solid content of 25 wt%;
(c) uniformly mixing the polytetrafluoroethylene emulsion prepared in the step (a) of the example 3 and the tetrafluoroethylene-acrylic acid copolymer emulsion prepared in the step (b) of the example in a mass ratio of 3:1 to obtain an oxygen composite channel former emulsion with the solid content of 25 wt%;
(d) adding an oxygen composite channel forming agent emulsion into a 52.6 wt% sulfuric acid solution under stirring, wherein the mass ratio of the sulfuric acid solution to the oxygen composite channel forming agent emulsion is 24:1, and uniformly dispersing to obtain paste acid.
Example 5
This example differs from example 4 only in that the oxygen recombination channel former consists of polytetrafluoroethylene and tetrafluoroethylene-acrylic acid copolymer in a mass ratio of 4: 1.
Comparative example 1
This comparative example used a conventional negative electrode formulation (6-DZM-20 Ah).
Comparative example 2
This comparative example differs from example 1 only in that the negative electrode lead paste for a lead-acid battery contains 96 parts by weight of pure water and also 32 parts by weight of a polytetrafluoroethylene emulsion having a solid content of 25% by weight (prepared in step (a) of example 3). In the step (2), 96 parts of pure water is added into the mixture, 32 parts of polytetrafluoroethylene emulsion is added, and 80 parts of paste acid is slowly added.
Comparative example 3
This comparative example differs from example 4 only in that the oxygen composite channel former consists of polytetrafluoroethylene and tetrafluoroethylene-acrylic acid copolymer in a mass ratio of 2: 1.
Comparative example 4
This comparative example differs from example 4 only in that the oxygen composite channel former consists of polytetrafluoroethylene and tetrafluoroethylene-acrylic acid copolymer in a mass ratio of 5: 1.
Application example
The negative electrode lead pastes of examples 1 to 5 and comparative examples 1 to 4 were coated to prepare a negative electrode, and the negative electrode was then prepared into a lead-acid battery according to a conventional method.
Test example 1: effect of the formulation
The lead-acid batteries manufactured using the negative electrode lead pastes of example 1 and comparative example 1 were subjected to room temperature capacity, low temperature-10 ℃ capacity, 1C quick charge and cycle life tests, and the results are shown in table 1.
TABLE 1
Figure BDA0003165361920000071
As can be seen from table 1, the lead-acid battery of example 1 has higher normal and low temperature capacities, faster charge speed, and longer cycle life, compared to comparative example 1. The composition and the proportion of the negative electrode additive can improve the performance of the negative electrode, thereby endowing the lead-acid storage battery with better performance.
Test example 2: action of oxygen complex channel formers
The lead-acid batteries manufactured from the negative electrode lead pastes of examples 1, 3 to 5 and comparative examples 2 to 4 were subjected to cycle life tests, and after 300 cycles, the water loss of the lead-acid batteries was measured, and the results are shown in table 2.
TABLE 2
Cycle life (times) Loss of water (g)
Example 1 538 136
Example 3 682 59
Example 4 701 63
Example 5 697 65
Comparative example 2 670 80
Comparative example 3 683 62
Comparative example 4 680 71
Analyzing the data of table 2, the following conclusions can be drawn:
(1) in example 1, no polytetrafluoroethylene was added, and in example 3, polytetrafluoroethylene was added to the kneading cream acid. The cycle life of the battery of example 3 was significantly extended and the water loss at 200 cycles was significantly reduced compared to example 1. The reason is that: the polytetrafluoroethylene can form a cross-linked network in the negative lead plaster, and the polytetrafluoroethylene has strong hydrophobicity and poor wettability of electrolyte, so that the function of an oxygen composite channel can be exerted in the negative electrode, oxygen and hydrogen can be diffused along the polytetrafluoroethylene cross-linked network, the compounding of the oxygen and the hydrogen is promoted, the water loss phenomenon of the lead-acid storage battery is reduced, and the cycle life of the battery is prolonged.
(2) Comparative example 2 the polytetrafluoroethylene emulsion was added separately from the cream acid (dilute sulfuric acid), and example 3 the polytetrafluoroethylene was added mixed in the cream acid. The cycle life of the cell of example 3 was longer and the water loss at 200 cycles was significantly reduced compared to comparative example 2. The reason is that: the function of reducing water loss of the battery by polytetrafluoroethylene has higher requirement on the dispersibility of the polytetrafluoroethylene in the lead-acid storage battery, and if the polytetrafluoroethylene is independently added into negative lead paste in the paste mixing process, due to the poor dispersibility of the polytetrafluoroethylene, the polytetrafluoroethylene is not beneficial to forming a hydrophobic cross-linking network with higher cross-linking degree and uniform distribution, so that oxygen composite channels cannot be communicated with each other, and the effect of reducing the water loss of the battery is difficult to effectively play. Therefore, in the invention, the polytetrafluoroethylene is added into the diachylon, and in the diachylon process, the polytetrafluoroethylene can enter between solid raw materials such as lead powder along with the diachylon, and is uniformly dispersed and crosslinked in the negative electrode to form an oxygen composite channel with relatively uniform distribution, thereby effectively reducing the water loss phenomenon of the lead-acid storage battery.
(3) Examples 4 and 5 the polytetrafluoroethylene of example 3 was replaced with polytetrafluoroethylene and a tetrafluoroethylene-acrylic acid copolymer. The cycle life of the batteries of examples 4 and 5 was longer compared to that of example 3. The reason is that: carboxyl in the molecular chain of the tetrafluoroethylene-acrylic acid copolymer can be complexed with lead powder, so that the bonding strength between the hydrophobic cross-linking network and the lead powder is further improved, the falling of a negative active substance in the battery circulation process is reduced, and the cycle life of the lead-acid storage battery is prolonged.
(4) The mass ratios of polytetrafluoroethylene and tetrafluoroethylene-acrylic acid copolymer in examples 4, 5 and comparative examples 3, 4 were 3:1, 4:1, 2:1, 5:1, respectively. The cycle life of the batteries of examples 4 and 5 was longer than that of comparative examples 3 and 4. The reason is that: when the relative dosage of the tetrafluoroethylene-acrylic acid copolymer is too high, the hydrophobicity of a cross-linked network is influenced, and further the diffusion of hydrogen and oxygen in an oxygen composite channel is influenced, so that the water loss of the battery is more; when the relative amount of the tetrafluoroethylene-acrylic acid copolymer is too low, the bonding strength between the crosslinked network and the lead powder is too low, so that the negative active material is easy to fall off, and the cycle life of the battery is further influenced.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.

Claims (10)

1. The lead-acid storage battery negative electrode lead plaster is characterized by comprising the following raw materials in parts by weight: 1000 parts of lead powder, 8-12 parts of barium sulfate, 1-5 parts of humic acid, 1-5 parts of sodium lignosulfonate, 1-5 parts of mixed carbon, 1-5 parts of bismuth trioxide, 0.5-1.5 parts of conductive fiber, 130 parts of water and 80-90 parts of paste acid.
2. The negative electrode lead paste of claim 1, wherein:
the mixed carbon comprises acetylene black and also comprises one or more of activated carbon, graphene and carbon nano tubes; the specific surface area of the mixed carbon is 100-1500m2(ii)/g; and/or
The conductive fibers comprise polyester fibers and/or polyacrylonitrile fibers; and/or
The oxidation degree of the lead powder is 70-80%, and the apparent density is 1.30-1.40g/cm3The particle size is D50 less than 2.8 μm; and/or
The water is pure water with the conductivity less than 2 mu S/cm.
3. The negative electrode lead paste of claim 1, wherein the paste acid is dilute sulfuric acid; h2SO4The mass fraction in the paste acid is 45-51 wt%.
4. The negative electrode lead paste of claim 3, wherein the paste acid further comprises an oxygen recombination channel former; the mass fraction of the oxygen composite channel forming agent in the paste acid is 0.5-1.5 wt%; the oxygen recombination channel former comprises polytetrafluoroethylene.
5. The negative electrode lead paste of claim 4, wherein the preparation method of the diacidic acid comprises the following steps: adding an oxygen composite channel forming agent emulsion into a sulfuric acid solution under stirring, wherein the mass ratio of the sulfuric acid solution to the oxygen composite channel forming agent emulsion is 20-30:1, and uniformly dispersing to obtain paste acid.
6. The negative lead paste of claim 5, wherein the oxygen recombination channel former further comprises a tetrafluoroethylene-acrylic acid copolymer; the mass ratio of the polytetrafluoroethylene to the tetrafluoroethylene-acrylic acid copolymer is 3-4: 1.
7. The negative electrode lead paste of claim 6, wherein the tetrafluoroethylene-acrylic acid copolymer is formulated as an oxygen composite channel former emulsion prepared by the following method:
(a) adding ammonium perfluorooctanoate, paraffin, ammonium persulfate and water into a reaction vessel, uniformly mixing, replacing air in the reaction vessel with inert gas, introducing tetrafluoroethylene, and carrying out a first polymerization reaction at 70-80 ℃ for 30-40 min;
(b) adding acrylic acid, wherein the mass volume ratio of the acrylic acid to the water in the step (1) is 1g:70-80mL, uniformly mixing, and continuing to perform a second polymerization reaction at 70-80 ℃ for 50-60min to obtain a tetrafluoroethylene-acrylic acid copolymer emulsion;
in the first polymerization reaction and the second polymerization reaction, the pressure in the reaction vessel is controlled to 1.0 to 1.5MPa by controlling the flow rate of tetrafluoroethylene.
8. A method for preparing a negative electrode lead paste according to any one of claims 1 to 7, comprising the steps of:
(1) adding lead powder accounting for 40-60wt% of the total mass of the lead powder into a paste mixing device, sequentially adding barium sulfate, sodium lignosulphonate, humic acid, bismuth trioxide, conductive fiber and mixed carbon, finally adding the rest lead powder, and uniformly stirring to obtain a mixture;
(2) and adding water into the mixture, adding paste acid, uniformly stirring, cooling, and discharging paste to obtain the lead-acid storage battery negative electrode lead paste.
9. A lead-acid battery comprising a negative electrode made from the negative electrode lead paste of any one of claims 1 to 8.
10. An electric vehicle comprising the lead-acid storage battery of claim 9.
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CN104377359A (en) * 2014-10-15 2015-02-25 超威电源有限公司 Deep-cycle-resistant lead-acid storage battery anode lead paste formula and preparation process thereof
CN105355912A (en) * 2015-11-23 2016-02-24 江苏海德森能源有限公司 Surface mount lead carbon battery electrode
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