CN116742005A - Lead-carbon battery negative electrode material and negative electrode with zinc bismuthate as hydrogen evolution inhibitor - Google Patents
Lead-carbon battery negative electrode material and negative electrode with zinc bismuthate as hydrogen evolution inhibitor Download PDFInfo
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- CN116742005A CN116742005A CN202310898376.8A CN202310898376A CN116742005A CN 116742005 A CN116742005 A CN 116742005A CN 202310898376 A CN202310898376 A CN 202310898376A CN 116742005 A CN116742005 A CN 116742005A
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- lead
- carbon
- zinc
- bismuthate
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- 239000011701 zinc Substances 0.000 title claims abstract description 80
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 79
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 60
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 54
- 239000001257 hydrogen Substances 0.000 title claims abstract description 54
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000003112 inhibitor Substances 0.000 title claims abstract description 22
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000000835 fiber Substances 0.000 claims abstract description 27
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 22
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004021 humic acid Substances 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 239000010405 anode material Substances 0.000 claims abstract description 9
- 229920005610 lignin Polymers 0.000 claims abstract description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 40
- 238000001035 drying Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000011505 plaster Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 239000004246 zinc acetate Substances 0.000 claims description 7
- 238000010335 hydrothermal treatment Methods 0.000 claims description 6
- 239000011812 mixed powder Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- PNYYBUOBTVHFDN-UHFFFAOYSA-N sodium bismuthate Chemical compound [Na+].[O-][Bi](=O)=O PNYYBUOBTVHFDN-UHFFFAOYSA-N 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 238000001723 curing Methods 0.000 claims description 5
- -1 polypropylene Polymers 0.000 claims description 5
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- 239000004917 carbon fiber Substances 0.000 claims description 4
- 238000002386 leaching Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 238000007711 solidification Methods 0.000 claims description 3
- 230000008023 solidification Effects 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 238000013461 design Methods 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 229920002821 Modacrylic Polymers 0.000 claims 1
- 238000005554 pickling Methods 0.000 claims 1
- 239000003575 carbonaceous material Substances 0.000 abstract description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 5
- 239000011787 zinc oxide Substances 0.000 abstract description 5
- 230000002401 inhibitory effect Effects 0.000 abstract description 4
- 229910000416 bismuth oxide Inorganic materials 0.000 abstract description 3
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004146 energy storage Methods 0.000 abstract description 2
- 239000007772 electrode material Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 43
- 238000012360 testing method Methods 0.000 description 15
- 239000000654 additive Substances 0.000 description 14
- 238000002484 cyclic voltammetry Methods 0.000 description 14
- 230000000996 additive effect Effects 0.000 description 13
- 230000002829 reductive effect Effects 0.000 description 13
- 239000000203 mixture Substances 0.000 description 10
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000007600 charging Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- VNFKQMOYAXLCJT-UHFFFAOYSA-N [O].[Zn].[Bi] Chemical compound [O].[Zn].[Bi] VNFKQMOYAXLCJT-UHFFFAOYSA-N 0.000 description 4
- ONVGHWLOUOITNL-UHFFFAOYSA-N [Zn].[Bi] Chemical compound [Zn].[Bi] ONVGHWLOUOITNL-UHFFFAOYSA-N 0.000 description 4
- 239000013543 active substance Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- VSXUJIASYQUBSV-UHFFFAOYSA-N bismuth zinc oxygen(2-) Chemical compound [O--].[Zn++].[Bi+3] VSXUJIASYQUBSV-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 229910000464 lead oxide Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- GACUIHAEKGVEIC-UHFFFAOYSA-L [Bi+2]=O.C([O-])([O-])=O Chemical compound [Bi+2]=O.C([O-])([O-])=O GACUIHAEKGVEIC-UHFFFAOYSA-L 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- FSAJRXGMUISOIW-UHFFFAOYSA-N bismuth sodium Chemical compound [Na].[Bi] FSAJRXGMUISOIW-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229920005552 sodium lignosulfonate Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
Classifications
-
- 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
- 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
- H01M4/14—Electrodes for lead-acid accumulators
- H01M4/16—Processes of manufacture
- H01M4/20—Processes of manufacture of pasted 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
- H01M4/16—Processes of manufacture
- H01M4/20—Processes of manufacture of pasted electrodes
- H01M4/21—Drying of pasted 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
-
- 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)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a lead-carbon battery negative electrode material and a negative electrode using zinc bismuthate as a hydrogen evolution inhibitor, and relates to the technical field of battery energy storage. The lead-carbon battery anode material provided by the invention comprises the following components in parts by weight: 0.06-0.12 part of short fiber, 0.5-1.5 parts of barium sulfate, 0.3-1.5 parts of carbon, 0.1-0.15 part of lignin, 0.15-0.35 part of humic acid, 0.5-3 parts of zinc bismuthate and 93-98 parts of lead powder. The zinc bismuthate is prepared by a hydrothermal method, has a simpler process and has better hydrogen evolution inhibiting effect than single materials (bismuth oxide and zinc oxide). According to the invention, the zinc bismuthate bimetallic material is added for preparing the electrode material, so that the hydrogen evolution reaction brought by the carbon material can be restrained, and the cycle life is excellent.
Description
Technical Field
The invention relates to the technical field of battery energy storage, in particular to a lead-carbon battery negative electrode material and a negative electrode taking zinc bismuthate as a hydrogen evolution inhibitor.
Background
The lead-acid battery is a storage battery with positive electrode material mainly of lead oxide, negative electrode material mainly of lead and electrolyte solution of sulfuric acid. Under the discharge state of the lead-acid battery, the anode material and the cathode material react with sulfuric acid to generate lead sulfate; in the charged state, lead sulfate on the positive and negative plates begins to be converted into lead oxide and lead. When the lead-acid battery is recycled under the high-rate partial state of charge (HRPSC), aggregation of lead sulfate can occur, long-time charge and discharge are difficult to realize, lead sulfate generated by a negative electrode is difficult to be completely converted into active substance sponge lead, and finally an irreversible compact lead sulfate layer is formed on the surface of the negative electrode, so that the utilization rate of polar plate active substances is low, the cycle life of the battery is short, and the application of the lead-acid battery is affected.
The lead-carbon battery is based on lead-acid battery research, carbon materials are introduced into the anode material, and the high specific surface area and the porous structure of the carbon materials are utilized to provide more interfaces for lead/lead sulfate reaction, so that aggregation of lead sulfate is reduced, and the generation of a lead sulfate layer is effectively hindered; in addition, the lead sulfate small particles which are difficult to agglomerate are more easily converted into active material sponge lead in the charging process, so that the utilization rate of the negative electrode active material is improved. The double-electric-layer capacitor made of the carbon material can effectively relieve the impact of large current on the polar plate during charge and discharge, so that the polar plate structure is more stable.
The lead-carbon battery has higher capacity, cycle life and better charge-discharge receiving capability than lead-acid batteries. Compared with new energy batteries such as lithium batteries, the lead-carbon battery has the advantages of good stability, low price, mature process, high recycling rate and the like. In particular, in the field of new energy automobiles, lead-carbon batteries are used in hybrid automobiles. Particularly in the application field of starting power supplies of automobiles, the lead-carbon battery is more widely applied.
Patent CN 110739457B discloses a lead-carbon battery negative electrode lead plaster and a preparation method thereof, a lead-carbon battery negative electrode plate and a lead-carbon battery, wherein the lead-carbon battery negative electrode lead plaster comprises lead powder, ordered mesoporous carbon powder, a binder, sodium lignosulfonate, humic acid, barium sulfate, a hydrogen inhibitor and sulfuric acid, wherein the mass of the ordered mesoporous carbon powder is 0.008-0.012 of the mass of the lead powder. According to the lead-carbon battery negative electrode lead plaster, the ordered mesoporous carbon powder is adopted to replace the traditional common carbon material, and the ordered mesoporous carbon has larger surface area, so that the contact area with electrolyte can be increased, the adsorption of the electrolyte is facilitated, and the specific capacity of the lead-carbon battery can be further improved.
Patent CN 103811752A discloses a lead-carbon battery negative electrode lead plaster, which comprises the following raw materials: 100 parts of lead powder, 4-100 parts of sulfuric acid, 0.1-8 parts of binder, 0.1-2 parts of barium sulfate, 0.01-2 parts of hydrogen evolution inhibitor, 50-100 parts of graphene oxide, 0.05-1 part of acetylene black, 1-4 parts of humic acid, 5-15 parts of red lead, 12-21 parts of water and 0.1-0.2 part of short fiber are added into a negative electrode lead plaster, and the graphene oxide contains more oxygen-containing functional groups and can generate more pseudo-capacitance in sulfuric acid, so that the use amount of lead powder in a negative electrode material can be reduced, meanwhile, the current on a lead negative electrode can be shared under the condition of high-current charge and discharge, the sulfation of a storage battery is slowed down, and the service life of the storage battery is prolonged.
Lead-carbon batteries are improved in capacity and cycle life, but the lower hydrogen evolution overpotential of the carbon material can lead to the accelerated hydrogen evolution rate of the negative plate of the battery, so that the water loss of the battery is faster and the internal pressure of the battery is higher. The separated hydrogen can impact the electrode plate as well, and damage the structure of the electrode plate, thereby affecting the excellent effect of the carbon material.
The hydrogen evolution inhibitor is the most direct method for improving the problem of hydrogen evolution caused by carbon materials in the negative electrode of the lead-carbon battery, and mainly uses metals or metal oxides with high hydrogen evolution overpotential to replace hydrogen evolution reaction or retard the hydrogen evolution reaction. The main principle is that the hydrogen evolution inhibitor with high hydrogen evolution overpotential is used for converting metal atoms/ions preferentially to convert hydrogen ions in the charging process, so that hysteresis of hydrogen evolution reaction is realized or the hydrogen evolution inhibitor is completely replaced, the occurrence of the hydrogen evolution reaction is greatly reduced, the generation of hydrogen is further reduced, and the excellent effect of the carbon material in a negative plate is further improved.
Bismuth and zinc materials are the main directions of research on hydrogen evolution inhibitors of lead-carbon batteries, wherein zinc oxide, zinc simple substances, bismuth oxide carbonate and the like are all studied in inhibiting hydrogen evolution of negative electrodes of lead-carbon batteries.
At present, partial two hydrogen evolution inhibitors are added into the cathode material simultaneously to generate a synergistic effect, so that a better hydrogen evolution inhibition effect is realized, and the performance of the battery is improved greatly. However, there is a problem in that the amount of the additive is increased.
Zinc bismuthate is a binary metal oxide containing both bismuth and zinc elements. The zinc bismuthate is prepared mainly by a hydrothermal method, the preparation method is simple, and the zinc bismuthate gradually grows into a tablet or rod-shaped structure from nano particles in the hydrothermal treatment process.
At present, the problem of too fast hydrogen evolution rate of the lead-carbon battery needs to be solved, so that the beneficial effect of the carbon material in the anode material is better exerted, and the cycle life and charge-discharge acceptance of the battery are further improved. Zinc bismuthate has not been studied in the field of batteries as a bimetallic oxide, nor has it been studied in comparison with a monometal oxide hydrogen evolution inhibitor.
Therefore, it is highly desirable to develop a lead-carbon battery negative electrode material and a negative electrode using a bi-metal oxide-zinc bismuthate as a hydrogen evolution inhibitor, which solve the above-mentioned problems.
Disclosure of Invention
The invention aims at the problems and provides a lead-carbon battery negative electrode material and a negative electrode which are long in battery cycle life and good in charge acceptance after deep discharge and take zinc bismuthate as a hydrogen evolution inhibitor in order to overcome the defects of the prior art. The invention provides a lead-carbon battery formula, which further improves the battery performance and the cycle life, and optimizes the function of carbon materials in the negative electrode. The zinc bismuthate hydrogen evolution inhibitor which can inhibit hydrogen evolution and greatly improve the battery performance and the cycle life is prepared by adopting sodium bismuthate and zinc acetate as raw materials to prepare a zinc bismuthate material containing bimetal.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
on the one hand, the invention provides a lead-carbon battery anode material taking zinc bismuthate as a hydrogen evolution inhibitor, which comprises the following components in parts by weight: 0.06-0.12 part of short fiber, 0.5-1.5 parts of barium sulfate, 0.3-1.5 parts of carbon, 0.1-0.15 part of lignin, 0.15-0.35 part of humic acid, 0.5-3 parts of zinc bismuthate and 93-98 parts of lead powder.
Preferably, the composition comprises the following components in parts by weight: 0.08-0.11 part of short fiber, 0.8-1.2 parts of barium sulfate, 0.4-1.2 parts of carbon, 0.1-0.12 part of lignin, 0.2-0.32 part of humic acid, 1-3 parts of zinc bismuthate and 94-97 parts of lead powder.
Further preferably, the composition comprises the following components in parts by weight: 0.1 part of short fiber, 1 part of barium sulfate, 1 part of carbon, 0.1 part of lignin, 0.3 part of humic acid, 2 parts of zinc bismuthate and 95.5 parts of lead powder.
Preferably, the short fiber can be at least one selected from polyester fiber, polypropylene fiber, polyacrylonitrile fiber, nitrilo-chloridized fiber, polyethylene fiber and polyamide fiber; further preferably, the short fibers may be selected from polyester fibers.
Preferably, the carbon can be at least one selected from activated carbon, carbon black, superconducting carbon black, carbon fiber, graphite and carbon nano tube; further preferably, the carbon may be at least one of activated carbon, carbon black, and carbon fiber.
On the other hand, the invention provides a preparation method of the zinc bismuthate, which is prepared by a hydrothermal method and comprises the following steps:
1) Adding sodium bismuthate and zinc acetate into water, stirring, and transferring into a reaction kettle;
2) Carrying out hydrothermal treatment on the reaction kettle at 120-210 ℃ for 12-24 hours, and cooling to room temperature; filtering, washing and drying.
Preferably, the temperature of the hydrothermal treatment in the step 2) is 160-200 ℃ and the treatment time is 18-24 hours.
Preferably, the drying temperature in step 2) is 50-70 ℃.
Preferably, the mass ratio of the sodium bismuthate to the zinc acetate in the step 1) is 1:1-1.5; it is further preferred that the mass ratio of sodium bismuthate to zinc acetate in step 1) is 1:1.
In yet another aspect, the invention provides a lead-carbon battery negative electrode comprising the lead-carbon battery negative electrode material described above.
In still another aspect, the invention provides a method for preparing a negative electrode of a lead-carbon battery, comprising the following steps:
1) Firstly mixing short fibers, barium sulfate, carbon, lignin, humic acid and zinc bismuthate, and stirring to obtain mixed powder A;
2) Adding lead powder into the powder A, and stirring to obtain mixed powder B;
3) Putting the powder B into a paste mixing machine, sequentially adding water and dilute sulfuric acid, and stirring until the density is 4.1-4.5g/mL to obtain uniformly mixed lead paste C;
4) And uniformly coating the lead plaster C on the negative plate, and carrying out acid leaching, curing and drying.
Preferably, the specific operation of stirring in step 1) is: mechanically stirring for 1-2h to obtain mixed powder A with uniform dispersion.
Preferably, the specific operation of stirring in step 2) is: mechanically stirring for 0.5-1.5h to obtain uniformly dispersed mixed powder B. The powder A and the lead powder are mechanically stirred to realize premixing, which is beneficial to improving the dispersion of each additive and improving the dispersibility of each additive in the final lead paste.
Preferably, the mass ratio of the water added in the step 3) to the lead powder in the step 2) is 0.12-0.15:1.
preferably, the mass ratio of the addition amount of the dilute sulfuric acid in the step 3) to the lead powder in the step 2) is 0.072-0.087:1.
preferably, the specific operation of the step 3) is as follows: the uniformly dispersed powder B was mixed with water, and then a sulfuric acid solution having a concentration of 1.4g/mL was slowly added thereto, and the temperature was controlled at 25 ℃.
Preferably, the specific operation of the step 4) is as follows: and (3) coating the lead plaster C on a negative plate grid, wherein the weight of the negative plate grid is about 17.18g, the plaster amount of the lead plaster C of each negative plate is 38-42.5g according to design requirements, and the coated negative plate is subjected to acid leaching in sulfuric acid with the density of 1.10-1.20g/mL, the temperature is controlled to be 25 ℃, and then the negative plate is placed into a constant temperature and humidity chamber for solidification and drying.
Preferably, the specific operation of the drying is as follows: the acid leached negative plate is immediately placed in a surface drying kiln and dried at 100-120 ℃ for 2-5min.
More preferably, the water content of the surface lead paste is controlled between 8% and 11% when the surface drying kiln is removed from the polar plate, so that the subsequent curing process can be realized.
More preferably, the curing and drying should be changed with time, and the temperature and humidity should be adjusted to realize further oxidation of free lead in the lead plaster, and the solid active substance and good appearance are obtained after molding; the adhesive force between the grids and the active substances is enhanced by forming the corrosion film on the surfaces of the grids, so that cracks are prevented from being generated between the grids and the lead plaster, and the stability of the electrode plate is damaged.
Compared with the prior art, the invention has the following beneficial effects:
(1) The zinc bismuthate is prepared by a hydrothermal method, the process is simpler, and the product with complete crystal form, uniform particle size distribution and good dispersibility can be obtained without high-temperature treatment, so that the energy consumption is relatively reduced; the reaction and crystal growth can be effectively controlled in the hydrothermal process by changing the factors such as the reaction temperature, the pressure, the reaction time and the like.
(2) The zinc bismuthate can obtain different morphologies by adjusting the temperature and the hydrothermal time.
(3) The zinc bismuthate with the same addition amount has better hydrogen evolution inhibiting effect than single materials (bismuth oxide and zinc oxide).
(4) The zinc bismuthate is mixed with the carbon material and added into the anode material, so that the hydrogen evolution reaction brought by the carbon material can be inhibited, and the beneficial effect of the carbon material is improved.
(5) Compared with bismuth oxide and zinc oxide, the zinc bismuthate has smaller addition amount, and can reduce the influence on the structural stability of the negative plate.
(6) Compared with bismuth zinc oxide prepared by an ultrasonic liquid phase method, the effect of inhibiting negative hydrogen evolution reaction of zinc bismuthate by a hydrothermal method is better.
(7) The specific capacitance and initial capacity of the battery plate added with the zinc bismuthate additive (based on the AC) are obviously improved, the impedance is reduced, the hydrogen evolution is reduced, and the service life of the battery is prolonged.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of zinc bismuthate obtained in example 1.
FIG. 2 is a Scanning Electron Microscope (SEM) photograph of zinc bismuthate obtained in example 1.
Fig. 3 is a Cyclic Voltammetry (CV) image of a negative plate with zinc bismuthate as a hydrogen evolution inhibitor prepared in example 1.
Fig. 4 is a Cyclic Voltammetry (CV) image of a negative plate with zinc bismuthate as a hydrogen evolution inhibitor prepared in example 2.
Fig. 5 is a Cyclic Voltammetry (CV) image of a negative plate with zinc bismuthate as a hydrogen evolution inhibitor prepared in example 3.
Fig. 6 is a Cyclic Voltammetry (CV) image of a negative plate with zinc bismuthate as a hydrogen evolution inhibitor prepared in example 4.
Fig. 7 is a Cyclic Voltammetry (CV) image of a negative plate with AC as a carbon source prepared in comparative example 1.
Fig. 8 is a Cyclic Voltammetry (CV) image of the negative plate of the control of comparative example 2.
Fig. 9 is a cathode polarization test (LSV) image of the negative plate manufactured in example 3, comparative example 1.
Fig. 10 is a cathode polarization test (LSV) image of the negative plates prepared in example 3 and comparative example 5.
Fig. 11 is a cathode polarization test (LSV) image of the negative plate manufactured in example 3, comparative example 3, and comparative example 4.
Fig. 12 is an ac impedance test image of the negative electrode plate manufactured in example 3 and comparative example 1.
Fig. 13 is a battery charging performance test image obtained in example 3, comparative example 1, comparative example 2.
Fig. 14 is a test image of the discharge performance of the battery prepared in example 3, comparative example 1, comparative example 2.
Fig. 15 is a battery cycle life performance test image obtained in example 3, comparative example 1, comparative example 2.
Fig. 16 is an SEM image of the negative plate after the battery cycle test prepared in example 3.
Fig. 17 is an SEM image of the negative plate after the battery cycle test of comparative example 1.
Fig. 18 is an SEM image of the negative plate after the battery cycle test of comparative example 2.
Detailed Description
In order to make the technical means, the creation features, the achievement of the purpose and the effect of the present invention easy to understand, the present invention will be further elucidated with reference to the specific embodiments, but the following embodiments are only preferred embodiments of the present invention, not all of them. Based on the examples in the embodiments, those skilled in the art can obtain other examples without making any inventive effort, which fall within the scope of the invention. It is to be noted that the raw materials used in the present invention are all common commercial products, and the sources thereof are not particularly limited. Technical and scientific terms used in the examples have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
Example 1
The lead-carbon battery negative electrode material taking zinc bismuthate as a hydrogen evolution inhibitor comprises the following components in parts by weight: 0.1 part of lignin, 0.3 part of humic acid, 0.1 part of composite conductive fiber (formed by compounding carbon fiber and polyaniline fiber), 1 part of barium sulfate, 1 part of AC, 0.5 part of zinc bismuthate additive and 97 parts of lead powder.
The preparation process of the zinc bismuthate additive comprises the following steps:
sodium bismuth (NaBiO) 3 ·2H 2 O) and zinc acetate (C) 4 H 6 O 4 Zn·2H 2 O) adding the mixture into deionized water, fully stirring to obtain a uniform mixture, and transferring the uniform mixture into a high-temperature high-pressure reaction kettle; placing the high-temperature high-pressure reaction kettle in an oven, performing hydrothermal treatment at 180 ℃ for 24 hours, and then naturally cooling to room temperature; the white precipitate was obtained by filtration, washed with ethanol and deionized water and dried at 60 ℃.
A preparation method of a lead-carbon battery cathode comprises the following steps:
(1) Adding lignin, humic acid, short fiber, barium sulfate, AC (activated carbon) and zinc bismuthate additive into 10 times of water, and carrying out ultrasonic treatment for 2 hours to obtain a mixed solution A;
(2) Adding the mixed solution A into lead powder to obtain a mixture B;
(3) Adding the mixture B and water into a paste mixing machine, wherein the mass ratio of the added amount of water to the lead powder in the step (2) is 0.12-0.13:1, so as to obtain a lead-carbon battery anode material, at the moment, the lead paste is in a slurry state, slowly adding sulfuric acid with the concentration of 1.4g/mL into the lead paste, wherein the mass ratio of the added amount of sulfuric acid to the lead powder in the step (2) is 0.078:1, releasing heat to 40 ℃, and stirring until the density is 4.4g/mL, so as to obtain a mixture C;
(4) Coating the mixture C onto a negative plate having a weight of about 25.5g, pasting 26.8g of the mixture on each negative plate, and applying H having a density of 1.12g/mL (25 ℃ C.) 2 SO 4 Acid spraying, surface drying for 2-3min in a surface drying kiln, and then transferring into a constant temperature and humidity box for curing and drying to obtain the qualified negative plate.
Example 2
This example differs from example 1 only in that zinc bismuthate is used in an amount of 1 part.
Example 3
This example differs from example 1 only in that zinc bismuthate is used in an amount of 2 parts.
Example 4
This example differs from example 1 only in that zinc bismuthate is used in an amount of 3 parts.
Comparative example 1
The comparative example differs from example 1 only in that the amount of AC used is 1 part, the zinc bismuthate additive being replaced by an equivalent amount of lead powder.
Comparative example 2
The only difference of this comparative example compared to example 1 is that the AC and zinc bismuthate additives were replaced with equivalent amounts of lead powder.
Comparative example 3
The comparative example differs from example 3 only in that the zinc bismuthate additive was replaced with 2 parts of ZnO.
Comparative example 4
The comparative example differs from example 3 only in that the zinc bismuthate additive was replaced with 2 parts of Bi 2 O 3 。
Comparative example 5
The comparative example differs from example 3 in that zinc bismuthate prepared by the hydrothermal method is replaced by 2 parts of bismuth zinc oxide prepared by the ultrasonic liquid phase method.
Experimental example 1
(1) XRD testing was performed on the zinc bismuthate prepared in example 1, and the results are shown in fig. 1: the synthesized zinc bismuthate has a good crystal structure.
(2) The zinc bismuthate prepared in example 1 was subjected to SEM test as shown in fig. 2. The results show that: the prepared zinc bismuthate has a sheet structure, the specific surface area of the zinc bismuthate is greatly increased, and the reaction contact surface is improved.
(3) The lead-carbon battery cathodes prepared in example 14 and comparative example 1 and comparative example 2 were placed in 1.25g/mL sulfuric acid as a working electrode, hg/Hg 2 SO 4 The reference electrode was made and Pt was the counter electrode. The scanning range is 1.20.2V, the scanning speed is 10mV/s, and the cyclic voltammogram of the negative plate is measured;
the test results were as follows:
FIG. 3 is a Cyclic Voltammetry (CV) image of a negative plate incorporating 0.5 part zinc bismuthate of example 1;
FIG. 4 is a Cyclic Voltammetry (CV) image of a negative plate with 1 part zinc bismuth oxide added in example 2;
FIG. 5 is a Cyclic Voltammetry (CV) image of a negative plate with 2 parts zinc bismuth oxide added in example 3;
FIG. 6 is a Cyclic Voltammetry (CV) image of a negative plate with 3 parts zinc bismuth oxide added in example 4;
FIG. 7 is a Cyclic Voltammetry (CV) image of a negative plate with 1 part AC added to comparative example 1;
fig. 8 is a Cyclic Voltammetry (CV) image of the negative plate of the control of comparative example 2.
(4) Calculating the specific capacitance according to the specific capacitance calculation formulaWherein S is the scanning speedA is the rectangular area in the cyclic voltammogram, deltaV is the sweep voltage range, and m is the mass of the active species.
The specific capacitance test results are shown in table 1.
TABLE 1
Table 1 shows that the specific capacitance of each electrode was the smallest, and comparative example 2 (blank) and comparative example 1 (AC added) showed that the addition of carbon material improved the specific capacitance characteristics of the electrode. Comparing examples 1-4, it is known that zinc bismuthate can further increase the specific capacitance of the electrode on the basis of the carbon material, and the addition amount of zinc bismuthate affects the specific capacitance of the electrode plate, and the specific capacitance of the electrode of example 3 (2 parts of zinc bismuthate is added) is the largest; comparative example 3 As known from comparative examples 3 to 5, the same amounts of zinc bismuthate, znO, bi were added 2 O 3 And the bismuth zinc oxide prepared by the ultrasonic liquid phase method, example 3 (2 parts of zinc bismuthate) has the highest specific capacitance, which shows that the zinc bismuthate prepared by the hydrothermal method has the best effect of improving the specific capacitance of the electrode.
(5) The lead-carbon battery cathodes prepared in example 3 and comparative example 1 were placed in 1.23g/mL sulfuric acid as the working electrode, hg/Hg 2 SO 4 The reference electrode was made and Pt was the counter electrode. The constant current volt-ampere curve of the negative plate is shown in figure 9, the electrode added with the AC shows larger hydrogen evolution current, the hydrogen evolution potential of the battery added with the zinc bismuthate moves negatively, and the hydrogen evolution reaction of the negative electrode is reduced.
(6) The lead-carbon battery cathodes prepared in example 3 and comparative example 5 were placed in 1.23g/mL sulfuric acid as the working electrode, hg/Hg 2 SO 4 The reference electrode was made and Pt was the counter electrode. The constant current volt-ampere curve of the measured negative plate is shown in figure 10, the hydrogen evolution potential of the zinc bismuthate battery prepared by the hydrothermal method is shifted negatively, the hydrogen evolution reaction of the negative electrode is reduced, and the zinc bismuthate battery has a better hydrogen evolution inhibition effect.
(7) The lead-carbon battery cathodes prepared in example 3 and comparative examples 3 and 4 were placed in 1.23g/mL sulfuric acid as a working electrode, hg/Hg 2 SO 4 The reference electrode was made and Pt was the counter electrode.The constant current volt-ampere curve of the measured negative plate is shown in figure 11, the hydrogen evolution potential of the battery with the zinc bismuthate added is shifted negatively, the hydrogen evolution reaction of the negative electrode is reduced, and the negative electrode has better hydrogen evolution inhibition effect than that of a single additive.
(8) The lead-carbon battery cathodes prepared in example 3 and comparative example 1 were placed in 1.23g/mL sulfuric acid as the working electrode, hg/Hg 2 SO 4 The reference electrode was made and Pt was the counter electrode. The impedance of the negative plate was measured as shown in fig. 12. The resistance of the zinc bismuthate is smaller. The semicircle in the nyquist plot is depressed, which may be due to the variation of the resistive and capacitive components of the electrode/electrolyte interface with electrode position, electrode thickness non-uniformity, etc.
(9) The lead-carbon batteries prepared in example 3 and comparative examples 1 and 2 were prepared into a battery with a positive electrode ratio, and the battery was tested for charge acceptance, and as a result, as shown in fig. 13, the battery charge ability was improved by adding AC, and further improved by adding zinc bismuthate based on AC.
(10) The lead-carbon battery prepared in example 3 and comparative examples 1 and 2 was prepared into a battery with a positive electrode ratio, and the high-current discharge acceptance of the battery was tested, and as shown in fig. 14, the addition of AC can improve the discharge capacity of the battery, and the further addition of zinc bismuthate on the basis of AC can further improve the discharge performance of the battery and reduce the polarization phenomenon during the discharge.
(11) The lead-carbon batteries prepared in examples 1 to 4 and comparative examples 1 and 2 were prepared into batteries by proportioning positive electrode plates, and the cycle life of the batteries was tested.
The specific test steps of the battery are as follows:
1) Standing for 10s;
2) Charging to 2.4V at 0.1C constant current;
3) Constant voltage charging for 12h at 2.4V;
4) Discharging to 50% SoC state with 1C constant current;
5) Placing for 10s;
6) Charging for 60s with a constant current of 2C;
7) Placing for 10s;
8) Discharging for 60s at a constant current of 2C;
9) Starting the cycle from 5) to 8) ending the discharge voltage below 1.7V.
The test results are shown in fig. 15 and table 2.
TABLE 2
| Battery type | Number of cycles |
| Blank group | 2236 |
| Control group (AC) | 3748 |
| 0.5% Zinc bismuth (containing AC) | 3948 |
| 1.0% Zinc bismuth (containing AC) | 4625 |
| 2.0% Zinc bismuth (containing AC) | 8699 |
| 3.0% Zinc bismuth (containing AC) | 7740 |
From the above, it is clear that the zinc bismuthate battery exhibits better battery performance. The zinc bismuthate additive can further improve the cycle life of the battery on the basis of AC.
(12) The lead-carbon batteries prepared in example 1 and comparative examples 1 and 2 were recycled, disassembled, and SEM tested on the negative electrode material.
The test results were as follows:
fig. 16 is a Scan (SEM) image of a negative plate after example 3 was cycled with 2 parts zinc bismuth oxide cells;
fig. 17 is a Scanning (SEM) image of the negative plate after 1 AC battery cycle was added to comparative example 2;
fig. 18 is a negative plate Scan (SEM) image of a comparative example 1 blank cell after cycling.
From the graph, the blank battery cathode generates large-particle irreversible PbSO 4 Large-particle irreversible PbSO (PbSO) for negative electrode of AC (alternating current) battery 4 The negative electrode of the zinc bismuthate battery is reduced, and the negative electrode of the zinc bismuthate battery more presents small particle products.
Experiments show that the specific capacitance and initial capacity of the battery plate added with the zinc bismuthate additive (based on the AC) are obviously improved, the impedance is reduced, the hydrogen evolution is reduced, and the service life of the battery is prolonged.
The foregoing detailed description is directed to one of the possible embodiments of the present invention, which is not intended to limit the scope of the invention, but is to be accorded the full scope of all such equivalents and modifications so as not to depart from the scope of the invention.
Claims (10)
1. The lead-carbon battery negative electrode material taking zinc bismuthate as a hydrogen evolution inhibitor is characterized by comprising the following components in parts by weight: 0.06-0.12 part of short fiber, 0.5-1.5 parts of barium sulfate, 0.3-1.5 parts of carbon, 0.1-0.15 part of lignin, 0.15-0.35 part of humic acid, 0.5-3 parts of zinc bismuthate and 93-98 parts of lead powder.
2. The lead-carbon battery anode material according to claim 1, wherein the short fiber is at least one selected from the group consisting of polyester fiber, polypropylene fiber, polyacrylonitrile fiber, modacrylic fiber, polyethylene fiber, and polyamide fiber; the carbon is at least one selected from activated carbon, carbon black, superconducting carbon black, carbon fiber, graphite and carbon nano tube.
3. The process for the preparation of zinc bismuthate according to any of claims 1 to 2, characterized in that it is prepared by a hydrothermal process comprising the steps of:
1) Adding sodium bismuthate and zinc acetate into water, stirring, and transferring into a reaction kettle;
2) Carrying out hydrothermal treatment on the reaction kettle at 120-210 ℃ for 12-24 hours, and cooling to room temperature; filtering, washing and drying.
4. The method for preparing zinc bismuthate according to claim 3, wherein the mass ratio of sodium bismuthate to zinc acetate in the step 1) is 1:1-1.5.
5. The method for preparing zinc bismuthate according to claim 3, wherein the hydrothermal treatment in step 2) is carried out at a temperature of 160-200 ℃ for 18-24 hours; the drying temperature in the step 2) is 50-70 ℃.
6. A lead-carbon battery anode comprising the lead-carbon battery anode material of any one of claims 1-2.
7. The preparation method of the lead-carbon battery cathode is characterized by comprising the following steps:
1) Firstly mixing short fibers, barium sulfate, carbon, lignin, humic acid and zinc bismuthate, and stirring to obtain mixed powder A;
2) Adding lead powder into the powder A, and stirring to obtain mixed powder B;
3) Putting the powder B into a paste mixing machine, sequentially adding water and dilute sulfuric acid, and stirring until the density is 4.1-4.5g/mL to obtain uniformly mixed lead paste C;
4) And uniformly coating the lead plaster C on the negative plate, and carrying out acid leaching, curing and drying.
8. The method for preparing the negative electrode of the lead-carbon battery according to claim 7, wherein the mass ratio of the water added in the step 3) to the lead powder in the step 2) is 0.12-0.15:1, a step of; the mass ratio of the addition amount of the dilute sulfuric acid in the step 3) to the lead powder in the step 2) is 0.072-0.087:1.
9. the method for preparing the negative electrode of the lead-carbon battery according to claim 7, wherein the specific operation of the step 3) is as follows: mixing the uniformly dispersed powder B with water, slowly adding a sulfuric acid solution with the concentration of 1.4g/mL, and controlling the temperature to be 25 ℃; the specific operation of the step 4) is as follows: and (3) coating the lead plaster C on a negative plate grid, wherein the weight of the negative plate grid is about 17.18g, the plaster amount of the lead plaster C of each negative plate is 38-42.5g according to design requirements, and the coated negative plate is subjected to acid leaching in sulfuric acid with the density of 1.10-1.20g/mL, the temperature is controlled to be 25 ℃, and then the negative plate is placed into a constant temperature and humidity chamber for solidification and drying.
10. The method for preparing the lead-carbon battery cathode according to claim 7, wherein the specific operations of surface drying and then solidification drying after pickling are as follows: the acid leached negative plate is immediately placed in a surface drying kiln and dried at 100-120 ℃ for 2-5min.
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