CN106252609A - Slow down the lead-acid accumulator anode diachylon that positive active material comes off - Google Patents

Slow down the lead-acid accumulator anode diachylon that positive active material comes off Download PDF

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Publication number
CN106252609A
CN106252609A CN201610723854.1A CN201610723854A CN106252609A CN 106252609 A CN106252609 A CN 106252609A CN 201610723854 A CN201610723854 A CN 201610723854A CN 106252609 A CN106252609 A CN 106252609A
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CN
China
Prior art keywords
active material
lead
positive active
slow down
anode diachylon
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201610723854.1A
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Chinese (zh)
Inventor
张燕
王军
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Sichuan United Electronic Technology Co Ltd
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Sichuan United Electronic Technology Co Ltd
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Publication date
Application filed by Sichuan United Electronic Technology Co Ltd filed Critical Sichuan United Electronic Technology Co Ltd
Priority to CN201610723854.1A priority Critical patent/CN106252609A/en
Publication of CN106252609A publication Critical patent/CN106252609A/en
Pending legal-status Critical Current

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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
    • H01M4/14—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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/56—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead
    • H01M4/57—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead of "grey lead", i.e. powders containing lead and lead oxide
    • 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

Abstract

The invention discloses and slow down the lead-acid accumulator anode diachylon that positive active material comes off, it is characterized in that, mixed by the raw material of following weight: Hydrocerussitum (Ceruse) 100, sulphuric acid 4～10, carbon materials 0.5, phosphoric acid 0.6, synthetic fibers 0.5, magnesium sulfate 0.3, wherein said synthetic fibers are 3～10 daniers.It is an object of the invention to provide and slow down the lead-acid accumulator anode diachylon that positive active material comes off, to alleviate in prior art along with losing connection between charge and discharge cycles, positive active material, holding caducous problem, realize slowing down coming off of positive active material, improve the purpose of service lifetime of accumulator.

Description

Slow down the lead-acid accumulator anode diachylon that positive active material comes off
Technical field
The present invention relates to lead plaster field, concretely relate to slow down the lead acid battery positive electrode that positive active material comes off Lead plaster.
Background technology
Positive/negative plate is parts the most crucial in accumulator, and the quality of positive/negative plate directly determines the electric discharge of accumulator Capacity and service life cycle.Along with the fast development of auto industry, more and more higher to the performance requirement of lead battery, wherein One of exactly accumulator is had higher requirement in service life under the high temperature conditions.Alkali formula sulphuric acid in anode diachylon The formation process again such as lead, lead oxide, lead sulfate is oxidized to PbO2Microporosity aggregation, and mutually knot becomes a continuous print Overall.Under normal circumstances, the cellular structure of positive active material can keep basicly stable, it is possible to stands the charge and discharge of thousands of times Electricity circulation.But under different ambient temperatures and discharge and recharge system, accumulator there will be different failure modes, and once active The structure of material is badly damaged, and discharge process is difficult to proceed.Under normal temperature condition, along with charge and discharge cycles, positive-active Substance P bO2Granule can taper into, and is reduced to PbSO4, gradually lose connection, the change of active substance aperture between granule greatly, macroscopic view Showing as active substance argillization, come off, time serious, pole plate overall structure is destroyed, it is impossible to be continuing with.
Summary of the invention
It is an object of the invention to provide and slow down the lead-acid accumulator anode diachylon that positive active material comes off, existing to alleviate Have in technology along with losing connection between charge and discharge cycles, positive active material, holding caducous problem, it is achieved slow down positive-active Coming off of material, improves the purpose of service lifetime of accumulator.
The present invention is achieved through the following technical solutions:
Slow down the lead-acid accumulator anode diachylon that positive active material comes off, it is characterised in that former by following weight Material mixes: Hydrocerussitum (Ceruse) 100, sulphuric acid 4～10, carbon materials 0.5, phosphoric acid 0.6, synthetic fibers 0.5, magnesium sulfate 0.3, Qi Zhongsuo Stating synthetic fibers is 3～10 daniers.
For in prior art along with losing connection between charge and discharge cycles, positive active material, holding caducous problem, this Invention proposition is a kind of slows down the lead-acid accumulator anode diachylon that positive active material comes off, wherein said carbon materials, phosphoric acid, conjunction Fiber, magnesium sulfate is become all to use as additive.Carbon materials belongs to high surface material, has higher adsorptivity, energy Well adsorbing electrolyte, thus improve sulfuric acid electrolyte to the contact of plate active material, infiltration, this improves work the most relatively The utilization rate of property material.Further, since the granule of carbon materials is very thin, in charge and discharge process, volume does not changes, It is possible to prevent contraction and the caking of active substance.The present invention adds phosphoric acid especially in formula, after phosphoric acid adds anode diachylon, Lead and metal can generate a kind of intermediate product Pb with phosphatizing3(PO4)2, the existence of this intermediate product, it is suppressed that grid Alloy and positive plate active substance PbO2PbO on interface2It is reduced to PbSO4Speed, particularly grid alloy with corrosion produce Transition zone between thing, in the presence of transition zone, grid alloy and the α-PbO of corrosion product internal layer2Between adhesion obtain Improve, so that corrosion product has preferable protective layer, the service life of grid alloy can be extended.Intermediate product Pb3(PO4)2 Generation, also improve grid corrosion internal layer α-PbO simultaneously2β-PbO with outer layer2Between adhesion, thus improve activity Substance P bO2With the cohesive force of grid, decrease coming off of active substance.It addition, the addition of phosphoric acid is to PbO2Electric discharge with sulphuric acid Course of reaction also has certain inhibitory action, thus can reduce PbO2Self discharge, improve battery charge capacity.Additionally, for increasing Adding the intensity of positive plate, prevent lead plaster from coming off, be additionally added synthetic fibers, wherein the consumption of synthetic fibers does not has enhancing pole very little The effect of plate intensity, consumption can fill more difficult too much to pole plate.Additionally, applicant finds the most afterwards, synthetic fibers Its effect increasing positive plate intensity is also had a significant impact by fineness degree, the synthetic fibers in specially 3～10 daniers, its lead Cream comes off and substantially slows down.Wherein danier is that textile industry commonly uses line density unit, characterizes fineness.Described magnesium sulfate is as one-tenth Hole agent adds, and it has good bonding capacity, magnesium sulfate and the lead oxide effect in anode diachylon, can generate lead oxide hydration Thing, this hydrate is when pole plate is dried, it is possible to generates crystalline texture in pole plate, therefore has good bonding effect, energy Coming off of enough reduction positive active materials further.
Further, one or more during described carbon materials is acetylene black, graphite, polyacene, carbon fiber.
Further, described carbon materials is graphite.In various carbon materialses, the resistance to oxidation degree of graphite is the highest, energy Enough make positive active material keep high porosity and strengthen electric conductivity, thus the initial capacity of battery can be improved and obtain preferably Charge acceptance.
Further, described graphite is can be by the superfine graphite of 200 eye mesh screens.To guarantee that graphite divides in additive Cloth is full and uniform, guarantees that graphite granule is sufficiently fine simultaneously, it is to avoid the contraction of active substance and caking.
Further, described synthetic fibers are acrylon or polypropylene.
Further, a length of the 3～5mm of described synthetic fibers.
The present invention compared with prior art, has such advantages as and beneficial effect:
1, the present invention slows down the lead-acid accumulator anode diachylon that positive active material comes off, and weight proportion is Hydrocerussitum (Ceruse) 100, sulphuric acid 4 ～10, carbon materials 0.5, phosphoric acid 0.6, synthetic fibers 0.5, magnesium sulfate 0.3；After phosphoric acid adds anode diachylon, lead and metal A kind of intermediate product Pb can be generated with phosphatizing3(PO4)2, the existence of this intermediate product, it is suppressed that grid alloy and positive pole Plate active substance PbO2PbO on interface2It is reduced to PbSO4Speed, the particularly mistake between grid alloy and corrosion product Cross layer, in the presence of transition zone, grid alloy and the α-PbO of corrosion product internal layer2Between adhesion improved so that Corrosion product has preferable protective layer, can extend the service life of grid alloy.Intermediate product Pb3(PO4)2Generation, simultaneously Also improve grid corrosion internal layer α-PbO2β-PbO with outer layer2Between adhesion, thus improve active substance PbO2With The cohesive force of grid, decreases coming off of active substance.It addition, the addition of phosphoric acid is to PbO2With the exoelectrical reaction process of sulphuric acid also There is certain inhibitory action, thus PbO can be reduced2Self discharge, improve battery charge capacity；Additionally, the synthetic fibers added Being the synthetic fibers in 3～10 daniers, its lead plaster comes off and substantially slows down.
Detailed description of the invention
For making the object, technical solutions and advantages of the present invention clearer, below in conjunction with embodiment, the present invention is made Further describing in detail, the exemplary embodiment of the present invention and explanation thereof are only used for explaining the present invention, are not intended as this The restriction of invention.
Embodiment 1:
Slow down the lead-acid accumulator anode diachylon that positive active material comes off, following raw materials according mix: Hydrocerussitum (Ceruse) 100g, sulphuric acid 4g, acetylene black 0.5g, phosphoric acid 0.6g, acrylon 0.5g, magnesium sulfate 0.3g；Wherein the fineness degree of acrylon is 3 daniers, the length of acrylon Degree is 3mm.
Embodiment 2:
Slow down the lead-acid accumulator anode diachylon that positive active material comes off, following raw materials according mix: Hydrocerussitum (Ceruse) 100g, sulphuric acid 4g, graphite 0.5g, phosphoric acid 0.6g, acrylon 0.5g, magnesium sulfate 0.3g；Wherein the fineness degree of acrylon is 3 daniers, the length of acrylon For 3mm.
Embodiment 3:
Slow down the lead-acid accumulator anode diachylon that positive active material comes off, following raw materials according mix: Hydrocerussitum (Ceruse) 100g, sulphuric acid 10g, graphite 0.5g, phosphoric acid 0.6g, acrylon 0.5g, magnesium sulfate 0.3g；Wherein the fineness degree of acrylon is 10 daniers, the length of acrylon Degree is 5mm.
Embodiment 4:
Slow down the lead-acid accumulator anode diachylon that positive active material comes off, following raw materials according mix: Hydrocerussitum (Ceruse) 100g, sulphuric acid 10g, polyacene 0.5g, phosphoric acid 0.6g, polypropylene 0.5g, magnesium sulfate 0.3g；Wherein the fineness degree of polypropylene is 6 daniers, polypropylene A length of 4mm.
With reference to embodiment 1:
Slow down the lead-acid accumulator anode diachylon that positive active material comes off, following raw materials according mix: Hydrocerussitum (Ceruse) 100g, sulphuric acid 4g, graphite 0.5g, acrylon 0.5g, magnesium sulfate 0.3g；Wherein the fineness degree of acrylon is 3 daniers, a length of 3mm of acrylon.
With reference to embodiment 2:
Slow down the lead-acid accumulator anode diachylon that positive active material comes off, following raw materials according mix: Hydrocerussitum (Ceruse) 100g, sulphuric acid 4g, graphite 0.5g, phosphoric acid 0.6g, acrylon 0.5g, magnesium sulfate 0.3g；Wherein the fineness degree of acrylon is 1 danier, the length of acrylon For 3mm.
With reference to embodiment 3:
Slow down the lead-acid accumulator anode diachylon that positive active material comes off, following raw materials according mix: Hydrocerussitum (Ceruse) 100g, sulphuric acid 4g, graphite 0.5g, phosphoric acid 0.6g, acrylon 0.5g, magnesium sulfate 0.3g；Wherein the fineness degree of acrylon is 12 daniers, the length of acrylon Degree is 3mm.
With reference to embodiment 4:
Slow down the lead-acid accumulator anode diachylon that positive active material comes off, following raw materials according mix: Hydrocerussitum (Ceruse) 100g, sulphuric acid 10g, graphite 0.5g, phosphoric acid 0.7g, polypropylene 0.5g, magnesium sulfate 0.3g；Wherein the fineness degree of polypropylene is 6 daniers, the length of polypropylene Degree is 4mm.
With reference to embodiment 5:
Slow down the lead-acid accumulator anode diachylon that positive active material comes off, following raw materials according mix: Hydrocerussitum (Ceruse) 100g, sulphuric acid 10g, graphite 0.5g, phosphoric acid 0.5g, polypropylene 0.5g, magnesium sulfate 0.3g；Wherein the fineness degree of polypropylene is 8 daniers, the length of polypropylene Degree is 4mm.
Table 1
Table 2
Wherein:
Table 1 is to use each embodiment and the lead-acid accumulator that is made with reference to anode diachylon in embodiment through 200 Positive active material expulsion rate after secondary discharge and recharge, on anode diachylon；
Table 2 is to use each embodiment and the lead-acid accumulator that is made with reference to anode diachylon in embodiment filling through 500 times Positive active material expulsion rate after electric discharge, on anode diachylon.
Embodiment 2 is whether add phosphoric acid with reference to embodiment 1 difference, experimental data can find, after adding phosphoric acid Additive, the expulsion rate of the positive active material on its anode diachylon substantially reduces, and shows to add in additive in the present invention Enter phosphoric acid and there is remarkable result.
Embodiment 1 is selected carbon materials with the difference of embodiment 2.Preferably graphite is as carbon materials, its effect Fruit is better than acetylene black.
Interval at claimed fineness degree with reference to the fineness degree of synthetic fibers in embodiment 2, reference embodiment 3 Outside, its effect has notable difference.
With reference to embodiment 4, do not meet the scope of protection of present invention with reference to phosphoric acid accounting in embodiment 5, its positive pole lead On cream, the positive active material degree that comes off is less than without degree during phosphoric acid, but also relative in the present invention, protected ratio is relatively High.
As it has been described above, the present invention can preferably realize reducing coming off of positive active material, improve service lifetime of accumulator Purpose.
Above-described detailed description of the invention, has been carried out the purpose of the present invention, technical scheme and beneficial effect further Describe in detail, be it should be understood that the detailed description of the invention that the foregoing is only the present invention, be not intended to limit the present invention Protection domain, all within the spirit and principles in the present invention, any modification, equivalent substitution and improvement etc. done, all should comprise Within protection scope of the present invention.

Claims (6)

1. slow down the lead-acid accumulator anode diachylon that positive active material comes off, it is characterised in that by following weight Raw material mixes: Hydrocerussitum (Ceruse) 100, sulphuric acid 4～10, carbon materials 0.5, phosphoric acid 0.6, synthetic fibers 0.5, magnesium sulfate 0.3, wherein Described synthetic fibers are 3～10 daniers.
The most according to claim 1 slow down the lead-acid accumulator anode diachylon that positive active material comes off, it is characterised in that: Described carbon materials is one or more in acetylene black, graphite, polyacene, carbon fiber.
The most according to claim 1 slow down the lead-acid accumulator anode diachylon that positive active material comes off, it is characterised in that: Described carbon materials is graphite.
The most according to claim 3 slow down the lead-acid accumulator anode diachylon that positive active material comes off, it is characterised in that: Described graphite is can be by the superfine graphite of 200 eye mesh screens.
The most according to claim 1 slow down the lead-acid accumulator anode diachylon that positive active material comes off, it is characterised in that: Described synthetic fibers are acrylon or polypropylene.
The most according to any one of claim 1 to 5 slow down the lead-acid accumulator anode diachylon that positive active material comes off, It is characterized in that: a length of the 3 of described synthetic fibers～5mm.
CN201610723854.1A 2016-08-25 2016-08-25 Slow down the lead-acid accumulator anode diachylon that positive active material comes off Pending CN106252609A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113675397A (en) * 2021-08-23 2021-11-19 浙江巨江电源制造有限公司 Deep-cycle long-life lead-acid storage battery lead paste for parking, battery thereof and manufacturing process method of battery

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58147963A (en) * 1982-02-25 1983-09-02 Shin Kobe Electric Mach Co Ltd Electrode plate for lead storage battery
JP2002141066A (en) * 2000-10-31 2002-05-17 Shin Kobe Electric Mach Co Ltd Control valve type lead acid battery
CN101707249A (en) * 2009-11-26 2010-05-12 风帆股份有限公司 Storage battery anode lead plaster capable of enhancing SAE standard high temperature service life and preparation method
CN103811751A (en) * 2012-11-13 2014-05-21 海洋王照明科技股份有限公司 Lead carbon battery anode diachylon as well as preparation method thereof, lead carbon battery anode plate as well as lead carbon battery

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58147963A (en) * 1982-02-25 1983-09-02 Shin Kobe Electric Mach Co Ltd Electrode plate for lead storage battery
JP2002141066A (en) * 2000-10-31 2002-05-17 Shin Kobe Electric Mach Co Ltd Control valve type lead acid battery
CN101707249A (en) * 2009-11-26 2010-05-12 风帆股份有限公司 Storage battery anode lead plaster capable of enhancing SAE standard high temperature service life and preparation method
CN103811751A (en) * 2012-11-13 2014-05-21 海洋王照明科技股份有限公司 Lead carbon battery anode diachylon as well as preparation method thereof, lead carbon battery anode plate as well as lead carbon battery

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113675397A (en) * 2021-08-23 2021-11-19 浙江巨江电源制造有限公司 Deep-cycle long-life lead-acid storage battery lead paste for parking, battery thereof and manufacturing process method of battery

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Application publication date: 20161221