CN105858717A - Preparation method of nano-scale tetrabasic lead sulfate storage battery additive - Google Patents

Preparation method of nano-scale tetrabasic lead sulfate storage battery additive Download PDF

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Publication number
CN105858717A
CN105858717A CN201610193257.2A CN201610193257A CN105858717A CN 105858717 A CN105858717 A CN 105858717A CN 201610193257 A CN201610193257 A CN 201610193257A CN 105858717 A CN105858717 A CN 105858717A
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lead
preparation
filtrate
nanoscale
battery additive
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CN105858717B (en
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王双印
严学庆
许文勇
赵荣兴
谭乃云
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Jiangsu Oliter Energy Technology Co., Ltd.
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Yangzhou Kaben Carbon Energy Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G21/00—Compounds of lead
    • C01G21/20—Sulfates
    • 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
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)

Abstract

The invention discloses a preparation method of a nano-scale tetrabasic lead sulfate storage battery additive. The preparation method comprises the following steps: 1) crushing waste lead acid storage batteries, adding the crushed batteries into a complex solution, performing stirring at 60-65 DEG C for 30-40 minutes, performing vacuum filtration, and removing filter residues; 2) keeping the temperature of the filtrate obtained in the step 1) at 60-65 DEG C, introducing carbon dioxide, then keeping the reaction temperature at 60-65 DEG C to perform a reaction for 30-40 minutes, and performing vacuum filtration to obtain a lead salt deposit and a complex filtrate; 3) returning the complex filtrate obtained in the step 2) to the step 1) for complex dissolution of a pretreated lead-containing material; and 4) dissolving the lead salt deposit obtained in the step 2) in sulfuric acid, performing stirring at a constant temperature of 75-80 DEG C for 30-35 minutes at a rotating speed of 600-1000r/min, then adding lead sulfate, performing stirring continuously for 3-4 hours, drying the mixture, and performing grinding and crushing to obtain powdery tetrabasic lead sulfate.

Description

A kind of preparation method of nanoscale four basic lead sulphate battery additive
Technical field
The invention belongs to lead-acid battery technical field of material, be specifically related to a kind of nanoscale four basic lead sulphate battery The preparation method of additive.
Background technology
Lead accumulator is because of its powerful, and abundant raw materials, the advantage such as cheap is all widely used in multiple fields. But using and storing process exists capacitance loss in early days, causing electrical property to decline rapidly, so preferably solving electricity Pond capacitance loss in early days is greatly improved every electrical property and the cycle life of battery.
Four basic lead sulphates (hereinafter referred to as 4BS) exist as intermediate forms in positive pole, and lead-acid accumulator can be avoided to hold Amount decay in early days.The most generally improve 4BS content in lead plaster, in Battery formation mistake with raising and cream or solidification temperature Cheng Zhong, 4BS can occur oxidation reaction to be converted into a large amount of compact grained PbO2, it is linked to be porous PbO2Fine grain gathers Collective. this aggregation is plesiomorphism original with 4BS in terms of configuration.The PbO that this process obtains2Structural strength Than the PbO come by 3BS inversion of phases2Much bigger, the pole plate mechanical strength of formation increases, thus extends battery and use Life-span.It addition, application 4BS presses in a certain amount of addition anode diachylon as additive, it is possible to achieve both increased battery and held Amount extends again the effect of battery life.
Commonly used along with lead-acid accumulator, the problem that the recovery of lead-acid accumulator is also become social concerns.At present Lead-acid accumulator recovery method mostly be hydrometallurgic recovery lead.Concrete processing method is: lead mud separating reducing takes off Sulfur recovery lead product and accessory substance.In patent CN101514395A " method of recovering lead oxide by waste lead-acid storage battery " In mention Reducing Lead mud method use oxalic acid reducing process, desulfurization use ammonium carbonate method, the weak point of this method be raw material grass Acid and ammonium carbonate price are high, cause production cost high.The production method of tribasic lead sulfate is to make lead sulfate and burning in water Alkali reacts, and generates tribasic lead sulfate and sal glauberi, owing to sal glauberi dehydration expends energy anhydrous slufuric acid simultaneously Sodium (glauber salt) is cheap, causes byproduct sal glauberi to process and has difficulties.
Summary of the invention
Goal of the invention: for weak point of the prior art, the invention provides a kind of nanoscale four basic lead sulphate and stores The preparation method of additives for battery.
Technical scheme: the preparation method of nanoscale four basic lead sulphate battery additive of the present invention, including walking as follows Rapid:
Step 1) waste and old lead-acid accumulator is pulverized, add in complex solution, at 60～65 DEG C, stir 30～40min, Filtration under diminished pressure, removes filter residue；
Step 2) by step 1) in the filtrate that obtains keep 60～65 DEG C and be passed through carbon dioxide, then keep 60～65 DEG C Reaction temperature reaction 30～40min, filtration under diminished pressure, obtain lead salt precipitation and complexing filtrate；
Step 3) by above-mentioned steps 2) in complexing filtrate be back to step 1) in be used for being complexed dissolving after pretreatment Lead-containing material.
Step 4) by above-mentioned steps 2) in lead salt precipitation vitriolization in, at 75～80 DEG C constant temperature stirring, rotating speed is 600-1000 rev/min, add lead sulfate after stirring 30～35min, continue stirring 3～4h；Mixture is dried, Grind, obtain powder four basic lead sulphate.
Described complex solution is: concentration is the arginine of 1.25mol/L and mixing water that concentration is 0.5mol/L histidine Solution.
The carbon dioxide being passed through meets following condition: relative to the dissoluble lead ion in the above-mentioned leaded filtrate of 1mol, The consumption of carbon dioxide is 0.5mol.
Lead salt is 9:1 with the mol ratio of sulfuric acid.Lead sulfate is 1:1 with the mol ratio of sulfuric acid.
After adding lead sulfate, mend and add deionized water dilution so that mixture presents half suspended state in mixing container.
Further, the present invention another characteristic is that after being dried by mixture, at being placed in-20 DEG C, freezes 2h, Being ground pulverizing, obtained product pellet is thinner, and purity is higher again.
Beneficial effect: 1, with waste and old lead acid accumulator as raw material, final product is applied in lead-acid accumulator, battery system Other impurity are not introduced, to battery performance without any harmful effect in Bei.Raw material is identical with lead-acid storage battery production raw material, Be suitable to lead-acid battery enterprise produce, during design production line, Minifab can be separated on production line for manufacturing battery limit, it is easier to Industrialization.Product purity is high, particle diameter is little, particle diameter distribution is homogeneous, can significantly improve battery pole plates intensity as additive, Reduce the loss of battery initial capacity, extend battery cycle life.
Detailed description of the invention:
Embodiment 1
Step 1) waste and old lead-acid accumulator to be pulverized, in addition complex solution, (concentration is the arginine of 1.25mol/L With the mixed aqueous solution that concentration is 0.5mol/L histidine), at 60 DEG C, stir 30min, filtration under diminished pressure, remove filter residue.
Step 2) by step 1) in the filtrate that obtains keep 60 DEG C and be passed through carbon dioxide (above-mentioned relative to 1mol Dissoluble lead ion in leaded filtrate, the consumption of carbon dioxide is 0.5mol), then keep the reaction temperature of 60 DEG C Reaction 30min, decompression comes, and obtains lead salt precipitation and complexing filtrate.
Step 3) by above-mentioned steps 2) in complexing filtrate be back to step 1) in be used for being complexed warp in dissolving the present embodiment Cross pretreated lead-containing material.
Step 4) by above-mentioned steps 2) in lead salt precipitation vitriolization (lead with sulfate radical mol ratio be 9:1) in, Constant temperature stirring at 75 DEG C, rotating speed is 600-1000 rev/min, adds lead sulfate, mend and add deionized water after stirring 30min Dilution so that mixture presents half suspended state in mixing container, continues stirring 3h；Carry out mixture drying, grinding Abrasive dust is broken, obtains powder four basic lead sulphate.
Embodiment 2
Step 1) waste and old lead-acid accumulator to be pulverized, in addition complex solution, (concentration is the arginine of 1.25mol/L With the mixed aqueous solution that concentration is 0.5mol/L histidine), at 65 DEG C, stir 40min, filtration under diminished pressure, remove filter residue.
Step 2) by step 1) in the filtrate that obtains keep 65 DEG C and be passed through carbon dioxide (above-mentioned relative to 1mol Dissoluble lead ion in leaded filtrate, the consumption of carbon dioxide is 0.5mol), the reaction temperature then keeping 65 DEG C is anti- Answer 40min, decompression to come, obtain lead salt precipitation and complexing filtrate.
Step 3) by above-mentioned steps 2) in complexing filtrate be back to step 1) in be used for being complexed warp in dissolving the present embodiment Cross pretreated lead-containing material.
Step 4) by above-mentioned steps 2) in lead salt precipitation vitriolization (lead with sulfate radical mol ratio be 9:1) in, Constant temperature stirring at 80 DEG C, rotating speed is 600-1000 rev/min, adds lead sulfate, mend and add deionized water after stirring 40min Dilution so that mixture presents half suspended state in mixing container, continues stirring 4h；Carry out mixture drying, grinding Abrasive dust is broken, obtains powder four basic lead sulphate.
Embodiment 3
Step 1) waste and old lead-acid accumulator to be pulverized, in addition complex solution, (concentration is the arginine of 1.25mol/L With the mixed aqueous solution that concentration is 0.5mol/L histidine), at 60 DEG C, stir 30min, filtration under diminished pressure, remove filter residue.
Step 2) by step 1) in the filtrate that obtains keep 60 DEG C and be passed through carbon dioxide (above-mentioned relative to 1mol Dissoluble lead ion in leaded filtrate, the consumption of carbon dioxide is 0.5mol), then keep the reaction temperature of 60 DEG C Reaction 30min, decompression comes, and obtains lead salt precipitation and complexing filtrate.
Step 3) by above-mentioned steps 2) in complexing filtrate be back to step 1) in be used for being complexed warp in dissolving the present embodiment Cross pretreated lead-containing material.
Step 4) by above-mentioned steps 2) in lead salt precipitation vitriolization (lead with sulfate radical mol ratio be 9:1) in, Constant temperature stirring at 75 DEG C, rotating speed is 600-1000 rev/min, adds lead sulfate, mend and add deionized water after stirring 30min Dilution so that mixture presents half suspended state in mixing container, continues stirring 3h；Mixture is dried, puts At-20 DEG C, freeze 2h, grind, obtain powder four basic lead sulphate.
Embodiment 4
Step 1) waste and old lead-acid accumulator to be pulverized, in addition complex solution, (concentration is the arginine of 1.25mol/L With the mixed aqueous solution that concentration is 0.5mol/L histidine), at 65 DEG C, stir 40min, filtration under diminished pressure, remove filter residue.
Step 2) by step 1) in the filtrate that obtains keep 65 DEG C and be passed through carbon dioxide (above-mentioned relative to 1mol Dissoluble lead ion in leaded filtrate, the consumption of carbon dioxide is 0.5mol), the reaction temperature then keeping 65 DEG C is anti- Answer 40min, decompression to come, obtain lead salt precipitation and complexing filtrate.
Step 3) by above-mentioned steps 2) in complexing filtrate be back to step 1) in be used for being complexed warp in dissolving the present embodiment Cross pretreated lead-containing material.
Step 4) by above-mentioned steps 2) in lead salt precipitation vitriolization (lead with sulfate radical mol ratio be 9:1) in, Constant temperature stirring at 80 DEG C, rotating speed is 600-1000 rev/min, adds lead sulfate, mend and add deionized water after stirring 40min Dilution so that mixture presents half suspended state in mixing container, continues stirring 4h；Mixture is dried, puts At-20 DEG C, freeze 2h, grind, obtain powder four basic lead sulphate.
In embodiment 1～embodiment 4, the purity of products obtained therefrom see table
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4
Purity 95.1% 97.8% 98.4% 99.2%

Claims (7)

1. the preparation method of a nanoscale four basic lead sulphate battery additive, it is characterised in that comprise the steps:
Step 1) waste and old lead-acid accumulator is pulverized, add in complex solution, at 60～65 DEG C, stir 30～40min, Filtration under diminished pressure, removes filter residue；
Step 2) by step 1) in the filtrate that obtains keep 60～65 DEG C and be passed through carbon dioxide, then keep 60～65 DEG C Reaction temperature reaction 30～40min, filtration under diminished pressure, obtain lead salt precipitation and complexing filtrate；
Step 3) by above-mentioned steps 2) in complexing filtrate be back to step 1) in be used for being complexed dissolving after pretreatment Lead-containing material；
Step 4) by above-mentioned steps 2) in lead salt precipitation vitriolization in, at 75～80 DEG C constant temperature stirring, rotating speed is 600-1000 rev/min, add lead sulfate after stirring 30～40min, continue stirring 3～4h；Mixture is dried, Grind, obtain powder four basic lead sulphate.
The preparation method of nanoscale four basic lead sulphate battery additive the most according to claim 1, its feature It is that described complex solution is: concentration is the arginine of 1.25mol/L and mixing water that concentration is 0.5mol/L histidine Solution.
The preparation method of nanoscale four basic lead sulphate battery additive the most according to claim 1, its feature It is that be passed through carbon dioxide meets following condition: relative to the dissoluble lead ion in the above-mentioned leaded filtrate of 1mol, The consumption of carbon dioxide is 0.5mol.
The preparation method of nanoscale four basic lead sulphate battery additive the most according to claim 1, its feature It is that lead salt is 9:1 with the mol ratio of sulfuric acid.
The preparation method of nanoscale four basic lead sulphate battery additive the most according to claim 1, its feature It is that lead sulfate is 1:1 with the mol ratio of sulfuric acid.
The preparation method of nanoscale four basic lead sulphate battery additive the most according to claim 1, its feature After being to add lead sulfate, mend and add deionized water dilution so that mixture presents half suspended state in mixing container.
The preparation method of nanoscale four basic lead sulphate battery additive the most according to claims 1 to 6, it is special Levy after being to dry mixture, at being placed in-20 DEG C, freeze 2h, then be ground pulverizing.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109052458A (en) * 2018-10-19 2018-12-21 阳煤集团山西吉天利科技有限公司 The preparation process of four basic lead sulphate crystal seed of nanoscale is prepared using waste lead accumulator

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103413937A (en) * 2013-08-29 2013-11-27 天能集团江苏特种电源有限公司 Method for synthesizing high-purity four-basic lead sulfate and application thereof
CN103526016A (en) * 2012-07-02 2014-01-22 张超 Method for recovering lead-containing raw material by using wet process
CN103803641A (en) * 2012-12-17 2014-05-21 天能电池(芜湖)有限公司 Preparation method of four-alkali sulfuric acid lead
CN104789776A (en) * 2014-01-16 2015-07-22 北京化工大学 Method for recovering lead oxide from waste containing lead oxide

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103526016A (en) * 2012-07-02 2014-01-22 张超 Method for recovering lead-containing raw material by using wet process
CN103803641A (en) * 2012-12-17 2014-05-21 天能电池(芜湖)有限公司 Preparation method of four-alkali sulfuric acid lead
CN103413937A (en) * 2013-08-29 2013-11-27 天能集团江苏特种电源有限公司 Method for synthesizing high-purity four-basic lead sulfate and application thereof
CN104789776A (en) * 2014-01-16 2015-07-22 北京化工大学 Method for recovering lead oxide from waste containing lead oxide

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109052458A (en) * 2018-10-19 2018-12-21 阳煤集团山西吉天利科技有限公司 The preparation process of four basic lead sulphate crystal seed of nanoscale is prepared using waste lead accumulator

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