CN105006546A - Technology for preparing antimony-carbon composite fiber electrode material by using lead anode mud - Google Patents
Technology for preparing antimony-carbon composite fiber electrode material by using lead anode mud Download PDFInfo
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- CN105006546A CN105006546A CN201510397210.3A CN201510397210A CN105006546A CN 105006546 A CN105006546 A CN 105006546A CN 201510397210 A CN201510397210 A CN 201510397210A CN 105006546 A CN105006546 A CN 105006546A
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a technology for preparing an antimony-carbon composite fiber electrode material by using lead anode mud. The technology comprises the following steps: processing the lead anode mud by using diluted nitric acid, hydrochloric acid and tartaric acid to obtain a tartaric acid-containing antimony chloride solution; adding a carbon agent and a fiber forming agent to the solution to prepare a precursor solution, pouring the precursor solution into a double-stick thread throwing centrifuge, and carrying out thread throwing to obtain raw electrode threads; and drying the raw electrode threads, and calcining in hydrogen atmosphere to obtain the electrode material. The technology has the characteristics of simplicity, low cost, and good performances of the above obtained product.
Description
Technical field
The present invention relates to the electrode fabrication techniques of battery, particularly one is used for the preparation method of the electrode material of lithium (sodium) battery.
Background technology
At present, the research of high performance lithium ion battery (lithium battery) and electrode material thereof is the focus of the area researches such as electrochemistry, materials chemistry, physics, and the character of the sodium ion and lithium ion that are all periodic table of elements I main group has many similarities, sodium ion equally with lithium ion can construct a kind of widely used secondary cell completely.And sodium-ion battery is compared with lithium ion battery, the cost of raw material is lower than lithium battery, half-cell prtential (E higher than lithium battery
0Na+/ Na=E
0Li+/ Li+0.3V), be applicable to adopting the lower electrolyte of decomposition voltage, thus security performance better [Jia Xuping, Chen Mei. sodium ion battery electrode material progress [J]. research institute of China Electronics journal, 2012,7 (6): 581-585].
Compared with material with carbon element, metal and alloy have higher theoretical capacity, and higher intercalation potential has good security performance, has caused the attention of people.Particularly tin pewter because tin and antimony two kinds of elements can with lithium generation alloying reaction (Li
22sn
5: 994mAh/g, Li
3sb:660mAh/g), there is higher theoretical capacity, show good electrochemical behavior, a kind of kamash alloy class negative material [Wang Zhong got a good chance of, Tian Wenhuai, Li Xingguo. tin pewter/graphite composite material is as the research [J] of lithium ion battery negative. functional material, 2007,38 (1): 109-112].
Because the radius of sodium ion is large compared with lithium ion radius, sodium-ion battery is when discharge and recharge, when sodium ion embed and embedding go out in process, the change of electrode material lattice parameter, and the crystal transfer (as being noncrystal from crystalline transformation) that some electrode material occurs, can stress be produced in electrode material, even cause the change of electrode material granules diameter or volume.The change of this stress and volume, will cause electrode material to ftracture, disintegrate and come off, and lose the connection with current collector, expose the surface made new advances in the electrolyte, finally cause losing of electrochemistry capacitance.
For improving the change in volume problem that electrode material produces in charge and discharge process, current development trend is: the active material of electrode material is prepared into nano particle.But the particle diameter of nano particle is less, the activity substance content of unit volume is lower, causes volume energy density lower.
Waste residue (hereinafter referred to as antimony slag) after plumbous electrolysis anode sludge integrated treatment, antimony content is about 50%, all the other are insoluble impurities (as silt etc.) and soluble impurity (mainly iron ion, arsenic ion, lead ion etc.) [Wang Xiran, Wang Jin, storehouse is to brightness. the technical study [J] that after plumbous electrolysis anode sludge integrated treatment, antimony reclaims. and coloured mining and metallurgy, 2008,24 (6): 30-32].
With the antimony in the antimony slag after the integrated treatment of Leaching in Hydrochloric Acid lead anode slurry, then utilize hydrolysis removing impurities ion, trivalent antimony hydrolysis is produced solid compounds and is entered slag, and other foreign ion stays in the solution.Recycling ammonia neutralization, obtain after washing drying stibium trioxide product [the bright brightness of grain, Liu Wanli, Xie Zhaofeng, etc. reclaim the method [P] of antimony a kind of antimony slag after lead anode slurry integrated treatment, Chinese patent 201410246801.6,2014.06.06].
Also have a kind of method being produced silver nitrate, recovery copper, lead, antimony by lead anode slurry, be made up of following steps: (1) nitric acid leaches; (2) filter residue uses Leaching in Hydrochloric Acid again; (3) filtrate sulfuric acid depositing; (4) hydrochloric acid leachate is hydrolyzed; (5) alkali cleaning hydrolysis gained filter residue; (6), in the filtrate after sulfuric acid depositing, the heavy silver of hydrochloric acid is carried out; (7) merge (2), (8) gained filter residue, carry out ammonia leaching, complexing, reduction, produces silver nitrate; (8) add alkali neutralization in the filtrate obtained (five), then add sulfide for precipitation of copper; (9) filtrate that merging (5), (8) obtain, dearsenification, obtained clear liquid and arsenic slag; The slag that this patent step (5) obtains is mainly the hydrolysate of antimony.[Li Xinyong, Zheng Lide, Pei Houlong. produced silver nitrate by lead anode slurry, reclaimed the method [P] of copper, lead, antimony, Chinese patent CN90109944.9,1990.12.06].
Above two patent documentations, after being all hydrolyzed by the hydrochloric acid solution of antimony, obtaining the hydrolysate of antimony, then are neutralized, dry, obtain antimony oxide product.As being that electrode material prepared by raw material with antimony oxide product, with hydrochloric acid, antimony oxide need being dissolved again, obtaining antimony chloride solution.As the antimony chloride solution that direct lead anode slurry leaches, will technological process be reduced, reduce costs.
Summary of the invention
The object of this invention is to provide a kind of method directly preparing electrode material with the antimony chloride solution that lead anode slurry leaches.
For reaching above object, the present invention takes following technical scheme to be achieved:
Lead anode slurry prepares a technique for antimony-carbon composite fibre electrode material, it is characterized in that, comprises the steps:
(1) fall iron in lead anode slurry and lead with dilute nitric acid dissolution, after solid-liquor separation, then use the antimony in dissolving with hydrochloric acid solid phase and arsenic, obtain the mixed solution of arsenic and antimony;
(2) in the solution of arsenic and antimony, add tartaric acid and water, obtain the hydrolytic precipitation thing of arsenic and tartrated antimony chloride solution;
(3) add the processbearing astrocyte agent of the carbon agent of 200% of antimony quality and the 10-50% of antimony quality at tartrated antimony chloride solution, be uniformly mixed, obtain precursor solution;
(4) precursor solution is poured in two rod tumbling machine and get rid of silk, obtain fibrous electrodes precursor;
(5) fibrous electrodes precursor is dry, be then heated to 600 DEG C in a hydrogen atmosphere and burn till, be incubated 1 hour, the final fiber electrode material obtaining antimony and carbon compound.
In above-mentioned technique, in described tartrated antimony chloride solution, the molar concentration of antimony is 1mol/L, and tartaric molar concentration is 2mol/L.Described carbon agent is the one in sucrose, glucose.Described processbearing astrocyte agent is any one in polyvinylpyrrolidone, polyvinyl alcohol, macrogol.
Advantage of the present invention is:
1, because antimony dissolves in tartaric acid solution, arsenic can only be dissolved in concentrated hydrochloric acid solution, therefore adds tartaric acid and water in the solution, obtains the hydrolytic precipitation of tartrated antimony chloride solution and arsenic.This method can reduce technological process, reduces costs.
2, in precursor solution, add carbon agent and processbearing astrocyte agent, two kinds of materials are organic substance, after fiber calcination, cushioning the mutually main form with carbon is present in fiber, be conducive to the stress alleviating antimony volumetric expansion generation, also can retrain the cracking that electrode material antimony particle produces, improve electrode material cycle performance, improve the useful life of battery.The carbon cushioned in phase forming agent has good electric conductivity in addition, when preparing battery, without the need to adding conductive agent and binding agent, further simplify preparation technology.
3, adopt two rod to get rid of a technique, obtain superfine fibre, be conducive to electrode material and contact with electrolytical, shorten the migration distance of sodium ion, be conducive to the charge-discharge velocity improving battery.
According to method of the present invention, by adjustment formula composition, the combination electrode material fibre diameter obtained is 2-8 μm, and circulate after 50 times, charge/discharge capacity is up to 460mAh/g, and properties of product are good.
To sum up, present invention process is simple, cost is low, good product performance, and adopts industrial residue to prepare the electrode material of high added value, has good economic benefit and environmental benefit.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail.
Lead anode slurry prepares a technique for antimony-carbon composite fibre electrode material, comprises the steps:
(1) fall iron in lead anode slurry and lead with dilute nitric acid dissolution, after solid-liquor separation, then use the antimony in dissolving with hydrochloric acid solid phase and arsenic, obtain the mixed solution of arsenic and antimony;
(2) in the solution of arsenic and antimony, add tartaric acid and water, obtain the hydrolytic precipitation thing of arsenic and tartrated antimony chloride solution, wherein the molar concentration of antimony is 1mol/L, and tartaric molar concentration is 2mol/L;
(3) preparation of precursor solution
Add carbon agent and processbearing astrocyte agent at tartrated antimony chloride solution, obtain precursor solution, wherein, carbon agent is the one in sucrose, glucose, and addition is 200% of antimony quality; Processbearing astrocyte agent is any one in polyvinylpyrrolidone, polyvinyl alcohol, macrogol, and addition is the 10-50% of antimony quality;
Table 1 lists the formula composition of 9 embodiments being numbered 1-9.
The formula of table 1 raw material
Note: the quality of antimony, according in tartrated antimony chloride solution, the concentration (100g/L) of antimony calculates.
(4) precursor solution of step (3) gained is poured in two rod tumbling machine, adopt to obtain the precursor of fibrous electrodes;
(5) fibrous electrodes precursor step (4) obtained is dry, is then heated to 600 DEG C in a hydrogen atmosphere, is incubated and burns till for 1 hour, the final fiber electrode material obtaining antimony and carbon compound.
The fibre diameter of above different embodiment gained composite fibre electrode material lists in table 2.Be to electrode with these composite fibre electrode materials as negative pole, sodium metal, after being assembled into battery, carry out cycle charge discharge electrical testing, the circulate charge/discharge capacity after 50 times and capability retention are shown in table 2.
The performance of table 2 combination electrode material fiber
| Embodiment | Diameter (μm) | Charge/discharge capacity (mAh/g) | Capability retention (%) |
| 1 | 2 | 460 | 96 |
| 2 | 8 | 410 | 90 |
| 3 | 3 | 460 | 95 |
| 4 | 4 | 450 | 92 |
| 5 | 5 | 440 | 93 |
| 6 | 8 | 400 | 90 |
| 7 | 4 | 460 | 95 |
| 8 | 6 | 420 | 91 |
| 9 | 7 | 420 | 90 |
As can be seen from Table 2, combination electrode fiber prepared by the inventive method, wherein the composite fibre discharge capacity of embodiment 5 can up to 460mAh/g, and capability retention can reach 96%.
Claims (4)
1. prepare a technique for antimony-carbon composite fibre electrode material with lead anode slurry, it is characterized in that, comprise the steps:
(1) fall iron in lead anode slurry and lead with dilute nitric acid dissolution, after solid-liquor separation, then use the antimony in dissolving with hydrochloric acid solid phase and arsenic, obtain the mixed solution of arsenic and antimony;
(2) in the solution of arsenic and antimony, add tartaric acid and water, obtain the hydrolytic precipitation thing of arsenic and tartrated antimony chloride solution;
(3) add the processbearing astrocyte agent of the carbon agent of 200% of antimony quality and the 10-50% of antimony quality at tartrated antimony chloride solution, be uniformly mixed, obtain precursor solution;
(4) precursor solution is poured in two rod tumbling machine and get rid of silk, obtain fibrous electrodes precursor;
(5) fibrous electrodes precursor is dry, be then heated to 600 DEG C in a hydrogen atmosphere and burn till, be incubated 1 hour, the final fiber electrode material obtaining antimony and carbon compound.
2. lead anode slurry as claimed in claim 1 prepares the technique of antimony-carbon composite fibre electrode material, it is characterized in that, in described tartrated antimony chloride solution, the molar concentration of antimony is 1mol/L, and tartaric molar concentration is 2mol/L.
3. lead anode slurry as claimed in claim 1 prepares the technique of antimony-carbon composite fibre electrode material, it is characterized in that, described carbon agent is the one in sucrose, glucose.
4. lead anode slurry as claimed in claim 1 prepares the technique of antimony-carbon composite fibre electrode material, it is characterized in that, described processbearing astrocyte agent is any one in polyvinylpyrrolidone, polyvinyl alcohol, macrogol.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1062175A (en) * | 1990-12-06 | 1992-06-24 | 昆明化工厂 | Produce the method for Silver Nitrate, recovery copper, lead, antimony by lead anode slurry |
| CN101787440A (en) * | 2010-03-29 | 2010-07-28 | 广西华锡集团股份有限公司 | Method for wet processing of high antimony-lead anode mud |
| JP2012119078A (en) * | 2010-11-29 | 2012-06-21 | Asahi Glass Co Ltd | Method for manufacturing electrode mixture for power storage device |
| CN104046796A (en) * | 2014-06-06 | 2014-09-17 | 郴州市金贵银业股份有限公司 | Method for recovering antimony from antimony slag after comprehensive treatment of lead anode sludge |
| CN104157841A (en) * | 2014-08-14 | 2014-11-19 | 陕西理工学院 | Preparation process of composite fiber electrode material for sodium-ion battery |
-
2015
- 2015-07-08 CN CN201510397210.3A patent/CN105006546B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1062175A (en) * | 1990-12-06 | 1992-06-24 | 昆明化工厂 | Produce the method for Silver Nitrate, recovery copper, lead, antimony by lead anode slurry |
| CN101787440A (en) * | 2010-03-29 | 2010-07-28 | 广西华锡集团股份有限公司 | Method for wet processing of high antimony-lead anode mud |
| JP2012119078A (en) * | 2010-11-29 | 2012-06-21 | Asahi Glass Co Ltd | Method for manufacturing electrode mixture for power storage device |
| CN104046796A (en) * | 2014-06-06 | 2014-09-17 | 郴州市金贵银业股份有限公司 | Method for recovering antimony from antimony slag after comprehensive treatment of lead anode sludge |
| CN104157841A (en) * | 2014-08-14 | 2014-11-19 | 陕西理工学院 | Preparation process of composite fiber electrode material for sodium-ion battery |
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