CN105006546B - 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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- CN105006546B CN105006546B CN201510397210.3A CN201510397210A CN105006546B CN 105006546 B CN105006546 B CN 105006546B CN 201510397210 A CN201510397210 A CN 201510397210A CN 105006546 B CN105006546 B CN 105006546B
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- antimony
- electrode material
- lead anode
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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
- H01M4/139—Processes of manufacture
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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
- 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 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, more particularly to a kind of system of the electrode material for lithium (sodium) battery
Preparation Method.
Background technology
At present, the research of high performance lithium ion battery (lithium battery) and its electrode material is electrochemistry, materials chemistry, physics
Learn etc. area research focus, and the property of the sodium ion and lithium ion for being all periodic table of elements I main groups have it is many it is similar it
Place, sodium ion is can to construct a kind of widely used secondary cell as lithium ion completely.And sodium-ion battery and lithium
Ion battery is compared, and the cost of raw material is lower than lithium battery, half-cell prtential (E higher than lithium battery0Na+/ Na=E0Li+/ Li+0.3V),
Be adapted to using the lower electrolyte of decomposition voltage, thus security performance more preferably [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 safety
Performance, has caused the attention of people.Particularly tin pewter, because two kinds of elements of tin and antimony can occur alloying reaction with lithium
(Li22Sn5：994mAh/g, Li3Sb：660mAh/g), there is higher theoretical capacity, it is shown that preferable electrochemical behavior, is one
Kind get a good chance of kamash alloy class negative material [Wang Zhong, Tian Wenhuai, Li Xingguo. tin pewter/graphite composite material is used as lithium
The research [J] of ion battery negative pole. functional material, 2007,38 (1)：109-112].
Due to the radius of sodium ion it is big compared with lithium ion radius, sodium-ion battery in discharge and recharge, when sodium ion it is embedded and embedding
During going out, the change of electrode material lattice parameter, and the crystal transfer that some electrode materials occur (is non-such as from crystalline transformation
Crystal), stress, or even the change for causing electrode material granules diameter or volume can be produced in electrode material.This stress and
The change of volume, will cause electrode material cracking, disintegrates and come off, and lose the connection with current collector, in the electrolyte cruelly
Expose new surface, finally result in losing for electrochemistry capacitance.
To improve the Volume Changes problem that electrode material is produced in charge and discharge process, current development trend is：By electricity
The active material of pole material is prepared into nano particle.But the particle diameter of nano particle is less, the activity substance content of unit volume compared with
It is low, cause volume energy density relatively low.
Waste residue (hereinafter referred to as antimony slag) after lead electrolysis anode sludge integrated treatment, 50% or so, remaining is not for for antimony content
Solubility impurity (such as silt) and soluble impurity (mainly iron ion, arsenic ion, lead ion etc.) [Wang Xiran, Wang Jin, storehouse to
Brightness. the technical study [J] that antimony is reclaimed after lead electrolysis anode sludge integrated treatment. coloured mining and metallurgy, 2008,24 (6)：30-32].
With the antimony in the antimony slag after salt Ore Leaching lead anode slurry integrated treatment, then using hydrolysis separate impurity from
Son, trivalent antimony hydrolysis production solid compounds enter slag, and other foreign ions are stayed in the solution.Ammoniacal liquor neutralization, Jing is recycled to wash
Wash be dried after obtain stibium trioxide product [the bright brightness of grain, Liu Wanli, Xie Zhaofeng, etc. in the antimony slag after a kind of integrated treatment from lead anode slurry
Reclaim the method [P] of antimony, Chinese patent 201410246801.6,2014.06.06].
Also a kind of method produced silver nitrate by lead anode slurry, reclaim copper, lead, antimony, comprises the steps of：(1) nitre
Ore Leaching；(2) filter residue uses again salt Ore Leaching；(3) filtrate sulfuric acid depositing；(4) hydrochloric acid leachate is hydrolyzed；(5) alkali cleaning hydrolysis institute
Obtain 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
Go out, be complexed, silver nitrate is produced in reduction；(8) add alkali neutralization in the filtrate that (five) obtain, add sulfide for precipitation of copper；(9) close
And (5), filtrate obtained in (8), dearsenification, clear liquid and arsenic slag is obtained；The slag that the patent step (5) is obtained is mainly the hydrolysis of antimony and produces
Thing.[Li Xinyong, Zheng Lide, Pei Houlong. produced silver nitrate, reclaimed the method [P] of copper, lead, antimony, Chinese patent by lead anode slurry
CN90109944.9,1990.12.06].
Two above patent document, by the hydrolysis of the hydrochloric acid solution of antimony after, obtain the hydrolysate of antimony, then neutralized,
Drying, obtains aoxidizing antimony product.It is that raw material prepares electrode material such as with oxidation antimony product, again need to be dissolved antimony oxide with hydrochloric acid,
Obtain antimony chloride solution.Such as the antimony chloride solution for directly being leached with lead anode slurry, technological process, reduces cost will be reduced.
The content of the invention
It is an object of the invention to provide a kind of directly prepare electrode material with the antimony chloride solution of lead anode slurry leaching
Method.
To reach object above, the present invention is adopted the following technical scheme that and is achieved：
The technique that a kind of lead anode slurry prepares antimony-carbon composite fibre electrode material, it is characterised in that including following steps
Suddenly：
(1) iron and lead in lead anode slurry is fallen with dilute nitric acid dissolution, after solid-liquor separation, then with the antimony in dissolving with hydrochloric acid solid phase
And arsenic, obtain the mixed solution of arsenic and antimony；
(2) tartaric acid and water are added in the solution of arsenic and antimony, the hydrolytic precipitation thing of arsenic and tartrated chlorination is obtained
Antimony solution；
(3) fibre of the 10-50% of the carbon agent and antimony quality of the 200% of antimony quality is added in tartrated antimony chloride solution
Dimension forming agent, is uniformly mixed, and obtains precursor solution；
(4) precursor solution is poured in double rod tumbling machines and gets rid of silk, obtain fibrous electrodes precursor；
(5) fibrous electrodes precursor is dried, 600 DEG C is then heated in a hydrogen atmosphere and is burnt till, be incubated 1 hour, most
The fiber electrode material that antimony is combined with carbon is obtained eventually.
In above-mentioned technique, in the tartrated antimony chloride solution, the molar concentration of antimony is 1mol/L, tartaric to rub
Your concentration is 2mol/L.The carbon agent is the one kind in sucrose, glucose.The fiber forming agent be polyvinylpyrrolidone,
Any one in polyvinyl alcohol, macrogol.
The method have the advantages that：
1st, because antimony dissolves in tartaric acid solution, arsenic can only be dissolved in concentrated hydrochloric acid solution, therefore add tartaric acid in the solution
And water, obtain the hydrolytic precipitation of tartrated antimony chloride solution and arsenic.This method can reduce technological process, reduces cost.
2nd, carbon agent and fiber forming agent are added in precursor solution, two kinds of materials are organic matter, after fiber calcination, is delayed
Punching mutually mainly in the form of carbon in fiber, is conducive to alleviating the stress that antimony volumetric expansion is produced, and can also constrain electrode material
The cracking that material antimony particle is produced, improves electrode material cycle performance, improves the service life of battery.In addition in buffering phase forming agent
Carbon have preferable electric conductivity, when battery is prepared, without the need for adding conductive agent and binding agent, further simplify preparation work
Skill.
3rd, get rid of a technique using double rods, obtain superfine fibre, be conducive to contact of the electrode material with electrolyte, shortening sodium from
The migration distance of son, is conducive to improving the charge-discharge velocity of battery.
According to the method for the present invention, by adjustment formula composition, the combination electrode material fibre diameter for obtaining is 2-8 μm,
After circulation 50 times, charge/discharge capacity is up to 460mAh/g, and properties of product are good.
To sum up, present invention process is simple, low cost, good product performance, and prepares high added value using industrial residue
Electrode material, with preferable economic benefit and environmental benefit.
Specific embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail.
A kind of lead anode slurry prepares the technique of antimony-carbon composite fibre electrode material, comprises the steps：
(1) iron and lead in lead anode slurry is fallen with dilute nitric acid dissolution, after solid-liquor separation, then with the antimony in dissolving with hydrochloric acid solid phase
And arsenic, obtain the mixed solution of arsenic and antimony；
(2) tartaric acid and water are added in the solution of arsenic and antimony, the hydrolytic precipitation thing of arsenic and tartrated chlorination is obtained
The molar concentration of antimony solution, wherein antimony is 1mol/L, and tartaric molar concentration is 2mol/L；
(3) preparation of precursor solution
Carbon agent and fiber forming agent are added in tartrated antimony chloride solution, precursor solution is obtained, wherein, carbon agent is
One kind in sucrose, glucose, addition is the 200% of antimony quality；Fiber forming agent is polyvinylpyrrolidone, polyethylene
Any one in alcohol, macrogol, addition is the 10-50% of antimony quality；
Table 1 lists the formula composition of 9 embodiments that numbering is 1-9.
The formula of the raw material of table 1
Note：The quality of antimony, according in tartrated antimony chloride solution, the concentration (1mol/L) of antimony is calculated.
(4) precursor solution obtained by step (3) is poured in double rod tumbling machines, adopt fibrous electrodes precursor；
(5) the fibrous electrodes precursor for obtaining step (4) is dried, and 600 DEG C is then heated in a hydrogen atmosphere, insulation
Burn till within 1 hour, it is final to obtain the fiber electrode material that antimony is combined with carbon.
The fibre diameter of different embodiments above gained composite fibre electrode material is listed in table 2.With these composite fibre electricity
Pole material is, to electrode, after being assembled into battery, to be circulated charge-discharge test as negative pole, metallic sodium, circulates filling after 50 times
Discharge capacity and capability retention are shown in table 2.
The performance of the combination electrode material fiber of table 2
| 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 |
From table 2 it can be seen that the composite fibre electric discharge of combination electrode fiber prepared by the inventive method, wherein embodiment 1
Capacity may be up to 460mAh/g, and capability retention is up to 96%.
Claims (4)
1. the technique that a kind of lead anode slurry prepares antimony-carbon composite fibre electrode material, it is characterised in that comprise the steps：
(1) fall the iron and lead in lead anode slurry with dilute nitric acid dissolution, after solid-liquor separation, then with the antimony in dissolving with hydrochloric acid solid phase and
Arsenic, obtains the mixed solution of arsenic and antimony；
(2) tartaric acid and water are added in the solution of arsenic and antimony, the hydrolytic precipitation thing and tartrated antimony chloride for obtaining arsenic is molten
Liquid；
(3) the fiber shape of the 10-50% of the carbon agent and antimony quality of the 200% of antimony quality is added in tartrated antimony chloride solution
Into agent, it is uniformly mixed, obtains precursor solution；
(4) precursor solution is poured in double rod tumbling machines and gets rid of silk, obtain fibrous electrodes precursor；
(5) fibrous electrodes precursor is dried, 600 DEG C is then heated in a hydrogen atmosphere and is burnt till, be incubated 1 hour, finally obtained
Obtain the fiber electrode material that antimony is combined with carbon.
2. the technique for preparing antimony-carbon composite fibre electrode material with lead anode slurry as claimed in claim 1, it is characterised in that
In the tartrated antimony chloride solution, the molar concentration of antimony is 1mol/L, and tartaric molar concentration is 2mol/L.
3. the technique for preparing antimony-carbon composite fibre electrode material with lead anode slurry as claimed in claim 1, it is characterised in that
The carbon agent is the one kind in sucrose, glucose.
4. the technique for preparing antimony-carbon composite fibre electrode material with lead anode slurry as claimed in claim 1, it is characterised in that
The fiber forming agent is any one in polyvinylpyrrolidone, polyvinyl alcohol, macrogol.
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Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1025921C (en) * | 1990-12-06 | 1994-09-14 | 昆明化工厂 | Method for producing silver nitrate and reclaiming copper, lead and antimony from lead anode mud |
| CN101787440B (en) * | 2010-03-29 | 2011-08-10 | 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 |
| CN104046796B (en) * | 2014-06-06 | 2015-08-26 | 郴州市金贵银业股份有限公司 | The method of antimony is reclaimed a kind of antimony slag after lead anode slurry comprehensive treating process |
| CN104157841B (en) * | 2014-08-14 | 2016-03-23 | 陕西理工学院 | For the composite fibre electrode material preparation technology of sodium-ion battery |
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