CN104638243B - The technique preparing pyrophosphate sodium ion battery electrode material with sodium jarosite - Google Patents
The technique preparing pyrophosphate sodium ion battery electrode material with sodium jarosite Download PDFInfo
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- CN104638243B CN104638243B CN201510076027.3A CN201510076027A CN104638243B CN 104638243 B CN104638243 B CN 104638243B CN 201510076027 A CN201510076027 A CN 201510076027A CN 104638243 B CN104638243 B CN 104638243B
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- electrode material
- sodium
- jarosite
- ion battery
- acid
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses the technique that a kind of sodium jarosite prepares pyrophosphate sodium ion battery electrode material, it is characterized in that, sodium jarosite adds dilution heat of sulfuric acid, stirring is after sodium jarosite dissolving, add stabilizing agentof sol, strong phosphoric acid, Natrii Sulfas and become fine agent, obtain precursor sol；Precursor sol is put in spinning-drawing machine after concentrating, and obtains electrode material cotton presoma；Electrode material cotton presoma is dried, then calcining under the protective atmosphere producing, the final sodium ion battery electrode material obtaining cotton shape is being decomposed by kerosene.The present invention adopts industrial residue to prepare the electrode material of high added value, low cost, and performance is good, process is simple, has good economic benefit and environmental benefit.
Description
Technical field
The present invention relates to a kind of sodium ion battery electrode material preparation method, particularly to a kind of discharge of utilization zine-smelting plant
The method to prepare pyrophosphate sodium ion battery electrode material for the waste residue-sodium jarosite.
Background technology
The research of high performance lithium ion battery and its electrode material is the area researches such as electrochemistry, materials chemistry, physicss
Focus, and the property of the sodium ion and lithium ion being all periodic table of elements I main group has many similarities, and sodium ion is complete
Have and the same with lithium ion battery can construct a kind of widely used secondary cell.And sodium-ion battery and lithium ion battery phase
The cost of raw material is lower than lithium ion battery, half-cell prtential (E for ratio0Na+/ Na=E0Li+/ Li+0.3V) higher than lithium ion battery, fit
Close using the lower electrolyte of decomposition voltage, thus security performance more preferably [Jia Xuping, Chen Mei. sodium ion battery electrode material is ground
Study carefully progress [J]. research institute of China Electronics journal, 2012,7 (6)：581-585].
At present, the raw material preparing sodium ion electrode material is mainly industrial chemicals, relatively costly, and in order to improve electrode material
The performance of material, generally adds multiple element and carries out multi-element doping, such as Wu Feng et al. is prepared for yNaFe1/2Ni1/2O2-(1-y)
Na2MnO3Electrode material, performance is better than unit material, and wherein y is only 88% for capability retention after 0.1～0.5,50 circulations
[Wu Feng, thanks, Wang Xiaoming etc. a kind of sodium ion battery electrode material and preparation method thereof [p] .CN201210567797].Many
Unit mixes and further increases preparation cost.
Content of the invention
In hydrometallurgy and inorganic chemical production, when there being larger amount of ferrum to need to remove, widely used generation at present
There is the ihleite deferrization process of good strainability.Iron vitriol dreg of yellow sodium method is sixties electricity Xin company of Australia Reston
Electricity Xin factory, through grow up after experimental study for many years, is initially applied to a kind of method for removing iron of zinc metallurgical process.With this
Meanwhile, Na Weixin company and Hispanic A Situliyana zinc company have also developed this method, respectively from this sodium jarosite
Method is promoted quickly in world's zinc abstraction and applies.The chemical formula of sodium jarosite is [NaFe3(SO4)2(OH)6], Zhi Neng
PH only for stablizing during 1.5-2.5, in addition contains the heavy metals such as a small amount of Zn, Cu, Cd in sodium jarosite, belongs to the model of hazardous waste
Farmland, if do not processed to it, will pollute environment.
It is an object of the invention to provide sodium jarosite prepares high added value sodium ion in a kind of hydrometallurgy based on process
The method of battery electrode material, has good energy-saving, emission-reducing, environment friendly benefit.
For reaching object above, the present invention adopts the following technical scheme that and is achieved：
A kind of sodium jarosite prepare pyrophosphate sodium ion battery electrode material technique it is characterised in that include under
State step：
(1) add dilution heat of sulfuric acid in sodium jarosite, stir after sodium jarosite dissolving, addition stabilizing agentof sol,
Strong phosphoric acid, Natrii Sulfas with become fine agent, obtain precursor sol：Wherein, stabilizing agentof sol be oxalic acid, citric acid, in tartaric acid one
Kind, addition is the 200mol% of sodium jarosite mole；In strong phosphoric acid, the addition of phosphoric acid is sodium jarosite mole
600mol%；Natrii Sulfas addition is the 250mol% of sodium jarosite mole；Fine agent is become to be Polyvinylpyrrolidone, polyethylene
One of alcohol, polyacrylic acid, addition is the 1-5mol% of sodium jarosite mole；
(2) step (1) gained precursor sol is concentrated；
(3) precursor sol after concentrating is passed through centrifugal box-spinning machine spinning, obtain electrode material cotton presoma；
(4) the electrode material cotton presoma that step (3) obtains is dried, then the protective atmosphere producing is being decomposed by kerosene
Under be heated to 900 DEG C and burn till, be incubated 6 hours, the final sodium ion battery electrode material obtaining cotton shape.
In above-mentioned technique, in described dilute sulfuric acid, the addition of sulphuric acid is the 300mol% of sodium jarosite mole；Dilute sulfuric acid
The mass concentration of solution is 10%.
The mass concentration of described strong phosphoric acid is 85%.
The present invention to prepare the electrode material of high added value due to employing industrial residue-sodium jarosite, so having into
This low, feature that process is simple, environmental benefit highlight.Meanwhile, the electrode material performance of preparation is good, during assembled battery, need not add
Conductive agent and binding agent.
Specific embodiment
A kind of sodium jarosite prepares the technique of pyrophosphate sodium ion battery electrode material, comprises the steps：
(1) preparation of precursor sol：Add dilution heat of sulfuric acid in sodium jarosite, stirring is until sodium jarosite dissolving
Afterwards, add stabilizing agentof sol, strong phosphoric acid, Natrii Sulfas (sodium sulfate) and become fine agent (formula is shown in Table 1)；
(2) precursor sol concentrates under the conditions of 60 DEG C；
(3) precursor sol after concentrating is put in centrifugal box-spinning machine, electrode material is obtained using centrifugal spinning process
Material cotton presoma；
(4) electrode material cotton presoma is dried, then under the protective atmosphere that generation is decomposed by kerosene, is heated to 900 DEG C
Burn till, and be incubated 6 hours under firing temperature, the final sodium ion battery electrode material obtaining cotton shape.
Using this cellucotton be negative pole, sodium be that battery is dressed up to electrode group, it is circulated with charge-discharge test, circulates 50
Discharge capacity after secondary is all higher than 90mAh/g, and capability retention is all higher than 90% (being shown in Table 2).
The formula of table 1 preparation technology
Note：The concentration of dilute sulfuric acid is 10%, and the addition in table is according to the H in solution2SO4Calculate；The concentration of strong phosphoric acid is
85%, the addition in table is according to the H in solution3PO4Calculate
The performance of table 2 electrode material
| Embodiment | Discharge capacity (mAh/g) | Capability retention (%) |
| 1 | 91 | 91 |
| 2 | 93 | 96 |
| 3 | 91 | 96 |
| 4 | 92 | 94 |
| 5 | 99 | 95 |
| 6 | 98 | 96 |
| 7 | 97 | 92 |
| 8 | 92 | 94 |
| 9 | 95 | 95 |
Sodium jarosite is decomposed by present invention sulphuric acid, obtains the mixed solution of iron sulfate and sodium sulfate, and iron sulfate is electrode
Material provides source of iron, and sodium sulfate provides part sodium source for electrode material, and the other metal ions in sodium jarosite provide doping
Phase.Prepare precursor sol when, add stabilizing agentof sol, can hinder the growth of micelle, improve the stability of colloidal sol, favorably
In application in industrialized production for the colloidal sol.When stabilizing agentof sol and fiber forming agent are calcined under the conditions of protective atmosphere, become
Carbon is wrapped in around electrode material, will improve the electric conductivity of electrode material, the grain growth of impeded electrode material, thus carry
The performance of high electrode material.After electrode material calcining, obtaining main thing phase is Ferric sodium pyrophosphate [Na2FeP2O7] and carbon is compound
Electrode material.
Claims (4)
1. a kind of sodium jarosite prepares the technique of pyrophosphate sodium ion battery electrode material it is characterised in that including following
Step：
(1) add dilution heat of sulfuric acid in sodium jarosite, stirring, after sodium jarosite dissolving, adds stabilizing agentof sol, dense phosphorus
Acid, Natrii Sulfas and becomes fibre agent, obtain precursor sol：Wherein, stabilizing agentof sol is one of oxalic acid, citric acid, tartaric acid, plus
Enter the 200mol% that amount is sodium jarosite mole；In strong phosphoric acid, the addition of phosphoric acid is sodium jarosite mole
600mol%；Natrii Sulfas addition is the 250mol% of sodium jarosite mole；Fine agent is become to be Polyvinylpyrrolidone, polyethylene
One of alcohol, polyacrylic acid, addition is the 1-5mol% of sodium jarosite mole；
(2) step (1) gained precursor sol is concentrated；
(3) precursor sol after concentrating is passed through centrifugal box-spinning machine spinning, obtain electrode material cotton presoma；
(4) the electrode material cotton presoma that step (3) obtains is dried, then adds under the protective atmosphere that generation is decomposed by kerosene
Heat is burnt till to 900 DEG C, is incubated 6 hours, the final sodium ion battery electrode material obtaining cotton shape.
2. the technique preparing pyrophosphate sodium ion battery electrode material with sodium jarosite as claimed in claim 1, its feature
It is, in described dilute sulfuric acid, the addition of sulphuric acid is the 300mol% of sodium jarosite mole.
3. the technique preparing pyrophosphate sodium ion battery electrode material with sodium jarosite as claimed in claim 2, its feature
It is, the mass concentration of described dilution heat of sulfuric acid is 10%.
4. the technique preparing pyrophosphate sodium ion battery electrode material with sodium jarosite as claimed in claim 1, its feature
It is, the mass concentration of described strong phosphoric acid is 85%.
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| CN201510076027.3A CN104638243B (en) | 2015-02-12 | 2015-02-12 | The technique preparing pyrophosphate sodium ion battery electrode material with sodium jarosite |
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| CN201510076027.3A CN104638243B (en) | 2015-02-12 | 2015-02-12 | The technique preparing pyrophosphate sodium ion battery electrode material with sodium jarosite |
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| CN104638243B true CN104638243B (en) | 2017-03-08 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104638244B (en) * | 2015-02-12 | 2017-03-15 | 陕西理工学院 | The technique that sodium ion battery electrode material is prepared with ammonium jarosite and Chalcanthitum |
| CN105810910B (en) * | 2016-04-20 | 2018-02-16 | 中南大学 | A kind of Na2‑2xFe1+xP2O7/ carbon composite and its preparation method and application |
| CN108039491B (en) * | 2017-11-30 | 2020-05-22 | 华南理工大学 | Sodium iron triphosphate as cathode material of sodium ion battery and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100814540B1 (en) * | 2001-04-06 | 2008-03-17 | 발렌스 테크놀로지, 인코포레이티드 | Sodium Ion Batteries |
| CN103896339B (en) * | 2012-12-27 | 2016-08-24 | 北京汉能创昱科技有限公司 | A kind of preparation method of sodium manganese oxide |
| CN104167541B (en) * | 2014-08-14 | 2016-03-23 | 陕西理工学院 | For the positive electrode preparation technology of sodium-ion battery |
| 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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