CN103058160A - Preparation method of low cost battery level iron phosphate based on ferrous powder corrosion - Google Patents
Preparation method of low cost battery level iron phosphate based on ferrous powder corrosion Download PDFInfo
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- CN103058160A CN103058160A CN2012104373257A CN201210437325A CN103058160A CN 103058160 A CN103058160 A CN 103058160A CN 2012104373257 A CN2012104373257 A CN 2012104373257A CN 201210437325 A CN201210437325 A CN 201210437325A CN 103058160 A CN103058160 A CN 103058160A
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Abstract
The invention provides a preparation method of low cost battery level iron phosphate based on ferrous powder corrosion. The method comprises the following steps of: under the alkaline condition of enough oxygen and water and the condition of mixing starch, corroding the ferrous powder to generate iron rust of which the main component is hydroxyl ferric oxide, wherein the existence of the starch is beneficial for forming a microporous loose structure; and acidizing the product by phosphoric acid and oxidizing the product by hydrogen peroxide to get the high-purity iron phosphate. The preparation method is simple and easy in technology, and needs less simple equipment; the production process is environment-friendly, production of waste is avoided; the cost is low, fewer raw materials is needed and the raw materials is cheap; in the production process of the preparation method, other ions are not introduced, the produced product is excellent in structure, low in impurity content, uniform in granularity and suitable for industrial large-scale production. Lithium iron phosphate prepared by using the iron phosphate which is prepared by the preparation method as raw material has the advantages of being high in first charge and discharge specific capacity, excellent in high rate cycling performance, low in self discharge rate, high in tap density, high in batch stability and excellent in processing performance, and so on.
Description
Technical field
The present invention relates to a kind of active compound lithium iron phosphate of lithium ion secondary battery anode (LiFePO
4) precursor (FePO
4) the preparation method, it is particularly a kind of that to generate main component based on iron powder corrosion is that the iron rust of hydrous iron oxide (FeO (OH)) is as the preparation method of tertiary iron phosphate precursor and tertiary iron phosphate.
Background technology
Lithium ion battery has the voltage height as the new generation of green high tension battery, and energy density is large, good cycle, and self-discharge is little, memory-less effect, the advantage that operating temperature range is wide and being widely used.Positive electrode material is the important component part of lithium ion battery, and iron lithium phosphate becomes the focus of current research as positive electrode material of new generation.Olivine-type iron lithium phosphate (LiFePO
4) can reversiblely take off the whole lithium ions of embedding, form constitutionally stable tertiary iron phosphate (FePO
4), and discharge reversible capacity up to 170mAh/g, its advantage as anode material for lithium-ion batteries is mainly manifested in the following aspects: (1) adopts phosphate radical to replace oxonium ion, under extreme conditions can precipitated oxygen, and safety performance improves greatly; (2) ferro element content in the earth's crust is very abundant, and raw material sources are extensive, and are cheap.(3) nontoxic, pollution-free; (4) have extended cycle life, can satisfy the needs that power truck frequently discharges and recharges.Iron lithium phosphate is synthetic take solid phase method as main at present; namely be that the carbonate of lithium (or oxyhydroxide, phosphoric acid salt), Ferrox (or ferrous acetate, ferrous phosphate, tertiary iron phosphate) and primary ammonium phosphate (or Secondary ammonium phosphate, phosphoric acid) are mixed, the protection sintering forms under inert atmosphere.Industrialized high temperature solid-state method production technique can be divided into by its source of iron that adopts at present: (1) Ferrox operational path.This method is the synthetic route of at present main flow, but the equipment interdependency is higher, and the production cycle is longer, and pattern regulation and control problem is the difficult point of this route, causes stability undesirable.(2) red iron oxide operational path.The red iron oxide production technique is having certain advantage aspect raw-material stability and the equipment investment, but it is higher and easily generate iron phosphide and affect performance and batch stability of iron lithium phosphate in the carbothermic reduction process to can be used as the price of the red iron oxide of producing the iron lithium phosphate raw material.(3) tertiary iron phosphate operational path.This route meets the power cell industry to the demand of positive electrode material.The technique of this method is simple, be fit to the industrialization batch production, raw material type is few, the subsequent process regulation and control are more simplified, and the gram volume of the iron lithium phosphate of preparation is higher, good processability, particle diameter are even.It is the preferred option for preparing on a large scale LiFePO 4 material.
But tertiary iron phosphate route cost compare is high, and only one of tertiary iron phosphate just reaches more than 50% of material cost, and significantly cutting down cost could allow the electrical property of its high-quality and market value be complementary.Mostly the preparation of tertiary iron phosphate in the document is to adopt ferrous sulfate (FeSO
4) and phosphoric acid or primary ammonium phosphate (NH
4H
2PO
4) in the aqueous phase pre-mixing, then under agitation add hydrogen peroxide oxidation and obtain the tertiary iron phosphate precipitation.There are the shortcomings such as production cost height, complex process, cost control difficulty in this technique.
Summary of the invention
Purpose of the present invention overcomes defects of the prior art exactly, and a kind of preparation method of eco-friendly low-cost cell-grade tertiary iron phosphate based on iron powder corrosion is provided.For this reason, the present invention is by the following technical solutions: it is under the alkaline condition of oxygen G﹠W abundance and under the condition of mixing starch, it is the iron rust of hydrous iron oxide that iron powder is corroded the generation main component, having of starch helps form the short texture with a lot of microporositys, the compound of the iron that obtains not only activity is higher, and helps subsequent disposal; Again products therefrom is obtained high-purity phosphoric acid iron behind phosphoric acid acidifying and hydrogen peroxide oxidation.
The chemical equation of the principal reaction that relates in the process is as follows:
2Fe＋O
2＋2H
2O= 2Fe(OH)
2 (1)
4Fe(OH)
2+O
2+2H
2O =4Fe(OH)
3 (2)
Fe(OH)
3=FeO(OH) + H
2O (3)
FeO(OH)+H
3PO
4=FePO
4+2H
2O (4)
On the basis of adopting technique scheme, the present invention also can adopt following further technical scheme:
It may further comprise the steps:
(1), zeroth order iron powder, starch and ammonium salt three are mixed, zeroth order iron powder and starch 1:0.4 ~ 0.8 in mass ratio wherein, the mol ratio 1:0.1 of zeroth order iron powder and ammonium ion ~ 1; And add suitable quantity of water material soaked, after put into the water-bath heating in water bath, the temperature that described water-bath adds is 50 ~ 80 ℃, until powder becomes uniform redness, described ammonium salt be in volatile salt and the bicarbonate of ammonia one of them or all;
(2), powder that step (1) is obtained adds with the phosphoric acid of iron powder Isoequivalent weight in, and add 5 ~ 10 times distilled water, 50 ~ 80 ℃ of constant temperature stir;
(3), solution that step (2) is obtained under agitation condition, slowly add in batches hydrogen peroxide, the hydrogen peroxide add-on of every mole of material is 80 ~ 150ml, reacts to obtain the tertiary iron phosphate white precipitate after 24 ~ 96 hours;
(4), tertiary iron phosphate throw out that step (3) is obtained is through 60 ~ 100 ℃ of forced air dryings 5 ~ 15 hours, obtains pure product F ePO
42H
2O.
Technical scheme of the present invention has following distinguishing feature: simple for process, required equipment is few and simple; The production process environmental friendliness produces without waste material; Cost is low, and desired raw material is few and cheap; The present invention does not introduce other ions in process of production, and made product structure is good and impurity is few, and epigranular is fit to industrial scale production.By the tertiary iron phosphate of the present invention preparation as raw material, the advantages such as the iron lithium phosphate of preparation has first charge-discharge specific storage height, high rate cyclic excellent performance, self-discharge rate is low, tap density is large, batch stable height and good processability.
Description of drawings
Fig. 1 is the x-ray diffraction pattern of the tertiary iron phosphate of embodiment 1 preparation.Can find out that prepared powder is FePO
4, there is not impurity peaks in the spectrogram, product purity is high.
Fig. 2 is the scanning electron microscope diagram of the tertiary iron phosphate of embodiment 1 preparation.Can find out that particle size distribution is even, and particle diameter is about 0.4 μ m.
Fig. 3 (detains electrical testing voltage range 2-4V for the iron lithium phosphate that the tertiary iron phosphate by embodiment 1 preparation makes in room temperature; Rate of charge 0.2C; Discharge-rate is pressed the arrow direction, is followed successively by 0.2C, 0.8C, 2C) charging and discharging curve figure under the condition.
Embodiment
Embodiment 1:
56g reduced iron powder (iron level 98%), 14.0g starch and 8.0g bicarbonate of ammonia are stirred, with water-soaked and 60 ℃ of water-bath arrest reactions 80 hours.Then reaction product is slowly joined in the phosphoric acid of 115.29g 85% of 12 times of equal-volume dilutions, and under agitation condition, add the 40ml hydrogen peroxide in batches, react and obtain tertiary iron phosphate after 60 hours and precipitate.Obtained product F ePO in 6 hours 80 ℃ of lower forced air dryings
42H
2O.
Embodiment 2:
14g reduced iron powder (iron level 98%), 3.5g starch and 6.0g bicarbonate of ammonia are stirred, with water-soaked and 60 ℃ of water-bath arrest reactions 28 hours.Then reaction product is slowly joined in the phosphoric acid of 28.82g 85% of 6 times of equal-volume dilutions, and under agitation condition, add the 25ml hydrogen peroxide in batches, react and obtain tertiary iron phosphate after 36 hours and precipitate.Obtained product F ePO in 5 hours 50 ℃ of lower forced air dryings
42H
2O.
Embodiment 3:
14g reduced iron powder (iron level 98%), 5.6g starch and 4.0g bicarbonate of ammonia are stirred, with water-soaked and 70 ℃ of water-bath arrest reactions 20 hours.Then reaction product is slowly joined in the phosphoric acid of 28.82g 85% of 8 times of equal-volume dilutions, and under agitation condition, add the 20ml hydrogen peroxide in batches, react and obtain tertiary iron phosphate after 40 hours and precipitate.Obtained product F ePO in 6 hours 60 ℃ of lower forced air dryings
42H
2O.
Embodiment 4:
28g reduced iron powder (iron level 98%), 22.4g starch and 3.9g volatile salt are stirred, with water-soaked and 80 ℃ of water-bath arrest reactions 75 hours.Then reaction product is slowly joined in the phosphoric acid of 57.65g 85% of 10 times of equal-volume dilutions, and under agitation condition, add the 40ml hydrogen peroxide in batches, react and obtain tertiary iron phosphate after 48 hours and precipitate.Obtained product F ePO in 6 hours 60 ℃ of lower forced air dryings
42H
2O.
Embodiment 5:
5.6g reduced iron powder (iron level 98%), 2.8g starch and 0.8g bicarbonate of ammonia are stirred, with water-soaked and 50 ℃ of water-bath arrest reactions 16 hours.Then reaction product is slowly joined in the phosphoric acid of 11.5g 85% of 5 times of equal-volume dilutions, and under agitation condition, add the 10ml hydrogen peroxide in batches, react and obtain tertiary iron phosphate after 24 hours and precipitate.Obtained product F ePO in 4 hours 50 ℃ of lower forced air dryings
42H
2O.
Embodiment 6:
56g spheroidal graphite cast iron powder (iron level 95%), 14.0g starch and 7.8g volatile salt are stirred, with water-soaked and 60 ℃ of water-bath arrest reactions 96 hours.Then reaction product is slowly joined in the phosphoric acid of 115.29g 85% of 10 times of equal-volume dilutions, and under agitation condition, add the 100ml hydrogen peroxide in batches, react and obtain tertiary iron phosphate after 60 hours and precipitate.Obtained product F ePO in 8 hours 80 ℃ of lower forced air dryings
42H
2O.
Embodiment 7:
112g spheroidal graphite cast iron powder (iron level 95%), 56g starch and 8.0g bicarbonate of ammonia are stirred, with water-soaked and 60 ℃ of water-bath arrest reactions 80 hours.Then reaction product is slowly joined in the phosphoric acid of 230.58g 85% of 8 times of equal-volume dilutions, and under agitation condition, add the 200ml hydrogen peroxide in batches, react and obtain tertiary iron phosphate after 60 hours and precipitate.Obtained product F ePO in 6 hours 80 ℃ of lower forced air dryings
42H
2O.
Embodiment 8:
112g reduced iron powder (iron level 98%), 80g starch and 15.7g volatile salt are stirred, with water-soaked and 60 ℃ of water-bath arrest reactions 96 hours.Then reaction product is slowly joined in the phosphoric acid of 230.58g 85% of 6 times of equal-volume dilutions, and under agitation condition, add the 300ml hydrogen peroxide in batches, react and obtain tertiary iron phosphate after 80 hours and precipitate.Obtained product F ePO in 10 hours 80 ℃ of lower forced air dryings
42H
2O.
Claims (2)
1. preparation method based on the low-cost cell-grade tertiary iron phosphate of iron powder corrosion, it is characterized in that it is under the alkaline condition of oxygen G﹠W abundance and under the condition of mixing starch, it is the iron rust of hydrous iron oxide that iron powder is corroded the generation main component, again products therefrom is obtained high-purity phosphoric acid iron behind phosphoric acid acidifying and hydrogen peroxide oxidation.
2. the preparation method of a kind of low-cost cell-grade tertiary iron phosphate based on iron powder corrosion as claimed in claim 1 is characterized in that it may further comprise the steps:
(1), zeroth order iron powder, starch and ammonium salt three are mixed, zeroth order iron powder and starch 1:0.4 ~ 0.8 in mass ratio wherein, the mol ratio 1:0.1 of zeroth order iron powder and ammonium ion ~ 1; And add suitable quantity of water material soaked, after put into the water-bath heating in water bath, the temperature of described heating in water bath is 50 ~ 80 ℃, until powder becomes uniform redness, described ammonium salt be in volatile salt and the bicarbonate of ammonia one of them or all;
(2), powder that step (1) is obtained adds with the phosphoric acid of iron powder Isoequivalent weight in, and add 5 ~ 10 times distilled water, 50 ~ 80 ℃ of constant temperature stir;
(3), solution that step (2) is obtained under agitation condition, slowly add in batches hydrogen peroxide, the hydrogen peroxide add-on of every mole of material is 80 ~ 150ml, reacts to obtain the tertiary iron phosphate white precipitate after 24 ~ 96 hours;
(4), tertiary iron phosphate throw out that step (3) is obtained is through 60 ~ 100 ℃ of forced air dryings 5 ~ 15 hours, obtains pure product F ePO
42H
2O.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110152667A (en) * | 2019-04-23 | 2019-08-23 | 同济大学 | A kind of modified method for forming γ-FeOOH in iron filings surface |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1226876A (en) * | 1967-04-01 | 1971-03-31 | ||
| CN101172595A (en) * | 2007-10-12 | 2008-05-07 | 杭州电子科技大学 | Process for producing iron phosphate |
| CN102333725A (en) * | 2009-02-26 | 2012-01-25 | 化学制造布敦海姆两合公司 | The preparation of Orthophosphoric acid Ferrum |
| CN102431988A (en) * | 2011-10-12 | 2012-05-02 | 浙江南都电源动力股份有限公司 | New process for preparing low-cost cell-grade iron phosphate material from basic iron acetate |
-
2012
- 2012-11-06 CN CN2012104373257A patent/CN103058160A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1226876A (en) * | 1967-04-01 | 1971-03-31 | ||
| CN101172595A (en) * | 2007-10-12 | 2008-05-07 | 杭州电子科技大学 | Process for producing iron phosphate |
| CN102333725A (en) * | 2009-02-26 | 2012-01-25 | 化学制造布敦海姆两合公司 | The preparation of Orthophosphoric acid Ferrum |
| CN102431988A (en) * | 2011-10-12 | 2012-05-02 | 浙江南都电源动力股份有限公司 | New process for preparing low-cost cell-grade iron phosphate material from basic iron acetate |
Non-Patent Citations (1)
| Title |
|---|
| 韩顺昌等: "《金属腐蚀显微组织图谱》", 30 November 2008, 国防工业出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110152667A (en) * | 2019-04-23 | 2019-08-23 | 同济大学 | A kind of modified method for forming γ-FeOOH in iron filings surface |
| CN110152667B (en) * | 2019-04-23 | 2021-09-03 | 同济大学 | Method for forming gamma-FeOOH by modifying iron chip surface |
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| C53 | Correction of patent of invention or patent application | ||
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Address after: 311305, No. 72, landscape Avenue, Qingshan Town, Ling'an Economic Development Zone, Zhejiang, Hangzhou Applicant after: Nandu Electric Power Co., Ltd., Zhejiang Applicant after: Hangzhou Narada Battery Co., Ltd Applicant after: Hangzhou Nandu Energy Technology Co., Ltd. Address before: 310013 No. 50 Bauhinia Road, Zhejiang, Hangzhou Applicant before: Nandu Electric Power Co., Ltd., Zhejiang Applicant before: Hangzhou Narada Battery Co., Ltd Applicant before: Hangzhou Nandu Energy Technology Co., Ltd. |
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Address after: 311305 Ling'an Qingshan Lake Street landscape Avenue, No. 72, No. Applicant after: Nandu Electric Power Co., Ltd., Zhejiang Applicant after: Hangzhou Narada Battery Co., Ltd Applicant after: Hangzhou Nandu Energy Technology Co., Ltd. Address before: 311305, No. 72, landscape Avenue, Qingshan Town, Ling'an Economic Development Zone, Zhejiang, Hangzhou Applicant before: Nandu Electric Power Co., Ltd., Zhejiang Applicant before: Hangzhou Narada Battery Co., Ltd Applicant before: Hangzhou Nandu Energy Technology Co., Ltd. |
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Application publication date: 20130424 |