CN102897739A - Novel process for preparing battery-grade iron phosphate material by using iron hydroxide - Google Patents
Novel process for preparing battery-grade iron phosphate material by using iron hydroxide Download PDFInfo
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- CN102897739A CN102897739A CN2012104469832A CN201210446983A CN102897739A CN 102897739 A CN102897739 A CN 102897739A CN 2012104469832 A CN2012104469832 A CN 2012104469832A CN 201210446983 A CN201210446983 A CN 201210446983A CN 102897739 A CN102897739 A CN 102897739A
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Abstract
The invention discloses a novel process for preparing a low-cost battery-grade iron phosphate material by using iron hydroxide. The process comprises the following steps: mixing a zero-valent iron source and corrosive acid in a molar ratio, and adding a certain amount of primary water and ammonia water; stirring to react for 0 to 24 hours, and slowly adding hydrogen peroxide until the iron source disappears and the solution turns to orange; adding surfactant which is 1 to 5 percent that of the mass of the iron source into the solution; adding a reagent containing phosphate radicals into the solution according to a certain molar ratio of iron element to phosphor element under a stirring condition to obtain iron phosphate precipitate; filtering and washing the product 3 to 5 times with the primary water which is 3 to 7 times the weight of the iron phosphate; drying in vacuum for 4 to 12 hours at 50 and 80 DEG C to obtain FePO4.2H2O. The process for preparing battery grade iron phosphate is simple and easy to carry out and low in cost; and the prepared product has good product crystal structure, few impurities and uniform granularity and is suitable for industrial scale production; moreover, the lithium iron phosphate prepared by the process has high specific capacity, low self-discharge, high tap density, stable product performance and good processing performance.
Description
Technical field
The invention relates to a kind of preparation method of active material for anode of Li-ion secondary battery presoma tertiary iron phosphate, especially about a kind of active compound lithium iron phosphate of lithium ion secondary battery anode (LiFePO
4) the preparation method of presoma.
Background technology
Traditional lead-acid cell, nickel-cadmium cell and nickel metal hydride battery etc., the problem such as the low and environmental pollution demand of satisfying the market well because of energy density.Compare with other secondary cell, lithium ion battery has high volume energy density and mass energy density, and have memory-less effect, self-discharge rate low, have extended cycle life and the advantage such as environmentally safe and become a kind of advanced person's secondary cell.
The iron lithium phosphate crystalline structure is stable, specific storage is high, discharge platform is steady and have extended cycle life, and is one of first-selected positive electrode material of lithium-ion-power cell, it seems that at present it is power lithium-ion battery and the only material of energy storage lithium ion battery.
The production technique that existing iron lithium phosphate technology of preparing is fit to suitability for industrialized production the most is high temperature solid-state method.Industrialized high temperature solid-state method production technique can be divided into again by the source of iron classification that it adopts at present: 1, Ferrox production technique, and current, scale operation LiFePO over half is arranged
4Producer substantially all adopt this method.The shortcoming of the method is that raw material Ferrox price is higher, the synthetic product particle diameter is wayward, pattern is irregular, product stability is short of, poor processability, and needs second heat treatment and grinding in the production process, and unit consumption of energy is high, and discharge amount of exhaust gas is large.2, the ferric oxide production technique is current, and the ferric oxide production technique is having certain advantage aspect raw-material stability and the equipment investment.Its shortcoming is that the iron lithium phosphate electrical property of producing is relatively poor, and easily generates iron phosphide and affect performance and batch stability of iron lithium phosphate in the carbothermic reduction process.3, tertiary iron phosphate production technique, the advantage of tertiary iron phosphate route is very obvious: technique is simple, be fit to industrialization batch production, raw material type still less, higher, the good processability of the gram volume of the subsequent process control iron lithium phosphate more simplifying, prepare, particle diameter be even, be the prefered method that novel large-scale prepares LiFePO 4 material, adopt at present that the representative enterprise of this route has that Taiwan is vertical triumphant, the Shangzhi of Datong District, Ou Sai etc.
But the tertiary iron phosphate route is high to the quality requirements of starting material (tertiary iron phosphate), the tertiary iron phosphate supplier quality of the U.S. and Germany is higher now, but price is suitable with the iron lithium phosphate finished product, so the gordian technique of this route largely depends on the technology of preparing of presoma tertiary iron phosphate.Through inspection information, in the production method of present industrialized tertiary iron phosphate, a kind of method is to be formed by wustite and the reaction of phosphoric acid salt hydrothermal method, and another kind of method is first then the ferrous salt oxidation to be added phosphoric acid with oxygenant to prepare.All there are the shortcomings such as production cost is high, complex process, Composition Control is difficult, three waste discharge is large.
Summary of the invention
The objective of the invention is for a kind of novel process that is prepared the ferric lithium phosphate precursor tertiary iron phosphate by hydrous iron oxide is provided, should preparation is simple, cost is low, the product crystal structure is good, impurity is less, epigranular, be fit to carry out industrial scale production.For this reason, the present invention is by the following technical solutions:
This technique synthesis step comprises:
, zeroth order source of iron, corrosive acid mixed and add water and ammoniacal liquor, slowly add hydrogen peroxide behind the stirring reaction, add the hydrogen peroxide time more than or equal to 2 hours, until the zeroth order source of iron disappears, solution becomes safran, reaction generates hydrous iron oxide, and the reaction under the effect of corrosive acid is: Fe+2H
2O → FeOOH+2H
2
(2), the solution that step (1) is obtained adds the tensio-active agent with respect to source of iron zeroth order quality 1～5%;
(3), solution that step (2) is obtained under stirring state, splash into ammoniacal liquor and adjust the pH value in 1.1～2.4, the reagent that adds phosphorous acid group obtains the tertiary iron phosphate precipitation;
(4), the tertiary iron phosphate sedimentable matter is filtered, the tertiary iron phosphate that leaches is with 3～7 times of water washings of its weight 3～5 times, and vacuum-drying is 4～12 hours under 50～90 ℃ of conditions, obtains product F ePO
42H
2O.
On the basis of adopting technique scheme, the present invention also can adopt following further technical scheme:
Described zeroth order source of iron refers to one or more in the spheroidal graphite cast iron powder of mass content 95% of the reduced iron powder of mass content 92% of reduced iron powder, iron of the mass content 98% of iron and iron.
The hydrogen ion mol ratio of described zeroth order source of iron and corrosive acid is 1:2～4.
Used corrosive acid is one or more in dilute hydrochloric acid, dilute sulphuric acid, hexenoic acid, rare nitric acid, citric acid, the tartrate.
Used tensio-active agent is one or more in tween-80, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, cetyl trimethylammonium bromide, polyoxyethylene glycol, the peregal.
The mol ratio of ferro element and phosphoric is 1:0.9～1.1 in the step (3).
The reagent of phosphorous acid group refers to one or more in phosphoric acid, ammonium phosphate, Secondary ammonium phosphate and the primary ammonium phosphate.
Hydrous iron oxide (FeOOH) has higher specific surface area and trickle grain pattern, is a kind of effective sorbent material, and the research of using its characterization of adsorption processing heavy metal contamination has obtained good success.Hydrous iron oxide is because size is little, and surperficial shared percent by volume is larger.The key attitudes, electronic state, Atomic coordinate on surface etc. are different from granule interior, thereby cause the active sites on surface to increase, and this just makes it possess primary condition as catalyzer.Along with reducing of particle diameter, smooth surface degree variation has formed scraggly atomic steps, thereby has increased the contact surface of chemical reaction.Its chemical catalysis effect mainly can be summed up as three aspects: the one, improve speed of response; The 2nd, reduce temperature of reaction; The 3rd, determine response path, improve selectivity.Hydrous iron oxide is used for the catalyzer of high molecular polymer oxidation, reduction and building-up reactions at present, can greatly improve reaction efficiency.At high temperature react the generation tertiary iron phosphate with respect to wustite and source of phosphoric acid, the reactive behavior of hydrous iron oxide own is higher, can be used as the source of iron of producing battery-grade iron phosphate, hydrous iron oxide is processed at low temperatures and can be obtained the tertiary iron phosphate precipitation, has simple, easily row, characteristic with low cost.
Owing to adopting technical scheme of the present invention, the present invention is simple for process, cost is low, the product crystal structure is good, impurity is less, epigranular, be fit to carry out industrial scale production.Iron lithium phosphate by the preparation of this tertiary iron phosphate has: the first charge-discharge specific storage is high, efficient is high, self-discharge rate is low, tap density is large, batch stability is high and the advantage such as good processability.
Description of drawings
Fig. 1 is X-ray diffraction (XRD) figure of the tertiary iron phosphate of embodiment 1 preparation;
Fig. 2 is scanning electronic microscope (SEM) figure of the tertiary iron phosphate of embodiment 1 preparation;
Fig. 3 is X-ray diffraction (XRD) figure by the iron lithium phosphate that tertiary iron phosphate synthesized of embodiment 1 preparation;
Fig. 4 is the first charge-discharge graphic representation by the iron lithium phosphate that tertiary iron phosphate synthesized of embodiment 1 preparation;
Embodiment
With 2.8g reduced iron powder (iron level 98%), 6g Glacial acetic acid and 10g citric acid standing and reacting 2 hours in water of 200 ml.Reduced iron powder reacts completely and then slowly adds hydrogen peroxide (massfraction 10%), and adding the hydrogen peroxide time is 2 hours, until the zeroth order source of iron disappears, solution becomes safran, generates hydrous iron oxide this moment.In solution, add the 0.14g Sodium dodecylbenzene sulfonate again.After 5.65g strong phosphoric acid dilution is 2 times of volumes, under agitation condition, slowly join in the solution, add weak ammonia and regulate pH value 1.5, obtain tertiary iron phosphate and precipitate.Obtained product F ePO with a water washing of 52g 4 times in 4 hours 90 ℃ of lower vacuum-dryings at last
42H
2O.Carry out the analysis of X-ray powder diffraction after 6 hours at 600 ℃ of lower sintering, the result shows that (Fig. 1) prepared powder is FeP0
4, there is not impurity peaks in the spectrogram, product purity is high.Fig. 2 is that the tertiary iron phosphate powder of preparation amplifies 30,000 times electron micrograph, and the product particle size is substantially at 0.2 μ m.XRD(Fig. 3 by iron phosphate powder) sample is pure phase as can be known.Detect through the tap density instrument, the iron lithium phosphate tap density of this method preparation is at 1.05, D
50At 4.2 microns, processing characteristics is excellent.Fig. 4 is for take the tertiary iron phosphate of preparation as the first charge-discharge curve of iron lithium phosphate under 0.2C that raw material synthesize, its first efficient be 98%, the discharge gram volume is 156mAh/g, has first discharge specific capacity high, first the high advantage of coulomb efficient.Owing to being pure phase, do not use other doped with metal elements, guaranteed the stability of product batches, and structure is constant in the working cycle, possess the advantage of long service life.
Embodiment 2:
With 14g reduced iron powder (iron level 98%), 15g dilute hydrochloric acid, 0.56g hexenoic acid and 26.3g citric acid standing and reacting 2 hours in water 2000ml.Then slowly add hydrogen peroxide (massfraction 10%), adding the hydrogen peroxide time is 3 hours, until reduced iron powder reacts completely, generates hydrous iron oxide this moment.。In solution, add the 0.14g tween-80 again.After 28.25g strong phosphoric acid dilution is 3 times of volumes, under agitation condition, slowly join in the solution, add weak ammonia and regulate pH value 1.8, obtain tertiary iron phosphate and precipitate.Obtained product F ePO with a water washing of 112g 3 times in 12 hours 50 ℃ of lower vacuum-dryings at last
42H
2O.
Embodiment 3:
With 14g reduced iron powder (iron level 98%), 45g dilute sulphuric acid and 5 g citric acids stirring reaction 4 hours in water 2000ml.Then slowly add hydrogen peroxide (massfraction 10%), adding the hydrogen peroxide time is 3 hours, until reduced iron powder reacts completely, generates hydrous iron oxide this moment.In solution, add the 0.3g sodium lauryl sulphate again.After 32g ammonium phosphate is mixed with 1mol/L solution, under agitation condition, slowly joins and obtain the tertiary iron phosphate precipitation in the solution, add weak ammonia and regulate the pH value 1.6.Obtained product F ePO with a water washing of 150g 4 times in 10 hours 80 ℃ of lower vacuum-dryings at last
42H
2O.
Embodiment 4:
With 14g spheroidal graphite cast iron powder (iron level 95%), the rare nitric acid of 63g and 0.5g hexenoic acid stirring reaction 24 hours in water 1500ml.Then slowly add hydrogen peroxide (massfraction 10%), adding the hydrogen peroxide time is 2.5 hours, until the spheroidal graphite cast iron powder reacts completely, generates hydrous iron oxide this moment.In solution, add the 0.3g cetyl trimethylammonium bromide again.After 28.25g strong phosphoric acid dilution is 4 times of volumes, adds weak ammonia and regulate pH value 1.3, under agitation condition, slowly join and obtain tertiary iron phosphate in the solution and precipitate.Obtained product F ePO with a water washing of 180g 5 times in 5 hours 90 ℃ of lower vacuum-dryings at last
42H
2O.
Embodiment 5:
With 7g spheroidal graphite cast iron powder (iron level 95%), 35g Glacial acetic acid and 5ml concentrated nitric acid stirring reaction 18 hours in water 800ml.Then slowly add hydrogen peroxide (massfraction 10%), adding the hydrogen peroxide time is 2.5 hours, until the spheroidal graphite cast iron powder reacts completely, generates hydrous iron oxide this moment.In solution, add the 0.2g polyoxyethylene glycol again.After 15g strong phosphoric acid dilution is 3 times of volumes, adds weak ammonia and regulate pH value 1.5, under agitation condition, slowly join and obtain tertiary iron phosphate in the solution and precipitate.Obtained product F ePO with a water washing of 138g 5 times in 8 hours 70 ℃ of lower vacuum-dryings at last
42H
2O.
Embodiment 6:
With 7g spheroidal graphite cast iron powder (iron level 95%), 35g oxalic acid and 5ml concentrated nitric acid stirring reaction 15 hours in water 800ml.Then slowly add hydrogen peroxide (massfraction 10%), adding the hydrogen peroxide time is 2.5 hours, until the spheroidal graphite cast iron powder reacts completely, generates hydrous iron oxide this moment.In solution, add the 0.2g peregal again.After being mixed with the 15g primary ammonium phosphate behind the 1 mol/L solution, adding weak ammonia and regulate pH value 1.8, under agitation condition, slowly join and obtain tertiary iron phosphate in the solution and precipitate.Obtained product F ePO with a water washing of 138g 5 times in 5 hours 90 ℃ of lower vacuum-dryings at last
42H
2O.
Embodiment 7:
With 7g reduced iron powder (iron level 98%) and 28g Glacial acetic acid stirring reaction 24 hours in water 500ml.Then slowly add hydrogen peroxide (massfraction 10%), until reduced iron powder reacts completely, adding the hydrogen peroxide time is 2 hours, generates hydrous iron oxide this moment.In solution, add the 0.4g sodium lauryl sulphate again.After 14.6g strong phosphoric acid dilution is 3 times of volumes, under agitation condition, slowly joins and obtain the tertiary iron phosphate precipitation in the solution.Obtained product F ePO with a water washing of 100g 3 times in 5 hours 90 ℃ of lower vacuum-dryings at last
42H
2O.
Embodiment 8:
With 14g reduced iron powder (iron level 92%), 55g Glacial acetic acid and 10g tartrate stirring reaction 24 hours in water 1500 ml.Then slowly add hydrogen peroxide (massfraction 10%), adding the hydrogen peroxide time is 2.5 hours, until reduced iron powder reacts completely, generates hydrous iron oxide this moment.In solution, add the 0.7g sodium lauryl sulphate again.The 30.4g Secondary ammonium phosphate is diluted for behind the 1mol/L solution, under agitation condition, slowly join and obtain the tertiary iron phosphate precipitation in the solution.Obtained product F ePO with a water washing of 240g 5 times in 7 hours 80 ℃ of lower vacuum-dryings at last
42H
2O.
Claims (7)
1. a novel process that is prepared low-cost cell-grade tertiary iron phosphate material by hydrous iron oxide is characterized in that, this technique synthesis step comprises:
(1), zeroth order source of iron, corrosive acid are mixed and are added water and ammoniacal liquor, slowly add hydrogen peroxide behind the stirring reaction, add the hydrogen peroxide time more than or equal to 2 hours, until the zeroth order source of iron disappears, solution becomes safran, reaction generates hydrous iron oxide, and the reaction under the effect of corrosive acid is: Fe+2H
2O → FeOOH+2H
2
(2), the solution that step (1) is obtained adds the tensio-active agent with respect to source of iron zeroth order quality 1～5%;
(3), solution that step (2) is obtained under stirring state, splash into ammoniacal liquor and adjust the pH value in 1.1～2.4, the reagent that adds phosphorous acid group obtains the tertiary iron phosphate precipitation;
(4), the tertiary iron phosphate sedimentable matter is filtered, the tertiary iron phosphate that leaches is with 3～7 times of water washings of its weight 3～5 times, and vacuum-drying is 4～12 hours under 50～90 ℃ of conditions, obtains product F ePO
42H
2O.
2. method according to claim 1 is characterized in that, described zeroth order source of iron refers to one or more in the spheroidal graphite cast iron powder of mass content 95% of the reduced iron powder of mass content 92% of reduced iron powder, iron of the mass content 98% of iron and iron.
3. novel process according to claim 1 is characterized in that, the hydrogen ion mol ratio of described zeroth order source of iron and corrosive acid is 1:2～4.
4. novel process according to claim 1 is characterized in that, used corrosive acid is one or more in dilute hydrochloric acid, dilute sulphuric acid, hexenoic acid, rare nitric acid, citric acid, the tartrate.
5. novel process according to claim 1 is characterized in that, used tensio-active agent is one or more in tween-80, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, cetyl trimethylammonium bromide, polyoxyethylene glycol, the peregal.
6. novel process according to claim 1 is characterized in that, the mol ratio of ferro element and phosphoric is 1:0.9～1.1 in the step (3).
7. novel process according to claim 1 is characterized in that, the reagent of phosphorous acid group refers to one or more in phosphoric acid, ammonium phosphate, Secondary ammonium phosphate and the primary ammonium phosphate.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107046132A (en) * | 2017-04-26 | 2017-08-15 | 浙江米粒新能源科技有限公司 | A kind of preparation method of high pure and ultra-fine LITHIUM BATTERY manganese phosphate |
| 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 |
| CN111180708A (en) * | 2020-01-16 | 2020-05-19 | 昆明理工大学 | Lithium ion battery ferrous oxalate composite negative electrode material and preparation method thereof |
| CN113666351A (en) * | 2021-08-31 | 2021-11-19 | 广东邦普循环科技有限公司 | Method for preparing iron phosphate by recycling nickel iron slag |
| CN114715868A (en) * | 2022-03-16 | 2022-07-08 | 桂林理工大学 | Method for preparing spherical high-density low-impurity lithium iron phosphate precursor from goethite |
| CN116605916A (en) * | 2023-05-31 | 2023-08-18 | 湖北虹润高科新材料有限公司 | Preparation method of alpha-FeOOH and preparation method of ferric phosphate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102101662A (en) * | 2011-04-01 | 2011-06-22 | 四川大学 | Preparation method and product of ferric phosphate |
| 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 |
| CN102515129A (en) * | 2011-12-20 | 2012-06-27 | 江苏中电长迅能源材料有限公司 | Preparation method for submicron battery-grade ferric phosphate |
-
2012
- 2012-11-09 CN CN2012104469832A patent/CN102897739A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102101662A (en) * | 2011-04-01 | 2011-06-22 | 四川大学 | Preparation method and product of ferric phosphate |
| 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 |
| CN102515129A (en) * | 2011-12-20 | 2012-06-27 | 江苏中电长迅能源材料有限公司 | Preparation method for submicron battery-grade ferric phosphate |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107046132A (en) * | 2017-04-26 | 2017-08-15 | 浙江米粒新能源科技有限公司 | A kind of preparation method of high pure and ultra-fine LITHIUM BATTERY manganese phosphate |
| CN107046132B (en) * | 2017-04-26 | 2019-09-06 | 浙江米粒新能源科技有限公司 | A kind of preparation method of high pure and ultra-fine LITHIUM BATTERY manganese phosphate |
| 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 |
| CN111180708A (en) * | 2020-01-16 | 2020-05-19 | 昆明理工大学 | Lithium ion battery ferrous oxalate composite negative electrode material and preparation method thereof |
| CN111180708B (en) * | 2020-01-16 | 2022-04-08 | 昆明理工大学 | Lithium ion battery ferrous oxalate composite negative electrode material and preparation method thereof |
| CN113666351A (en) * | 2021-08-31 | 2021-11-19 | 广东邦普循环科技有限公司 | Method for preparing iron phosphate by recycling nickel iron slag |
| WO2023029571A1 (en) * | 2021-08-31 | 2023-03-09 | 广东邦普循环科技有限公司 | Method for preparing iron phosphate by recycling ferronickel slag |
| CN113666351B (en) * | 2021-08-31 | 2023-12-12 | 广东邦普循环科技有限公司 | Method for preparing ferric phosphate by recycling ferronickel slag |
| CN114715868A (en) * | 2022-03-16 | 2022-07-08 | 桂林理工大学 | Method for preparing spherical high-density low-impurity lithium iron phosphate precursor from goethite |
| CN116605916A (en) * | 2023-05-31 | 2023-08-18 | 湖北虹润高科新材料有限公司 | Preparation method of alpha-FeOOH and preparation method of ferric phosphate |
| CN116605916B (en) * | 2023-05-31 | 2024-02-20 | 湖北虹润高科新材料有限公司 | Preparation method of alpha-FeOOH and preparation method of ferric phosphate |
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Application publication date: 20130130 |