CN102807203A - Preparation method for nanocluster structure iron phosphate - Google Patents
Preparation method for nanocluster structure iron phosphate Download PDFInfo
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- CN102807203A CN102807203A CN2012102329141A CN201210232914A CN102807203A CN 102807203 A CN102807203 A CN 102807203A CN 2012102329141 A CN2012102329141 A CN 2012102329141A CN 201210232914 A CN201210232914 A CN 201210232914A CN 102807203 A CN102807203 A CN 102807203A
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- iron
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- structure preparation
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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 relates to a preparation method for nanocluster structure iron phosphate, which comprises the following steps of: 1) adding ferric salt solution and inorganic phosphorous compound into a percussion flow device to be mixed, or adding ferrous salt solution and inorganic phosphorous compound into the percussion flow device, meanwhile, adding oxidant into ferrous salt solution, mixing after the ferrous salt solution is completely oxidized, and obtaining mixed solution containing ferric iron ions; and 2) keeping the stirring state, regulating and controlling a reaction system by alkaline solution at a certain reaction temperature, meanwhile controlling the percussion flow speed to be 1000-3000rmp, continuously stirring after the alkaline solution is added, ageing, separating, washing with pure water, and drying to obtain the nanocluster structure iron phosphate. The preparation method for the nanocluster structure iron phosphate has the beneficial effect of simple technical process, and the good-dispersibility nanocluster structure iron phosphate of which the primary particle diameter is 10-100nm and the secondary particle diameter is 1-3mu m can be obtained.
Description
Technical field
The invention belongs to inorganic chemical industry material technology field, relate to a kind of method and technology field of preparation nanocluster structure tertiary iron phosphate in enormous quantities.
Background technology
Tertiary iron phosphate is mainly used in ceramic industry, food service industry, is widely used in the production of lithium ion battery anode material lithium iron phosphate in recent years.At battery industry; The tertiary iron phosphate route synthesizes battery anode material of lithium iron phosphate, is a kind of novel and competitive route, wherein the main raw material tertiary iron phosphate except that ferro element is provided, the phosphoric; Because the crystalline structure of tertiary iron phosphate and the crystalline structure of iron lithium phosphate are basic identical; Make the effect that tertiary iron phosphate also plays provides the basic skeleton of iron lithium phosphate, so character such as pattern of tertiary iron phosphate, structure, element proportioning, have a strong impact on the chemical property of iron lithium phosphate.
Domestic research of in industry, using for the tertiary iron phosphate with special construction is more, particularly for the tertiary iron phosphate with nanometer and vesicular structure, has syntheticly obtained some achievements in research with performance study for it.This tertiary iron phosphate with nanometer and vesicular structure generally be by molysite and phosphoric acid salt in solution state, it is synthetic via hydrothermal method to add template, mineralizer, tensio-active agent etc., is widely used at aspects such as Industrial Catalysis, surface passivation and IXs.But in the battery material field; Patent is said at present all is to adopt traditional liquid phase-precipitator method to prepare the tertiary iron phosphate precursor basically; And study the control that generally concentrates on synthetic middle impurity ion content, ignored control to this body structure of material and pattern, and relatively large, the skewness of tertiary iron phosphate precursor particle of preparation under traditional alr mode; Agglomeration is serious, is not easy to mix with the lithium source.
Summary of the invention
The present invention proposes a kind of nanocluster structure preparation method of ferric phosphate, it adopts impact flow reactor can realize the continuous large batch of production of nanocluster structure tertiary iron phosphate.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: nanocluster structure preparation method of ferric phosphate,
It is characterized in that including following steps:
1) adopting the percussion flow device, is that the 1:1 adding wherein mixes with iron salt solutions and inorganic phosphorus compound by the mol ratio of iron phosphorus; Or adopt the percussion flow device, with ferrous salt solution and inorganic phosphorus compound by the mol ratio of iron phosphorus be the 1:1 adding wherein, mix after adding oxygenant to ferrous salt solution complete oxidation simultaneously, obtain containing the mixing solutions of ferric ion;
2) keep whipped state; Under certain temperature of reaction; Through pH value to 1.5 ~ 3.0 of basic soln regulation and control reaction system, control percussion flow speed 1000 ~ 3000rmp simultaneously, add basic soln and finish continued stirring 15 ~ 90min; Through overaging, separation, pure water washing and oven dry, obtain nanocluster structure tertiary iron phosphate.
Press such scheme, described iron salt solutions is ferric sulfate, iron nitrate, iron(ic)chloride or iron acetate solution, and described ferrous salt solution is ferrous sulfate, Iron nitrate, iron protochloride or Iron diacetate.
Press such scheme, described inorganic phosphorus compound is phosphoric acid, primary ammonium phosphate or SODIUM PHOSPHATE, MONOBASIC.
Press such scheme, described oxygenant is air, oxygen, Youxiaolin, VAL-DROP or ydrogen peroxide 50.
Press such scheme, described basic soln is sodium hydroxide, Pottasium Hydroxide or ammoniacal liquor, and the mass percent concentration of basic soln is 0.5 ~ 15%.
Press such scheme, described iron salt solutions or ferrous salt solution are the saturated solution of at room temperature preparing.
Press such scheme, step 2) described range of reaction temperature is 60 ~ 95 ℃, and the percussion flow time is 30 ~ 180 min, and digestion time is 30 ~ 240 min.
Press such scheme, it is 25 ~ 60 ℃ that the pure water temperature is used in described washing.
Press such scheme, described bake out temperature is 120 ~ 600 ℃, and drying time is 120 ~ 300 min.
In liquid-phase reaction system, material is done liquid motion under anchor formula or slurry formula whipped state, and its mode of motion is decided by alr mode, also influences collision of molecules mode, streaming fluid structure and blending state, thus the state of aggregation of the decision product that forms.The employing impact flow reactor carries out intermolecular collision by material and reacts under the percussion flow state, for granularity, the pattern of controlling product unique effect is arranged.
Beneficial effect of the present invention is: preparing method's technological process of the present invention is simple; Can obtain the primary particle particle diameter between 10 ~ 100 nm; The offspring particle diameter between 1 ~ 3 μ m, the nanocluster tertiary iron phosphate of good dispersivity; It can be used for the preparation of lithium ion battery anode material lithium iron phosphate, also can be used for fields such as foodstuff additive, biological medicine.
Description of drawings
Fig. 1 is the particle size distribution figure and the sem photograph of embodiment 1 tertiary iron phosphate;
Fig. 2 is the LiFePO 4 sem photograph of embodiment 1.
Embodiment
are done further detailed explanation below in conjunction with embodiment to the present invention, but this explanation can not be construed as limiting the invention.
Embodiment 1
Get 5.5kg iron nitrate (Fe (NO
3)
39H
2O) in the 4L deionized water dissolving, more slowly to wherein adding 1.56kg NH
4H
2PO
4, transfer in the impact flow reactor, be heated to 80 ℃ after; Regulating percussion flow speed is 1000 rpm, and time 120min is under whipped state; Using mass percent concentration is after 10% aqueous sodium hydroxide solution is regulated pH=1.80; Continue to stir 30 min, behind aging then 240 min, using temperature is that 30 ℃ of pure water are washed till liquid effluent pH=5.5.Filter cake obtains white anhydrous tertiary iron phosphate powder, productive rate 99.5% at 600 ℃ of thermal treatment 200min.Product electromicroscopic photograph and size-grade distribution are seen accompanying drawing 1, product good dispersivity, primary particle particle diameter between 10 ~ 100nm, offspring D
50Be 2.0 μ m.Prepare iron lithium phosphate with this tertiary iron phosphate and see accompanying drawing 2, good dispersivity, even particle size distribution, button cell 0.1C loading capacity can reach 165mAh/g.
Get 2.59kg ferrous sulfate (FeSO
47H
2O) add the 4L dissolved in purified water, slowly transfer in the impact flow reactor again, add the sodium chlorate aqueous solution to the ferrous sulfate complete oxidation to wherein adding 1.13kg phosphoric acid (mass percent 85%); After being heated to 90 ℃, regulate percussion flow speed 3000 rpm, time 60min; Under whipped state; Using mass percent concentration is after 8% potassium hydroxide aqueous solution is regulated pH=2.50, to continue to stir 15 min, aging then 150 min; Filter, using temperature is that 30 ℃ of pure water are washed till liquid effluent pH=5.0.Throw out is obtained phosphate dihydrate iron powder, productive rate 99.5% 120 ℃ of dryings after 120 minutes.Product good dispersivity, primary particle particle diameter between 10 ~ 100nm, offspring D
50Be 1.0 μ m.Prepare iron lithium phosphate with this tertiary iron phosphate, good dispersivity, even particle size distribution, the 0.1C charge/discharge capacity reaches 160 mAh/g.
Embodiment 3
Get 2.59kg ferrous sulfate (FeSO
47H
2O) use the 4L dissolved in purified water, more slowly to wherein adding 0.68L H
3PO
4(mass percent 85%) transferred to impact flow reactor, slowly adds ydrogen peroxide 50 to complete oxidation, be heated to 85 ℃ after; Regulate percussion flow speed 2000 rpm, time 90min is under the whipped state; Using concentration is after 15% ammonia soln is regulated pH=2.00; Continue to stir 90 min, behind aging then 30 min, be washed till liquid effluent pH=6.0 with 50 ℃ of pure water.Throw out is obtained white anhydrous tertiary iron phosphate powder 450 ℃ of dryings after 240 minutes, productive rate 99.5%, product good dispersivity, primary particle particle diameter between 10 ~ 100nm, offspring D
50Be 3.0 μ m.Prepare iron lithium phosphate with this tertiary iron phosphate, good dispersivity, even particle size distribution, button cell 0.1C charge/discharge capacity reaches 160 mAh/g.
Get 3.64kg iron nitrate (Fe (NO
3)
39H
2O) in the 4L deionized water dissolving, more slowly to wherein adding 1.1 kg H
3PO
4(mass percent 85%) transferred in the impact flow reactor, be heated to 80 ℃ after; Regulating percussion flow speed is 1500 rpm, and time 60min is under whipped state; Using mass percent concentration is after 15% ammoniacal liquor is regulated pH=3.0; Continue to stir 60 min, behind aging then 240 min, using temperature is that 50 ℃ of pure water are washed till liquid effluent pH=6.0.Filter cake obtains white anhydrous tertiary iron phosphate powder, productive rate 99.5% at 550 ℃ of thermal treatment 200min.Product through with preparation LiFePO 4 after lithium source, carbon source are mixed, the ferrousphosphate lithium material good processability that obtains, button cell 0.1C loading capacity can reach 165mAh/g.
Claims (9)
1. nanocluster structure preparation method of ferric phosphate is characterized in that including following steps:
1) adopting the percussion flow device, is that the 1:1 adding wherein mixes with iron salt solutions and inorganic phosphorus compound by the mol ratio of iron phosphorus; Or adopt the percussion flow device, with ferrous salt solution and inorganic phosphorus compound by the mol ratio of iron phosphorus be the 1:1 adding wherein, mix after adding oxygenant to ferrous salt solution complete oxidation simultaneously, obtain containing the mixing solutions of ferric ion;
2) keep whipped state; Under certain temperature of reaction; Through pH value to 1.5 ~ 3.0 of basic soln regulation and control reaction system, control percussion flow speed 1000 ~ 3000rmp simultaneously, add basic soln and finish continued stirring 15 ~ 90min; Through overaging, separation, pure water washing and oven dry, obtain nanocluster structure tertiary iron phosphate.
2. nanocluster structure preparation method of ferric phosphate according to claim 1; It is characterized in that: described iron salt solutions is ferric sulfate, iron nitrate, iron(ic)chloride or iron acetate solution, and described ferrous salt solution is ferrous sulfate, Iron nitrate, iron protochloride or Iron diacetate.
3. nanocluster structure preparation method of ferric phosphate according to claim 1 and 2 is characterized in that: described inorganic phosphorus compound is phosphoric acid, primary ammonium phosphate or SODIUM PHOSPHATE, MONOBASIC.
4. nanocluster structure preparation method of ferric phosphate according to claim 1 and 2 is characterized in that: described oxygenant is air, oxygen, Youxiaolin, VAL-DROP or ydrogen peroxide 50.
5. nanocluster structure preparation method of ferric phosphate according to claim 1 and 2 is characterized in that: described basic soln is sodium hydroxide, Pottasium Hydroxide or ammoniacal liquor, and the mass percent concentration of basic soln is 0.5 ~ 15%.
6. nanocluster structure preparation method of ferric phosphate according to claim 1 and 2 is characterized in that: described iron salt solutions or the ferrous salt solution saturated solution at room temperature preparing.
7. nanocluster structure preparation method of ferric phosphate according to claim 1 and 2 is characterized in that: step 2) described range of reaction temperature is 60 ~ 95 ℃, and the percussion flow time is 30 ~ 180 min, and digestion time is 30 ~ 240 min.
8. nanocluster structure preparation method of ferric phosphate according to claim 1 and 2 is characterized in that: it is 25 ~ 60 ℃ that the pure water temperature is used in described washing.
9. nanocluster structure preparation method of ferric phosphate according to claim 1 and 2 is characterized in that: described bake out temperature is 120 ~ 600 ℃, and drying time is 120 ~ 300 min.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103011119A (en) * | 2012-12-17 | 2013-04-03 | 南京工业大学 | Preparation method of nano ferric phosphate |
| CN104505495A (en) * | 2014-12-09 | 2015-04-08 | 山东精工电子科技有限公司 | Method for ultrasonic preparation of nano iron phosphate of lithium iron phosphate |
| CN110304617A (en) * | 2019-08-01 | 2019-10-08 | 湖北昊瑞新能源有限公司 | A kind of preparation method of low cost ferric orthophosphate |
| CN114074934A (en) * | 2020-08-14 | 2022-02-22 | 中国科学院上海硅酸盐研究所 | Amorphous inorganic solid electrolyte and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60226572A (en) * | 1984-04-24 | 1985-11-11 | Sanyo Chem Ind Ltd | Resin composition for coating compound of anode electrodeposition |
| US6447697B1 (en) * | 1999-03-03 | 2002-09-10 | Astaris, Llc | Colorant liquid, method of use, and wildland fire retardant liquids containing same |
| CN102009967A (en) * | 2010-12-23 | 2011-04-13 | 武汉大学 | Method for preparing iron phosphate with micro/nano structure |
-
2012
- 2012-07-06 CN CN2012102329141A patent/CN102807203A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60226572A (en) * | 1984-04-24 | 1985-11-11 | Sanyo Chem Ind Ltd | Resin composition for coating compound of anode electrodeposition |
| US6447697B1 (en) * | 1999-03-03 | 2002-09-10 | Astaris, Llc | Colorant liquid, method of use, and wildland fire retardant liquids containing same |
| CN102009967A (en) * | 2010-12-23 | 2011-04-13 | 武汉大学 | Method for preparing iron phosphate with micro/nano structure |
Non-Patent Citations (2)
| Title |
|---|
| 伍沅 等: "液体连续相撞击流强化过程特性及相关技术装备的研发和作用", 《化工进展》 * |
| 周玉新 等: "撞击流反应制备纳米磷酸锌改进工艺研究", 《武汉理工大学学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103011119A (en) * | 2012-12-17 | 2013-04-03 | 南京工业大学 | Preparation method of nano ferric phosphate |
| CN104505495A (en) * | 2014-12-09 | 2015-04-08 | 山东精工电子科技有限公司 | Method for ultrasonic preparation of nano iron phosphate of lithium iron phosphate |
| CN110304617A (en) * | 2019-08-01 | 2019-10-08 | 湖北昊瑞新能源有限公司 | A kind of preparation method of low cost ferric orthophosphate |
| CN114074934A (en) * | 2020-08-14 | 2022-02-22 | 中国科学院上海硅酸盐研究所 | Amorphous inorganic solid electrolyte and preparation method thereof |
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