CN102675083A - Preparation method of ferrous oxalate - Google Patents
Preparation method of ferrous oxalate Download PDFInfo
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- CN102675083A CN102675083A CN2011100667204A CN201110066720A CN102675083A CN 102675083 A CN102675083 A CN 102675083A CN 2011100667204 A CN2011100667204 A CN 2011100667204A CN 201110066720 A CN201110066720 A CN 201110066720A CN 102675083 A CN102675083 A CN 102675083A
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Abstract
The invention discloses a preparation method of ferrous oxalate. The preparation method includes step (1), mixing 0.05-1.5mol/L of ferrous ion water solution and 0.05-2.0mol/L of oxalic acid ion water solution under the reaction temperature of 5-95 DEG C to obtain mixed solution; and step (2), conducting aging on the mixed solution obtained in the step (1) under the reaction temperature. When the reaction temperature is 5-70 DEG C, the aging time is 1 hour to 24 hours. When the reaction temperature is 70-95 DEG C, the aging time is 0.5-1 hour. The preparation method is convenient to operate. The purity of the prepared ferrous oxalate is over 99.3%. The prepared ferrous oxalate is controllable in particle size, single in crystal form and capable of meeting requirements of combining of anode material ferrous phosphate of a lithium ion battery.
Description
Technical field
The present invention relates to a kind of preparation method of Ferrox.
Background technology
Lithium ion battery, particularly lithium-ion-power cell are to receive whole world extensive concern also by the chemical energy source system of studying energetically, and its application on power car will be alleviated the day by day exhausted crisis of global petroleum resources to a certain extent.
In the positive electrode material of existing lithium-ion-power cell, iron lithium phosphate obtains researchist's extensive approval and primary study owing to having good safety performance and high-rate discharge ability.During synthesizing iron lithium phosphate; Molysite commonly used is a Ferrox; Because the valence state of iron is identical with iron lithium phosphate in the Ferrox, need change the chemical reaction of iron ion valence state, and be that raw material can not introduced other independent elements in the iron lithium phosphate that makes with the Ferrox.Yet, the defective that existing Ferrox product ubiquity granularity is bigger than normal, purity is on the low side.Mixing of materials was irregular when the existence of these defectives can cause synthesizing iron lithium phosphate on the one hand, and the iron lithium phosphate purity that makes is not high, and electrochemical properties is not good; On the other hand, impure its thermal process reactor that also can make of Ferrox crystal formation is unstable, and then influences the performance of the iron lithium phosphate that makes.Therefore, preparation high purity, small particle size, the single Ferrox of crystal formation, significant for synthesizing lithium ion power battery anode material iron lithium phosphate.
Chinese patent CN101376626A discloses a kind of preparation method of Ferrox hydrated salt crystal.This method is carried out short-time contact reaction (be 10 seconds～1 minute duration of contact) with divalent iron salt solution and oxalic acid or oxalate solution, makes the Ferrox particle of particle diameter less than 10m, is used for the synthetic of lithium ion battery anode material lithium iron phosphate.The advantage of this method is that material duration of contact short, and shortcoming is to be difficult to make mixing of materials evenly and generate the Ferrox particle of quality homogeneous the so short time, and simultaneously, variation of temperature also can cause the generation of heterogeneous structure.
Chinese patent CN100488937C discloses the working method of the special-purpose Ferrox of a kind of iron lithium phosphate.This method is regulated the reaction of oxalate denominationby and ferrous ion through the ratio of control oxalic acid and ammonium oxalate, synthesizes the Ferrox particle with different crystal structure with this.This method realizes the adjusting of ammonium ion through the mode that imports ammonia, complicated operation, and its particle diameter that obtains particle is unfavorable for that greater than 10 μ m iron lithium phosphate prepares the uniform mixing of material in the process.
Summary of the invention
Technical problem to be solved by this invention is to have overcome prior art mesoxalic acid ferrous preparation method complicated operation; The Ferrox particle mass that obtains is inhomogeneous, purity is low; Be unfavorable for preparing the defective of the good iron lithium phosphate of electrochemical properties; Provide a kind of easy and simple to handle, and the Ferrox purity that makes is high, size is controlled, the preparation method of the single Ferrox of crystal formation.
The preparation method of Ferrox of the present invention comprises the steps:
Step (1) is under 5～95 ℃ in temperature of reaction, with the ferrous ion aqueous solution of 0.05～1.5mol/L and the oxalate denominationby aqueous solution of 0.05～2.0mol/L, gets mixing solutions; Wherein, Describedly be mixed into the ferrous ion aqueous solution with 0.05～1.5mol/L (preferred 5～80mL/min) speed joins in the oxalate denominationby aqueous solution of 0.05～2.0mol/L with 1～100mL/min; Perhaps, (preferred 5～80mL/min) speed joins in the ferrous ion aqueous solution of 0.05～1.5mol/L with 1～100mL/min with the oxalate denominationby aqueous solution of 0.05～2.0mol/L.
Step (2) is carried out ageing with step (1) gained mixing solutions under the described temperature of reaction of step (1), get final product; When temperature of reaction was 5～70 ℃, the described aged time was 1～24 hour; When temperature of reaction was 70～95 ℃, the described aged time was 0.5～1 hour.
Preferably, the consumption of the ferrous ion aqueous solution of the described 0.05～1.5mol/L of step (1) is 0.8～1.2L; The consumption of the oxalate denominationby aqueous solution of described 0.05～2.0mol/L is 0.8～1.2L.
Preferably, step (2) gained mixture is filtered,, get final product the washing of precipitate that obtains, drying.
Among the present invention, the source of described ferrous ion can be the soluble salt of the conventional ferrous ion that uses in this area, and preferable is ferrous sulfate and/or iron protochloride.
Among the present invention, the source of described oxalate denominationby can be the conventional soluble compound that contains oxalate denominationby that uses in this area, one or more that preferable is in oxalic acid, ammonium oxalate and the sodium oxalate.
On the basis of this area general knowledge, but above-mentioned each preferred feature arbitrary combination among the present invention promptly gets each preferred embodiment of the present invention.
Raw material described in the present invention or reagent except that specifying, all commercially available getting.
Positive progressive effect of the present invention is: the preparation method who the invention provides a kind of Ferrox.This method is easy and simple to handle; The Ferrox purity that makes reaches more than 99.3%, crystal formation is single; Also can obtain the Ferrox particle of different-grain diameter as required, particle size range can be controlled in 2～5 μ m, can satisfy the requirement of lithium ion battery anode material lithium iron phosphate synthetic.
Description of drawings
The XRD spectra of the Ferrox that Fig. 1 makes for embodiment 1.
The SEM photo of the Ferrox that Fig. 2 makes for embodiment 1.
The XRD spectra of the Ferrox that Fig. 3 makes for embodiment 3.
The SEM photo of the Ferrox that Fig. 4 makes for embodiment 3.
The SEM photo of the Ferrox that Fig. 5 makes for embodiment 4.
The XRD spectra of the Ferrox that Fig. 6 makes for embodiment 5.
The SEM photo of the Ferrox that Fig. 7 makes for embodiment 5.
The XRD spectra of the Ferrox that Fig. 8 makes for Comparative Examples 1.
Embodiment
Further specify the present invention with embodiment below, but the present invention is not limited.
Used raw material or reagent is except that specifying among the embodiment, all commercially available getting.
Embodiment 1
Respectively with respectively 1 liter of the oxalic acid aqueous solution of the ferrous sulfate aqueous solution of zero(ppm) water preparation 0.05mol/L and 0.05mol/L.Controlled temperature is 5 ℃, under the whipped state, ferrous sulfate aqueous solution is joined in the oxalic acid aqueous solution with the speed of 5mL/min react.Mixing of materials with system ageing 4 hours, then with after mother liquor filtration, washing, the drying, obtains yellow Ferrox powder after finishing.
Through test, the Ferrox for preparing through above-mentioned condition is single iris type (see figure 1), and the yield of Ferrox is 99.5%, and purity is 99.5%, and median size is 4.0 μ m, and particle is single cubic particle (see figure 2).
Embodiment 2
Respectively with respectively 1 liter of the ammonium oxalate aqueous solution of the ferrous sulfate aqueous solution of zero(ppm) water preparation 0.5mol/L and 0.5mol/L.Controlled temperature is 45 ℃, under the whipped state, ferrous sulfate aqueous solution is joined in the ammonium oxalate aqueous solution with the speed of 50mL/min react.Mixing of materials with system ageing 0.5 hour, then with after mother liquor filtration, washing, the drying, obtains yellow Ferrox powder after finishing.
Through test, the Ferrox for preparing through above-mentioned condition is single iris type, and the yield of Ferrox is 99.0%, and purity is 99.5%, and median size is 2.0 μ m, and particle is single cubic particle.
Embodiment 3
Respectively with respectively 1 liter of the sodium oxalate aqueous solution of the ferrous sulfate aqueous solution of zero(ppm) water preparation 1.0mol/L and 1.0mol/L.Controlled temperature is 25 ℃, under the whipped state, the sodium oxalate aqueous solution is joined in the ferrous sulfate aqueous solution with the speed of 50mL/min react.Mixing of materials with system ageing 2 hours, then with after mother liquor filtration, washing, the drying, obtains yellow Ferrox powder after finishing.
Through test, the Ferrox for preparing through above-mentioned condition is single iris type (see figure 3), and the yield of Ferrox is 99.2%, and purity is 99.4%, and median size is 3.7 μ m, and particle is single cubic particle (see figure 4).
Embodiment 4
Respectively with respectively 1 liter of the ammonium oxalate aqueous solution of the ferrous chloride aqueous solution of zero(ppm) water preparation 1.5mol/L and 1.5mol/L.Controlled temperature is 95 ℃, under the whipped state, the ammonium oxalate aqueous solution is joined in the solution of ferrous chloride with the speed of 100mL/min react.Mixing of materials with system ageing 0.5 hour, then with after mother liquor filtration, washing, the drying, obtains yellow Ferrox powder after finishing.
Through test, the Ferrox for preparing through above-mentioned condition also is single iris type, and the yield of Ferrox is 99.2%, and purity is 99.4%, and median size is 3.0 μ m, and particle is cubic particle (see figure 5).
Embodiment 5
Respectively with respectively 1 liter of the oxalic acid aqueous solution of the ferrous chloride aqueous solution of zero(ppm) water preparation 1.5mol/L and 1.5mol/L.Controlled temperature is 95 ℃, under the whipped state, oxalic acid aqueous solution is joined in the solution of ferrous chloride with the speed of 100mL/min react.Mixing of materials with system ageing 1.0 hours, then with after mother liquor filtration, washing, the drying, obtains yellow Ferrox powder after finishing.
Through test, the Ferrox for preparing through above-mentioned condition also is single iris type (see figure 6), and the yield of Ferrox is 99.1%, and purity is 99.4%, and median size is 2.5 μ m, and particle is cubic particle (see figure 7).
Embodiment 6
Respectively with respectively 1 liter of the ammonium oxalate aqueous solution of the ferrous sulfate aqueous solution of zero(ppm) water preparation 0.5mol/L and 0.5mol/L.Controlled temperature is 70 ℃, under the whipped state, ferrous sulfate aqueous solution is joined in the ammonium oxalate aqueous solution with the speed of 50mL/min react.Mixing of materials with system ageing 1 hour, then with after mother liquor filtration, washing, the drying, obtains yellow Ferrox powder after finishing.
Through test, the Ferrox for preparing through above-mentioned condition is single iris type, and the yield of Ferrox is 99.2%, and purity is 99.3%, and median size is 3.1 μ m, and particle is single cubic particle.
Embodiment 7
Respectively with respectively 1 liter of the sodium oxalate aqueous solution of the ferrous sulfate aqueous solution of zero(ppm) water preparation 1.0mol/L and 1.0mol/L.Controlled temperature is 25 ℃, under the whipped state, the sodium oxalate aqueous solution is joined in the ferrous sulfate aqueous solution with the speed of 1mL/min react.Mixing of materials with system ageing 24 hours, then with after mother liquor filtration, washing, the drying, obtains yellow Ferrox powder after finishing.
Through test, the Ferrox for preparing through above-mentioned condition is single iris type, and the yield of Ferrox is 99.6%, and purity is 99.5%, and median size is 4.2 μ m, and particle is single cubic particle.
Respectively with respectively 1 liter of the ammonium oxalate aqueous solution of the ferrous chloride aqueous solution of zero(ppm) water preparation 1.5mol/L and 2.0mol/L.Controlled temperature is 85 ℃, under the whipped state, the ammonium oxalate aqueous solution is joined in the solution of ferrous chloride with the speed of 80mL/min react.Mixing of materials with system ageing 1 hour, then with after mother liquor filtration, washing, the drying, obtains yellow Ferrox powder after finishing.
Through test, the Ferrox for preparing through above-mentioned condition also is single iris type, and the yield of Ferrox is 99.5%, and purity is 99.4%, and median size is 2.9 μ m, and particle is cubic particle.
Comparative Examples 1
Respectively with respectively 1 liter of the ammonium oxalate aqueous solution of the ferrous chloride aqueous solution of zero(ppm) water preparation 1.5mol/L and 1.5mol/L.Controlled temperature is 95 ℃, under the whipped state, the ammonium oxalate aqueous solution is joined in the solution of ferrous chloride with the speed of 100mL/min react.Mixing of materials with system ageing 2.5 hours, then with after mother liquor filtration, washing, the drying, obtains yellow Ferrox powder after finishing.
Through test, the dephasign (see figure 8) has appearred in the crystal formation of the Ferrox through the preparation of above-mentioned condition.
Comparative Examples 2
Respectively with respectively 1 liter of the ammonium oxalate aqueous solution of the ferrous chloride aqueous solution of zero(ppm) water preparation 1.5mol/L and 1.5mol/L.Controlled temperature is 50 ℃, under the whipped state, the ammonium oxalate aqueous solution is joined in the solution of ferrous chloride with the speed of 200mL/min react.Mixing of materials with system ageing 2 hours, then with after mother liquor filtration, washing, the drying, obtains yellow Ferrox powder after finishing.Through purity test, the purity of Ferrox is 96.7%.
Claims (7)
1. the preparation method of a Ferrox is characterized in that comprising the steps:
Step (1) is under 5～95 ℃ in temperature of reaction, with the ferrous ion aqueous solution of 0.05～1.5mol/L and the oxalate denominationby aqueous solution of 0.05～2.0mol/L, gets mixing solutions; Wherein, Described being mixed into joins the ferrous ion aqueous solution of the 0.05～1.5mol/L speed with 1～100mL/min in the oxalate denominationby aqueous solution of 0.05～2.0mol/L; Perhaps, the oxalate denominationby aqueous solution of the 0.05～2.0mol/L speed with 1～100mL/min is joined in the ferrous ion aqueous solution of 0.05～1.5mol/L;
Step (2) is carried out ageing with step (1) gained mixing solutions under the described temperature of reaction of step (1), get final product; When temperature of reaction was 5～70 ℃, the described aged time was 1～24 hour; When temperature of reaction was 70～95 ℃, the described aged time was 0.5～1 hour.
2. preparation method as claimed in claim 1 is characterized in that: the consumption of the ferrous ion aqueous solution of the described 0.05～1.5mol/L of step (1) is 0.8～1.2L; The consumption of the oxalate denominationby aqueous solution of the described 0.05～2.0mol/L of step (1) is 0.8～1.2L.
3. according to claim 1 or claim 2 preparation method is characterized in that: step (2) gained mixture is filtered, with the washing of precipitate that obtains, drying, get final product.
4. like each described preparation method of claim 1～3, it is characterized in that: being mixed into described in the step (1) joins the ferrous ion aqueous solution of the 0.05～1.5mol/L speed with 5～80mL/min in the oxalate denominationby aqueous solution of 0.05～2.0mol/L.
5. like each described preparation method of claim 1～3, it is characterized in that: being mixed into described in the step (1) joins the oxalate denominationby aqueous solution of the 0.05～2.0mol/L speed with 5～80mL/min in the ferrous ion aqueous solution of 0.05～1.5mol/L.
6. like each described preparation method of claim 1～5, it is characterized in that: the source of described ferrous ion is ferrous sulfate and/or iron protochloride.
7. like each described preparation method of claim 1～6, it is characterized in that: the source of described oxalate denominationby is one or more in oxalic acid, ammonium oxalate and the sodium oxalate.
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| CN2011100667204A CN102675083A (en) | 2011-03-18 | 2011-03-18 | Preparation method of ferrous oxalate |
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| CN2011100667204A CN102675083A (en) | 2011-03-18 | 2011-03-18 | Preparation method of ferrous oxalate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103276402A (en) * | 2013-05-21 | 2013-09-04 | 山西大学 | Method for treating waste liquor obtained in pickling of hot-rolled chromium stainless steel wire rod by using sulfuric acid process |
| CN106478407A (en) * | 2016-09-07 | 2017-03-08 | 昆明理工大学 | A kind of preparation method of lamellar structure Ferrox. |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101376626A (en) * | 2007-08-28 | 2009-03-04 | 比亚迪股份有限公司 | Preparation of iron oxalate hydrous salt crystal |
| CN101386575A (en) * | 2008-07-04 | 2009-03-18 | 合肥国轩高科动力能源有限公司 | Method for preparing iron oxalate |
| US20090252668A1 (en) * | 2008-04-07 | 2009-10-08 | Byd Company Limited | Methods For Preparing Iron Source Material And Ferrous Oxalate for Lithium Ferrous Phosphate |
-
2011
- 2011-03-18 CN CN2011100667204A patent/CN102675083A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101376626A (en) * | 2007-08-28 | 2009-03-04 | 比亚迪股份有限公司 | Preparation of iron oxalate hydrous salt crystal |
| US20090252668A1 (en) * | 2008-04-07 | 2009-10-08 | Byd Company Limited | Methods For Preparing Iron Source Material And Ferrous Oxalate for Lithium Ferrous Phosphate |
| CN101386575A (en) * | 2008-07-04 | 2009-03-18 | 合肥国轩高科动力能源有限公司 | Method for preparing iron oxalate |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103276402A (en) * | 2013-05-21 | 2013-09-04 | 山西大学 | Method for treating waste liquor obtained in pickling of hot-rolled chromium stainless steel wire rod by using sulfuric acid process |
| CN106478407A (en) * | 2016-09-07 | 2017-03-08 | 昆明理工大学 | A kind of preparation method of lamellar structure Ferrox. |
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Application publication date: 20120919 |