CN101376626A - Preparation of iron oxalate hydrous salt crystal - Google Patents
Preparation of iron oxalate hydrous salt crystal Download PDFInfo
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- CN101376626A CN101376626A CNA2007101475915A CN200710147591A CN101376626A CN 101376626 A CN101376626 A CN 101376626A CN A2007101475915 A CNA2007101475915 A CN A2007101475915A CN 200710147591 A CN200710147591 A CN 200710147591A CN 101376626 A CN101376626 A CN 101376626A
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Abstract
The invention provides a method for preparing ferrous oxalate hydrated salt crystals. The method comprises the following steps: carrying out the contact reaction between a solution A and a solution B. The contact manner and condition of the solution A and the solution B are provided to allow the produced ferrous oxalate hydrated salt to be supersaturated in the reaction mixed solution of the solution A and the solution B. By adopting the method, the prepared ferrous oxalate hydrated salt crystals have smaller average particle size and higher purity.
Description
Technical field
The invention relates to a kind of preparation method of Ferrox hydrated salt crystal.
Background technology
At present, the positive electrode material that lithium cell is commonly used is cobalt acid lithium (LiCoO
2), lithium nickel cobalt dioxide (LiNi
xCo
1-xO
2), nickle cobalt lithium manganate (LiNi
xCo
yMn
1-x-yO
2) and lithium manganate (LiMn
2O
4).LiCoO
2, LiNi
xCo
1-xO
2And LiNi
xCo
yMn
1-x-yO
2Have higher electroconductibility and lithium ion and take off the embedding reversibility, but safety performance is relatively poor, and the cost height.Lithium manganate (LiMn
2O
4Though) comparatively cheap and safety, but not only loading capacity is less for it, and the cycle life under hot conditions is relatively poor, and its cycle life can't satisfy the needs of actual use.
In order to solve the problem that exists in the above-mentioned lithium battery material, (A.K.Padhi such as texas,U.S college professor J.B.Goodenough, K.S.Najundaswamy, C.Masqueslier, S.Okadaand J.B.Goodenough, J.Electrochem.Soc.144,1609-1613 (1997)) a kind of new lithium intercalation compound is disclosed: lithium iron phosphate LiFePO in the academic article of delivering in 1997 on U.S.'s electrochemistry magazine
4Polycrystal.Its theoretical loading capacity can reach 170 MAH/grams, and has good safety performance, therefore is very suitable for the positive electrode material as the high-power drive pond.And lithium, iron and phosphorus all are the abundant elements of reserves on the earth, so its production cost is very low.
Usually with Ferrox as one of starting material of synthesizing lithium ferrous phosphate, its particle diameter is very big to the LiFePO 4 Effect on Performance.Because the electronics of LiFePO 4 itself and ionic electric conductivity are all very low, solving one of low method of ionic conductivity is exactly to reduce grain diameter, therefore also strict more to the requirement of raw material particle size, usually need raw material particle size less than 10 microns, the employing particle diameter is a raw material less than 10 microns ultra-fine Ferrox, can control the particle diameter of LiFePO 4 effectively.
" to the improvement of " three oxalic acid close the preparation of the sour potassium of iron (III) " " (Zheng Chenmou etc., university chemistry, 1999,14 (2)) put down in writing a kind of preparation method of Ferrox in the literary composition, this method is to add oxalic acid or potassium oxalate is made Ferrox in containing the solution of ferrous ion.But the Ferrox hydrated salt crystal median size of using this method to obtain is the 20-80 micron, and easily produces dephasign in the process of preparation Ferrox hydrated salt crystal.Therefore, such Ferrox is not suitable for use in the synthesis material of the positive active material LiFePO 4 of lithium-ion secondary cell.
Summary of the invention
The Ferrox hydrated salt crystal granularity that the objective of the invention is to overcome existing method preparation is bigger, and in the process of preparation Ferrox hydrated salt crystal, be easy to generate the defective of dephasign, a kind of preparation method that can obtain the Ferrox hydrated salt crystal that grain graininess is less and purity is higher is provided.
The invention provides a kind of preparation method of Ferrox hydrated salt crystal, this method comprises that this method comprises solution A and solution B contact reacts, described solution A is the solution that contains oxalic acid and/or oxalate, described solution B is the solution that contains divalent iron salt, wherein, the way of contact of described solution A and solution B and contact conditions make the Ferrox salt hydrate of reaction generation reach supersaturation in the reaction mixture of solution A and solution B.
Adopting the median size of the Ferrox hydrated salt crystal of method preparation provided by the invention is the 6-9 micron, and the purity of the Ferrox hydrated salt crystal of preparation is higher, and resulting Ferrox hydrated salt crystal is particularly suitable as the positive active material LiFePO of preparation lithium-ion secondary cell
4Or LiFeMePO
4The raw material of (Me is one or more among Mn, Co, Ni, the Al).
Description of drawings
The SEM figure of the Ferrox hydrated salt crystal that Fig. 1 obtains for embodiment 1;
The SEM figure of the Ferrox hydrated salt crystal that Fig. 2 obtains for embodiment 2;
The SEM figure of the Ferrox hydrated salt crystal that Fig. 3 obtains for embodiment 3;
The SEM figure of the Ferrox hydrated salt crystal that Fig. 4 obtains for Comparative Examples 1;
The SEM figure of the Ferrox hydrated salt crystal that Fig. 5 obtains for Comparative Examples 2;
The XRD diffractogram of the Ferrox hydrated salt crystal that Fig. 6 obtains for embodiment 1;
The XRD diffractogram of the Ferrox hydrated salt crystal that Fig. 7 obtains for embodiment 2;
The XRD diffractogram of the Ferrox hydrated salt crystal that Fig. 8 obtains for embodiment 3;
The XRD diffractogram of the Ferrox hydrated salt crystal that Fig. 9 obtains for Comparative Examples 1;
The XRD diffractogram of the Ferrox hydrated salt crystal that Figure 10 obtains for Comparative Examples 2.
Embodiment
Method provided by the invention comprises that this method comprises solution A and solution B contact reacts, described solution A is the solution that contains oxalic acid and/or oxalate, described solution B is the solution that contains divalent iron salt, wherein, the way of contact of described solution A and solution B and contact conditions make the Ferrox salt hydrate of reaction generation reach supersaturation in the reaction mixture of solution A and solution B.
The way of contact of described solution A and solution B is for adding solution A in the solution B or solution B is added in the solution A, and the joining day is 10 seconds-1 minute; Perhaps, the liquid flow of solution A contacts with the liquid flow of solution B, and the ratio of the flow velocity of the liquid flow of the liquid flow of solution A and solution B is 0.8-1.2.
When the liquid flow of described solution A contacted with the liquid flow of solution B, the present invention had no particular limits the flow velocity size of the liquid flow of the liquid flow of solution A and solution B, was 0.8-1.2 as long as make the ratio of flow velocity of the liquid flow of the liquid flow of solution A and solution B.Under the preferable case, the liquid flow of solution A contacts in 10 minutes with the liquid flow of solution B and finishes.
The concentration of described solution A and solution B is the 1.2-3 mol, and catalytic temperature is 25-60 ℃; Perhaps, the concentration of solution A and solution B is greater than 3 mol to 10 mol, and catalytic temperature is greater than 60 ℃ to 95 ℃.Under the preferable case, the concentration of described solution A is the 1.8-2.0 mol, and the concentration of described solution B is the 1.5-2.0 mol, and described catalytic temperature is 45-55 ℃.
Method provided by the invention is by the way of contact and the contact conditions of control solution A and solution B, the Ferrox salt hydrate that reaction is generated is in hypersaturated state in the reaction mixture of above-mentioned solution A and solution B, like this, the Ferrox salt hydrate will spontaneously be separated out a large amount of tiny nucleus, the formation speed of nucleus is very fast, be far longer than crystalline growth speed, therefore crystal also has little time to grow up, crystallisation process just is through with, so the crystal size that obtains is little, and, very fast because crystal is separated out, so the crystal purity that obtains is higher.
The mol ratio of the divalent iron salt in oxalic acid in the described solution A and/or oxalate and the solution B can be their conventional ratio, for example can be 0.6-1.0, is preferably 0.8-1.0.
Oxalate used in the present invention has no particular limits, and can select conventional various water-soluble oxalate for use, and for example, described oxalate can be in potassium oxalate, sodium oxalate and the ammonium oxalate one or more.Two oxalic acid hydrate (H wherein
2C
2O
42H
2O) obtain easily for industrial, and solubleness being higher, is particularly preferred therefore.
Divalent iron salt used in the present invention has no particular limits, and can select conventional various water-soluble divalent iron salt for use, and for example, described divalent iron salt can be ferrous sulfate and/or iron protochloride.Ferrous sulfate (FeSO wherein
47H
2O) obtain easily for industrial, and very cheap, be particularly preferred therefore.
This method also comprises the product solid-liquid separation after described solution A and the solution B contact reacts, with solid product washing and dry.
Described separation can utilize ordinary method to carry out as filtration and/or centrifugation method.
Described washing can be adopted washing or use the organic solvent washing solid product, and the time and the number of times of washing have no particular limits.
Described drying temperature is 50-90 ℃, is preferably 70-80 ℃; Can be 5-18 hour time of drying, is preferably 8-15 hour.Because if drying temperature is lower than 50 ℃, the then dry time that needs is oversize; If drying temperature is higher than 90 ℃, the phenomenon that ferrous iron is oxidized or crystal water breaks away from will take place.
Adopt embodiment that the present invention is explained in further detail below.
Embodiment 1
Stir down, with the ferrous sulfate (FeSO of 20 liter of 2.0 mol
47H
2O) solution joins the two oxalic acid hydrate (H that 20 liter of 1.8 mol is housed in 1 minute
2C
2O
4H
2O) in the reaction vessel of solution, adding finishes, and the temperature of reaction mixture is 50 ℃, and the Ferrox hydrated salt crystal is separated out thereupon, ageing 30 minutes.
Then, the filtered and recycled Ferrox is with the Ferrox of three washing and recycling of 60 liters of deionization moisture.Then, dry 12 hours of the Ferrox after will washing under 80 ℃ obtains 5.85 kilograms of dry products (yield 90.3%).
The SEM figure that adopts this Ferrox hydrated salt crystal that the JSM-5610-LV type scanning electron microscope of Japanese JEOL company records as shown in Figure 1.
The XRD diffractogram that adopts this LiFePO 4 dry product that the D/MAX2200PC type x-ray powder diffraction instrument of Japanese company of science records as shown in Figure 6.
Prepare FeC according to the method identical with embodiment 1
2O
42H
2O, different is, with two oxalic acid hydrate (H of 20 liter of 1.3 mol
2C
2O
4H
2O) solution joins the ferrous sulfate (FeSO of 20 liter of 1.5 mol
47H
2O) in the solution, the joining day is 10 seconds, and the temperature of reaction mixture is 30 ℃.After filtration, washing and dry, obtain 4.19 kilograms of dry products (yield 89.6%).
The SEM figure that adopts this Ferrox hydrated salt crystal that the JSM-5610-LV type scanning electron microscope of Japanese JEOL company records as shown in Figure 2.
The XRD diffractogram that adopts this LiFePO 4 dry product that the D/MAX2200PC type x-ray powder diffraction instrument of Japanese company of science records as shown in Figure 7.
Embodiment 3
Prepare FeC according to the method identical with embodiment 1
2O
42H
2O, different is, by the ferrous sulfate (FeSO of a volume pump with 20 liter of 5 mol
47H
2O) solution pumps in the reactor evenly with 20 liters/minute speed, simultaneously by the two oxalic acid hydrate (H of a volume pump with 20 liter of 5 mol
2C
2O
4H
2O) solution pumps in the reactor evenly with 20 liters/minute speed, and the temperature of reaction mixture is 70 ℃.After filtration, washing and dry, obtain 15.62 kilograms of dry products (yield 86.8%).
The SEM figure that adopts this Ferrox hydrated salt crystal that the JSM-5610-LV type scanning electron microscope of Japanese JEOL company records as shown in Figure 3.
The XRD diffractogram that adopts this LiFePO 4 dry product that the D/MAX2200PC type x-ray powder diffraction instrument of Japanese company of science records as shown in Figure 8.
Comparative Examples 1
Prepare FeC according to the method identical with embodiment 1
2O
42H
2O, different is, with two oxalic acid hydrate (H of 20 liter of 1.0 mol
2C
2O
4H
2O) solution joins the ferrous sulfate (FeSO of 20 liter of 1.0 mol
47H
2O) in the solution, the temperature of reaction mixture is 25 ℃.After filtration, washing and dry, obtain 2.73 kilograms of dry product FeC
2O
42H
2O (yield 75.9%).
The SEM figure that adopts this Ferrox hydrated salt crystal that the JSM-5610-LV type scanning electron microscope of Japanese JEOL company records as shown in Figure 4.
The XRD diffractogram that adopts this LiFePO 4 dry product that the D/MAX2200PC type x-ray powder diffraction instrument of Japanese company of science records as shown in Figure 9.
Comparative Examples 2
Prepare FeC according to the method identical with embodiment 1
2O
42H
2O, different is, with two oxalic acid hydrate (H of 20 liter of 2.8 mol
2C
2O
4H
2O) solution joins the ferrous sulfate (FeSO of 20 liter of 2.8 mol
47H
2O) in the solution, the temperature of reaction mixture is 70 ℃.After filtration, washing and dry, obtain 7.84 kilograms of dry product FeC
2O
42H
2O (yield 77.8%).
The SEM figure that adopts this Ferrox hydrated salt crystal that the JSM-5610-LV type scanning electron microscope of Japanese JEOL company records as shown in Figure 5.
The XRD diffractogram that adopts this LiFePO 4 dry product that the D/MAX2200PC type x-ray powder diffraction instrument of Japanese company of science records as shown in figure 10.
For the prepared dry product of embodiment 1-3, Comparative Examples 1-2, the X100 type particles distribution instrument that adopts U.S. HONEYWELL company is obtained separately median size respectively with laser diffractometry.The results are shown in Table 1.
Table 1
| Embodiment 1 | |
Embodiment 3 | Comparative example 1 | Comparative example 2 | |
| Median size (micron) | 8.85 | 6.42 | 6.12 | 21.75 | 26.40 |
Fig. 6, Fig. 7, Fig. 8 are respectively the XRD diffractogram of the Ferrox hydrated salt crystal that embodiment 1,2,3 makes, wherein, the collection of illustrative plates of Ferrox hydrated salt crystal is represented on top, and the collection of illustrative plates (JCPDS figure number 23-0293) of standard Ferrox hydrated salt crystal is represented in the bottom.From Fig. 6, Fig. 7, Fig. 8 as can be known, the XRD figure spectrum of the Ferrox hydrated salt crystal of embodiment 1,2,3 preparations is consistent with the 23-0293 collection of illustrative plates, and the thing that the material of surveying has been described is pure Ferrox hydrated salt crystal thing phase mutually.That is to say, the Ferrox salt hydrate that reaction generates among the embodiment 1,2,3 has all reached supersaturation, and crystal is separated out very fast, so crystal particle diameter is also less, median size is respectively 8.85 microns, 6.42 microns, 6.12 microns, sees Fig. 1,2,3 and table 1 respectively.
The XRD diffractogram of the Ferrox hydrated salt crystal that Fig. 9 makes for Comparative Examples 1, wherein, the collection of illustrative plates of Ferrox hydrated salt crystal is represented on top, the collection of illustrative plates (JCPDS figure number 22-0635) of the another kind of crystal formation of standard Ferrox is represented in the bottom.As can be seen from Figure 9, the XRD diffractogram and the 22-0635 collection of illustrative plates of the Ferrox hydrated salt crystal that Comparative Examples 1 makes are very approaching, and the thing that the material of surveying has been described is to be the dephasign of another crystal formation substantially mutually.That is to say that the Ferrox salt hydrate that reaction generates in the Comparative Examples 1 does not reach supersaturation in the time of 25 ℃, crystal is separated out slowly, so crystal particle diameter is also bigger, and median size is 21.75 microns, sees Fig. 4 and table 1.
The XRD diffractogram of the Ferrox hydrated salt crystal that Figure 10 makes for Comparative Examples 2, wherein, the collection of illustrative plates of Ferrox hydrated salt crystal is represented on top, the collection of illustrative plates (JCPDS figure number 23-0293) of middle part expression standard Ferrox hydrated salt crystal, the collection of illustrative plates (JCPDS figure number 22-0635) of the another kind of crystal formation of standard Ferrox is represented in the bottom.As can be seen from Figure 10, the XRD diffractogram of the Ferrox hydrated salt crystal that Comparative Examples 2 makes has more some assorted peaks than standard Ferrox hydrated salt crystal 23-0293 collection of illustrative plates, and there is correspondence at these assorted peaks in the 22-0635 collection of illustrative plates, thereby there is dephasign in the thing of judging Comparative Examples 2 material of surveying in mutually.That is to say that the Ferrox salt hydrate that reaction generates in the Comparative Examples 2 does not reach supersaturation in the time of 70 ℃, crystal is separated out slowly, so crystal particle diameter is also bigger, and median size is 26.40 microns, sees Fig. 5 and table 1.
Claims (10)
1, a kind of preparation method of Ferrox hydrated salt crystal, this method comprises solution A and solution B contact reacts, described solution A is the solution that contains oxalic acid and/or oxalate, described solution B is the solution that contains divalent iron salt, it is characterized in that the Ferrox salt hydrate that the way of contact of described solution A and solution B and contact conditions generate reaction reaches supersaturation in reaction mixture.
2, method according to claim 1, wherein, the way of contact of described solution A and solution B is for adding solution A in the solution B or solution B is added in the solution A, and the joining day is 10 seconds-1 minute; Perhaps, the liquid flow of solution A contacts with the liquid flow of solution B, and the ratio of the flow velocity of the liquid flow of the liquid flow of solution A and solution B is 0.8-1.2.
3, method according to claim 1, wherein, the contact conditions of described solution A and solution B comprises: the concentration of solution A and solution B is the 1.2-3 mol, and catalytic temperature is 25-60 ℃; Perhaps, the concentration of solution A and solution B is greater than 3 mol to 10 mol, and catalytic temperature is greater than 60 ℃ to 95 ℃.
4, according to claim 1 or 3 described methods, wherein, the contact conditions of described solution A and solution B comprises: the concentration of solution A is the 1.8-2.0 mol, and the concentration of solution B is the 1.5-2.0 mol, and described catalytic temperature is 45-55 ℃.
5, method according to claim 1, wherein, the mol ratio of the divalent iron salt in oxalic acid in the described solution A and/or oxalate and the solution B is 0.6-1.0.
6, method according to claim 5, wherein, the mol ratio of the divalent iron salt in oxalic acid in the described solution A and/or oxalate and the solution B is 0.8-1.0.
7, according to claim 1,5 or 6 described methods, wherein, described oxalate is one or more in potassium oxalate, sodium oxalate and the ammonium oxalate, and described divalent iron salt is ferrous sulfate and/or iron protochloride.
8, method according to claim 1, wherein, this method also comprises the product solid-liquid separation after described solution A and the solution B contact reacts, with solid product washing and dry.
9, method according to claim 8, wherein, described drying temperature is 50-90 ℃, be 5-18 hour time of drying.
10, method according to claim 9, wherein, described drying temperature is 70-80 ℃, be 8-15 hour time of drying.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102336646A (en) * | 2010-07-21 | 2012-02-01 | 宁波杉杉新材料科技有限公司 | Preparation method of ferrous oxalate |
| CN102675083A (en) * | 2011-03-18 | 2012-09-19 | 上海杉杉科技有限公司 | Preparation method of ferrous oxalate |
| CN115141096A (en) * | 2022-05-16 | 2022-10-04 | 江苏中天药业有限公司 | Ferrous succinate tetrahydrate crystal form, preparation method thereof, raw material composition containing crystal form and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2531260B1 (en) * | 1982-07-29 | 1986-04-11 | Centre Nat Rech Scient | FERROMAGNETIC MATERIALS DERIVED FROM IRON NITRIDES, THEIR PREPARATION AND THEIR APPLICATION AS MAGNETIC RECORDING MATERIAL |
| CN100418252C (en) * | 2005-01-28 | 2008-09-10 | 比亚迪股份有限公司 | Preperative method for ferrous phosphate radical lithium salt of lithium ion secondary cell active material |
-
2007
- 2007-08-28 CN CN2007101475915A patent/CN101376626B/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102336646A (en) * | 2010-07-21 | 2012-02-01 | 宁波杉杉新材料科技有限公司 | Preparation method of ferrous oxalate |
| CN102675083A (en) * | 2011-03-18 | 2012-09-19 | 上海杉杉科技有限公司 | Preparation method of ferrous oxalate |
| CN115141096A (en) * | 2022-05-16 | 2022-10-04 | 江苏中天药业有限公司 | Ferrous succinate tetrahydrate crystal form, preparation method thereof, raw material composition containing crystal form and application thereof |
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