CN110436428A - A kind of preparation method of sheet-form iron phosphate, sheet-form iron phosphate obtained and its application - Google Patents
A kind of preparation method of sheet-form iron phosphate, sheet-form iron phosphate obtained and its application Download PDFInfo
- Publication number
- CN110436428A CN110436428A CN201910612406.8A CN201910612406A CN110436428A CN 110436428 A CN110436428 A CN 110436428A CN 201910612406 A CN201910612406 A CN 201910612406A CN 110436428 A CN110436428 A CN 110436428A
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- sheet
- iron phosphate
- form iron
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- acid
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
Abstract
The invention discloses a kind of preparation method of sheet-form iron phosphate, sheet-form iron phosphate obtained and its applications, comprising the following steps: prepares ferrous salt solution, after phosphoric acid is added, adds oxidant for ferrous ions into iron ion；Phosphoric acid and sodium hydroxide is taken to be prepared into mixed solution；After mixed solution is heated to (90~100) DEG C, ferric ion solutions are added；The sheet-form iron phosphate will be obtained after product obtained calcining.The present invention program is fed at high temperature so that almost without the generation of yellow intermediate during feeding, the positive sheet-form iron phosphate product of white is quickly formed during charging, Mr.'s yellowly intermediate gradually turns white again after avoiding traditional addition molysite by microcosmic salt, the grinding efficiency of sheet-form iron phosphate made from scheme is higher through the invention, and S content is lower so that it, which is applied to, can obtain higher battery capacity in LiFePO4 preparation process.
Description
Technical field
The present invention relates to field of new energy technologies, and in particular to a kind of preparation method of sheet-form iron phosphate, sheet obtained
Ferric phosphate and its application.
Background technique
As country vigorously supports new-energy automobile industry, the market scale of global lithium ion battery expands at double
.Currently, applying in lithium ion battery at most is LiMn2O4, LiFePO4 and ternary, wherein ferric phosphate lithium cell is due to tool
Have the advantages that raw material sources it is extensive, it is cheap, have a safety feature and have extended cycle life, become lithium ion battery of new generation
Ideal positive electrode.Ferric phosphate is the important presoma for preparing LiFePO4, and performance determines a variety of masters of LiFePO4
Performance is wanted, therefore, the excellent ferric phosphate of processability is of great significance for the preparation of LiFePO4.Although both domestic and external grind
The person of studying carefully has carried out a large amount of research to ferric phosphate aspect of performance is promoted, and also achieves some good effects, but still existing defects,
The problems such as grinding efficiency is poor when S content height, ferric phosphate synthesizing iron lithium phosphate during such as ferrous sulfate being used to prepare ferric phosphate.
Synthesize a kind of sheet-form iron phosphate that the low high grinding efficiency of S content is high for the both of these problems present invention.
Summary of the invention
The first technical problem to be solved by the present invention is: provide one kind can reduce in sheet-form iron phosphate S content and
Improve the preparation method of the sheet-form iron phosphate of grinding efficiency.
Second technical problem to be solved by this invention is: providing sheet-form iron phosphate made from a kind of above method.
Third technical problem to be solved by this invention is: providing a kind of application of above-mentioned sheet-form iron phosphate.
In order to solve above-mentioned first technical problem, the technical solution adopted by the present invention are as follows: a kind of system of sheet-form iron phosphate
Preparation Method, comprising the following steps:
S1, prepare ferrous salt solution, be added acid after, add oxidant by ferrous ions at iron ion be made iron from
Sub- solution；
S2, phosphoric acid and sodium hydroxide is taken to be prepared by mixing into mixed solution；
S3, after mixed solution made from step S2 to be heated to (90~100) DEG C, it is molten that iron ion made from step S1 is added
Liquid；
S4, the sheet-form iron phosphate is obtained after step S3 has been reacted rear product calcining obtained.
Preferably, the addition speed of the ferric ion solutions in the step S3 is (0.5~1.5) L/h.
Further, the ferrous salt includes frerrous chloride and/or ferrous sulfate.Further, lead in the step S1
It crosses addition acid and the pH value of solution is adjusted to 1.5~1.8.
Further, the acid is acid corresponding with acid ion in the ferrous salt, preferably sulfuric acid or hydrochloric acid；Most
Preferably sulfuric acid, if sulfuric acid, then the ratio between amount of substance of the ferrous salt in the step S1 and sulfuric acid is (10~15): 1.
Further, in the step S2, the ratio between amount of substance of the phosphoric acid and sodium hydroxide is 1:(0.8-1).
Further, the ratio between amount of substance of the ferrous salt and phosphoric acid is 1:(1~1.2).
Further, the calcination temperature in the step S4 is (500~600) DEG C, and the time is (4~6) h.
The beneficial effects of the present invention are: the present invention program adjusts the preparation process of traditional flake ferric phosphate,
Traditional flake ferric phosphate precipitating preparation method has been abandoned, feed way is changed, after ferrous salt is first oxidized to molysite, then
Molysite is added in the microcosmic salt solution for being heated to (90~100) DEG C, at high temperature charging so that during charging almost without
Yellow intermediate generates, and the positive sheet-form iron phosphate product of white is quickly formed during charging, avoids and traditional adds microcosmic salt
Mr.'s yellowly intermediate gradually turns white again after entering molysite, reduces the probability that sulfate radical is entered by package in sheet-form iron phosphate,
And then greatly reduce S content in finished product.The grinding efficiency of sheet-form iron phosphate made from scheme is higher through the invention, and then makes
It is obtained to be applied to that more high discharge capacity can be obtained in LiFePO4 preparation process.
In order to solve above-mentioned second technical problem, the technical solution adopted by the present invention are as follows: one kind passes through above method system
The sheet-form iron phosphate obtained.
In order to solve above-mentioned third technical problem, the technical solution adopted by the present invention are as follows: a kind of above-mentioned sheet-form iron phosphate
Application in the preparation of LiFePO4.
A kind of LiFePO4, the LiFePO4 are prepared in raw material comprising above-mentioned sheet-form iron phosphate.
The beneficial effects of the present invention are: it is excellent that chemical property can be made in the sheet-form iron phosphate as made from the above method
Good LiFePO4 and corresponding battery.
Detailed description of the invention
Fig. 1 is SEM figure of the sheet-form iron phosphate made from the embodiment of the present invention 1 under 50K multiplying power；
Fig. 2 is SEM figure of the sheet-form iron phosphate made from the embodiment of the present invention 1 under 30K multiplying power；
Fig. 3 is SEM figure of the sheet-form iron phosphate made from the embodiment of the present invention 1 under 10K multiplying power；
Fig. 4 is SEM figure of the sheet-form iron phosphate made from the embodiment of the present invention 1 under 1K multiplying power
Fig. 5 is SEM figure of the sheet-form iron phosphate made from reference examples 1 of the present invention under 50K multiplying power；
Fig. 6 is SEM figure of the sheet-form iron phosphate made from reference examples 1 of the present invention under 30K multiplying power；
Fig. 7 is SEM figure of the sheet-form iron phosphate made from reference examples 1 of the present invention under 10K multiplying power.
Specific embodiment
To explain the technical content, the achieved purpose and the effect of the present invention in detail, below in conjunction with embodiment and cooperate attached
Figure is explained.
A kind of the embodiment of the present invention one are as follows: preparation method of sheet-form iron phosphate, comprising the following steps:
(1) 0.6mol sulfuric acid is added in the molysite 4L for configuring 1.5mol/L, and 500g hydrogen peroxide (mass fraction 27%) is molten
Liquid is slowly added in molysite, until oxidation is complete.
(2) 795.5g phosphoric acid (commercially available concentrated phosphoric acid, mass fraction 85%) is weighed, 720g sodium hydroxide is weighed and is added in phosphoric acid
And it is settled to 4L.
(3) it microcosmic salt will have been configured pours into 10L reaction kettle and be warming up to 96 DEG C, configured molysite has been added with the speed of 1L/h
Microcosmic salt.
(4) sample 550 DEG C × 5h calcined crystalline in atmosphere furnace polymerize, and obtains the sheet-form iron phosphate.
(5) sheet-form iron phosphate made from aforesaid operations is taken to carry out through scanning electron microscope (scanning electron
Microscope, SEM) observe its microscopic appearance.
Shape appearance figure under different multiplying as shown in figures 1-4, it can be seen from the figure that sheet phosphorus made from the present invention program
In the form of sheets, morphology stability are good for sour iron.Similarly, referring to the charging sequence of the present invention program, according to other of the present invention program
After ratio addition, ferric phosphate obtained is equally in the form of sheets.
Reference examples one of the invention are as follows: a kind of preparation method of ferric phosphate conventionally prepares sheet-form iron phosphate, tool
Steps are as follows for body:
(1) the molysite 4L for configuring 1.5mol/L, is added 0.6mol sulfuric acid, 500g hydrogen peroxide (27%) solution is slowly added to
In molysite, until oxidation is complete.
(2) 795.5g phosphoric acid (commercially available concentrated phosphoric acid, mass fraction 85%) is weighed, 720g sodium hydroxide is weighed and is added in phosphoric acid
And it is settled to 4L.
(3) molysite is poured into 10L reaction kettle with conventional method, microcosmic salt is added in molysite at normal temperature.
(4) sample 550 DEG C × 5h calcined crystalline in atmosphere furnace polymerize, and obtains the ferric phosphate.
(5) ferric phosphate made from aforesaid operations is taken to carry out through scanning electron microscope (scanning electron
Microscope, SEM) observe its microscopic appearance.
Shape appearance figure under different multiplying is as shown in Fig. 5~7, it can be seen from the figure that ferric phosphate made from the present invention program
It is serious in cotton-shaped and reunion.
This practical example scheme makes sheet-form iron phosphate turn white while charging by way of crystallizing at high temperature, changes
Yellow intermediate can only be made after the completion of traditional charging, through the invention the feed way of scheme enables to sheet phosphoric acid
Iron particle develops to sheet, and the present invention program is by the way that the preparation process of traditional flake ferric phosphate to be adjusted, by material proportion
And feed way makes change, by slow-addition, and the molysite in the microcosmic salt solution being added under high temperature is anti-with microcosmic salt rapidly
White plates ferric phosphate should be generated, reduces the process of yellow intermediate package S, overcomes traditional approach and prepare sheet-form iron phosphate
When the problems such as existing grinding efficiency is low and S content is difficult to control, high capacity can be made in scheme through the invention and S content is low
Sheet-form iron phosphate.
Ferric phosphate obtained after phosphate dihydrate iron made from before taking the embodiment of the present invention 1 and reference examples 1 to calcine and calcining, In
Sulfur content is measured under equal conditions, measurement result is as shown in table 1 below:
1 finished product sulfur content contrast table of table
| Sample number into spectrum | Phosphate dihydrate iron S content (ppm) | Anhydrous iron phosphate sulfur content S |
| Embodiment 1 | 35.0 | 27.0 |
| Reference examples 1 | 629.9 | 383.0 |
As can be seen from the above table, compared with prior synthesizing method, two water tablets shape phosphoric acid made from the embodiment of the present invention
S content is greatly lowered in iron and anhydrous sheet-form iron phosphate.
Ferric phosphate made from sheet-form iron phosphate made from above-described embodiment and reference examples is conventionally prepared into phosphorus
Sour iron lithium repeats the operation four times, and can be carried out test to the electrochemistry of LiFePO4 obtained respectively, as a result such as the following table 2
It is shown:
2 electrochemical performances of lithium iron phosphate contrast table of table
As can be seen from Table 2, after being prepared into LiFePO4 using sheet-form iron phosphate made from the embodiment of the present invention
With good chemical property, the multiple performances such as compacted density, specific capacity are obviously improved, similarly, will be referring to this hair
After sheet-form iron phosphate made from other ratios of bright scheme feed way is prepared into LiFePO4, equally there is similar property.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair
Equivalents made by bright specification and accompanying drawing content are applied directly or indirectly in relevant technical field, similarly include
In scope of patent protection of the invention.
Claims (10)
1. a kind of preparation method of sheet-form iron phosphate, it is characterised in that: the following steps are included:
S1, ferrous salt solution is prepared, after acid is added, adding oxidant, that iron ion is made at iron ion in ferrous ions is molten
Liquid；
S2, phosphoric acid and sodium hydroxide is taken to be prepared by mixing into mixed solution；
S3, after mixed solution made from step S2 to be heated to (90~100) DEG C, ferric ion solutions made from step S1 are added；
S4, the sheet-form iron phosphate is obtained after step S3 has been reacted rear product calcining obtained.
2. the preparation method of sheet-form iron phosphate according to claim 1, it is characterised in that: the iron ion in the step S3
The addition speed of solution is (0.5~1.5) L/h.
3. the preparation method of sheet-form iron phosphate according to claim 1, it is characterised in that: pass through addition in the step S1
The pH value of solution is adjusted to 1.5~1.8 by acid.
4. the preparation method of sheet-form iron phosphate according to claim 1, it is characterised in that: the acid is sulfuric acid, the Asia
The ratio between amount of substance of molysite and sulfuric acid is (10~15): 1.
5. the preparation method of sheet-form iron phosphate according to claim 1, it is characterised in that: in the step S2, the phosphorus
The ratio between acid and the amount of substance of sodium hydroxide are 1:(0.8-1).
6. the preparation method of sheet-form iron phosphate according to claim 1, it is characterised in that: the object of the ferrous salt and phosphoric acid
The ratio between amount of matter is 1:(1~1.2).
7. the preparation method of sheet-form iron phosphate according to claim 1, it is characterised in that: the calcining temperature in the step S4
Degree is (500~600) DEG C, and the time is (4~6) h.
8. a kind of sheet-form iron phosphate as made from method as described in any one of claims 1 to 7.
9. a kind of application of sheet-form iron phosphate as claimed in claim 8 in the preparation of LiFePO4.
10. a kind of LiFePO4, it is characterised in that: the LiFePO4 is prepared in raw material comprising as claimed in claim 8
Sheet-form iron phosphate.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110902666A (en) * | 2019-12-26 | 2020-03-24 | 湖南雅城新材料有限公司 | Preparation method of flaky ferric phosphate dihydrate |
| CN111704121A (en) * | 2020-06-17 | 2020-09-25 | 湖南雅城新材料有限公司 | Preparation method of iron phosphate and lithium iron phosphate |
| CN112811405A (en) * | 2020-12-30 | 2021-05-18 | 林州市赋通新能源材料科技有限公司 | Preparation method of ferric phosphate with controllable morphology |
| CN115676793A (en) * | 2022-09-30 | 2023-02-03 | 山东精工电子科技股份有限公司 | Preparation method of leaf-shaped lithium iron phosphate material and leaf-shaped lithium iron phosphate material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110902666A (en) * | 2019-12-26 | 2020-03-24 | 湖南雅城新材料有限公司 | Preparation method of flaky ferric phosphate dihydrate |
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| CN112811405A (en) * | 2020-12-30 | 2021-05-18 | 林州市赋通新能源材料科技有限公司 | Preparation method of ferric phosphate with controllable morphology |
| CN115676793A (en) * | 2022-09-30 | 2023-02-03 | 山东精工电子科技股份有限公司 | Preparation method of leaf-shaped lithium iron phosphate material and leaf-shaped lithium iron phosphate material |
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Application publication date: 20191112 |