CN111732089A - Preparation method of lithium iron phosphate - Google Patents
Preparation method of lithium iron phosphate Download PDFInfo
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- CN111732089A CN111732089A CN202010874135.6A CN202010874135A CN111732089A CN 111732089 A CN111732089 A CN 111732089A CN 202010874135 A CN202010874135 A CN 202010874135A CN 111732089 A CN111732089 A CN 111732089A
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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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
- C01P2004/01—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
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/10—Solid density
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the technical field of lithium ion battery materials, and particularly provides a preparation method of lithium iron phosphate. The method takes the lithium-rich waste liquid as a lithium source, only needs to detect and determine the lithium content in the lithium-rich waste liquid, and can synthesize the lithium iron phosphate material by supplementing corresponding iron source, carbon source and the like. The method does not need to carry out purification, concentration, filtration, heating and the like for many times, and only needs to carry out sintering and crushing for one time. The method has simple production process, and the prepared lithium iron phosphate material has good comprehensive performance, low production cost and environmental friendliness.
Description
Technical Field
The invention relates to the technical field of lithium ion battery materials, in particular to a preparation method of lithium iron phosphate.
Background
Since the first commercialization of lithium ion batteries in the 90 s of the 20 th century, lithium ion batteries have exhibited unique advantages in the fields of energy density, power density, service life, safety and the like in the field of chemical energy storage batteries. Currently, common positive electrode materials in the lithium ion battery market are a series of ternary derivatives of lithium cobaltate, lithium manganate, lithium iron phosphate and lithium nickel cobalt manganese. Because the lithium iron phosphate and the iron phosphate material both have olivine crystal structures, have stable P-O bonds, are easy to obtain and have low price, the lithium iron phosphate material has the characteristics of high safety, long service life and low cost which are incomparable with other materials. With the further improvement of battery technology and material technology, the cell energy density of the current mainstream lithium iron phosphate single battery reaches 200wh/kg, the system energy density reaches 160wh/kg, and the performance is close to that of the conventional ternary 523 material, even 622 material. At present, the performance of lithium iron phosphate materials of various manufacturers is close, the technology is basically mature, and price competition is mainly achieved. Therefore, how to reduce the cost is the most critical subject for the survival and development of the iron phosphate lithium material enterprises at present.
Patent application publication No. CN111137869A discloses a preparation method of lithium iron phosphate, which comprises the steps of preparing lithium iron phosphate by taking crude lithium phosphate as a raw material, obtaining a pure lithium solution by stirring, acid dissolving, phosphorus removal and step-by-step impurity removal, then adding an iron source, a phosphorus source and a carbon source, and obtaining the lithium iron phosphate by mixing treatment. Although the preparation method reduces the loss of lithium to the minimum, and obtains the lithium iron phosphate with high purity and good performance by taking the low-cost rough lithium phosphate as the raw material, the production process in the reaction process is complex, the requirement on production equipment is high (in the process of preparing the lithium iron phosphate by the rough lithium phosphate, a plurality of raw materials, liquid phase and solid phase synthesis equipment are required to be purified, concentrated, filtered, heated and the like for many times), the difficulty in mass production is high, and in addition, the environmental protection requirements of waste water, waste gas and the like are met.
In conclusion, the development of the preparation method of the lithium iron phosphate, which has the advantages of simple process flow, easy industrial production, low cost, safety and environmental protection, has very important significance in the field.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the preparation method of the lithium iron phosphate is simple in process flow, easy for industrial production, low in cost, safe and environment-friendly.
The solution of the invention is realized by the following steps:
a preparation method of lithium iron phosphate takes lithium-rich waste liquid as a lithium source, and comprises the following steps:
(1) detecting the concentration of Li in the lithium-rich waste liquid;
(2) adding a certain volume of lithium-rich waste liquid into a stirring tank, adding a certain mass of phosphoric acid or phosphate according to the Li concentration in the step (1) and the molar ratio of Li to P, and stirring to fully mix the mixture to obtain mixed slurry A;
(3) adding an iron source, a carbon source, an additive and pure water into the mixed slurry A in the step (2) according to the molar ratio of Li/Fe, and fully stirring to uniformly mix the iron source, the carbon source, the additive and the pure water to obtain mixed slurry B;
(4) and (4) respectively carrying out grinding treatment, drying treatment, heat treatment and crushing on the mixed slurry B obtained in the step (3) to obtain the lithium iron phosphate.
Further, the phosphate in step (2) refers to one or more of diammonium hydrogen phosphate, ammonium dihydrogen phosphate, lithium dihydrogen phosphate and ammonium phosphate.
Further, in the step (2), the molar ratio of Li/P is 1.0 to 1.2, preferably 1.0 to 1.1.
Further, the iron source in the step (3) refers to one or more of ferric oxide, ferrous oxalate, ferric phosphate, ferric nitrate, ferrous chloride and ferrous sulfate.
Further, in the step (3), the molar ratio of Li/Fe is 1.0 to 1.2, preferably 1.0 to 1.1.
Further, the carbon source in the step (3) is one or more of glucose, citric acid, starch, sucrose, polyethylene glycol, phenolic resin, polyvinyl alcohol, oxalic acid and graphite; the mass percentage of the carbon source to the iron source is 8-20: 100.
further, the additive in the step (3) refers to one or more of oxides of Mg, Ti, Zr, W, Al or Nb; the mass percentage of the additive to the iron source is 0.1-1: 100.
further, the process indexes of the grinding treatment in the step (4) are as follows: wet grinding is used until the particle size of the slurry is 0.2-1.5 μm, preferably 0.5-1.0. mu.m.
Further, the process conditions of the heat treatment in the step (4) are as follows: the reaction temperature is 600-1000 ℃, preferably 700-900 ℃; the constant temperature time is 5-15h, preferably 7-10 h.
Further, the heat treatment in the step (4) is performed in an inert atmosphere, and the inert gas is one or more of nitrogen, argon and helium.
The invention has the following beneficial effects:
(1) the production process is simple: the lithium-rich waste liquid is directly used as a lithium source for synthesizing the lithium iron phosphate material, and the lithium iron phosphate material can be synthesized by detecting and determining the lithium content in the waste liquid and supplementing corresponding iron source, carbon source and the like. The method does not need to carry out purification, concentration, filtration, heating and the like for many times, and only needs to carry out sintering and crushing for one time.
(2) The production cost is low: the method is suitable for a solid-phase synthesis production line of the lithium iron phosphate material, does not need liquid-phase synthesis equipment, has low requirement on production equipment, has simple process flow and is easy for industrial production.
(3) Safety and environmental protection: no wastewater, waste gas and the like are discharged in the preparation process, and the preparation method is safe and environment-friendly; meanwhile, the comprehensive utilization value of the lithium-containing waste liquid is improved, and the resource recycling and the environmental protection are facilitated.
(4) The material has excellent comprehensive properties: the compacted density of the prepared lithium iron phosphate material is 2.5-2.7g/cm3And the 1C capacity is more than 147 mAh/g.
Drawings
Fig. 1 is an SEM image of lithium iron phosphate prepared in example 1;
fig. 2 is a charge-discharge curve diagram of the lithium iron phosphate prepared in example 1.
Detailed Description
The present invention will now be described in detail with reference to the drawings, which are given by way of illustration and explanation only and should not be construed to limit the scope of the present invention in any way.
Example 1:
lithium-rich waste liquid is used as a lithium source to prepare lithium iron phosphate,
(1) detecting the concentration of Li in the lithium-rich waste liquid to be 2.5 g/L;
(2) adding 50L of lithium-rich waste liquid into a stirring tank, adding 2661g of ammonium phosphate according to the molar ratio of Li to P of 1.0, and stirring to fully mix the lithium-rich waste liquid and the ammonium phosphate to obtain mixed slurry A;
(3) adding 2857g of iron oxide, 285g of carbon source, 28g of additive and pure water into the mixed slurry A in the step (2) according to the molar ratio of Li to Fe of 1.0, and fully stirring to uniformly mix the mixture to obtain mixed slurry B;
(4) and (3) grinding the mixed slurry B by a wet method until the particle size of the slurry is 1 mu m, drying, and then carrying out heat treatment at 800 ℃ for 9 h. The heat treatment was performed in a nitrogen atmosphere. Then, the resultant was crushed to obtain lithium iron phosphate.
Example 2:
lithium-rich waste liquid is used as a lithium source to prepare lithium iron phosphate,
(1) detecting the concentration of Li in the lithium-rich waste liquid to be 3.3 g/L;
(2) adding 50L of lithium-rich waste liquid into a stirring tank, adding 2464g of ammonium dihydrogen phosphate according to the molar ratio of Li to P of 1.1, and stirring to fully mix to obtain mixed slurry A;
(3) adding 2845g of ferrous chloride, 228g of carbon source, 15g of additive and pure water into the mixed slurry A in the step (2) according to the molar ratio of Li to Fe of 1.05, and fully stirring to uniformly mix the materials to obtain mixed slurry B;
(4) and (3) carrying out wet grinding on the mixed slurry B until the particle size of the slurry is 0.8 mu m, drying, and carrying out heat treatment at the temperature of 830 ℃ for 7 h. The heat treatment was performed in a nitrogen atmosphere. Then, the resultant was crushed to obtain lithium iron phosphate.
Comparative example:
(1) the method comprises the steps of mixing pure water, iron phosphate, a lithium source, a carbon source and an additive according to a formula with a mass ratio of 180:100:25:10:0.5, and stirring to fully mix the materials to obtain mixed slurry with the particle size of 0.8 mu m;
(2) the mixed slurry A was dried and then heat-treated at 760 ℃ for 10 hours. The heat treatment was performed in a nitrogen atmosphere. Then, the resultant was crushed to obtain lithium iron phosphate.
The compacted density and 1C capacity of the lithium iron phosphate prepared in example 1, example 2 and comparative example were further compared, and the results are shown in table 1.
TABLE 1 lithium iron phosphate Performance and production cost comparison
In addition, as can be seen from fig. 1, the large particles of the lithium iron phosphate prepared in this example 1 are micron-sized, which can improve the compaction density of the material; the small particles are nano-sized and are filled in the gaps among the large particles, so that the capacity of the material can be further improved; as can be seen from fig. 2, the lithium iron phosphate prepared in example 1 has good charge and discharge performance.
In addition, the production costs of example 1, example 2 and comparative example were further calculated, and it was found that the production costs of example 1 and example 2 were reduced by 4000-.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of lithium iron phosphate is characterized in that lithium-rich waste liquid is used as a lithium source, and comprises the following steps:
(1) detecting the concentration of Li in the lithium-rich waste liquid;
(2) adding a certain volume of lithium-rich waste liquid into a stirring tank, adding a certain mass of phosphoric acid or phosphate according to the Li concentration in the step (1) and the molar ratio of Li to P, and stirring to fully mix the mixture to obtain mixed slurry A;
(3) adding an iron source, a carbon source, an additive and pure water into the mixed slurry A in the step (2) according to the molar ratio of Li/Fe, and fully stirring to uniformly mix the iron source, the carbon source, the additive and the pure water to obtain mixed slurry B; the additive refers to one or more of oxides of Mg, Ti, Zr, W, Al or Nb;
(4) and (4) respectively carrying out grinding treatment, drying treatment, heat treatment and crushing on the mixed slurry B obtained in the step (3) to obtain the lithium iron phosphate.
2. The method for producing lithium iron phosphate according to claim 1, wherein in the step (2), the molar ratio of Li/P is 1.0 to 1.2.
3. The method for preparing lithium iron phosphate according to claim 1 or 2, wherein the phosphate in step (2) is one or more of diammonium hydrogen phosphate, ammonium dihydrogen phosphate, lithium dihydrogen phosphate and ammonium phosphate.
4. The method for preparing lithium iron phosphate according to claim 1, wherein in the step (3), the molar ratio of Li/Fe is 1.0 to 1.2.
5. The method for preparing lithium iron phosphate according to claim 1 or 4, wherein the iron source in step (3) is one or more of iron oxide, ferrous oxalate, iron phosphate, ferric nitrate, ferrous chloride, and ferrous sulfate.
6. The method for preparing lithium iron phosphate according to claim 1, wherein the carbon source in step (3) is one or more of glucose, citric acid, starch, sucrose, polyethylene glycol, phenolic resin, polyvinyl alcohol, oxalic acid, and graphite; the mass percentage of the carbon source to the iron source is 8-20: 100.
7. the method for preparing lithium iron phosphate according to claim 1, wherein the additive accounts for 0.1-1% of the iron source in the step (3).
8. The method for preparing lithium iron phosphate according to claim 1, wherein the process indexes of the grinding treatment in the step (4) are as follows: wet grinding is adopted until the particle size of the slurry is 0.2-1.5 mu m.
9. The method for preparing lithium iron phosphate according to claim 1, wherein the heat treatment in the step (4) is performed under the following process conditions: the reaction temperature is 600 ℃ and 1000 ℃, and the constant temperature time is 5-15 h.
10. The method for preparing lithium iron phosphate according to claim 1 or 9, wherein the heat treatment in step (4) is performed in an inert atmosphere, and the inert gas is one or more of nitrogen, argon, and helium.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024021233A1 (en) * | 2022-07-28 | 2024-02-01 | 广东邦普循环科技有限公司 | Method for preparing lithium iron phosphate by means of comprehensive recovery of lithium-containing wastewater and use thereof |
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| CN101154722A (en) * | 2007-09-13 | 2008-04-02 | 广西师范大学 | Core-shell type nano-scale carbon-covered iron lithium phosphate compound anode material and method for preparing the same |
| CN106276842A (en) * | 2016-08-02 | 2017-01-04 | 北京北大明德科技发展有限公司 | Method by the LiFePO4 reclaiming in waste and old lithium ion battery |
| CN106495122A (en) * | 2016-11-03 | 2017-03-15 | 王坚 | A kind of method that waste lithium iron phosphate positive plate reclaims iron phosphate presoma |
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- 2020-08-27 CN CN202010874135.6A patent/CN111732089A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101154722A (en) * | 2007-09-13 | 2008-04-02 | 广西师范大学 | Core-shell type nano-scale carbon-covered iron lithium phosphate compound anode material and method for preparing the same |
| CN106276842A (en) * | 2016-08-02 | 2017-01-04 | 北京北大明德科技发展有限公司 | Method by the LiFePO4 reclaiming in waste and old lithium ion battery |
| CN106495122A (en) * | 2016-11-03 | 2017-03-15 | 王坚 | A kind of method that waste lithium iron phosphate positive plate reclaims iron phosphate presoma |
Non-Patent Citations (2)
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2024021233A1 (en) * | 2022-07-28 | 2024-02-01 | 广东邦普循环科技有限公司 | Method for preparing lithium iron phosphate by means of comprehensive recovery of lithium-containing wastewater and use thereof |
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Application publication date: 20201002 |