CN110857216B - Battery-grade iron phosphate precursor, lithium iron phosphate, and preparation method and application thereof - Google Patents
Battery-grade iron phosphate precursor, lithium iron phosphate, and preparation method and application thereof Download PDFInfo
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- CN110857216B CN110857216B CN201910934641.7A CN201910934641A CN110857216B CN 110857216 B CN110857216 B CN 110857216B CN 201910934641 A CN201910934641 A CN 201910934641A CN 110857216 B CN110857216 B CN 110857216B
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- 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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- C—CHEMISTRY; METALLURGY
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- 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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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
Abstract
The invention discloses a battery-grade iron phosphate precursor, lithium iron phosphate and a preparation method and application thereof. The iron phosphate obtained by the method has uniform distribution of iron and phosphorus elements, is particularly suitable for being used as a raw material of lithium iron phosphate which is a high-rate lithium battery positive electrode material, and the preparation method has the advantages of mild reaction conditions, simple and flexible operation, low cost, improved yield, mass production and wide application prospect.
Description
Technical Field
The invention relates to the field of lithium battery materials, and particularly relates to a battery-grade iron phosphate precursor, lithium iron phosphate, and preparation methods and applications thereof.
Background
Lithium ion batteries have been rapidly popularized and developed since the time comes because of their characteristics of high specific energy, long service life, no pollution and the like, and currently, lithium battery positive electrode materials mainly comprise lithium cobaltate, lithium iron phosphate, lithium manganate and ternary materials.
In recent years, with the wide application of lithium iron phosphate lithium ion batteries in the industries of new energy automobiles, wind and light energy storage, communication base stations, large database storage and the like, the production and manufacture of lithium iron phosphate cathode materials are also greatly developed. Lithium iron phosphate is a battery material with an olivine structure, has a stable and reliable structure, small deformation and long service life in a circulation process, but has low intrinsic conductivity and small ion diffusion coefficient, so that the low-temperature performance and the high-rate performance of the lithium iron phosphate are poor. Under the condition of high-rate discharge, the internal impedance of the battery is high, so that the voltage of the lithium battery is reduced quickly at the initial stage of large-current discharge, and the use of the lithium battery under the condition of high-rate discharge is limited.
Various technological routes exist for the preparation of the lithium iron phosphate anode material, wherein the industrialized technological routes include an iron oxide red route, a ferrous oxalate route, a hydrothermal synthesis route, an iron orthophosphate route and the like. Through practices and verification of industries and markets after 2012, the lithium iron phosphate prepared by the ferric orthophosphate route has the outstanding advantages of good electrical property, low magazine content, simple process steps and the like, and gradually becomes a technical trend of uniform industries. Under the background, huge development opportunities are brought to the manufacturing industry of ferric orthophosphate.
However, the research and production of battery grade ferric orthophosphate at home and abroad are late, and especially the realization of the large-scale production of the commercialized ferric orthophosphate is realized only in recent years. However, the technology of battery-grade ferric orthophosphate in the prior art is based on early low-level ceramic-grade and food-grade product modes, so that the rate performance of the battery-grade ferric orthophosphate is poor due to the problems of purity fluctuation, undefined crystal structure and the like, and a phenomenon of disjointing with the preparation of a cathode material exists in the product and technology open stage, so that the defect of poor rate performance of the lithium iron phosphate cannot be solved from the source.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a preparation method of a battery-grade iron phosphate precursor, and the battery-grade iron phosphate precursor prepared by the method can be used for preparing high-rate lithium iron phosphate.
The invention also provides the iron phosphate precursor prepared by the method.
The invention also provides a lithium iron phosphate anode material prepared by using the iron phosphate precursor.
The invention also provides a method for preparing the lithium iron phosphate cathode material by using the iron phosphate precursor.
The invention also provides application of the lithium iron phosphate anode material in a lithium battery.
A method of making a battery grade iron phosphate precursor according to an embodiment of the first aspect of the invention comprises the steps of:
s1, adding a surfactant into ferrous sulfate solution, adding a phosphorus salt solution and a gas oxidant, stirring uniformly after the addition is finished, injecting alkali liquor and adjusting the pH value of the reaction solution to be 2.6-2.9 to obtain a mixed solution, controlling the temperature of the mixed solution of the reaction system to be (40-60) DEG C, continuing stirring after the addition is finished, and then standing and aging the mixed solution after the reaction under the stirring condition;
s2, performing filter pressing, washing and drying on the aged reaction product in the step S1 to obtain a ferric phosphate dihydrate precursor;
and S3, calcining the ferric phosphate dihydrate precursor obtained in the step S2 to obtain an anhydrous ferric phosphate precursor.
According to the method for preparing the battery-grade iron phosphate precursor, in step S1, the gaseous oxidant includes at least one of oxygen or ozone.
According to the method for preparing the battery-grade iron phosphate precursor, in the step S1, the surfactant is a nonionic surfactant; preferably, the surfactant includes at least one of sorbitan ester, sucrose fatty acid ester, polyoxyethylene alkylphenol ether, or alkylolamide.
According to the method for preparing the battery-grade iron phosphate precursor, in step S1, the phosphorus salt includes at least one of sodium phosphate, sodium monohydrogen phosphate, sodium dihydrogen phosphate, ammonium monohydrogen phosphate, or ammonium dihydrogen phosphate.
According to the method for preparing the battery-grade iron phosphate precursor, in step S1, the gaseous oxidant includes at least one of oxygen or ozone.
According to the preparation method of the battery-grade iron phosphate precursor, in the step S3, the calcination temperature is (750-850) ° c, and the calcination time is (1-2) h.
According to the preparation method of the battery-grade iron phosphate precursor, the alkali liquor comprises at least one of ammonia water, liquid ammonia and sodium hydroxide solution.
A method of making a battery grade iron phosphate precursor according to an embodiment of the first aspect of the invention comprises the steps of:
s1, adding a surfactant into a continuously stirred kettle filled with (185-3Adding a gas oxidant at a flow rate of/h, stirring for 5-10 h after the addition is finished, injecting 45% alkali liquor at a flow rate of (150-;
s2, carrying out filter pressing, washing and drying on a reaction product obtained after the reaction in the step S1 to obtain a ferric phosphate dihydrate precursor;
and S3, calcining the dihydrate ferric phosphate precursor to obtain the anhydrous ferric phosphate precursor with the structure.
According to the method for preparing the battery-grade iron phosphate precursor, in step S1, the concentration of the phosphorus salt in the phosphorus salt solution is (40-55)%, and the concentration of the gaseous oxidant is (1 × 10)5-1.5×105)ppm。
According to the method for preparing the battery-grade iron phosphate precursor, provided by the embodiment of the first aspect of the invention, the speed in all stirring operations is (45-55) Hz.
According to the iron phosphate precursor of the embodiment of the second aspect of the invention, the iron phosphate precursor is prepared by the method.
According to the lithium iron phosphate of the embodiment of the third aspect of the present invention, the raw material for preparing the lithium iron phosphate contains the above-described iron phosphate precursor.
The preparation method of the lithium iron phosphate according to the embodiment of the fourth aspect of the invention comprises the following steps:
and adding deionized water, a lithium source and a composite carbon source into the iron phosphate precursor to obtain a mixture, sanding the mixture, spray-drying the sanded mixture, and calcining the dried material to obtain the lithium iron phosphate.
According to the preparation method of lithium iron phosphate provided by the embodiment of the fourth aspect of the invention, the composite carbon source is glucose and citric acid, and the molar ratio of the glucose to the citric acid is X: (1-X), wherein the value range of X is more than or equal to 0.3 and less than or equal to 0.7.
According to the method for preparing lithium iron phosphate of the embodiment of the fourth aspect of the invention, the lithium source is lithium carbonate.
According to the preparation method of lithium iron phosphate of the fourth aspect of the present invention, in the calcination operation, the calcination temperature is 650 to 700 ℃ and the calcination time is 10 to 14 hours.
According to the preparation method of lithium iron phosphate of the fourth aspect of the present invention, the particle size of the mixture after the sanding operation is 650nm (450-.
According to the lithium ion battery of the embodiment of the fifth aspect of the invention, the cathode material of the lithium ion battery is the lithium iron phosphate.
The preparation method of the battery-grade iron phosphate precursor provided by the embodiment of the invention at least has the following beneficial effects: according to the method, a phosphorus salt is used for reaction, the pH value in the reaction process is controlled to be (2.6-2.9), the acidity in the reaction process is weaker than that of phosphoric acid, the reaction is carried out slowly, and further iron and phosphorus in the prepared iron phosphate precursor are uniformly distributed and have few surface defects. The lithium iron phosphate material prepared by the iron phosphate precursor has excellent crystal dynamic performance, high ion transmission rate and excellent rate performance. The iron phosphate obtained by the method has uniform distribution of iron and phosphorus elements, and is particularly suitable for being used as a raw material of lithium iron phosphate serving as a high-rate lithium battery positive electrode material; the preparation method has the advantages of mild reaction conditions, simple and flexible operation, low cost, high yield, large-scale mass production and wide application prospect in the field of lithium batteries.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is an SEM electron micrograph of iron phosphate prepared in example 1 of the present invention;
FIG. 2 is a distribution characterization map of Fe elements at different depths as measured by a high-precision transmission electron microscope in example 1 of the present invention;
FIG. 3 is a distribution characterization map of O elements at different depths as measured by a high-precision transmission electron microscope in example 1 of the present invention;
FIG. 4 is a distribution characterization map of P elements at different depths as measured by a high-precision transmission electron microscope in example 1 of the present invention;
fig. 5 is a graph showing the rate performance of the lithium iron phosphate cathode material prepared in example 1 of the present invention.
Detailed Description
The embodiments of the invention will be described in detail hereinafter, examples of which are illustrated in the accompanying drawings, and the embodiments described hereinafter with reference to the drawings are illustrative only and are not to be construed as limiting the invention.
The first embodiment of the invention is as follows: a preparation process of a high-rate lithium battery iron phosphate precursor and a lithium iron phosphate positive electrode material and a lithium battery prepared by the preparation process are disclosed:
firstly, preparing an iron phosphate precursor, specifically comprising the following steps:
s1-1, adding sucrose fatty acid ester into a kettle which is filled with 205g/L ferrous sulfate solution and continuously stirred at the frequency of 55Hz, adding 55 percent ammonium monohydrogen phosphate solution at the flow rate of 120L/h by a peristaltic pump and at the flow rate of 5m by a gas flow meter3The flow rate of the feed solution is 1.5X 105ppm oxygen, stirring for 10h after the addition is finished, injecting 45% ammonia water at the flow rate of 150L/h by adopting a peristaltic pump, adjusting the pH value of the reaction solution to be 2.9, and controllingThe temperature of the reaction system is 60 ℃, and after the addition is finished, the reaction system is stirred for 1 hour and then stands for 4 hours.
S1-2, then carrying out filter pressing, washing and drying on the reaction product of S1-1 to obtain a ferric phosphate dihydrate precursor;
and S1-3, calcining the dihydrate ferric phosphate precursor of S1-2 at 800 ℃ for 2h to obtain the anhydrous ferric phosphate precursor.
The ferric orthophosphate precursor prepared by the above operation is taken to be subjected to SEM characterization and high-precision transmission electron microscope test, and the results are shown in figures 1 to 4. As can be seen from fig. 2 to 4, the iron, oxygen and phosphorus elements in the iron phosphate are uniformly distributed, which indicates that the iron phosphate prepared by the embodiment of the present invention has no defect in element distribution, and is favorable for the synthesis of lithium iron phosphate. In summary, the iron phosphate with few (even no) surface defects can be prepared by the method of the above embodiment.
Secondly, preparing the lithium iron phosphate anode material, which comprises the following specific steps:
s2-1, adding deionized water, lithium carbonate, glucose and citric acid (mixed according to a molar ratio of 1:1) into an iron phosphate precursor to obtain a mixed carbon source, sanding the mixture, controlling the sanding granularity to be 650nm, spray-drying the sanded mixture, and then placing the dried material in a nitrogen atmosphere to calcine at 700 ℃ for 14h to obtain the lithium iron phosphate.
Thirdly, preparing the lithium battery and testing the performance of the lithium battery:
and (3) carrying out electrochemical cycle performance test on the lithium iron phosphate material synthesized by the prepared ferric orthophosphate in the button type lithium ion battery. The result is shown in fig. 5, and it can be seen from fig. 5 that the ferric phosphate prepared by the invention is synthesized into the lithium iron phosphate material with 0.2C first-cycle charging capacity of 159.1mAh/g, first-cycle discharging capacity of 158.4mAh/g, 1C discharging capacity of 151.9mAh/g, 2C discharging capacity of 145.8mAh/g, 3C discharging capacity of 143.8mAh/g, and first-effect of 99.7%.
The second embodiment of the invention is as follows: a preparation process of a high-rate lithium battery iron phosphate precursor and a lithium iron phosphate cathode material comprises the following steps:
firstly, preparing an iron phosphate precursor, specifically comprising the following steps:
s1-1, adding alkylolamide into a continuous stirring kettle which is filled with 185g/L ferrous sulfate solution and has the frequency of 45Hz, adding 40 percent sodium phosphate solution at the flow rate of 90L/h by using a peristaltic pump, and adding 3m of sodium phosphate solution at the flow rate of 3m by using a gas flow meter3The flow rate of the feed is 1X 105And ppm ozone is stirred for 5 hours after the addition is finished, then 45 percent sodium hydroxide is injected into the reaction solution at the flow rate of 150L/h by adopting a peristaltic pump, the pH value of the reaction solution is adjusted to be 2.6, the temperature of the reaction system is controlled to be 40 ℃, the reaction solution is stirred for 1 hour after the addition is finished, and the reaction solution is kept still for 2 hours after the stirring is finished.
S1-2, then carrying out filter pressing, washing and drying on the reaction product of S1-1 to obtain a ferric phosphate dihydrate precursor;
and S1-3, calcining the dihydrate ferric phosphate precursor of S1-2 at 750 ℃ for 1h to obtain the anhydrous ferric phosphate precursor.
Secondly, preparing the lithium iron phosphate anode material, which comprises the following specific steps:
s2-1, adding deionized water, lithium carbonate and a mixed carbon source of glucose and citric acid (according to a molar ratio of 7: 3) into an iron phosphate precursor to prepare a mixture, sanding the mixture, controlling the sanding granularity to be 450nm, spray-drying the sanded mixture, and then placing the dried material in a nitrogen atmosphere to calcine at a high temperature of 650 ℃ for 10 hours to obtain the lithium iron phosphate.
The third embodiment of the invention is as follows: a preparation process of a high-rate lithium battery iron phosphate precursor and a lithium iron phosphate cathode material comprises the following steps:
firstly, preparing an iron phosphate precursor, specifically comprising the following steps:
s1-1, adding alkylphenol polyoxyethylene into a kettle which is filled with 195g/L ferrous sulfate solution and continuously stirred at the frequency of 50Hz, adding 45 percent ammonium dihydrogen phosphate solution at the flow rate of 110L/h by a peristaltic pump and 4m by a gas flow meter3The flow rate of the feed solution is 1.2X 105Stirring for 8h after the addition of ppm ozone, injecting 45% ammonia water at 200L/h by using a peristaltic pump, adjusting the pH value of the reaction solution to 2.7, controlling the temperature of the reaction system to 50 ℃, stirring for 1.5h after the addition is finished, standing for 3h after the stirring is finished。
S1-2, then carrying out filter pressing, washing and drying on the reaction product of S1-1 to obtain a ferric phosphate dihydrate precursor;
and S1-3, calcining the dihydrate ferric phosphate precursor of S1-2 at 800 ℃ for 1.5h to obtain the anhydrous ferric phosphate precursor.
Secondly, preparing the lithium iron phosphate anode material, which comprises the following specific steps:
s2-1, adding deionized water, lithium carbonate and a mixed carbon source of glucose and citric acid (mixed according to a molar ratio of 8: 2) into an iron phosphate precursor to prepare a mixture, sanding the mixture, controlling the sanding granularity to be 550nm, spray-drying the sanded mixture, and then placing the dried material in a nitrogen atmosphere to calcine at 680 ℃ for 12 hours to obtain the lithium iron phosphate.
The fourth embodiment of the invention is as follows: a preparation process of a high-rate lithium battery iron phosphate precursor and a lithium iron phosphate cathode material comprises the following steps:
firstly, preparing an iron phosphate precursor, specifically comprising the following steps:
s1-1, adding sorbitan ester into a kettle which is filled with 205g/L ferrous sulfate solution and continuously stirred at the frequency of 45Hz, adding 50 percent sodium phosphate and ammonium dihydrogen phosphate solution at the flow rate of 100L/h by a peristaltic pump and 4m by a gas flow meter3The flow rate of the feed solution is 1.5X 105And (2) stirring a ppm oxygen-ozone mixture (the volume ratio of oxygen to ozone in the mixture is 1:1) for 7 hours after the addition is finished, injecting 45% sodium hydroxide at the flow rate of 250L/h by using a peristaltic pump, adjusting the pH value of the reaction solution to 2.8, controlling the temperature of the reaction system to be 50 ℃, stirring for 2 hours after the addition is finished, and standing for 4 hours after the stirring is finished.
S1-2, then carrying out filter pressing, washing and drying on the reaction product of S1-1 to obtain a ferric phosphate dihydrate precursor;
and S1-3, calcining the dihydrate ferric phosphate precursor of S1-2 at 800 ℃ for 2h to obtain the anhydrous ferric phosphate precursor.
Secondly, preparing the lithium iron phosphate anode material, which comprises the following specific steps:
s2-1, adding deionized water, lithium carbonate and a mixed carbon source of glucose and citric acid (mixed according to a molar ratio of 6: 4) into an iron phosphate precursor to prepare a mixture, sanding the mixture, controlling the sanding granularity to be 600nm, spray-drying the sanded mixture, and then placing the dried material in a nitrogen atmosphere to calcine at a high temperature of 700 ℃ for 12 hours to obtain the lithium iron phosphate.
The scheme of the invention uses the gas oxidant for oxidation, and has at least the following advantages compared with the liquid oxidant:
first, liquid oxidants such as hydrogen peroxide have concentration problems, and the concentration can be further diluted in the reaction process, so that concentration difference is caused, the purity and uniformity of the product can be reduced, the yield of Fe can be reduced, and the cost is increased. The above problems can be avoided by using a gaseous oxidizing agent.
Secondly, the liquid oxidant is easy to decompose in the storage process, so that the oxidation capacity is insufficient, the limitation is that the reaction system cannot be added in excess, the gaseous oxidant can be added in a supersaturated manner through the air flow, and the oxidation capacity is further ensured.
Third, it is difficult to recover the unreacted portion of the liquid oxidizing agent if it is added in excess, and the excess portion of the gaseous oxidizing agent can be easily recovered by a gas recovery device.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be able to cover the technical scope of the present invention and the equivalent alternatives or modifications according to the technical solution and the inventive concept of the present invention within the technical scope of the present invention.
Claims (7)
1. A preparation method of a battery-grade iron phosphate precursor is characterized by comprising the following steps:
s1, adding a nonionic surfactant into the ferrous salt solution, adding the phosphorus salt solution and a gas oxidant, then injecting alkali liquor, adjusting the pH value of the reaction solution to 2.6-2.9 to obtain a mixed solution, controlling the temperature of the mixed solution to be (40-60) DEG C, reacting the mixed solution under a stirring condition, and standing and aging;
s2, carrying out filter pressing, washing and drying on the reaction product aged in the step S1 to obtain a dihydrate ferric phosphate precursor;
s3, calcining the ferric phosphate dihydrate precursor obtained in the step S2 to obtain an anhydrous ferric phosphate precursor;
the nonionic surfactant in the step S1 includes at least one of sorbitan ester, sucrose fatty acid ester, polyoxyethylene alkylphenol ether, or alkylolamide;
the gaseous oxidant in said step S1 comprises at least one of oxygen or ozone;
the calcination temperature in the step S3 is 750-850 ℃ for 1-2 h.
2. The method according to claim 1, wherein the phosphorus salt in step S1 comprises at least one of sodium phosphate, sodium monohydrogen phosphate, sodium dihydrogen phosphate, ammonium monohydrogen phosphate, or ammonium dihydrogen phosphate.
3. An iron phosphate precursor prepared by the method of claim 1 or 2.
4. A lithium iron phosphate characterized in that a raw material for producing the lithium iron phosphate contains the iron phosphate precursor according to claim 3.
5. The preparation method of the lithium iron phosphate is characterized by comprising the following steps:
adding deionized water, a lithium source and a composite carbon source to the iron phosphate precursor according to claim 3 to obtain a mixture, sanding the mixture, spray-drying the sanded mixture, and calcining the dried material to obtain lithium iron phosphate.
6. The method for preparing lithium iron phosphate according to claim 5, wherein the composite carbon source is glucose and citric acid, and the molar ratio of glucose to citric acid is X: (1-X), wherein the value range of X is more than or equal to 0.3 and less than or equal to 0.7.
7. A lithium ion battery, characterized in that the positive electrode material of the lithium ion battery is the lithium iron phosphate according to claim 4.
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| CN111847415A (en) * | 2020-07-21 | 2020-10-30 | 合肥国轩高科动力能源有限公司 | Battery-grade ferric orthophosphate and preparation method and application thereof |
| CN113479861B (en) * | 2021-07-01 | 2023-02-14 | 广东邦普循环科技有限公司 | Preparation method of low-sulfur-content nano iron phosphate |
| CN114132910B (en) * | 2021-12-30 | 2023-03-31 | 河南佰利新能源材料有限公司 | Method for preparing large-aperture iron phosphate |
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Address after: 410600 Xinkang Road, Ningxiang Economic and Technological Development Zone, Changsha City, Hunan Province Patentee after: Hunan Yacheng New Energy Co.,Ltd. Address before: 410600 Xinkang Road, Ningxiang Economic and Technological Development Zone, Changsha City, Hunan Province Patentee before: HUNAN YACHENG NEW MATERIAL CO.,LTD. |