CN114572955B - Battery-grade aluminum-containing ferric phosphate and preparation method thereof, lithium iron phosphate positive electrode material and preparation method thereof, and battery - Google Patents

Battery-grade aluminum-containing ferric phosphate and preparation method thereof, lithium iron phosphate positive electrode material and preparation method thereof, and battery Download PDF

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CN114572955B
CN114572955B CN202210292144.3A CN202210292144A CN114572955B CN 114572955 B CN114572955 B CN 114572955B CN 202210292144 A CN202210292144 A CN 202210292144A CN 114572955 B CN114572955 B CN 114572955B
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iron phosphate
battery
aluminum
phosphate
lithium
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CN114572955A (en
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郑靭
陈汉昭
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Zhuhai Zhongli New Energy Materials Co ltd
GUANGDONG GUANGHUA SCI-TECH CO LTD
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GUANGDONG GUANGHUA SCI-TECH CO LTD
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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
    • 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
    • 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
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • 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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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
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    • C01P2006/40—Electric properties
    • 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 relates to a battery-grade aluminum-containing ferric phosphate and a preparation method thereof, a lithium iron phosphate anode material and a preparation method thereof, and a battery. The preparation method of the battery-level aluminum-containing ferric phosphate comprises the following steps: providing an iron phosphate coarse material, wherein the iron phosphate coarse material contains aluminum impurities, and the content of the aluminum impurities is 500 ppm-5000 ppm; and (3) heating the coarse iron phosphate material to 600-650 ℃ for calcination, and then cooling to prepare the battery-grade aluminum-containing iron phosphate, wherein the cooling treatment comprises the step of cooling from 600-650 ℃ to 400-450 ℃ at a speed of 1-3 ℃/min. The preparation method provided by the invention is simple and controllable in process, low in environmental pressure, low in cost, good in atomic economy, easy to industrialize and good in performance of the final product, and the battery-grade aluminum-containing ferric phosphate can not have great adverse effect on the performance of a downstream battery.

Description

Battery-grade aluminum-containing ferric phosphate and preparation method thereof, lithium iron phosphate positive electrode material and preparation method thereof, and battery
Technical Field
The invention relates to the technical field of battery materials, in particular to a battery-grade aluminum-containing ferric phosphate and a preparation method thereof, a lithium iron phosphate positive electrode material and a preparation method thereof, and a battery.
Background
Lithium iron phosphate is one of the main positive electrode materials of lithium ion batteries at present because of the advantages of safety in use and low production cost. With the continuous retirement or scrapping of the lithium iron phosphate batteries which are already put on the market, the recycling problem of the lithium iron phosphate batteries becomes an industrial problem which needs to be solved urgently. Because the anode of the lithium iron phosphate battery adopts an aluminum foil current collector, the recovered lithium iron phosphate material inevitably contains a large amount of impurity aluminum. The presence of these aluminum impurities, whether it is direct regeneration of lithium iron phosphate or hydrometallurgical recovery of lithium iron phosphate, can have a significant impact on the electrical performance of downstream batteries, especially, can result in a significant reduction in the specific discharge capacity of the battery.
Typically, when lithium iron phosphate is recovered by hydrometallurgical processes, substantially all of the aluminum impurities are incorporated into the iron phosphate coarse material. The aluminum content in commercial iron phosphate coarse materials with recovery value is generally about 500ppm to 5000 ppm. The current method for removing aluminum from iron phosphate coarse materials can be acid leaching or alkaline leaching or through phosphoric acid precipitation, and all the purposes are to completely separate aluminum from the iron phosphate coarse materials, reduce the aluminum content to below 500ppm, and reduce the adverse effect of impurity aluminum on the electrical performance of downstream batteries. However, the aluminum removal method generally has the defects of large reagent consumption, environmental protection, low ferrophosphorus recovery rate, large reagent treatment or recovery difficulty, high process cost and the like.
Disclosure of Invention
Based on the above, the invention provides a battery-grade aluminum-containing ferric phosphate and a preparation method thereof, a lithium iron phosphate positive electrode material and a preparation method thereof, and a battery. The method breaks through the thought formula of thoroughly removing aluminum impurities from the coarse iron phosphate material, but prepares the battery-grade aluminum-containing iron phosphate which does not have great adverse effect on the performance of a downstream battery.
The first aspect of the invention provides a method for preparing battery-grade aluminum-containing ferric phosphate, which comprises the following steps:
providing an iron phosphate coarse material, wherein the iron phosphate coarse material contains aluminum impurities, and the content of the aluminum impurities is 500 ppm-5000 ppm;
and (3) heating the coarse iron phosphate material to 600-650 ℃ for calcination, and then cooling to prepare the battery-grade aluminum-containing iron phosphate, wherein the cooling treatment comprises the step of cooling from 600-650 ℃ to 400-450 ℃ at a speed of 1-3 ℃/min.
In some of these embodiments, the cooling process further comprises the step of cooling from the 400 ℃ to 450 ℃ to room temperature at an arbitrary rate.
In some of these embodiments, the calcination is for a period of time ranging from 5 hours to 10 hours.
The second aspect of the invention provides battery-grade aluminum-containing ferric phosphate prepared by the preparation method.
The third aspect of the invention provides a lithium iron phosphate positive electrode material, which is prepared from the battery-grade aluminum-containing ferric phosphate, a lithium source, a dispersing agent and a carbon source.
In some embodiments, the lithium source is selected from at least one of lithium carbonate, lithium hydroxide, and lithium dihydrogen phosphate.
In some embodiments, the dispersant is selected from at least one of polyethylene glycol, polyacrylamide, and polyethyleneimine.
In some embodiments, the carbon source is selected from at least one of glucose, sucrose, and starch.
The fourth aspect of the present invention provides a method for preparing a lithium iron phosphate positive electrode material, comprising the steps of:
mixing the battery-grade aluminum-containing ferric phosphate, a lithium source, a dispersing agent, a carbon source and water to obtain mixed slurry, and grinding the mixed slurry to the particle size D of a solid mixture in the mixed slurry 50 Obtaining primary slurry with the diameter of 0.5-0.7 mu m, taking out 10-15% of the total mass from the primary slurry, and continuously grinding to the particle diameter D of the solid mixture 50 And the size is 0.1-0.25 mu m, so as to obtain secondary slurry, mixing the primary slurry and the secondary slurry, drying, roasting under the protection of non-reducing gas, and crushing and screening to obtain the lithium iron phosphate anode material.
In some embodiments, the molar ratio of iron phosphate, lithium source, and carbon source in the battery-grade aluminum-containing iron phosphate is 1: (1.01-1.05): (0.35-0.4).
In some embodiments, the dispersant comprises 2% -3% by mass of the battery grade aluminum-containing iron phosphate.
In some embodiments, the mixed slurry has a solids content of 45% to 55%.
In some embodiments, the milling is ball milling.
In some embodiments, the step of firing includes: first, roasting for 3-5 h at 300-350 ℃ and then roasting for 4-8 h at 740-760 ℃ for two stages.
In a fifth aspect, the present invention provides a battery, which is prepared from the above lithium iron phosphate cathode material, anode material and electrolyte.
Compared with the traditional scheme, the invention has the following beneficial effects:
the inventor of the present invention has found through research that a main solid solution of hydrated iron aluminum phosphate exists in commercial iron phosphate coarse materials, and most of the solid solution exists in the form of a solid solution of dihydrate iron aluminum phosphate, and aluminum impurities are doped in the crystal lattice of iron phosphate. The invention breaks through the thinking that aluminum impurities are thoroughly removed from the coarse iron phosphate material, but separates out the aluminum impurities from the hydrated aluminum ferric phosphate solid solution to form an independent aluminum phosphate phase through heating to 600-650 ℃ for calcination, and simultaneously controls the technological parameters of cooling treatment, so that the separated aluminum phosphate phase is prevented from undergoing phase transition and returning to the iron phosphate phase, the battery-grade aluminum-containing iron phosphate is prepared, the independent aluminum phosphate phase does not need to be separated from an iron phosphate product, can coexist with the lithium iron phosphate phase, the independent aluminum phosphate phase does not have great adverse effect on the downstream battery performance, and the battery-grade aluminum-containing iron phosphate can be directly utilized to prepare the lithium iron phosphate anode material meeting the requirements of high compaction density and high specific discharge capacity.
The method has high tolerance to aluminum in the coarse ferric phosphate material, simple and controllable process, low environmental pressure, low cost, good atomic economy, high utilization rate of ferrophosphorus, easy industrialization, good performance of the final product and great economic benefit.
According to the invention, the battery-level aluminum-containing ferric phosphate is used for preparing the lithium iron phosphate anode material, in the preparation process, first primary slurry is obtained by grinding, then a part of primary slurry is taken to be continuously ground to obtain secondary slurry, and the two slurries are mixed for subsequent process treatment, so that a particle mechanism with complementary size can be effectively formed, and a foundation is laid for subsequently obtaining the high-compaction-density lithium iron phosphate anode material. In addition, in the roasting stage, carbon coated with the lithium iron phosphate material is fully graphitized through two-stage roasting treatment, so that the conductivity of the material is improved. While the temperature of the calcination is controlled within the above range, not too high, to avoid the formation of excessively large sintered particles, deteriorating the electrochemical properties of the lithium iron phosphate product.
Drawings
FIG. 1 is an XRD contrast pattern of battery grade aluminum-containing ferric phosphate of examples 1-3 and comparative examples 1-2;
fig. 2 is an SEM image of the lithium iron phosphate cathode material of example 1.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Terminology
Unless otherwise indicated or contradicted, terms or phrases used herein have the following meanings:
as used herein, the term "and/or," and/or, "and/or" includes any one of two or more of the listed items and also includes any and all combinations of the listed items, including any two or more of the listed items, any or all of the listed items.
In the present invention, "at least one" means any one, any two or more of the listed items.
In the present invention, "optional" means optional or not, that is, means any one selected from two parallel schemes of "with" or "without". If multiple "alternatives" occur in a technical solution, if no particular description exists and there is no contradiction or mutual constraint, then each "alternative" is independent.
In the present invention, "preferred" is merely to describe embodiments or examples that are more effective, and it should be understood that they are not intended to limit the scope of the present invention.
In the invention, the technical characteristics described in an open mode comprise a closed technical scheme composed of the listed characteristics and also comprise an open technical scheme comprising the listed characteristics.
In the present invention, the numerical range is referred to, and both ends of the numerical range are included unless otherwise specified.
In the present invention, the content of the components is referred to as mass percent for solid-liquid mixing and solid-solid mixing, and volume percent for liquid-liquid mixing unless otherwise specified.
In the present invention, the term "percent concentration" refers to the final concentration unless otherwise specified. The final concentration refers to the ratio of the additive component in the system after the component is added.
In the present invention, the temperature parameter is not particularly limited, and it is allowed to perform the constant temperature treatment or the treatment within a predetermined temperature range. The constant temperature process allows the temperature to fluctuate within the accuracy of the instrument control.
In the present invention, "drying" is to maintain the product in a loose particulate state by methods including, but not limited to, vacuum freeze drying, heat drying under nitrogen or inert gas, microwave drying, spray drying or flash drying, and the like, preferably spray or flash drying. It can be carried out under conventional process conditions, the temperature range of the reference is 200-220 ℃, the drying process can be completed very rapidly or can last for a period of time, in the case of industrial mass production, the drying time is the yield divided by the production rate, in the embodiment of the invention, the operating time of the reference is preferably 3-20 minutes.
The invention provides a preparation method of battery-grade aluminum-containing ferric phosphate, which comprises the following steps:
providing an iron phosphate coarse material, wherein the iron phosphate coarse material contains aluminum impurities, and the content of the aluminum impurities is 500 ppm-5000 ppm;
and (3) heating the coarse iron phosphate material to 600-650 ℃ for calcination, and then cooling to prepare the battery-grade aluminum-containing iron phosphate, wherein the cooling treatment comprises the step of cooling from 600-650 ℃ to 400-450 ℃ at a speed of 1-3 ℃/min.
The inventor of the present invention has found through research that a main solid solution of hydrated iron aluminum phosphate exists in commercial iron phosphate coarse materials, and most of the solid solution exists in the form of a solid solution of dihydrate iron aluminum phosphate, and aluminum impurities are doped in the crystal lattice of iron phosphate. The invention breaks through the thinking that aluminum impurities are thoroughly removed from the coarse iron phosphate material, but separates out the aluminum impurities from the hydrated aluminum ferric phosphate solid solution to form an independent aluminum phosphate phase through heating to 600-650 ℃ for calcination, and simultaneously controls the technological parameters of cooling treatment, so that the separated aluminum phosphate phase is prevented from undergoing phase transition and returning to the iron phosphate phase, the battery-grade aluminum-containing iron phosphate is prepared, the independent aluminum phosphate phase does not need to be separated from an iron phosphate product, can coexist with the lithium iron phosphate phase, the independent aluminum phosphate phase does not have great adverse effect on the downstream battery performance, and the battery-grade aluminum-containing iron phosphate can be directly utilized to prepare the lithium iron phosphate anode material meeting the requirements of high compaction density and high specific discharge capacity.
Alternatively, the coarse iron phosphate material may be obtained by recycling upstream waste lithium iron phosphate.
And heating the coarse iron phosphate material to 600-650 ℃ for calcination. Including but not limited to heating the iron phosphate coarse to 600 ℃, 610 ℃, 620 ℃, 630 ℃, 640 ℃, 650 ℃.
Optionally, the calcination time is 5-10 h. Including but not limited to 5h, 6h, 7h, 8h, 9h, 10h.
Optionally, the cooling treatment further comprises the step of cooling from 400 ℃ to 450 ℃ to room temperature at an arbitrary rate.
It is understood that any rate may refer to natural cooling to room temperature.
The method has high tolerance to aluminum in the coarse ferric phosphate material, simple and controllable process, low environmental pressure, low cost, good atomic economy, high utilization rate of ferrophosphorus, easy industrialization, good performance of the final product and great economic benefit.
The second aspect of the invention provides battery-grade aluminum-containing ferric phosphate prepared by the preparation method. In the battery-grade aluminum-containing ferric phosphate, aluminum phosphate and ferric phosphate are not present in the form of a solid co-solution, but are each independently present. The iron phosphate may be completely converted into lithium iron phosphate upon subsequent preparation of the lithium iron phosphate cathode material. Furthermore, the aluminum phosphate phase and the lithium iron phosphate phase are different in crystal system, and are not mutually soluble in nature. And the melting point of the aluminum phosphate phase is far higher than the roasting temperature for preparing the lithium iron phosphate, and the phenomenon that aluminum returns to the lithium iron phosphate crystal lattice again can not occur in the cooling link after the preparation of the lithium iron phosphate. The aluminum phosphate impurities in the battery-level aluminum-containing ferric phosphate exist independently in the lithium iron phosphate positive electrode material, so that the great loss of the discharge specific capacity of the material is avoided.
The third aspect of the invention provides a lithium iron phosphate positive electrode material, which is prepared from the battery-grade aluminum-containing ferric phosphate, a lithium source, a dispersing agent and a carbon source.
Optionally, the lithium source is selected from at least one of lithium carbonate, lithium hydroxide, and lithium dihydrogen phosphate.
Optionally, the dispersing agent is selected from at least one of polyethylene glycol, polyacrylamide and polyethyleneimine.
Further alternatively, the polyethylene glycol may be selected from at least one of polyethylene glycol 1000, polyethylene glycol 1500, and polyethylene glycol 10000.
Optionally, the carbon source is selected from at least one of glucose, sucrose and starch.
The fourth aspect of the present invention provides a method for preparing a lithium iron phosphate positive electrode material, comprising the steps of:
mixing the battery-grade aluminum-containing ferric phosphate, a lithium source, a dispersing agent, a carbon source and water to obtain mixed slurry, and grinding the mixed slurry to the particle size D of a solid mixture in the mixed slurry 50 Obtaining primary slurry with the diameter of 0.5-0.7 mu m, taking out 10-15% of the total mass from the primary slurry, and continuously grinding to the particle diameter D of the solid mixture 50 The size of the slurry is 0.1-0.25 mu m, secondary slurry is obtained, the primary slurry and the secondary slurry are mixed, dried and then non-reducedRoasting under the protection of gas, and crushing and sieving to obtain the lithium iron phosphate anode material.
Optionally, the molar ratio of the iron phosphate, the lithium source and the carbon source in the battery-grade aluminum-containing iron phosphate is 1: (1.01-1.05): (0.35-0.4).
Optionally, the mass of the dispersing agent accounts for 2-3% of the mass of the battery-grade aluminum-containing ferric phosphate.
Optionally, the solid content of the mixed slurry is 45% -55%.
Optionally, the milling is ball milling.
In preparing the lithium iron phosphate positive electrode material, the material has the particle diameter D 50 The primary slurry and the secondary slurry are mixed, so that a particle mechanism with complementary size can be effectively formed, and a foundation is laid for the subsequent preparation of the high-compaction-density lithium iron phosphate material.
It will be appreciated that the primary slurry and the secondary slurry are mixed and then enter the spraying process.
Optionally, the step of firing includes: first, roasting for 3-5 h at 300-350 ℃ and then roasting for 4-8 h at 740-760 ℃ for two stages. In the roasting stage, carbon coated with the lithium iron phosphate material is fully graphitized through the first-stage roasting and the second-stage roasting treatment of two temperature sections, so that the conductivity of the material is improved, and meanwhile, the roasting temperature of each section is controlled within the range and is not excessively high, so that oversized sintered particles are avoided to be formed, and the electrochemical performance of the lithium iron phosphate product is deteriorated.
In a fifth aspect, the present invention provides a battery, which is prepared from the above lithium iron phosphate cathode material, anode material and electrolyte.
The following examples are further offered by way of illustration, and the materials used in the following examples are commercially available unless otherwise indicated, and the apparatus used is commercially available unless otherwise indicated, and the processes involved, unless otherwise indicated, are routine selections by those skilled in the art.
The "coarse iron phosphate" used in the following specific examples and comparative examples was obtained by purchasing "Jiangxi gold lithium science and technology Co., ltd.
Example 1
The embodiment provides a battery-level aluminum-containing ferric phosphate and a preparation method thereof, a lithium iron phosphate positive electrode material and a preparation method thereof, and the steps are as follows:
1) The iron phosphate coarse material was taken and the aluminum impurity content was measured to be 3213ppm.
2) Preparation of Battery grade aluminum-containing iron phosphate
Calcining the iron phosphate coarse material obtained in the step 1) at 600 ℃ for 5 hours, wherein the aluminum impurities are separated out and form AlPO 4 The phase is cooled to 450 ℃ at a speed of 1 ℃/min, and then naturally cooled to room temperature, so as to obtain the battery-grade aluminum-containing ferric phosphate, the XRD pattern of the obtained battery-grade aluminum-containing ferric phosphate is shown as figure 1, and the XRD pattern is matched with AlPO 4 And FePO 4 As can be seen from a comparison of the standard cards of (a), the battery-grade aluminum-containing iron phosphate contains an independent AlPO 4 Phase and FePO 4 And (3) phase (C).
3) Preparation of lithium iron phosphate cathode material
Crushing and sieving the battery-grade aluminum-containing iron phosphate obtained in the step 2), and then mixing the crushed and sieved aluminum-containing iron phosphate with the following components: lithium carbonate: glucose was 1:1.01: and (3) mixing the battery-level aluminum-containing ferric phosphate, lithium carbonate and glucose according to the molar ratio of 0.35, adding polyethylene glycol 1500 according to the amount accounting for 2% of the mass of the battery-level aluminum-containing ferric phosphate, and adding a proper amount of deionized water to obtain the mixed slurry with the solid content of 45%.
Ball milling the mixed slurry to obtain particle size distribution D 50 Taking 10% of the mass of the primary slurry, and continuing ball milling to form particle size distribution D 50 And (3) uniformly mixing the primary slurry and the secondary slurry, spray-drying at 210 ℃ for 5 minutes, roasting at 300 ℃ for 3 hours at a first stage and then at 740 ℃ for 4 hours at a second stage under the protection of nitrogen, and naturally cooling to obtain the lithium iron phosphate anode material. An SEM image of the obtained lithium iron phosphate positive electrode material is shown in fig. 2.
Example 2
The present embodiment provides a battery-grade aluminum-containing iron phosphate and a preparation method thereof, and a lithium iron phosphate positive electrode material and a preparation method thereof, which are mainly different from those of embodiment 1 in process parameters of each step. The method comprises the following steps:
1) The iron phosphate coarse material was taken and the aluminum impurity content was determined to be 4870ppm.
2) Preparation of Battery grade aluminum-containing iron phosphate
Calcining the iron phosphate coarse material obtained in the step 1) at 650 ℃ for 10 hours, wherein the aluminum impurities are separated out and form AlPO 4 The phase is cooled to 450 ℃ at a speed of 3 ℃/min, and then naturally cooled to room temperature, so as to obtain the battery-grade aluminum-containing ferric phosphate, the XRD pattern of the obtained battery-grade aluminum-containing ferric phosphate is shown as figure 1, and the battery-grade aluminum-containing ferric phosphate is matched with AlPO 4 And FePO 4 As can be seen from a comparison of the standard cards of (a), the battery-grade aluminum-containing iron phosphate contains an independent AlPO 4 Phase and FePO 4 And (3) phase (C).
3) Preparation of lithium iron phosphate cathode material
Crushing and sieving the battery-grade aluminum-containing iron phosphate obtained in the step 2), and then mixing the crushed and sieved aluminum-containing iron phosphate with the following components: lithium carbonate: glucose was 1:1.05: and (3) mixing the battery-level aluminum-containing ferric phosphate, lithium carbonate and glucose according to the molar ratio of 0.4, adding polyethylene glycol 1500 according to the amount accounting for 3% of the mass of the battery-level aluminum-containing ferric phosphate, and adding a proper amount of deionized water to obtain the mixed slurry with the solid content of 55%.
Ball milling the mixed slurry to obtain particle size distribution D 50 Taking 15% of the mass of the primary slurry, and continuing ball milling to form particle size distribution D 50 And (3) uniformly mixing the primary slurry and the secondary slurry, spray-drying at 200 ℃ for 8 minutes, roasting at 350 ℃ for 5 hours at first and then roasting at 760 ℃ for 8 hours at second under the protection of nitrogen, and naturally cooling to obtain the lithium iron phosphate anode material.
Example 3
The present embodiment provides a battery-grade aluminum-containing iron phosphate and a preparation method thereof, and a lithium iron phosphate positive electrode material and a preparation method thereof, which are mainly different from those of embodiment 1 in process parameters of each step. The method comprises the following steps:
1) The iron phosphate coarse material was taken and the aluminum impurity content was determined to be 527ppm.
2) Preparation of Battery grade aluminum-containing iron phosphate
Calcining the iron phosphate coarse material obtained in the step 1) at 630 ℃ for 8 hours, wherein the aluminum impurities are separated out and form AlPO 4 The phase is cooled to 430 ℃ at a speed of 2 ℃/min, and then naturally cooled to room temperature to obtain battery-grade aluminum-containing ferric phosphate, the XRD pattern of the obtained battery-grade aluminum-containing ferric phosphate is shown as figure 1, and the XRD pattern is matched with AlPO 4 And FePO 4 As can be seen from a comparison of the standard cards of (a), the battery-grade aluminum-containing iron phosphate contains an independent AlPO 4 Phase and FePO 4 And (3) phase (C).
3) Preparation of lithium iron phosphate cathode material
Crushing and sieving the battery-grade aluminum-containing iron phosphate obtained in the step 1), and then mixing the crushed and sieved aluminum-containing iron phosphate with the following components: lithium carbonate: glucose was 1:1.03: and (3) mixing the battery-level aluminum-containing ferric phosphate, lithium carbonate and glucose according to the molar ratio of 0.38, adding polyethylene glycol 1500 according to the amount accounting for 2.5% of the mass of the battery-level aluminum-containing ferric phosphate, and adding a proper amount of deionized water to obtain the slurry with the solid content of 50%.
Ball milling the mixed slurry to obtain particle size distribution D 50 Taking 13% of primary slurry with the mass of 0.6 μm, and continuing ball milling to form particle size distribution D 50 And (3) uniformly mixing the primary slurry and the secondary slurry, spray-drying at 220 ℃ for 10 minutes, roasting at 330 ℃ for 4 hours at first and then at 750 ℃ for 6 hours in a first stage under the protection of nitrogen, and naturally cooling to obtain the lithium iron phosphate anode material.
Example 4
The embodiment provides a battery-level aluminum-containing ferric phosphate and a preparation method thereof, a lithium iron phosphate positive electrode material and a preparation method thereof, which are basically the same as the embodiment 1, and the proportion of secondary slurry is different, and the steps are as follows:
1) The same coarse iron phosphate as in example 1 was used.
2) Battery grade aluminum-containing iron phosphate was prepared in the same manner as in example 1.
3) Preparation of lithium iron phosphate cathode material
Crushing and sieving the battery-grade aluminum-containing iron phosphate obtained in the step 2), and then mixing the crushed and sieved aluminum-containing iron phosphate with the following components: lithium carbonate: glucose was 1:1.01: and (3) mixing the battery-level aluminum-containing ferric phosphate, lithium carbonate and glucose according to the molar ratio of 0.35, adding polyethylene glycol 1500 according to the amount accounting for 2% of the mass of the battery-level aluminum-containing ferric phosphate, and adding a proper amount of deionized water to obtain the mixed slurry with the solid content of 45%.
Ball milling the mixed slurry to obtain particle size distribution D 50 Taking 20% of the mass of the primary slurry, and continuing ball milling to form particle size distribution D 50 And (3) uniformly mixing the primary slurry and the secondary slurry, spray-drying at 210 ℃ for 5 minutes, roasting at 300 ℃ for 3 hours at a first stage and then at 740 ℃ for 4 hours at a second stage under the protection of nitrogen, and naturally cooling to obtain the lithium iron phosphate anode material.
Example 5
The present example provides a battery-grade aluminum-containing iron phosphate and a method for preparing the same, a lithium iron phosphate positive electrode material and a method for preparing the same, which are basically the same as example 1, without secondary slurry, and the steps are as follows:
1) The same coarse iron phosphate as in example 1 was used.
2) Battery grade aluminum-containing iron phosphate was prepared in the same manner as in example 1.
3) Preparation of lithium iron phosphate cathode material
Crushing and sieving the battery-grade aluminum-containing iron phosphate obtained in the step 2), and then mixing the crushed and sieved aluminum-containing iron phosphate with the following components: lithium carbonate: glucose was 1:1.01: and (3) mixing the battery-level aluminum-containing ferric phosphate, lithium carbonate and glucose according to the molar ratio of 0.35, adding polyethylene glycol 1500 according to the amount accounting for 2% of the mass of the battery-level aluminum-containing ferric phosphate, and adding a proper amount of deionized water to obtain the mixed slurry with the solid content of 45%.
Ball milling the mixed slurry to obtain particle size distribution D 50 The slurry with the particle size of 0.5 μm is spray dried for 5 minutes at 210 ℃, and then is roasted for 3 hours at 300 ℃ for a first period of time and then is roasted for 4 hours at 740 ℃ for a second period of time under the protection of nitrogen, and the lithium iron phosphate anode material is obtained after natural cooling.
Example 6
This example provides a battery-grade aluminum-containing ferric phosphate, a preparation method thereof, a lithium iron phosphate positive electrode material and a preparation method thereofPreparation method, essentially the same as in example 1, primary slurry particle size D 50 The steps are different as follows:
1) The same coarse iron phosphate as in example 1 was used.
2) Battery grade aluminum-containing iron phosphate was prepared in the same manner as in example 1.
3) Preparation of lithium iron phosphate cathode material
Crushing and sieving the battery-grade aluminum-containing iron phosphate obtained in the step 2), and then mixing the crushed and sieved aluminum-containing iron phosphate with the following components: lithium carbonate: glucose was 1:1.01: and (3) mixing the battery-level aluminum-containing ferric phosphate, lithium carbonate and glucose according to the molar ratio of 0.35, adding polyethylene glycol 1500 according to the amount accounting for 2% of the mass of the battery-level aluminum-containing ferric phosphate, and adding a proper amount of deionized water to obtain the mixed slurry with the solid content of 45%.
Ball milling the mixed slurry to obtain particle size distribution D 50 Taking 10% of the mass of the primary slurry, and continuing ball milling to form particle size distribution D 50 And (3) uniformly mixing the primary slurry and the secondary slurry, spray-drying at 210 ℃ for 5 minutes, roasting at 300 ℃ for 3 hours at a first stage and then at 740 ℃ for 4 hours at a second stage under the protection of nitrogen, and naturally cooling to obtain the lithium iron phosphate anode material.
Comparative example 1
The comparative example provides a battery-grade aluminum-containing iron phosphate and a preparation method thereof, a lithium iron phosphate positive electrode material and a preparation method thereof, which are basically the same as those of example 1, and are mainly different in that the content of aluminum impurities in the iron phosphate coarse material is 6435ppm, and the steps are as follows:
1) The iron phosphate coarse material was taken and the aluminum impurity content was measured to be 6435ppm.
2) Preparation of Battery grade aluminum-containing iron phosphate
As in example 1, the XRD pattern of the resulting battery grade aluminum-containing iron phosphate is shown in FIG. 1, and is the same as AlPO 4 And FePO 4 As can be seen from a comparison of the standard cards of (a), the battery-grade aluminum-containing iron phosphate contains an independent AlPO 4 Phase and FePO 4 The phase, however, the peak intensity corresponding to the aluminum phosphate phase is significantly more prominent in the 2 theta angle range of 21 deg. to 24 deg..
3) A lithium iron phosphate positive electrode material was prepared in the same manner as in example 1.
Comparative example 2
The comparative example provides a battery-grade aluminum-containing ferric phosphate and a preparation method thereof, and a lithium iron phosphate positive electrode material and a preparation method thereof, which are basically the same as those of the embodiment 1, and mainly differ in the process parameters of cooling treatment as follows:
1) The same coarse iron phosphate as in example 1 was used.
2) Preparation of Battery grade aluminum-containing iron phosphate
Calcining the coarse iron phosphate material obtained in the step 1) at 600 ℃ for 5 hours, naturally cooling to room temperature to obtain battery-grade aluminum-containing iron phosphate, wherein the XRD pattern of the obtained battery-grade aluminum-containing iron phosphate is shown as figure 1, and the XRD pattern is matched with AlPO 4 And FePO 4 As can be seen from a comparison of standard cards of (a), the battery-grade aluminum-containing iron phosphate did not form AlPO 4 And (3) phase (C).
3) A lithium iron phosphate positive electrode material was prepared in the same manner as in example 1.
Comparative example 3
The comparative example provides a preparation method of battery-grade aluminum-containing ferric phosphate, a lithium iron phosphate positive electrode material and a preparation method thereof, which are basically the same as the example 1, and mainly differ in the process parameters of cooling treatment as follows:
1) The same coarse iron phosphate as in example 1 was used.
2) Preparation of Battery grade aluminum-containing iron phosphate
Calcining the coarse iron phosphate material obtained in the step 1) at 600 ℃ for 5 hours to precipitate aluminum impurities and form AlPO 4 And cooling to 450 ℃ at a speed of 5 ℃/min, and naturally cooling to room temperature to obtain the battery-grade aluminum-containing ferric phosphate.
3) A lithium iron phosphate positive electrode material was prepared in the same manner as in example 1.
Comparative example 4
The comparative example provides a preparation method of battery-grade aluminum-containing ferric phosphate, a lithium iron phosphate positive electrode material and a preparation method thereof, which are basically the same as the example 1, and mainly differ in the process parameters of cooling treatment as follows:
1) The same coarse iron phosphate as in example 1 was used.
2) Preparation of Battery grade aluminum-containing iron phosphate
Calcining the coarse iron phosphate material obtained in the step 1) at 600 ℃ for 5 hours to precipitate aluminum impurities and form AlPO 4 And (3) cooling to 500 ℃ at a speed of 1 ℃/min, and naturally cooling to room temperature to obtain the battery-grade aluminum-containing ferric phosphate.
3) A lithium iron phosphate positive electrode material was prepared in the same manner as in example 1.
Comparative example 5
The comparative example provides a preparation method of battery-grade aluminum-containing ferric phosphate, a lithium iron phosphate positive electrode material and a preparation method thereof, and the preparation method is basically the same as that of the example 1, wherein the calcination temperature of the coarse material of the ferric phosphate is 550 ℃, and the steps are as follows:
1) The same coarse iron phosphate as in example 1 was used.
2) Preparation of Battery grade aluminum-containing iron phosphate
And (3) placing the coarse iron phosphate material obtained in the step (1) at 550 ℃ for calcination for 5 hours, then cooling to 450 ℃ at a speed of 1 ℃/min, and naturally cooling to room temperature to obtain the battery-grade aluminum-containing iron phosphate.
3) A lithium iron phosphate positive electrode material was prepared in the same manner as in example 1.
Comparative example 6
The comparative example provides a preparation method of battery-grade aluminum-containing ferric phosphate, a lithium iron phosphate positive electrode material and a preparation method thereof, and the preparation method is basically the same as that of the example 1, wherein the calcination temperature of the coarse material of the ferric phosphate is 700 ℃, and the steps are as follows:
1) The same coarse iron phosphate as in example 1 was used.
2) Preparation of Battery grade aluminum-containing iron phosphate
And (3) placing the coarse iron phosphate material obtained in the step (1) at 700 ℃ for calcination for 5 hours, then cooling to 450 ℃ at a speed of 1 ℃/min, and naturally cooling to room temperature to obtain the battery-grade aluminum-containing iron phosphate.
3) A lithium iron phosphate positive electrode material was prepared in the same manner as in example 1.
Compaction density and discharge Performance test
The testing method comprises the following steps: the compacted density of the lithium iron phosphate cathode material powders obtained in each of the above examples and comparative examples was tested according to the test method specified in annex L in the national standard GB/T24533-2009. The lithium iron phosphate materials of the above examples and comparative examples were tested for 0.1C discharge performance according to the test method specified in the national standard GB/T30835-2014, and the test results are shown in Table 1.
And (5) qualification standard: currently in the industry, the positive electrode material of lithium iron phosphate has a compact density standard of greater than 2.38 g/cc and a specific discharge capacity standard of greater than 155 ma/g at 0.1C.
TABLE 1
Figure BDA0003561945090000161
The above results show that in examples 1-3, although the raw material iron phosphate coarse material contains a higher content of impurity aluminum, the final prepared lithium iron phosphate positive electrode material after the treatment of the invention simultaneously meets the requirements of the industry on compaction density and discharge specific capacity, and achieves the aim of preparing the high-performance lithium iron phosphate positive electrode material from the battery-grade aluminum-containing iron phosphate.
In examples 4-6, the proportion and the particle size of the secondary slurry are not within the preferred range of the invention when preparing the lithium iron phosphate positive electrode material, and no perfect size complementation effect is formed between the primary and secondary slurry particles, resulting in low compaction density of the subsequent lithium iron phosphate material. And, primary slurry particle D in example 6 50 =0.8 μm, oversized particles, resulting in a severe mismatch in secondary slurry particle size, resulting in low compaction density.
In comparative example 1, the impurity aluminum content reaches 6435ppm, resulting in a higher impurity content of aluminum phosphate existing alone in lithium iron phosphate, which reduces the specific discharge capacity of the material.
In comparative example 2, after calcination, the process parameters of the cooling treatment are not controlled, so that aluminum phosphate is converted into aluminum and returns to the crystal lattice of iron phosphate again, and the aluminum phosphate cannot be completely separated from the iron phosphate phase, thereby adversely affecting the specific discharge capacity of the subsequent lithium iron phosphate product.
In comparative example 3, the first stage of the coarse iron phosphate material is cooled too rapidly, and the quenching causes the aluminum phosphate to change phase and form solid solution with the iron phosphate, thereby adversely affecting the electrical properties of the material. In comparative example 4, the first stage of the coarse iron phosphate material has a higher cooling end point, which also causes solid solution formation between aluminum phosphate and iron phosphate, and adversely affects the electrical properties of the material.
In comparative example 5, the calcination temperature of the iron phosphate coarse material was 550 ℃, aluminum did not precipitate from the iron aluminum phosphate solid solution and formed an independent aluminum phosphate phase, and the aluminum that did not precipitate in the iron phosphate hindered the subsequent lithium iron phosphate calcination process, which in turn adversely affected the electrochemical properties of the material. In comparative example 6, the calcination temperature of the iron phosphate coarse material was 700 ℃, so that the specific surface area of the prepared battery-grade aluminum-containing iron phosphate was too small, and finally the electrolyte in the battery could not fully infiltrate the lithium iron phosphate material, and the discharge capacity of the material was reduced.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims (10)

1. The preparation method of the battery-grade aluminum-containing ferric phosphate is characterized by comprising the following steps of:
providing an iron phosphate coarse material, wherein the iron phosphate coarse material contains aluminum impurities, and the content of the aluminum impurities is 500 ppm-5000 ppm;
and (3) heating the coarse iron phosphate material to 600-650 ℃ for calcination, and then cooling to prepare the battery-grade aluminum-containing iron phosphate, wherein the cooling treatment comprises the step of cooling from 600-650 ℃ to 400-450 ℃ at a speed of 1-3 ℃/min.
2. The method of claim 1, wherein the cooling process further comprises the step of cooling from 400 ℃ to 450 ℃ to room temperature at an arbitrary rate.
3. The method for preparing battery-grade aluminum-containing ferric phosphate according to claim 1, wherein the calcination time is 5 to 10 hours.
4. A battery grade aluminum-containing iron phosphate prepared by the method of any one of claims 1 to 3.
5. A lithium iron phosphate positive electrode material, which is characterized in that the preparation raw materials comprise the battery-grade aluminum-containing ferric phosphate, a lithium source, a dispersing agent and a carbon source.
6. The lithium iron phosphate positive electrode material according to claim 5, wherein the lithium source is selected from at least one of lithium carbonate, lithium hydroxide, and lithium dihydrogen phosphate; and/or
The dispersing agent is at least one selected from polyethylene glycol, polyacrylamide and polyethyleneimine; and/or
The carbon source is at least one selected from glucose, sucrose and starch.
7. The preparation method of the lithium iron phosphate anode material is characterized by comprising the following steps of:
mixing the battery-grade aluminum-containing ferric phosphate, a lithium source, a dispersing agent, a carbon source and water in the lithium iron phosphate positive electrode material according to claim 5 or 6 to obtain a mixed slurry, and grinding the mixed slurry to the particle size D of a solid mixture in the mixed slurry 50 Is 0.5-0.7 mu m to obtain primary slurry, and then taking out 10-15% of the total mass from the primary slurry and continuously grinding to the particle diameter D of the solid mixture 50 And the size is 0.1-0.25 mu m, so as to obtain secondary slurry, mixing the primary slurry and the secondary slurry, drying, roasting under the protection of non-reducing gas, and crushing and screening to obtain the lithium iron phosphate anode material.
8. The method of preparing according to claim 7, wherein the step of firing comprises: first, roasting for 3-5 h at 300-350 ℃ and then roasting for 4-8 h at 740-760 ℃ for two stages.
9. The method of claim 7 or 8, wherein the molar ratio of iron phosphate, lithium source and carbon source in the battery-grade aluminum-containing iron phosphate is 1: (1.01-1.05): (0.35 to 0.4); and/or
The mass of the dispersing agent accounts for 2% -3% of the mass of the battery-grade aluminum-containing ferric phosphate; and/or
The solid content of the mixed slurry is 45-55%.
10. A battery, characterized in that the preparation raw materials comprise the lithium iron phosphate positive electrode material, the negative electrode material and the electrolyte prepared by the preparation method according to any one of claims 7 to 9.
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