CN114864930A - Method for recycling waste lithium iron phosphate - Google Patents

Method for recycling waste lithium iron phosphate Download PDF

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CN114864930A
CN114864930A CN202210652044.7A CN202210652044A CN114864930A CN 114864930 A CN114864930 A CN 114864930A CN 202210652044 A CN202210652044 A CN 202210652044A CN 114864930 A CN114864930 A CN 114864930A
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iron phosphate
lithium iron
lithium
sintering
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黄长靓
高伟
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Jiangsu Gcl Lithium Battery Technology Co ltd
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Jiangsu Gcl Lithium Battery Technology Co ltd
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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
    • 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
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • 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
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

Abstract

The invention discloses a method for recycling waste lithium iron phosphate, and belongs to the technical field of lithium ion battery anode materials. The method comprises the following steps: (1) mixing waste lithium iron phosphate, a lithium source, an iron source, a phosphorus source and an additive, grinding and drying, and sintering the obtained dry powder in an aerobic atmosphere to obtain oxidized lithium iron phosphate powder; (2) and mixing the oxidized lithium iron phosphate powder, an additive and a carbon source, grinding for the second time, drying, sintering the obtained dry powder in an inert atmosphere, and after sintering, carrying out graded crushing to finally obtain the regenerated lithium iron phosphate/carbon composite material. The whole preparation process avoids acid and alkali treatment, reduces the generation of waste acid, waste alkali and waste water, and simultaneously improves the surface smoothness of the particles on the surface of the lithium iron phosphate and the compacted density of the lithium iron phosphate.

Description

Method for recycling waste lithium iron phosphate
Technical Field
The invention belongs to the technical field of lithium ion battery anode materials, and particularly relates to a method for recycling waste lithium iron phosphate.
Background
Because the raw materials are low in price, the theoretical capacity is high (170mAh/g), the structure is stable, the working voltage is stable, the lithium iron phosphate is nontoxic and environment-friendly, safe and long in cycle life and the like, the lithium iron phosphate is widely favored by power and energy storage markets all the time. With the rapid development of new energy industry, the lithium battery industry is also developing to be more vigorous, especially in the fields of electric automobiles and energy storage markets, so that the yield of lithium iron phosphate is rapidly increased. In the processes of producing lithium iron phosphate materials and lithium iron phosphate batteries in a large scale, a large amount of unqualified lithium iron phosphate waste materials, waste pole pieces and leftover materials can be generated, and in addition, a large amount of battery pole pieces in the waste lithium iron phosphate batteries generated every year are used up, so that the quantity value is very large. How to maximize the utilization of these large quantities of waste materials has been a great deal of work related to many scholars and enterprises.
The traditional method for recycling the waste lithium iron phosphate material mainly adopts roasting, acid leaching or combination of the roasting and the acid leaching. Adding acid and oxidant, heating and dissolving to obtain lithium, iron and phosphorus solution, then adding alkali to adjust the pH value to form iron phosphate, filtering, then adding sodium carbonate into the filtrate, filtering and purifying to finally obtain lithium carbonate and iron phosphate. However, the recovery process is complex, the investment in equipment is large, byproducts are easily generated in the whole process, and a large amount of waste acid, waste alkali and waste water are generated, so that the recovery process is not environment-friendly.
In order to avoid the disadvantages in the liquid phase recycling process, many techniques remove residual carbon in the lithium iron phosphate waste material by a roasting method to obtain oxidized lithium iron phosphate (mainly containing Li as a main component) 3 Fe 2 (PO 4 ) 3 And Fe 2 O 3 ) Then adding a small amount of lithium source and carbon source, mixing again, and carrying out primary mixing and primary burning to obtain the regenerated lithium iron phosphate. However, the lithium iron phosphate prepared by the process has low compacted density, poorer electrochemical capacity and high impurity content, and can not meet the requirements of the power battery market at all.
In view of the above, on the basis of the above, the regenerated lithium iron phosphate/carbon composite material with high compaction density, good processing performance and excellent electrochemical performance can be prepared by mixing the waste lithium iron phosphate powder with a lithium source, an iron source and a phosphorus source, sintering in an aerobic atmosphere to obtain oxidized lithium iron phosphate, mixing the oxidized lithium iron phosphate powder with a carbon source, sintering, and finally carrying out double mixing and double sintering.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a method for recycling waste lithium iron phosphate, which is more environment-friendly (acid leaching is not needed, and generation of waste acid and waste water is avoided), has low cost and is suitable for large-scale production. The oxidized lithium iron phosphate is obtained by mixing waste lithium iron phosphate powder with a lithium source, an iron source and a phosphorus source and sintering the mixture in an aerobic atmosphere, and then the oxidized lithium iron phosphate powder is mixed with a carbon source and sintered.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for recycling waste lithium iron phosphate comprises the following steps:
(1) mixing waste lithium iron phosphate, a lithium source, an iron source, a phosphorus source and an additive, grinding and drying, and sintering the obtained dry powder in an aerobic atmosphere to obtain oxidized lithium iron phosphate powder;
(2) and mixing the oxidized lithium iron phosphate powder, an additive and a carbon source, grinding for the second time, drying, sintering the obtained dry powder in an inert atmosphere, and after sintering is finished, carrying out graded crushing to finally obtain the regenerated lithium iron phosphate/carbon composite material.
Preferably, in the step (1), the waste lithium iron phosphate is selected from one or two of unqualified products produced by lithium iron phosphate manufacturers or black lithium iron phosphate powder stripped from lithium iron phosphate pole pieces, and the carbon content of the waste lithium iron phosphate is 1.2-6%, and more preferably 1.5-4%.
Preferably, in the step (1), the addition amount of the waste lithium iron phosphate accounts for 30-60% of the mass of the oxidized lithium iron phosphate.
Preferably, in the step (1), when the lithium source, the iron source and the phosphorus source are added, the molar ratio of lithium, iron and phosphorus elements is controlled to be 1-1.1: 0.9-1.1: 1-1.1.
Preferably, in the step (1), the additive is at least one selected from zirconium dioxide, titanium dioxide, tetrabutyl titanate, magnesium acetate, magnesium hydroxide, magnesium oxide, zirconium hydroxide, niobium pentoxide, niobium hydroxide, nickel acetate, manganese acetate, aluminum oxide, molybdenum oxide and ammonium molybdate; more preferably at least one of magnesium oxide, titanium dioxide, zirconium dioxide and ammonium molybdate.
Preferably, in the step (1), the mass of the additive accounts for 0-0.5% of the mass of the oxidized lithium iron phosphate powder.
Preferably, in step (1), the milling is performed to a particle size of 350-500nm, and more preferably to 450 nm.
Preferably, in step (1) or step (2), the grinding process is: firstly, coarse grinding is carried out at the rotation speed of 1500-.
Preferably, in step (1) or step (2), the drying includes, but is not limited to, static drying, spray drying, and the like.
Preferably, in step (1), the aerobic atmosphere includes an air atmosphere and an oxygen atmosphere.
Preferably, in the step (1), the sintering temperature is 650-750 ℃, and the sintering time is 3-6 hours.
Preferably, in step (1) or step (2), the solvent used in the mixing is at least one selected from the group consisting of water, methanol, ethanol, acetone, and NMP (N-methylpyrrolidone).
Preferably, in the step (2), the additive is a combination of at least one of zirconium dioxide, titanium dioxide, tetrabutyl titanate, magnesium acetate, magnesium hydroxide, magnesium oxide, zirconium hydroxide, niobium pentoxide, niobium hydroxide, nickel acetate, manganese acetate, aluminum oxide, molybdenum oxide and ammonium molybdate, and at least one of glucose, cyclodextrin, polyethylene glycol 20000, sucrose, rock candy and starch; further preferably, the titanium dioxide and/or niobium pentoxide may be combined with at least one of glucose, cyclodextrin, polyethylene glycol 20000, sucrose, crystal sugar, and starch.
Preferably, in the step (2), the mass of the additive accounts for 0-0.5% of the mass of the regenerated lithium iron phosphate/carbon composite material.
Preferably, in the step (2), the inert atmosphere gas is at least one of nitrogen, argon, helium and carbon dioxide.
Preferably, in the step (2), the sintering temperature is 700-780 ℃, and the sintering time is 6-10 h.
Preferably, in the step (2), the mass fraction of carbon in the regenerated lithium iron phosphate/carbon composite material is 1.4-2.5%.
The invention has the beneficial effects that:
(1) the method provided by the invention has the characteristics of low cost, simple process and capability of large-scale production, acid and alkali are not required to be used for leaching in the production process, no waste water, waste acid or waste alkali is generated in the whole regeneration process, the method is environment-friendly, the quality selectivity of the recycled lithium iron phosphate product is wider, and particularly, the treatment effect on high-carbon waste lithium iron phosphate is good.
(2) The invention is beneficial to improving the purity of the lithium iron phosphate product, the growth of crystal form, carbon coating and compaction density through the two-mixing and two-sintering process, and is also beneficial to improving the processing performance of the lithium iron phosphate material. The primary mixing is favorable for uniformly mixing lithium, iron, phosphorus and additive metal elements, and the waste lithium iron phosphate primary particles are reshaped by grinding, so that the surface smoothness of the lithium iron phosphate precursor is improved; the one-time sintering under the aerobic atmosphere is beneficial to completely burning out carbon and organic matters contained in the waste lithium iron phosphate material and improving the growth and surface smoothness of the one-time particles in the one-time sintering process, and the one-time sintering is beneficial to reducing the impurity content (such as sulfate radicals, organic matters and the like in the raw materials are volatilized through sintering or discharged in a gas form after being oxidized) in the newly added lithium iron phosphate raw materials (lithium source, iron source and phosphorus source) and improving the purity of the product, so that the full reaction of the raw materials is facilitated, and the generation of some side reactions is reduced; and through secondary mixed material secondary sintering, on one hand, the adhesion of a carbon source on the smooth surface of the oxidized lithium iron phosphate is facilitated, the coating uniformity of the carbon source is improved, and on the other hand, the fusion uniformity and the compaction density of the lithium iron phosphate and the additive are improved.
(3) The invention obtains oxidized lithium iron phosphate (the main component is Li) by one-time sintering 3 Fe 2 (PO4) 3 And Fe 2 O 3 ) Is a precursor, reduces the emission of gas in the reaction in the secondary sintering, and the phase change is beneficial to improving the coating uniformity and the density of the carbon layer.
(4) The regenerated lithium iron phosphate/carbon composite electrode material has good processing performance, electrochemical performance and high compaction density, and can be applied to power batteries and high-end energy storage markets.
Drawings
Fig. 1 is an SEM photograph of a lithium iron phosphate precursor prepared according to example 1;
fig. 2 is a graph showing verification of electrochemical properties of the lithium iron phosphate/carbon composite material prepared according to example 1.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way. The following is merely an exemplary illustration of the scope of the invention as claimed, and various changes and modifications of the invention of the present application may be made by those skilled in the art based on the disclosure, which also fall within the scope of the invention as claimed.
The present invention will be further described below by way of specific examples. The various chemicals used in the examples of the present invention were obtained by conventional commercial routes unless otherwise specified. Unless otherwise specified, the contents are all mass contents hereinafter. Unless otherwise specified, it is understood to be carried out at room temperature.
Example 1
(1) Preparation of lithium iron phosphate precursor
39.35g of lithium carbonate (99.5 wt%), 89.29g of iron oxyhydroxide (99.5 wt%), 119.12g of ammonium dihydrogen phosphate (99.5 wt%), 165g of waste lithium iron phosphate powder with a carbon content of 3%, and 0.8g of magnesium oxide were sequentially added to a 2L basket mill containing 1000mL of absolute ethanol, wherein the molar ratio of the newly added lithium source, iron source and phosphorus source Li: fe: p is 1.06:1:1.03, after the material is added, starting to carry out coarse grinding at the rotating speed of 2000r/min, transferring the slurry to a sand mill for fine grinding when the granularity D50 of the slurry is less than 1 mu m, controlling the granularity of the slurry to be 450nm, and (3) carrying out static drying, placing the obtained dry powder into an atmosphere furnace blown into the air atmosphere for sintering, wherein the sintering temperature is 710 ℃, the constant temperature time is 4h, and after the temperature of the tube furnace is naturally reduced to 80 ℃, taking out and crushing the material to obtain 300g of red oxidized lithium iron phosphate precursor.
(2) Preparation of lithium iron phosphate material
Adding 300g of oxidized lithium iron phosphate precursor, 25g of glucose, 5g of cyclodextrin and 0.8g of titanium dioxide into a 2L basket mill containing 1000mL of absolute ethyl alcohol in sequence, starting coarse milling at the rotating speed of 2000r/min after the materials are added, and finishing the coarse milling until the granularity of the slurry is D50<1 mu m of the powder is transferred into a sand mill for fine grinding, after the granularity of slurry is controlled at 450nm, the powder is statically dried, the obtained dried powder is placed into a tubular furnace under the nitrogen atmosphere for sintering, the sintering temperature is 780 ℃, the constant temperature time is 8h, when the temperature of the tubular furnace is naturally reduced to 80 ℃, the material is taken out and crushed in a grading way, the regenerated lithium iron phosphate with the carbon content of 1.5 percent is obtained, and after analysis, the molar ratio of lithium, iron and phosphorus of the regenerated lithium iron phosphate is Li: Fe: P: 1:1.025, and the powder is compacted to 2.58g/cm 3 。
The obtained regenerated lithium iron phosphate material was observed by a scanning electron microscope, and the result is shown in fig. 1. As can be seen from FIG. 1, the size of the prepared primary particles is in the range of about 0.2 to 1 μm, and most of the particles are mainly concentrated in the range of about 0.5 to 0.6. mu.m.
The prepared lithium iron phosphate/carbon composite material for the lithium ion battery anode is taken as an anode material, acetylene black is taken as a conductive agent, polytetrafluoroethylene is taken as a binder, electrode plates are prepared, and metallic lithium is taken as a cathode to assemble the simulated button cell. The test is carried out under the conditions of 2-3.75V and normal temperature and different charging and discharging currents, and the result is shown in figure 2. As can be seen from FIG. 2, the initial reversible capacity was 158.3mAh/g in charge and discharge at 0.1C, 156.2mAh/g in charge and discharge at 0.2C, and 144.9mAh/g in charge and discharge at 1C (see Table 1).
Example 2
(1) Preparation of lithium iron phosphate precursor
39.72g of lithium carbonate (99.5 wt%), 80.24 g of iron oxide (99.6 wt%), 119.12g of ammonium dihydrogen phosphate (99.5 wt%), 180g of waste lithium iron phosphate with 2% of carbon content and 1.4g of titanium dioxide are sequentially added into a 2L basket mill containing 1000mL of water, wherein the molar ratio of a newly added lithium source to an iron source to a phosphorus source Li: Fe: P is 1.07:1:1.03, after the addition of the materials, coarse milling is started at the rotating speed of 2000r/min, after the slurry granularity D50<1 μm, the slurry is transferred into a sand mill for fine milling, after the slurry granularity is controlled at 450nm, spray drying is carried out, the obtained dried powder is placed into an atmosphere furnace under an air atmosphere for sintering, the sintering temperature is 700 ℃, the constant temperature time is 4h, after the atmosphere furnace is naturally cooled to 80 ℃, the materials are taken out and crushed, and 300g of red oxidized lithium iron phosphate precursor is obtained.
(2) Preparation of lithium iron phosphate material
Adding 300g of oxidized lithium iron phosphate precursor, 25g of rock sugar, 4g of cyclodextrin, 2g of starch and 0.5g of niobium pentoxide into a 2L basket mill containing 1000mL of absolute ethyl alcohol in sequence, and after the materials are added, carrying out coarse grinding at the rotating speed of 2000r/min until the granularity of the slurry is D50<Transferring the powder with the particle size of 1 mu m into a sand mill for fine grinding, statically drying after the particle size of slurry is controlled to be 450nm, putting the obtained dry powder into a tube furnace under the nitrogen atmosphere for sintering, wherein the sintering temperature is 760 ℃, the constant temperature time is 8h, naturally cooling the tube furnace to 80 ℃, taking out the material, and carrying out grading crushing to obtain regenerated lithium iron phosphate with the carbon content of 1.6%, and analyzing the regenerated lithium iron phosphate to obtain the regenerated lithium iron phosphate with the lithium, iron and phosphorus molar ratio of Li to Fe to P of 1.06 to 1 to 1.035, and compacting the powder to 2.56g/cm 3 。
The prepared lithium iron phosphate/carbon composite material for the lithium ion battery anode is taken as an anode material, acetylene black is taken as a conductive agent, polytetrafluoroethylene is taken as a binder, electrode plates are prepared, and metallic lithium is taken as a cathode to assemble the simulated button cell. Under the conditions of 2-3.75V and normal temperature and different charging and discharging current tests, the initial reversible capacity of charging and discharging at 0.1C is 158.4mAh/g, the initial reversible capacity of charging and discharging at 0.2C is 155.3mAh/g, and the initial reversible capacity of charging and discharging at 1C is 142.1mAh/g (see table 1).
Example 3
(1) Preparation of lithium iron phosphate precursor
40.10g of lithium carbonate (99.5 wt%), 188.85g of iron oxalate (99.5 wt%), 137.22g of diammonium phosphate (99.6 wt%), 120g of waste lithium iron phosphate powder (from a lithium iron phosphate pole piece) with the carbon content of 4% and 1g of zirconium dioxide are sequentially added into a 2L British grinder containing 1200ml of absolute ethyl alcohol, wherein the molar ratio of the newly added lithium source, iron source and phosphorus source Li: fe: after the materials are added, the ratio of P to P is 1.08:1:1.035, starting to carry out coarse grinding at the rotating speed of 2000r/min, transferring the slurry to a sand mill for fine grinding when the granularity D50 of the slurry is less than 1 mu m, controlling the granularity of the slurry to be 450nm, and (3) carrying out static drying, placing the obtained dry powder into an atmosphere furnace blown with air for sintering, wherein the sintering temperature is 680 ℃, the constant temperature time is 4h, and when the atmosphere furnace naturally cools to 80 ℃, taking out and crushing the material to obtain 250g of red oxidized lithium iron phosphate precursor.
(2) Preparation of phosphate cathode material
Adding 250g of lithium iron phosphate precursor, 23g of sucrose, 8g of polyethylene glycol 20000 and 1g of niobium pentoxide into a 2L basket mill containing 1200mL of deionized water in sequence, after the materials are added, starting coarse milling at the rotating speed of 2000r/min, and after the materials are milled for several minutes, waiting for the granularity D50 of the slurry<Transferring the powder with the particle size of 1 mu m into a sand mill for fine grinding, performing spray drying after the particle size of slurry is controlled to be 450nm, putting the obtained dried powder into a tube furnace under the argon atmosphere for sintering, wherein the sintering temperature is 770 ℃, the constant temperature time is 8h, naturally cooling the tube furnace to 80 ℃, taking out the material, and performing grading crushing to obtain regenerated lithium iron phosphate with the carbon content of 1.6 wt%, and analyzing the regenerated lithium iron phosphate to obtain the regenerated lithium iron phosphate with the lithium-iron-phosphorus molar ratio of Li to Fe to P of 1.06 to 1 to 1.03, and compacting the powder to be 2.51g/cm 3 。
The prepared lithium iron phosphate/carbon composite material for the lithium ion battery anode is taken as an anode material, acetylene black is taken as a conductive agent, polytetrafluoroethylene is taken as a binder, electrode plates are prepared, and metallic lithium is taken as a cathode to assemble the simulated button cell. Under the conditions of 2-3.75V and normal temperature and different charging and discharging current tests, the initial reversible capacity of charging and discharging at 0.1C is 158.6mAh/g, the initial reversible capacity of charging and discharging at 0.2C is 156.5mAh/g, and the initial reversible capacity of charging and discharging at 1C is 144.1mAh/g (see table 1).
Example 4
(1) Preparation of lithium iron phosphate precursor
38.98g of lithium carbonate (99.5 wt%), 77.56g of ferroferric oxide (99.5 wt%), 117.8g of ammonium dihydrogen phosphate (99.6 wt%), 200g of waste lithium iron phosphate powder with 1.5% of carbon content and 1.2g of ammonium molybdate are sequentially added into a 2L Lane mill containing 1200ml of deionized water, wherein the molar ratio of the newly added lithium source, iron source and phosphorus source Li: fe: p is 1.05:1:1.02, after the material is added, starting to carry out coarse grinding at the rotating speed of 2000r/min, transferring the slurry to a sand mill for fine grinding when the granularity D50 of the slurry is less than 1 mu m, controlling the granularity of the slurry to be 450nm, and (3) carrying out spray drying, placing the obtained dried powder into an atmosphere furnace blown with air for sintering, wherein the sintering temperature is 730 ℃, the constant temperature time is 3 hours, and when the atmosphere furnace is naturally cooled to 80 ℃, taking out and crushing the material to obtain 330g of red oxidized lithium iron phosphate precursor.
(2) Preparation of lithium iron phosphate material
Adding 300g of lithium iron phosphate precursor, 24g of glucose, 4g of cyclodextrin, 8g of polyethylene glycol 20000 and 0.5g of titanium dioxide into a 2L basket mill containing 1200mL of deionized water in sequence, starting coarse milling at the rotating speed of 2000r/min after the materials are added, and after the materials are milled for several minutes, waiting for the granularity D50 of the slurry<Transferring the powder with the particle size of 1 mu m into a sand mill for fine grinding, performing spray drying after the particle size of slurry is controlled to be 450nm, putting the obtained dried powder into a tube furnace under the argon atmosphere for sintering, wherein the sintering temperature is 760 ℃, the constant temperature time is 10 hours, naturally cooling the tube furnace to 80 ℃, taking out the material, and performing grading crushing to obtain regenerated lithium iron phosphate with the carbon content of 1.4 wt%, and analyzing and regenerating the lithium iron phosphateThe molar ratio of lithium, iron and phosphorus of the lithium iron to the iron to the phosphorus is Li, Fe and P is 1.05 to 1 to 1.035, and the powder is compacted to 2.53g/cm 3 。
The prepared lithium iron phosphate/carbon composite material for the lithium ion battery anode is taken as an anode material, acetylene black is taken as a conductive agent, polytetrafluoroethylene is taken as a binder, electrode plates are prepared, and metallic lithium is taken as a cathode to assemble the simulated button cell. Under the conditions of 2-3.75V and normal temperature and different charging and discharging current tests, the initial reversible capacity of charging and discharging at 0.1C is 158.9mAh/g, the initial reversible capacity of charging and discharging at 0.2C is 154.8mAh/g, and the initial reversible capacity of charging and discharging at 1C is 144.9mAh/g (see table 1).
Example 5
The difference from example 1 is that the additive in step (1) is 0.8g of ammonium molybdate, and the rest is the same.
(1) Preparation of lithium iron phosphate precursor
39.35g of lithium carbonate (99.5 wt%), 89.29g of iron oxyhydroxide (99.5 wt%), 119.12g of ammonium dihydrogen phosphate (99.5 wt%), 165g of waste lithium iron phosphate powder with a carbon content of 3%, and 0.8g of ammonium molybdate were sequentially added to a 2L basket mill containing 1000mL of absolute ethanol, wherein the molar ratio of the newly added lithium source, iron source and phosphorus source Li: fe: p is 1.06:1:1.03, after the material is added, starting to carry out coarse grinding at the rotating speed of 2000r/min, transferring the slurry to a sand mill for fine grinding when the granularity D50 of the slurry is less than 1 mu m, controlling the granularity of the slurry to be 450nm, and (3) carrying out static drying, placing the obtained dry powder into an atmosphere furnace blown into the air atmosphere for sintering, wherein the sintering temperature is 710 ℃, the constant temperature time is 4h, and after the temperature of the tube furnace is naturally reduced to 80 ℃, taking out and crushing the material to obtain 300g of red oxidized lithium iron phosphate precursor.
(2) Preparation of lithium iron phosphate material
Adding 300g of oxidized lithium iron phosphate precursor, 25g of glucose, 5g of cyclodextrin and 0.8g of titanium dioxide into a 2L basket mill containing 1000mL of absolute ethyl alcohol in sequence, starting coarse milling at the rotating speed of 2000r/min after the materials are added, and finishing the coarse milling until the granularity of the slurry is D50<Transferring the powder into a sand mill for fine grinding with the particle size of 1 mu m, performing static drying after the particle size of the slurry is controlled to be 450nm, and placing the obtained dry powder into a containerSintering in a tubular furnace under the atmosphere of nitrogen, wherein the sintering temperature is 780 ℃, the constant temperature time is 8h, when the temperature of the tubular furnace is naturally reduced to 80 ℃, the materials are taken out and crushed in a grading way to obtain regenerated lithium iron phosphate with the carbon content of 1.5%, through analysis, the molar ratio of lithium, iron and phosphorus of the regenerated lithium iron phosphate is Li, Fe, P is 1.05:1:1.025, and the powder is compacted to be 2.63g/cm 3 。
The prepared lithium iron phosphate/carbon composite material for the lithium ion battery anode is taken as an anode material, acetylene black is taken as a conductive agent, polytetrafluoroethylene is taken as a binder, electrode plates are prepared, and metallic lithium is taken as a cathode to assemble the simulated button cell. Under the conditions of 2-3.75V and normal temperature and different charging and discharging current tests, the initial reversible capacity of charging and discharging at 0.1C is 158.5mAh/g, the initial reversible capacity of charging and discharging at 0.2C is 156.6mAh/g, and the initial reversible capacity of charging and discharging at 1C is 145.2mAh/g (see table 1).
Example 6
In contrast to example 1, the additives in step (2) were 25g of glucose, 5g of cyclodextrin and 0.8g of niobium pentoxide, the rest being the same.
(1) Preparation of lithium iron phosphate precursor
39.35g of lithium carbonate (99.5 wt%), 89.29g of iron oxyhydroxide (99.5 wt%), 119.12g of ammonium dihydrogen phosphate (99.5 wt%), 165g of waste lithium iron phosphate powder with a carbon content of 3%, and 0.8g of magnesium oxide were sequentially added to a 2L basket mill containing 1000mL of absolute ethanol, wherein the molar ratio of the newly added lithium source, iron source and phosphorus source Li: fe: p is 1.06:1:1.03, after the material is added, starting to carry out coarse grinding at the rotating speed of 2000r/min, transferring the slurry to a sand mill for fine grinding when the granularity D50 of the slurry is less than 1 mu m, controlling the granularity of the slurry to be 450nm, and (3) carrying out static drying, placing the obtained dry powder into an atmosphere furnace blown into the air atmosphere for sintering, wherein the sintering temperature is 710 ℃, the constant temperature time is 4h, and after the temperature of the tube furnace is naturally reduced to 80 ℃, taking out and crushing the material to obtain 300g of red oxidized lithium iron phosphate precursor.
(2) Preparation of lithium iron phosphate material
Adding 300g of oxidized lithium iron phosphate precursor, 25g of glucose, 5g of cyclodextrin and 0.8g of niobium pentoxide into the solution in sequenceAfter the addition of the slurry in a 2L basket mill containing 1000mL of absolute ethanol, coarse grinding was started at 2000r/min until the particle size of the slurry was D50<Transferring the powder with the particle size of 1 mu m into a sand mill for fine grinding, statically drying after the particle size of slurry is controlled to be 450nm, putting the obtained dry powder into a tube furnace under the nitrogen atmosphere for sintering, wherein the sintering temperature is 780 ℃, the constant temperature time is 8h, naturally cooling the tube furnace to 80 ℃, taking out the material, and carrying out grading crushing to obtain regenerated lithium iron phosphate with the carbon content of 1.5%, and analyzing the regenerated lithium iron phosphate to obtain the regenerated lithium iron phosphate with the lithium, iron and phosphorus molar ratio of Li to Fe to P of 1.05 to 1 to 1.025, and compacting the powder to be 2.61g/cm 3 。
The prepared lithium iron phosphate/carbon composite material for the lithium ion battery anode is taken as an anode material, acetylene black is taken as a conductive agent, polytetrafluoroethylene is taken as a binder, electrode plates are prepared, and metallic lithium is taken as a cathode to assemble the simulated button cell. Under the conditions of 2-3.75V and normal temperature and different charging and discharging current tests, the initial reversible capacity of charging and discharging at 0.1C is 159.1mAh/g, the initial reversible capacity of charging and discharging at 0.2C is 156.8mAh/g, and the initial reversible capacity of charging and discharging at 1C is 146.9mAh/g (see table 1).
Comparative example 1
Compared with the example 1, the raw material of the comparative example 1 adopts the single waste product of the lithium iron phosphate, and the lithium source, the phosphorus source and the iron source are not added, and other steps are the same as the example 1.
(1) Adding 310g of waste lithium iron phosphate powder with 3% of carbon content and 0.8g of magnesium oxide into a 2L basket mill containing 1000mL of absolute ethyl alcohol, after the materials are added, starting coarse grinding at the rotating speed of 2000r/min, transferring the slurry into a sand mill for fine grinding when the slurry granularity D50 is less than 1 mu m, controlling the slurry granularity at 450nm, carrying out static drying, blowing the obtained dry powder into an atmosphere furnace in the air atmosphere for sintering at the sintering temperature of 710 ℃ for constant temperature of 4h, naturally cooling the powder to 80 ℃ in a tubular furnace, taking out the material, and crushing to obtain 300g of red oxidized lithium iron phosphate precursor.
(2) Preparation of lithium iron phosphate material
300g of oxidized lithium iron phosphate precursor, 25g of glucose and,5g of cyclodextrin and 0.8g of titanium dioxide are added to a 2L basket mill containing 1000mL of absolute ethanol, after the addition of the cyclodextrin and the titanium dioxide, coarse grinding is started at 2000r/min until the particle size of the slurry is D50<Transferring the powder with the particle size of 1 mu m into a sand mill for fine grinding, statically drying after the particle size of slurry is controlled to be 450nm, putting the obtained dry powder into a tube furnace under the nitrogen atmosphere for sintering, wherein the sintering temperature is 780 ℃, the constant temperature time is 8h, naturally cooling the tube furnace to 80 ℃, taking out the material, and carrying out classification crushing to obtain regenerated lithium iron phosphate with the carbon content of 1.5%, and analyzing the regenerated lithium iron phosphate with the molar ratio of lithium to iron to phosphorus of Li to Fe to P of 1.04 to 1 to 1.05 and powder compaction of 2.42g/cm 3 。
The prepared lithium iron phosphate/carbon composite material for the lithium ion battery anode is taken as an anode material, acetylene black is taken as a conductive agent, polytetrafluoroethylene is taken as a binder, electrode plates are prepared, and metallic lithium is taken as a cathode to assemble the simulated button cell. Under the conditions of 2-3.75V and normal temperature and different charging and discharging current tests, the initial reversible capacity of charging and discharging at 0.1C is 138.5mAh/g, the initial reversible capacity of charging and discharging at 0.2C is 132.3mAh/g, and the initial reversible capacity of charging and discharging at 1C is 120.1mAh/g (see table 1).
Comparative example 2
Compared with the embodiment 1, the difference of the comparative example 2 is that a small amount of lithium and phosphorus elements and waste lithium iron phosphate are added and mixed in the first mixing process to achieve the same proportion of the lithium iron phosphate synthesized in the embodiment 1, and other steps are the same as those in the embodiment 1.
(1) Adding 310g of waste lithium iron phosphate powder with the carbon content of 3%, 1.2g of lithium carbonate (99.5 wt%), 0.8g of ammonium dihydrogen phosphate and 0.8g of magnesium oxide into a 2L basket mill containing 1000mL of absolute ethyl alcohol, after the materials are added, starting to perform coarse grinding at the rotating speed of 2000r/min, transferring the slurry to a sand mill for fine grinding when the slurry granularity D50 is less than 1 mu m, performing static drying after the slurry granularity is controlled to be 450nm, blowing the obtained dried powder into an atmosphere furnace in the air atmosphere for sintering, wherein the sintering temperature is 710 ℃, the constant temperature time is 4h, naturally cooling the tubular furnace to 80 ℃, taking out and crushing the materials to obtain 300g of red oxidized lithium iron phosphate precursor.
(2) Preparation of lithium iron phosphate material
Adding 300g of oxidized lithium iron phosphate precursor, 25g of glucose, 5g of cyclodextrin and 0.8g of titanium dioxide into a 2L basket mill containing 1000mL of absolute ethyl alcohol in sequence, starting coarse milling at the rotating speed of 2000r/min after the materials are added, and finishing the coarse milling until the granularity of the slurry is D50<Transferring the powder with the particle size of 1 mu m into a sand mill for fine grinding, statically drying after the particle size of slurry is controlled to be 450nm, putting the obtained dry powder into a tube furnace under the nitrogen atmosphere for sintering, wherein the sintering temperature is 780 ℃, the constant temperature time is 8h, naturally cooling the tube furnace to 80 ℃, taking out the material, and carrying out grading crushing to obtain regenerated lithium iron phosphate with the carbon content of 1.5%, and analyzing the regenerated lithium iron phosphate to obtain the regenerated lithium iron phosphate with the lithium, iron and phosphorus molar ratio of Li to Fe to P of 1.05 to 1 to 1.025, and compacting the powder to be 2.45g/cm 3 。
The prepared lithium iron phosphate/carbon composite material for the lithium ion battery anode is taken as an anode material, acetylene black is taken as a conductive agent, polytetrafluoroethylene is taken as a binder, electrode plates are prepared, and metallic lithium is taken as a cathode to assemble the simulated button cell. Under the conditions of 2-3.75V and normal temperature and different charging and discharging current tests, the initial reversible capacity of charging and discharging at 0.1C is 145.5mAh/g, the initial reversible capacity of charging and discharging at 0.2C is 140.3mAh/g, and the initial reversible capacity of charging and discharging at 1C is 130.3mAh/g (see table 1).
Comparative example 3
In comparison with example 1, the atmosphere of primary sintering in comparative example 3 is nitrogen, which is an inert gas, and the quality of the carbon source in the mixture is different, but the final carbon content is the same as that in example 1, and the other steps are the same as those in experimental example 1.
(1) Preparation of lithium iron phosphate precursor
39.35g of lithium carbonate (99.5 wt%), 89.29g of iron oxyhydroxide (99.5 wt%), 119.12g of ammonium dihydrogen phosphate (99.5 wt%), 165g of waste lithium iron phosphate powder with a carbon content of 3% and 0.8g of magnesium oxide were sequentially added to a 2L basket mill containing 1000mL of absolute ethanol, wherein the molar ratio of the newly added lithium source, iron source and phosphorus source Li: fe: p is 1.06:1:1.03, after the material is added, starting to carry out coarse grinding at the rotating speed of 2000r/min, transferring the slurry to a sand mill for fine grinding when the granularity D50 of the slurry is less than 1 mu m, controlling the granularity of the slurry to be 450nm, and (3) carrying out static drying, placing the obtained dry powder in an atmosphere furnace in a nitrogen atmosphere for sintering, wherein the sintering temperature is 710 ℃, the constant temperature time is 4h, and taking out and crushing the material when the temperature of the tube furnace is naturally reduced to 80 ℃ to obtain 300g of gray black lithium iron phosphate precursor with the carbon content of 1.1%.
(2) Preparation of lithium iron phosphate material
Adding 300g of oxidized lithium iron phosphate precursor, 8g of glucose, 1.6g of cyclodextrin and 0.8g of titanium dioxide into a 2L basket mill containing 1000mL of absolute ethyl alcohol in sequence, starting coarse milling at the rotating speed of 2000r/min after the materials are added, and waiting for the granularity D50 of the slurry<Transferring the powder with the particle size of 1 mu m into a sand mill for fine grinding, statically drying after the particle size of slurry is controlled to be 450nm, putting the obtained dry powder into a tube furnace under the nitrogen atmosphere for sintering, wherein the sintering temperature is 780 ℃, the constant temperature time is 8h, naturally cooling the tube furnace to 80 ℃, taking out the material, and carrying out grading crushing to obtain regenerated lithium iron phosphate with the carbon content of 1.5%, and analyzing the regenerated lithium iron phosphate to obtain the regenerated lithium iron phosphate with the lithium, iron and phosphorus molar ratio of Li to Fe to P of 1.05 to 1 to 1.025, and compacting the powder to be 2.38g/cm 3 。
The prepared lithium iron phosphate/carbon composite material for the lithium ion battery anode is taken as an anode material, acetylene black is taken as a conductive agent, polytetrafluoroethylene is taken as a binder, electrode plates are prepared, and metallic lithium is taken as a cathode to assemble the simulated button cell. Under the conditions of 2-3.75V and normal temperature and different charging and discharging current tests, the initial reversible capacity of charging and discharging at 0.1C is 154.1mAh/g, the initial reversible capacity of charging and discharging at 0.2C is 150.1mAh/g, and the initial reversible capacity of charging and discharging at 1C is 138.5mAh/g (see table 1).
TABLE 1 chemical Properties and powder compaction results for examples and comparative examples
Figure BDA0003686516710000121
As can be seen from the results of table 1, example 1 significantly improved the discharge capacity and the powder compacted density as compared to the regenerated product of comparative example 1 in which no lithium source, phosphorus source, iron source were added. Comparative example 2 data shows that the discharge capacity and powder compaction were all decreased compared to the example with the addition of only a small amount of lithium source and phosphorus source and no addition of iron source, demonstrating that the addition of a large amount of lithium source, iron source and phosphorus source in example 1 has the effect of improving the discharge performance and powder compaction, and comparative example 3 selects inert atmosphere sintering in step (1), although the final carbon content is the same, the discharge performance and powder compaction are inferior to those of example 1 compared to atmospheric aerobic sintering.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. A method for recycling waste lithium iron phosphate is characterized by comprising the following steps:
(1) mixing waste lithium iron phosphate, a lithium source, an iron source, a phosphorus source and an additive, grinding and drying, and sintering the obtained dry powder in an aerobic atmosphere to obtain oxidized lithium iron phosphate powder;
(2) and mixing the oxidized lithium iron phosphate powder, an additive and a carbon source, grinding for the second time, drying, sintering the obtained dry powder in an inert atmosphere, and after sintering, carrying out graded crushing to finally obtain the regenerated lithium iron phosphate/carbon composite material.
2. The method according to claim 1, wherein in the step (1), the waste lithium iron phosphate is selected from one or two of unqualified products produced by lithium iron phosphate manufacturers or black lithium iron phosphate powder stripped from lithium iron phosphate pole pieces, and the carbon content of the waste lithium iron phosphate is 1.2-6%.
3. The method according to claim 1, wherein in the step (1), the addition amount of the waste lithium iron phosphate accounts for 30-60% of the mass of the oxidized lithium iron phosphate.
4. The method according to claim 1, wherein in the step (1), when the lithium source, the iron source and the phosphorus source are added, the molar ratio of the lithium, the iron and the phosphorus elements is controlled to be 1-1.1: 0.9-1.1: 1-1.1.
5. The method according to claim 1, wherein in the step (1), the additive is at least one selected from the group consisting of zirconium dioxide, titanium dioxide, tetrabutyl titanate, magnesium acetate, magnesium hydroxide, magnesium oxide, zirconium hydroxide, niobium pentoxide, niobium hydroxide, nickel acetate, manganese acetate, aluminum oxide, molybdenum oxide, ammonium molybdate; the mass of the additive accounts for 0-0.5% of the mass of the oxidized lithium iron phosphate powder.
6. The method according to claim 1, wherein in step (1), the aerobic atmosphere comprises an air atmosphere, an oxygen atmosphere; in the step (2), the gas in the inert atmosphere is at least one of nitrogen, argon, helium and carbon dioxide.
7. The method as claimed in claim 1, wherein in step (1), the sintering temperature is 650-750 ℃ and the sintering time is 3-6 hours.
8. The method of claim 1, wherein in step (2), the additive is a combination of at least one of zirconium dioxide, titanium dioxide, tetrabutyl titanate, magnesium acetate, magnesium hydroxide, magnesium oxide, zirconium hydroxide, niobium pentoxide, niobium hydroxide, nickel acetate, manganese acetate, aluminum oxide, molybdenum oxide, ammonium molybdate, and at least one of glucose, cyclodextrin, polyethylene glycol 20000, sucrose, rock candy, starch; more preferably, the composite material is a combination of at least one of titanium dioxide and niobium pentoxide and at least one of glucose, cyclodextrin, polyethylene glycol 20000, sucrose, rock candy and starch, wherein the mass of the additive accounts for 0-0.5% of the mass of the regenerated lithium iron phosphate/carbon composite material.
9. The method as claimed in claim 1, wherein in step (2), the sintering temperature is 700-780 ℃ and the sintering time is 6-10 h.
10. The method according to claim 1, wherein in step (2), the mass fraction of carbon in the regenerated lithium iron phosphate/carbon composite material is 1.4-2.5%.
CN202210652044.7A 2022-06-09 2022-06-09 Method for recycling waste lithium iron phosphate Pending CN114864930A (en)

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