CN114592128B - Method for preparing high-value material by recycling waste nickel-iron alloy - Google Patents

Method for preparing high-value material by recycling waste nickel-iron alloy Download PDF

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CN114592128B
CN114592128B CN202210202950.7A CN202210202950A CN114592128B CN 114592128 B CN114592128 B CN 114592128B CN 202210202950 A CN202210202950 A CN 202210202950A CN 114592128 B CN114592128 B CN 114592128B
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CN114592128A (en
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代德明
叶建
周雷军
卜相楠
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Cornex New Energy Co ltd
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    • C—CHEMISTRY; METALLURGY
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    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
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    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22B23/04—Obtaining nickel or cobalt by wet processes
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    • C22B23/0423—Halogenated acids or salts thereof
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
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    • C22B23/043—Sulfurated acids or salts thereof
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    • C22B23/0438—Nitric acids or salts thereof
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Abstract

The invention provides a method for preparing a high-value material by recycling waste nickel-iron alloy, which comprises the steps of firstly dissolving the waste nickel-iron alloy under an acidic condition, filtering, adding lithium salt into filtrate, dropwise adding phosphate solution to obtain white supernatant, mixing filter residue and a carbon source, performing sand grinding treatment, performing spray drying to obtain precursor powder, sintering the precursor powder under a nitrogen atmosphere, crushing, screening, deironing and packaging to obtain the anode material. The invention provides a method for recycling waste nickel-iron alloy, and the method can be used for preparing a lithium nickel iron phosphate cathode material with excellent performance, and the obtained cathode material has excellent electrical properties.

Description

Method for preparing high-value material by recycling waste nickel-iron alloy
Technical Field
The invention relates to the technical field of new materials, in particular to a method for preparing a high-value material by recycling waste nickel-iron alloy.
Background
The waste ferronickel alloy material is ferronickel alloy with 20-60% of nickel content, the melting point of ferronickel is 1430-1480 ℃, and the density is 8.1-8.4. The main constituents of the nickel-iron alloy are nickel and iron, and secondly a certain amount of carbon is contained. The ferronickel alloy is scrapped in a large amount every year, and meanwhile, part of waste materials also exist in the production and forming processes of producing the ferronickel alloy. The existing method for recycling waste nickel-iron alloy is furnace-returning reconstruction, and the value of the product obtained by the method is low.
Lithium iron phosphate has good cycle performance, and thus becomes a hot spot in the power market and the energy storage market in recent years. However, the existing capacity of lithium iron phosphate is basically close to the theoretical value, and the future trend is to develop a novel high-voltage phosphate anode material, wherein the voltage platform of lithium manganese phosphate is 4.1V, the voltage platform of lithium cobalt phosphate is 4.8V, and the voltage platform of lithium nickel phosphate is 5.1V. The lithium manganese phosphate has poor cycle performance, the lithium cobalt phosphate needs cobalt element, and cobalt resource is relatively scarce, so that the lithium cobalt phosphate battery has high price and low popularization value, and the lithium nickel phosphate has high voltage but poor conductivity and is difficult to meet the requirement of power on material performance.
In recent years, various new energy manufacturers have studied composite phosphate anode materials, and some manufacturers have proposed lithium iron manganese phosphate materials which have a 4.1V voltage platform relative to lithium iron phosphate, have an overall energy density 10-15% higher than that of lithium iron phosphate, but have a certain difference compared with high nickel ternary batteries. The novel lithium nickel iron phosphate has a 5.1V voltage platform, the composite material also has an olivine structure similar to lithium iron phosphate, and the performance of the lithium nickel iron phosphate is greatly improved through coating and modification, so that the lithium nickel iron phosphate has basic conditions for popularization and application.
Therefore, a method for preparing lithium nickel iron phosphate by recycling waste nickel-iron alloy is needed for recycling waste nickel-iron alloy and preparing lithium nickel iron phosphate cathode material.
Disclosure of Invention
In view of this, the invention provides a method for preparing a high-value material by recycling waste nickel-iron alloy, which can realize the recycling of waste materials, is low in cost, and has high value and high performance.
The technical scheme of the invention is realized as follows: the invention provides a method for preparing a high-value material by recycling waste nickel-iron alloy, which comprises the following steps:
s1, mixing waste nickel-iron alloy with water, adding acid, adjusting the pH value to 0-4, heating to 20-80 ℃, keeping the temperature, reacting for 1-5 hours, and filtering after complete reaction to obtain a first filtrate and a first filter residue;
s2, adding soluble lithium salt into the first filtrate, heating to 20-80 ℃, and keeping the temperature and stirring to obtain a first solution;
s3, adding phosphate solution into the first solution until the supernatant of the solution is white, stopping adding the phosphate solution, keeping the temperature of 20-80 ℃, stirring for 1-4 hours, and filtering to obtain a second filtrate and a second filter residue;
s4, mixing the first filter residue, the second filter residue and a carbon source, then sanding, and after sanding, performing spray drying to obtain powder;
s5, calcining the powder in a nitrogen atmosphere to obtain a sintered material;
s6, crushing, screening, deironing and packaging the sintered material to obtain the lithium nickel iron phosphate anode material.
On the basis of the above technical scheme, preferably, in step S1, the mass ratio of the waste nickel-iron alloy to water is 1: (1-5).
On the basis of the above technical scheme, preferably, in step S1, the waste ferronickel alloy includes one or more of scrap ferronickel alloy, waste material for producing ferronickel alloy, and scrap material for cutting ferronickel alloy.
On the basis of the above technical solution, preferably, in step S1, the acid is one or a combination of several of sulfuric acid, nitric acid, hydrochloric acid, or other strong acids.
On the basis of the above technical solution, preferably, in step S2, before heating, a first additive is further added, where the first additive is one or more soluble salts of titanium, magnesium, aluminum, zirconium, iron and rare earth metal materials.
On the basis of the above technical solution, preferably, the stoichiometric ratio of the metal element of the first additive to the nickel and iron in the first filtrate is (0.001-0.01): 1.
still more preferably, in the step S2, the first additive of the rare earth metal material includes soluble salts of praseodymium, samarium and neodymium.
Still more preferably, in step S2, the stoichiometric ratio of the lithium element in the soluble lithium salt to the sum of the nickel and iron elements in the first filtrate is (1-1.1): 1.
based on the above technical solution, in step S2, the stirring speed is preferably 200 to 1000rpm.
On the basis of the above technical solution, preferably, in step S3, the phosphate is one or more of monohydrogen phosphate, dihydrogen phosphate, and a soluble salt of phosphate, and the cation of the phosphate is one or more of ammonium ion, sodium ion, and potassium ion.
On the basis of the above technical solution, preferably, in step S3, the stirring speed is 200 to 600rpm.
On the basis of the above technical solution, preferably, in step S4, before the sanding, the sanding is further performed, and after a second additive is added and mixed, the sanding is performed, where the second additive is one or more of nano aluminum oxide, nano titanium oxide, nano zirconium oxide, nano magnesium oxide, nano tungsten oxide, boric acid, and nano rare earth oxide.
Based on the above technical solution, it is preferable that the second additive is added in an amount of 0.01 to 1% by weight of the powder in step S4.
On the basis of the above technical solution, preferably, in step S4, the mass ratio of the carbon source to the final nickel iron phosphate positive electrode material is 0.5-3%.
On the basis of the above technical solution, preferably, in step S4, the carbon source is one or more of first filter residue, graphite, carbon nanotubes, graphene, glucose, sucrose, white granulated sugar, and polyethylene glycol.
On the basis of the technical scheme, the sand grinding particle size is preferably 100-500nm.
On the basis of the above technical solution, preferably, the solid content of the sand is 30-50%.
On the basis of the above technical solution, preferably, the particle size of the powder is 5 to 15 μm.
On the basis of the above technical solution, preferably, in step S5, a 200-400 mesh ultrasonic vibration sieve is used for the sieving.
On the basis of the above technical scheme, preferably, in step S5, the calcination temperature is 650 to 850 ℃, and the calcination time is 5 to 20 hours.
Compared with the prior art, the method for preparing the high-value material by recycling the waste nickel-iron alloy has the following beneficial effects:
(1) On one hand, the waste nickel-iron alloy can be leached and recycled, meanwhile, leachate is used as a raw material, soluble lithium and other doping elements are added, the nickel-iron, the lithium and the other doping elements are solidified and precipitated in a coprecipitation mode to form atomic-level mixture, and a cladding machine and a doping agent are added through sanding to improve the ionic point and the electronic conductivity of the material, so that the rate capability of the finally obtained material is improved, and meanwhile, the waste nickel-iron alloy is recycled;
(2) According to the invention, the waste nickel-iron alloy is used as a raw material, and nickel, iron and even carbon in the material can be recycled to synthesize the lithium nickel iron phosphate, so that the paste recycling rate of the waste nickel-iron alloy can be realized, and the synthesis cost of the lithium nickel iron phosphate can be reduced;
(3) In the invention, a one-step coprecipitation mode is adopted, so that different elements in the material are mixed at an atomic level, and the electrochemical performance of the material is greatly improved;
(4) The carbon source adopted in the invention can also simultaneously comprise organic carbon and inorganic carbon, the inorganic carbon elements are uniformly mixed among the nickel lithium iron phosphate, the electronic conduction among particles is improved, the organic carbon source is uniformly coated on the surface of the material after carbonization, the conductivity of the material is further improved, and the contact between the material and the electrolyte and the side reaction between the material and the electrolyte are reduced due to the coating of the carbon source;
(5) The invention also improves the preparation process, and the in-situ doping mode and the surface phase doping mode are adopted simultaneously, so that doping elements among atoms are uniformly mixed, different elements can be formed among particles of the formed anode material by the surface phase doping, the crystal cell structure is improved, and the electrical property of the anode material is improved.
(6) The invention adopts a sanding mode to control the particle size of the particles, thereby leading the small particle material to have the internal resistance of bottom crossing, ensuring the rate performance of the material, then coating a carbon source, ensuring the electrical performance and simultaneously avoiding the reaction of the anode material and the electrolyte.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is an electron micrograph of a positive electrode material obtained in example 29 of the present invention;
FIG. 2 is a graph of cycle performance of example 1 of the present invention;
FIG. 3 is a graph showing the cycle performance of example 17 of the present invention;
FIG. 4 is a graph showing cycle performance of example 29 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments of the present invention, belong to the protection scope of the present invention.
Example 1
Weighing 1 part of waste nickel-iron alloy, adding 1 part of water, adding sulfuric acid to adjust the pH value of the solution to 0, keeping the temperature at 20 ℃, keeping the temperature for reaction for 2 hours, and filtering after the reaction is completed to obtain a first filtrate and a first filter residue;
adding 0.89 part of lithium sulfate into the first filtrate, wherein the stoichiometric ratio of lithium element to the sum of nickel element and iron element in the obtained solution is 1;
adding a 2M diammonium hydrogen phosphate solution into the first solution until the supernatant of the solution turns white, stopping adding the diammonium hydrogen phosphate solution, keeping the temperature at 20 ℃, stirring at 200rpm for 4 hours, and filtering to obtain a second filtrate and a second filter residue;
weighing 1 part of dried second filter residue and 0.005 part of graphite, mixing, adding water to adjust the solid content to 30%, sanding the obtained slurry until the particle size is 500nm, and then performing spray drying to obtain powder, wherein the particle size of the obtained powder is 15 microns.
Heating the obtained powder to 650 ℃ in a nitrogen atmosphere, and calcining for 20 hours to obtain a sintered material;
and coarsely crushing the sintered material by using a pair of rollers, conveying the crushed material to an airflow crusher by using airflow, crushing the crushed material to the granularity of 1.2 mu m, conveying the crushed material to a packaging machine, and carrying out screening, iron removal and packaging treatment to obtain the lithium nickel iron phosphate anode material.
Example 2
Weighing 1 part of waste nickel-iron alloy, adding 2 parts of water, adding nitric acid to adjust the pH value of the solution to 1, keeping the temperature at 40 ℃, keeping the temperature for reaction for 3 hours, and filtering after the reaction is completed to obtain a first filtrate and a first filter residue;
adding 1.2 parts of lithium nitrate into the first filtrate, wherein the stoichiometric ratio of lithium element to the sum of nickel element and iron element in the obtained solution is 1.02;
adding 2M sodium dihydrogen phosphate solution into the first solution until the supernatant becomes white, stopping adding the sodium dihydrogen phosphate solution, maintaining the temperature at 40 deg.C, stirring at 400rpm for 3h, and filtering to obtain a second filtrate and a second filter residue;
weighing 1 part of dried second filter residue and 0.01 part of carbon nano tube, mixing, adding water to adjust the solid content to 40%, sanding the obtained slurry until the particle size is 400nm, and then performing spray drying to obtain powder, wherein the particle size of the obtained powder is 12 microns.
Heating the obtained powder to 700 ℃ in a nitrogen atmosphere, and calcining for 15h to obtain a sintered material;
and coarsely crushing the sintered material by using a pair of rollers, conveying the crushed material to an airflow crusher by using airflow, crushing the crushed material to the granularity of 1.2 mu m, conveying the crushed material to a packaging machine, and carrying out screening, iron removal and packaging treatment to obtain the lithium nickel iron phosphate anode material.
Example 3
Weighing 1 part of waste nickel-iron alloy, adding 3 parts of water, adding hydrochloric acid to adjust the pH value of the solution to 2, keeping the temperature at 60 ℃, keeping the temperature for reaction for 3 hours, and filtering after the reaction is completed to obtain a first filtrate and a first filter residue;
adding 1.07 part of lithium chloride into the first filtrate, wherein the stoichiometric ratio of lithium element to the sum of nickel element and iron element in the obtained solution is 1.04;
adding 2M potassium phosphate solution into the first solution until the supernatant of the solution becomes white, stopping adding the potassium phosphate solution, keeping the temperature at 60 ℃, stirring at 600rpm for 2 hours, and filtering to obtain a second filtrate and a second filter residue;
weighing 1 part of dried second filter residue and 0.02 part of glucose, mixing, adding water to adjust the solid content to 50%, sanding the obtained slurry until the particle size is 300nm, and then performing spray drying to obtain powder, wherein the particle size of the obtained powder is 10 microns.
Heating the obtained powder to 750 ℃ in a nitrogen atmosphere, and calcining for 10 hours to obtain a sintered material;
and (3) roughly crushing the sintered material by a pair of rollers, conveying the crushed sintered material to an airflow crusher by airflow to crush the crushed sintered material to the particle size of 1.2 mu m, conveying the crushed sintered material to a packaging machine, and performing screening, iron removal and packaging treatment to obtain the lithium nickel iron phosphate anode material.
Example 4
Weighing 1 part of waste nickel-iron alloy, adding 4 parts of water, adding nitric acid to adjust the pH value of the solution to 3, keeping the temperature at 80 ℃, keeping the temperature for reaction for 1 hour, and filtering after the reaction is completed to obtain a first filtrate and first filter residue;
adding 1.26 parts of lithium nitrate into the first filtrate, wherein the stoichiometric ratio of lithium element to the sum of nickel element and iron element in the obtained solution is 1.06;
adding a mixed solution of disodium hydrogen phosphate and potassium phosphate into the first solution until the supernatant of the solution turns white, stopping adding the mixed solution of disodium hydrogen phosphate and potassium phosphate, keeping the temperature at 80 ℃, stirring at 600rpm for 1h, and filtering to obtain a second filtrate and a second filter residue;
weighing 1 part of dried second filter residue, 0.01 part of first filter residue and 0.01 part of polyethylene glycol, mixing, adding water to adjust the solid content to 40%, sanding the obtained slurry until the particle size is 200nm, and then performing spray drying to obtain powder, wherein the particle size of the obtained powder is 8 microns.
Heating the obtained powder to 800 ℃ in a nitrogen atmosphere, and calcining for 10 hours to obtain a sintered material;
and coarsely crushing the sintered material by using a pair of rollers, conveying the crushed material to an airflow crusher by using airflow, crushing the crushed material to the granularity of 1.1 mu m, conveying the crushed material to a packaging machine, and carrying out screening, iron removal and packaging treatment to obtain the lithium nickel iron phosphate anode material.
Example 5
Weighing 1 part of waste nickel-iron alloy, adding 5 parts of water, adding nitric acid to adjust the pH value of the solution to 4, keeping the temperature at 60 ℃, keeping the temperature for reaction for 3 hours, and filtering after the reaction is completed to obtain a first filtrate and a first filter residue;
adding 1.3 parts of lithium nitrate into the first filtrate, wherein the stoichiometric ratio of lithium element to the sum of nickel element and iron element in the obtained solution is 1.1, maintaining the temperature of the obtained solution at 60 ℃, and stirring for 2 hours under the condition of 800rpm to obtain a first solution;
adding a 2M disodium hydrogen phosphate mixed solution into the first solution until the supernatant of the solution becomes white, stopping adding the disodium hydrogen phosphate solution, keeping the temperature at 60 ℃, stirring at 400rpm for 2 hours, and filtering to obtain a second filtrate and a second filter residue;
weighing 1 part of dried second filter residue, 0.01 part of graphene and 0.02 part of sucrose, mixing, adding water to adjust the solid content to 40%, sanding the obtained slurry until the particle size is 100nm, and then performing spray drying to obtain powder, wherein the particle size of the obtained powder is 5 microns.
Heating the obtained powder to 850 ℃ in a nitrogen atmosphere, and calcining for 5 hours to obtain a sintered material;
and coarsely crushing the sintered material by using a pair of rollers, conveying the crushed material to an airflow crusher by using airflow, crushing the crushed material to the granularity of 1.1 mu m, conveying the crushed material to a packaging machine, and carrying out screening, iron removal and packaging treatment to obtain the lithium nickel iron phosphate anode material.
Example 6
Weighing 1 part of waste nickel-iron alloy, adding 5 parts of water, adding nitric acid to adjust the pH value of the solution to 4, keeping the temperature at 60 ℃, keeping the temperature for reaction for 3 hours, and filtering after the reaction is completed to obtain a first filtrate and a first filter residue;
adding 1.3 parts of lithium nitrate and 0.001 part of titanium nitrate into the first filtrate, wherein the stoichiometric ratio of lithium element to the sum of nickel element and iron element in the obtained solution is 1.1, keeping the obtained solution at 60 ℃, and stirring for 2 hours under the condition of 800rpm to obtain a first solution;
adding a 2M disodium hydrogen phosphate mixed solution into the first solution until the supernatant of the solution becomes white, stopping adding the disodium hydrogen phosphate solution, keeping the temperature at 60 ℃, stirring at 400rpm for 2 hours, and filtering to obtain a second filtrate and a second filter residue;
weighing 1 part of dried second filter residue, 0.01 part of graphite and 0.02 part of white granulated sugar, mixing, adding water to adjust the solid content to 40%, sanding the obtained slurry until the particle size is 100nm, and then performing spray drying to obtain powder, wherein the particle size of the obtained powder is 5 microns.
Heating the obtained powder to 850 ℃ in a nitrogen atmosphere, and calcining for 5 hours to obtain a sintered material;
and coarsely crushing the sintered material by using a pair of rollers, conveying the crushed material to an airflow crusher by using airflow, crushing the crushed material to the granularity of 1.1 mu m, conveying the crushed material to a packaging machine, and carrying out screening, iron removal and packaging treatment to obtain the lithium nickel iron phosphate anode material.
Example 7
Weighing 1 part of waste nickel-iron alloy, adding 5 parts of water, adding nitric acid to adjust the pH value of the solution to 4, keeping the temperature at 60 ℃, keeping the temperature for reaction for 3 hours, and filtering after the reaction is completed to obtain a first filtrate and a first filter residue;
adding 1.3 parts of lithium nitrate and 0.005 part of titanium nitrate into the first filtrate, wherein the stoichiometric ratio of lithium element to the sum of nickel element and iron element in the obtained solution is 1.1;
adding a 2M disodium hydrogen phosphate mixed solution into the first solution until the supernatant of the solution becomes white, stopping adding the disodium hydrogen phosphate solution, keeping the temperature at 60 ℃, stirring at 400rpm for 2 hours, and filtering to obtain a second filtrate and a second filter residue;
weighing 1 part of dried second filter residue, 0.01 part of graphite and 0.02 part of white granulated sugar, mixing, adding water to adjust the solid content to 40%, sanding the obtained slurry until the particle size is 100nm, and then performing spray drying to obtain powder, wherein the particle size of the obtained powder is 5 microns.
Heating the obtained powder to 850 ℃ in a nitrogen atmosphere, and calcining for 5 hours to obtain a sintered material;
and coarsely crushing the sintered material by using a pair of rollers, conveying the crushed material to an airflow crusher by using airflow, crushing the crushed material to the granularity of 1.1 mu m, conveying the crushed material to a packaging machine, and carrying out screening, iron removal and packaging treatment to obtain the lithium nickel iron phosphate anode material.
Example 8
Weighing 1 part of waste nickel-iron alloy, adding 5 parts of water, adding nitric acid to adjust the pH value of the solution to 4, keeping the temperature at 60 ℃, keeping the temperature for reaction for 3 hours, and filtering after the reaction is completed to obtain a first filtrate and a first filter residue;
adding 1.3 parts of lithium nitrate and 0.01 part of titanium nitrate into the first filtrate, wherein the stoichiometric ratio of lithium element to the sum of nickel element and iron element in the obtained solution is 1.1, keeping the temperature of the obtained solution at 60 ℃, and stirring for 2 hours under the condition of 800rpm to obtain a first solution;
adding a 2M disodium hydrogen phosphate mixed solution into the first solution until the supernatant of the solution becomes white, stopping adding the disodium hydrogen phosphate solution, keeping the temperature at 60 ℃, stirring at 400rpm for 2 hours, and filtering to obtain a second filtrate and a second filter residue;
weighing 1 part of dried second filter residue, 0.01 part of graphite and 0.02 part of white granulated sugar, mixing, adding water to adjust the solid content to 40%, sanding the obtained slurry until the particle size is 100nm, and then performing spray drying to obtain powder, wherein the particle size of the obtained powder is 5 microns.
Heating the obtained powder to 850 ℃ in a nitrogen atmosphere, and calcining for 5 hours to obtain a sintered material;
and coarsely crushing the sintered material by using a pair of rollers, conveying the crushed material to an airflow crusher by using airflow, crushing the crushed material to the granularity of 1.1 mu m, conveying the crushed material to a packaging machine, and carrying out screening, iron removal and packaging treatment to obtain the lithium nickel iron phosphate anode material.
Example 9
Weighing 1 part of waste nickel-iron alloy, adding 5 parts of water, adding nitric acid to adjust the pH value of the solution to 4, keeping the temperature at 60 ℃, keeping the temperature for reaction for 3 hours, and filtering after the reaction is completed to obtain a first filtrate and a first filter residue;
adding 1.3 parts of lithium nitrate and 0.005 part of magnesium nitrate into the first filtrate, wherein the stoichiometric ratio of lithium element to the sum of nickel element and iron element in the obtained solution is 1.1, keeping the obtained solution at 60 ℃, and stirring for 2 hours under the condition of 800rpm to obtain a first solution;
adding a 2M disodium hydrogen phosphate mixed solution into the first solution until the supernatant of the solution turns white, stopping adding the disodium hydrogen phosphate solution, keeping the temperature at 60 ℃, stirring at 400rpm for 2 hours, and filtering to obtain a second filtrate and a second filter residue;
weighing 1 part of dried second filter residue, 0.01 part of graphite and 0.02 part of white granulated sugar, mixing, adding water to adjust the solid content to 40%, sanding the obtained slurry until the particle size is 100nm, and then performing spray drying to obtain powder, wherein the particle size of the obtained powder is 5 microns.
Heating the obtained powder to 850 ℃ in a nitrogen atmosphere, and calcining for 5 hours to obtain a sintered material;
and (3) roughly crushing the sintered material by a pair of rollers, conveying the crushed sintered material to an airflow crusher by airflow to crush the crushed sintered material to the particle size of 1.2 mu m, conveying the crushed sintered material to a packaging machine, and performing screening, iron removal and packaging treatment to obtain the lithium nickel iron phosphate anode material.
Example 10
Weighing 1 part of waste nickel-iron alloy, adding 5 parts of water, adding nitric acid to adjust the pH value of the solution to 4, keeping the temperature at 60 ℃, keeping the temperature for reaction for 3 hours, and filtering after the reaction is completed to obtain a first filtrate and a first filter residue;
adding 1.3 parts of lithium nitrate and 0.005 part of aluminum nitrate into the first filtrate, wherein the stoichiometric ratio of lithium element to the sum of nickel element and iron element in the obtained solution is 1.1, keeping the obtained solution at 60 ℃, and stirring for 2 hours under the condition of 800rpm to obtain a first solution;
adding a 2M disodium hydrogen phosphate mixed solution into the first solution until the supernatant of the solution turns white, stopping adding the disodium hydrogen phosphate solution, keeping the temperature at 60 ℃, stirring at 400rpm for 2 hours, and filtering to obtain a second filtrate and a second filter residue;
weighing 1 part of dried second filter residue, 0.01 part of graphite and 0.02 part of white granulated sugar, mixing, adding water to adjust the solid content to 40%, sanding the obtained slurry until the particle size is 100nm, and then performing spray drying to obtain powder, wherein the particle size of the obtained powder is 5 microns.
Heating the obtained powder to 850 ℃ in a nitrogen atmosphere, and calcining for 5 hours to obtain a sintered material;
and coarsely crushing the sintered material by using a pair of rollers, conveying the crushed material to an airflow crusher by using airflow, crushing the crushed material to the granularity of 1.2 mu m, conveying the crushed material to a packaging machine, and carrying out screening, iron removal and packaging treatment to obtain the lithium nickel iron phosphate anode material.
Example 11
Weighing 1 part of waste nickel-iron alloy, adding 5 parts of water, adding nitric acid to adjust the pH value of the solution to 4, keeping the temperature at 60 ℃, keeping the temperature for reaction for 3 hours, and filtering after the reaction is completed to obtain a first filtrate and a first filter residue;
adding 1.3 parts of lithium nitrate and 0.005 part of zirconium nitrate into the first filtrate, wherein the stoichiometric ratio of lithium element to the sum of nickel element and iron element in the obtained solution is 1.1, keeping the obtained solution at 60 ℃, and stirring for 2 hours under the condition of 800rpm to obtain a first solution;
adding a 2M disodium hydrogen phosphate mixed solution into the first solution until the supernatant of the solution turns white, stopping adding the disodium hydrogen phosphate solution, keeping the temperature at 60 ℃, stirring at 400rpm for 2 hours, and filtering to obtain a second filtrate and a second filter residue;
weighing 1 part of dried second filter residue, 0.01 part of graphite and 0.02 part of white granulated sugar, mixing, adding water to adjust the solid content to 40%, sanding the obtained slurry until the particle size is 100nm, and then performing spray drying to obtain powder, wherein the particle size of the obtained powder is 5 microns.
Heating the obtained powder to 850 ℃ in a nitrogen atmosphere, and calcining for 5 hours to obtain a sintered material;
and (3) roughly crushing the sintered material by a pair of rollers, conveying the crushed sintered material to an airflow crusher by airflow to crush the crushed sintered material to the particle size of 1.2 mu m, conveying the crushed sintered material to a packaging machine, and performing screening, iron removal and packaging treatment to obtain the lithium nickel iron phosphate anode material.
Example 12
Weighing 1 part of waste nickel-iron alloy, adding 5 parts of water, adding nitric acid to adjust the pH value of the solution to 4, keeping the temperature at 60 ℃, keeping the temperature for reaction for 3 hours, and filtering after the reaction is completed to obtain a first filtrate and a first filter residue;
adding 1.3 parts of lithium nitrate and 0.005 part of ferric nitrate into the first filtrate, wherein the stoichiometric ratio of lithium element to the sum of nickel element and iron element in the obtained solution is 1.1, keeping the temperature of the obtained solution at 60 ℃, and stirring for 2 hours under the condition of 800rpm to obtain a first solution;
adding a 2M disodium hydrogen phosphate mixed solution into the first solution until the supernatant of the solution turns white, stopping adding the disodium hydrogen phosphate solution, keeping the temperature at 60 ℃, stirring at 400rpm for 2 hours, and filtering to obtain a second filtrate and a second filter residue;
weighing 1 part of dried second filter residue, 0.01 part of graphite and 0.02 part of white granulated sugar, mixing, adding water to adjust the solid content to 40%, sanding the obtained slurry until the particle size is 100nm, and then performing spray drying to obtain powder, wherein the particle size of the obtained powder is 5 microns.
Heating the obtained powder to 850 ℃ in a nitrogen atmosphere, and calcining for 5 hours to obtain a sintered material;
and (3) roughly crushing the sintered material by a pair of rollers, conveying the crushed sintered material to an airflow crusher by airflow to crush the crushed sintered material to the particle size of 1.2 mu m, conveying the crushed sintered material to a packaging machine, and performing screening, iron removal and packaging treatment to obtain the lithium nickel iron phosphate anode material.
Example 13
Weighing 1 part of waste nickel-iron alloy, adding 5 parts of water, adding nitric acid to adjust the pH value of the solution to 4, keeping the temperature at 60 ℃, keeping the temperature for reaction for 3 hours, and filtering after the reaction is completed to obtain a first filtrate and a first filter residue;
adding 1.3 parts of lithium nitrate and 0.005 part of praseodymium nitrate into the first filtrate, wherein the stoichiometric ratio of the lithium element to the sum of the nickel element and the iron element in the obtained solution is 1.1;
adding a 2M disodium hydrogen phosphate mixed solution into the first solution until the supernatant of the solution turns white, stopping adding the disodium hydrogen phosphate solution, keeping the temperature at 60 ℃, stirring at 400rpm for 2 hours, and filtering to obtain a second filtrate and a second filter residue;
weighing 1 part of dried second filter residue, 0.01 part of graphite and 0.02 part of white granulated sugar, mixing, adding water to adjust the solid content to 40%, sanding the obtained slurry until the particle size is 100nm, and then performing spray drying to obtain powder, wherein the particle size of the obtained powder is 5 microns.
Heating the obtained powder to 850 ℃ in a nitrogen atmosphere, and calcining for 5 hours to obtain a sintered material;
and coarsely crushing the sintered material by using a pair of rollers, conveying the crushed material to an airflow crusher by using airflow, crushing the crushed material to the granularity of 1.2 mu m, conveying the crushed material to a packaging machine, and carrying out screening, iron removal and packaging treatment to obtain the lithium nickel iron phosphate anode material.
Example 14
Weighing 1 part of waste nickel-iron alloy, adding 5 parts of water, adding nitric acid to adjust the pH value of the solution to 4, keeping the temperature at 60 ℃, keeping the temperature for reaction for 3 hours, and filtering after the reaction is completed to obtain a first filtrate and a first filter residue;
adding 1.3 parts of lithium nitrate and 0.005 part of samarium nitrate into the first filtrate, wherein the stoichiometric ratio of lithium element to the sum of nickel element and iron element in the obtained solution is 1.1;
adding a 2M disodium hydrogen phosphate mixed solution into the first solution until the supernatant of the solution becomes white, stopping adding the disodium hydrogen phosphate solution, keeping the temperature at 60 ℃, stirring at 400rpm for 2 hours, and filtering to obtain a second filtrate and a second filter residue;
weighing 1 part of dried second filter residue, 0.01 part of graphite and 0.02 part of white granulated sugar, mixing, adding water to adjust the solid content to 40%, sanding the obtained slurry until the particle size is 100nm, and then performing spray drying to obtain powder, wherein the particle size of the obtained powder is 5 microns.
Heating the obtained powder to 850 ℃ in a nitrogen atmosphere, and calcining for 5 hours to obtain a sintered material;
and (3) roughly crushing the sintered material by a pair of rollers, conveying the crushed sintered material to an airflow crusher by airflow to crush the crushed sintered material to the particle size of 1.2 mu m, conveying the crushed sintered material to a packaging machine, and performing screening, iron removal and packaging treatment to obtain the lithium nickel iron phosphate anode material.
Example 15
Weighing 1 part of waste nickel-iron alloy, adding 5 parts of water, adding nitric acid to adjust the pH value of the solution to 4, keeping the temperature at 60 ℃, keeping the temperature for reaction for 3 hours, and filtering after the reaction is completed to obtain a first filtrate and a first filter residue;
adding 1.3 parts of lithium nitrate and 0.005 part of neodymium nitrate into the first filtrate, wherein the stoichiometric ratio of lithium element to the sum of nickel element and iron element in the obtained solution is 1.1;
adding a 2M disodium hydrogen phosphate mixed solution into the first solution until the supernatant of the solution turns white, stopping adding the disodium hydrogen phosphate solution, keeping the temperature at 60 ℃, stirring at 400rpm for 2 hours, and filtering to obtain a second filtrate and a second filter residue;
weighing 1 part of dried second filter residue, 0.01 part of graphite and 0.02 part of white granulated sugar, mixing, adding water to adjust the solid content to 40%, sanding the obtained slurry until the particle size is 100nm, and then performing spray drying to obtain powder, wherein the particle size of the obtained powder is 5 microns.
Heating the obtained powder to 850 ℃ in a nitrogen atmosphere, and calcining for 5 hours to obtain a sintered material;
and (3) roughly crushing the sintered material by a pair of rollers, conveying the crushed sintered material to an airflow crusher by airflow to crush the crushed sintered material to the particle size of 1.2 mu m, conveying the crushed sintered material to a packaging machine, and performing screening, iron removal and packaging treatment to obtain the lithium nickel iron phosphate anode material.
Example 16
Weighing 1 part of waste nickel-iron alloy, adding 5 parts of water, adding nitric acid to adjust the pH value of the solution to 4, keeping the temperature at 60 ℃, keeping the temperature for reaction for 3 hours, and filtering after the reaction is completed to obtain a first filtrate and a first filter residue;
adding 1.3 parts of lithium nitrate, 0.003 part of titanium nitrate and 0.003 part of aluminum nitrate into the first filtrate, wherein the stoichiometric ratio of lithium element to the sum of nickel element and iron element in the obtained solution is 1.1, and keeping the temperature of the obtained solution at 60 ℃ and stirring at 800rpm for 2 hours to obtain a first solution;
adding a 2M disodium hydrogen phosphate mixed solution into the first solution until the supernatant of the solution turns white, stopping adding the disodium hydrogen phosphate solution, keeping the temperature at 60 ℃, stirring at 400rpm for 2 hours, and filtering to obtain a second filtrate and a second filter residue;
weighing 1 part of dried second filter residue, 0.01 part of graphite and 0.02 part of white granulated sugar, mixing, adding water to adjust the solid content to 40%, sanding the obtained slurry until the particle size is 100nm, and then performing spray drying to obtain powder, wherein the particle size of the obtained powder is 5 microns.
Heating the obtained powder to 850 ℃ in a nitrogen atmosphere, and calcining for 5 hours to obtain a sintered material;
and coarsely crushing the sintered material by using a pair of rollers, conveying the crushed material to an airflow crusher by using airflow, crushing the crushed material to the granularity of 1.2 mu m, conveying the crushed material to a packaging machine, and carrying out screening, iron removal and packaging treatment to obtain the lithium nickel iron phosphate anode material.
Example 17
Weighing 1 part of waste nickel-iron alloy, adding 5 parts of water, adding nitric acid to adjust the pH value of the solution to 4, keeping the temperature at 60 ℃, keeping the temperature for reaction for 3 hours, and filtering after the reaction is completed to obtain a first filtrate and a first filter residue;
adding 1.3 parts of lithium nitrate, 0.003 part of titanium nitrate and 0.003 part of neodymium nitrate into the first filtrate, wherein the stoichiometric ratio of lithium element to the sum of nickel element and iron element in the obtained solution is 1.1, keeping the obtained solution at 60 ℃, and stirring for 2 hours under the condition of 800rpm to obtain a first solution;
adding a 2M disodium hydrogen phosphate mixed solution into the first solution until the supernatant of the solution turns white, stopping adding the disodium hydrogen phosphate solution, keeping the temperature at 60 ℃, stirring at 400rpm for 2 hours, and filtering to obtain a second filtrate and a second filter residue;
weighing 1 part of dried second filter residue, 0.01 part of graphite and 0.02 part of white granulated sugar, mixing, adding water to adjust the solid content to 40%, sanding the obtained slurry until the particle size is 100nm, and then performing spray drying to obtain powder, wherein the particle size of the obtained powder is 5 microns.
Heating the obtained powder to 850 ℃ in a nitrogen atmosphere, and calcining for 5 hours to obtain a sintered material;
and (3) roughly crushing the sintered material by a pair of rollers, conveying the crushed sintered material to an airflow crusher by airflow to crush the crushed sintered material to the particle size of 1.2 mu m, conveying the crushed sintered material to a packaging machine, and performing screening, iron removal and packaging treatment to obtain the lithium nickel iron phosphate anode material.
Example 18
Weighing 1 part of waste nickel-iron alloy, adding 5 parts of water, adding nitric acid to adjust the pH value of the solution to 4, keeping the temperature at 60 ℃, keeping the temperature for reaction for 3 hours, and filtering after the reaction is completed to obtain a first filtrate and a first filter residue;
adding 1.3 parts of lithium nitrate, 0.003 part of titanium nitrate and 0.003 part of praseodymium nitrate into the first filtrate, wherein the stoichiometric ratio of lithium element to the sum of nickel element and iron element in the obtained solution is 1.1, and keeping the temperature of the obtained solution at 60 ℃ under the condition of 800rpm and stirring for 2 hours to obtain a first solution;
adding a 2M disodium hydrogen phosphate mixed solution into the first solution until the supernatant of the solution turns white, stopping adding the disodium hydrogen phosphate solution, keeping the temperature at 60 ℃, stirring at 400rpm for 2 hours, and filtering to obtain a second filtrate and a second filter residue;
weighing 1 part of dried second filter residue, 0.01 part of graphite and 0.02 part of white granulated sugar, mixing, adding water to adjust the solid content to 40%, sanding the obtained slurry until the particle size is 100nm, and then performing spray drying to obtain powder, wherein the particle size of the obtained powder is 5 microns.
Heating the obtained powder to 850 ℃ in a nitrogen atmosphere, and calcining for 5 hours to obtain a sintered material;
and coarsely crushing the sintered material by using a pair of rollers, conveying the crushed material to an airflow crusher by using airflow, crushing the crushed material to the granularity of 1.2 mu m, conveying the crushed material to a packaging machine, and carrying out screening, iron removal and packaging treatment to obtain the lithium nickel iron phosphate anode material.
Example 19
Weighing 1 part of waste nickel-iron alloy, adding 5 parts of water, adding nitric acid to adjust the pH value of the solution to 4, keeping the temperature at 60 ℃, keeping the temperature for reaction for 3 hours, and filtering after the reaction is completed to obtain a first filtrate and a first filter residue;
adding 1.3 parts of lithium nitrate, 0.003 part of titanium nitrate and 0.003 part of neodymium nitrate into the first filtrate, wherein the stoichiometric ratio of lithium element to the sum of nickel element and iron element in the obtained solution is 1.1, keeping the obtained solution at 60 ℃, and stirring for 2 hours under the condition of 800rpm to obtain a first solution;
adding a 2M disodium hydrogen phosphate mixed solution into the first solution until the supernatant of the solution turns white, stopping adding the disodium hydrogen phosphate solution, keeping the temperature at 60 ℃, stirring at 400rpm for 2 hours, and filtering to obtain a second filtrate and a second filter residue;
weighing 1 part of dried second filter residue, 0.01 part of graphite, 0.02 part of white granulated sugar and 0.0001 part of nano-alumina, mixing, adding water to adjust the solid content to 40%, sanding the obtained slurry until the particle size is 100nm, and then performing spray drying to obtain powder, wherein the particle size of the obtained powder is 5 microns.
Heating the obtained powder to 850 ℃ in a nitrogen atmosphere, and calcining for 5 hours to obtain a sintered material;
and coarsely crushing the sintered material by using a pair of rollers, conveying the crushed material to an airflow crusher by using airflow, crushing the crushed material to the granularity of 1.2 mu m, conveying the crushed material to a packaging machine, and carrying out screening, iron removal and packaging treatment to obtain the lithium nickel iron phosphate anode material.
Example 20
Weighing 1 part of waste nickel-iron alloy, adding 5 parts of water, adding nitric acid to adjust the pH value of the solution to 4, keeping the temperature at 60 ℃, keeping the temperature for reaction for 3 hours, and filtering after the reaction is completed to obtain a first filtrate and a first filter residue;
adding 1.3 parts of lithium nitrate, 0.003 part of titanium nitrate and 0.003 part of neodymium nitrate into the first filtrate, wherein the stoichiometric ratio of lithium element to the sum of nickel element and iron element in the obtained solution is 1.1, keeping the obtained solution at 60 ℃, and stirring for 2 hours under the condition of 800rpm to obtain a first solution;
adding a 2M disodium hydrogen phosphate mixed solution into the first solution until the supernatant of the solution turns white, stopping adding the disodium hydrogen phosphate solution, keeping the temperature at 60 ℃, stirring at 400rpm for 2 hours, and filtering to obtain a second filtrate and a second filter residue;
weighing 1 part of dried second filter residue, 0.01 part of graphite, 0.02 part of white granulated sugar and 0.001 part of nano-alumina, mixing, adding water to adjust the solid content to 40%, sanding the obtained slurry until the particle size is 100nm, and then performing spray drying to obtain powder, wherein the particle size of the obtained powder is 5 microns.
Heating the obtained powder to 850 ℃ in a nitrogen atmosphere, and calcining for 5 hours to obtain a sintered material;
and coarsely crushing the sintered material by using a pair of rollers, conveying the crushed material to an airflow crusher by using airflow, crushing the crushed material to the granularity of 1.2 mu m, conveying the crushed material to a packaging machine, and carrying out screening, iron removal and packaging treatment to obtain the lithium nickel iron phosphate anode material.
Example 21
Weighing 1 part of waste nickel-iron alloy, adding 5 parts of water, adding nitric acid to adjust the pH value of the solution to 4, keeping the temperature at 60 ℃, keeping the temperature for reaction for 3 hours, and filtering after the reaction is completed to obtain a first filtrate and a first filter residue;
adding 1.3 parts of lithium nitrate, 0.003 part of titanium nitrate and 0.003 part of neodymium nitrate into the first filtrate, wherein the stoichiometric ratio of lithium element to the sum of nickel element and iron element in the obtained solution is 1.1, keeping the obtained solution at 60 ℃, and stirring for 2 hours under the condition of 800rpm to obtain a first solution;
adding a 2M disodium hydrogen phosphate mixed solution into the first solution until the supernatant of the solution becomes white, stopping adding the disodium hydrogen phosphate solution, keeping the temperature at 60 ℃, stirring at 400rpm for 2 hours, and filtering to obtain a second filtrate and a second filter residue;
weighing 1 part of dried second filter residue, 0.01 part of graphite, 0.02 part of white granulated sugar and 0.01 part of nano-alumina, mixing, adding water to adjust the solid content to 40%, sanding the obtained slurry until the particle size is 100nm, and then performing spray drying to obtain powder, wherein the particle size of the obtained powder is 5 mu m.
Heating the obtained powder to 850 ℃ in a nitrogen atmosphere, and calcining for 5 hours to obtain a sintered material;
and (3) roughly crushing the sintered material by a pair of rollers, conveying the crushed sintered material to an airflow crusher by airflow to crush the crushed sintered material to the particle size of 1.2 mu m, conveying the crushed sintered material to a packaging machine, and performing screening, iron removal and packaging treatment to obtain the lithium nickel iron phosphate anode material.
Example 22
Weighing 1 part of waste nickel-iron alloy, adding 5 parts of water, adding nitric acid to adjust the pH value of the solution to 4, keeping the temperature at 60 ℃, keeping the temperature for reaction for 3 hours, and filtering after the reaction is completed to obtain a first filtrate and a first filter residue;
adding 1.3 parts of lithium nitrate, 0.003 part of titanium nitrate and 0.003 part of neodymium nitrate into the first filtrate, wherein the stoichiometric ratio of lithium element to the sum of nickel element and iron element in the obtained solution is 1.1, keeping the obtained solution at 60 ℃, and stirring for 2 hours under the condition of 800rpm to obtain a first solution;
adding a 2M disodium hydrogen phosphate mixed solution into the first solution until the supernatant of the solution turns white, stopping adding the disodium hydrogen phosphate solution, keeping the temperature at 60 ℃, stirring at 400rpm for 2 hours, and filtering to obtain a second filtrate and a second filter residue;
weighing 1 part of dried second filter residue, 0.01 part of graphite, 0.02 part of white granulated sugar and 0.001 part of nano titanium oxide, mixing, adding water to adjust the solid content to 40%, sanding the obtained slurry until the particle size is 100nm, and then performing spray drying to obtain powder, wherein the particle size of the obtained powder is 5 microns.
Heating the obtained powder to 850 ℃ in a nitrogen atmosphere, and calcining for 5 hours to obtain a sintered material;
and coarsely crushing the sintered material by using a pair of rollers, conveying the crushed material to an airflow crusher by using airflow, crushing the crushed material to the granularity of 1.2 mu m, conveying the crushed material to a packaging machine, and carrying out screening, iron removal and packaging treatment to obtain the lithium nickel iron phosphate anode material.
Example 23
Weighing 1 part of waste nickel-iron alloy, adding 5 parts of water, adding nitric acid to adjust the pH value of the solution to 4, keeping the temperature at 60 ℃, keeping the temperature for reaction for 3 hours, and filtering after the reaction is completed to obtain a first filtrate and a first filter residue;
adding 1.3 parts of lithium nitrate, 0.003 part of titanium nitrate and 0.003 part of neodymium nitrate into the first filtrate, wherein the stoichiometric ratio of lithium element to the sum of nickel element and iron element in the obtained solution is 1.1, keeping the obtained solution at 60 ℃, and stirring for 2 hours under the condition of 800rpm to obtain a first solution;
adding a 2M disodium hydrogen phosphate mixed solution into the first solution until the supernatant of the solution becomes white, stopping adding the disodium hydrogen phosphate solution, keeping the temperature at 60 ℃, stirring at 400rpm for 2 hours, and filtering to obtain a second filtrate and a second filter residue;
weighing 1 part of dried second filter residue, 0.01 part of graphite, 0.02 part of white granulated sugar and 0.001 part of nano zirconia, mixing, adding water to adjust the solid content to 40%, sanding the obtained slurry until the particle size is 100nm, and then performing spray drying to obtain powder, wherein the particle size of the obtained powder is 5 microns.
Heating the obtained powder to 850 ℃ in a nitrogen atmosphere, and calcining for 5 hours to obtain a sintered material;
and coarsely crushing the sintered material by using a pair of rollers, conveying the crushed material to an airflow crusher by using airflow, crushing the crushed material to the granularity of 1.2 mu m, conveying the crushed material to a packaging machine, and carrying out screening, iron removal and packaging treatment to obtain the lithium nickel iron phosphate anode material.
Example 24
Weighing 1 part of waste nickel-iron alloy, adding 5 parts of water, adding nitric acid to adjust the pH value of the solution to 4, keeping the temperature at 60 ℃, keeping the temperature for reaction for 3 hours, and filtering after the reaction is completed to obtain a first filtrate and a first filter residue;
adding 1.3 parts of lithium nitrate, 0.003 part of titanium nitrate and 0.003 part of neodymium nitrate into the first filtrate, wherein the stoichiometric ratio of lithium element to the sum of nickel element and iron element in the obtained solution is 1.1, keeping the obtained solution at 60 ℃, and stirring for 2 hours under the condition of 800rpm to obtain a first solution;
adding a 2M disodium hydrogen phosphate mixed solution into the first solution until the supernatant of the solution turns white, stopping adding the disodium hydrogen phosphate solution, keeping the temperature at 60 ℃, stirring at 400rpm for 2 hours, and filtering to obtain a second filtrate and a second filter residue;
weighing 1 part of dried second filter residue, 0.01 part of graphite, 0.02 part of white granulated sugar and 0.001 part of nano magnesium oxide, mixing, adding water to adjust the solid content to 40%, sanding the obtained slurry until the particle size is 100nm, and then performing spray drying to obtain powder, wherein the particle size of the obtained powder is 5 microns.
Heating the obtained powder to 850 ℃ in a nitrogen atmosphere, and calcining for 5 hours to obtain a sintered material;
and (3) roughly crushing the sintered material by a pair of rollers, conveying the crushed sintered material to an airflow crusher by airflow to crush the crushed sintered material to the particle size of 1.2 mu m, conveying the crushed sintered material to a packaging machine, and performing screening, iron removal and packaging treatment to obtain the lithium nickel iron phosphate anode material.
Example 25
Weighing 1 part of waste nickel-iron alloy, adding 5 parts of water, adding nitric acid to adjust the pH value of the solution to 4, keeping the temperature at 60 ℃, keeping the temperature for reaction for 3 hours, and filtering after the reaction is completed to obtain a first filtrate and a first filter residue;
adding 1.3 parts of lithium nitrate, 0.003 part of titanium nitrate and 0.003 part of neodymium nitrate into the first filtrate, wherein the stoichiometric ratio of lithium element to the sum of nickel element and iron element in the obtained solution is 1.1, and keeping the temperature of the obtained solution at 60 ℃ and stirring at 800rpm for 2h to obtain a first solution;
adding a 2M disodium hydrogen phosphate mixed solution into the first solution until the supernatant of the solution turns white, stopping adding the disodium hydrogen phosphate solution, keeping the temperature at 60 ℃, stirring at 400rpm for 2 hours, and filtering to obtain a second filtrate and a second filter residue;
weighing 1 part of dried second filter residue, 0.01 part of graphite, 0.02 part of white granulated sugar and 0.001 part of nano tungsten oxide, mixing, adding water to adjust the solid content to 40%, sanding the obtained slurry until the particle size is 100nm, and then performing spray drying to obtain powder, wherein the particle size of the obtained powder is 5 microns.
Heating the obtained powder to 850 ℃ in a nitrogen atmosphere, and calcining for 5 hours to obtain a sintered material;
and coarsely crushing the sintered material by using a pair of rollers, conveying the crushed material to an airflow crusher by using airflow, crushing the crushed material to the granularity of 1.2 mu m, conveying the crushed material to a packaging machine, and carrying out screening, iron removal and packaging treatment to obtain the lithium nickel iron phosphate anode material.
Example 26
Weighing 1 part of waste nickel-iron alloy, adding 5 parts of water, adding nitric acid to adjust the pH value of the solution to 4, keeping the temperature at 60 ℃, keeping the temperature for reaction for 3 hours, and filtering after the reaction is completed to obtain a first filtrate and a first filter residue;
adding 1.3 parts of lithium nitrate, 0.003 part of titanium nitrate and 0.003 part of neodymium nitrate into the first filtrate, wherein the stoichiometric ratio of lithium element to the sum of nickel element and iron element in the obtained solution is 1.1, keeping the obtained solution at 60 ℃, and stirring for 2 hours under the condition of 800rpm to obtain a first solution;
adding a 2M disodium hydrogen phosphate mixed solution into the first solution until the supernatant of the solution turns white, stopping adding the disodium hydrogen phosphate solution, keeping the temperature at 60 ℃, stirring at 400rpm for 2 hours, and filtering to obtain a second filtrate and a second filter residue;
weighing 1 part of dried second filter residue, 0.01 part of graphite, 0.02 part of white granulated sugar and 0.001 part of boric acid, mixing, adding water to adjust the solid content to 40%, sanding the obtained slurry until the particle size is 100nm, and then performing spray drying to obtain powder, wherein the particle size of the obtained powder is 5 microns.
Heating the obtained powder to 850 ℃ in a nitrogen atmosphere, and calcining for 5 hours to obtain a sintered material;
and coarsely crushing the sintered material by using a pair of rollers, conveying the crushed material to an airflow crusher by using airflow, crushing the crushed material to the granularity of 1.2 mu m, conveying the crushed material to a packaging machine, and carrying out screening, iron removal and packaging treatment to obtain the lithium nickel iron phosphate anode material.
Example 27
Weighing 1 part of waste nickel-iron alloy, adding 5 parts of water, adding nitric acid to adjust the pH value of the solution to 4, keeping the temperature at 60 ℃, keeping the temperature for reaction for 3 hours, and filtering after the reaction is completed to obtain a first filtrate and a first filter residue;
adding 1.3 parts of lithium nitrate, 0.003 part of titanium nitrate and 0.003 part of neodymium nitrate into the first filtrate, wherein the stoichiometric ratio of lithium element to the sum of nickel element and iron element in the obtained solution is 1.1, and keeping the temperature of the obtained solution at 60 ℃ and stirring at 800rpm for 2h to obtain a first solution;
adding a 2M disodium hydrogen phosphate mixed solution into the first solution until the supernatant of the solution turns white, stopping adding the disodium hydrogen phosphate solution, keeping the temperature at 60 ℃, stirring at 400rpm for 2 hours, and filtering to obtain a second filtrate and a second filter residue;
weighing 1 part of dried second filter residue, 0.01 part of graphite, 0.02 part of white granulated sugar and 0.001 part of nano samarium oxide, mixing, adding water to adjust the solid content to 40%, sanding the obtained slurry until the particle size is 100nm, and then performing spray drying to obtain powder, wherein the particle size of the obtained powder is 5 microns.
Heating the obtained powder to 850 ℃ in a nitrogen atmosphere, and calcining for 5 hours to obtain a sintered material;
and coarsely crushing the sintered material by using a pair of rollers, conveying the crushed material to an airflow crusher by using airflow, crushing the crushed material to the granularity of 1.2 mu m, conveying the crushed material to a packaging machine, and carrying out screening, iron removal and packaging treatment to obtain the lithium nickel iron phosphate anode material.
Example 28
Weighing 1 part of waste nickel-iron alloy, adding 5 parts of water, adding nitric acid to adjust the pH value of the solution to 4, keeping the temperature at 60 ℃, keeping the temperature for reaction for 3 hours, and filtering after the reaction is completed to obtain a first filtrate and a first filter residue;
adding 1.3 parts of lithium nitrate, 0.003 part of titanium nitrate and 0.003 part of neodymium nitrate into the first filtrate, wherein the stoichiometric ratio of lithium element to the sum of nickel element and iron element in the obtained solution is 1.1, and keeping the temperature of the obtained solution at 60 ℃ and stirring at 800rpm for 2h to obtain a first solution;
adding a 2M disodium hydrogen phosphate mixed solution into the first solution until the supernatant of the solution turns white, stopping adding the disodium hydrogen phosphate solution, keeping the temperature at 60 ℃, stirring at 400rpm for 2 hours, and filtering to obtain a second filtrate and a second filter residue;
weighing 1 part of dried second filter residue, 0.01 part of graphite, 0.02 part of white granulated sugar, 0.002 part of nano zirconia and 0.001 part of nano magnesia, mixing, adding water to adjust the solid content to 40%, sanding the obtained slurry until the particle size is 100nm, and then performing spray drying to obtain powder with the particle size of 5 microns.
Heating the obtained powder to 850 ℃ in a nitrogen atmosphere, and calcining for 5 hours to obtain a sintered material;
and (3) roughly crushing the sintered material by a pair of rollers, conveying the crushed sintered material to an airflow crusher by airflow to crush the crushed sintered material to the particle size of 1.2 mu m, conveying the crushed sintered material to a packaging machine, and performing screening, iron removal and packaging treatment to obtain the lithium nickel iron phosphate anode material.
Weighing 1 part of waste nickel-iron alloy, adding 5 parts of water, adding nitric acid to adjust the pH value of the solution to 4, keeping the temperature at 60 ℃, keeping the temperature for reaction for 3 hours, and filtering after the reaction is completed to obtain a first filtrate and a first filter residue;
adding 1.3 parts of lithium nitrate, 0.003 part of titanium nitrate and 0.003 part of neodymium nitrate into the first filtrate, wherein the stoichiometric ratio of lithium element to the sum of nickel element and iron element in the obtained solution is 1.1, keeping the obtained solution at 60 ℃, and stirring for 2 hours under the condition of 800rpm to obtain a first solution;
adding a 2M disodium hydrogen phosphate mixed solution into the first solution until the supernatant of the solution becomes white, stopping adding the disodium hydrogen phosphate solution, keeping the temperature at 60 ℃, stirring at 400rpm for 2 hours, and filtering to obtain a second filtrate and a second filter residue;
weighing 1 part of dried second filter residue, 0.01 part of graphite, 0.02 part of white granulated sugar, 0.002 part of nano zirconia and 0.001 part of nano samarium oxide, mixing, adding water to adjust the solid content to 40%, sanding the obtained slurry until the particle size is 100nm, and then performing spray drying to obtain powder with the particle size of 5 microns.
Heating the obtained powder to 850 ℃ in a nitrogen atmosphere, and calcining for 5 hours to obtain a sintered material;
and coarsely crushing the sintered material by using a pair of rollers, conveying the crushed material to an airflow crusher by using airflow, crushing the crushed material to the granularity of 1.2 mu m, conveying the crushed material to a packaging machine, and carrying out screening, iron removal and packaging treatment to obtain the lithium nickel iron phosphate anode material.
Comparative example 1
In addition to example 5, the amount of titanium nitrate added was 0.02 part.
Comparative example 2
In addition to example 17, the amount of nano alumina added was 0.02 part.
The cycle performance and the rate capability of the lithium iron nickel phosphate cathode material obtained in the above embodiment and the comparative example were respectively tested, and the specific results are as follows:
Figure BDA0003528086530000281
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Figure BDA0003528086530000291
it can be seen that the method can directly recycle nickel-iron elements from waste nickel-iron alloy to prepare the lithium iron nickel phosphate cathode material, and the obtained cathode material has certain cycle performance, good electrical performance and certain stability, and the comparison of examples 4 and 5 with examples 1, 2 and 3 shows that the multiplying power of the obtained cathode material is improved to a certain extent by adopting the combined coating of organic carbon and inorganic carbon, and has certain reinforcing effect on cycle performance.
Compared with the embodiments before and after doping, the obtained anode material not only keeps excellent cycle performance after other metal elements are doped in the extracting solution, but also improves the rate capability of the battery to a certain extent, and after the doping treatment of titanium, neodymium, titanium and praseodymium is adopted, the electrical performance of the obtained anode material is relatively obviously optimized, the cycle performance is improved, and the rate capability is relatively improved.
The application also carries out nano metal oxide doping treatment in the coating process, particularly, after the surface phase doping treatment, the cycle performance of the anode material is also obviously improved, and as can be seen from the data of the embodiments 19 to 29, after the mixed doping treatment of zirconium oxide and samarium oxide is adopted, the cycle performance of the anode material is improved to a certain extent, and meanwhile, the rate performance of the anode material is also improved to a certain extent, and compared with the conventional single nano metal oxide surface phase doping, the rate performance effect is improved by 10 to 20 percent.
According to comparative examples 1 and 2, it can be seen that, when the doping element is excessive, the performance of the obtained cathode material is greatly reduced, and it is considered that the excessive doping element may affect the cell structure in the cathode material, thereby affecting the original performance of the cathode material.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the scope of the present invention, which is intended to cover any modifications, equivalents, improvements, etc. within the spirit and scope of the present invention.

Claims (8)

1. A method for preparing high-value materials by recycling waste ferronickel alloys is characterized by comprising the following steps:
s1, mixing waste nickel-iron alloy with water, adding acid, adjusting the pH value to 0-4, heating to 20-80 ℃, keeping the temperature, reacting for 1-5 hours, and filtering to obtain a first filtrate and a first filter residue after complete reaction;
s2, adding soluble lithium salt into the first filtrate, heating to 20-80 ℃, and keeping the temperature and stirring to obtain a first solution;
s3, adding phosphate solution into the first solution until the supernatant of the solution is white, stopping adding the phosphate solution, keeping the temperature of 20-80 ℃, stirring for 1-4 hours, and filtering to obtain a second filtrate and a second filter residue;
s4, mixing the second filter residue and a carbon source, sanding, and spray drying after sanding to obtain powder;
s5, calcining the powder in a nitrogen atmosphere to obtain a sintered material;
s6, crushing, screening, deironing and packaging the sintered material to obtain a lithium nickel iron phosphate anode material;
in the step S1, the acid is one or a combination of more of sulfuric acid, nitric acid and hydrochloric acid; in step S2, the soluble lithium salt is one of lithium sulfate, lithium nitrate and lithium chloride, wherein the stoichiometric ratio of the lithium element to the sum of the nickel and iron elements in the first filtrate is (1.02-1.1): 1.
2. the method for preparing high-value materials by recycling waste ferronickel alloy according to claim 1, wherein in the step S1, the mass ratio of the waste ferronickel alloy to water is 1: (1-5).
3. The method for preparing high-value materials by recycling waste ferronickel alloys according to claim 1, wherein in step S2, before heating, a first additive is added, wherein the first additive is one or more soluble salts of titanium, magnesium, aluminum, zirconium and rare earth metal materials.
4. The method for preparing high-value materials by recycling waste ferronickel alloy according to claim 1, wherein in step S3, the phosphate is solubleHPO 4 2- Salt (I)、H 2 PO 4 - Salt (salt)AndPO 4 3- salt (I)The cation of the phosphate is one or more of ammonium ion, sodium ion and potassium ion.
5. The method for preparing high-value materials by recycling waste ferronickel alloys according to claim 1, wherein step S4 further comprises adding a second additive to the waste ferronickel alloys, mixing the second additive with the waste ferronickel alloys, and then performing sand grinding, wherein the second additive is one or more of nano aluminum oxide, nano titanium oxide, nano zirconium oxide, nano magnesium oxide, nano tungsten oxide, boric acid and nano rare earth oxide.
6. The method for preparing high-value materials by recycling waste ferronickel alloys according to claim 5, wherein in the step S4, the second additive is added in an amount of 0.01-1% by weight of the powder.
7. The method for preparing high-value materials by recycling waste ferronickel alloys according to claim 1, wherein in the step S4, the carbon source accounts for 0.5-3% of the final lithium iron nickel phosphate cathode material by mass.
8. The method for preparing high-value materials by recycling waste ferronickel alloys according to claim 1, wherein in the step S5, the calcining temperature is 650-850 ℃ and the calcining time is 5-20h.
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