CN109231181A - Processing method, ternary precursor, battery-grade iron phosphate and the lithium ion battery of iron vitriol dreg of yellow sodium - Google Patents

Processing method, ternary precursor, battery-grade iron phosphate and the lithium ion battery of iron vitriol dreg of yellow sodium Download PDF

Info

Publication number
CN109231181A
CN109231181A CN201811419087.0A CN201811419087A CN109231181A CN 109231181 A CN109231181 A CN 109231181A CN 201811419087 A CN201811419087 A CN 201811419087A CN 109231181 A CN109231181 A CN 109231181A
Authority
CN
China
Prior art keywords
manganese
iron
sodium
cobalt
vitriol dreg
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201811419087.0A
Other languages
Chinese (zh)
Other versions
CN109231181B (en
Inventor
陈耀
吴理觉
文定强
郭欢
高琦
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangdong Jiana Energy Technology Co Ltd
Original Assignee
Guangdong Jiana Energy Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Guangdong Jiana Energy Technology Co Ltd filed Critical Guangdong Jiana Energy Technology Co Ltd
Priority to CN201811419087.0A priority Critical patent/CN109231181B/en
Publication of CN109231181A publication Critical patent/CN109231181A/en
Application granted granted Critical
Publication of CN109231181B publication Critical patent/CN109231181B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/37—Phosphates of heavy metals
    • C01B25/375—Phosphates of heavy metals of iron
    • 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
    • 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
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention provides a kind of processing method of iron vitriol dreg of yellow sodium, ternary precursor, battery-grade iron phosphate and lithium ion batteries, are related to iron vitriol dreg of yellow sodium processing technology field.Leachate and leached mud is made after being first ultrasonically treated the iron vitriol dreg of yellow sodium of crushing in the processing method, it is different according to the type of contained valuable metal and content, by leachate, by manganese and manganous fluoride, the scavenging solution of nickeliferous, cobalt and manganese is made in purified treatment twice, the raw material that the scavenging solution of nickeliferous, cobalt and manganese can be used as many kinds of substance is widely used in each field, the scavenging solution of preferably nickeliferous, cobalt and manganese as ternary precursor reaction raw materials to be applied to field of lithium ion battery；The processing method of the iron vitriol dreg of yellow sodium can sufficiently be recycled the valuable metal in leachate, and process flow is simple, and easily operated, production cost is low, be suitable for industrial volume production.The present invention also provides a kind of ternary precursor, battery-grade iron phosphate or lithium ion batteries.

Description

Processing method, ternary precursor, battery-grade iron phosphate and the lithium ion of iron vitriol dreg of yellow sodium Battery
Technical field
The present invention relates to iron vitriol dreg of yellow sodium processing technology field, in particular to iron vitriol dreg of yellow sodium processing method, three First presoma, battery-grade iron phosphate and lithium ion battery.
Background technique
In the hydrometallurgy of cobalt nickel, iron is the impurity for needing to remove, and it is good that generation strainability is widely used at present Sodium jarosite deferrization process.It is heavy using the iron hydroxide for having part in this technique iron removal but when iron content is higher It forms sediment and generates, this precipitating has the adsorption property of colloid, is easy to generate suction-operated to the metal ion in solution.Therefore, cobalt Containing non-ferrous metals such as a certain amount of cobalt, nickel, copper, manganese, lead in the iron vitriol dreg of yellow sodium that nickel hydrometallurgy is generated except iron, to cause The loss of non-ferrous metal.In addition, after a large amount of iron vitriol dreg of yellow sodium is stacked for a long time, not only land occupation and waste of resource, Er Qieqi In heavy metal chemical change can occur under field conditions (factors), serious pollution is caused to environment.For these problems, yellow sodium iron The recycling development and utilization of alum slag is concerned.
Currently, main for the processing of iron vitriol dreg of yellow sodium, there are two directions: one, using iron vitriol dreg of yellow sodium as construction material The construction materials such as brick are made by adding other raw materials in raw material；Two, therein have by the techniques such as roasting, being electrolysed and be separately recovered Valence metal, or prepare the products such as various metal salts or oxide.The above method can handle and utilize to a certain extent yellow sodium Iron vitriol slag solves the problems, such as that slag muck is deposited and brings, but related process flow is complex, high production cost, and cannot be right Various composition in iron vitriol dreg of yellow sodium is efficiently used.
In view of this, the present invention is specifically proposed at least one of to solve the above technical problems.
Summary of the invention
The first purpose of this invention is to provide a kind of processing method of iron vitriol dreg of yellow sodium, can surpass iron vitriol dreg of yellow sodium warp The valuable metal in leachate obtained after sonication is recycled, and product obtained is made to can be applied to multiple fields, Reduce environmental pollution caused by iron vitriol dreg of yellow sodium accumulation.
Second object of the present invention is to provide a kind of ternary precursor, using the processing method of above-mentioned iron vitriol dreg of yellow sodium It is made.
Third object of the present invention is to provide a kind of battery-grade iron phosphate, using the processing side of above-mentioned iron vitriol dreg of yellow sodium Method is made.
Fourth object of the present invention is to provide a kind of lithium ion battery, using above-mentioned ternary precursor or LITHIUM BATTERY phosphorus Sour iron is made.
Of the invention the 5th be designed to provide a kind of electronic device comprising above-mentioned lithium ion battery, electric tool, Electric vehicle or power storage system.
In order to realize above-mentioned purpose of the invention, the following technical scheme is adopted:
The present invention provides a kind of processing methods of iron vitriol dreg of yellow sodium, comprising the following steps:
The iron vitriol dreg of yellow sodium of crushing is added to the water and is ultrasonically treated, leachate and leached mud are obtained；
Successively leachate is purified using manganese simple substance and manganous fluoride, obtains the scavenging solution of nickeliferous, cobalt and manganese；
Optionally, nickel source, cobalt source and manganese source are added into the scavenging solution of nickeliferous, cobalt and manganese, and it is made be co-precipitated instead It answers, obtains ternary precursor.
Further, on the basis of technical solution of the present invention, crude ferric sulfate that leached mud is obtained through Ore Leaching Solution is restored using reducing agent, obtains crude ferrous sulfate solution；
Crude ferrous sulfate solution is purified using fluoride, is purified ferrous sulfate solution；
Purification ferrous sulfate solution is aoxidized, ferrum sulfuricum oxydatum solutum is obtained；
Optionally, phosphate is added into ferrum sulfuricum oxydatum solutum, and it is made to carry out reactive crystallization, the sediment of generation is forged It burns, obtains battery-grade iron phosphate.
Further, on the basis of technical solution of the present invention, manganese simple substance powder is used to purify to remove leachate The copper ion in leachate is removed, primary purification liquid is obtained, wherein the additional amount of manganese simple substance powder is that copper ion mole contains in leachate 1.1~1.3 times of amount；
Preferably, manganous fluoride is used to purify primary purification liquid with remove calcium ion in primary purification liquid and magnesium from Son obtains the scavenging solution of nickeliferous, cobalt and manganese, wherein the additional amount of manganous fluoride is the calcium and magnesium ion total moles in primary purification liquid 1.1~1.4 times of content.
Further, on the basis of technical solution of the present invention, in the scavenging solution of nickeliferous, cobalt and manganese be added nickel source, Cobalt source and manganese source keep nickel salt, cobalt salt and manganese salt in the mixed solution of the scavenging solution of nickel source, cobalt source, manganese source and nickeliferous, cobalt and manganese dense Degree summation is 1~2.5mol/L；
Preferably, the coprecipitation reaction carries out in an inert atmosphere；
Preferably, the coprecipitation reaction carries out under alkaline condition；
Preferably, the mixed solution pH of the scavenging solution of nickel source, cobalt source, manganese source and nickeliferous, cobalt and manganese is 10.5~12, ammonium root Concentration is 0.2~0.5mol/L.
Further, on the basis of technical solution of the present invention, leached mud is leached using sulfuric acid, leached mud and The solid-liquid mass ratio of sulfuric acid is 1:4~6, preferably 1:4.5~6；
Preferably, leaching process and adjoint stirring, mixing speed are 250~350r/min, 1~3h of extraction time；
Preferably, reducing agent includes any one in iron powder, hydrogen sulfide or vulcanized sodium；
Preferably, reducing agent is iron powder, and the additional amount of iron powder is iron ion theoretical reduction dosage in crude ferrum sulfuricum oxydatum solutum 1.05~1.2 times；
Preferably, fluoride includes sodium fluoride or potassium fluoride, preferably sodium fluoride；
Preferably, fluoride additional amount is 1.2~1.35 times of calcium ion theoretical amount in crude ferrous sulfate solution；
Preferably, fluoride is sodium fluoride, pH value of solution when sodium fluoride purifies crude ferrous sulfate solution be 5~ 6.5, purification temperature is 40~60 DEG C, and the clarification time is 2~3h；
Preferably, oxidant includes any one in sodium chlorate, sodium peroxydisulfate or hydrogen peroxide；
Preferably, the additional amount of oxidant be purify ferrous sulfate solution ferrous ions theoretical oxidation dosage 1.05~ 1.2 again；
Preferably, oxidization time is 0.5~1h；
Preferably, phosphate include in sodium phosphate, potassium phosphate, ammonium dihydrogen phosphate or ammonium phosphate any one or at least Two kinds of combination；
Preferably, phosphatic feed time is 0.5~1h, and reactive crystallization temperature is 60~80 DEG C；
Preferably, calcination temperature is 500~600 DEG C, and calcination time is 2~3h.
Further, on the basis of technical solution of the present invention, iron vitriol dreg of yellow sodium includes the chemistry of following mass fraction Ingredient: Fe:20~26%, Na:4~7%, Si:4~8%, Ni:2~4%, Co:0.5~1%, Mn:0.3~0.8%, Cu:1 ~3%, Ca:0.1~0.3%, Mg:0.2~0.4% and other metallic elements < 0.1%；
Preferably, the partial size of the iron vitriol dreg of yellow sodium of crushing is less than 75 μm；
Preferably, compressed air is passed through while ultrasonic treatment；
Preferably, the flow of compressed air is 0.5~2m3/h；
It preferably, further include adding iron vitriol dreg of yellow sodium water to size mixing then to be freeze-dried before crushing iron vitriol dreg of yellow sodium The step of；
Preferably, during adding water to size mixing, the mass ratio of iron vitriol dreg of yellow sodium and water is 1:0.3~0.8；
Preferably, the temperature of freeze-drying is -10~-30 DEG C, and the pressure of freeze-drying is 1.5~15Pa.
The present invention also provides a kind of ternary precursors, are made using the processing method of above-mentioned iron vitriol dreg of yellow sodium.
The present invention also provides a kind of battery-grade iron phosphates, are made using the processing method of above-mentioned iron vitriol dreg of yellow sodium.
The present invention also provides a kind of lithium ion batteries, are made of above-mentioned ternary precursor or battery-grade iron phosphate.
The present invention also provides the electronic device comprising above-mentioned lithium ion battery, electric tool, electric vehicle or electric power to deposit Storage system.
Compared with prior art, the processing method of iron vitriol dreg of yellow sodium provided by the invention, ternary precursor, LITHIUM BATTERY phosphoric acid Iron and lithium ion battery have the advantage that
(1) the present invention provides a kind of processing methods of iron vitriol dreg of yellow sodium, first surpass the iron vitriol dreg of yellow sodium of crushing Leachate and leached mud are made after sonication, it is different according to the type of contained valuable metal and content, leachate is passed through into manganese Purified treatment is made the scavenging solution of nickeliferous, cobalt and manganese twice with manganous fluoride, and the scavenging solution of the nickeliferous, cobalt and manganese can be used as a variety of objects The raw material of matter is widely used in each field, the scavenging solution of preferably nickeliferous, cobalt and manganese as ternary precursor reaction raw materials from And it is applied to field of lithium ion battery；The processing method of the iron vitriol dreg of yellow sodium can carry out the valuable metal in leachate abundant It recycles, process flow is simple, and easily operated, production cost is low, is suitable for industrial volume production.
The typical way of the processing method of present invention offer iron vitriol dreg of yellow sodium is not only can be by the valuable gold in leachate Category is recycled, and the iron in leached mud can also be made to useful chemical products, can both reduce iron vitriol dreg of yellow sodium in this way Environmental pollution caused by accumulation, moreover it is possible to which economic benefit is brought to enterprise by addition product.
(2) the present invention provides a kind of ternary precursors, are made by the processing method of above-mentioned iron vitriol dreg of yellow sodium.The ternary Presoma also has lower production cost, is suitable for industrialized production while with good product characteristic.
(3) the present invention provides a kind of battery-grade iron phosphates, are made by the processing method of above-mentioned iron vitriol dreg of yellow sodium.The electricity Pond grade ferric phosphate also has good product characteristic, realizes the low cost production of battery-grade iron phosphate.
(4) the present invention provides a kind of lithium ion batteries, are made of above-mentioned ternary precursor or battery-grade iron phosphate.Mirror The advantage possessed by above-mentioned ternary precursor or battery-grade iron phosphate, so that the lithium ion battery is with good electrochemistry Also there is lower production cost while energy.
(5) the present invention provides the electronic device comprising above-mentioned lithium ion battery, electric tool, electric vehicle or electric power to deposit Storage system.In view of advantage possessed by above-mentioned lithium ion battery, in the electronic device comprising above-mentioned lithium ion battery, electronic work Identical effect can also be obtained in tool, electric vehicle and electric power storage system.
Detailed description of the invention
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor It puts, is also possible to obtain other drawings based on these drawings.
Fig. 1 is the process flow diagram of the processing method for the iron vitriol dreg of yellow sodium that one embodiment of the present invention provides.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is The conventional products that can be obtained by commercially available purchase.
It should be understood that in the present invention, if without particularly illustrating, all embodiments mentioned in this article and Preferred implementation method can be combined with each other to form new technical solution.
In the present invention, if without particularly illustrating, all technical characteristics and preferred feature mentioned in this article can be with Intercombination forms new technical solution.
In the present invention, if percentage (%) or part refer to the weight relative to composition without particularly illustrating Percentage or parts by weight.
In the present invention, if related each component or its preferred ingredient can be combined with each other shape without particularly illustrating The technical solution of Cheng Xin.
In the present invention, unless otherwise indicated, numberical range " a~b " indicates the contracting of any real combinings between a to b Sketch form shows that wherein a and b is real number.Such as numberical range " 6~22 " indicate herein all listed " 6~22 " it Between whole real numbers, " 6~22 " be these combinations of values breviary indicate.
" range " disclosed in this invention can be respectively one or more lower limits and one in the form of lower and upper limit A or multiple upper limits.
In the present invention, unless otherwise indicated, it is each reaction or operating procedure can sequentially carry out, can also in sequence into Row.Preferably, reaction method herein is that sequence carries out.
Unless otherwise indicated, profession used herein and meaning phase known to scientific term and one skilled in the art Together.In addition, any method similar to or equal to what is recorded or material can also be applied in the present invention.
According to an aspect of the invention, there is provided the processing method of iron vitriol dreg of yellow sodium, comprising the following steps:
The iron vitriol dreg of yellow sodium of crushing is added to the water and is ultrasonically treated, leachate and leached mud are obtained；
Successively leachate is purified using manganese simple substance and manganous fluoride, obtains the scavenging solution of nickeliferous, cobalt and manganese；
Optionally, nickel source, cobalt source and manganese source are added into the scavenging solution of nickeliferous, cobalt and manganese, and it is made be co-precipitated instead It answers, obtains ternary precursor.
Specifically, containing soluble-salts such as cobalt salt, nickel salt, manganese salt, mantoquita or magnesium salts in iron vitriol dreg of yellow sodium, by sodium jarosite It is added to the water and is ultrasonically treated after ground-slag is broken, soluble-salt can be made to be dissolved in the water, to realize part valuable metal Separation.It for the mode of crushing, is not especially limited herein, can be grinding.
Nickel, cobalt, manganese, copper, calcium, magnesium plasma are mainly contained after sonicated, in leachate, are mainly contained in leached mud Iron, calcium, silicon plasma.It is different according to species of metal ion specific in leachate and content, after being carried out accordingly to leachate Processing.
Due to be added first into leachate using nickel, cobalt and the manganese Metal ion in leachate in subsequent processing Enter manganese simple substance, the purpose is to not introduce new impurity again while replacing copper, obtains blister copper and primary purification liquid；So After continue to carry out removal of impurities processing to primary purification liquid, i.e., manganous fluoride is added into primary purification liquid, the purpose is to by calcium, magnesium from Son cements out while not introducing new impurity again, obtains the purification of calcirm-fluoride, magnesium fluoride solid impurity and nickeliferous, cobalt and manganese Liquid.The scavenging solution of obtained nickeliferous, cobalt and manganese is the sulfate liquor of nickel, cobalt and manganese, other metal ion contents are less than 0.001%.
In carrying out removal of impurities treatment process twice to leachate, using manganese simple substance, manganous fluoride as precipitating reagent, it is not introduced His foreign ion, and manganese ion can be used as one of the raw material of next step synthetic material.
It should be noted that heretofore described the step of " optionally " referring to optionally later, can carry out, it can also not It carries out.Needle for the purpose of the present invention, refers to that the processing method of iron vitriol dreg of yellow sodium can handle to obtain the scavenging solution of nickeliferous, cobalt and manganese, The scavenging solution of nickeliferous, cobalt and manganese can be further processed, ternary precursor is prepared.
In other words, the scavenging solution of the nickeliferous, cobalt and manganese that obtain can be used as independent product and sell, and can also be used as a variety of The reaction raw materials of product.For example, the scavenging solution of nickel source, cobalt source, manganese source and nickeliferous, cobalt and manganese can be mixed, be co-precipitated anti- It answers, ternary precursor is prepared.
Ternary precursor is nickel cobalt manganese hydroxide, chemical formula NixCoyMnz(OH)2, exactly with nickel source, cobalt source and Manganese source is raw material, and the ratio (x:y:z) of nickel, cobalt and manganese then adjusts according to actual needs.Using the processing method of iron vitriol dreg of yellow sodium The main metal ions such as nickeliferous, cobalt and manganese of the scavenging solution of nickeliferous, cobalt and manganese obtained, therefore can be as the original of ternary precursor Material.Due to the possible lower or nickel of the content of nickel, cobalt and manganese Metal ion in the scavenging solution of nickeliferous, cobalt and manganese, cobalt and three kinds of manganese Proportion between metal ion may not meet the requirement of x, y, z in ternary precursor, therefore need to add a certain amount of nickel source, cobalt Source, manganese source are mixed with the scavenging solution of nickeliferous, cobalt and manganese, then carry out coprecipitation reaction, and ternary precursor is prepared.
Reaction raw materials using the scavenging solution of nickeliferous, cobalt and manganese as ternary precursor, so that being recycled in iron vitriol dreg of yellow sodium Valuable metal be utilized effectively, simultaneously because other metal ion contents are very low in the scavenging solution of nickeliferous, cobalt and manganese, therefore not Coprecipitation process and the ternary precursor of generation can be adversely affected.
The processing method of iron vitriol dreg of yellow sodium provided by the invention, after being first ultrasonically treated the iron vitriol dreg of yellow sodium of crushing Leachate and leached mud is made, it is different according to the type of contained valuable metal and content, leachate is passed through into manganese and manganous fluoride The scavenging solution of nickeliferous, cobalt and manganese is made in purified treatment twice.The raw material that the scavenging solution of nickeliferous, cobalt and manganese can be used as many kinds of substance is wide It is general to be applied to each field, preferably field of lithium ion battery, it can be using the scavenging solution of nickeliferous, cobalt and manganese as the anti-of ternary precursor Answer raw material.The processing method of the iron vitriol dreg of yellow sodium can sufficiently be recycled the valuable metal in leachate, technique Process is simple, easily operated, and production cost is low, is suitable for industrial volume production.
Explanation is needed further exist for, valuable metal contained by the iron vitriol dreg of yellow sodium of different manufacturers and impurity component may not Together, therefore to it treatment process carried out may be also different, need to use corresponding treatment process according to the ingredient of iron vitriol dreg of yellow sodium.
As a kind of optional embodiment of the invention, iron vitriol dreg of yellow sodium includes the chemical component of following mass fraction: Fe: 20~26%, Na:4~7%, Si:4~8%, Ni:2~4%, Co:0.5~1%, Mn:0.3~0.8%, Cu:1~3%, Ca:0.1~0.3%, Mg:0.2~0.4% and other metallic elements < 0.1%.
Iron vitriol dreg of yellow sodium is the complicated salt of sulfate, oxide or hydroxide, and wherein metal part is containing there are many chemistry Ingredient.Wherein, the typical but non-limiting mass fraction of Fe is 20%, 22%, 24%, 25% or 26%；Na typical case but non-limit The mass fraction of property processed is 4%, 5%, 6% or 7%；The typical but non-limiting mass fraction of Si is 4%, 5%, 6%, 7% Or 8%；The typical but non-limiting mass fraction of Ni is 2%, 3% or 4%；The typical but non-limiting mass fraction of Co is 0.5%, 0.6%, 0.7%, 0.8%, 0.9% or 1%；The typical but non-limiting mass fraction of Mn be 0.3%, 0.4%, 0.5%, 0.6%, 0.7% or 0.8%；The typical but non-limiting mass fraction of Cu is 1%, 2% or 3%；Ca is typical but non- Restrictive mass fraction is 0.1%, 0.2% or 0.3%；The typical but non-limiting mass fraction of Mg is 0.2%, 0.3% Or 0.4%；Other metallic elements refer to other metallic elements in addition to above-mentioned Fe, Na, Si, Ni, Co, Mn, Cu, Ca and Mg, The mass fraction of such as Al, K, As etc., other metallic elements is lower, and generally less than 0.1%.
Using the processing method of iron vitriol dreg of yellow sodium provided by the invention for the yellow sodium iron with above-mentioned chemical composition content Alum slag has good effect.
Since the particle of iron vitriol dreg of yellow sodium is larger, the dissolution that ultrasonic treatment is unfavorable for solable matter is directly carried out, Therefore it needs to crush it.Crushing can use lapping mode commonly used in the art.As a kind of optional implementation of the invention Mode crushes iron vitriol dreg of yellow sodium using ball milling.
The size and quantity of ball-milling medium in mechanical milling process are not especially limited.For example, the ruler of ball-milling medium Very little is tetra- kinds of sizes of 20mm, 10mm, 5mm and 2mm, and every kind of size accounts for 1/4.Ball-milling medium can be selected from Ceramic Balls, stainless steel ball Or any one in sintered carbide ball.
For iron vitriol dreg of yellow sodium after pulverization process, granularity is smaller.As a kind of optional embodiment of the invention, crushing The partial size of iron vitriol dreg of yellow sodium is less than 75 μm；
Iron vitriol dreg of yellow sodium is ground into molecule, the leaching velocity of soluble-salt in iron vitriol dreg of yellow sodium can be promoted, is shortened Sonication treatment time.
It further include by sodium jarosite before crushing iron vitriol dreg of yellow sodium as a kind of optional embodiment of the invention The step of slag adds water to size mixing and then be freeze-dried；
Preferably, during adding water to size mixing, the mass ratio of iron vitriol dreg of yellow sodium and water is 1:0.3~0.8, preferably 1:0.4 ~0.7；
Preferably, the temperature of freeze-drying is -10~-30 DEG C, and the pressure of freeze-drying is 1.5~15Pa.
Iron vitriol dreg of yellow sodium and water are sized mixing and are tuned into paste, is then freeze-dried again.Freeze-drying is conducive to promote Huang Natrojarosite is loose porous, and the soluble-salt of inside absorption is exposed, and then facilitates solvable in subsequent ultrasonic treatment process The abundant leaching of property salt.
When iron vitriol dreg of yellow sodium is sized mixing with water, the mass ratio of iron vitriol dreg of yellow sodium and water is typical but non-limiting to be, for example, 1:0.3,1:0.4,1:0.5,1:0.6,1:0.7 or 1:0.8.
After iron vitriol dreg of yellow sodium and water sized mixing forming paste, quick freeze ice under conditions of -10~-30 DEG C, so So that ice is distilled under conditions of 1.5~15Pa again afterwards, achievees the purpose that dry.The temperature of typical but non-limiting freeze-drying It is -10 DEG C, -15 DEG C, -20 DEG C, -25 DEG C or -30 DEG C；The pressure of typical but non-limiting freeze-drying be 1.5Pa, 2Pa, 4Pa, 5Pa, 6Pa, 8Pa, 10Pa, 12Pa, 14Pa or 15Pa.
By to add water size mixing and freezing dry process in technological parameter restriction so that iron vitriol dreg of yellow sodium be more likely formed it is thin The porous structure of pine, is conducive to the leaching of soluble-salt.
As a kind of optional embodiment of the invention, while ultrasonic treatment and it is passed through compressed air；Preferably, it compresses The flow of air is 0.5~2m3/h；
Being passed through compressed air, mainly there are two purposes: first is that playing stirring action；Second is that promoting ultrasonic cavitation.It is typical but The flow of unrestricted compressed air is 0.5m3/h、0.6m3/h、0.8m3/h、1.0m3/h、1.2m3/h、1.4m3/h、 1.5m3/h、1.6m3/h、1.8m3/ h or 2.0m3/h.By controlling the flow of compressed air, so as to the ultrasonic cavitation journey of solution Degree reaches suitable level.
As a kind of optional embodiment of the invention, manganese simple substance powder is used to purify to remove leachate leachate In copper ion, obtain primary purification liquid, wherein the additional amount of manganese simple substance powder be leachate in copper ion molar content 1.1 ~1.3 times；
Displacement removal of impurities is carried out to the copper ion in leachate using manganese simple substance powder, is not drawn again while to purification of leaching liquor Enter new impurity.Stoichiometric ratio is followed between copper ion molar content in the additional amount and leachate of manganese simple substance powder.To make Copper ion is sufficiently removed in leachate, and the additional amount of manganese simple substance powder can be slightly higher than the theoretical amount of manganese simple substance powder, typical but non- The additional amount of restrictive manganese simple substance powder is that the multiple of copper ion molar content in leachate is, for example, 1.1 times, 1.2 times or 1.3 Times.
As a kind of optional embodiment of the invention, manganous fluoride is used to purify primary purification liquid primary to remove Calcium ion and magnesium ion in scavenging solution, obtain the scavenging solution of nickeliferous, cobalt and manganese, wherein the additional amount of manganous fluoride is primary net 1.1~1.4 times for changing the calcium ion in liquid and magnesium ion total moles content.Typical but non-limiting manganous fluoride additional amount is one The multiple of calcium and magnesium ion total moles content in secondary scavenging solution is, for example, 1.1 times, 1.2 times, 1.3 times or 1.4 times.
By being defined respectively to manganese simple substance powder and manganous fluoride dosage, make it possible to leachate and primary purification liquid In metal ion to be cleaned realize good impurity-eliminating effect.
As a kind of optional embodiment of the invention, to addition nickel source, cobalt source and manganese in the scavenging solution of nickeliferous, cobalt and manganese Source makes nickel salt in the mixed solution of the scavenging solution of nickel source, cobalt source, manganese source and nickeliferous, cobalt and manganese, cobalt salt and manganese salt concentration summation 1~2.5mol/L；
The additional amount of nickel source, cobalt source and manganese source is needed according to nickel, cobalt and manganese ion content in the scavenging solution of nickeliferous, cobalt and manganese And nickel, cobalt, manganese three proportion are adjusted in ternary precursor.
Nickel salt, cobalt salt and manganese salt concentration summation refer to that the scavenging solution of nickel source, cobalt source, manganese source and nickeliferous, cobalt and manganese is formed Mixed solution in nickel salt, cobalt salt and manganese salt concentration summation.Illustrative nickel salt, cobalt salt and manganese salt concentration summation be 1mol/L, 1.5mol/L, 2.0mol/L or 2.5mol/L.It should be noted that the nickel source being added, cobalt source and manganese source are art technology The common substance classes of personnel, are not construed as limiting herein.
As a kind of optional embodiment of the present invention, coprecipitation reaction carries out in an inert atmosphere, preferably nitrogen atmosphere Middle progress.
As a kind of optional embodiment of the present invention, coprecipitation reaction carries out under alkaline condition；Preferably, nickel source, cobalt The mixed solution pH of the scavenging solution of source, manganese source and nickeliferous, cobalt and manganese is 10.5~12, and ammonium root concentration is 0.2~0.5mol/L.Allusion quotation Type but unrestricted mixed solution pH are 10.5,11,11.5 or 12, and typical but non-limiting ammonium root concentration is 0.2mol/ L, 0.3mol/L, 0.4mol/L or 0.5mol/L.
By to nickel salt, cobalt salt and manganese salt concentration summation, protective atmosphere and mixing in mixed solution in coprecipitation process The restriction of pH value of solution and ammonium root concentration so that nickel salt, cobalt salt and manganese salt can realize uniform co-precipitation under the above conditions, and precipitates Object narrow particle size distribution, tap density are high.
In addition to being recycled to the valuable metal in leachate, recycling benefit can also be carried out to the substance in leached mud With.As a kind of preferred embodiment of the invention, the crude ferrum sulfuricum oxydatum solutum that leached mud is obtained through Ore Leaching is using reduction Agent reduction, obtains crude ferrous sulfate solution；
Crude ferrous sulfate solution is purified using fluoride, is purified ferrous sulfate solution；
Purification ferrous sulfate solution is aoxidized, ferrum sulfuricum oxydatum solutum is obtained；
Optionally, phosphate is added into ferrum sulfuricum oxydatum solutum, and it is made to carry out reactive crystallization, the sediment of generation is forged It burns, obtains battery-grade iron phosphate.
When handling leached mud, the iron in leached mud is mainly made to the form of ferric sulfate using acid, then adopted Crude ferrum sulfuricum oxydatum solutum is reduced into crude ferrous sulfate solution with reducing agent.It is few due to also containing in crude ferrous sulfate solution Calcium ion is measured, therefore fluoride is added thereto, calcium ion is cleaned in the form of calcirm-fluoride, to be purified sulfuric acid Asia Ferrous solution.In order to convert iron ion for the ferrous ion purified in ferrous sulfate solution, therefore oxidant is added to purification sulfuric acid Ferrous iron solution is aoxidized, and ferrum sulfuricum oxydatum solutum is obtained.
It should be noted that when the classification to reducing agent selects, in addition to consider can efficiently by ferric iron also Except original is at ferrous iron, it is also necessary to consider not introduce the precipitating of other possibilities, excessive influence cannot be generated on whole system. It is that fluoride should be soluble in water and the fluoride of side reaction does not occur in addition, according to needs are specifically used.
The leached mud obtained using the processing method of iron vitriol dreg of yellow sodium provided by the invention, using acidleach, reduction, net Ferrum sulfuricum oxydatum solutum is made in change, oxidation, and obtained ferrum sulfuricum oxydatum solutum can be used as independent product and sell, and can also be used as multiple product Reaction raw materials.Ferric phosphate is generated for example, can react under certain condition ferrum sulfuricum oxydatum solutum with phosphate, ferric phosphate can be used as Prepare the good raw material of lithium ion battery anode material lithium iron phosphate.
The preparation method of battery-grade iron phosphate has very much, and it is normal for directly reacting generation ferric phosphate with ferric sulfate using phosphate A kind of method seen.And impurity content is lower in ferrum sulfuricum oxydatum solutum made from the processing method of use iron vitriol dreg of yellow sodium, therefore can incite somebody to action It is as the raw material for preparing battery-grade iron phosphate.
Reaction raw materials of the ferrum sulfuricum oxydatum solutum made from processing method using iron vitriol dreg of yellow sodium as ferric phosphate, so that yellow sodium Iron in iron vitriol slag is utilized effectively, simultaneously because other metal ion contents are very low in ferrum sulfuricum oxydatum solutum, therefore will not be to life At battery-grade iron phosphate adversely affect.
Similar with the processing mode of leachate, leached mud is also required to carry out purification and impurity removal processing.As one kind of the invention Optional embodiment leaches leached mud using sulfuric acid, and the solid-liquid mass ratio of leached mud and sulfuric acid is 1:4~6, preferably The solid-liquid mass ratio of 1:4.5~6, typical but non-limiting leached mud and sulfuric acid is 1:4,1:4.5,1:5 or 1:6.
As a kind of optional embodiment of the invention, leaching process and with stirring, mixing speed is 250~350r/ Min, 1~3h of extraction time；
Typical but non-limiting mixing speed is 250r/min, 260r/min, 270r/min, 280r/ in leaching process Min, 290r/min, 300r/min, 320r/min, 340r/min or 350r/min, typical but non-limiting extraction time are 1h, 2h or 3h.
By the restriction to specific process parameter in leaching process, so that the iron in leached mud to the greatest extent may be used in the form of ferric sulfate It can sufficiently be leached, to improve the leaching rate of iron in leaching process.
As a kind of optional embodiment of the invention, reducing agent includes any one in iron powder, hydrogen sulfide or vulcanized sodium Kind, preferably iron powder.
Iron ion molar content can follow stoichiometric ratio in the dosage of iron powder and crude ferrum sulfuricum oxydatum solutum, crude to make Iron ion is reduced sufficiently in ferrum sulfuricum oxydatum solutum, therefore the dosage of iron powder is slightly above iron ion theoretical reduction dosage.As the present invention A kind of optional embodiment, the additional amount of iron powder be iron ion theoretical reduction dosage in crude ferrum sulfuricum oxydatum solutum 1.05~ 1.2 again；The additional amount of typical but non-limiting iron powder is the multiple of iron ion theoretical reduction dosage in crude ferrum sulfuricum oxydatum solutum For example, 1.05 times, 1.1 times, 1.15 times or 1.2 times.
By the restriction to iron powder additional amount, ferric ion in crude ferrum sulfuricum oxydatum solutum is enabled sufficiently to be reduced to divalent Ferrous ion.
As a kind of optional embodiment of the invention, fluoride includes sodium fluoride or potassium fluoride, preferably sodium fluoride.
Stoichiometric ratio relationship is followed between calcium ion in fluoride additional amount and crude ferrous sulfate solution.Sufficiently to go Except the calcium ion in crude ferrous sulfate solution, fluoride additional amount can be slightly higher than calcium ion theoretical amount.As of the invention A kind of optional embodiment, fluoride additional amount are 1.2~1.35 times of calcium ion theoretical amount in crude ferrous sulfate solution； The additional amount of typical but non-limiting fluoride is that the multiple of calcium ion theoretical amount in crude ferrous sulfate solution is, for example, 1.2 times, 1.25 times, 1.3 times or 1.35 times.
As a kind of optional embodiment of the invention, fluoride is sodium fluoride, and sodium fluoride is to crude ferrous sulfate solution PH value of solution when being purified is 5~6.5, and typical but non-limiting pH is 5,5.5,6 or 6.5；
As a kind of optional embodiment of the invention, purification temperature is 40~60 DEG C, and the clarification time is 2~3h；It is typical But unrestricted purification temperature be 40 DEG C, 45 DEG C, 50 DEG C, 55 DEG C or 60 DEG C, the typical but non-limiting clarification time be 2h, 2.5h or 3h.
When by being purified to crude ferrous sulfate solution when the additional amount of sodium fluoride, pH value of solution, purification temperature and purification Between restriction realize from crude ferrous sulfate to purification sulfuric acid so that the impurity such as calcium ion of crude ferrous sulfate can be removed Ferrous conversion.
As a kind of optional embodiment of the invention, oxidant includes appointing in sodium chlorate, sodium peroxydisulfate or hydrogen peroxide It anticipates one kind；
The additional amount and purification ferrous sulfate solution ferrous ions content of oxidant follow stoichiometric ratio relationship.It is preferred that Ground, the additional amount of oxidant are 1.05~1.2 times for purifying ferrous sulfate solution ferrous ions theoretical oxidation dosage；It is typical but The additional amount of unrestricted oxidant is that the multiple of purification ferrous sulfate solution ferrous ions theoretical oxidation dosage is, for example, 1.05 times, 1.1 times, 1.15 times or 1.2 times；
Preferably, oxidization time is 0.5~1h, and typical but non-limiting oxidization time is 0.5h, 0.75h or 1h.
By the restriction of type to oxidant, dosage and oxidization time, so that divalent in purification ferrous sulfate solution Ferrous ion can sufficiently be oxidized to ferric ion.
As a kind of optional embodiment of the invention, phosphate includes sodium phosphate, potassium phosphate, ammonium dihydrogen phosphate or phosphoric acid In ammonium any one or at least two combination；
Preferably, phosphatic feed time is 0.5~1h, and reaction temperature is 60~80 DEG C；Phosphate typical case but non-limit The feed time of property processed is 0.5h, 0.75h or 1h, and typical but non-limiting reaction temperature is 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C Or 80 DEG C.
Preferably, calcination temperature is 500~600 DEG C, and calcination time is 2~3h；Typical but non-limiting calcination temperature Be 500 DEG C, 520 DEG C, 540 DEG C, 550 DEG C, 560 DEG C, 580 DEG C or 600 DEG C, typical but non-limiting calcination time be 2h, 2.5h or 3h.
By the restriction to each technological parameter during battery-grade iron phosphate is prepared, so that obtained phosphoric acid iron product product Matter is higher, meets the needs of battery production.
Furthermore it is possible to by the preparation method and battery-grade iron phosphate of the processing method of iron vitriol dreg of yellow sodium and ternary precursor Preparation method combines.As a kind of optional embodiment of the invention, the processing method of the iron vitriol dreg of yellow sodium includes following step Suddenly, process flow is as shown in Figure 1:
(a) add water to size mixing iron vitriol dreg of yellow sodium to be freeze-dried, be added to the water and be ultrasonically treated after then crushing, Obtain leachate and leached mud；
(b) leachate is cleaned using manganese simple substance powder, obtains primary purification liquid；Primary purification liquid is removed using manganous fluoride It is miscellaneous, obtain the scavenging solution of nickeliferous, cobalt and manganese；
The scavenging solution of nickeliferous, cobalt and manganese is mixed with nickel source, cobalt source, manganese source, so that it is carried out coprecipitation reaction, obtains ternary Presoma；
The crude ferrum sulfuricum oxydatum solutum that leached mud is obtained through sulfuric acid leaching uses iron powder reducing, and it is molten to obtain crude ferrous sulfate Liquid；Crude ferrous sulfate solution is purified using sodium fluoride, is purified ferrous sulfate solution；It is molten to purification ferrous sulfate Oxidant is added in liquid, obtains ferrum sulfuricum oxydatum solutum；
Phosphate progress reactive crystallization is added to ferrum sulfuricum oxydatum solutum, the sediment high-temperature calcination of generation is obtained into LITHIUM BATTERY Ferric phosphate.
The iron vitriol dreg of yellow sodium that the processing method of the iron vitriol dreg of yellow sodium is generated using cobalt nickel fibers as raw material, by freeze-drying, Valuable metal in the methods of ultrasonic treatment, co-precipitation, reactive crystallization effectively recycling iron vitriol dreg of yellow sodium, high-valued preparation is for lithium electricity The ternary precursor and battery-grade iron phosphate of industry.During processing, Freeze Drying Technique is efficiently used, sodium jarosite is promoted It is loose porous, the water soluble salt of inside absorption is exposed；Using ultrasonic cavitation, make the solubility in iron vitriol dreg of yellow sodium Salt completely dissolves in water, and realizes being kept completely separate for water-insoluble (leached mud) and the hydrotrope (leachate), is conducive under raising The purity of one step ternary precursor and ferric phosphate.Leachate is cleaned using manganese simple substance powder and manganous fluoride, and the manganese of introducing can be used as three One of the raw material of first presoma, achievees the purpose that effective use.According to the spy for mainly containing nickel, cobalt and manganese in purified solution Point prepares ternary precursor by coprecipitation.For the acid solution of leached mud, by controlling Fe3+It is reduced to Fe2+, fluoride process Impurity calcium is effectively removed, then again by Fe2+It is oxidized to Fe3+, by control phosphate charging process, prepare unformed phosphoric acid Iron particle then after high-temperature calcination, obtains crystallinity height, the perfect battery-grade iron phosphate of crystal form.
The processing method of the iron vitriol dreg of yellow sodium can reduce environmental pollution caused by iron vitriol dreg of yellow sodium accumulation, while can recycle Ternary precursor is prepared using the valuable metal in leachate, goes back the iron standby LITHIUM BATTERY phosphoric acid in recoverable leached mud Iron, and the quality of the prepared ternary precursor come out and battery-grade iron phosphate can satisfy in lithium ion battery production It is required that.Therefore the processing method of the iron vitriol dreg of yellow sodium can real environment and economic benefit double receipts.
According to the second aspect of the invention, a kind of ternary precursor is additionally provided, using the place of above-mentioned iron vitriol dreg of yellow sodium Reason method is made.
Advantage possessed by processing method in view of above-mentioned iron vitriol dreg of yellow sodium has ternary precursor obtained well While product characteristic, also there is certain economic benefit.
According to the third aspect of the present invention, a kind of battery-grade iron phosphate is additionally provided, using above-mentioned iron vitriol dreg of yellow sodium Processing method is made.
Advantage possessed by processing method in view of above-mentioned iron vitriol dreg of yellow sodium has battery-grade iron phosphate obtained also good Good product characteristic realizes the low cost production of battery-grade iron phosphate.
According to the fourth aspect of the present invention, a kind of lithium ion battery is additionally provided, using above-mentioned ternary precursor or electricity Pond grade ferric phosphate is made.
In view of advantage possessed by above-mentioned ternary precursor or battery-grade iron phosphate, so that the lithium ion battery is with good Also there is lower production cost while good chemical property.
According to the fifth aspect of the present invention, additionally provide the electronic device comprising above-mentioned lithium ion battery, electric tool, Electric vehicle or power storage system.In view of advantage possessed by above-mentioned lithium ion battery, embodiment of the present invention is being used Identical effect can also be obtained in the electronic device of lithium ion battery, electric tool, electric vehicle and electric power storage system.
Electronic device is the electricity for using lithium ion battery to perform various functions (for example, performing music) as the power supply of operation Sub-device.Electric tool is the electric tool for using lithium ion battery to carry out moving parts (for example, drill bit) as driving power.Electricity Motor-car is the electric vehicle run by lithium ion battery as driving power, and be can be other than lithium ion battery It is also equipped with the automobile (including hybrid electric vehicle) of other driving sources.Electric power storage system is to use lithium ion battery as electric power The electric power storage system of storage source.For example, making electric power be stored in the lithium as electric power storage source in household power stocking system In ion battery, and the electric power that consumption is stored in lithium ion battery as needed is to be able to use such as domestic electronic appliances Various devices.
Combined with specific embodiments below and comparative example, the invention will be further described.
Embodiment 1
Present embodiments provide a kind of processing method of iron vitriol dreg of yellow sodium, comprising the following steps:
(a) iron vitriol dreg of yellow sodium is mixed with water with mass ratio for 1:0.4 and is tuned into paste, the quick freeze under the conditions of -15 DEG C Ice, it is then dry under the pressure of 5Pa, ball-milling medium then is done with the Ceramic Balls of diameter 20mm, 10mm, 5mm and 2mm, often The ball of kind diameter respectively accounts for 1/4, carries out ball mill grinding to the iron vitriol dreg of yellow sodium after drying, smashed sodium jarosite solid impurity particle is less than 75μm；
Smashed iron vitriol dreg of yellow sodium is mixed with water with mass ratio 1:4 and is sized mixing, be ultrasonically treated and is passed through compression is simultaneously empty Gas, the flow of compressed air are 1m3After ultrasonic, leachate and leached mud is made in/h, ultrasonic time 0.8h；
(b) leachate is handled: 1.1 times of manganese simple substance powder of copper molar content being added to leachate, obtain one after replacing copper removal Secondary scavenging solution；Then into primary purification liquid be added 1.2 times of Ca and Mg precipitating ion theoretical amount manganous fluoride, pH be 4, temperature 1.5h is purified under conditions of 55 DEG C of degree, obtains the scavenging solution of nickeliferous, cobalt and manganese；
To in the scavenging solution of nickeliferous, cobalt and manganese be added nickel source, cobalt source, manganese source with adjust nickel salt in mixed solution, cobalt salt and Manganese salt concentration summation is 1.5mol/L, in nitrogen protection atmosphere, controls pH10.5~11, ammonium root 0.2~0.3mol/L of concentration, Coprecipitation obtains ternary precursor；
Leaching residue treating: by leached mud and sulfuric acid solid-liquid mass ratio 1:4 that leached mud acid is molten, mixing speed 250r/min, Leaching time 1.5h obtains crude ferrum sulfuricum oxydatum solutum；Ferric ion theoretical reduction dosage is added into crude ferrum sulfuricum oxydatum solutum 1.1 times of iron powder adds the sodium fluoride of 1.2 times of Ca precipitating ion theoretical amount after reduction filtering, is 5.5,45 DEG C in pH Under the conditions of purify 2h, ferrous sulfate solution must be purified after filtering；Then to purification ferrous sulfate solution in be added divalent ferrous iron from 1.05 times of sodium chlorate of sub- theoretical oxidation dosage react 0.5h, obtain ferrum sulfuricum oxydatum solutum；
Sodium phosphate crystalline deposit is added to ferrum sulfuricum oxydatum solutum, the feed time of sodium phosphate is 0.5h, precipitated crystal reaction temperature Degree is 65 DEG C, and filtering drying calcines 2.5h at 550 DEG C, obtains battery-grade iron phosphate.
Embodiment 2
Present embodiments provide a kind of processing method of iron vitriol dreg of yellow sodium, comprising the following steps:
(a) iron vitriol dreg of yellow sodium is mixed with water with mass ratio for 1:0.6 and is tuned into paste, the quick freeze under the conditions of -20 DEG C Ice, it is then dry under the pressure of 10Pa, ball-milling medium then is done with the Ceramic Balls of diameter 20mm, 10mm, 5mm and 2mm, often The ball of kind diameter respectively accounts for 1/4, carries out ball mill grinding to the iron vitriol dreg of yellow sodium after drying, smashed sodium jarosite solid impurity particle is less than 75μm；
Smashed iron vitriol dreg of yellow sodium is mixed with water with mass ratio 1:5 and is sized mixing, be ultrasonically treated and is passed through compression is simultaneously empty Gas, the flow of compressed air are 1m3After ultrasonic, leachate and leached mud is made in/h, ultrasonic time 1h；
(b) leachate is handled: 1.2 times of manganese simple substance powder of copper molar content being added to leachate, obtain one after replacing copper removal Secondary scavenging solution；Then into primary purification liquid be added 1.2 times of Ca and Mg precipitating ion theoretical amount manganous fluoride, pH be 4.5, 1.5h is purified under conditions of temperature 60 C, obtains the scavenging solution of nickeliferous, cobalt and manganese；To nickel is added in the scavenging solution of nickeliferous, cobalt and manganese Source, cobalt source, manganese source are to adjust nickel salt in mixed solution, cobalt salt and manganese salt concentration summation for 1.5mol/L, in nitrogen protection atmosphere In, pH 10.9~11.5, ammonium root 0.3~0.4mol/L of concentration are controlled, coprecipitation obtains ternary precursor；
Leaching residue treating: by leached mud and sulfuric acid solid-liquid mass ratio 1:5 that leached mud acid is molten, mixing speed 300r/min, Leaching time 2h obtains crude ferrum sulfuricum oxydatum solutum；The 1.1 of ferric ion theoretical reduction dosage is added into crude ferrum sulfuricum oxydatum solutum Iron powder again adds 1.25 times of sodium fluorides of Ca precipitating ion theoretical amount after reduction filtering, the condition for being 5.5,55 DEG C in pH Lower purification 2h, must purify ferrous sulfate solution after filtering；Then divalent ferrous ion reason is added into purification ferrous sulfate solution By 1.1 times of sodium chlorate of oxidation dosage, 0.8h is reacted, ferrum sulfuricum oxydatum solutum is obtained；
Sodium phosphate crystalline deposit is added to ferrum sulfuricum oxydatum solutum, the feed time of sodium phosphate is 0.5h, precipitated crystal reaction temperature Degree is 70 DEG C, and filtering drying calcines 2h at 600 DEG C, obtains battery-grade iron phosphate.
Embodiment 3
Present embodiments provide a kind of processing method of iron vitriol dreg of yellow sodium, comprising the following steps:
(a) iron vitriol dreg of yellow sodium is mixed with water with mass ratio for 1:0.7 and is tuned into paste, the quick freeze under the conditions of -20 DEG C Ice, it is then dry under the pressure of 12Pa, ball-milling medium then is done with the Ceramic Balls of diameter 20mm, 10mm, 5mm and 2mm, often The ball of kind diameter respectively accounts for 1/4, carries out ball mill grinding to the iron vitriol dreg of yellow sodium after drying, smashed sodium jarosite solid impurity particle is less than 75μm；
Smashed iron vitriol dreg of yellow sodium is mixed with water with mass ratio 1:6 and is sized mixing, be ultrasonically treated and is passed through compression is simultaneously empty Gas, the flow of compressed air are 1.5m3After ultrasonic, leachate and leached mud is made in/h, ultrasonic time 1.5h；
(b) leachate is handled: 1.3 times of manganese simple substance powder of copper molar content being added to leachate, obtain one after replacing copper removal Secondary scavenging solution；Then into primary purification liquid be added 1.3 times of Ca and Mg precipitating ion theoretical amount manganous fluoride, pH be 5, temperature 1.5h is purified under conditions of 65 DEG C of degree, obtains the scavenging solution of nickeliferous, cobalt and manganese；To in the scavenging solution of nickeliferous, cobalt and manganese be added nickel source, Cobalt source, manganese source are to adjust nickel salt in mixed solution, cobalt salt and manganese salt concentration summation as 1.8mol/L, in nitrogen protection atmosphere, PH 11.2~11.8, ammonium root 0.4~0.5mol/L of concentration are controlled, coprecipitation obtains ternary precursor.
Leaching residue treating: by leached mud and sulfuric acid solid-liquid mass ratio 1:6 that leached mud acid is molten, mixing speed 300r/min, Leaching time 2.5h obtains crude ferrum sulfuricum oxydatum solutum；Ferric ion theoretical reduction dosage is added into crude ferrum sulfuricum oxydatum solutum 1.2 times of iron powder adds 1.3 times of sodium fluorides of Ca precipitating ion theoretical amount after reduction filtering, the condition for being 6,55 DEG C in pH Lower purification 2.5h, must purify ferrous sulfate solution after filtering；Then divalent ferrous ion is added into purification ferrous sulfate solution 1.1 times of sodium chlorate of theoretical oxidation dosage react 1h, obtain ferrum sulfuricum oxydatum solutum；
Sodium phosphate crystalline deposit is added to ferrum sulfuricum oxydatum solutum, the feed time of sodium phosphate is 0.7h, precipitated crystal reaction temperature Degree is 75 DEG C, and filtering drying calcines 2.5h at 600 DEG C, obtains battery-grade iron phosphate.
Embodiment 4
Present embodiments provide a kind of processing method of iron vitriol dreg of yellow sodium, comprising the following steps:
(a) iron vitriol dreg of yellow sodium is mixed with water with mass ratio for 1:0.8 and is tuned into paste, the quick freeze under the conditions of -30 DEG C Ice, it is then dry under the pressure of 15Pa, ball-milling medium then is done with the Ceramic Balls of diameter 20mm, 10mm, 5mm and 2mm, often The ball of kind diameter respectively accounts for 1/4, carries out ball mill grinding to the iron vitriol dreg of yellow sodium after drying, smashed sodium jarosite solid impurity particle is less than 75μm；
Smashed iron vitriol dreg of yellow sodium is mixed with water with mass ratio 1:6 and is sized mixing, be ultrasonically treated and is passed through compression is simultaneously empty Gas, the flow of compressed air are 2m3After ultrasonic, leachate and leached mud is made in/h, ultrasonic time 1.5h；
(b) leachate is handled: 1.3 times of manganese simple substance powder of copper molar content being added to leachate, obtain one after replacing copper removal Secondary scavenging solution；Then into primary purification liquid be added 1.4 times of Ca and Mg precipitating ion theoretical amount manganous fluoride, pH be 5, temperature 1.5h is purified under conditions of 65 DEG C of degree, obtains the scavenging solution of nickeliferous, cobalt and manganese；To in the scavenging solution of nickeliferous, cobalt and manganese be added nickel source, Cobalt source, manganese source are to adjust nickel salt in mixed solution, cobalt salt and manganese salt concentration summation as 2.5mol/L, in nitrogen protection atmosphere, PH 11.2~11.8, ammonium root 0.4~0.5mol/L of concentration are controlled, coprecipitation obtains ternary precursor.
Leaching residue treating: by leached mud and sulfuric acid solid-liquid mass ratio 1:6 that leached mud acid is molten, mixing speed 350r/min, Leaching time 2.5h obtains crude ferrum sulfuricum oxydatum solutum；Ferric ion theoretical reduction dosage is added into crude ferrum sulfuricum oxydatum solutum 1.05 times of vulcanized sodium adds 1.35 times of potassium fluorides of Ca precipitating ion theoretical amount after reduction filtering, is 6,55 DEG C in pH Under the conditions of purify 2.5h, ferrous sulfate solution must be purified after filtering；Then it is ferrous divalent to be added into purification ferrous sulfate solution Ionic theory aoxidizes 1.1 times of hydrogen peroxide of dosage, reacts 1h, obtains ferrum sulfuricum oxydatum solutum；
Ammonium phosphate crystalline deposit is added to ferrum sulfuricum oxydatum solutum, the feed time of sodium phosphate is 1h, precipitated crystal reaction temperature It is 80 DEG C, filtering drying calcines 2h at 500 DEG C, obtains battery-grade iron phosphate.
Embodiment 5
The processing method for present embodiments providing a kind of iron vitriol dreg of yellow sodium, in addition to replacing with freeze-drying in step (a) Oven drying, drying temperature are 110 DEG C, drying time 15h, remaining step is same as Example 2.
Embodiment 6
The processing method for present embodiments providing a kind of iron vitriol dreg of yellow sodium, in addition in step (a) in ultrasonication not It is passed through compressed air, remaining step is same as Example 2.
Embodiment 7
The processing method for present embodiments providing a kind of iron vitriol dreg of yellow sodium, in addition to phosphorus is added to ferrum sulfuricum oxydatum solutum in step (b) In sour sodium reaction crystallization process, the feed time of sodium phosphate is 0.2h, remaining step is same as Example 2.
Comparative example 1
This comparative example provides a kind of processing method of iron vitriol dreg of yellow sodium, in addition to replacing with ultrasonic treatment in step (a) Mechanical stirring, speed of agitator 150r/min, remaining step are same as Example 2.
Comparative example 2
This comparative example provides a kind of processing method of iron vitriol dreg of yellow sodium, in addition in step (b) in leachate treatment process Manganese is replaced with into iron, remaining step is same as Example 2.
Comparative example 3
This comparative example provides a kind of processing method of iron vitriol dreg of yellow sodium, in addition in step (b) in leachate treatment process Manganous fluoride is replaced with into sodium fluoride, remaining step is same as Example 2.
Comparative example 4
This comparative example provides a kind of processing method of iron vitriol dreg of yellow sodium, during leaching residue treating in step (b) Crude ferrous sulfate solution is not purified using sodium fluoride, remaining step is same as Example 2.
For the effect for verifying embodiment and comparative example, ad hoc following experimental example.
Experimental example 1
The product quality of ternary precursor made from each embodiment and comparative example and battery-grade iron phosphate is measured, is had Body the results are shown in Table 1 and table 2.
The product quality of ternary precursor made from each embodiment and comparative example of table 1
It can be seen from the data in Table 1 that the product quality of ternary precursor prepared by various embodiments of the present invention reaches Standard GB/T/T 26300-2010 qualified products requirement.
The product quality of ferric phosphate made from each embodiment and comparative example of table 2
Through data analysis in table 2 it is found that the product quality of battery-grade iron phosphate prepared by the embodiment of the present invention reaches state Family's chemical industry standard HG/T 4701-2014 qualified products requirement.
Specifically, from Tables 1 and 2 data can be seen that embodiment 1-4 obtain qualified ternary precursor product and Battery-grade iron phosphate product.Embodiment 5-7 is the control experiment of embodiment 2, different from embodiment 2, and embodiment 5 uses baking oven Dry, embodiment 6 is not passed through compressed air when being ultrasonically treated, and embodiment 7 shortens the feed time of sodium phosphate.By 1 He of table Data can be seen that the change of processing method in embodiment 5-7 in table 2, the main quality for influencing battery-grade iron phosphate product.Phase For 2 battery-grade iron phosphate product quality of embodiment, embodiment 5-7 can make the raising of impurity content in battery-grade iron phosphate, The content of corresponding ferric phosphate is relative reduction, but embodiment 5-7 ternary precursor product obtained and LITHIUM BATTERY phosphoric acid Iron product quality is still able to meet respective standard.
Ultrasonic treatment condition is changed into mechanical stirring by comparative example 1, and as a result the iron content in ferric phosphate is 28.5%, ferrophosphorus Than being 0.94, the requirement of qualified products is not met, this shows that mechanical stirring is not completely separated the solubility in iron vitriol dreg of yellow sodium Sulfate causes ferric phosphate impurity content to increase, and iron content accordingly reduces.Manganese is replaced in 2 leachate treatment process of comparative example For iron, as a result iron content is 0.25% in ternary precursor, and manganous fluoride is replaced with fluorine in 3 leachate treatment process of comparative example Change sodium, as a result sodium content is 0.023% in ternary precursor, does not meet qualified products requirement, this shows impurity in treatment process Introducing will lead to the generation of substandard product.It is sub- to crude sulfuric acid not using sodium fluoride during 4 leaching residue treating of comparative example Ferrous solution is purified, and as a result impurity calcium and content of magnesium are respectively 0.011% and 0.008%, does not meet qualified products requirement, This shows that purification and impurity removal is the necessary condition for preparing spec battery grade ferric phosphate.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution The range of scheme.

Claims (10)

1. a kind of processing method of iron vitriol dreg of yellow sodium, which comprises the following steps:
The iron vitriol dreg of yellow sodium of crushing is added to the water and is ultrasonically treated, leachate and leached mud are obtained；
Successively leachate is purified using manganese simple substance and manganous fluoride, obtains the scavenging solution of nickeliferous, cobalt and manganese；
Optionally, nickel source, cobalt source and manganese source are added into the scavenging solution of nickeliferous, cobalt and manganese, and it is made to carry out coprecipitation reaction, obtains To ternary precursor.
2. the processing method of iron vitriol dreg of yellow sodium according to claim 1, which is characterized in that obtain leached mud through Ore Leaching Crude ferrum sulfuricum oxydatum solutum using reducing agent restore, obtain crude ferrous sulfate solution；
Crude ferrous sulfate solution is purified using fluoride, is purified ferrous sulfate solution；
Purification ferrous sulfate solution is aoxidized, ferrum sulfuricum oxydatum solutum is obtained；
Optionally, phosphate is added into ferrum sulfuricum oxydatum solutum, and it is made to carry out reactive crystallization, the sediment of generation is calcined, is obtained To battery-grade iron phosphate.
3. the processing method of iron vitriol dreg of yellow sodium according to claim 1 or 2, which is characterized in that using manganese simple substance powder to leaching Liquid is purified to remove the copper ion in leachate out, obtains primary purification liquid, wherein the additional amount of manganese simple substance powder is to leach 1.1~1.3 times of copper ion molar content in liquid；
Preferably, manganous fluoride is used to purify primary purification liquid to remove the calcium ion and magnesium ion in primary purification liquid, Obtain the scavenging solution of nickeliferous, cobalt and manganese, wherein the additional amount of manganous fluoride is that the calcium and magnesium ion total moles in primary purification liquid contain 1.1~1.4 times of amount.
4. the processing method of iron vitriol dreg of yellow sodium according to claim 1 or 2, which is characterized in that the net of nickeliferous, cobalt and manganese Change and nickel source, cobalt source and manganese source are added in liquid, makes nickel in the mixed solution of the scavenging solution of nickel source, cobalt source, manganese source and nickeliferous, cobalt and manganese Salt, cobalt salt and manganese salt concentration summation are 1~2.5mol/L；
Preferably, the coprecipitation reaction carries out in an inert atmosphere；
Preferably, the coprecipitation reaction carries out under alkaline condition；
Preferably, the mixed solution pH of the scavenging solution of nickel source, cobalt source, manganese source and nickeliferous, cobalt and manganese is 10.5~12, ammonium root concentration For 0.2~0.5mol/L.
5. the processing method of iron vitriol dreg of yellow sodium according to claim 2, which is characterized in that carried out using sulfuric acid to leached mud It leaches, the solid-liquid mass ratio of leached mud and sulfuric acid is 1:4~6, preferably 1:4.5~6；
Preferably, leaching process and adjoint stirring, mixing speed are 250~350r/min, 1~3h of extraction time；
Preferably, reducing agent includes any one in iron powder, hydrogen sulfide or vulcanized sodium；
Preferably, reducing agent is iron powder, and the additional amount of iron powder is iron ion theoretical reduction dosage in crude ferrum sulfuricum oxydatum solutum 1.05~1.2 times；
Preferably, fluoride includes sodium fluoride or potassium fluoride, preferably sodium fluoride；
Preferably, fluoride additional amount is 1.2~1.35 times of calcium ion theoretical amount in crude ferrous sulfate solution；
Preferably, fluoride is sodium fluoride, and pH value of solution when sodium fluoride purifies crude ferrous sulfate solution is 5~6.5, Purification temperature is 40~60 DEG C, and the clarification time is 2~3h；
Preferably, oxidant includes any one in sodium chlorate, sodium peroxydisulfate or hydrogen peroxide；
Preferably, the additional amount of oxidant is purify ferrous sulfate solution ferrous ions theoretical oxidation dosage 1.05~1.2 Times；
Preferably, oxidization time is 0.5~1h；
Preferably, phosphate includes any one in sodium phosphate, potassium phosphate, ammonium dihydrogen phosphate or ammonium phosphate or at least two Combination；
Preferably, phosphatic feed time is 0.5~1h, and reactive crystallization temperature is 60~80 DEG C；
Preferably, calcination temperature is 500~600 DEG C, and calcination time is 2~3h.
6. the processing method of iron vitriol dreg of yellow sodium according to claim 1 or 2, which is characterized in that iron vitriol dreg of yellow sodium include with The chemical component of lower mass fraction: Fe:20~26%, Na:4~7%, Si:4~8%, Ni:2~4%, Co:0.5~1%, Mn:0.3~0.8%, Cu:1~3%, Ca:0.1~0.3%, Mg:0.2~0.4% and other metallic elements < 0.1%；
Preferably, the partial size of the iron vitriol dreg of yellow sodium of crushing is less than 75 μm；
Preferably, compressed air is passed through while ultrasonic treatment；
Preferably, the flow of compressed air is 0.5~2m3/h；
It preferably, further include the step for adding iron vitriol dreg of yellow sodium water to size mixing and then be freeze-dried before crushing iron vitriol dreg of yellow sodium Suddenly；
Preferably, during adding water to size mixing, the mass ratio of iron vitriol dreg of yellow sodium and water is 1:0.3~0.8；
Preferably, the temperature of freeze-drying is -10~-30 DEG C, and the pressure of freeze-drying is 1.5~15Pa.
7. a kind of ternary precursor, which is characterized in that using the processing of iron vitriol dreg of yellow sodium as claimed in any one of claims 1 to 6 Method is made.
8. a kind of battery-grade iron phosphate, which is characterized in that using the place of iron vitriol dreg of yellow sodium described in claim 2-6 any one Reason method is made.
9. a kind of lithium ion battery, which is characterized in that using described in ternary precursor as claimed in claim 7 or claim 8 Battery-grade iron phosphate be made.
10. electronic device, electric tool, electric vehicle comprising lithium ion battery as claimed in claim 9 or electric power storage system System.
CN201811419087.0A 2018-11-26 2018-11-26 Processing method, ternary precursor, battery-grade iron phosphate and the lithium ion battery of iron vitriol dreg of yellow sodium Active CN109231181B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811419087.0A CN109231181B (en) 2018-11-26 2018-11-26 Processing method, ternary precursor, battery-grade iron phosphate and the lithium ion battery of iron vitriol dreg of yellow sodium

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811419087.0A CN109231181B (en) 2018-11-26 2018-11-26 Processing method, ternary precursor, battery-grade iron phosphate and the lithium ion battery of iron vitriol dreg of yellow sodium

Publications (2)

Publication Number Publication Date
CN109231181A true CN109231181A (en) 2019-01-18
CN109231181B CN109231181B (en) 2019-08-02

Family

ID=65073528

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811419087.0A Active CN109231181B (en) 2018-11-26 2018-11-26 Processing method, ternary precursor, battery-grade iron phosphate and the lithium ion battery of iron vitriol dreg of yellow sodium

Country Status (1)

Country Link
CN (1) CN109231181B (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110358925A (en) * 2019-07-29 2019-10-22 中南大学 A kind of method of chemistry freeze thawing treatment iron vitriol slag
CN113184821A (en) * 2021-05-11 2021-07-30 蜂巢能源科技有限公司 Method for preparing iron phosphate by using iron-containing slag
CN113430390A (en) * 2021-07-12 2021-09-24 深圳市贝特瑞纳米科技有限公司 Treatment method of laterite-nickel ore high-pressure acid leaching slag and positive electrode material
CN113851618A (en) * 2021-08-10 2021-12-28 桂林理工大学 Method for preparing high-performance iron phosphate/graphene composite negative electrode material by using iron vitriol slag hydrochloric acid leaching solution and application
CN115196609A (en) * 2022-09-15 2022-10-18 中国科学院过程工程研究所 Method for recovering iron phosphate from lithium iron phosphate lithium extraction slag and application thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101066827A (en) * 2007-06-05 2007-11-07 台州盛世环境工程有限公司 Electroplating sludge treating and utilizing process
CN103384002A (en) * 2012-05-04 2013-11-06 湖南科飞特高新技术有限公司 Method for preparing electronic ternary material precursor from Ni-Co residues
CN104480317A (en) * 2014-11-13 2015-04-01 朱蕾 Cobalt nickel metallurgy wastewater sludge recycling method
CN104701524A (en) * 2015-03-03 2015-06-10 中南大学 Method for directly preparing nickel-cobalt-manganese ternary cathode material precursor from nickel electrolyte
CN107058745A (en) * 2017-04-21 2017-08-18 青海快驴电动汽车科技有限公司 A kind of method that valuable metal is extracted in cobalt metallurgical waste
CN108649195A (en) * 2018-04-28 2018-10-12 成都新柯力化工科技有限公司 A kind of nickelic ternary lithium battery material of polythiophene base and preparation method

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101066827A (en) * 2007-06-05 2007-11-07 台州盛世环境工程有限公司 Electroplating sludge treating and utilizing process
CN103384002A (en) * 2012-05-04 2013-11-06 湖南科飞特高新技术有限公司 Method for preparing electronic ternary material precursor from Ni-Co residues
CN104480317A (en) * 2014-11-13 2015-04-01 朱蕾 Cobalt nickel metallurgy wastewater sludge recycling method
CN104701524A (en) * 2015-03-03 2015-06-10 中南大学 Method for directly preparing nickel-cobalt-manganese ternary cathode material precursor from nickel electrolyte
CN107058745A (en) * 2017-04-21 2017-08-18 青海快驴电动汽车科技有限公司 A kind of method that valuable metal is extracted in cobalt metallurgical waste
CN108649195A (en) * 2018-04-28 2018-10-12 成都新柯力化工科技有限公司 A kind of nickelic ternary lithium battery material of polythiophene base and preparation method

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110358925A (en) * 2019-07-29 2019-10-22 中南大学 A kind of method of chemistry freeze thawing treatment iron vitriol slag
CN113184821A (en) * 2021-05-11 2021-07-30 蜂巢能源科技有限公司 Method for preparing iron phosphate by using iron-containing slag
CN113184821B (en) * 2021-05-11 2023-07-14 蜂巢能源科技有限公司 Method for preparing ferric phosphate from iron-containing slag
CN113430390A (en) * 2021-07-12 2021-09-24 深圳市贝特瑞纳米科技有限公司 Treatment method of laterite-nickel ore high-pressure acid leaching slag and positive electrode material
CN113851618A (en) * 2021-08-10 2021-12-28 桂林理工大学 Method for preparing high-performance iron phosphate/graphene composite negative electrode material by using iron vitriol slag hydrochloric acid leaching solution and application
CN113851618B (en) * 2021-08-10 2023-06-23 桂林理工大学 Method for preparing high-performance ferric phosphate/graphene composite anode material by utilizing hydrochloric acid leaching solution of iron vitriol slag and application of high-performance ferric phosphate/graphene composite anode material
CN115196609A (en) * 2022-09-15 2022-10-18 中国科学院过程工程研究所 Method for recovering iron phosphate from lithium iron phosphate lithium extraction slag and application thereof

Also Published As

Publication number Publication date
CN109231181B (en) 2019-08-02

Similar Documents

Publication Publication Date Title
CN109231181B (en) Processing method, ternary precursor, battery-grade iron phosphate and the lithium ion battery of iron vitriol dreg of yellow sodium
Wang et al. Recent progress on the recycling technology of Li-ion batteries
Xiao et al. Challenges to future development of spent lithium ion batteries recovery from environmental and technological perspectives
KR101682217B1 (en) A Method Of Manufacturing A Lithium Carbonate With High Purity By Recycling A Lithium From A Anode Material Of Used Lithium Ion Secondary Battery
EP4286325A1 (en) Method for resource recycling of nickel-iron alloy and use thereof
Zhu et al. Recovery of Co and Li from spent lithium-ion batteries by combination method of acid leaching and chemical precipitation
CN104805299B (en) Method for preparing lithium battery electrode materials LiFePO4 and Li4Ti5O12 from vanadium extraction slag
CN113277489A (en) Method for preparing high-purity iron phosphate by using ferrophosphorus waste
CN101717858B (en) Method for extracting molybdenum, nickel, vanadium and ferrum from polymetallic black-shale paragentic minerals
CA3143966C (en) Methods for extracting lithium from spodumene
CN102828025A (en) Method for extracting V2O5 from stone coal navajoite
US11909041B2 (en) Method to produce cathode materials for Li-ion batteries
Shen et al. Recycling cathodes from spent lithium-ion batteries based on the selective extraction of lithium
CN114506834A (en) Treatment method of waste lithium iron phosphate powder and carbon-coated lithium iron phosphate
CN110482515B (en) Preparation method of low-cost lithium iron phosphate
Chen et al. Hydrometallurgical processes for valuable metals recycling from spent lithium-ion batteries
CN112725621B (en) Method for separating nickel, cobalt and manganese from waste lithium battery based on carbonate solid-phase conversion method
CN108751234A (en) A kind of method of purification of lithium fluoride
CN115709979B (en) Method for preparing battery-grade manganese iron phosphate by taking high-iron manganese ore as raw material
CN115196609B (en) Method for recovering iron phosphate from lithium iron phosphate lithium extraction slag and application thereof
CN109319843A (en) A method of high purity manganese sulfate is prepared from poor manganese spar
CN115652077A (en) Method for selectively separating and recovering lithium and manganese from waste lithium manganate battery
CN115074540A (en) Comprehensive recovery method for valuable components of waste power battery
CN110257851B (en) Special electrolytic manganese dioxide for lithium manganate battery and preparation method thereof
KR102228192B1 (en) Preparing method of nickel-cobalt-manganese complex sulphate solution by recycling wasted electrode material

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant