CN109231181B - 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 PDFInfo
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- CN109231181B CN109231181B CN201811419087.0A CN201811419087A CN109231181B CN 109231181 B CN109231181 B CN 109231181B CN 201811419087 A CN201811419087 A CN 201811419087A CN 109231181 B CN109231181 B CN 109231181B
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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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
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 (34)
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;
To addition nickel source, cobalt source and manganese source in the scavenging solution of nickeliferous, cobalt and manganese, and its is made to carry out coprecipitation reaction, obtains ternary
Presoma.
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;
Phosphate is added into ferrum sulfuricum oxydatum solutum, and it is made to carry out reactive crystallization, the sediment of generation is calcined, LITHIUM BATTERY is obtained
Ferric 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.
4. the processing method of iron vitriol dreg of yellow sodium according to claim 3, which is characterized in that using manganous fluoride to primary purification
Liquid is purified to remove the calcium ion and magnesium ion in primary purification liquid, obtains the scavenging solution of nickeliferous, cobalt and manganese, wherein fluorine
The additional amount for changing manganese is 1.1~1.4 times of the calcium and magnesium ion total moles content in primary purification liquid.
5. 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.
6. the processing method of iron vitriol dreg of yellow sodium according to claim 5, which is characterized in that the coprecipitation reaction is in inertia
It is carried out in atmosphere.
7. the processing method of iron vitriol dreg of yellow sodium according to claim 5, which is characterized in that the coprecipitation reaction is in alkalinity
Under the conditions of carry out.
8. the processing method of iron vitriol dreg of yellow sodium according to claim 5, which is characterized in that nickel source, cobalt source, manganese source and contain
The mixed solution pH of the scavenging solution of nickel, cobalt and manganese is 10.5~12, and ammonium root concentration is 0.2~0.5mol/L.
9. 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.
10. the processing method of iron vitriol dreg of yellow sodium according to claim 9, which is characterized in that the solid-liquid of leached mud and sulfuric acid
Mass ratio is 1:4.5~6.
11. the processing method of iron vitriol dreg of yellow sodium according to claim 9, which is characterized in that leaching process and adjoint stirring,
Mixing speed is 250~350r/min, 1~3h of extraction time.
12. the processing method of iron vitriol dreg of yellow sodium according to claim 2, which is characterized in that reducing agent includes iron powder, vulcanization
Any one in hydrogen or vulcanized sodium.
13. the processing method of iron vitriol dreg of yellow sodium according to claim 12, which is characterized in that reducing agent is iron powder, iron powder
Additional amount be 1.05~1.2 times of iron ion theoretical reduction dosage in crude ferrum sulfuricum oxydatum solutum.
14. the processing method of iron vitriol dreg of yellow sodium according to claim 2, which is characterized in that fluoride include sodium fluoride or
Potassium fluoride.
15. the processing method of iron vitriol dreg of yellow sodium according to claim 14, which is characterized in that fluoride is sodium fluoride.
16. the processing method of iron vitriol dreg of yellow sodium according to claim 14, which is characterized in that fluoride additional amount is crude
1.2~1.35 times of calcium ion theoretical amount in ferrous sulfate solution.
17. the processing method of iron vitriol dreg of yellow sodium according to claim 14, which is characterized in that fluoride is sodium fluoride, fluorine
Changing pH value of solution when sodium purifies crude ferrous sulfate solution is 5~6.5, and purification temperature is 40~60 DEG C, the clarification time
For 2~3h.
18. the processing method of iron vitriol dreg of yellow sodium according to claim 2, which is characterized in that purification ferrous sulfate solution
When being aoxidized, oxidant includes any one in sodium chlorate, sodium peroxydisulfate or hydrogen peroxide.
19. the processing method of iron vitriol dreg of yellow sodium according to claim 18, which is characterized in that the additional amount of oxidant is net
1.05~1.2 times for changing ferrous sulfate solution ferrous ions theoretical oxidation dosage.
20. the processing method of iron vitriol dreg of yellow sodium according to claim 18, which is characterized in that oxidization time is 0.5~1h.
21. the processing method of iron vitriol dreg of yellow sodium according to claim 2, which is characterized in that phosphate includes sodium phosphate, phosphorus
In sour potassium, ammonium dihydrogen phosphate or ammonium phosphate any one or at least two combination.
22. the processing method of iron vitriol dreg of yellow sodium according to claim 21, which is characterized in that phosphatic feed time is
0.5~1h, reactive crystallization temperature are 60~80 DEG C.
23. the processing method of iron vitriol dreg of yellow sodium according to claim 2, which is characterized in that calcination temperature is 500~600
DEG C, calcination time is 2~3h.
24. 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%.
25. the processing method of iron vitriol dreg of yellow sodium according to claim 1 or 2, which is characterized in that the iron vitriol dreg of yellow sodium of crushing
Partial size less than 75 μm.
26. the processing method of iron vitriol dreg of yellow sodium according to claim 1 or 2, which is characterized in that lead to while ultrasonic treatment
Enter compressed air.
27. the processing method of iron vitriol dreg of yellow sodium according to claim 26, which is characterized in that the flow of compressed air is
0.5~2m3/h.
28. the processing method of iron vitriol dreg of yellow sodium according to claim 1 or 2, which is characterized in that by sodium jarosite ground-slag
Before broken, further include the steps that adding iron vitriol dreg of yellow sodium water to size mixing then is freeze-dried.
29. the processing method of iron vitriol dreg of yellow sodium according to claim 28, which is characterized in that yellow during adding water to size mixing
The mass ratio of natrojarosite slag and water is 1:0.3~0.8.
30. the processing method of iron vitriol dreg of yellow sodium according to claim 28, which is characterized in that the temperature of freeze-drying be-
10~-30 DEG C, the pressure of freeze-drying is 1.5~15Pa.
31. a kind of ternary precursor, which is characterized in that using the place of iron vitriol dreg of yellow sodium described in claim 1-30 any one
Reason method is made.
32. a kind of battery-grade iron phosphate, which is characterized in that using iron vitriol dreg of yellow sodium described in claim 2-30 any one
Processing method is made.
33. a kind of lithium ion battery, which is characterized in that using described in claim 31 ternary precursor or claim 32 institute
The battery-grade iron phosphate stated is made.
34. electronic device, electric tool, electric vehicle comprising lithium ion battery described in claim 33 or electric power storage system
System.
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