CN109354002A - The method of lithium phosphate, the preparation method of iron manganese phosphate for lithium and lithium iron phosphate positive material are prepared by phosphorus ore - Google Patents
The method of lithium phosphate, the preparation method of iron manganese phosphate for lithium and lithium iron phosphate positive material are prepared by phosphorus ore Download PDFInfo
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- CN109354002A CN109354002A CN201810990504.0A CN201810990504A CN109354002A CN 109354002 A CN109354002 A CN 109354002A CN 201810990504 A CN201810990504 A CN 201810990504A CN 109354002 A CN109354002 A CN 109354002A
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- 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
- C01B25/30—Alkali metal phosphates
- C01B25/305—Preparation from phosphorus-containing compounds by alkaline treatment
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- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
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- C01B25/45—Phosphates containing plural metal, or metal and ammonium
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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Abstract
The present invention provides a kind of methods for preparing lithium phosphate by phosphorus ore, comprising: obtains ground phosphate rock after being crushed rock phosphate in powder, ground phosphate rock is dissolved in acid, is then filtered, filtrate A is obtained；Alkaline matter is added into filtrate A, stirs simultaneously, until resulting pH value of solution is 6.0-8.5, carbonate is then added, is filtered after the reaction was continued 30-120min, obtains liquor B；Soluble lithium salt is added into liquor B, while alkaline matter is added, stirs, until resulting pH value of solution is 9.0-12.0, after filtration drying, obtains lithium phosphate.Phosphorus ore is rationally utilized in the method provided by the invention for preparing lithium phosphate by phosphorus ore, and low cost is prepared for lithium phosphate, simple process.The present invention also lithium phosphate made from phosphorus ore prepares iron manganese phosphate for lithium and lithium iron phosphate positive material as raw material, and obtained positive electrode energy density is higher, electrochemical performance.
Description
Technical field
The present invention relates to field of lithium ion battery anode, and in particular to it is a kind of by phosphorus ore prepare lithium phosphate method,
The preparation method of iron manganese phosphate for lithium and lithium iron phosphate positive material.
Background technique
Phosphorus ore is the mineral of calcic, phosphorus and a large amount of impurity, is a kind of important chemical industry raw mineral materials, is widely used in
Each industrial department.Although China's phosphate rock resource is abundant, 80% the above are the mid low grade phosphate rocks for being difficult to directly utilize.Existing skill
Art is often lower to the utilization rate of rock phosphate in powder, and the pollutant of pollution environment is often generated during utilization.Therefore, how
Rationally become necessary using phosphorus ore.
Summary of the invention
To solve the above problems, the present invention provides a kind of methods for preparing lithium phosphate by phosphorus ore, and by the phosphoric acid
Lithium is used to prepare iron manganese phosphate for lithium and lithium iron phosphate positive material.
First aspect present invention provides a kind of method for preparing lithium phosphate by phosphorus ore, comprising the following steps:
Ground phosphate rock is obtained after rock phosphate in powder is crushed, the ground phosphate rock is dissolved in acid, is then filtered, filtrate A is obtained；
Alkaline matter is added into the filtrate A, stirs simultaneously, until resulting pH value of solution is 6.0-8.5, is then added
Carbonate filters after the reaction was continued 30-120min, obtains liquor B；
Soluble lithium salt is added into the liquor B, while alkaline matter is added, stirs, until resulting pH value of solution is
9.0-12.0 filtering, obtains lithium phosphate filter residue；After drying, lithium phosphate is obtained.
Wherein, the carbonate includes at least one of ammonium carbonate, sodium carbonate and potassium carbonate.
Wherein, the additional amount of the carbonate are as follows: the calcium ion contained in the mole of the carbonate and the filtrate A
It is 1:1 with the ratio between the integral molar quantity of magnesium ion.
Wherein, the soluble lithium salt includes at least one of lithium sulfate, lithium nitrate, lithium acetate and lithium chloride.
Wherein, by phosphorus: lithium molar ratio is that the soluble lithium salt is added into the liquor B by 1:3.
Wherein, the alkaline matter is added into the liquor B, until continuing after resulting pH value of solution is 9.0-12.0
30-120min is stirred, then carries out the filtering again.
Wherein, the operation of the drying include: by the lithium phosphate filter residue in air atmosphere at a temperature of 60-200 DEG C
After dry 6-20h, then it is placed in vacuum environment dry 2-10h at a temperature of 120-200 DEG C, the lithium phosphate is obtained after crushing.
Wherein, the acid includes at least one of sulfuric acid, nitric acid and hydrochloric acid.
Second aspect of the present invention provides a kind of preparation method of lithium iron manganese phosphate anode material, comprising:
Ground phosphate rock is obtained after rock phosphate in powder is crushed, the ground phosphate rock is dissolved in acid, is then filtered, filtrate A is obtained；
Alkaline matter is added into the filtrate A, stirs simultaneously, until resulting pH value of solution is 6.0-8.5, is then added
Carbonate filters after the reaction was continued 30-120min, obtains liquor B；
Soluble lithium salt is added into the liquor B, while alkaline matter is added, stirs, until resulting pH value of solution is
9.0-12.0 filtering, obtains lithium phosphate filter residue；After drying, lithium phosphate is obtained；
According to the molar ratio of each element in iron manganese phosphate for lithium, the lithium phosphate, source of iron, manganese source and phosphorus source are mixed, obtained
Mixing material；
Iron manganese phosphate for lithium presoma will be obtained after the mixing material ball milling, drying；By the iron manganese phosphate for lithium presoma
Lithium iron manganese phosphate anode material is obtained after calcining.
Third aspect present invention provides a kind of preparation method of lithium iron phosphate positive material, comprising:
Ground phosphate rock is obtained after rock phosphate in powder is crushed, the ground phosphate rock is dissolved in acid, is then filtered, filtrate A is obtained；
Alkaline matter is added into the filtrate A, stirs simultaneously, until resulting pH value of solution is 6.0-8.5, is then added
Carbonate filters after the reaction was continued 30-120min, obtains liquor B；
Soluble lithium salt is added into the liquor B, while alkaline matter is added, stirs, until resulting pH value of solution is
9.0-12.0 filtering, obtains lithium phosphate filter residue；After drying, lithium phosphate is obtained；
According to the molar ratio of each element in lithium iron phosphate positive material, the lithium phosphate, source of iron and phosphorus source are mixed, obtained
Mixing material；
Ferric lithium phosphate precursor will be obtained after the mixing material ball milling, drying；The ferric lithium phosphate precursor is calcined
After obtain lithium iron phosphate positive material.
To sum up, beneficial effect of the present invention includes the following aspects:
1, the present invention provides a kind of methods for preparing lithium phosphate by phosphorus ore, and phosphorus ore, and low cost preparation is rationally utilized
Lithium phosphate, simple process.
2, the present invention is as preparing iron manganese phosphate for lithium as lithium source and partial phosphorus source for the lithium phosphate made from phosphorus ore
Positive electrode, preparation cost is lower and environmental-friendly, and obtained lithium iron manganese phosphate anode material energy density is higher, electrochemistry
It can be excellent；
3, the present invention is as preparing LiFePO4 as lithium source and partial phosphorus source just for the lithium phosphate made from phosphorus ore
Pole material, preparation cost is lower and environmental-friendly, and obtained lithium iron phosphate positive material energy density is higher, and chemical property is excellent
It is different.
Detailed description of the invention
Fig. 1 is the method flow schematic diagram that lithium phosphate is prepared by phosphorus ore that an embodiment of the present invention provides；
Fig. 2 is iron manganese phosphate for lithium (LiFe prepared by the embodiment of the present invention 40.2Mn0.8PO4) positive electrode scanning electron microscope
Figure；
Fig. 3 is the X ray diffracting spectrum of iron manganese phosphate for lithium (XRD) positive electrode made from the embodiment of the present invention 4；
Fig. 4 is iron manganese phosphate for lithium (LiFe prepared by the embodiment of the present invention 40.2Mn0.8PO4) positive electrode discharge curve
Figure.
Specific embodiment
The following is a preferred embodiment of the present invention, it is noted that for those skilled in the art
For, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also considered as
Protection scope of the present invention.
Referring to Fig. 1, first aspect present invention provides a kind of method for preparing lithium phosphate by phosphorus ore, including following step
It is rapid:
S01 obtains ground phosphate rock after being crushed rock phosphate in powder, the ground phosphate rock is dissolved in acid, is then filtered, filtrate is obtained
A；
S02 is added alkaline matter into the filtrate A, stirs simultaneously, until resulting pH value of solution is 6.0-8.5, then
Carbonate is added, is filtered after the reaction was continued 30-120min, obtains liquor B；
Soluble lithium salt is added into the liquor B, while alkaline matter is added by S03, stirring, until resulting solution
PH is 9.0-12.0, and filtering obtains lithium phosphate filter residue；After drying, lithium phosphate is obtained.
In embodiment of the present invention, in step S01, the rock phosphate in powder can be directly commercially available.
In embodiment of the present invention, in step S01, is sieved with 100 mesh sieve after the rock phosphate in powder is crushed, obtain the phosphorus ore
Powder.
In embodiment of the present invention, in step S01, the main component of the ground phosphate rock includes P2O5、CaO、Fe2O3、MgO、
SiO2Deng.
In embodiment of the present invention, in step S01, the acid includes at least one of sulfuric acid, nitric acid and hydrochloric acid.
In embodiment of the present invention, in step S01, the acid is concentrated acid, for example in the concentrated sulfuric acid, concentrated nitric acid and concentrated hydrochloric acid
It is at least one.These concentrated acids can be directly commercially available.If the acid is the concentrated sulfuric acid that mass fraction is 98%.
In embodiment of the present invention, in step S01, the additional amount of the acid is CaO, MgO, Al in rock phosphate in powder2O3、Fe2O3
The 100%-120% of required acid amount when being reacted completely with acid.
It in embodiment of the present invention, is heated in the course of dissolution, the temperature of the heating is 40-100 DEG C.
In embodiment of the present invention, the time of the dissolution reaction is 1-6h.
In embodiment of the present invention, in step S02, the alkaline matter includes in ammonium hydroxide, sodium hydroxide and potassium hydroxide
At least one.Optionally, the alkaline matter is ammonium hydroxide, and the concentration of the ammonium hydroxide is regular industrial ammonia concn.It is optional
Ground is slowly added to alkaline matter into the filtrate A, is stirred simultaneously, and detects the pH variation of the filtrate A simultaneously, directly
It is 6.0-8.5 to resulting pH value of solution, stops that the alkaline matter is added.
In embodiment of the present invention, in step S02, the mixing speed is 100-400r/min.
In embodiment of the present invention, in step S02, alkaline matter is added into the filtrate A, until resulting pH value of solution
For 6.0-7.5 or 7.5-8.5.Optionally, the pH is 6.0,6.5,7.0,7.5,8.0 or 8.5.
In embodiment of the present invention, in step S02, alkaline matter, which is added, can make the aluminium ion in filtrate A form aluminum phosphate
Precipitating, iron ion form ferric hydroxide precipitate, to remove aluminium ion and iron ion from filtrate A.In the method for the present invention, pass through
Alkaline matter is added into the filtrate A, until resulting pH value of solution is 6.0-8.5, can preferably sink within the scope of the pH
Aluminium ion and iron ion in the filtrate of shallow lake farthest remove aluminium ion and iron ion in filtrate.
In embodiment of the present invention, in step S02, alkaline matter is slowly added into the filtrate A, stirring is until gained
PH value of solution be 6.0-8.5 after, stop that alkaline matter is added, and continue stirring a period of time to add carbonate.Optionally, after
Continuous stirring 30-120min.Reaction can be made more abundant in this way.
In embodiment of the present invention, in step S02, the carbonate include in ammonium carbonate, sodium carbonate and potassium carbonate extremely
Few one kind.
In embodiment of the present invention, in step S02, calcium ion and magnesium ion, the carbonate are also contained in the filtrate A
Additional amount be that all calcium ions and all magnesium ions can be made to form the precipitating of calcium carbonate and magnesium carbonate to remove from filtrate.
Optionally, the content of Ca and Mg in the filtrate A is measured according to ICP (inductively coupled plasma body), is then added corresponding mole
The carbonate of amount is to generate calcium carbonate and carbonic acid magnesium precipitate.I.e. according in calcium carbonate each element molar ratio be added carbonate and
Carbonate is added according to the molar ratio of each element in magnesium carbonate.Optionally, the additional amount of the carbonate are as follows: the carbonate
The ratio between integral molar quantity of calcium ion and magnesium ion contained in mole and the filtrate A is 1:1.
In embodiment of the present invention, in step S02, after carbonate is added, stirring, the reaction was continued 60-120min.It is optional
Ground, after carbonate is added, stirring, the reaction was continued 100-120min.
In embodiment of the present invention, in step S02, the liquor B containing monoammonium phosphate and ammonium phosphate is obtained by filtration and contains
There is the mixed precipitation of aluminum phosphate, iron hydroxide, calcium carbonate and magnesium carbonate.
In embodiment of the present invention, the step S02 is to operate at room temperature.
In embodiment of the present invention, in step S03, the soluble lithium salt includes lithium sulfate, lithium nitrate, lithium acetate and chlorine
Change at least one of lithium.
In embodiment of the present invention, measured in the liquor B according to ICP (inductively coupled plasma body) or quinoline molybdenum lemon ketone method
The concentration of phosphorus, then according to lithium: phosphorus molar ratio is that soluble lithium salt is added into the liquor B by 3:1, and final filtration obtains phosphoric acid
Lithium filter residue.
In embodiment of the present invention, in step S03, the mixing speed is 100-400r/min.
In embodiment of the present invention, in step S03, it is added into the liquor B during the soluble lithium salt, simultaneously
Alkaline matter is added, until the pH of acquired solution is 9.0-12.0.Optionally, the alkaline matter includes ammonium hydroxide, sodium hydroxide
At least one of with potassium hydroxide.Optionally, the alkaline matter is ammonium hydroxide, and the concentration of the ammonium hydroxide is regular industrial ammonia
Water concentration.Optionally, it is slowly added to alkaline matter into the liquor B, is stirred simultaneously, and detects the liquor B simultaneously
PH variation until resulting pH value of solution is 9.0-12.0 stop that the alkaline matter is added.
In embodiment of the present invention, in step S03, until continuing to stir 30- after resulting pH value of solution is 9.0-12.0
120min, then be filtered.
In embodiment of the present invention, in step S03, the operation of the drying includes: by the lithium phosphate filter residue in air
In atmosphere at a temperature of 60-200 DEG C after dry 6-20h, then it is placed in vacuum environment in 120-200 DEG C of dry 2-10h, after crushing
Obtain the lithium phosphate.In embodiment of the present invention, first dry in air atmosphere, then dry under vacuum conditions, Ke Yigeng
Dry lithium phosphate well.
System of the present invention is taller compared with commercialization lithium phosphate purity by the lithium phosphate that phosphorus ore is prepared, and commercialization lithium phosphate is pure
Degree is 97% or so, and lithium phosphate purity produced by the present invention is up to 99.5% or more.
The present invention provides a kind of methods for preparing lithium phosphate by phosphorus ore, phosphorus ore are rationally utilized, and low cost is prepared for
Lithium phosphate, simple process, and 85% or more can achieve to the phosphorus recovery rate in phosphorus ore, recovery rate is higher.In addition, of the invention
Method is environmentally friendly, and waste liquid, the waste residue that pollution is generated to environment are not generated during preparing lithium phosphate.Phosphoric acid obtained
Lithium purity is higher, can be used for the preparation of anode material for lithium-ion batteries.
Second aspect of the present invention provides a kind of preparation method of lithium iron manganese phosphate anode material, comprising:
S10 obtains ground phosphate rock after being crushed rock phosphate in powder, the ground phosphate rock is dissolved in acid, is then filtered, filtrate is obtained
A；
S11 is added alkaline matter into the filtrate A, stirs simultaneously, until resulting pH value of solution is 6.0-8.5, then
Carbonate is added, is filtered after the reaction was continued 30-120min, obtains liquor B；
Soluble lithium salt is added into the liquor B, while alkaline matter is added by S12, stirring, until resulting solution
PH is 9.0-12.0, and filtering obtains lithium phosphate filter residue；After drying, lithium phosphate is obtained；
S13 mixes the lithium phosphate, source of iron, manganese source and phosphorus source according to the molar ratio of each element in iron manganese phosphate for lithium,
Obtain mixing material；
S14 will obtain iron manganese phosphate for lithium presoma after the mixing material ball milling, drying；Before the iron manganese phosphate for lithium
Lithium iron manganese phosphate anode material is obtained after driving body calcining.
In embodiment of the present invention, the concrete operations technique of described S10, S11 and S12 can be found in each step of first aspect
Suddenly.
In embodiment of the present invention, the chemical formula of the lithium iron manganese phosphate anode material obtained is LiFe1-xMnxPO4,
The range of middle x is 0.5≤x≤0.8.
In embodiment of the present invention, in the step S13, nLi:nFe:nP:nMn=(1.0-1.1) in molar ratio:
(0.2-0.5): (0.95-1): (0.5-0.8) is added the lithium phosphate and source of iron, phosphorus source, manganese source is added, and obtains mixing material.
It, will be in lithium phosphate made from lithium phosphate made from above-mentioned first aspect or step S12 in embodiment of the present invention
P elements phosphorus source as part of the elemental lithium as lithium source, in lithium phosphate.In addition, a part of phosphorus source is added additionally with completion
The amount of phosphorus in iron manganese phosphate for lithium.
In embodiment of the present invention, phosphorus source includes in phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate and lithium dihydrogen phosphate
At least one.
In embodiment of the present invention, the source of iron includes ferrous carbonate, ferrous hydroxide, ferrous nitrate, ferrous oxalate, hydrogen
At least one of iron oxide, ferric nitrate, ironic citrate and di-iron trioxide.
In embodiment of the present invention, the manganese source includes manganese dioxide, manganese sesquioxide managnic oxide, mangano-manganic oxide, manganese oxalate, vinegar
At least one of sour manganese and manganese nitrate.
In embodiment of the present invention, in the step S13, carbon source is also added into form mixing material, the carbon source packet
It includes in citric acid, malic acid, tartaric acid, oxalic acid, salicylic acid, succinic acid, glycine, ethylenediamine tetra-acetic acid, sucrose and glucose
At least one.Optionally, the quality that the carbon source is added is the 10%-50% of target product iron manganese phosphate for lithium quality.This hair
After bright addition carbon source, the carbon source can form carbon coating layer on iron manganese phosphate for lithium surface, improve the electric conductivity of iron manganese phosphate for lithium.
In embodiment of the present invention, in the step S13, solvent is also added into form mixing material, the solvent packet
Include water, methanol, ethyl alcohol, propyl alcohol, isopropanol, n-butanol, isobutanol, n-amyl alcohol, n-hexyl alcohol, n-heptanol, acetone, butanone, fourth two
Ketone, pentanone, cyclopentanone, at least one of ketone, cyclohexanone and cycloheptanone.Optionally, the mixing material after addition solvent
Solid content be 30%-60%.
In embodiment of the present invention, in the step S13, metallic compound can also be added in the iron manganese phosphate for lithium
Doped metallic elements in positive electrode.Optionally, the type and additional amount of the metallic compound can carry out according to the actual situation
Selection.If the metal of doping can be aluminium, the chemical formula of the lithium iron manganese phosphate anode material of aluminium doping is (LiAlyFe1-x- yMnxPO4) wherein the range of x be 0.5≤x≤0.8, the range of y is 0.002≤y≤0.02.
In embodiment of the present invention, in the step S14, the Ball-milling Time is 10-48 hours.
In embodiment of the present invention, in the step S14, it is dried the mixing material after ball milling to obtain powder.It can
The operation of selection of land, the drying includes: that the mixing material after ball milling is placed in air dry oven, 80-300 DEG C at a temperature of it is dry
Dry 2-20 hours obtains powder.
In embodiment of the present invention, in the step S14, after gained powder is crushed with disintegrating apparatus, at 400-600 DEG C
At a temperature of pre-process 2-10 hours, obtain iron manganese phosphate for lithium presoma.Optionally, the partial size of the iron manganese phosphate for lithium presoma
For nanoscale.
Temperature in embodiment of the present invention, in the step S14, by the iron manganese phosphate for lithium presoma at 500-900 DEG C
Degree lower sintering 10-30 hours, obtain iron manganese phosphate for lithium powder body material (LiFe1-xMnxPO4) or aluminium doping iron manganese phosphate powder for lithium
Material (LiAlyFe1-x-yMnxPO4), wherein the range of x is 0.5≤x≤0.8, and the range of y is 0.002≤y≤0.02.
In embodiment of the present invention, in the step S14, the pretreatment and calcine technology are carried out under protective atmosphere
, the gas of the protective atmosphere includes at least one of nitrogen and argon gas.
In embodiment of the present invention, the partial size of the lithium iron manganese phosphate anode material is nanoscale.Optionally, the phosphoric acid
The partial size of manganese iron lithium anode material is 100-200nm.
The present invention prepares iron manganese phosphate for lithium anode material as lithium source and partial phosphorus source by lithium phosphate obtained above
Material, preparation cost is lower, and does not generate waste liquid, the waste residue that pollution is generated to environment during the preparation process, environmental-friendly, obtains
Lithium iron manganese phosphate anode material energy density it is higher, electrochemical performance.
Third aspect present invention provides a kind of preparation method of lithium iron phosphate positive material, comprising:
S20 obtains ground phosphate rock after being crushed rock phosphate in powder, the ground phosphate rock is dissolved in acid, is then filtered, filtrate is obtained
A；
S21 is added alkaline matter into the filtrate A, stirs simultaneously, until resulting pH value of solution is 6.0-8.5, then
Carbonate is added, is filtered after the reaction was continued 30-120min, obtains liquor B；
Soluble lithium salt is added into the liquor B, while alkaline matter is added by S22, stirring, until resulting solution
PH is 9.0-12.0, and filtering obtains lithium phosphate filter residue；After drying, lithium phosphate is obtained；
S23 mixes the lithium phosphate, source of iron and phosphorus source according to the molar ratio of each element in lithium iron phosphate positive material,
Obtain mixing material；
S24 will obtain ferric lithium phosphate precursor after the mixing material ball milling, drying；By the ferric lithium phosphate precursor
Lithium iron phosphate positive material is obtained after calcining.
In embodiment of the present invention, the concrete operations technique of described S20, S21 and S22 can be found in each step of first aspect
Suddenly.
In embodiment of the present invention, according to the molar ratio of each element in lithium iron phosphate positive material, by the lithium phosphate, iron
Source and phosphorus source mixing, obtain mixing material.Optionally, molar ratio nLi:nFe:nP=(1.0-1.1): (0.95- of each element
1): (0.95-1).
In embodiment of the present invention, the source of iron and phosphorus source can be source of iron and the phosphorus described in above-mentioned second aspect
Source.
In embodiment of the present invention, in the step S23, carbon source is also added into form mixing material, the carbon source packet
It includes in citric acid, malic acid, tartaric acid, oxalic acid, salicylic acid, succinic acid, glycine, ethylenediamine tetra-acetic acid, sucrose and glucose
At least one.Optionally, the quality that the carbon source is added is the 10%-50% of target product LiFePO4 quality.The present invention
After carbon source is added, the carbon source can form carbon coating layer on LiFePO4 surface, improve the electric conductivity of LiFePO4.
In embodiment of the present invention, in the step S23, solvent is also added into form mixing material, the solvent packet
Include water, methanol, ethyl alcohol, propyl alcohol, isopropanol, n-butanol, isobutanol, n-amyl alcohol, n-hexyl alcohol, n-heptanol, acetone, butanone, fourth two
Ketone, pentanone, cyclopentanone, at least one of ketone, cyclohexanone and cycloheptanone.Optionally, the mixing material after addition solvent
Solid content be 30%-60%.
In embodiment of the present invention, in the step S23, can also be added metallic compound with the LiFePO4 just
Doped metallic elements in the material of pole.Optionally, the type and additional amount of the metallic compound can be selected according to the actual situation
It selects.If the metal of doping can be aluminium, the chemical formula of the lithium iron phosphate positive material of aluminium doping is (LiAlyFe1-yPO4) wherein y
Range be 0.002≤y≤0.02.
In embodiment of the present invention, in the step S24, the Ball-milling Time is 10-48 hours.
In embodiment of the present invention, in the step S24, it is dried the mixing material after ball milling to obtain powder.It can
The operation of selection of land, the drying includes: that the mixing material after ball milling is placed in air dry oven, 80-300 DEG C at a temperature of it is dry
Dry 2-20 hours obtains powder.
In embodiment of the present invention, in the step S24, after gained powder is crushed with disintegrating apparatus, at 400-600 DEG C
At a temperature of pre-process 2-10 hours, obtain ferric lithium phosphate precursor.Optionally, the partial size of the ferric lithium phosphate precursor is to receive
Meter level.
Temperature in embodiment of the present invention, in the step S24, by the ferric lithium phosphate precursor at 500-900 DEG C
Sintering 10-30 hours, obtains LiFePO 4 powder material.
In embodiment of the present invention, in the step S24, the pretreatment and calcine technology are carried out under protective atmosphere
, the gas of the protective atmosphere includes at least one of nitrogen and argon gas.
In embodiment of the present invention, the partial size of the lithium iron phosphate positive material is nanoscale.
The present invention prepares lithium iron phosphate positive material as lithium source and part phosphorus source by lithium phosphate obtained above, this
Outside, a part of phosphorus source is added additionally with the amount of phosphorus in completion LiFePO4.
The preparation method for the lithium iron phosphate positive material that third aspect present invention provides, passes through the phosphoric acid as made from phosphorus ore
Lithium prepares lithium iron phosphate positive material as lithium source and partial phosphorus source, and preparation cost is lower, and during the preparation process not
Waste liquid, the waste residue that pollution is generated to environment are generated, environmental-friendly, obtained lithium iron phosphate positive material energy density is higher, electricity
Chemical property is excellent.
It is understood that the lithium phosphate that the present invention is prepared by phosphorus ore, can also be used to preparing other lithium ion batteries just
Pole material.
Embodiment 1:
A method of lithium phosphate is prepared by phosphorus ore, comprising the following steps:
(1) it is sieved with 100 mesh sieve after being crushed rock phosphate in powder, obtains ground phosphate rock, in concentrated sulfuric acid by ground phosphate rock dissolution, at 100 DEG C
Under carry out dissolution reaction 1h, after filtering, obtain filtrate A；
(2) ammonium hydroxide is added into filtrate A, stirs simultaneously, mixing speed 100r/min, until resulting pH value of solution is
6.0, continue stirring 30min then according to the content of the calcium ion and magnesium ion that measure in filtrate A and corresponding mole is added
Ammonium carbonate, i.e., the ratio between integral molar quantity of calcium ion and magnesium ion contained in the mole of ammonium carbonate and filtrate A is 1:1, after
It is filtered after continuous reaction 30min, obtains the liquor B containing monoammonium phosphate and ammonium phosphate；
(3) phosphorus is pressed into liquor B: lithium molar ratio is that lithium sulfate is added in 1:3, while ammonium hydroxide is added, and is stirred, until resulting
PH value of solution is 9.0, continues to stir 30min, and then mixing speed 100r/min is filtered, obtain lithium phosphate filter residue；By lithium phosphate
After filter residue dries 20h at a temperature of 60 DEG C in air atmosphere, then it is placed in vacuum environment in 120 DEG C of dry 10h, after crushing
To lithium phosphate.
The present embodiment can achieve 85% or more to the phosphorus recovery rate in phosphorus ore.
Embodiment 2:
A method of lithium phosphate is prepared by phosphorus ore, comprising the following steps:
(1) it is sieved with 100 mesh sieve after being crushed rock phosphate in powder, obtains ground phosphate rock, ground phosphate rock is dissolved in concentrated nitric acid, at 40 DEG C
Dissolution reaction 6h is carried out, after filtering, obtains filtrate A；
(2) ammonium hydroxide is added into filtrate A, stirs simultaneously, mixing speed 400r/min, until resulting pH value of solution is
8.5, continue stirring 60min then according to the content of the calcium ion and magnesium ion that measure in filtrate A and corresponding mole is added
Ammonium carbonate, i.e., the ratio between integral molar quantity of calcium ion and magnesium ion contained in the mole of ammonium carbonate and filtrate A is 1:1, after
It is filtered after continuous reaction 120min, obtains the liquor B containing monoammonium phosphate and ammonium phosphate；
(3) phosphorus is pressed into liquor B: lithium molar ratio is that lithium sulfate is added in 1:3, while ammonium hydroxide is added, and is stirred, until resulting
PH value of solution is 12.0, continues to stir 60min, and then mixing speed 400r/min is filtered, obtain lithium phosphate filter residue；By phosphoric acid
After lithium filter residue dries 6h at a temperature of 200 DEG C in air atmosphere, then it is placed in vacuum environment in 200 DEG C of dry 2h, after crushing
Obtain lithium phosphate；
The present embodiment can achieve 85% or more to the phosphorus recovery rate in phosphorus ore.
Embodiment 3:
A method of lithium phosphate is prepared by phosphorus ore, comprising the following steps:
(1) it is sieved with 100 mesh sieve after being crushed rock phosphate in powder, obtains ground phosphate rock, ground phosphate rock is dissolved in concentrated hydrochloric acid, at 60 DEG C
Dissolution reaction 3h is carried out, after filtering, obtains filtrate A；
(2) ammonium hydroxide is added into filtrate A, stirs simultaneously, mixing speed 300r/min, until resulting pH value of solution is
7.5, continue stirring 120min then according to the content of the calcium ion and magnesium ion that measure in filtrate A and corresponding mole is added
Ammonium carbonate, i.e., the ratio between integral molar quantity of calcium ion and magnesium ion contained in the mole of ammonium carbonate and filtrate A is 1:1, after
It is filtered after continuous reaction 60min, obtains the liquor B containing monoammonium phosphate and ammonium phosphate；
(3) phosphorus is pressed into liquor B: lithium molar ratio is that lithium sulfate is added in 1:3, while ammonium hydroxide is added, and is stirred, until resulting
PH value of solution is 10.5, continues to stir 120min, and then mixing speed 300r/min is filtered, obtain lithium phosphate filter residue；By phosphoric acid
After lithium filter residue dries 10h at a temperature of 100 DEG C in air atmosphere, then it is placed in vacuum environment in 150 DEG C of dry 5h, after crushing
Obtain lithium phosphate；
The present embodiment can achieve 85% or more to the phosphorus recovery rate in phosphorus ore.
Embodiment 4:
A kind of preparation method of lithium iron manganese phosphate anode material, comprising:
(1) nLi:nFe:nP:nMn=1.0:0.2:1.0:0.8 in molar ratio, be added lithium phosphate made from embodiment 1 with
And ferrous carbonate, phosphoric acid and manganese dioxide, and citric acid and solvent is added, obtain mixing material；
(2) it by after mixing material ball milling 10 hours, is placed in air dry oven, was obtained at 80 DEG C of temperature dry 20 hours
Powder is placed in nitrogen furnace after crushing gained powder with disintegrating apparatus, 400 DEG C at a temperature of pre-process 10 hours, obtain
Nano lithium iron manganese presoma；
(3) nano lithium iron manganese presoma is placed in nitrogen furnace, 500 DEG C at a temperature of be sintered 30 hours, obtain
Nano lithium iron manganese powder body material LiFe0.2Mn0.8PO4。
Fig. 2 is lithium iron manganese phosphate anode material LiFe made from the embodiment of the present invention 40.2Mn0.8PO4Scanning electron microscope (SEM) photograph；
From figure 2 it can be seen that the partial size of lithium iron manganese phosphate anode material is 100-200nm.
X-ray diffraction test is carried out to (XRD) positive electrode of iron manganese phosphate for lithium made from the embodiment of the present invention 4；Fig. 3 is this
The X ray diffracting spectrum of iron manganese phosphate for lithium made from inventive embodiments 4 (XRD) positive electrode；By anode obtained by embodiment 4
Material and standard card compare, it is seen that and iron manganese phosphate for lithium peak is obtained, illustrates to have prepared lithium iron manganese phosphate anode material, and
And the peak of the XRD obtained is more sharp, illustrates that crystallinity is relatively good.
Embodiment 5:
A kind of preparation method of lithium iron manganese phosphate anode material, comprising:
(1) nLi:nFe:nP:nMn=1.1:0.5:0.95:0.5 in molar ratio, be added lithium phosphate made from embodiment 2,
Ferrous hydroxide, diammonium hydrogen phosphate and manganese sesquioxide managnic oxide, and malic acid and solvent is added, obtain mixing material；
(2) it by after mixing material ball milling 48 hours, is placed in air dry oven, was obtained at 300 DEG C of temperature dry 2 hours
Powder is placed in nitrogen furnace after crushing gained powder with disintegrating apparatus, 600 DEG C at a temperature of pre-process 2 hours, obtain
Nano lithium iron manganese presoma；
(3) nano lithium iron manganese presoma is placed in nitrogen furnace, 900 DEG C at a temperature of be sintered 10 hours, obtain
Nano lithium iron manganese powder body material LiFe0.5Mn0.5PO4。
Embodiment 6:
A kind of preparation method of lithium iron manganese phosphate anode material, comprising:
(1) lithium phosphate, lemon made from embodiment 3 is added in nLi:nFe:nP:nMn=1.0:0.4:1.0:0.6 in molar ratio
Lemon acid iron, ammonium dihydrogen phosphate and mangano-manganic oxide, and oxalic acid and solvent is added, obtain mixing material；
(2) by after mixing material ball milling 30 hours, be placed in air dry oven, 200 DEG C at a temperature of it is 10 hours dry
Obtain powder, after gained powder is crushed with disintegrating apparatus, be placed in nitrogen furnace, 500 DEG C at a temperature of pre-process 8 hours,
Obtain nano lithium iron manganese presoma；
(3) nano lithium iron manganese presoma is placed in nitrogen furnace, 700 DEG C at a temperature of be sintered 20 hours, obtain
Nano lithium iron manganese powder body material LiFe0.4Mn0.6PO4。
Embodiment 7:
A kind of preparation method of lithium iron manganese phosphate anode material, comprising:
(1) aluminium hydroxide, reality is added in nAl:nLi:nFe:nP:nMn=0.005:1.0:0.195:1.0:0.8 in molar ratio
It applies lithium phosphate made from example 1 and ferric nitrate, lithium dihydrogen phosphate and manganese oxalate and salicylic acid and solvent is added, obtain mixing material
Material；
(2) by after mixing material ball milling 30 hours, be placed in air dry oven, 200 DEG C at a temperature of it is 10 hours dry
Obtain powder, after gained powder is crushed with disintegrating apparatus, be placed in nitrogen furnace, 500 DEG C at a temperature of pre-process 8 hours,
Obtain nano lithium iron manganese presoma；
(3) nano lithium iron manganese presoma is placed in nitrogen furnace, 700 DEG C at a temperature of be sintered 20 hours, obtain
Nano lithium iron manganese powder body material LiAl0.005Fe0.195Mn0.8PO4。
Effect example
Lithium iron manganese phosphate anode material, polyvinylidene fluoride binder and carbon black conductive agent obtained above are taken, by the phosphoric acid
Manganese iron lithium anode material, the adhesive and the conductive agent are mixed with mass ratio for the ratio of 93:3:4, and mixture is obtained, and
It adds this mixture in NMP (N-Methyl pyrrolidone) solvent, obtains mixed slurry, be then coated in the mixed slurry
The surface of aluminium base obtains positive plate after dry；Wherein, according to mixture in the solution content 60% ratio be added NMP it is molten
Agent, and ball grinding stirring 1 hour is mixed into slurry.Drying temperature is 110 DEG C；
The positive plate, cathode pole piece, diaphragm and electrolyte are assembled into lithium ion battery, which includes ethylene carbonate
Ester, methyl ethyl carbonate and lithium hexafluoro phosphate, wherein the volume ratio of the ethylene carbonate and the methyl ethyl carbonate is 3:7, the hexafluoro
The concentration of lithium phosphate is 1M.
The battery being assembled into nano lithium iron manganese phosphate anode material prepared by the embodiment of the present invention 4 carries out chemical property
Test, wherein Discharge test is as shown in Figure 4.According to test result it can be seen that battery 1.0C electric discharge gram volume is reachable
140mAh/g, mean voltage can achieve 3.85V or more, illustrate the excellent material performance.
Lithium iron phosphate positive material is prepared according to the similar method of above-described embodiment 4-7, and just by LiFePO4 obtained
The battery that pole material is assembled into carries out electrochemical property test, according to test result it is found that lithium iron phosphate positive material obtained
Performance is also very excellent.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
Limitations on the scope of the patent of the present invention therefore cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention
Protect range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of method for preparing lithium phosphate by phosphorus ore, which comprises the following steps:
Ground phosphate rock is obtained after rock phosphate in powder is crushed, the ground phosphate rock is dissolved in acid, is then filtered, filtrate A is obtained；
Alkaline matter is added into the filtrate A, stirs simultaneously, until resulting pH value of solution is 6.0-8.5, carbonic acid is then added
Salt filters after the reaction was continued 30-120min, obtains liquor B；
Soluble lithium salt is added into the liquor B, while alkaline matter is added, stirs, until resulting pH value of solution is 9.0-
12.0, filtering obtains lithium phosphate filter residue；After drying, lithium phosphate is obtained.
2. the method for preparing lithium phosphate by phosphorus ore as described in claim 1, which is characterized in that the carbonate includes carbonic acid
At least one of ammonium, sodium carbonate and potassium carbonate.
3. the method for preparing lithium phosphate by phosphorus ore as described in claim 1, which is characterized in that the additional amount of the carbonate
Are as follows: the ratio between integral molar quantity of calcium ion and magnesium ion contained in the mole of the carbonate and the filtrate A is 1:1.
4. the method for preparing lithium phosphate by phosphorus ore as described in claim 1, which is characterized in that the soluble lithium salt includes sulphur
At least one of sour lithium, lithium nitrate, lithium acetate and lithium chloride.
5. the method for preparing lithium phosphate by phosphorus ore as described in claim 1, which is characterized in that press phosphorus: lithium molar ratio be 1:3 to
The soluble lithium salt is added in the liquor B.
6. the method for preparing lithium phosphate by phosphorus ore as described in claim 1, which is characterized in that institute is added into the liquor B
Alkaline matter is stated, until continuing to stir 30-120min, then carrying out the filtering again after resulting pH value of solution is 9.0-12.0.
7. the method for preparing lithium phosphate by phosphorus ore as described in claim 1, which is characterized in that the operation of the drying includes:
By the lithium phosphate filter residue in air atmosphere, at a temperature of 60-200 DEG C after dry 6-20h, then it is placed in vacuum environment
Dry 2-10h, obtains the lithium phosphate at a temperature of 120-200 DEG C after crushing.
8. the method for preparing lithium phosphate by phosphorus ore as described in claim 1, which is characterized in that the acid includes sulfuric acid, nitric acid
At least one of with hydrochloric acid.
9. a kind of preparation method of lithium iron manganese phosphate anode material characterized by comprising
Ground phosphate rock is obtained after rock phosphate in powder is crushed, the ground phosphate rock is dissolved in acid, is then filtered, filtrate A is obtained；
Alkaline matter is added into the filtrate A, stirs simultaneously, until resulting pH value of solution is 6.0-8.5, carbonic acid is then added
Salt filters after the reaction was continued 30-120min, obtains liquor B；
Soluble lithium salt is added into the liquor B, while alkaline matter is added, stirs, until resulting pH value of solution is 9.0-
12.0, filtering obtains lithium phosphate filter residue；After drying, lithium phosphate is obtained；
According to the molar ratio of each element in iron manganese phosphate for lithium, the lithium phosphate, source of iron, manganese source and phosphorus source are mixed, mixed
Material；
Iron manganese phosphate for lithium presoma will be obtained after the mixing material ball milling, drying；The iron manganese phosphate for lithium presoma is calcined
After obtain lithium iron manganese phosphate anode material.
10. a kind of preparation method of lithium iron phosphate positive material characterized by comprising
Ground phosphate rock is obtained after rock phosphate in powder is crushed, the ground phosphate rock is dissolved in acid, is then filtered, filtrate A is obtained；
Alkaline matter is added into the filtrate A, stirs simultaneously, until resulting pH value of solution is 6.0-8.5, carbonic acid is then added
Salt filters after the reaction was continued 30-120min, obtains liquor B；
Soluble lithium salt is added into the liquor B, while alkaline matter is added, stirs, until resulting pH value of solution is 9.0-
12.0, filtering obtains lithium phosphate filter residue；After drying, lithium phosphate is obtained；
According to the molar ratio of each element in lithium iron phosphate positive material, the lithium phosphate, source of iron and phosphorus source are mixed, mixed
Material；
Ferric lithium phosphate precursor will be obtained after the mixing material ball milling, drying；It will be obtained after ferric lithium phosphate precursor calcining
To lithium iron phosphate positive material.
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