CN109231182A - The method of ammonium dihydrogen 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 ammonium dihydrogen 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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Abstract
The present invention provides a kind of methods for preparing ammonium dihydrogen phosphate by phosphorus ore, comprising: obtains ground phosphate rock after being crushed rock phosphate in powder, ground phosphate rock is dissolved in nitric acid, filtrate A is then obtained by filtration；Ammonium sulfate is added into filtrate A, after stirring 30-60min, liquor B is obtained by filtration；Barium salt is added into liquor B, is filtered after stirring 30-60min, obtains liquor C；Ammonium hydroxide is added into liquor C, is stirred simultaneously, until the pH of acquired solution is 3.8-7.0, filtrate D is obtained by filtration；Ammonium carbonate is added into filtrate D, after stirring 30-60min, filtrate E is obtained by filtration；It is dry after filtrate E is concentrated and is crystallized, obtain ammonium dihydrogen phosphate.Phosphorus ore is rationally utilized in the method provided by the invention for preparing ammonium dihydrogen phosphate by phosphorus ore, and low cost is prepared for ammonium dihydrogen phosphate, simple process.The present invention also prepares the positive electrodes such as iron manganese phosphate for lithium as raw material as the ammonium dihydrogen phosphate made from phosphorus ore.
Description
Technical field
The present invention relates to field of lithium ion battery anode, and in particular to a kind of side that ammonium dihydrogen phosphate is prepared by phosphorus ore
The preparation method of method, 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 ammonium dihydrogen phosphate by phosphorus ore, and will be described
Ammonium dihydrogen phosphate 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 ammonium dihydrogen 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 nitric acid, is then filtered, filtrate A is obtained；
Ammonium sulfate is added into the filtrate A, after stirring 30-60min, filtering obtains liquor B；
Barium salt is added into the liquor B, after stirring 30-60min, filtering obtains liquor C；
Ammonium hydroxide is added into the liquor C, is stirred simultaneously, until the pH of acquired solution is 3.8-7.0, then filters
Obtain filtrate D；
Ammonium carbonate is added into the filtrate D, after stirring 30-60min, filtering obtains filtrate E；
The filtrate E is concentrated and is crystallized, then dries, obtains ammonium dihydrogen phosphate.
Wherein, the additional amount of the ammonium sulfate are as follows: the calcium ion contained in the mole of the ammonium sulfate and the filtrate A
The ratio between mole be (1-1.05): 1.
Wherein, the barium salt includes at least one of barium carbonate, barium nitrate and barium hydroxide.
Wherein, the additional amount of the barium salt are as follows: the sulfate ion contained in the mole of the barium salt and the liquor B
The ratio between mole be 1:1.
Wherein, the additional amount of the ammonium carbonate are as follows: the calcium ion contained in the mole of the ammonium carbonate and the filtrate D
It is (1-1.1) with the ratio between the integral molar quantity of magnesium ion: 1.
Wherein, the operation of the drying includes: to be dried in vacuo 6-12h at a temperature of 110-130 DEG C.
Wherein, ammonium hydroxide is added into the liquor C, until continuing to stir 30- after the pH of acquired solution is 3.8-7.0
After 60min, then carry out the filtering.
Wherein, it is heated in the course of dissolution, the temperature of the heating is 40-100 DEG C, the dissolution reaction
Time is 1-6h.
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 nitric acid, is then filtered, filtrate A is obtained；
Ammonium sulfate is added into the filtrate A, after stirring 30-60min, filtering obtains liquor B；
Barium salt is added into the liquor B, after stirring 30-60min, filtering obtains liquor C；
Ammonium hydroxide is added into the liquor C, is stirred simultaneously, until the pH of acquired solution is 3.8-7.0, then filters
Obtain filtrate D；
Ammonium carbonate is added into the filtrate D, after stirring 30-60min, filtering obtains filtrate E；
The filtrate E is concentrated and is crystallized, then dries, obtains ammonium dihydrogen phosphate；
According to the molar ratio of each element in iron manganese phosphate for lithium, the ammonium dihydrogen phosphate, lithium source, source of iron and manganese source are mixed,
Obtain 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 nitric acid, is then filtered, filtrate A is obtained；
Ammonium sulfate is added into the filtrate A, after stirring 30-60min, filtering obtains liquor B；
Barium salt is added into the liquor B, after stirring 30-60min, filtering obtains liquor C；
Ammonium hydroxide is added into the liquor C, is stirred simultaneously, until the pH of acquired solution is 3.8-7.0, then filters
Obtain filtrate D；
Ammonium carbonate is added into the filtrate D, after stirring 30-60min, filtering obtains filtrate E；
The filtrate E is concentrated and is crystallized, then dries, obtains ammonium dihydrogen phosphate；
According to the molar ratio of each element in lithium iron phosphate positive material, the ammonium dihydrogen phosphate, source of iron and lithium source are mixed,
Obtain 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 ammonium dihydrogen phosphate by phosphorus ore, and phosphorus ore, and low cost is rationally utilized
It is prepared for ammonium dihydrogen phosphate, simple process.
2, the present invention prepares lithium iron manganese phosphate anode material as phosphorus source as the ammonium dihydrogen phosphate made from phosphorus ore,
Preparation cost is lower and environmental-friendly, and obtained lithium iron manganese phosphate anode material energy density is higher, electrochemical performance；
3, the present invention prepares lithium iron phosphate positive material as phosphorus source as the ammonium dihydrogen phosphate made from phosphorus ore, makes
Standby cost is relatively low and environmental-friendly, and obtained lithium iron phosphate positive material energy density is higher, electrochemical performance.
Detailed description of the invention
Fig. 1 is the method flow schematic diagram that ammonium dihydrogen 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 ammonium dihydrogen phosphate by phosphorus ore, including following
Step:
S01 obtains ground phosphate rock after being crushed rock phosphate in powder, the ground phosphate rock is dissolved in nitric acid, is then filtered, is filtered
Liquid A；
Ammonium sulfate is added into the filtrate A by S02, and after stirring 30-60min, filtering obtains liquor B；
Barium salt is added into the liquor B by S03, and after stirring 30-60min, filtering obtains liquor C；
Ammonium hydroxide is added into the liquor C, is stirred simultaneously by S04, until the pH of acquired solution is 3.8-7.0, then
Filtrate D is obtained by filtration；
Ammonium carbonate is added into the filtrate D by S05, and after stirring 30-60min, filtering obtains filtrate E；
Then S06 dries after the filtrate E is concentrated and is crystallized, obtains ammonium dihydrogen phosphate.
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 present invention selects nitric acid to dissolve ground phosphate rock, will not introduce other in this way
Anion.The nitrate anion that addition nitric acid introduces is subsequent can to form ammonium nitrate, and then is got rid of by heat resolve.Optionally,
The nitric acid is concentrated acid.Still optionally further, the mass fraction of the concentrated nitric acid is 65%-68%.In the matter of the concentrated nitric acid
It measures under score, ground phosphate rock can be completely dissolved, and improve the recovery rate of phosphorus.
In embodiment of the present invention, in step S01, the additional amount of the nitric acid is CaO, MgO, Al in phosphorus ore2O3、Fe2O3
The 100%-120% of required nitric acid amount when being reacted completely with nitric acid.
It in embodiment of the present invention, in step S01, is heated in the course of dissolution, the temperature of the heating is
40-100℃。
In embodiment of the present invention, in step S01, the time of the dissolution reaction is 1-6h.
In embodiment of the present invention, in step S02, the mixing speed is 100-400r/min.
In embodiment of the present invention, calcium ion is contained in the filtrate A, the additional amount of the ammonium sulfate is that can make calcium ion
Calcium sulfate precipitation is formed to remove calcium ion from filtrate.Optionally, institute is measured according to spectrophotometry or volumetric precipitation method
The content of Ca in filtrate is stated, the ammonium sulfate of corresponding mole is added then to generate calcium sulfate precipitation.I.e. according to each in calcium sulfate
Ammonium sulfate is added in the molar ratio of element.Optionally, the additional amount of the ammonium sulfate are as follows: the mole of the ammonium sulfate and the filter
The ratio between mole of calcium ion contained in liquid is (1-1.05): 1.Still optionally further, the mole of the ammonium sulfate and institute
Stating the ratio between mole of calcium ion contained in filtrate is 1:1.
In embodiment of the present invention, the addition of ammonium sulfate removes calcium ion well, at the same will not introduce again other it is miscellaneous from
Son.
In embodiment of the present invention, the barium salt is the barium salt for dissolving in acid solution.Optionally, the barium salt includes carbon
At least one of sour barium, barium nitrate and barium hydroxide.
In embodiment of the present invention, sulfate ion is contained in the liquor B, the additional amount of the barium salt is that can make to own
Sulfate ion forms barium sulfate precipitate to remove sulfate ion from filtrate.Optionally, according to spectrophotometry or appearance
Amount titration measures the content of sulfate radical in the liquor B, the barium salt of corresponding mole is added then to generate barium sulfate precipitate.
Barium salt is added according to the molar ratio of each element in barium sulfate.Optionally, the additional amount of the barium salt are as follows: mole of the barium salt
The ratio between mole of sulfate ion contained in amount and the liquor B is 1:1.
In embodiment of the present invention, in step S03, the mixing speed is 100-400r/min.
Liquor C and barium sulfate precipitate in embodiment of the present invention, after sulphur removal is obtained in step S03, after filtering.
In embodiment of the present invention, in step S04, the concentration of the ammonium hydroxide is regular industrial ammonia concn.
In embodiment of the present invention, in step S04, the mixing speed is 100-400r/min.
In embodiment of the present invention, in step S04, be added ammonium hydroxide after reaction until resulting pH value of solution be 3.8-5.0 or
5.0-7.0.Optionally, reaction is until resulting pH value of solution is 3.8-4.2 after ammonium hydroxide is added.Still optionally further, the pH is
3.8,4.0,4.5,5.0,5.5,6.0,6.5 or 7.0.
In embodiment of the present invention, in step S04, it is slowly added to ammonium hydroxide into the liquor C, is stirred simultaneously, directly
After pH to acquired solution is 3.8-7.0, stop that ammonium hydroxide is added, continue after stirring 30-120min, then carry out the filtering.
In embodiment of the present invention, in step S04, after filtering, filtrate D and phosphoric acid aluminum precipitation are obtained.The filtrate D be containing
There is the ammonium dihydrogen phosphate of a small amount of calcium, magnesium addition.
In embodiment of the present invention, in step S05, calcium ion and magnesium ion are contained in the filtrate D, the ammonium carbonate
Additional amount is that the calcium ion and the magnesium ion can be made to form precipitation of calcium carbonate and carbonic acid magnesium precipitate to remove from filtrate
The calcium ion and the magnesium ion.Optionally, it is measured according to spectrophotometry or volumetric precipitation method and to be contained in the filtrate D
Then the ammonium carbonate of corresponding mole is added to generate precipitation of calcium carbonate and carbonic acid magnesium precipitate in the content of calcium ion and magnesium ion.
Optionally, the ratio between integral molar quantity of calcium ion and magnesium ion contained in the mole of the ammonium carbonate and the filtrate D is (1-
1.1):1.Still optionally further, the additional amount of the ammonium carbonate are as follows: contain in the mole of the ammonium carbonate and the filtrate D
Calcium ion and the ratio between the integral molar quantity of magnesium ion be 1:1.
In embodiment of the present invention, the addition of ammonium carbonate removes calcium ion and the magnesium ion well, while again will not
Introduce other heteroions.
In embodiment of the present invention, in step S05, the mixing speed is 100-400r/min.
In embodiment of the present invention, in step S05, the filtrate E containing ammonium dihydrogen phosphate and ammonium nitrate is obtained by filtration and contains
There are calcium carbonate and magnesium carbonate mixed precipitation.
In embodiment of the present invention, in step S06, after the filtrate E is concentrated and is crystallized, the concentration and crystallization
Operation can be routine operation, crystallize the filtrate E.
In embodiment of the present invention, in step S06, after crystallization, obtained crystal is dried.Optionally, described dry
Dry operation includes: to be dried in vacuo 6-12h at a temperature of 110-130 DEG C.Nitre in the drying process, in the filtrate E
Sour ammonium, which decomposes, to disappear, to obtain pure ammonium dihydrogen phosphate powder.
In embodiment of the present invention, the purity of ammonium dihydrogen phosphate obtained is 99.5% or more.
The present invention provides a kind of methods for preparing ammonium dihydrogen phosphate by phosphorus ore, and phosphorus ore, and low cost system is rationally utilized
For ammonium dihydrogen phosphate, simple process, and 85% or more can achieve to the phosphorus recovery rate in phosphorus ore, recovery rate is higher.In addition,
Method of the invention is environmentally friendly, during preparing ammonium dihydrogen phosphate and can not generate to environment generate pollution waste liquid,
Waste residue.Ammonium dihydrogen phosphate purity obtained 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 nitric acid, is then filtered, is filtered
Liquid A；
Ammonium sulfate is added into the filtrate A by S11, and after stirring 30-60min, filtering obtains liquor B；
Barium salt is added into the liquor B by S12, and after stirring 30-60min, filtering obtains liquor C；
Ammonium hydroxide is added into the liquor C, is stirred simultaneously by S13, until the pH of acquired solution is 3.8-7.0, then
Filtrate D is obtained by filtration；
Ammonium carbonate is added into the filtrate D by S14, and after stirring 30-60min, filtering obtains filtrate E；
The filtrate E is concentrated and is crystallized, then dried, obtain ammonium dihydrogen phosphate by S15；
S16 mixes the ammonium dihydrogen phosphate, lithium source, source of iron and manganese source according to the molar ratio of each element in iron manganese phosphate for lithium
It closes, obtains mixing material；
S17 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, S12, S13, S14 and S15 can be found in first
Each step of aspect.
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 S16, nLi:nFe:nP:nMn=(1.0-1.1) in molar ratio:
(0.2-0.5): (0.95-1): lithium source, source of iron, ammonium dihydrogen phosphate and manganese source is added in (0.5-0.8), obtains mixing material.
In embodiment of the present invention, by phosphoric acid made from ammonium dihydrogen phosphate made from above-mentioned first aspect or step S15
Ammonium dihydrogen is as phosphorus source.
In embodiment of the present invention, the lithium source includes lithia, lithium hydroxide, lithium acetate, lithium carbonate, lithium nitrate, Asia
At least one of lithium nitrate, lithium phosphate, lithium dihydrogen phosphate and lithium oxalate.
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 S16, 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 S16, 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 S16, 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 S17, the Ball-milling Time is 10-48 hours.
In embodiment of the present invention, in the step S17, 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 S17, 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 S17, 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 S17, 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 lithium iron manganese phosphate anode material as phosphorus source by ammonium dihydrogen phosphate obtained above, is prepared into
This is lower, and does not generate waste liquid, the waste residue that pollution is generated to environment, environmental-friendly, obtained manganese phosphate during the preparation process
Iron lithium anode material energy density 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 nitric acid, is then filtered, is filtered
Liquid A；
Ammonium sulfate is added into the filtrate A by S21, and after stirring 30-60min, filtering obtains liquor B；
Barium salt is added into the liquor B by S22, and after stirring 30-60min, filtering obtains liquor C；
Ammonium hydroxide is added into the liquor C, is stirred simultaneously by S23, until the pH of acquired solution is 3.8-7.0, then
Filtrate D is obtained by filtration；
Ammonium carbonate is added into the filtrate D by S24, and after stirring 30-60min, filtering obtains filtrate E；
The filtrate E is concentrated and is crystallized, then dried, obtain ammonium dihydrogen phosphate by S25；
S26, according to the molar ratio of each element in lithium iron phosphate positive material, by the ammonium dihydrogen phosphate, lithium source and source of iron
Mixing, obtains mixing material；
S27 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, S22, S23, S24 and S25 can be found in first
Each step of aspect.
In embodiment of the present invention, in step S26, according to the molar ratio of each element in lithium iron phosphate positive material, by lithium
Source, source of iron and ammonium dihydrogen phosphate mixing, obtain mixing material.Optionally, the molar ratio nLi:nFe:nP=of each element
(1.0-1.1): (0.95-1): (0.95-1).
In embodiment of the present invention, in step S26, the source of iron and the lithium source can be iron described in above-mentioned second aspect
Source and phosphorus source.
In embodiment of the present invention, in the step S26, 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 S26, 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 S26, 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 S27, the Ball-milling Time is 10-48 hours.
In embodiment of the present invention, in the step S27, 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
Obtain powder within dry 2-20 hours.
In embodiment of the present invention, in the step S27, 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 S27, 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 S27, 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 phosphorus source by ammonium dihydrogen phosphate obtained above.
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
Ammonium dihydrogen prepares lithium iron phosphate positive material as phosphorus source, and preparation cost is lower, and does not generate to ring during the preparation process
Border generates the waste liquid of pollution, waste residue, and environmental-friendly, obtained lithium iron phosphate positive material energy density is higher, chemical property
It is excellent.
It is understood that present invention ammonium dihydrogen phosphate as made from phosphorus ore, can also be used to prepare other lithium-ion electrics
Pond positive electrode.
Embodiment 1:
A method of ammonium dihydrogen 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, it is 65% dense that ground phosphate rock, which is dissolved in mass fraction,
In nitric acid, dissolution reaction 1h is carried out at 100 DEG C, mixed solution is obtained, after filtering, obtains filtrate A；
(2) then according to the content of the calcium ion measured in filtrate A, by the calcium ion molar ratio in ammonium sulfate and filtrate A
Ammonium sulfate is added into filtrate A for 1:1, stirs simultaneously, mixing speed 100r/min, mixing time 30min, then mistake
Filter, obtains liquor B and calcium sulfate filter residue；
(3) it according to the content of the sulfate ion measured in liquor B, rubs by barium carbonate and the sulfate ion in liquor B
Your ratio is that barium carbonate is added into liquor B by 1:1, is stirred simultaneously, mixing speed 400r/min, mixing time 30min,
Then it filters, liquor C and barium sulfate precipitate after obtaining sulphur removal；
(4) ammonium hydroxide is added into liquor C, is stirred simultaneously, mixing speed 100r/min, until the pH of acquired solution
It is 3.8, is filtered after then proceeding to stirring 30min, obtain the filtrate D and phosphoric acid aluminum precipitation of a small amount of calcium, magnesium addition；
(5) total by ammonium carbonate and calcium ion in filtrate D and magnesium ion according to the content of calcium ion and magnesium ion in filtrate D
The molar ratio of amount is that ammonium carbonate solid is added into filtrate D by 1:1, is filtered after stirring 30min, mixing speed 100r/min is obtained
To the mixed precipitation of filtrate E and calcium carbonate containing ammonium dihydrogen phosphate and ammonium nitrate and magnesium carbonate；
(6) filtrate E is concentrated and is crystallized, then in 110 DEG C of vacuum drying 12h, obtain ammonium dihydrogen phosphate powder.
The present embodiment can achieve 85% or more to the phosphorus recovery rate in phosphorus ore.
Embodiment 2:
A method of ammonium dihydrogen 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, it is 68% dense that ground phosphate rock, which is dissolved in mass fraction,
In nitric acid, dissolution reaction 6h is carried out at 40 DEG C, mixed solution is obtained, after filtering, obtains filtrate A；
(2) then according to the content of the calcium ion measured in filtrate A, by the calcium ion molar ratio in ammonium sulfate and filtrate A
Ammonium sulfate is added into filtrate A for 1:1, stirs simultaneously, mixing speed 200r/min, mixing time 40min, then mistake
Filter, obtains liquor B and calcium sulfate filter residue；
(3) it according to the content of the sulfate ion measured in liquor B, rubs by barium nitrate and the sulfate ion in liquor B
Your ratio is that barium nitrate is added into liquor B by 1:1, is stirred simultaneously, mixing speed 200r/min, mixing time 40min,
Then it filters, liquor C and barium sulfate precipitate after obtaining sulphur removal；
(4) ammonium hydroxide is added into liquor C, is stirred simultaneously, mixing speed 200r/min, until the pH of acquired solution
It is 4.2, is filtered after then proceeding to stirring 60min, obtain the filtrate D and phosphoric acid aluminum precipitation of a small amount of calcium, magnesium addition；
(5) total by ammonium carbonate and calcium ion in filtrate D and magnesium ion according to the content of calcium ion and magnesium ion in filtrate D
The molar ratio of amount is that ammonium carbonate solid is added into filtrate D by 1:1, is filtered after stirring 40min, mixing speed 100r/min is obtained
To the mixed precipitation of filtrate E and calcium carbonate containing ammonium dihydrogen phosphate and ammonium nitrate and magnesium carbonate；
(6) filtrate E is concentrated and is crystallized, then in 130 DEG C of vacuum drying 6h, obtain ammonium dihydrogen phosphate powder.
The present embodiment can achieve 85% or more to the phosphorus recovery rate in phosphorus ore.
Embodiment 3:
A method of ammonium dihydrogen 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, it is 66% dense that ground phosphate rock, which is dissolved in mass fraction,
In nitric acid, dissolution reaction 4h is carried out at 60 DEG C, mixed solution is obtained, after filtering, obtains filtrate A；
(2) then according to the content of the calcium ion measured in filtrate A, by the calcium ion molar ratio in ammonium sulfate and filtrate A
Ammonium sulfate is added into filtrate A for 1:1, stirs simultaneously, mixing speed 100r/min, mixing time 60min, then mistake
Filter, obtains liquor B and calcium sulfate filter residue；
(3) it according to the content of the sulfate ion measured in liquor B, rubs by barium carbonate and the sulfate ion in liquor B
Your ratio is that barium carbonate is added into liquor B by 1:1, is stirred simultaneously, mixing speed 100r/min, mixing time 60min,
Then it filters, liquor C and barium sulfate precipitate after obtaining sulphur removal；
(4) ammonium hydroxide is added into liquor C, is stirred simultaneously, mixing speed 100r/min, until the pH of acquired solution
It is 7.0, is filtered after then proceeding to stirring 120min, obtain the filtrate D and phosphoric acid aluminum precipitation of a small amount of calcium, magnesium addition；
(5) total by ammonium carbonate and calcium ion in filtrate D and magnesium ion according to the content of calcium ion and magnesium ion in filtrate D
The molar ratio of amount is that ammonium carbonate solid is added into filtrate D by 1:1, is filtered after stirring 60min, mixing speed 100r/min is obtained
To the mixed precipitation of filtrate E and calcium carbonate containing ammonium dihydrogen phosphate and ammonium nitrate and magnesium carbonate；
(6) filtrate E is concentrated and is crystallized, then in 120 DEG C of vacuum drying 8h, obtain ammonium dihydrogen phosphate powder.
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) lithia, ferrous carbonate, embodiment is added in nLi:nFe:nP:nMn=1.0:0.2:1.0:0.8 in molar ratio
Ammonium dihydrogen phosphate made from 1, 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 the X ray diffracting spectrum of iron manganese phosphate for lithium (XRD) positive electrode made from the embodiment of the present invention 4；It will implement
Positive electrode obtained by example 4 and standard card compare, it is seen that obtain iron manganese phosphate for lithium peak, illustrate to have prepared manganese phosphate
Iron lithium anode material, 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 hydroxide, ferrous hydroxide,
Ammonium dihydrogen phosphate made from embodiment 2, 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 acetate, ironic citrate, embodiment 3 is added in nLi:nFe:nP:nMn=1.0:0.4:1.0:0.6 in molar ratio
Ammonium dihydrogen phosphate obtained, 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, carbon is added in nAl:nLi:nFe:nP:nMn=0.005:1.0:0.195:1.0:0.8 in molar ratio
Simultaneously salicylic acid and solvent is added in sour lithium, ferric nitrate, ammonium dihydrogen phosphate made from embodiment 1, manganese oxalate, obtains 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 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 that the material electrochemical performance is excellent.
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
Chemical property 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 ammonium dihydrogen 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 nitric acid, is then filtered, filtrate A is obtained；
Ammonium sulfate is added into the filtrate A, after stirring 30-60min, filtering obtains liquor B；
Barium salt is added into the liquor B, after stirring 30-60min, filtering obtains liquor C；
Ammonium hydroxide is added into the liquor C, is stirred simultaneously, until the pH of acquired solution is 3.8-7.0, is then obtained by filtration
Filtrate D；
Ammonium carbonate is added into the filtrate D, after stirring 30-60min, filtering obtains filtrate E；
The filtrate E is concentrated and is crystallized, then dries, obtains ammonium dihydrogen phosphate.
2. the method for preparing ammonium dihydrogen phosphate by phosphorus ore as described in claim 1, which is characterized in that the addition of the ammonium sulfate
Amount are as follows: the ratio between mole of calcium ion contained in the mole of the ammonium sulfate and the filtrate A is (1-1.05): 1.
3. the method for preparing ammonium dihydrogen phosphate by phosphorus ore as described in claim 1, which is characterized in that the barium salt includes carbonic acid
At least one of barium, barium nitrate and barium hydroxide.
4. the method for preparing ammonium dihydrogen phosphate by phosphorus ore as described in claim 1, which is characterized in that the additional amount of the barium salt
Are as follows: the ratio between mole of sulfate ion contained in the mole of the barium salt and the liquor B is 1:1.
5. the method for preparing ammonium dihydrogen phosphate by phosphorus ore as described in claim 1, which is characterized in that the addition of the ammonium carbonate
Amount are as follows: the ratio between integral molar quantity of calcium ion and magnesium ion contained in the mole of the ammonium carbonate and the filtrate D is (1-
1.1):1。
6. the method for preparing ammonium dihydrogen phosphate by phosphorus ore as described in claim 1, which is characterized in that the operation packet of the drying
It includes: being dried in vacuo 6-12h at a temperature of 110-130 DEG C.
7. the method for preparing ammonium dihydrogen phosphate by phosphorus ore as described in claim 1, which is characterized in that add into the liquor C
Enter ammonium hydroxide, until continuing after stirring 30-60min, then carry out the filtering after the pH of acquired solution is 3.8-7.0.
8. the method for preparing ammonium dihydrogen phosphate by phosphorus ore as described in claim 1, which is characterized in that in the course of dissolution
It is heated, the temperature of the heating is 40-100 DEG C, and the time of the dissolution reaction is 1-6h.
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 nitric acid, is then filtered, filtrate A is obtained；
Ammonium sulfate is added into the filtrate A, after stirring 30-60min, filtering obtains liquor B；
Barium salt is added into the liquor B, after stirring 30-60min, filtering obtains liquor C；
Ammonium hydroxide is added into the liquor C, is stirred simultaneously, until the pH of acquired solution is 3.8-7.0, is then obtained by filtration
Filtrate D；
Ammonium carbonate is added into the filtrate D, after stirring 30-60min, filtering obtains filtrate E；
The filtrate E is concentrated and is crystallized, then dries, obtains ammonium dihydrogen phosphate；
According to the molar ratio of each element in iron manganese phosphate for lithium, the ammonium dihydrogen phosphate, lithium source, source of iron and manganese source are mixed, obtained
Mixing 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 nitric acid, is then filtered, filtrate A is obtained；
Ammonium sulfate is added into the filtrate A, after stirring 30-60min, filtering obtains liquor B；
Barium salt is added into the liquor B, after stirring 30-60min, filtering obtains liquor C；
Ammonium hydroxide is added into the liquor C, is stirred simultaneously, until the pH of acquired solution is 3.8-7.0, is then obtained by filtration
Filtrate D；
Ammonium carbonate is added into the filtrate D, after stirring 30-60min, filtering obtains filtrate E；
The filtrate E is concentrated and is crystallized, then dries, obtains ammonium dihydrogen phosphate；
According to the molar ratio of each element in lithium iron phosphate positive material, the ammonium dihydrogen phosphate, source of iron and lithium source are mixed, obtained
Mixing 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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