CN103825024B - A kind of battery-grade iron phosphate and preparation method thereof - Google Patents

A kind of battery-grade iron phosphate and preparation method thereof Download PDF

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CN103825024B
CN103825024B CN201410062178.9A CN201410062178A CN103825024B CN 103825024 B CN103825024 B CN 103825024B CN 201410062178 A CN201410062178 A CN 201410062178A CN 103825024 B CN103825024 B CN 103825024B
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iron
phosphate
source
battery
preparation
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CN103825024A (en
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应皆荣
陈韶峰
王顺林
沈震雷
陈明锋
沙金
陈炼
芦亚婷
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Ningbo Jinhe New Materials Co Ltd
Ningbo University of Technology
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Ningbo Jinhe New Materials Co Ltd
Ningbo University of Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a kind of battery-grade iron phosphate and preparation method thereof.This battery-grade iron phosphate is anhydrous iron phosphate FePO 4, powder is made up of the single dispersing olive shape particle of pattern rule, and bulk density is high, and tap density is up to 1.5-1.6g/cm 3.Its preparation method is with trivalent iron salt ferric nitrate for source of iron, with phosphoric acid or ammonium dihydrogen phosphate or diammonium hydrogen phosphate or ammonium phosphate for phosphorus source; In the mixed aqueous solution in source of iron and phosphorus source, add ammonia spirit as pH value regulator, stirring reaction ageing generate the high density olive shape crystalline state compound NH containing ammonium root, hydroxyl and the crystallization water 4fe 2(OH) (PO 4) 22H 2o; Prepare through Separation of Solid and Liquid, Roasting Decomposition and obtain again.This battery-grade iron phosphate is the desirable feedstock preparing lithium ion battery anode material lithium iron phosphate.This preparation method be suitable for the scale of high-quality high density battery-grade iron phosphate, economy, stable, reliably produce, non-wastewater discharge, there is obvious advantage, very with practical value.

Description

A kind of battery-grade iron phosphate and preparation method thereof
Technical field
The invention belongs to technical field of energy material preparation, relate to a kind of high density olive shape battery-grade anhydrous iron phosphate and preparation method thereof, this battery-grade iron phosphate is the desirable presoma preparing lithium ion battery anode material lithium iron phosphate.
Background technology
Lithium ion battery is the green high-capacity battery of a new generation, there is the many merits such as voltage is high, energy density large, good cycle, self discharge is little, memory-less effect, operating temperature range are wide, be widely used in mobile phone, notebook computer, digital camera, video camera, electronic instrument etc., also there is in fields such as UPS, electric tool, electric bicycle, electric automobile, energy-storage batteries bright application prospect.In recent years, the output of lithium ion battery rapidly increases, and application constantly expands, and has become in 21st century national economy and the significant new high-tech product of people's lives.
At present, lithium ion battery reaches its maturity in the compact battery field of portable type electronic product, range of application just progressively to middle Large Copacity, in high-power power type and accumulation energy type field of batteries expand.Positive electrode is the important component part of lithium ion battery, and its performance determines the combination property of battery to a great extent.Positive electrode research and improvement in performance are one of cores of lithium ion battery development.Concerning power type and accumulation energy type lithium ion battery, the cost of positive electrode, high-temperature behavior, fail safe are very important.The lithium be applied in compact battery field-compound transition metal oxide positive electrode, comprises cobalt acid lithium (LiCoO 2), lithium nickelate (LiNiO 2), LiMn2O4 (LiMn 2o 4) and the derivative of above three kinds of materials, as lithium nickel cobalt dioxide (LiNi 0.8co 0.2o 2), nickle cobalt lithium manganate (LiNi 1/3co 1/3mn 1/3o 2) etc. still can not meet the demands.
The lithium iron phosphate positive material of orthogonal olivine structural has become study hotspot both domestic and external.The respective advantage of cobalt acid lithium, lithium nickelate, LiMn2O4 and derivative positive electrode thereof concentrated by this material: not containing noble element, cheaper starting materials, resource extreme enrichment; Stability Analysis of Structures, security performance is splendid, LiFePO 4in O and P with strong covalent bond strong bonded, make material be difficult to analyse oxygen and decompose; High-temperature behavior and thermal stability are obviously better than other known positive electrode; Good cycle; Volume-diminished during charging, bulk effect when coordinating with carbon negative pole material is good; Good with most of electrolyte system compatibility, storge quality is good; Nontoxic, be real green material.Compared with cobalt acid lithium, lithium nickelate, LiMn2O4 and derivative positive electrode thereof, lithium iron phosphate positive material has outstanding advantage in cost, high-temperature behavior, fail safe, is expected to become power type and the desirable positive electrode of accumulation energy type lithium ion battery.The industrialization of lithium iron phosphate positive material and popularization and application, to reduction lithium ion battery cost, improve battery security, expand lithium ion battery industry, promote that lithium ion battery maximizes, high power has very great meaning; The application making lithium ion battery in middle large-capacity ups, medium-and-large-sized energy-storage battery, electric tool, electric automobile is become a reality.
Along with petering out of fossil energy, new forms of energy are all more and more paid attention to as the exploitation of solar energy, wind energy, tidal energy in the whole world, and using the research of new forms of energy as new subject growth point.Solar energy, wind energy, tidal energy etc., except can generating electricity by way of merging two or more grid systems, need the electrical power storage sending in a lot of situation.Only solve the storage problem of electric energy, solar energy, wind energy, tidal power ability flexible Application, move towards practical on a large scale.Therefore, the research of energy-storage battery and critical material thereof is significant for the development and application of new forms of energy.
The perfect match of to take LiFePO4 as the lithium-ion energy storage battery of positive electrode may be solar energy, wind energy, tidal power system.Therefore, the research of lithium iron phosphate positive material not only has important value in field of lithium ion battery, is of great significance the development and application of the new energy technologies such as solar energy, wind energy, tidal energy also tool.
It seems at present, LiFePO4 is most possible real large-scale application in the ideal material of power type and accumulation energy type lithium ion battery.Since professor JohnB.Goodenough of the U.S. in 1997 proposes this material, both at home and abroad to this has been extensive and deep research.People by carrying out surperficial bag conductive carbon to material, inside mixes the means such as conductive materials, crystal grain nanometer and improves the conductivity of material; By the particle shape of optimal control powder, the bulk density of particles size and distribution raising material.People develop multiple preparation technology, and some is applied to reality.
Be summed up, the main flow preparation technology of current LiFePO4 is following four kinds or its mutation:
1. Whote-wet method technique
This method is dispersed in water or in other solvents, by hydro-thermal or solvent heat process, reacts one-step synthesis LiFePO4, then make through subsequent treatment at relatively low temperature and high pressure in lithium source, source of iron, phosphorus source.This method concise in technology, can be made into nano-grade lithium iron phosphate; But discharging of waste liquid amount is large, need high pressure resistant equipment, industry is amplified not easily.
2. ferrous oxalate technique
This method is the classical technology of synthesizing iron lithium phosphate.With ferrous oxalate (FeC 2o 42H 2o) be source of iron, mix with ammonium dihydrogen phosphate or diammonium hydrogen phosphate, lithium salts, carbon source, under reduction or inert atmosphere protection, make LiFePO4 through predecomposition, high-temperature roasting.Have a large amount of ammonia to generate in preparation process, contaminated environment, etching apparatus, ferrous oxalate raw material is more expensive simultaneously.Though this method uses at present in a large number, being considered to is not a kind of competitive technology.
3. iron oxide red technique
This method is with iron oxide red (Fe 2o 3) be source of iron, with lithium dihydrogen phosphate (LiH 2pO 4), carbon source mixes through wet grinding, spraying dry, under reduction or inert atmosphere protection, make LiFePO4 through pyrocarbon thermal reduction reaction.This method compares environmental protection, but lithium dihydrogen phosphate raw material is more expensive and not bery stable.The LiFePO 4 material usual performance obtained by this method is general, belongs to low-and-medium-grade products.
4. ferric phosphate technique
With ferric phosphate (FePO 4) be raw material, with lithium carbonate (Li 2cO 3), carbon source Homogeneous phase mixing, reduction or inert atmosphere protection under make LiFePO4 through pyrocarbon thermal reduction reaction.By the usual better performances of LiFePO 4 material that this method is obtained, be suitable for preparing medium and high-grade goods.This synthesis technique compares science, but its advantage plays not yet completely, is worth further investigation.
We think, ferric phosphate technique has following advantage:
1. ferric phosphate (FePO 4), lithium carbonate (Li 2cO 3), the carbothermic reduction process of carbon source is similar to discharge process in battery: FePO 4skeleton motionless, ferric iron back is ferrous iron, Li +insert FePO 4lattice in, FePO 4become LiFePO 4.This course of reaction is more simply too much than the course of reaction of Whote-wet method technique, ferrous oxalate technique, iron oxide red technique, and ferric phosphate technique is more easily realized, and reaction condition is looser, and controllability is stronger.
2. wet chemical method can be utilized to synthesize ferric phosphate presoma, accuracy controlling is carried out to its composition, structure, pattern; As precursor synthesis LiFePO4, realize the accuracy controlling of the composition to target product, structure, pattern; The most of technology content prepared by LiFePO4 is transferred to ferric phosphate presoma; Soft chemical synthesis advantage can be given full play to, there is wide skill upgrading space.
At present, the advantage of ferric phosphate technique obtains generally acknowledging of people gradually, likely develops into standard technology prepared by LiFePO4.The new preparation technology of high-quality battery-grade iron phosphate comes into one's own day by day.
The existing history for many years of industrial production of ferric phosphate, usually adopts trivalent iron salt or divalent iron salt to be raw material, adds phosphoric acid or phosphate, be made into mixed solution, then obtain by alkali solution precipitate.
As with trivalent iron salt ferric nitrate (Fe (NO 3) 3), ferric trichloride (FeCl 3), ferric sulfate (Fe 2(SO 4) 3) be source of iron, with phosphoric acid (H 3pO 4) mix by a certain percentage, be made into mixed solution, add NaOH (NaOH) solution, regulate temperature and pH value, make Fe 3+with PO 4 3-in conjunction with and precipitate, obtain the ferric phosphate (FePO containing the crystallization water 4xH 2o, x=2-4).
Or with divalent iron salt ferrous sulfate (FeSO 4), frerrous chloride (FeCl 2) be source of iron, with phosphoric acid (H 3pO 4) mix by a certain percentage, be made into mixed solution, add oxidant as hydrogen peroxide (H 2o 2), clorox (NaClO), sodium chlorate (NaClO 3), ammonium persulfate ((NH 4) 2s 2o 8) etc., make Fe 2+be oxidized to Fe 3+, add NaOH (NaOH) solution simultaneously, regulate temperature and pH value, make the Fe that oxidation generates 3+with PO 4 3-in conjunction with and precipitate, obtain the ferric phosphate FePO containing the crystallization water 4xH 2o(x=2-4).
There is common shortcoming in said method:
One is that course of reaction all has byproduct salt to produce, as NaNO 3, NaCl, Na 2sO 4deng, byproduct salt is present in the mother liquor of reaction generation, also exists in a large number in the cleaning solution of ferric phosphate product, and directly discharge is by serious environment pollution, and liquid waste processing will cause cost to increase, and accessory substance is again low-value product;
Two is that the ferric phosphate generated all contains certain crystallization water, is generally two, is FePO 42H 2o; Product, except the crystallization water, also contains a small amount of adsorbed water usually; Due to containing the crystallization water and adsorbed water, the actual constituent of ferric phosphate is not extremely determined reliably, for accurate dosing when producing LiFePO4 brings certain difficulty;
In addition, the product containing the crystallization water, in long-term storage process, may produce the moisture absorption or weathering phenomenon, product composition is changed in time, has a negative impact to the stability of technique and homogeneity of product; Therefore, FePO 42H 2o is unsuitable for the raw material being directly used as to produce lithium iron phosphate positive material, generally will carry out necessary preliminary treatment.
Industrial production FePO 42H 2o generally adopts ferrous sulfate (FeSO 4) be raw material, cost is lower.But adopt existing technique, a large amount of oxidant must be consumed as hydrogen peroxide (H 2o 2), clorox (NaClO), sodium chlorate (NaClO 3), ammonium persulfate ((NH 4) 2s 2o 8) etc., increase cost to a certain extent.
We have invented a kind of battery-grade anhydrous iron phosphate with rhombic form in granted patent " battery-grade anhydrous iron phosphate and preparation method thereof; patent No. ZL201110419619.2 ", its preparation method is that to adopt take air as the oxidation-precipitation method of oxidant, divalent iron salt and phosphoric acid or phosphatic mixture aqueous solution are added pH value regulator solution control ph, pass into air, stir, reaction generates the crystalline state compound containing ammonium root, hydroxyl and the crystallization water, then obtains NH through Separation of Solid and Liquid, washing, oven dry 4fe 2(OH) (PO 4) 22H 2o powder; The roasting in air atmosphere of this powder, decomposes removing ammonium root, hydroxyl and the crystallization water, obtains the battery-grade anhydrous iron phosphate with rhombic form.
This invention has certain beneficial effect: preparing gained is the anhydrous iron phosphate not containing the crystallization water and adsorbed water, and composition is determined reliably, to stablize save-resistant, is the desirable feedstock preparing LiFePO4, is conducive to the stability and the homogeneity of product that improve technique; With the divalent iron salt ferrous sulfate of cheapness, frerrous chloride for raw material, preparation process take air as oxidant, without the need to consuming extra oxidant, and can be significantly cost-saving; Only contain ammonium salt in the mother liquor produced and cleaning solution, can be used as nitrogenous fertilizer and be directly used in agricultural and forestry production.
But also there are some shortcomings in this invention, mainly contains:
1, gained NH is prepared 4fe 2(OH) (PO 4) 22H 2the pattern of O and anhydrous iron phosphate powder granule is irregular, and bulk density is lower.Usual NH 4fe 2(OH) (PO 4) 22H 2the tap density of O is less than 0.8g/cm 3, the tap density of anhydrous phosphoric acid iron powder body is less than 1.0g/cm 3.When the major defect that bulk density is low is product roasting, boat charge is little, and baking furnace production capacity is little; During follow-up batching grinding, the solid content of slurry is low, and grinder production capacity is little, and spray dryer solvent evaporation amount is large, and energy consumption is high, and productive rate is low.
2, be source of iron with divalent iron salt, need continue to pass into air and be oxidized, reactor complex structure, large quantity of air can take away heat, and energy consumption increases to some extent.
3, contain ammonium chloride, ammonium sulfate etc. in mother liquor, fully must wash solid product, clean Cl -and SO 4 2-, a large amount of washings need be consumed.
Though only containing ammonium salt in the mother liquor 4, produced and cleaning solution, can be used as nitrogenous fertilizer and be directly used in agricultural and forestry production, liquid form product freight volume is large, and ammonium chloride and ammonium sulfate reduce gradually as the application of nitrogenous fertilizer, and the process problem of waste water still exists.
Summary of the invention
The present invention in order to solve the deficiency of above-mentioned existing ferric phosphate and preparation method thereof, and propose a kind of high density anhydrous iron phosphate of being made up of the single dispersing olive shape particle of pattern rule and can Simplified flowsheet, reduce costs, effectively solve the preparation method of this battery-grade iron phosphate of waste water handling problem.
The present invention is achieved by the following scheme:
Battery-grade iron phosphate of the present invention is anhydrous iron phosphate FePO 4, powder is made up of the single dispersing olive shape particle of pattern rule, and bulk density is high, and tap density is up to 1.5-1.6g/cm 3.
The preparation method of battery-grade iron phosphate of the present invention is with trivalent iron salt ferric nitrate for source of iron, with phosphoric acid or ammonium dihydrogen phosphate or diammonium hydrogen phosphate or ammonium phosphate for phosphorus source; The mixed aqueous solution in preparation source of iron and phosphorus source; In the mixed aqueous solution in source of iron and phosphorus source, add ammonia spirit as pH value regulator, stirring reaction generates the crystalline state compound containing ammonium root, hydroxyl and the crystallization water, then through Separation of Solid and Liquid, dry and obtain NH 4fe 2(OH) (PO 4) 22H 2o powder, the mol ratio of Qi Zhongtie, phosphorus is 0.99-1.01:1, and powder is made up of the single dispersing olive shape particle of pattern rule, and tap density is up to 1.2-1.3g/cm 3; The roasting in air atmosphere of this powder, decomposes removing ammonium root, hydroxyl and the crystallization water, obtains battery-grade anhydrous iron phosphate FePO 4, powder is also made up of the single dispersing olive shape particle of pattern rule, and tap density is up to 1.5-1.6g/cm 3; Mother liquor after Separation of Solid and Liquid isolates ammonium nitrate solid through freezing and crystallizing, the mixed aqueous solution in the multiplexing preparation source of iron of weary mother liquor and phosphorus source and pH value regulator solution, and the closed circulation realizing mother liquor utilizes.
The preparation method of battery-grade iron phosphate of the present invention, its concrete steps are as follows:
The mixed aqueous solution in a, preparation source of iron and phosphorus source, i.e. the mixed aqueous solution of preparation trivalent iron salt ferric nitrate and phosphoric acid or ammonium dihydrogen phosphate or diammonium hydrogen phosphate or ammonium phosphate, wherein the concentration of iron is 0.2-2 mol/L, and the mol ratio of phosphorus and iron is 0.95-1.05: 1;
B, preparation ammonia spirit are as pH value regulator solution, and wherein the concentration of ammonia is 0.5-12 mol/L;
C, the mixed aqueous solution in the above-mentioned source of iron for preparing and phosphorus source, pH value regulator solution pump are input in the reactor be with and stirred respectively continuously; By water bath with thermostatic control, in regulating and controlling reactor reactant liquor temperature and remain within the scope of 60-98 DEG C constant; The flow of the mixed aqueous solution in constant source of iron and phosphorus source, in regulating and controlling reactor, the pH value of reactant liquor is 0.5-5.5 and keeps constant; Feed in raw material, continued to stir ageing, generated crystalline state compound NH 4fe 2(OH) (PO 4) 22H 2o;
D, to be proceeded in solid-liquid separator by upper step gained material and carry out Separation of Solid and Liquid, gained solid product, without the need to washing, in an oven in 80-120 DEG C of dry 2-10 hour, obtains NH 4fe 2(OH) (PO 4) 22H 2o powder, the mol ratio of Qi Zhongtie, phosphorus is 0.99-1.01:1, and powder is made up of the single dispersing olive shape particle of pattern rule, and tap density is up to 1.2-1.3g/cm 3;
E, by NH 4fe 2(OH) (PO 4) 22H 2o powder is in air atmosphere, and 500-700 DEG C of roasting 2-24 hour, decomposes removing ammonium root, hydroxyl and the crystallization water, obtain battery-grade anhydrous iron phosphate FePO 4, powder is also made up of the single dispersing olive shape particle of pattern rule, and tap density is up to 1.5-1.6g/cm 3;
F, d walked the mother liquor after gained Separation of Solid and Liquid in crystallization tank in 1-5 DEG C of freezing and crystallizing, centrifugation goes out ammonium nitrate solid, weary mother liquor returns a step, b step is multiplexing, the mixed aqueous solution in preparation source of iron and phosphorus source and pH value regulator solution, and the closed circulation realizing mother liquor utilizes.
Beneficial effect:
The present invention, is also oxidized without the need to blowing air without the need to oxidant for high-quality battery-grade anhydrous iron phosphate prepared by raw material with trivalent iron salt ferric nitrate, simplifies reactor structure.Ferric nitrate can be prepared with the iron oxide red of nitric acid dissolve cheapness or metallic iron, and cost is lower.
Preparing gained is the anhydrous iron phosphate not containing the crystallization water and adsorbed water, and be made up of the single dispersing olive shape particle of pattern rule, tap density is up to 1.5-1.6g/cm 3, bulk density, degree of crystallinity and reactivity are high.During high density product roasting, boat charge is large, and baking furnace production capacity is large; During follow-up batching grinding, the solid content of slurry is high, and grinder production capacity is large, and spray dryer solvent evaporation amount is little, and energy consumption reduces, and productive rate improves.
Only be mingled with a small amount of ammonium nitrate in solid product after Separation of Solid and Liquid, can decompose completely in follow-up Roasting Decomposition, without any residue, therefore product is without the need to washing, can save a large amount of washings.
Only containing ammonium nitrate in mother liquor, after freezing and crystallizing, obtain ammonium nitrate solid, can be used as byproduct; Mother liquor can return multiplexing batching, and the closed circulation realizing mother liquor utilizes, and accomplishes wastewater zero discharge.
Anhydrous phosphoric acid ferrous components prepared by the present invention is determined reliably, to stablize save-resistant, is the desirable feedstock preparing LiFePO4, is conducive to the stability and the homogeneity of product that improve technique.
This preparation method be suitable for the scale of high-quality high density battery-grade iron phosphate, economy, stable, reliably produce, non-wastewater discharge, there is obvious advantage, very with practical value.
Explanation of nouns
Weary mother liquor: described " weary mother liquor " refers to following liquid herein: by the mother liquor freezing and crystallizing obtained after described steps d Separation of Solid and Liquid, centrifugation is remaining liquid after going out ammonium nitrate solid, is " weary mother liquor ".
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph (9.5mm × 2.00k) of embodiment 1 battery-grade iron phosphate.
Fig. 2 is the scanning electron microscope (SEM) photograph (9.5mm × 5.00k) of embodiment 1 battery-grade iron phosphate.
Fig. 3 is the scanning electron microscope (SEM) photograph (9.5mm × 100k) of embodiment 1 battery-grade iron phosphate.
Embodiment
Battery-grade iron phosphate of the present invention is anhydrous iron phosphate FePO 4, powder is made up of the single dispersing olive shape particle of pattern rule, and bulk density is high, and tap density is up to 1.5-1.6g/cm 3.This battery-grade anhydrous iron phosphate is the desirable feedstock preparing lithium iron phosphate positive material.
The preparation method of this battery-grade iron phosphate is with trivalent iron salt ferric nitrate for source of iron, with phosphoric acid or ammonium dihydrogen phosphate or diammonium hydrogen phosphate or ammonium phosphate for phosphorus source; The mixed aqueous solution in preparation source of iron and phosphorus source; In the mixture aqueous solution in source of iron and phosphorus source, add ammonia spirit as pH value regulator, stirring reaction generates the crystalline state compound containing ammonium root, hydroxyl and the crystallization water, then through Separation of Solid and Liquid, dry and obtain NH 4fe 2(OH) (PO 4) 22H 2o powder, the mol ratio of Qi Zhongtie, phosphorus is 0.99-1.01:1, and powder is made up of the single dispersing olive shape particle of pattern rule, and tap density is up to 1.2-1.3g/cm 3; The roasting in air atmosphere of this powder, decomposes removing ammonium root, hydroxyl and the crystallization water, obtains battery-grade anhydrous iron phosphate FePO 4, powder is also made up of the single dispersing olive shape particle of pattern rule, and tap density is up to 1.5-1.6g/cm 3; Mother liquor after Separation of Solid and Liquid isolates ammonium nitrate solid through freezing and crystallizing, the mixed aqueous solution in the multiplexing preparation source of iron of weary mother liquor and phosphorus source and pH value regulator solution, and the closed circulation realizing mother liquor utilizes.
The concrete steps of the preparation method of above-mentioned battery-grade iron phosphate are as follows:
The mixed aqueous solution in a, preparation source of iron and phosphorus source, i.e. the mixed aqueous solution of preparation trivalent iron salt ferric nitrate and phosphoric acid or ammonium dihydrogen phosphate or diammonium hydrogen phosphate or ammonium phosphate, wherein the concentration of iron is 0.2-2 mol/L, and the mol ratio of phosphorus and iron is 0.95-1.05: 1;
B, preparation ammonia spirit are as pH value regulator solution, and wherein the concentration of ammonia is 0.5-12 mol/L;
C, the mixed aqueous solution in the above-mentioned source of iron for preparing and phosphorus source, pH value regulator solution pump are input in the reactor be with and stirred respectively continuously; By water bath with thermostatic control, in regulating and controlling reactor reactant liquor temperature and remain within the scope of 60-98 DEG C constant; The flow of the mixed aqueous solution in constant source of iron and phosphorus source, in regulating and controlling reactor, the pH value of reactant liquor is 0.5-5.5 and keeps constant; Feed in raw material, continued to stir ageing, generated crystalline state compound NH 4fe 2(OH) (PO 4) 22H 2o;
D, to be proceeded in solid-liquid separator by upper step gained material and carry out Separation of Solid and Liquid, gained solid product, without the need to washing, in an oven in 80-120 DEG C of dry 2-10 hour, obtains NH 4fe 2(OH) (PO 4) 22H 2o powder, the mol ratio of Qi Zhongtie, phosphorus is 0.99-1.01:1, and powder is made up of the single dispersing olive shape particle of pattern rule, and tap density is up to 1.2-1.3g/cm 3;
E, by NH 4fe 2(OH) (PO 4) 22H 2o powder is in air atmosphere, and 500-700 DEG C of roasting 2-24 hour, decomposes removing ammonium root, hydroxyl and the crystallization water, obtain battery-grade anhydrous iron phosphate FePO 4, powder is also made up of the single dispersing olive shape particle of pattern rule, and tap density is up to 1.5-1.6g/cm 3.
F, by the mother liquor after described steps d gained Separation of Solid and Liquid in crystallization tank in 1-5 DEG C of freezing and crystallizing, centrifugation goes out ammonium nitrate solid, weary mother liquor returns described step a, described step b is multiplexing, the mixed aqueous solution in preparation source of iron and phosphorus source and pH value regulator solution, the closed circulation realizing mother liquor utilizes.
The present invention is further described below in conjunction with embodiment:
Embodiment 1
Preparation ferric nitrate and phosphoric acid mixed aqueous solution, wherein iron nitrate concentration is 2.0 mol/L, phosphoric acid concentration is 2.0 mol/L, and the mol ratio of phosphorus and iron is 1: 1;
Compound concentration is that the ammonia spirit of 10.0 mol/L is as pH value regulator;
Be add 2 liters of deionized waters in advance, strong agitation in the reactor of 7 liters at volume, and pass into thermostatted water in reacting kettle jacketing, controlling water temperature in reactor is 95 DEG C;
Ferric nitrate and phosphoric acid mixed aqueous solution, ammonia spirit pump are input in reactor respectively continuously, the flow controlling ferric nitrate and phosphoric acid mixed aqueous solution is 20 ml/min, regulate the flow of ammonia spirit, the pH value controlling reactant liquor in reactor is 1.60 ± 0.05;
By water bath with thermostatic control, in regulating and controlling reactor reactant liquor temperature and remain within the scope of 94-96 DEG C;
Stop reinforced after adding 2 liters of ferric nitrates and phosphoric acid mixed aqueous solution toward reactor, continue to stir ageing 10 hours; In ageing process, should remain that the temperature of reactant liquor is within the scope of 94-96 DEG C, and add ammonia spirit in good time, the pH value controlling reactant liquor in reactor is 1.60 ± 0.05;
After ageing terminates, the material in reactor is discharged, carries out Separation of Solid and Liquid with centrifuge;
By solid product under the condition of 105 DEG C dry 4 hours in an oven, obtain NH 4fe 2(OH) (PO 4) 22H 2o powder, the mol ratio of Qi Zhongtie, phosphorus is 1:1, and powder is made up of the single dispersing olive shape particle of pattern rule, and tap density is up to 1.3g/cm 3;
By NH 4fe 2(OH) (PO 4) 22H 2o powder is placed in corundum crucible, 580 DEG C of roastings 4 hours in air atmosphere muffle furnace, decomposes removing ammonium root, hydroxyl and the crystallization water, obtains battery-grade anhydrous iron phosphate FePO 4, powder is also made up of the single dispersing olive shape particle of pattern rule, and tap density is up to 1.6g/cm 3.
Only containing ammonium nitrate in mother liquor after centrifugation, by mother liquor in crystallization tank in 1-5 DEG C of freezing and crystallizing, centrifugation goes out ammonium nitrate solid, and weary mother liquor returns multiplexing, the mixed aqueous solution in preparation source of iron and phosphorus source and pH value regulator solution, the closed circulation realizing mother liquor utilizes.
Embodiment 2
Preparation ferric nitrate and ammonium phosphate mixed aqueous solution, wherein iron nitrate concentration is 0.2 mol/L, ammonium phosphate concentration is 0.2 mol/L, and the mol ratio of phosphorus and iron is 1: 1;
Compound concentration is that the ammonia spirit of 0.5 mol/L is as pH value regulator;
Be add 2 liters of deionized waters in advance, strong agitation in the reactor of 7 liters at volume, and pass into thermostatted water in reacting kettle jacketing, controlling water temperature in reactor is 60 DEG C;
Ferric nitrate and ammonium phosphate mixed aqueous solution, ammonia spirit pump are input in reactor respectively continuously, the flow controlling ferric nitrate and ammonium phosphate mixed aqueous solution is 20 ml/min, regulate the flow of ammonia spirit, the pH value controlling reactant liquor in reactor is 5.50 ± 0.05;
By water bath with thermostatic control, in regulating and controlling reactor reactant liquor temperature and remain within the scope of 59-61 DEG C;
Stop reinforced after adding 2 liters of ferric nitrates and ammonium phosphate mixed aqueous solution toward reactor, continue to stir ageing 10 hours; In ageing process, should remain that the temperature of reactant liquor is within the scope of 59-61 DEG C, and add ammonia spirit in good time, the pH value controlling reactant liquor in reactor is 5.50 ± 0.05;
After ageing terminates, the material in reactor is discharged, carries out Separation of Solid and Liquid with centrifuge;
By solid product under the condition of 80 DEG C dry 10 hours in an oven, obtain NH 4fe 2(OH) (PO 4) 22H 2o powder, the mol ratio of Qi Zhongtie, phosphorus is 1.01:1, and powder is made up of the single dispersing olive shape particle of pattern rule, and tap density is up to 1.2g/cm 3;
By NH 4fe 2(OH) (PO 4) 22H 2o powder is placed in corundum crucible, 520 DEG C of roastings 24 hours in air atmosphere muffle furnace, decomposes removing ammonium root, hydroxyl and the crystallization water, obtains battery-grade anhydrous iron phosphate FePO 4, powder is also made up of the single dispersing olive shape particle of pattern rule, and tap density is up to 1.5g/cm 3.
Only containing ammonium nitrate in mother liquor after centrifugation, by mother liquor in crystallization tank in 1-5 DEG C of freezing and crystallizing, centrifugation goes out ammonium nitrate solid, and weary mother liquor returns multiplexing, the mixture aqueous solution in preparation source of iron and phosphorus source and pH value regulator solution, the closed circulation realizing mother liquor utilizes.
Embodiment 3
Preparation ferric nitrate and ammonium dihydrogen phosphate mixed aqueous solution, wherein iron nitrate concentration is 1.0 mol/L, biphosphate ammonium concentration is 1.0 mol/L, and the mol ratio of phosphorus and iron is 1: 1;
Compound concentration is that the ammonia spirit of 4.0 mol/L is as pH value regulator;
Be add 2 liters of deionized waters in advance, strong agitation in the reactor of 7 liters at volume, and pass into thermostatted water in reacting kettle jacketing, controlling water temperature in reactor is 85 DEG C;
Ferric nitrate and ammonium dihydrogen phosphate mixed aqueous solution, ammonia spirit pump are input in reactor respectively continuously, the flow controlling ferric nitrate and ammonium dihydrogen phosphate mixed aqueous solution is 20 ml/min, regulate the flow of ammonia spirit, the pH value controlling reactant liquor in reactor is 2.50 ± 0.05;
By water bath with thermostatic control, in regulating and controlling reactor reactant liquor temperature and remain within the scope of 84-86 DEG C;
Stop reinforced after adding 2 liters of ferric nitrates and ammonium dihydrogen phosphate mixed aqueous solution toward reactor, continue to stir ageing 10 hours; In ageing process, should remain that the temperature of reactant liquor is within the scope of 84-86 DEG C, and add ammonia spirit in good time, the pH value controlling reactant liquor in reactor is 2.50 ± 0.05;
After ageing terminates, the material in reactor is discharged, carries out Separation of Solid and Liquid with centrifuge;
By solid product under the condition of 100 DEG C dry 8 hours in an oven, obtain NH 4fe 2(OH) (PO 4) 22H 2o powder, the mol ratio of Qi Zhongtie, phosphorus is 0.99:1, and powder is made up of the single dispersing olive shape particle of pattern rule, and tap density is up to 1.24g/cm 3;
By NH 4fe 2(OH) (PO 4) 22H 2o powder is placed in corundum crucible, 650 DEG C of roastings 6 hours in air atmosphere muffle furnace, decomposes removing ammonium root, hydroxyl and the crystallization water, obtains battery-grade anhydrous iron phosphate FePO 4, powder is also made up of the single dispersing olive shape particle of pattern rule, and tap density is up to 1.56g/cm 3.
Only containing ammonium nitrate in mother liquor after centrifugation, by mother liquor in crystallization tank in 1-5 DEG C of freezing and crystallizing, centrifugation goes out ammonium nitrate solid, and weary mother liquor returns multiplexing, the mixed aqueous solution in preparation source of iron and phosphorus source and pH value regulator solution, the closed circulation realizing mother liquor utilizes.
Embodiment 4
Preparation ferric nitrate and diammonium hydrogen phosphate mixed aqueous solution, wherein iron nitrate concentration is 1.5 mol/L, diammonium hydrogen phosphate concentration is 1.5 mol/L, and the mol ratio of phosphorus and iron is 1: 1;
Compound concentration is that the ammonia spirit of 12.0 mol/L is as pH value regulator;
Be add 2 liters of deionized waters in advance, strong agitation in the reactor of 7 liters at volume, and pass into thermostatted water in reacting kettle jacketing, controlling water temperature in reactor is 75 DEG C;
Ferric nitrate and diammonium hydrogen phosphate mixed aqueous solution, ammonia spirit pump are input in reactor respectively continuously, the flow controlling ferric nitrate and diammonium hydrogen phosphate mixed aqueous solution is 20 ml/min, regulate the flow of ammonia spirit, the pH value controlling reactant liquor in reactor is 1.00 ± 0.05;
By water bath with thermostatic control, in regulating and controlling reactor reactant liquor temperature and remain within the scope of 74-76 DEG C;
Stop reinforced after adding 2 liters of ferric nitrates and diammonium hydrogen phosphate mixed aqueous solution toward reactor, continue to stir ageing 10 hours; In ageing process, should remain that the temperature of reactant liquor is within the scope of 74-76 DEG C, and add ammonia spirit in good time, the pH value controlling reactant liquor in reactor is 1.00 ± 0.05;
After ageing terminates, the material in reactor is discharged, carries out Separation of Solid and Liquid with centrifuge;
By solid product under the condition of 120 DEG C dry 2 hours in an oven, obtain NH 4fe 2(OH) (PO 4) 22H 2o powder, the mol ratio of Qi Zhongtie, phosphorus is 1:1, and powder is made up of the single dispersing olive shape particle of pattern rule, and tap density is up to 1.22g/cm 3;
By NH 4fe 2(OH) (PO 4) 22H 2o powder is placed in corundum crucible, 700 DEG C of roastings 2 hours in air atmosphere muffle furnace, decomposes removing ammonium root, hydroxyl and the crystallization water, obtains battery-grade anhydrous iron phosphate FePO 4, powder is also made up of the single dispersing olive shape particle of pattern rule, and tap density is up to 1.54g/cm 3.
Only containing ammonium nitrate in mother liquor after centrifugation, by mother liquor in crystallization tank in 1-5 DEG C of freezing and crystallizing, centrifugation goes out ammonium nitrate solid, and weary mother liquor returns multiplexing, the mixed aqueous solution in preparation source of iron and phosphorus source and pH value regulator solution, the closed circulation realizing mother liquor utilizes.
Embodiment 5
Preparation ferric nitrate, phosphoric acid, diammonium hydrogen phosphate mixed aqueous solution, wherein iron nitrate concentration is 1.0 mol/L, phosphoric acid concentration is 0.5 mol/L, diammonium hydrogen phosphate concentration is 0.5 mol/L, and the mol ratio of phosphorus and iron is 1: 1; Replace the ferric nitrate in embodiment 3 and ammonium dihydrogen phosphate mixed aqueous solution, prepare battery-grade anhydrous iron phosphate FePO by same process condition 4, powder is also made up of the single dispersing olive shape particle of pattern rule, and tap density is up to 1.55g/cm 3.
Embodiment 6
Preparation ferric nitrate, phosphoric acid, ammonium phosphate mixed aqueous solution, wherein iron nitrate concentration is 1.5 mol/L, phosphoric acid concentration is 0.75 mol/L, ammonium phosphate concentration is 0.75 mol/L, and the mol ratio of phosphorus and iron is 1: 1; Replace the ferric nitrate in embodiment 4 and diammonium hydrogen phosphate mixed aqueous solution, prepare battery-grade anhydrous iron phosphate FePO by same process condition 4, powder is also made up of the single dispersing olive shape particle of pattern rule, and tap density is up to 1.53g/cm 3.
As mentioned above, just the present invention can be realized preferably.

Claims (1)

1. a preparation method for battery-grade iron phosphate, is characterized in that: this battery-grade iron phosphate is anhydrous iron phosphate FePO 4, powder is made up of the single dispersing olive shape particle of pattern rule, and bulk density is high, and tap density is up to 1.5-1.6g/cm 3;
Described preparation method is with trivalent iron salt ferric nitrate for source of iron, with phosphoric acid or ammonium dihydrogen phosphate or diammonium hydrogen phosphate or ammonium phosphate for phosphorus source; The mixed aqueous solution in preparation source of iron and phosphorus source; In the mixed aqueous solution in source of iron and phosphorus source, add ammonia spirit as pH value regulator, stirring reaction generates the crystalline state compound containing ammonium root, hydroxyl and the crystallization water, then through Separation of Solid and Liquid, dry and obtain NH 4fe 2(OH) (PO 4) 22H 2o powder, the mol ratio of Qi Zhongtie, phosphorus is 0.99-1.01:1, and powder is made up of the single dispersing olive shape particle of pattern rule, and tap density is up to 1.2-1.3g/cm 3; The roasting in air atmosphere of this powder, decomposes removing ammonium root, hydroxyl and the crystallization water, obtains battery-grade anhydrous iron phosphate FePO 4, powder is also made up of the single dispersing olive shape particle of pattern rule, and tap density is up to 1.5-1.6g/cm 3;
Described preparation method, its concrete steps are as follows:
The mixed aqueous solution in a, preparation source of iron and phosphorus source, i.e. the mixed aqueous solution of preparation trivalent iron salt ferric nitrate and phosphoric acid or ammonium dihydrogen phosphate or diammonium hydrogen phosphate or ammonium phosphate, wherein the concentration of iron is 0.2-2 mol/L, and the mol ratio of phosphorus and iron is 0.95-1.05: 1;
B, preparation ammonia spirit are as pH value regulator solution, and wherein the concentration of ammonia is 0.5-12 mol/L;
C, the mixed aqueous solution in the above-mentioned source of iron for preparing and phosphorus source, pH value regulator solution pump are input in the reactor be with and stirred respectively continuously; By water bath with thermostatic control, in regulating and controlling reactor reactant liquor temperature and remain within the scope of 60-98 DEG C constant; The flow of the mixed aqueous solution in constant source of iron and phosphorus source, in regulating and controlling reactor, the pH value of reactant liquor is 0.5-5.5 and keeps constant; Feed in raw material, continued to stir ageing, generated crystalline state compound NH 4fe 2(OH) (PO 4) 22H 2o;
D, to be proceeded in solid-liquid separator by described step c gained material and carry out Separation of Solid and Liquid, obtain solid product and mother liquor, gained solid product, without the need to washing, in an oven in 80-120 DEG C of dry 2-10 hour, obtains NH 4fe 2(OH) (PO 4) 22H 2o powder, the mol ratio of Qi Zhongtie, phosphorus is 0.99-1.01:1, and powder is made up of the single dispersing olive shape particle of pattern rule, and tap density is up to 1.2-1.3g/cm 3;
E, by described steps d gained NH 4fe 2(OH) (PO 4) 22H 2o powder is in air atmosphere, and 500-700 DEG C of roasting 2-24 hour, decomposes removing ammonium root, hydroxyl and the crystallization water, obtain described battery-grade anhydrous iron phosphate FePO 4, powder is also made up of the single dispersing olive shape particle of pattern rule, and tap density is up to 1.5-1.6g/cm 3;
F, d walked the mother liquor after gained Separation of Solid and Liquid in crystallization tank after 1-5 DEG C of freezing and crystallizing, centrifugation obtains ammonium nitrate solid and weary mother liquor, and described weary mother liquor is remaining liquid after described mother liquor centrifugation ammonium nitrate solid; Described weary mother liquor returns a step, b step is multiplexing in mixed aqueous solution and the pH value regulator solution of preparing source of iron and phosphorus source, and the closed circulation realizing mother liquor utilizes.
CN201410062178.9A 2014-02-24 2014-02-24 A kind of battery-grade iron phosphate and preparation method thereof Expired - Fee Related CN103825024B (en)

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JP6083425B2 (en) * 2014-10-17 2017-02-22 トヨタ自動車株式会社 Positive electrode mixture paste, positive electrode, non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery manufacturing method
CN104860285A (en) * 2015-04-10 2015-08-26 合肥国轩高科动力能源股份公司 Drying method for lithium iron phosphate precursor slurry
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101244813A (en) * 2007-02-15 2008-08-20 比亚迪股份有限公司 Alkali type iron ammonium phosphate and production method, production method of iron phosphate and production method of ferrous lithium phosphate
CN101269807A (en) * 2008-03-05 2008-09-24 广州融捷材料科技有限公司 High-density spherical iron phosphate and manufacture method thereof
CN101979313A (en) * 2010-11-03 2011-02-23 江苏方舟新能源股份有限公司 Simple synthesis method of spherical-like iron phosphate
CN102583291A (en) * 2011-01-06 2012-07-18 南通宝聚颜料有限公司 Preparation process of ferric phosphate capable of simultaneously obtaining nitric acid and ammonium nitrate

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101294335B1 (en) * 2012-05-25 2013-08-16 한국과학기술연구원 Fabricating method of lifepo4 cathode electroactive material for lithium secondary battery by recycling, lifepo4 cathode electroactive material for lithium secondary battery, lifepo4 cathode and lithium secondary battery fabricated thereby

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101244813A (en) * 2007-02-15 2008-08-20 比亚迪股份有限公司 Alkali type iron ammonium phosphate and production method, production method of iron phosphate and production method of ferrous lithium phosphate
CN101269807A (en) * 2008-03-05 2008-09-24 广州融捷材料科技有限公司 High-density spherical iron phosphate and manufacture method thereof
CN101979313A (en) * 2010-11-03 2011-02-23 江苏方舟新能源股份有限公司 Simple synthesis method of spherical-like iron phosphate
CN102583291A (en) * 2011-01-06 2012-07-18 南通宝聚颜料有限公司 Preparation process of ferric phosphate capable of simultaneously obtaining nitric acid and ammonium nitrate

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