CN109546140A - A kind of method that water/solvent-thermal method largely prepares carbon coating iron manganese phosphate for lithium - Google Patents
A kind of method that water/solvent-thermal method largely prepares carbon coating iron manganese phosphate for lithium Download PDFInfo
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- 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
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
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Abstract
The invention discloses a kind of methods that water/solvent-thermal method largely prepares carbon coating iron manganese phosphate for lithium, phosphorus source, source of iron, manganese source, part lithium source and stirring solvent are formed uniformly the first suspension by this method, remaining lithium source and stirring solvent are formed uniformly the second suspension, the first suspension and the second suspension reactor tank is squeezed into again to mix, part lithium source in first suspension is the 15%~33.3% of lithium source total amount, the solvent be water, ethylene glycol, ethyl alcohol, acetone it is one or more than one kinds of.Method of the invention makes raw material be in for a long time dissolution saturation state in a manner of preparing raw material suspension, and reaction is promoted to carry out, and saves solvent cost, improves the production quantity of principal product in the unit time, inhibits the generation of impurity, improves product yield and purity；Meanwhile lithium source being divided into two parts and is launched respectively, conducive to perfect crystal particle is formed, centralized particle diameter, gram volume is big, electrochemical performance, is conducive to quantify amplification production in the industry.
Description
Technical field
The invention belongs to technical field of energy material, and in particular to a kind of water/solvent-thermal method largely prepares lithium battery anode
The method of material phosphoric acid manganese iron lithium.
Background technique
As secondary cell of new generation, lithium ion battery because its output voltage is high, density small in size is big, energy density is high,
The advantages that self discharge is few, memory-less effect, long storage life, be widely used in mobile electronic product, powered vehicle and
Energy storage device.It is with the development of science and technology and progressive, the new demand of high-energy density is proposed to lithium ion battery.It is high
Specific capacity and high voltage become two paths for realizing high-energy density.
The positive electrode of lithium ion battery is the key that determine its performance, mainly there is stratiform cobalt acid lithium (LCO), nickel cobalt at present
LiMn2O4 (NCM) and nickel cobalt lithium aluminate (NCA), spinelle shape LiMn2O4 (LMO) and lithium nickelate (LNO), olivine shape ferric phosphate
Lithium (LFP) etc..LCO actual specific capacity is 140mAh/g, and electrode cycle performance deteriorates rapidly when overcharge, and safety is poor；Cobalt money
Source is short, at high cost, toxicity is big.The ternary materials such as NCM and NCA become power lithium battery with advantages such as height ratio capacity, tap densities
The main positive electrode in pond, but its safety and cycle life limit it and are used for electric bus.LMO discharge voltage is higher,
Safety is preferable, low in cost, but its specific capacity is lower, and thermodynamic property is unstable, capacity attenuation quickly, cycle performance compared with
Difference.LFP has preferable security performance and cycle life, but its discharge voltage and tap density are lower.
Lithium manganese phosphate (LiMnPO4, LMP) and LiFePO4 (LiFePO4, LFP) and it is all olivine shape crystal structure, belong to
Orthorhombic system (space group: Pmnb).The theoretical charge/discharge capacity of LMP is 171mAh/g, and discharge platform is 4.1V (vs Li/Li+), theoretical energy density 700Whkg-1, about 20% is improved than LFP.But its intrinsic lower electronic conductivity (<
10-10S·cm-1) and lithium ion mobility rate (< 10-16cm2·s-1) to result in practical charge/discharge capacity lower, and high rate performance
It is poor.Iron manganese phosphate for lithium (LiMnxFe1-xPO4, 0 < x < 1, LMFP) and operating voltage and energy density with higher, preferable
Cyclical stability and security performance, environmentally friendly, cheap, these advantages make LMFP become lithium ion cell positive material
The strong candidate of material.
The main preparation methods of iron manganese phosphate for lithium are solid phase method and liquid phase method.Solid phase method using solid lithium salts, manganese salt and
Phosphate is mixed by high-energy ball milling and encloses lower high temperature sintering, such as CN102738465A in inert protective atmosphere.Liquid phase method divides again
For coprecipitation, sol-gal process, spray pyrolysis, hydrothermal/solvent thermal method etc..Compared with solid phase method, liquid phase method preparation
LMFP material, purity is higher, and particle is smaller, particle diameter distribution is uniform, and chemical property is preferable.Hydrothermal/solvent heat in liquid phase method
Method is reacted under high-temperature and high-pressure conditions in closed reactor by dissolution of raw material in water or solvent.The method can be controlled preferably
Prepared material pattern, and material crystalline is good, and lattice defect is few, purity is high.Patent CN101807698A disclose it is a kind of will be former
Feed liquid is divided into three fluid streams and is injected separately into the method that mixer reaction prepares the lesser iron manganese phosphate for lithium of partial size, but this method walks
Rapid cumbersome, condition is harsh, is not suitable for quantization production.For these problems, patent CN104752720A discloses a kind of new system
The method of standby iron manganese phosphate for lithium, method is by the first solution for having dissolved manganese source, source of iron and phosphorus source and has dissolved the second of lithium source
Solution cocurrent mixing, and strict control pH6.5~7.5 so that iron manganese phosphate for lithium particle diameter distribution uniformly, electrochemical performance.But
It is existing hydrothermal/solvent thermal method is all to be completely dissolved raw material to react again in a solvent, one side solvent-oil ratio is big,
Costly, unit volume reaction solution volume production is low；On the other hand solvent increases environmental burden and wastewater treatment after a large amount of reaction
Cost is unfavorable for promoting and applying.
Summary of the invention
In view of the problems of the existing technology, the present invention provides a kind of water/solvent-thermal methods largely to prepare carbon coating phosphoric acid
The method of manganese iron lithium.Suspension is made in raw material to this method rather than solution participates in reaction, at low cost, volume production is high, environmental protection pressure pole
It is big to reduce.
The technical solution adopted by the invention is as follows:
A kind of method that water/solvent-thermal method largely prepares carbon coating iron manganese phosphate for lithium, including by phosphorus source, source of iron, manganese source, portion
Point lithium source and stirring solvent are formed uniformly the first suspension, and remaining lithium source and stirring solvent are formed uniformly the second suspension, will
First suspension and the second suspension squeeze into reactor tank mixing, and the part lithium source in first suspension is lithium source total amount
15%~33.3%, the solvent be water, ethylene glycol, ethyl alcohol, acetone it is one or more than one kinds of.
In above-mentioned preparation method of the invention, there are part phosphorus source, source of iron, manganese source and lithium source incomplete in the first suspension
Be dissolved into solvent or phosphorus source, source of iron, manganese source and lithium source in both at least form sediment, have part lithium in the second suspension
Source is not completely dissolved, to form suspension.Existing water/solvothermal preparation method is that whole materials are added together stirring, or
Person is divided into several bursts of stirrings, and raw material is needed to be completely dissolved, and suspended matter does not occur, and such mode makes the concentration of reaction raw materials
It carries out with reaction and sharply declines, especially the mode of multiply hybrid reaction, mix the reduction that further dilution causes concentration, no
Conducive to the progress of main reaction, conversion rate of products is low, if in order to allow raw material sufficiently to react the extension time, and will lead to by-product
Content is high, influences purity.Method of the invention makes raw material in solution be in dissolution saturation state, solution within the longer reaction time
In consumption of raw materials after have suspended state solid dissolution supplemented, reaction solution for a long time be in high concentration of feed state, favorably
In promoting reaction to carry out to main reaction direction, the production quantity of principal product in the unit time is improved, inhibits by-product increase with time,
And the generation of secondary by-product, improve product yield and purity.Some preferred embodiments according to the present invention, using the present invention
Method prepares solid content >=90g/L of iron manganese phosphate for lithium product, the 0.5C gram volume > 145mAh/g of material.And existing water/molten
The solid content of the iron manganese phosphate for lithium product of agent thermal method preparation is generally 20-40g/L, 0.5C gram volume < 130mAh/g.And product
It is mingled with more impurity in particle.In addition, to produce in terms of equivalent iron manganese phosphate for lithium, method of the invention compared with the conventional method,
60% or more solvent can be saved, more save the cost occupies obvious price advantage in plant produced.
Above-mentioned preparation method of the invention, is also divided into two parts for lithium source and launches, the lithium in preferably the first suspension
Source is the 15%~33.3% of lithium source total amount.If all lithium sources and phosphorus source, source of iron, manganese source are mixed simultaneously, meeting is operated
Simpler but reaction product precipitating is quickly generated, and a large amount of impurity of package or raw material, influence the chemical property of product in crystal.
If all lithium sources are used to the second suspension of preparation, two strands of materials form solid product, solid material dispersion when mixing
Unevenly, the crystal perfection degree of formation is poor, and product gram volume is lower.Through the inventors of the present invention discovered through researches that, it is first that lithium source is total
The 15%~33.3% of amount is mixed with phosphorus source, source of iron, manganese source, and a small amount of uniform crystal dispersion is initially formed when being sufficiently stirred in solution
In, when with the second suspension hybrid reaction, this part molding crystal phosphoric acid that inductive formation form, size is similar
Manganese iron lithium particle, particle diameter distribution high concentration, crystal perfection degree is high, and gram volume is big, electrochemical performance.
Further, the method that above-mentioned water/solvent-thermal method largely prepares carbon coating iron manganese phosphate for lithium, comprising the following steps:
1) phosphorus source, source of iron, manganese source, part lithium source and stirring solvent are formed uniformly the first suspension, by remaining lithium source and
Stirring solvent is formed uniformly the second suspension, total molar ratio of material Li:(Fe+Mn): P=2.9~3.0:1:1, products molecule formula
For LiMnxFe1-xPO4, 0 < x < 1；
2) the first suspension acid and the second suspension are squeezed into reactor tank and is mixed, mixed slurry is under an inert atmosphere
After stirring, 130~240 DEG C of reactions is warming up to, and kept for 2~10 hours, is down to room temperature, obtains iron manganese phosphate for lithium slurry；
3) iron manganese phosphate for lithium slurry is separated by solid-liquid separation, carbon source is added in wet solid (moisture content 50-90%) to containing,
It dries after mixing；
4) material after drying is sintered under an inert atmosphere, crushes, sieves, dries, obtain carbon coating manganese phosphate
Iron lithium electrode material.
Phosphorus source of the present invention includes phosphoric acid, lithium dihydrogen phosphate, ammonium di-hydrogen phosphate, preferably phosphoric acid.
Source of iron of the present invention includes ferrous sulfate, ferrous oxalate, frerrous chloride, preferably ferrous sulfate.
Manganese source of the present invention includes manganese sulfate, manganese acetate, manganese chloride, preferably manganese sulfate.
Lithium source of the present invention includes lithium hydroxide, lithium carbonate, lithium acetate, preferably lithium carbonate, lithium hydroxide.
Preferably, the method that above-mentioned water/solvent-thermal method largely prepares carbon coating iron manganese phosphate for lithium, it is outstanding that step 1) prepares first
When turbid and the second suspension, 20~40 DEG C of temperature of charge are controlled, 0.5~5h of mixing time；(Mn+Fe) is dense in first suspension
Degree is 1~3mol/L, 4~8mol/L of Li concentration in the second suspension.Selection Mn, Fe, Li concentration, can effectively protect
Card using suspension reacted possessed by advantage more preferably.If concentration is too low, low output is at high cost；Excessive concentration, will be unfavorable
It is carried out in production.
Preferably, the method that above-mentioned water/solvent-thermal method largely prepares carbon coating iron manganese phosphate for lithium, the solvent are water and second
The mixed solvent of glycol.
Preferably, the method that above-mentioned water/solvent-thermal method largely prepares carbon coating iron manganese phosphate for lithium, when the step 2) stirring
Between be 0.5~6h, 10~60Hz of stirring frequency, control 20~60 DEG C of temperature of charge.Obtain uniform water/solvent thermal reaction forerunner
Somaplasm material (suspension).More preferably, the mixing time of step 2) is 4h, stirring frequency 50Hz.Mixing time and frequency are by shadow
The effect for ringing material dispersion, to influence the chemical property of product；And the too high oxidation for being easy to cause iron and manganese of temperature, thus
Influence the chemical property of product.
Preferably, the method that above-mentioned water/solvent-thermal method largely prepares carbon coating iron manganese phosphate for lithium, step 2) are warming up to 130
~240 DEG C of control heating rates are 1~5 DEG C/min.When cooling, preferably 1~5 DEG C/min of cooling rate.
Preferably, the method that above-mentioned water/solvent-thermal method largely prepares carbon coating iron manganese phosphate for lithium, the step 3) solid-liquid point
From mode include but is not limited to centrifuge centrifugation and micro porous filtration.
Preferably, the method that above-mentioned water/solvent-thermal method largely prepares carbon coating iron manganese phosphate for lithium, the step 3) carbon source:
Solid=3~15g:100g.
Carbon coating iron manganese phosphate for lithium sintered precursor water content≤1% after step 3 is dry.The carbon source can be respectively
Kind carbohydrate or other carbonaceous organic materials.Drying mode includes but is not limited to be spray-dried.Spray drying exit temperature is 80~125
℃。
Preferably, the method that above-mentioned water/solvent-thermal method largely prepares carbon coating iron manganese phosphate for lithium, step 4) sintering temperature are
It 500~800 DEG C, is kept for 2~10 hours, 2~10 DEG C/min of heating rate.
More preferably, the method that above-mentioned water/solvent-thermal method largely prepares carbon coating iron manganese phosphate for lithium, in step 4) temperature-rise period
It keeps being further continued for being warming up to 500~800 DEG C for 1~8 hour at 250~350 DEG C.In 250-350 DEG C of holding a period of time, make to coat
Material resistivity it is lower, the chemical property of material is more excellent.
Using preparation method of the invention, have the advantages that
1, operating procedure is easy to control in the industrial production, it is easier to realize automation.
2, iron manganese phosphate for lithium solid content >=90g/L after the completion of water/solvent thermal reaction in slurry suspension, chemical property
It is excellent.
3, the lesser positive electrode carbon coating iron manganese phosphate for lithium of size, average grain diameter about 50nm, particle size distribution are obtained
Compared with concentration, uniformity is good.
4, it can according to need, adjustment raw material feed ratio synthesizes the carbon coating iron manganese phosphate of different Fe/ (Mn+Fe) ratios
Lithium, rolled product variety adjustment is flexible, stay in grade.
5, the electrode obtained material discharging capacity is higher, and high rate performance is preferable, electrochemical performance.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of carbon coating iron manganese phosphate for lithium prepared by embodiment 1；
Fig. 2 is the charging and discharging curve figure of carbon coating iron manganese phosphate for lithium prepared by embodiment 1, to embody carbon coating manganese phosphate
The gram volume of iron lithium.
Specific embodiment
It is illustrated below by way of specific embodiment is further to summary of the invention of the invention, but should not be construed as the present invention
Range be only limitted to example below, invention thinking according to the present invention and entire contents, can will be each in following instance
Technical characteristic makes combination/replacement/adjustment/modification appropriate etc., this is will be obvious to those skilled in the art that still
Belong to the scope that the present invention protects.
Embodiment 1
Weigh 85% phosphoric acid of 18.7kg, 5.4kg LiOHH2O、16.4kg MnSO4·H2O、18.0kg FeSO4·
7H2115L water-ethylene glycol mixed solvent (volume ratio of water and ethylene glycol is 2:3) is added in O, controls 20~40 DEG C of temperature of charge,
Stirring 2 hours, as slurry A.Weigh 14.8kg LiOHH2115L water-ethylene glycol mixed solvent (water and ethylene glycol is added in O
Volume ratio be 2:3), control 20~40 DEG C of temperature of charge, stir 2 hours, as slurry B.Throw slurry A and B into reactor tank
In, advanced slurry A, laggard slurry B, coutroi velocity is consistent.Mixed slurry continues stirring 4 hours under an inert atmosphere, so
180 DEG C are warming up to the rate of 3 DEG C/min afterwards, and is kept for 3 hours, room temperature is then down to.Filtering, filtering stock, until cleaning solution
In sulfate concentration be lower than 200ppm, obtain contain wet iron manganese phosphate for lithium slurry, solid-to-liquid ratio 30%.Iron manganese phosphate for lithium is obtained to produce
The solid content of product is 94.3g/L.According to quality than glucose: iron manganese phosphate for lithium=15:100 ratio weighs glucose, is added
That has washed contains in wet iron manganese phosphate for lithium slurry, stirs 1 hour.100 DEG C of outlet temperature of setting is spray-dried, and drying is obtained
Iron manganese phosphate for lithium sintered precursor.Under nitrogen protection, heating rate is 8 DEG C/min, and 300 DEG C are calcined 4 hours, continues to heat up
It is sintered 8 hours to 700 DEG C, then through crushing, screening, drying, obtains carbon coating lithium iron manganese phosphate anode material finished product.
By obtained carbon coating lithium iron manganese phosphate anode material carry out electron-microscope scanning, the result is shown in Figure 1, material be it is rodlike, it is short
Diameter about 50nm, dimensional homogeneity is good, and distribution is relatively concentrated.
Button cell R2032 is assembled using the carbon coating iron manganese phosphate for lithium as positive electrode, the discharge capacity of 0.5C is
147mAh/g, charging and discharging curve are as shown in Figure 2.
Embodiment 2
Weigh 85% phosphoric acid of 18.7kg, 6.1kg LiOHH2O、19.2kg MnSO4·H2O、13.5kg FeSO4·
7H2115L water-ethylene glycol mixed solvent (volume ratio of water and ethylene glycol is 1:1) is added in O, controls 20~40 DEG C of temperature of charge,
Stirring 1 hour, as slurry A.Weigh 14.1kg LiOHH2115L water-ethylene glycol mixed solvent (water and ethylene glycol is added in O
Volume ratio be 1:1), control 20~40 DEG C of temperature of charge, stir 0.5 hour, as slurry B.Slurry A and B are thrown into simultaneously
In reactor tank, coutroi velocity makes the two while having beaten.Mixed slurry continues stirring 6 hours under an inert atmosphere, then
240 DEG C are warming up to the rate of 5 DEG C/min, and is kept for 2 hours, room temperature is then down to.Filtering, filtering stock, until in cleaning solution
Sulfate concentration be lower than 200ppm, obtain contain wet iron manganese phosphate for lithium slurry, solid-to-liquid ratio 30%.Obtain iron manganese phosphate for lithium product
Solid content be 94.8g/L.According to quality than glucose: iron manganese phosphate for lithium=7:100 ratio weighs glucose, and washing is added
Good contains in wet iron manganese phosphate for lithium slurry, stirs 1 hour.105 DEG C of outlet temperature of setting is spray-dried, and dry phosphorus is obtained
Sour manganese iron lithium sintered precursor.Under nitrogen protection, heating rate is 8 DEG C/min, and 250 DEG C are calcined 4 hours, is continuously heating to
500 DEG C are sintered 10 hours, then through crushing, screening, drying, obtain carbon coating lithium iron manganese phosphate anode material finished product.
Through electron-microscope scanning, carbon coating iron manganese phosphate for lithium be it is rodlike, the minor axis of particle about 50nm, dimensional homogeneity is good, distribution
Compared with concentration.
Button cell R2032 is assembled using carbon coating iron manganese phosphate lithium material as positive electrode, the discharge capacity of 0.5C is
146mAh/g。
Embodiment 3
Weigh 85% phosphoric acid of 18.7kg, 3.4kg LiOHH2O、21.9kg MnSO4·H2O、9kg FeSO4·7H2O adds
Enter 100L water-ethylene glycol mixed solvent (volume ratio of water and ethylene glycol is 3:2), controls 20~40 DEG C of temperature of charge, stirring 1 is small
When, as slurry A.Weigh 16.8kg LiOHH2The 100L water-ethylene glycol mixed solvent (volume ratio of water and ethylene glycol is added in O
For 1:1), 20~40 DEG C of temperature of charge are controlled, is stirred 5 hours, as slurry B.Slurry A and B is thrown into reactor tank simultaneously, is controlled
Flow velocity processed makes the two while having beaten.Mixed slurry continues stirring 2 hours under an inert atmosphere, then with 4 DEG C/min's
Rate is warming up to 130 DEG C, and is kept for 10 hours, is then down to room temperature.Filtering, filtering stock, until the sulfate radical in cleaning solution is dense
Degree is lower than 200ppm, obtains and contains wet iron manganese phosphate for lithium slurry, solid-to-liquid ratio 30%.Obtain iron manganese phosphate for lithium product solid content be
107.4g/L.According to quality than glucose: iron manganese phosphate for lithium=15:100 ratio weighs glucose, and what addition had been washed contains wet phosphorus
In sour manganese iron lithium slurry, stir 1 hour.110 DEG C of outlet temperature of setting is spray-dried, and is obtained dry iron manganese phosphate for lithium and is burnt
Tie presoma.Under nitrogen protection, heating rate is 8 DEG C/min, and 350 DEG C are calcined 3 hours, and it is small to be continuously heating to 720 DEG C of sintering 8
When, then through crushing, screening, drying, obtain carbon coating lithium iron manganese phosphate anode material finished product.
Through electron-microscope scanning, carbon coating iron manganese phosphate for lithium be it is rodlike, the minor axis of particle about 50nm, dimensional homogeneity is good, distribution
Compared with concentration.
Button cell R2032 is assembled using carbon coating iron manganese phosphate lithium material as positive electrode, the discharge capacity of 0.5C is
145mAh/g。
Comparative example 1
Weigh 85% phosphoric acid of 6.57kg, 1.9kg LiOHH2O、5.76kg MnSO4·H2O、6.32kg FeSO4·
7H2115L water-ethylene glycol mixed solvent (volume ratio of water and ethylene glycol is 2:3) is added in O, controls 20~40 DEG C of temperature of charge,
Stirring 2 hours, material is completely dissolved, as slurry A.Weigh 5.2kg LiOHH2115L water-ethylene glycol mixed solvent is added in O
(volume ratio of water and ethylene glycol is 2:3), controls 20~40 DEG C of temperature of charge, stirs 2 hours, material is completely dissolved, as slurry
Expect B.Slurry A and B are thrown into reactor tank, advanced slurry A, laggard slurry B, coutroi velocity is consistent.Mixed slurry is lazy
Property atmosphere under continue stirring 4 hours, be then warming up to 180 DEG C with the rate of 3 DEG C/min, and kept for 3 hours, be then down to room
Temperature.Filtering, filtering stock obtain until the sulfate concentration in cleaning solution is lower than 200ppm and contain wet iron manganese phosphate for lithium slurry, solid-liquid
Than being 30%.The solid content for obtaining iron manganese phosphate for lithium product is 36.7g/L.According to quality than glucose: iron manganese phosphate for lithium=15:
100 ratio weighs glucose, and what addition had been washed contains in wet iron manganese phosphate for lithium slurry, stirs 1 hour.Outlet temperature is set
100 DEG C are spray-dried, and dry iron manganese phosphate for lithium sintered precursor is obtained.Under nitrogen protection, heating rate be 8 DEG C/
Min, 300 DEG C are calcined 4 hours, are continuously heating to 700 DEG C and are sintered 8 hours, then through crushing, screening, drying, obtain carbon coating phosphorus
Sour manganese iron lithium anode material finished product.
Button cell R2032, the electric discharge of 0.5C are assembled using the carbon coating iron manganese phosphate lithium material of preparation as positive electrode
Capacity is 138mAh/g.
The comparative experiments, by lithium hydroxide etc., all in a solvent, solvent usage amount is big, at high cost, and makes raw material for dissolution
Concentration it is low, obtain iron manganese phosphate for lithium product solid content be 36.7g/L, hence it is evident that lower than embodiment 1 iron manganese phosphate for lithium produce
The solid content of product is 94.3g/L, and chemical property also has reduction.
Comparative example 2
Weigh 85% phosphoric acid of 18.7kg, 16.4kg MnSO4·H2O、18.0kg FeSO4·7H2115L water-second is added in O
Glycol mixed solvent (volume ratio of water and ethylene glycol is 2:3), controls 20~40 DEG C of temperature of charge, stirs 2 hours, as slurry
A.Weigh 20.2kg LiOHH2115L water-ethylene glycol mixed solvent (volume ratio of water and ethylene glycol is 2:3), control is added in O
It 20~40 DEG C of temperature of charge, stirs 2 hours, as slurry B.Slurry A and B are thrown into reactor tank, advanced slurry A, laggard slurry
Expect that B, coutroi velocity are consistent.Mixed slurry continues stirring 4 hours under an inert atmosphere, then with the rate liter of 3 DEG C/min
Temperature is kept for 3 hours to 180 DEG C, is then down to room temperature.Filtering, filtering stock, until the sulfate concentration in cleaning solution is lower than
200ppm is obtained and is contained wet iron manganese phosphate for lithium slurry, solid-to-liquid ratio 30%.The solid content for obtaining iron manganese phosphate for lithium product is 94.3g/
L.According to quality than glucose: iron manganese phosphate for lithium=15:100 ratio weighs glucose, and what addition had been washed contains wet manganese phosphate
In iron lithium slurry, stir 1 hour.100 DEG C of outlet temperature of setting is spray-dried, before obtaining dry iron manganese phosphate for lithium sintering
Drive body.Under nitrogen protection, heating rate is 8 DEG C/min, and 300 DEG C are calcined 4 hours, is continuously heating to 700 DEG C and is sintered 8 hours,
Then through crushing, screening, drying, carbon coating lithium iron manganese phosphate anode material finished product is obtained.
Button cell R2032, the electric discharge of 0.5C are assembled using the carbon coating iron manganese phosphate lithium material of preparation as positive electrode
Capacity is 140mAh/g.
The comparative experiments, by lithium hydroxide all investment slurry B, when slurry A and slurry B is mixed, material mixing divides
It dissipates unevenly, the crystal perfection degree of formation is poor, and product gram volume reduces.
Claims (10)
1. a kind of method that water/solvent-thermal method largely prepares carbon coating iron manganese phosphate for lithium characterized by comprising by phosphorus source, iron
Source, manganese source, part lithium source and stirring solvent are formed uniformly the first suspension, and remaining lithium source and stirring solvent are formed uniformly second
First suspension and the second suspension are squeezed into reactor tank hybrid reaction, the part lithium source in first suspension by suspension
Be the 15%~33.3% of lithium source total amount, the solvent be water, ethylene glycol, ethyl alcohol, acetone it is one or more than one kinds of.
2. the method that water/solvent-thermal method according to claim 1 largely prepares carbon coating iron manganese phosphate for lithium, feature exist
In, comprising the following steps:
1) phosphorus source, source of iron, manganese source, part lithium source and stirring solvent are formed uniformly the first suspension, by remaining lithium source and solvent
Stir evenly to form the second suspension, total molar ratio of material Li:(Fe+Mn): P=2.9~3.0:1:1；
2) the first suspension and the second suspension are squeezed into reactor tank and is mixed, mixed slurry stirs under an inert atmosphere
Afterwards, 130~240 DEG C of reactions are warming up to, and are kept for 2~10 hours, room temperature is down to, obtains iron manganese phosphate for lithium slurry；
3) iron manganese phosphate for lithium slurry is separated by solid-liquid separation, to containing carbon source is added in wet solid, is dried after mixing；
4) material after drying is sintered under an inert atmosphere, crushes, sieves, dries, obtain carbon coating iron manganese phosphate for lithium
Electrode material, products molecule formula are LiMnxFe1-xPO4, 0 < x < 1.
3. the method that water/solvent-thermal method according to claim 2 largely prepares carbon coating iron manganese phosphate for lithium, feature exist
In, when step 1) prepares the first suspension and the second suspension, 20~40 DEG C of temperature of charge of control, 0.5~5h of mixing time；The
(Mn+Fe) concentration is 1~3mol/L, 4~8mol/L of Li concentration in the second suspension in one suspension.
4. the method that water/solvent-thermal method according to claim 1 largely prepares carbon coating iron manganese phosphate for lithium, feature exist
In the solvent is the mixed solvent of water and ethylene glycol.
5. the method that water/solvent-thermal method according to claim 2 largely prepares carbon coating iron manganese phosphate for lithium, feature exist
In step 2) mixing time is 0.5~6h, 10~60Hz of stirring frequency, controls 20~60 DEG C of temperature of charge.
6. the method that water/solvent-thermal method according to claim 5 largely prepares carbon coating iron manganese phosphate for lithium, feature exist
In step 2) mixing time is 4h, stirring frequency 50Hz.
7. the method that water/solvent-thermal method according to claim 2 largely prepares carbon coating iron manganese phosphate for lithium, feature exist
In step 2) heating rate is 1~5 DEG C/min, 1~5 DEG C/min of cooling rate.
8. the method that water/solvent-thermal method according to claim 2 largely prepares carbon coating iron manganese phosphate for lithium, feature exist
In the mass ratio of the step 3) carbon source and the solid is 3~15:100.
9. the method that water/solvent-thermal method according to claim 2 largely prepares carbon coating iron manganese phosphate for lithium, feature exist
In step 4) sintering temperature is 500~800 DEG C, is kept for 2~10 hours, 2~10 DEG C/min of heating rate.
10. the method that water/solvent-thermal method according to claim 9 largely prepares carbon coating iron manganese phosphate for lithium, feature exist
In keeping being further continued for being warming up to 500~800 DEG C for 1~8 hour at 250~350 DEG C in step 4) temperature-rise period.
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| US20140356720A1 (en) * | 2010-01-28 | 2014-12-04 | Sued-Chemie Ip Gmbh & Co. Kg | Substituted lithium-manganese metal phosphate |
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Denomination of invention: A method for preparing carbon coated lithium manganese iron phosphate in bulk by water/solvothermal method Effective date of registration: 20230306 Granted publication date: 20210330 Pledgee: China Co. truction Bank Corp Deyang branch Pledgor: DEYANG WEIXU LITHIUM BATTERY TECHNOLOGY CO.,LTD. Registration number: Y2023980034175 |