CN102255078A - Coordinated method for preparing nanometer spherical iron phosphate and then using carbon fusion method to prepare nanometer spherical lithium iron phosphate - Google Patents
Coordinated method for preparing nanometer spherical iron phosphate and then using carbon fusion method to prepare nanometer spherical lithium iron phosphate Download PDFInfo
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Abstract
The invention provides a coordinated method for preparing nanometer spherical iron phosphate by using simple substance iron and then using a carbon fusion method to prepare nanometer spherical lithium iron phosphate, which is characterized by comprising the following steps: 1, preparing a nanometer spherical iron phosphate sizing agent; 2, preparing nanometer spherical iron phosphate powder 3, preparing an initially-fused nanometer spherical lithium iron phosphate anode material with high multiplying power; and 4, smashing to form the nanometer spherical lithium iron phosphate anode material with high multiplying power. In the coordinated method, the simple substance iron with low price is taken as the initial raw material, thus greatly reducing the production cost; and by using the coordinated method, the multiplying power performance, the low temperature performance, the cyclicity and the compacted density are improved greatly; the consistency and the stability are controlled effectively; the secondary pollution of a semi-production link can be avoided, thus minimizing the self discharge of the materials; and the coating finish performance is good.
Description
Technical field
The invention belongs to the new energy materials technical field, particularly a kind ofly prepare the nanometer spherical ferric phosphate with fe one continuous line and prepare the method for nanometer spherical LiFePO4 continuously, can be used as the positive electrode of production lithium ion battery to the carbon fusion method.
Technical background
LiFePO4 is a kind of positive electrode of novel lithium ion battery, and its theoretical gram volume is 170mAh/g, and voltage platform is 3.5V, LiFePO4 (LiFePO
4) and cobalt acid lithium (LiCoO
2), LiMn2O4 (LiMn
2O
4), lithium nickelate (LiNiO
2), element material (LiNi
0.3Co
0.3Mn
0.3O
2) wait lithium ion anode material to compare, have that raw material resources is abundant, cheap, Heat stability is good, have extended cycle life and advantages of environment protection, particularly its olivine structural makes it to possess the superior characteristic with safety of cycle performance.And the positive electrode that uses in the present commercial lithium ion battery is with cobalt acid lithium (LiCoO
2) be main, possess excellent chemical property, but cycle life is short, and cobalt is scarce resource, shortcomings such as on the high side, toxicity height, and limited its popularization and use.Element material (LiNi
0.3Co
0.3Mn
0.3O
2) equally because of cobalt element restriction, the difficulty of popularization is arranged.LiMn2O4 (LiMn
2O
4) the structure less stable, and capacity is relatively low, cycle life is poor.Lithium nickelate (LiNiO
2) because synthetic difficulty relatively, and cycle life is poor, so LiFePO4 is expected to become the anode material for lithium-ion batteries of latest generation.
Because the characteristics such as semiconductor that LiFePO 4 material itself possesses will realize successfully that commercialization must solve following six big problems:
1. need significantly improve the electric conductivity of LiFePO 4 material, make high rate performance and cryogenic property obtain synchronous raising;
2. by control harmful substance and then strict control self discharge and cycle performance;
3. the particle diameter of synthetic with the synthetic pattern of control nano-grade lithium iron phosphate and LiFePO4 is to improve cycle life and compacted density;
4. need to solve the cost control that material nanoization is brought;
5. the stability when the big production of scale prepares LiFePO4, conforming control;
6. solve the processing characteristics difficult problem of nano-grade lithium iron phosphate when making the lithium ion cell positive coating.
The method of synthesizing iron lithium phosphate is a lot, include high temperature solid-state method and wet method (microwave process for synthesizing, the precipitation method, hydro thermal method, sol-gal process, oxidation-reduction method, carbon fusion method) or the like, the advantage of solid phase method is that equipment is simple, but because of batch mixing even inadequately, so chemical property difference and instability, consistency are very poor, its synthesis temperature height, time are long, and it is higher to make it production cost; The advantage of wet method is that batch mixing is even, sufficient reacting, and the synthetic temperature time lower, insulation is shorter, and energy consumption is lower, has good stability and consistency, is present main production technology direction, and the approach that improves the conductivity of ferric phosphate now mainly contains:
1. carbon doping process;
2. micro-doping process;
3. carbon cladding process;
4. carbon coating+micro-doping process.
The raw material of traditional preparation process lithium iron phosphate positive material are generally ferrous oxalate, ferrous acetate, iron oxide, ferric phosphate, ferrous phosphate etc., they generally all are the micron order materials, because the characteristic of semiconductor of LiFePO4, cause and use their synthetic material electrochemical performances relatively poor, especially high power is forthright poorer with cryogenic property.This is the difficult point of synthesizing iron lithium phosphate positive electrode.
The conductivity of LiFePO4 is low, can improve by coated with carbon or ion doping, but Li
+Diffusion velocity in LiFePO4 is slow, makes battery can only be fit to little electric current and discharges and recharges, and under the identical situation of other condition, initial size is at the LiFePO4 low range poor-performing of 1 μ m-5 μ m, the non-constant of high magnification and cryogenic property; Initial size is general in the LiFePO4 low range performance of 500nm-1000nm, high magnification and poor performance at low temperatures; Initial size is in the LiFePO4 low range better performances of 100nm-500nm, but high rate capability and cryogenic property are better; Initial size is at the LiFePO4 of 10nm-100nm, and the low range performance is very good, and high rate capability and cryogenic property are also very good; Initial size below 10nm, theoretical performance excellence, but because synthetic difficulty, cost is very high, be not suitable for commercialization, thereby therefore have only the initial size of control raw material ferric phosphate to reach the synthetic initial size of control lithium iron phosphate positive material, make it nanometer; Under the identical situation of condition, initial size is more little, Li
+Diffusion velocity fast more, suitable more high-multiplying power discharge, thus the high magnification specific capacity is also high more; And the original grain of nanometer spherical LiFePO4 is the circular granule of nanometer, can be more conducive to carbon and merge coating, and nanometer spherical LiFePO4 spheroid has the bulk density height, the specific area maximum, cause the particle contact tightr, the electric conductivity excellence also is more suitable for high-multiplying power discharge; The spheroidal pattern of nanometer spherical LiFePO4 particle, make it to have the most stable contour structures, in the expansion and contraction process when the discharging and recharging of battery, have minimum expansion and shrinkage ratio, thereby have excellent material fatigue resistance, have excellent battery cycle life.
Summary of the invention
The objective of the invention is to begin the streamlined nanometer spherical ferric phosphate prepares high magnification nanometer spherical LiFePO4 continuously to the carbon fusion method the method for preparing from fe in order to provide a kind of; have with low cost, synthesis technique simple, be fit to extensive chemical industry production; and have extraordinary consistency and stability, high rate capability, cycle performance, low temperature performance excellent.
Above-describedly begin one continuous line with fe and prepare the nanometer spherical ferric phosphate and may further comprise the steps to the method that the carbon fusion method prepares high magnification nanometer spherical LiFePO4 continuously:
1), (iron content is greater than 99.8% with high purity elemental iron, iron sheet, iron filings etc.) put into the reactive tank that fills acid solution, heating (60-95 ℃) was fully reacted (20-60 hour, pH value 3-7), degaussing, filter, impurity elimination obtains pure ferrous salt solution (100-300g/L), (300-800L) squeezes into stills for air blowing with ferrous salt solution, to dissolve good phosphate (60-90kg) simultaneously and add stills for air blowing with oxidant (25-45kg) (adding in 5-60 minute), fully decontamination is cleaned in reaction back press filtration, obtain initial pure nano ferric phosphate slurry (conductivity 3-100ms, pH value 3-7).
2), regulate the acidity (pH value 1-5) of initial slurry and fully degaussing dispersion, squeeze into reactor, (60-95 ℃) moulding of heating is firm, make that initial nano ferric phosphate crystal grain is shaped in order, particle diameter is stable and full and spheroidization, degaussing, filtration, rinsing (conductivity 50-1000 μ s, pH value 1-5), oven dry (50-200 ℃ of vacuum, microwave, far-infrared ray drying) obtains nanometer spherical ferric phosphate powder (moisture 0.1%-5%, particle shape are sphere or class sphere, and particle diameter is 1-300nm).
3); with nanometer spherical ferric phosphate and lithium salts (iron phosphorus mol ratio 0.9-1.1; lithium phosphorus mol ratio 0.9-1.1); dopant ion compound (accounting for the 0.1-2% of nanometer spherical ferric phosphate powder); carbon fusion agent (accounting for the 1-5% of nanometer spherical ferric phosphate powder); carbon source (water system or the solvent that account for the 1-20% of nanometer spherical ferric phosphate powder are carbon source) adds in the Scattered Kettle that pure water or solvent are housed and fully disperses; degaussing (1-10 hour; rotating speed 300-2000 changes); squeeze into ball milling unit mahine degaussing (zirconium spherolite footpath 0.1-10mm) ball milling (0.5-50 hour); dry (spraying; microwave; far infrared vacuumize); put into compressing tablet comminutor compressing tablet secondary granulation; (300-900 ℃ of inert atmosphere sintering furnace sintering; 5-15 hour); obtain initial carbon and merge nanometer spherical high magnification lithium iron phosphate positive material (particle shape is sphere or class sphere, and particle diameter is 1nm-300nm).
4), initial carbon merged nanometer spherical high magnification lithium iron phosphate positive material pulverize (comminution by gas stream, mechanical crushing) classification, the carbon that obtains being fit to the lithium ion cell positive coating performance merges nanometer spherical high magnification lithium iron phosphate positive material.
In above-mentioned:
1. high purity elemental iron is the few high purity iron of impurity content, iron sheet, iron filings;
2. acid is sulfuric acid, phosphoric acid, hydrochloric acid, nitric acid;
3. ferrous salt is ferrous sulfate, frerrous chloride, ferrous nitrate;
4. phosphate is sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, ammonium dihydrogen phosphate;
5. oxidant is hydrogen peroxide, clorox, potassium chlorate;
6. the particle shape of nanometer spherical ferric phosphate is sphere or class sphere, and particle diameter is 1nm-300nm;
7. the particle shape of nanometer spherical LiFePO4 is sphere or class sphere, and particle diameter is 1nm-300nm;
8. carbon source is carbohydrate, PVA, PVB, gelatin, pectin, gelatine;
9. used liquid medium is high purity water or solvent, and solvent is ethanol, acetone, isopropyl alcohol;
10. lithium salts is lithium hydroxide, lithium carbonate, lithium dihydrogen phosphate, lithium oxalate, lithium acetate or lithium chloride;
11. the ion doping compound is to contain the compound that element is Ti, V, Cr, Mn, Co, Ni, Mg, Na;
12. inert protective gas is nitrogen, argon gas; The mist of the mist of nitrogen and hydrogen, argon gas and hydrogen (hydrogen content is 1%-15%);
13. the nano-sized carbon fusion agent is different high molecular polymer KH550, KH560, among KH570, the CG602 one or more.
The present invention prepares the nanometer spherical ferric phosphate with fe one continuous line and prepares the method for high magnification nanometer spherical LiFePO4 continuously to the carbon fusion method, and its advantage is:
1. having adopted cheap fe is that initial raw materials one continuous line is produced the nanometer spherical ferric phosphate to producing high magnification nanometer spherical LiFePO4 continuously, greatly reduces cost;
2. particle diameter and the particle shape by control nanometer spherical ferric phosphate reaches particle diameter and the particle shape of controlling nano-grade lithium iron phosphate, makes multiplying power, low temperature properties, cyclicity, compacted density obtain improving greatly;
3. adding trace compound by ion doping is better improved performances such as multiplying power, cyclicity, low temperature;
4. by preparing high magnification nanometer spherical LiFePO4 continuously to the carbon fusion method, make consistency and stability obtain effective control and assurance with fe one continuous line preparation nanometer spherical ferric phosphate;
5. produce continuously to make by one continuous line and remove objectionable impurities and better guaranteed, effectively prevented the secondary pollution of middle production link, thereby it is lower that the self discharge of material is dropped to, and cycle performance is better guaranteed;
6. make nanometer spherical LiFePO4 possess good coating processing characteristics by secondary granulation, crushing and classification technology with nano material characteristic.
Description of drawings
Accompanying drawing 1 is high-purity source of iron photo;
Accompanying drawing 2-1,2-2,2-3,2-4 are the TEM Electronic Speculum figure of nanometer spherical ferric phosphate;
Accompanying drawing 3-1,3-2,3-3,3-4 are the TEM Electronic Speculum figure of nanometer spherical LiFePO4;
Accompanying drawing 4 is nanometer spherical LiFePO4 Fe
2+The Mo﹠4﹠ssbauer spectrum curve chart of content;
Accompanying drawing 5-1,5-2,5-3,5-4 are the charging and discharging curve figure under each multiplying power.
Embodiment
The preparation of nanometer spherical ferric phosphate:
High purity iron content is put into the reactive tank that fills acid solution greater than 99.8% iron sheet (shown in Figure 1), be heated to 95 ℃, fully reaction is 30 hours, pH value is 3, filter impurity elimination and obtain pure ferrous salt solution 170g/L, 480L squeezes into stills for air blowing with ferrous salt solution, to dissolve good diammonium hydrogen phosphate 72kg and oxidant hydrogen peroxide 40kg simultaneously and in 10 minutes, add stills for air blowing, fully reaction back press filtration, degaussing, cleaning, decontamination, obtain initial pure nano ferric phosphate slurry, conductivity is 15ms, and pH value is 4.5.
The acid pH value of regulating initial slurry is 2.5, and fully disperse, squeeze into reactor, it is firm to 95 ℃ of moulding to heat, and makes that initial nano ferric phosphate crystal grain is shaped in order, particle diameter is stable and full and spheroidization, filtration, degaussing, rinsing, conductivity 500 μ s, 4.5,100 ℃ of oven dry of pH value obtain nanometer spherical ferric phosphate powder, moisture 2.5%, particle diameter, particle shape are seen accompanying drawing 2-1.
The preparation of nanometer spherical LiFePO4:
(iron phosphorus mol ratio is 1:1 with nanometer spherical ferric phosphate and lithium salts; lithium phosphorus mol ratio 1:1); doping V ionic compound 2.5kg; carbon fusion agent KH550 3kg; carbon source PVB 6 kg add in the Scattered Kettle that pure water or solvent are housed and fully disperse; degaussing 3 hours; rotating speed 800 changes; squeeze into ball milling unit mahine degaussing (zirconium spherolite footpath 7mm; 1.2mm ball milling (6 hours) and 0.5mm); spray drying; put into compressing tablet comminutor compressing tablet secondary granulation; 750 ℃ of inert atmosphere sintering furnace sintering; time is 12 hours; obtain initial carbon and merge nanometer spherical high magnification lithium iron phosphate positive material, simple substance; the ferric iron impurity content is seen accompanying drawing 4.
Initial carbon is merged nanometer spherical high magnification lithium iron phosphate positive material pulverize (comminution by gas stream, mechanical crushing) classification, obtain being fit to the carbon fusion nanometer spherical high magnification lithium iron phosphate positive material of lithium ion cell positive coating performance, see accompanying drawing 3-1.
Under 25 ℃ of room temperatures, be that negative pole is made button cell with the lithium sheet, its FCC0.5C initial charge 163mAh/g, 0.5C 157 mAh/g that discharge, 10C 138 mAh/g that discharge, charging and discharging curve is seen accompanying drawing 5-1.
The preparation of nanometer spherical ferric phosphate:
High purity iron content is put into the reactive tank that fills acid solution greater than 99.8% iron sheet (shown in Figure 1), be heated to 90 ℃, fully reaction is 35 hours, and pH value 3.5 filters impurity elimination and obtains pure ferrous salt solution 198g/L, 390L squeezes into stills for air blowing with ferrous salt solution, to dissolve good diammonium hydrogen phosphate 68kg and hydrogen peroxide 38kg simultaneously and add stills for air blowing in 15 minutes, fully decontamination is cleaned in reaction back press filtration, obtains initial pure nano ferric phosphate slurry, conductivity is 20ms, and pH value is 4.8.
The acid pH value of regulating initial slurry is 3.0, and fully disperse, squeeze into reactor, it is firm to 95 ℃ of moulding to heat, and makes that initial nano ferric phosphate crystal grain is shaped in order, particle diameter is stable and full and spheroidization, filter rinsing, conductivity 500 μ s, 4.5,120 ℃ of vacuum dryings of pH value obtain nanometer spherical ferric phosphate powder, moisture 2.5%, particle diameter, particle shape are seen accompanying drawing 2-2.
The preparation of nanometer spherical LiFePO4:
(iron phosphorus mol ratio is 0.98:1 with nanometer spherical ferric phosphate and lithium salts; lithium phosphorus mol ratio 1.02:1); doped with Mg ionic compound 2.5kg; carbon fusion agent KH560 2.5kg; carbon source gelatin 8kg adds in the Scattered Kettle that pure water or solvent are housed and fully disperseed 4 hours; rotating speed 900 changes; squeeze into ball milling unit mahine (zirconium spherolite footpath 7mm; 1.2mm ball milling (5 hours) and 0.5mm); spray drying; put into compressing tablet comminutor compressing tablet secondary granulation; 750 ℃ of inert atmosphere sintering furnace sintering; time is 10 hours; obtain initial carbon and merge nanometer spherical high magnification lithium iron phosphate positive material, simple substance; the ferric iron impurity content is seen accompanying drawing 4.
Initial carbon is merged nanometer spherical high magnification lithium iron phosphate positive material pulverize (comminution by gas stream, mechanical crushing) classification, obtain being fit to the carbon fusion nanometer spherical high magnification lithium iron phosphate positive material of lithium ion cell positive coating performance, see accompanying drawing 3-2.
Under 25 ℃ of room temperatures, be that negative pole is made button cell with the lithium sheet, its FCC0.5C charging 157mAh/g, 0.5C 150 mAh/g that discharge, 10C 125 mAh/g that discharge, charging and discharging curve is seen accompanying drawing 5-2.
The preparation of nanometer spherical ferric phosphate:
High purity iron content is put into the reactive tank that fills acid solution greater than 99.8% iron sheet (shown in Figure 1), be heated to 85 ℃, fully reaction is 45 hours, and pH value 4 filters impurity elimination and obtains pure ferrous salt solution 209g/L, 360L squeezes into stills for air blowing with ferrous salt solution, to dissolve good diammonium hydrogen phosphate 66kg and hydrogen peroxide 37kg simultaneously and add stills for air blowing in 25 minutes, fully decontamination is cleaned in reaction back press filtration, obtains initial pure nano ferric phosphate slurry, conductivity is 20ms, and pH value is 4.8.
The acid pH value of regulating initial slurry is 3.0, and fully disperse, squeeze into reactor, it is firm to 95 ℃ of moulding to heat, and makes that initial nano ferric phosphate crystal grain is shaped in order, particle diameter is stable and full and spheroidization, filter rinsing, conductivity 500 μ s, 4.5,120 ℃ of vacuum dryings of pH value obtain nanometer spherical ferric phosphate powder, moisture 2.5%, particle diameter, particle shape are seen accompanying drawing 2-3.
The preparation of nanometer spherical LiFePO4:
(iron phosphorus mol ratio is 0.98:1 with nanometer spherical ferric phosphate and lithium salts; lithium phosphorus mol ratio 1.02:1); doping V ionic compound 2.5kg; carbon fusion agent KH560 3kg; carbon source PVB 8 kg add in the Scattered Kettle that pure water or solvent are housed and fully disperseed 6 hours; rotating speed 900 changes; squeeze into ball milling combination still (zirconium spherolite footpath 7mm; 1.2mm ball milling (8 hours) and 0.5mm); spray drying; put into compressing tablet comminutor compressing tablet secondary granulation; 750 ℃ of inert atmosphere sintering furnace sintering; time is 9 hours; obtain initial carbon and merge nanometer spherical high magnification lithium iron phosphate positive material, simple substance; the ferric iron impurity content is seen accompanying drawing 4.
Initial carbon is merged nanometer spherical high magnification lithium iron phosphate positive material pulverize (comminution by gas stream, mechanical crushing) classification, obtain being fit to the carbon fusion nanometer spherical high magnification lithium iron phosphate positive material of lithium ion cell positive coating performance, see accompanying drawing 3-3.
Under 25 ℃ of room temperatures, be that negative pole is made button cell with the lithium sheet, its FCC0.5C charging 156mAh/g, 0.5C 152 mAh/g that discharge, 10C 127 mAh/g that discharge, charging and discharging curve is seen accompanying drawing 5-3.
The preparation of nanometer spherical ferric phosphate:
High purity iron content is put into the reactive tank that fills acid solution greater than 99.8% iron sheet (shown in Figure 1), be heated to 80 ℃, fully reaction is 48 hours, and pH value 4.5 filters impurity elimination and obtains pure ferrous salt solution 228g/L, 335L squeezes into stills for air blowing with ferrous salt solution, to dissolve good diammonium hydrogen phosphate 67kg and hydrogen peroxide 38kg simultaneously and add stills for air blowing in 30 minutes, fully decontamination is cleaned in reaction back press filtration, obtains initial pure nano ferric phosphate slurry, conductivity is 15ms, and pH value is 3.8.
The acid pH value of regulating initial slurry is 3.0, and fully disperse, squeeze into reactor, it is firm to 95 ℃ of moulding to heat, and makes that initial nano ferric phosphate crystal grain is shaped in order, particle diameter is stable and full and spheroidization, filter rinsing, conductivity 300 μ s, 3.8,120 ℃ of vacuum dryings of pH value obtain nanometer spherical ferric phosphate powder, moisture 1.5%, particle diameter, particle shape are seen accompanying drawing 2-4.
The preparation of nanometer spherical LiFePO4:
(iron phosphorus mol ratio is 0.96:1 with nanometer spherical ferric phosphate and lithium salts; lithium phosphorus mol ratio 1.05:1); doping V ionic compound 3kg; carbon fusion agent KH560 3.5kg; carbon source PVB 5 kg add in the Scattered Kettle that pure water or solvent are housed and fully disperseed 6 hours; rotating speed 900 changes; squeeze into ball milling combination still (zirconium spherolite footpath 7mm; 1.2mm ball milling (8 hours) and 0.5mm); spray drying; put into compressing tablet comminutor compressing tablet secondary granulation; 750 ℃ of inert atmosphere sintering furnace sintering; time is 11 hours; obtain initial carbon and merge nanometer spherical high magnification lithium iron phosphate positive material, simple substance; the ferric iron impurity content is seen accompanying drawing 4.
Initial carbon is merged nanometer spherical high magnification lithium iron phosphate positive material pulverize (comminution by gas stream, mechanical crushing) classification, obtain being fit to the carbon fusion nanometer spherical high magnification lithium iron phosphate positive material of lithium ion cell positive coating performance, see accompanying drawing 3-4.
Under 25 ℃ of room temperatures, be that negative pole is made button cell with the lithium sheet, its FCC0.5C charging 161mAh/g, the 0.5C 156mAh/g that discharges, 10C 135 mAh/g that discharge, charging and discharging curve is seen accompanying drawing 5-4.
Claims (14)
1. one kind prepares the method for nanometer spherical LiFePO4 from preparing the nanometer spherical ferric phosphate continuously to the carbon fusion method, it is characterized in that: may further comprise the steps
:
1), preparation nanometer spherical ferric phosphate slurry: high-purity iron sheet or iron filings are put into the reactive tank that fills acid solution, are heated to 60-95 ℃, fully reacted 20-60 hour, pH value 3-7, filtration, degaussing, impurity elimination obtain pure ferrous salt solution 100-300g/L; Ferrous salt solution is squeezed into stills for air blowing, will dissolve good phosphate and oxidant simultaneously and join stills for air blowing at 5-60 minute, fully reaction back press filtration, cleaning, degaussing, decontamination obtain initial pure nano ferric phosphate slurry;
2), preparation nanometer spherical ferric phosphate powder: the acidity of regulating initial slurry is to pH value 1-5, and fully disperse, squeeze into reactor, it is firm to be warmed to 60-95 ℃ of moulding, make that initial nano ferric phosphate crystal grain is shaped in order, particle diameter is stable and full and spheroidization, it is sphere or class sphere that degaussing, filtration, rinsing, oven dry obtain nanometer spherical ferric phosphate powder, and particle diameter is 1nm-300nm;
3), the preparation initial carbon merges nanometer spherical high magnification lithium iron phosphate positive material: with nanometer spherical ferric phosphate and lithium salts: iron phosphorus mol ratio 0.9-1.1, lithium phosphorus mol ratio 0.9-1.1, doping accounts for the ionic compound of nanometer spherical ferric phosphate powder 0.1-2%, account for the carbon fusion agent of nanometer spherical ferric phosphate powder 1-5%, the water system or the solvent that account for nanometer spherical ferric phosphate powder 1-20% are that carbon source adds fully dispersion in the Scattered Kettle that pure water or solvent are housed, degaussing 1-10 hour, rotating speed 300-2000 changes, squeeze into ball milling combination still ball milling degaussing 0.5-50 hour, dry, carry out the compressing tablet secondary granulation, under inert atmosphere 300-900 ℃ sintering 5-15 hour, obtain initial carbon and merge nanometer spherical high magnification lithium iron phosphate positive material, its particle shape is sphere or class sphere, and particle diameter is 1nm-300nm;
4), pulverize moulding nanometer spherical high magnification lithium iron phosphate positive material: initial carbon is merged nanometer spherical high magnification lithium iron phosphate positive material crushing and classification, obtain being fit to the carbon fusion nanometer spherical high magnification lithium iron phosphate positive material of lithium ion cell positive coating performance.
2. according to claim 1ly a kind ofly prepare the method for nanometer spherical LiFePO4 from preparing the nanometer spherical ferric phosphate continuously to the carbon fusion method, it is characterized in that: the high-purity iron sheet described in the step 1) or its iron content of iron filings are greater than 99.8%.
3. according to claim 1ly a kind ofly prepare the method for nanometer spherical LiFePO4 continuously to the carbon fusion method, it is characterized in that: step 1) or step 2 from preparing the nanometer spherical ferric phosphate) in acid be acid one of them for sulfuric acid, phosphoric acid, hydrochloric acid or nitric acid.
4. according to claim 1ly a kind ofly prepare the method for nanometer spherical LiFePO4 from preparing the nanometer spherical ferric phosphate continuously to the carbon fusion method, it is characterized in that: the phosphate in the step 1) is one of them of sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, ammonium dihydrogen phosphate.
5. according to claim 1ly a kind ofly prepare the method for nanometer spherical LiFePO4 from preparing the nanometer spherical ferric phosphate continuously to the carbon fusion method, it is characterized in that: the ferrous salt in the step 1) is one of them of ferrous sulfate, frerrous chloride or ferrous nitrate.
6. according to claim 1ly a kind ofly prepare the method for nanometer spherical LiFePO4 from preparing the nanometer spherical ferric phosphate continuously to the carbon fusion method, it is characterized in that: the oxidant in the step 1) is one of them of hydrogen peroxide, clorox or potassium chlorate.
7. according to claim 1ly a kind ofly prepare the method for nanometer spherical LiFePO4 continuously to the carbon fusion method, it is characterized in that: step 2 from preparing the nanometer spherical ferric phosphate) in the particle shape of the nanometer spherical ferric phosphate that obtains be that sphere or class sphere, particle diameter are 1nm-300nm.
8. according to claim 1ly a kind ofly prepare the method for nanometer spherical LiFePO4 from preparing the nanometer spherical ferric phosphate continuously to the carbon fusion method, it is characterized in that: the carbon source in the step 3) is one of them of carbohydrate, PVA, PVB, gelatin, pectin or gelatine.
9. according to claim 1 a kind of from preparing the nanometer spherical ferric phosphate prepares the nanometer spherical LiFePO4 continuously to the carbon fusion method method, it is characterized in that: the liquid medium in the step 3) is high purity water or solvent, and solvent is one of them of ethanol, acetone or isopropyl alcohol.
10. according to claim 1ly a kind ofly prepare the method for nanometer spherical LiFePO4 from preparing the nanometer spherical ferric phosphate continuously to the carbon fusion method, it is characterized in that: the lithium salts in the step 3) is one of them of lithium hydroxide, lithium carbonate, lithium dihydrogen phosphate, lithium oxalate, lithium acetate or lithium chloride.
11. according to claim 1ly a kind ofly prepare the method for nanometer spherical LiFePO4 from preparing the nanometer spherical ferric phosphate continuously to the carbon fusion method, it is characterized in that: the protective gas in the step 3) is nitrogen, argon gas; One of them of the mist of the mist of nitrogen and hydrogen or argon gas and hydrogen.
12. it is according to claim 1 a kind of from preparing the nanometer spherical ferric phosphate prepares the nanometer spherical LiFePO4 continuously to the carbon fusion method method, it is characterized in that: the nanometer spherical LiFePO4 that obtains in the step 3), its particle shape are that sphere or class sphere, particle diameter are 1nm-300nm.
13. according to claim 1ly a kind ofly prepare the method for nanometer spherical LiFePO4 continuously to the carbon fusion method, it is characterized in that from preparing the nanometer spherical ferric phosphate: step 1), 2), 3) in degaussing be to use 3000-35000 Gausses' magnetic filter or magnetic filter combination to remove fe, ferric iron impurity in the material.
14. according to claim 1ly a kind ofly prepare the method for nanometer spherical LiFePO4 continuously to the carbon fusion method, it is characterized in that from preparing the nanometer spherical ferric phosphate: step 1), 2), 3), 4) in the ionic compound element of doping be at least a or several in Ti, V, Cr, Mn, Co, Ni, Mg, the Na compound.
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| PCT/CN2011/001139 WO2012162861A1 (en) | 2011-05-27 | 2011-07-11 | Method for preparing nanometric spherical iron phosphate followed by carbon fusion process to continuously prepare nanometric spherical lithium iron phosphate |
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