CN102856545A - Preparation method of micro-nano-grade metal-ion-doped lithium iron phosphate anode material - Google Patents
Preparation method of micro-nano-grade metal-ion-doped lithium iron phosphate anode material Download PDFInfo
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Abstract
The invention belongs to the technical field of lithium ion battery anode material preparation, and discloses a preparation method of a micro-nano-grade metal-ion-doped lithium iron phosphate anode material. According to the invention, an accurate iron-phosphorus ratio is realized through a liquid phase homogenization reaction; doping metal ions are added simultaneously during a continuous liquid phase reaction process, such that material conductivity and tap density are improved; during subsequent preparation processes, through accurate controlling over lithium-iron-phosphorus ratio and carbon content, good dispersion, and rapid spray drying, precursor material uniform dispersion and good carbon coating are realized; and under atmosphere protection, the micro-nano-grade metal-ion-doped lithium iron phosphate anode material with narrow particle-size distribution, high tap density, and good fluidity is obtained through a heat treatment of a relatively short time under a relatively low temperature. The preparation method provided by the invention has the advantages of suitability for large-scale productions, simple technology, and low cost. The method has great application value and good application prospect in the respect of preparation of high-power lithium ion batteries applied in fields of solar energy, wind energy, electric vehicles, and the like.
Description
Technical field
The invention belongs to chargeable chemical electric power source electrode technical field of material, particularly a kind of high power lithium ion cell preparation method of micro-nano-scale doped lithium iron phosphate anode material.
Background technology
LiFePO 4 (LiFePO
4) be a kind of lithium ion battery novel anode material that grew up in recent years.Its raw material source is abundant, and specific capacity is high, has extended cycle life, and environmental pollution is little.At present, power type of new generation or accumulation energy type lithium ion battery have been widely used in.
Yet, most of business-like LiFePO4s are owing to directly adopt the solid phase high-sintering process, there is defective at aspects such as raw material mixing, drying, sintering, therefore, the performance of mass production of products is stable not, and consistency is relatively poor in batches, cause the material manufacturing cost to increase, add different manufacturers battery preparation technique difference, applying of product is affected, thereby also seriously restricted its large-scale production; In addition, show still Shortcomings of the aspects such as its high rate during charging-discharging, cryogenic property, cause power of battery density, operating characteristics and the scope of application also to be restricted.Therefore, must propose a cover innovative technology route and fundamentally solve the above-mentioned bottleneck problem that LiFePO 4 material exists.
Preparation technology is simple for the high temperature solid-state method LiFePO 4 material, but reactant is difficult for mixing, some process using ball milling mixes, sintering time is long, time consumption and energy consumption, synthetic product broad particle distribution, granule size is micro-meter scale, pattern is irregular, and the chemical property of different batches material differs greatly.This is that the control of product composition, purity, crystallization shape, granule size also has great difficulty, causes the batch less stable of product, and whole production process flow process is long because solid phase method is difficult to control accurately lithium, iron, phosphorus ratio, and energy consumption is larger.Existing many patents have carried out improving research to the synthesis technique of LiFePO4 both at home and abroad, but are the improvement on the solid phase method basis mostly.Also have and adopt microwave method, hydro thermal method and some liquid phase method synthetic methods, but that these methods are not suitable for extensive preparation, some complex process, some cost a bit is higher.Therefore, the present invention is intended to seek a kind of on a large scale preparation, process stabilizing, liquid phase homogeneous phase method simple to operate, lower-cost in conjunction with the process route of solid-phase sintering synthesizing iron lithium phosphate.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of micro-nano doped metal ion lithium iron phosphate positive material.
A kind of preparation method of micro-nano doped metal ion lithium iron phosphate positive material, this lithium iron phosphate positive material granularity are 50nm～6 μ m, and the doping metals amount is 0.5 ~ 5%, and carbon content is 0.5～5%, and tap density is 1.1 ~ 1.6g/cm
2, the method may further comprise the steps:
(1) mol ratio according to Fe and doped metal ion sum and P is 1:1 weighing source of iron, phosphorus source and doped metal ion compound, with three's water-soluble solution that is mixed with respectively, then with source of iron with phosphorus source solution is mixed to get Fe and the P total concentration is the mixed solution of 0.75-2mol/L, the doped metal ion amount is 0.01 ~ 0.05 of doped metal ion and the total mole of Fe, and the concentration of doped metal ion compound solution is 0.1 ~ 1mol/L; Compound concentration is the alkaline solution of 0.1-3mol/L;
(2) dispersant of adding deionized water and the theoretical ferric phosphate quality 0.1% ~ 0.5% that generates in reactor is even with the speed dispersed with stirring of 200-2000r/min, reacts 0.5-4 hour;
(3) the phosphorus source in the step (1) and source of iron mixed solution, doped metal ion compound solution, aqueous slkali are distinguished in the reactor of input step (2), and mix with the speed of 200-2000r/min, reacted 0.5-4 hour, reaction temperature is 15-80 ℃; Wherein the charging rate of phosphorus source and source of iron mixed solution is 2-15ml/min, and doped metal ion compound solution charging rate is 1-10ml/min, and the alkaline solution charging rate is regulated by the pH of system, and the pH control range is 1.5-6.0;
(4) step (3) products therefrom is filtered, wash 3 times with deionized water, wash 1 time with ethanol, 80 ℃, dry 4-8 hour; Then, under 350-550 ℃, obtained containing the ferric phosphate of doped metal ion in sintering 4-8 hour;
(5) mol ratio by Li, Fe, P three is (1 ~ 1.05): (0.95 ~ 1): 1 takes by weighing respectively the ferric phosphate of lithium source and step (4) preparation; By the ferric phosphate quality 0.5 ~ 5% take by weighing carbon source, lithium source, ferric phosphate, carbon source are added and contain in the aqueous solution of dispersant, in with the blender that stirs, disperseed 0.25-2 hour take mixing speed as 200-800r/min, and to adjust solid content with deionized water be 10%-50%; Wherein the consumption of dispersant is theoretical 0.1% ~ 0.5% of the ferric phosphate quality that generates;
(6) with the input of the mixed material in the step (5) spray dryer, carry out spray drying; The control inlet temperature is 180-250 ℃, and outlet temperature is 90-120 ℃;
(7) be under 400-700 ℃ with step (6) gained dried material in sintering temperature under the inert gas, sintering time is 8-12 hour, and the sintered products cooling is namely got micro-nano doped metal ion lithium iron phosphate positive material.
Above-mentioned source of iron is ferric nitrate, iron chloride, ferric sulfate or ironic citrate.
The above-mentioned phosphorus source of stating is phosphoric acid, ammonium dihydrogen phosphate, sodium dihydrogen phosphate or potassium dihydrogen phosphate;
Above-mentioned doped metal ion compound is cobalt nitrate, manganese nitrate, zinc nitrate, ammonium molybdate, ammonium tungstate, ammonium titanium fluoride, strontium nitrate, nickel nitrate, magnesium nitrate or zirconium nitrate.
Above-mentioned lithium source is lithium hydroxide, lithium carbonate, lithium acetate, lithium nitrate, lithium oxalate or lithium sulfate.
Above-mentioned carbon source is one or more in acetylene black, electrically conductive graphite, carbon nano-tube, Graphene, sucrose, glucose, fructose, citric acid, pentaerythrite, vitamin C, polyvinyl alcohol, polyethylene glycol and the polyethers.
Alkali compounds in the above-mentioned alkaline solution is carbonic hydroammonium, ammonium carbonate, sodium acid carbonate, sodium carbonate, saleratus, potash, NaOH, potassium hydroxide or ammoniacal liquor.
Above-mentioned dispersant is that lauryl sodium sulfate, dodecyl sodium sulfate, APES 10, dioctyl sodium sulfosuccinate, Sucrose Fatty Acid Ester, aliphatic acid sorb are smooth, in the polysorbate, polyoxyethylene, polyvinyl alcohol, methyl anyl alcohol, cellulose derivative, fatty acid polyethylene glycol ester one or more.
Reactor described in the step (2) is the stainless steel reactor with chuck, charging aperture, discharging opening, overfall, blender and PH meter, but this reactor continuous discharge.
Lithium source described in the step (5) adds with powder or is configured to the aqueous solution and adds.
Inert gas described in the step (7) is high pure nitrogen, high-purity argon gas or to contain volume be that the High Purity Hydrogen of 2% hydrogen is argon-mixed.
Beneficial effect of the present invention is: use relatively cheap ferric iron to replace the divalence source of iron to make raw material, not only reduced production cost, and avoided the easy oxidation of ferrous iron to generate the impurity that is difficult to remove and cause product impure; In liquid phase, can realize accurate-metering and the doping of source of iron, phosphorus source and metal ion, iron, phosphorus and metallic atom distribute very evenly and proportion of composing is fixed; Adding a small amount of dispersant in liquid-phase system can make source of iron, phosphorus source and doping metals compound fully mix the product Uniform Dispersion before reaction; Ferric phosphate, lithium source and carbon source only do not need ball milling just can realize that good homogeneous phase mixes by stirring, saved the energy, have greatly shortened incorporation time, have improved production efficiency; Adopt spray-dired method, the wink-dry slurry is avoided segregation in the composition dry run, products obtained therefrom homogeneous chemical composition, in batches good stability; In liquid phase reaction course, realize the even carbon dope of metal ion mixing and granule interior, material tap density and conductivity raising are highly profitable; The precursor material granularity of the method preparation is less, narrow distribution, and therefore, required sintering temperature descends, and sintering time shortens, and has further reduced power consumption.This reaction method technique is simple, is easy to control, but continuous discharge, production efficiency is high, the product quality high conformity, and stable electrochemical property, preparation cost is low, and is easy to large-scale continuous production.The micro-nano-scale doped iron lithium phosphate material of the method preparation has good chemical property as anode material for lithium-ion batteries, at room temperature 0.1C multiplying power discharging specific capacity is greater than 155mAh/g, 10C multiplying power discharging specific capacity is greater than 100mAh/g, and cycle performance is good, and the positive electrode that is suitable as high power type lithium ion cell uses.
Description of drawings
Fig. 1 is scanning electron microscopy (SEM) figure and the X-ray energy spectrum figure (EDS) that mixes the cobalt ferric phosphate.
Fig. 2 is the SEM figure that mixes the cobalt lithium iron phosphate positive material.
Fig. 3 is the cycle performance curve of mixing the discharge of cobalt lithium iron phosphate positive material under different multiplying that room temperature records.
Embodiment
Below in conjunction with drawings and Examples technical scheme of the present invention is described further.
(1) mol ratio according to Fe and doped metal ion sum and P is 1:1, prepare respectively 1mol/L iron nitrate solution and 1mol/L phosphoric acid solution, two solution are mixed, obtaining Fe and P total concentration is the mixed solution of 1mol/L, and compound concentration is that 0.5mol/L cobalt nitrate solution and concentration are the 3mol/L ammonia spirit.
(2) the 0.25g polyvinyl alcohol is dispersed in the 100ml deionized water, stirs in the 1L stainless steel reactor of adding with chuck and stirring, mixing speed is 200r/min, and control chuck circulating water temperature is 25 ℃.
(3) with the mixed solution of iron nitrate solution and phosphoric acid solution with 5ml/min charging rate input reactor, with the 0.5mol/L cobalt nitrate solution with 2ml/min charging rate input reactor.Simultaneously, with the ammonia spirit input reactor of 3mol/L, control pH is 1.5, regulates the charging rate of ammonia spirit.The adjusting mixing speed is 1500r/min, reacts beginning discharging in 1.5 hours.With material filtering, wash 3 times with deionized water, wash 1 time with ethanol, under 80 ℃, dried by the fire 4 hours, 350 ℃ of sintering 8 hours, obtain mixing the cobalt ferric phosphate again.
(4) take by weighing 50g and mix the cobalt ferric phosphate, the 14.4g lithium carbonate, 12.6g sucrose and 0.15g polyvinyl alcohol add in the blender, add 180ml water, and transferring solid content is 30%, stirs with the mixing speed of 800r/min to stop to stir after 0.5 hour.With this material input spray dryer, control drying machine inlet temperature is 220 ℃, and 110 ℃ of outlet temperatures are carried out spray drying.
(5) the gained dried material is placed the high pure nitrogen sintering furnace, 500 ℃ of sintering of sintering temperature 4 hours are set, 600 ℃ of sintering 6 hours obtain mixing the cobalt lithium iron phosphate positive material.
Utilize and mix cobalt ferric phosphate granule size and pattern in the sem test preparation process, and mix the cobalt ferric phosphate with the test of X-ray energy spectrum analytic approach, the result as shown in Figure 1.
Utilize sem test to mix cobalt lithium iron phosphate positive material granule size and pattern and analytical test material tap density, mix cobalt amount and carbon content.Recording this, to mix cobalt lithium iron phosphate positive material particle size range be 80nm～3 μ m, and mixing the cobalt amount is 3.2%, and carbon content of lithium iron phosphate is 4.5%.The material tap density is 1.2g/cm
3, as shown in Figure 2.
This is mixed the in mass ratio 8:1:1 mixing of cobalt LiFePO 4 material, Super-P conductive carbon black, PVDF binding agent, make uniform slurry take NMP as solvent, then with its blade coating on the aluminium foil of 20 micron thickness, after 120 ℃ of vacuumize, obtain anode pole piece, cut into suitable diameter, take the lithium paper tinsel as to electrode, in being full of the glove box of argon gas, be assembled into button cell, carry out charge-discharge test with constant current, charging/discharging voltage is 2.5-4.2V, specific capacity and the cycle performance of the different discharge-rates of test material.As shown in Figure 3, average specific discharge capacity is more than the 142mAh/g under the 1C multiplying power, and average specific discharge capacity is higher than 110mAh/g under the 10C multiplying power.
(1) mol ratio according to Fe and doped metal ion sum and P is 1:1, prepares respectively 2mol/L ferric chloride solution and 2mol/L ammonium dihydrogen phosphate, and two solution are mixed, and obtaining Fe and P total concentration is the 2mol/L mixed solution.Prepare 1mol/L ammonium molybdate solution and 2mol/L sal volatile.
(2) with load weighted 0.1g polyethylene glycol and 0.05g polyvinyl alcohol in advance dispersant in the 100ml deionized water, stir in the 1L stainless steel reactor of adding with chuck and stirring, mixing speed is 600r/min, and control chuck circulating water temperature is 15 ℃.
(3) with the mixed solution of ferric chloride solution and ammonium dihydrogen phosphate with 15ml/min charging rate input reactor, with the 1mol/L ammonium molybdate solution with 10ml/min charging rate input reactor.Simultaneously, with 2mol/L sal volatile input reactor, control pH is 4.0, regulates the charging rate of 2mol/L sal volatile.The adjusting mixing speed is 2000r/min, reacts beginning discharging in 0.5 hour.With material filtering, wash 3 times with deionized water, wash 1 time with ethanol, under 80 ℃, dried by the fire 6 hours, 450 ℃ of sintering 6 hours, obtain mixing molybdophosphate iron again.
(4) take by weighing 50g and mix molybdophosphate iron, the 8.4g lithium hydroxide, the 4.6g electrically conductive graphite, 0.2g polyethylene glycol and 0.05g polyvinyl alcohol add in the blender, add 570ml water, and transferring solid content is 10%, stirs with the mixing speed of 500r/min to stop to stir after 1.5 hours.With this material input spray dryer, control drying machine inlet temperature is 180 ℃, and 90 ℃ of outlet temperatures are carried out spray drying.
(5) the gained dried material is placed the high-purity argon gas sintering furnace, 400 ℃ of sintering of sintering temperature 6 hours are set, 700 ℃ of sintering 6 hours obtain mixing molybdophosphate iron lithium anode material.
This mixes molybdophosphate iron lithium anode material granule size and pattern to utilize sem test, the test material tap density, mixes molybdenum amount and carbon content.
This is mixed the in mass ratio 8:1:1 mixing of molybdophosphate iron lithium material, Super-P conductive carbon black, PVDF binding agent, make uniform slurry take NMP as solvent, then with its blade coating on the aluminium foil of 20 micron thickness, after 120 ℃ of vacuumize, obtain anode pole piece, cut into suitable diameter, take the lithium paper tinsel as to electrode, in being full of the glove box of argon gas, be assembled into button cell, carry out charge-discharge test with constant current, charging/discharging voltage is 2.5-4.2V, specific capacity and the cycle performance of the different discharge-rates of test material.
Recording this, to mix molybdophosphate iron lithium anode material particle size range be 50nm～1 μ m, and mixing the molybdenum amount is 4.5%, and carbon content of lithium iron phosphate is 0.5%.The material tap density is 1.4g/cm
3Room temperature records mixes the discharge performance of molybdophosphate iron lithium under different multiplying, and average specific discharge capacity is more than the 140mAh/g under the 1C multiplying power, and average specific discharge capacity is higher than 105mAh/g under the 10C multiplying power.
(1) mol ratio according to Fe and doped metal ion sum and P is 1:1, prepares respectively 0.5mol/L ferric oxalate solution and 1mol/L phosphoric acid solution, and two solution are mixed, and obtaining Fe and P total concentration is the 0.75mol/L mixed solution.Prepare 0.1mol/L zinc nitrate solution and 0.1mol/L sodium hydroxide solution.
(2) with load weighted 0.05g lauryl sodium sulfate in advance dispersant in the 100ml deionized water, add in the 1L stainless steel reactor with chuck and stirring and stir, mixing speed is 800r/min, control chuck circulating water temperature is 60 ℃.
(3) with the mixed solution of ferric oxalate solution and phosphoric acid solution with 2ml/min charging rate input reactor, with the 0.1mol/L zinc nitrate solution with 1ml/min charging rate input reactor.Simultaneously, with the sodium hydroxide solution input reactor of 0.1mol/L, control pH is 5.0, regulates the charging rate of sodium hydroxide solution.The adjusting mixing speed is 600r/min, reacts beginning discharging in 4 hours.With material filtering, wash 3 times with deionized water, wash 1 time with ethanol, under 80 ℃, dried by the fire 5 hours, 550 ℃ of sintering 4 hours, obtain mixing the zinc ferric phosphate again.
(4) take by weighing 50g and mix the zinc ferric phosphate, the 17.7g lithium oxalate, 29.8g glucose and 0.05g lauryl sodium sulfate add in the blender, add 98ml water, and transferring solid content is 50%, stirs with the mixing speed of 400r/min to stop to stir after 2.0 hours.With this material input spray dryer, control drying machine inlet temperature is 250 ℃, and 120 ℃ of outlet temperatures are carried out spray drying.
(5) the gained dried material is placed the high pure nitrogen sintering furnace, 450 ℃ of sintering of sintering temperature 6 hours are set, 650 ℃ of sintering 5 hours obtain mixing the zinc lithium iron phosphate positive material.
This mixes zinc lithium iron phosphate positive material granule size and pattern to utilize sem test, tests this material tap density, mixes zinc amount and carbon content.
This is mixed the in mass ratio 8:1:1 mixing of zinc LiFePO 4 material, Super-P conductive carbon black, PVDF binding agent, make uniform slurry take NMP as solvent, then with its blade coating on the aluminium foil of 20 micron thickness, after 120 ℃ of vacuumize, obtain anode pole piece, cut into suitable diameter, take the lithium paper tinsel as to electrode, in being full of the glove box of argon gas, be assembled into button cell, carry out charge-discharge test with constant current, charging/discharging voltage is 2.5-4.2V, specific capacity and the cycle performance of the different discharge-rates of test material.
Recording this, to mix zinc lithium iron phosphate positive material particle size range be 1 μ m～6 μ m, and mixing the zinc amount is 0.5%, and carbon content of lithium iron phosphate is 3.5%.The material tap density is 1.1g/cm
3Average specific discharge capacity is more than the 140mAh/g under the 1C multiplying power, and average specific discharge capacity is higher than 100mAh/g under the 10C multiplying power.
The step of preparation micro-nano-scale LiFePO4 is as follows:
(1) mol ratio according to Fe and doped metal ion sum and P is 1:1, through stoichiometry accurately, prepare respectively 1mol/L ironic citrate solution and 1mol/L potassium dihydrogen phosphate, two solution are mixed, obtaining Fe and P total concentration is the 1mol/L mixed solution.Prepare 0.5mol/L manganese nitrate solution and 0.5mol/L potassium bicarbonate solution.
(2) with load weighted 0.20g polysorbate in advance dispersant in the 100ml deionized water, add in the 1L stainless steel reactor with chuck and stirring and stir, mixing speed is 400r/min, control chuck circulating water temperature is 80 ℃.
(3) with the mixed solution of 1mol/L ironic citrate solution and 1mol/L potassium dihydrogen phosphate with 2ml/min charging rate input reactor, with the 0.5mol/L manganese nitrate solution with 1ml/min charging rate input reactor.Simultaneously, with the potassium bicarbonate solution input reactor of 0.5mol/L, control pH is 6.0, regulates the charging rate of potassium bicarbonate solution.The adjusting mixing speed is 1000r/min, reacts beginning discharging in 3 hours.With material filtering, wash 3 times with deionized water, wash 1 time with ethanol, under 80 ℃, dried by the fire 7 hours, 400 ℃ of sintering 6 hours, obtain mixing the manganese ferric phosphate again.
(4) take by weighing 50g and mix the manganese ferric phosphate, the 19.4g lithium acetate, 31.3g fructose and 0.15g polysorbate add in the blender, add 152ml water, and transferring solid content is 40%, stirs with the mixing speed of 500r/min to stop to stir after 1.5 hours.With this material input spray dryer, control drying machine inlet temperature is 230 ℃, and 110 ℃ of outlet temperatures are carried out spray drying.
(5) the gained dried material is placed hydrogen-argon-mixed (hydrogen that contains cumulative volume 2%) sintering furnace, 450 ℃ of sintering of sintering temperature 5 hours are set, 700 ℃ of sintering 4 hours obtain mixing the manganese lithium iron phosphate positive material.
This mixes manganese lithium iron phosphate positive material granule size and pattern to utilize sem test, the test material tap density, mixes manganese amount and carbon content.
This is mixed the in mass ratio 8:1:1 mixing of manganese LiFePO 4 material, Super-P conductive carbon black, PVDF binding agent, make uniform slurry take NMP as solvent, then with its blade coating on the aluminium foil of 20 micron thickness, after 120 ℃ of vacuumize, obtain anode pole piece, cut into suitable diameter, take the lithium paper tinsel as to electrode, in being full of the glove box of argon gas, be assembled into button cell, carry out charge-discharge test with constant current, charging/discharging voltage is 2.5-4.2V, specific capacity and the cycle performance of the different discharge-rates of test material.
Recording this, to mix manganese lithium iron phosphate positive material particle size range be 200nm～4 μ m, and mixing the manganese amount is 5.0%, and carbon content of lithium iron phosphate is 1.9%.The material tap density is 1.5g/cm
3Room temperature records mixes the discharge performance of manganese LiFePO4 under different multiplying, and average specific discharge capacity is more than the 140mAh/g under the 1C multiplying power, and average specific discharge capacity is higher than 100mAh/g under the 10C multiplying power.
The step of preparation micro-nano-scale doped iron lithium phosphate is as follows:
(1) mol ratio according to Fe and doped metal ion sum and P is 1:1, prepares respectively 1mol/L iron nitrate solution and 1mol/L phosphoric acid solution, and two solution are mixed, and obtaining Fe and P total concentration is the 1mol/L mixed solution.Prepare 0.1mol/L ammonium tungstate solution and 2mol/L ammonia spirit.
(2) with load weighted 0.15g pentaerythrite in advance dispersant in the 100ml deionized water, add in the 1L stainless steel reactor with chuck and stirring and stir, mixing speed is 700r/min, control chuck circulating water temperature is 35 ℃.
(3) with the mixed solution of 1mol/L iron nitrate solution and 1mol/L phosphoric acid solution with 10ml/min charging rate input reactor, with the 0.1mol/L ammonium tungstate solution with 5ml/min charging rate input reactor.Simultaneously, with the ammonia spirit input reactor of 2mol/L, control pH is 3.0, regulates the charging rate of ammonia spirit.The adjusting mixing speed is 1200r/min, reacts beginning discharging in 1.2 hours.With material filtering, wash 3 times with deionized water, wash 1 time with ethanol, under 80 ℃, dried by the fire 8 hours, 550 ℃ of sintering 4 hours, obtain mixing tungstophosphoric acid iron again.
(4) take by weighing 50g and mix tungstophosphoric acid iron, the 22.8g lithium nitrate, 20.6g polyethylene glycol (molecular weight 4000) and 0.25g pentaerythrite add in the blender, add 375ml water, and transferring solid content is 20%, stirs with the mixing speed of 700r/min to stop to stir after 1.0 hours.With this material input spray dryer, control drying machine inlet temperature is 240 ℃, and 120 ℃ of outlet temperatures are carried out spray drying.
(5) the gained dried material is placed the high-purity argon gas sintering furnace, 500 ℃ of sintering of sintering temperature 4 hours are set, 700 ℃ of sintering 4 hours obtain mixing tungstophosphoric acid iron lithium anode material.
This mixes tungstophosphoric acid iron lithium anode material granule size and pattern to utilize sem test, the test material tap density, mixes tungsten amount and carbon content.
This is mixed the in mass ratio 8:1:1 mixing of tungstophosphoric acid iron lithium material, Super-P conductive carbon black, PVDF binding agent, make uniform slurry take NMP as solvent, then with its blade coating on the aluminium foil of 20 micron thickness, after 120 ℃ of vacuumize, obtain anode pole piece, cut into suitable diameter, take the lithium paper tinsel as to electrode, in being full of the glove box of argon gas, be assembled into button cell, carry out charge-discharge test with constant current, charging/discharging voltage is 2.5-4.2V, specific capacity and the cycle performance of the different discharge-rates of test material.
Recording this, to mix tungstophosphoric acid iron lithium anode material particle size range be 80nm～3 μ m, and mixing the tungsten amount is 2.7%, and carbon content of lithium iron phosphate is 1.5%, and the material tap density is 1.6g/cm
3Room temperature records mixes the discharge performance of tungstophosphoric acid iron lithium under different multiplying, and average specific discharge capacity is more than the 145mAh/g under the 1C multiplying power, and average specific discharge capacity is higher than 110mAh/g under the 10C multiplying power.
Claims (11)
1. the preparation method of a micro-nano doped metal ion lithium iron phosphate positive material is characterized in that, the method may further comprise the steps:
(1) mol ratio according to Fe and doped metal ion sum and P is 1:1 weighing source of iron, phosphorus source and doped metal ion compound, with three's water-soluble solution that is mixed with respectively, then with source of iron with phosphorus source solution is mixed to get Fe and the P total concentration is the mixed solution of 0.75-2mol/L, the doped metal ion amount is 0.01 ~ 0.05 of doped metal ion and the total mole of Fe, and the concentration of doped metal ion compound solution is 0.1 ~ 1mol/L; Compound concentration is the alkaline solution of 0.1-3mol/L;
(2) dispersant of adding deionized water and the theoretical ferric phosphate quality 0.1% ~ 0.5% that generates in reactor is even with the speed dispersed with stirring of 200-2000r/min, reacts 0.5-4 hour;
(3) the phosphorus source in the step (1) and source of iron mixed solution, doped metal ion compound solution, aqueous slkali are distinguished in the reactor of input step (2), and mix with the speed of 200-2000r/min, reacted 0.5-4 hour, reaction temperature is 15-80 ℃; Wherein the charging rate of phosphorus source and source of iron mixed solution is 2-15ml/min, and doped metal ion compound solution charging rate is 1-10ml/min, and the alkaline solution charging rate is regulated by the pH of system, and the pH control range is 1.5-6.0;
(4) step (3) products therefrom is filtered, wash 3 times with deionized water, wash 1 time with ethanol, 80 ℃, dry 4-8 hour; Then, under 350-550 ℃, obtained containing the ferric phosphate of doped metal ion in sintering 4-8 hour;
(5) mol ratio by Li, Fe, P three is (1 ~ 1.05): (0.95 ~ 1): 1 takes by weighing respectively the ferric phosphate of lithium source and step (4) preparation; By the ferric phosphate quality 0.5 ~ 5% take by weighing carbon source, lithium source, ferric phosphate, carbon source are added and contain in the aqueous solution of dispersant, in with the blender that stirs, disperseed 0.25-2 hour take mixing speed as 200-800r/min, and to adjust solid content with deionized water be 10%-50%; Wherein the consumption of dispersant is theoretical 0.1% ~ 0.5% of the ferric phosphate quality that generates;
(6) with the input of the mixed material in the step (5) spray dryer, carry out spray drying; The control inlet temperature is 180-250 ℃, and outlet temperature is 90-120 ℃;
(7) be under 400-700 ℃ with step (6) gained dried material in sintering temperature under the inert gas, sintering time is 8-12 hour, and the sintered products cooling is namely got micro-nano doped metal ion lithium iron phosphate positive material.
2. preparation method according to claim 1 is characterized in that, described source of iron is ferric nitrate, iron chloride, ferric sulfate or ironic citrate.
3. preparation method according to claim 1 is characterized in that, described phosphorus source is phosphoric acid, ammonium dihydrogen phosphate, sodium dihydrogen phosphate or potassium dihydrogen phosphate.
4. preparation method according to claim 1 is characterized in that, described doped metal ion compound is cobalt nitrate, manganese nitrate, zinc nitrate, ammonium molybdate, ammonium tungstate, ammonium titanium fluoride, strontium nitrate, nickel nitrate, magnesium nitrate or zirconium nitrate.
5. preparation method according to claim 1 is characterized in that, described lithium source is lithium hydroxide, lithium carbonate, lithium acetate, lithium nitrate, lithium oxalate or lithium sulfate.
6. preparation method according to claim 1, it is characterized in that described carbon source is one or more in acetylene black, electrically conductive graphite, carbon nano-tube, Graphene, sucrose, glucose, fructose, citric acid, pentaerythrite, vitamin C, polyvinyl alcohol, polyethylene glycol and the polyethers.
7. preparation method according to claim 1 is characterized in that, the alkali compounds in the described alkaline solution is carbonic hydroammonium, ammonium carbonate, sodium acid carbonate, sodium carbonate, saleratus, potash, NaOH, potassium hydroxide or ammoniacal liquor.
8. preparation method according to claim 1, it is characterized in that described dispersant is that lauryl sodium sulfate, dodecyl sodium sulfate, APES 10, dioctyl sodium sulfosuccinate, Sucrose Fatty Acid Ester, aliphatic acid sorb are smooth, in the polysorbate, polyoxyethylene, polyvinyl alcohol, methyl anyl alcohol, cellulose derivative, fatty acid polyethylene glycol ester one or more.
9. preparation method according to claim 1 is characterized in that, reactor described in the step (2) is the stainless steel reactor with chuck, charging aperture, discharging opening, overfall, blender and PH meter, but this reactor continuous discharge.
10. preparation method according to claim 1 is characterized in that, lithium source described in the step (5) adds with powder or is configured to the aqueous solution and adds.
11. preparation method according to claim 1 is characterized in that, inert gas described in the step (7) is high pure nitrogen, high-purity argon gas or to contain volume be that the High Purity Hydrogen of 2% hydrogen is argon-mixed.
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