CN103303893B - Preparation method of lithium iron phosphate - Google Patents
Preparation method of lithium iron phosphate Download PDFInfo
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- CN103303893B CN103303893B CN201310253068.6A CN201310253068A CN103303893B CN 103303893 B CN103303893 B CN 103303893B CN 201310253068 A CN201310253068 A CN 201310253068A CN 103303893 B CN103303893 B CN 103303893B
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Abstract
The invention provides a preparation method and system of lithium iron phosphate. The preparation system comprises a ball mill, a cyclone preheating device used for preheating a material through the afterheat of the system, a ball mill rotary kiln used for milling the preheated material in grades and dynamically sintering at the same time, and a cooler. The method comprises the following steps of: mixing ferric salt, lithium salt and phosphate in molar ratio of Fe: Li: P of (0.8-1.2): (0.8-1.2): 1; adding a solvent which is 2 to 5 times the total weight of the mixture; performing ball milling for 2 to 20 hours through the ball mill; dispersing to feed into the cyclone preheating device for preheating and predecomposition; transferring into the ball mill rotary kiln for sintering and milling in grades at the same time; and discharging and feeding the product meeting the particle size requirement into the cooler for cooling to reach the room temperature so as to obtain the finished lithium iron phosphate. The preparation method is a continuous full-dynamic sintering method, and the product prepared by such method is less in agglomeration, small in particle size, high in uniformity and relatively high in quality and stability of batches.
Description
Technical field
The present invention relates to the method for production of phosphate salt containing two or more metals, relate in particular to a kind of method for preparing solid phase of iron lithium phosphate.
Background technology
Lithium-ion secondary cell is as new generation of green battery, has that energy density is large, operating voltage is high, an advantage such as memory-less effect, self-discharge are little, good cycle, operating temperature range are wide and being widely used.Safety performance is good, cheap, thermostability is high because having for lithium ion secondary battery anode material ferric lithium phosphate, good cycle, high theoretical capacity, higher charge and discharge platform, memory-less effect, advantages of environment protection, becomes the research emphasis of lithium ion secondary battery anode material.
The method of suitability for industrialized production iron lithium phosphate at present, or synthesize master with solid phase method.Mostly adopt atmosphere protection type pushed bat kiln or the semicontinuous production of roller kiln (tunnel furnace); Adopt atmosphere protection type elevator furnace or pit furnace gap to produce.If publication number is the method for announcing in the patent application of CN1581537, CN1753216, CN1762798 and CN1767238, mix by lithium source, source of iron and phosphoric acid salt, under protection of inert gas, high-temperature roasting forms.Preparation technology is simple for this method, and reaction conditions is easily controlled, and is convenient to suitability for industrialized production.But existing technique belongs to static sintering processing mostly, in sintering process, material is actionless, and material exists the sintering process half-cooked phenomenons such as heterogeneity, burning and raw burn of being heated like this.Easily there is the defects such as particle abnormal growth, crystallization be bad.Also there is the shortcomings such as sintering time is long, energy consumption is high, production efficiency is low in static sintering processing simultaneously.
Summary of the invention
The object of the present invention is to provide a kind of lithium iron phosphate preparation method and preparation system, solve the large and skewness of the iron lithium phosphate product cut size of preparing in prior art, the problem of batch poor stability.
Lithium iron phosphate preparation method of the present invention is as follows:
A kind of lithium iron phosphate preparation method, comprises the following steps:
S1, ball milling: after molysite, lithium salts and phosphoric acid salt being mixed according to the mol ratio of Fe:Li:P=0.8～1.2:0.8～1.2:1, add the solvent of 2～5 times of said mixture gross weights, then ball milling 2～20 hours;
S2, preheating and predecomposition: the slurry after ball milling is carried out in inert atmosphere to preheating and predecomposition, so that solvent evaporates and removes the by product atmosphere that preheating and predecomposition produce, obtain into kiln presoma; Described by product atmosphere is mainly water vapor, carbon monoxide, carbonic acid gas, ammonia etc.
S3, sintering: described in inciting somebody to action, enter kiln presoma and in inert atmosphere, carry out high temperature sintering, in high temperature sintering, the lithium iron phosphate particles generating is ground, and carry out classified grinding step by step by particle diameter
S4, cooling: step S3 gained material is cooled to room temperature, makes iron lithium phosphate finished product.
Preferably:
Described step S2 carries out in cyclone preheating device, and described cyclone preheating device is to comprise decomposition chamber and the sealing suspension preheating system of one-level heat exchange unit at least, and described heat exchange unit comprises heat transfer tube and cyclone cylinder;
Described step S2 comprises:
S2-1, heat exchange: the material after ball milling enters the heat transfer tube of the described heat exchange unit that is positioned at described cyclone preheating device top, carry out heat exchange with the hot gas flow that is flowed to top by described heat transfer tube bottom, and brought into the cyclone cylinder of described heat exchange unit by described hot gas flow;
S2-2, gas solid separation: the cyclone cylinder top of described heat exchange unit is connected to vapor pipe, discharge or escape and enter the heat transfer tube of the described heat exchange unit on upper level cyclone preheating device top through described vapor pipe with hot gas flow after material-heat-exchanging, material particles after preheating, through described cyclone cylinder gas solid separation, is entered the heat transfer tube of the described heat exchange unit on next stage cyclone preheating device top by the cyclone cylinder bottom of described cyclone preheating device; ;
S2-3, decomposition: described material obtains into kiln presoma after cyclone preheating device high temperature preheating and predecomposition.Preferably:
Described step S3 carries out in ball milling rotary kiln, in described ball milling rotary kiln, is provided with well heater and temperature controller, and kiln intracoelomic cavity is equipped with a point sieve plate that grinds medium and had a different pore size and is divided into multiple storehouses; Described ball milling rotary kiln has kiln tail and kiln hood, and described kiln tail is provided with opening for feed, and described kiln hood is equipped with discharging grate plate and is connected to cooler;
Described step S3 comprises:
S3-1, enter kiln: described in enter kiln presoma and enter the described ball milling rotary kiln that is full of rare gas element;
S3-2, grinding and sintering: described in enter kiln presoma at described kiln intracoelomic cavity high temperature sintering, simultaneously through described in grind medium milling, through point sieve plate sub-sieve step by step of described different pore size, grind step by step and sintering;
Material by step S3-2 gained enters described cooler through described discharging grate plate, is cooled to room temperature, obtains iron lithium phosphate finished product.
Preferably: the kiln intracoelomic cavity of described ball milling rotary kiln is divided into three storehouses by first point of sieve plate and second point of sieve plate of different pore size, be followed successively by the first storehouse, the second storehouse, the 3rd storehouse by kiln tail to kiln hood, described the first storehouse and the second storehouse inwall are provided with ladder lining board, and described the 3rd storehouse inwall is provided with flat liner plate; Described temperature controller can be set different temperature of reaction to described the first storehouse, the second storehouse and the 3rd storehouse.The screen-aperture of first point of sieve plate and second point of sieve plate is between 1-100 micron, and the screen-aperture of second point of sieve plate is less than the screen-aperture of first point of sieve plate.Ladder lining board preferably adopts the liner plate with different surfaces shape to strengthen grinding, improve mill efficiency, simultaneously with respect to flat liner plate, in the one the second bulkheads, adopt ladder lining board, even if can ensure that, in the time that kiln body does not have angle of inclination, material also can be advanced to kiln hood.
Preferably:
Described molysite is any one or multiple combination in ironic oxalate, Ferrox, iron nitrate, iron acetate, Iron diacetate, ferric oxide, ironic hydroxide, ironic citrate, iron stearate;
Described lithium salts is any one or two or more combination in Quilonum Retard, Lithium Acetate, lithium nitrate, lithium hydroxide, lithium fluoride, monometallic;
Described phosphoric acid salt is any one or two or more combinations in primary ammonium phosphate, Secondary ammonium phosphate, triammonium phosphate, phosphoric acid, Vanadium Pentoxide in FLAKES;
Described solvent is at least one in deionized water, distilled water, dehydrated alcohol, acetone.
Preferably: the kiln body speed of rotation of described ball milling rotary kiln is 1～30 rev/min, and adjustable continuously; The kiln body integral inclination angle of described ball milling rotary kiln is adjustable continuously within the scope of 0～60 degree, and the having of this inclination angle helps material and advance after sub-sieve from kiln Caudad kiln hood.
Preferably: described ball milling rotary kiln feeding manner is spiral charging.
Preferably: described in to grind medium be steel ball, rod iron or zirconia ball.
Preferably: described hot gas flow comes from the two or more combination in the high-temperature gas that in described ball milling rotary kiln, in the rare gas element in high-temperature sintering process, cooler, in the rare gas element of cooling material discharge, warm, material decomposition produces.
A kind of iron lithium phosphate preparation system, comprises ball mill, cooler:
Also comprise primary heater unit, described primary heater unit, for the slurry after ball milling is carried out to preheating and predecomposition so that solvent evaporates and removes the by product atmosphere that preheating and predecomposition produce at inert atmosphere, obtains into kiln presoma
Also comprise ball milling rotary kiln, the kiln intracoelomic cavity of described ball milling rotary kiln is split into for the material of different-grain diameter and grinds and at least two storehouses of sintering, and be equipped with and grind medium, for by described enter kiln presoma inert atmosphere by size grading grind in carry out dynamic high temperature sintering.
Material after described ball mill ball milling enters described primary heater unit and carries out preheating and predecomposition, described in obtaining, enter the kiln tail that kiln presoma enters described ball milling rotary kiln, the material after classified grinding while sintering enters described cooler by the kiln hood of described ball milling rotary kiln and carries out cooling.
Preferably: described primary heater unit is cyclone preheating device, described cyclone preheating device is to comprise decomposition chamber and the suspension heat exchange system of one-level heat exchange unit at least, and described heat exchange unit comprises cyclone cylinder and heat transfer tube; Described ball milling rotary kiln has kiln tail and kiln hood, and described kiln tail is connected with described cyclone preheating device so that the material after preheating enters described ball milling rotary kiln, and described kiln hood is connected and carries out cooling with discharging with described cooler.
Preferably: the kiln intracoelomic cavity of described ball milling rotary kiln is divided into three storehouses by first point of sieve plate and second point of sieve plate of different pore size, be followed successively by the first storehouse, the second storehouse, the 3rd storehouse by kiln tail to kiln hood, described the first storehouse and the second storehouse inwall are provided with ladder lining board, in order to increasing mill efficiency, advance material advance and avoid described in grind the direct shock of medium and kiln body, described the 3rd storehouse inwall is provided with flat liner plate; Described ball milling rotary kiln also comprises temperature controller, so that different temperature of reaction is set in described the first storehouse, the second storehouse and the 3rd storehouse.
Preferably: described kiln tail is provided with opening for feed and spiral feeding-passage, so that the material after preheating, from described opening for feed enters, is entered the kiln intracoelomic cavity of described ball milling rotary kiln by described spiral feeding-passage; Described kiln hood is provided with discharging grate plate, has supplied the material dispersion of grinding and sintering evenly to enter described cooler.
Preferably: between described cooler and described decomposition chamber, be communicated with by a waste heat reclaiming flue, between described kiln tail and described decomposition chamber, be communicated with by a funnel uptake, so that unnecessary system heat energy is carried out to material preheating for described cyclone preheating device.
Lithium iron phosphate preparation method provided by the invention, raw mixture solubilizing agent is carried out to wet-milling, the material again particle diameter after wet-milling being reduced to some extent carries out preheating and predecomposition, make solvent evaporation, the pyrolysis that carries out organo-functional group decomposition and deamination etc., material particular diameter further reduces, and has ensured the anti-oxidant environment in follow-up sintering process simultaneously, what obtain that temperature is higher, particle diameter is less enters kiln presoma, can reduce follow-up sintering time and milling time; Described in inciting somebody to action, enter kiln presoma by size grading, grinding limit, limit dynamic sinter, overcome the existing static sintering processing inequality of being heated, the shortcoming of burning or raw burn, avoided the trouble that needs double sintering because of undesirable, efficiently make particle diameter evenly, high-quality and the high iron lithium phosphate finished product of batch stability.
In preferred version, use cyclone preheating device to carry out preheating and predecomposition, because vapor pipe can produce negative pressure, hot gas flow can drive slurry motion, and constantly carry out heat exchange, the temperature of slurry constantly raises, pyrolytic decomposition, evaporation, dry gradually, material has become high temperature dry powder entering before kiln body, and due to through decomposition chamber, carries out that organo-functional group decomposes and the pyrolysis of deamination etc., by product atmosphere is together discharged with hot gas flow, and remaining high temperature dry powder enters kiln body sintering.Preheating has improved the temperature that enters kiln presoma, has reduced particle diameter, has reduced sintering time in kiln, has improved efficiency, and meanwhile, cyclone preheating device has effectively utilized the heat energy in each stage in preparation process, greatly reduces energy consumption.When entering kiln presoma and entering kiln body, by the mode of spiral charging, make material can be in order, disperse, send in kiln equably, prevent putty.Utilize point sieve plate kiln body to be separated into the storehouse of different lengths, complete the function of different sintering temperature control, different residence time of material, different grind size classification, realize corase grind, fine grinding is to the grinding step by step of fine grinding, realize LiFePO 4 material sintering, grinding, classification one time to produce, reduced or remitted subsequent handling, improved production efficiency, reduce cost, reduced the secondary pollution to material and environment.
In the scheme being more preferably, sub-sieve buttress screens according to particle diameter, and the material that does not meet particle diameter requirement is left to continuation grinding and sintering, until meet the requirements, has ensured the particle size uniformity of the finished product.In whole process, kiln body rotates with given pace, has realized the continous way full dynamic system that grinding, classification and sintering carry out simultaneously standby, without sintering repeatedly, also without manpower intervention, has improved to a great extent production efficiency and has reduced energy consumption.
In the scheme being more preferably, on kiln body inwall, interior lining panel is housed, mill efficiency can be increased, advance material to carry out and the direct shock of medium (as steel ball) and kiln body can be effectively avoided grinding, extend the work-ing life of kiln body.The speed of rotation of kiln body, integral inclination angle is adjustable, thereby makes ball milling rotary kiln entirety flexibility ratio higher, and controllability is strong.
Iron lithium phosphate preparation system provided by the invention carries out classified grinding, dynamic sinter to material with ball milling rotary kiln simultaneously, is heated evenly, and has guaranteed the thing phase of iron lithium phosphate finished product and the homogeneity of granularity.Use cyclone preheating device to carry out preheating, dispersion, decomposition to entering kiln presoma, improved the temperature that enters kiln presoma, reduce particle diameter, reduced material sintering time, improved production efficiency; Utilize the thermal source of the unnecessary heat energy of system as primary heater unit, reduced widely energy consumption.
In a word, utilize iron lithium phosphate product that preparation method of the present invention and preparation facilities make to have thing phase and the narrower more uniform size distribution of special homogeneous, show as better materials processing performance and outstanding chemical property, batch stability is high.
Brief description of the drawings
Fig. 1 is the lithium iron phosphate preparation method process flow sheet of the specific embodiment of the invention;
Fig. 2 is the structural representation of cyclone preheating device one-level heat exchange unit in the specific embodiment of the invention;
Fig. 3 is ball milling rotary structure schematic diagram in preparation method of the present invention;
Fig. 4 is ball milling rotary kiln tailing stream of the present invention, air-flow schematic diagram.
Description of reference numerals:
10 ball mills
20 coolers
30 decomposition chambers
40 vapor pipes
50 ball milling rotary kilns
501 kiln tails
5011 opening for feeds
5012 spiral feeding-passages
502 kiln bodies
5021 first points of sieve plates
5022 second points of sieve plates
5023 ladder lining boards
503 kiln hoods
5031 discharging grate plates
60 funnel uptakes
70 waste heat reclaiming flues
C1～C5 cyclone cylinder
A1～A5 heat transfer tube
X streams flow to
Y hot gas flow flows to
Area1 heat transfer zone
Area2 gas solid separation district
Embodiment
Preferred embodiment the invention will be further described to contrast accompanying drawing combination below, but not limit the invention.
The lithium iron phosphate preparation method of the present embodiment is to carry out in a set of ball milling rotary system as shown in Figure 1, described ball milling rotary system comprises ball mill 10, cyclone preheating device, ball milling rotary kiln and cooler 20, wherein cyclone preheating device is the suspension heat exchange system that comprises Pyatyi heat exchange unit and a decomposition chamber 30, the quantity that it should be noted that heat exchange unit and decomposition chamber is not limited to this.As shown in Figure 1, take ground as benchmark, be followed successively by first step heat exchange unit from top to bottom to level V heat exchange unit, each heat exchange unit includes a cyclone cylinder and heat transfer tube, cyclone cylinder is followed successively by C1, C2, C3, C4, C5, and heat transfer tube is followed successively by A1, A2, A3, A4, A5.The cyclone cylinder of heat exchange units at different levels is funnel-form, its upper port is communicated with this grade of heat transfer tube sealing, lower port is communicated with the heat transfer tube sealing of next stage heat exchange unit, the upper port of cyclone cylinder C1 is also provided with vapor pipe 40, and the upper port of all the other four cyclone cylinders is also communicated with the heat transfer tube sealing of upper level heat exchange unit.Illustrate for:
Heat transfer tube A1 is communicated with the upper port of cyclone cylinder C1 and the upper port of cyclone cylinder C2, and the upper port of cyclone cylinder C1 is provided with vapor pipe 40, and lower port is communicated with heat transfer tube A2;
Heat transfer tube A2 is communicated with the upper port of cyclone cylinder C2 and the upper port of cyclone cylinder C3, and the upper port of cyclone cylinder C2 is also communicated with heat transfer tube A1, and lower port is communicated with heat transfer tube A3;
Heat transfer tube A3 is communicated with the upper port of cyclone cylinder C3 and the upper port of cyclone cylinder C4, and the upper port of cyclone cylinder C3 is also communicated with heat transfer tube A2, and lower port is communicated with heat transfer tube A4;
Heat transfer tube A4 is communicated with the upper port of cyclone cylinder C4 and the upper port of cyclone cylinder C5, and the upper port of cyclone cylinder C4 is also communicated with heat transfer tube A3, and lower port is communicated with decomposition chamber 30;
Heat transfer tube A5 is communicated with upper port and the decomposition chamber 30 of cyclone cylinder C5, and the upper port of cyclone cylinder C5 is also communicated with heat transfer tube A4, and lower port is connected to the kiln tail 501 of described ball milling rotary kiln 50.
Between described decomposition chamber 30 and described kiln tail 501, be provided with funnel uptake 60, and between cooler 20, be provided with waste heat reclaiming flue 70, described funnel uptake 60 and waste heat reclaiming flue 70 all for by the unnecessary heat energy recycle of system to cyclone preheating device, be to be that decomposition chamber 30 flows to top first step heat exchange unit direction by the bottom of cyclone preheating device for the hot gas flow of preheating, and material is to flow to bottom by top first step heat exchange unit to enter in ball milling rotary kiln 50 again, carry out sintering.Specifically flow to and illustrate with certain one-level heat exchange unit, as shown in Figure 2, material enters after the heat transfer tube of certain one-level heat exchange unit, flow to and illustrate with X, carry out heat exchange at heat exchange zone Area1 and hot gas flow, entering afterwards cyclone cylinder is gas solid separation district Area2, carries out gas solid separation at this.
Provide a kind of method of preferably preparing iron lithium phosphate below:
After Ferrox, monometallic and phosphoric acid salt directly being mixed according to the mol ratio of Fe:Li:P=1:1:1, add the dehydrated alcohol of 3 times of said mixture gross weights, ball milling 5 hours in ball mill 10, slurry after ball milling enters described heat transfer tube A1, because this heat transfer tube A1 is connected between cyclone cylinder C1 upper port and cyclone cylinder C2 upper port, and hot gas flow is to flow to cyclone cylinder C1 direction by cyclone cylinder C2, the slurry adding thus can enter cyclone cylinder C1 under the drive of hot gas flow, in this heat transfer tube A1, also carry out heat exchange simultaneously, as shown in Figure 2, in the process of heat exchange, follow high temperature evaporation, slurry slowly becomes dry, become the siccative that particle diameter is less, siccative enters cyclone cylinder C1, carry out gas solid separation at this, as shown in Figure 2, under the effect of self gravitation, siccative falls into described heat transfer tube A2, carry out again heat exchange and under the drive of hot gas flow, enter cyclone cylinder C2, and discharge via vapor pipe 40 from cyclone cylinder C1 through the hot gas flow of heat exchange.In the same way to cyclone cylinder C4, the temperature of siccative constantly raises, particle diameter constantly diminishes, as shown in Figure 4, siccative enters decomposition chamber 30, decomposes, because decomposition chamber 30 is connected with funnel uptake 60 and pre-recovery of heat flue 70, and the siccative after decomposing, because having become dust through multistage preheating, can enter into cyclone cylinder C5 by decomposition chamber 30 through heat transfer tube A5, then be entered the kiln tail 501 of ball milling rotary kiln 50 by this cyclone cylinder C5 lower port under the drive of hot gas flow.Dispersion step by step, preheating and decomposition, improved the temperature that enters kiln presoma, reduced particle diameter, reduces the sintering time in kiln.As shown in Figure 3, dry particulate dust enters spiral feeding-passage 5012 from opening for feed 5011, enters into the kiln body 502 of ball milling rotary kiln 50, and the hot gas flow in kiln and particulate dust are reverse to be flowed out by kiln tail 501, enters cyclone preheating device through funnel uptake 60.
In described ball milling rotary kiln 50, be provided with temperature controller and well heater, be also placed with the steel ball of different size ratio and ratio of grinding media to material, also can use rod iron or zirconia ball, as grinding medium.As shown in Figure 3, kiln body 502 inner chambers are divided into by a point sieve plate for different pore size three storehouses that length diminishes successively, and the longest the first position in storehouse of length is in kiln tail 501 1 sides, and the 3rd the shortest position in storehouse is in kiln hood 503 1 sides; First point of sieve plate 5021 aperture between described the first storehouse and the second storehouse are 70 microns, second point of sieve plate 5022 aperture between described the second storehouse and the 3rd storehouse are 20 microns, the first storehouse and the second storehouse inwall are equipped with ladder lining board 5023, to grind the direct shock of the inwall of medium and kiln body 502 described in avoiding, and ladder lining board can be made as non-made of one piece, to change flexibly wherein a certain.Steel ball in three storehouses, the first storehouse to the diminishes gradually, has realized corase grind and has arrived the process of lapping refining to fine grinding again.In certain embodiments, steel ball can not be put in the 3rd storehouse, can not place liner plate or place flat liner plate.Kiln body 502 rotates with the speed of 1～30 rev/min, and kiln hood one end is downward-sloping, angle of inclination is continuous adjustable at 0～60 °, material enters after kiln body 502, in 400 DEG C, the first storehouse ball milling, after sintering 1 hour, through first point of sieve plate 5021 sub-sieve, the material that meets particle diameter requirement enters the second storehouse, in 700 DEG C of ball millings, after sintering 2 hours, through second point of sieve plate 5022 sub-sieve, the material that meets particle diameter requirement enters the 3rd storehouse, in 650 DEG C of ball millings, after sintering 2 hours, screen through the discharging grate plate 5031 of being located at kiln hood 503, enter described cooler 20, be cooled to room temperature, obtain particle diameter even, few reunion, batch high iron lithium phosphate finished product of stability.
It should be noted in the discussion above that sintering temperature can according to actual needs, adjust by temperature controller, meanwhile, because the length in each storehouse is different, the time of material stop can be therefore different.Above-mentioned said, the length in the first storehouse is the longest, and sintering temperature is lower, and residence time of material is just longer, can make more materials be ground, and obtains less more uniform particle diameter.The discharging grate plate of kiln hood, with dispersing mode discharging, is convenient to coolingly while making discharging, has also ensured to a certain extent that product reunites less.
The preparation method of above-mentioned embodiment, raw mixture solubilizing agent is carried out to wet-milling, the material again particle diameter after wet-milling being reduced to some extent carries out preheating and predecomposition, make solvent evaporation, material particular diameter further reduces, and decomposes and removes aerobic crystal powder, has ensured the anti-oxidant environment in follow-up sintering process, what obtain that temperature is higher, particle diameter is less enters kiln presoma, can reduce follow-up sintering time and milling time; Described in inciting somebody to action, enter kiln presoma by size grading, grinding limit, limit dynamic sinter, overcome the existing static sintering processing inequality of being heated, the shortcoming of burning or raw burn, avoid the trouble that needs double sintering because of undesirable, efficiently make particle diameter evenly, high-quality and the high iron lithium phosphate finished product of batch stability, thing phase and narrower more uniform size distribution that it has special homogeneous, show as better materials processing performance and outstanding chemical property.
Moreover, reduce the manpower intervention degree of traditional technology, improve efficiency, reduced costs, disposable preheating, grinding, the sintering, cooling of completing continuously; Meanwhile, utilize the waste heat of system to carry out preheating, greatly reduce energy consumption.
In above-described embodiment, molysite, lithium salts and phosphatic proportioning can be selected according to the characteristic demand of lithium ion battery in the scope of Fe:Li:P=0.8～1.2:0.8～1.2:1; And quantity of solvent is also not limited to 3 times that above-described embodiment provides, but quantity of solvent generally should be 2-5 times of molysite, lithium salts and phosphate mixt total amount; Ball-milling Time can be set at 2～20 hours according to the factor such as material particular diameter, inventory.
In the system of above-described embodiment, the aperture of first point of sieve plate and second point of sieve plate all needs to be arranged between 1-100 micron, and wherein the aperture of second point of sieve plate need be less than the aperture of first point of sieve plate.
Above content is in conjunction with concrete preferred implementation further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For those skilled in the art, without departing from the inventive concept of the premise, can also make some being equal to substitute or obvious modification, and performance or purposes identical, all should be considered as belonging to protection scope of the present invention.
Claims (14)
1. a preparation method for iron lithium phosphate, is characterized in that, comprises the following steps:
S1, ball milling: after molysite, lithium salts and phosphoric acid salt being mixed according to the mol ratio of Fe:Li:P=0.8～1.2:0.8～1.2:1, add the solvent of 2～5 times of said mixture gross weights, then ball milling 2～20 hours;
S2, preheating and predecomposition: the slurry after ball milling is carried out in inert atmosphere to preheating and predecomposition, so that solvent evaporates and removes the by product atmosphere that preheating and predecomposition produce, obtain into kiln presoma;
S3, sintering: described in inciting somebody to action, enter kiln presoma and in inert atmosphere, carry out high temperature sintering, in high temperature sintering, the lithium iron phosphate particles generating is ground, and carry out classified grinding step by step by particle diameter;
S4, cooling: step S3 gained material is cooled to room temperature, makes iron lithium phosphate finished product;
Wherein, described step S3 carries out in ball milling rotary kiln, in described ball milling rotary kiln, is provided with well heater and temperature controller, and kiln intracoelomic cavity is equipped with a point sieve plate that grinds medium and had a different pore size and is divided into multiple storehouses; Described ball milling rotary kiln has kiln tail and kiln hood, and described kiln tail is provided with opening for feed, and described kiln hood is equipped with discharging grate plate and is connected to cooler;
Described step S3 comprises:
S3-1, enter kiln: described in enter kiln presoma and enter the described ball milling rotary kiln that is full of rare gas element;
S3-2, grinding and sintering: described in enter kiln presoma at described kiln intracoelomic cavity high temperature sintering, simultaneously through described in grind medium milling, through point sieve plate sub-sieve step by step of described different pore size, grind step by step and sintering;
Material by step S3-2 gained enters described cooler through described discharging grate plate, is cooled to room temperature, obtains iron lithium phosphate finished product.
2. the preparation method of iron lithium phosphate as claimed in claim 1, is characterized in that:
Described step S2 carries out in cyclone preheating device, and described cyclone preheating device is to comprise decomposition chamber and the sealing suspension preheating system of one-level heat exchange unit at least, and described heat exchange unit comprises heat transfer tube and cyclone cylinder;
Described step S2 comprises:
S2-1, heat exchange: the material after ball milling enters the heat transfer tube of the described heat exchange unit that is positioned at described cyclone preheating device top, carry out heat exchange with the hot gas flow that is flowed to top by described heat transfer tube bottom, and brought into the cyclone cylinder of described heat exchange unit by described hot gas flow;
S2-2, gas solid separation: the cyclone cylinder top of described heat exchange unit is connected to vapor pipe, discharge or escape and enter the heat transfer tube of the described heat exchange unit on upper level cyclone preheating device top through described vapor pipe with hot gas flow after material-heat-exchanging; Material particles after preheating, through described cyclone cylinder gas solid separation, is entered the heat transfer tube of the described heat exchange unit on next stage cyclone preheating device top by the cyclone cylinder bottom of described cyclone preheating device;
S2-3, decomposition: described material obtains into kiln presoma after cyclone preheating device high temperature preheating and predecomposition.
3. the preparation method of iron lithium phosphate as claimed in claim 1, it is characterized in that: the kiln intracoelomic cavity of described ball milling rotary kiln is divided into three storehouses by first point of sieve plate and second point of sieve plate of different pore size, be followed successively by the first storehouse, the second storehouse, the 3rd storehouse by kiln tail to kiln hood, described the first storehouse and the second storehouse inwall are provided with ladder lining board, and described the 3rd storehouse inwall is provided with flat liner plate; Described temperature controller can be set different temperature of reaction to described the first storehouse, the second storehouse and the 3rd storehouse, the screen-aperture of described first point of sieve plate and second point of sieve plate is between 1～100 micron, and the screen-aperture of described second point of sieve plate is less than the screen-aperture of described first point of sieve plate.
4. the preparation method of iron lithium phosphate as claimed in claim 1, is characterized in that:
Described molysite is any one or multiple combination in ironic oxalate, Ferrox, iron nitrate, iron acetate, Iron diacetate, ironic citrate, iron stearate;
Described lithium salts is any one or two or more combination in Quilonum Retard, Lithium Acetate, lithium nitrate, lithium fluoride, monometallic;
Described phosphoric acid salt is any one or two or more combinations in primary ammonium phosphate, Secondary ammonium phosphate, triammonium phosphate;
Described solvent is at least one in deionized water, distilled water, dehydrated alcohol, acetone.
5. the preparation method of iron lithium phosphate as claimed in claim 1, is characterized in that: the kiln body speed of rotation of described ball milling rotary kiln is 1～30 rev/min, and adjustable continuously; The kiln body integral inclination angle of described ball milling rotary kiln is adjustable continuously within the scope of 0～60 degree.
6. the preparation method of iron lithium phosphate as claimed in claim 1, is characterized in that: described ball milling rotary kiln feeding manner is spiral charging.
7. the preparation method of iron lithium phosphate as claimed in claim 1, is characterized in that: described in to grind medium be any one or two or more combinations in steel ball, rod iron or zirconia ball.
8. the preparation method of iron lithium phosphate as claimed in claim 2, is characterized in that: described hot gas flow comprises one or more the combination coming from the rare gas element that in the rare gas element in high-temperature sintering process, cooler, cooling material is discharged in described ball milling rotary kiln.
9. the preparation method of iron lithium phosphate as claimed in claim 8, is characterized in that: described hot gas flow also comprises that coming from material in warm decomposes the high-temperature gas producing.
10. a preparation system for iron lithium phosphate, comprises ball mill, cooler, it is characterized in that:
Also comprise primary heater unit, described primary heater unit, for the slurry after ball milling is evaporated and removes the by product that preheating and predecomposition produce at the inert atmosphere solvent that carries out preheating and predecomposition so that solvent evaporates, obtains into kiln presoma;
Also comprise ball milling rotary kiln, the kiln intracoelomic cavity of described ball milling rotary kiln is split into for the material of different-grain diameter and grinds and at least two storehouses of sintering, and is equipped with and grinds medium, grinds for the iron lithium phosphate that high temperature sintering is produced.
The preparation system of 11. iron lithium phosphates as claimed in claim 10, it is characterized in that: described primary heater unit is cyclone preheating device, described cyclone preheating device is to comprise decomposition chamber and the suspension heat exchange system of one-level heat exchange unit at least, and described heat exchange unit comprises cyclone cylinder and heat transfer tube; Described ball milling rotary kiln has kiln tail and kiln hood, and described kiln tail is connected with described cyclone preheating device so that the material after preheating enters described ball milling rotary kiln, and described kiln hood is connected and carries out cooling with discharging with described cooler.
The preparation system of 12. iron lithium phosphates as claimed in claim 11, it is characterized in that: the kiln intracoelomic cavity of described ball milling rotary kiln is divided into three storehouses by first point of sieve plate and second point of sieve plate of different pore size, be followed successively by the first storehouse, the second storehouse, the 3rd storehouse by kiln tail to kiln hood, described the first storehouse and the second storehouse inwall are provided with ladder lining board, in order to increasing mill efficiency, advance material advance and avoid described in grind the direct shock of medium and kiln body, described the 3rd storehouse inwall is provided with flat liner plate; Described ball milling rotary kiln also comprises temperature controller, so that different temperature of reaction is set in described the first storehouse, the second storehouse and the 3rd storehouse; The screen-aperture of described first point of sieve plate and second point of sieve plate is between 1～100 micron, and the screen-aperture of described second point of sieve plate is less than the screen-aperture of described first point of sieve plate.
The preparation system of 13. iron lithium phosphates as claimed in claim 11, it is characterized in that: described kiln tail is provided with opening for feed and spiral feeding-passage, so that the material after preheating, from described opening for feed enters, is entered the kiln intracoelomic cavity of described ball milling rotary kiln by described spiral feeding-passage; Described kiln hood is provided with discharging grate plate, has supplied the material dispersion of grinding and sintering evenly to enter described cooler.
The preparation system of 14. iron lithium phosphates as described in claim 10 to 12 any one, it is characterized in that: between described cooler and described decomposition chamber, be communicated with by a waste heat reclaiming flue, between described kiln tail and described decomposition chamber, be communicated with by a funnel uptake, so that unnecessary system heat energy is carried out to material preheating for described cyclone preheating device.
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| CN105295930A (en) * | 2014-07-21 | 2016-02-03 | 山西云大中天环境科技有限公司 | Acid soil conditioner and preparation method thereof |
| CN113130875B (en) * | 2021-04-19 | 2022-03-25 | 浙江浩越能源科技有限公司 | Lithium vanadium phosphate battery positive electrode material and preparation process thereof |
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| CN1581537A (en) * | 2004-05-20 | 2005-02-16 | 上海交通大学 | Method for preparing lithiumion cell positive material Iron-lithium phosphate |
| CN1821065A (en) * | 2006-03-20 | 2006-08-23 | 清华大学 | Process for preparing high density spherical lithium ferric phosphate |
| CN102097616A (en) * | 2011-01-11 | 2011-06-15 | 清华大学深圳研究生院 | Preparation method of high-energy and high-power density nano-scale lithium iron phosphate powder |
| CN102637856A (en) * | 2012-04-12 | 2012-08-15 | 东南大学 | Converter type production process and device of lithium battery positive/negative electrode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1581537A (en) * | 2004-05-20 | 2005-02-16 | 上海交通大学 | Method for preparing lithiumion cell positive material Iron-lithium phosphate |
| CN1821065A (en) * | 2006-03-20 | 2006-08-23 | 清华大学 | Process for preparing high density spherical lithium ferric phosphate |
| CN102097616A (en) * | 2011-01-11 | 2011-06-15 | 清华大学深圳研究生院 | Preparation method of high-energy and high-power density nano-scale lithium iron phosphate powder |
| CN102637856A (en) * | 2012-04-12 | 2012-08-15 | 东南大学 | Converter type production process and device of lithium battery positive/negative electrode material |
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