CN100528746C - Wet method of preparing lithium ferrous phosphate and its prepared lithium ferrous phosphate - Google Patents
Wet method of preparing lithium ferrous phosphate and its prepared lithium ferrous phosphate Download PDFInfo
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- CN100528746C CN100528746C CNB2006101114452A CN200610111445A CN100528746C CN 100528746 C CN100528746 C CN 100528746C CN B2006101114452 A CNB2006101114452 A CN B2006101114452A CN 200610111445 A CN200610111445 A CN 200610111445A CN 100528746 C CN100528746 C CN 100528746C
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
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Abstract
The present invention provides a method for preparing ferrous lithium phosphate by using wet method. Said method includes the following steps: making required water-soluble compounds containing Li, Fe and P and containing alloying element M respectively be dissolved in water; stirring them and placing them into a reactor to obtain a suspension, in which the Li content, Fe content and P content must be met with the following formula: [mLi+n(1-m)/n M]; pFe:qPO4=1:1:1, in said formula n is chemical valence of alloying element M, m is mole number of Li, (1-m)/n is mole number of alloying element M and the P and q respectively are mole numbers of Fe and PO4; adding reduction electro-conductive additive, spray drying suspension, roasting and pulverizing so as to obtain the invented product.
Description
Technical field
The present invention relates to a kind of preparation method of energy and material, relate in particular to a kind of preparation method of lithium ion cell positive actives-LiFePO 4.
Background technology
Lithium-ion secondary cell is the new generation of green energy, has advantages such as high-energy-density, high cycle performance, low self-discharge rate, memory-less effect, operating temperature range be wide.In numerous areas widespread uses such as mobile telephone, laptop computer, pick up camera, power tools.March to electric automobiles.But the research and the application of anode material for lithium-ion batteries focus mostly in LiC at present
oO
2, LiNiO
2And LiMn
2O
4Deng.Spinel LiMn wherein
2O
4Cost is low, and security is better, but cycle performance and high-temperature behavior are poor; LiNiO
2Cost is lower, and capacity is higher, but the preparation difficulty, material consistence and poor reproducibility, and have serious safety problem; LiC
oO
2Because high comprehensive performance, thus be the anode material for lithium-ion batteries of present unique large-scale commercial production, but cost an arm and a leg, certain toxicity is arranged and have certain safety problem.
Padhi in 1997 and Goodenoagh report the LiFePO of olivine structural first
4Have to insert and take off the lithium function, make LiFePO
4The class material is subjected to extensive concern and actively research and development.Because raw material resources are rich and easy to get, LiFePO
4, FePO
4Structure is all being stablized below 400 ℃.The theoretical specific discharge capacity 170mAh/g and the overwhelming majority can develop, operating voltage 3.0 (high magnification)-3.4V (low range) is very steady, good with the electrolytic solution consistency, volume only reduces 6.5% during charging, little the increasing of volume is complementary when charging with the carbon negative pole, particularly nontoxic, high-temperature behavior, good cycle and security are good, and power truck is popularized hope.Therefore people expect LiFePO
4To make lithium ion battery revolutionary variation occur, lithium ion battery widespread usage in power truck is become a reality.
The method of actual fabrication LiFePO 4 mostly is high temperature solid-state method at present.So-called solid phase method, refer to solid-state Li source, Fe source, P source compound, doping element compound and reduction conductive additive, long-time in ball mill (for example: have 18-36 hour with solid material in proportion, also have 18-48 hour etc.) ground and mixed, get middle and high two temperature sections then and burn till once or twice.This method has following shortcoming:
1, the time that mixes be difficult for to determine, can not continuous production;
2, would rather prolong milling time for guaranteeing to mix, time-consuming;
3, it is inhomogeneous etc. each batch products to take place easily.
Summary of the invention
The purpose of this invention is to provide a kind of wet method and prepare the method for LiFePO 4 and the LiFePO 4 of preparation thereof.The method technology that wet method of the present invention prepares LiFePO 4 is simple, the suitability for industrialized serialization is produced, and raw material mixes, the product performance uniformity, prepared LiFePO 4 steady quality, thus overcome the problem that present production LiFePO 4 exists.
Wet method of the present invention prepares the method for LiFePO 4, and its step is as follows:
1. the liquid deposition preparation contains Li
mM
(1-m)/nFePO
4The suspension liquid of compound crystallite or nucleus
1) compound that contains lithium, iron, phosphorus and doped element M in the suspension liquid meets following formula:
[mLi+(1-m)/nM]∶pFe∶qPO
4＝1∶1∶1 (1)
(1) n is the valency of doped element M in the formula, and m is the mole number that contains the compound of Li, (1-m)/n is the mole number that contains the compound of doped element M, p, q contain Fe and PO
4The mole number of compound, when (1-m)/n=0, the mole number that contains the compound of doped element M is zero, does not promptly contain the compound of doped element in the suspension liquid, then the mol ratio of Li: Fe: P meets the requirement of following formula:
mLi∶pFe∶qPO
4＝1∶1∶1 (2)
The mole number of solid chemical compound=(weight of compound * its content)/molar mass;
2) water-soluble each compound that contains lithium, iron, phosphorus and doped element M of required weight is calculated and taken by weighing to basis (1) formula respectively, is dissolved in the water respectively then, makes each solution; Contain that the compound of doped element M is water-fast to be powder;
Described water dissolvable contains Li
+Compound is one of Lithium Acetate, lithium hydroxide, lithium oxalate, Lithium Citrate de, monometallic, lithium chloride or lithium nitrate; Water dissolvable contains Fe
2+Compound is one of Iron diacetate, iron lactate, ferrous citrate, ferrous ammonium citrate, iron protochloride or Iron nitrate; Water dissolvable contains PO
4 3-Compound is one of phosphoric acid, monometallic, primary ammonium phosphate, Secondary ammonium phosphate or ammonium phosphate; Remove the product that generates expectation in a word, other by product is that each allied compound of removing easily in preparation process all can;
The compound that contains doped element M is selected from and contains ionic radius near Li
+The high valence elements of radius such as Mg
2+, Al
3+, Zr
4+Or Nb
5+Deng compound, the compound that contains doped element M is the oxide compound that contains doped element M, oxyhydroxide, muriate, one of nitrate, organic acid salt or organometallics;
3) above-mentioned each solution and stream are added in the reactor, under 120 rev/mins of speed conditions of agitator, add the water-fast powder that contains the compound of doped element M, uniform mixing, carry out the liquid deposition reaction, since precipitin reaction carry out not exclusively and by product water-soluble, so what make is to contain deposited compound Li
mM
(1-m)/nFePO
4The outstanding turbid mixed solution of crystallite or nucleus and by-product solution;
Because during liquid deposition, most of lithium iron connects with phosphate radical, the volatilization of lithium when having significantly reduced high-temperature roasting, institute's lithium needn't be excessive, so [m+n (1-m)/n]=p=q is arranged and make it equal 1, (3) formula that makes is set up:
mLi
++(1-m)/n?M
n++pFe
2++qPO
4 3--＝Li
mM
(1-m)/n?FePO
4(3)
(1) promptly by ideal deposition reaction (3) decision, when not containing doped element M, (1) formula becomes (2) to formula:
mLi∶pFe∶qP＝1∶1∶1 (2)
At this moment, m=p=q, deposition reaction (3) becomes reaction (4)
Li
++Fe
2++PO4
3-＝LiFePO
4(4)
Prepare the concentration of each solution, both relevant with starting compound solubleness, the solid-to-liquid ratio in the time of also will considering spraying drying is in suitable scope, and this will be according to the spray drying device type that is had through the debugging decision.
2. add the reduction conductive additive
Under 120 rev/mins of speed conditions of agitator, in above-mentioned suspension liquid, add the reduction conductive additive while stirring, continue again to stir 1-3 hour, make the suspension liquid uniform mixing; The reduction conductive additive is that charcoal or pyrolysis can produce one of carbon compound or its arbitrary combination, and the conductive additive that perhaps reduces is that charcoal or pyrolysis can produce in the powder of one of carbon compound or its arbitrary combination and thin inert metal or the subsequent technique and can be reduced to one of inert metal compound of this metal-powder; Add charcoal or pyrolysis and can produce the amount of one of carbon compound or its arbitrary combination for estimating the 3-15% of product weight, the amount that adds the powder of thin inert metal is 1% of expectation product weight, and the content of inert metal is for estimating 1% of product weight in the inert metal compound of adding; Wherein, charcoal is superconduction carbon black or superfine graphite; Wherein can to produce carbon compound be organic compound-sucrose or one of citric acid, natural high moleculer eompound-starch or synthetic macromolecular compound-polyethylene powders or polyvinyl alcohol in pyrolysis; Wherein the powder of thin inert metal is the powder of Ag or Cu; The inert metal compound that can be reduced to this metal-powder in subsequent technique is oxide compound, the oxyhydroxide of Ag or Cu, one of nitrate, organic acid salt or organometallics;
3. spraying drying suspension liquid
With volume pump above-mentioned mixed uniformly suspension liquid is delivered to the spraying drying top of tower, it through rotating speed 18000-24000 rev/min centrifugal energy nozzle atomizing, be mixed into the promoting the circulation of qi fluidized drying at the spray-drying tower inlet with 260-310 ℃ of warm air, dried powder is that 100-120 ℃ bag filter is collected through cyclonic separator and temperature in, must comprise the mix powder of each reaction product and by product;
4. roasting, pulverizing
The mix powder that above-mentioned dust-precipitator is collected is sent in the High Temperature Furnaces Heating Apparatus, under nonoxidizing atmosphere after 350-500 ℃ of constant temperature calcining 5-20 hour, again at 600-800 ℃ of constant temperature calcining 5-20 hour, take out after being cooled to normal temperature then, promptly get lithium ion cell positive actives LiFePO 4 crystalline powder through pulverizing, cross 300 mesh sieves; Or under nonoxidizing atmosphere in 350-500 ℃ of constant temperature calcining 5-25 hour, take out after being cooled to normal temperature then, blend together powder through grinding, sent into again in the High Temperature Furnaces Heating Apparatus in nonoxidizing atmosphere in 600-800 ℃ of constant temperature calcining 5-20 hour, take out after being cooled to normal temperature, promptly get lithium ion cell positive actives ferrous phosphate lithium powder through pulverizing, cross 300 mesh sieves.
Described mixed reaction solution carries out being suspension liquid after the abundant deposition reaction, is meant that the solid precipitation reaction precipitation that is undertaken by (2) formula is abundant inadequately or says product Li in mixed solution
mM
(1-m)/nFePO
4(or LiFePO
4) be partly dissolved and hydrolysis, by product is dissolved in water, and reaction product and by product form the complicated outstanding turbid mixed solution of component together.Each feed composition solution is also stream adding reactor and powerful stirring fast, keeps making Li than big degree of supersaturation
mM
(1-m)/nFePO
4(or LiFePO
4) the nucleus formation speed is much larger than crystal grain-growth speed, can keep crystal grain in the nano level scope, the accumulative particle is in the micron order scope.
Carbon that described reduction conductive additive is meant adding or that pyrolysis produces is that conductive agent can at high temperature reduce Fe again
3+Be Fe
2+, the dual function of have reduction, conducting electricity.
The spraying drying gained is with Li
mM
(1-m)/nFePO
4(or LiFePO
4) nucleus or crystallite be each reaction product at center and the uniform mixture powder of by product, by product can be removed in follow-up roasting process fully.
Described High Temperature Furnaces Heating Apparatus is one of tube furnace, box-type furnace, continuous tunnel furnace or vertical heater, and the latter two can also be two kinds of discontinuous or continous ways.
Described nonoxidizing atmosphere is oxygen-free N
2Atmosphere, Ar atmosphere, N
2With H
2Mixed-gas atmosphere or Ar and H
2One of mixed-gas atmosphere.
Wet method of the present invention prepares the method for LiFePO 4, but the simple continuous production of technology; Raw material mixes, the product performance uniformity, can avoid the inhomogeneous uneven drawback of product performance that makes of dry method batch mixing, makes Li
+, Fe
2+, PO
4 3-And M
N+Uniform mixing on ion (being equivalent to atom) level, and tentatively generate LiFePO
4The deposition reaction of nucleus or crystallite, spraying drying and roasting then makes the good carbon uniformly of chemical property easily and coats Li
mM
(1-m)/nFePO
4(or LiFePO
4) product.
The crystal grain of the lithium ion battery F utmost point actives LiFePO 4 that the method that adopts wet method of the present invention to prepare LiFePO 4 is prepared is nano level, the particle size of its reunion is below 10 μ m, can find out that from its x-ray diffraction pattern it is an olivine-type structure, and not have the dephasign peak; Can find out the even and most＜10 μ m of particle from its stereoscan photograph, its size distribution figure proves that further particle diameter is below 10 μ m; Adopt the lithium ion battery of the present invention's assembling higher capacity to be arranged, high-rate discharge ability and cycle performance are preferably arranged.
Description of drawings
Fig. 1 is for pressing the LiFePO of embodiment 1 preparation
4X-ray diffracting spectrum.
Fig. 2 is for pressing the prepared LiFePO of embodiment 1
4Stereoscan photograph.
Fig. 3 is for pressing the prepared LiFePO of embodiment 1
4Size distribution figure.
Fig. 4 is for pressing the prepared LiFePO of embodiment 1
4Make the 14500-500mAh cylindrical lithium ion battery 0.2C charging and discharging curve of positive electrode active material preparation.
Fig. 5 is for pressing the prepared LiFePO of embodiment 1
4Make each multiplying power discharging curve of 14500-500mAh cylindrical lithium ion battery of positive electrode active material preparation.
Fig. 6 is for pressing the prepared LiFePO of embodiment 1
4Make the 14500-500mAh cylindrical lithium ion battery 1C/1C cycle life curve (not intact) of positive electrode active material preparation.
Raw material required for the present invention, equipment all have commercially available.
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described.
1. prepare the Li that contains of m=p=q=126.77 mole at first respectively, Fe, the solution of P-compound is about to LiOH.H
2O (99.8%) 5.33kg, Fe (CH
3COO)
2.4H
2O (99%) 31.50kg, H
3PO
4(85%) 14.62kg is dissolved in 40,50 respectively, 30kg and temperature be to make solution in 50 ℃ the water; Above-mentioned three kinds of solution and stream are added 240 liters of reactors, under 120 rev/mins of stirring velocitys, it are mixed and carry out the deposition reaction of (4) formula fast:
Li
++Fe
2++PO
4 3-＝LiFePO
4(4)
Principal product and each by product form suspension liquid together;
2. under 120 rev/mins of speed conditions of agitator, add the reduction conductive additive, estimate LiFePO
4Output=126.77 * 157.76, about 20kg; The content that pyrolysis that add to estimate finished weight 15%-3.0kg while stirring in above-mentioned suspension liquid can produce inert metal in the inert metal compound of carbon compound and adding is 0.51kg inert metal compound for the 1%-that estimates product weight, i.e. citric acid 3.0Kg and CuC
2O
4.1/2H
2O 0.51kg continues to stir 1-3 hour again, makes the suspension liquid uniform mixing;
3. with volume pump above-mentioned mixed uniformly suspension liquid is delivered to the spraying drying top of tower, it through rotating speed 18000-24000 rev/min centrifugal energy nozzle atomizing, be mixed into the promoting the circulation of qi fluidized drying at the spray-drying tower inlet with 260-280 ℃ of warm air, dried powder is collected through the bag filter of cyclonic separator and 100-120 ℃ of inlet, must comprise the mix powder of each reaction product and by product;
4. with above-mentioned pulverulent mixture, move on in the box High Temperature Furnaces Heating Apparatus in (90%Ar+10%H
2) after 20 hours, be warmed up to 710 ± 15 ℃ of constant temperature calcinings 10 hours at 360 ± 10 ℃ of constant temperature calcinings under the mixed atmosphere, take out after being cooled to normal temperature then, pulverize, cross 300 mesh sieves and get the LiFePO 4 powder-product.
Fig. 1 is the prepared LiFePO of embodiment 1
4The X-ray diffracting spectrum of actives proves that it is olivine structural and inclusion-free phase.Fig. 2 is the prepared LiFePO of embodiment 1
4The stereoscan photograph of actives can be found out most of particle＜10 μ m.Fig. 3 is the prepared LiFePO of EXAMPLE l
4The size distribution figure of actives proves that further particle diameter branch is below 10 μ m.Fig. 4 is by the prepared LiFePO of actuator's human embodiment 1
4Make the positive electrode active material anodal 14500-500mAh cylindrical lithium ion battery 0.2C charging and discharging curve of joining the graphite cathode preparation of production technique preparation routinely.Specific storage 134mAhg, discharge platform voltage is greater than 3.2V and very steady.Fig. 5 is 14500-500mAh cylindrical battery 0.2C, 1.0C, 3.0C, 5.0C, 7.0C, the 10.0C discharge curve with Fig. 4, calculates each multiplying power discharging specific storage and is summarized in the table 1.Fig. 6 for fill with the 14500-500mAh cylindrical lithium ion battery 1C of Fig. 4/1C puts cycle life curve (intact).
Each multiplying power discharging specific storage (mAh/g) of LiFePO 4 of table 1, embodiment preparation
Sample 0.2C 0.5 C 1C 3C 5C 7C 10C
Data in the table 1 and Fig. 6 proof not only has height ratio capacity and charges and discharge efficient by the ferrousphosphate lithium material of embodiment 1 preparation, with and also good high-rate discharge ability and cycle performance arranged.
1. prepare the m=124.27 mole at first respectively, the p=q=126.80 mole contain Li, Fe, the solution of P-compound is about to 124.26 moles LiCl (99.6%) 5.29kg, 126.80 moles FeCl
2.4H
2O (99.5%) 25.34kg, 126.80 moles (NH
4)
3PO
4.3H
2O (99.5%) 25.89kKg is dissolved in 15,30 respectively, 80Kg and temperature be to make solution in 50 ℃ the water, and 1.268 moles MgCl
2.6H
2O (98%) 263.05g is dissolved in FeCl
2In the solution; Under 120 rev/mins of stirring velocitys, divide will above-mentioned three kinds of solution and 240 liters of reactors of stream adding in, it mixed and carry out (3 fast
1) deposition reaction of formula:
0.98Li
++0.01Mg
2++Fe
2++PO
4 3+＝Li
0.98Mg
0.01FePO
4(3
1)
This moment, reaction product and by product formed suspension liquid together;
2. under 120 rev/mins of speed conditions of agitator, add the reduction conductive additive, estimate Li
0.98Mg
0.01Fe PO
4Output approximates 126.8 * 157.76, i.e. 20kg; In above-mentioned suspension liquid, add while stirring and estimate that finished weight 3%-0.6kg charcoal and pyrolysis can produce the 1%-0.2kg inert metal powder of carbon compound and expectation finished weight, be superconduction carbon black 0.3kg and sucrose 0.3kg and 0.2kg super fine silver powder, continue again to stir 1-3 hour, make the suspension liquid uniform mixing;
3. with volume pump above-mentioned mixed uniformly suspension liquid is delivered to the spraying drying top of tower, it through rotating speed 18000-24000 rev/min centrifugal energy nozzle atomizing, be mixed into the promoting the circulation of qi fluidized drying at the spray-drying tower inlet with 290-310 ℃ of warm air, dried powder is that 100-120 ℃ bag filter is collected through cyclonic separator and temperature in, must comprise the mix powder of each reaction product and by product;
4. above-mentioned pulverulent mixture is spread out on the flitch, sends in the high temp tunnel stove of high pure nitrogen atmosphere, in 490 ± 10 ℃ of constant temperature calcinings 25 hours, take out after being cooled to normal temperature then, ball milling is sent into (90%N after grinding and mixing
2+ 10%H
2) in the high temp tunnel stove of mixed atmosphere, in 700 ± 10 ℃ of constant temperature calcinings 10 hours, take out after being cooled to normal temperature then, pulverize, cross the LiFePO 4 (Li that 300 mesh sieves get doped with Mg
0.98Mg
0.01FePO
4) material.
Listed each high-multiplying power discharge capacity of doing the 1450-500mAh cylindrical lithium ion battery 1C charging of positive electrode active material and the preparation of graphite carbon negative pole by embodiment 2 prepared LiFePO 4s in the table 1.
1. prepare the m=120.96 mole at first respectively, the q=p=126.00 mole contain Li, Fe, the solution of P-compound and contain the Zr1.26 molar solution is about to contain the LiH of 120.96 moles of Li and P
2PO
4(98.8%) 12.724kg and phosphorous 5.04 moles (NH
4) H
2PO
4(99.5%) 0.583kg contains the Fe (C of 126.00 moles of Fe together
3H
5O
3)
2.3H
2O (containing Fe 18.9%) 37.23kg and contain the Zr (NO of 1.26 moles of Zr
3)
45H
2O (99%) 0.546.5kg is dissolved in 60,60 respectively, 5kg and temperature are to make solution in 50 ℃ the hot water; Under 120 rev/mins of stirring velocitys, above-mentioned three kinds of solution and stream mode are added in 240 liters of reactors, it is mixed and carry out (3 fast
2) deposition reaction of formula:
0.96Li
++0.01Zr
4++Fe
2++PO
4 3+＝Li
0.96Zr
0.01FePO
4(3
2)
This moment, reaction product and by product formed suspension liquid together;
2. under 120 rev/mins of speed conditions of agitator, add the reduction conductive additive, estimate Li
0.96Zr
0.01FePO output is about (126 * 157.76) 20Kg; Add charcoal and the pyrolysis of estimating finished weight 10%-2.0Kg while stirring and can produce carbon compound in above-mentioned suspension liquid, promptly the polyethylene powders of 0.4Kg starch and 1.6Kg continues to stir 1-3 hour again, makes the suspension liquid uniform mixing;
3. with volume pump above-mentioned mixed uniformly suspension liquid is delivered to the spraying drying top of tower, it through rotating speed 18000-24000 rev/min centrifugal energy nozzle atomizing, be mixed into the promoting the circulation of qi fluidized drying at the spray-drying tower inlet with 290-310 ℃ of warm air, dried powder is that 100-120 ℃ bag filter is collected through cyclonic separator and temperature in, must comprise the mix powder of each reaction product and by product;
4. with above-mentioned pulverulent mixture, move on in the tube type high-temperature furnace under the argon atmospher at 490 ± 10 ℃ of constant temperature calcinings after 5 hours, be warmed up to 610 ± 10 ℃ of constant temperature calcinings 20 hours, take out after being cooled to normal temperature then, pulverize, cross must the mix LiFePO 4 powder-product of zirconium of 300 mesh sieves.
Listed each high-multiplying power discharge capacity of doing the 1450-500mAh cylindrical lithium ion battery 1C charging of positive electrode active material and the preparation of graphite carbon negative pole by embodiment 3 prepared LiFePO 4s in the table 1.
Embodiment 4:
1. prepare the m=120.43 mole at first respectively, the p=q=126.77 mole contain Li, Fe, the solution of P-compound is about to contain the Li (CH of 120.43 moles of Li
3COO) .2H
2O (99.8%) 12.31jg contains the Fe (C of 126.77 moles of Fe
6H
6O
7) (containing Fe16.8%) 42.14kg, contain (the NH of 126.77 moles of P
4)
2HPO
4(99.5%) 16.83kg is dissolved in 10,70 respectively, and 40kg and temperature are to make solution in 50 ℃ the water; Under 120 rev/mins of stirring velocitys, above-mentioned three kinds of solution and stream are added 240 liters of reactors, then with 1.2677 moles of Nb
2O
5(content 99.5%) powder 338.66g adds, and it is mixed and carries out (3 fast
3) deposition reaction of formula:
0.95Li
++0.05H
++Fe
2++PO
4 3--＝Li
0.95H
0.05FePO
4(3
3)
Li when high-temperature roasting
0.95H
0.05FePO
4Middle 0.05H
+By 0.01Nb
5+Displacement, final product is (Li
0.95Nb
0.01FePO
4), this moment, reaction product and by product formed suspension liquid together.
2. under 120 rev/mins of speed conditions of agitator, add the reduction conductive additive, estimate Li
0.95Nb
0.01FePO
4Output is about (126.77 * 157.76) 20kg, in above-mentioned suspension liquid, add charcoal and the pyrolysis of estimating finished weight 10%-2.0Kg while stirring and can produce carbon compound, be that 0.35Kg superfine graphite and weight percent concentration are 7.5% polyvinyl alcohol water solution 22kg (wherein containing polyvinyl alcohol 1.65kg), continue again to stir 1-3 hour, make the suspension liquid uniform mixing.
3. with volume pump above-mentioned mixed uniformly suspension liquid is delivered to the spraying drying top of tower, it through rotating speed 18000-24000 rev/min centrifugal energy nozzle atomizing, be mixed into the promoting the circulation of qi fluidized drying at the spray-drying tower inlet with 280-310 ℃ of warm air, dried powder is that 100-120 ℃ bag filter is collected through cyclonic separator and temperature in, must comprise the mix powder of each reaction product and by product;
4. with above-mentioned pulverulent mixture, move on in the high temp, vertical stove under the high pure nitrogen atmosphere 490 ± 10 ℃ of constant temperature calcinings 5 hours, take out after being cooled to normal temperature then, ball milling is sent into the high temp tunnel stove at (90%N after 1 hour
2+ 10%H
2) 610 ± 10 ℃ of constant temperature calcinings 20 hours under the mixed atmosphere, take out after being cooled to normal temperature then, pulverize, cross the 300 mesh sieves niobium LiFePO 4 (Li that must mix
0.95Nb
0.01FePO
4) powder-product.
Listed each high-multiplying power discharge capacity of doing the 1450-500mAh cylindrical lithium ion battery 1C charging of positive electrode active material and the preparation of graphite carbon negative pole by embodiment 4 prepared LiFePO 4s in the table 1.
Listed each high-multiplying power discharge capacity of doing the 1450-500mAh cylindrical lithium ion battery 1C charging of positive electrode active material and the preparation of graphite carbon negative pole by embodiment 5 prepared LiFePO 4s in the table 1.
Listed each high-multiplying power discharge capacity of doing the 1450-500mAh cylindrical lithium ion battery 1C charging of positive electrode active material and the preparation of graphite carbon negative pole by embodiment 6 prepared LiFePO 4s in the table 1.
Claims (5)
1. a wet method prepares the method for LiFePO 4, and its step is as follows
1) the liquid deposition preparation contains Li
mM
(1-m)/nFePO
4The suspension liquid of compound crystallite or nucleus
(1) contain lithium, iron, phosphorus and doped element M in the suspension liquid liquid and meet following formula:
[mLi+(1-m)/n?M]∶pFe∶qPO
4＝1∶1∶1 (i)
(i) n is the valency of doped element M in the formula, and m is the mole number that contains the compound of Li, (1-m)/n is the mole number that contains the compound of doped element M, p, q contain Fe and PO
4The mole number of compound, when (1-m)/n=0, the mole number that contains the compound of doped element M is zero, does not promptly contain the compound of doped element in the suspension liquid, then the mol ratio of Li: Fe: P meets the requirement of following formula:
mLi∶pFe∶qPO
4＝1∶1∶1 (ii)
(2) water-soluble each compound that contains lithium, iron, phosphorus of required weight is calculated and taken by weighing to basis (i) formula respectively, is dissolved in the water respectively then, makes each solution; Take by weighing the compound that contains doped element M of required weight, if its water soluble is made solution, water-fast as if it is powder;
(3) above-mentioned each solution and stream are added in the reactor, under 120 rev/mins of speed conditions of agitator, if the compound that contains doped element M then adds its powder water insoluble, and uniform mixing carries out the liquid deposition reaction, makes to contain Li
mM
(1-m)/nFePO
4The mixing suspension liquid of compound crystallite or nucleus;
2) add the reduction conductive additive
Under 120 rev/mins of speed conditions of agitator, in above-mentioned suspension liquid, add the reduction conductive additive while stirring, continue again to stir 1-3 hour, make the suspension liquid uniform mixing; The reduction conductive additive is that charcoal or pyrolysis can produce one of carbon compound or its arbitrary combination, and the conductive additive that perhaps reduces is that charcoal or pyrolysis can produce in the powder of one of carbon compound or its arbitrary combination and thin inert metal or the subsequent technique and can be reduced to one of inert metal compound of this metal-powder; Described charcoal or pyrolysis can produce the add-on of one of carbon compound or its arbitrary combination for estimating the 3-15% of product weight, the add-on of the powder of described thin inert metal is for estimating 1% of product weight, and the add-on of described inert metal compound is that the content of metal in this inert metal compound is 1% of expectation product weight;
3) spraying drying suspension liquid
With volume pump above-mentioned mixed uniformly suspension liquid is delivered to the spraying drying top of tower, it through rotating speed 18000-24000 rev/min centrifugal energy nozzle atomizing, be mixed into the promoting the circulation of qi fluidized drying at the spray-drying tower inlet with 260-310 ℃ of warm air, dried powder is that 100-120 ℃ bag filter is collected through cyclonic separator and temperature in, must comprise the mix powder of each reaction product and by product;
4) roasting, pulverizing
The mix powder that above-mentioned dust-precipitator is collected is sent in the High Temperature Furnaces Heating Apparatus, under nonoxidizing atmosphere after 350-500 ℃ of constant temperature calcining 5-20 hour, again at 600-800 ℃ of constant temperature calcining 5-20 hour, take out after being cooled to normal temperature then, promptly get lithium ion cell positive actives LiFePO 4 crystalline powder through pulverizing, cross 300 mesh sieves; Or under nonoxidizing atmosphere in 350-500 ℃ of constant temperature calcining 5-25 hour, take out after being cooled to normal temperature then, blend together powder through grinding, sent into again in the High Temperature Furnaces Heating Apparatus in nonoxidizing atmosphere in 600-800 ℃ of constant temperature calcining 5-20 hour, take out after being cooled to normal temperature, promptly get lithium ion cell positive actives ferrous phosphate lithium powder through pulverizing, cross 300 mesh sieves.
2. wet method prepares the method for LiFePO 4 according to claim 1, it is characterized in that described water-soluble compound that contains lithium is one of Lithium Acetate, lithium hydroxide, lithium oxalate, Lithium Citrate de, monometallic, lithium chloride or lithium nitrate; Water-soluble ferruginous compound is one of Iron diacetate, iron lactate, ferrous citrate, ferrous ammonium citrate, iron protochloride or Iron nitrate; Water-soluble phosphorated compound is one of phosphoric acid, monometallic, primary ammonium phosphate, Secondary ammonium phosphate or ammonium phosphate; The compound that contains doped element M is for containing ionic radius near Li
+The Mg of radius
2+, Al
3+, Zr
4+Or Nb
5+One of compound, the compound that contains doped element M is the oxide compound that contains doped element M, oxyhydroxide, muriate, one of nitrate, organic acid salt or organometallics.
3. prepare the method for LiFePO 4 as wet method as described in the claim 2, it is characterized in that charcoal is superconduction carbon black or superfine graphite in the described reduction conductive additive; It is one of sucrose, citric acid, starch, polyethylene powders or polyvinyl alcohol that described pyrolysis can produce carbon compound; The powder of described thin inert metal is the powder of Ag or Cu; The inert metal compound that can be reduced to this metal-powder in subsequent technique is oxide compound, the oxyhydroxide of Ag or Cu, one of nitrate, organic acid salt or organometallics.
4. prepare the method for LiFePO 4 as wet method as described in the claim 3, it is characterized in that described High Temperature Furnaces Heating Apparatus is one of tube furnace, box-type furnace, continuous tunnel furnace or vertical heater, wherein continuous tunnel furnace or vertical heater are one of intermittent type or continous way.
5. prepare the method for LiFePO 4 as wet method as described in the claim 4, it is characterized in that described nonoxidizing atmosphere is oxygen-free N
2Atmosphere, Ar atmosphere, N
2With H
2Mixed-gas atmosphere, or Ar and H
2One of mixed-gas atmosphere.
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| CNB2006101114452A CN100528746C (en) | 2006-08-18 | 2006-08-18 | Wet method of preparing lithium ferrous phosphate and its prepared lithium ferrous phosphate |
| PCT/CN2007/000577 WO2008022508A1 (en) | 2006-08-18 | 2007-02-16 | Method for preparing lithium iron phosphate through wet process and lithium iron phosphate prepared by the same |
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| CNB2006101114452A CN100528746C (en) | 2006-08-18 | 2006-08-18 | Wet method of preparing lithium ferrous phosphate and its prepared lithium ferrous phosphate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107611427A (en) * | 2016-07-12 | 2018-01-19 | 南通亨利锂电新材料有限公司 | A kind of microstructure metal phosphate and preparation method thereof |
| CN109336078A (en) * | 2012-08-10 | 2019-02-15 | 三星Sdi株式会社 | The manufacturing method of lithium metal phosphates |
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| CN101533912B (en) * | 2008-03-11 | 2012-07-25 | 比亚迪股份有限公司 | Method for preparing lithium iron phosphate used as positive active material of lithium ion secondary battery |
| CN102381693A (en) * | 2010-09-06 | 2012-03-21 | 李文宝 | Preparation method of lithium iron phosphate |
| CN101935029B (en) * | 2010-09-29 | 2012-01-04 | 彩虹集团公司 | Method for preparing lithium iron phosphate material |
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| CN104752717B (en) * | 2013-12-27 | 2017-05-03 | 比亚迪股份有限公司 | Lithium iron phosphate and its preparation method and use |
| CN115180608A (en) * | 2022-07-26 | 2022-10-14 | 江西赣锋锂电科技股份有限公司 | Preparation method of spherical lithium iron manganese phosphate with high tap density |
| CN115566307B (en) * | 2022-11-15 | 2023-03-24 | 湖南五创循环科技有限公司 | Method for recovering high-purity lithium oxalate and high-purity lithium hydroxide from waste lithium battery |
| CN116692911A (en) * | 2023-08-07 | 2023-09-05 | 赣州市力道新能源有限公司 | Process for reducing magnetic substances in battery-grade lithium carbonate |
| CN116902946B (en) * | 2023-09-14 | 2023-11-14 | 北京林立新能源有限公司 | Method for preparing ferric phosphate from iron black |
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| CN1208241C (en) * | 2003-02-17 | 2005-06-29 | 郑绵平 | Wet chemistry method for preparing lithium iron phosphate |
| DE10353266B4 (en) * | 2003-11-14 | 2013-02-21 | Süd-Chemie Ip Gmbh & Co. Kg | Lithium iron phosphate, process for its preparation and its use as electrode material |
| CN1773751A (en) * | 2004-11-11 | 2006-05-17 | 大同股份有限公司 | Production of olivine structural lithium ferric phospate lithium battery anode material by solution method |
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| CN109336078A (en) * | 2012-08-10 | 2019-02-15 | 三星Sdi株式会社 | The manufacturing method of lithium metal phosphates |
| CN107611427A (en) * | 2016-07-12 | 2018-01-19 | 南通亨利锂电新材料有限公司 | A kind of microstructure metal phosphate and preparation method thereof |
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| CN1903708A (en) | 2007-01-31 |
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