CN102468479A - Manufacturing method for lithium iron phosphate cathode material - Google Patents

Manufacturing method for lithium iron phosphate cathode material Download PDF

Info

Publication number
CN102468479A
CN102468479A CN2010105484510A CN201010548451A CN102468479A CN 102468479 A CN102468479 A CN 102468479A CN 2010105484510 A CN2010105484510 A CN 2010105484510A CN 201010548451 A CN201010548451 A CN 201010548451A CN 102468479 A CN102468479 A CN 102468479A
Authority
CN
China
Prior art keywords
lithium
iron
water
compound
iron phosphate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN2010105484510A
Other languages
Chinese (zh)
Inventor
林居南
张成裕
林荣正
赖怡文
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
GREEN ENERGY ELECTRODE Inc
Original Assignee
GREEN ENERGY ELECTRODE Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by GREEN ENERGY ELECTRODE Inc filed Critical GREEN ENERGY ELECTRODE Inc
Priority to CN2010105484510A priority Critical patent/CN102468479A/en
Priority to TW100137433A priority patent/TW201221469A/en
Publication of CN102468479A publication Critical patent/CN102468479A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Landscapes

  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention relates to a manufacturing method for a lithium iron phosphate cathode material. The reactivity and the uniformity of raw materials are improved by adopting a semi-chemical method, and the raw materials used for manufacturing lithium iron phosphate materials are divided into water-soluble raw materials and water-insoluble raw materials. The manufacturing method comprises the following steps of: firstly, dissolving the water-soluble raw materials into water, adding the water-insoluble raw materials, adding a dispersing agent, a carbon source and a compound of iron position substituting elements, and grinding and uniformly mixing the raw materials to form slurry with all components of lithium iron phosphate; secondly, preparing the uniformly mixed slurry into precursor powder in a spray granulation manner; and finally, calcining the precursor powder at the temperature of between 600 and 800 DEG C for 1 to 24 hours in reducing atmosphere, and crushing the calcined powder to obtain finished products. The manufacturing process is simple and suitable for mass production, the raw materials are uniformly mixed, the properties of the products are consistent, the prepared lithium iron phosphate has stable quality characteristics, and the products have long charge and discharge service life and higher charge and discharge capacity, so that related problems of the conventional lithium iron phosphate production are solved.

Description

The manufacturing approach of lithium iron phosphate positive material
Technical field
Present invention is directed to a kind of manufacturing approach of lithium iron phosphate positive material, the manufacturing approach of outstanding reference and a kind of anode material of lithium battery means that especially half chemical method prepares the method for lithium iron phosphate positive material.
Background technology
When electronics industry was flourish, the 3C electronic product grew with each passing day to portable type demands for energy degree in using in a large number, adds the trend of advocating carbon reduction in recent years, drives the fast development of electric automobile more, impels battery industry flourish.In the various battery, lithium secondary battery has high-energy-density, discharging voltage balance, have extended cycle life and advantage such as memory-less effect, therefore has been widely used on each field.
Lithium iron phosphate positive material has advantages such as high weight energy density, high charge-discharge life-span, big charging and discharging capabilities, nontoxic and low price, and being considered to is most possible power battery material.Yet because pure iron lithium phosphate electrical conductivity is not good, its characteristic is not suitable for being used as battery material and uses; So this material is since 1997 are found by people such as Goodenough; Existing considerable method is suggested the electrical characteristic of improving iron lithium phosphate, and for example carbon coats and the replacement of lithium (Li), iron (Fe), phosphorus lattice positions such as (P) etc., via the replacement of said process; Improve the conductivity of phosphoric acid body lithium widely, make this product have excellent electric characteristics.
The manufacturing approach of iron lithium phosphate has solid state process, hot carbon reduction method, coprecipitation method and hydro thermal method etc. at present, and wherein solid state process is mainly chosen lithium carbonate (Li 2CO 3), ferrous oxalate (FeC 2O 4.2H 20) and ammonium di-hydrogen phosphate ((NH 4) H 2PO 4) under the solvent situation, mix together, dry, and then calcining, because adopting solid-state mode, mixes in powder, so the uniformity of raw material is relatively poor relatively, and, can decomposes under the high temperature and emit ammonia (NH because of using ammonium di-hydrogen phosphate to work as raw material 3), the problem of environmental protection is arranged.The source of iron that hot carbon reduction method is used is di-iron trioxide (Fe 2O 3), at this moment, iron is the compound of 3 valencys; And the iron of the LiFePO 4 material that produces is the divalent compound; So the carbon source material that adds is except being used as the carbon source, still some need be used as the reducing agent use, therefore; The carbon source addition that adds needs more than conventional method, and so productive rate relatively can less and wayward Fe + 3Residual quantity.Coprecipitation method then uses ferrous sulfate (FeSO 4), lithium hydroxide (LiOH) and phosphoric acid (H 3PO 4) wait raw material, with the pH value of ammoniacal liquor regulation and control solution, make elements such as Li, Fe, P produce deposition, precisely because the processing procedure relative complex need just to can be made into high-quality product through the multiple tracks cleaning step, and this method also has the big problem of waste water treatment in addition.In addition; Hydrothermal synthesis method then is to utilize material under high pressure, middle temperature situation; Have high-dissolvability and degree of reaction is made iron lithium phosphate, but because reaction temperature is lower, about 100～200 ° of C; Though so the structural intergrity of material all have out, precisely because the hot properties of product is relatively poor relatively and water heating apparatus volume production is relatively costly.In a word; Above-mentioned general common lithium iron phosphate positive material manufacturing approach; Though wherein the solid state process processing procedure is simple, because of using micron-sized raw material, so material can't fully evenly mix; Adding needs long heat treatment just can reach characteristic preferably, so needs relatively in the processing procedure to use the particle size distribution of more protective gas and product wider; Hot carbon reduction method also is a kind of of solid state process basically, and difference is that the raw material that uses is not quite alike; Coprecipitation method or hydrothermal synthesis method then have the long or apparatus expensive of processing procedure, cause can't volume production puzzlement.
Chinese patent CN101714658 proposes half wet process and prepares LiFePO 4 material; In the compound of Li, Fe, appoint and get a kind of water-fast compound; Other is water-soluble compound; Above-mentioned water-fast compound is put into above-mentioned water-soluble compound process suspension-turbid liquid, wherein the lithium in the suspension-turbid liquid, iron, phosphorus need meet following formula:
Figure 821754DEST_PATH_IMAGE001
(formula one)
In the above-mentioned formula one, n is the chemical valence of doped chemical M; M is the not ear number of Li; (1-m)/n is the not ear number of doped chemical M; And p and q are respectively Fe and PO 4Not ear number.Afterwards, add the reduction conductive additive, the spray pyrolysis suspension-turbid liquid makes the precursor powder, this precursor powder of roast, pulverize product.This method technology is simple; The suitability for industrialized serialization is produced, and the LiFePO4 steady quality that makes has good high-rate discharge ability and cycle performance; Precisely because because the doping elements position is the Li position, so the gram volume of the LiFePO 4 material of making is less relatively.
Because pure LiFePO4 electrical conductivity is not good, about 10 -9Ohm-m, the method that generally increases electrical conductivity include that carbon coats, high valence ion mixes or add metallic particles such as copper or silver how a rice particle improves electrical conductivity.By early stage document sight; It is main that the increase electrical conductivity is all only done single kind of method, recently, and in order further to increase electrical conductivity; Two kinds of occupation modes of combination are arranged then; For example: carbon coats and adds the high valence ion doping, is main with the lithium position mostly yet mix, and the doping of Li position can reduce effective gram volume of lithium battery.In addition, even if the minority paper adopts the iron position to mix, its doping also only has 1～2at%.So, general can't meet user required when reality is used with person system; In fact be necessary to develop that a kind of tool processing procedure is simple, but the cheap industrialization volume production of manufacturing cost and the high gram volume of product tool, high-rate discharge ability and cycle life are this patent problem to be solved preferably.
Summary of the invention
Main purpose of the present invention is; Overcome the problems referred to above that known skill meets with and provide a kind of half chemical method to prepare the method for lithium iron phosphate positive material, the simple and suitable industrial mass production of making technology, its raw materials mix is even; Properties of product are consistent; Prepared LiFePO4 mass property is stable, makes product have favorable charge-discharge life-span and charging and discharging capabilities preferably, thereby can overcome the relevant issues that present production LiFePO4 exists.
For reaching the above object, the manufacturing approach of a kind of lithium iron phosphate positive material provided by the invention, it comprises the following step at least:
(A) former material is selected: in lithium, iron, phosphorus three compounds, choose any one kind of them water-insoluble compound as water-fast former material; Select water soluble compound as water-soluble former material for other two kinds; And choose the doped chemical (M) of iron position substituted compound in addition, and choose carbon-source cpd as carbon source material as displacement iron;
(B) slurry preparation: the addition of calculating each material according to the proportioning of solid content and each element; Weigh above-mentioned water soluble compound, water-insoluble compound, iron position substituted compound and carbon-source cpd and dispersant and deionized water respectively, and the adding proportion of above-mentioned lithium, iron, phosphorus and doped chemical system meets mLi+ [nFe+ (1-n) M]: qPO 4=0.95～1.1:1:1～1.05 scopes, wherein m is the not ear number of Li, and n is the not ear number of Fe, and 1-n is the not ear number of doped chemical M, and q is PO 4Not ear number, continue, this water soluble compound, this carbon-source cpd and this dispersant are dissolved in earlier in this deionized water, and then add this water-insoluble compound and this iron position substituted compound;
(C) slurry grinds: in order to the granular size of controlling water-insoluble compound in above-mentioned phosphorous, iron, the lithium slurry and the uniformity of each raw material; Use grinder that the composition in the slurry is mixed; Simultaneously the solids in the slurry are ground to below 2 microns (μ m), in order to do electrical characteristic with the enhancement final products;
(D) mist projection granulating: will pass through ground and mixed, levigate phosphoric acid iron lithium slurry; Send into and carry out granulation in the sponging granulator; Utilize the parameters such as charging rate, temperature, pressure or rotating speed of control sponging granulator, the granularity of adjustment prilling powder is to process precursor powder;
(E) reducing atmosphere calcining: this precursor powder is sent in the kiln of protection of reducing atmosphere and calcined, at the calcination time that between between 600～800 ° of C calcining heats, carries out 1～24 hour; And
(F) pulverize: will calcine cooled powder and take out, and be crushed to powder with pulverizer and can cross 325 eye mesh screens, and promptly get tool carbon and coat and the substituted lithium iron phosphate positive material in iron position.
For reaching the above object, the manufacturing approach of another kind of lithium iron phosphate positive material provided by the invention is to prepare LiFePO4 with half chemical method, and it comprises the following step at least:
(A) former material is selected: select the water-insoluble compound of iron content to be used as source of iron; Lithium carbonate is used as the lithium source, phosphoric acid is used as the phosphorus source; And choose the doped chemical M of iron position substituted compound in addition, and choose carbon-source cpd as carbon source material as displacement iron;
(B) slurry preparation: the addition of calculating each material according to the proportioning of solid content and each element; Weigh water-insoluble compound, iron position substituted compound and carbon-source cpd and the dispersant and the deionized water of above-mentioned lithium carbonate, phosphoric acid, iron content respectively, and the adding proportion of above-mentioned lithium, iron, phosphorus and doped chemical meets mLi+ [nFe+ (1-n) M]: qPO 4=0.95～1.1:1:1～1.05 scopes, wherein m is the not ear number of Li, and n is the not ear number of Fe, and 1-n is the not ear number of doped chemical M, and q is PO 4Not ear number, again this lithium carbonate is added in this deionized water, add phosphoric acid down in stirring condition, add this carbon-source cpd and this dispersant again, add the water-insoluble compound and the iron position substituted compound of iron content at last again;
(C) slurry grinds: in order to the granular size of controlling water-insoluble compound in above-mentioned phosphorous, iron, the lithium slurry and the uniformity of each raw material, use grinder that the composition in the slurry is mixed, simultaneously the solids in the slurry are ground to below the 2 μ m;
(D) mist projection granulating: will pass through ground and mixed, levigate phosphoric acid iron lithium slurry; Send into and carry out granulation in the sponging granulator; Utilize charging rate, temperature, pressure or the rotating speed of control sponging granulator, the granularity of adjustment prilling powder is to process precursor powder;
(E) reducing atmosphere calcining: above-mentioned precursor powder is sent in the kiln of protection of reducing atmosphere and calcined, at the calcination time that between between 600～800 ° of C calcining heats, carries out 1～24 hour; And
(F) pulverize: will calcine cooled powder and take out, and be crushed to powder with pulverizer and can cross 325 eye mesh screens, and promptly get and have carbon coating and the substituted lithium iron phosphate positive material in iron position.
Compared with prior art; The beneficial effect that the present invention had is: the present invention prepares lithium iron phosphate positive material with half chemical method; Simple and the suitable industrial mass production of making technology, its raw materials mix is even, and properties of product are consistent; Prepared LiFePO4 mass property is stable, makes product have favorable charge-discharge life-span and charging and discharging capabilities preferably.
Description of drawings
Fig. 1 is a making schematic flow sheet of the present invention.
Fig. 2 is the x x-ray diffraction sketch map that contains the zinc iron phosphate powder that the present invention prepares.
Fig. 3 is the discharge capability sketch map of assembly of the present invention.
Fig. 4 is the cycle life sketch map that assembly of the present invention discharges and recharges.
Label declaration:
The former material of step (A) selects 11;
Step (B) slurry preparation 12;
Step (C) ground and mixed 13;
Step (D) mist projection granulating 14;
Step (E) reducing atmosphere calcining 15;
Step (F) pulverizes 16;
Charging and discharging curve 21～28.
Embodiment
As previously mentioned, essence spirit of the present invention system hopes that the mixing of material can reach near chemical grade to be mixed, and whole processing procedure hope can the same simple and low price with general solid state process processing procedure.Therefore, the inventor proposes to prepare lithium iron phosphate positive material with the theory of half chemical method.
Seeing also Fig. 1～shown in Figure 4, is to be respectively the discharge capability sketch map that contains the x x-ray diffraction sketch map of zinc iron phosphate powder, assembly of the present invention of making schematic flow sheet of the present invention, the present invention's preparation and the cycle life sketch map that assembly of the present invention discharges and recharges.As shown in the figure: the present invention is a kind of manufacturing approach of lithium iron phosphate positive material, is to utilize the mode of half chemical method to improve the reactivity and the uniformity of raw material, and the former material that generally is used for making the iron lithium phosphate material is divided into water-soluble and water-insoluble two types.It comprises the following step at least:
(A) former material selects 11: in LiFePO4 principal component lithium (Li), iron (Fe), phosphorus (P) three compounds, choose any one kind of them water-insoluble compound as water-fast former material; Select water soluble compound as water-soluble former material for other two kinds; And choose the doped chemical (M) of iron position substituted compound in addition, and choose carbon-source cpd as carbon source material as displacement iron;
(B) the slurry preparation 12: the addition of calculating each material according to the proportioning of solid content and each element; Weigh above-mentioned water soluble compound, water-insoluble compound, iron position substituted compound and carbon-source cpd and dispersant and deionized water respectively, and the adding proportion of above-mentioned lithium, iron, phosphorus and doped chemical system meets mLi+ [nFe+ (1-n) M]: qPO 4=0.95～1.1:1:1～1.05 scopes, wherein m is the not ear number of Li, and n is the not ear number of Fe, and 1-n is the not ear number of doped chemical M, and q is PO 4Not ear number; Continue it, this water soluble compound, this carbon-source cpd and this dispersant are dissolved in earlier in this deionized water, and then add this water-insoluble compound and this iron position substituted compound;
(C) ground and mixed 13: in order to the granular size of controlling water-insoluble compound in above-mentioned phosphorous, iron, the lithium slurry and the uniformity of each raw material; Use grinder; The ball mill of for example generally having seen, stir grinding machine (Attritor) or ball mill (Bead miller); Composition in the slurry is mixed, simultaneously the solids in the slurry are ground to below 2 microns (μ m), to promote the electrical characteristic of final products;
(D) mist projection granulating 14: will pass through that ball milling or pearl mill mixes, levigate phosphoric acid iron lithium slurry; Send into and carry out granulation in the sponging granulator; Utilize the parameters such as charging rate, temperature, pressure or rotating speed of control sponging granulator, the granularity of adjustment prilling powder is to process precursor powder; Wherein the pattern of sponging granulator system can be general pressure type, rotating disc type or jet flow (Twin jet type), and central is again best especially with the latter;
(E) reducing atmosphere calcining 15: this precursor powder is sent in the kiln of protection of reducing atmosphere and calcined, at the calcination time that between between 600～800 ° of C calcining heats, carries out 1～24 hour, wherein the protective atmosphere of kiln system can be nitrogen (N 2), argon (Ar), nitrogen argon (N 2-Ar) or hydrogen argon (H 2-Ar) select one of which in the gas; And
(F) pulverize 16: will calcine cooled powder and take out, and be crushed to powder with pulverizer and can cross 300～325 eye mesh screens, and promptly get tool carbon and coat and the substituted lithium iron phosphate positive material in iron position.This powder has carbon to coat simultaneously and the iron position replaces, thus the lithium iron phosphate positive material of processing have high discharge and recharge gram volume, cycle life reaches bigger charging and discharging capabilities.
In the above-mentioned steps (A), the water soluble compound of lithium is selected from lithium hydroxide (LiOH), lithium acetate (CH 3COOLi), lithium dihydrogen phosphate (LiH 2PO 4, the phosphorus source can be provided simultaneously), lithium nitrate (LiNO 3), lithium chloride (LiCl) or lithium citrate (Li 3C 6H 5O 7) in select one of which; The water soluble compound of this iron is selected from ferrous acetate ((CH 3COO) 2Fe), ferric nitrate (Fe (NO 3) 3), iron chloride (FeCl 3), ferric oxalate, frerrous chloride (FeCl 2) or ferrous nitrate (Fe (NO 3) 2) in select one of which; And the water soluble compound of this phosphorus is selected from phosphoric acid (H 3PO 4), lithium dihydrogen phosphate (the lithium source can be provided simultaneously), ammonium di-hydrogen phosphate (NH 4H 2PO 4), DAP ((NH 4) 2HPO 4) or phosphoric acid ammonia ((NH 4) 3PO 4) in select one of which.
In the above-mentioned steps (A), the water-insoluble compound of lithium is selected from lithium fluoride (LiF), lithium carbonate (Li 2CO 3) or phosphatization lithium (Li 3P can provide the phosphorus source simultaneously) in select one of which; The water-insoluble compound of this iron is selected from ferrous carbonate (FeCO 3), ferrous oxide (FeO), di-iron trioxide (Fe 2O 3), ferrous oxalate (FeC 2O 4.2H 2O), ferrous phosphate (Fe 3(PO 4) 2, the phosphorus source can be provided simultaneously) or ferric phosphate (FePO 4, the phosphorus source can be provided simultaneously) in select one of which; And the water-insoluble series of compounds of this phosphorus is selected from lithium phosphate (Li 3PO 4, the lithium source can be provided simultaneously), select one of which in ferrous phosphate (source of iron can be provided simultaneously) or the ferric phosphate (source of iron can be provided simultaneously).
The doped chemical of above-mentioned steps (A) iron position substituted compound is selected from oxide, carbonic acid thing, hydroxide, nitrate, organo-metallic compound or the chloride of magnesium (Mg), zinc (Zn), titanium (Ti), zirconium (Zr), tungsten (W), manganese (Mn), nickel (Ni), cobalt (Co), chromium (Cr) and vanadium (V) and selects one of which.
Above-mentioned steps (A) carbon-source cpd is water miscible carbon containing organic compound; And can be sucrose, fructose, glucose, citric acid, polyvinylpyrrolidone (Polyvinyl pyrrolidone; PVP), cyclodextrin, polyvinyl alcohol (Polyvinyl Alcohol; PVA) or polyethylene glycol (Polyethylene Glycols selects one of which or any two mixture in PEG).
The addition of above-mentioned steps (B) iron position substituted compound is 1～15mol%, and the addition of carbon-source cpd is 2～15wt% of LiFePO4.
In a preferred embodiment, when the source of iron of above-mentioned steps (A) is selected the water-insoluble compound of iron content for use, can select lithium carbonate to be used as the lithium source; Phosphoric acid is used as the phosphorus source, produces water miscible lithium dihydrogen phosphate by phosphoric acid and lithium carbonate reaction, and whole material framework is still kept the essence spirit of half chemical method basically; Be that the principal component element is kept a first prime system solid; Two elements exist with water miscible form in addition, and so the composition of material can reach well-mixed purpose.
The object of the invention, feature and advantage please refer to following examples, will do more detailed explanation.
[embodiment 1]
In the compound that contains Li, Fe, P, choose FeC 2O 4.2H 2O is as water-insoluble compound, LiH 2PO 4As water soluble compound, and with zinc oxide (ZnO) as iron position substituted compound (mixing element), PVP with what Zn was used as displacement iron as carbon source.This LiH wherein 2PO 4Preparation comprise: get the lithium carbonate of 3.794kg earlier, add the deionized water of 20kg,, add 85% H of 11.76kg stirring simultaneously 3PO 4, by Li 2CO 3Meeting and H 3PO 4Reaction generates water miscible LiH 2PO 4And carbon dioxide (CO 2).Then, in aqueous solution, add the dispersant FN265 of 0.26Kg and the carbon source material PVP of 0.905Kg, stir together, add the FeC of 17.194Kg again 2O 4.2H 2The ZnO of O and 0.407Kg.Continue, aforementioned mixed slurry is ground 4 times with ball mill, to make the ceramic size of the homodisperse Li of containing, Fe, P element, at this moment, the granularity D50=1.9 μ m of this ceramic size.Then, with above-mentioned uniform and stable aqueous dispersion slurry, send into the wriggling pumping and to carry out powder granulation processing procedure in the NB-12 type sponging granulator and get precursor powder, wherein the inlet temperature of comminutor is between 210～230 ° of C, and outlet temperature is between 100～120 ° of C; At last, above-mentioned precursor powder moved in the atmosphere calciner heat-treat, be warming up to 720 ° of C with the speed of 5 ° of C of per minute; Constant temperature kept 4 hours; Product is taken out in the cold back of stove, through pulverizing, crossing 300 mesh sieves, can obtain to contain the carbon-coated LiFePO 4 for lithium ion batteries material of zinc.
As shown in Figure 2, be the prepared x x-ray diffraction figure that contains the zinc iron phosphate powder of the foregoing description 1.Show that by result among the figure it is for the tool olivine structural and do not have the existence of miscellaneous peak, and shows that zinc atom replaces the iron position as expection.At this, the present invention more is used in battery with it to test for understanding the powder characteristics of making, and is testing with button cell CR2032 mode down, and the discharge capability of assembly 0.2 coulomb (C) is 138.6mAh/g.Assembly is as shown in Figure 3 at the discharge capability of 0.1C～12C again; By 0.1C charging and discharging curve 21,0.2C charging and discharging curve 22,0.2C-1C charging and discharging curve 23,0.2C-2C charging and discharging curve 24,0.2C-3C charging and discharging curve 25,0.2C-5C charging and discharging curve 26,0.2C-8C charging and discharging curve 27 and 28 sights of 0.2C-12C charging and discharging curve, this result also display module has good large current discharging capability.The cycle life result that Fig. 4 then discharges and recharges for assembly 1C is by display module can be less than 1.5% in the electrical attenuation of going through 100 circulations as a result.
[embodiment 2]
Method of the present invention also can be the material framework of another embodiment, and its difference is except that the foregoing description is carried the material framework, select FeC 2O 4.2H 2O is as water-insoluble compound, LiH 2PO 4As water soluble compound, titanium dioxide (TiO 2) as iron position substituted compound (mixing element) and ascorbic acid with what Ti was used as displacement iron as carbon source.When preparation, weigh the LiH of 10.50Kg 2PO 4, be dissolved in the deionized water of 18Kg, add the dispersant B YK180 of 0.28Kg then, and carbon source material-ascorbic acid of 1.80Kg, after stirring, add the FeC of 16.76Kg again 2O 4.2H 2The TiO of O and 0.60kg 2Then, as above-mentioned embodiment 1, carry out processing procedures such as ground and mixed, mist projection granulating, reducing atmosphere calcining and pulverizing, process the carbon-coated LiFePO 4 for lithium ion batteries powder of titaniferous, wherein the condition system of reducing atmosphere calcining was with 700 ° of C sintering 16 hours.
The 0.2C discharge capability of above-mentioned prescription powder is 153.1mAh/g; And 1C discharges and recharges after going through 100 circulations, and its electrical attenuation is less than 0.1%.
[embodiment 3]
Method of the present invention also can be the material framework of another embodiment, and its difference is except that the foregoing description is carried the material framework, select Li 3PO 4As water-insoluble Li source and P source, (CH 3COO) 2Fe is as water-soluble source of iron, manganese carbonate (MnCO 3) as iron position substituted compound (mixing element) and glucose with what Mn was used as displacement iron as carbon source.When preparation, be (the CH that weighs 17.393Kg 3COO) 2Fe is dissolved in the deionized water of 22Kg, adds the glucose of 1.6Kg and the dispersant 1221 of 0.32Kg then, after stirring, adds the Li of 10.85Kg again 3PO 4And the MnCO of 0.92Kg 3Then, as above-mentioned embodiment 1, carry out processing procedures such as ground and mixed, mist projection granulating, reducing atmosphere calcining and pulverizing, process the carbon-coated LiFePO 4 for lithium ion batteries powder that contains manganese, wherein the condition system of reducing atmosphere calcining was with 720 ° of C sintering 8 hours.
The 0.2C discharge capability of above-mentioned prescription powder is 143.1mAh/g; And 1C discharges and recharges after going through 100 circulations, and electrically attenuation is less than 2.1%.
Embodiment 4
Method of the present invention also can be the material framework of another embodiment, and its difference is, in the compound that contains Li, Fe, P, selects FeC except that the foregoing description is carried the material framework 2O 4.2H 2O is as water-insoluble compound, LiOH.H 2O and H 3PO 4Mix element, cyclodextrin as carbon source respectively as water miscible Li source and P source, and with Ti as what replaced the iron position.When preparation, weigh the LiOH.H of 4.366Kg 2The H of O and 11.529Kg 3PO 4, dissolve in the deionized water of 21.5Kg, add the dispersant B YK-180 of 0.39Kg and carbon source material-cyclodextrin of 1.8Kg again.Then, those raw materials are carried out processing procedures such as ground and mixed, mist projection granulating, reducing atmosphere calcining and pulverizing as above-mentioned embodiment 1 same way as, process the carbon-coated LiFePO 4 for lithium ion batteries material of titaniferous.
The 0.2C discharge capability of above-mentioned material is 148.1mAh/g; And 1C discharges and recharges after going through 100 circulations, and its electrical attenuation is less than 2.8%.
The present invention is a kind of method of making the iron lithium phosphate positive electrode; Its characteristic comprises: adopt the mode with half chemical method; Utilize the mode of granularity of solid liquid interface effect and control solid to make that each composition can reach the mixture homogeneity near chemical method in the slurry, simultaneously, select suitable water-soluble raw material; Product in the processing procedure need only carry out mist projection granulating can carry out follow-up calcining processing procedure; Needn't need cleaning step repeatedly as chemical method, can reach high-quality characteristic, promptly this method can have the inhomogeneity characteristics of the convenience and the chemical method of solid state process simultaneously; In addition, aspect relevant raising LiFePO4 electrical conductivity, the present invention system adopts and adds the substituted mode of carbon source and iron position simultaneously and improve electrical conductivity.Wherein relevant carbon source part is to adopt water-soluble organic additive, and so carbon source and other raw-material mixture homogeneity are fairly good; The present invention mixes also inequality with the iron position of generally having seen in addition; The present invention system with the mode of height replacement amount (1～15at%) improves the electrical conductivity of product, simultaneously, the substituted element of iron position; Use 2～5 valency elements can, be not to adopt the high price element; At last, for keeping the uniformity of product, the present invention adopts the mode of mist projection granulating, to avoid generally drying the issuable raw material lamination problem of processing procedure.
In sum, the present invention is a kind of manufacturing approach of lithium iron phosphate positive material, can effectively improve the various shortcoming of usefulness; System prepares the method for lithium iron phosphate positive material with half chemical method, the simple and suitable industrial mass production of making technology, and its raw materials mix is even; Properties of product are consistent, and prepared LiFePO4 mass property is stable, make product have favorable charge-discharge life-span and charging and discharging capabilities preferably; Thereby can overcome the relevant issues that present production LiFePO4 exists; And then making generation of the present invention can more progressive, more practical, more meet institute's palpus of user, the true important document that has met application for a patent for invention hence proposes patent application in accordance with the law.

Claims (19)

1. the manufacturing approach of a lithium iron phosphate positive material is to prepare LiFePO4 with half chemical method, and it comprises the following step at least:
(A) former material is selected: in lithium Li, iron Fe, phosphorus P three compounds, choose any one kind of them water-insoluble compound as water-fast former material; Select water soluble compound as water-soluble former material for other two kinds in lithium Li, iron Fe, phosphorus P three compounds; And choose the doped chemical M of iron position substituted compound in addition, and choose carbon-source cpd as carbon source material as displacement iron;
(B) slurry preparation: the addition of calculating each material according to the proportioning of solid content and each element; Weigh above-mentioned water soluble compound, water-insoluble compound, iron position substituted compound and carbon-source cpd and dispersant and deionized water respectively, and the adding proportion of above-mentioned lithium, iron, phosphorus and doped chemical meets mLi+ [nFe+ (1-n) M]: qPO 4=0.95～1.1:1:1～1.05 scopes, wherein m is the not ear number of Li, and n is the not ear number of Fe, and 1-n is the not ear number of doped chemical M, and q is PO 4Not ear number; Again this water soluble compound, this carbon-source cpd and this dispersant are dissolved in earlier in this deionized water, and then add this water-insoluble compound and this iron position substituted compound;
(C) ground and mixed: in order to the granular size of controlling water-insoluble compound in above-mentioned phosphorous, iron, the lithium slurry and the uniformity of each raw material, use grinder that the composition in the slurry is mixed, simultaneously the solids in the slurry are ground to below 2 microns;
(D) mist projection granulating: will pass through ground and mixed, levigate phosphoric acid iron lithium slurry; Send into and carry out granulation in the sponging granulator; Utilize charging rate, temperature, pressure or the rotating speed of control sponging granulator, the granularity of adjustment prilling powder is to process precursor powder;
(E) reducing atmosphere calcining: this precursor powder is sent in the kiln of protection of reducing atmosphere and calcined, at the calcination time that between between 600～800 ° of C calcining heats, carries out 1～24 hour; And
(F) pulverize: will calcine cooled powder and take out, and be crushed to powder with pulverizer and can cross 300～325 eye mesh screens, and promptly get and have carbon coating and the substituted lithium iron phosphate positive material in iron position.
2. the manufacturing approach of lithium iron phosphate positive material according to claim 1 is characterized in that, the water soluble compound of this lithium is selected from lithium hydroxide, lithium acetate, lithium dihydrogen phosphate, lithium nitrate, lithium chloride or the lithium citrate and selects one of which; The water soluble compound of this iron is selected from ferrous acetate, ferric nitrate, iron chloride, ferric oxalate, frerrous chloride or the ferrous nitrate and selects one of which; And the water soluble compound of this phosphorus is selected from phosphoric acid, lithium dihydrogen phosphate, ammonium di-hydrogen phosphate, DAP or the phosphoric acid ammonia and selects one of which.
3. the manufacturing approach of lithium iron phosphate positive material according to claim 1 is characterized in that, the water-insoluble compound of this lithium is selected from lithium fluoride, lithium carbonate or the phosphatization lithium and selects one of which; The water-insoluble compound of this iron is selected from ferrous carbonate, ferrous oxide, di-iron trioxide, ferrous oxalate, ferrous phosphate or the ferric phosphate selects one of which; And the water-insoluble compound of this phosphorus is selected from lithium phosphate, ferrous phosphate or the ferric phosphate and selects one of which.
4. the manufacturing approach of lithium iron phosphate positive material according to claim 1; It is characterized in that the doped chemical of this iron position substituted compound is selected from the oxide of magnesium, zinc, titanium, zirconium, tungsten, manganese, nickel, cobalt, chromium and vanadium, carbonic acid thing, hydroxide, nitrate, organo-metallic compound or the chloride selects one of which.
5. the manufacturing approach of lithium iron phosphate positive material according to claim 1; It is characterized in that; This carbon-source cpd is water miscible carbon containing organic compound, and can be and select one of which or any two mixture in sucrose, fructose, glucose, citric acid, polyvinylpyrrolidone, cyclodextrin, polyvinyl alcohol or the polyethylene glycol.
6. the manufacturing approach of lithium iron phosphate positive material according to claim 1 is characterized in that, the addition of this iron position substituted compound is 1～15mol%.
7. the manufacturing approach of lithium iron phosphate positive material according to claim 1 is characterized in that, the addition of this carbon-source cpd is 2～15wt% of LiFePO4.
8. the manufacturing approach of lithium iron phosphate positive material according to claim 1 is characterized in that, the protective atmosphere of this kiln is to select one of which in nitrogen, argon, nitrogen argon or the hydrogen argon gas body.
9. the manufacturing approach of lithium iron phosphate positive material according to claim 1 is characterized in that, this grinder is ball mill, stir grinding machine or ball mill.
10. the manufacturing approach of lithium iron phosphate positive material according to claim 1 is characterized in that, the pattern of this sponging granulator is general pressure type, rotating disc type or jet flow.
11. the manufacturing approach of a lithium iron phosphate positive material is to prepare LiFePO4 with half chemical method, it comprises the following step at least:
(A) former material is selected: select the water-insoluble compound of iron content to be used as source of iron; Lithium carbonate is used as the lithium source, phosphoric acid is used as the phosphorus source; And choose the doped chemical M of iron position substituted compound in addition, and choose carbon-source cpd as carbon source material as displacement iron;
(B) slurry preparation: the addition of calculating each material according to the proportioning of solid content and each element; Weigh water-insoluble compound, iron position substituted compound and carbon-source cpd and the dispersant and the deionized water of above-mentioned lithium carbonate, phosphoric acid, iron content respectively, and the adding proportion of above-mentioned lithium, iron, phosphorus and doped chemical meets mLi+ [nFe+ (1-n) M]: qPO 4=0.95～1.1:1:1～1.05 scopes, wherein m is the not ear number of Li, and n is the not ear number of Fe, and 1-n is the not ear number of doped chemical M, and q is PO 4Not ear number, again this lithium carbonate is added in this deionized water, add phosphoric acid down in stirring condition, add this carbon-source cpd and this dispersant again, add the water-insoluble compound and the iron position substituted compound of iron content at last again;
(C) slurry grinds: in order to the granular size of controlling water-insoluble compound in above-mentioned phosphorous, iron, the lithium slurry and the uniformity of each raw material, use grinder that the composition in the slurry is mixed, simultaneously the solids in the slurry are ground to below the 2 μ m;
(D) mist projection granulating: will pass through ground and mixed, levigate phosphoric acid iron lithium slurry; Send into and carry out granulation in the sponging granulator; Utilize charging rate, temperature, pressure or the rotating speed of control sponging granulator, the granularity of adjustment prilling powder is to process precursor powder;
(E) reducing atmosphere calcining: above-mentioned precursor powder is sent in the kiln of protection of reducing atmosphere and calcined, at the calcination time that between between 600～800 ° of C calcining heats, carries out 1～24 hour; And
(F) pulverize: will calcine cooled powder and take out, and be crushed to powder with pulverizer and can cross 325 eye mesh screens, and promptly get and have carbon coating and the substituted lithium iron phosphate positive material in iron position.
12. the manufacturing approach of lithium iron phosphate positive material according to claim 11 is characterized in that, the water-insoluble compound of this iron content is selected from ferrous carbonate, ferrous oxide, di-iron trioxide or the ferrous oxalate selects one of which.
13. the manufacturing approach of lithium iron phosphate positive material according to claim 11; It is characterized in that the doped chemical of this iron position substituted compound is selected from the oxide of magnesium, zinc, titanium, zirconium, tungsten, manganese, nickel, cobalt, chromium and vanadium, carbonic acid thing, hydroxide, nitrate, organo-metallic compound or the chloride selects one of which.
14. the manufacturing approach of lithium iron phosphate positive material according to claim 11; It is characterized in that; This carbon-source cpd is water miscible carbon containing organic compound, and can be and select one of which or any two mixture in sucrose, fructose, glucose, citric acid, polyvinylpyrrolidone, cyclodextrin, polyvinyl alcohol or the polyethylene glycol.
15. the manufacturing approach of lithium iron phosphate positive material according to claim 11 is characterized in that, the addition of this iron position substituted compound is 1～15mol%.
16. the manufacturing approach of lithium iron phosphate positive material according to claim 11 is characterized in that, the addition of this carbon-source cpd is 2～15wt% of LiFePO4.
17. the manufacturing approach of lithium iron phosphate positive material according to claim 11 is characterized in that, the protective atmosphere of this kiln is to select one of which in nitrogen, argon, nitrogen argon or the hydrogen argon gas body.
18. the manufacturing approach of lithium iron phosphate positive material according to claim 11 is characterized in that, this grinder is ball mill, stir grinding machine or ball mill.
19. the manufacturing approach of lithium iron phosphate positive material according to claim 11 is characterized in that, the pattern of this sponging granulator is general pressure type, rotating disc type or jet flow.
CN2010105484510A 2010-11-18 2010-11-18 Manufacturing method for lithium iron phosphate cathode material Pending CN102468479A (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN2010105484510A CN102468479A (en) 2010-11-18 2010-11-18 Manufacturing method for lithium iron phosphate cathode material
TW100137433A TW201221469A (en) 2010-11-18 2011-10-14 Manufacturing method for lithium iron phosphate material and lithium iron phosphate powder produced thereby

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2010105484510A CN102468479A (en) 2010-11-18 2010-11-18 Manufacturing method for lithium iron phosphate cathode material

Publications (1)

Publication Number Publication Date
CN102468479A true CN102468479A (en) 2012-05-23

Family

ID=46071811

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2010105484510A Pending CN102468479A (en) 2010-11-18 2010-11-18 Manufacturing method for lithium iron phosphate cathode material

Country Status (2)

Country Link
CN (1) CN102468479A (en)
TW (1) TW201221469A (en)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014180333A1 (en) * 2013-05-08 2014-11-13 台湾立凯电能科技股份有限公司 Battery composite material and preparation method of precursor thereof
CN104891467A (en) * 2015-05-11 2015-09-09 吉林化工学院 LiMnyFe(1-y)PO4 micron material, preparation method thereof and application thereof
WO2015169132A1 (en) * 2014-05-09 2015-11-12 湖南顶立科技有限公司 Method for preparing wc-co powder used for thermal spraying
CN105449206A (en) * 2015-12-23 2016-03-30 邬石根 LiFe1-xZrxPO4 electrode material and preparation method thereof
CN109336077A (en) * 2018-08-29 2019-02-15 深圳市德方纳米科技股份有限公司 A kind of lithium iron phosphate positive material and preparation method thereof
CN110620217A (en) * 2019-06-28 2019-12-27 湖北虹润高科新材料有限公司 Zinc-doped lithium iron phosphate/carbon composite material and preparation method thereof
CN110828823A (en) * 2019-11-19 2020-02-21 湖北理工学院 Preparation method of lithium manganese borate/carbon composite material
CN114105117A (en) * 2021-10-20 2022-03-01 合肥国轩高科动力能源有限公司 Preparation method of precursor and nickel lithium iron phosphate cathode material
WO2022144917A1 (en) * 2020-12-28 2022-07-07 International Advanced Research Centre For Powder Metallurgy And New Materials (Arci) Method of producing in-situ carbon coated lithium iron phosphate cathode material for lithium-ion batteries and the product thereof
CN116845235A (en) * 2023-08-29 2023-10-03 深圳海辰储能控制技术有限公司 Positive electrode material, positive electrode sheet and battery

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103682251B (en) * 2013-12-10 2016-06-15 浙江大学 A kind of porous iron sesquioxide/carbon nanosheet composite and preparation method thereof and its application in preparing lithium ion battery
TWI621298B (en) * 2016-04-01 2018-04-11 創奕能源科技股份有限公司 Method for manufacturing cathode material with high power of lithium ion battery and lithium ion battery

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101314463A (en) * 2007-05-28 2008-12-03 上海比亚迪有限公司 Method of producing active compound lithium iron phosphate of lithium ion secondary battery anode

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101162776B (en) * 2007-10-26 2010-06-02 深圳市贝特瑞新能源材料股份有限公司 Lithium iron phosphate suitable for high multiplying power electrokinetic cell and method for producing the same
CN101436667A (en) * 2007-11-14 2009-05-20 中国科学院理化技术研究所 Anode polyporous material of lithium ion cell and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101314463A (en) * 2007-05-28 2008-12-03 上海比亚迪有限公司 Method of producing active compound lithium iron phosphate of lithium ion secondary battery anode

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10236512B2 (en) 2013-05-08 2019-03-19 Advanced Lithium Electrochemistry Co., Ltd. Preparation method of battery composite material and precursor thereof
CN105409033A (en) * 2013-05-08 2016-03-16 台湾立凯电能科技股份有限公司 Battery composite material and preparation method of precursor thereof
JP2016522965A (en) * 2013-05-08 2016-08-04 台湾立凱電能科技股▲ふん▼有限公司 Battery composite material and method for producing precursor thereof
EP2996179A4 (en) * 2013-05-08 2017-01-18 Advanced Lithium Electrochemistry Co., Ltd. Battery composite material and preparation method of precursor thereof
TWI617074B (en) * 2013-05-08 2018-03-01 台灣立凱電能科技股份有限公司 Preparation method of battery composite material and precursor thereof
WO2014180333A1 (en) * 2013-05-08 2014-11-13 台湾立凯电能科技股份有限公司 Battery composite material and preparation method of precursor thereof
WO2015169132A1 (en) * 2014-05-09 2015-11-12 湖南顶立科技有限公司 Method for preparing wc-co powder used for thermal spraying
CN104891467A (en) * 2015-05-11 2015-09-09 吉林化工学院 LiMnyFe(1-y)PO4 micron material, preparation method thereof and application thereof
CN105449206A (en) * 2015-12-23 2016-03-30 邬石根 LiFe1-xZrxPO4 electrode material and preparation method thereof
CN109336077A (en) * 2018-08-29 2019-02-15 深圳市德方纳米科技股份有限公司 A kind of lithium iron phosphate positive material and preparation method thereof
CN110620217A (en) * 2019-06-28 2019-12-27 湖北虹润高科新材料有限公司 Zinc-doped lithium iron phosphate/carbon composite material and preparation method thereof
CN110828823A (en) * 2019-11-19 2020-02-21 湖北理工学院 Preparation method of lithium manganese borate/carbon composite material
WO2022144917A1 (en) * 2020-12-28 2022-07-07 International Advanced Research Centre For Powder Metallurgy And New Materials (Arci) Method of producing in-situ carbon coated lithium iron phosphate cathode material for lithium-ion batteries and the product thereof
CN114105117A (en) * 2021-10-20 2022-03-01 合肥国轩高科动力能源有限公司 Preparation method of precursor and nickel lithium iron phosphate cathode material
CN114105117B (en) * 2021-10-20 2024-02-20 合肥国轩高科动力能源有限公司 Preparation method of precursor and lithium nickel iron phosphate positive electrode material
CN116845235A (en) * 2023-08-29 2023-10-03 深圳海辰储能控制技术有限公司 Positive electrode material, positive electrode sheet and battery
CN116845235B (en) * 2023-08-29 2024-04-02 深圳海辰储能控制技术有限公司 Positive electrode material, positive electrode sheet and battery

Also Published As

Publication number Publication date
TW201221469A (en) 2012-06-01
TWI450856B (en) 2014-09-01

Similar Documents

Publication Publication Date Title
CN102468479A (en) Manufacturing method for lithium iron phosphate cathode material
JP6196175B2 (en) Method for producing positive electrode active material for lithium secondary battery and active material precursor powder used therefor
US10763499B2 (en) Cathode active material for all-solid-state lithium secondary battery
CN101186290B (en) Anode material vanadium lithium phosphate and preparation method thereof
US9391313B2 (en) Lithium metal composite oxide powder
US10468677B2 (en) Spinel-type lithium-manganese-containing complex oxide
CN101106194B (en) Cathode material Li3V2(PO4)3 of lithium ion battery and its making method
JP6335276B2 (en) Positive electrode active material for lithium secondary battery
CN102725887B (en) Comprise the lithium storage battery of ferric phosphate containing lithium and carbon
CN101597048B (en) Method for preparing anode material lithium iron phosphate
CN111033828A (en) Positive electrode active material for all-solid-state lithium secondary battery
JP5830179B2 (en) Method for producing positive electrode active material for lithium secondary battery and active material precursor powder used therefor
EP3351510B1 (en) Spinel type lithium nickel manganese-containing composite oxide
WO2019044734A1 (en) Positive electrode active substance for all solid-state lithium secondary battery
EP2725642A1 (en) Spinel lithium-manganese-nickel-containing composite oxide
JP6008024B2 (en) Method for producing olivine type lithium transition metal oxide
CN107074584B (en) The composite oxides of 5V grades of spinel-type lithium-magnesium containings
CN102468489B (en) Method for producing lithium iron phosphate material and lithium iron phosphate powder produced thereby
EP3597603A1 (en) Spinel type lithium nickel manganese-containing composite oxide
JP2012190648A (en) Lithium transition metal-based compound manufacturing method
WO2013127251A1 (en) Method for preparing electrochemically active material
CN115535991A (en) Nanocrystalline phosphoric acid series anode material and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20120523