CN102683674A - Preparation methods of nano iron phosphate precursors and ultra-fine nano lithium iron phosphate usable for electrode material - Google Patents
Preparation methods of nano iron phosphate precursors and ultra-fine nano lithium iron phosphate usable for electrode material Download PDFInfo
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Abstract
The invention provides a preparation method of nano iron phosphate precursors, and a preparation method of ultra-fine nano lithium iron phosphate usable for electrode material using the precursors. Firstly, the nano iron phosphate precursors (FP) are prepared and then the ultra-fin nano lithium iron phosphate cathode material with smaller size is prepared by the nano iron phosphate precursors (FP). The production technology of the FP is simple, the obtained nano precursors are used for furthermore preparing the finer nano spherical or near-spherical lithium iron phosphate particles, thus the electrode material made of the precursors has features of good performance, high capacity, good discharge capacity and voltage platform property under high scaling factor, as well as long cycle life.
Description
Technical field
The invention belongs to battery active electrode material technical field.Be particularly related to nano ferric phosphate presoma preparation method, and prepare the method for nano-grade lithium iron phosphate electrode material with obtained presoma.
Technical background
Goodenough in 1997 etc. have reported a kind of LiFePO4 (LiFePO of novel olivine-type structure
4) be used for anode material for lithium-ion batteries; It has high theoretical capacity (170mAh/g), excellent cycle performance, abundant raw material sources, good security performance and characteristic such as environmentally friendly; LiFePO4 is counted as one of the most promising lithium ion anode material; It both can be widely used in electronic and the hybrid vehicle high power battery, also can be used as the energy-storage battery of regenerative resource (like wind energy, solar energy and water can wait).Yet, LiFePO
4Because the restriction of structure makes it have low electron conduction and low ion migration rate, seriously restricted the high rate performance of this kind material on the one hand, during high power charging-discharging, its actual specific capacity is low, causes the specific power density of battery low.On the basis of LiFePO 4 material being carried out traditional modification understanding, people recognize that gradually nanometer technology is one of important method that improves its multiplying power property and physical and chemical performance thereof.Research shows, no matter is to adopt the carbon coating or do not adopt carbon to coat, as long as material granule refine to about 140 nanometers or littler, this material all has extremely excellent high rate performance.When lithium iron phosphate positive material is carried out the C clad nanoization, in conjunction with adopting metal ion mixing technology, between these nano particles, set up conductive network, can further improve the high rate capability of material.
China's new-energy automobile planning proposes to reach 120Wh/kg to the specific energy of high-energy Vehicular battery system in 2015; Price is lower than 3 yuan/Wh; Distance travelled reaches the requirement of 150,000 km; The performance that this just needs further to improve existing lithium iron phosphate positive material reduces positive electrode and production cost of cells simultaneously.Electric motor car ferric phosphate lithium ion electrokinetic cell requires lithium iron phosphate positive material to have characteristics such as high-energy-density, high-specific-power, long-life, safety and environmental protection, high conformity, low cost.
Research open source literature about the LiFePO4 electrode material has following reports at present, for example:
1, Chinese patent CN101172594 " is used to prepare the preparation method of ferric phosphate of LiFePO 4 material "; It relates to heavy metal phosphate; The steps include: to analyze pure soluble ferric iron salt and be dissolved in distilled water; Be mixed with the aqueous solution of 0.05～5M, adding quality is the anion surfactant of molysite quality 0.01～3%, is Fe according to mol ratio then
3+: PO4
3-=1: 0.8～1.2 ratio adds the analysis pure phosphoric acid and stirs, and under stirring, slowly adding concentration is the alkaline solution of 1～9M, and the reinforced time was greater than 1 hour; Reach 6～7 up to the pH value of solution value; The ferric phosphate deposit is filtered, and the ferric phosphate that filters out washs 3～5 times with the distilled water of 2～5 times of its weight, under vacuum condition; In 60～90 ℃ of scopes, dry, obtain product F ePO
42H
2The O powder.The ferric phosphate product that has two crystallizations water that makes has very high reactivity, and the LiFePO 4 material performance of processing with it is superior to the LiFePO 4 material processed with commercially available ferric phosphate product.
2, " method for preparing ferrous phosphate lithium/carbon composite material with the unordered ferric phosphate of high activity " of Chinese patent CN101237043A; This method is mixed back with phosphorus source solution by stoichiometric proportion with the divalence source of iron and is added hydrogen peroxide; Control pH value stirs and makes highly active unordered ferric phosphate.Ferric phosphate, lithium source and carbon source are mixed in proportion; Ball milling is the back spray drying evenly; Under protective atmosphere, obtaining average grain diameter through high-temperature heat treatment is 200-500nm, and 0.25C multiplying power discharging specific capacity reaches 145-150mAh/g; 1C multiplying power discharging specific capacity reaches 130-140mAh/g, and 5C multiplying power discharging specific capacity reaches the height ratio capacity ferrous phosphate lithium/carbon composite material of 105-110mAh/g.
3, Chinese patent title: a kind of preparation method's application (patent) of nano ferric phosphate number: the CN200910093734.8 applying date: 2009.10.16 open (bulletin) number: CN101693531A open (bulletin) day: 2010.04.14 apply for (patent right) people: the Tsing-Hua University address: (design) people: Pu Weihua is invented in the Box 82, No.100084 Mailbox, Patent Office, Tsinghua University, Beijing City; Appoint and found the state; Wu Yuling; He Xiangming; Wang Li; Li JianJun; Gao Jian; Yang Yu gives birth to; Wan Chunrong; Jiang Changyin summary: a kind of preparation method of nano ferric phosphate; Belong to the anode material for lithium-ion batteries preparing technical field; It is characterized in that with phosphoric acid or soluble phosphoric acid salting liquid both one of, water-soluble divalent iron salt and one of oxidant or water-soluble trivalent ferric salt solution, the mixed solution and the alkaline aqueous solution that form with water soluble dispersing agent be input in the RPB layer with certain charging rate with measuring pump; Regulate the rotating speed of RPB; PH value with aqueous slkali control reaction system; The nano ferric phosphate particle that reactive crystallization generates is discharged by the discharging opening of RPB with mixed liquor, after filtration, washing, drying, obtains nanoscale ferric phosphate (FePO42H2O) powder.The inventive method is easy, easy to operate, efficient is high, and the ferric phosphate that makes reaches nanoscale, and size is even, narrow distribution range, is applicable to suitability for industrialized production.This nano ferric phosphate is the good persursor material of preparation high power power type lithium-ion battery anode material ferric lithium phosphate.
4, Chinese patent title: anode material for lithium-ion batteries of nanostructure and preparation method thereof application number: the CN201010281627.0 applying date: 2010.09.15 open (bulletin) number: CN101944593A open (bulletin) day: 2011.01.12 applied for (patent right) people: University Of Tianjin, address: No. 92, Weijin Road, Nankai District, Tianjin City invention (design) people: Yang Quanhong; Wei Wei; The Soviet side is far away; Chen Xuecheng; Lv Wei, summary: anode material for lithium-ion batteries of a kind of nanostructure and preparation method thereof.The positive electrode of telling is the granular pattern nucleocapsid structure, and nuclear material is by nano-grade lithium iron phosphate, and phosphoric acid vanadium lithium or cobalt-lithium oxide and Graphene are formed; The shell material is a porous carbon.Preparation method's process comprises; With lithium acetate, lithium oxalate, ammonium dihydrogen phosphate, metavanadic acid ammonia, phosphoric acid, lithium nitrate, cobalt nitrate and graphite oxide is that raw material adopts the method for collosol and gel or ball milling to make compound; Compound is carried out vacuum presintering; Obtain nuclear material, obtain the positive electrode of granular pattern nucleocapsid structure again with the calcining of organic carbon source mixed grinding.Its advantage is that positive electrode has good conductivity, good cycle, and capacity is high, the little and even characteristics of grain diameter.And preparation technology is simple for this positive electrode, is easy to suitability for industrialized production.Principal claim: a kind of nanostructure anode material for lithium-ion batteries; It is characterized in that; This positive electrode is the granular pattern nucleocapsid structure; Wherein nuclear material is the LiFePO4 by particle diameter 20～300nm, and phosphoric acid vanadium lithium or cobalt-lithium oxide and Graphene are pressed mass ratio and be (50～1): 1, and the interlayer that is uniformly distributed in Graphene is formed; The shell material is the porous carbon that comes from glucose, sucrose or citric acid carbon source, and the porous carbon layer thickness is 1～20nm, and quality is 1～30% of nuclear material amount.
5, Chinese patent title: a kind of nano lithium iron phosphate material and preparation method thereof application (patent) number: the CN200810029616.6 applying date: 2008.07.19; Open (bulletin) number: CN101546830 open (bulletin) day: 2009.09.30, apply for (patent right) people: Shenzhen Dynanonic Co., Ltd. address: (design) people: Kong Lingyong is invented in No. 1 Technology Pineeering Service Centre in QiLin Road, Nanshan District, Shenzhen City, GuangDong Province 914-915 chamber; He Yanyan; Ji Xuewen; Wang Yunshi; Appoint really; Huang Rong, summary: a kind of nano lithium iron phosphate material and preparation method thereof.By stoichiometric proportion lithium source, source of iron, phosphoric acid root, doping element compound are dissolved in the aqueous solution that contains complexing agent; And adding is done clad material through the high conductive carbon nanotube that auxiliary agent disperses; With gained solution sintering in the inert atmosphere stove; Reaction temperature is 500-900 ℃, and the reaction time is 3-16 hour.The present invention has controlled chemical composition, phase constituent and the particle diameter of LiFePO4 effectively; The gained LiFePO4 is the nano-grade lithium iron phosphate that CNT coats; Particle is tiny, even, purity is high; Having higher charge/discharge capacity, good high rate performance and good circulation performance, is the ideal material of making lithium ion battery.Principal claim: 1. the nano lithium iron phosphate material that coats of a CNT, it is characterized in that with the CNT being clad material, add doped chemical and improve conductivity, and the LiFePO4 particle diameter is a nano-scale.
The weak point that the product that the ferric lithium phosphate precursor preparation methods of above-mentioned open source literature report obtains exists is that technology is complicated; Product purity is not high; Particle is big, distribution of particles is inhomogeneous, thus cause that its electron-ion conductivity is not good, capacity, multiplying power and cycle life performance also have with a certain distance from the requirement that is applied to production practices.
Summary of the invention
Shortcoming such as the purpose of this invention is to provide that a kind of ferric lithium phosphate precursor preparation technology that can overcome prior art is complicated, product purity is not high, particle is big and distribution of particles is inhomogeneous; The electrode material function admirable that the presoma of feasible preparation is processed; It is good to have under high power capacity, the high magnification discharge capacity and voltage platform property; The nano ferric phosphate presoma preparation method who has extended cycle life, and the method for preparing the nano-grade lithium iron phosphate electrode material with obtained presoma.
The present invention is based on such discovery: have the LiFePO4 electrode material that the nano-scale iron phosphate grains is done the presoma preparation, both kept the pattern of ferric phosphate presoma basically, have the meticulous nano particle littler again than presoma.In fact, 95% weight is to be made up of ferric phosphate in the LiFePO4 electrode material, and therefore, preparation earlier has the ferric phosphate presoma of nano-scale, prepares the nano-grade lithium iron phosphate with meticulousr nano-scale structure again, has special advantages undoubtedly.
Technical scheme of the present invention is achieved in that the ferric phosphate presoma FP that at first preparation has nano-scale or nanometer size particles, and then makes the LiFePO4 electrode material with superfine nano size (particle diameter is less than 100nm) sphere or torispherical or spherical particle with FP.Specifically comprise the following steps:
(1) reacts in water with the Fe source compound of certain mol proportion and P source compound and make band crystallization water nanometer presoma series FP1, make waterless nano presoma series FP2 through the crystallization water that adds among the heat abstraction FP1;
(2) the mixed nano ferric phosphate series of Li source compound in molar ratio with certain carbon-source cpd, hybrid reaction in water or organic solvent forms the first ferric lithium phosphate precursor LFP1 with nano-scale size;
(3) in inert atmosphere, calcine LFP1, can make the second ferric lithium phosphate precursor LFP2 with nano-scale size;
(4) in inert atmosphere, calcine presoma LFP1 or LFP2, can make superfine nano sphere or spherical particle electrode material LiFePO4 electrode material.
Wherein nano ferric phosphate presoma FP preparation can divide the following step:
(1) prep solution A and B:A are phosphorus source thing and water mixed liquid, and B is source of iron thing and water mixed liquid;
(2) A and B press certain mol proportion and mix, and add oxidant, become ferric iron to the ferrous oxidation that possibly exist in the mixed liquor with oxidant after; Stir about 2～5 hours also transfers pH value extremely between about 1～6.5; Continue agitating heating, temperature is controlled between 25 ℃～100 ℃, reacts about 1～10 hour;
(3) stop reaction, be cooled to room temperature, precipitation and centrifugal separation is dryouied promptly to get with water washing and is had the crystallization water, has the presoma FP1 of nano-scale;
(4) heating FP1 temperature is controlled between about 250 ℃～600 ℃, and the time is controlled between about 2～20 hours, promptly gets waterless nano ferric phosphate presoma FP2.
Said preparation nano ferric phosphate reaction PH is controlled between about 1～6.5; Iron phosphorus mol ratio is about Fe/P=1.
Described source of iron is iron powder, di-iron trioxide, tri-iron tetroxide, ferric iron source compound such as ferric sulfate, ferric nitrate, ferric nitrate, iron hydroxide, iron chloride etc., one or more mixing in ferrous iron source compound such as ferrous sulfate, ferrous oxide, ferrous nitrate, ferrous hydroxide, the frerrous chloride etc.As having the ferrous iron available oxidant to change into ferric iron to all ferrous irons in the reaction.Described oxidant is H
2O
2, Na
2O
2, NaClO
3In one or more mixing.
Said Fe source compound and P source compound mixing afterreaction temperature are controlled between the room temperature to 100 ℃, and the reaction time is controlled between about 1～10 hour.The gained sediment contains crystallization water ferric phosphate presoma FP1 through centrifugalizing, making after water washing and the drying.
Gained precursor FP1 heating and temperature control is controlled between about 2～20 hours between about 250 ℃～600 ℃ heating time, can make anhydrous iron phosphate presoma FP2.Obtained presoma FP1 and FP2 have the primary granule of about 100～800nm, and primary granule is formed the secondary granule with about 1～100 μ m of micron-scale particle diameter, and tap density is about 0.5～2.5g/cm
3
Have superfine nano sphere or spherical particle LiFePO4 electrode active material with made nano ferric phosphate presoma FP1 or FP2 preparation, its step is following:
(1) Li source compound and ferric phosphate presoma are with certain mol proportion; Mix in water or organic solvent with a certain amount of carbon-source cpd; Temperature is controlled between about room temperature to the solution boiling point, and the time is controlled between about 2～8 hours, forms the first nano-grade lithium iron phosphate presoma LFP1.
(2) gained LFP1 has been placed inert atmosphere furnace, under inert gas shielding, temperature is controlled at about 2～10 hours of 300 ℃～450 ℃ calcinings.Cooling back crushing screening makes the second nano-grade lithium iron phosphate presoma LFP2.
(3) gained LFP1 or LFP2 are placed inert atmosphere furnace; Under inert gas shielding, calcined 2～5 hours in about 300 ℃～450 ℃; Continue to be warming up to about 2～15 hours of about 500 ℃～800 ℃ calcinings, make after the cooling and have superfine nano particle sphere or spherical particle lithium iron phosphate positive material LFP.
Described Li source compound is one or more mixing in lithium carbonate, lithia, lithium acetate, lithium hydroxide, lithium oxalate, lithium formate, lithium phosphate, lithium fluoride, lithium iodide, lithium nitrate, lithium chloride, lithium sulfate and the lithium dihydrogen phosphate.
Said ferric phosphate presoma be the present invention prepared contain crystallization water ferric phosphate FP1 (FePO
4NH
2O) and anhydrous iron phosphate FP2 (FePO
4).
Said solution is that water is or/and organic solvent comprises one or more combinations in methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, n-butanol, isobutanol, acetone, butanone, diacetyl, ethylene glycol, dimethylformamide (DMF) and the acetonitrile.
Described carbon-source cpd is DIC, organic carbon, high molecular polymer or natural extract carbon compound, and carbon-source cpd is every moles iron weight 1-30g.Wherein inorganic carbon source comprises wherein one or more combinations of conductive carbon black, acetylene carbon black, nano-sized carbon, CNT, Graphene and graphene complex; Organic carbon source comprises wherein one or more combinations of sucrose, fructose, glucose hexadecanol, carboxylic acid compound malonic acid, adipic acid, acrylic acid, salicylic acid, laurate, ascorbic acid, oleic acid, isocaproic acid and citric acid; High molecular polymer be gather ethanol (PEG), polyvinyl alcohol (PVA), gather ethanol butyral (PVB), polypropylene, polyvinylpyrrolidone (PUP) and polyacrylic wherein one or more combinations; Described natural extract carbon source is wherein one or more combinations of oleum sojae, cellulose and cellulose derivative thereof, chitin, starch and kerosene.
Said inert gas is that oxygen-free atmosphere can charge into inert gas such as argon gas, nitrogen and reducibility gas hydrogen are realized through vacuumizing.
Said Li: Fe: the P mol ratio approximately is: 1: 1: 1.
The obtained nano ferric phosphate presoma of the present invention specifically has following characteristic: the primary granule with the about 100～800nm of nano-scale particle diameter.The nanometer primary granule is formed the secondary granule of about 1～100 μ m of micron-scale particle diameter, the about 0.5～2.0g/cm of nano ferric phosphate presoma tap density
3
The above superfine nano LiFePO4 electrode material preparation method; Obtained electrode material product has following characteristic: particle keeps the pattern of nano ferric phosphate presoma basically; Its primary granule is superfine nano sphere or the torispherical particle littler than presoma primary granule, the about 10～100nm of its particle diameter; The primary granule composition has the secondary granule that the nano-scale particle diameter is about 100～800nm; Secondary granule is formed the particle with about 1～100 μ m of micron-scale particle diameter, and superfine nano LiFePO4 electrode material tap density is about 0.7～2.5g/cm
3Products made thereby not only has higher charge/discharge capacity, good multiplying power property and cycle performance, and also the preparation method is simple, is easy to realize industrialization.
Lithium iron phosphate positive material with such spherical super fine nano particle has excellent chemical property: higher charge/discharge capacity, taller and bigger multiplying power discharging platform, better charge-discharge magnification and excellent cycle performance.
The lithium iron phosphate positive material that the ferric phosphate presoma for preparing with the present invention further makes is compared with existing nano-lithium ion electrode active material, and its outstanding substantive distinguishing features and marked improvement is:
Can significantly improve chemical property, it is little to have a particle, high power capacity, and high magnification, the high magnification voltage platform is good, advantage such as have extended cycle life, and also preparation method's technology is simple, and preparation cost is low, is easy to large-scale industrialization production.
The obtained LiFePO4 electrode material of the ferric phosphate presoma that utilizes the present invention to prepare not only has the good electric chemical property, and the preparation process is simple, efficient, environmental protection, safety.
Description of drawings
Fig. 1 is the simple sketch map of technical process of the present invention: the ferric lithium phosphate precursor FP1 or the FP2 of the present invention's preparation, preparation has superfine nano size, sphere or torispherical particle lithium iron phosphate positive material LFP.
Fig. 2: the present invention's preparation contains crystallization water ferric phosphate presoma FP1 (FePO
42H
2O) X-ray powder diffraction figure.
Fig. 3: the present invention prepares anhydrous iron phosphate presoma FP2 (FePO4) X-ray powder diffraction figure.
The present invention shown in Fig. 4 A, the 4B prepares ferric phosphate presoma FP1 different resolution Electronic Speculum figure.
The present invention shown in Fig. 5 A, the 5B prepares anhydrous iron phosphate presoma FP2 different resolution Electronic Speculum figure.
Shown in Figure 6, with the obtained lithium iron phosphate positive material X-ray powder diffraction of the ferric phosphate presoma figure of the present invention's preparation.
Shown in Fig. 7 A, 7B, the 7C, prepare the obtained lithium iron phosphate positive material different resolution of ferric phosphate presoma Electronic Speculum figure with the present invention.
Fig. 8 gained lithium iron phosphate positive material is processed button cell different multiplying charging and discharging curve figure.
Shown in Fig. 1 schematic drawing; Have superfine nano sphere or torispherical LiFePO4 electrode material synthetic schemes: with the superfine nano ferric phosphate presoma FP1 or the FP2 of the present invention's preparation; Mix in molar ratio with Li source compound, add LiFePO4 first presoma LFP1 or the LFP2 that carbon-source cpd makes nano-scale.FP1 or FP2 calcined under inert gas shielding make lithium iron phosphate positive material LFP with superfine nano sphere or torispherical particle.
Fig. 2 has provided the present invention's preparation and has contained crystallization water ferric phosphate presoma FP1 (FePO
42H
2O) X-ray powder diffraction figure has shown FePO among the figure
42H
2The peak value of O.
Fig. 3 has provided the present invention and has prepared anhydrous iron phosphate presoma FP2 (FePO
4) X-ray powder diffraction figure, shown the peak value of FePO4 among the figure.
Fig. 4 A, 4B, 5A, 5B diagram, the present invention made ferric phosphate presoma FP1 and FP2 different resolution Electronic Speculum figure.By the visible FP1 and FP2 primary granule of figure is the ultra-fine grain that particle diameter is about 100～800nm, and it is the secondary granule of 1～100 μ m that such primary granule is formed particle diameter.
Fig. 7 A, 7B, the present invention of 7C diagram prepare the Electronic Speculum figure of LiFePO4 electrode material LFP different resolution.It is thus clear that LiFePO4 keeps the pattern of ferric phosphate presoma basically, its primary granule is the further sphere or the torispherical particle of segmentation of presoma primary granule, the about 10～100nm of its particle diameter by figure; Primary granule is formed the secondary granule that particle diameter is about 100～800nm, and secondary granule is formed the micron particles that particle diameter is about 1～100 μ m.
Therefore, prepare earlier and have certain pattern and superior in quality ferric phosphate presoma FP, further preparation is had meticulousr nano-scale and the good lithium iron phosphate positive material of chemical property has special advantages.
Shown in Figure 8, the present invention makes positive electrode and processes high rate charge-discharge capacity and the good discharge voltage conservation rate that button cell has excellence.Here describe charging/discharging voltage with discharge capacitance and lie prostrate at 2.0-4.2, measured capacity is with respect to the percentage of the capacity under the 0.2C multiplying power when some discharge-rate C.Can know at 0.2C by Fig. 8,1C, 3C, 5C, 10C 20C, under 30C, 40C and the 50C discharge-rate, its corresponding capacity (mAh/g) is about 164,155,142,139,131,119,110,100,92 respectively.The capacity of relative 0.2C, the discharge-rate capability retention is about respectively: 1C95%, 3C 87%, 5C 85%, 10C 80%, 20C 73%, and 30C 67%, 40C 61% and 50C 56%.
Embodiment
Embodiment 1:
Solution A 1:55.8 restrains NH
4H
2PO
4Mix with 400ml water.Solution B 1:139g FeSO
47H
2O mixes with 500ml water.Under agitation pour solution B 1 into A1, under agitation slowly add 27%H after mixing
2O
2Solution or etc. mole powder NaClO
3After being converted into ferric iron to all ferrous irons, regulate about PH=2.5, the gained mixed solution heat about 90 ℃ about 4 hours.With precipitation and centrifugal separation, use deionized water wash, 104 ℃ of oven for drying promptly get the ferric phosphate presoma FP1 that contains the crystallization water.
Gained FP1 about 5 hours of about 500 ℃ of heating, is promptly got the anhydrous iron phosphate presoma FP2 of the water that decrystallizes.
The presoma primary granule that obtains is about the 100-500 nanometer, and such primary granule is formed the secondary granule that particle diameter is about 1～100 μ m.
Use Li: Fe: the P mol ratio is about 1: 1: 1 Li
2CO
3And FP2, and the cellulose acetate of the every moles iron of about 15g mixes in isopropyl alcohol, stirs about 40 ℃ of heating down and promptly gets ferric lithium phosphate precursor LFP1 in about 4 hours.LFP2 was being calcined about 5 hours at about 350 ℃ under the argon shield, and crushing screening behind the natural cooling promptly makes LFP2.LFP2 was calcined about 12 hours at 700 ℃ under argon shield, promptly make lithium iron phosphate positive material LFP.
Basically keep the pattern of nano ferric phosphate presoma by the visible LFP particle of Fig. 6, Fig. 7 A, 7B, 7C, but its primary granule is superfine spherical or the torispherical particle littler than presoma primary granule, its size is about 15～70nm; The primary granule composition has the secondary granule that the nano-scale particle diameter is about 100～800nm; Secondary granule is formed the particle with about 1～100 μ m of micron-scale particle diameter, and the material tap density is about 0.95g/cm
3It is as shown in Figure 8 that the different multiplying of the button cell that makes with positive electrode with gained LFP charges and discharge electrograph.Under the 2.0-4.2V charging/discharging voltage, under 0.2C, 3C, 5C, 10C, 20C, 30C, 40C, the 50C discharge-rate, its respective volume is respectively 164,155,142,139,131,119,110,100,92.
Embodiment 2:
Solution A 2:135 restrains FeCl
36H
2O mixes with about 700ml water.Solution B 2:57.7g85% phosphoric acid mixes with 200ml water.Mixed solution B2 is under agitation poured in the A2 mixed liquor, and it is 2.80 that pH value is transferred in the back that stirs, and the step that repeats example one then prepares FP1, FP2, LFP1, LFP2 and LFP.
The X-ray powder diffraction figure of obtained FP2, FP2, LFP and different resolution Electronic Speculum figure and example one obtained FP1, FP2, LFP are same or similar.The button cell 0.2C multiplying power discharging capacity that the LFP positive electrode is processed is 158mAh/g.
Embodiment 3:
Solution A 3: about 57.6g phosphoric acid mixes with 300ml water.Solution B 3: about 192g ferric nitrate mixes with 400ml water.After under agitation pouring B1 into A1 solution, regulate PH and be about 2.0, heat about 70 ℃ about 4 hours, precipitation and centrifugal separation is used water washing, must contain the ferric phosphate presoma FP1 of the crystallization water after the oven dry.
With prepared ferric phosphate presoma FP1; After equimolar lithium source mixture (mol ratio is 1: 1 lithium acetate and a lithium hydroxide mixture) mixes in water; Every mole of phosphoric acid iron adds the polypropylene of 20g, dries behind the mixing mixing, promptly gets ferric lithium phosphate precursor LFP1.LFP1 was calcined about 5 hours at about 350 ℃ under argon shield, be warming up to about 12 hours of 700 ℃ of calcinings then, promptly make lithium iron phosphate positive material LFP.
The button cell 0.2C multiplying power discharging capacity that uses prepared LFP to process as positive electrode is 150mAh/g.
Embodiment 4:
Solution A 4:1.2kg 85% phosphoric acid mixes with 10L water.0.5kg iron powder under agitation slowly adds among the A4, does not stop to be stirred to till all iron powder dissolvings, slowly adds 27%H then
2O
2After solution is converted into ferric iron to all ferrous irons, regulates PH and be about 3.0, be heated to 50 ℃ of insulations after about 4 hours with sediment centrifugal filtration, with deionized water wash clean back oven dry, make band crystallization water ferric phosphate presoma FP1.
Moles of hydrogen lithia and FP1 such as use in water, to mix, every mole of FP1 adds the cellulose acetate of about 30g weight.Make the LiFePO4 first presoma LFP1.LFP1 about 350 ℃ of calcinings 5 hours, is warming up to about 700 ℃ again and continues about 12 hours of calcining under argon shield, makes lithium iron phosphate positive material LFP behind the natural cooling.Figure is identical with Fig. 7 for its X-ray powder diffraction of obtained LFP.Different resolution Electronic Speculum figure and Fig. 7 A, 7B, 7C are similar.The LFP particle keeps the pattern of nano ferric phosphate presoma basically, but its primary granule is sphere or the torispherical particle littler than presoma primary granule, the about 15～70nm of its particle diameter; The primary granule composition has the secondary granule that the nano-scale particle diameter is about 100～800nm; Secondary granule is formed the particle with about 1～100 μ m of micron-scale particle diameter, and the material tap density is about 0.90g/cm
3The button cell 0.2C multiplying power discharging capacity of processing as positive electrode with prepared LFP is about 155mAh/g.
Claims (7)
1. superfine nano electrode material method preparing phosphate iron lithium; It is characterized in that: at first prepare ferric phosphate presoma FP with nano-scale or nanometer size particles; And then make with FP and to have particle diameter less than the superfine nano sphere of 100nm or the LiFePO4 electrode material of torispherical or spherical particle, specifically comprise the following steps:
(1) reacts in water with the Fe source compound of certain mol proportion and P source compound and make band crystallization water nanometer presoma series FP1, make waterless nano presoma series FP2 through the crystallization water that adds among the heat abstraction FP1;
(2) the mixed nano ferric phosphate series of Li source compound in molar ratio with certain carbon-source cpd, hybrid reaction in water or organic solvent forms the first ferric lithium phosphate precursor LFP1 with nano-scale size;
(3) in inert atmosphere, calcine LFP1, make the second ferric lithium phosphate precursor LFP2 with nano-scale size;
(4) in inert atmosphere, calcine presoma LFP1 or LFP2, make superfine nano sphere or spherical particle electrode material LiFePO4 electrode material.
2. the described superfine nano electrode material of claim 1 method preparing phosphate iron lithium is characterized in that: nano ferric phosphate presoma FP preparation comprises the following steps:
(1) prep solution A and B:A are phosphorus source thing and water mixed liquid, and B is source of iron thing and water mixed liquid;
(2) A and B press certain mol proportion and mix, and add oxidant, become ferric iron to the ferrous oxidation that possibly exist in the mixed liquor with oxidant after; Stir about 2～5 hours is also transferred between pH value to 1～6.5; Continue agitating heating, temperature is controlled between 25 ℃～100 ℃, reacts 1～10 hour;
(3) stop reaction, be cooled to room temperature, precipitation and centrifugal separation is dryouied promptly to get with water washing and is had the crystallization water, has the presoma FP1 of nano-scale;
(4) heating FP1 temperature is controlled between about 250 ℃～600 ℃, and the time promptly gets waterless nano ferric phosphate presoma FP2 between controlling 2～20 hours;
Said preparation nano ferric phosphate reaction PH is controlled between about 1～6.5; Iron phosphorus mol ratio is Fe/P=1;
Described source of iron is iron powder, di-iron trioxide, tri-iron tetroxide, ferric iron source compound and one or more mixing of ferrous iron source compound; Ferrous iron need change into ferric iron with oxidant;
Described oxidant is H
2O
2, Na
2O
2And NaClO
3In one or more mixing.
3. the described superfine nano electrode material of claim 2 method preparing phosphate iron lithium is characterized in that:
Said Fe source compound and P source compound mixing afterreaction temperature are controlled between the room temperature to 100 ℃, between 1～10 hour reaction time.
4. the described superfine nano electrode material of claim 1 method preparing phosphate iron lithium is characterized in that: have superfine nano sphere or spherical particle LiFePO4 electrode active material with made nano ferric phosphate presoma FP1 or FP2 preparation, its step is following:
(1) Li source compound and ferric phosphate presoma are with certain mol proportion; Mix in water or organic solvent with a certain amount of carbon-source cpd; Temperature is controlled between room temperature to the solution boiling point, and the time was controlled between 2～8 hours, forms the first nano-grade lithium iron phosphate presoma LFP1;
(2) gained LFP1 has been placed inert atmosphere furnace, under inert gas shielding, temperature is controlled at 300 ℃～450 ℃ calcinings 2～10 hours, and cooling back crushing screening makes the second nano-grade lithium iron phosphate presoma LFP2;
(3) gained LFP1 or LFP2 are placed inert atmosphere furnace; Under inert gas shielding, calcined 2～5 hours in 300 ℃～450 ℃; Continue to be warming up to 500 ℃～800 ℃ calcinings 2～15 hours, make after the cooling and have superfine nano particle sphere or spherical particle lithium iron phosphate positive material LFP;
Described Li source compound is one or more mixing in lithium carbonate, lithia, lithium acetate, lithium hydroxide, lithium oxalate, lithium formate, lithium phosphate, lithium fluoride, lithium iodide, lithium nitrate, lithium chloride, lithium sulfate and the lithium dihydrogen phosphate;
Said ferric phosphate presoma be the present invention prepared contain crystallization water ferric phosphate FP1 (FePO
4NH
2O) and anhydrous iron phosphate FP2 (FePO
4);
Said Li: Fe: the P mol ratio is: 1: 1: 1.
5. the described superfine nano electrode material of claim 4 method preparing phosphate iron lithium, it is characterized in that: said solution is that water is or/and organic solvent comprises one or more combinations in methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, n-butanol, isobutanol, acetone, butanone, diacetyl, ethylene glycol, dimethylformamide (DMF) and the acetonitrile.
6. the described superfine nano electrode material of claim 4 method preparing phosphate iron lithium; It is characterized in that: described carbon-source cpd is DIC, organic carbon, high molecular polymer or natural extract carbon compound; Carbon-source cpd is every moles iron weight 1-30g, and wherein inorganic carbon source comprises wherein one or more combinations of conductive carbon black, acetylene carbon black, nano-sized carbon, CNT, Graphene and graphene complex; Organic carbon source comprises wherein one or more combinations of sucrose, fructose, glucose hexadecanol, carboxylic acid compound malonic acid, adipic acid, acrylic acid, salicylic acid, laurate, ascorbic acid, oleic acid, isocaproic acid and citric acid; High molecular polymer be gather ethanol (PEG), polyvinyl alcohol (PVA), gather ethanol butyral (PVB), polypropylene, polyvinylpyrrolidone (PUP) and polyacrylic wherein one or more combinations; Described natural extract carbon source is wherein one or more combinations of oleum sojae, cellulose and cellulose derivative thereof, chitin, starch and kerosene.
7. the described superfine nano electrode material of claim 4 method preparing phosphate iron lithium is characterized in that: inert gas is oxygen-free atmosphere or charges into inert gas and realize that described inert gas is argon gas, nitrogen or reducibility gas through vacuumizing.
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| US13036566 | 2011-02-28 | ||
| US13/036,566 US9139429B2 (en) | 2010-03-02 | 2011-02-28 | High performance cathode material LiFePO4, its precursors and methods of making thereof |
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Citations (4)
| 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 |
| CN101378125A (en) * | 2007-08-28 | 2009-03-04 | 比亚迪股份有限公司 | Method for preparing active substance lithium iron phosphate for lithium ion secondary battery anode |
| JP2010218884A (en) * | 2009-03-17 | 2010-09-30 | Nippon Chem Ind Co Ltd | Lithium phosphorous complex oxide-carbon composite and method of manufacturing the same, positive electrode active material for lithium secondary battery, and lithium secondary battery |
| CN101859891A (en) * | 2010-06-03 | 2010-10-13 | 清华大学 | Lithium battery electrode material |
-
2011
- 2011-07-23 CN CN2011102188276A patent/CN102683674A/en active Pending
Patent Citations (5)
| 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 |
| CN101568489A (en) * | 2007-05-28 | 2009-10-28 | 比亚迪股份有限公司 | Method for preparing lithium iron phosphate as a positive electrode active material for a lithium ion secondary battery |
| CN101378125A (en) * | 2007-08-28 | 2009-03-04 | 比亚迪股份有限公司 | Method for preparing active substance lithium iron phosphate for lithium ion secondary battery anode |
| JP2010218884A (en) * | 2009-03-17 | 2010-09-30 | Nippon Chem Ind Co Ltd | Lithium phosphorous complex oxide-carbon composite and method of manufacturing the same, positive electrode active material for lithium secondary battery, and lithium secondary battery |
| CN101859891A (en) * | 2010-06-03 | 2010-10-13 | 清华大学 | Lithium battery electrode material |
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