CN102381692A - High-performance lithium ion phosphate materials prepared by microwave method and preparation method of high-performance lithium ion phosphate materials - Google Patents
High-performance lithium ion phosphate materials prepared by microwave method and preparation method of high-performance lithium ion phosphate materials Download PDFInfo
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- CN102381692A CN102381692A CN2010102722502A CN201010272250A CN102381692A CN 102381692 A CN102381692 A CN 102381692A CN 2010102722502 A CN2010102722502 A CN 2010102722502A CN 201010272250 A CN201010272250 A CN 201010272250A CN 102381692 A CN102381692 A CN 102381692A
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Abstract
The invention discloses high-performance lithium ion phosphate materials prepared by a microwave method and a preparation method of the high-performance lithium ion phosphate materials. Under the condition of microwave heating, microwave absorption is added into a precursor to prepare the high-performance lithium ion phosphate materials, the microwave absorption can be used as a heat source during heating, and a lithium ion phosphate end product can be used as a doping substance or a complex. The microwave absorption is divided into a magnetic material and a polarity material, includes the magnetic materials comprising transition elements and rare earth elements, and also includes polarity compounds such as non-face-centered cubic-structure compounds, non-polarity carbonaceous organic materials, metal organic compounds and the like. When the lithium ion phosphate materials are prepared by the method, heat treatment time can be shortened, heat utilization efficiency is improved, the materials have higher electric conductivity and electrochemical performance, and comprehensive performance indexes of the high-performance lithium ion phosphate materials are higher than materials prepared by means of resistance type heating and in an inert atmosphere protection environment under equal conditions. The preparation method is simple and convenient in operation and easy for massive production.
Description
Technical field
The invention belongs to the energy storage material technical field, be specifically related under the microwave selective heating condition, select suitable microwave absorption, the microwave absorbing material when this absorption agent both can be used as heating improves heating efficiency; Can be used as the part of end product again, improve the chemical property of LiFePO 4 material.
Background technology
With one of electromobile, gordian technique that power tool is relevant is energy storage technology.At present, the energy storage technology with commercial value and excellent combination property is the power lithium battery pool technology, and wherein positive electrode material is on the high side owing to it, specific storage is on the low side, harsh the becoming of performance requriements restricts lithium ion battery by the bottleneck of large-scale promotion application.Comparatively sophisticated in the market lithium cell commodity adopt LiCoO more
2Material is as positive pole, yet in the face of high-power electric appliance such as electromobile the time, LiCoO
2Exist thermostability not enough, be easy to potential safety hazard such as blast.This moment spinel type LiMn
2O
4And polyanionic compound is (like LiFePO
4) highlight certain security advantages, for example polyanion type compound adopts anion structure unit (XO
m)
N-(X=P, S, As, Mo and W) replaces stratiform LiCoO
2Oxygen in the structure can effectively prevent the release of oxygen in the charge and discharge process, improves safety performance.But above-mentioned two kinds of equivalent material still exist essential defective separately, for example LiMn
2O
4Poor stability, life-span weak point; Polyanion type LiFePO
4Shortcoming such as conductivity, poor processability.Comparatively speaking, present people are to LiFePO
4The modification exploitation of material shows bigger interest.
Though LiFePO
4Have plurality of advantages, but also there is self inherent shortcoming in it, relatively poor (electric conductivity is 10 like electroconductibility
-9-10
-10S/cm), the lithium ion velocity of diffusion slow (10
-14Cm
2/ s), low, the poor processability of tap density etc., seriously restricted LiFePO
4The practicalization of material.In process of production, the traditional resistor formula type of heating material that needs a person with the qualifications of a general is heated to about 700 degree, and sintering time is not less than 5 hours, and this can make production cost improve greatly, and is unfavorable for the energy-conserving and environment-protective expanding economy.
Microwave heating is a kind of heat treating method that is different from traditional resistor formula type of heating, has characteristics:
(1) rate of heating is fast.Conventional heating all is to utilize heat conducting principle to import heat into inside from the heating object outside like heating such as flame, hot blast, electric heating, steams, and the object core temperature is raise, and is referred to as indirect heating.To make the centre reach required temperature in the process, need the regular hour, need higher outside temperature simultaneously; The relatively poor required time of object of thermal conductivity is just grown.Microwave heating is to make heating object itself become thermal objects, is referred to as whole type of heating, does not need heat conducting process, therefore can cross even heating at short notice.These characteristics can make the relatively poor material of thermal conduction get heat drying at short notice, and energy utilization ratio is improved, and can also make the size of process furnace littler than normal reheating furnace.
(2) even heating.Use the indirect heating mode,, just need the rising outside temperature, be easy to generate outer knot " shell " like this and internal layer folder " life " phenomenon for improving rate of heating.No matter each position shape of object is how during microwave heating, ability uniformly penetrating hertzian wave is all arranged usually, with the generation heat, so the ineffectivity of dielectric material heating is improved greatly.
(3) efficient energy-saving.Microwave has different effects to different substances, contains the polar material and absorbs microwave energy easily and generate heat.Do not contain polarity and then seldom absorb microwave heating.During microwave heating, being heated material generally all is in the heating chamber that is placed on made, and heating chamber is a sealed hollow to electric wave; Microwave can not leak; Can only the heating object bulk absorption, air and cell therefor in the heating chamber all do not have and can generate heat, so thermo-efficiency is high; Therefore the envrionment temperature at workshop can not raise yet simultaneously, and the work production environment is obviously improved.
(4) be easy to control.Compare with conventional heating means, the control of microwave heating can reach the purpose of up-down, start-stop moment as long as controlling power is controlled knob.Because only to object heating itself, air heats hardly in body of heater, the furnace chamber, so thermal inertia is minimum when heating, appliance computer control is suitable for the standard and the robotization control of heat-processed and heating process especially.
(5) selectivity heating.Microwave has different effects to the material of different media characteristic; Microwave is a kind of high-frequency hertzian wave, its range of frequency about 300～300 000MHz (corresponding wavelength is 100～0.1cm) between the 300MHz to 300GHz. it has fluctuation, high frequency property, thermal property and non-thermal property four big fundamental characteristics.Microwave also has wave-particle parallelism as a kind of hertzian wave. and the energy of microwave quantum is 199 * 10
-25～1.99 * 10
-22J. microwave can make the dipole molecule polar side chain with high hunting of frequency, causes the effects such as electromagnetic oscillation of molecule, increases the motion of molecule, causes the generation of heat.
Can know according to physical theory; Medium molecule can be divided into two big types of polar molecule and non-polar molecules. and the center of the positive and negative electric charge of polar molecule does not overlap, and a segment distance is arranged therebetween, can equivalence is that an electricdipole (like water) is outside under the effect of electric field; Make the directional steering of original rambling polar molecule along external electric field; Generation turn to polarization (the positive and negative charge-site of non-polar molecule overlaps, and makes the positive and negative charge center in the molecule only produce displacement polarization along direction of an electric field outside under the effect of electric field) if. external electric field is an alternation, and turning to also of polar molecule will constantly change direction with the variation of electric field so. in this process; Because intermolecular mutual collision; With making electric energy be converted into the kinetic energy of molecule, and then be converted into heat energy, the temperature of object is raise. this shows; Object for the polar molecule composition; Alternating electric field just heats it easily. and the physical quantity of characterized medium degree of polarization under External Electrical Field is specific inductivity. (under action of alternative electric field, the specific inductivity of medium is a plural number, and imaginary component has reflected the loss of medium). in fact; Specific inductivity is not a constant number; Under various conditions, its specific inductivity is also inequality. and therefore for example specific inductivity and the loss ratio general material of water under microwave condition is a lot of greatly, is easier to absorb microwave energy and is heated. and microwave is a kind of hertzian wave of very high frequency; Being radiated at will be by total reflection on the ideal conducting metallic surface. and being radiated at dielectric surface then has sub-fraction to be reflected; And major part can be penetrated into medium inside, and is absorbed by medium gradually in inside and change heat energy into, and its penetration depth depends mainly on the specific inductivity and the electromagnetic frequency of medium. under microwave frequency, can reach several centimetres to its penetration depth of general object.
The present invention proposes in the LiFePO 4 material heat treatment process, to adopt microwave heating simultaneously, selects suitable microwave absorption, and the microwave absorbing material when this absorption agent both can be used as heating improves heating efficiency; Can be used as the part of end product again, improve the chemical property of LiFePO 4 material.
As microwave absorbing material,, can be divided into magnetic microwave absorbing material and electric dipole moment class absorbing material according to the magnetic field and the electric field component of microwave.The former mainly realizes wave-absorbing effect through the magnetic domain " friction " of magneticsubstance, and the latter realizes wave-absorbing effect through " friction " in electric dipole moment and outfield.In order to improve the penetrativity of microwave, reduce surface reflection simultaneously, employed absorbing material can use nano-powder material.
Summary of the invention
First technical problem to be solved by this invention provides a kind of high-performance iron phosphate lithium material of microwave method preparation, and through adding suitable microwave absorption, the microwave absorbing material when this absorption agent both can be used as heating improves heating efficiency; Can be used as the part of end product again, improve the chemical property of LiFePO 4 material.
Second technical problem to be solved by this invention provides a kind of high-performance iron phosphate lithium preparation methods of microwave method preparation, and this method is simple, easy to operate, practical.
The present invention solves the technical scheme that above-mentioned first technical problem adopts: a kind of high-performance iron phosphate lithium material of microwave method preparation; It is characterized in that this high-performance iron phosphate lithium material is through in containing lithium, iron content, phosphorous presoma, adding microwave absorption; Through compound being prepared from, wherein the amount of microwave absorption is 0.05%～50% of a presoma quality summation.
As preferably; Said microwave absorption comprise magneticsubstance perhaps/and polar material; Wherein magneticsubstance is to comprise the magneticsubstance that contains transition group, rare earth element, and polar material is for comprising non-face-centred cubic structure compound, nonpolar carbonaceous organic material or organometallics;
Wherein, said non-face-centred cubic structure compound is for comprise the one or more combination of the compound of Sr, Ca, Mg, Na, Nd, V, Cr, Mn, Fe, Ni, Co, Cu, Mo at least;
Said nonpolar carbonaceous organic material is one or more combination of carbohydrate, ester class, macromolecular compound;
Said organometallics is ferrocene or hydroxy metal salt.
The present invention solves above-mentioned second technical scheme that technical problem adopted: a kind of high-performance iron phosphate lithium preparation methods of microwave method preparation; It is characterized in that step is: will contain lithium, iron content, phosphorous presoma and take by weighing by a certain percentage and be placed in the solvent; And add an amount of microwave absorption and mix; Dry; Place the nonoxidizing atmosphere stove to heat-treat with the mode of microwave heating then and obtain required high-performance iron phosphate lithium material, the amount of wherein said microwave absorption is 0.05%～50% of a presoma quality summation.
Preferably; Said microwave absorption comprise magneticsubstance perhaps/and polar material; Wherein magneticsubstance is to comprise the magneticsubstance that contains transition group, rare earth element, and polar material is for comprising non-face-centred cubic structure compound, nonpolar carbonaceous organic material or organometallics;
Wherein, said non-face-centred cubic structure compound is for comprise the one or more combination of the compound of Sr, Ca, Mg, Na, Nd, V, Cr, Mn, Fe, Ni, Co, Cu, Mo at least;
Said nonpolar carbonaceous organic material is one or more combination of carbohydrate, ester class, macromolecular compound;
Said organometallics is ferrocene or hydroxy metal salt.
As improvement, the temperature of said microwave heating is a room temperature to 900 ℃, and be 10 minutes～24 hours heat-up time; Preferred temperature is 500～800 ℃, 1～5 hour time.
As improvement, said heat treatment process is divided into two sections, and wherein first section temperature is room temperature to 500 ℃, and sintering time is 1～10 hour; Second section temperature is 500～900 ℃, and sintering time is 10 minutes～10 hours.
Preferably, the mol ratio of the said lithium that contains lithium, iron content, phosphorous presoma, iron, phosphorus is 0.8～1.2: 0.8～1.2: 0.8～1.2; The said lithium presoma that contains is one or more the combination in Lithium Hydroxide MonoHydrate, Quilonum Retard, Lithium Acetate, lithium nitrate, Lithium Sulphate, lithium chloride, lithiumbromide, lithium fluoride, lithium nitride, phosphoric acid hydrogen two lithiums, monometallic, the Trilithium phosphate; Said iron content presoma is one or more the combination in iron, iron protoxide, red oxide of iron, ferrous sulfate, tertiary iron phosphate, Iron nitrate, ferrous phosphate, Ferrox, Iron diacetate, the ferrous citrate; Said phosphorous presoma is one or more the combination in phosphoric acid, primary ammonium phosphate, Secondary ammonium phosphate, monometallic, ferrous ammonium phosphate, phosphoric acid hydrogen two lithiums, the Vanadium Pentoxide in FLAKES.
Further preferred, said lithium: iron: the mol ratio of phosphorus is 0.95～1.05: 1: 1.
As preferably, described solvent is inorganic or organic reagent or mixed solution, comprises one or more of water, alcohols, ketone, ethers, acids, macromolecular solution, and the quality of solvent is 0.3～10 times of other reactant presoma quality sums.
Improve, described mixing is carried out through the mode of mechanical stirring or high energy milling again, and mixing time is 1～24 hour.
Improve, the said dry means of spraying drying, direct drying or vacuum filtration that adopt are carried out again.
At last, described non-oxidizing atmosphere is to carry out under one or more inert atmospheres in argon gas, helium, neon, krypton gas, xenon, radon gas or nitrogen, or comprises in hydrogen or the carbon monoxide at reducing gas and to carry out, or carries out in a vacuum.
Compared with prior art; The invention has the advantages that: adopt microwave heating; And adding special absorbing material, this absorption agent can be used as microwave absorption in heat-processed, in the iron lithium phosphate end product, can be used as doped compound or complex chemical compound; Reach all higher effect of ionic conductivity and electronic conductivity, improve the chemical property of matrix material; Can make simultaneously the material property that burns till within a short period of time obviously be superior to adopting traditional heating mode heating gained material, significantly reduce production cost; The composite ferric lithium phosphate material high rate performance that the present invention makes is excellent, and its specific conductivity can surpass 10
- 4S/cm, preparation method used in the present invention is simple, easy to operate, practical, and effect is remarkable, is suitable for the industrialization running.
Description of drawings
Fig. 1 is the XRD figure that embodiment 1 resistance-type heats the LiFePO 4 material of 650 ℃ (a) and 650 ℃ of (b) thermal treatments of embodiment 2 microwave heatings preparation in 1 hour;
Fig. 2 is that the chemical property of corresponding sample among Fig. 1 compares.
Embodiment
Embodiment describes in further detail the present invention below in conjunction with accompanying drawing.
Choose lithium source, source of iron, phosphorus source and microwave absorption presoma, take by weighing by a certain percentage and be placed in the solvent, after in high energy ball mill, mixing; Dry; And place the nonoxidizing atmosphere stove in 350 ℃ of thermal treatment 2h, and then heating was cooled to room temperature to 24 hours in 10 minutes between 500 ℃～900 ℃; Obtain required LiFePO 4 material, microwave heating is used in thermal treatment wherein.
In the said heat treatment process, use microwave as heating source, microwave heater can be selected common equipment on the market for use, and Heating temperature is a room temperature to 900 ℃, and preferred temperature is 500～800 ℃, and be 10 minutes to 24 hours heat-up time.
Said microwave absorption comprise magneticsubstance perhaps/and polar material.Therefore this absorption agent comprises the magneticsubstance (one or more combination in metal, alloy and intermetallic compound, MOX, calcium titanium ore structure, spinel structure, the inverse spinel structure material) that contains transition group, rare earth element; Also may further include polar compound or only use polar compound: like non-face-centred cubic structure compound (one or more combination that comprises the compound of Sr, Ca, Mg, Na, Nd, V, Cr, Mn, Fe, Ni, Co, Cu, Mo at least), nonpolar carbonaceous organic material (combinations of one or more of carbohydrate, ester class, macromolecular compound etc.); Perhaps organometallics (like ferrocene, hydroxy metal salt etc.).This microwave absorption accounts for 0.05%～50% of presoma quality summation.Microwave absorbing material when this microwave absorption both can be used as thermal treatment can be used as doped compound or complex chemical compound again in the iron lithium phosphate end product.
At least comprise in the described presoma containing lithium, iron content and phosphorated compound, its mol ratio is 0.8～1.2: 0.8～1.2: 0.8～1.2, and lithium in the preferred version: iron: the mol ratio of phosphorus is 0.95～1.05: 1: 1.The described lithium presoma that contains is one or more the combination in Lithium Hydroxide MonoHydrate, Quilonum Retard, Lithium Acetate, lithium nitrate, Lithium Sulphate, lithium chloride, lithiumbromide, lithium fluoride, lithium nitride, phosphoric acid hydrogen two lithiums, monometallic, the Trilithium phosphate.Described iron content presoma is one or more the combination in iron, iron protoxide, red oxide of iron, ferrous sulfate, tertiary iron phosphate, Iron nitrate, ferrous phosphate, Ferrox, Iron diacetate, the ferrous citrate.Described phosphorous presoma is one or more the combination in phosphoric acid, primary ammonium phosphate, Secondary ammonium phosphate, monometallic, ferrous ammonium phosphate, phosphoric acid hydrogen two lithiums, the Vanadium Pentoxide in FLAKES.
Said solvent comprises inorganic and organic reagent or mixed solution, and like water, alcohols, ketone, ethers, acids, macromolecular solution etc. one or more, solvent quality is 0.3～10 times of other reactant presoma sums.
Described mixing is carried out through the mode of mechanical stirring or high energy milling.
Described drying can adopt means such as spraying drying, direct drying or vacuum filtration to carry out.
Further specify with specific examples below
Embodiment 1 (simultaneous test)
Choose Z 250, Lithium Hydroxide MonoHydrate and primary ammonium phosphate raw material, Fe in molar ratio: Li: P=1: 1.02: 1 ratio takes by weighing and is placed in the aqueous solution, makes solid content reach 40%; In high energy ball mill, mix 7 hours after evenly; Spraying drying places the resistance-type process furnace then, under argon shield at 350 ℃ of thermal treatment 2h; Then at 650 ℃ of thermal treatment 1h postcooling to room temperature, obtain required LiFePO 4 material.
The XRD of gained material sees Fig. 1 a, can see that wherein material is pure phase LiFePO
4
Electro-chemical test shows that (Fig. 2 a), the capacity of this material was 101mAh/g when 5C discharged and recharged, and conductivity of electrolyte materials is 2X10
-6S/cm.
Embodiment 2
Choose Z 250, Lithium Hydroxide MonoHydrate and primary ammonium phosphate raw material, Fe in molar ratio: Li: P=1: 1.02: 1 ratio takes by weighing and is placed in the aqueous solution, makes solid content reach 40%; In high energy ball mill, mix 7 hours after evenly; Spraying drying places microwave oven (wherein Z 250 is main microwave absorption) then, under argon shield at 350 ℃ of thermal treatment 2h; Then at 650 ℃ of thermal treatment 1h postcooling to room temperature, obtain required LiFePO 4 material.
The XRD of gained material sees Fig. 1 b, can see that wherein material is pure phase LiFePO
4
Electro-chemical test shows (Fig. 2 b), and the capacity of this material was 144mAh/g when 5C discharged and recharged, and conductivity of electrolyte materials is 3.8X10
-5S/cm.
Embodiment 3
Choose Ferrox, lithium nitrate and primary ammonium phosphate raw material, Fe in molar ratio: Li: P=1: 1.02: 1 ratio takes by weighing and is placed in the acetone soln, makes solid content reach 40%, adds the Co of above-mentioned raw materials quality 1% then
3O
4, in high energy ball mill, mix 7 hours after evenly, spraying drying places microwave oven (Co wherein then
3O
4Be main microwave absorption), under argon shield at 350 ℃ of thermal treatment 2h, then at 650 ℃ of thermal treatment 2h postcooling to room temperature, obtain required LiFePO 4 material.
The gained material is pure phase LiFePO
4Electro-chemical test shows when 5C discharges and recharges that the capacity of this material is 150mAh/g, and conductivity of electrolyte materials is 5.1X10
-4S/cm.
Embodiment 4
Choose Ferrox, Lithium Acetate, primary ammonium phosphate, Vanadium Pentoxide in FLAKES raw material; Fe: Li: P: V=0.99 in molar ratio: 1.05: 1: 0.01 ratio takes by weighing and is placed in the aqueous solution, makes solid content reach 40%, adds the sucrose of above-mentioned raw materials quality 8% then; In high energy ball mill, mix 7 hours after evenly; Spraying drying places microwave oven (wherein Vanadium Pentoxide in FLAKES, sucrose are main microwave absorption) then, under argon shield at 350 ℃ of thermal treatment 1h; Then at 700 ℃ of thermal treatment 1.5h postcooling to room temperature, obtain required LiFePO 4 material.
The gained material is pure phase LiFePO
4Electro-chemical test shows when 5C discharges and recharges that the capacity of this material is 158mAh/g, and conductivity of electrolyte materials is 7.2X10
-2S/cm.
Embodiment 5
Choose tertiary iron phosphate, Quilonum Retard, magnesium acetate raw material; Fe: Li: P: Mg=0.99 in molar ratio: 1.02: 1: 0.01 ratio takes by weighing and is placed in the aqueous solution, makes solid content reach 40%, adds the sucrose of above-mentioned raw materials quality 8% then; In high energy ball mill, mix 7 hours after evenly; Spraying drying places microwave oven (wherein sucrose is main microwave absorption) then, under argon shield at 350 ℃ of thermal treatment 2h; Then at 700 ℃ of thermal treatment 2h postcooling to room temperature, obtain required LiFePO 4 material.
The gained material is pure phase LiFePO
4Electro-chemical test shows when 5C discharges and recharges that the capacity of this material is 158mAh/g, and conductivity of electrolyte materials is 7.2X10
-2S/cm.
Embodiment 6
Choose tertiary iron phosphate, Quilonum Retard, magnesium acetate raw material; Fe: Li: P: Mg=1.03 in molar ratio: 1.02: 1: 0.01 ratio takes by weighing and is placed in the ethanolic soln, makes solid content reach 40%, adds the ferrocene of above-mentioned raw materials quality 0.5% and 0.5% iron carbonyl then; In high energy ball mill, mix 7 hours after evenly; Spraying drying places microwave oven (wherein ferrocene, iron carbonyl are main microwave absorption) then, under argon shield at 350 ℃ of thermal treatment 2h; Then at 680 ℃ of thermal treatment 2h postcooling to room temperature, obtain required LiFePO 4 material.
The gained material is pure phase LiFePO
4Electro-chemical test shows when 5C discharges and recharges that the capacity of this material is 160mAh/g, and conductivity of electrolyte materials is 8.0X10
-2S/cm.
Embodiment 7
Choose tertiary iron phosphate, Lithium Hydroxide MonoHydrate, nano oxidized magnesium raw material; Fe: Li: P: Mg=0.93 in molar ratio: 1.02: 1: 0.01 ratio takes by weighing in the mixing solutions that is placed on water and ether (both mass ratioes are 1: 1); Make solid content reach 40%, add the resol of above-mentioned raw materials quality 8% then, the nano level iron protoxide of adding above-mentioned raw materials quality 0.3%, 0.3% nano level nickel oxide and 0.3% nano level red oxide of iron; In high energy ball mill, mix 7 hours after evenly; Spraying drying places microwave oven (wherein resol, nano level iron protoxide, nano level nickel oxide, nano level red oxide of iron are main microwave absorption) then, under argon shield at 350 ℃ of thermal treatment 2h; Then at 650 ℃ of thermal treatment 1.5h postcooling to room temperature, obtain required LiFePO 4 material.
The gained material is pure phase LiFePO
4Electro-chemical test shows when 5C discharges and recharges that the capacity of this material is 159mAh/g, and conductivity of electrolyte materials is 6.7X10
-2S/cm.
Embodiment 8
Choose tertiary iron phosphate, Quilonum Retard, SODIUMNITRATE raw material; Fe: Li: P: Na=0.98 in molar ratio: 1.02: 1: 0.01 ratio takes by weighing in the mixing solutions that is placed on second alcohol and water (both mass ratioes are 1: 1); Make solid content reach 40%; Add the metal iron powder of above-mentioned raw materials quality 0.3% and 0.3% metal cobalt powder, 0.3% Manganse Dioxide then, in high energy ball mill, mix 7 hours after evenly, spraying drying; Place microwave oven (wherein metal iron powder, metal cobalt powder, Manganse Dioxide are main microwave absorption) then; Under argon shield at 350 ℃ of thermal treatment 2h, then at 680 ℃ of thermal treatment 2h postcooling to room temperature, obtain required LiFePO 4 material.
The gained material is pure phase LiFePO
4Electro-chemical test shows when 5C discharges and recharges that the capacity of this material is 154mAh/g, and conductivity of electrolyte materials is 4.3X10
-3S/cm.
Embodiment 9
Choose Ferrox, Z 250, lithium nitrate and primary ammonium phosphate raw material; Fe: Li: P=0.9 in molar ratio: 1.02: 1 ratio takes by weighing in the mixing solutions that is placed on acetone and water (both mass ratioes are 1: 1), makes solid content reach 40%, and wherein the mass ratio of Ferrox and Z 250 is 1: 1; The resol that adds above-mentioned raw materials quality 10% then; In high energy ball mill, mix 7 hours after evenly, spraying drying, (wherein resol, Z 250 are main microwave absorption to place microwave oven then; Both quality be about the presoma quality and 40%); Under argon shield at 450 ℃ of thermal treatment 5h, then at 750 ℃ of thermal treatment 4h postcooling to room temperature, obtain required LiFePO 4 material.
The gained material is pure phase LiFePO
4Electro-chemical test shows when 5C discharges and recharges that the capacity of this material is 138mAh/g, and conductivity of electrolyte materials is 5.3X10
-2S/cm.
Choose Ferrox, Z 250, lithium nitrate and primary ammonium phosphate raw material; Fe: Li: P=1 in molar ratio: 1.02: 1 ratio takes by weighing and is placed in the acetone soln, makes solid content reach 40%, and wherein the mass ratio of Ferrox and Z 250 is 1: 1; The resol that adds above-mentioned raw materials quality 10% then; In high energy ball mill, mix 7 hours after evenly, spraying drying, (wherein resol, Z 250 are main microwave absorption to place microwave oven then; Both quality be about the presoma quality and 25%); Under argon shield at 450 ℃ of thermal treatment 5h, then at 750 ℃ of thermal treatment 3.5h postcooling to room temperature, obtain required LiFePO 4 material.
The gained material is pure phase LiFePO
4Electro-chemical test shows when 5C discharges and recharges that the capacity of this material is 140mAh/g, and conductivity of electrolyte materials is 3.9X10
-2S/cm.
Embodiment 11
Choose iron carbonyl, lithium nitrate and primary ammonium phosphate raw material; Fe: Li: P=1 in molar ratio: 1.1: 1 ratio takes by weighing (wherein the mass ratio of oleic acid and water is 1: 2) in the mixing solutions that is placed on oleic acid and water; Make solid content reach 20%, in high energy ball mill, mix 3 hours then after evenly, spraying drying; Place microwave oven (wherein iron carbonyl, oleic acid are main microwave absorption) then; Under the nitrogen gas shiled at 400 ℃ of thermal treatment 10h, then at 750 ℃ of thermal treatment 4h postcooling to room temperature, obtain required LiFePO 4 material.
The gained material is pure phase LiFePO
4Electro-chemical test shows when 5C discharges and recharges that the capacity of this material is 142mAh/g, and conductivity of electrolyte materials is 5.3X10
-2S/cm.
Embodiment 12
Choose iron carbonyl, lithium nitrate and primary ammonium phosphate raw material; Fe: Li: P=1 in molar ratio: 1.05: 1 ratio takes by weighing and is placed in the acetone soln, makes solid content reach 5%, adds the oleic acid of above-mentioned raw materials quality 10% then; In high energy ball mill, mix 3 hours after evenly; Spraying drying places microwave oven (wherein iron carbonyl, oleic acid are main microwave absorption) then, under argon shield at 300 ℃ of thermal treatment 10h; Then at 700 ℃ of thermal treatment 6h postcooling to room temperature, obtain required LiFePO 4 material.
The gained material is pure phase LiFePO
4Electro-chemical test shows when 5C discharges and recharges that the capacity of this material is 145mAh/g, and conductivity of electrolyte materials is 8.7X10
-2S/cm.
Embodiment 13
Choose iron carbonyl, lithium nitrate and primary ammonium phosphate raw material; Fe: Li: P=1 in molar ratio: 1.02: 1 ratio takes by weighing and is placed in the acetone soln, makes solid content reach 70%, adds the oleic acid of above-mentioned raw materials quality 10% then; In high energy ball mill, mix 3 hours after evenly; Spraying drying places microwave oven (wherein iron carbonyl, oleic acid are main microwave absorption) then, under argon shield at 500 ℃ of thermal treatment 10h; Then at 700 ℃ of thermal treatment 8h postcooling to room temperature, obtain required LiFePO 4 material.
The gained material is pure phase LiFePO
4Electro-chemical test shows when 5C discharges and recharges that the capacity of this material is 140mAh/g, and conductivity of electrolyte materials is 7.6X10
-2S/cm.
Embodiment 14
Choose red stone, lithium nitrate and primary ammonium phosphate raw material; Fe: Li: P=1 in molar ratio: 1.02: 1 ratio takes by weighing and is placed in the ethanolic soln, makes solid content reach 13%, adds the Z 150PH of above-mentioned raw materials quality 10% then; In high energy ball mill, mix 3 hours after evenly; Spraying drying places microwave oven (wherein Z 150PH is main microwave absorption) then, under argon shield at 500 ℃ of thermal treatment 10h; Then at 800 ℃ of thermal treatment 7h postcooling to room temperature, obtain required LiFePO 4 material.
The gained material is pure phase LiFePO
4Electro-chemical test shows when 5C discharges and recharges that the capacity of this material is 120mAh/g, and conductivity of electrolyte materials is 9.3X10
-3S/cm.
Embodiment 15
Choose iron nitrate, lithium nitrate and primary ammonium phosphate raw material; Fe: Li: P=1.06 in molar ratio: 1.02: 1 ratio takes by weighing and is placed in the acetone soln, makes solid content reach 10%, adds the PEG 400 of above-mentioned raw materials quality 15% then; In high energy ball mill, mix 8 hours after evenly; Spraying drying places microwave oven (wherein PEG 400 is main microwave absorption) then, under argon shield at 500 ℃ of thermal treatment 10h; Then at 600 ℃ of thermal treatment 10h postcooling to room temperature, obtain required LiFePO 4 material.
The gained material is pure phase LiFePO
4Electro-chemical test shows when 5C discharges and recharges that the capacity of this material is 123mAh/g, and conductivity of electrolyte materials is 3.1X10
-3S/cm.
Embodiment 16
Choose iron carbonyl, lithium nitrate and primary ammonium phosphate raw material; Fe: Li: P=1.06 in molar ratio: 1.02: 1 ratio takes by weighing and is placed in acetone and ether (mass ratio is 1: the 1) mixing solutions, makes solid content reach 10%, adds the Vestolen PP 7052 of above-mentioned raw materials quality 10% then; In high energy ball mill, mix 8 hours after evenly; Spraying drying places microwave oven (wherein iron carbonyl, Vestolen PP 7052 are main microwave absorption) then, under nitrogen protection at 500 ℃ of thermal treatment 10h; Then at 630 ℃ of thermal treatment 10h postcooling to room temperature, obtain required LiFePO 4 material.
The gained material is pure phase LiFePO
4Electro-chemical test shows when 5C discharges and recharges that the capacity of this material is 125mAh/g, and conductivity of electrolyte materials is 5.3X10
-2S/cm.
Following instance carries out electrochemical property test after above-mentioned LiFePO 4 material is assembled into battery
Embodiment 17
With positive electrode active materials, PVDF, conductive acetylene black be to join in N-Methyl pyrrolidone at 80: 5: 15 by mass ratio; Magnetic agitation evenly after, positive plate is processed in oven dry, and with glove box in be assembled into 2032 button cells; Wherein negative pole is the lithium sheet; Barrier film is a Vestolen PP 7052, and ionogen is 1M LiPF6, and electrolyte quality is than being EC: DMC: EMC=1: 1: 1.
Probe temperature is 25 ℃ of room temperatures, and voltage range is 2.0-4.2V, and current density is 5C=850mA/g.
Above embodiment explains employing microwave heating, and adds special microwave absorption, can reach all higher effect of ionic conductivity and electronic conductivity, improves the electric conductivity and the capacity of LiFePO 4 material.
Claims (12)
1. the high-performance iron phosphate lithium material of microwave method preparation; It is characterized in that this high-performance iron phosphate lithium material is through in containing lithium, iron content, phosphorous presoma, adding microwave absorption; Through compound being prepared from, wherein the amount of microwave absorption is 0.05%～50% of a presoma quality summation.
2. high-performance iron phosphate lithium material according to claim 1; It is characterized in that said microwave absorption comprise magneticsubstance perhaps/and polar material; Wherein magneticsubstance is to comprise the magneticsubstance that contains transition group, rare earth element, and polar material comprises non-face-centred cubic structure compound, nonpolar carbonaceous organic material or organometallics;
Wherein, said non-face-centred cubic structure compound is for comprise the one or more combination of the compound of Sr, Ca, Mg, Na, Nd, V, Cr, Mn, Fe, Ni, Co, Cu, Mo at least;
Said nonpolar carbonaceous organic material is one or more combination of carbohydrate, ester class, macromolecular compound;
Said organometallics is ferrocene or hydroxy metal salt.
3. the high-performance iron phosphate lithium preparation methods of microwave method preparation; It is characterized in that step is: will contain lithium, iron content, phosphorous presoma and take by weighing by a certain percentage and be placed in the solvent; And add an amount of microwave absorption and mix; Drying places the nonoxidizing atmosphere stove to heat-treat with the mode of microwave heating then and obtains required high-performance iron phosphate lithium material, and the amount of wherein said microwave absorption is 0.05%～50% of a presoma quality summation.
4. preparation method according to claim 3; It is characterized in that said microwave absorption comprise magneticsubstance perhaps/and polar material; Wherein magneticsubstance is to comprise the magneticsubstance that contains transition group, rare earth element, and polar material comprises non-face-centred cubic structure compound, nonpolar carbonaceous organic material or organometallics;
Wherein, said non-face-centred cubic structure compound is for comprise the one or more combination of the compound of Sr, Ca, Mg, Na, Nd, V, Cr, Mn, Fe, Ni, Co, Cu, Mo at least;
Said nonpolar carbonaceous organic material is one or more combination of carbohydrate, ester class, macromolecular compound;
Said organometallics is ferrocene or hydroxy metal salt.
5. preparation method according to claim 3, the temperature that it is characterized in that said microwave heating are room temperature to 900 ℃, and be 10 minutes～24 hours heat-up time.
6. preparation method according to claim 5 is characterized in that said heat treatment process is divided into two sections, and wherein first section temperature is room temperature to 500 ℃, and sintering time is 1～10 hour; Second section temperature is 500～900 ℃, and sintering time is 10 minutes～10 hours.
7. preparation method according to claim 3 is characterized in that the mol ratio of the said lithium that contains lithium, iron content, phosphorous presoma, iron, phosphorus is 0.8～1.2: 0.8～1.2: 0.8～1.2; The said lithium presoma that contains is one or more the combination in Lithium Hydroxide MonoHydrate, Quilonum Retard, Lithium Acetate, lithium nitrate, Lithium Sulphate, lithium chloride, Potassium Bromide, lithium fluoride, lithium nitride, phosphoric acid hydrogen two lithiums, monometallic, the Trilithium phosphate; Said iron content presoma is one or more the combination in iron, iron protoxide, red oxide of iron, ferrous sulfate, tertiary iron phosphate, Iron nitrate, ferrous phosphate, Ferrox, Iron diacetate, the ferrous citrate; Said phosphorous presoma is one or more the combination in phosphoric acid, primary ammonium phosphate, Secondary ammonium phosphate, monometallic, ferrous ammonium phosphate, phosphoric acid hydrogen two lithiums, the Vanadium Pentoxide in FLAKES.
8. preparation method according to claim 7 is characterized in that said lithium: iron: the mol ratio of phosphorus is 0.95～1.05: 1: 1
9. preparation method according to claim 3; It is characterized in that described solvent is inorganic or organic reagent or mixed solution; Comprise one or more of water, alcohols, ketone, ethers, acids, macromolecular solution, the quality of solvent is 0.3～10 times of other reactant presoma quality sums.
10. preparation method according to claim 3 is characterized in that described mixing carries out through the mode of mechanical stirring or high energy milling, and mixing time is 1～24 hour.
11. preparation method according to claim 3 is characterized in that the said dry means that sparge dry, direct drying or vacuum filtration that adopt carry out.
12. preparation method according to claim 3; It is characterized in that described non-oxidizing atmosphere is to carry out under one or more inert atmospheres in argon gas, helium, neon, krypton gas, xenon, radon gas or nitrogen; Or comprise in hydrogen or the carbon monoxide at reducing gas and to carry out, or carry out in a vacuum.
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| CN112492869A (en) * | 2020-12-15 | 2021-03-12 | 合肥工业大学 | Prussian blue redox-derived iron-based wave-absorbing material and preparation method thereof |
| CN115744865A (en) * | 2022-12-09 | 2023-03-07 | 山西大学 | Preparation method of vanadium sodium phosphate cathode material based on iron doping and carbon coating |
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| CN101397131A (en) * | 2008-11-04 | 2009-04-01 | 辽宁石油化工大学 | Method for synthesizing doped type lithium iron phosphate |
| CN101764226A (en) * | 2009-01-08 | 2010-06-30 | 横店集团东磁股份有限公司 | Oxygen vacancy-contained and Fe site-doped lithium ferric phosphate and rapid solid-phase sintering method thereof |
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| CN115744865A (en) * | 2022-12-09 | 2023-03-07 | 山西大学 | Preparation method of vanadium sodium phosphate cathode material based on iron doping and carbon coating |
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