CN101931073B - Preparation method of lithium iron phosphate/carbon composite cathode material - Google Patents
Preparation method of lithium iron phosphate/carbon composite cathode material Download PDFInfo
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- CN101931073B CN101931073B CN2009100875110A CN200910087511A CN101931073B CN 101931073 B CN101931073 B CN 101931073B CN 2009100875110 A CN2009100875110 A CN 2009100875110A CN 200910087511 A CN200910087511 A CN 200910087511A CN 101931073 B CN101931073 B CN 101931073B
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Abstract
The invention discloses a preparation method of a lithium iron phosphate/carbon composite cathode material. The method comprises the following steps: 1) mixing materials for carrying out ball milling treatment, wherein the materials comprises a lithium source, an iron source, a phosphorus source and a carbon source, and the iron source is ferric oxide and/or ferroferric oxide; 2) drying the materials after the ball milling, pressing into tablets, and carrying out presintering on the tablets in a tubular furnace under a non-oxidizing atmosphere; and 3) smashing the obtained tablets, then carrying out re-grinding, pressing into the tablets, carrying out secondary sintering on the tablets in the tubular furnace under the non-oxidizing atmosphere and obtaining the composite cathode material. The Cu or Mg-doped lithium iron phosphate/carbon composite material can be obtained by adding doping elements into the materials. The method utilizes the raw materials with simplicity and low price, has simple preparation process conditions and low sintering temperature, and can greatly reduce the production cost and be conductive to industrial implementation. Furthermore, the method utilizes an in-situ formed carbon material to control the particle size of lithium iron phosphate, and the actual capacity of the obtained lithium iron phosphate/carbon composite cathode material is high.
Description
Technical field
The present invention relates to a kind of preparation method of LiFePO4/carbon composite anode material.
Background technology
Operating voltage height, specific energy are high, capacity is big, self discharge is little, cyclicity is good because of having for lithium ion battery, the ideal source of long service life, in light weight, outstanding advantage becomes portable electric appts such as mobile phone, notebook computer such as volume is little.Meanwhile, for alleviating ambient pressure, electronic and hybrid-electric car is competitively developed in countries in the world.Core technology wherein is exactly the high-performance secondary cell.According to the market prediction of day USA and Europe, Vehicular battery will be main with lithium ion battery after 2010.
Relative negative material, the development of positive electrode is comparatively slow, and that can commercially produce in a large number at present still mainly is cobalt acid lithium (LiCoO
2).This material will use expensive cobalt resource, and is not only poisonous and have a safety issue under the overcharge conditions.Except that the cobalt acid lithium of layer structure, the lithium nickelate (LiNiO of transition metal oxide such as layer structure
2) and the LiMn2O4 (LiMn of spinel structure
2O
4) also be main positive electrode.LiNiO wherein
2Theoretical capacity is higher, but poor heat stability, preparation difficulty, is prone to side reaction takes place, thereby influences the capacity and the cycle performance of battery.LiMn
2O
4Cycle performance is poor, specific capacity is lower.LiFePO4 (the LiFePO of olivine-type structure in recent years
4) positive electrode causes people's extensive concern.This material has plurality of advantages such as specific capacity height, environmental friendliness and thermal stability height, is expected to become anode material for lithium-ion batteries of new generation.
But LiFePO
4Itself electronic conductivity and lithium ion conductivity are all too low, have limited making full use of of its active material, are badly in need of improving its actual specific capacity.Research shows that carbon coats the performance that can improve material greatly, and therefore, the focus of research mostly concentrates on the compound positive electrode of carbon-coated LiFePO 4 for lithium ion batteries at present.
LiFePO
4The preparation method mainly be high temperature solid phase synthesis, the lithium source of use mainly is a lithium carbonate, source of iron mainly is a ferrous oxalate, carbon source mainly is a sucrose.But be to use feedstock production LiFePO such as ferrous oxalate
4Costing an arm and a leg of LiFePO4 be can cause, its competitive advantage and application widely limited.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing LiFePO4/carbon composite anode material.
The method for preparing LiFePO4/carbon composite anode material provided by the present invention comprises the steps:
1) with carrying out ball-milling treatment after the mixing of materials; Said material comprises lithium source, source of iron, phosphorus source and carbon source, and wherein, said source of iron is di-iron trioxide and/or tri-iron tetroxide;
2) with the drying materials behind the step 1) ball milling, compressing tablet is in tube furnace, slice, thin piece being carried out presintering under the non-oxidizing atmosphere;
3) with step 2) slice, thin piece that obtains grinds after pulverizing once more, and compressing tablet in tube furnace, slice, thin piece being carried out double sintering under the non-oxidizing atmosphere, obtains said composite positive pole.
Wherein, the time of ball-milling treatment described in the step 1) specifically can be 1-30h, and the rotating speed of ball mill can be 200-2000 rev/min in the said ball-milling treatment.
The detailed process of carrying out presintering step 2) is following: the temperature of tube furnace is risen to pre-sintering temperature 250-450 ℃ by room temperature, keep said pre-sintering temperature, sintering 1-30h cools the temperature to room temperature then; In the said presintering process, heating rate and rate of temperature fall are 1-50 ℃/min.
The detailed process of carrying out double sintering in the step 3) is following: the temperature of tube furnace is risen to sintering temperature 500-800 ℃ by room temperature, keep said sintering temperature, sintering 1-30h cools the temperature to room temperature then; In the said double sintering process, heating rate and rate of temperature fall are 1-50 ℃/min.
Form step 2) and step 3) described in the gas of non-oxidizing atmosphere be at least a in the following gas: nitrogen, argon gas, hydrogen, helium and carbon dioxide.
Step 2) pressure of compressing tablet can be 1-30Mpa and in the process of compressing tablet described in the step 3).
In step 3), carbon source had not only played the effect of reducing atmosphere but also had limited the growth of ferric phosphate lithium grain, also increased the conductivity of final material.
Among the present invention, said material can only be made up of lithium source, source of iron, phosphorus source and carbon source, also can comprise mantoquita or magnesium salts.
When said material was made up of lithium source, source of iron, phosphorus source and carbon source, stoichiometric proportion Li: Fe: P=1 was pressed in lithium source, source of iron and phosphorus source in the said material: mix at 1: 1, the quality of carbon source is the 5%-35% of said material gross mass in the said material.The composite positive pole that obtain this moment is LiFePO4/carbon composite anode material.
When said material is made up of lithium source, source of iron, phosphorus source, mantoquita and carbon source; Lithium source, source of iron, phosphorus source and mantoquita are pressed stoichiometric proportion Li: Fe: P: Cu=1: (1-x) in the said material: 1: x mixes; Wherein, 0.01≤x≤0.1, the quality of carbon source is the 5%-35% of said material gross mass in the said material.The composite positive pole that obtain this moment is copper doped iron phosphate lithium/carbon composite anode material.
In said material, comprise magnesium salts; Lithium source, source of iron, phosphorus source and magnesium salts are pressed stoichiometric proportion Li: Fe: P: Mg=1: (1-x) in the said material: 1: x mixes; Wherein, 0.01≤x≤0.1, the quality of carbon source is the 5%-35% of said material gross mass in the said material.The composite positive pole that obtain this moment is magnesium doped iron phosphate lithium/carbon composite anode material.
Among the present invention, said lithium source specifically can be one or more in lithium carbonate, lithium chloride, lithium nitrate, lithium fluoride, lithium sulfate and the lithium hydroxide; Said phosphorus source specifically can be one or more in ammonium dihydrogen phosphate, ammonium hydrogen phosphate and the ammonium phosphate; Said carbon source specifically can be one or more in sucrose, glucose, alginic acid and the starch; Said mantoquita specifically can be one or more in cupric oxide, copper chloride, copper nitrate, copper sulphate and the alginic acid copper; Said magnesium salts specifically can be one or more in magnesia, magnesium chloride, magnesium nitrate, magnesium sulfate and the alginic acid magnesium.
The invention provides the method that a kind of large-scale low-cost prepares the compound positive electrode of LiFePO4/carbon of height ratio capacity.This method is compared with existing solid phase synthesis process, and its outstanding advantage is: selecting cheap di-iron trioxide or tri-iron tetroxide for use is source of iron, and process conditions are simple relatively, greatly reduce production cost; And utilize the particle diameter of the cheap material with carbon element control LiFePO4 of environmental protection; Thereby obtain the LiFePO4/carbon composite anode material of height ratio capacity; Can reach 162mAh/g like the specific discharge capacity of non-doped samples under the 0.1C multiplying power, the specific discharge capacity of doped samples under the 0.1C multiplying power can reach 167mAh/g.
Description of drawings
Fig. 1 is the X ray diffracting spectrum (XRD) of lithium iron phosphate among the embodiment 1.
Fig. 2 is the electron scanning micrograph of lithium iron phosphate among the embodiment 1.
Fig. 3 be among the embodiment 1 lithium iron phosphate as anode material for lithium-ion batteries, the discharge curve under the 0.1C multiplying power.
Fig. 4 is the X ray diffracting spectrum (XRD) of Cu doped iron lithium phosphate/carbon composite among the embodiment 10.
Fig. 5 is the electron scanning micrograph of Cu doped iron lithium phosphate/carbon composite among the embodiment 10.
Fig. 6 is the X ray diffracting spectrum (XRD) of Mg doped iron lithium phosphate/carbon composite among the embodiment 16.
Fig. 7 is the electron scanning micrograph of Mg doped iron lithium phosphate/carbon composite among the embodiment 16.
Embodiment
Below in conjunction with specific embodiment the present invention is described further, but the present invention is not limited to following examples.
Experimental technique described in the following embodiment like no specified otherwise, is conventional method; Said reagent and material like no specified otherwise, all can obtain from commercial sources.
By Li: Fe: P=1: 1: 1 mol ratio takes by weighing Li
2CO
3, Fe
2O
3And NH
4H
2PO
4, add simultaneously that to account for all material mass fractions be 25% alginic acid.With mixed material in ball mill with 1000 rev/mins rotating speed, be placed in 60 ℃ of baking ovens dry behind the ball milling 15h.The gained material carries out compressing tablet with 20Mpa again, is placed on then to carry out presintering in the tube furnace, and the speed with 10 ℃/min under the nitrogen protection rises to 350 ℃ by room temperature, reduces to room temperature with the speed of 15 ℃/min behind the constant temperature 12h.With above-mentioned material ball milling (rotating speed is 1000 rev/mins, ball milling 3 hours) once more, compressing tablet (pressure is 20Mpa), and under nitrogen protection, in tube furnace, carry out sintering once more.Sintering step is: the speed with 5 ℃/min rises to 600 ℃ by room temperature, reduces to room temperature with the speed of 10 ℃/min behind the constant temperature 15h.Obtain lithium iron phosphate thus.
The sign of lithium iron phosphate:
With powder x-ray diffraction (Rigaku DmaxrB, CuK
αRay) crystal structure of analysis lithium iron phosphate.The result is as shown in Figure 1.As can be seen from the figure, there is not impurity peaks in the spectrogram, explains that product purity is high.Because the carbon of gained is noncrystalline structure, so there is not its diffraction maximum.
Characterized the pattern of this lithium iron phosphate with scanning electron microscopy (JEOL-6700F), as shown in Figure 2.Visible by figure, the particle of this material is very little and relatively more even.
The chemical property of lithium iron phosphate characterizes:
The lithium iron phosphate for preparing among the embodiment 1, acetylene black and Kynoar binding agent are made into slurry with mass ratio mixing in 80: 10: 10, are coated to equably and obtain anodal diaphragm on the aluminum foil current collector.As negative pole, polypropylene microporous barrier (Celgard 2400) is as barrier film with metal lithium sheet, 1mol/L LiPF
6(solvent is that volume ratio is 1: 1 ethylene carbonate and a dimethyl carbonate mixed liquor) is assembled into the Swagelok pattern and intends battery as electrolyte in the glove box of argon shield.
The battery of above-mentioned assembling is carried out the constant current charge-discharge test on Arbin BT2000 charge-discharge test appearance, charge-discharge magnification is 0.1C, and the charging/discharging voltage interval is 2.5-4.2V.The 5th time discharge curve is as shown in Figure 3, can find out that by figure the discharge capacity of this LiFePO4/carbon composite anode material can reach 162mAh/g.The composition of the lithium iron phosphate for preparing in the present embodiment and simulated battery test result are listed in table 1.
By Li: Fe: P=1: 1: 1 mol ratio takes by weighing Li
2CO
3, Fe
2O
3And NH
4H
2PO
4, add mass fraction simultaneously and be 20% sucrose.Prepare lithium iron phosphate by method identical among the embodiment 1 then, different is that sintering temperature is 650 ℃ for the second time, and constant temperature time is 10h.
The positive pole of simulated battery, negative pole, electrolyte and battery assembling are identical with embodiment 1, and the composition of gained LiFePO4/carbon composite anode material reaches and lists in table 1 in the test result of simulated battery.
Embodiment 3, preparation lithium iron phosphate
By Li: Fe: P=1: 1: 1 mol ratio takes by weighing Li
2CO
3, Fe
2O
3(NH
4)
2HPO
4, add mass fraction simultaneously and be 10% alginic acid.Prepare lithium iron phosphate by method identical among the embodiment 1 then, different is that sintering temperature is 625 ℃ for the second time, and constant temperature time is 10h.
The positive pole of simulated battery, negative pole, electrolyte and battery assembling are identical with embodiment 1, and the composition of gained LiFePO4/carbon composite anode material reaches and lists in table 1 in the test result of simulated battery.
Embodiment 4, preparation lithium iron phosphate
By Li: Fe: P=1: 1: 1 mol ratio takes by weighing Li
2CO
3, Fe
3O
4And NH
4H
2PO
4, add mass fraction simultaneously and be 5% glucose.Prepare lithium iron phosphate by method identical among the embodiment 1 then, different is that sintering temperature is 700 ℃ for the second time, and constant temperature time is 8h.
The positive pole of simulated battery, negative pole, electrolyte and battery assembling are identical with embodiment 1, and the composition of gained LiFePO4/carbon composite anode material reaches and lists in table 1 in the test result of simulated battery.
Embodiment 5, preparation lithium iron phosphate
By Li: Fe: P=1: 1: 1 mol ratio takes by weighing LiOH, Fe
3O
4(NH
4)
2HPO
4, add mass fraction simultaneously and be 30% starch.Prepare lithium iron phosphate by method identical among the embodiment 1 then, different is that sintering temperature is 500 ℃ for the second time, and constant temperature time is 30h.
The positive pole of simulated battery, negative pole, electrolyte and battery assembling are identical with embodiment 1, and the composition of gained LiFePO4/carbon composite anode material reaches and lists in table 1 in the test result of simulated battery.
Embodiment 6, preparation lithium iron phosphate
By Li: Fe: P=1: 1: 1 mol ratio takes by weighing LiNO
3, Fe
2O
3(NH
4)
2HPO
4, add mass fraction simultaneously and be 35% alginic acid.Prepare lithium iron phosphate by method identical among the embodiment 1 then, different is that sintering temperature is 800 ℃ for the second time, and constant temperature time is 3h.
The positive pole of simulated battery, negative pole, electrolyte and battery assembling are identical with embodiment 1, and the composition of gained LiFePO4/carbon composite anode material reaches and lists in table 1 in the test result of simulated battery.
Embodiment 7, preparation lithium iron phosphate
By Li: Fe: P=1: 1: 1 mol ratio takes by weighing Li
2SO
4, Fe
2O
3And NH
4H
2PO
4, add mass fraction simultaneously and be 25% alginic acid.Prepare lithium iron phosphate by method identical among the embodiment 1 then, different is that sintering temperature is 600 ℃ for the second time, and constant temperature time is 12h.
The positive pole of simulated battery, negative pole, electrolyte and battery assembling are identical with embodiment 1, and the composition of gained LiFePO4/carbon composite anode material reaches and lists in table 1 in the test result of simulated battery.
Embodiment 8, preparation lithium iron phosphate
By Li: Fe: P=1: 1: 1 mol ratio takes by weighing LiCl, Fe
2O
3(NH
4)
2HPO
4, add mass fraction simultaneously and be 15% glucose.Prepare lithium iron phosphate by method identical among the embodiment 1 then, different is that sintering temperature is 650 ℃ for the second time, and constant temperature time is 12h.
The positive pole of simulated battery, negative pole, electrolyte and battery assembling are identical with embodiment 1, and the composition of gained LiFePO4/carbon composite anode material reaches and lists in table 1 in the test result of simulated battery.
Embodiment 9, preparation lithium iron phosphate
By Li: Fe: P=1: 1: 1 mol ratio takes by weighing Li
2CO
3, Fe
2O
3(NH
4)
3PO
4, add mass fraction simultaneously and be 25% alginic acid.Prepare lithium iron phosphate by method identical among the embodiment 1 then, different is that sintering temperature is 600 ℃ for the second time, and constant temperature time is 10h.
The positive pole of simulated battery, negative pole, electrolyte and battery assembling are identical with embodiment 1, and the composition of gained LiFePO4/carbon composite anode material reaches and lists in table 1 in the test result of simulated battery.
Embodiment 10, preparation Cu doped iron lithium phosphate/carbon composite
By Li: Fe: Cu: P=1: 0.93: 0.07: 1 mol ratio takes by weighing Li
2CO
3, Fe
2O
3, Cu (NO
3)
2And NH
4H
2PO
4, add mass fraction simultaneously and be 25% alginic acid.Prepare Cu doped iron lithium phosphate/carbon composite by method identical among the embodiment 1 then.
The sign of Cu doped iron lithium phosphate/carbon composite:
With powder x-ray diffraction (Rigaku DmaxrB, CuK
αRay) crystal structure of analysis Cu doped iron lithium phosphate/carbon composite.The result is as shown in Figure 4.As can be seen from the figure, each diffraction maximum is consistent basically with the LiFePO4 of unadulterated olivine structural, does not have impurity peaks, explains that the Cu element has been doped in the lattice of LiFePO4 effectively.
Characterized the pattern of this Cu doped iron lithium phosphate/carbon composite with scanning electron microscopy (JEOL-6700F), as shown in Figure 5.Visible by figure, the smoother that becomes of the lithium iron phosphate surface after Cu mixes.
The positive pole of simulated battery, negative pole, electrolyte and battery assembling are identical with embodiment 1, and the composition of gained Cu doped iron lithium phosphate/carbon composite anode material reaches and lists in table 1 in the test result of simulated battery.
Embodiment 11, preparation Cu doped iron lithium phosphate/carbon composite
By Li: Fe: Cu: P=1: 0.95: 0.05: 1 mol ratio takes by weighing Li
2CO
3, Fe
2O
3, CuSO
4(NH
4)
2HPO
4, add mass fraction simultaneously and be 10% alginic acid.Prepare Cu doped iron lithium phosphate/carbon composite by method identical among the embodiment 1 then, different is that sintering temperature is 625 ℃ for the second time, and constant temperature time is 10h.
The positive pole of simulated battery, negative pole, electrolyte and battery assembling are identical with embodiment 1, and the composition of gained Cu doped iron lithium phosphate/carbon composite anode material reaches and lists in table 1 in the test result of simulated battery.
Embodiment 12, preparation Cu doped iron lithium phosphate/carbon composite
By Li: Fe: Cu: P=1: 0.92: 0.08: 1 mol ratio takes by weighing Li
2CO
3, Fe
2O
3, CuSO
4And NH
4H
2PO
4, add mass fraction simultaneously and be 20% sucrose.Prepare Cu doped iron lithium phosphate/carbon composite by method identical among the embodiment 1 then, different is that sintering temperature is 650 ℃ for the second time, and constant temperature time is 10h.
The positive pole of simulated battery, negative pole, electrolyte and battery assembling are identical with embodiment 1, and the composition of gained Cu doped iron lithium phosphate/carbon composite anode material reaches and lists in table 1 in the test result of simulated battery.
Embodiment 13, preparation Cu doped iron lithium phosphate/carbon composite
By Li: Fe: Cu: P=1: 0.97: 0.03: 1 mol ratio takes by weighing LiOH, Fe
3O
4, CuCl
2(NH
4)
2HPO
4, add mass fraction simultaneously and be 30% starch.Prepare Cu doped iron lithium phosphate/carbon composite by method identical among the embodiment 1 then, different is that sintering temperature is 550 ℃ for the second time, and constant temperature time is 12h.
The positive pole of simulated battery, negative pole, electrolyte and battery assembling are identical with embodiment 1, and the composition of gained Cu doped iron lithium phosphate/carbon composite anode material reaches and lists in table 1 in the test result of simulated battery.
Embodiment 14, preparation Cu doped iron lithium phosphate/carbon composite
By Li: Fe: Cu: P=1: 0.99: 0.01: 1 mol ratio takes by weighing LiCl, Fe
2O
3, Cu (NO
3)
2(NH
4)
2HPO
4, add mass fraction simultaneously and be 15% glucose.Prepare Cu doped iron lithium phosphate/carbon composite by method identical among the embodiment 1 then, different is that sintering temperature is 650 ℃ for the second time, and constant temperature time is 12h.
The positive pole of simulated battery, negative pole, electrolyte and battery assembling are identical with embodiment 1, and the composition of gained Cu doped iron lithium phosphate/carbon composite anode material reaches and lists in table 1 in the test result of simulated battery.
Embodiment 15, preparation Cu doped iron lithium phosphate/carbon composite
By Li: Fe: Cu: P=1: 0.9: 0.1: 1 mol ratio takes by weighing LiF, Fe
2O
3, CuCl
2(NH
4)
3PO
4, add mass fraction simultaneously and be 15% glucose.Prepare Cu doped iron lithium phosphate/carbon composite by method identical among the embodiment 1 then, different is that sintering temperature is 625 ℃ for the second time, and constant temperature time is 20h.
The positive pole of simulated battery, negative pole, electrolyte and battery assembling are identical with embodiment 1, and the composition of gained Cu doped iron lithium phosphate/carbon composite anode material reaches and lists in table 1 in the test result of simulated battery.
Embodiment 16, preparation Mg doped iron lithium phosphate/carbon composite
By Li: Fe: Mg: P=1: 0.93: 0.07: 1 mol ratio takes by weighing Li
2CO
3, Fe
2O
3, Mg (NO
3)
2And NH
4H
2PO
4, add mass fraction simultaneously and be 25% alginic acid.Prepare Mg doped iron lithium phosphate/carbon composite by method identical among the embodiment 1 then.
The sign of Mg doped iron lithium phosphate/carbon composite:
With powder x-ray diffraction (Rigaku DmaxrB, CuK
αRay) crystal structure of analysis Mg doped iron lithium phosphate/carbon composite.The result is as shown in Figure 6.As can be seen from the figure, each diffraction maximum is consistent basically with the LiFePO4 of unadulterated olivine structural, does not have impurity peaks, explains that the Mg element has been doped in the lattice of LiFePO4 effectively.
Characterized the pattern of this Mg doped iron lithium phosphate/carbon composite with scanning electron microscopy (JEOL-6700F), as shown in Figure 7.Visible by figure, the smoother that becomes of the lithium iron phosphate surface after Mg mixes.
The positive pole of simulated battery, negative pole, electrolyte and battery assembling are identical with embodiment 1, and the composition of gained Mg doped iron lithium phosphate/carbon composite anode material reaches and lists in table 1 in the test result of simulated battery.
Embodiment 17, preparation Mg doped iron lithium phosphate/carbon composite
By Li: Fe: Mg: P=1: 0.95: 0.05: 1 mol ratio takes by weighing Li
2CO
3, Fe
2O
3, MgSO
4(NH
4)
2HPO
4, add mass fraction simultaneously and be 10% alginic acid.Prepare Mg doped iron lithium phosphate/carbon composite by method identical among the embodiment 1 then, different is that sintering temperature is 625 ℃ for the second time, and constant temperature time is 10h.
The positive pole of simulated battery, negative pole, electrolyte and battery assembling are identical with embodiment 1, and the composition of gained Mg doped iron lithium phosphate/carbon composite anode material reaches and lists in table 1 in the test result of simulated battery.
Embodiment 18, preparation Mg doped iron lithium phosphate/carbon composite
By Li: Fe: Mg: P=1: 0.92: 0.08: 1 mol ratio takes by weighing Li
2CO
3, Fe
2O
3, MgSO
4And NH
4H
2PO
4, add mass fraction simultaneously and be 20% sucrose.Prepare Mg doped iron lithium phosphate/carbon composite by method identical among the embodiment 1 then, different is that sintering temperature is 650 ℃ for the second time, and constant temperature time is 10h.
The positive pole of simulated battery, negative pole, electrolyte and battery assembling are identical with embodiment 1, and the composition of gained Mg doped iron lithium phosphate/carbon composite anode material reaches and lists in table 1 in the test result of simulated battery.
Embodiment 19, preparation Mg doped iron lithium phosphate/carbon composite
By Li: Fe: Mg: P=1: 0.97: 0.03: 1 mol ratio takes by weighing LiOH, Fe
3O
4, MgCl
2(NH
4)
2HPO
4, add mass fraction simultaneously and be 30% starch.Prepare Mg doped iron lithium phosphate/carbon composite by method identical among the embodiment 1 then, different is that sintering temperature is 550 ℃ for the second time, and constant temperature time is 12h.
The positive pole of simulated battery, negative pole, electrolyte and battery assembling are identical with embodiment 1, and the composition of gained Mg doped iron lithium phosphate/carbon composite anode material reaches and lists in table 1 in the test result of simulated battery.
By Li: Fe: Mg: P=1: 0.99: 0.01: 1 mol ratio takes by weighing LiCl, Fe
2O
3, Mg (NO
3)
2(NH
4)
2HPO
4, add mass fraction simultaneously and be 15% glucose.Prepare Mg doped iron lithium phosphate/carbon composite by method identical among the embodiment 1 then, different is that sintering temperature is 650 ℃ for the second time, and constant temperature time is 12h.
Embodiment 21, preparation Mg doped iron lithium phosphate/carbon composite
By Li: Fe: Mg: P=1: 0.9: 0.1: 1 mol ratio takes by weighing LiF, Fe
2O
3, MgCl
2(NH
4)
3PO
4, add mass fraction simultaneously and be 15% glucose.Prepare Mg doped iron lithium phosphate/carbon composite by method identical among the embodiment 1 then, different is that sintering temperature is 625 ℃ for the second time, and constant temperature time is 20h.
The test result of the composition of table 1, LiFePO4/carbon composite anode material, preparation condition and simulated battery
Result based on table 1 can find out that the present invention utilizes cheap di-iron trioxide or tri-iron tetroxide can conveniently prepare LiFePO4/carbon and doped iron phosphate lithium/carbon composite anode material for source of iron.Utilize the present invention not only can reduce the preparation cost of material greatly, and LiFePO4/carbon and doped iron phosphate lithium/carbon composite anode material that the present invention obtains have all shown higher lithium storage content.
Claims (4)
1. the preparation method of a composite positive pole comprises the steps:
1) with carrying out ball-milling treatment after the mixing of materials; Said material comprises lithium source, source of iron, phosphorus source and carbon source, and wherein, said source of iron is a di-iron trioxide; Said lithium source is a lithium carbonate; Said phosphorus source is an ammonium dihydrogen phosphate; Said carbon source is an alginic acid;
2) with the drying materials behind the step 1) ball milling, compressing tablet is in tube furnace, slice, thin piece being carried out presintering under the non-oxidizing atmosphere;
3) with step 2) slice, thin piece that obtains grinds after pulverizing once more, and compressing tablet in tube furnace, slice, thin piece being carried out double sintering under the non-oxidizing atmosphere, obtains said composite positive pole;
The time of ball-milling treatment described in the step 1) is 1-30h, and the rotating speed of ball mill is 200-2000 rev/min in the said ball-milling treatment;
The process of carrying out presintering step 2) is following: the temperature of tube furnace is risen to pre-sintering temperature 250-450 ℃ by room temperature, keep said pre-sintering temperature, sintering 1-30h cools the temperature to room temperature then; In the said presintering process, heating rate and rate of temperature fall are 1-50 ℃/min;
The process of carrying out double sintering in the step 3) is following: the temperature of tube furnace is risen to sintering temperature 500-800 ℃ by room temperature, keep said sintering temperature, sintering 1-30h cools the temperature to room temperature then; In the said double sintering process, heating rate and rate of temperature fall are 1-50 ℃/min;
Step 2) pressure of compressing tablet is 1-30Mpa and in the process of compressing tablet described in the step 3);
Said material is lithium source, source of iron, phosphorus source and carbon source, and stoichiometric proportion Li: Fe: P=1 is pressed in lithium source, source of iron and phosphorus source in the said material: mix at 1: 1, the quality of carbon source is the 5%-35% of said material gross mass in the said material.
2. method according to claim 1 is characterized in that: form step 2) and step 3) described in the gas of non-oxidizing atmosphere be at least a in the following gas: nitrogen, argon gas, hydrogen, helium and carbon dioxide.
3. method according to claim 1 is characterized in that: said material also comprises mantoquita or magnesium salts;
When said material is made up of lithium source, source of iron, phosphorus source, mantoquita and carbon source; Lithium source, source of iron, phosphorus source and mantoquita are pressed stoichiometric proportion Li: Fe: P: Cu=1: (1-x) in the said material: 1: x mixes; Wherein, 0.01≤x≤0.1, the quality of carbon source is the 5%-35% of said material gross mass in the said material;
When said material is made up of lithium source, source of iron, phosphorus source, magnesium salts and carbon source; Lithium source, source of iron, phosphorus source and magnesium salts are pressed stoichiometric proportion Li: Fe: P: Mg=1: (1-x) in the said material: 1: x mixes; Wherein, 0.01≤x≤0.1, the quality of carbon source is the 5%-35% of said material gross mass in the said material.
4. method according to claim 3 is characterized in that: said mantoquita is following at least a: cupric oxide, copper chloride, copper nitrate, copper sulphate and alginic acid copper; Said magnesium salts is following at least a: magnesia, magnesium chloride, magnesium nitrate, magnesium sulfate and alginic acid magnesium.
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| CN102097617A (en) * | 2011-01-12 | 2011-06-15 | 福建师范大学 | Method for depositing silicon thin film on surface of lithium iron phosphate anode in lithium ion battery |
| KR101345559B1 (en) * | 2011-12-21 | 2014-01-02 | 한국기초과학지원연구원 | Recovery method of lithium using electrochemistry process |
| CN102745663B (en) * | 2012-07-09 | 2014-12-17 | 四川金网通电子科技有限公司 | Method for preparing lithium iron phosphate material |
| CN102731082A (en) * | 2012-07-10 | 2012-10-17 | 李永康 | High-performance lithium iron phosphate material and synthesis method thereof |
| CN103618083B (en) * | 2013-11-16 | 2015-11-18 | 河南福森新能源科技有限公司 | The production method of high-capacity high-compaction lithium iron phosphate anode material |
| JP6156823B2 (en) * | 2014-03-28 | 2017-07-05 | 学校法人 関西大学 | Binders, electrodes and electrochemical devices |
| CN109192924A (en) * | 2018-09-30 | 2019-01-11 | 山东精工电子科技有限公司 | A kind of method of carbon encapsulated material destressing and residual carbon |
| CN112563472A (en) * | 2020-12-16 | 2021-03-26 | 远景动力技术(江苏)有限公司 | Polymer composite lithium iron phosphate anode material and preparation method thereof |
| CN115632131A (en) * | 2022-11-18 | 2023-01-20 | 洲际高能科技(北京)有限公司 | Lithium ion battery anode material and preparation method thereof |
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