CN102386396A - Preparation method of niobium and barium activated lithium iron phosphate anode materials - Google Patents
Preparation method of niobium and barium activated lithium iron phosphate anode materials Download PDFInfo
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- CN102386396A CN102386396A CN2011103357055A CN201110335705A CN102386396A CN 102386396 A CN102386396 A CN 102386396A CN 2011103357055 A CN2011103357055 A CN 2011103357055A CN 201110335705 A CN201110335705 A CN 201110335705A CN 102386396 A CN102386396 A CN 102386396A
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Abstract
The invention relates to a preparation method of niobium and barium activated lithium iron phosphate anode materials, which includes mixing raw materials of a lithium source, an iron source, a phosphoric acid root source, a niobium source and a barium source according to the following ratio by mole: 1 part of lithium, 0.00002 to 0.00005 part of niobium, 0.0003 to 0.003 part of barium, 1 part of iron and 1 part of phosphoric acid root, milling the raw materials in an absolute ethyl alcohol medium for 20 hours through a high-speed ball with 200r/mimn rotating speed, drying the raw materials under the temperature between 105 DEG C and 120 DEG C to obtain a precursor, placing the precursor obtained by drying in a high-temperature furnace and conducting high-temperature calcination on the precursor under the temperature between 500 DEG C and 750 DEG C for 24 hours in an atmosphere of nitrogen to obtain the niobium and barium activated lithium iron phosphate anode materials. Due to the fact that a small quantity of niobium and barium is mingled for replacement, appearance and particle diameter of products can be favorably controlled to obtain stable lithium iron phosphate compound. Lattice of the products is activated, diffusion coefficient of lithium ions is improved, and first discharging capacity of obtained materials reaches 160.52mAh/g. Electrode potential of a charging-discharging platform is about 3.5V relative to lithium, initial discharging capacity surpasses 168mAh/g, and the capacity attenuates by about 1.2% after 100 times of charging-discharging circulation. Compared with an unmingled LiFePO4 contrast embodiment, specific capacity and circulation stability are greatly improved.
Description
Technical field
Niobium of the present invention, barium activation lithium iron phosphate positive material preparation method belong to a kind of anode material of lithium battery preparation method, particularly a kind of ferric phosphate lithium cell method for preparing anode material.
Background technology
At present; The research present situation of LiFePO4 doping vario-property: LiFePO4 LiFePO4 is because of it is nontoxic, environmentally friendly, safe, abundant, high, the stable cycle performance, cheap of specific capacity in raw material source; Steady discharge platform with theoretical capacity 3.5V of 170mAh/g; LiFePO 4 material has high energy density, cheap price, excellent security, is specially adapted to electrokinetic cell.But its resistivity is bigger.Because LiFePO4; Under the normal temperature, the dynamics of LiFePO4 is bad, the high rate performance extreme difference; Domestic and international research persons have used such as methods such as coating, doping, nanometerizations and have improved high rate performance, and basic idea improves conductivity exactly and shortens ion, electric transmission path.Doping is one type of important material modification method.2002, reported first lithium position doping vario-properties such as Massachusetts science and engineering Chiang professor Yet-Ming can improve the LiFePO4 electronic conductivity greatly.They carry out the doping of high volence metal ion (Mg2+, Al3+, Ti4+, Zr4+, Nb5+ and W6+) solid solution in the lithium position, electronic conductivity has improved 8 one magnitude.Sample through above-mentioned doping has better electrochemical performance, and particularly high-rate performance discharges under the electric current of 21.5C (3225mA/g), still can obtain the capacity of 60mAh/g.Doping carbon: carbon has good electric conductivity and lower mass density, adds a spot of carbon of people, can improve the electric conductivity of material on the one hand, can reduce the particle diameter yardstick of material on the other hand.Xxx has studied different phase and has mixed the influence of people's carbon to material electrochemical performance.Shi Zhicong etc. " adopt solid phase reaction to combine the high speed ball-milling method, synthetic positive electrode LiFePO4, experiment shows: LiFePO4 has the discharge voltage plateau of 3.4V, and discharge capacity only decays 9.5% after reaching 147mAh/g charge and discharge cycles 100 times first.LiFePO4/C composite material behind the carbon dope, the granule-morphology rule, spherical for class, particle is little, and particle size distribution is all colluded.Carbon is scattered between the crystal grain, has strengthened the electrical conductance between the particle.LiFePO4 specific discharge capacity and cycle performance behind the carbon dope all significantly improve.Mix in the lithium position: the LiFePO4 crushed grain is assorted to be a kind of important method of improving chemical property.Mix and can improve the conductivity of LiFePO4 in the lithium position.Tan Xianyan etc. " " adopt the calcination method synthesizing lithium ionic cell positive pole material lithium iron phosphate, mix a spot of Mg2+ and have significantly improved conductivity of electrolyte materials, have improved the chemical property of LiFePO4.After the doping, LiFePO4 discharge capacity first reaches 135.52mAh/g; Unadulterated LiFePO4 discharge capacity first has only 116.25mAh/g.Conductivity after the doping has obtained certain raising.This is because doping little metal ion replaces the Li+ position, constitutes the p N-type semiconductor N, has increased the conductivity of material.The identical ^ of Liu adopts that improved solid phase method has prepared that particle is fine, the uniform LiFePO4 of particle size distribution and Li0,98Mn, and the o.o2LiFePO4 compound, mixing helps controlling the pattern and the particle diameter of product on a small quantity, obtains stable LiFePO4 compound.Because Mn2+ octahedral coordination radius, can think that magnesium ion occupies the replacement lithium ion less than Fe2+.The result shows: the relative lithium electrode current potential of the charge and discharge platform of lithium ion is about 3.5V in the material, and initial discharge capacity surpasses 160mAh/g, and capacity only decays 5.5% after 50 charge and discharge cycles, shows that this method has improved specific energy and cyclical stability.The iron position is assorted disastrously: can improve conductivity of electrolyte materials though mix in the lithium position, because foreign atom can hinder the diffusion of lithium ion in the one dimension passage, thereby be unfavorable for improving the high-rate charge-discharge capability of material.And the rate charge-discharge performance of iron position doping can improvement LiFePO4 improves cycle performance.^ such as Liu Fangling adopt parcel carbon to improve its surface electronic conductivity, and doped metal ion is to improve its body electronic conductivity.Chosen ionic radius near and 4 different metal ion species Ca3+ of valence state; Ti5+, Ta5+, mix in the Fe position of MO6+; Sample unit cell volume after the doping all has minimizing; Electronic conductivity has improved the 4-6 one magnitude than the electronic conductivity of LiFePO4, and its impedance in electrolyte solution is significantly reduced, and chemical property also obviously improves.^ such as Hu Huanyu adopt the synthetic particle tiny and uniform nanoscale positive electrode LiFePO4 of high-temperature solid phase reaction method, have good capacity cycle performance, but its high rate capability are poor.Mix a spot of manganese and can reduce the polarization of material, improve the high rate capability of material.This mainly is because the doping of manganese has increased the unit cell volume of LiFePO4; More help deviating from of lithium; The doping of manganese has caused sintering process to produce crystal structure defects in addition, has improved the electron conduction of material, thereby has made the high-rate charge-discharge capability of material make moderate progress.The phosphate potential crushed grain is assorted: P site doped is feasible in theory, but the doping of carrying out phosphate potential is separately seldom arranged.^ such as Zhang Yurong have studied olivine structural Li2+2xTi2-xCu2x (NbO) 2, and having obtained conductivity through Ti and Cu replacement P is that 1.26 * 10-6S/cm-adds, and initial discharge capacity is the positive electrode of 805.8mAh/g.Said material has higher conductivity, but owing to Fe is all replaced by Ti and Cu, ' guiding discharge voltage is lower, and cycle performance is poor.Though phosphate potential is feasible in theory, study less relatively.
Through retrieval, put down in writing 1043 of relevant lithium battery applications for a patent for invention, 2181 of lithium ion battery applications for a patent for invention at present, wherein having a great deal of is relevant method of mixing.
Confirm it is the lithium position in theory, or the iron position, or phosphate potential obtains mixing and role, and relevant authoritative experts still have different separately brilliant idea, also constantly studying, exploring.
Present more consistent viewpoint is, LiFePO4 has that fail safe is good, pollution-free, stable cycle performance, specific capacity is high and advantage such as cheap, but also has poorly conductive and the lower shortcoming of tap density.Poorly conductive is to influence the biggest factor that LiFePO4 is used, and can conductivity be improved through mixing, and high-rate charge-discharge capability also improves, and has suppressed the effect of capacity attenuation to a certain extent.The doping approach can improve, improve the lithium ion anode material performance, has been a kind of feasible mode of generally acknowledging.
Summary of the invention
The objective of the invention is to: based on the structural limitations of the lithium iron phosphate positive material (LiFePO4) of prior art; There are its poorly conductive and the low deficiency of lithium ion diffusion coefficient, propose niobium, barium activation lithium iron phosphate positive material preparation method that a kind of niobium, barium activation improve its performance.
The present invention can improve, improve the lithium ion anode material performance in view of the doping approach, has been a kind of feasible mode of generally acknowledging.According to the chemical property of barium/lithium, electric property, crystal structure characteristic is the characteristics of akin element:
Barium is element the most active in the alkaline-earth metal, because it is very active, and oxidized easily, should be kept in kerosene and the atoleine.
5.212 electron-volts of ionization energy, the first ionization energy 502.9kJ/mol;
Crystal structure: structure cell is a body centred cubic cell, and each structure cell contains 2 metallic atoms;
Cell parameter: a=502.8pm; B=502.8pm; C=502.8pm; α=90 °; β=90 °; γ=90 °.
Lithium, metallic element can react with a large amount of inorganic reagents and organic reagent.With equal ability such as oxygen, nitrogen, sulphur chemical combination, the deepening owing to be prone to oxidated, and density is littler than kerosene, so should deposit in the atoleine.
5.392 electron-volts of ionization energy, the first ionization energy 520.2kJ/mol;
Crystal structure: structure cell is a body centred cubic cell, and each structure cell contains 2 metallic atoms;
Cell parameter: a=351pm; B=351pm; C=351pm; α=90 °; β=90 °; γ=90 °.
Think that barium should be to be easy to the doping effect of lithium position most.The present invention be mix through barium make an experiment, in the situation of mixing with barium, can add 1-2 other element again, constitute 2 yuan or 3 yuan of doping, with obtained performance anode material of lithium battery preferably.
Niobium of the present invention, barium activation lithium iron phosphate positive material, it is characterized in that: its chemical composition or chemical general formula can be expressed as: LiNbxBayFePO
4, x=0.00002-0.00005, y=0.0003-0.003; Wherein the mol of Li, Nb, Ba, Fe, P ratio is: 1mol Li: 0.00002-0.00005mol Nb: 0.0003-0.003mol Ba: 1mol Fe: 1mol P.
Niobium of the present invention, barium activation lithium iron phosphate positive material preparation method is characterized in that: the raw material in its lithium source, source of iron, phosphoric acid root, niobium source, barium source, according to 1mol Li: 0.00002-0.00005mol Nb: 0.0003-0.003mol Ba: 1mol Fe: after the 1mol P mixed; In ethanol medium; Rotating speed 200-800r/mimn high speed ball milling 15-20h with 105-120 ℃ of oven dry, obtains presoma; The presoma that oven dry is obtained places in the high temperature furnace; In blanket of nitrogen,, promptly get niobium of the present invention, barium activation lithium iron phosphate positive material through 500-750 ℃ of high-temperature calcination 16-24h.Its chemical composition is: Li Nb x Bay Fe PO4, x=0.00002-0.00005, y=0.0003-0.003; Wherein the mol of Li, Nb, Ba, Fe, P ratio is: 1mol Li: 0.00002-0.00005mol Nb: 0.0003-0.003mol Ba: 1mol Fe: 1mol P.Its lithium source is one of lithium carbonate, lithium hydroxide or lithium dihydrogen phosphate; Source of iron is a ferrous oxalate; The phosphoric acid root is one of ammonium dihydrogen phosphate or diammonium hydrogen phosphate; The niobium source is one of niobic acid, niobium pentaoxide, sodium niobate, and the barium source is one of brium carbonate, barium hydroxide, barium chloride, barium nitrate, barium monoxide, barium sulphide.
The present invention's beneficial effect compared with prior art: niobium of the present invention, barium activation lithium iron phosphate positive material preparation method; The gained material is perhaps because mix a small amount of substitute niobium, barium; Help controlling the pattern and the particle diameter of product, obtain stable LiFePO4 compound, niobium, barium ions occupy the replacement lithium ion; Its lattice has obtained activation, has improved the lithium ion diffusion coefficient; Product unit cell volume after niobium mixes all has minimizing, and electronic conductivity improves than the electronic conductivity of LiFePO4, and its impedance in electrolyte solution is significantly reduced, and chemical property also obviously improves; Its first discharge capacity reach 160.52mAh/g; The relative lithium electrode current potential of its charge and discharge platform is about 3.5V, and initial discharge capacity surpasses 168mAh/g, and capacity decays about 1.2% approximately after 100 charge and discharge cycles; Specific capacity and cyclical stability and unadulterated LiFePO4 discharge capacity first have only 116.25mAh/g to compare, and are greatly improved.
Embodiment
Below in conjunction with embodiment the present invention is described further, but execution mode of the present invention is not limited thereto.
Below adopt the calcination method synthetic method,, be illustrated niobium of the present invention, barium activation lithium iron phosphate positive material preparation method.
Niobium of the present invention, barium activation lithium iron phosphate positive material preparation method, its lithium source can be used: lithium salts such as lithium carbonate, lithium hydroxide or lithium dihydrogen phosphate, source of iron can be used: ferrous oxalate etc.; The phosphoric acid root can be used: ammonium dihydrogen phosphate or diammonium hydrogen phosphate etc.; The niobium source is niobium sodium niobate (NaNbO3), niobic acid NbO3; Niobium pentaoxide (Nb2O5), the barium source can be used: barium salts such as brium carbonate, barium hydroxide, barium chloride, barium nitrate, barium monoxide, barium sulphide etc.Select for use: lithium carbonate (Li2CO3) (99.73%), niobium pentaoxide (Nb2O5) (AR), brium carbonate (BaCO3) (99.8%), ferrous oxalate (FeC2O4.2H2O) (99.06%), diammonium hydrogen phosphate (NH4H2PO4) (98%) is a raw material; According to 1mol Li: 0.00002-0.00005mol Nb: 0.0003-0.003mol Ba: 1mol Fe: after the 1mol P mixed, in ethanol medium, rotating speed 200-800r/mimn high speed ball milling 15-20h; With 105-120 ℃ of oven dry; Obtain presoma, the presoma that oven dry is obtained places in the high temperature furnace, in blanket of nitrogen; Through 500-750 ℃ of high-temperature calcination 16-24h, promptly get niobium of the present invention, barium activation lithium iron phosphate positive material.
Embodiment 1
With Li2CO3 (99.73%); Niobium pentaoxide (Nb2O5) (AR), BaCO3 (99.8%), FeC2O4.2H2O (99.06%); NH4H2PO4 (98%) raw material; According to 1mol Li: 0.00002mol Nb: 0.0003mol Ba: 1mol Fe: after the 1mol P mixed, in absolute ethyl alcohol (AR) medium, high speed ball milling 20h (rotating speed 200r/mimn.After the 105-120 ℃ of oven dry, obtain presoma, the presoma that oven dry is obtained places in the high temperature furnace, in common purity nitrogen (＞99.5%) atmosphere, and through 500-750 ℃, high-temperature calcination 24h.Promptly get niobium of the present invention, barium activation lithium iron phosphate positive material.
Embodiment 2
With Li2CO3 (99.73%); Niobium pentaoxide (Nb2O5) (AR), BaCO3 (99.8%), FeC2O4.2H2O (99.06%); NH4H2PO4 (98%) raw material; According to 1mol Li: 0.00004mol Nb: 0.001mol Ba: 1mol Fe: after the 1mol P mixed, in absolute ethyl alcohol (AR) medium, high speed ball milling 20h (rotating speed 200r/mimn.After the 105-120 ℃ of oven dry, obtain presoma, the presoma that oven dry is obtained places in the high temperature furnace, in common purity nitrogen (＞99.5%) atmosphere, and through 500-750 ℃, high-temperature calcination 24h.Promptly get niobium of the present invention, barium activation lithium iron phosphate positive material.
Embodiment 3
With Li2CO3 (99.73%); Niobium pentaoxide (Nb2O5) (AR), BaCO3 (99.8%), FeC2O4.2H2O (99.06%); NH4H2PO4 (98%) raw material; According to 1mol Li: 0.00005mol Nb: 0.003mol Ba: 1mol Fe: after the 1mol P mixed, in absolute ethyl alcohol (AR) medium, high speed ball milling 20h (rotating speed 200r/mimn.After the 105-120 ℃ of oven dry, obtain presoma, the presoma that oven dry is obtained places in the high temperature furnace, in common purity nitrogen (＞99.5%) atmosphere, and through 500-750 ℃, high-temperature calcination 24h.Promptly get niobium of the present invention, barium activation lithium iron phosphate positive material.
Embodiment 4 (not mixing contrast)
With Li2CO3 (99.73%), FeC2O4.2H2O (99.06%), NH4H2PO4 (98%) raw material, according to 1molLi: 1mol Fe: after the 1mol P mixed, in absolute ethyl alcohol (AR) medium, high speed ball milling 20h (rotating speed 200r/mimn.After the 105-120 ℃ of oven dry, obtain presoma, the presoma that oven dry is obtained places in the high temperature furnace, in common purity nitrogen (＞99.5%) atmosphere, and through 500-750 ℃, high-temperature calcination 24h.Promptly get lithium ion anode material.
Adopt the testing equipment of prior art and the method for testing of prior art,, carry out test result with the control Example of not mixing 4 and be niobium, the barium activation lithium iron phosphate positive material of above embodiment 1-3:
The niobium of embodiment of the invention 1-3, barium activation lithium iron phosphate positive material, discharge capacity reaches more than the 155.52mAh/g first; Unadulterated LiFePO4 discharge capacity first has only in the 116.25mAh/g.
The barium activation lithium iron phosphate positive material of embodiment of the invention 1-3, the relative lithium electrode current potential of its charge and discharge platform is about 3.5V, and initial discharge capacity surpasses 164mAh/g, and capacity decays about 3.0% approximately after 100 charge and discharge cycles.
Barium activation lithium iron phosphate positive material preparation method of the present invention, the back of mixing is assorted, the raising of gained material specific capacity and cyclical stability; Perhaps this be because mix a small amount of substitute niobium, barium; Help controlling the pattern and the particle diameter of product, obtain stable LiFePO4 compound, barium ions occupies the replacement lithium ion; Its lattice has obtained activation, has improved the lithium ion diffusion coefficient; Dopant ion though mixing, barium lithium position can improve conductivity of electrolyte materials, owing to can hinder the diffusion of lithium ion in the one dimension passage, thereby be unfavorable for improving the high-rate charge-discharge capability of material.And the rate charge-discharge performance of iron position doping can improvement LiFePO4 improves cycle performance.Product unit cell volume after niobium mixes all has minimizing, and electronic conductivity improves than the electronic conductivity of LiFePO4, and its impedance in electrolyte solution is significantly reduced, and chemical property also obviously improves; Its first discharge capacity reach 155.52mAh/g; The relative lithium electrode current potential of its charge and discharge platform is about 3.5V, and initial discharge capacity surpasses 164mAh/g, and capacity decays about 3.0% approximately after 100 charge and discharge cycles; Specific capacity and cyclical stability and unadulterated LiFePO4 discharge capacity first have only 116.25mAh/g to compare, and are greatly improved.Be owing to a small amount of substitute niobium, the barium of mixing, help controlling the pattern and the particle diameter of product, obtain stable LiFePO4 compound, its lattice has obtained activation, has improved the result of lithium ion diffusion coefficient.
Claims (2)
1. a niobium, barium activation lithium iron phosphate positive material preparation method is characterized in that: the raw material in its lithium source, source of iron, phosphoric acid root, niobium source, barium source, according to 1mol Li: 0.00002-0.00005mol Nb: 0.0003-0.003mol Ba: 1mol Fe: after the 1mol P mixed; In ethanol medium; Rotating speed 200-800r/mimn high speed ball milling 15-20h with 105-120 ℃ of oven dry, obtains presoma; The presoma that oven dry is obtained places in the high temperature furnace; In blanket of nitrogen,, promptly get niobium, barium activation lithium iron phosphate positive material through 500-750 ℃ of high-temperature calcination 16-24h.
2. niobium according to claim 1, barium activation lithium iron phosphate positive material preparation method; It is characterized in that: its lithium source is one of lithium carbonate, lithium hydroxide, lithium dihydrogen phosphate; Source of iron is a ferrous oxalate; The phosphoric acid root is one of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, and the niobium source is one of niobic acid, niobium pentaoxide, sodium niobate, and the barium source is one of brium carbonate, barium hydroxide, barium chloride, barium nitrate, barium monoxide, barium sulphide.
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Citations (3)
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| JP2006048991A (en) * | 2004-08-02 | 2006-02-16 | Sumitomo Osaka Cement Co Ltd | Positive electrode active material for lithium battery, its manufacturing method, and lithium battery |
| CN101393982A (en) * | 2008-10-28 | 2009-03-25 | 南京海泰纳米材料有限公司 | Method for producing carbon coated nano stage lithium iron phosphate by precipitation |
| CN101582498A (en) * | 2009-06-18 | 2009-11-18 | 东北师范大学 | Method for preparing nanometer ferrous phosphate lithium /carbon composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2006048991A (en) * | 2004-08-02 | 2006-02-16 | Sumitomo Osaka Cement Co Ltd | Positive electrode active material for lithium battery, its manufacturing method, and lithium battery |
| CN101393982A (en) * | 2008-10-28 | 2009-03-25 | 南京海泰纳米材料有限公司 | Method for producing carbon coated nano stage lithium iron phosphate by precipitation |
| CN101582498A (en) * | 2009-06-18 | 2009-11-18 | 东北师范大学 | Method for preparing nanometer ferrous phosphate lithium /carbon composite material |
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