CN100551821C - The preparation method of rare earth doped iron lithium phosphate powder - Google Patents
The preparation method of rare earth doped iron lithium phosphate powder Download PDFInfo
- Publication number
- CN100551821C CN100551821C CNB2005101324297A CN200510132429A CN100551821C CN 100551821 C CN100551821 C CN 100551821C CN B2005101324297 A CNB2005101324297 A CN B2005101324297A CN 200510132429 A CN200510132429 A CN 200510132429A CN 100551821 C CN100551821 C CN 100551821C
- Authority
- CN
- China
- Prior art keywords
- lithium
- hours
- rare earth
- preparation
- oven dry
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The invention discloses the preparation method of a kind of rare earth doped iron lithium phosphate powder that belongs to the electrochemical power source technical field of material.This lithium ion battery anode material lithium iron phosphate molecular formula Li
1-xRE
xFePO
4Expression, its concrete preparation method hotchpotch and parent stock mixed once, synthetic through the solid phase method of secondary clacining.Promptly press lithium salts, ferrous salt and phosphoric acid salt and hotchpotch batch mixing in molar ratio, oven dry, low temperature presintering and high temperature secondary calcining obtain rare earth doped iron lithium phosphate powder.With the lanthanide series rare-earth elements compound is hotchpotch, be easy to realize effectively mixing by traditional solid phase method, significantly improve cell container and cycle electric performance, very with practical value, have wide application prospect at secondary lithium battery commonly used and power source cell positive material field.
Description
Technical field
The invention belongs to the electrochemical power source technical field of material.Be particularly related to as using secondary lithium battery or power source preparation method always with a kind of rare earth doped iron lithium phosphate powder of modification lithium-ion battery anode material.
Technical background
Lithium ion battery is the novel green high-power rechargeable battery that occurs early 1990s, numerous advantages such as have that voltage height, energy density are big, good cycle, self-discharge are little, memory-less effect, operating temperature range are wide, be widely used in mobile telephone, notebook computer, portable power tool, electronic instrument, weaponry etc., in electromobile, also have a good application prospect, become the emphasis that competitively research and develop countries in the world at present.Positive electrode material is an important component part of lithium ion battery, in the lithium ion battery charge and discharge process, not only to be provided in the positive and negative electrode lithium intercalation compound the needed lithium of back and forth embedding/take off, form the needed lithium of SEI film but also will bear the negative material surface, therefore, research and develop the key point that high performance positive electrode material has become the lithium ion battery development.Present research mainly concentrates on the lithium-containing transition metal oxide aspect, and transition metal is mainly cobalt, nickel, manganese.In recent years, based on Fe
3+/ Fe
2+The material of redox couple causes people's very big interest, particularly has the iron lithium phosphate (LiFePO of olivine crystal structure
4) become the most promising alternative positive electrode material of recent research.
LiFePO
4That material has is cheap, nontoxic, nonhygroscopic, Environmental compatibility is fine, rich in mineral resources, multiple advantage such as capacity is higher, stability is fine.Goodenough[J.Electrochem.Soc., 144 (1997) 1188] research group has synthesized iron lithium phosphate (LiFePO at first
4), this material has high theoretical specific storage (170mAh/g) as anode material for lithium-ion batteries, greater than commercial LiCoO
2Actual discharge specific storage 140mAh/g, so cause investigator's very big concern.But the electronic conductivity of this material is relatively poor, has greatly limited the application of material under higher current density.The method about this material property of improvement raising of report mainly contains the surface and mixes or coated with conductive carbon material or conductive metal particle at present, improves the intergranular electronic conductivity of fertile material; Relatively large transition element replaces Fe
2+The position, the ionic conductivity of raising material; Partly replace Li and mix micro-high volence metal ion
+Electronic conductivity in the precursor granule can be improved in the position, is a kind of important method of modifying.Chung, S.Y., Chiang, Y.M. etc. (nature material version, Nature materials,, 1 volume, October, 123 pages in 2003) at first use a small amount of high volence metal ion Mg
2+, Al
3+, Ti
4+, Zr
2+, Nb
5+, W
6+Li doped FePO
4, the bigger LiFePO that improved
4Specific conductivity, make LiFePO
4Under high charge-discharge magnification, also have the capacity more than the 60mAh/g, and proposed correspondence
Middle LiFePO
4And FePO
4Two-phase changes the electrical conduction mechanism of the p-n junction transformation that takes place; Shi.S.Q., Chen, L.Q. etc. (physical comment B, Physical Review B, 68 volumes, 19 phases, 195108-1 page or leaf) utilization first principle has calculated the trace Cr Li doped
1-3xCr
xFePO
4Density of electronic states, fermi level, the new electrical conduction mechanism based on the conduction tunnel of dopant ion 3d energy level and Fe, O energy level hydridization has been proposed; Hu, Y.Q., Doeff, M.M., Kostecki, R., Finones, R. (electrochemistry journal, Journal of theElectrochemical Society, 151 volumes, 8 phases, A1279 page or leaf) uses sol-gel method to prepare adulterated Li first
0.98Mg
0.01FePO
4And Li
0.96Ti
0.01FePO
4Positive electrode material has improved LiFePO equally
4The base batteries performance; Ni, J.F. etc. (material wall bulletin, Materials Letters, 59 volumes, 18 phases, 2361 pages) utilization coprecipitation method has prepared mixes Mg
2+, Cu
2+, Zn
2+LiFePO
4Positive pole powder discharges under the C/10 multiplying power, obtains the above capacity of 120mAh/g.In other positive electrode materials, as spinel lithium manganate LiMn
2O
4, Peng Zhengshun [Chinese rare-earth journal, 18 volumes,, 1 phase: 48 in 2000] has studied rare earth Nd, and Ce substitutes the LiMn of Mn position
2O
4Positive electrode material; Yang Shuting etc. [Chinese rare-earth journal, 21 volumes,, 4 phases: 414 in 2003] utilize microwave heating technique to synthesize rear-earth-doped basic LiMn
2-xRE
xO
4(RE=Y, Nd, Gd, Ce) material has been studied different dopant ions and the different doping action rule to its electrochemical reversibility and electrochemical specific capacity.Cobalt acid lithium LiCoO and for example
2In the system, advance equality [JOURNAL OF RARE EARTHS, 21 volumes,, 4 phases: 466 in 2000] Wei and studied LiCo
1-xRE
xO
2(x=0101～0.03), RE=Y, La, Tm and Gd serial rare-earth dopant material.LiNi for another example
0.8Co
0.2O
2In the system, the LiNi of Ce replacement Co has been studied in beans will river etc. [JOURNAL OF RARE EARTHS, 22 volumes,, 5 phases: 644 in 2004]
0.95Ce
0.05O
2Material.Up to now, relevant rare earth element is to iron lithium phosphate LiFePO
4Modifying function research do not appear in the newspapers as yet.
It is doped raw material that the present invention proposes with rare earth lanthanide compound (being designated as RE, down together), utilizes conventional solid-state method to prepare oxygen place doped iron lithium phosphate Li
1-xRE
xFePO
4(0＜x≤0.05) has improved the basic electrical property of this material, makes it have higher charge/discharge capacity and good cycle performance of battery.
Summary of the invention
The object of the present invention is to provide a kind of compound dopedly, significantly improve the preparation method of a kind of rear-earth-doped type LiFePO 4 powder of the anode material for lithium ion battery of parent basis electrical property by rare earth lanthanide.It is characterized in that described lithium ion battery anode material lithium iron phosphate molecular formula Li
1-xRE
xFePO
4Expression, wherein RE is the doped source element, 0＜x≤0.05;
The preparation method's of described rear-earth-doped type LiFePO 4 powder concrete mode is as follows:
Lithium salts, ferrous salt and phosphoric acid salt and rare-earth dopant are pressed element Li: Fe: P: RE=(1-x): 1: 1: batch mixing of the mol ratio of x, added mix grinding medium mixing and ball milling 6～12 hours, after drying under 40～70 ℃, under inert atmosphere or reducing atmosphere, be heated to 400～550 ℃, be incubated 5～10 hours and carry out precalcining; With pre-imitation frosted glass secondary ball milling 6～12 hours, 40～70 ℃ of oven dry down, under inert atmosphere or reducing atmosphere, 550～850 ℃ of secondary clacinings obtained rear-earth-doped iron lithium phosphate Li then
1-xRE
xFePO
4Powder.
Described blending agent is at least a in deionized water, industrial spirit and the dehydrated alcohol.
Described hotchpotch is at least a in oxide compound, oxyhydroxide, muriate, nitrate, vitriol, carbonate, fluorochemical and the organic salt of the lanthanum except that the radioactivity promethium, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium in the lanthanon.
Described lithium salts is Li
2CO
3, LiOH, lithium oxalate, at least a in the Lithium Acetate.
Described ferrous salt is a Ferrox, and Iron diacetate is at least a in iron protochloride, the ferrous sulfate.
Described phosphoric acid salt comprises ammonium phosphate, and Secondary ammonium phosphate is at least a in the primary ammonium phosphate.
Described inert atmosphere or reducing atmosphere are nitrogen, argon gas, at least a in the nitrogen and hydrogen mixture.
The invention has the beneficial effects as follows and utilize the solid phase method that is easy to commercially produce, the doping various widely lanthanide compounds of drawing materials, through the simple stoving process that mixes, by control thermal treatment temp and time, it is good to prepare crystal property, composition is even, rear-earth-doped anode material for lithium ion battery iron lithium phosphate Li
1- xRE
xFePO
4(0＜x≤0.05) powder, first discharge specific capacity can reach 90-140mAh/g under the room temperature.Compare with other metallic cation doping routes, the present invention can significantly improve parent base batteries capacity and capacity cycle performance more, has clear superiority, and is very with practical value, has wide application prospect at secondary lithium battery, particularly power source commonly used with the cell positive material field.
Embodiment
The invention provides a kind of compound dopedly, significantly improve a kind of preparation method of rare earth doped iron lithium phosphate powder of the anode material for lithium ion battery of parent basis electrical property by rare earth lanthanide.Described lithium ion battery anode material lithium iron phosphate molecular formula Li
1-xRE
xFePO
4Expression, wherein RE is the doped source element, 0＜x≤0.05;
The concrete mode of preparation method that described rare earth is mixed LiFePO 4 powder is as follows:
Lithium salts, ferrous salt and phosphoric acid salt and rare-earth dopant are pressed element Li: Fe: P: RE=(1-x): 1: 1: the mol ratio of x is once reinforced, add at least a in deionized water, industrial spirit and the dehydrated alcohol then as the mix grinding medium, mixing and ball milling 6～12 hours, 40～70 ℃ of oven dry; Oven dry back powder is heated to 400～550 ℃ under inert atmosphere or reducing atmosphere, be incubated 5～10 hours and carry out precalcining; With pre-imitation frosted glass secondary ball milling 6～12 hours, 40～70 ℃ of oven dry down, under inert atmosphere or reducing atmosphere, 550～850 ℃ of secondary clacinings obtained rear-earth-doped iron lithium phosphate Li then
1-xRE
xFePO
4Powder.
Described hotchpotch is at least a in oxide compound, oxyhydroxide, muriate, nitrate, vitriol, carbonate, fluorochemical and the organic salt of the lanthanum except that the radioactivity promethium, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium in the lanthanon.
Described lithium salts is Li
2CO
3, LiOH, at least a in lithium oxalate and the Lithium Acetate.
Described ferrous salt is a Ferrox, and Iron diacetate is at least a in iron protochloride, the ferrous sulfate.
Described phosphoric acid salt comprises ammonium phosphate, and Secondary ammonium phosphate is at least a in the primary ammonium phosphate.
Described blending agent is at least a in deionized water, industrial spirit and the dehydrated alcohol.
Described inert atmosphere or reducing atmosphere are nitrogen, argon gas, at least a in the nitrogen and hydrogen mixture.
With rare-earth doped lithium iron phosphate and conductive carbon black, polyvinylidene difluoride (PVDF), by (9～16): (0.875～2.2): 1 mass ratio is coated on the collector aluminium flake after grinding evenly, makes electrode slice, is negative pole with the metal lithium sheet, with the LiPF of 1.0mol/L
6Being dissolved in the solvent with 1: 1 blended ethyl-carbonate of volume ratio and methylcarbonate is electrolytic solution, and polypropylene microporous film is a barrier film, is assembled into the simulation Li-Ion rechargeable battery.
The system of discharging and recharging of the respective battery of described assembling is: press 0.05-0.2C multiplying power constant current charge-discharge under the 2.5V-4.2V stopping potential.
Below by embodiment, further illustrate outstanding feature of the present invention and marked improvement, only be the present invention is described and never limit the present invention.
Embodiment 1
With 0.0975 moles of hydrogen Lithium Oxide 98min LiOHH
2O, 0.1 mole of Ferrox Fe (C
2O
4) 2H
2O and 0.1 mole of phosphoric acid ammonium dihydrogen NH
4H
2PO
4With 0.00125 mole of nine water lanthanum oxalate La
2(C
2O
4)
39H
2O mixes and adds in the polyester jar, add the 70ml raw spirit, sealing back ball milling on planetary ball mill mixed 10 hours, discharging oven dry back is under 0.3 liter/minute nitrogen atmosphere, rise to 400 ℃ with 5 ℃/minute temperature rise rates, be incubated 8 hours, be cooled to room temperature with stove, obtaining pre-imitation frosted glass, is medium ball milling 6 hours with the industrial spirit, and discharging oven dry back is under 0.3 liter/minute nitrogen atmosphere, rise to 700 ℃ with 4 ℃/minute temperature rise rates, be incubated 8 hours, be cooled to room temperature, gained positive electrode material Li with stove
0.975La
0.025FePO
4
Take by weighing the above-mentioned positive electrode material powder of 0.9g, add the 0.19g carbon black, the 0.096g polyvinylidene difluoride (PVDF) is made dispersion agent with dehydrated alcohol, ultra-sonic oscillation are mixed 30min, it is even to make it thorough mixing, after 80 ℃ of dryings, adds N-Methyl pyrrolidone furnishing slurry, be coated on equably on the collector aluminium foil, after 80 ℃ of dryings, on roll squeezer, flatten, make the anode thin film of the about 200 μ m of thickness.On anode thin film, go out 1cm
2The size disk, after weighing, with it more than 140 ℃ of vacuum-drying 12h, behind the vacuum chamber naturally cooling, as backup electrode.Electrolytic solution adopts 1mol/L LiPF
6Ethyl-carbonate EC: methylcarbonate DMC=1: 1 mixed solution; Polypropylene microporous film is a barrier film; Metal lithium sheet is as negative pole.Packaged battery in the glove box of argon gas atmosphere, ageing 6 hours charges to 4.2 volts by the speed of 20mA/g (in positive pole), is discharged to 2.5 volts, and reversible first specific discharge capacity is about 117mAh/g.Through 20 circulations, specific discharge capacity remains on more than the 118mAh/g.
Embodiment 2
With 0.04975 mole of Quilonum Retard Li
2CO
3, the ferrous Fe (CH of 0.1 molar acetate
3COO)
22H
2O and 0.1 mole of phosphoric acid ammonium (NH
4)
3PO
4With 0.00025 mole of lanthanum trioxide La
2O
3Mix, add in the polyester jar, add the 100ml industrial spirit, mixed 6 hours on planetary ball mill the sealing back, discharging oven dry back is under 0.3 liter/minute nitrogen atmosphere, rise to 430 ℃ with 5 ℃/minute temperature rise rates, be incubated 7.5 hours, cool to room temperature with the furnace, obtain pre-imitation frosted glass, with water is medium ball milling 10 hours, and discharging oven dry back is under 0.3 liter/minute nitrogen and hydrogen mixture atmosphere (nitrogen: hydrogen=9: 1, volume ratio), rise to 720 ℃ with 4 ℃/minute temperature rise rates, be incubated 7 hours, be cooled to room temperature, obtain positive electrode material Li with stove
0.995La
0.005FePO
4
Take by weighing 1.125g positive electrode material powder, add the 0.169g carbon black, the 0.12g polyvinylidene difluoride (PVDF), press embodiment 1 method system electrode slice and assembled battery, speed in 10mA/g (with positive pole) charges to 4.2 volts, is discharged to 2.5 volts, and the reversible first specific discharge capacity that obtains battery is about 120mAh/g.Through 20 circulations, specific discharge capacity remains on more than the 120mAh/g.
Embodiment 3
With 0.099 molar acetate lithium Li (CH
3COO), 0.1 mole of iron protochloride FeCl
2And 0.1 mole of phosphoric acid hydrogen, two ammoniums and 0.0005 mole of nine water Sedemesis Ce
2(C
2O
4)
39H
2O mixes, add in the polyester jar, add the 75ml raw spirit, mixed 7 hours on planetary ball mill the sealing back, discharging oven dry back is under 0.3 liter/minute nitrogen atmosphere, rise to 450 ℃ with 5 ℃/minute temperature rise rates, be incubated 9 hours, be cooled to room temperature, obtain pre-imitation frosted glass with stove, with the industrial spirit is medium ball milling 10 hours, discharging oven dry back rose to 700 ℃ with 4 ℃/minute temperature rise rates under 0.3 liter/minute nitrogen atmosphere, this temperature insulation 8 hours, be cooled to room temperature with stove, obtain positive electrode material Li
0.99Ce
0.01FePO
4
Take by weighing 1.02g positive electrode material powder, add the 0.184g carbon black, the 0.096g polyvinylidene difluoride (PVDF), press embodiment 1 method system electrode slice and assembled battery, speed in 10mA/g (with positive pole) charges to 4.2 volts, is discharged to 2.5 volts, and the reversible first specific discharge capacity that obtains battery is about 137mAh/g.Through 20 circulations, specific discharge capacity remains on more than the 130mAh/g.
Embodiment 4
With 0.0475 mole of Quilonum Retard, the ferrous FeSO of 0.1 mol sulfuric acid
47H
2O and 0.1 mole of phosphoric acid hydrogen, two ammoniums and 0.005 mol sulfuric acid cerium Ce (SO
4)
22H
2O mixes, add in the polyester jar, add the 100ml raw spirit, mixed 11 hours on planetary ball mill the sealing back, discharging oven dry back is under 0.3 liter/minute nitrogen atmosphere, rise to 480 ℃ with 5 ℃/minute temperature rise rates, be incubated 5 hours, be cooled to room temperature, obtain pre-imitation frosted glass with stove, with water is medium ball milling 5 hours, discharging oven dry back rose to 680 ℃ with 4 ℃/minute temperature rise rates under 0.3 liter/minute decomposed ammonia atmosphere, this temperature insulation 11 hours, be cooled to room temperature with stove, obtain positive electrode material Li
0.95Ce
0.05FePO
4
Take by weighing 0.9g positive electrode material powder, add the 0.16g carbon black, the 0.096g polyvinylidene difluoride (PVDF), press embodiment 1 method system electrode slice and assembled battery, speed in 10mA/g (with positive pole) charges to 4.2 volts, is discharged to 2.5 volts, obtains the reversible first specific discharge capacity 137mAh/g of battery.Through 20 circulations, the specific discharge capacity that respective material shows remains on more than the 130mAh/g.
Embodiment 5
With 0.099 moles of hydrogen Lithium Oxide 98min, 0.1 mole of iron protochloride and 0.1 mole of phosphoric acid ammonium dihydrogen and 0.001 mole of praseodymium chloride PrCl
3Mix, add in the polyester jar, add the 55ml industrial spirit, mixed 6.5 hours on planetary ball mill the sealing back, discharging oven dry back is under 0.3 liter/minute nitrogen atmosphere, rise to 400 ℃ with 5 ℃/minute temperature rise rates, be incubated 8.5 hours, be cooled to room temperature, obtain pre-imitation frosted glass with stove, with water be medium ball milling 5.5 hours, discharging oven dry back rose to 700 ℃ with 4 ℃/minute temperature rise rates under 0.3 liter/minute nitrogen atmosphere, this temperature insulation 8 hours, be cooled to room temperature with stove, obtain positive electrode material Li
0.99Pr
0.01FePO
4
Take by weighing 0.537g positive electrode material powder, add the 0.066g carbon black, the 0.036g polyvinylidene difluoride (PVDF), press embodiment 1 method system electrode slice and assembled battery, speed in 34mA/g (with positive pole) charges to 4.2 volts, is discharged to 2.5 volts, obtains the reversible first specific discharge capacity 100mAh/g of battery.Through 20 circulations, the specific discharge capacity that respective material shows remains on more than the 100mAh/g.
Embodiment 6
With 0.0498 mole of Quilonum Retard, 0.1 mole of Ferrox and 0.1 mole of phosphoric acid ammonium and 0.0004 mole of neodymium fluoride NdF
3Mix, add in the polyester jar, add 130ml water, mixed 6 hours on planetary ball mill the sealing back, discharging oven dry back is under 0.3 liter/minute nitrogen atmosphere, rise to 400 ℃ with 5 ℃/minute temperature rise rates, be incubated 8 hours, cool to room temperature with the furnace, obtain pre-imitation frosted glass, with water is medium ball milling 8 hours, and discharging oven dry back is under 0.3 liter/minute nitrogen and hydrogen mixture atmosphere (nitrogen: hydrogen=9: 1, volume ratio), rise to 700 ℃ with 4 ℃/minute temperature rise rates, this temperature insulation 8 hours, be cooled to room temperature with stove, obtain positive electrode material Li
0.996Nd
0.004FePO
4
Take by weighing 1.325g positive electrode material powder, add the 0.263g carbon black, the 0.12g polyvinylidene difluoride (PVDF), press embodiment 1 method system electrode slice and assembled battery, speed in 10mA/g (with positive pole) charges to 4.2 volts, is discharged to 2.5 volts, obtains the reversible first specific discharge capacity 94mAh/g of battery.Through 20 circulations, the specific discharge capacity that respective material shows remains on more than the 90mAh/g.
Embodiment 7
With 0.099 molar acetate lithium, 0.1 mole of Ferrox and 0.1 mole of phosphoric acid ammonium dihydrogen and 0.0005 mole of Samarium trioxide (Sm
2O
3) mix, add in the polyester jar, add the 80ml raw spirit, mixed 7 hours on planetary ball mill the sealing back, discharging oven dry back is under 0.3 liter/minute nitrogen atmosphere, rise to 400 ℃ with 5 ℃/minute temperature rise rates, be incubated 8 hours, be cooled to room temperature, obtain pre-imitation frosted glass with stove, with water is medium ball milling 6 hours, discharging oven dry back rose to 700 ℃ with 4 ℃/minute temperature rise rates under 0.3 liter/minute nitrogen atmosphere, this temperature insulation 8 hours, be cooled to room temperature with stove, obtain positive electrode material Li
0.99Sm
0.01FePO
4
Take by weighing 0.45g positive electrode material powder, add the 0.078g carbon black, the 0.032g polyvinylidene difluoride (PVDF), press embodiment 1 method system electrode slice and assembled battery, speed in 20mA/g (with positive pole) charges to 4.2 volts, is discharged to 2.5 volts, obtains the reversible first specific discharge capacity 123mAh/g of battery.Through 20 circulations, the specific discharge capacity that respective material shows remains on more than the 120mAh/g.
Embodiment 8
With 0.097 moles of hydrogen Lithium Oxide 98min, 0.1 mole of Ferrox and 0.1 mole of phosphoric acid hydrogen, two ammoniums and 0.0015 mole of oxalic acid europium Eu
2(C
2O
4)
310H
2O mixes, add in the polyester jar, add the 60ml raw spirit, mixed 6 hours on planetary ball mill the sealing back, discharging oven dry back is under 0.3 liter/minute nitrogen atmosphere, rise to 420 ℃ with 5 ℃/minute temperature rise rates, be incubated 9 hours, be cooled to room temperature, obtain pre-imitation frosted glass with stove, with the industrial spirit be medium ball milling 6 hours, discharging oven dry back rose to 700 ℃ with 3 ℃/minute temperature rise rates under 0.3 liter/minute decomposed ammonia atmosphere, this temperature insulation 7 hours, be cooled to room temperature with stove, obtain positive electrode material Li
0.97Eu
0.03FePO
4
Take by weighing 0.45g positive electrode material powder, add the 0.0448g carbon black, the 0.032g polyvinylidene difluoride (PVDF), press embodiment 1 method system electrode slice and assembled battery, speed in 34mA/g (with positive pole) charges to 4.2 volts, is discharged to 2.5 volts, obtains the reversible first specific discharge capacity 121mAh/g of battery.Through 20 circulations, the specific discharge capacity that respective material shows remains on more than the 120mAh/g.
Embodiment 9
With 0.048 mole of Quilonum Retard, 0.1 mole of Ferrox and 0.1 mole of phosphoric acid ammonium dihydrogen and 0.004 molar nitric acid gadolinium Gd (NO
3)
3Mix, add in the polyester jar, add the 60ml raw spirit, mixed 7 hours on planetary ball mill the sealing back, discharging oven dry back is under 0.3 liter/minute nitrogen atmosphere, rise to 400 ℃ with 5 ℃/minute temperature rise rates, be incubated 8 hours, be cooled to room temperature, obtain pre-imitation frosted glass with stove, with water be medium ball milling 6 hours, discharging oven dry back rose to 750 ℃ with 4 ℃/minute temperature rise rates under 0.3 liter/minute nitrogen atmosphere, this temperature insulation 8 hours, be cooled to room temperature with stove, obtain positive electrode material Li
0.96Gd
0.04FePO
4
Take by weighing the 0.45g positive powder, add the 0.06g carbon black, the 0.032g polyvinylidene difluoride (PVDF), press embodiment 1 method system electrode slice and assembled battery, speed in 25mA/g (with positive pole) charges to 4.2 volts, is discharged to 2.5 volts, obtains the reversible first specific discharge capacity 111mAh/g of battery.Through 20 circulations, the specific discharge capacity that respective material shows remains on more than the 109mAh/g.
Embodiment 10
With 0.096 molar acetate lithium, 0.1 molar acetate is ferrous and 0.1 mole of phosphoric acid ammonium and 0.001 mole of terbium sesquioxide (Tb
4O
7) mix, add in the polyester jar, add the 80ml raw spirit, mixed 7 hours on planetary ball mill the sealing back, discharging oven dry back is under 0.3 liter/minute nitrogen atmosphere, rise to 400 ℃ with 5 ℃/minute temperature rise rates, this temperature insulation 8 hours, be cooled to room temperature with stove, obtain pre-imitation frosted glass, with water be medium ball milling 6 hours, discharging oven dry back rose to 700 ℃ with 4 ℃/minute temperature rise rates under 0.3 liter/minute nitrogen atmosphere, this temperature insulation 8 hours, be cooled to room temperature with stove, obtain positive electrode material Li
0.96Tb
0.04FePO
4
Take by weighing 0.45g positive electrode material powder, add the 0.078g carbon black, the 0.032g polyvinylidene difluoride (PVDF), press embodiment 1 method system electrode slice and assembled battery, speed in 30mA/g (with positive pole) charges to 4.2 volts, is discharged to 2.5 volts, obtains the reversible first specific discharge capacity 123mAh/g of battery.Through 20 circulations, the specific discharge capacity that respective material shows remains on more than the 120mAh/g.
Embodiment 11
With 0.0499 mole of Quilonum Retard, 0.1 mole of iron protochloride and 0.1 mole of phosphoric acid ammonium dihydrogen and 0.0002 mole of Dysprosium trichloride DyCl
3Mix, add in the polyester jar, add the 80ml raw spirit, mixed 7 hours on planetary ball mill the sealing back, discharging oven dry back is under 0.3 liter/minute nitrogen atmosphere, rise to 400 ℃ with 5 ℃/minute temperature rise rates, this temperature insulation 8 hours, be cooled to room temperature with stove, obtain pre-imitation frosted glass, with water be medium ball milling 6 hours, discharging oven dry back rose to 700 ℃ with 4 ℃/minute temperature rise rates under 0.3 liter/minute nitrogen atmosphere, this temperature insulation 8 hours, be cooled to room temperature with stove, obtain positive electrode material Li
0.998Dy
0.002FePO
4
Take by weighing the 0.843g positive powder, add the 0.078g carbon black, the 0.062g polyvinylidene difluoride (PVDF), press embodiment 1 method system electrode slice and assembled battery, speed in 40mA/g (with positive pole) charges to 4.2 volts, is discharged to 2.5 volts, obtains the reversible first specific discharge capacity 113mAh/g of battery.Through 20 circulations, the specific discharge capacity that respective material shows remains on more than the 110mAh/g.
Embodiment 12
With 0.0994 moles of hydrogen Lithium Oxide 98min, 0.1 mole of Ferrox and 0.1 mole of phosphoric acid hydrogen, two ammoniums and 0.0003 mole of Holmium trioxide Ho
2O
3Mix, add in the polyester jar, add the 50ml water-alcohol, mixed 7 hours on planetary ball mill the sealing back, discharging oven dry back is under 0.3 liter/minute nitrogen atmosphere, rise to 400 ℃ with 5 ℃/minute temperature rise rates, be incubated 8 hours, be cooled to room temperature, obtain pre-imitation frosted glass with stove, with water be medium ball milling 6 hours, discharging oven dry back rose to 700 ℃ with 4 ℃/minute temperature rise rates under 0.3 liter/minute decomposed ammonia atmosphere, this temperature insulation 8 hours, be cooled to room temperature with stove, obtain positive electrode material Li
0.994Ho
0.006FePO
4
Take by weighing 0.624g positive electrode material powder, add the 0.09g carbon black, the 0.052g polyvinylidene difluoride (PVDF), press embodiment 1 method system electrode slice and assembled battery, speed in 20mA/g (with positive pole) charges to 4.2 volts, is discharged to 2.5 volts, obtains the reversible first specific discharge capacity 148mAh/g of battery.Through 20 circulations, the specific discharge capacity that shows remains on more than the 135mAh/g.
Embodiment 13
With 0.0493 mole of Quilonum Retard, 0.1 mole of Ferrox and 0.1 mole of phosphoric acid ammonium and 0.0007 mole of Erbium trioxide (Er
2O
3) mix, add in the polyester jar, add the 80ml raw spirit, mixed 7 hours on planetary ball mill the sealing back, discharging oven dry back is under 0.3 liter/minute nitrogen atmosphere, rise to 400 ℃ with 5 ℃/minute temperature rise rates, be incubated 8 hours, be cooled to room temperature, obtain pre-imitation frosted glass with stove, with water be medium ball milling 6 hours, discharging oven dry back rose to 700 ℃ with 4 ℃/minute temperature rise rates under 0.3 liter/minute nitrogen atmosphere, this temperature insulation 8 hours, be cooled to room temperature with stove, obtain positive electrode material Li
0.986Er
0.014FePO
4
Take by weighing 0.734g positive electrode material powder, add the 0.085g carbon black, the 0.052g polyvinylidene difluoride (PVDF), press embodiment 1 method system electrode slice and assembled battery, speed in 20mA/g (with positive pole) charges to 4.2 volts, is discharged to 2.5 volts, obtains the reversible first specific discharge capacity 118mAh/g of battery.Through 20 circulations, the specific discharge capacity that shows remains on more than the 120mAh/g.
Embodiment 14
With 0.098 molar acetate lithium, 0.1 mole of Ferrox and 0.1 mole of phosphoric acid ammonium dihydrogen and 0.002 mole of thulium chloride TmCl
3Mix, add in the polyester jar, add the 80ml raw spirit, mixed 7 hours on planetary ball mill the sealing back, discharging oven dry back is under 0.3 liter/minute decomposed ammonia atmosphere, rise to 400 ℃ with 3 ℃/minute temperature rise rates, be incubated 7 hours, be cooled to room temperature, obtain pre-imitation frosted glass with stove, with the industrial spirit be medium ball milling 6 hours, discharging oven dry back rose to 750 ℃ with 4 ℃/minute temperature rise rates under 0.3 liter/minute decomposed ammonia atmosphere, this temperature insulation 6 hours, be cooled to room temperature with stove, obtain positive electrode material Li
0.98Tm
0.02FePO
4
Take by weighing 0.45g positive electrode material powder, add the 0.078g carbon black, the 0.042g polyvinylidene difluoride (PVDF), press embodiment 1 method system electrode slice and assembled battery, speed in 20mA/g (with positive pole) charges to 4.2 volts, is discharged to 2.5 volts, obtains the reversible first specific discharge capacity 123mAh/g of battery.Through 20 circulations, the specific discharge capacity that respective material shows remains on more than the 120mAh/g.
Embodiment 15
With 0.04825 mole of Quilonum Retard, 0.1 mole of Ferrox and 0.1 mole of phosphoric acid ammonium dihydrogen and 0.00175 mole of ytterbium oxide (Yb
2O
3) mix, add in the polyester jar, add the 80ml raw spirit, mixed 7 hours on planetary ball mill the sealing back, discharging oven dry back is under 0.3 liter/minute nitrogen atmosphere, rise to 400 ℃ with 5 ℃/minute temperature rise rates, this temperature insulation 8 hours, be cooled to room temperature with stove, obtain pre-imitation frosted glass, with water be medium ball milling 6 hours, discharging oven dry back rose to 730 ℃ with 4 ℃/minute temperature rise rates under 0.3 liter/minute nitrogen atmosphere, this temperature insulation 8 hours, be cooled to room temperature with stove, obtain positive electrode material Li
0.965Yb
0.035FePO
4
Take by weighing 0.45g positive electrode material powder, add the 0.078g carbon black, the 0.032g polyvinylidene difluoride (PVDF), press embodiment 1 method system electrode slice and assembled battery, speed in 20mA/g (with positive pole) charges to 4.2 volts, is discharged to 2.5 volts, obtains the reversible first specific discharge capacity 122mAh/g of battery.Through 20 circulations, the specific discharge capacity that shows remains on more than the 125mAh/g.
Embodiment 16
With 0.0975 molar acetate lithium, 0.1 mole of Ferrox and 0.1 mole of phosphoric acid ammonium dihydrogen and 0.0025 molar nitric acid lutetium Lu (NO
3)
3Mix, add in the polyester jar, add the 80ml raw spirit, mixed 6 hours on planetary ball mill the sealing back, discharging oven dry back is under 0.3 liter/minute nitrogen atmosphere, rise to 400 ℃ with 5 ℃/minute temperature rise rates, this temperature insulation 8 hours, be cooled to room temperature with stove, obtain pre-imitation frosted glass, with the raw spirit be medium ball milling 6 hours, discharging oven dry back rose to 700 ℃ with 4 ℃/minute temperature rise rates under 0.3 liter/minute nitrogen atmosphere, this temperature insulation 8 hours, be cooled to room temperature with stove, obtain positive electrode material Li
0.975Lu
0.025FePO
4
Take by weighing 0.45g positive electrode material powder, add the 0.078g carbon black, the 0.032g polyvinylidene difluoride (PVDF), press embodiment 1 method system electrode slice and assembled battery, speed in 20mA/g (with positive pole) charges to 4.2 volts, is discharged to 2.5 volts, obtains the reversible first specific discharge capacity 123mAh/g of battery.Through 20 circulations, the specific discharge capacity that respective material shows remains on more than the 120mAh/g.
Claims (5)
1. the preparation method of a rare earth doped iron lithium phosphate powder is characterized in that, is used for the described iron lithium phosphate molecular formula Li of anode material for lithium-ion batteries
1-xRE
xFePO
4Expression, wherein 0＜x≤0.05; RE is the element of rare-earth dopant, and the element of this rare-earth dopant is by the rare earth lanthanide compound: the oxide compound of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium, oxyhydroxide, muriate, nitrate, vitriol, carbonate, fluorochemical or organic salt are adulterated;
Concrete preparation method is as follows:
Lithium salts, ferrous salt and phosphoric acid salt and rare-earth dopant are pressed element Li: Fe: P: RE=(1-x): 1: 1: the mol ratio of x is once reinforced, adds the mix grinding medium, and 6～12 hours ball milling time is 40～70 ℃ of oven dry down; Oven dry back powder is heated to 400～550 ℃ under inert atmosphere or reducing atmosphere, be incubated 5～10 hours and carry out precalcining; Secondary ball milling 6～12 hours, 40～70 ℃ of oven dry down, under inert atmosphere or reducing atmosphere, 550～850 ℃ of secondary clacinings obtain rear-earth-doped iron lithium phosphate Li then
1-xRE
xFePO
4Powder.
2. according to the preparation method of the described rare earth doped iron lithium phosphate powder of claim 1, it is characterized in that described lithium salts is Li
2CO
3, at least a in lithium oxalate and the Lithium Acetate.
3. according to the preparation method of the described rare earth doped iron lithium phosphate powder of claim 2, it is characterized in that described lithium salts substitutes with LiOH.
4. according to the preparation method of the described rare earth doped iron lithium phosphate powder of claim 1, it is characterized in that described ferrous salt is at least a in Ferrox, Iron diacetate, iron protochloride and the ferrous sulfate.
5. according to the preparation method of the described rare earth doped iron lithium phosphate powder of claim 1, it is characterized in that described phosphoric acid salt is at least a in ammonium phosphate, Secondary ammonium phosphate and the primary ammonium phosphate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101324297A CN100551821C (en) | 2005-12-23 | 2005-12-23 | The preparation method of rare earth doped iron lithium phosphate powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101324297A CN100551821C (en) | 2005-12-23 | 2005-12-23 | The preparation method of rare earth doped iron lithium phosphate powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1785800A CN1785800A (en) | 2006-06-14 |
| CN100551821C true CN100551821C (en) | 2009-10-21 |
Family
ID=36783420
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005101324297A Expired - Fee Related CN100551821C (en) | 2005-12-23 | 2005-12-23 | The preparation method of rare earth doped iron lithium phosphate powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100551821C (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100450920C (en) * | 2006-11-24 | 2009-01-14 | 中南大学 | Method for preparing powder of lithium iron phosphate |
| CN100450919C (en) * | 2006-11-24 | 2009-01-14 | 中南大学 | Method for synthesizing Nano level powder of lithium iron phosphate |
| KR100821832B1 (en) * | 2007-04-20 | 2008-04-14 | 정성윤 | Method for making nanoparticles of lithium transition metal phosphates |
| US8480987B2 (en) | 2007-04-20 | 2013-07-09 | Sung Yoon Chung | Method of preparing nanoparticles of lithium transition metal phosphates, lithium transition metal phosphates, and method of preparing the same |
| CN101841027A (en) * | 2010-05-13 | 2010-09-22 | 湘西自治州矿产与新材料技术创新服务中心 | Method for preparing lithium position rare earth-doped lithium vanadyl phosphate cathode material for lithium ion battery |
| CN101931075B (en) * | 2010-06-28 | 2013-07-03 | 彩虹集团公司 | Rare earth-doped power battery anode material and preparation method thereof |
| CN102044660A (en) * | 2010-10-30 | 2011-05-04 | 华南理工大学 | Rare-earth element samarium-doped modified lithium ion battery anode material and preparation method thereof |
| CN102633243A (en) * | 2012-04-26 | 2012-08-15 | 张健 | Barium iron phosphate product and preparation method and application of barium iron phosphate product |
| CN103400982A (en) * | 2013-07-26 | 2013-11-20 | 烟台卓能电池材料有限公司 | Nanometer lithium zirconate modified lithium iron phosphate composite material and preparation method thereof |
| CN105720305A (en) * | 2014-12-03 | 2016-06-29 | 中兴通讯股份有限公司 | Preparation method of lithium ion polymer battery |
| CN107834059A (en) * | 2017-07-08 | 2018-03-23 | 郑春燕 | A kind of preparation technology of novel composite electrode material |
| CN107827092A (en) * | 2017-07-08 | 2018-03-23 | 郑春燕 | A kind of electrode material |
| CN107834066A (en) * | 2017-07-09 | 2018-03-23 | 郑春燕 | A kind of high conductivity combination electrode material and technique for adulterating manganese |
| CN107834026A (en) * | 2017-07-09 | 2018-03-23 | 郑春燕 | The combination electrode material and its preparation technology of a kind of high conductivity |
| CN110474099A (en) * | 2019-07-12 | 2019-11-19 | 大连恒超锂业科技有限公司 | A kind of preparation method of lithium ion battery anode glue size |
| CN112607725A (en) * | 2020-12-17 | 2021-04-06 | 合肥国轩电池材料有限公司 | Nitrogen-doped carbon nanotube/rare earth metal ion-doped lithium iron phosphate composite positive electrode material and preparation method thereof |
-
2005
- 2005-12-23 CN CNB2005101324297A patent/CN100551821C/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| 镁离子掺杂对LiFePO4/C 材料电池性能的影响. 卢俊彪等.物理化学学报，第21卷第3期. 2005 |
| 镁离子掺杂对LiFePO4/C 材料电池性能的影响. 卢俊彪等.物理化学学报，第21卷第3期. 2005 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1785800A (en) | 2006-06-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100551821C (en) | The preparation method of rare earth doped iron lithium phosphate powder | |
| CN1332878C (en) | Prepn process of oxygen place doped lithium ferric phosphate powder | |
| CN100470894C (en) | Preparation method of phosphorus position partly substituted iron lithium phosphate powder | |
| CN101339994B (en) | Preparation of multi-position doped lithium iron phosphate positive electrode material and application thereof | |
| CN101800315A (en) | Multielement-doped lithium iron phosphate positive electrode material and preparation method thereof | |
| CN102104148A (en) | Mixed rare earth compound-doped and modified lithium iron phosphate cathode material and preparation method thereof | |
| CN100418255C (en) | Method for preparing lithium enriched lithium ion phosphate powder | |
| CN102738451A (en) | Modified positive electrode material of lithium ion battery and preparation method of modified positive electrode material | |
| CN104795560A (en) | Sodium-rich P2-phase layered oxide material and preparation method and application thereof | |
| CN101752562B (en) | Compound doped modified lithium ion battery anode material and preparation method thereof | |
| CN101540400A (en) | Lithic natrium doping type lithium iron phosphate cathode material for lithium-ion battery and preparation method thereof | |
| CN100537418C (en) | Preparation method of transition element doped iron lithium phosphate powder | |
| CN103887483A (en) | Doped and modified ternary positive electrode material and preparation method thereof | |
| CN105185954A (en) | LiAlO2 coated LiNi1-xCoxO2 lithium-ion battery positive electrode material and preparation method thereof | |
| CN103474646B (en) | A kind of mesh structural porous lithium-rich manganese-based anode material for lithium-ion batteries and preparation method thereof | |
| CN104393234A (en) | Modified lithium ion battery composite positive pole material and preparation method thereof | |
| CN102751481A (en) | Li2MnO3 and LiCoO2 composite anode material | |
| CN103794776A (en) | High-voltage high-compaction composite positive electrode material of lithium ion battery and preparation method | |
| CN104979549A (en) | Sheet lithium-enriched manganese-based anode material for lithium-ion battery as well as preparation method and application of sheet lithium-enriched manganese-based anode material | |
| CN103078099A (en) | Anode material for lithium ion cell and preparation method thereof | |
| CN115207340A (en) | Sodium ion battery layered oxide positive electrode material and preparation method and application thereof | |
| CN100490221C (en) | Composite doped modified lithium-ion battery anode material and its manufacture method | |
| CN102185146B (en) | Rare-earth doped manganese-lithium phosphate anode material and preparation method thereof | |
| CN102163709B (en) | Cobalt nickel manganese lithium oxide-cooper oxide compound positive material for lithium ion battery and preparation method thereof | |
| CN106410180A (en) | Lithium ion battery positive pole material, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20091021 Termination date: 20151223 |
|
| EXPY | Termination of patent right or utility model |