CN100494052C - LiFePO4 cathode material based on P site doping and preparation method thereof - Google Patents
LiFePO4 cathode material based on P site doping and preparation method thereof Download PDFInfo
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Abstract
Disclosed is a phosphorus-doped lithium iron phosphate positive electrode material and a preparation method of the same, which relates to a positive electrode materials of lithium ion batteries. The present invention provides a phosphorus-doped lithium iron phosphate positive electrode material of lithium ion batteries with higher charge-discharge capacity, excellent multiplying power performance and cycle performance, and a preparation method of the same. The positive electrode material has a formula of LiyFe(P1-xMx)O4, wherein M is doping element of Ge, Sn, Se, Te or Bi. The preparation method comprises the steps of mixing the ferrite and phosphate with dopant; adding at least one of the water, alcohol, acetone serving as ball mill solvent; scrubbing and filtrating after ball milling; vacuum drying the filtration product to obtain the intermediate product which is mixed with lithium salt; adding ball mill solvent to ball mill again; drying the product and then heating calcining in the presence of inert gas or reducing atmosphere to obtain doping type lithium iron phosphate LiyFe(P1-xMx)O4 powder.
Description
Technical field
The present invention relates to a kind of anode material for lithium-ion batteries, especially relate to a kind of lithium iron phosphate positive material that replaces (doping) based on phosphate potential and preparation method thereof.
Background technology
At present, China's low capacity lithium cell---the production as battery of mobile phone, cells in notebook computer etc. is tending towards saturated substantially, but jumbo power lithium-ion battery does not but still come into the market.Traditional small-scale lithium ion cell has been taken as the leading factor with lithium cobaltate cathode material since coming out always, because cobalt acid lithium self-security is poor, and shortcoming such as cost an arm and a leg, therefore can't really be suitable for the lithium-ion-power cell industry need.Though the price of spinel lithium-manganese oxide positive electrode material is low, good rate capability, the defective of its high temperature circulation poor stability still do not have suitable method and solve.The lithium electricity LiFePO 4 of anode material (LiFePO of a new generation
4) after overcoming the shortcoming of self, really represented the broad space for the development and the renewal of large vol lithium dynamical battery.
The iron lithium phosphate that Goodenough group reported first in 1997 has olivine structural can reversibly embed and the removal lithium embedded ion, has caused people's very big concern.That this material has is nontoxic, pollution-free, power cell is needed just for advantages such as safety performance is good, starting material wide material sources, low price, therefore is considered to the desirable positive electrode material of lithium-ion-power cell.US5910382,6085015, No. 6514640 patent disclosures manufacturing LiFePO
4The method of series material, material little electric current discharge and recharge condition (～0.1C) can provide down～loading capacity of 150mAh/g.
Pure LiFePO
4Material exists the shortcoming of self, shows: (1) electronic conductivity is low.This causes its rate charge-discharge poor performance, only is applicable to little current work condition, can't adapt to the work under the big current condition, is unfavorable for being used on the power-type power cell; (2) tap density is low.This causes the battery volume energy density made with this material on the low side, and the pole piece difficulty of processing is big, has influenced the practicalization of this material.
At present, at LiFePO
4The work that the above shortcoming of material is carried out is a lot, in order to solve the problem of poorly conductive, has proposed surperficial coating (as carbon coating etc.) and element doping methods such as (Li position, Fe positions); At the low problem of tap density, methods such as crystal formation control growing are proposed.These work have all greatly suppressed LiFePO
4The shortcoming of material.Can estimate, solve LiFePO
4After above-mentioned two shortcomings, this material will have great application prospect in the power cell market in future.
Summary of the invention
The present invention aim to provide a kind ofly have higher charge/discharge capacity, better the lithium ion battery of high rate performance and good circulation performance is with P site doped lithium iron phosphate positive material and preparation method thereof.
Technical scheme of the present invention is with Ge, and Sn, Se, Te, elements such as Bi partly substitute iron lithium phosphate (LiFePO
4) in phosphorus, by control lithium ion content compensate intramolecular charge balance, utilize simple two single-step solid phase reaction methods to prepare P site doped iron lithium phosphate Li
yFe (P
1-xM
x) O
4(M=Ge, Sn, Se, Te, the Bi) method of powder to reach the remarkable chemical property that improves this material, makes it have higher charge/discharge capacity, the purpose of high rate performance and excellent cycle performance preferably.
Described molecular formula based on P site doped lithium iron phosphate positive material is Li
yFe (P
1-xM
x) O
4, wherein M is doped element (being alternate source), M is Ge, and Sn, Se, Te or Bi, 0＜x＜0.5, y is a lithium content, 0.7＜y＜2.0.
Described preparation method based on P site doped lithium iron phosphate positive material may further comprise the steps:
1) ferrous salt, phosphoric acid salt are mixed with hotchpotch, add at least a in entry, ethanol, the acetone, behind ball milling 6～12h as the ball milling solvent, washing, filter, filtration product obtains intermediate product behind 60～80 ℃ of vacuum drying 5～8h, by quality than ferrous salt: phosphoric acid salt: hotchpotch=m
1: m
2(1-x): (m
3X/n
1), m wherein
1Be the molecular weight of ferrous salt, m
2Be phosphatic molecular weight, m
3Be the molecular weight of hotchpotch, n
1Atomicity for M in the hotchpotch;
2) intermediate product and lithium salts are carried out rerolling, add entry or organic solvent as the ball milling solvent, ball milling mixes 6～12h again, and 500～800 ℃ of calcinings are heated in product oven dry back under inert atmosphere or reducing atmosphere, obtain doped lithium ferric phosphate Li
yFe (P
1-xM
x) O
4Powder, wherein M is Ge, Sn, Se, Te or Bi, y are lithium content, 0.7＜y＜2.0, by quality than intermediate product: lithium salts=169: (m
4Y/n
2), m wherein
4Be the molecular weight of lithium salts, y is a lithium content, 0.7＜y＜2.0, n
2Atomicity for the lithium in the lithium salts molecular formula.
Described ferrous salt is Iron diacetate, iron protochloride or ferrous sulfate.Described phosphoric acid salt is ammonium phosphate, primary ammonium phosphate or Secondary ammonium phosphate.Described lithium salts is Quilonum Retard, lithium hydroxide, lithium oxalate or Lithium Acetate.Described hotchpotch is Ge-doped thing, tin dope thing, selenium hotchpotch, tellurium hotchpotch or bismuth hotchpotch.Described Ge-doped thing is germanium dioxide or sodium germanate.Described tin dope thing is tindioxide or sodium stannate.Described selenium hotchpotch is tin anhydride or sodium selenate.Described tellurium hotchpotch is three oxidations, two telluriums or sodium tellurate.Described bismuth hotchpotch is a bismuthous oxide bismuth trioxide.
In step 2) in, organic solvent can adopt at least a in dehydrated alcohol, the acetone; The temperature of product oven dry is preferably 40～120 ℃; Preferably be incubated 5～12h after the calcining.Described inert atmosphere or reducing atmosphere are at least a in nitrogen, argon gas, nitrogen and hydrogen mixture and the argon hydrogen gas mixture.
Utilization of the present invention is easy to the solid phase method of suitability for industrialized production, adopt the cheap vitriol of raw material, phosphoric acid salt, metal oxide or corresponding salt, through simple uniform mixing, filtration, stoving process, by control thermal treatment temp and time, it is good to prepare crystal property, composition is even, the iron lithium phosphate Li that the part phosphate potential replaces
yFe (P
1-xM
x) O
4(M=Ge, Sn, Se, Te, Bi) powder.The material that utilizes the present invention to prepare has higher loading capacity, and good multiplying power discharging property is very with practical value, and at secondary lithium battery commonly used, particularly the power battery anode material field is with a wide range of applications.
Description of drawings
Fig. 1 is the first discharge curve of B0 material under different discharge-rates.In Fig. 1, X-coordinate is loading capacity (mAh/g), and ordinate zou is voltage (V), and the multiplying power of each curve correspondence is respectively 0.1C, 0.2C, 0.5C, 1C, 2C, 4C, 5C.Wherein the B0 material is positive electrode material LiFePO
4
Fig. 2 is capability retention (with 0.1C multiplying power the is benchmark) curve of B1 material under different discharge-rates.In Fig. 2, X-coordinate is discharge-rate (C), and ordinate zou is capability retention (%).
Embodiment
Following examples will be in conjunction with the accompanying drawings to content of the present invention with and outstanding feature and marked improvement be further described.
Embodiment 1: with 8.34g ferrous sulfate FeSO
47H
2O, 3.45g primary ammonium phosphate NH
4H
2PO
4Mix, add in the agate jar, add the 5ml dehydrated alcohol as the ball milling solvent, sealing back speed with 500rpm on planetary ball mill is mixed 8h, with deionized water dissolving, filtration, be the nitrate of baryta Ba (NO of 1mol/L extremely 3～4 times after the discharging with concentration with deionized water wash
3)
2Solution detects less than sulfate ion SO
4 2-Filtration product obtains intermediate product behind 60 ℃ of vacuum drying 8h.With 3.06g Lithium Acetate CH
3COOLi2H
2O and intermediate product add in the ball grinder, add the 5ml dehydrated alcohol as the ball milling solvent, the sealing back continues to mix 10h with the speed of 500rpm on planetary ball mill, after the discharging at 80 ℃ of vacuum drying 2h, then under the nitrogen and hydrogen mixture atmosphere of 10ml/s, rise to 600 ℃ with the temperature rise rate of 5 ℃/min, under this temperature, be incubated 10h, drop to room temperature with stove, obtain positive electrode material LiFePO
4, be designated as B0.
The chemical property of gained sample is measured as follows: take by weighing 0.78g iron lithium phosphate LiFePO
4Anodal powder, add 0.12g acetylene black as conductive agent, add mass concentration again and be 10% PVDF solution (N-Methyl pyrrolidone NMP makees solvent) 1.0g as cakingagent, add 1g NMP as dispersion agent, seal back speed ball milling mixing 3h with 500rpm on planetary ball mill, the slurry that obtains is coated on the aluminium collector uniformly, flattens behind the oven dry 30min down at 100 ℃, obtains positive plate.With the metal lithium sheet is negative pole, with the LiPF of 1.0mol/L
6/ EC+DMC (1: 1) is an electrolytic solution, and the Celgard2300 film is a barrier film, is assembled into the CR2025 button cell in being full of the glove box of argon gas, and ageing 8h carries out charge-discharge test.
Fig. 1 has provided the first discharge curve of battery under different discharge-rates, and the charging/discharging voltage scope is 2.0～4.2V.Battery discharges under different electric currents after being charged to 4.2V with the 0.2C multiplying power.Battery loading capacity under the 0.1C multiplying power is 155mAh/g, and along with the increase of discharge-rate, capacity descends very fast, and the loading capacity under the 1C multiplying power is 130mAh/g, and the loading capacity under the 5C multiplying power drops to 103mAh/g.
Embodiment 2: with 16.80g two hydration Iron diacetate Fe (CH
3COO)
22H
2O, 11.93g ammonium phosphate (NH
4)
3PO
4Mix, add in the agate jar, adding 5ml dehydrated alcohol is as the ball milling solvent, and sealing back speed with 500rpm on planetary ball mill is mixed 8h, with deionized water dissolving, filtration, uses deionized water wash 3～4 times after the discharging.Filtration product obtains intermediate product behind 80 ℃ of vacuum drying 6h.With 2.96g Quilonum Retard Li
2CO
3Add in the ball grinder with intermediate product, add the 5ml dehydrated alcohol as the ball milling solvent, the sealing back continues to mix 10h with the speed of 500rpm on planetary ball mill, after the discharging at 80 ℃ of vacuum drying 2h, then under the nitrogen atmosphere of 15ml/s, temperature rise rate with 5 ℃/min rises to 700 ℃, is incubated 5h under this temperature, drops to room temperature with stove and gets iron lithium phosphate LiFePO
4Powder is designated as B1.Method according to embodiment 1 is assembled into the CR2025 button cell, and ageing 8h carries out charge-discharge test, and test condition is identical with embodiment 1.Fig. 2 has provided capability retention (with 0.1C multiplying power the is benchmark) curve of B1 material under different discharge-rates.Along with the increase of discharge-rate, cell container keeps better, 0.1C, and 0.2C and 0.5C capacity are almost constant, and the loading capacity under the 1C multiplying power remains on (0.1C loading capacity relatively) more than 95%, and the loading capacity under the 5C multiplying power still remains on more than 80%.
Embodiment 3: with 16.80g two hydration Iron diacetate Fe (CH
3COO)
22H
2O, 11.33g ammonium phosphate (NH
4)
3PO
4With 0.60g tindioxide SnO
2Mix, add in the agate jar, adding 5ml acetone is as the ball milling solvent, and sealing back speed with 500rpm on planetary ball mill is mixed 8h, with deionized water dissolving, filtration, uses deionized water wash 3～4 times after the discharging.Filtration product behind 100 ℃ of vacuum drying 6h, the intermediate product that obtains.With 3.10g Quilonum Retard Li
2CO
3Add in the ball grinder with intermediate product, add 5ml acetone as the ball milling solvent, the sealing back continues to mix 10h with the speed of 500rpm on planetary ball mill, after the discharging at 80 ℃ of vacuum drying 2h, then under the nitrogen and hydrogen mixture atmosphere of 10ml/s, rise to 700 ℃ with the temperature rise rate of 5 ℃/min, under this temperature, be incubated 5h, drop to room temperature with stove, obtain the iron lithium phosphate Li that phosphate potential replaces Sn
1.05Fe (P
0.95Sn
0.05) O
4Powder.Method according to embodiment 1 is assembled into the CR2025 button cell, and ageing 8h carries out charge-discharge test, and test condition is identical with embodiment 1.
Embodiment 4: with 21.00g two hydration Iron diacetate Fe (CH
3COO)
22H
2O, 11.93g ammonium phosphate (NH
4)
3PO
4With 5.33g sodium stannate Na
2SnO
33H
2O mixes, and adds in the agate jar, and adding 5ml acetone is as the ball milling solvent, and sealing back speed with 500rpm on planetary ball mill is mixed 8h, with deionized water dissolving, filtration, uses deionized water wash 3～4 times after the discharging.Filtration product behind 80 ℃ of vacuum drying 6h, the intermediate product that obtains.With 4.43g Quilonum Retard Li
2CO
3Add in the ball grinder with intermediate product, add 5ml acetone as the ball milling solvent, the sealing back continues to mix 10h with the speed of 500rpm on planetary ball mill, after the discharging at 80 ℃ of vacuum drying 2h, then under the nitrogen atmosphere of 10ml/s, rise to 700 ℃ with the temperature rise rate of 5 ℃/min, under this temperature, be incubated 5h, drop to room temperature with stove, obtain the iron lithium phosphate Li that phosphate potential replaces Sn
1.2Fe (P
0.8Sn
0.2) O
4Powder.Method according to embodiment 1 is assembled into the CR2025 button cell, and ageing 8h carries out charge-discharge test, and test condition is identical with embodiment 1.
Embodiment 5: with 27.80g ferrous sulfate FeSO
47H
2O, 11.89g Secondary ammonium phosphate (NH
4)
2HPO
4Sodium tellurate Na with 2.38g
2TeO
4Mix, add in the agate jar, add the 5ml deionized water as the ball milling solvent, sealing back speed with 500rpm on planetary ball mill is mixed 8h, with deionized water dissolving, filtration, extremely use 1mol/L nitrate of baryta Ba (NO for 3～4 times after the discharging with deionized water wash
3)
2Solution detects less than sulfate ion SO
4 2-Filtration product obtains intermediate product behind 120 ℃ of vacuum drying 5h.With 3.78g lithium hydroxide LiOHH
2O and intermediate product add in the ball grinder, add the 5ml deionized water as the ball milling solvent, the sealing back continues to mix 10h with the speed of 500rpm on planetary ball mill, after the discharging at 80 ℃ of vacuum drying 2h, then under the argon hydrogen gas mixture atmosphere of 15ml/s, rise to 700 ℃ with the temperature rise rate of 5 ℃/min, under this temperature, be incubated 5h, drop to room temperature with stove, obtain the iron lithium phosphate Li that phosphate potential replaces Te
0.9Fe (P
0.9Te
0.1) O
4Powder.Method according to embodiment 1 is assembled into the CR2025 button cell, and ageing 8h carries out charge-discharge test, and test condition is identical with embodiment 1.
Embodiment 6: with 8.34g ferrous sulfate FeSO
47H
2O, 3.57g Secondary ammonium phosphate (NH
4)
2HPO
4Three oxidations, two tellurium Te with 0.45g
2O
3Mix, add in the agate jar, add the 5ml deionized water as the ball milling solvent, sealing back speed with 500rpm on planetary ball mill is mixed 8h, with deionized water dissolving, filtration, extremely use 1mol/L nitrate of baryta Ba (NO for 3～4 times after the discharging with deionized water wash
3)
2Solution detects less than sulfate ion SO
4 2-Filtration product obtains intermediate product behind 120 ℃ of vacuum drying 8h.With 1.51g lithium hydroxide LiOHH
2O and intermediate product add in the ball grinder, add the 5ml deionized water as the ball milling solvent, the sealing back continues to mix 10h with the speed of 500rpm on planetary ball mill, after the discharging at 80 ℃ of vacuum drying 2h, then under the argon hydrogen gas mixture atmosphere of 15ml/s, rise to 700 ℃ with the temperature rise rate of 5 ℃/min, under this temperature, be incubated 5h, drop to room temperature with stove, obtain the iron lithium phosphate Li that phosphate potential replaces Te
1.2Fe (P
0.9Te
0.1) O
4Powder.Method according to embodiment 1 is assembled into the CR2025 button cell, and ageing 8h carries out charge-discharge test, and test condition is identical with embodiment 1.
Embodiment 7: with 9.94g Iron dichloride tetrahydrate FeCl
24H
2O, 6.71g ammonium phosphate (NH
4)
3PO
4Sodium Selenite Na with 0.86g
2SeO
3Mix, add in the agate jar, adding 5ml dehydrated alcohol is as the ball milling solvent, and sealing back speed with 500rpm on planetary ball mill is mixed 8h, with deionized water dissolving, filtration, uses deionized water wash 3～4 times after the discharging.Filtration product obtains intermediate product behind 80 ℃ of vacuum drying 5h.With 2.03g Quilonum Retard Li
2CO
3Add in the ball grinder with intermediate product, add the 5ml dehydrated alcohol as the ball milling solvent, the sealing back continues to mix 10h with the speed of 500rpm on planetary ball mill, after the discharging at 80 ℃ of vacuum drying 2h, then under the nitrogen atmosphere of 20ml/s, rise to 800 ℃ with the temperature rise rate of 5 ℃/min, under this temperature, be incubated 8h, drop to room temperature with stove, obtain the iron lithium phosphate Li that phosphate potential replaces Se
1.1Fe (P
0.9Se
0.1) O
4Powder.Method according to embodiment 1 is assembled into the CR2025 button cell, and ageing 8h carries out charge-discharge test, and test condition is identical with embodiment 1.
Embodiment 8: with 19.88g Iron dichloride tetrahydrate FeCl
24H
2O, 13.41g ammonium phosphate (NH
4)
3PO
4Tin anhydride SeO with 1.11g
2Mix, add in the agate jar, adding 5ml dehydrated alcohol is as the ball milling solvent, and sealing back speed with 500rpm on planetary ball mill is mixed 12h, with deionized water dissolving, filtration, uses deionized water wash 3～4 times after the discharging.Filtration product obtains intermediate product behind 80 ℃ of vacuum drying 5h.With 4.06g Quilonum Retard Li
2CO
3Add in the ball grinder with intermediate product, add the 5ml dehydrated alcohol as the ball milling solvent, the sealing back continues to mix 10h with the speed of 500rpm on planetary ball mill, after the discharging at 80 ℃ of vacuum drying 2h, then under the nitrogen atmosphere of 20ml/s, rise to 800 ℃ with the temperature rise rate of 5 ℃/min, under this temperature, be incubated 8h, drop to room temperature with stove, obtain the iron lithium phosphate Li that phosphate potential replaces Se
1.1Fe (P
0.9Se
0.1) O
4Powder.Method according to embodiment 1 is assembled into the CR2025 button cell, and ageing 8h carries out charge-discharge test, and test condition is identical with embodiment 1.
Embodiment 9: with 27.80g ferrous sulfate FeSO
47H
2O, 12.67g ammonium phosphate (NH
4)
3PO
4Germanium dioxide GeO with 1.57g
2Mix, add in the agate jar, add 5ml acetone as the ball milling solvent, sealing back speed with 500rpm on planetary ball mill is mixed 8h, after the discharging with deionized water dissolving, filtration, with deionized water wash 3～4 times to 1mol/L nitrate of baryta Ba (NO
3)
2Solution detects less than sulfate ion SO
4 2-Filtration product obtains intermediate product behind 80 ℃ of vacuum drying 5h.With 5.86g lithium oxalate Li
2C
2O
4Add in the ball grinder with intermediate product, add 5ml acetone as the ball milling solvent, the sealing back continues to mix 10h with the speed of 500rpm on planetary ball mill, after the discharging at 80 ℃ of vacuum drying 2h, then under the nitrogen atmosphere of 15ml/s, rise to 750 ℃ with the temperature rise rate of 5 ℃/min, under this temperature, be incubated 5h, drop to room temperature with stove, obtain the iron lithium phosphate Li that phosphate potential replaces Ge
1.15Fe (P
0.85Ge
0.15) O
4Powder.Method according to embodiment 1 is assembled into the CR2025 button cell, and ageing 8h carries out charge-discharge test, and test condition is identical with embodiment 1.
Embodiment 10: with 13.90g ferrous sulfate FeSO
47H
2O, 6.71g ammonium phosphate (NH
4)
3PO
4Sodium germanate Na with 0.83g
2GeO
3Mix, add in the agate jar, add 5ml acetone as the ball milling solvent, sealing back speed with 500rpm on planetary ball mill is mixed 12h, after the discharging with deionized water dissolving, filtration, with deionized water wash 3～4 times to 1mol/L nitrate of baryta Ba (NO
3)
2Solution detects less than sulfate ion SO
4 2-Filtration product obtains intermediate product behind 80 ℃ of vacuum drying 8h.With 2.80g lithium oxalate Li
2C
2O
4Add in the ball grinder with intermediate product, add 5ml acetone as the ball milling solvent, the sealing back continues to mix 10h with the speed of 500rpm on planetary ball mill, after the discharging at 80 ℃ of vacuum drying 2h, then under the nitrogen atmosphere of 20ml/s, rise to 750 ℃ with the temperature rise rate of 5 ℃/min, under this temperature, be incubated 5h, drop to room temperature with stove, obtain the iron lithium phosphate Li that phosphate potential replaces Ge
1.1Fe (P
0.9Ge
0.1) O
4Powder.Method according to embodiment 1 is assembled into the CR2025 button cell, and ageing 8h carries out charge-discharge test, and test condition is identical with embodiment 1.
Embodiment 11: with 27.80g ferrous sulfate FeSO
47H
2O, 10.35g primary ammonium phosphate NH
4H
2PO
4Bismuthous oxide bismuth trioxide Bi with 2.33g
2O
3Mix, add in the agate jar, add the 5ml deionized water as the ball milling solvent, sealing back speed with 500rpm on planetary ball mill is mixed 8h, with deionized water dissolving, filtration, extremely use 1mol/L nitrate of baryta Ba (NO for 3～4 times after the discharging with deionized water wash
3)
2Solution detects less than sulfate ion SO
4 2-Filtration product obtains intermediate product behind 80 ℃ of vacuum drying 8h.With 5.03g lithium hydroxide LiOHH
2O and intermediate product add in the ball grinder, add the 5ml deionized water as the ball milling solvent, the sealing back continues to mix 10h with the speed of 500rpm on planetary ball mill, after the discharging at 80 ℃ of vacuum drying 2h, then under the nitrogen and hydrogen mixture atmosphere of 20ml/s, rise to 700 ℃ with the temperature rise rate of 5 ℃/min, under this temperature, be incubated 5h, drop to room temperature with stove, obtain the iron lithium phosphate Li that phosphate potential replaces Bi
1.2Fe (P
0.9Bi
0.1) O
4Powder.Method according to embodiment 1 is assembled into the CR2025 button cell, and ageing 8h carries out charge-discharge test, and test condition is identical with embodiment 1.
Claims (10)
1. based on P site doped lithium iron phosphate positive material, it is characterized in that its molecular formula is Li
yFe (P
1-xM
x) O
4, wherein M is a doped element, M is Ge, and Sn, Se, Te or Bi, 0＜x＜0.5, y is a lithium content, 0.7＜y＜2.0.
2. the preparation method based on P site doped lithium iron phosphate positive material as claimed in claim 1 is characterized in that may further comprise the steps:
1) ferrous salt, phosphoric acid salt are mixed with hotchpotch, add at least a in entry, ethanol, the acetone, behind ball milling 6～12h as the ball milling solvent, washing, filter, filtration product obtains intermediate product behind 60～80 ℃ of vacuum drying 5～8h, by quality than ferrous salt: phosphoric acid salt: hotchpotch=m
1: m
2(1-x): (m
3X/n
1), m wherein
1Be the molecular weight of ferrous salt, m
2Be phosphatic molecular weight, m
3Be the molecular weight of hotchpotch, n
1Atomicity for M in the hotchpotch;
2) intermediate product and lithium salts are carried out rerolling, add entry or organic solvent as the ball milling solvent, ball milling mixes 6～12h again, and 500～800 ℃ of calcinings are heated in product oven dry back under inert atmosphere or reducing atmosphere, obtain doped lithium ferric phosphate Li
yFe (P
1-xM
x) O
4Powder, wherein M is Ge, Sn, Se, Te or Bi, y are lithium content, quality is pressed than intermediate product: lithium salts=169:(m in 0.7＜y＜2.0
4Y/n
2), m wherein
4Be the molecular weight of lithium salts, y is a lithium content, 0.7＜y＜2.0, n
2Atomicity for the lithium in the lithium salts molecular formula.
3. the preparation method based on P site doped lithium iron phosphate positive material as claimed in claim 2 is characterized in that described ferrous salt is Iron diacetate, iron protochloride or ferrous sulfate.
4. the preparation method based on P site doped lithium iron phosphate positive material as claimed in claim 2 is characterized in that described phosphoric acid salt is ammonium phosphate, primary ammonium phosphate or Secondary ammonium phosphate.
5. the preparation method based on P site doped lithium iron phosphate positive material as claimed in claim 2 is characterized in that described lithium salts is Quilonum Retard, lithium hydroxide, lithium oxalate or Lithium Acetate.
6. the preparation method based on P site doped lithium iron phosphate positive material as claimed in claim 2 is characterized in that described hotchpotch is Ge-doped thing, tin dope thing, selenium hotchpotch, tellurium hotchpotch or bismuth hotchpotch; Described Ge-doped thing is germanium dioxide or sodium germanate; Described tin dope thing is tindioxide or sodium stannate; Described selenium hotchpotch is tin anhydride or sodium selenate; Described tellurium hotchpotch is three oxidations, two telluriums or sodium tellurate; Described bismuth hotchpotch is a bismuthous oxide bismuth trioxide.
7. the preparation method based on P site doped lithium iron phosphate positive material as claimed in claim 2 is characterized in that in step 2) in, organic solvent is at least a in dehydrated alcohol, the acetone.
8. the preparation method based on P site doped lithium iron phosphate positive material as claimed in claim 2 is characterized in that in step 2) in, the temperature of product oven dry is 40～120 ℃.
9. the preparation method based on P site doped lithium iron phosphate positive material as claimed in claim 2 is characterized in that in step 2) in, calcining back insulation 5～12h.
10. the preparation method based on P site doped lithium iron phosphate positive material as claimed in claim 2 is characterized in that in step 2) in, described inert atmosphere or reducing atmosphere are at least a in nitrogen, argon gas, nitrogen and hydrogen mixture and the argon hydrogen gas mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100087132A CN100494052C (en) | 2007-03-16 | 2007-03-16 | LiFePO4 cathode material based on P site doping and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100087132A CN100494052C (en) | 2007-03-16 | 2007-03-16 | LiFePO4 cathode material based on P site doping and preparation method thereof |
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| CN101844756B (en) * | 2009-03-25 | 2012-01-11 | 宝山钢铁股份有限公司 | Method for preparing lithium iron phosphate by using steel slag |
| CN101898757B (en) * | 2009-05-26 | 2011-12-21 | 宝山钢铁股份有限公司 | Method for preparing multi-component doped lithium ferrous phosphate by utilizing high phosphorus slag |
| CN101989656A (en) * | 2009-07-30 | 2011-03-23 | 河南新飞科隆电源有限公司 | Lithium ion battery phosphate anode material and preparation method thereof |
| CN101651204B (en) * | 2009-09-24 | 2012-11-14 | 安徽工业大学 | Method for preparing multi-element doping lithium iron phosphate by taking ferrous metallurgy sludge as main raw material |
| CN102376980A (en) * | 2010-08-07 | 2012-03-14 | 孙美红 | Cell with carbon-free lithium iron phosphate as anode and manufacturing method thereof |
| CN102208598B (en) | 2011-05-12 | 2014-03-12 | 中国科学院宁波材料技术与工程研究所 | Electrode plate of graphene coating modified lithium secondary battery and manufacturing method thereof |
| CN102992295A (en) * | 2011-09-09 | 2013-03-27 | 江西省金锂科技有限公司 | Manufacturing method of high-activity lithium iron phosphate positive pole material |
| CN102364734B (en) * | 2011-10-26 | 2013-02-13 | 黄景诚 | Method for preparing antimony and barium activated lithium iron phosphate cathode material |
| JP6302751B2 (en) * | 2014-06-03 | 2018-03-28 | シャープ株式会社 | Positive electrode active material, positive electrode and non-aqueous electrolyte secondary battery |
| CN108539178B (en) * | 2018-04-25 | 2020-11-13 | 广东工业大学 | Novel phosphorus-sulfur-selenium composite negative electrode material for ion battery and preparation method thereof |
| CN111342018B (en) * | 2020-03-10 | 2022-09-16 | 四川联伍新能源科技有限公司 | Carbon-coated lithium-containing transition metal phosphate positive electrode material and preparation method thereof |
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