CN103346316A - Doped lithium iron phosphate and preparation method thereof - Google Patents
Doped lithium iron phosphate and preparation method thereof Download PDFInfo
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- CN103346316A CN103346316A CN2013102642272A CN201310264227A CN103346316A CN 103346316 A CN103346316 A CN 103346316A CN 2013102642272 A CN2013102642272 A CN 2013102642272A CN 201310264227 A CN201310264227 A CN 201310264227A CN 103346316 A CN103346316 A CN 103346316A
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- doped lithium
- powder
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- lithium ferric
- ferric phosphate
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses doped lithium iron phosphate and a preparation method thereof. The method comprises the following steps of: respectively weighing and mixing Li3PO4, Fe2O3, Nb2O5, and Ta2O5, adding acetone in the powder, and placing the mixture into a ball grinder for uniformly grinding, so as to obtain grinding slurry; drying the slurry, and adding a citric acid saturated water solution into the dried slurry, so as to obtain a rheological-phase precursor; under the protection of an inert gas, raising the temperature of the rheological-phase precursor to 300 DEG C, roasting for 5-8 hours, and withdrawing the precursor after the temperature is reduced down with a furnace, and uniformly grinding; pressing the ground grinding powder into blocks, roasting the blocks for 15-24 hours at the constant temperature of 600 DEG C under the protection of the inert gas, and reducing the temperature of the blocks to the ambient temperature, thereby obtaining the doped lithium iron phosphate. The doped lithium iron phosphate is good in electrochemical performance and material crystal form, and uniform in particle size, and has the chemical expression of LiFe1-x-yNbxTayPO4/C, where x is larger than 0 but less than or equal to 0.02, and y is larger than 0 but less than or equal to 0.02.
Description
Technical field
The invention belongs to the lithium ion battery field, relate in particular to a kind of doped lithium ferric phosphate and preparation method thereof.
Technical background
Environment in recent years pressure continues to increase, and developing into of new-energy automobile is inevitable, and the fail safe of new forms of energy car is problem demanding prompt solution, fundamentally improve the fail safe that the fail safe of battery still will improve material, LiFePO
4Material be in the battery material than safe material, but this material also has some shortcomings that self exist, and shows that mainly discharge capacity is little under the relatively lower and high magnification of conductivity.
Summary of the invention
The object of the present invention is to provide a kind of doped lithium ferric phosphate and preparation method thereof, doped lithium ferric phosphate charging and discharging capacity, material crystal formation that this method obtains are better, and particle diameter is even.
In order to achieve the above object, the chemical expression of doped lithium ferric phosphate of the present invention is: LiFe
1-x-yNb
xTa
yPO
4/ C, wherein, 0＜x≤0.02,0＜y≤0.02.
A kind of preparation method of doped lithium ferric phosphate may further comprise the steps:
1) by the phosphorus lithium: iron: niobium: tantalum=1:(1-x-y): the mol ratio of x:y takes by weighing Li respectively
3PO
4, Fe
2O
3, Nb
2O
5And Ta
2O
5, mix then, get powder; 0＜x≤0.02,0＜y≤0.02 wherein;
2) add powder in the acetone and place grinding in ball grinder even, obtain ground slurry; With ground slurry 100 ℃ down dry, add the saturated aqueous solution of citric acid then in the powder that obtains, obtain the precursor of rheology phase; Li in the contained carbon of citric acid and the powder in the saturated aqueous solution of the citric acid that wherein, adds
3PO
4The mol ratio of contained phosphorus is 1:1;
3) under the protection of inert gas, the precursor of rheology phase is warming up to 300 ℃ of constant temperature calcining 5-8h, take out with stove cooling back then and grind evenly; The grinding powder that grinding is obtained is pressed into blocks, and blocks in 600 ℃ of constant temperature calcining 15-24h, is cooled to room temperature with stove then under the protection of inert gas, namely get doped lithium ferric phosphate.
Described step 2) volume of acetone is 2 times of powder volume in.
Described step 2) rotating speed of ball mill is 500-800rpm/min, and rotational time is 3-6h.
Described step 2) ground slurry is to adopt oven drying, and baking temperature is 100 ℃.
Inert gas in the described step 3) is nitrogen.
The presoma of rheology phase is that speed with 4 ℃/min is warming up to 300 ℃ in the described step 3).
Grind powder in the described step 3) and under 300MPa pressure, be pressed into blocks.
Blocks in the described step 3) is cylindric.
Compared with prior art, beneficial effect of the present invention is: the present invention mix in LiFePO4 Nb, Ta, the doped lithium ferric phosphate (LiFe that makes preparation
1-x-yTi
xOs
yPO
4/ C anode material for lithium-ion batteries) have bigger charging and discharging capacity, and the material crystal formation that this method is synthesized is better, particle diameter is even.
Description of drawings
Fig. 1 is the SEM photo of the doped lithium ferric phosphate of the present invention's preparation; Wherein, the SEM photo of the doped lithium ferric phosphate that a makes for embodiment 1, the SEM photo of the doped lithium ferric phosphate that b makes for embodiment 2, the SEM photo of the doped lithium ferric phosphate that c makes for embodiment 3, the SEM photo of the doped lithium ferric phosphate that d makes for embodiment 4;
Fig. 2 is the first charge-discharge curve of doped lithium ferric phosphate under 2C of embodiment of the invention 1-4 preparation.
Embodiment
Embodiment 1:
The chemical expression of the doped lithium ferric phosphate of present embodiment is as follows: LiFe
0.98Nb
0.01Ta
0.01PO
4/ C.
The preparation method of present embodiment doped lithium ferric phosphate may further comprise the steps:
1) by phosphorus: the mol ratio of iron: niobium: tantalum=1:0.98:0.01:0.01 takes by weighing Li respectively
3PO
4, Fe
2O
3, Nb
2O
5And Ta
2O
5, mix then, get powder;
2) powder is added in the acetone of 2 times of powder volumes and place ball mill with the speed rotation 3h of 500rpm/min powder to be mixed, obtain ground slurry; Ground slurry is taken out from ball grinder, then in baking oven in 100 ℃ down dry, add the saturated aqueous solution of citric acid in the powder that obtains, obtain the precursor of rheology phase; Li in the contained carbon of citric acid and the powder in the saturated aqueous solution of the citric acid that wherein, adds
3PO
4The mol ratio of contained phosphorus is 1:1;
3) under the protection of high pure nitrogen atmosphere, the precursor of rheology phase is warming up to 300 ℃ with the 4 ℃/min rate of heat addition, constant temperature calcining 5h takes out with stove cooling back then and grinds evenly; The grinding powder that grinding is obtained depresses to cylinder at 300MPa pressure, and cylinder in 600 ℃ of constant temperature calcining 15h, is cooled to room temperature with stove then under the protection of high pure nitrogen atmosphere, namely get doped lithium ferric phosphate.
Embodiment 2:
The chemical expression of present embodiment doped lithium ferric phosphate is as follows: LiFe
0.97Nb
0.01Ta
0.02PO
4/ C.
The preparation method of present embodiment doped lithium ferric phosphate may further comprise the steps:
1) by phosphorus: the mol ratio of iron: niobium: tantalum=1:0.97:0.01:0.02 takes by weighing Li respectively
3PO
4, Fe
2O
3, Nb
2O
5And Ta
2O
5, mix then, get powder;
2) powder is added in the acetone of 2 times of powder volumes and place ball mill with the speed rotation 4h of 600rpm/min powder to be mixed, obtain ground slurry; Ground slurry is taken out from ball grinder, then in baking oven in 100 ℃ down dry, add the saturated aqueous solution of citric acid in the powder that obtains, obtain the precursor of rheology phase; Li in the contained carbon of citric acid and the powder in the saturated aqueous solution of the citric acid that wherein, adds
3PO
4The mol ratio of contained phosphorus is 1:1;
3) under the protection of high pure nitrogen atmosphere, the precursor of rheology phase is warming up to 300 ℃ with the 4 ℃/min rate of heat addition, constant temperature calcining 6h takes out with stove cooling back then and grinds evenly; The grinding powder that grinding is obtained depresses to cylinder at 300MPa pressure, and cylinder in 600 ℃ of constant temperature calcining 18h, is cooled to room temperature with stove then under the protection of high pure nitrogen atmosphere, namely get doped lithium ferric phosphate.
Embodiment 3:
The chemical expression of present embodiment doped lithium ferric phosphate is as follows: LiFe
0.97Nb
0.02Ta
0.01PO
4/ C.
The preparation method of present embodiment doped lithium ferric phosphate may further comprise the steps:
1) by phosphorus: the mol ratio of iron: niobium: tantalum=1:0.97:0.02:0.01 takes by weighing Li respectively
3PO
4, Fe
2O
3, Nb
2O
5And Ta
2O
5, mix then, get powder;
2) powder is added in the acetone of 2 times of powder volumes and place ball mill with the speed rotation 5h of 700rpm/min, powder is mixed, obtain ground slurry; Ground slurry is taken out from ball grinder, then in baking oven in 100 ℃ down dry, add the saturated aqueous solution of citric acid in the powder that obtains, obtain the precursor of rheology phase; Li in the contained carbon of citric acid and the powder in the saturated aqueous solution of the citric acid that wherein, adds
3PO
4The mol ratio of contained phosphorus is 1:1;
3) under the protection of high pure nitrogen atmosphere, the precursor of rheology phase is warming up to 300 ℃ with the 4 ℃/min rate of heat addition, constant temperature calcining 7h takes out with stove cooling back then and grinds evenly; The grinding powder that grinding is obtained depresses to cylinder at 300MPa pressure, and cylinder in 600 ℃ of constant temperature calcining 21h, is cooled to room temperature with stove then under the protection of high pure nitrogen atmosphere, namely get doped lithium ferric phosphate.
Embodiment 4
The chemical expression of present embodiment doped lithium ferric phosphate is as follows: LiFe
0.96Nb
0.02Ta
0.02PO
4/ C.
The preparation method of present embodiment doped lithium ferric phosphate may further comprise the steps:
1) by phosphorus: the mol ratio of iron: niobium: tantalum=1:0.96:0.02:0.02 takes by weighing Li respectively
3PO
4, Fe
2O
3, Nb
2O
5And Ta
2O
5, mix then, get powder;
2) powder is added in the acetone of 2 times of powder volumes and place ball mill with the speed rotation 6h of 800rpm/min, powder is mixed, obtain ground slurry; Ground slurry is taken out from ball grinder, then in baking oven in 100 ℃ down dry, add the saturated aqueous solution of citric acid in the powder that obtains, obtain the precursor of rheology phase; Li in the contained carbon of citric acid and the powder in the saturated aqueous solution of the citric acid that wherein, adds
3PO
4The mol ratio of contained phosphorus is 1:1;
3) under the protection of high pure nitrogen atmosphere, the precursor of rheology phase is warming up to 300 ℃ with the 4 ℃/min rate of heat addition, constant temperature calcining 8h takes out with stove cooling back then and grinds evenly; The grinding powder that grinding is obtained depresses to cylinder at 300MPa pressure, and cylinder in 600 ℃ of constant temperature calcining 24h, is cooled to room temperature with stove then under the protection of high pure nitrogen atmosphere, namely get doped lithium ferric phosphate.
The present invention has carried out the SEM detection to the doped lithium ferric phosphate that embodiment 1-4 obtains, and its result is shown in Fig. 1 a-1d.By Fig. 1 a-1d as can be seen, the particle diameter of the doped lithium ferric phosphate that embodiment 3 obtains is less and relatively more even, the particle diameter of the doped lithium ferric phosphate that embodiment 4 obtains is bigger, passes through fast and smaller particle size is conducive to lithium ion, can improve the high rate performance of material.
First the charging and discharging curve of doped lithium ferric phosphate under 2C that Fig. 2 obtains for embodiment 1-4, from curve as can be seen the chemical expression that obtains of embodiment 1 be LiFe
0.98Nb
0.01Ta
0.01PO
4The first charge-discharge capacity minimum of the doped lithium ferric phosphate of/C under 2C is about 95mAh/g; The chemical expression that embodiment 3 obtains is LiFe
0.97Nb
0.02Ta
0.01PO
4The first charge-discharge capacity maximum of the doped lithium ferric phosphate of/C under 2C is about 120mAh/g; The chemical expression that embodiment 2 obtains is LiFe
0.97Nb
0.01Ta
0.02PO
4The chemical expression that the doped lithium ferric phosphate of/C and embodiment 4 obtain is LiFe
0.96Nb
0.02Ta
0.02PO
4The doped lithium ferric phosphate of/C first charge-discharge capacity under 2C is more or less the same, about 100mAh/g.
Claims (9)
1. a doped lithium ferric phosphate is characterized in that, chemical expression is: LiFe
1-x-yNb
xTa
yPO
4/ C, wherein, 0＜x≤0.02,0＜y≤0.02.
2. the preparation method of a doped lithium ferric phosphate as claimed in claim 1 is characterized in that, may further comprise the steps:
1) by phosphorus: iron: niobium: tantalum=1:(1-x-y): the mol ratio of x:y takes by weighing Li respectively
3PO
4, Fe
2O
3, Nb
2O
5And Ta
2O
5, mix then, get powder; 0＜x≤0.02,0＜y≤0.02 wherein;
2) add powder in the acetone and place grinding in ball grinder even, obtain ground slurry; With the ground slurry drying, add the saturated aqueous solution of citric acid then in the powder that obtains, obtain the precursor of rheology phase; Li in the contained carbon of citric acid and the powder in the saturated aqueous solution of the citric acid that wherein, adds
3PO
4The mol ratio of contained phosphorus is 1:1;
3) under the protection of inert gas, the precursor of rheology phase is warming up to 300 ℃ of constant temperature calcining 5-8h, take out with stove cooling back then and grind evenly; The grinding powder that grinding is obtained is pressed into blocks, and blocks in 600 ℃ of constant temperature calcining 15-24h, is cooled to room temperature with stove then under the protection of inert gas, namely get doped lithium ferric phosphate.
3. the preparation method of doped lithium ferric phosphate according to claim 2 is characterized in that: the volume of acetone is 2 times of powder volume described step 2).
4. according to the preparation method of claim 2 or 3 described doped lithium ferric phosphates, it is characterized in that: described step 2) rotating speed of ball mill is 500-800rpm/min, and rotational time is 3-6h.
5. the preparation method of doped lithium ferric phosphate according to claim 2 is characterized in that: described step 2) ground slurry is to adopt oven drying, and baking temperature is 100 ℃.
6. the preparation method of doped lithium ferric phosphate according to claim 2, it is characterized in that: the inert gas in the described step 3) is nitrogen.
7. the preparation method of doped lithium ferric phosphate according to claim 2 is characterized in that: the presoma of rheology phase is that speed with 4 ℃/min is warming up to 300 ℃ in the described step 3).
8. the preparation method of doped lithium ferric phosphate according to claim 2 is characterized in that: grind powder in the described step 3) and be pressed into blocks under 300MPa pressure.
9. according to the preparation method of claim 2 or 8 described doped lithium ferric phosphates, it is characterized in that: the blocks in the described step 3) is cylindric.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111653772A (en) * | 2020-05-28 | 2020-09-11 | 武汉理工大学 | Flexible iron niobate nanowire array electrode and preparation method and application thereof |
| CN112786859A (en) * | 2021-01-22 | 2021-05-11 | 合肥国轩高科动力能源有限公司 | Preparation method of tantalum-doped/porous metal nanoparticle-coated modified lithium iron phosphate material |
Citations (3)
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|---|---|---|---|---|
| CN103000889A (en) * | 2012-12-04 | 2013-03-27 | 彩虹集团公司 | Preparation method of positive pole material of lithium-ion battery doped with lithium iron phosphate in lithium position |
| CN103053052A (en) * | 2011-04-28 | 2013-04-17 | 昭和电工株式会社 | Method for manufacturing positive electrode active material for lithium secondary cell, positive electrode active material for lithium secondary cell, and lithium secondary cell |
| CN103098263A (en) * | 2010-09-09 | 2013-05-08 | 加州理工学院 | Electrochemical energy storage systems and methods |
-
2013
- 2013-06-27 CN CN2013102642272A patent/CN103346316A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103098263A (en) * | 2010-09-09 | 2013-05-08 | 加州理工学院 | Electrochemical energy storage systems and methods |
| CN103053052A (en) * | 2011-04-28 | 2013-04-17 | 昭和电工株式会社 | Method for manufacturing positive electrode active material for lithium secondary cell, positive electrode active material for lithium secondary cell, and lithium secondary cell |
| CN103000889A (en) * | 2012-12-04 | 2013-03-27 | 彩虹集团公司 | Preparation method of positive pole material of lithium-ion battery doped with lithium iron phosphate in lithium position |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111653772A (en) * | 2020-05-28 | 2020-09-11 | 武汉理工大学 | Flexible iron niobate nanowire array electrode and preparation method and application thereof |
| CN112786859A (en) * | 2021-01-22 | 2021-05-11 | 合肥国轩高科动力能源有限公司 | Preparation method of tantalum-doped/porous metal nanoparticle-coated modified lithium iron phosphate material |
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Application publication date: 20131009 |