CN103337630A - Metal-doped carbon-coated lithium iron phosphate and preparation method thereof - Google Patents

Metal-doped carbon-coated lithium iron phosphate and preparation method thereof Download PDF

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CN103337630A
CN103337630A CN2013102646875A CN201310264687A CN103337630A CN 103337630 A CN103337630 A CN 103337630A CN 2013102646875 A CN2013102646875 A CN 2013102646875A CN 201310264687 A CN201310264687 A CN 201310264687A CN 103337630 A CN103337630 A CN 103337630A
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metal
powder
bag carbon
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method preparing
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靳素芳
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Irico Group Corp
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Irico Group Corp
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention relates to metal-doped carbon-coated lithium iron phosphate and a preparation method thereof. The preparation method comprises the following steps: respectively weighing Li3PO4, Fe2O3, Nb2O5 and RuO2, then mixing, adding the obtained powder into acetone, arranging in a ball grinder, and uniformly grinding to obtain ground slurry; drying the ground slurry, and then adding a saturated water solution of citric acid into the obtained powder to obtain a rheological phase precursor; under the protection of inert gas, heating the rheological phase precursor to 300 DEG C, performing constant-temperature roasting, then cooling in a furnace, taking out, and uniformly grinding; and pressing the ground powder obtained by grinding into blocks, performing constant-temperature roasting on the blocks at 600 DEG C under the protection of the inert gas, and then cooling to room temperature in the furnace, thus obtaining the metal-doped carbon-coated lithium iron phosphate. The chemical expression of the metal-doped carbon-coated lithium iron phosphate obtained by the invention is LiFe1-x-yNbxRuyPO4/C, wherein 0<x<=0.02 and 0<y<=0.02. The metal-doped carbon-coated lithium iron phosphate has a small particle size, has high specific discharge capacity under the condition of heavy current, and can effectively solve the problem that a battery prepared from the material is poor in low-temperature performance.

Description

A kind of metal-doped bag carbon LiFePO4 and preparation method thereof
Technical field
The invention belongs to the ferric phosphate lithium cell field, relate in particular to a kind of metal-doped bag carbon LiFePO4 and preparation method thereof.
Technical background
In today of social high speed development, the use of automobile is inevitable, and coal-fired this road is passless, fuel cell uses hydrogen gas generation also unworkable, can only walk this road of electric motor car from energy angle, and electrokinetic cell is the nucleus equipment of electric automobile, thereby developing into of lithium ion battery is inevitable, ferric phosphate lithium cell is compared with other lithium ion battery material has fail safe preferably, but this material also has some shortcomings that self exists, and shows that mainly the cryogenic property of material is poor.
Summary of the invention
The object of the present invention is to provide a kind of metal-doped bag carbon LiFePO4 and preparation method thereof, the metal-doped bag carbon LiFePO4 that this method obtains can solve this material effectively and prepare the relatively poor problem of cryogenic property that battery produces.
A kind of chemical expression of metal-doped bag carbon LiFePO4 is: LiFe 1-x-yNb xRu yPO 4/ C; Wherein, 0＜x≤0.02,0＜y≤0.02.
A kind of this metal-doped bag carbon method preparing phosphate iron lithium may further comprise the steps:
1) by phosphorus: iron: niobium: ruthenium=1:(1-x-y): the mol ratio of x:y takes by weighing Li respectively 3PO 4, Fe 2O 3, Nb 2O 5And RuO 2, mix then, get powder; Wherein, 0＜x≤0.02,0＜y≤0.02;
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 gets metal-doped bag carbon LiFePO4.
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 is by doping Nb and Ru in LiFePO4, the metal-doped bag carbon LiFePO4 particle diameter of preparation is less, specific discharge capacity at big electric current and 0 ℃ of following this material making battery is bigger, can solve this material effectively and prepare the relatively poor problem of battery cryogenic property
Description of drawings
Fig. 1 is the SEM photo of the metal-doped bag carbon LiFePO4 of the present invention's preparation; Wherein, the SEM photo of the metal-doped bag carbon LiFePO4 that a makes for embodiment 1, the SEM photo of the metal-doped bag carbon LiFePO4 that b makes for embodiment 2, the SEM photo of the metal-doped bag carbon LiFePO4 that the SEM photo of the metal-doped bag carbon LiFePO4 that c makes for embodiment 3, d make for embodiment 4;
Fig. 2 for the metal-doped bag carbon LiFePO4 of embodiment of the invention 1-4 preparation at 0 ℃, the first charge-discharge curve under the 3C.
Embodiment
Embodiment 1:
The chemical expression of the metal-doped bag carbon of present embodiment LiFePO4 is as follows:
LiFe 0.98Nb 0.01Ru 0.01PO 4/C。
The metal-doped bag carbon of present embodiment method preparing phosphate iron lithium may further comprise the steps:
1) by phosphorus: the mol ratio of iron: niobium: ruthenium=1:0.98:0.01:0.01 takes by weighing Li respectively 3PO 4, Fe 2O 3, Nb 2O 5And RuO 2, 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 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 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 gets metal-doped bag carbon LiFePO4.
Embodiment 2:
The chemical expression of the metal-doped bag carbon of present embodiment LiFePO4 is as follows:
LiFe 0.97Nb 0.01Ru 0.02PO 4/C。
The metal-doped bag carbon of present embodiment method preparing phosphate iron lithium may further comprise the steps:
1) by phosphorus: the mol ratio of iron: niobium: ruthenium=1:0.97:0.01:0.02 takes by weighing Li respectively 3PO 4, Fe 2O 3, Nb 2O 5And RuO 2, 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 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 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 gets metal-doped bag carbon LiFePO4.
Embodiment 3:
The chemical expression of the metal-doped bag carbon of present embodiment LiFePO4 is as follows:
LiFe 0.97Nb 0.02Ru 0.01PO 4/C。
The metal-doped bag carbon of present embodiment method preparing phosphate iron lithium may further comprise the steps:
1) by phosphorus: the mol ratio of iron: niobium: ruthenium=1:0.97:0.02:0.01 takes by weighing Li respectively 3PO 4, Fe 2O 3, Nb 2O 5And RuO 2, 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 gets metal-doped bag carbon LiFePO4.
Embodiment 4:
The chemical expression of the metal-doped bag carbon of present embodiment LiFePO4 is as follows:
LiFe 0.96Nb 0.02Ru 0.02PO 4/C。
The metal-doped bag carbon of present embodiment method preparing phosphate iron lithium may further comprise the steps:
1) by phosphorus: the mol ratio of iron: niobium: ruthenium=1:0.96:0.02:0.02 takes by weighing Li respectively 3PO 4, Fe 2O 3, Nb 2O 5And RuO 2, 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 gets metal-doped bag carbon LiFePO4.
The present invention has carried out the SEM detection to the metal-doped bag carbon LiFePO4 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 metal-doped bag carbon LiFePO4 that embodiment 3 obtains is less and relatively more even, the particle diameter of the metal-doped bag carbon LiFePO4 that embodiment 4 obtains is bigger, and smaller particle size is conducive to lithium ion to be passed through fast, can improve the high rate performance of material.
First the charging and discharging curve of metal-doped bag carbon LiFePO4 under 3C that Fig. 2 obtains for embodiment 1-4, from the curve first charge-discharge capacity minimum of metal-doped bag carbon LiFePO4 under 3C that obtain of embodiment 1 as can be seen, at 120mAh/g, the first charge-discharge capacity maximum of metal-doped bag carbon LiFePO4 under 3C that embodiment 4 obtains, about 140mAh/g, the metal-doped bag carbon LiFePO4 that embodiment 3 obtains the first charge-discharge capacity also less, the metal-doped bag carbon LiFePO4 that embodiment 2 obtains the first charge-discharge capacity placed in the middle, at 140mAh/g.

Claims (9)

1. metal-doped bag carbon LiFePO4, it is characterized in that: chemical expression is: LiFe 1-x-yNb xRu yPO 4/ C; Wherein, 0＜x≤0.02,0＜y≤0.02.
2. a metal-doped bag carbon method preparing phosphate iron lithium as claimed in claim 1 is characterized in that, may further comprise the steps:
1) by phosphorus: iron: niobium: ruthenium=1:(1-x-y): the mol ratio of x:y takes by weighing Li respectively 3PO 4, Fe 2O 3, Nb 2O 5And RuO 2, mix then, get powder; Wherein, 0＜x≤0.02,0＜y≤0.02;
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 gets metal-doped bag carbon LiFePO4.
3. metal-doped bag carbon method preparing phosphate iron lithium according to claim 2 is characterized in that: the volume of acetone is 2 times of powder volume described step 2).
4. metal-doped bag carbon method preparing phosphate iron lithium according to claim 2, it is characterized in that: described step 2) rotating speed of ball mill is 500-800rpm/min, rotational time is 3-6h.
5. metal-doped bag carbon method preparing phosphate iron lithium according to claim 2 is characterized in that: described step 2) ground slurry is to adopt oven drying, and baking temperature is 100 ℃.
6. metal-doped bag carbon method preparing phosphate iron lithium according to claim 2, it is characterized in that: the inert gas in the described step 3) is nitrogen.
7. metal-doped bag carbon method preparing phosphate iron lithium 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. metal-doped bag carbon method preparing phosphate iron lithium 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 claim 2 or 8 described metal-doped bag carbon method preparing phosphate iron lithium, it is characterized in that: the blocks in the described step 3) is cylindric.
CN2013102646875A 2013-06-27 2013-06-27 Metal-doped carbon-coated lithium iron phosphate and preparation method thereof Pending CN103337630A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090117020A1 (en) * 2007-11-05 2009-05-07 Board Of Regents, The University Of Texas System Rapid microwave-solvothermal synthesis and surface modification of nanostructured phospho-olivine cathodes for lithium ion batteries
CN102299331A (en) * 2011-07-19 2011-12-28 彩虹集团公司 Carbon-coated lithium iron phosphate-doped lithium ion battery anode material and preparation method thereof
CN103038162A (en) * 2010-05-27 2013-04-10 苏德化学专利两合有限公司 Composite material containing a mixed lithium metal phosphate

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090117020A1 (en) * 2007-11-05 2009-05-07 Board Of Regents, The University Of Texas System Rapid microwave-solvothermal synthesis and surface modification of nanostructured phospho-olivine cathodes for lithium ion batteries
CN103038162A (en) * 2010-05-27 2013-04-10 苏德化学专利两合有限公司 Composite material containing a mixed lithium metal phosphate
CN102299331A (en) * 2011-07-19 2011-12-28 彩虹集团公司 Carbon-coated lithium iron phosphate-doped lithium ion battery anode material and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
唐红等: "掺Nb5+对LiFePO4高倍率性能的影响", 《电源技术》, vol. 35, no. 3, 31 March 2011 (2011-03-31), pages 268 - 2 *

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Application publication date: 20131002