CN102583299A - Method for preparing nano pure phase LiFePO4 by using different Li source, Fe source, P source and reductive atmosphere - Google Patents
Method for preparing nano pure phase LiFePO4 by using different Li source, Fe source, P source and reductive atmosphere Download PDFInfo
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- CN102583299A CN102583299A CN2012100419054A CN201210041905A CN102583299A CN 102583299 A CN102583299 A CN 102583299A CN 2012100419054 A CN2012100419054 A CN 2012100419054A CN 201210041905 A CN201210041905 A CN 201210041905A CN 102583299 A CN102583299 A CN 102583299A
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Abstract
The invention discloses a method for preparing nano pure phase LiFePO4 by using different Li source, Fe source, P source and reductive atmosphere. The method comprises the following steps of: 1) preparing a mixture; 2) presintering at a low temperature; and 3) sintering at a high temperature. According to the invention, a composite nano-structured carbon layer is adopted to coat a lithium iron phosphate material, thereby improving the multiplying power property and the energy density of the existing phosphate material battery; a secondary lithium ion battery using the material as a positive electrode has the advantages of large power density, good low temperature property, high specific capacity and the like; and the material nano pure phase LiFePO4is especially applied to a high-power dynamic battery and the fields of motor-driven tools, motor-driven automobiles, hybrid cars, motor-driven torpedo, energy-storing power supplies and the like.
Description
Technical field
The present invention relates to a kind of positive electrode material of secondary lithium battery, specifically relate to a kind of composite nanostructure carbon-coating coated LiFePO 4 for lithium ion batteries electrode materials that is used for secondary lithium battery with the pure phase LiFePO of nanometer
4And preparation method thereof.
Background technology
LiFePO
4Have that cost is low, aboundresources and structural stability and thermostability advantages of higher, but LiFePO under the normal temperature
4Dynamics bad, the high rate performance extreme difference has greatly limited the application of this material in reality.In order to improve specific conductivity and the transmission route that shortens ion, electronics, improve high rate performance, people have adopted such as methods such as coating, doping, nanometer it have been carried out modification.Armand proposes to coat one deck conductive layer at material surface and improves electronic conductivity, in polymer battery 80 ℃ with the 1C multiplying power under reversible capacity reach 160 mAh/g.Chiang Yet-Ming research group through different valency element (Mg, Al, Zr, Ti, Nb W) substitutes the electronic conductivity that improves material to the Li among the LiFePO4.The result shows that the material electric conductivity after the doping can improve 8 one magnitude; When charge-discharge magnification was C/10, capacity can reach 150mAh/g, when multiplying power is 40C, still kept the capacity of 60 mAh/g; And, show excellent electrochemical properties through the almost not decay of 60 all circulation volumes.1997, M.Armand etc. were at U.S. Pat A6, disclosed LiFePO in 514,640
4Carrying out the iron position mixes and phosphate potential alternate material.Yet reduce the granularity of phosphate material and improve the electrical contact performance between the particle at its coated with carbon through nanometer; But increased considerably the specific surface area of material; Need add more sticker when causing material coating pole piece; Influence the electroconductibility of pole piece, also make the density of pole piece and the activity substance content of unit volume reduce significantly.So just be unfavorable for producing the battery of high-energy-density.Therefore how at the LiFePO of hundreds of nanometer particle sizes
4Particle surface coats fine and close thin carbon layer uniformly and forms conductive network through carbochain, is to realize superpower LiFePO
4The gordian technique that electrode is made.
Summary of the invention
It is poor to the objective of the invention is when overcoming existing LiFePO 4 material as the positive electrode material of serondary lithium battery multiplying power property; And process the low density shortcoming of pole piece; A kind of composite nanostructure carbon-coating coated LiFePO 4 for lithium ion batteries electrode materials is provided, and is to adopt Different L i source, Fe source, P source to prepare the pure phase LiFePO of nanometer
4Method, obtain the electrode anode material of composite nanostructure carbon-coating coated LiFePO 4 for lithium ion batteries, to improve the high rate performance and the energy density of phosphate material battery.
Preparing method of the present invention realizes in the following manner: adopt different Li sources, Fe source, P source to prepare the pure phase LiFePO of nanometer
4Method, may further comprise the steps: 1) configuration mixture; 2) low temperature presintering; 3) high temperature sintering; It is characterized in that:
1), configuration mixture: adopt different Li sources, Fe source, P source to prepare the pure phase LiFePO of nanometer
4: take by weighing Li source, Fe source, P source and C according to mol ratio 0.5-1:1/3-1:1:0.3
6H
8O
7Be placed in the deionized water solvent, adopt the super grinder nanometer to handle: rotating speed is 3000 rev/mins, and 6 hours, mill was situated between and is the zirconia ball of diameter 0.3mm, and oven dry and hand lapping are pulverized and be mixture;
Described Li source is LiOH or L i
2CO
3
Described Fe source is FeOOH, Fe
3O
4Or Fe
2O
3
Described P source is H
3PO
4Or NH
4H
2PO
4
2), low temperature presintering: with mixture high-purity be to carry out low temperature presintering under high-purity protection of reducing atmosphere of 5%: be warming up to 350 ℃ with 1 hour from room temperature, at 350 ℃ of constant temperature after 4 hours, drop to room temperature with 10 hours, hand lapping is pulverized;
3), high temperature sintering: mixture is high temperature sintering under high-purity protection of reducing atmosphere of 5%: be warming up to 650 ℃ with 4 hours from room temperature; At 650 ℃ of constant temperature after 10 hours; With dropping to room temperature in 18 hours, obtain the pure phase LiFePO of nanometer that the particle median size is 100-2000nm after again the solid hand lapping being pulverized
4
Described step 2), 3) in, reducing atmosphere is Ar, CO or Ar+H
2.
With the composite nanostructure carbon-coating coated LiFePO 4 for lithium ion batteries material that the present invention makes, can improve the high rate performance and the energy density of existing phosphate material battery.Doing the anodal secondary lithium battery with said material, to have power density big, and low-temperature performance is good, remarkable advantages such as specific storage height.Be specially adapted to the superpower power cell, as be used in power tool, electromobile, PHEV, electric topedo, fields such as accumulation power supply.
Embodiment
Embodiment 1
A kind of Different L i source of adopting prepares the pure phase LiFePO of nanometer that is used for serondary lithium battery of the present invention
4Method: at first, take by weighing LiOH or L i according to mol ratio 1:0.5:1:0.3
2CO
3, Fe
2O
3, H
3PO
4, C
6H
8O
7(Hydrocerol A) also put into deionized water solvent, adopts the super grinder nanometer to handle back (rotating speed is 3000 rev/mins, and 6 hours, mill was situated between and is the zirconia ball of diameter 0.3mm), after oven dry and hand lapping are pulverized.With this mixture at high-purity Ar+H
2(5%) thermal treatment under the gas shiled (heat treated step is: be warming up to 350 ℃ with 1 hour from room temperature, at 350 ℃ of constant temperature after 4 hours, with dropping to room temperature in ten hours), after hand lapping was pulverized, mixture was at high-purity Ar+H
2Under the gas shiled once more sintering (sintering step is: be warming up to 650 ℃ with 4 hours from room temperature, at 650 ℃ of constant temperature after 10 hours, with dropping to room temperature in 18 hours.The back is pulverized in the solid hand lapping just can obtain the pure phase LiFePO of nanometer that the primary particle particle diameter is 300 nm
4
Embodiment 2
Adopt different Fe source to prepare the pure phase LiFePO of nanometer that is used for serondary lithium battery of the present invention
4Method: at first, 0.5:1:1:0.3 takes by weighing Li according to mol ratio
2CO
3, FeOOH, NH
4H
2PO
4, C
6H
8O
7(Hydrocerol A) also put into deionized water solvent, adopts the super grinder nanometer to handle back (rotating speed is 3000 rev/mins, and 6 hours, mill was situated between and is the zirconia ball of diameter 0.3mm), after oven dry and hand lapping are pulverized.With this mixture at high-purity Ar+H
2(5%) thermal treatment under the gas shiled (heat treated step is: be warming up to 350 ℃ with 1 hour from room temperature, at 350 ℃ of constant temperature after 4 hours, with dropping to room temperature in ten hours), after hand lapping was pulverized, mixture was at high-purity Ar+H
2Under the gas shiled once more sintering (sintering step is: be warming up to 650 ℃ with 4 hours from room temperature, at 650 ℃ of constant temperature after 10 hours, with dropping to room temperature in 18 hours.The back is pulverized in the solid hand lapping just can obtain the pure phase LiFePO of nanometer that the primary particle particle diameter is 400 nm
4
Embodiment 3:
Adopt different Fe source to prepare the pure phase LiFePO of nanometer that is used for serondary lithium battery of the present invention
4Method: at first, 0.5:1/3:1:0.3 takes by weighing Li according to mol ratio
2CO
3, Fe
3O
4, NH
4H
2PO
4, C
6H
8O
7(Hydrocerol A) also put into deionized water solvent, adopts the super grinder nanometer to handle back (rotating speed is 3000 rev/mins, and 6 hours, mill was situated between and is the zirconia ball of diameter 0.3mm), after oven dry and hand lapping are pulverized.With this mixture at high-purity Ar+H
2(5%) thermal treatment under the gas shiled (heat treated step is: be warming up to 350 ℃ with 1 hour from room temperature, at 350 ℃ of constant temperature after 4 hours, with dropping to room temperature in ten hours), after hand lapping was pulverized, mixture was at high-purity Ar+H
2(5%) under the gas shiled once more sintering (sintering step is: be warming up to 650 ℃ with 4 hours from room temperature, at 650 ℃ of constant temperature after 10 hours, with dropping to room temperature in 18 hours.The back is pulverized in the solid hand lapping just can obtain the pure phase LiFePO of nanometer that the primary particle particle diameter is 300 nm
4
Embodiment 4:
Adopt different Fe source to prepare the pure phase LiFePO of nanometer that is used for serondary lithium battery of the present invention
4Method: at first, 0.5:0.5:1:0.3 takes by weighing Li according to mol ratio
2CO
3, Fe
2O
3, H
3PO
4, C
6H
8O
7(Hydrocerol A) also put into deionized water solvent, adopts the super grinder nanometer to handle back (rotating speed is 3000 rev/mins, and 6 hours, mill was situated between and is the zirconia ball of diameter 0.3mm), after oven dry and hand lapping are pulverized.(heat treated step is: be warming up to 350 ℃ with 1 hour from room temperature with the thermal treatment under high-purity CO (5%) gas shiled of this mixture; At 350 ℃ of constant temperature after 4 hours; With dropping to room temperature in ten hours), after hand lapping is pulverized, mixture under high-purity CO gas shiled once more sintering (sintering step is: be warming up to 650 ℃ with 4 hours from room temperature; At 650 ℃ of constant temperature after 10 hours, with dropping to room temperature in 18 hours.The back is pulverized in the solid hand lapping just can obtain the pure phase LiFePO of nanometer that the primary particle particle diameter is 300 nm
4
Implement 5:
Adopt different reducing atmospheres to prepare the pure phase LiFePO of nanometer that is used for serondary lithium battery of the present invention
4Method: at first, 0.5:0.5:1:0.3 takes by weighing LiOH according to mol ratio, Fe
2O
3, NH
4H
2PO
4, C
6H
8O
7(Hydrocerol A) also put into deionized water solvent, adopts the super grinder nanometer to handle back (rotating speed is 3000 rev/mins, and 6 hours, mill was situated between and is the zirconia ball of diameter 0.3mm), after oven dry and hand lapping are pulverized.With this mixture at high-purity Ar+H
2Down thermal treatment of protection (heat treated step is: be warming up to 350 ℃ with 1 hour from room temperature, at 350 ℃ of constant temperature after 4 hours, with dropping to room temperature in ten hours), after the hand lapping pulverizing, mixture is at high-purity Ar+H
2Under the gas shiled once more sintering (sintering step is: be warming up to 650 ℃ with 4 hours from room temperature, at 650 ℃ of constant temperature after 10 hours, with dropping to room temperature in 18 hours.The back is pulverized in the solid hand lapping just can obtain the pure phase LiFePO of nanometer that the primary particle particle diameter is 300 nm
4
Embodiment 6:
Adopt different reducing atmospheres to prepare the pure phase LiFePO of nanometer that is used for serondary lithium battery of the present invention
4Method: at first, 0.5:0.5:1:0.3 takes by weighing Li according to mol ratio
2CO
3, Fe
2O
3, NH
4H
2PO
4, C
6H
8O
7(Hydrocerol A) also put into deionized water solvent, adopts the super grinder nanometer to handle back (rotating speed is 3000 rev/mins, and 6 hours, mill was situated between and is the zirconia ball of diameter 0.3mm), after oven dry and hand lapping are pulverized.With this mixture at high-purity N H
3Thermal treatment under the gas shiled (heat treated step is: be warming up to 350 ℃ with 1 hour from room temperature, at 350 ℃ of constant temperature after 4 hours, with dropping to room temperature in ten hours), after hand lapping was pulverized, mixture was at high-purity N H
3Under the gas shiled once more sintering (sintering step is: be warming up to 650 ℃ with 4 hours from room temperature, at 650 ℃ of constant temperature after 10 hours, with dropping to room temperature in 18 hours.The back is pulverized in the solid hand lapping just can obtain the pure phase LiFePO of nanometer that the primary particle particle diameter is 200 nm
4
The nano lithium iron phosphate material principal character:
| Embodiment | The Li source | The Fe source | The P source | Reducing atmosphere | Primary particle |
| 1 | Li 2CO 3 | Fe 2O 3 | H 3PO 4 | Ar+H 2（5%） | 300 nm |
| 2 | Li 2CO 3 | FeOOH | NH 4H 2PO 4 | Ar+H 2（5%） | 400 nm |
| 3 | Li 2CO 3 | Fe 3O 4 | NH 4H 2PO 4 | Ar+H 2（5%） | 200 nm |
| 4 | Li 2CO 3 | Fe 2O 3 | H 3PO 4 | CO（5%） | 300 um |
| 5 | LiOH | Fe 2O 3 | NH 4H 2PO 4 | Ar+H 2（5%） | 100 nm |
| 6 | Li 2CO 3 | Fe 2O 3 | NH 4H 2PO 4 | NH 3 | 200 nm |
Claims (5)
1. adopt different Li sources, Fe source, P source to prepare the pure phase LiFePO of nanometer
4Method, may further comprise the steps: 1) configuration mixture; 2) low temperature presintering; 3) high temperature sintering; It is characterized in that:
1), configuration mixture: adopt different Li sources, Fe source, P source to prepare the pure phase LiFePO of nanometer
4: take by weighing Li source, Fe source, P source and C according to mol ratio 0.5-1:1/3-1:1:0.3
6H
8O
7Be placed in the deionized water solvent, adopt the super grinder nanometer to handle: rotating speed is 3000 rev/mins, and 6 hours, mill was situated between and is the zirconia ball of diameter 0.3mm, and oven dry and hand lapping are pulverized and be mixture;
2), low temperature presintering: with mixture high-purity be to carry out low temperature presintering under high-purity protection of reducing atmosphere of 5%: be warming up to 350 ℃ with 1 hour from room temperature, at 350 ℃ of constant temperature after 4 hours, drop to room temperature with 10 hours, hand lapping is pulverized;
3), high temperature sintering: mixture is high temperature sintering under high-purity protection of reducing atmosphere of 5%: be warming up to 650 ℃ with 4 hours from room temperature; At 650 ℃ of constant temperature after 10 hours; With dropping to room temperature in 18 hours, obtain the pure phase LiFePO of nanometer that the particle median size is 100-2000nm after again the solid hand lapping being pulverized
4
2. different Li source, Fe source, the P sources of employing according to claim 1 prepares the pure phase LiFePO of nanometer
4Method, it is characterized in that: the Li source in the described step 1) is LiOH or L i
2CO
3
3. different Li source, Fe source, the P sources of employing according to claim 1 prepares the pure phase LiFePO of nanometer
4Method, it is characterized in that: the Fe source in the described step 1) is FeOOH, Fe
3O
4Or Fe
2O
3
4. different Li source, Fe source, the P sources of employing according to claim 1 prepares the pure phase LiFePO of nanometer
4Method, it is characterized in that: the P source in the described step 1) is H
3PO
4Or NH
4H
2PO
4
5. different Li source, Fe source, the P sources of employing according to claim 1 prepares the pure phase LiFePO of nanometer
4Method, described step 2), 3) in, high-purity reducing atmosphere is Ar, CO or Ar+H
2
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103094568A (en) * | 2013-01-29 | 2013-05-08 | 河北师范大学 | Preparation method for lithium iron phosphate |
| CN103515601A (en) * | 2013-10-28 | 2014-01-15 | 金瑞新材料科技股份有限公司 | Positive pole material LiFePO4 for lithium ion battery and preparation method thereof |
| CN103531794A (en) * | 2013-10-28 | 2014-01-22 | 金瑞新材料科技股份有限公司 | Lithium ion battery positive material lithium ferrous phosphate and preparation method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101378125A (en) * | 2007-08-28 | 2009-03-04 | 比亚迪股份有限公司 | Method for preparing active substance lithium iron phosphate for lithium ion secondary battery anode |
| CN101950801A (en) * | 2010-09-21 | 2011-01-19 | 新疆金盛科达有色金属新材料有限责任公司 | Preparation method of positive electrode material LiFePO4/C of lithium ion battery |
-
2012
- 2012-02-23 CN CN2012100419054A patent/CN102583299A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101378125A (en) * | 2007-08-28 | 2009-03-04 | 比亚迪股份有限公司 | Method for preparing active substance lithium iron phosphate for lithium ion secondary battery anode |
| CN101950801A (en) * | 2010-09-21 | 2011-01-19 | 新疆金盛科达有色金属新材料有限责任公司 | Preparation method of positive electrode material LiFePO4/C of lithium ion battery |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103094568A (en) * | 2013-01-29 | 2013-05-08 | 河北师范大学 | Preparation method for lithium iron phosphate |
| CN103515601A (en) * | 2013-10-28 | 2014-01-15 | 金瑞新材料科技股份有限公司 | Positive pole material LiFePO4 for lithium ion battery and preparation method thereof |
| CN103531794A (en) * | 2013-10-28 | 2014-01-22 | 金瑞新材料科技股份有限公司 | Lithium ion battery positive material lithium ferrous phosphate and preparation method |
| CN103531794B (en) * | 2013-10-28 | 2015-12-02 | 金瑞新材料科技股份有限公司 | Lithium ferrous phosphate as anode material of lithium ion battery and preparation method thereof |
| CN103515601B (en) * | 2013-10-28 | 2016-03-02 | 金瑞新材料科技股份有限公司 | A kind of anode material for lithium ion battery LiFePO 4 and preparation method thereof |
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