CN102079517A - Method for preparing fluorizated lithium vanadium phosphate as lithium-ion battery anode material by using spray pyrolysis method - Google Patents
Method for preparing fluorizated lithium vanadium phosphate as lithium-ion battery anode material by using spray pyrolysis method Download PDFInfo
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- CN102079517A CN102079517A CN2009102528872A CN200910252887A CN102079517A CN 102079517 A CN102079517 A CN 102079517A CN 2009102528872 A CN2009102528872 A CN 2009102528872A CN 200910252887 A CN200910252887 A CN 200910252887A CN 102079517 A CN102079517 A CN 102079517A
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Abstract
The invention discloses a method for preparing fluorizated lithium vanadium phosphate as a lithium-ion battery anode material by using a spray pyrolysis method. The preparation method comprises the following steps of: respectively adding a phosphate source, a vanadium source, a lithium source, a fluorine source, hydrazine hydrate and additives in a certain stoichiometric proportion to water, stirring for 30min to uniformly mix after adding each substance, and finally, forming a mixed solution with the metal ion concentration of 0.2-1.0mol/L; then, putting the mixed solution in a hydrogen airflow spray dryer, spraying and drying at 200-300 DEG C and collecting the product to obtain precursor powder; and tabletting the precursor powder at the pressure of 20MPa, then, sintering at 600-800 DEG C for 10h under hydrogen protection and naturally cooling to a room temperature to obtain LiVPO4F. The method has low raw material cost, simple operation process, strong controllability and high reproduction, effectively shortens the synthesis period of the material and saves the production cost. The fluorizated lithium vanadium phosphate synthesized by applying the method has the grain diameter of 60-500nm, good grain dispersibility, high crystallinity degree, higher reversible capacity and favorable cycle life, can meet various needs of the practical applications of the lithium-ion battery and can be directly used for the mass production of the lithium-ion battery anode material.
Description
Technical field
The present invention relates to a kind of method for preparing anode material for lithium-ion batteries, particularly utilize spray pyrolysis to prepare the method for anode material for lithium-ion batteries fluorinated phosphate vanadium lithium.
Background technology
Lithium ion battery has high workload current potential, high-energy-density, high-specific-power, has extended cycle life and advantage such as pollution-free is widely used on portable electric appts, power tool, energy storage device, power truck and the hybrid electric vehicle because of it.Lithium ion battery generally is made up of a plurality of parts such as positive and negative electrode active material, electrolytic solution, barrier film, collectors, among these integral parts, active material is the crucial active site of main integral part of lithium ion battery and energy storage, positive electrode material particularly, its cost accounts for about 40% of entire cell, so composition design, preparation technology and the performance of positive electrode material have determined the final performance and the price of lithium ion battery to a great extent.Though, cobalt acid lithium is a kind of the most frequently used commercial li-ion cell positive material at present, but cobalt is a kind of rare strategic resource, make that cobalt acid lithium is higher as the cost of the lithium ion battery of positive electrode material, particularly because China cobalt resource country extremely in short supply, explored cobalt resource workable reserves only accounts for 1.03% of world's cobalt resource, and the most of cobalt ore resources relies on foreign import, therefore is necessary very much to seek and the cheap anode material for lithium-ion batteries of development of new.By contrast, vanadium is China's advantage mineral products, and explored vanadium resource reserves occupy the third place in the world, account for global total reserves 18.7%, therefore, exploitation lithium ion battery vanadium is that positive electrode material not only has the important strategic meaning, also has great economic and social benefit.
At the lithium ion battery vanadium is in the positive electrode material, fluorinated phosphate vanadium lithium (LiVPO
4F) be a kind of novel polyanion material, its structure be one by PO
4Tetrahedron and VO
4F
2The octahedra three-dimensional framework network that makes up makes LiVPO just because of this structural advantage
4F has very high average operating potential (4.3V), height reversible lithium ion transport characteristic, high energy density (667Wh/kg), good chemistry and electrochemical stability, thermostability particularly, people such as J.R.Dahn (F.Zhou, X.M.Zhao, J.R.Dahn, Electrochem.Commun., 2009,11:589.) utilize accelerating calorimeter to find LiVPO
4F compares LiFePO
4Have better thermostability, show that the battery with this type of material construction has very high security.Therefore, LiVPO
4F is a kind of anode material for lithium-ion batteries that DEVELOPMENT PROSPECT is arranged very much.At present, synthetic LiVPO
4The main method of F is the high temperature solid-state polystep reaction method under protection of inert gas; but this class preparation technology has, and process is complicated and changeable, the cycle is long, energy consumption is excessive, the more high shortcoming of cost; and resulting material purity is not high, particle is poor than big and skewness, chemical property, is unfavorable for realizing large-scale industrial production.
Summary of the invention
The purpose of this invention is to provide a kind of method of utilizing spray pyrolysis to prepare anode material for lithium-ion batteries fluorinated phosphate vanadium lithium.Raw material sources of the present invention are extensive, and are easy and simple to handle, controllability good, circulation ratio is high, and resulting material granule is less, size distribution is even, degree of crystallinity is high, thereby when reducing the material preparation cost, improved the chemical property of material.
Concrete implementation step of the present invention is:
(1) phosphoric acid root, vanadium source, lithium source, fluorine source, hydrazine hydrate and the additive with certain stoichiometric ratio is added to the water respectively, stirring made it to mix in 30 minutes behind a kind of material of every adding, finally made it to form the mixing solutions of concentration of metal ions between 0.2-1.0mol/L.
The mol ratio of the phosphoric acid root described in the present invention, vanadium source, lithium source, fluorine source, hydrazine hydrate and additive is (1-4): (1-2): (1-2): (1-2): 2: (1-4).
Phosphoric acid root described in the present invention is a kind of in phosphoric acid, primary ammonium phosphate, the Secondary ammonium phosphate.
Vanadium source described in the present invention is a kind of in Vanadium Pentoxide in FLAKES, vanadous oxide, the ammonium meta-vanadate.
Lithium source described in the present invention is a kind of in lithium fluoride, lithium oxalate, Lithium Acetate, the lithium nitrate.
Fluorine source described in the present invention is a kind of in Neutral ammonium fluoride, the lithium fluoride.
Additive described in the present invention is a kind of in maltose, sucrose, the glucose.
(2) then mixing solutions is put into the argon stream spray-dryer,, collect product and get the presoma powder 200-300 ℃ of following spraying drying.
(3) the presoma powder is pressed into sheet under 20MPa pressure, then under argon shield in 600-800 ℃ of sintering 10 hours, promptly get LiVPO after naturally cooling to room temperature
4F.
Characteristics of the present invention are: (1) has simplified LiVPO
4The preparation process of F, controllability is good, and the circulation ratio height has shortened the synthesis cycle of material, has saved production cost.(2) utilize this method synthetic material granule uniformity, good dispersity, degree of crystallinity height, and, also can obtain the material of different-grain diameter by regulating the concentration of mixing solutions.(3) resulting material has very high average operating potential (4.3V), considerable reversible capacity, the high rate performance of excellence and stable cycle life among the present invention, make this material have very high actual use value, can effectively satisfy the actual requirement of the various application of lithium ion battery.(4) the present invention's navajoite resource of having made full use of China's abundant is developed lithium ion battery, has reduced the real cost of lithium ion battery from the source of manufactured materials, is particularly suitable for large-scale industrialization production.
Description of drawings
Fig. 1 is gained LiVPO in the embodiment of the invention 1
4The XRD figure of F.
Fig. 2 is gained LiVPO in the embodiment of the invention 1
4The SEM figure of F.
Fig. 3 is gained LiVPO in the embodiment of the invention 1
4The first charge-discharge curve of F.
Fig. 4 is gained LiVPO in the embodiment of the invention 1
4The cycle performance curve of F.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail.
Examples of implementation 1
0.4mol primary ammonium phosphate, 0.2mol ammonium meta-vanadate, 0.2mol lithium oxalate, 0.2mol Neutral ammonium fluoride, 0.2mol hydrazine hydrate, 0.4mol maltose are added to the water respectively, stirred 30 minutes with mechanical stirrer behind a kind of material of every adding, make it to mix, the cumulative volume of final gained mixing solutions is 400mL, then mixing solutions is put into the argon stream spray-dryer, 300 ℃ of following spraying dryings, collect product and get the presoma powder.The presoma powder of gained is pressed into sheet under 20MPa pressure, then under argon shield in 800 ℃ of sintering 10 hours, promptly get LiVPO after naturally cooling to room temperature
4F.The product of X-ray powder diffraction analysis revealed gained is pure LiVPO
4F does not have other any dephasigns, the degree of crystallinity height; Learn the even particle size unanimity of products therefrom from scanning electron microscope analysis, particle diameter is 500nm.With the product of gained as positive electrode material, in being full of the glove box of argon gas, be assembled into experiment buckle type lithium-ion battery, multiplying power with 0.1C is carried out charge and discharge cycles between 3.2-4.5V, the initial charge capacity is 150.7mAh/g, loading capacity is 143.9mAh/g, the reversible capacity that circulates after 30 weeks is 139.3mAh/g, has shown excellent chemical property.
Examples of implementation 2
0.4mol phosphoric acid, 0.1mol vanadous oxide, 0.2mol lithium fluoride, 0.2mol hydrazine hydrate, 0.2mol sucrose are added to the water respectively, stirred 30 minutes with mechanical stirrer behind a kind of material of every adding, make it to mix, the cumulative volume of final gained mixing solutions is 2000mL, then mixing solutions is put into the argon stream spray-dryer, 200 ℃ of following spraying dryings, collect product and get the presoma powder.The presoma powder of gained is pressed into sheet under 20MPa pressure, then under argon shield in 600 ℃ of sintering 10 hours, promptly get LiVPO after naturally cooling to room temperature
4F.X ray powder art diffraction analysis shows that the product of gained is pure LiVPO
4F does not have other any dephasigns, the degree of crystallinity height; Learn the even particle size unanimity of products therefrom from scanning electron microscope analysis, particle diameter is 60nm.With the product of gained as positive electrode material, in being full of the glove box of argon gas, be assembled into experiment buckle type lithium-ion battery, multiplying power with 0.1C is carried out charge and discharge cycles between 3.2-4.5V, the initial charge capacity is 153.2mAh/g, loading capacity is 142.7mAh/g, the reversible capacity that circulates after 30 weeks is 139.2mAh/g, has shown excellent chemical property.
Examples of implementation 3
0.1mol Secondary ammonium phosphate, 0.1mol ammonium meta-vanadate, 0.1mol Lithium Acetate, 0.1mol Neutral ammonium fluoride, 0.2mol hydrazine hydrate, 0.1mol glucose are added to the water respectively, stirred 30 minutes with mechanical stirrer behind a kind of material of every adding, make it to mix, the cumulative volume of final gained mixing solutions is 500mL, then mixing solutions is put into the argon stream spray-dryer, 250 ℃ of following spraying dryings, collect product and get the presoma powder.The presoma powder of gained is pressed into sheet under 20MPa pressure, then under argon shield in 700 ℃ of sintering 10 hours, promptly get LiVPO after naturally cooling to room temperature
4F.The product of X-ray powder diffraction analysis revealed gained is pure LiVPO
4F does not have other any dephasigns, the degree of crystallinity height; Learn the even particle size unanimity of products therefrom from scanning electron microscope analysis, particle diameter is 120nm.With the product of gained as positive electrode material, in being full of the glove box of argon gas, be assembled into experiment buckle type lithium-ion battery, multiplying power with 0.1C is carried out charge and discharge cycles between 3.2-4.5V, the initial charge capacity is 152.8mAh/g, loading capacity is 146.4mAh/g, the reversible capacity that circulates after 30 weeks is 140.1mAh/g, has shown excellent chemical property.
Examples of implementation 4
0.4mol phosphoric acid, 0.1mol Vanadium Pentoxide in FLAKES, 0.2mol lithium fluoride, 0.2mol hydrazine hydrate, 0.2mol sucrose are added to the water respectively, stirred 30 minutes with mechanical stirrer behind a kind of material of every adding, make it to mix, the cumulative volume of final gained mixing solutions is 1000mL, then mixing solutions is put into the argon stream spray-dryer, 200 ℃ of following spraying dryings, collect product and get the presoma powder.The presoma powder of gained is pressed into sheet under 20MPa pressure, then under argon shield in 700 ℃ of sintering 10 hours, promptly get LiVPO after naturally cooling to room temperature
4F.The product of X-ray powder diffraction analysis revealed gained is pure LiVPO
4F does not have other any dephasigns, the degree of crystallinity height; Learn the even particle size unanimity of products therefrom from scanning electron microscope analysis, particle diameter is 180nm.With the product of gained as positive electrode material, in being full of the glove box of argon gas, be assembled into experiment buckle type lithium-ion battery, multiplying power with 0.1C is carried out charge and discharge cycles between 3.2-4.5V, the initial charge capacity is 150.5mAh/g, loading capacity is 141.8mAh/g, the reversible capacity that circulates after 30 weeks is 133.4mAh/g, has shown excellent chemical property.
Examples of implementation 5
0.15mol primary ammonium phosphate, 0.15mol ammonium meta-vanadate, 0.15mol lithium nitrate, 0.15mol Neutral ammonium fluoride, 0.2mol hydrazine hydrate, 0.15mol glucose are added to the water respectively, stirred 30 minutes with mechanical stirrer behind a kind of material of every adding, make it to mix, the cumulative volume of final gained mixing solutions is 400mL, then mixing solutions is put into the argon stream spray-dryer, 300 ℃ of following spraying dryings, collect product and get the presoma powder.The presoma powder of gained is pressed into sheet under 20MPa pressure, then under argon shield in 600 ℃ of sintering 10 hours, promptly get LiVPO after naturally cooling to room temperature
4F.The product of X-ray powder diffraction analysis revealed gained is pure LiVPO
4F does not have other any dephasigns, the degree of crystallinity height; Learn the even particle size unanimity of products therefrom from scanning electron microscope analysis, particle diameter is 300nm.With the product of gained as positive electrode material, in being full of the glove box of argon gas, be assembled into experiment buckle type lithium-ion battery, multiplying power with 0.1C is carried out charge and discharge cycles between 3.2-4.5V, the initial charge capacity is 145.9mAh/g, loading capacity is 141.1mAh/g, the reversible capacity that circulates after 30 weeks is 132.5mAh/g, has shown excellent chemical property.
Claims (7)
1. a spray pyrolysis prepares the method for anode material for lithium-ion batteries fluorinated phosphate vanadium lithium, it is characterized in that concrete implementation step is: phosphoric acid root, vanadium source, lithium source, fluorine source, hydrazine hydrate and the additive of certain stoichiometric ratio are added to the water, stirring made it to mix in 30 minutes behind a kind of material of every adding, finally made it to form the mixing solutions of concentration of metal ions between 0.2-1.0mol/L; Then mixing solutions is put into the argon stream spray-dryer,, collect product and get the presoma powder 200-300 ℃ of following spraying drying; The presoma powder is pressed into sheet under 20MPa pressure, then under argon shield in 600-800 ℃ of sintering 10 hours, promptly get LiVPO after naturally cooling to room temperature
4F.
2. a kind of spray pyrolysis according to claim 1 prepares the method for anode material for lithium-ion batteries fluorinated phosphate vanadium lithium, it is characterized in that the mol ratio of described phosphoric acid root, vanadium source, lithium source, fluorine source, hydrazine hydrate and additive is (1-4): (1-2): (1-2): (1-2): 2: (1-4).
3. a kind of spray pyrolysis according to claim 1 prepares the method for anode material for lithium-ion batteries fluorinated phosphate vanadium lithium, it is characterized in that described phosphoric acid root is a kind of in phosphoric acid, primary ammonium phosphate, the Secondary ammonium phosphate.
4. a kind of spray pyrolysis according to claim 1 prepares the method for anode material for lithium-ion batteries fluorinated phosphate vanadium lithium, it is characterized in that described vanadium source is a kind of in Vanadium Pentoxide in FLAKES, vanadous oxide, the ammonium meta-vanadate.
5. a kind of spray pyrolysis according to claim 1 prepares the method for anode material for lithium-ion batteries fluorinated phosphate vanadium lithium, it is characterized in that described lithium source is a kind of in lithium fluoride, lithium oxalate, Lithium Acetate, the lithium nitrate.
6. a kind of spray pyrolysis according to claim 1 prepares the method for anode material for lithium-ion batteries fluorinated phosphate vanadium lithium, it is characterized in that described fluorine source is a kind of in Neutral ammonium fluoride, the lithium fluoride.
7. a kind of spray pyrolysis according to claim 1 prepares the method for anode material for lithium-ion batteries fluorinated phosphate vanadium lithium, it is characterized in that described additive is a kind of in maltose, sucrose, the glucose.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103864045A (en) * | 2014-03-28 | 2014-06-18 | 张宝 | Preparation method of porous channel-shaped lithium ion battery negative electrode material VPO4 |
| CN103872324A (en) * | 2014-03-28 | 2014-06-18 | 郑俊超 | Preparation method of petaloid lithium ion battery negative electrode material VPO4 |
| CN104157917A (en) * | 2014-07-14 | 2014-11-19 | 宁波大学 | LiV3O8/Li:BPO4|Al<3+> doped Li7La3Zr2o12/Li4Ti5O12 all-solid-state thin film battery and preparation method |
| CN104835960A (en) * | 2015-05-08 | 2015-08-12 | 中南大学 | Preparation method for lithium ion battery cathode material VPO4F |
| CN105226275A (en) * | 2015-07-15 | 2016-01-06 | 徐茂龙 | A kind of modification fluorophosphoric acid vanadium lithium anode material of lithium battery and preparation method thereof |
| CN108878875A (en) * | 2018-06-19 | 2018-11-23 | 中南大学 | The preparation method of fluorophosphoric acid vanadium sodium |
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2009
- 2009-11-29 CN CN2009102528872A patent/CN102079517A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103864045A (en) * | 2014-03-28 | 2014-06-18 | 张宝 | Preparation method of porous channel-shaped lithium ion battery negative electrode material VPO4 |
| CN103872324A (en) * | 2014-03-28 | 2014-06-18 | 郑俊超 | Preparation method of petaloid lithium ion battery negative electrode material VPO4 |
| CN103872324B (en) * | 2014-03-28 | 2016-08-24 | 中南大学 | A kind of petal-shaped lithium ion battery negative material VPO4preparation method |
| CN104157917A (en) * | 2014-07-14 | 2014-11-19 | 宁波大学 | LiV3O8/Li:BPO4|Al<3+> doped Li7La3Zr2o12/Li4Ti5O12 all-solid-state thin film battery and preparation method |
| CN104835960A (en) * | 2015-05-08 | 2015-08-12 | 中南大学 | Preparation method for lithium ion battery cathode material VPO4F |
| CN104835960B (en) * | 2015-05-08 | 2017-08-25 | 中南大学 | A kind of preparation method of lithium ion battery negative material fluorophosphoric acid vanadium |
| CN105226275A (en) * | 2015-07-15 | 2016-01-06 | 徐茂龙 | A kind of modification fluorophosphoric acid vanadium lithium anode material of lithium battery and preparation method thereof |
| CN108878875A (en) * | 2018-06-19 | 2018-11-23 | 中南大学 | The preparation method of fluorophosphoric acid vanadium sodium |
| CN108878875B (en) * | 2018-06-19 | 2020-12-08 | 中南大学 | Preparation method of sodium vanadium fluorophosphate |
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Application publication date: 20110601 |