CN102079518A - Low-temperature liquid-phase preparation method for LiVPo4F as lithium-ion battery cathode material - Google Patents
Low-temperature liquid-phase preparation method for LiVPo4F as lithium-ion battery cathode material Download PDFInfo
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- CN102079518A CN102079518A CN2009102535113A CN200910253511A CN102079518A CN 102079518 A CN102079518 A CN 102079518A CN 2009102535113 A CN2009102535113 A CN 2009102535113A CN 200910253511 A CN200910253511 A CN 200910253511A CN 102079518 A CN102079518 A CN 102079518A
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Abstract
The invention discloses a low-temperature liquid-phase preparation method for LiVPo4F as the lithium-ion battery cathode material. The preparation method is characterized by the following steps: adding phosphoric acid source, vanadium source, lithium source, fluorine source and reducing agent at a certain stoichiometric ratio to a water/polyol mixture system at a certain volume ratio, stirring uniformly for 30 minutes after each substance is added, then pouring the finally formed mixed solution into an autoclave, subjecting the mixed solution to reaction for 5 hours to 7 days at 100-190 DEG C, cooling the autoclave to the room temperature, taking out the product of reaction and washing several times with ethanol and distilled water, and drying to obtain the LiVPO4F. The method has the advantages of a wide source of raw materials, simple operating process, good controllability, high reproducibility and can reduce the synthesis temperature of the material and save the cost of production. Through the method, the size of the grain of LiVPo4F is 20-300 nanometers. With good particle dispersion, high crystalline, high reversible capacity and good cycle life, the LiVPo4F can meet the various practical needs for lithium-ion battery in application. The preparation method is suitable for the mass production of lithium-ion battery cathode materials.
Description
Technical field
The present invention relates to a kind of method for preparing anode material for lithium-ion batteries, particularly under low temperature liquid phase, utilize polyol 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., 2009,11:589-591.) 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, energy consumption is excessive, the more high shortcoming of cost; and resulting material purity is not high, particle is big, chemical property is poor, 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 under low temperature liquid phase, utilizing polyol to prepare anode material for lithium-ion batteries fluorinated phosphate vanadium lithium.Raw material sources of the present invention are extensive, easy and simple to handle, controllability good, circulation ratio is high, avoided the high-temperature sintering process of high energy consumption, 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:
Phosphoric acid root, vanadium source, lithium source, fluorine source and the reductive agent of certain stoichiometric ratio joined respectively in the water/polyol mixed system of certain volume ratio, stir behind a kind of material of every adding and made it to mix in 30 minutes, then the mixing solutions that will finally form is poured in the autoclave, reacted 5 hours to 7 days down at 100-190 ℃, subsequently autoclave is naturally cooled to room temperature, take out product and also clean repeatedly, promptly get LiVPO after the drying with ethanol and distilled water
4F.
The mol ratio of the phosphoric acid root described in the present invention, vanadium source, lithium source, fluorine source and reductive agent is (1-4): (1-2): (1-2): (1-2): (1-2).
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.
Reductive agent described in the present invention is a kind of in hydrazine hydrate, the formaldehyde.
The volume ratio of water described in the present invention and polyvalent alcohol is 1: (1-5).
Polyol described in the present invention is a kind of in ethylene glycol, glycol ether, triglycol, the Tetraglycol 99.
Characteristics of the present invention are: (1) has simplified LiVPO
4The preparation process of F, controllability is good, and the circulation ratio height has reduced the synthesis temperature 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 the conditioned reaction temperature and time.(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
It is in water/Tetraglycol 99 mixing solutions of 1: 1 that 0.4mol primary ammonium phosphate, 0.2mol ammonium meta-vanadate, 0.2mol lithium oxalate, 0.2mol Neutral ammonium fluoride, 0.2mol formaldehyde are joined volume ratio respectively, made it to mix in 30 minutes with the mechanical stirrer stirring behind a kind of material of every adding, then the mixing solutions that will finally form is poured in the autoclave, reacted 7 days down at 190 ℃, then autoclave is naturally cooled to room temperature, take out product and also clean repeatedly, promptly get LiVPO after the drying with ethanol and distilled water
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 154.8mAh/g, loading capacity is 150.0mAh/g, the reversible capacity that circulates after 30 weeks is 145.6mAh/g, has shown excellent chemical property.
Examples of implementation 2
It is in water/glycol ether mixing solutions of 1: 5 that 0.4mol phosphoric acid, 0.1mol vanadous oxide, 0.2mol lithium fluoride, 0.2mol hydrazine hydrate are joined volume ratio respectively, made it to mix in 30 minutes with the mechanical stirrer stirring behind a kind of material of every adding, then the mixing solutions that will finally form is poured in the autoclave, reacted 5 hours down at 180 ℃, then autoclave is naturally cooled to room temperature, take out product and also clean repeatedly, promptly get LiVPO after the drying with ethanol and distilled water
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 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 152.5mAh/g, loading capacity is 145.4mAh/g, the reversible capacity that circulates after 30 weeks is 141.8mAh/g, has shown excellent chemical property.
Examples of implementation 3
It is in water/triglycol mixing solutions of 1: 3 that 0.1mol Secondary ammonium phosphate, 0.1mol ammonium meta-vanadate, 0.1mol Lithium Acetate, 0.1mol Neutral ammonium fluoride, 0.1mol formaldehyde are joined volume ratio respectively, made it to mix in 30 minutes with the mechanical stirrer stirring behind a kind of material of every adding, then the mixing solutions that will finally form is poured in the autoclave, reacted 2 days down at 100 ℃, then autoclave is naturally cooled to room temperature, take out product and also clean repeatedly, promptly get LiVPO after the drying with ethanol and distilled water
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 20nm.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 157.8mAh/g, loading capacity is 150.4mAh/g, the reversible capacity that circulates after 30 weeks is 148.5mAh/g, has shown excellent chemical property.
Examples of implementation 4
It is in water/ethylene glycol mixing solutions of 1: 2 that 0.4mol phosphoric acid, 0.1mol Vanadium Pentoxide in FLAKES, 0.2mol lithium nitrate, 0.2mol hydrazine hydrate are joined volume ratio respectively, made it to mix in 30 minutes with the mechanical stirrer stirring behind a kind of material of every adding, then the mixing solutions that will finally form is poured in the autoclave, reacted 5 days down at 150 ℃, then autoclave is naturally cooled to room temperature, take out product and also clean repeatedly, promptly get LiVPO after the drying with ethanol and distilled water
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 150nm.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 151.9mAh/g, loading capacity is 142.7mAh/g, the reversible capacity that circulates after 30 weeks is 135.6mAh/g, has shown excellent chemical property.
Examples of implementation 5
It is to stir 30 minutes with mechanical stirrer behind a kind of material of every adding in water/glycol ether mixing solutions of 1: 4 that 0.15mol primary ammonium phosphate, 0.15mol ammonium meta-vanadate, 0.15mol lithium nitrate, 0.15mol Neutral ammonium fluoride, 0.15mol formaldehyde are joined volume ratio respectively, make it to mix, then the mixing solutions that will finally form is poured in the autoclave, reacted 1 day down at 120 ℃, then autoclave is naturally cooled to room temperature, take out product and also clean repeatedly, promptly get LiVPO after the drying with ethanol and distilled water
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 80nm.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 148.7mAh/g, loading capacity is 140.0mAh/g, the reversible capacity that circulates after 30 weeks is 133.8mAh/g, has shown excellent chemical property.
Claims (9)
1. a low temperature liquid phase prepares the method for anode material for lithium-ion batteries fluorinated phosphate vanadium lithium, it is characterized in that concrete implementation step is: with the phosphoric acid root of certain stoichiometric ratio, the vanadium source, the lithium source, fluorine source and reductive agent join respectively in the water/polyol mixed system of certain volume ratio, stir behind a kind of material of every adding and made it to mix in 30 minutes, then the mixing solutions that will finally form is poured in the autoclave, reacted 5 hours to 7 days down at 100-190 ℃, subsequently autoclave is naturally cooled to room temperature, take out product and also clean repeatedly, promptly get LiVPO after the drying with ethanol and distilled water water
4F.
2. a kind of low temperature liquid phase 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 and reductive agent is (1-4): (1-2): (1-2): (1-2): (1-2).
3. a kind of low temperature liquid phase 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 low temperature liquid phase 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 low temperature liquid phase 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 low temperature liquid phase 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 low temperature liquid phase according to claim 1 prepares the method for anode material for lithium-ion batteries fluorinated phosphate vanadium lithium, it is characterized in that described reductive agent is a kind of in hydrazine hydrate, the formaldehyde.
8. a kind of low temperature liquid phase according to claim 1 prepares the method for anode material for lithium-ion batteries fluorinated phosphate vanadium lithium, and the volume ratio that it is characterized in that described water and polyvalent alcohol is 1: (1-5).
9. a kind of low temperature liquid phase according to claim 1 prepares the method for anode material for lithium-ion batteries fluorinated phosphate vanadium lithium, it is characterized in that described polyol is a kind of in ethylene glycol, glycol ether, triglycol, the Tetraglycol 99.
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| CN2009102535113A CN102079518A (en) | 2009-11-29 | 2009-11-29 | Low-temperature liquid-phase preparation method for LiVPo4F as lithium-ion battery cathode material |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103872289A (en) * | 2014-03-28 | 2014-06-18 | 张宝 | Preparation method of spherical lithium ion battery positive electrode material LiVPO4F |
| CN104401957A (en) * | 2014-10-13 | 2015-03-11 | 济南大学 | Hydrothermally preparing method of lithium secondary battery anode material cobalt lithium fluorophosphate |
| US11955624B2 (en) | 2020-10-29 | 2024-04-09 | Saft America | Blended cathode materials for secondary batteries |
-
2009
- 2009-11-29 CN CN2009102535113A patent/CN102079518A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103872289A (en) * | 2014-03-28 | 2014-06-18 | 张宝 | Preparation method of spherical lithium ion battery positive electrode material LiVPO4F |
| CN103872289B (en) * | 2014-03-28 | 2017-04-05 | 中南大学 | A kind of ball-shaped lithium-ion battery anode material LiVPO4The preparation method of F |
| CN104401957A (en) * | 2014-10-13 | 2015-03-11 | 济南大学 | Hydrothermally preparing method of lithium secondary battery anode material cobalt lithium fluorophosphate |
| US11955624B2 (en) | 2020-10-29 | 2024-04-09 | Saft America | Blended cathode materials for secondary batteries |
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Application publication date: 20110601 |