CN102509789A - Method for preparing positive material fluorine-doped sodium vanadium phosphate of sodium-containing lithium ion battery - Google Patents
Method for preparing positive material fluorine-doped sodium vanadium phosphate of sodium-containing lithium ion battery Download PDFInfo
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- CN102509789A CN102509789A CN201110315076XA CN201110315076A CN102509789A CN 102509789 A CN102509789 A CN 102509789A CN 201110315076X A CN201110315076X A CN 201110315076XA CN 201110315076 A CN201110315076 A CN 201110315076A CN 102509789 A CN102509789 A CN 102509789A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a method for preparing positive material fluorine-doped sodium vanadium phosphate of a sodium-containing lithium ion battery, and particularly relates to a method for preparing Na3V2(PO4)3-x/3Fx (x is not smaller than 0 and not less than 6) by mechanical activation-assisted one-step high-temperature solid state reaction. The method comprises the following steps: dispersing sodium (Na) source, vanadium (V) source, phosphorus (P) source, fluorine (F) source, and carbon (C) source with reducing and conductive effect in a certain amount of liquid dispersion medium; high-speed ball milling the blended materials for mechanical activation; calcining the activated material at 450 to 1000 DEG C for 1 to 72 hours in an inert or reducing atmosphere; and cooling to obtain the final product. The positive material Na3V2(PO4)3-x/3Fx prepared by the method has good electrochemical property. The method provided by the invention has the advantages of simple and convenient process, easy control, low cost, and friendly environment, and the synthesis process is simplified so as to facilitate large-scale production.
Description
Technical field
The present invention relates to a kind of preparation method who contains the sodium anode material for lithium-ion batteries, promptly prepare a kind of method that the sodium anode material for lithium-ion batteries is mixed fluorophosphoric acid vanadium sodium that contains through the auxiliary step high temperature solid-state method of mechanical activation, it belongs to the new energy materials preparing technical field.
Background technology
Along with the rise of continuous development, the especially electric automobile of lithium ion battery industry, in continuous increase, this has just brought the tight demand to lithium resource to the demand of lithium ion battery in market.Yet lithium resource is contained in the salt lake more at present, from the salt lake, extracts lithium and is still an expensive process, and this just becomes the bottleneck of limiting lithium ion cell industry fast development.If can consider to replace lithium, will break the constraint of lithium resource, for country and society bring huge interests to the lithium ion battery industry with other more cheap elements.
The phosphoric acid vanadium sodium salt of mixing fluorine belongs to the polyanion type material, at first is used as the sodium-ion battery positive electrode.Because the stability of its crystal structure makes it compare with other sodium-ion battery positive electrodes, has longer cycle life.But people are for the understanding of sodium-ion battery system, and picture is not sound so to lithium-ion battery system.Consider that sodium-ion battery and lithium ion battery have identical principle, people are attempting the sodium-ion battery positive electrode is applied in the lithium ion battery.
2005, people such as J.Baker at first proposed the notion of mixed type lithium ion battery, and they use Na
3V
2(PO
4)
2F
3As positive pole, contain LiPF
6Organic liquor as electrolyte, graphite has constituted the mixed type lithium ion battery as negative pole, finds the work that this system can not only be stable, and has shown good electrochemical, its initial reversible specific capacity reaches 120mAhg
-1, circulation is 100 times under the 0.5C multiplying power, specific capacity conservation rate about 96%.2010, people such as Jiangqing Zhao also did the similar research about the mixed type lithium ion battery, had obtained result preferably equally.In order to ensure the valence state of vanadium in material is+3 valencys, and the two-step method that is that they adopt prepares material, promptly prepares VPO earlier
4Precursor is reduced to the vanadium of high valence state+3 valencys, is fixed in VPO
4In, and then by VPO
4React with synthetic final products with NaF.Adopt this kind synthetic method, technological process is longer, and operating procedure is more, and energy consumption is bigger.
Show according to patent CN101369661A, adopt a kind of sol-gel process, the fluorophosphoric acid vanadium sodium material Na that step preparation carbon coats
3V
2(PO
4)
2F
3/ C.Adopt this synthetic method, though be that a step is synthetic, because sol-gel is when handling; Requiring raw material is solubility; And disposable raw material input amount is unsuitable excessive, operation inconvenience, and have the large amount of organic decomposition to cause to the waste of resource and the pollution of environment; Cost is higher, is difficult to accomplish scale production.
Summary of the invention
The objective of the invention is to overcome and avoid the shortcoming and defect of prior art; Provide a kind of simple, condition is easy to control, and reactivity strengthens; Synthetic product has excellent electrochemical properties, contains the sodium lithium ion cell positive and mixes fluorophosphoric acid vanadium sodium preparation methods.
The positive electrode that is used to contain the sodium lithium ion battery through this method prepares has stable electrochemical property, good rate capability, and characteristics such as security performance is good can be used for preparing the electrokinetic cell that satisfies the electric tool needs.
The present invention adopts following processing step to realize goal of the invention.
Method of the present invention may further comprise the steps:
(1) mechanical activation
Na: V: P: F=3 in molar ratio: 2: (3-x/3): x (wherein 0≤x≤6) takes by weighing and is used for preparation and mixes fluorophosphoric acid vanadium sodium (Na
3V
2(PO
4)
3-x/3F
x) the raw material in sodium source, vanadium source, phosphorus source and fluorine source, mix with the carbon source that plays reduction and electric action that accounts for raw material total weight 10%～30%; Mixed raw material is scattered in liquid phase dispersion medium, through ball milling mechanical activation 5～48h;
(2) high temperature solid state reaction
Material behind the mechanical activation is placed inertia or reducing atmosphere protection down, and roasting 1～72h after 450～1000 ℃ is chilled to room temperature at last, promptly obtains Na
3V
2(PO
4)
3-x/3F
xPositive electrode.
The present invention preferred said 1) the ball milling time in step is 5～24h.
Described mechanical activation is in high speed ball mill, to carry out, and the preferred rotating speed of ball mill is 500～1200 commentaries on classics/min, and ball/material is than being 8～10: 1.
Described 2) step is preferably carried out warming temperature with the heating rate of 2～3 ℃/min.
Described 2) preferred sintering temperature is 500～900 ℃ in the step.
Preferred version of the present invention also comprises:
Described sodium source is one or more in sodium nitrate, sodium acetate, sodium acid carbonate, sodium fluoride, sodium carbonate and the NaOH; Described vanadium source is one or more in vanadic sulfide, vanadium trioxide, vanadium oxytrichloride, vanadic oxide and the ammonium metavanadate; Said phosphorus source is one or more in diammonium hydrogen phosphate, phosphoric acid, ammonium dihydrogen phosphate, phosphorus pentoxide and the sodium phosphate; Described fluorine source is one or more in hydrofluoric acid, ammonium fluoride and the sodium fluoride; Described carbon source is one or more in white sugar, polyacrylamide, glucose, polyvinyl alcohol, sucrose and the starch.
Described liquid phase dispersion medium is one or more in ethylene glycol, deionized water, ethanol, butanols and the butanediol.
Described inert atmosphere is a kind of in nitrogen and the argon gas; Described reducing atmosphere is N
2/ H
2Mist, N
2: H
2=6: 4,7: 3,8: 2,9: 1, flow was 10～1000mL/min.
The auxiliary step high temperature solid-state method of the mechanical activation that the present invention proposes, method is simple, and condition is easy to control; Mechanical activation can make that reactant fully mixes, reactivity strengthens, thereby impels solid phase reaction can more be prone to carry out; Synthetic product has excellent electrochemical properties; Simultaneously, synthesis technique is simple, and production cost is low, and environmental pollution is little, is convenient to accomplish scale production.
Description of drawings
The Na of Fig. 1: embodiment 1 preparation
3V
2(PO
4)
2F
3The X-ray diffraction of/C material (XRD) collection of illustrative plates;
The Na of Fig. 2: embodiment 1 preparation
3V
2(PO
4)
2F
3The charge-discharge magnification curve chart of/C material;
The Na of Fig. 3: embodiment 2 preparations
3V
2(PO
4)
3The first charge-discharge curve chart of/C material;
The Na of Fig. 4: embodiment 2 preparations
3V
2(PO
4)
3The ESEM of/C material (SEM) collection of illustrative plates;
The Na of Fig. 5: embodiment 3 preparations
3V
2(PO
4)
2.5F
1.5/ C material 0.5C first charge-discharge curve chart;
The Na of Fig. 6: embodiment 3 preparations
3V
2(PO
4)
2.5F
1.5/ C material 5C multiplying power cyclic curve figure;
The Na of Fig. 7: embodiment 4 preparations
3V
2(PO
4)
1.5F
4.5The different multiplying cyclic curve figure of/C material.
Embodiment
Below in conjunction with embodiment the present invention is further described, following examples are intended to illustrate the present invention, rather than to further qualification of the present invention.
Embodiment 1:
0.052mol vanadic oxide, 0.156mol ammonium fluoride, 0.156mol sodium acid carbonate, 0.104mol ammonium dihydrogen phosphate and 6g glucose mixed and dispersed in ethanol, are placed ball mill, under 600 commentaries on classics/min velocities of rotation, mechanical activation 8h.With the material behind the mechanical activation under argon shield in 600 ℃ of roasting 24h, be product Na after the cooling
3V
2(PO
4)
2F
3/ C.The X-ray diffraction analysis of products therefrom is as shown in Figure 1, analyzes to show that the product by this kind formulation also has minor N a
3V
2(PO
4)
3Dephasign, not carbon peak existence in the collection of illustrative plates, this explanation glucose is to resolve into for amorphous carbon at high temperature.Resulting product is assembled into the experiment button cell, tests it and discharge and recharge chemical property, test result shows: the first discharge specific capacity of material under the multiplying power of 0.5C, 1C, 2C, 5C, 10C is respectively 107mAhg
-1, 105.8mAhg
-1, 102.9mAhg
-1, 97.9mAhg
-1, 90.4mAhg
-1, the specific discharge capacity conservation rate from 0.5C to 10C is 84.5%, and near 4.2V and 3.7V voltage, has two constant voltage platforms.Material first charge-discharge curve under each multiplying power is as shown in Figure 2.
Embodiment 2:
0.052mol vanadic oxide, 0.156mol ammonium dihydrogen phosphate, 0.156mol NaOH and 6g glucose mixed and dispersed in ethanol, are placed ball mill, under 800 commentaries on classics/min velocities of rotation, mechanical activation 8h.With the material behind the mechanical activation under argon shield in 900 ℃ of roasting 8h, be product Na after the cooling
3V
2(PO
4)
3/ C.The sem analysis of material is as shown in Figure 3, and the particle diameter that analysis shows product is about 1 μ m.Resulting product is assembled into the experiment button cell, under the 0.1C multiplying power, tests it and discharge and recharge chemical property, test result shows: first discharge specific capacity is 109mAhg
-1, and a constant voltage platform appears near 3.7V voltage, near 4.2V voltage, there is not tangible constant voltage platform.Material is as shown in Figure 4 at 0.1C first charge-discharge curve.
Embodiment 3:
0.052mol vanadic oxide, 0.13mol ammonium dihydrogen phosphate, 0.156mol NaOH, 0.075mol ammonium fluoride and 6g glucose mixed and dispersed in ethanol, are placed ball mill, under 1000 commentaries on classics/min velocities of rotation, mechanical activation 10h.With the material behind the mechanical activation under argon shield in 700 ℃ of roasting 12h, be product Na after the cooling
3V
2(PO
4)
2.5F
1.5/ C.Resulting product is assembled into the experiment button cell, material is carried out electrochemical property test, the result shows: materials is except occurring near 3.7V voltage the constant voltage platform, and one the constant voltage platform occurs near 4.2V voltage.The first charge-discharge curve of material under the 0.5C multiplying power is as shown in Figure 5, and the cyclic curve of material under the 5C multiplying power is as shown in Figure 6.
Embodiment 4:
0.052mol vanadic oxide, 0.156mol NaOH, 0.078mol ammonium dihydrogen phosphate, 0.185mol ammonium fluoride and 6g glucose mixed and dispersed in ethanol, are placed ball mill, under 1100 commentaries on classics/min velocities of rotation, mechanical activation 10h.With the material behind the mechanical activation under argon shield in 500 ℃ of roasting 36h, be product Na after the cooling
3V
2(PO
4)
1.5F
4.5/ C.Resulting product is assembled into the experiment button cell; Material is discharged and recharged electrochemical property test; Fig. 6 is the cyclic curve figure of material, and test result shows: the first discharge specific capacity of material under 0.1C, 0.5C, 1C, 2C, 5C, 10C, 0.1C multiplying power is respectively 103.1mAhg
-1, 101.3mAhg
-1, 99.4mAhg
-1, 96.1mAhg
-1, 81.5mAhg
-1, 51.3mAhg
-1, 95.6mAhg
-1Under different multiplying powers, material all shows cyclical stability preferably.
Claims (8)
1. one kind prepares and contains the method that the sodium anode material for lithium-ion batteries is mixed fluorophosphoric acid vanadium sodium, it is characterized in that, comprises following processing step:
1) mechanical activation
Na: V: P: F=3 in molar ratio: 2: (3-x/3): x, 0≤x≤6 wherein take by weighing and are used for preparation and mix fluorophosphoric acid vanadium sodium Na
3V
2(PO
4)
3-x/3F
xThe raw material in sodium source, vanadium source, phosphorus source and fluorine source, mix with the carbon source that plays reduction and electric action that accounts for raw material total weight 10%～30%; Mixed material is scattered in the liquid phase dispersion medium, through ball milling mechanical activation 5～48h;
2) high temperature solid state reaction
Material behind the mechanical activation is placed inertia or reducing atmosphere protection down, be warming up to 450～1000 ℃ of roasting 1～72h, stove is chilled to room temperature, promptly gets.
2. method according to claim 1 is characterized in that, said 1) the step mechanical activation is 5～24h.
3. according to claim 1 or claim 2 method, it is characterized in that: described mechanical activation carries out in high speed ball mill, and drum's speed of rotation is 500～1200 commentaries on classics/min, and ball/material is than being 8～10: 1.
4. method according to claim 1 is characterized in that, described 2) step is that heating rate with 2～3 ℃/min carries out warming temperature.
5. method according to claim 4 is characterized in that, described 2) in the step in 500～900 ℃ of roastings.
6. the method for claim 1, it is characterized in that: described sodium source is one or more in sodium nitrate, sodium acetate, sodium acid carbonate, sodium fluoride, sodium carbonate and the NaOH; Described vanadium source is one or more in vanadic sulfide, vanadium trioxide, vanadium oxytrichloride, vanadic oxide and the ammonium metavanadate; Said phosphorus source is one or more in diammonium hydrogen phosphate, phosphoric acid, ammonium dihydrogen phosphate, phosphorus pentoxide and the sodium phosphate; Described fluorine source is one or more in hydrofluoric acid, ammonium fluoride and the sodium fluoride; Described carbon source is one or more in white sugar, polyacrylamide, glucose, polyvinyl alcohol, sucrose and the starch.
7. the method for claim 1, it is characterized in that: described liquid phase dispersion medium is one or more in ethylene glycol, deionized water, ethanol, butanols and the butanediol.
8. the method for claim 1 is characterized in that: described inert atmosphere is a kind of in nitrogen and the argon gas; Described reducing atmosphere is N
2/ H
2Mist, N
2: H
2=6: 4,7: 3,8: 2,9: 1, flow was 10～1000mL/min.
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| CN102903916A (en) * | 2012-10-09 | 2013-01-30 | 江苏科捷锂电池有限公司 | Preparation method of nickel-doped sodium ferrous fluorophosphate cathode material |
| CN103022490A (en) * | 2012-12-31 | 2013-04-03 | 广西地博矿业集团股份有限公司 | Method for preparing sodium fluorophosphate vanadium for positive pole material of sodium-ion battery |
| CN104769757A (en) * | 2012-11-08 | 2015-07-08 | 丰田自动车株式会社 | Positive electrode active material and hybrid ion battery |
| CN105336924A (en) * | 2015-09-25 | 2016-02-17 | 中南大学 | Preparation method of carbon coated vanadium sodium phosphate positive electrode material |
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| CN105552328A (en) * | 2015-12-24 | 2016-05-04 | 华中科技大学 | Sodium vanadium phosphate sodium ion battery positive electrode material and preparation method therefor |
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| CN106848310A (en) * | 2017-02-21 | 2017-06-13 | 东南大学 | A kind of high-energy ball milling preparation method of non-stoichiometric vanadium phosphate sodium |
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