CN110931728B - Lithium vanadium fluorophosphate-lithium vanadyl phosphate composite cathode material, and preparation method and application thereof - Google Patents
Lithium vanadium fluorophosphate-lithium vanadyl phosphate composite cathode material, and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a lithium vanadium fluorophosphate-lithium vanadyl phosphate composite anode material, a preparation method and application thereof, wherein the general formula of the lithium vanadium fluorophosphate-lithium vanadyl phosphate composite anode material is as follows: xLiVOPO4·LiVPO4F, wherein x is more than or equal to 0.05 and less than or equal to 0.40. The preparation method of the lithium vanadium fluorophosphate-lithium vanadyl phosphate composite cathode material comprises the following steps of: weighing a lithium source, a vanadium source, a phosphorus source and a fluorine source according to a general formula, and mixing; adding an additive, a carbon source and a dispersing agent into the mixture for grinding, and drying in vacuum to obtain amorphous state roasting precursor powder; and tabletting the non-crystalline state roasting precursor powder, sintering in a non-reducing atmosphere, and cooling to obtain the lithium vanadium fluorophosphate-lithium vanadyl phosphate composite anode material. The material can be prepared by high-temperature calcination in the air atmosphere, and the higher voltage and capacity of the lithium vanadium fluorophosphate are still maintained while the usage amount of the raw material villaumite is reduced.
Description
Technical Field
The invention relates to a lithium ion battery anode material technology, in particular to a lithium vanadium fluorophosphate-lithium vanadyl phosphate composite anode material, a preparation method and application thereof.
Background
Lithium vanadium fluorophosphate (LiVPO)4F) The material is a novel triclinic lithium ion battery anode material. LiVPO as a phosphate polyanionic positive electrode material4F has the advantages of safe polyanion structural material, small structural change in the charge-discharge process, good cycle stability and the like. Simultaneous LiVPO4F has a higher potential plateau (4.2 V.s.Li/Li)+) And a higher theoretical specific capacity (156 mAh/g). The electrochemical performance of the lithium vanadium fluorophosphate material can be effectively improved through material improvement processes such as carbon coating and the like, and the actual charge-discharge capacity of the lithium vanadium fluorophosphate material can reach more than 90% of the theoretical capacity. In addition, excellent thermal stability and excellent rate capability and cycle performance, so that LiVPO4F has more advantages and potentials in practical application as the anode material of the lithium ion battery. However, in the production process of lithium vanadium fluorophosphate, the material is usually prepared by a high-temperature solid-phase sintering process under the protection of inert gas, and the main raw materials used are fluorine salts such as lithium fluoride and the like due to high price and high-temperature calcination processThe inert gas protection and fluorine volatilization are needed, and the like, so that pure-phase LiVPO is caused4The production cost of F is high, and the production process has strict requirements, so that the F can not be widely applied to lithium ion batteries as an anode material at present.
Disclosure of Invention
The invention aims to provide a lithium vanadium fluorophosphate-lithium vanadyl phosphate composite anode material, which can be prepared by high-temperature calcination in the air atmosphere and can still keep higher voltage and capacity of the lithium vanadium fluorophosphate while reducing the using amount of fluorine salt serving as a raw material, aiming at the problems that the preparation cost of the lithium vanadium fluorophosphate of a lithium ion battery anode material is high, the inert gas protection is needed in the calcination preparation process and the like.
In order to achieve the purpose, the invention adopts the technical scheme that: a lithium vanadium fluorophosphate-lithium vanadyl phosphate composite cathode material is provided, which has a general formula as follows: xLiVOPO4·LiVPO4F, wherein x is more than or equal to 0.05 and less than or equal to 0.40.
Furthermore, x is more than or equal to 0.10 and less than or equal to 0.35 in the general formula.
The invention also discloses a preparation method of the lithium vanadium fluorophosphate-lithium vanadyl phosphate composite anode material, which comprises the following steps:
step (1) according to the general formula of xLiVOPO4·LiVPO4Weighing a lithium source, a vanadium source, a phosphorus source and a fluorine source according to the proportion of F, and mixing, wherein x is more than or equal to 0.05 and less than or equal to 0.40;
adding 1-15% (preferably 1-10%) of additive for preventing excessive reduction of vanadium and 1-40% (preferably 10-30%) of carbon source by mass into the mixture, then adding 50% of ball-milling dispersant by mass for grinding, and performing vacuum drying to obtain amorphous state roasting precursor powder, wherein the addition sequence of the additive, the carbon source and the ball-milling dispersant is not required;
and (3) tabletting the amorphous state roasting precursor powder, and sintering in a non-reducing atmosphere at the sintering temperature of 400-650 ℃, wherein the heat preservation time is 1-5 h, and naturally cooling to obtain the lithium vanadium fluorophosphate-lithium vanadyl phosphate composite anode material.
Further, the lithium source in the step (1) is one or more of lithium hydroxide, lithium phosphate, lithium fluoride, lithium carbonate and lithium acetate; the vanadium source is one or more of vanadium phosphate, ammonium metavanadate, vanadyl oxalate, vanadium pentoxide, vanadium tetraoxide and vanadium trioxide; the phosphorus source is one or more of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate and phosphoric acid; the fluorine source is one or more of lithium fluoride and vanadium fluoride.
Further, the additive in the step (2) is one or more of tributyl borate, diethyl borate, boric acid and lithium borohydride.
Further, the carbon source in the step (2) is one or more of citric acid, polyvinyl alcohol, glucose, phenolic resin and graphene conductive slurry, and the graphene conductive slurry is an alcohol system or an N-methyl pyrrolidone system with a solid content of 1% -8%.
Further, the dispersant in the step (2) is one or more of isopropanol, ethanol and methanol.
Further, the grinding in the step (2) is high-energy ball milling, and the particle size after grinding is not higher than 5 μm.
Further, the tabletting pressure in the step (3) is 20-50 MPa.
Further, the non-reducing atmosphere in the step (3) is one or more of argon, nitrogen or air.
Further, the sintering temperature in the step (3) is 400-650 ℃, and the heat preservation time is 1-5 h, preferably 1-3 h.
The invention also provides application of the lithium vanadium fluorophosphate-lithium vanadyl phosphate composite cathode material in the field of lithium ion batteries.
Compared with the prior art, the lithium vanadium fluorophosphate-lithium vanadyl phosphate composite cathode material and the preparation method thereof have the following advantages:
1) the invention prepares a lithium vanadyl phosphate-lithium vanadium fluorophosphate composite anode material (xLiVOPO) which can be used for a lithium ion battery composite anode4·LiVPO4F, x is more than or equal to 0.05 and less than or equal to 0.40). The lithium vanadyl phosphate in the composite anode material is a doping phase of lithium vanadium fluorophosphate, and LiVOPO4And LiVPO4F belongs to phosphate polyanion anode material, the charge-discharge platform of the composite anode material is 3.95 V.s.Li/Li +, the theoretical specific capacity is 159mAh/g, and the theoretical specific capacity is equivalent to LiVPO4F is similar.
2) The calcining process of the lithium vanadyl phosphate is simple and easy to implement, and the synthesis condition does not need high-temperature sintering and harsh reducing atmosphere like LiVOPO in the calcining process of the lithium vanadyl fluorophosphate4The sintering atmosphere of (2) is generally air, but the low electronic conductivity of the sintering atmosphere severely limits the exertion of electrochemical performance. The invention organically combines lithium vanadyl phosphate-lithium vanadium fluorophosphate, and the addition of the additive effectively controls the valence state of vanadium, thereby ensuring the effective synthesis of the composite material, leading the composite material to have the good electrochemical properties of high voltage and high capacity of the lithium vanadyl fluorophosphate material, and the characteristics of easy obtaining and low price of the lithium vanadyl phosphate, effectively improving the doping item LiVOPO while realizing the reduction of fluorine salt and the simplification of the calcining process difficulty4The performance of the composite cathode material is expressed, so that the electrochemical performance of the composite cathode material is fully exerted;
3) the preparation method of the lithium vanadium phosphate-lithium vanadium fluorophosphate composite material has the advantages of easily obtained and accessible raw materials, simple process, non-harsh environment and lower production comprehensive cost.
Drawings
FIG. 1 is an XRD spectrum of a lithium vanadium fluorophosphate-lithium vanadyl phosphate composite cathode material of example 1;
fig. 2 is a button cell charge-discharge curve for the lithium vanadium fluorophosphate-lithium vanadyl phosphate composite of example 1.
Detailed Description
The invention is further illustrated by the following examples:
example 1
The embodiment discloses a preparation method of lithium ion battery composite anode material lithium vanadium fluorophosphate-lithium vanadyl phosphate, which comprises the following steps:
lithium carbonate, vanadium pentoxide, ammonium dihydrogen phosphate and lithium fluoride are mixed according to a molar ratio of Li: v: p: f ═ 1.15:1.15:1.15:1, and a composite component of 0.15LiVOPO was prepared4·LiVPO4And F, adding tributyl borate accounting for 3% of the total mass of the mixture, glucose accounting for 30% of the total mass of the mixture and citric acid accounting for 10%, then adding a dispersing agent to perform high-energy ball milling, performing tabletting on the pre-roasting body after vacuum drying at 120 ℃, placing the pre-roasting body in an air atmosphere to perform sintering treatment, wherein the sintering temperature is 650 ℃, the heat preservation time is 3 hours, and naturally cooling to obtain the lithium vanadium fluorophosphate-lithium vanadyl phosphate composite anode material.
Analysis of the XRD spectrum (as shown in figure 1) shows that the prepared material is LiVOPO4·LiVPO4F composite material, LiVPO4F is the main phase.
The obtained product lithium vanadium phosphate is used as the lithium ion battery anode material, a lithium sheet is used as a counter electrode to assemble a lithium ion button battery, as shown in figure 2, a charge-discharge test is carried out at a voltage of 3.0-4.5V, the charging specific capacity under a 1C multiplying power is 130.1mAh/g, and the discharging capacity is 129.5 mAh/g.
Example 2
The embodiment discloses a preparation method of lithium ion battery composite anode material lithium vanadium fluorophosphate-lithium vanadyl phosphate, which comprises the following steps:
lithium carbonate, vanadium phosphate and lithium fluoride are mixed in a molar ratio of Li: v: p: f1.15: 1.15:1 to prepare a composite component of 0.30LiVOPO4·LiVPO4And F, adding tributyl borate accounting for 7% of the total mass of the mixture, glucose accounting for 20% of the total mass of the mixture and graphene conductive slurry accounting for 5% (an ethanol system accounting for 5% of the mass of the mixture), adding a dispersing agent, carrying out high-energy ball milling, carrying out vacuum drying at 120 ℃, tabletting the roasted precursor, placing the tablet in an air atmosphere, carrying out sintering treatment, wherein the sintering temperature is 550 ℃, the heat preservation time is 3 hours, and naturally cooling to obtain the lithium vanadium fluorophosphate-lithium vanadyl phosphate composite anode material.
The lithium sheet is used as a counter electrode to assemble the lithium ion button cell, the charging specific capacity is 121.2mAh/g under the 1C multiplying power, and the discharging capacity is 119.5 mAh/g.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (9)
1. The lithium vanadium fluorophosphate-lithium vanadyl phosphate composite cathode material is characterized by having a general formula as follows: xLiVOPO4·LiVPO4F, wherein x is more than or equal to 0.05 and less than or equal to 0.40;
the preparation method of the lithium vanadium fluorophosphate-lithium vanadyl phosphate composite cathode material comprises the following steps of:
step (1) according to the general formula of xLiVOPO4·LiVPO4F, weighing a lithium source, a vanadium source, a phosphorus source and a fluorine source, and mixing, wherein x is more than or equal to 0.05 and less than or equal to 0.40;
adding 1-15% of additive for preventing excessive reduction of vanadium and 1-40% of carbon source by mass into the mixture, then adding a dispersing agent for grinding, and performing vacuum drying to obtain amorphous state roasting precursor powder;
and (3) tabletting the amorphous state roasting precursor powder, sintering in a non-reducing atmosphere at the sintering temperature of 400-650 ℃, keeping the temperature for 1-5 h, and cooling to obtain the lithium vanadium fluorophosphate-lithium vanadyl phosphate composite anode material.
2. The lithium vanadium fluorophosphate-lithium vanadyl phosphate composite positive electrode material according to claim 1, wherein x is 0.10. ltoreq. x.ltoreq.0.35 in the general formula.
3. The lithium vanadium fluorophosphate-lithium vanadyl phosphate composite cathode material according to claim 1, wherein the lithium source in step (1) is one or more of lithium hydroxide, lithium phosphate, lithium fluoride, lithium carbonate and lithium acetate; the vanadium source is one or more of vanadium phosphate, ammonium metavanadate, vanadyl oxalate, vanadium pentoxide, vanadium tetraoxide and vanadium trioxide; the phosphorus source is one or more of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate and phosphoric acid; the fluorine source is one or more of lithium fluoride and vanadium fluoride.
4. The lithium vanadium fluorophosphate-lithium vanadyl phosphate composite cathode material according to claim 1, wherein the additive in the step (2) is one or more of tributyl borate, diethyl borate, boric acid and lithium borohydride.
5. The lithium vanadium fluorophosphate-lithium vanadyl phosphate composite cathode material according to claim 1, wherein the carbon source in the step (2) is one or more of citric acid, polyvinyl alcohol, glucose, phenolic resin and graphene conductive slurry.
6. The lithium vanadium fluorophosphate-lithium vanadyl phosphate composite cathode material according to claim 1, wherein the dispersant in the step (2) is one or more of isopropanol, ethanol and methanol.
7. The lithium vanadium fluorophosphate-lithium vanadyl phosphate composite cathode material according to claim 1, wherein the tabletting pressure in step (3) is 20 to 50 MPa.
8. The lithium vanadium fluorophosphate-lithium vanadyl phosphate composite cathode material according to claim 1, wherein the non-reducing atmosphere in step (3) is one or more of argon, nitrogen or air.
9. Use of the lithium vanadium fluorophosphate-lithium vanadyl phosphate composite cathode material according to any one of claims 1 to 2 in the field of lithium ion batteries.
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CN103650214A (en) * | 2011-07-12 | 2014-03-19 | 应用材料公司 | Methods to fabricate variations in porosity of lithium ion battery electrode films |
CN103887497A (en) * | 2014-03-28 | 2014-06-25 | 郑俊超 | Preparation method of multi-core type phosphate compound positive electrode material with core-shell structure for lithium ion battery |
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CN105591055A (en) * | 2015-12-17 | 2016-05-18 | 中南大学 | High-multiplying power lithium ion battery and preparation method thereof |
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CN101663710A (en) * | 2007-02-20 | 2010-03-03 | 威伦斯技术公司 | Electrodes comprising mixed active particles |
CN103493258A (en) * | 2011-02-25 | 2014-01-01 | 应用材料公司 | Lithium ion cell design apparatus and method |
CN103650214A (en) * | 2011-07-12 | 2014-03-19 | 应用材料公司 | Methods to fabricate variations in porosity of lithium ion battery electrode films |
CN103367794A (en) * | 2012-03-27 | 2013-10-23 | Tdk株式会社 | Lithium-ion secondary battery |
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