CN107768663B - Method for preparing transition metal oxide having oxygen defect - Google Patents
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- H—ELECTRICITY
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Abstract
The present invention relates to a method of preparing a transition metal oxide having an oxygen defect, a transition metal oxide having an oxygen defect prepared therefrom, an electrode comprising the transition metal oxide having an oxygen defect lithium ion battery, and a lithium ion battery comprising the electrode. The method comprises the following steps: a) fully mixing a transition metal oxide or a precursor thereof with a modifier to obtain a uniform mixture; b) heating the mixture at 360 ℃ to 550 ℃ under inert atmosphere or vacuum conditions to obtain a transition metal oxide having oxygen defects; wherein the modifier is selected from simple substance phosphorus with reducibility or low-valence phosphorus compounds with the valence state of the phosphorus less than 5.
Description
Technical Field
The invention belongs to the field of new energy materials, and relates to a preparation method of an electrode material of a lithium ion battery, in particular to a method for preparing a transition metal oxide with oxygen defects, a transition metal oxide with oxygen defects prepared by the method, an electrode containing the transition metal oxide with oxygen defects, and a lithium ion battery comprising the electrode.
Background
The lithium ion battery is one of the most successful batteries commercialized so far, has the advantages of high voltage, high energy density, low self-discharge rate, long service life and the like, and is widely applied to the fields of mobile phones, notebook computers, electric vehicles and the like in quantity or in future.
With the development of technology and the expansion of application fields, the requirements for the performance of lithium ion batteries have been greatly improved, wherein for electric vehicles, the power density is one of the very important aspects, and determines the speed of the vehicle. The power density of the battery is determined by the rate capability of the electrode material to a large extent, and the electrode material with high conductivity and capable of rapidly transferring electrons and lithium ions can have very excellent rate capability and very high power density. There are many methods for increasing the electron ion migration rate, including surface conductive material coating, lattice ion doping, etc. The purpose of doping is primarily to create certain defects, including lithium ion defectsAnd (4) trapping, so that the lithium ion migration rate is improved. In addition, the mixed valence of transition metal ions can be caused, and the electronic conductivity of the material is improved, for example, in TiO2Or Li4Ti5O12In which Ti is introduced3+The ions can greatly improve the electronic conductivity of the material, so that the rate capability of the material is obviously improved.
Oxygen defects are a type of defects commonly found in oxide materials, and particularly, oxygen ions easily lose electrons to become oxygen at high temperatures, thereby causing the generation of oxygen defects. The presence of oxygen defects may improve the electronic conductivity of the material to some extent, e.g. TiO2-x，MoO3-xThe electronic conductivity of the alloy is obviously higher than that of TiO2And MoO3. The oxygen defects can be produced by ion doping or by chemical reduction. Wherein the chemical reduction is carried out in an inert atmosphere using carbon or a reducing gas, for strongly oxidizing oxides, e.g. MnO2，MoO3And the like, the reduction of the high-valence metal is easily achieved. But for TiO2For the oxide with weaker reducibility, higher temperature and stronger reducing gas are needed to realize Ti4+To Ti3+Is performed. Thereby causing the increase of the cost in the preparation process of the material, easily causing the growth of particles at high temperature, and being not beneficial to improving the rate capability of the material.
The invention skillfully provides a novel method for preparing transition metal oxide with oxygen defects, which mainly utilizes the low boiling point of phosphorus pentoxide and adopts simple substance phosphorus or low-valence phosphorus compounds to reduce the oxide to obtain the transition metal oxide material with certain oxygen defects. The reaction temperature of the method is low and generally does not exceed 500 ℃. Therefore, on one hand, the energy consumption is saved, on the other hand, the growth of the material at high temperature can be inhibited, a product with smaller particles is obtained, meanwhile, the amount of phosphorus or phosphorus compounds required in the reaction is less, the cost of raw materials is lower, and the commercialization of the preparation method is facilitated.
Disclosure of Invention
The technical problem to be solved by the invention is to provide an electrode material of transition metal oxide with oxygen defect and better rate property.
In order to solve the above technical problems, the present invention provides a method of preparing a transition metal oxide having an oxygen defect.
According to an aspect of the present invention, there is provided a method of preparing a transition metal oxide having an oxygen defect, including:
a) fully mixing a transition metal oxide or a precursor thereof with a modifier to obtain a uniform mixture;
b) heating the mixture at 360 ℃ to 550 ℃ under inert atmosphere or vacuum conditions to obtain a transition metal oxide having oxygen defects;
wherein the modifier is selected from simple substance phosphorus with reducibility or low-valence phosphorus compounds with the valence state of the phosphorus less than 5;
the modifier is used in an amount of 0.2 to 15 wt%, preferably 0.5 to 10 wt%, more preferably 0.5 to 8 wt%, based on 100 wt% of the transition metal oxide or the precursor thereof.
Preferably, the phosphorus compound in a lower valence state, wherein the phosphorus valence state is less than 5, is selected from NaH2PO2,PH3,H3PO3And the like.
Wherein the transition metal oxide is selected from titanium dioxide, lithium titanate, molybdenum trioxide, vanadium pentoxide, niobium pentoxide and the like.
The precursor is a material that is decomposed to obtain the transition metal oxide, and examples thereof include, for example, ammonium molybdate, ammonium vanadate and the like as a precursor of molybdenum trioxide.
Preferably, in step b), the mixture is heated at a temperature of 360 to 450 ℃, preferably for more than 10 minutes.
In the present invention, it is very important to sufficiently and uniformly mix the transition metal oxide or its precursor and the modifier, and they can be sufficiently mixed using a conventional method in the art.
For example, the transition metal oxide or a precursor thereof and the modifier are subjected to grinding and mixing for a long time (e.g., 24 hours or more) using a grinder, a mixer, a ball mill, or the like to achieve sufficient mixing thereof.
Alternatively, a modifier is dissolved in a suitable solvent, the resulting solution is mixed with the transition metal oxide or a precursor thereof, and the mixture is heated and dried with stirring to obtain a uniform mixture.
Preferably, the transition metal oxide having an oxygen defect is used as an electrode material, generally as an anode material, further preferably, it is used as an electrode material of a lithium ion battery.
According to another aspect of the present invention, there is provided a transition metal oxide having an oxygen defect prepared by the method. The transition metal oxide having oxygen defects has the advantages of high purity and good electrochemical properties.
According to still another aspect of the present invention, there is provided an electrode for a lithium ion battery, comprising the transition metal oxide having an oxygen defect.
According to yet another aspect of the present invention, there is provided a lithium ion battery including an electrode of the lithium ion battery.
In the present invention, the transition metal oxide refers to a compound of one transition metal element and oxygen, or a compound of two or more transition metal elements and oxygen, or a compound of one or more transition metal elements and other metal elements and oxygen, and the latter two are also referred to as a composite oxide.
In the invention, simple substance phosphorus or low-valence state phosphorus compound is used as a modification additive, partial reduction of transition metal and oxygen defect production can be realized at lower temperature by utilizing the reducibility of phosphorus, and the reaction product is easy to purify and recover due to the easy sublimability of phosphorus pentoxide. The lithium ion battery material prepared by the method has obviously improved electronic conductivity and improved electrochemical performance. The method uses cheap phosphorus as a reducing agent, reduces at low temperature, greatly reduces the production cost and is beneficial to realizing industrialization.
Drawings
Fig. 1 is an XRD pattern showing untreated lithium titanate and an XRD pattern showing lithium titanate with oxygen defects obtained according to example 1, respectively;
FIG. 2 is an XPS plot of a lithium titanate with oxygen defects obtained according to example 1;
fig. 3 is an electrochemical curve of a lithium ion battery comprising untreated lithium titanate as electrode material at different charging currents;
fig. 4 is an electrochemical curve at different charging currents for a lithium ion battery comprising as electrode material a lithium titanate with oxygen defects obtained according to example 1;
FIG. 5 is an electrochemical curve of a lithium ion battery comprising untreated molybdenum trioxide as an electrode material at different charging currents;
fig. 6 is an electrochemical curve of a lithium ion battery with oxygen-deficient molybdenum trioxide as an electrode material obtained in example 2 at different charging currents.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate the features and advantages of the invention and is not intended to limit the scope of the invention.
The present invention provides a method for preparing a transition metal oxide having an oxygen defect. In the present invention, a mixed-valence transition metal oxide is prepared by forming oxygen defects in a transition metal oxide, and when it is used as an electrode material, the conductivity of the material can be greatly improved. For example, as titanium-containing oxide materials, when incorporated with a certain amount of Ti3+When ionic, the conductivity can be greatly improved. Oxygen defects can be obtained by reaction under an inert gas or a reducing gas, for Ti4+In terms of ions, the reduction needs to be carried out under a reducing gas at a high temperature to realize Ti3+The energy consumption and the cost are higher. The invention provides a novel low-temperature reducing agent with low cost, which realizes the reduction of transition metal ions at low temperature by utilizing the volatility of a product. According to the bookIn the invention, the modifier is preferably elemental phosphorus or a low-valence phosphorus compound, and the compound can be oxidized at low temperature, and then the generated phosphorus pentoxide can be sublimated and removed, so that the reaction can be continuously performed. The method requires low reaction temperature, low energy consumption and high safety, and in addition, the modifier is very small in use amount, the cost is lower, and the method has industrial application value.
The equipment used for drying in the process according to the invention is drying equipment well known to the person skilled in the art, such as infrared ovens, forced air ovens, etc., preferably muffle ovens are used for calcination. Other equipment which is not particularly limited as long as it can perform the preparation step and which can achieve the effects of the present invention by equipment known to those skilled in the art is within the scope of protection.
The following are specific examples of the present invention and illustrate the technical solutions of the present invention in detail.
Example 1
Preparation of lithium titanate with oxygen defects
1g of commercial lithium titanate (LTO 1, Shenzhen Beibei New energy materials Co., Ltd.) and 0.05g of red phosphorus (national drug group chemical reagent Co., Ltd.) were weighed, ground uniformly, and then treated at 400 ℃ for 10 minutes in argon atmosphere to obtain a lithium titanate material with oxygen defects. The color of the treated lithium titanate is changed from white to blue.
Electrochemical performance test
According to the transition metal oxide: super conductive carbon black: PVDF (polyvinylidene fluoride) (75: 15: 10) is mixed with N-methylpyrrolidone as a solvent to prepare slurry, a copper foil is uniformly coated with the slurry to serve as a working electrode, a counter electrode is made of high-purity metal lithium, a diaphragm is made of Celgard 2400, electrolyte is a mixed solution of ethylene carbonate and dimethyl carbonate of 1M LiPF6 according to a volume ratio of 1:1, and the mixed solution is assembled into a 2032 type button cell in a glove box filled with argon to carry out electrochemical performance testing.
Table 1: electrochemical performance of unmodified lithium titanate at different currents
Specific experimental data may be looked at the electrochemical curves of figure 3 at different charging current densities.
Table 2: electrochemical performance of modified lithium titanate under different currents
Specific experimental data may be looked at the electrochemical curves of figure 4 at different charging current densities.
Example 2
Preparation of molybdenum trioxide with oxygen defects
1g of commercially available pale yellow molybdenum trioxide (national chemical Co., Ltd.) and 0.01g of red phosphorus (national chemical Co., Ltd.) were weighed, mixed and ground uniformly, and reacted under vacuum at 400 ℃ for 1 hour to obtain bluish black molybdenum trioxide having oxygen defects.
Electrochemical testing
The same method as in example 1 was performed to test the rate capability of the molybdenum trioxide material before and after modification, and the results are shown in tables 3 and 4 below, and fig. 5.
Table 3: electrochemical performance of unmodified molybdenum trioxide under different currents
Specific experimental data the electrochemical curves of figure 5 at different charge current densities can be looked at.
Table 4: electrochemical performance of modified molybdenum trioxide under different currents
Specific experimental data may be looked at the electrochemical curves of figure 6 at different charging current densities.
Example 3
Preparation of titanium dioxide having oxygen deficiency
1g of nano titanium dioxide (national chemical group, chemical Co., Ltd., P25) was weighed in a crucible, and 0.1g of NaH was placed at the position of the upper tuyere2PO2Heating to 400 deg.C for two hours in a nitrogen-filled tube furnace, and utilizing the pH obtained by decomposition3The titanium dioxide is reduced to obtain a bluish-black titanium dioxide with oxygen defects.
Electrochemical testing
The rate capability of the titania material before and after modification was tested in the same manner as in example 1, and the results are shown in tables 5 and 6 below.
Table 5: electrochemical performance of unmodified titanium dioxide at different currents
Table 6: electrochemical performance of modified titanium dioxide under different currents
Example 4
Preparation of vanadium pentoxide with oxygen defect
1g of ammonium metavanadate (national chemical group chemical Co., Ltd.) was weighed into a crucible, and 0.1g of NaH was placed at the position of the upper tuyere2PO2Heating to 450 deg.C for half an hour in a nitrogen-filled tube furnace, and decomposing to obtain pH3And reducing the vanadium pentoxide to obtain the vanadium pentoxide with oxygen defects.
Electrochemical testing
The rate capability of the vanadium pentoxide material before and after modification was tested in the same manner as in example 1, and the results are shown in tables 7 and 8 below.
Table 7: electrochemical performance of unmodified vanadium pentoxide under different currents
Table 8: electrochemical performance of modified vanadium pentoxide under different currents
From the above results, it can be seen that: the method has good effect on some nanometer oxides which are difficult to reduce, can realize the reduction of the oxides on the premise of keeping the particle size, and better improves the electrochemical performance of the material. Depending on the redox activity of the raw materials and the requirement for homogeneity, we use different raw materials for material modification to obtain optimized electrochemical performance.
The method for preparing transition metal oxide with oxygen defect provided by the present invention is described in detail above, and the principle and the embodiment of the present invention are illustrated herein by using specific examples, and the above description of the examples is only for helping understanding the method of the present invention and the core idea thereof, it should be noted that, for those skilled in the art, it is possible to make several improvements and modifications to the present invention without departing from the principle of the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.
Claims (8)
1. A method of preparing a transition metal oxide having an oxygen defect, comprising:
a) fully mixing a transition metal oxide or a precursor thereof with a modifier to obtain a uniform mixture;
b) heating the mixture at 360 ℃ to 550 ℃ under inert atmosphere or vacuum conditions to obtain a transition metal oxide having oxygen defects;
wherein the modifier is simple substance phosphorus with reducibility,
the transition metal oxide is selected from titanium dioxide, lithium titanate, molybdenum trioxide, vanadium pentoxide and niobium pentoxide.
2. The method according to claim 1, wherein the modifier is used in an amount of 0.2 to 15 wt% based on 100 wt% of the transition metal oxide or the precursor thereof.
3. The method according to claim 2, wherein the modifier is used in an amount of 0.5 to 10 wt% based on 100 wt% of the transition metal oxide or the precursor thereof.
4. The method according to claim 2, wherein the modifier is used in an amount of preferably 0.5 to 8 wt% based on 100 wt% of the transition metal oxide or the precursor thereof.
5. The process of claim 1, wherein in step b), the mixture is heated at a temperature of 360 ℃ to 450 ℃.
6. A transition metal oxide having oxygen defects prepared according to the method of any one of claims 1 to 5.
7. An electrode of a lithium ion battery comprising the transition metal oxide having an oxygen defect of claim 6.
8. A lithium ion battery comprising an electrode of the lithium ion battery of claim 7.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101682028A (en) * | 2007-01-17 | 2010-03-24 | 埃纳戴尔公司 | Lithium titanate and lithium cells and batteries including the same |
| CN101883735A (en) * | 2007-10-01 | 2010-11-10 | 巴斯夫欧洲公司 | Process for the preparation of crystalline lithium-, vanadium- and phosphate-comprising materials |
| CN103476494A (en) * | 2011-03-24 | 2013-12-25 | 国立大学法人横浜国立大学 | Oxygen reduction catalyst and methods for preparing same |
| CN102642867B (en) * | 2012-04-24 | 2014-01-01 | 四川大学 | Method for preparing nanometer Ti4O7 powder |
| CN106277042A (en) * | 2016-08-29 | 2017-01-04 | 湖南科莱新材料有限公司 | One prepares Ti4o7method |
| CN106477633A (en) * | 2015-09-01 | 2017-03-08 | 北京化工大学 | A kind of bimetal-doped group vib metal oxide nano-material and preparation method and application |
| CN106861681A (en) * | 2015-12-10 | 2017-06-20 | 中国科学院上海硅酸盐研究所 | A kind of method that efficient hydrogen reduction prepares transition metal oxide defect |
-
2017
- 2017-09-28 CN CN201710901861.0A patent/CN107768663B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101682028A (en) * | 2007-01-17 | 2010-03-24 | 埃纳戴尔公司 | Lithium titanate and lithium cells and batteries including the same |
| CN101883735A (en) * | 2007-10-01 | 2010-11-10 | 巴斯夫欧洲公司 | Process for the preparation of crystalline lithium-, vanadium- and phosphate-comprising materials |
| CN103476494A (en) * | 2011-03-24 | 2013-12-25 | 国立大学法人横浜国立大学 | Oxygen reduction catalyst and methods for preparing same |
| CN102642867B (en) * | 2012-04-24 | 2014-01-01 | 四川大学 | Method for preparing nanometer Ti4O7 powder |
| CN106477633A (en) * | 2015-09-01 | 2017-03-08 | 北京化工大学 | A kind of bimetal-doped group vib metal oxide nano-material and preparation method and application |
| CN106861681A (en) * | 2015-12-10 | 2017-06-20 | 中国科学院上海硅酸盐研究所 | A kind of method that efficient hydrogen reduction prepares transition metal oxide defect |
| CN106277042A (en) * | 2016-08-29 | 2017-01-04 | 湖南科莱新材料有限公司 | One prepares Ti4o7method |
Non-Patent Citations (1)
| Title |
|---|
| "微纳结构及缺陷二氧化钛包覆层对锂/钠二次电池负极材料的改性研究";王娜娜;《中国博士学位论文全文数据库 工程科技Ⅱ辑》;20061115;第C042-6页 * |
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