CN112678876B - Application of LiFe4Mo5O20 in lithium ion battery cathode - Google Patents
Application of LiFe4Mo5O20 in lithium ion battery cathode Download PDFInfo
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- CN112678876B CN112678876B CN202010971182.2A CN202010971182A CN112678876B CN 112678876 B CN112678876 B CN 112678876B CN 202010971182 A CN202010971182 A CN 202010971182A CN 112678876 B CN112678876 B CN 112678876B
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Abstract
The invention relates to LiFe 4 Mo 5 O 20 The lithium ion battery cathode is applied to the lithium ion battery cathode. The LiFe 4 Mo 5 O 20 The compound is used as an active material applied to the negative electrode of the lithium ion battery, has better charge and discharge performance of the lithium ion battery, and is circulatedThe lithium ion battery cathode material has good stability and proper working voltage and can be used as a lithium ion battery cathode material.
Description
Technical Field
The invention relates to a chemical formula of LiFe 4 Mo 5 O 20 The lithium ion battery cathode material, the preparation method and the lithium ion battery manufactured by the material.
Background
With the increasing severity of energy problems, the increasing scarcity of non-renewable resources, and the increasing awareness of people on the importance of environmental protection, the social demand for new energy is increasing, and stored energy plays an increasingly important role in energy systems. Previously, lithium ion batteries, which are important energy storage devices in new energy, have attracted a great deal of research resources.
The cathode materials currently applied to lithium ion batteries mainly include graphite, carbon, lithium titanate and the like. However, these materials still suffer from a number of problems: poor specific capacity, poor cycling stability, difficulty in preparation and the like, which severely limits the practical application of these materials. Therefore, the search for new lithium ion battery negative electrode materials remains a hotspot and difficulty of lithium ion battery research. Among polyanionic negative electrode materials, molybdate has gained more and more attention due to its higher specific capacity.
Disclosure of Invention
In view of the above-mentioned technical problems, the present invention aims to provide a LiFe 4 Mo 5 O 20 The material is used as a negative electrode material in a lithium ion battery;
the specific technical scheme is as follows:
LiFe 4 Mo 5 O 20 Application of the LiFe in lithium ion battery cathode 4 Mo 5 O 20 The compound is used as an active material to be applied to a lithium ion battery cathode.
The lithium ion battery cathode active material is LiFe 4 Mo 5 O 20 A material.
The invention provides LiFe 4 Mo 5 O 20 A lithium ion battery cathode material.
Preparation of LiFe by solid-phase reaction method 4 Mo 5 O 20 The method comprises the following steps:
1) Preparing materials: mixing and pretreating a Li-containing compound, a Fe-containing compound and a Mo-containing compound according to the molar ratio of Li to Fe to Mo of (1-1.1) 4:5;
the pretreatment is to uniformly mix the prepared raw materials, pour the mixture into a crucible, heat the mixture for 2 to 10 hours in a muffle furnace from room temperature to 200 to 500 ℃, and then cool the mixture to room temperature;
2) Controlling various parameters to synthesize the material: placing the crucible containing the ingredients in a muffle furnace; raising the temperature from room temperature to 600-1000 ℃ at the rate of 1-10 ℃; preserving the heat for 10-40 hours; after the reaction is fully carried out, the temperature is reduced to room temperature at the speed of 1-50 ℃/h to obtain LiFe 4 Mo 5 O 20 A material;
the Li-containing compound is one or more than two of Li oxide, li carbonate, li borate, li nitrate or Li oxalate;
the Fe-containing compound is one or more than two of Fe oxide and Fe oxalate;
the Mo-containing compound is MoO 2 Or MoO 3 One or two of them.
Preparation of LiFe by sol-gel method 4 Mo 5 O 20 The lithium ion battery negative electrode material comprises the following steps:
1) Preparing materials: mixing a Li-containing compound, a divalent Fe-containing compound and a Mo-containing compound according to the weight ratio of Li: fe: mo: adding oxalic acid into deionized water at 50-100 ℃ according to a molar ratio of (1-1.1) to 4:5, stirring until a uniform light green solution is formed, and continuing stirring until sol is formed; the molar concentration of the Li-containing compound in deionized water is 0.1-0.5mol/L.
2) Transferring the sol to a drying oven at 100-150 ℃, drying to gel, grinding the gel into powder, transferring the powder to a porcelain boat, and performing pretreatment;
the pretreatment is that the raw materials in the porcelain boat are heated from room temperature to 200-500 ℃ in a muffle furnace for more than 2-10 hours, and then cooled to room temperature;
3) Controlling various parameters to synthesize the material: placing the porcelain boat containing the ingredients in a muffle furnace; raising the temperature to 600-1000 ℃ at the rate of 1-10 ℃; keeping the temperature for 10 to 40 hours(ii) a After the reaction is fully carried out, the temperature is reduced to room temperature at the speed of 1-50 ℃/h to obtain LiFe 4 Mo 5 O 20 A material;
the Li-containing compound is one or more than two of Li oxide, li carbonate, li borate, li nitrate or Li oxalate;
the Fe-containing compound is one or more than two of Fe oxide and Fe oxalate;
the Mo-containing compound is MoO 2 Or MoO 3 One or two of them.
A few typical available LiFe are listed below 4 Mo 5 O 20 Chemical reaction formula of the compound:
(1) Li 2 CO 3 +6FeO+Fe 2 O 3 +10MoO 3 =2LiFe 4 Mo 5 O 20 +CO 2
(2) 2LiNO 3 +8FeO +10MoO 3 ＝2LiFe 4 Mo 5 O 20 +2NO 2
(3) 2Li 2 CO 3 +16FeC 2 O 4 +20MoO 3 +O 2 ＝4LiFe 4 Mo 5 O 20 +32CO 2
the invention has the advantages that: the obtained LiFe 4 Mo 5 O 20 The negative electrode material has high specific capacity, rate capability and cycling stability. LiFe 4 Mo 5 O 20 The lithium ion battery cathode material has higher specific capacity reaching 950mAh/g; the working voltage is between 0.05 and 3.0V, and the specific capacity can still be kept above 95 percent after 100 cycles.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
FIG. 1 is a LiFe according to the present invention 4 Mo 5 O 20 SEM pictures of lithium ion battery negative electrode materials.
FIG. 2 is a LiFe according to the present invention 4 Mo 5 O 20 The polycrystalline powder X-ray diffraction pattern of (a).
FIG. 3 is a LiFe according to the present invention 4 Mo 5 O 20 Crystal structure of lithium.
FIG. 4 is a LiFe according to the present invention 4 Mo 5 O 20 The lithium negative electrode material has a charge-discharge curve of 0.1C multiplying power and 1.5-4.2V.
FIG. 5 is a LiFe according to the present invention 4 Mo 5 O 20 Rate performance curve of lithium negative electrode material.
Detailed Description
The present invention will now be described in more detail with reference to the accompanying drawings, in which preferred embodiments of the invention are shown, it being understood that one skilled in the art may modify the invention herein described while still achieving the beneficial results of the present invention. Accordingly, the following description should be construed as broadly as possible to those skilled in the art and not as limiting the invention.
Example 1LiFe 4 Mo 5 O 20 High temperature solid phase preparation of anode materials
0.01mol of Li 2 CO 3 0.06mol of FeO and 0.1mol of MoO 3 Put into an agate mortar and ground for half an hour. Transferred to a crucible and placed in a muffle furnace. The furnace is heated to 300 ℃ at the heating rate of 5 ℃/min, the temperature is kept for 5 hours, and finally the temperature is reduced to the room temperature at the speed of 20 ℃/min. And taking out the synthesized material, grinding the synthesized material into powder, transferring the powder into the crucible again, and putting the crucible into a muffle furnace. The furnace is heated to 800 ℃ at the heating rate of 5 ℃/min, the temperature is preserved for 20 hours, and finally the temperature is reduced to the room temperature at the speed of 20 ℃/min. Taking out the obtained product and grinding the product to obtain the LiFe 4 Mo 5 O 20 A compound is provided.
As shown in the figure1, it is a gray green powder with a tap density of 2.0g/cm 3 . The X-ray diffraction spectrum is shown in figure 2, and the crystal structure diagram is shown in figure 3. As can be seen from FIG. 3, the basic structural unit is FeO 6 And MoO 4 Polyhedron, moO 4 The polyhedrons are connected to form a three-dimensional network structure.
Example 2LiFe 4 Mo 5 O 20 Sol-gel preparation of negative electrode materials
0.03mol of oxalic acid was dissolved in a beaker containing 150ml of deionized water, and then 0.04mol of Fe (NO) was added 3 ) 3 Stirring the mixture in a constant-temperature water bath at 70-80 ℃ until the mixture turns into a blue solution, and then adding 0.05mol of MoO 3 0.01mol of Li 2 CO 3 And continuously stirring to form the blue-green lithium iron molybdate sol. And (3) placing the sol in an oven at 80 ℃ for drying for about 10 hours to obtain a blue fluffy precursor, grinding the precursor into powder, placing the powder in a crucible, and placing the crucible in a muffle furnace. The furnace is heated to 300 ℃ at the heating rate of 5 ℃/min, the temperature is kept for 5 hours, and finally the temperature is reduced to the room temperature at the speed of 20 ℃/min. And taking out the synthesized material, grinding the synthesized material into powder, transferring the powder into the crucible again, and putting the crucible into a muffle furnace. The furnace is heated to 800 ℃ at the heating rate of 5 ℃/min, the temperature is preserved for 20 hours, and finally the temperature is reduced to the room temperature at the speed of 20 ℃/min. Taking out the obtained product and grinding the product to obtain the LiFe 4 Mo 5 O 20 A compound is provided.
Dissolving the materials obtained in the examples 1 and 2 in a proper amount of N-methylpyrrolidone according to the mass ratio of 8. Meanwhile, a lithium sheet is used as a negative electrode, celgard 2500 is used as a diaphragm, and 1mol/L LiPF 6 The EC + DMC (1:1 by volume) solution of (A) was used as an electrolyte, and a coin cell was assembled in an argon-filled glove box. The assembled cells were then subjected to electrochemical testing, each at 0.05-3.0V constant current. The results of the tests are shown in FIGS. 4 and 5, where it can be seen that LiFe 4 Mo 5 O 20 Has high specific discharge capacity up to 950mAhg -1 And has good rate-following performance, and 500mAhg is still available under 20C rate -1 The specific capacity of (A).
The LiFe 4 Mo 5 O 20 The compound is used as an active material to be applied to a lithium ion battery cathode, has better charge and discharge performance of the lithium ion battery, good cycle stability and proper working voltage, and can be used as a lithium ion battery cathode material.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, changes and equivalent structural changes made to the above embodiment according to the technical spirit of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (2)
1. LiFe 4 Mo 5 O 20 The application in the negative electrode of the lithium ion battery is characterized in that: the LiFe 4 Mo 5 O 20 The compound is used as an active material to be applied to a lithium ion battery cathode;
and, the LiFe 4 Mo 5 O 20 The preparation of the compounds is as follows:
preparation of LiFe by solid-phase reaction method 4 Mo 5 O 20 A compound comprising the steps of:
1) Preparing materials: mixing and pretreating a Li-containing compound, a Fe-containing compound and a Mo-containing compound according to the molar ratio of Li to Fe to Mo of (1-1.1) 4:5;
the pretreatment is that the prepared raw materials are uniformly mixed, heated from room temperature to 200-500 ℃ for 2-10 hours, and then cooled to room temperature;
2) Controlling various parameters to synthesize the material: heating the pretreated ingredients from room temperature to 600-1000 ℃ at the speed of 1-10 ℃/min; preserving the heat for 10-40 hours; after the reaction is fully carried out, the temperature is reduced to the room temperature at the speed of 1-50 ℃/h,obtaining LiFe 4 Mo 5 O 20 A material;
the Li-containing compound is one or more than two of Li oxide, li carbonate, li borate, li nitrate or Li oxalate;
the Fe-containing compound is one or more than two of Fe oxide and Fe oxalate;
the Mo-containing compound is MoO 2 Or MoO 3 One or two of them;
alternatively, the LiFe is prepared by a sol-gel method 4 Mo 5 O 20 A compound comprising the steps of:
1) Preparing materials: mixing a Li-containing compound, a divalent Fe-containing compound and a Mo-containing compound in the ratio of Li: fe: mo: adding oxalic acid into deionized water at 50-100 ℃ according to a molar ratio of (1-1.1) to 4:5, stirring until a uniform light green solution is formed, and continuing stirring until sol is formed;
2) Drying the sol at 100-200 ℃ to obtain gel, grinding the gel into powder and then carrying out pretreatment;
the pretreatment is to heat the mixture from room temperature to 200-500 ℃ for more than 2-10 hours, and then cool the mixture to room temperature;
3) Controlling various parameters to synthesize the material: the material pretreated in the step 2); raising the temperature to 600-1000 ℃ at the rate of 1-10 ℃; preserving the heat for 10-40 hours; after the reaction is fully carried out, the temperature is reduced to room temperature at the speed of 1-50 ℃/h to obtain LiFe 4 Mo 5 O 20 A material;
the Li-containing compound is one or more than two of Li oxide, li carbonate, li borate, li nitrate or Li oxalate;
the Fe-containing compound is one or more than two of Fe oxide and Fe oxalate;
the Mo-containing compound is MoO 2 Or MoO 3 One or two of them.
2. Use according to claim 1, characterized in that:
the mol concentration of the Li-containing compound in the step 1) of the sol-gel method in the deionized water is 0.1-0.5mol/L.
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| JP3928032B2 (en) * | 1999-09-17 | 2007-06-13 | 独立行政法人産業技術総合研究所 | Electrode active material for non-aqueous electrolyte battery, electrode and battery including the same |
| CN103985865B (en) * | 2014-05-16 | 2016-08-24 | 吉林大学 | A kind of molybdate polyanionic lithium cell cathode material and preparation method thereof |
| CN107302091A (en) * | 2016-08-03 | 2017-10-27 | 桐城市宇洁机动车尾气检测有限公司 | A kind of preparation method and applications of LiFe (MoO) material |
| CN107275629B (en) * | 2017-05-08 | 2021-01-05 | 武汉工程大学 | High-power charge-discharge lithium ion battery anode material and preparation method thereof |
| CN107026268B (en) * | 2017-05-27 | 2019-06-04 | 中南大学 | A kind of preparation method of anode material for lithium-ion batteries iron molybdate lithium |
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