CN115528228A - Lithium molybdate coated modified lithium manganate material and preparation method and application thereof - Google Patents
Lithium molybdate coated modified lithium manganate material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a lithium molybdate coated modified lithium manganate material and a preparation method and application thereof, belonging to the technical field of lithium ion batteries. The lithium molybdate coated modified lithium manganate material provided by the invention comprises molybdenum-doped lithium manganate and lithium molybdate coated on the surface of the molybdenum-doped lithium manganate. According to the invention, molybdenum is used for doping the lithium manganate, so that the structural defects of the lithium manganate can be effectively improved, and the structural stability of the lithium manganate is improved; the surface of the molybdenum-doped lithium manganate is coated with a layer of lithium molybdate, so that the side reaction between the lithium manganate and the electrolyte can be effectively reduced, and the cycling stability of the material in the cycling process is improved. The embodiment result shows that the discharge specific capacity of the lithium molybdate-coated modified lithium manganate material provided by the invention is 88.9-95.8% after being cycled for 100 circles, the capacity retention rate is 81.3-87.4%, and the cycle performance is obviously improved compared with that of a simple lithium manganate material.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a lithium molybdate coated modified lithium manganate material and a preparation method and application thereof.
Background
Lithium Ion Batteries (LIBs) have dominated the energy storage field as an energy storage device that is different from conventional energy sources. In the modern portable application product market, lithium ion batteries are widely used for 3C digital products, mobile power sources, electric tools, wearable electronic products, and the like. The lithium ion battery has the advantages of high specific energy, low self-discharge, good cycle performance, no memory effect, environmental protection and the like, and is a high-efficiency secondary battery with the greatest development prospect and a fastest-developed chemical energy storage power supply.
Spinel lithium manganate has become one of the most potential lithium ion battery electrode materials due to its advantages of high working voltage, good stability, low cost and the like. Compared with the ternary material which is hot, the cobalt resource and the nickel resource are in short supply, the price is high, the manganese resource is rich, and the price is only one tenth of that of the cobalt-nickel material. Compared with a lithium iron phosphate material, the lithium manganate has good low-temperature performance and mature preparation process. Therefore, spinel lithium manganate materials have been receiving much attention from researchers.
However, the lithium manganate material has poor cycle performance, and the major problem faced by the lithium manganate material is large capacity loss after each cycle. To this end, chen Ruifang et al (see: chen Ruifang, wen Bixia, tian Liang, et al. Citric acid vs. spinel type LiMn 2 O 4 Effect of Performance [ J]The chemical novel material 2020) explores the influence of citric acid on the performance of spinel type lithium manganate, and by optimizing the dosage of additive citric acid, the capacity retention rate of the material is only 53.4% under the optimal addition amount after 300 cycles, and the average volume loss rate per cycle is 1.55 per mill.
Disclosure of Invention
In view of the above, the invention aims to provide a lithium molybdate coated modified lithium manganate material and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a lithium molybdate coated modified lithium manganate material, which comprises molybdenum-doped lithium manganate and lithium molybdate coated on the surface of the molybdenum-doped lithium manganate;
the chemical composition of the molybdenum-doped lithium manganate is as follows: liMn 2-x Mo x O 4 ，0＜x≤0.02。
Preferably, the molar ratio of the lithium molybdate to the molybdenum-doped lithium manganate is 0.01-0.02.
Preferably, the lithium manganate is spinel lithium manganate.
Preferably, the lithium molybdate coated modified lithium manganate material is characterized in that the particle size of the lithium molybdate coated modified lithium manganate material is 5-30 μm.
The invention provides a preparation method of the lithium molybdate coated modified lithium manganate material, which comprises the following steps:
mixing manganese dioxide, soluble molybdate and soluble manganous salt with water, and carrying out coprecipitation reaction to obtain manganese molybdate coated manganese dioxide;
and mixing the manganese molybdate coated manganese dioxide with a lithium source, and calcining in an oxygen-containing atmosphere to obtain the lithium molybdate coated modified lithium manganate material.
Preferably, the molar ratio of the manganese dioxide, the soluble molybdate and the soluble manganous salt is (50-100): 1 (1-1.2).
Preferably, the temperature of the coprecipitation reaction is 80-100 ℃ and the time is 2-8 h.
Preferably, the molar ratio of the lithium source to the manganese dioxide is (1.08-1.12): 2.
Preferably, the calcining temperature is 700-1000 ℃, and the holding time is 4-20 h.
The invention provides an application of the lithium molybdate coated modified lithium manganate material as a lithium ion battery anode active material.
The invention providesA lithium molybdate coated modified lithium manganate material comprises molybdenum-doped lithium manganate and lithium molybdate coated on the surface of the molybdenum-doped lithium manganate; the chemical composition of the molybdenum-doped lithium manganate is LiMn 2-x Mo x O 4 X is more than 0 and less than or equal to 0.02. According to the method, the molybdenum element is used for doping the lithium manganate, and the molybdenum element is easy to change the oxidation state of the lithium manganate, so that the molybdenum element can play a role in protecting the manganese element in the electrochemical reaction process, namely the chemical structure of the lithium manganese spinel is relatively stabilized, the structural defects of the lithium manganate can be effectively improved, and the structural stability of the lithium manganate is improved; the surface of the molybdenum-doped lithium manganate is coated with a layer of lithium molybdate, so that the side reaction between the lithium manganate and the electrolyte can be effectively reduced, and the cycling stability of the material in the cycling process is improved. The embodiment result shows that the discharge specific capacity of the lithium molybdate-coated modified lithium manganate material is 88.9-95.8% after being cycled for 100 circles, the capacity retention rate is 81.3-87.4%, and the cycle performance is obviously improved compared with that of a pure lithium manganate material.
The invention provides a preparation method of the lithium molybdate coated modified lithium manganate material, which comprises the following steps: mixing manganese dioxide, soluble molybdate, soluble manganous salt and water, and carrying out coprecipitation reaction to obtain manganese molybdate coated manganese dioxide; and mixing the manganese molybdate coated manganese dioxide with a lithium source, and calcining in an oxygen-containing atmosphere to obtain the lithium molybdate coated modified lithium manganate material. According to the invention, manganese molybdate can be coated on the surface of manganese dioxide in situ by adopting a coprecipitation mode of manganese dioxide, soluble molybdate and soluble manganous salt, and elements are uniformly distributed in the coating process; according to the invention, lithium ions are introduced into manganese molybdate-coated manganese dioxide in a calcining manner, so that the lithium molybdate-coated modified lithium manganate material is obtained. Meanwhile, the preparation method is simple, low in cost and easy to realize industrial mass production.
Drawings
FIG. 1 shows Li obtained in example 1 2 MoO 4 @LiMn 1.99 Mo 0.01 O 4 SEM picture of (1);
FIG. 2 shows Li obtained in example 1 2 MoO 4 @LiMn 1.99 Mo 0.01 O 4 The charge and discharge test result of (1);
FIG. 3 shows Li in comparative example 1 2 MoO 4 The charge and discharge test results of (1).
Detailed Description
The invention provides a lithium molybdate coated modified lithium manganate material, which comprises molybdenum-doped lithium manganate and lithium molybdate coated on the surface of the molybdenum-doped lithium manganate;
the chemical composition of the molybdenum-doped lithium manganate is as follows: liMn 2-x Mo x O 4 0 < x.ltoreq.0.02, preferably 0.005. Ltoreq.x.ltoreq.0.015, more preferably 0.01. Ltoreq.x.ltoreq.0.012.
As a specific embodiment of the invention, the chemical composition of the lithium molybdate coated modified lithium manganate material is Li 2 MoO 4 @LiMn 1.995 Mo 0.005 O 4 、Li 2 MoO 4 @LiMn 1.99 Mo 0.01 O 4 Or Li 2 MoO 4 @LiMn 1.98 Mo 0.02 O 4 .
In the invention, the molar ratio of the lithium molybdate to the molybdenum-doped lithium manganate is preferably 0.01-0.02, more preferably 0.015-0.018.
In the present invention, the lithium manganate is preferably spinel lithium manganate. In the invention, the molybdenum-doped lithium manganate is preferably a lithium manganate with a surface layer doped with molybdenum element.
In the invention, the medium particle size of the lithium molybdate-coated modified lithium manganate material is preferably 5 to 30 μm, and more preferably 10 to 20 μm. In the present invention, the thickness of the lithium molybdate is preferably 5 to 200nm, more preferably 10 to 150nm, and still more preferably 50 to 100nm.
The invention provides a preparation method of the lithium molybdate coated modified lithium manganate material, which comprises the following steps:
mixing manganese dioxide, soluble molybdate and soluble manganous salt with water, and carrying out coprecipitation reaction to obtain manganese molybdate coated manganese dioxide;
and mixing the manganese molybdate coated manganese dioxide with a lithium source, and calcining in an oxygen-containing atmosphere to obtain the lithium molybdate coated modified lithium manganate material.
Manganese dioxide, soluble molybdate, soluble manganous salt and water are mixed for coprecipitation reaction, and manganese molybdate coated manganese dioxide is obtained. In the present invention, the particle diameter of the manganese dioxide is preferably 5 to 30 μm, and more preferably 10 to 20 μm.
In the invention, the soluble molybdate is preferably one or more of lithium molybdate, sodium molybdate and potassium molybdate, and the soluble manganous salt is preferably manganese chloride.
In the present invention, the molar ratio of manganese dioxide, soluble molybdate and soluble divalent manganese salt is preferably (50 to 100): 1 (1 to 1.2), and more preferably (60 to 80): 1:1.
In the present invention, the concentration of manganese dioxide in the mixed solution obtained by mixing the manganese dioxide, soluble molybdate and soluble manganous salt with water is preferably 0.05 to 0.2g/mL, more preferably 0.1 to 0.15g/mL.
The invention does not require any particular mixing means, such as stirring, known to the person skilled in the art.
In the present invention, the temperature of the coprecipitation reaction is preferably 80 to 100 ℃, and more preferably 90 ℃; the time is preferably 2 to 8 hours, more preferably 4 to 6 hours.
In the invention, in the coprecipitation reaction process, manganese dioxide is uniformly distributed in the solution, wherein the surface charge of the manganese dioxide is negative, and Mn in the solution is easily attracted 2+ To the surface of the particles, and molybdate anions will neutralize Mn 2+ The coprecipitation reaction occurs to uniformly deposit on the surface of the manganese dioxide.
After the coprecipitation reaction, the present invention preferably performs a post-treatment on the obtained coprecipitation reaction, and the post-treatment preferably includes:
and carrying out solid-liquid separation, washing and drying on the coprecipitation reaction liquid ethylene to obtain manganese molybdate coated manganese dioxide.
In the present invention, the solid-liquid separation is preferably filtration; the washing is preferably water washing. The present invention does not require any particular manner of drying, and the solids may be dried to constant weight using drying means well known to those skilled in the art.
After the manganese molybdate-coated manganese dioxide is obtained, mixing the manganese molybdate-coated manganese dioxide with a lithium source, and calcining in an oxygen-containing atmosphere to obtain the lithium molybdate-coated modified lithium manganate material. In the present invention, the lithium source is preferably lithium carbonate and/or lithium hydroxide.
In the present invention, the molar ratio of the lithium source to manganese dioxide is preferably (1.08 to 1.12): 2, and more preferably 1:2.
The invention does not require any particular mixing means, such as stirring, known to the person skilled in the art.
In the present invention, the calcination is preferably carried out in a muffle furnace. In the present invention, the oxygen-containing atmosphere is preferably oxygen or air.
In the present invention, the temperature of the calcination is preferably 700 to 1000 ℃, more preferably 800 to 900 ℃; the holding time is preferably 4 to 20 hours, more preferably 6 to 15 hours, and still more preferably 10 to 12 hours. In the present invention, the rate of temperature increase to the calcination temperature is preferably 100 ℃/h.
In the invention, because the manganese molybdate coated on the surface of the manganese molybdate coated manganese dioxide material is very thin and is attached to the surface of the manganese dioxide in the form of nano particles, a large number of channels are provided to enable lithium ions to react with the manganese dioxide. During the calcining process, manganese molybdate can react with lithium ions to generate lithium molybdate; meanwhile, lithium ions can penetrate through the lithium molybdate layer to contact with manganese dioxide, and the molybdenum-doped lithium manganate is generated through oxidation and calcination.
The invention provides an application of the lithium molybdate coated modified lithium manganate material as a lithium ion battery anode active material. When the lithium molybdate-coated modified lithium manganate material provided by the invention is used as a lithium ion battery anode active material, the lithium molybdate-coated modified lithium manganate material has good cycling stability.
The following will describe the lithium molybdate coated modified lithium manganate material and the preparation method and application thereof in detail with reference to the examples, but they should not be construed as limiting the scope of the present invention.
Example 1
(1) Adding 0.1mol of MnO 2 Dispersing in 100mL of aqueous solution, adding 2mmol of sodium molybdate and 2mmol of manganese chloride, heating at 100 ℃ for reaction for 2 hours, filtering, washing and drying to obtain manganese molybdate coated manganese dioxide crystals;
(2) Uniformly mixing the manganese molybdate-coated manganese dioxide crystal and 0.055mol of LiOH in a mortar, and calcining at 800 ℃ for 8 hours in a muffle furnace to obtain a lithium molybdate-coated modified lithium manganate material, which is recorded as Li 2 MoO 4 @LiMn 1.99 Mo 0.01 O 4 。
Obtained Li 2 MoO 4 @LiMn 1.99 Mo 0.01 O 4 Is shown in fig. 1. As can be seen from FIG. 1, the material is in the form of polycrystalline grains having a grain size corresponding to that of the starting material MnO 2 The size of primary crystal grains is about 0.5-2 mu m, the distribution is uniform and compact, the particle surface is smooth, and the interface stability is good.
The synthesized lithium molybdate coated modified lithium manganate material is used as an active substance of a positive electrode material, and is mixed with Acetylene Black (AB) as a conductive agent and polyvinylidene fluoride (PVDF) as a binder in a mass ratio of 8. Coating the slurry on a current collector aluminum foil by using an automatic coating machine, flatly placing the current collector aluminum foil on toughened glass, transferring the current collector aluminum foil to a vacuum drying oven at 85 ℃ for drying for 4h, preparing a pole piece with the diameter of 14mm by punching, drying for 4h at 105 ℃ in the vacuum drying oven, placing the pole piece in a glove box with the water content and the oxygen content both lower than 0.1ppm and filled with argon atmosphere for 4h to reduce the water absorbed by the pole piece in the transferring process, and then assembling the pole piece into a CR2032 type button cell in the glove box. The battery uses a pure metal lithium sheet with the diameter of 16mm and the thickness of 0.5mm as a negative electrode, and a porous polyethylene film with the diameter of 18mm and the model of Celgard2300 as a diaphragm.
After the battery is assembled and aged for 12 hours, the charging and discharging tests of different potentials are carried out. The results are shown in FIG. 2. As can be seen from fig. 2, the sample was activated at 4.3V, 3 cycles at 0.1C,and circulating for 100 circles at the magnification of 1C. The specific discharge capacity after 100 cycles is 94.6mA h g -1 The capacity retention rate was 86.9%.
Comparative example 1
Adding 0.1mol of MnO 2 Evenly mixing the mixture with 0.055mol of LiOH in a mortar, and then placing the mixture in a muffle furnace to calcine for 8 hours at 800 ℃ to obtain LiMn 2 O 4 。
LiMn as in example 1 2 O 4 A CR2032 type button cell was assembled as a positive electrode material active material.
After the battery assembly was aged for 12 hours, charge and discharge tests at different potentials were performed, and the results are shown in fig. 3. As can be seen in fig. 3, the sample was activated at 4.3V for 3 cycles at 0.1C and then cycled for 100 cycles at 1C rate. The specific discharge capacity after 100 cycles is 72.1mA h g -1 The capacity retention rate was 68.6%.
Example 2
(1) Adding 0.1mol of MnO 2 Dispersing in 100mL of aqueous solution, adding 2mmol of sodium molybdate and 2mmol of manganese chloride, heating at 100 ℃ for reaction for 2 hours, filtering, washing and drying to obtain manganese molybdate coated manganese dioxide crystals;
(2) Uniformly mixing the manganese molybdate-coated manganese dioxide crystal and 0.054mol of LiOH in a mortar, and calcining the mixture in a muffle furnace at 800 ℃ for 8 hours to obtain Li 2 MoO 4 @LiMn 1.99 Mo 0.01 O 4 。
In the manner of example 1 with Li 2 MoO 4 @LiMn 1.99 Mo 0.01 O 4 A CR2032 type button cell was assembled as a positive electrode material active material.
After the battery is assembled and aged for 12 hours, the charging and discharging tests of different potentials are carried out. The sample was activated at 4.3V for 3 cycles at 0.1C and then cycled at 1C rate for 100 cycles. The specific discharge capacity after 100 cycles is 87.6mA h g -1 The capacity retention rate was 80.4%.
Example 3
(1) Adding 0.1mol of MnO 2 Dispersing in 100mL of aqueous solution, adding 2mmol of sodium molybdate and 2mmol of manganese chloride, and heating at 90 ℃ for reactionAfter 4 hours, filtering, washing and drying to obtain manganese molybdate coated manganese dioxide crystals;
(2) Uniformly mixing the manganese molybdate-coated manganese dioxide crystal and 0.056mol of LiOH in a mortar, and calcining the mixture in a muffle furnace at 850 ℃ for 10 hours to obtain Li 2 MoO 4 @LiMn 1.99 Mo 0.01 O 4 。
In the manner of example 1 with Li 2 MoO 4 @LiMn 1.99 Mo 0.01 O 4 A CR2032 type button cell was assembled as a positive electrode material active material.
And after the battery is assembled and aged for 12 hours, carrying out charge and discharge tests of different potentials. The sample was activated at 4.3V for 3 cycles at 0.1C and then cycled at 1C rate for 100 cycles. The specific discharge capacity after 100 cycles is 92.5mA h g -1 The capacity retention rate was 85.1%.
Example 4
(1) Adding 0.1mol of MnO 2 Dispersing in 100mL of aqueous solution, adding 1mmol of sodium molybdate and 1mmol of manganese chloride, heating at 100 ℃ for reaction for 2 hours, filtering, washing and drying to obtain manganese molybdate coated manganese dioxide crystals;
(2) Uniformly mixing the manganese molybdate-coated manganese dioxide crystal and 0.055mol of LiOH in a mortar, and calcining in a muffle furnace at 800 ℃ for 8h to obtain Li 2 MoO 4 @LiMn 1.995 Mo 0.005 O 4 。
In the manner of example 1 with Li 2 MoO 4 @LiMn 1.995 Mo 0.005 O 4 A CR2032 type button cell was assembled as a positive electrode material active material.
After the battery is assembled and aged for 12 hours, the charging and discharging tests of different potentials are carried out. The sample was activated at 4.3V for 3 cycles at 0.1C and then cycled at 1C rate for 100 cycles. The specific discharge capacity after 100 cycles is 95.8mA h g -1 The capacity retention rate was 87.4%.
Example 5
(1) Adding 0.1mol of MnO 2 Dispersing in 100mL aqueous solution, adding 1mmol sodium molybdate and 1mmol manganese chloride, heating at 90 deg.C for 2 hr, reacting, and filteringFiltering, washing and drying to obtain manganese molybdate coated manganese dioxide crystals;
(2) Uniformly mixing the manganese molybdate-coated manganese dioxide crystal and 0.055mol of LiOH in a mortar, and calcining in a muffle furnace at 750 ℃ for 9h to obtain Li 2 MoO 4 @LiMn 1.995 Mo 0.005 O 4 。
In the manner of example 1 with Li 2 MoO 4 @LiMn 1.995 Mo 0.005 O 4 A CR2032 type button cell was assembled as a positive electrode material active material.
After the battery is assembled and aged for 12 hours, the charging and discharging tests of different potentials are carried out. The sample was activated at 4.3V for 3 cycles at 0.1C and then cycled at 1C rate for 100 cycles. The specific discharge capacity after 100 cycles is 88.9mA h g -1 The capacity retention rate was 81.3%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.
Claims (10)
1. A lithium molybdate coated modified lithium manganate material comprises molybdenum-doped lithium manganate and lithium molybdate coated on the surface of the molybdenum-doped lithium manganate;
the chemical composition of the molybdenum-doped lithium manganate is as follows: liMn 2-x Mo x O 4 ，0＜x≤0.02。
2. The lithium molybdate coated modified lithium manganate material as claimed in claim 1, wherein the molar ratio of lithium molybdate to molybdenum doped lithium manganate is 0.01-0.02.
3. The lithium molybdate coated modified lithium manganate material according to claim 1 or 2, wherein said lithium manganate is spinel lithium manganate.
4. The lithium molybdate-coated modified lithium manganate material according to claim 1 or 2, wherein the medium particle size of the lithium molybdate-coated modified lithium manganate material is 5 to 30 μm.
5. The method for preparing the lithium molybdate-coated modified lithium manganate material of any one of claims 1 to 4, comprising the following steps:
mixing manganese dioxide, soluble molybdate and soluble manganous salt with water, and carrying out coprecipitation reaction to obtain manganese molybdate coated manganese dioxide;
and mixing the manganese molybdate coated manganese dioxide with a lithium source, and calcining in an oxygen-containing atmosphere to obtain the lithium molybdate coated modified lithium manganate material.
6. The method according to claim 5, wherein the molar ratio of the manganese dioxide, the soluble molybdate and the soluble manganous salt is (50-100): 1- (1-1.2).
7. The preparation method according to claim 5 or 6, wherein the temperature of the coprecipitation reaction is 80-100 ℃ and the time is 2-8 h.
8. The method according to claim 5, wherein the molar ratio of the lithium source to manganese dioxide is (1.08-1.12): 2.
9. The preparation method according to claim 5 or 8, characterized in that the calcination temperature is 700-1000 ℃ and the holding time is 4-20 h.
10. The use of the lithium molybdate-coated modified lithium manganate material according to any one of claims 1 to 4 or the lithium molybdate-coated modified lithium manganate material prepared by the preparation method according to any one of claims 5 to 9 as a positive electrode active material of a lithium ion battery.
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