CN113104895A - Preparation method of manganous oxide/carbon composite material, negative electrode and lithium ion battery - Google Patents

Preparation method of manganous oxide/carbon composite material, negative electrode and lithium ion battery Download PDF

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CN113104895A
CN113104895A CN202010032356.9A CN202010032356A CN113104895A CN 113104895 A CN113104895 A CN 113104895A CN 202010032356 A CN202010032356 A CN 202010032356A CN 113104895 A CN113104895 A CN 113104895A
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negative electrode
manganous oxide
carbon composite
composite material
layer
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洪晔
董海勇
胡倩倩
长世勇
吴春宇
胡志鹏
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Guangzhou Automobile Group Co Ltd
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Guangzhou Automobile Group Co Ltd
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Abstract

The invention provides a preparation method of a manganous oxide/carbon composite material, the manganous oxide/carbon composite material, a negative electrode and a lithium ion battery. The preparation method of the manganous oxide/carbon composite material comprises the following steps: obtaining manganese carbonate microspheres; mixing the manganese carbonate microspheres and polyacrylonitrile to prepare slurry; forming a negative electrode active precursor layer on the surface of a negative electrode current collector by using the slurry; the negative electrode active precursor layer is carbonized in an oxygen-free environment, and the manganous oxide/carbon composite material has the advantages of high compaction density, stable structure and the like. The active material contained in the negative electrode active layer of the negative electrode is the manganous oxide/carbon composite material of the invention. The negative electrode is applied to the lithium ion battery and can provide higher specific capacity and excellent cycle performance.

Description

Preparation method of manganous oxide/carbon composite material, negative electrode and lithium ion battery
Technical Field
The invention belongs to the technical field of chemical power supplies, and particularly relates to a preparation method of a manganous oxide/carbon composite material, the manganous oxide/carbon composite material, a negative electrode and a lithium ion battery.
Background
With the wide application of lithium ion batteries in the industries of portable electronic products, new energy vehicles, electric power storage devices and the like, high specific energy, high power, low cost, long service life and high safety have become targets for future development of lithium ion batteries. The negative electrode of the lithium ion battery is an important component of the battery, and the structure and the performance of the negative electrode directly influence the capacity and the cycle performance of the battery. At present, most of commercial lithium ion batteries adopt graphite materials as negative electrodes, the theoretical specific capacity is only 372mAh/g, and the development requirements of the lithium ion batteries are difficult to meet. The theoretical specific capacity of manganous oxide (MnO) is up to 756mAh/g, and the manganous oxide is wide in source, low in price, environment-friendly and good in safety, and is a potential negative electrode material of a lithium ion battery. However, the conductivity of manganous oxide is poor, volume expansion is easy to occur in the charging and discharging process, electrodes are pulverized and fall off, and the gram capacity of the battery is low and the cycle stability is poor.
In order to improve the electrochemical performance of the manganous oxide material, the composite structure design of the manganous oxide material by using a carbon material is reported at present. In practical application, the volume expansion phenomenon can be relieved to a certain extent through the nanocrystallization of the active material, and the specific capacity of the battery is improved, but the nano material usually has the defect of large specific surface area, so that the electrode compaction density is low, and the exertion of the whole energy density of the battery is limited.
The existing graphite/manganous oxide composite material with a core-shell structure has the advantages that the spherical core is manganous oxide with the particle size of less than 100nm, the spherical shell is a graphite carbon layer with the thickness of less than 10nm, the electrochemical performance is improved through the nanocrystallization of the manganous oxide, and the electrical conductivity of the composite material is improved through the graphite carbon layer. Although the electrochemical performance of the composite negative electrode is improved to a certain extent by the manganous oxide composite electrode material, the ball core of the existing scheme is solid manganous oxide nano-particles, and the nano-material has the defect of large specific surface area, so that the electrode compaction density is low, and the problem of large volume change exists in the battery circulation process.
According to the existing three-dimensional manganous oxide/porous carbon material, manganous oxide particles are loaded in a porous carbon skeleton, the size of manganous oxide microspheres reaches 800nm, the primary particle size is about 50nm, and the thickness of a surface carbon layer is 4-7 nm. The structure is helpful for relieving the volume change of the manganous oxide in the circulating process, but the primary particle size of the manganous oxide microsphere is relatively large, and the volume expansion of the manganous oxide in the circulating process is still large. From the application of electrode materials, the existing manganous oxide composite material needs to be mixed with a certain amount of adhesive to form slurry subsequently, and the slurry is coated on a copper foil to form a negative electrode plate, so that the process is complicated, and the introduced non-conductive adhesive (such as polyvinylidene fluoride (PVDF) and the like) is not beneficial to improving the overall conductivity of the electrode.
In addition, in the prior art related to the present application, a method of mixing an active material and polyacrylonitrile to prepare a slurry, coating the slurry on a copper current collector, drying and performing heat treatment has been found to improve the specific capacity of the material. However, the coating layer formed by carbonizing polyacrylonitrile is relatively dense, and the volume expansion of the active material is increased along with the increase of the number of cycles, so that the coating layer on the surface is broken, and the cycle performance of the material is deteriorated. Therefore, if polyacrylonitrile and a manganous oxide material are directly mixed to prepare slurry, and the slurry is coated on a copper foil and subjected to heat treatment, the problem of volume expansion of manganous oxide in the circulation process is difficult to effectively solve, and a more ingenious structural design is required.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a manganous oxide/carbon composite material to solve the technical problems that the existing manganous oxide material has low electrode compaction density or has large volume expansion in the charging and discharging process.
The invention also aims to provide a negative electrode, a preparation method and application thereof, so as to solve the technical problems of low gram capacity and poor cycle stability of the conventional manganous oxide negative electrode when the conventional manganous oxide negative electrode is used for a lithium ion battery.
In order to achieve the object of the present invention, the present invention provides a method for preparing a manganous oxide/carbon composite material, comprising the steps of:
obtaining manganese carbonate microspheres;
mixing the manganese carbonate microspheres and polyacrylonitrile to prepare slurry;
forming a negative electrode active precursor layer on the surface of a negative electrode current collector by using the slurry;
and carbonizing the negative electrode active precursor layer in an oxygen-free environment.
In yet another aspect of the present invention, a manganous oxide/carbon composite is provided. The manganous oxide/carbon composite material comprises:
the core body is a microsphere consisting of a plurality of manganous oxide particles, the microsphere is of a porous structure, the particle size of the manganous oxide particles is in a nanometer level, and the diameter of the microsphere is in a micrometer level;
the shell layer coats the core body and is a nitrogen-doped carbon material thin layer.
In another aspect of the present invention, a negative electrode is provided. The negative electrode comprises a negative electrode current collector and a negative electrode active layer formed on the surface of the current collector, wherein the active material of the negative electrode active layer is prepared by adopting the preparation method of the manganous oxide/carbon composite material, or the active material of the negative electrode active layer is the manganous oxide/carbon composite material.
In yet another aspect of the invention, a lithium ion battery is provided that includes a negative electrode, such as the negative electrode of the invention.
Different from the prior art, the negative electrode preparation method comprises the steps of firstly preparing manganese carbonate microspheres, directly forming slurry by the manganese carbonate microspheres and polyacrylonitrile, enabling the polyacrylonitrile to wrap the manganese carbonate microspheres and forming a negative electrode active precursor layer, directly decomposing the manganese carbonate microspheres in the negative electrode active precursor layer into a porous structure core body in the carbonization process, and carbonizing the polyacrylonitrile coated on the surfaces of the manganese carbonate microspheres to form a nitrogen-doped carbon coated shell layer, thereby forming the manganous oxide/carbon composite material. Therefore, the preparation method of the negative electrode can ensure the formation of a porous structure in the core body and has a buffering effect on the volume change of the microsphere core body in the charging and discharging processes.
The manganous oxide/carbon composite material directly forms a negative electrode active layer on the surface of the negative electrode current collector, so that the negative electrode has excellent electrochemical performance, additional addition of a binder can be avoided, the preparation process is simplified, and the production efficiency is improved.
Compared with the prior art, the manganous oxide/carbon composite material forms the porous microsphere core body by using a plurality of nano-scale manganous oxide particles, the compaction density of the manganous oxide/carbon composite material is greatly improved, and meanwhile, the porous structure of the core body can provide a buffer space for the volume change of manganous oxide in the charge and discharge process, so that the volume change of the microsphere core body in the charge and discharge process is reduced as much as possible; a shell layer coated by nitrogen-doped carbon is formed on the surface of a manganous oxide microsphere core body and is used as an electron transmission channel between manganous oxide and a copper current collector, so that the conductivity of the manganous oxide/carbon composite material is obviously improved under the condition of not additionally adding a conductive agent; the gaps formed between the shell layer and the core body and the porous structure in the core body effectively relieve the volume change of the microsphere core body in the charging and discharging process, and ensure the structural stability and the electrochemical stability of the manganous oxide/carbon composite material.
The negative electrode of the invention is characterized in that a negative electrode active layer formed by the manganous oxide/carbon composite material of the invention is combined on the surface of a negative electrode current collector. Therefore, the negative electrode of the present invention has electrochemical properties of the manganous oxide/carbon composite material of the present invention, so that the negative electrode of the present invention has excellent conductivity and structural stability, thereby having high specific capacity and excellent cycle performance.
Because the lithium ion battery of the invention contains the negative electrode of the invention, the lithium ion battery of the invention has the characteristics of high specific capacity and excellent cycle performance.
Drawings
FIG. 1 is a schematic structural diagram of an exemplary manganous oxide/carbon composite of the present invention;
FIG. 2 is a schematic diagram of the structure of an example negative electrode of the present invention;
FIG. 3 is a schematic process flow diagram of an example negative electrode fabrication method of the present invention;
fig. 4 is an XRD pattern of a manganous oxide/carbon composite negative electrode prepared in accordance with example one of the present invention;
fig. 5 is an SEM photograph of a manganous oxide/carbon composite negative electrode prepared in the first example of the present invention;
fig. 6 is a TEM photograph of a manganous oxide/carbon composite anode prepared in the first example of the present invention;
FIG. 7 is a graph showing cycle characteristics at a current density of 0.1A/g of composite negative electrodes prepared in example one of the present invention and comparative examples one to two;
fig. 8 is a graph of the cycle performance of the manganous oxide/carbon composite anode prepared in the first embodiment of the invention under different current densities.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a preparation method of a manganous oxide/carbon composite material. The preparation method of the manganous oxide/carbon composite material has the process flow as shown in figure 3, and comprises the following steps:
step S01: obtaining manganese carbonate microspheres;
step S02: mixing the manganese carbonate microspheres and polyacrylonitrile to prepare slurry;
step S03: forming a negative electrode active precursor layer on the surface of a negative electrode current collector by using the slurry;
step S04: and carbonizing the negative electrode active precursor layer in an oxygen-free environment.
Among these, the manganese carbonate microspheres in S01 are to be understood as manganese carbonate particles, which are precursors of the nucleus body 11 of the manganous oxide/carbon composite 1 described above. In one embodiment, the particle size of the manganese carbonate microspheres is 0.2-10 μm, preferably 0.5-5 μm. After the carbonization treatment in step S04, the particles are decomposed into a plurality of manganous oxide particles 111, and the plurality of manganous oxide particles 111 are stacked to form a manganous oxide microsphere core body 11.
In one embodiment, the method for obtaining the manganese carbonate microspheres in step S01 includes the following steps:
under the condition of stirring, the carbonate solution is dripped into the manganese salt solution for precipitation reaction, and then solid-liquid separation treatment, washing treatment and drying treatment are carried out.
In a specific embodiment, the carbonate solution is a solution prepared by dissolving 0.1mol of carbonate in 100-800 mL of deionized water. The carbonate includes, but is not limited to, water-soluble carbonates such as sodium bicarbonate, sodium carbonate, ammonium bicarbonate, ammonium carbonate, potassium carbonate, etc., and preferably ammonium bicarbonate.
The manganese salt solution is formed by dissolving 0.01mol of manganese salt in 100-800 mL of a mixed solution of absolute ethyl alcohol and deionized water. The manganese salt includes, but is not limited to, water-soluble manganese salts such as manganese chloride, manganese sulfate, manganese nitrate, and the like, and preferably manganese sulfate.
And in the precipitation reaction process, dropwise adding the carbonate solution into the manganese salt solution at a dropwise adding rate of 1-50 mL/min, and stirring in the dropwise adding process. By controlling the preparation process method and process conditions of the manganese carbonate microsphere, the manganese carbonate microsphere with proper particle size, namely a precursor of a manganous oxide microsphere nucleus body 11, is obtained. The precipitation reaction should be sufficient, for example, the carbonate solution is completely added dropwise and then the reaction is continued for 0.5 to 6 hours at room temperature. The solid-liquid separation treatment after the precipitation reaction can be, but not only, suction filtration, and the washing treatment can be, but not only, washing by using deionized water and absolute ethyl alcohol.
In the step S02, the polyacrylonitrile serves not only as a carbon source compound, but also as a nitrogen source compound, that is, as an organic carbon source of nitrogen-doped carbon, and also serves as a binder, thereby effectively avoiding influence on the conductivity of the active layer due to additional addition of the binder. In one embodiment, the mass ratio of the manganese carbonate microspheres to the polyacrylonitrile is 95: 5-60: 40, preferably 90:10 to 70: 30. In the slurry, the polyacrylonitrile coats the manganese carbonate microspheres. Of course, the two should be well mixed. In another embodiment, the solvent of the slurry may be a dimethylformamide solvent, but may of course be another solvent capable of dissolving the polyacrylonitrile. The concentration of the slurry may be that of a conventional electrode active layer slurry, such as a slurry concentration that is advantageous for cast film formation.
In S03, the slurry may be cast on the surface of the negative electrode current collector to form a negative electrode active precursor layer, such as by doctor blade casting. Because the slurry contains polyacrylonitrile, the polyacrylonitrile simultaneously serves as a binder, and good adhesion among manganese carbonate particles and between manganese carbonate and a negative electrode current collector is realized. After the negative electrode active precursor layer is formed, before the step S04, the negative electrode active precursor layer is dried, for example, but not limited to, dried at 60 to 100 ℃.
Before S04 is performed, the electrode sheet including the negative electrode active precursor layer may be cut.
In S04, during the carbonization of the negative electrode active precursor layer in an oxygen-free environment, manganese carbonate in the negative electrode active precursor layer is decomposed during the heat treatment to generate manganous oxide and carbon dioxide gas, and the carbon dioxide gas is removed to leave pores between manganous oxide particles, thereby forming the porous structure core body 11 shown in fig. 1. Meanwhile, the polyacrylonitrile is pyrolyzed to generate nitrogen-doped carbon, and the nitrogen-doped carbon is coated on the surface of the manganous oxide microsphere 11 shown in fig. 1 to form a shell layer 12.
In one embodiment, the temperature of the carbonization treatment is 350 to 650 ℃, preferably 400 to 500 ℃. In the temperature range, manganese carbonate is decomposed to generate manganous oxide, and the primary particle size of the manganous oxide is small, so that the volume expansion generated in the circulation process is relieved. Below this temperature range, the manganese carbonate is not completely decomposed, above this temperature, the sample mass changes greatly before and after heat treatment, resulting in a loose structure of the manganous oxide/carbon composite material, i.e. a loose structure of the negative electrode active layer, the active substance is easy to fall off from the negative electrode current collector, at the same time, the size of the manganous oxide grain is greatly increased, the volume expansion during the cycle is large, and the electrochemical performance is rather reduced. In addition, the carbonization treatment is carried out for a time at least sufficient to completely decompose manganese carbonate and completely carbonize polyacrylonitrile. The preferable carbonization time is 0.5 to 5 hours. In another embodiment, the temperature of the carbonization treatment is increased to the carbonization treatment temperature at a rate of 2 to 10 ℃/min.
In addition, the oxygen-free environment is preferably an inert gas protected environment. So as to ensure the carbonization and cracking of the polyacrylonitrile.
Therefore, the preparation method of the manganous oxide/carbon composite material can ensure that the active layer of the manganous oxide/carbon composite material is directly formed on the surface of the negative electrode current collector, endows the negative electrode with excellent electrochemical performance, can effectively avoid additional addition of a binder, simplifies the preparation process and improves the production efficiency.
The embodiment of the invention also provides a manganous oxide/carbon composite material. The microstructure of the manganous oxide/carbon composite material is a core-shell structure shown in figure 1. The manganous oxide/carbon composite material 1 comprises a core body 11 and a shell layer 12 coated outside the core body 11.
The core body 11 is a microsphere formed by a plurality of manganous oxide particles 111, the microsphere is of a porous structure, namely, a plurality of pores 112 are formed, and the particle size of the manganous oxide particles 111 is in a nanometer scale, specifically 5-35 nm, preferably 10-20 nm. The diameter of the microsphere, namely the core body 11, is micron-sized, specifically 0.2-10 μm, and preferably 0.5-5 μm. The structure can effectively relieve the volume change of the manganous oxide nucleus body 11 in the charging and discharging process.
The shell layer 12 is a nitrogen-doped carbon thin layer, and the thickness of the shell layer is 1-15 nm, preferably 3-8 nm. The nitrogen-doped carbon thin layer has excellent conductivity, and can form a protective layer on the surface of the manganous oxide microsphere to inhibit side reaction between the manganous oxide microsphere and electrolyte.
Because the shell layer 12 covers the core body 11, a volume of void 13 may also exist between the shell layer 12 and the core body 11. The voids 13 are naturally formed during the preparation of the manganous oxide/carbon composite material 1, and can effectively buffer the volume change of the core body 11 during the charge and discharge processes.
The components act synergistically to endow the manganous oxide/carbon composite material 1 with higher compaction density, excellent conductivity, structural stability and cycle performance.
The manganous oxide/carbon composite material can be prepared according to the preparation method of the manganous oxide/carbon composite material.
On the basis of the manganous oxide/carbon composite material 1, the embodiment of the invention also provides a negative electrode. The structure of the negative electrode is shown in fig. 2, and the negative electrode comprises a negative electrode current collector 01 and a negative electrode active layer 02 formed on the surface of the current collector 01.
The negative electrode current collector 01 may be a conventional negative electrode current collector, such as a copper foil, but not exclusively. And the thickness of the negative electrode current collector 01 may be, but not limited to, 8 to 20 μm.
The active material of the negative electrode active layer 02 is the manganous oxide/carbon composite material described above. The thickness thereof may be a conventional adjustable thickness of the negative electrode active layer.
Since the negative electrode is a negative electrode active layer 02 formed by bonding the above-described manganous oxide/carbon composite material 1 on the surface of a negative electrode current collector 01. Therefore, the negative electrode has the electrochemical properties of the manganous oxide/carbon composite material 1 described above, so that the negative electrode has excellent conductivity and structural stability, thereby having high specific capacity and excellent cycle performance.
Meanwhile, the embodiment of the invention also provides a lithium ion battery. The lithium ion battery naturally includes necessary components, such as a cell formed of a positive electrode, a negative electrode, and a separator. Wherein the negative electrode is the negative electrode described above. The other components may be conventional components contained in conventional lithium ion batteries. Thus, since the negative electrode of the lithium ion battery is a negative electrode comprising the above-described manganous oxide/carbon composite, the lithium ion battery has a high specific capacity and excellent cycle performance.
The manganese oxide/carbon composite material, the preparation method and the application thereof according to the embodiment of the present invention are illustrated by a plurality of specific examples.
Example one
The first embodiment provides a negative electrode containing a manganous oxide/carbon composite material and a preparation method thereof. The structure of the negative electrode is shown in fig. 2, and comprises a copper foil 01 and an active layer 02 formed by a manganous oxide/carbon composite uniformly distributed on the copper foil, wherein the thickness of the copper foil is 16 mu m, and the structure of the manganous oxide/carbon composite is shown in fig. 1 and comprises a manganous oxide microsphere core body 11 and a nitrogen-doped carbon coating layer 12. The size of the manganous oxide microspheres is 0.8-1.5 mu m, the particle size of small particles 111 forming the microspheres is about 12nm, and certain pores 112 exist among the particles. The thickness of the nitrogen-doped carbon thin layer uniformly wrapped on the surface of the manganous oxide microsphere is about 4nm, and the carbon layer realizes good electric contact between the manganous oxide microsphere and the copper foil.
The negative electrode is prepared according to a method comprising the steps of:
s11, preparing manganese carbonate microspheres:
dissolving 0.01mol of manganese sulfate in a mixed solution of 150mL of anhydrous ethanol and 150mL of deionized water; meanwhile, 0.1mol of ammonium bicarbonate is dissolved in 150mL of deionized water; dropwise adding the ammonium bicarbonate solution into the manganese sulfate solution under vigorous stirring, wherein the dropwise adding speed is 6mL/min, and continuously reacting for 3 hours at room temperature after all the ammonium bicarbonate solution is added; and after the reaction is finished, carrying out suction filtration on the solution, washing the solution by using deionized water and absolute ethyl alcohol, and drying the solution to obtain the manganese carbonate microspheres.
S12, preparing slurry of manganese carbonate microspheres and polyacrylonitrile:
weighing the manganese carbonate microspheres prepared by S11 and commercial polyacrylonitrile powder according to the mass ratio of 9:1, adding the manganese carbonate microspheres and the commercial polyacrylonitrile powder into a dimethylformamide solvent, and stirring to prepare slurry with good fluidity;
s13, forming a manganese carbonate/polyacrylonitrile composite negative electrode:
and carrying out doctor-blade casting on the copper foil to form a uniform thin layer, and drying at 80 ℃ to obtain the manganese carbonate/polyacrylonitrile composite negative electrode.
S14, carbonizing the manganese carbonate/polyacrylonitrile composite negative electrode:
cutting the prepared manganese carbonate/polyacrylonitrile composite negative electrode into small disks with the diameter of 12mm, putting the small disks into a tubular furnace, heating the small disks to 400 ℃ at the speed of 5 ℃/min under the nitrogen atmosphere, and carbonizing the small disks at constant temperature for 3 hours to obtain the manganous oxide/carbon composite negative electrode.
Various test methods were used to characterize the phase and morphology of the manganous oxide/carbon composite negative electrode, with the results shown in fig. 4-6. The XRD pattern (fig. 4) shows that the composite negative electrode contains XRD peaks of copper foil (Cu) and manganous oxide (MnO), where the manganous oxide diffraction peak is broad, indicating that the MnO grain size is small. As can be seen from the SEM image (FIG. 5), the size of the manganous oxide microspheres is about 0.8-1.5 μm. From the TEM image (FIG. 6), it can be seen that the manganous oxide microspheres are formed by stacking a plurality of small particles, the particle size of the small particles is about 12nm, and a carbon-coated thin layer with the thickness of about 4nm can be observed on the outer layer of the microspheres. It was further confirmed by XPS characterization that nitrogen introduced by decomposition of polyacrylonitrile exists in the composite negative electrode and the valence of the manganese element is + 2. The characterization results show that the manganous oxide microsphere with the micro-nano structure is synthesized by the preparation method, and the nitrogen-doped carbon coating layer with high conductivity is distributed on the surface layer of the manganous oxide microsphere.
Example one the prepared manganous oxide/carbon composite negative electrode shows excellent electrochemical performance when applied to a lithium ion battery. The first and second discharge specific capacities of the composite negative electrode under the current density of 0.1A/g are 1467mAh/g and 1039mAh/g respectively, and the specific capacity is stabilized at 943mAh/g after 40 times of circulation (figure 7). Fig. 8 is a graph of cycling performance of a composite negative electrode at different current densities. As can be seen from fig. 8, the composite negative electrode can provide higher specific capacity when cycled under different current densities, and can be stably tested after high-current charge and discharge, and shows excellent cycling stability.
Example two
This example provides a negative electrode for a lithium ion battery having substantially the same structure as in the first example, except that the particle size of the small particles constituting the manganous oxide microspheres is about 16 nm.
The preparation method is different from the first embodiment in that the heat treatment temperature of the manganese carbonate/polyacrylonitrile composite negative electrode is 500 ℃, and other process steps are the same as the first embodiment.
EXAMPLE III
This example provides a negative electrode for a lithium ion battery having substantially the same structure as in the first example, except that the particle size of the small particles constituting the manganous oxide microspheres is about 35 nm.
The preparation method is different from the first embodiment in that the heat treatment temperature of the manganese carbonate/polyacrylonitrile composite negative electrode is 600 ℃, and other process steps are the same as the first embodiment. This indicates that when the heat treatment temperature is increased to 600 c, the particle size of the small particles constituting the manganous oxide microspheres is significantly increased.
Example four
The embodiment provides a negative electrode of a lithium ion battery, which has a structure basically the same as that of the first embodiment, and is different from the first embodiment in that the size of manganous oxide microspheres is 2-5 mu m.
The preparation method is different from the first embodiment in that the synthesis conditions of the manganese carbonate microspheres are different, and other process steps are the same as those in the first embodiment. The size of the manganous oxide microspheres can be adjusted and controlled by changing the synthesis conditions of the manganese carbonate.
The synthesis process of the manganese carbonate microspheres comprises the following steps:
dissolving 0.01mol of manganese sulfate in a mixed solution of 60mL of absolute ethyl alcohol and 600mL of deionized water; meanwhile, 0.1mol of ammonium bicarbonate is dissolved in 600mL of deionized water; dropwise adding the ammonium bicarbonate solution into the manganese sulfate solution under vigorous stirring, wherein the dropwise adding speed is 30mL/min, and continuously reacting for 2 hours at room temperature after all the ammonium bicarbonate solution is added; and after the reaction is finished, carrying out suction filtration on the solution, washing the solution by using deionized water and absolute ethyl alcohol, and drying the solution to obtain the manganese carbonate microspheres.
EXAMPLE five
This example provides a negative electrode for a lithium ion battery, which has substantially the same structure as in example 4, except that the nitrogen-doped carbon thin layer uniformly coated on the surface of the manganous oxide microspheres has a thickness of about 8 nm.
The preparation method is different from the fourth embodiment in that the mass ratio of the manganese carbonate used for preparing the pole piece to the commercialized polyacrylonitrile powder is 8:2, and other process steps are the same as those in the fourth embodiment. The thickness of the nitrogen-doped carbon thin layer can be regulated and controlled by changing the dosage of the polyacrylonitrile powder.
The composite negative electrodes prepared in the second to fifth examples listed above were assembled into button cells using the same process conditions as in the first example and the cells were tested for cycling performance at a current density of 0.1A/g, with the results shown in table 1. As can be seen from table 1, both the manganous oxide/carbon composite negative electrode prepared by the present invention can realize high specific capacity and good cycling stability. Meanwhile, in order to illustrate the advantages of the composite electrode structure design of the present invention, the inventors also conducted the following comparative tests:
comparative example 1
The structural difference between this comparative example and first example is that the final electrode consists of a copper foil and a manganese carbonate/carbon composite uniformly distributed on the copper foil.
The difference in the preparation method is that the heat treatment temperature of the manganese carbonate/polyacrylonitrile composite negative electrode is 300 ℃, and other process steps are the same as those in the first embodiment.
The XRD pattern shows that the composite negative electrode obtained by the comparative example contains copper foil and manganese carbonate (MnCO)3) The diffraction peak of (2) indicates that manganese carbonate is not decomposed to form manganous oxide at a heat treatment temperature of 300 ℃. However, it is difficult for manganese carbonate itself to exhibit a high gram capacity as a battery active material. The cycle performance of the composite negative electrode at 0.1A/g is shown in FIG. 7. As can be seen from the figure, the initial specific discharge capacity of the composite negative electrode is 1003mAh/g, but the capacity value rapidly decays along with the increase of the cycle number.
Comparative example No. two
The present comparative example is structurally different from example one in that the final electrode is composed of a copper foil and a manganous oxide/polyacrylonitrile composite. Wherein, the surface of the manganous oxide microsphere is distributed with a polyacrylonitrile coating layer which is not carbonized.
The preparation method is different from the first embodiment in that after the manganese carbonate microspheres are synthesized, the powder is put into a tubular furnace, the temperature is raised to 400 ℃ at the speed of 5 DEG/min under the nitrogen atmosphere, and the constant-temperature carbonization time is 3 hours, so that the manganous oxide powder is obtained. Weighing the prepared manganous oxide powder and commercial polyacrylonitrile powder according to the mass ratio of 9:1, adding the manganous oxide powder and the commercial polyacrylonitrile powder into a dimethylformamide solvent, stirring to prepare slurry with good fluidity, performing doctor blade casting on a copper foil to form a uniform thin layer, and drying at 80 ℃ to obtain the manganous oxide/polyacrylonitrile composite negative electrode. The other process steps are the same as in the first embodiment. The cycle performance of the composite negative electrode at 0.1A/g is shown in FIG. 7. As can be seen from fig. 7, the initial specific discharge capacity of the composite negative electrode is high, but the specific discharge capacity is attenuated remarkably as the cycle number increases. The reason is that polyacrylonitrile is not carbonized, a nitrogen-doped carbon coating layer with high conductivity cannot be formed on the surface of the manganous oxide microsphere, the overall conductivity of the electrode is poor, the reversibility of the manganous oxide is reduced along with the increase of the cycle number, the activity is failed, and the specific capacity is rapidly attenuated.
TABLE 1 cyclability of composite negative electrodes prepared in examples one-five and comparative examples one-two at a current density of 0.1A/g
Figure BDA0002364770370000121
Figure BDA0002364770370000131
Table 1 lists the performance data for inventive examples one-five and comparative examples one-two. As can be seen from the table, the manganous oxide/carbon composite negative electrode prepared according to the present invention can realize higher specific capacity and more excellent cycle performance, which is inseparable from its unique composite structure, compared to the above comparative example. The manganous oxide micro-nano structure improves the overall higher compacted density of the electrode, meanwhile, the small-size manganous oxide nano particles formed inside the manganous oxide micro-nano structure have higher electrochemical activity, and the pores among the particles are favorable for relieving the volume expansion of the material in the charging and discharging process, so that the cycle performance of the composite negative electrode is improved. The nitrogen-doped carbon coating thin layer on the surface of the manganous oxide microsphere is beneficial to inhibiting the side reaction between the manganous oxide and the electrolyte, improving the overall conductivity of the electrode and contributing to the improvement of the capacity of the composite negative electrode greatly.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (10)

1. A preparation method of a manganous oxide/carbon composite material comprises the following steps:
obtaining manganese carbonate microspheres;
mixing the manganese carbonate microspheres and polyacrylonitrile to prepare slurry;
forming a negative electrode active precursor layer on the surface of a negative electrode current collector by using the slurry;
and carbonizing the negative electrode active precursor layer in an oxygen-free environment.
2. The method of claim 1, wherein: the mass ratio of the manganese carbonate microspheres to the polyacrylonitrile is 95: 5-60: 40; and/or
The oxygen-free environment is an environment protected by inert gas.
3. The method of claim 1, wherein: the temperature of the carbonization treatment is 350-650 ℃, and the time of the carbonization treatment is 0.5-5 hours; and/or
The carbonization treatment is carried out by raising the temperature to the carbonization treatment temperature at the speed of 2-10 ℃/min.
4. The production method according to any one of claims 1 to 3, wherein the method for obtaining the manganese carbonate microspheres comprises the steps of:
under the condition of stirring, the carbonate solution is dripped into the manganese salt solution for precipitation reaction, and then solid-liquid separation treatment, washing treatment and drying treatment are carried out.
5. The method of claim 4, wherein: the carbonate solution is formed by dissolving 0.1mol of carbonate in 100-800 mL of deionized water, the manganese salt solution is formed by dissolving 0.01mol of manganese salt in 100-800 mL of a mixed solution of absolute ethyl alcohol and deionized water, and the dropping rate is 1-50 mL/min.
6. A manganous oxide/carbon composite comprising:
the core body is a microsphere consisting of a plurality of manganous oxide particles, the microsphere is of a porous structure, the particle size of the manganous oxide particles is in a nanometer level, and the diameter of the microsphere is in a micrometer level;
the shell layer coats the core body and is a nitrogen-doped carbon thin layer.
7. The manganous oxide/carbon composite of claim 6, wherein: the particle size of the manganous oxide particles is 5-35 nm; and/or
The diameter of the microsphere is 0.2-10 μm.
8. The manganous oxide/carbon composite according to claim 6 or 7, wherein: the thickness of the shell layer is 1-15 nm.
9. A negative electrode comprising a negative electrode current collector and a negative electrode active layer formed on a surface of the current collector, characterized in that: the active material of the negative electrode active layer is prepared by the method for preparing a manganous oxide/carbon composite material according to any one of claims 1 to 5, or the active material of the negative electrode active layer is the manganous oxide/carbon composite material according to any one of claims 6 to 8.
10. A lithium ion battery comprising a negative electrode, characterized in that: the negative electrode is the negative electrode of claim 9.
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002050401A (en) * 2000-08-01 2002-02-15 Nissan Motor Co Ltd Nonaqueous electrolyte lithium ion secondary cell
CN1897336A (en) * 2005-05-27 2007-01-17 索尼株式会社 Cathode active material, method of manufacturing it, cathode, and battery
CN103779535A (en) * 2012-10-18 2014-05-07 三星精密化学股份有限公司 Lithium metal oxide composite, method for preparing the same, and lithium secondary battery including the same
CN104485456A (en) * 2014-11-20 2015-04-01 刘剑洪 Method for preparing carbon-coated manganous oxide and carbon-coated manganous oxide
CN105958027A (en) * 2016-06-22 2016-09-21 贵州玉屏迈威科技有限公司 Manganese-based composite positive electrode material and preparation method therefor
CN108808024A (en) * 2018-06-19 2018-11-13 合肥工业大学 A kind of preparation method and applications of MnO/C anode electrocatalysts
CN109148859A (en) * 2018-08-29 2019-01-04 中南大学 A kind of preparation method of double carbon-coating coated manganese oxide composite materials
CN110556517A (en) * 2018-06-01 2019-12-10 广州汽车集团股份有限公司 Negative electrode material, negative electrode and preparation method of negative electrode

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002050401A (en) * 2000-08-01 2002-02-15 Nissan Motor Co Ltd Nonaqueous electrolyte lithium ion secondary cell
CN1897336A (en) * 2005-05-27 2007-01-17 索尼株式会社 Cathode active material, method of manufacturing it, cathode, and battery
CN103779535A (en) * 2012-10-18 2014-05-07 三星精密化学股份有限公司 Lithium metal oxide composite, method for preparing the same, and lithium secondary battery including the same
CN104485456A (en) * 2014-11-20 2015-04-01 刘剑洪 Method for preparing carbon-coated manganous oxide and carbon-coated manganous oxide
CN105958027A (en) * 2016-06-22 2016-09-21 贵州玉屏迈威科技有限公司 Manganese-based composite positive electrode material and preparation method therefor
CN110556517A (en) * 2018-06-01 2019-12-10 广州汽车集团股份有限公司 Negative electrode material, negative electrode and preparation method of negative electrode
CN108808024A (en) * 2018-06-19 2018-11-13 合肥工业大学 A kind of preparation method and applications of MnO/C anode electrocatalysts
CN109148859A (en) * 2018-08-29 2019-01-04 中南大学 A kind of preparation method of double carbon-coating coated manganese oxide composite materials

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