CN107425181B - Preparation method of manganese oxide/starch-based hard carbon composite negative electrode material - Google Patents
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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Abstract
The invention relates to the technical field of lithium ion battery materials, in particular to a preparation method of a manganese oxide/starch-based hard carbon composite negative electrode material, which is characterized by comprising the following preparation steps: (1) pre-carbonizing to obtain black pre-carbonized powder product; (2) preparing a starch-based hard carbon material (3) and mixing; (4) carrying out hydrothermal reaction; (5) and obtaining a finished product. Compared with the prior art, the manganese oxide protective layer with an amorphous structure is formed on the surface of the starch-based hard carbon by a hydrothermal method, so that lithium ions consumed by an SEI (solid electrolyte interface) film formed by the surface of an electrode and an electrolyte are reduced, and the first coulombic efficiency of the negative electrode material is improved; the prepared manganese oxide/starch-based hard carbon for the lithium ion battery cathode material has the characteristics of good electrochemical performance, good cycling stability and excellent consistency of batch products; and the preparation method is simple, the production is environment-friendly, the large-scale production is easy, and the product quality is easy to control.
Description
Technical Field
The invention relates to the technical field of lithium ion battery materials, in particular to a preparation method of a manganese oxide/starch-based hard carbon composite negative electrode material.
Background
The lithium ion battery is a novel high-energy secondary battery which is put into practical use in the last 90 th century, and has the advantages of high working voltage, light weight, large specific energy, small self-discharge and cycleLong ring life, no memory effect, less environmental pollution, etc. The lithium ion battery negative electrode material mainly comprises carbon, and mainly comprises artificial graphite, natural graphite and amorphous carbon. However, the current graphite negative electrode has the following problems: 1. the potential platform is close to the potential of metal lithium, and dendrite Li is easy to separate out to cause short circuit; 2. the SEI film is unstable and Li is liable to occur+The graphite is embedded into a graphite layer together with an organic solvent, so that graphite is stripped and pulverized; 3. graphite C layer spacing (d)002≤0.34nm)＜LixC6(0.37 nm) and 8% volume change, which easily causes graphite layer stripping and pulverization; 4. the graphite and the organic solvent are subjected to exothermic reaction, combustible gas is easily generated, and the battery is easy to burn; 5. li+The diffusion coefficient is small and rapid charging is difficult.
Amorphous carbon can be classified into hard carbon and soft carbon according to the ease of graphitization. Compared with graphite, the hard carbon in the amorphous carbon has the advantages of small electrode expansion, no battery warpage, long cycle life, good rate capability and the like. The hard carbon can be divided into two types of biomass and fossil resources according to the source, and the biomass starch used as the hard carbon precursor has the advantages of environmental protection, low cost and the like. The starch-based hard carbon material is an amorphous carbon material prepared by taking starch as a raw material and performing heat treatment under certain conditions, and belongs to biomass hard carbon materials. Compared with fossil resource hard carbon, it has the following advantages: 1. the source is wide, and the raw material has reproducibility; 2. the preparation process is simple and convenient, and is environment-friendly; 3. low cost and suitability for industrialization.
At present, the disadvantages of the hard carbon anode material are mainly low first-time efficiency and voltage hysteresis.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, the hard carbon negative electrode material is compounded with other negative electrode materials to improve the orderliness of the surface of the hard carbon material, reduce lithium ions consumed by a stable SEI film formed by the surface of an electrode and electrolyte, facilitate the improvement of the first coulombic efficiency of the lithium ions, and improve the overall electrochemical performance of the composite electrode through the excellent electrical properties of other electrodes.
In order to realize the purpose, the preparation method of the manganese oxide/starch-based hard carbon composite negative electrode material is characterized by comprising the following preparation steps:
(1) and pre-carbonization: keeping the starch in a vacuum drying oven at the temperature of 200-250 ℃ for 24-48h at constant temperature to obtain a black pre-carbonized powder product;
(2) preparing a starch-based hard carbon material: heating the pre-carbonized powder product obtained by the preparation to 900-1100 ℃ at the temperature of 1-10 ℃/min in an inert atmosphere, keeping the temperature for 1-4h, and then cooling to room temperature along with the furnace to obtain a starch-based hard carbon material;
(3) and mixing: mixing manganese salt: starch-based hard carbon material: 5-15: 100: 800, mixing and stirring until the manganese salt is completely dissolved to obtain a mixture;
(4) and hydrothermal reaction: the mixture is thermally treated for 5 to 15 hours in a hydrothermal reaction kettle at the temperature of 150-;
(5) and obtaining a finished product: washing and drying the black product to obtain a manganese oxide/starch-based hard carbon composite negative electrode material;
the manganese salt is one of potassium permanganate, manganese nitrate and manganese hydroxide.
The inert atmosphere is one or two of nitrogen, argon and helium.
In the step of preparing the starch-based hard carbon material, the temperature is 1000 ℃.
In the hydrothermal reaction step, the mixture is subjected to heat treatment for 10 hours at 160 ℃ in a hydrothermal reaction kettle.
Compared with the prior art, the manganese oxide protective layer with an amorphous structure is formed on the surface of the starch-based hard carbon by a hydrothermal method, the amorphous crystallinity is low, the movement of ions is facilitated, the anisotropy of the surface of the starch-based hard carbon material can be eliminated, and lithium ions consumed by an SEI (solid electrolyte interface) film formed by the surface of an electrode and an electrolyte are reduced, so that the first coulombic efficiency of a negative electrode material is improved; the prepared manganese oxide/starch-based hard carbon for the lithium ion battery cathode material has the characteristics of good electrochemical performance, good cycling stability and excellent consistency of batch products; and the preparation method is simple, the production is environment-friendly, the large-scale production is easy, and the product quality is easy to control.
Drawings
Fig. 1 is an SEM image of a manganese oxide/starch-based hard carbon composite anode material prepared according to the present invention.
Fig. 2 is a comparison graph of 0.1C first cycle discharge curves of the manganese oxide/starch-based hard carbon composite negative electrode material prepared in example 2 of the present invention and the starch-based hard carbon negative electrode material obtained under the same preparation conditions.
Detailed Description
The present invention will now be further described with reference to examples.
Example 1
a. Pre-carbonization: keeping the starch in a vacuum drying oven at the constant temperature of 200 ℃ for 24 hours to obtain a black pre-carbonized powder product;
b. preparing a starch-based hard carbon material: and (3) heating the pre-carbonized powder product to 900 ℃ at the temperature of 10 ℃/min in the inert atmosphere of nitrogen, keeping for 1h, and then cooling to room temperature along with the furnace to obtain the starch-based hard carbon material.
c. Mixing: mixing potassium permanganate, a starch-based hard carbon material and distilled water according to a weight ratio of 5: 100: 800, and stirring until potassium permanganate is completely dissolved to obtain a mixture.
d. Hydrothermal reaction: and (3) carrying out heat treatment on the mixture in a hydrothermal reaction kettle at 150 ℃ for 5h to obtain a black product.
e. Obtaining a finished product: and washing and drying the black product to obtain the manganese oxide/starch-based hard carbon composite negative electrode material.
Example 2
a. Pre-carbonization: keeping the starch in a vacuum drying oven at 250 ℃ for 48 hours at a constant temperature to obtain a black pre-carbonized powder product;
b. preparing a starch-based hard carbon material: and (3) heating the pre-carbonized powder product to 1100 ℃ at 1 ℃/min under the inert atmosphere of argon, keeping the temperature for 4h, and then cooling the product to room temperature along with the furnace to obtain the starch-based hard carbon material.
c. Mixing: mixing manganese nitrate, a starch-based hard carbon material and distilled water according to a weight ratio of 15: 100: 800, and stirring until the manganese nitrate is completely dissolved to obtain a mixture.
d. Hydrothermal reaction: and (3) carrying out heat treatment on the mixture in a hydrothermal reaction kettle at 200 ℃ for 15h to obtain a black product.
e. Obtaining a finished product: and washing and drying the black product to obtain the manganese oxide/starch-based hard carbon composite negative electrode material.
Example 3
a. Pre-carbonization: keeping the starch in a vacuum drying oven at 220 ℃ for 36 hours at a constant temperature to obtain a black pre-carbonized powder product;
b. preparing a starch-based hard carbon material: and (3) heating the pre-carbonized powder product to 1000 ℃ at the temperature of 5 ℃/min in helium gas serving as inert atmosphere, keeping for 2h, and then cooling to room temperature along with the furnace to obtain the starch-based hard carbon material.
c. Mixing: mixing manganese hydroxide, a starch-based hard carbon material and distilled water according to a weight ratio of 10: 100: 800, stirring until the manganese hydroxide is completely dissolved to obtain a mixture.
d. Hydrothermal reaction: and (3) carrying out heat treatment on the mixture in a hydrothermal reaction kettle at 160 ℃ for 10h to obtain a black product.
e. Obtaining a finished product: and washing and drying the black product to obtain the manganese oxide/starch-based hard carbon composite negative electrode material.
Example 4
a. Pre-carbonization: keeping the starch in a vacuum drying oven at the constant temperature of 200 ℃ for 48 hours to obtain a black pre-carbonized powder product;
b. preparing a starch-based hard carbon material: and (3) heating the pre-carbonized powder product to 1050 ℃ at 7 ℃/min in a mixed gas of nitrogen and argon in an inert atmosphere, keeping for 3h, and then cooling to room temperature along with the furnace to obtain the starch-based hard carbon material.
c. Mixing: mixing potassium permanganate, a starch-based hard carbon material and distilled water according to a weight ratio of 6: 100: 800, and stirring until potassium permanganate is completely dissolved to obtain a mixture.
d. Hydrothermal reaction: and (3) carrying out heat treatment on the mixture in a hydrothermal reaction kettle at 170 ℃ for 9h to obtain a black product.
e. Obtaining a finished product: and washing and drying the black product to obtain the manganese oxide/starch-based hard carbon composite negative electrode material.
Example 5
a. Pre-carbonization: keeping the starch in a vacuum drying oven at 230 ℃ for 40h at constant temperature to obtain a black pre-carbonized powder product;
b. preparing a starch-based hard carbon material: and (3) heating the pre-carbonized powder product to 950 ℃ at the temperature of 7 ℃/min in a mixed gas of nitrogen and helium in an inert atmosphere, keeping the temperature for 4h, and then cooling to room temperature to obtain the starch-based hard carbon material.
c. Mixing: mixing manganese nitrate, a starch-based hard carbon material and distilled water according to a weight ratio of 12: 100: 800, and stirring until the manganese nitrate is completely dissolved to obtain a mixture.
d. Hydrothermal reaction: and (3) carrying out heat treatment on the mixture in a hydrothermal reaction kettle at 180 ℃ for 12h to obtain a black product.
e. Obtaining a finished product: and washing and drying the black product to obtain the manganese oxide/starch-based hard carbon composite negative electrode material.
Taking the manganese oxide/starch-based hard carbon composite negative electrode material prepared in example 2 as an example, the electrochemical performance of the material is tested, and the specific test results are as follows:
the manganese oxide/starch-based hard carbon composite negative electrode material prepared in example 2 and the starch-based hard carbon negative electrode material obtained under the same preparation conditions are respectively mixed with acetylene black serving as a conductive agent and polytetrafluoroethylene emulsion serving as a binder in an aqueous solution according to a weight ratio of 80:15:5 uniformly, then the mixture is pressed on copper foil to prepare a negative electrode sheet, a metal lithium sheet is taken as a negative electrode, a solution of ethylene carbonate and dimethyl carbonate of 1mol/L lithium hexafluorophosphate is taken as an electrolyte, a Celgard2400 polypropylene microporous membrane is taken as a diaphragm, a CR2025 type button lithium ion battery is assembled to carry out charging and discharging, the system is that the constant current is 0.1C to 2mV, the discharge is carried out to 1mV after the battery is placed for 10 minutes, and finally the charge is carried out to 2V at 0.1C to obtain a test curve, and the test curve is shown in figure 2. Wherein the first discharge specific capacity and the first coulombic efficiency of the starch-based hard carbon negative electrode material are 568.7/375.7mAh g respectively-1And 66.5%. The first charge-discharge specific capacity and the first coulombic efficiency of the manganese oxide/starch-based hard carbon composite negative electrode material are 746.7/508.1mAh g-1And 68.0%. The manganese oxide/starch-based hard carbon composite negative electrode material shows more excellent electrochemical performance than the starch-based hard carbon negative electrode material.
Claims (4)
1. A preparation method of a manganese oxide/starch-based hard carbon composite negative electrode material is characterized by comprising the following preparation steps:
(1) and pre-carbonization: keeping the starch in a vacuum drying oven at the temperature of 200-250 ℃ for 24-48h at constant temperature to obtain a black pre-carbonized powder product;
(2) preparing a starch-based hard carbon material: heating the pre-carbonized powder product obtained by the preparation to 900-1100 ℃ at the temperature of 1-10 ℃/min in an inert atmosphere, keeping the temperature for 1-4h, and then cooling to room temperature along with the furnace to obtain a starch-based hard carbon material;
(3) and mixing: mixing manganese salt: starch-based hard carbon material: 5-15: 100: 800, mixing and stirring until the manganese salt is completely dissolved to obtain a mixture;
(4) and hydrothermal reaction: the mixture is thermally treated for 5 to 15 hours in a hydrothermal reaction kettle at the temperature of 150-;
(5) and obtaining a finished product: washing and drying the black product to obtain a manganese oxide/starch-based hard carbon composite negative electrode material with an amorphous structure manganese oxide protective layer formed on the surface of the starch-based hard carbon;
the manganese salt is one of potassium permanganate, manganese nitrate and manganese hydroxide.
2. The method of claim 1, wherein: the inert atmosphere is one or two of nitrogen, argon and helium.
3. The method of claim 1, wherein: in the step of preparing the starch-based hard carbon material, the temperature is 1000 ℃.
4. The method of claim 1, wherein: in the hydrothermal reaction step, the mixture is subjected to heat treatment for 10 hours at 160 ℃ in a hydrothermal reaction kettle.
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| CN112547052A (en) * | 2020-12-25 | 2021-03-26 | 陕西科技大学 | Manganese oxide formaldehyde degradation material, preparation method thereof and catalyst |
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| CN101417820A (en) * | 2008-09-24 | 2009-04-29 | 上海大学 | Method for preparing multi-morphology nano manganese dioxide |
| CN104992852A (en) * | 2015-07-21 | 2015-10-21 | 湖北吉隆危废处理技术有限公司 | A method for preparing an electrode material with graphene coated with manganese dioxide |
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| CN102059082B (en) * | 2010-11-30 | 2012-06-27 | 重庆大学 | Method for preparing nano manganese dioxide/carbon composite microsphere |
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