CN113517441A - Method for modifying lithium manganese battery by graphene - Google Patents
Method for modifying lithium manganese battery by graphene Download PDFInfo
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- CN113517441A CN113517441A CN202110351164.9A CN202110351164A CN113517441A CN 113517441 A CN113517441 A CN 113517441A CN 202110351164 A CN202110351164 A CN 202110351164A CN 113517441 A CN113517441 A CN 113517441A
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- manganese dioxide
- graphene
- electrolytic manganese
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- lithium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
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Abstract
The invention discloses a method for modifying a lithium-manganese battery by graphene, which comprises the following operation steps: (1) mixing electrolytic manganese dioxide and graphene in proportion; (2) adding ethanol into the substances which are not obtained after mixing in the step (1), ball-milling for 1h, and cooling; (3) and (3) separating the substances obtained after cooling in the step (2) from the graphene modified electrolytic manganese dioxide (G-EMD) by using a sieve to obtain the graphene modified electrolytic manganese dioxide material. The graphene modified manganese dioxide material obtained by the method has good conductivity, and the preparation method is simple and is easy for batch production; the invention solves the problems of low conductivity, poor performance during high-rate discharge in the discharge process and the like when the current Electrolytic Manganese Dioxide (EMD) is used as a lithium-manganese dioxide electrode material; the method is simple and easy to implement, economic and environment-friendly, easy to scale, and wide in application prospect, economic benefit value and social environment-friendly value.
Description
Technical Field
The invention relates to a method for modifying a lithium-manganese battery, in particular to a method for modifying a lithium-manganese battery by graphene.
Background
Lithium-manganese dioxide batteries (abbreviated as lithium manganese batteries) are one of the most widely used three major systems of primary lithium batteries, and have been the focus of research in the electrochemical field due to their advantages of high voltage and specific energy, safety, reliability, wide operating temperature range, and low cost. While lithium-manganese dioxide batteries generally use Electrolytic Manganese Dioxide (EMD) as the positive electrode material, their wider use is limited due to their low conductivity and poor performance during high rate discharge.
In the aspect of improving the rate capability and conductivity of the anode material, the carbon material is coated by an effective method, such as Honma (Journal of Power Sources,2005,125, 85)]Equal use of ultrasonic methods for the preparation of carbon-coated amorphous MnO2The performance of the electrode is improved. Researchers such as Andre k.geim at manchester university, uk, in 2004, obtained independently existing graphene for the first time by a mechanical graphite exfoliation method, and characterized the basic properties of graphene [ Nature Materials,2007,6, 183; science,2009,324,1530]. Graphene has excellent electron conductivity and thermal conductivity, the former ensures a good electron transport channel, and the latter ensures the stability of the material, so that graphene is used for modifying MnO2The material is the first choice.
Disclosure of Invention
Aiming at the technical problems, the invention provides a method for modifying a lithium manganese dioxide battery by graphene, aiming at solving the problems of low conductivity, poor performance during high-rate discharge in the discharge process and the like when the current Electrolytic Manganese Dioxide (EMD) is used as a lithium-manganese dioxide electrode material.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
a method for modifying a lithium manganese battery by graphene comprises the following operation steps:
(1) mixing electrolytic manganese dioxide and graphene in proportion, wherein the total mass of the electrolytic manganese dioxide and the graphene is 1000 g;
(2) adding absolute ethyl alcohol into the substances which are not obtained after mixing in the step (1), carrying out ball milling for 1h, and cooling;
(3) and (3) separating the substances obtained after cooling in the step (2) from the graphene modified electrolytic manganese dioxide (G-EMD) by using a sieve to obtain the graphene modified electrolytic manganese dioxide material.
Preferably, the ratio of the electrolytic manganese dioxide to the graphene in the step (1) is 98:2 by mass.
Preferably, the ball milling speed in the step (2) is 200-300 r/min.
Preferably, the ball milling time in the step (2) is 0.5 to 1.5 h.
The graphene modified manganese dioxide prepared by the method is used for a lithium-manganese dioxide battery.
Compared with the prior art, the invention has the following beneficial effects:
the graphene modified manganese dioxide material obtained by the method has good conductivity, and the preparation method is simple and is easy for batch production; the invention solves the problems of low conductivity, poor performance during high-rate discharge in the discharge process and the like when the current Electrolytic Manganese Dioxide (EMD) is used as a lithium-manganese dioxide electrode material; the method is simple and easy to implement, economic and environment-friendly, easy to scale, and wide in application prospect, economic benefit value and social environment-friendly value.
Drawings
Fig. 1 is a scanning electron microscope image of graphene-modified manganese dioxide (G-EMD) prepared in example 1 of the present invention.
Fig. 2 is a constant current discharge curve of Electrolytic Manganese Dioxide (EMD) and graphene-modified manganese dioxide (G-EMD) prepared in example 1 of the present invention as a positive electrode of a lithium-manganese dioxide battery.
Detailed Description
The following detailed description is to be read in connection with the accompanying drawings, but it is to be understood that the scope of the invention is not limited to the specific embodiments. The raw materials and reagents used in the examples were all commercially available unless otherwise specified.
The electrolytic manganese dioxide used in the examples was produced by china manganese ore industries, llc, and graphene was purchased from graphene industries, development ltd, gulf north, Guangxi.
Example 1
A method for modifying a lithium manganese battery by graphene comprises the following specific operation steps:
(1) mixing electrolytic manganese dioxide and graphene according to the mass ratio of 98:2, wherein the total mass of the electrolytic manganese dioxide and the graphene is 1000 g;
(2) putting the substances which are not obtained after mixing in the step (1) into a ball milling tank, adding 50ml of absolute ethyl alcohol, carrying out ball milling for 1h at the rotating speed of 260r/min, and cooling;
(3) and (3) after the ball milling tank is cooled in the step (2), separating the grinding balls from the graphene modified electrolytic manganese dioxide (G-EMD) by using a standard sieve to obtain the graphene modified electrolytic manganese dioxide material.
Example 2
A method for modifying a lithium manganese battery by graphene comprises the following specific operation steps:
(1) mixing electrolytic manganese dioxide and graphene according to the mass ratio of 98:2, wherein the total mass of the electrolytic manganese dioxide and the graphene is 1000 g;
(2) putting the substances which are not obtained after mixing in the step (1) into a ball milling tank, adding 50ml of absolute ethyl alcohol, carrying out ball milling for-1.5 h at the rotating speed of 200r/min, and cooling;
(3) and (3) after the ball milling tank is cooled in the step (2), separating the grinding balls from the graphene modified electrolytic manganese dioxide (G-EMD) by using a standard sieve to obtain the graphene modified electrolytic manganese dioxide material.
Example 3
A method for modifying a lithium manganese battery by graphene comprises the following specific operation steps:
(1) mixing electrolytic manganese dioxide and graphene according to the mass ratio of 98:2, wherein the total mass of the electrolytic manganese dioxide and the graphene is 1000 g;
(2) putting the substances which are not obtained after mixing in the step (1) into a ball milling tank, adding 50ml of absolute ethyl alcohol, carrying out ball milling for 0.5 according to the rotating speed of 300r/min, and cooling;
(3) and (3) after the ball milling tank is cooled in the step (2), separating the grinding balls from the graphene modified electrolytic manganese dioxide (G-EMD) by using a standard sieve to obtain the graphene modified electrolytic manganese dioxide material.
The graphene modified electrolytic manganese dioxide material prepared in the embodiment 1 of the invention is used for scanning electron microscope and other tests.
From fig. 1, it can be seen that the micro-domain morphology of the sample is that the graphene (G) and the Electrolytic Manganese Dioxide (EMD) are broken after ball milling, the Electrolytic Manganese Dioxide (EMD) enters the pores of the macroporous graphene network, and the holes are broken and doped on the Electrolytic Manganese Dioxide (EMD), so that the graphene (G) is well mixed with the Electrolytic Manganese Dioxide (EMD).
FIG. 2 is a voltage-capacity discharge curve obtained by discharging Electrolytic Manganese Dioxide (EMD) and graphene-modified electrolytic manganese dioxide (G-EMD) under the same current condition, wherein the discharge is performed under a current of 100mA, the capacity of the Electrolytic Manganese Dioxide (EMD) is 4.57Ah, and the voltage plateau is 2.90V-2.66V. The capacity of the graphene modified electrolytic manganese dioxide (G-EMD) reaches 4.96Ah, and the voltage platform is 2.90V-2.68V. Compared with Electrolytic Manganese Dioxide (EMD), the graphene modified electrolytic manganese dioxide (G-EMD) has larger capacity and higher and more stable voltage platform.
In conclusion, the graphene modified manganese dioxide prepared by the invention has practical application value in the aspect of being used for lithium-manganese dioxide batteries.
The foregoing descriptions of specific exemplary embodiments of the present invention have been presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and its practical application to enable one skilled in the art to make and use various exemplary embodiments of the invention and various alternatives and modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (5)
1. A method for modifying a lithium manganese battery by graphene is characterized by comprising the following operation steps:
(1) mixing electrolytic manganese dioxide and graphene in proportion;
(2) adding ethanol into the substances which are not obtained after mixing in the step (1), ball-milling for 1h, and cooling;
(3) and (3) separating the substances obtained after cooling in the step (2) from the graphene modified electrolytic manganese dioxide (G-EMD) by using a sieve to obtain the graphene modified electrolytic manganese dioxide material.
2. The method of claim 1, wherein: the ratio of the electrolytic manganese dioxide to the graphene in the step (1) is 98:2 by mass.
3. The method of claim 1, wherein: the ball milling speed in the step (2) is 200-300 r/min.
4. The method of claim 1, wherein: the ball milling time in the step (2) is 0.5-1.5 h.
5. The application of the graphene modified manganese dioxide material prepared according to the method of any one of claims 1 to 4 in a lithium-manganese dioxide battery.
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| CN202110351164.9A CN113517441A (en) | 2021-03-31 | 2021-03-31 | Method for modifying lithium manganese battery by graphene |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103572315A (en) * | 2013-11-07 | 2014-02-12 | 广西桂柳化工有限责任公司 | Preparation method of special electrolytic manganese dioxide for button/manganese dioxide battery |
| CN103811757A (en) * | 2014-03-11 | 2014-05-21 | 中国第一汽车股份有限公司 | Graphene composite positive electrode material |
| CN107611407A (en) * | 2017-09-21 | 2018-01-19 | 江门市宏力能源有限公司 | A kind of positive pole of lithium manganese battery formula and preparation method |
| CN107732231A (en) * | 2017-09-27 | 2018-02-23 | 四川长虹新能源科技股份有限公司 | The positive electrode and alkaline zinc-manganese dioxide cell of alkaline zinc-manganese dioxide cell |
| CN111769255A (en) * | 2020-07-09 | 2020-10-13 | 四川虹微技术有限公司 | Positive pole piece for high-power lithium-manganese dioxide battery and preparation method thereof |
| CN112186149A (en) * | 2020-09-12 | 2021-01-05 | 宿迁德特材料科技有限公司 | Manganese dioxide/graphite nanosheet composite zinc ion positive electrode material and preparation method thereof |
-
2021
- 2021-03-31 CN CN202110351164.9A patent/CN113517441A/en not_active Withdrawn
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103572315A (en) * | 2013-11-07 | 2014-02-12 | 广西桂柳化工有限责任公司 | Preparation method of special electrolytic manganese dioxide for button/manganese dioxide battery |
| CN103811757A (en) * | 2014-03-11 | 2014-05-21 | 中国第一汽车股份有限公司 | Graphene composite positive electrode material |
| CN107611407A (en) * | 2017-09-21 | 2018-01-19 | 江门市宏力能源有限公司 | A kind of positive pole of lithium manganese battery formula and preparation method |
| CN107732231A (en) * | 2017-09-27 | 2018-02-23 | 四川长虹新能源科技股份有限公司 | The positive electrode and alkaline zinc-manganese dioxide cell of alkaline zinc-manganese dioxide cell |
| CN111769255A (en) * | 2020-07-09 | 2020-10-13 | 四川虹微技术有限公司 | Positive pole piece for high-power lithium-manganese dioxide battery and preparation method thereof |
| CN112186149A (en) * | 2020-09-12 | 2021-01-05 | 宿迁德特材料科技有限公司 | Manganese dioxide/graphite nanosheet composite zinc ion positive electrode material and preparation method thereof |
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