CN109192960A - A kind of MnO/ cellulose base porous carbon and preparation method thereof and the application in lithium ion battery negative material - Google Patents
A kind of MnO/ cellulose base porous carbon and preparation method thereof and the application in lithium ion battery negative material Download PDFInfo
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- CN109192960A CN109192960A CN201811089098.7A CN201811089098A CN109192960A CN 109192960 A CN109192960 A CN 109192960A CN 201811089098 A CN201811089098 A CN 201811089098A CN 109192960 A CN109192960 A CN 109192960A
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- 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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H01M4/00—Electrodes
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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Abstract
Application the invention discloses a kind of MnO/ cellulose base porous carbon and preparation method thereof and in lithium ion battery negative material, the MnO/ cellulose base porous carbon is using soluble manganese salt and cellulosic-based material as raw material, abundant absorption using cellulosic-based material to soluble manganese salting liquid forms well-mixed cellulose/manganese salt compound after drying.After drying, cellulose/manganese salt compound is synchronized into carbonization/crystallization under an inert atmosphere, obtains MnO- cellulose base carbon composite.It is mixed and made into electrode slice with MnO- cellulose base carbon composite obtained and acetylene black and binder, as lithium ion battery negative material.The method that the present invention prepares MnO- cellulose base carbon, it is easy to operation, operating time is short, without filtering, centrifugation, the complex operations such as washing, at low cost, carbon content is controllable, is easy to be mass produced, synthesized MnO- cellulose base carbon presents excellent chemical property, expands the type of lithium ion battery negative material.
Description
Technical field
The present invention relates to a kind of porous carbon and its preparation method and application more particularly to a kind of MnO/ cellulose base porous carbons
And preparation method thereof and the application in lithium ion battery negative material；Belong to composite material preparation and field of lithium ion battery.
Background technique
In order to meet application demand of the lithium ion battery in the fields such as smart grid, electric vehicle, military equipment and space flight,
Guarantee that lithium ion battery obtains that specific capacity is high, has extended cycle life, the feature that safety is good, exploitation new electrode materials are to closing weight
It wants.For lithium ion battery negative material, the transition metal oxide negative electrode material based on conversion reaction increasingly causes
The concern of numerous scholars.
Nano material based on conversion reaction is the lithium ion pond cathode material of a kind of height ratio capacity (500-1000mAh g-1)
Material.Transition metal oxide is the representative of this kind of materials, and French Tarascon group (Nature 2000,407:496.) is first
Secondary such material that reports can cause extensively as lithium ion battery negative material with late transition metal oxide negative electrode material
The interest of big scholar, though research finds that it has the advantages that height ratio capacity, there is also operating voltage height and cyclical stability compared with
Difference disadvantage, so reduce its charge and discharge platform voltage and improve its cyclical stability as such investigation of materials hot spot it
One.Scientific worker is it has also been found that transition metal oxide (such as Mn containing Mn3O4,Mn2O3,MnO2And MnO) there is good circulation
Stability, and charging voltage is than other metal oxide (such as Fe3O4And Co3O4) want low 0.5V or so, and lower charging voltage
Higher energy density can be provided when being assembled into full battery.Meanwhile it is multiple with carbon material to design Mn system transition metal oxide
It closes, using the good electric conductivity of carbon material and to the buffering effect of Mn system transition metal oxide charge and discharge process volume change,
The chemical property of material can further be promoted.
In conjunction with the above advantage, Mn system transition metal oxide/carbon composite designs and prepares technical research as lithium
The hot spot of ion battery cathode material exploitation.And how to construct with specific morphology structure, carbon content is controllable, carbon and oxide fill
One of the key points and difficulties for dividing compound composite material to become such developing material.
Summary of the invention
In view of this, the present invention provides a kind of MnO/ cellulose base porous carbon and preparation method thereof and in lithium ion battery
Application in negative electrode material, to overcome traditional carbon negative pole material specific capacity low and other transition metal oxide charging voltages are high
Disadvantage provides certain help to exploitation novel cathode material for lithium ion battery.
To achieve the goals above, the present invention adopts the following technical scheme: being made with soluble manganese salt and cellulosic-based material
For raw material, abundant absorption using cellulosic-based material to soluble manganese salting liquid forms well-mixed fiber after drying
Element/manganese salt compound.After drying, cellulose/manganese salt compound is synchronized into carbonization/crystallization under an inert atmosphere, obtains spy
Determine controllable appearance structure, carbon content, carbon and the abundant compound MnO- cellulose base carbon composite of oxide.Finally application is made
MnO- cellulose base carbon composite and acetylene black and binder be mixed and made into electrode slice, specifically include:
A kind of preparation method of MnO/ cellulose base porous carbon, comprising the following steps:
(1) soluble manganese salt is dissolved in deionized water, forms manganese salt solution；
(2) cellulosic-based material is added in manganese salt solution, dries after mixing evenly, obtains cellulose/manganese salt composite wood
Material；
(3) by the cellulose after drying/manganese salt composite material, carbonization/crystallization obtains MnO/ cellulose base under an inert atmosphere
Porous carbon, wherein carbonization/crystallization temperature is 300-700 DEG C, preferably 450-650 DEG C；Carbonization/crystallization time is 2-6h,
Preferably 3-5h.
The method that the present invention prepares MnO- cellulose base carbon, easy to operation, the operating time is short, without filtering, is centrifuged,
The complex operations such as washing, at low cost, carbon content is controllable, is easy to be mass produced, and synthesized MnO- cellulose base carbon presents
Excellent chemical property expands the type of lithium ion battery negative material.
Further, soluble manganese salt is any of manganese nitrate or manganese acetate, and cellulosic-based material is cotton, paper scrap, straw
Stalk it is any；The operation being dissolved in soluble manganese salt in step (1) in deionized water are as follows: add in every 2-10mL deionized water
Enter 0.2-1.0g solubility manganese salt, stirring and dissolving；The addition mass ratio of cellulosic-based material and soluble manganese salt in step (2)
Are as follows: 3-20:2-10.
It is that the characterization of adsorption of cellulose-based source material has obtained well-mixed fibre using above-mentioned further beneficial effect
Element/manganese salt compound is tieed up, so that MnO in MnO- cellulose base carbon composite be made to come into full contact with carbon, MnO has good knot
Crystalline substance and crystallite dimension, carbon content are rationally and sufficiently compound with MnO, pass through the additional amount and manganese salt and aqueous solvent of change cellulose
Additional amount with the content of carbon in Effective Regulation composite material and the pattern and porosity characteristic of composite material can be controlled, it is prepared
Composite material presents excellent chemical property.
The present invention also provides a kind of lithium ion battery negative materials, are prepared by above-mentioned MnO/ cellulose base porous carbon
It arrives, preparation method are as follows:
MnO/ cellulose base porous carbon, acetylene black and binder are put into crucible and grind 12-18min, wetting is added water,
Continue to grind 20-30min, gained pasty mixture is uniformly coated on copper foil and dry at 70-90 DEG C, later to painting
There is the copper foil of said mixture to be rolled, cut to get lithium ion battery negative material.
The mass ratio of MnO/ cellulose base carbon, acetylene black and binder is 7:2:1；Binder is sodium alginate or gathers inclined two
Vinyl fluoride it is any.
In the glove box full of argon gas, electrode slice, diaphragm, lithium piece and nickel foam are assembled into button electricity in conventional manner
Pond.Button cell charge/discharge capacity made of being measured at room temperature with test method and cycle performance examine MnO/ cellulose base
Chemical property of the carbon as lithium ion battery negative material, the results show that in 200mAg-1Rate under, for the first time with second
Secondary discharge capacity is respectively 1157.4 and 812.3mAhg-1, coulombic efficiency is up to 71% for the first time.It is followed by 50 constant current charge-discharges
After ring, capacity is also maintained at 775.9mAhg-1Left and right, presents good cycle performance, while average charging tension only has
1.25V。
The present invention is prepared for the ideal MnO- cellulose base carbon of chemical property by straightforward procedure, and has studied it
As the chemical property of lithium ion battery negative material, including its specific capacity and cycle performance, due to its good electrochemistry
Performance makes it have potential application in field of lithium ion battery.
Detailed description of the invention
Fig. 1 is X-ray diffraction (XRD) figure of MnO/ cellulose base porous carbon of the present invention；
Fig. 2 is scanning electron microscope (SEM) photo of MnO/ cellulose base porous carbon of the present invention；
Fig. 3 a is the nitrogen Adsorption and desorption isotherms of MnO/ cellulose base porous carbon of the present invention, and 3b is MnO/ cellulose of the present invention
The graph of pore diameter distribution of base porous carbon；
Fig. 4 a is the first charge-discharge curve of MnO/ cellulose base porous carbon of the present invention, and 4b is MnO/ cellulose base of the present invention
The cycle performance figure of porous carbon；
Fig. 5 is the high rate performance figure of MnO/ cellulose base porous carbon of the present invention.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Embodiment 1:
The preparation method of MnO/ cellulose base porous carbon, comprising the following steps:
Step (1): weighing the manganese nitrate solution of 1.0g 50wt%, and 5mL deionized water is added, it is molten that manganese nitrate is prepared
Liquid；
Step (2): 0.5g cotton is added into above-mentioned solution, cotton is made sufficiently to adsorb manganese nitrate solution；
Step (3): by obtained mixture it is dry after, carbonization/crystallization 4h obtains MnO/ cellulose base is porous at 600 DEG C
Carbon, color slightly celadon.
Fig. 1 is the x-ray diffraction pattern of the MnO/ cellulose base porous carbon of preparation, and Fig. 2 a and Fig. 2 b are that the MnO/ of preparation is fine
The SEM image for tieing up plain base porous carbon, can be seen from figure its be it is porous tubular structured, x=bg is its nitrogen adsorption desorption in Fig. 3 a
Thermoisopleth, Fig. 3 b are that its surface area is calculated in 20m as seen from the figure in its graph of pore diameter distribution2/ g or so, is adsorbed on higher-pressure region
Between ramp, and there are an adsorption hysteresis ring, illustrate in the presence of a large amount of mesoporous and macroporous structure.
Embodiment 2:
The preparation method of MnO/ cellulose base porous carbon, comprising the following steps:
Step (1): weighing the manganese nitrate solution of 0.5g 50wt%, and 2mL deionized water is added, it is molten that manganese nitrate is prepared
Liquid；
Step (2): 1g health paper scrap is added into above-mentioned solution, paper scrap is made sufficiently to adsorb manganese nitrate solution；
Step (3): after the drying of obtained mixture, carbonization/crystallization 6h obtains MnO/ cellulose base carbon mesh at 600 DEG C
Mark product.
Fig. 1 is the x-ray diffraction pattern of the MnO/ cellulose base porous carbon of preparation, and Fig. 2 c is the MnO/ cellulose base of preparation
The SEM image of carbon can see it from figure as porous class club shaped structure, and x=cg is its nitrogen Adsorption and desorption isotherms, figure in Fig. 3 a
3b is that its surface area is calculated in 80m as seen from the figure in its graph of pore diameter distribution2/ g or so, and there are a large amount of macroporous structures.
Embodiment 3:
The preparation method of MnO/ cellulose base porous carbon, comprising the following steps:
Step (1): weighing 1.0g manganese acetate, and 10mL deionized water is added, acetic acid manganese solution is prepared；
Step (2): 2g cotton is added into above-mentioned solution, cotton is made sufficiently to adsorb manganese nitrate solution；
Step (3): after the drying of obtained mixture, carbonization/crystallization 6h obtains MnO/ cellulose base carbon mesh at 550 DEG C
Mark product.
Fig. 1 is the x-ray diffraction pattern of the MnO/ cellulose base porous carbon of preparation, and Fig. 2 d is the MnO/ cellulose base of preparation
The SEM image of carbon can see it from figure as closed non-porous club shaped structure, and x=dg is its nitrogen adsorption desorption isothermal in Fig. 3 a
Line, Fig. 3 b are that its surface area is calculated in 130m as seen from the figure in its graph of pore diameter distribution2/ g or so, and exist a large amount of mesoporous
Structure.
Electro-chemical test:
In the glove box full of argon gas, electrode slice, diaphragm, lithium piece and nickel foam are assembled into CR2016 in conventional manner
Button cell.
The mixture formed with MnO/ cellulose base porous carbon, acetylene black and binder and the electrode slice being applied on copper foil
As battery cathode, using lithium piece be used as to and reference electrode, with polymer film (Celgarad 2400) and LiPF6Solution
(LBC-301, Shenzhen Capchem) respectively as diaphragm and electrolyte, at room temperature under different current densities, in 1.0-3.0V
In (to Li+/Li) voltage regime, constant current loop test is carried out on Neware CT-3008 battery test system, is examined
Chemical property of the MnO/ cellulose base carbon as lithium ion battery negative material, chemical property is as shown in Figures 4 and 5, by
Figure is it is found that in 200mAg-1Rate under, be respectively for the first time 1157.4 and 812.3mAhg with second of discharge capacity-1, for the first time
Coulombic efficiency is up to 71%.After 50 constant current charge-discharges recycle, capacity is also maintained at 775.9mAhg-1Left and right.By changing
Change condition can be improved the discharge capacity and starting coulombic efficiency of MnO/ cellulose base porous carbon.
Claims (10)
1. a kind of preparation method of MnO/ cellulose base porous carbon, which comprises the following steps:
(1) soluble manganese salt is dissolved in deionized water, forms manganese salt solution；
(2) cellulosic-based material is added in manganese salt solution, dries after mixing evenly, obtains cellulose/manganese salt composite material；
(3) by the cellulose after drying/manganese salt composite material, to obtain MnO/ cellulose base porous for carbonization/crystallization under an inert atmosphere
Carbon.
2. a kind of preparation method of MnO/ cellulose base porous carbon according to claim 1, which is characterized in that the step
(1) operation being dissolved in soluble manganese salt in deionized water are as follows: it is solvable that 0.2-1.0g is added in every 2-10mL deionized water
Property manganese salt, stirring and dissolving.
3. according to claim 1 or a kind of 2 described in any item preparation methods of MnO/ cellulose base porous carbon, feature exist
In the solubility manganese salt is any of manganese nitrate or manganese acetate.
4. a kind of preparation method of MnO/ cellulose base porous carbon according to claim 1, which is characterized in that step (2)
Described in cellulosic-based material and soluble manganese salt addition mass ratio are as follows: 3-20:2-10.
5. according to claim 1 or a kind of 4 described in any item preparation methods of MnO/ cellulose base porous carbon, feature exist
In, the cellulosic-based material be cotton, paper scrap, stalk it is any.
6. a kind of preparation method of MnO/ cellulose base porous carbon according to claim 1, which is characterized in that step (3)
The temperature of the carbonization/crystallization is 300-700 DEG C, and carbonization/crystallization time is 2-6h.
7. a kind of lithium ion battery negative material, which is characterized in that the lithium ion battery negative material includes claims
The preparation method of the MnO/ cellulose base porous carbon of any one of 1-6 prepares MnO/ cellulose base porous carbon.
8. a kind of lithium ion battery negative material according to claim 7, which is characterized in that the negative electrode of lithium ion battery
Material further includes acetylene black, binder and sheet metal, the preparation method comprises the following steps:
MnO/ cellulose base porous carbon, acetylene black and binder are put into crucible and are ground, wetting is added water, continues to grind, it will
Gained pasty mixture is uniformly coated on sheet metal and drying, grinds later the sheet metal for being coated with said mixture
Pressure is cut to get lithium ion battery negative material.
9. a kind of lithium ion battery negative material according to claim 8, which is characterized in that the MnO/ cellulose base
The mass ratio of carbon, acetylene black and binder is 7:2:1；The binder is any of sodium alginate or polyvinylidene fluoride；
The sheet metal is copper foil.
10. a kind of lithium ion battery negative material according to claim 8, which is characterized in that the time of the grinding is
12-18min；The time for continuing grinding is 20-30min；The drying is dry at 70-90 DEG C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110767883A (en) * | 2019-07-02 | 2020-02-07 | 罗宝林 | Modified fiber, preparation method and application |
| CN112436128A (en) * | 2020-12-01 | 2021-03-02 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of manganese-cobalt-oxygen composite two-dimensional carbon material for lithium ion battery cathode |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107492648A (en) * | 2017-08-18 | 2017-12-19 | 湖北文理学院 | Cotton base carbon fibre/MnO/C materials, preparation method and application |
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2018
- 2018-09-18 CN CN201811089098.7A patent/CN109192960A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107492648A (en) * | 2017-08-18 | 2017-12-19 | 湖北文理学院 | Cotton base carbon fibre/MnO/C materials, preparation method and application |
Non-Patent Citations (1)
| Title |
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| CHUNYU ZHU等: "Facile synthesis of MnO/carbon composites by a single-step nitratecellulose combustion synthesis for Li ion battery anode", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110767883A (en) * | 2019-07-02 | 2020-02-07 | 罗宝林 | Modified fiber, preparation method and application |
| CN110767883B (en) * | 2019-07-02 | 2023-07-04 | 罗宝林 | Modified fiber, preparation method and application |
| CN112436128A (en) * | 2020-12-01 | 2021-03-02 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of manganese-cobalt-oxygen composite two-dimensional carbon material for lithium ion battery cathode |
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Application publication date: 20190111 |