CN105826522B - A kind of preparation method of used as negative electrode of Li-ion battery in-situ carbon cladding manganese carbonate - Google Patents
A kind of preparation method of used as negative electrode of Li-ion battery in-situ carbon cladding manganese carbonate Download PDFInfo
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- CN105826522B CN105826522B CN201610333350.9A CN201610333350A CN105826522B CN 105826522 B CN105826522 B CN 105826522B CN 201610333350 A CN201610333350 A CN 201610333350A CN 105826522 B CN105826522 B CN 105826522B
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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
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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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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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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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
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Abstract
The invention discloses a kind of method that one-step method original position prepares used as negative electrode of Li-ion battery carbon coating manganese carbonate, specific steps include：(1) certain density liquor potassic permanganate and carbon source solution are prepared respectively, the molar concentration rate of the carbon source and liquor potassic permanganate is 1：2‑2.5；(2) carbon source solution is added in liquor potassic permanganate, be ultrasonically treated after being dispersed with stirring；(3) scattered solution is added in reactor and heated, heating-up temperature is 120 DEG C 180 DEG C, and the heat time is 3 24h；(4) reactor naturally cools to room temperature, cleaning, and gained powder is used as negative electrode of Li-ion battery in-situ carbon cladding manganese carbonate after drying.This method preparing raw material is cheap and easy to get, and simple to operate to consume energy less, be pollution-free, resulting manganese carbonate carbon coating is uniform, even particle size distribution, and purity is high, can effectively prevent particle collapse phenomenon in manganese carbonate charge and discharge process, improves lithium ion battery cyclical stability.
Description
Technical field
The present invention relates to battery material technical field, and in particular to a kind of used as negative electrode of Li-ion battery in-situ carbon coats carbonic acid
The preparation method of manganese.
Background technology
With lithium ion battery flourish and application it is more wide, market proposes to its portability and energy density
Higher requirement.The part important as lithium ion battery, influence of the negative material to performance are most important.However,
Existing commercialization negative material Carbon anode has been difficult to meet such requirement, therefore to various alternative type negative materials through row
Research and modification are the important methods for solving this problem.
At present, negative material can be divided into insert type, alloy-type and the class of conversion hysteria three from from storage lithium mechanism.And conversion hysteria is born
Pole has the advantages that high power capacity, discharge and recharge Volume Changes are smaller relative to alloy-type and insert type electrode, therefore is more suitable for not
The lithium electricity market come.Transition metal carbonate using manganese carbonate as representative is used as new conversion hysteria negative electrode of lithium ion battery material
Material, great concern has been obtained from 2007 since reporting for the first time, but with other materials based on conversion reaction mechanism
Similar, it is big that the transition metal carbonate negative material such as manganese carbonate equally exists the Volume Changes in charge and discharge process, structural collapse,
Capacity decline, and then cause lithium ion battery chemical property decay, had a strong impact on such material in lithium ion battery side
The practical application in face.Therefore, how by modified method overcome the transition metal carbonate negative material such as manganese carbonate it is above-mentioned lack
Point turns into now the emphasis of many scholar's research both at home and abroad.At present, conventional modified method has carbon coating, pattern control etc., so
And often preparation process is cumbersome, preparation condition is harsh, high energy consumption for these methods, resulting product is unsatisfactory, is unfavorable for industry
Change actual production.
The content of the invention
The purpose of the present invention is exactly to solve the above problems, there is provided a kind of one-step method original position prepares negative electrode of lithium ion battery
With the method for carbon coating manganese carbonate, this method preparing raw material is cheap and easy to get, the carbon of power consumption simple to operate less, pollution-free, resulting
Sour manganese carbon coating is uniform, even particle size distribution, and purity is high, can effectively prevent that particle collapse is existing in manganese carbonate charge and discharge process
As improving lithium ion battery cyclical stability.
To achieve these goals, the present invention adopts the following technical scheme that：
A kind of preparation method of used as negative electrode of Li-ion battery in-situ carbon cladding manganese carbonate, comprises the following steps：
(1) certain density liquor potassic permanganate and carbon source solution are prepared respectively, the carbon source and liquor potassic permanganate
Molar concentration rate is 1：2-2.5；
(2) carbon source solution is added in liquor potassic permanganate, be ultrasonically treated after being dispersed with stirring；
(3) scattered solution is added in reactor and heated, heating-up temperature is 120 DEG C -180 DEG C, and the heat time is
3-24h；
(4) reactor naturally cools to room temperature, cleaning, and gained powder is used as negative electrode of Li-ion battery in-situ carbon after drying
Coat manganese carbonate.
Carbon source wherein in step (1) includes glucose, the one or more in sucrose and oxalic acid；
Preferably, in the step (1), carbon source is glucose；
Preferably, in the step (1), carbon source solution concentration is 0.02~0.1 mol/L；
Preferably, in the step (2), supersound process frequency is 15~22Hz, and processing time is 5~20 minutes；
Preferably, in the step (3), heating-up temperature is 180 DEG C, heat time 6h.
The present invention also provides a kind of used as negative electrode of Li-ion battery in-situ carbon being prepared according to the above method and coats carbonic acid
Manganese material.
In addition, the present invention also provides a kind of negative electrode of lithium ion battery, the material of the GND is foregoing former
Position carbon coating carbonic acid manganese material.
Finally, the present invention also provides a kind of lithium ion battery, and the negative material of the lithium ion battery is former as previously described
Position carbon coating carbonic acid manganese material.
Beneficial effect：
1. carbon source of the present invention primarily serves two kinds of effects in preparation process, generation carbonic acid is on the one hand reacted with potassium permanganate
Manganese, another aspect carbon is evenly coated at the manganese carbonate surface to be formed and forms compound, while the presence of carbon source also effectively inhibits
The reunion of manganese carbonate crystal, therefore obtained carbon coating manganese carbonate even particle size distribution, realize that one-step method original position prepares lithium ion
GND carbon coating manganese carbonate, greatly simplifies preparation process, prepares that material is cheap and easy to get, and production cost is low, is advantageous to work
Industryization mass produces；
2. preparation method power consumption of the present invention is few, reaction is that can obtain final products only under relatively lower temp, and product is not
Need to post-process, course of reaction Environmental Safety, no poisonous and harmful substance produces；
3. gained manganese carbonate carbon coating of the invention is uniform, purity is high, can effectively prevent in manganese carbonate charge and discharge process
Grain collapse phenomenon, improves lithium ion battery cyclical stability.
Brief description of the drawings
Fig. 1 is the SEM figures of gained powder in embodiment 1；
Fig. 2 is the TEM figures of gained powder in embodiment 1；
Fig. 3 is the SEM figures of gained powder in embodiment 2；
Fig. 4 is the TEM figures of gained powder in embodiment 2.
Embodiment
The invention will be further described with embodiment below in conjunction with the accompanying drawings.It should be noted that the description below be only for
The present invention is explained, its content is not defined.
Embodiment 1
(1) compound concentration is the liquor potassic permanganate of 0.25 mol/L, is dispersed with stirring；
(2) glucose solution of 0.1 mol/L is prepared, is dispersed with stirring；
(3) above-mentioned glucose solution is added in liquor potassic permanganate, is ultrasonically treated 22Hz after being dispersed with stirring, during processing
Between be 5 minutes；
(4) scattered solution is added in reactor be heated to 180 DEG C keep 6 hours；
(5) reactor heated naturally cools to room temperature, cleaning, powder is finally obtained after drying.
Obtain the test result of powder:
As shown in fig. 1, carbon coating manganese carbonate crystal is in the spindle bodily form to SEM patterns, and carbon layer on surface uniformly coats, crystal grain
Degree is evenly distributed；TEM patterns are as shown in Fig. 2 the spindle bodily form is presented in carbon coating manganese carbonate crystal, it is evident that manganese carbonate crystal
It is made up of double-layer structure, wherein top layer is manganese carbonate particle for the carbon-coating and small manganese carbonate, internal core uniformly coated.
Tested using battery test system obtaining spindle bodily form manganese carbonate, in current density 100mAg-1Condition obtains
It is 1180mAh/g to initial capacity, capacity stationary value 450mAh/g after circulating 100 weeks.Prove that there is good electrochemistry to follow for it
Ring stability.
Embodiment 2
(1) compound concentration is the liquor potassic permanganate of 0.04 mol/L, is dispersed with stirring；
(2) oxalic acid solution of 0.02 mol/L is prepared, is dispersed with stirring；
(3) above-mentioned oxalic acid solution is added in liquor potassic permanganate, 15Hz, processing time is ultrasonically treated after being dispersed with stirring
For 20 minutes；
(4) scattered solution is added in reactor be heated to 120 DEG C keep 10 hours；
(5) reactor heated naturally cools to room temperature, cleaning, powder is finally obtained after drying.
Obtain the test result of powder：
As shown in Figure 3, carbon coating manganese carbonate crystal is square in regular shape, and carbon layer on surface uniformly wraps for SEM patterns
Cover, Lens capsule is uniform；TEM patterns have the square of regular shape as shown in figure 4, carbon coating manganese carbonate crystal is presented,
It is evident that manganese carbonate crystal is made up of double-layer structure, wherein top layer is the carbon-coating and small manganese carbonate uniformly coated, internal
Core is manganese carbonate particle.
Obtained square manganese carbonate is tested using battery test system, current density 100mAg-1Obtaining initial capacity is
998mAh/g, capacity stationary value 430mAh/g after circulating 100 weeks.Experiment proves that it has good electrochemical cycle stability.
Comparative example 1
Method is with embodiment 1, the difference is that replacing potassium permanganate using manganese sulfate, uses sodium acid carbonate to replace glucose.
Obtained manganese carbonate is tested using battery test system, current density 100mAg-1Under the conditions of, obtain initial capacity
For 950mAh/g, capacity stationary value 230mAh/g after circulating 100 weeks.
It is not difficult to find out by comparative example 1, it is steady using manganese carbonate made from manganese sulfate and sodium acid carbonate, its initial capacity and capacity
Definite value significantly declines compared with the application, and electrochemical cycle stability is poor.
Although above-mentioned the embodiment of the present invention is described with reference to accompanying drawing, model not is protected to the present invention
The limitation enclosed, one of ordinary skill in the art should be understood that on the basis of technical scheme those skilled in the art are not
Need to pay various modifications or deformation that creative work can make still within protection scope of the present invention.
Claims (9)
1. a kind of preparation method of used as negative electrode of Li-ion battery in-situ carbon cladding manganese carbonate, comprises the following steps：
（1）Certain density liquor potassic permanganate and carbon source solution are prepared respectively, the carbon source solution and liquor potassic permanganate
Molar concentration rate is 1：2-2.5；
（2）Carbon source solution is added in liquor potassic permanganate, is ultrasonically treated after being dispersed with stirring；
（3）Scattered solution is added in reactor and heated, heating-up temperature is 120 DEG C -180 DEG C, heat time 3-
24h；
（4）Reactor naturally cools to room temperature, cleaning, and gained powder is used as negative electrode of Li-ion battery original position carbon coating after drying
Manganese carbonate.
2. a kind of preparation method of used as negative electrode of Li-ion battery in-situ carbon cladding manganese carbonate as claimed in claim 1, its feature
It is, the step（1）In, carbon source solution concentration is 0.02 ~ 0.1 mol/L.
3. a kind of preparation method of used as negative electrode of Li-ion battery in-situ carbon cladding manganese carbonate as claimed in claim 1, its feature
It is, the step（1）In carbon source include glucose, the one or more in sucrose and oxalic acid.
4. a kind of preparation method of used as negative electrode of Li-ion battery in-situ carbon cladding manganese carbonate as claimed in claim 3, its feature
It is, the step（1）In, carbon source is glucose.
5. a kind of preparation method of used as negative electrode of Li-ion battery in-situ carbon cladding manganese carbonate as claimed in claim 1, its feature
It is, the step（2）In, supersound process frequency is 15 ~ 22Hz, and processing time is 5 ~ 20 minutes.
6. a kind of preparation method of used as negative electrode of Li-ion battery in-situ carbon cladding manganese carbonate as claimed in claim 1, its feature
It is, the step（3）In, heating-up temperature is 180 DEG C, and the heat time is 6 h.
A kind of 7. used as negative electrode of Li-ion battery original position carbon coating that method as claimed in any one of claims 1 to 6 is prepared
Carbonic acid manganese material.
8. a kind of negative electrode of lithium ion battery, it is characterised in that the material of the GND is as claimed in claim 7 in situ
Carbon coating carbonic acid manganese material.
9. a kind of lithium ion battery, it is characterised in that the negative material of the lithium ion battery is the original position described in claim 7
Carbon coating carbonic acid manganese material.
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| CN106784825A (en) * | 2017-03-15 | 2017-05-31 | 北京理工大学 | A kind of spherical nickeliferous carbonic acid manganese material and its preparation method and application |
| CN107910525B (en) * | 2017-11-16 | 2021-01-08 | 中山大学 | Preparation method of nitrogen-doped manganese carbonate and compound thereof |
| CN110504437B (en) * | 2019-08-30 | 2020-11-13 | 浙江大学山东工业技术研究院 | Polypyrrole-coated porous sodium manganate composite material and preparation method and application thereof |
| CN112661189A (en) * | 2020-12-25 | 2021-04-16 | 陕西科技大学 | Manganese carbonate nano material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102208610A (en) * | 2011-04-18 | 2011-10-05 | 北京工业大学 | Preparation method of carbon coated MnO cathode material |
| CN103500833A (en) * | 2013-10-23 | 2014-01-08 | 山东大学 | Method for preparing lithium iron phosphate positive electrode material coated by home position graphitization carbon |
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- 2016-05-18 CN CN201610333350.9A patent/CN105826522B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102208610A (en) * | 2011-04-18 | 2011-10-05 | 北京工业大学 | Preparation method of carbon coated MnO cathode material |
| CN103500833A (en) * | 2013-10-23 | 2014-01-08 | 山东大学 | Method for preparing lithium iron phosphate positive electrode material coated by home position graphitization carbon |
Non-Patent Citations (1)
| Title |
|---|
| Hydrothermal Fabrication of MnCO3@rGO Composite as an Anode;Liankai Zhou et.al.;《Inorganic Chemistry》;20140821;全文 * |
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