CN107706374A - A kind of preparation method of graphene/manganese oxide composite material - Google Patents
A kind of preparation method of graphene/manganese oxide composite material Download PDFInfo
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- CN107706374A CN107706374A CN201710870183.6A CN201710870183A CN107706374A CN 107706374 A CN107706374 A CN 107706374A CN 201710870183 A CN201710870183 A CN 201710870183A CN 107706374 A CN107706374 A CN 107706374A
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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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- 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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- 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
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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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
- H01M4/58—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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- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
It is a kind of layered solid dusty material for lithium ion battery negative material herein, belongs to ion cathode material lithium applied technical field, it specifically has consisting of：MnO/RGO, wherein, the mass percent of graphene oxide is：10%~20%.MnO architectural feature is nano level stratiform framework in the material, compared with the ion cathode material lithium reported at present, the material has more preferable normal temperature circulation stability and high rate performance, and the material raw materials have natural abundance height, price is low, it is environment-friendly the features such as.
Description
Technical field
The invention belongs to electrochemical power source technical field of material, more particularly to a kind of lithium ion battery negative material
The preparation method of graphene/manganese oxide metal oxide.In conventional secondary lithium battery and power source cell negative electrode material
Field is with a wide range of applications.
Background technology
Lithium ion battery has the advantages that high-energy-density and power density and to be widely used in energy storage material etc. each
The mobile devices such as field, such as mobile phone, computer, electric automobile.Determine that performance of lithium ion battery is positive and negative pole material, and with just
Pole material is compared, and influence of the negative material to capacity of lithium ion battery becomes apparent from, but commercialized negative material is main at present
For carbon negative pole material, its theoretical capacity only has 372mAh/g, therefore the chemical property for improving negative material is current lithium ion
The major issue that battery faces.
Graphene has very excellent electron conduction and thermal conductivity as lithium ion battery negative material；For electrode
Grapheme material can reach nano-scale so that the migration distance of lithium ion wherein is very short, is favorably improved battery
Power-performance；Meanwhile graphene also has high theoretical specific surface area (2600m2g-1), the advantages that good mechanical performance.This
A little features all make preferred research material of the graphene as lithium ion battery negative material, but graphene is born as lithium ion battery
There is also some problems for pole material：1st, graphene is not suitable for large-scale production；2nd, graphene is easy to because Van der Waals force weighs again
Newly it is stacked into the transmission for together, influenceing lithium ion in graphene.Metal oxide has high theoretical capacity and wide because of it
General is applied in lithium ion battery negative material, and in transition metal oxide, nanoscale manganese because environment-friendly,
Cost is low, and natural abundance height is extensively studied.But its as ion cathode material lithium there is also some it is intrinsic the shortcomings that, example
The efflorescence as caused by volumetric expansion and reunion, electric conductivity are poor etc. to limit its practical application.
The defects of in order to improve metal oxide and graphene, we are by two kinds of Material claddings.In the composite, a side
Face, graphene can provide a good support platform for the formation of the nucleation of metal oxide, growth and nanostructured,
So that scattered more homogeneous of the nanostructured formed, pattern is more controllable；On the other hand, graphene can improve entirely
The electric conductivity of composite, alleviate volumetric expansion of the metal oxide during embedding and removing.And metal oxide can be with
Higher capacity is provided, at the same can reduce graphene reunion and lamella between secondary stacking, so as to improve graphite
The effective ratio surface of alkene, obtain higher electro-chemical activity.
At present, the synthetic method of MnO quasi-metal oxides negative material mainly includes hydro-thermal method, coprecipitation and liquid phase
The precipitation method.Hydrothermal synthesis method can obtain the higher material of purity, and can control the knot of material by changing synthesis condition
Configuration looks, compared with other methods, such a method is simple.But hydro-thermal method needs to react under high-temperature and high-pressure conditions, because
This requirement to container is higher.
The content of the invention
For overcome the deficiencies in the prior art, our present invention MnO/RGO composites, wherein graphene oxide quality hundred
Fraction is：10%~20%, MnO are layer structure, and material forms nano-sized particles, improve the electrochemistry of material
Can, add the commercialized possibility of this kind of material.
In order to solve the above-mentioned technical problem, the present invention relates to technical scheme it is as follows：
The present invention is a kind of nano level layered solid dusty material for lithium ion battery negative material, is had following
Composition：MnO/RGO composites, wherein graphene oxide mass percent are：10%~20%.
The present invention prepares comprising the following steps that for graphene/manganese oxide composite material：
(1) it is in mass ratio 10%~20% mixing by graphene oxide, manganese salt, then adds reducing agent, stirring makes it
Put it into after fully mixing in water-bath, add precipitating reagent after being warming up to 80 DEG C, continue to be warming up to 90 DEG C, above-mentioned solution is equal
Even is transferred in ptfe autoclave, in an oven hydro-thermal 12h at 120 DEG C, by the solution deionized water after hydro-thermal
Centrifuge washing 3 times, 12h is dried at 60 DEG C in an oven, obtains solid powder.
(2) obtained presoma is placed on the lower 500 DEG C of calcinings 2h of nitrogen atmosphere in tube furnace, be fully ground after cooling
To solid powder MnO/RGO, wherein graphite oxide mass percent is：10%~20%.
Compared with prior art, the beneficial effects of the invention are as follows：
Solid powder material structure prepared by the present invention is nano level layer structure, and this structure design makes solid powder
The cyclical stability and high rate performance of material are enhanced.It is and natural because the cost of raw material of the material is cheap
Abundance is high, it is environment-friendly the features such as, can meet the needs of in the market is applied to negative electrode of lithium ion battery.
Brief description of the drawings
Fig. 1 is ESEM (SEM) photo of example 1.
Fig. 2 is the X ray diffracting spectrum of example 1.
Fig. 3 is the first charge-discharge curve of example 1.
Fig. 4 is the discharge cycles curve of example 1.
Fig. 5 is the multiplying power figure of example 1.
Embodiment
It is used for the method for further illustrating that the present invention describes below by way of specific embodiment, it is not intended that of the invention
It is confined to these embodiments.
Embodiment 1：
A kind of preparation method of graphene/manganese oxide composite material, comprises the following steps：
0.08g graphite oxides are weighed in beaker, add in the aqueous solution of 160ml ethanol (volume ratio is ethanol: water=2:
1), ultrasound makes it be uniformly dispersed, and the water manganese acetates of 0.9907g tetra- are added in 40ml absolute ethyl alcohols, magnetic agitation to dissolving
15min, scattered graphene solution is added drop-wise in the ethanol solution of four water manganese acetates, after being sufficiently stirred, by 2ml
(1mmol/ml)H2O2Add in above-mentioned mixed solution, magnetic agitation 1h under normal temperature, the solution after stirring is transferred to water-bath
In, 80 DEG C are warming up to, 10ml 8mmol/ml KOH solution is added, after being added dropwise, water-bath pot temperature is risen to 90 DEG C, will be molten
Liquid is transferred in ptfe autoclave, hydro-thermal 12h at 120 DEG C, resulting solution deionized water centrifuge washing 3 times, 60
12h is dried at DEG C and obtains presoma, then, presoma is put into tube furnace in nitrogen atmosphere at 500 DEG C and calcines 2h, is obtained
MnO/RGO solid powders, wherein graphene oxide mass percent are：10%~20%.From the scanning electron microscope (SEM) photograph (Fig. 1) of material
It can be seen that manganese oxide is evenly distributed in the surface of graphene.MnO in XRD (Fig. 2) display material of material is cube
Phase solid powder, do not find that other dephasigns are present.(Fig. 3) is as can be seen that material from material at normal temperatures first charge-discharge figure
0.1C first discharge specific capacity is 997mAh/g under 0.01-3V, and initial charge specific capacity is 727mAh/g.From material normal
The lower cyclic curve figure (Fig. 4) of temperature is it can be seen that specific discharge capacity still can reach 410mAh/g after circulating 50 weeks.Exist from material
High rate performance figure (Fig. 5) under normal temperature is it can be seen that current density specific discharge capacity in 1A/g still can reach 320mAh/
g。
Embodiment 2：
A kind of preparation method of graphene/mangano-manganic oxide composite, comprises the following steps：
0.08g graphite oxides are weighed in beaker, add in the aqueous solution of 160ml ethanol (volume ratio is ethanol: water=2:
1), ultrasound makes it be uniformly dispersed, and the water manganese acetates of 0.9907g tetra- are added in 40ml absolute ethyl alcohols, magnetic agitation to dissolving
15min, scattered graphene solution is added drop-wise in the ethanol solution of four water manganese acetates, after being sufficiently stirred, by 2ml
(1mmol/ml)H2O2Add in above-mentioned mixed solution, magnetic agitation 1h under normal temperature, the solution after stirring is transferred to water-bath
In, 80 DEG C are warming up to, adds 10ml 8mmol/ml KOH solution, after being added dropwise, stands 12h at room temperature, resulting solution is used
Deionized water centrifuge washing 3 times, 12h is dried at 60 DEG C.Mangano-manganic oxide is can be seen that in stone from the scanning electron microscope (SEM) photograph of material
Reunite on black alkene serious.The XRD display material of material is Tetragonal Mn3O4Solid powder, do not find that other dephasigns are present.From
The first charge-discharge it can be seen from the figure that of material at normal temperatures, material 0.1C first discharge specific capacity under 0.01-3V are
930mAh/g, initial charge specific capacity are 609mAh/g.Circulation 50 weeks is can be seen that from the cyclic curve figure of material at normal temperatures
Specific discharge capacity has 270mAh/g afterwards, and circulation conservation rate is 29.06%.Can from the high rate performance figure of material at normal temperatures
Go out, current density specific discharge capacity in 1A/g is 170mAh/g.
Embodiment 3：
A kind of preparation method of graphene/mangano-manganic oxide composite, comprises the following steps：
0.08g graphite oxides are weighed in beaker, add in the aqueous solution of 160ml ethanol (volume ratio is ethanol: water=2:
1), ultrasound makes it be uniformly dispersed, and the water manganese acetates of 0.9907g tetra- are added in 40ml absolute ethyl alcohols, magnetic agitation to dissolving
15min, scattered graphene solution is added drop-wise in the ethanol solution of four water manganese acetates, after being sufficiently stirred, by 2ml
(1mmol/ml)H2O2Add in above-mentioned mixed solution, magnetic agitation 1h under normal temperature, the solution after stirring is transferred to water-bath
In, 80 DEG C are warming up to, 10ml 8mmol/ml KOH solution is added, after being added dropwise, water-bath pot temperature is risen to 90 DEG C, will be molten
Liquid is transferred in ptfe autoclave, hydro-thermal 12h at 120 DEG C, resulting solution deionized water centrifuge washing 3 times, 60
12h is dried at DEG C.Mangano-manganic oxide is can be seen that from the scanning electron microscope (SEM) photograph of material on graphene to reunite seriously.The XRD of material
Figure display material is Tetragonal Mn3O4Solid powder, do not find that other dephasigns are present.From the first charge-discharge of material at normal temperatures
It can be seen from the figure that, material 0.1C under 0.01-3V first discharge specific capacity is 1173mAh/g, and initial charge specific capacity is
724mAh/.From material at normal temperatures cyclic curve figure can be seen that circulation 50 weeks after specific discharge capacity be 315mAh/g, circulate
Conservation rate is 26.84%.Current density specific discharge capacity in 1A/g is can be seen that from the high rate performance figure of material at normal temperatures
Still 202mAh/g can be reached.
Although above in conjunction with figure, invention has been described, and the invention is not limited in above-mentioned specific embodiment party
Formula, above-mentioned embodiment is only schematical, rather than restricted, and one of ordinary skill in the art is in this hair
Under bright enlightenment, without deviating from the spirit of the invention, many variations can also be made, these belong to the guarantor of the present invention
Within shield.
Claims (8)
1. a kind of material for negative electrode of lithium ion battery, it is characterised in that there is following molecular formula composition：MnO/RGO wherein,
Graphite oxide mass percent is：10%~20%.
2. solid material according to claim 1, it is characterised in that the structure of the material is layer structure.
3. solid material according to claim 1, it is characterised in that the voltage scope of application of the material is in 0.01V-
3V。
4. the preparation method of the solid material described in claim 1, methods described comprises the following steps that：
(1) it is in mass ratio 10%~20% mixing by graphene oxide, manganese salt, then adds reducing agent, stirring makes its abundant
Put it into after mixing in water-bath after being warming up to 80 DEG C and add precipitating reagent, continue to be warming up to 90 DEG C, above-mentioned solution is uniform
It is transferred in ptfe autoclave, in an oven hydro-thermal 12h at 120 DEG C, the solution deionized water centrifugation after hydro-thermal is washed
Wash 3 times, dry 12h at 60 DEG C in an oven, obtain solid powder.
(2) obtained presoma is placed on the lower 500 DEG C of calcinings 2h of nitrogen atmosphere in tube furnace, is fully ground and is consolidated after cooling
Body powder MnO/RGO, wherein graphite oxide mass percent are：10%~20%.
5. the preparation method of solid material according to claim 4, it is characterised in that the manganese salt is four water manganese acetates.
6. preparation method according to claim 4, it is characterised in that the graphene is graphene oxide.
7. preparation method according to claim 4, it is characterised in that the precipitating reagent is potassium hydroxide.
8. preparation method according to claim 4, it is characterised in that the reducing agent is hydrogen peroxide.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110317005A (en) * | 2018-03-30 | 2019-10-11 | 中国电力科学研究院有限公司 | A kind of preparation method of three-dimensional hierarchical porous structure Graphene electrodes material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102185143A (en) * | 2011-04-02 | 2011-09-14 | 浙江大学 | Transition metal oxide/ graphene composite material and preparation method thereof |
| CN106252628A (en) * | 2016-08-30 | 2016-12-21 | 安徽师范大学 | The preparation method of a kind of manganese oxide/graphene nanocomposite material, lithium ion battery negative, lithium ion battery |
| KR101721968B1 (en) * | 2015-12-22 | 2017-03-31 | 울산과학기술원 | HIERARCHICAL MATERIAL INCLUDING URCHIN SHAPED MnO2, METHODE FOR SYNTHESIS THE SAME, AND AIR ELECTRODE AND METAL-AIR BATTERY INCLUDING THE SAME |
-
2017
- 2017-09-20 CN CN201710870183.6A patent/CN107706374A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102185143A (en) * | 2011-04-02 | 2011-09-14 | 浙江大学 | Transition metal oxide/ graphene composite material and preparation method thereof |
| KR101721968B1 (en) * | 2015-12-22 | 2017-03-31 | 울산과학기술원 | HIERARCHICAL MATERIAL INCLUDING URCHIN SHAPED MnO2, METHODE FOR SYNTHESIS THE SAME, AND AIR ELECTRODE AND METAL-AIR BATTERY INCLUDING THE SAME |
| CN106252628A (en) * | 2016-08-30 | 2016-12-21 | 安徽师范大学 | The preparation method of a kind of manganese oxide/graphene nanocomposite material, lithium ion battery negative, lithium ion battery |
Non-Patent Citations (1)
| Title |
|---|
| 涂飞跃: "石墨烯-Mn_xO_y的制备及其电化学性能研究", 《中国博士学位论文全文数据库工程科技Ⅰ辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110317005A (en) * | 2018-03-30 | 2019-10-11 | 中国电力科学研究院有限公司 | A kind of preparation method of three-dimensional hierarchical porous structure Graphene electrodes material |
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