CN108365185A - The preparation method of porous manganese sulfide and graphene composite material - Google Patents
The preparation method of porous manganese sulfide and graphene composite material Download PDFInfo
- Publication number
- CN108365185A CN108365185A CN201810017807.4A CN201810017807A CN108365185A CN 108365185 A CN108365185 A CN 108365185A CN 201810017807 A CN201810017807 A CN 201810017807A CN 108365185 A CN108365185 A CN 108365185A
- Authority
- CN
- China
- Prior art keywords
- composite material
- graphene
- manganese
- manganese sulfide
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- H01M4/364—Composites as mixtures
-
- 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
-
- 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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- 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
-
- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
The present invention relates to a kind of porous manganese sulfide as lithium cell cathode material and graphene composite materials and preparation method thereof.The main process of the method for the present invention and steps are as follows：Using suitable manganese source and sulphur source, uniform mixed solution is formed with graphene oxide, using hydro-thermal method, the crystallinity of further calcination process raising composite material, finally obtains porous manganese sulfide and graphene composite material after reaction.Composite material, which is made, in the present invention has good electric conductivity and structural stability, manganese sulfide microsphere surface is with concaveconvex structure and inside with microcellular structure, microcellular structure reduces the transmission path of lithium ion, and concaveconvex structure provides the specific surface area of more sites and bigger to store lithium ion and be come into full contact with electrolyte.The volume change for being introduced as charge and discharge process of graphene provides cushion space, improves the cyclical stability of composite material.The present invention is made composite material and can be used for the preparation of lithium ion battery and the performance of lithium ion battery can be improved.
Description
Technical field
The present invention relates to a kind of preparation sides of porous manganese sulfide and graphene composite material as lithium cell cathode material
Method belongs to technical field of lithium ion battery negative.
Background technology
Now, due to the exhaustion of global fossil fuel energy and outstanding day by day problem of environmental pollution, such as：Haze and water are dirty
Dye etc., therefore the urgency for developing clean energy resource of new generation becomes more and more important.And chargeable lithium ion battery is as a new generation
Energy storage device is of increasing concern.So developing low-cost, environmental-friendly, there is long-time stable cycle, high power capacity and high power
The electrode material of rate is very important.Since electrode material plays important role in chargeable lithium ion battery.
It is well known that the cathode of commercial li-ion battery is graphite now, theoretical specific capacity only has 372mAh/g, this severely limits into
One step develops high-capacity lithium ion cell.And transition metal sulfide（MoS2,WS2,SnS2）Much there is 600mAh/g-
The reversible specific capacity of 1100mAh/g is the graphite negative material of lithium ion battery during ideal negative material replacement is commercial.Recently,
Sulfide causes the concern of researchers in numerous areas, for example, ultracapacitor, solar cell, semiconductor, lithium ion
Battery, gas sensitive, catalysis material etc..However, often being filled when the transition metal of pure phase is as lithium ion battery negative material
It discharges during lithium ion insertion abjection, material occurs volume and caves in, and structure breaking is easy to cause capacity attenuation and poor follows
Ring performance and high rate performance.In addition, having proven to effective by the negative material for constructing hollow structure or porous structure
Approach improve the cycle performance of material.Because hollow or porous structure can provide more active sites to store
Lithium ion can effectively improve its capacity, moreover, unique hollow or porous structure can effectively shorten lithium ion biography
Defeated path, in addition, there is pore passage structure the specific surface area of bigger electrode to be allowed to be come into full contact with electrolyte.For example, passing through no template
The NiS hollow spheres of method synthesis present outstanding performance in solar cells, the SnO synthesized by hydro-thermal method2Porous material
Material is demonstrated by good cycle performance in lithium ion battery, the hollow Copper-cladding Aluminum Bar Mn synthesized also by hydro-thermal method2O3Structure exist
The chemical property that lithium ion battery has been shown.
Graphene is ideal framework material as two-dimentional carbon material, wherein composite semiconductor, metal sulfide, can be with
As the electrode material of good lithium battery, because of the mechanically actuated that graphene has had, lighter weight, high stable structure
Many advantages, such as property, good chemical stability, high conductivity, high specific surface area.The sulfide of different negative materials, oxidation
Chemical property is all improved after object and alloy and graphene are compound.Recently, existing researcher points out to grow on the surface of graphene
Sulfide grain can effectively prevent volume change, increase conductivity, and active site can provide lithium to a certain extent
Ion storage ability and cycle performance.Such as：CoS is grown on the surface of graphene2, it is compound after electrical property be much better than pure phase
CoS2.It is follow-up also to have more researchers successfully by sulfide and graphene Application of composite on lithium ion battery.It is many at
Graphene is that matrix is applied to lithium cell cathode material with sulfide composite material by fruit, is the more of matrix based on sulfide
Porous materials also largely improve the chemical property of lithium battery.Therefore, we are synthesized by simple hydro-thermal method
Manganese sulfide microballoon with cavernous structure and graphene complex, and composite sample presents high specific volume in lithium battery
Amount, outstanding cycle performance are expected to become the negative material in lithium battery.
Invention content
In view of the defects existing in the prior art, the object of the present invention is to provide porous manganese sulfides and graphene composite wood
Material and preparation method thereof.First, the porous structure of manganese sulfide can reduce bulk effect of the material in charge and discharge process；Separately
Outside, graphene is a kind of carbon material with special two-dimensional structure, can there is the volume that manganese sulfide is buffered in charge and discharge process
Expansion further increases the structural stability of material, and graphene-structured can improve the electric conductivity of material and ion passes
Defeated performance is effectively improved the insertion and abjection of lithium ion.
In order to achieve the above objectives, the present invention adopts the following technical scheme that.
1. the preparation method of porous manganese sulfide and graphene composite material, which is characterized in that the preparation method include with
Lower process steps：
A. 10 ~ 50 ml graphene oxides are measured（A concentration of 5 ~ 10 mg/ml）It is added in the distilled water of 100 ~ 200ml, super
Ultrasound 1 ~ 3 hour, forms uniform graphene oxide suspension in the Ultrasound Instrument that acoustical power is 45W；
B. 3 ~ 5 grams of manganese source is then weighed, 2 ~ 5 grams of sulphur sources and 0.2 ~ 1 gram of urea are separately added into the oxidation that above-mentioned steps a is obtained
In graphene solution, which is placed in double aobvious constant temperature blender with magnetic force in magnetic agitation 0.5 hour, is formed uniform
Mixed liquor；
C. the obtained mixed liquors of above-mentioned steps b are then transferred to reaction kettle, place in baking oven and are maintained at 160 ~ 200 DEG C instead
It answers 24 hours；It waits for after reaction, being cooled to room temperature, take out reaction kettle and opens, washed respectively three times with water and ethyl alcohol, then will
Intermediate is transferred in vacuum drying chamber and is dried in vacuum overnight for 80 DEG C, obtains black solid powder；
D. then the obtained solid powders of above-mentioned steps c are placed in tube furnace, with 3 degree of heating rates per minute in nitrogen
Under the conditions of 300 ~ 500 DEG C calcine 4 hours；After calcining, sample is taken out, that is, obtains porous manganese sulfide and graphene composite wood
Material.
2. the preparation method of porous manganese sulfide and graphene composite material according to claim 1, feature exist
In the manganese source described in the step b is any one of manganese chloride, manganese nitrate, manganese sulfate, and the sulphur source is thiocarbamide, sulphur
For any one of acetamide, L-cysteine, carbon disulfide.
The advantages and features of the present invention
Compared with other manganese sulfide/graphene composite materials, the composite material that we prepare has structure following prominent and property
It can feature：
(1) prepare that composite porous preparation process is relatively easy, and cost is relatively low.
(2) for manganese sulfide microsphere surface with concaveconvex structure and internal with microcellular structure, microcellular structure reduces lithium ion
Transmission path, concaveconvex structure provide the specific surface area of more sites and bigger store lithium ion and with electrolyte it is abundant
Contact.
(3) structural stability of manganese sulfide microballoon is increased by introducing graphene, it is made in charge and discharge process to be volume
Variation provides cushion space, improves the cyclical stability of composite material.
(4) graphene introduces the conductivity for improving composite material, can improve the high rate performance of material.
Description of the drawings
Fig. 1 is the XRD spectrum of porous manganese sulfide and graphene composite material prepared by embodiment 1；
Fig. 2 is the SEM pictures of porous manganese sulfide and graphene composite material prepared by embodiment 1；
Fig. 3 is the TEM pictures of porous manganese sulfide and graphene composite material prepared by embodiment 1；
Fig. 4 is the BET curves of porous manganese sulfide and graphene composite material prepared by embodiment 1；
Fig. 5 is the curve of double curvature of porous manganese sulfide and graphene composite material prepared by embodiment 1；
Fig. 6 is the cyclic curve of porous manganese sulfide and graphene composite material prepared by embodiment 1.
Specific implementation mode
The method further illustrated the present invention below by embodiment.
Embodiment 1
One, preparing porous manganese sulfide and graphene composite material, steps are as follows：
Measure 10 ml graphene oxides（A concentration of 10 mg/ml）It is added in the distilled water of 150 ml, is 45 in ultrasonic power
Ultrasound 1 hour in the Ultrasound Instrument of W.
Then the 50% concentration manganese nitrate solution of 3 g is weighed, 3 g L-cysteines and 0.5 g urea are separately added into
In the graphite oxide solution stated, which is placed in double aobvious constant temperature blender with magnetic force in 0.5 h of magnetic agitation.Then will
Solution is transferred to reaction kettle, places in baking oven and is maintained at 160 DEG C and reacts 24 hours.
It waits for after reaction, being cooled to room temperature, take out reaction kettle and opens, washed respectively three times with water and ethyl alcohol, then will
Intermediate is transferred to 80 degree of one nights of vacuum drying in vacuum drying chamber, and then obtained solid powder is placed in tube furnace,
It is calcined 4 hours for 500 degree under a nitrogen atmosphere with 3 degree of heating rates per minute.After calcining, sample is taken out, that is, is obtained porous
Manganese sulfide and graphene composite material.
The electric performance test of material is made：
By the product of preparation with composite material：Carbon black：PTFE mass ratioes are 85:10:5 ratio, which is directly rolled, wears into piece, blunderbuss poling
Piece is pressed on copper mesh to get working electrode.Using metal lithium sheet as cathode, using microporous polypropylene membrane as diaphragm, l.0 electrolyte is
The EC/DMC solution of mol/L LiPF6（Volume ratio 1:1）, CR2032 type button cells are assembled in the glove box full of argon gas.
The XRD of product as shown in Figure 1, as seen from the figure we prepare composite material in the manganese sulfide containing pure phase, the product
It is middle without apparent impurity peaks.Fig. 2 is the scanning electron microscope of the composite material prepared（SEM）Photo, it can be seen that manganese sulfide microballoon it is straight
Diameter is about at 1-2 μm, and manganese sulfide microballoon is largely all grown in the hole that graphene is formed；The structure of this package can be with
Enhance the degree of adhesion of manganese sulfide on the surface of graphene, increase the conductivity of manganese sulfide, can be that charge and discharge process material structure collapses
It collapses and buffering is provided, to increase the stability of cyclic process；In addition manganese sulfide and surface of the graphene after compound are more coarse, tool
There are the surface area and electrolyte contacts of bigger, additionally it is possible to more sites are provided and facilitate Li+Storage and transmission.It is prepared by Fig. 3
The transmission electron microscope of composite material（TEM）Photo, it can be seen that graphene is covered in microsphere surface, and surface texture is uneven,
Ball center is relatively thin and has penetrating duct, so specific surface area and more active sites with stable structure and bigger.Fig. 4
It is the BET curves of the composite material prepared.As seen from the figure, according to International Union of Pure and Applied Chemistry (IUPAC) to absorption
The classification of desorption isotherm, sample belong to IV type adsorption/desorption isotherms.All there is the apparent capillary condensation stage, imply conjunction
At sphere material all there is mesoporous property, and retardant curve is very narrow and thin, implies in sample that there are poroid knots
Structure increases electro-chemical activity surface and increases lithium ion memory capacity.Fig. 5 is the curve of double curvature of the composite material prepared,
It is recycled 5 times under 0.1 A/g current densities, then recycles at 0.2 A/g, 0.5 A/g, 1 A/g, then restore again successively
0.1 A/g current densities recycle, and when current density increases to 1 A/g from 0.1 A/g, the specific capacity of composite material is from 1711
MAh/g is reduced to 970 mAh/g, and finally when current density is restored to 0.1 A/g, the specific capacity of composite material is being passed through 80 times
After cycle, and 1200 mAh/g can be reached, the state being restored to after initial 5th cycle, then during this, coulombic efficiency by
Step is stable at 100%.This illustrates that the cyclical stability under each current density of composite material and high rate performance are good, this with
The analysis of first-class means of testing is consistent.Fig. 6 is the cyclic curve of the composite material prepared, should under 100 mA/g current densities
Material is no in cyclic process to decay, and due to the activation of electrode, apparent rising occurs in capacity, is recycled at 90 times
Specific capacity can be maintained at 1300 mAh/g afterwards, show that this material has good cycle performance.
Embodiment 2
Measure 20 ml graphene oxides（A concentration of 10 mg/ml）It is added in the distilled water of 200 ml, is 45 in ultrasonic power
Ultrasound 1 hour in the Ultrasound Instrument of W.
Then the 50% concentration manganese nitrate solution of 3.58 g, 2.42 g L-cysteines and 0.60 g urea difference are weighed
It is added in above-mentioned graphite oxide solution, which is placed in double aobvious constant temperature blender with magnetic force in 0.5 h of magnetic agitation.
Then solution is transferred to reaction kettle, places in baking oven and be maintained at 160 DEG C and reacts 24 hours.
It waits for after reaction, being cooled to room temperature, take out reaction kettle and opens, washed respectively three times with water and ethyl alcohol, then will
Intermediate is transferred to 80 degree of one nights of vacuum drying in vacuum drying chamber, and then obtained solid powder is placed in tube furnace,
It is calcined 4 hours for 500 degree under a nitrogen atmosphere with 3 degree of heating rates per minute.After calcining, sample is taken out, that is, is obtained porous
Manganese sulfide and graphene composite material.
Embodiment 3
Measure 20 ml graphene oxides（A concentration of 5 mg/ml）It is added in the distilled water of 100 ml, is 45 W in ultrasonic power
Ultrasound Instrument in ultrasound 1 hour.
Then the 50% concentration manganese nitrate solution of 3.62 g is weighed, 2.62 g thiocarbamides and 0.60 g urea are separately added into
In the graphite oxide solution stated, which is placed in double aobvious constant temperature blender with magnetic force in 0.5 h of magnetic agitation.Then will
Solution is transferred to reaction kettle, places in baking oven and is maintained at 160 DEG C and reacts 24 hours.
It waits for after reaction, being cooled to room temperature, take out reaction kettle and opens, washed respectively three times with water and ethyl alcohol, then will
Intermediate is transferred to 80 degree of one nights of vacuum drying in vacuum drying chamber, and then obtained solid powder is placed in tube furnace,
It is calcined 4 hours for 300 degree under a nitrogen atmosphere with 3 degree of heating rates per minute.After calcining, sample is taken out, that is, is obtained porous
Manganese sulfide and graphene composite material.
Embodiment 4
Measure 20 ml graphene oxides（A concentration of 10 mg/ml）It is added in the distilled water of 200 ml, is 45 in ultrasonic power
Ultrasound 1 hour in the Ultrasound Instrument of W.
Then the 50% concentration sulphuric acid manganese solution of 3.76 g, 2.65 g thioacetamides and 0.80 g urea difference are weighed
It is added in above-mentioned graphite oxide solution, which is placed in double aobvious constant temperature blender with magnetic force in 0.5 h of magnetic agitation.
Then solution is transferred to reaction kettle, places in baking oven and be maintained at 180 DEG C and reacts 24 hours.
It waits for after reaction, being cooled to room temperature, take out reaction kettle and opens, washed respectively three times with water and ethyl alcohol, then will
Intermediate is transferred to 80 degree of one nights of vacuum drying in vacuum drying chamber, and then obtained solid powder is placed in tube furnace,
It is calcined 4 hours for 400 degree under a nitrogen atmosphere with 3 degree of heatings per minute.After calcining, sample is taken out, that is, obtains porous vulcanization
Manganese and graphene composite material.
Claims (2)
1. the preparation method of porous manganese sulfide and graphene composite material, which is characterized in that the preparation method includes following mistake
Journey step：
A. 10 ~ 50 ml graphene oxides are measured（A concentration of 5 ~ 10 mg/ml）It is added in the distilled water of 100 ~ 200ml, super
Ultrasound 1 ~ 3 hour, forms uniform graphene oxide suspension in the Ultrasound Instrument that acoustical power is 45W；
B. 3 ~ 5 grams of manganese source is then weighed, 2 ~ 5 grams of sulphur sources and 0.2 ~ 1 gram of urea are separately added into the oxidation that above-mentioned steps a is obtained
In graphene solution, which is placed in double aobvious constant temperature blender with magnetic force in magnetic agitation 0.5 hour, is formed uniform
Mixed liquor；
C. the obtained mixed liquors of above-mentioned steps b are then transferred to reaction kettle, place in baking oven and are maintained at 160 ~ 200 DEG C instead
It answers 24 hours；It waits for after reaction, being cooled to room temperature, take out reaction kettle and opens, washed respectively three times with water and ethyl alcohol, then will
Intermediate is transferred in vacuum drying chamber and is dried in vacuum overnight for 80 DEG C, obtains black solid powder；
D. then the obtained solid powders of above-mentioned steps c are placed in tube furnace, with 3 degree of heating rates per minute in nitrogen
Under the conditions of 300 ~ 500 DEG C calcine 4 hours；After calcining, sample is taken out, that is, obtains porous manganese sulfide and graphene composite wood
Material.
2. the preparation method of porous manganese sulfide and graphene composite material according to claim 1, which is characterized in that described
Manganese source described in step b is any one of manganese chloride, manganese nitrate, manganese sulfate, and the sulphur source is thiocarbamide, thioacetyl
Any one of amine, L-cysteine, carbon disulfide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810017807.4A CN108365185A (en) | 2018-01-09 | 2018-01-09 | The preparation method of porous manganese sulfide and graphene composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810017807.4A CN108365185A (en) | 2018-01-09 | 2018-01-09 | The preparation method of porous manganese sulfide and graphene composite material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108365185A true CN108365185A (en) | 2018-08-03 |
Family
ID=63011174
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810017807.4A Pending CN108365185A (en) | 2018-01-09 | 2018-01-09 | The preparation method of porous manganese sulfide and graphene composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108365185A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109473643A (en) * | 2018-10-17 | 2019-03-15 | 长沙学院 | A kind of CoSe2/ graphene composite material preparation method and purposes |
| CN109748322A (en) * | 2018-12-15 | 2019-05-14 | 河南大学 | The synthetic method and application of α-MnS nanoparticle and α-MnS/rGO composite material |
| CN110148717A (en) * | 2019-04-28 | 2019-08-20 | 东莞市戎科科技有限公司 | A kind of N doping graphene oxide/manganese sulfide carries sulphur composite material and preparation method and application |
| CN110828802A (en) * | 2019-11-07 | 2020-02-21 | 吉首大学 | Preparation method of high-power aqueous zinc ion battery positive electrode material |
| CN113329604A (en) * | 2021-05-18 | 2021-08-31 | 北京科技大学 | Preparation method of manganese sulfide and graphene electromagnetic wave absorption composite material |
| CN114229902A (en) * | 2021-12-20 | 2022-03-25 | 中原工学院 | Gamma/alpha heterogeneous-containing manganese sulfide and preparation method and application thereof |
| CN114686892A (en) * | 2022-03-03 | 2022-07-01 | 青岛理工大学 | Z-type graphene-sulfide composite photo-anode material and preparation method and application thereof |
| CN114725356A (en) * | 2022-05-06 | 2022-07-08 | 四川大学 | Mn-based heterogeneous compound/carbon composite material with limited domain structure and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106159239A (en) * | 2016-08-30 | 2016-11-23 | 安徽师范大学 | The preparation method of a kind of Manganese monosulfide ./graphene nanocomposite material, lithium ion battery negative, lithium ion battery |
-
2018
- 2018-01-09 CN CN201810017807.4A patent/CN108365185A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106159239A (en) * | 2016-08-30 | 2016-11-23 | 安徽师范大学 | The preparation method of a kind of Manganese monosulfide ./graphene nanocomposite material, lithium ion battery negative, lithium ion battery |
Non-Patent Citations (1)
| Title |
|---|
| XIJUN XU等: ""In Situ Synthesis of MnS Hollow Microspheres on Reduced Graphene Oxide Sheets as High-Capacity and Long-Life Anodes for Li- and Na-Ion Batteries"", 《APPLIED MATERIALS & INTERFACES》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109473643A (en) * | 2018-10-17 | 2019-03-15 | 长沙学院 | A kind of CoSe2/ graphene composite material preparation method and purposes |
| CN109473643B (en) * | 2018-10-17 | 2021-06-25 | 长沙学院 | CoSe2Preparation method and application of graphene composite material |
| CN109748322A (en) * | 2018-12-15 | 2019-05-14 | 河南大学 | The synthetic method and application of α-MnS nanoparticle and α-MnS/rGO composite material |
| CN110148717A (en) * | 2019-04-28 | 2019-08-20 | 东莞市戎科科技有限公司 | A kind of N doping graphene oxide/manganese sulfide carries sulphur composite material and preparation method and application |
| CN110828802A (en) * | 2019-11-07 | 2020-02-21 | 吉首大学 | Preparation method of high-power aqueous zinc ion battery positive electrode material |
| CN113329604A (en) * | 2021-05-18 | 2021-08-31 | 北京科技大学 | Preparation method of manganese sulfide and graphene electromagnetic wave absorption composite material |
| CN114229902A (en) * | 2021-12-20 | 2022-03-25 | 中原工学院 | Gamma/alpha heterogeneous-containing manganese sulfide and preparation method and application thereof |
| CN114229902B (en) * | 2021-12-20 | 2023-09-15 | 中原工学院 | Manganese sulfide containing gamma/alpha heterogeneous junction and preparation method and application thereof |
| CN114686892A (en) * | 2022-03-03 | 2022-07-01 | 青岛理工大学 | Z-type graphene-sulfide composite photo-anode material and preparation method and application thereof |
| CN114686892B (en) * | 2022-03-03 | 2023-11-03 | 青岛理工大学 | Z-type graphene-sulfide composite photo-anode material and preparation method and application thereof |
| CN114725356A (en) * | 2022-05-06 | 2022-07-08 | 四川大学 | Mn-based heterogeneous compound/carbon composite material with limited domain structure and preparation method and application thereof |
| CN114725356B (en) * | 2022-05-06 | 2023-04-07 | 四川大学 | Mn-based heterogeneous compound/carbon composite material with limited domain structure and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108365185A (en) | The preparation method of porous manganese sulfide and graphene composite material | |
| CN105845889B (en) | A kind of NiCo2O4Composite material and preparation method and its application on lithium ion battery | |
| RU2672675C2 (en) | Tungsten-based material, super battery and supercapacitor | |
| CN106914244B (en) | A kind of graphene-based metallic compound nano array material preparation and application | |
| CN105576223B (en) | A kind of tin oxide base negative electrode material and preparation method thereof with high reversible capacity | |
| CN111180709B (en) | Carbon nano tube and metal copper co-doped ferrous oxalate lithium battery composite negative electrode material and preparation method thereof | |
| CN110649271B (en) | Co-N/C @ MoS2Composite material, preparation method thereof and application thereof in lithium air battery | |
| CN108520944A (en) | A kind of nitrogen-doped carbon cladding mangano-manganic oxide composite material and preparation method and application | |
| CN113839038A (en) | MOF-derived Bi @ C nano composite electrode material and preparation method thereof | |
| CN110176601A (en) | A kind of carbon coating oxidation Asia silicium cathode material and its preparation method and application | |
| CN109301209B (en) | Preparation method of titanium dioxide modified phosphorus/carbon composite negative electrode material | |
| CN108630923A (en) | Nickel cobalt lithium aluminate cathode material, preparation method and the lithium battery of gradient sodium ion doping | |
| CN109671935B (en) | Preparation method and application of silicon dioxide/biochar composite material | |
| CN114300659B (en) | Method for synthesizing hard carbon coated sodium ion battery nanocomposite and application thereof | |
| CN115172709A (en) | High-performance strontium-doped ternary sodium-ion battery positive electrode material and preparation method thereof | |
| CN116314739B (en) | Manganese-based layered oxide positive electrode material and preparation method and application thereof | |
| CN107195884A (en) | A kind of lithium metasilicate doped graphene lithium ion battery negative material and preparation method thereof | |
| CN114256460B (en) | Large-scale preparation of high-crystallization Prussian blue analogues for sodium ion battery by using salt water-in-water microreactor principle | |
| CN110931726A (en) | Lithium titanate negative electrode composite material, preparation method thereof and lithium ion battery | |
| CN110336026A (en) | The preparation method and water system sodium-ion battery of water system sodium-ion battery positive material | |
| CN109192960A (en) | A kind of MnO/ cellulose base porous carbon and preparation method thereof and the application in lithium ion battery negative material | |
| CN111755691B (en) | Preparation method of bimetallic sulfide for sodium-sulfur secondary battery | |
| CN109873147B (en) | Carbon-modified porous ZnO nano material and preparation method and application thereof | |
| CN108198700B (en) | A kind of preparation method and applications of graphene-carbon nano tube/cobalt manganese alloy oxide nano-slice compound | |
| CN106299349B (en) | Lithium ion battery adulterates the preparation method of lithium nickelate material with holmium |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180803 |
|
| RJ01 | Rejection of invention patent application after publication |