CN110492071A - Inner wall is loaded with the hollow carbon sphere and preparation method and purposes of nickel hydroxide and sulphur - Google Patents
Inner wall is loaded with the hollow carbon sphere and preparation method and purposes of nickel hydroxide and sulphur Download PDFInfo
- Publication number
- CN110492071A CN110492071A CN201910764939.8A CN201910764939A CN110492071A CN 110492071 A CN110492071 A CN 110492071A CN 201910764939 A CN201910764939 A CN 201910764939A CN 110492071 A CN110492071 A CN 110492071A
- Authority
- CN
- China
- Prior art keywords
- sulphur
- loaded
- hollow carbon
- carbon sphere
- sio
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
-
- 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
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
-
- 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 hollow carbon sphere of nickel hydroxide and sulphur is loaded with the invention discloses a kind of inner wall and preparation method and purposes, this method include: (1) by SiO2Ball is dispersed in ethanol-water mixture, and nickel sulfate stirring is added, instills ammonium hydroxide, obtains SiO2/Ni(OH)2；(2) by SiO2/Ni(OH)2It is added with the mixture of dopamine into ethanol-water mixture, is added trishydroxymethylaminomethane, obtains composite material；(3) under atmosphere of inert gases, step (2) composite material is carbonized, HCl cleaning, strong base solution impregnates, and obtains composite material；(4) step (3) composite material and elemental sulfur are ground, is heated under atmosphere of inert gases at 150~170 DEG C, temperature is increased to 190~210 DEG C of heat preservations, obtains Ni (OH)2@HCS-S composite material.Material of the invention effectively can inhibit polysulfide to dissolve, and improve the long-term circulation specific capacitance of material.
Description
Technical field
The present invention relates to a kind of S composite materials, and in particular to a kind of inner wall be loaded with nickel hydroxide and sulphur hollow carbon sphere and
Preparation method and use.
Background technique
Demand of the electric car to high-energy density and long circulation life energy-storage system is higher and higher, in recent decades, people
Have studied a variety of energy storage devices, including lithium ion battery, lithium-air battery and lithium-sulfur cell.Since lithium-sulfur cell (Li-S) is managed
It is very high by specific capacity (1675mAh/g) and energy density (2600Wh/kg), it is most promising one of energy-storage system.
However, the dissolution of polysulfide and caused sulphur anode volume is swollen in electrochemistry cyclic process in lithium-sulfur cell
Swollen, the utilization rate that will lead to the serious capacity attenuation of lithium-sulfur cell and active material reduces, to the commercialization band of lithium ion battery
Huge difficulty is carried out.To solve these problems, scientific research personnel cathode material structure design, novel electrolytes use, every
The transformation of film, the protection of cathode of lithium etc. have carried out a large amount of research, to improve the chemical property of lithium ion battery.
In cathode material structure design method, scientific research personnel has studied various porous carbon materials in conjunction with sulphur, with enhancing
The chemical property of sulphur anode, including carbon nanotube, graphene, Nano carbon fibers peacekeeping other hollow carbon structures, sulphur/carbon of synthesis
Composite material improves circulating battery stability and specific capacity as anode.
But the combination of sulphur and carbon is that is relied on is the weak physical absorption that nonpolar carbon matrix provides, in charge and discharge cycles process
In cannot effectively inhibit the dissolution of polarity polysulfide, to limit further mentioning for circulating battery stability and specific capacity
It is high.
Summary of the invention
The object of the present invention is to provide hollow carbon sphere and preparation method and purposes that a kind of inner wall is loaded with nickel hydroxide and sulphur,
Solving the problems, such as that the combination of sulphur and carbon in current material is weak leads to that the dissolution of polarity polysulfide, Neng Gouyou cannot be effectively inhibited
Effect inhibits polysulfide dissolution, improves the coulombic efficiency of the long-term circulation specific capacitance of material, cyclical stability and charge/discharge.
In order to achieve the above object, the preparation of the hollow carbon sphere of nickel hydroxide and sulphur is loaded with the present invention provides a kind of inner wall
Method, this method include:
(1) by SiO2Ball is dispersed in ethanol-water mixture, and nickel sulfate stirring is added, instills ammonium hydroxide, is stirred at room temperature, receives
Collect deposit, obtains SiO2/Ni(OH)2；Wherein, the SiO2Quality, nickel sulfate mole and the ratio between the volume of ammonium hydroxide be
1g:0.004mol:10mL；
(2) by the SiO2/Ni(OH)2It is added with the mixture of dopamine into ethanol-water mixture, is added three hydroxyls
Aminomethane, stirring, resulting deposit are SiO2/Ni(OH)2@PDA composite material；Wherein, the SiO2/Ni
(OH)2, dopamine and trishydroxymethylaminomethane mass ratio be 1:(1.25~1.5): (0.3~0.5)；
(3) under atmosphere of inert gases, by the SiO2/Ni(OH)2@PDA composite material heats carbon at 700~800 DEG C
Change, after being carbonized, cleaned with HCl, then impregnated in strong base solution and remove silica, obtains Ni (OH)2@HCS is compound
Material；Wherein, the strong base solution includes: potassium hydroxide solution and/or Strong oxdiative sodium solution；
(4) by the Ni (OH)2@HCS composite material and elemental sulfur are obtained grinding with the mixed grinding of mass ratio 1:3~5
Mixture heated under atmosphere of inert gases at 150~170 DEG C, then raise the temperature to 190~210 DEG C heat preservation to go
Except being attached to Ni (OH)2The sulfur granules of@HCS composite material surface obtain the hollow carbon sphere that inner wall is loaded with nickel hydroxide and sulphur.
Preferably, in step (1), the volume ratio of ethyl alcohol and water is 0.6~1.2:1 in the ethanol-water mixture；In
In step (2), the volume ratio of ethyl alcohol and water is 0.4~0.8:1 in the ethanol-water mixture.
Preferably, described that the time is stirred at room temperature as 1~2h in step (1).
Preferably, in step (1), the ammonium hydroxide rate of addition is 10mL/h.
Preferably, in step (2), the mixing time is 5~8h.
Preferably, in step (3), the concentration of the HCl is 1.5~2mol/L；The concentration of the strong base solution be 8~
10mol/L。
Preferably, in step (3), the time of the heating carbonization is 2~4h；In the strong base solution impregnate 24~
30h。
Preferably, the inert gas includes: nitrogen, argon gas.
The present invention also provides the hollow carbon sphere that a kind of inner wall is loaded with nickel hydroxide and sulphur, which is using described
Method preparation.
The present invention also provides the purposes that the inner wall described in one kind is loaded with the hollow carbon sphere of nickel hydroxide and sulphur, the hollow carbon
Positive electrode of the ball as lithium-sulfur cell.
Inner wall of the invention is loaded with the hollow carbon sphere and preparation method and purposes of nickel hydroxide and sulphur, solves current material
The combination of middle sulphur and carbon is weak to lead to the problem of cannot effectively inhibiting the dissolution of polarity polysulfide, has the advantage that
Method of the invention is by Ni (OH)2It is deposited on SiO2On ball, the then carbon coated forerunner on poly bar amine (PDA) shell
Body has synthesized SiO2/Ni(OH)2@PDA composite material converts carbon for PDA by carbonization technique, by KOH erosion removal
Portion SiO2Core penetrates into sulphur in NH@HCS finally by heat treatment, so that obtaining inner wall is loaded with Ni (OH)2Nanoparticle and S's
Hollow carbon sphere.Due to Ni (OH)2It is excellent electrode material and contains abundant dynamic polarity/hydrophilic radical, is limited in conjunction with sulphur
The dissolution of polysulfide can provide physical absorption for the combination between mesoporous carbon spheres and polysulfides.Ni (OH) of the invention2@
HCS-S composite material is used as the electrode material of lithium-sulfur cell, and it is good that lithium-sulfur cell recycles the relatively high and stable property of specific capacitance for a long time, fill/
The coulombic efficiency of electric discharge is high.
Detailed description of the invention
Fig. 1 is the SEM figure of the NH@HCS-S compound of the embodiment of the present invention 3.
Fig. 2 is each element mapping reference figure in the NH@HCS-S compound of the embodiment of the present invention 3.
Fig. 3 is that the NH@HCS-S compound of the embodiment of the present invention 3 recycles 500 periods as anode at current density 1C
Specific capacity and coulombic efficiency figure.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
Embodiment 1
A kind of inner wall is loaded with the preparation method of the hollow carbon sphere of nickel hydroxide and sulphur, includes:
(1)SiO2/Ni(OH)2Synthesis:
By 1g SiO2Ball is dispersed in 60mL ethyl alcohol and the mixed liquor of 100mL deionized water, is then added 0.004mol's
NiSO4·6H2O stirs into stable solution.10mL ammonium hydroxide is instilled again, reacts ammonia sufficiently, prevents from largely volatilizing, rate of addition
1h is stirred at room temperature in 10mL/min in control.Hereafter, deposit, as SiO are collected by centrifugation2/Ni(OH)2,
It is washed and is dried with ethyl alcohol and deionized water.
(2)SiO2/Ni(OH)2@PDA synthesis:
By 1g SiO2/Ni(OH)280mL ethyl alcohol and 100mL deionized water is added in the mixture of powder and 1.5g dopamine
In mixed liquor, then it is added 0.5g trishydroxymethylaminomethane, and continuously stir 8h, it is resulting with deionized water centrifuge washing
Deposit is SiO after dry2/Ni(OH)2@PDA composite material.Wherein, trishydroxymethylaminomethane plays the role of buffer,
Be conducive to poly-dopamine and be wrapped in SiO2/Ni(OH)2Particle surface；
(3)Ni(OH)2The synthesis of@HCS composite material:
In a nitrogen atmosphere, by SiO2/Ni(OH)2@PDA composite material heats 2h at 700 DEG C and is carbonized.Carbonization knot
Shu Hou, with 1.5mol/L HCl cleaning sample, HCl solution non-oxidative is unable to the oxidizing H of apparatus2SO4And HNO3, HCl
For washing remaining Ni (OH)2, dopamine and trishydroxymethylaminomethane.Finally, in 8mol/L potassium hydroxide solution
Immersion removes silica for 24 hours, has obtained Ni (OH)2@HCS composite material.With deionized water centrifuge washing Ni (OH)2@HCS is multiple
Condensation material, and the dry 12h at 60 DEG C.Gained sample is expressed as NH@HCS composite material.
(4)Ni(OH)2The synthesis of@HCS-S composite material:
Using ethyl alcohol as dispersing agent, by Ni (OH)2@HCS composite material and elemental sulfur are ground with the ratio of mass ratio 1:3 in agate
Mixed grinding 30min in alms bowl.The mixture that grinding obtains is heated into 12h at 150 DEG C under an argon, S is made to penetrate into Ni
(OH)2Inside@HCS, 190 DEG C of heat preservation 2h are then raised the temperature to, Ni (OH) is attached to removal2@HCS composite material surface
Sulfur granules.Gained sample is expressed as NH@HCS-S compound.
Embodiment 2
A kind of inner wall is loaded with the preparation method of the hollow carbon sphere of nickel hydroxide and sulphur, basic with the preparation method of embodiment 1
Identical, difference is:
In step (1), SiO2Dosage is 2g, ethanol consumption 120mL, NiSO4·6H2The dosage of O is 0.008mol,
Ammonia volume is 20mL, and 2h is stirred at room temperature；
In step (3), by SiO2/Ni(OH)2@PDA composite material heats 4h at 800 DEG C and is carbonized；Use 2mol/L
HCl cleaning sample；30h is impregnated in 10mol/L potassium hydroxide solution removes silica；With deionized water centrifuge washing Ni
(OH)2@HCS composite material, and the dry 16h at 60 DEG C；
In step (4), Ni (OH)2The ratio of@HCS composite material and elemental sulfur is 1:5, mixed grinding 50min；It will grind
It grinds obtained mixture and heats 15h under an argon at 160 DEG C, temperature is increased to 200 DEG C of heat preservation 4h.
Embodiment 3
A kind of inner wall is loaded with the preparation method of the hollow carbon sphere of nickel hydroxide and sulphur, basic with the preparation method of embodiment 1
Identical, difference is:
In step (2), SiO2/Ni(OH)2Powder dosage is 0.5g, and dopamine dosage is 0.75g, and ethanol consumption is
40mL, trishydroxymethylaminomethane dosage are 0.25g, continuously stir 5h；
In step (3), impregnates 30h and remove silica；
In step (4), mixed grinding 30min.
Embodiment 4
A kind of inner wall is loaded with the preparation method of the hollow carbon sphere of nickel hydroxide and sulphur, basic with the preparation method of embodiment 1
Identical, difference is:
In step (1), SiO2Dosage is 1.5g, ethanol consumption 100mL, NiSO4·6H2The dosage of O is
0.006mol, ammonia volume 15mL, is stirred at room temperature 1.5h；
In step (2), SiO2/Ni(OH)2Powder dosage be 0.8g, dopamine dosage be 1g, ethanol consumption 60mL,
Trishydroxymethylaminomethane dosage is 0.3g, continuously stirs 6h；
In step (3), by SiO2/Ni(OH)2@PDA composite material heats 3h at 750 DEG C and is carbonized；With
1.8mol/L HCl cleaning sample；28h is impregnated in 9mol/L potassium hydroxide solution removes silica；It is centrifuged with deionized water
It washs Ni (OH)2@HCS composite material, and the dry 14h at 60 DEG C；
In step (4), Ni (OH)2The ratio of@HCS composite material and elemental sulfur is 1:4, mixed grinding 40min；It will grind
It grinds obtained mixture and heats 13h under an argon at 170 DEG C, temperature is increased to 210 DEG C of heat preservation 3h.
The structure of NH@HCS-S compound prepared by the embodiment of the present invention 3 is analyzed, as shown in Figure 1, for the present invention
The SEM of the NH@HCS-S compound of embodiment 3 schemes, it can be seen that NH@HCS-S compound is evident as hollow sphere structure.Such as Fig. 2 institute
Show, is that referring to figure, four kinds of elements of C, Ni, O, S uniformly divide for each element mapping in the NH@HCS-S compound of the embodiment of the present invention 3
Cloth shows that S can have been penetrated into the hollow structure of NH@HCS at 150 DEG C in the hollow structure of NH@HCS.
Electrochemical property test is carried out to NH@HCS-S compound prepared by the embodiment of the present invention 3, it is compound with NH@HCS-S
Object is that positive electrode assembles half-cell, carries out charge and discharge/electricity experiment.Specifically, by assembling CR2016 coin half-cell to it
Chemical property is tested:
Firstly, with N-Methyl pyrrolidone (NMP) for solvent, the NH@HCS-S prepared in 80%wt. embodiment 3 is compound
Object, 10%wt. conduction charcoal and 10%wt. Kynoar (PVDF) adhesive are mixed with electrode slurry；
Then, slurry is equably coated on aluminium foil, is dried for 24 hours at 70 DEG C；
Finally, the aluminium foil prepared the disk for striking out diameter 15mm is used as anode, lithium metal is cathode,
Using microporous polypropylene membrane (Celgard2300) diaphragm, constant current charge and discharge is tested using Land CT2001A type battery condition tester
Electric process has carried out cyclic voltammetry and electrochemical analysis on electrochemical workstation (CHI660E).
As shown in figure 3, the NH@HCS-S compound for the embodiment of the present invention 3 is recycled at current density 1C as anode
The specific capacity and coulombic efficiency figure in 500 periods, it can be seen from the figure that the initial specific capacities of embodiment 3 are 898.3mAh/g,
Continuous rating is 785.2Ah/g, and capacity retention ratio is the 87.41% of initial value, and harmonic(-)mean capacity attenuation rate is 0.025%, is followed
Ring stability further demonstrates the satisfactory electrical conductivity of NH@HCS-S combination electrode.The coulombic efficiency of NH@HCS-S combination electrode compared with
High and fluctuation shows that the electrode has preferable charge/discharge invertibity less (referring to Fig. 3).
As shown in table 1, it is compared for the specific capacity of the NH@HCS-S of the embodiment of the present invention 3 and other lithium sulfur battery anode materials
As a result, initial specific capacities are 800mAh/g, the specific capacity after composite material 500 periods of circulation are prepared in embodiment 3 is significantly high
In other lithium sulfur battery anode materials.
The NH@HCS-S of 1 embodiment of the present invention 3 of table and the specific capacity comparing result of other lithium sulfur battery anode materials
Note: [1] CO2,oxidation ofcarbon nanotubes for lithium-sulfur batteries
with improved electrochemical performance[J].Carbon,2018,132:370-379；[2]
Vulcanized polymeric cathode material featuring a polyaniline skeleton for
high-rate rechargeability and long-cycle stability lithium-sulfur batteries
[J].Electrochimica Acta,2018,276:111-117；[3]A multidimensional and nitrogen-
doped graphene/hierarchical porous carbonas a sulfur scaffoldforhighperforma
ncelithium sulfurbatteries[J].ElectrochimicaActa,2018,278:83-92；[4]Confine
sulfur in urchin-like nitrogen doped carbon particles for lithium-sulfur
batteries[J].MaterialsLetters,2018,228:195-198.
It is discussed in detail although the contents of the present invention have passed through above preferred embodiment, but it should be appreciated that above-mentioned
Description is not considered as limitation of the present invention.After those skilled in the art have read above content, for of the invention
A variety of modifications and substitutions all will be apparent.Therefore, protection scope of the present invention should be limited to the appended claims.
Claims (10)
1. the preparation method that a kind of inner wall is loaded with the hollow carbon sphere of nickel hydroxide and sulphur, which is characterized in that this method includes:
(1) by SiO2Ball is dispersed in ethanol-water mixture, and nickel sulfate stirring is added, instills ammonium hydroxide, is stirred at room temperature, collects deposition
Object obtains SiO2/Ni(OH)2；Wherein, the SiO2Quality, nickel sulfate mole and the ratio between the volume of ammonium hydroxide be 1g:
0.004mol:10mL；
(2) by the SiO2/Ni(OH)2It is added with the mixture of dopamine into ethanol-water mixture, is added trihydroxy methyl
Aminomethane, stirring, resulting deposit are SiO2/Ni(OH)2@PDA composite material；Wherein, the SiO2/Ni(OH)2, it is more
The mass ratio of bar amine and trishydroxymethylaminomethane is 1:(1.25~1.5): (0.3~0.5)；
(3) under atmosphere of inert gases, by the SiO2/Ni(OH)2@PDA composite material heats carbonization at 700~800 DEG C,
It after being carbonized, is cleaned with HCl, then is impregnated in strong base solution and remove silica, obtain Ni (OH)2@HCS composite wood
Material；Wherein, the strong base solution includes: potassium hydroxide solution and/or Strong oxdiative sodium solution；
(4) by the Ni (OH)2@HCS composite material and elemental sulfur are obtained grinding mixed with the mixed grinding of mass ratio 1:3~5
It closes object to heat under atmosphere of inert gases at 150~170 DEG C, it is attached to remove then to raise the temperature to 190~210 DEG C of heat preservations
At Ni (OH)2The sulfur granules of@HCS composite material surface obtain the hollow carbon sphere that inner wall is loaded with nickel hydroxide and sulphur.
2. the preparation method that inner wall according to claim 1 is loaded with the hollow carbon sphere of nickel hydroxide and sulphur, which is characterized in that
In step (1), the volume ratio of ethyl alcohol and water is 0.6~1.2:1 in the ethanol-water mixture；It is described in step (2)
The volume ratio of ethyl alcohol and water is 0.4~0.8:1 in ethanol-water mixture.
3. the preparation method that inner wall according to claim 1 is loaded with the hollow carbon sphere of nickel hydroxide and sulphur, which is characterized in that
It is described that the time is stirred at room temperature as 1~2h in step (1).
4. the preparation method that inner wall according to claim 1 is loaded with the hollow carbon sphere of nickel hydroxide and sulphur, which is characterized in that
In step (1), the ammonium hydroxide rate of addition is 10mL/h.
5. the preparation method that inner wall according to claim 1 is loaded with the hollow carbon sphere of nickel hydroxide and sulphur, which is characterized in that
In step (2), the mixing time is 5~8h.
6. the preparation method that inner wall according to claim 1 is loaded with the hollow carbon sphere of nickel hydroxide and sulphur, which is characterized in that
In step (3), the concentration of the HCl is 1.5~2mol/L；The concentration of the strong base solution is 8~10mol/L.
7. the preparation method that inner wall according to claim 1 is loaded with the hollow carbon sphere of nickel hydroxide and sulphur, which is characterized in that
In step (3), the time of the heating carbonization is 2~4h；24~30h is impregnated in the strong base solution.
8. the preparation method that inner wall according to claim 1 is loaded with the hollow carbon sphere of nickel hydroxide and sulphur, which is characterized in that
The inert gas includes: nitrogen, argon gas.
9. the hollow carbon sphere that a kind of inner wall is loaded with nickel hydroxide and sulphur, which is characterized in that the hollow carbon sphere is using as right is wanted
Method described in any one of 1-8 is asked to prepare.
10. the purposes that a kind of inner wall as claimed in claim 9 is loaded with the hollow carbon sphere of nickel hydroxide and sulphur, which is characterized in that
Positive electrode of the hollow carbon sphere as lithium-sulfur cell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910764939.8A CN110492071A (en) | 2019-08-19 | 2019-08-19 | Inner wall is loaded with the hollow carbon sphere and preparation method and purposes of nickel hydroxide and sulphur |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910764939.8A CN110492071A (en) | 2019-08-19 | 2019-08-19 | Inner wall is loaded with the hollow carbon sphere and preparation method and purposes of nickel hydroxide and sulphur |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110492071A true CN110492071A (en) | 2019-11-22 |
Family
ID=68551998
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910764939.8A Pending CN110492071A (en) | 2019-08-19 | 2019-08-19 | Inner wall is loaded with the hollow carbon sphere and preparation method and purposes of nickel hydroxide and sulphur |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110492071A (en) |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150221935A1 (en) * | 2014-02-05 | 2015-08-06 | GM Global Technology Operations LLC | Sulfur based active material for a positive electrode |
| CN105118972A (en) * | 2015-07-06 | 2015-12-02 | 浙江大学 | Metal hydroxide coated carbon and sulfur lithium-sulfur battery positive electrode material, and preparation method and application thereof |
| CN107069002A (en) * | 2017-04-10 | 2017-08-18 | 湖北大学 | A kind of lithium sulfur battery anode material and preparation method thereof and lithium-sulfur cell |
| CN107946557A (en) * | 2017-11-02 | 2018-04-20 | 东华大学 | A kind of preparation method of cobalt oxide modification Nano carbon balls electrode material |
| CN108258240A (en) * | 2017-12-06 | 2018-07-06 | 珠海格力电器股份有限公司 | Carbon ball, basis material, positive plate, battery and corresponding preparation or assemble method |
| CN108923026A (en) * | 2018-06-19 | 2018-11-30 | 大连理工大学 | A kind of preparation method of the rich nitrogen material of porous carbon nanosheet filling hollow carbon sphere |
| CN109461900A (en) * | 2018-09-27 | 2019-03-12 | 北京长城华冠汽车科技股份有限公司 | A kind of preparation method of the hollow Nano carbon balls combination electrode material of multi-pore channel |
| EP3454399A1 (en) * | 2016-05-06 | 2019-03-13 | Suzhou Hans Energy Storage Technology Co., Ltd. | Method for preparing boron-doped porous carbon sphere |
| CN109524637A (en) * | 2018-09-30 | 2019-03-26 | 肇庆市华师大光电产业研究院 | A kind of porous self-supporting flexible electrode material of lithium-sulfur cell and preparation method thereof |
| WO2019107752A1 (en) * | 2017-11-30 | 2019-06-06 | 주식회사 엘지화학 | Sulfur-carbon composite, method for manufacturing same and lithium secondary battery comprising same |
| CN110098396A (en) * | 2019-05-06 | 2019-08-06 | 广东工业大学 | A kind of lithium-sulfur battery composite cathode material and preparation method thereof and battery |
| CN110137475A (en) * | 2019-05-24 | 2019-08-16 | 西南大学 | A kind of hollow carbon sphere/molybdenum disulfide bipolarity composite material and preparation method and application |
-
2019
- 2019-08-19 CN CN201910764939.8A patent/CN110492071A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150221935A1 (en) * | 2014-02-05 | 2015-08-06 | GM Global Technology Operations LLC | Sulfur based active material for a positive electrode |
| CN105118972A (en) * | 2015-07-06 | 2015-12-02 | 浙江大学 | Metal hydroxide coated carbon and sulfur lithium-sulfur battery positive electrode material, and preparation method and application thereof |
| EP3454399A1 (en) * | 2016-05-06 | 2019-03-13 | Suzhou Hans Energy Storage Technology Co., Ltd. | Method for preparing boron-doped porous carbon sphere |
| CN107069002A (en) * | 2017-04-10 | 2017-08-18 | 湖北大学 | A kind of lithium sulfur battery anode material and preparation method thereof and lithium-sulfur cell |
| CN107946557A (en) * | 2017-11-02 | 2018-04-20 | 东华大学 | A kind of preparation method of cobalt oxide modification Nano carbon balls electrode material |
| WO2019107752A1 (en) * | 2017-11-30 | 2019-06-06 | 주식회사 엘지화학 | Sulfur-carbon composite, method for manufacturing same and lithium secondary battery comprising same |
| CN108258240A (en) * | 2017-12-06 | 2018-07-06 | 珠海格力电器股份有限公司 | Carbon ball, basis material, positive plate, battery and corresponding preparation or assemble method |
| CN108923026A (en) * | 2018-06-19 | 2018-11-30 | 大连理工大学 | A kind of preparation method of the rich nitrogen material of porous carbon nanosheet filling hollow carbon sphere |
| CN109461900A (en) * | 2018-09-27 | 2019-03-12 | 北京长城华冠汽车科技股份有限公司 | A kind of preparation method of the hollow Nano carbon balls combination electrode material of multi-pore channel |
| CN109524637A (en) * | 2018-09-30 | 2019-03-26 | 肇庆市华师大光电产业研究院 | A kind of porous self-supporting flexible electrode material of lithium-sulfur cell and preparation method thereof |
| CN110098396A (en) * | 2019-05-06 | 2019-08-06 | 广东工业大学 | A kind of lithium-sulfur battery composite cathode material and preparation method thereof and battery |
| CN110137475A (en) * | 2019-05-24 | 2019-08-16 | 西南大学 | A kind of hollow carbon sphere/molybdenum disulfide bipolarity composite material and preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| DAI, CL ET AL: ""Uniform alpha-Ni(OH)(2) hollow spheres constructed from ultrathin nanosheets as efficient polysulfide mediator for long-term lithium-sulfur batteries"", 《ENERGY STORAGE MATERIALS 》 * |
| TIAN, YX ET AL: ""Metal-organic framework derived yolk-shell NiS2/carbon spheres for lithium-sulfur batteries with enhanced polysulfide redox kinetics"", 《CHEMICAL COMMUNICATIONS》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yang et al. | YANG et al. | |
| CN106025200B (en) | A kind of preparation method and applications of N doping MXene cell negative electrode material | |
| CN105810914B (en) | A kind of sodium-ion battery sulfur doping porous carbon materials and preparation method thereof | |
| Xu et al. | Tri-functionalized polypropylene separator by rGO/MoO 2 composite for high-performance lithium–sulfur batteries | |
| CN104779376B (en) | A kind of lithium sulfur battery anode material, preparation method and lithium-sulfur cell | |
| CN105489901B (en) | A kind of preparation method and applications of lithium-sulfur cell three-dimensional carbon collector | |
| CN105932234A (en) | Doped porous carbon spheres used for negative electrode material of sodium ion battery and preparation method for doped porous carbon spheres | |
| CN104409733B (en) | Nitrogen doped porous carbon/sulfur composite positive material as well as preparation method and application thereof | |
| CN103545123A (en) | Hybrid energy storage device with zinc ion battery and supercapacitor | |
| CN106920941B (en) | A kind of cobalt, titanium, nitrogen co-doped carbon nanotube/sulphur composite positive pole and preparation method thereof | |
| CN106876673B (en) | The method that one-step method prepares the core-shell structure lithium sulfur battery anode material that titanium dioxide and graphene bilayer coat altogether | |
| CN106099108A (en) | A kind of preparation method of LITHIUM BATTERY graphite/absorbent charcoal composite material | |
| CN108321369A (en) | A kind of macropore carbon/zinc oxide/sulphur composite material and preparation method can be used for lithium-sulfur cell and application | |
| CN108807808A (en) | A kind of biomass carbon aeroge is modified lithium-sulfur cell dedicated diaphragm and preparation method thereof and lithium-sulfur cell | |
| CN103560019B (en) | A kind of zinc ion hybrid super capacitor | |
| CN110212180B (en) | Preparation method of lithium sulfide self-supporting carbon sphere/carbon nanofiber composite material and lithium-sulfur battery | |
| CN108963207A (en) | A kind of carbon composite material and its preparation method and application of porous metals doping | |
| CN108666570A (en) | Porous carbon nanobelts lithium sulfur battery anode material and its preparation method and application | |
| CN109817923A (en) | A kind of nitrogen-doped porous carbon material and its preparation method and application | |
| US20230183524A1 (en) | Polyamine composite material and preparation method therefor, slurry, separator, electrode sheet, and lithium-sulfur battery containing the same | |
| CN110148739A (en) | A kind of carbon@allyl sulfides itrile group polymer composite anode active material, anode and its preparation and the application in lithium-sulfur cell | |
| CN112117444A (en) | Carbon-coated cobalt sulfide positive electrode material, preparation method, positive electrode and aluminum ion battery | |
| CN108767203B (en) | Titanium dioxide nanotube-graphene-sulfur composite material and preparation method and application thereof | |
| CN108172406A (en) | One kind is with FeS2-xSexMaterial is the sodium ion capacitor of negative material | |
| CN110265633A (en) | A kind of micro-nano structure lithium-sulfur battery composite cathode material and preparation method thereof and battery |
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: 20191122 |
|
| RJ01 | Rejection of invention patent application after publication |