CN107863520A - A kind of lithium sulfur battery anode material and preparation method thereof - Google Patents
A kind of lithium sulfur battery anode material and preparation method thereof Download PDFInfo
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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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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
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- H01M10/052—Li-accumulators
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- H—ELECTRICITY
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- H—ELECTRICITY
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- 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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- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to lithium sulfur battery anode material and preparation method thereof, is formed by N layer graphite metal layers and sulphur layer alternative stacked, and the graphite metal layer includes nano-graphene and nano-metal-oxide, and the sulphur layer includes sulphur and nano-graphene；N>1, and N is natural number；The thickness of the lithium sulfur battery anode material is 1 200 μm, and the thickness of graphite metal layer or sulphur layer is 0.5 50 μm；The tridimensional network of UNICOM is intertwined to form between the graphite metal layer being separated by.The electric conductivity that the present invention can both improve electrode can also effectively obstruct dissolving of the polysulfide into electrolyte.
Description
Technical field
The present invention relates to a kind of lithium sulfur battery anode material and preparation method thereof.
Background technology
Lithium-sulfur cell has a height ratio capacity, aboundresources and the characteristic such as environment-friendly, be most potential lithium of new generation from
One of sub- battery.But also need to overcome some defects of its own to expand its application, such as (1) sulphur and discharging product sulphur
Change the electrochemicaUy inert of lithium；(2) in discharge process dissolving of the caused long-chain polysulfide in conventional organic solution liquid and
Shuttle between both positive and negative polarity；(3) volumetric expansion of active material in charge and discharge process etc..
Traditional lithium sulfur battery anode material be by sulphur and conductive carbon black, that binding agent is dissolved in 1-METHYLPYRROLIDONE is molten
It is coated with after being well mixed in liquid onto aluminium foil.In order to overcome the electrical insulating property of sulphur itself, and improve the electric conductivity of electrode, electrode
The content of sulphur is typically not over 70% in material.However, carbon black and binding agent are all the materials for not possessing electro-chemical activity, mistake
The material of more this electrochemicaUy inerts of addition will certainly cause the energy density of electrode to reduce, and weaken lithium-sulfur cell in reality
Advantage in.In recent years, researcher transfers to start to design and manufacture the lithium-sulphur cell positive electrode of self-supporting or binder free
Material.Most of electrode of this self-supporting is using the carbon film (paper) or other conductive self-supporting materials of conduction to collect sulphur body and sulphur
Carrier, then active material sulphur is deposited on to be made by face by method physically or chemically.Researcher in positive electrode and
The interlayer of conduction is added between barrier film can significantly improve the performance of lithium-sulfur cell, even to the battery using sulphur as positive pole
Also excellent chemical property is shown.But generally interlayer is that the part independent as one is added to lithium sulphur electricity
Inside pond, this undoubtedly adds the workload in cell assembling processes.
The content of the invention
The present invention provides a kind of lithium sulfur battery anode material and preparation method thereof, and it can both improve the electric conductivity of electrode
Dissolving of the polysulfide into electrolyte can also effectively be obstructed.
To solve above technical problem, the present invention provides the technical scheme of first aspect, i.e., a kind of lithium-sulphur cell positive electrode material
Material, is formed, the graphite-metal layer includes nano-graphene and nano metal by N layer graphite-metal layers and sulphur layer alternative stacked
Oxide, the sulphur layer include sulphur and nano-graphene；
N>1, and N is natural number；
The thickness of the lithium sulfur battery anode material is 1-200 μm, and the thickness of graphite-metal layer or sulphur layer is 0.5-50 μ
m；The tridimensional network of UNICOM is intertwined to form between the graphite-metal layer being separated by.
Preferably, N=2,3,4 or 5.
Preferably, the part by weight of nano-graphene and nano-metal-oxide is 1 in graphite metal layer:(1-5).
Preferably, nano-metal-oxide is the nano-oxide of manganese, vanadium or molybdenum.
Preferably, nano-graphene is graphene nano volume.
Preferably, nano-metal-oxide is metal oxide nano-wire or metal oxide nano band.
Preferably, the part by weight of sulphur and nano-graphene is 1 in sulphur layer：(0.05-0.1).
The application also provides the preparation method of foregoing any described lithium sulfur battery anode material, comprises the following steps,
(1) proportionally nano-graphene and nano-metal-oxide are scattered in water or organic solvent, that is, divided
Dispersion liquid A, be divided into more parts it is stand-by；
(2) sulphur is dissolved in ethylenediamine solution, and the concentration for obtaining sulphur is 20-50mg/mL sulphur-ethylenediamine solution, then will
The nano-graphene of the ratio is immersed in the sulphur-ethylenediamine solution, and hydrochloric acid solution is added dropwise thereto and adjusts pH to 5-6, is held
Be centrifuged after continuous stirring 2-10min, it is neutrality to wash to solution, finally by the material after washing be scattered in again water or
In organic solvent, obtain dispersion liquid B, be divided into more parts it is stand-by；
(3) more parts of dispersion liquid A and dispersion liquid B are alternately filtered into same container successively respectively, it is to be obtained suitable
To filtration cakes torrefaction after the number of plies, foregoing any described lithium sulfur battery anode material is obtained；Dispersion liquid A is filtered, dry graphite-metal
Layer, dispersion liquid B is filtered, dry sulphur layer.
Preferably, dispersion liquid A and dispersion liquid B concentration are 0.05-2.0mg/mL.
Preferably, the organic solvent is at least one of absolute ethyl alcohol, acetone, ethylene glycol.
Lithium sulfur battery anode material that the application provides and preparation method thereof, it is with specific structure using prepare gained
The cell positive material of N layer graphite-metal layers and sulphur layer alternative stacked, can also effectively it be obstructed so as to improve the electric conductivity of electrode
Dissolving of the polysulfide into electrolyte.
Brief description of the drawings
Fig. 1 is the graphene nano volume that in embodiment of the present invention one prepared by embodiment 1 and manganese dioxide nanowire or received
The ESEM and distribution diagram of element of double-layer structure positive pole of the rice with modification；
Fig. 2 is the graphene nano volume that in embodiment of the present invention one prepared by embodiment 2 and manganese dioxide nanowire or received
The scanning electron microscope (SEM) photograph of three-decker positive pole of the rice with modification；
Fig. 3 is the graphene nano volume that in embodiment of the present invention one prepared by embodiment 2 and manganese dioxide nanowire or received
The scanning of three-decker positive pole of the rice with modification and distribution diagram of element；
Fig. 4 is that embodiment 2 prepares graphene nano volume and manganese dioxide nanowire or nanometer in embodiment of the present invention one
Circulation schematic diagram of the three-decker positive pole with modification under 0.2C；
Fig. 5 is the graphene nano volume and vanadium pentoxide nanowires prepared in embodiment of the present invention two in embodiment 17
Or the ESEM and distribution diagram of element of the three-decker positive pole of nanobelt modification；
Fig. 6 be in embodiment of the present invention two embodiment 17 prepare graphene nano volume and vanadium pentoxide nanowires or
Circulation schematic diagram of the three-decker positive pole of nanobelt modification under 0.5C.
Fig. 7 is the graphene nano volume and the modification of molybdenum trioxide nano band that in embodiment of the present invention three prepared by embodiment 32
Circulation schematic diagram of the three-decker positive pole under 0.5C.
Embodiment
For the object, technical solutions and advantages of the present invention are more clearly understood, below in conjunction with embodiment of the present invention
In accompanying drawing, the technical scheme in embodiment of the present invention is clearly and completely described, it is clear that described embodiment party
Formula only a part of embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention, ability
The every other embodiment that domain those of ordinary skill is obtained under the premise of creative work is not made, belongs to the present invention
The scope of protection.In the case where not conflicting, the feature in embodiment and embodiment in the present invention can be mutually any
Combination.
The addition of no-bonder and conductive black can be saved using lithium sulfur battery anode material described herein, promotes list
The surface density of sulphur is larger on the positive plate of plane product, up to 6.2mgcm-2。
Lithium sulfur battery anode material described herein comprising sulphur body, active material and interlayer is collected, reduces battery in itself
Processing step in assembling process, only itself and lithium anode, barrier film and lithium-sulfur cell electrolyte electricity need to be assembled follow-up
Pond, you can lithium-sulfur cell is obtained, while also ensures the performance of gained battery, such as in high-sulfur carrying capacity (6.2mgcm-2) following table
Reveal good chemical property, in 0.2C, 403mAhg can be obtained by circulating 150 times-1Specific discharge capacity.
In addition, the three dimensional network that the application can be formed especially using graphene roll and metal oxide nano-wire (or nanobelt)
Shape structure, electrode conductivuty can not only be improved and also help the infiltration of electrolyte and the migration of lithium ion, so as to promote electrochemistry
The speed of reaction.In addition, graphene nano volume and metal oxide nano-wire are made to the physics and chemisorbed of polysulfide
With effectively fixing, and the polysulfide of dissolving is recycled, improve the utilization rate of sulphur so as to extend the cycle life of battery.
It is that corresponding lithium sulphur is made using the lithium sulfur battery anode material of preparation method described herein acquisition below
Every embodiment of battery.
Embodiment one
(1) graphene nano volume and manganese dioxide nanowire or nanobelt are scattered in water or organic according to part by weight x
In the liquid such as solvent m, that is, obtain concentration be l1mg/mL dispersion liquid A, be divided into more parts it is stand-by；
(2) sulphur is dissolved in ethylenediamine solution, and the concentration for obtaining sulphur is l2mg/mL sulphur-ethylenediamine solution, according still further to sulphur
The nano-graphene that part by weight with nano-graphene is y is immersed in the sulphur-ethylenediamine solution, and hydrochloric acid is added dropwise thereto
Solution adjusts pH to 5-6, is centrifuged after persistently stirring 2-10min, and it is neutrality to wash to solution, finally by the thing after washing
Material be scattered in again in water or organic solvent, obtain concentration be l 3mg/mL dispersion liquid B, be divided into more parts it is stand-by；
(3) more parts of dispersion liquid A and dispersion liquid B are alternately filtered into same container successively respectively, it is to be obtained suitable
To filtration cakes torrefaction after the number of plies, foregoing any described lithium sulfur battery anode material is obtained；Dispersion liquid A is filtered, dry graphite-metal
Layer, dispersion liquid B is filtered, dry sulphur layer.
According to above-mentioned steps, different every preparation parameters is respectively adopted and is prepared, the preparation parameter of each embodiment is such as
Shown in table 1 below；Preparation-obtained lithium sulfur battery anode material is subjected to coherent detection, such as the number of plies, gross thickness, sulphur thickness
Specific discharge capacity/the mAhg of 150 times is circulated under degree, graphite-metal thickness degree, sulphur aspect density, 0.2C-1, circulate under 0.5C
Specific discharge capacity/the mAhg of 190 times-1Deng；Acquired results see the table below 2.
Table 1
| Embodiment | x | m | l1 | l2 | y | l3 |
| 1 | 1:1 | Absolute ethyl alcohol | 0.05 | 20 | 1:0.1 | 0.05 |
| 2 | 1:2 | Absolute ethyl alcohol | 2.0 | 50 | 1:0.09 | 2.0 |
| 3 | 1:3 | Absolute ethyl alcohol | 0.1 | 30 | 1:0.08 | 0.1 |
| 4 | 1:4 | Absolute ethyl alcohol | 0.5 | 35 | 1:0.07 | 0.5 |
| 5 | 1:5 | Absolute ethyl alcohol | 1.0 | 40 | 1:0.05 | 1.0 |
| 6 | 1:1 | Acetone | 0.05 | 20 | 1:0.1 | 0.05 |
| 7 | 1:2 | Acetone | 2.0 | 50 | 1:0.09 | 2.0 |
| 8 | 1:3 | Acetone | 0.1 | 30 | 1:0.08 | 0.1 |
| 9 | 1:4 | Acetone | 0.5 | 35 | 1:0.07 | 0.5 |
| 10 | 1:5 | Acetone | 1.0 | 40 | 1:0.05 | 1.0 |
| 11 | 1:1 | Ethylene glycol | 0.05 | 20 | 1:0.1 | 0.05 |
| 12 | 1:2 | Ethylene glycol | 2.0 | 50 | 1:0.09 | 2.0 |
| 13 | 1:3 | Ethylene glycol | 0.1 | 30 | 1:0.08 | 0.1 |
| 14 | 1:4 | Ethylene glycol | 0.5 | 35 | 1:0.07 | 0.5 |
| 15 | 1:5 | Ethylene glycol | 1.0 | 40 | 1:0.05 | 1.0 |
Table 2
Embodiment two
(1) graphene nano volume and vanadium pentoxide nanowires or nanobelt are scattered in water according to part by weight x or had
In the liquid such as solvent m, that is, obtain concentration be l1mg/mL dispersion liquid A, be divided into more parts it is stand-by；
(2) sulphur is dissolved in ethylenediamine solution, and the concentration for obtaining sulphur is l2mg/mL sulphur-ethylenediamine solution, according still further to sulphur
The nano-graphene that part by weight with nano-graphene is y is immersed in the sulphur-ethylenediamine solution, and hydrochloric acid is added dropwise thereto
Solution adjusts pH to 5-6, is centrifuged after persistently stirring 2-10min, and it is neutrality to wash to solution, finally by the thing after washing
Material be scattered in again in water or organic solvent, obtain concentration be l3mg/mL dispersion liquid B, be divided into more parts it is stand-by；
(3) more parts of dispersion liquid A and dispersion liquid B are alternately filtered into same container successively respectively, it is to be obtained suitable
To filtration cakes torrefaction after the number of plies, foregoing any described lithium sulfur battery anode material is obtained；Dispersion liquid A is filtered, dry graphite-metal
Layer, dispersion liquid B is filtered, dry sulphur layer.
According to above-mentioned steps, different every preparation parameters is respectively adopted and is prepared, the preparation parameter of each embodiment is such as
Shown in table 3 below；Preparation-obtained lithium sulfur battery anode material is subjected to coherent detection, such as the number of plies, gross thickness, sulphur thickness
Specific discharge capacity/the mAhg of 150 times is circulated under degree, graphite-metal thickness degree, sulphur aspect density, 0.2C-1, circulate under 0.5C
Specific discharge capacity/the mAhg of 190 times-1Deng；Acquired results see the table below 4.
Table 3
| Embodiment | x | m | l1 | l2 | y | l 3 |
| 16 | 1:1 | Absolute ethyl alcohol | 0.05 | 20 | 1:0.1 | 0.05 |
| 17 | 1:2 | Absolute ethyl alcohol | 2.0 | 50 | 1:0.09 | 2.0 |
| 18 | 1:3 | Absolute ethyl alcohol | 0.1 | 30 | 1:0.08 | 0.1 |
| 19 | 1:4 | Absolute ethyl alcohol | 0.5 | 35 | 1:0.07 | 0.5 |
| 20 | 1:5 | Absolute ethyl alcohol | 1.0 | 40 | 1:0.05 | 1.0 |
| 21 | 1:1 | Acetone | 0.05 | 20 | 1:0.1 | 0.05 |
| 22 | 1:2 | Acetone | 2.0 | 50 | 1:0.09 | 2.0 |
| 23 | 1:3 | Acetone | 0.1 | 30 | 1:0.08 | 0.1 |
| 24 | 1:4 | Acetone | 0.5 | 35 | 1:0.07 | 0.5 |
| 25 | 1:5 | Acetone | 1.0 | 40 | 1:0.05 | 1.0 |
| 26 | 1:1 | Ethylene glycol | 0.05 | 20 | 1:0.1 | 0.05 |
| 27 | 1:2 | Ethylene glycol | 2.0 | 50 | 1:0.09 | 2.0 |
| 28 | 1:3 | Ethylene glycol | 0.1 | 30 | 1:0.08 | 0.1 |
| 29 | 1:4 | Ethylene glycol | 0.5 | 35 | 1:0.07 | 0.5 |
| 30 | 1:5 | Ethylene glycol | 1.0 | 40 | 1:0.05 | 1.0 |
Table 4
Embodiment three
(1) graphene nano volume and molybdenum trioxide nano-wire or nanobelt are scattered in water or organic according to part by weight x
In the liquid such as solvent m, that is, obtain concentration be l1mg/mL dispersion liquid A, be divided into more parts it is stand-by；
(2) sulphur is dissolved in ethylenediamine solution, and the concentration for obtaining sulphur is l2mg/mL sulphur-ethylenediamine solution, according still further to sulphur
The nano-graphene that part by weight with nano-graphene is y is immersed in the sulphur-ethylenediamine solution, and hydrochloric acid is added dropwise thereto
Solution adjusts pH to 5-6, is centrifuged after persistently stirring 2-10min, and it is neutrality to wash to solution, finally by the thing after washing
Material be scattered in again in water or organic solvent, obtain concentration be l3mg/mL dispersion liquid B, be divided into more parts it is stand-by；
(3) more parts of dispersion liquid A and dispersion liquid B are alternately filtered into same container successively respectively, it is to be obtained suitable
To filtration cakes torrefaction after the number of plies, foregoing any described lithium sulfur battery anode material is obtained；Dispersion liquid A is filtered, dry graphite-metal
Layer, dispersion liquid B is filtered, dry sulphur layer.
According to above-mentioned steps, different every preparation parameters is respectively adopted and is prepared, the preparation parameter of each embodiment is such as
Shown in table 5 below；Preparation-obtained lithium sulfur battery anode material is subjected to coherent detection, such as the number of plies, gross thickness, sulphur thickness
Specific discharge capacity/the mAhg of 150 times is circulated under degree, graphite-metal thickness degree, sulphur aspect density, 0.2C-1, circulate under 0.5C
Specific discharge capacity/the mAhg of 190 times-1Deng；Acquired results see the table below 6.
Table 5
| Embodiment | x | m | l1 | l2 | y | l 3 |
| 31 | 1:1 | Absolute ethyl alcohol | 0.05 | 20 | 1:0.1 | 0.05 |
| 32 | 1:2 | Absolute ethyl alcohol | 2.0 | 50 | 1:0.09 | 2.0 |
| 33 | 1:3 | Absolute ethyl alcohol | 0.1 | 30 | 1:0.08 | 0.1 |
| 34 | 1:4 | Absolute ethyl alcohol | 0.5 | 35 | 1:0.07 | 0.5 |
| 35 | 1:5 | Absolute ethyl alcohol | 1.0 | 40 | 1:0.05 | 1.0 |
| 36 | 1:1 | Acetone | 0.05 | 20 | 1:0.1 | 0.05 |
| 37 | 1:2 | Acetone | 2.0 | 50 | 1:0.09 | 2.0 |
| 38 | 1:3 | Acetone | 0.1 | 30 | 1:0.08 | 0.1 |
| 39 | 1:4 | Acetone | 0.5 | 35 | 1:0.07 | 0.5 |
| 40 | 1:5 | Acetone | 1.0 | 40 | 1:0.05 | 1.0 |
| 41 | 1:1 | Ethylene glycol | 0.05 | 20 | 1:0.1 | 0.05 |
| 42 | 1:2 | Ethylene glycol | 2.0 | 50 | 1:0.09 | 2.0 |
| 43 | 1:3 | Ethylene glycol | 0.1 | 30 | 1:0.08 | 0.1 |
| 44 | 1:4 | Ethylene glycol | 0.5 | 35 | 1:0.07 | 0.5 |
| 45 | 1:5 | Ethylene glycol | 1.0 | 40 | 1:0.05 | 1.0 |
Table 6
Embodiment four
(1) graphene nano particle and manganese dioxide nanowire or nanobelt are scattered in water according to part by weight x or had
In the liquid such as solvent m, that is, obtain concentration be l1mg/mL dispersion liquid A, be divided into more parts it is stand-by；
(2) sulphur is dissolved in ethylenediamine solution, and the concentration for obtaining sulphur is l2mg/mL sulphur-ethylenediamine solution, according still further to sulphur
The nano-graphene that part by weight with nano-graphene is y is immersed in the sulphur-ethylenediamine solution, and hydrochloric acid is added dropwise thereto
Solution adjusts pH to 5-6, is centrifuged after persistently stirring 2-10min, and it is neutrality to wash to solution, finally by the thing after washing
Material be scattered in again in water or organic solvent, obtain concentration be l3mg/mL dispersion liquid B, be divided into more parts it is stand-by；
(3) more parts of dispersion liquid A and dispersion liquid B are alternately filtered into same container successively respectively, it is to be obtained suitable
To filtration cakes torrefaction after the number of plies, foregoing any described lithium sulfur battery anode material is obtained；Dispersion liquid A is filtered, dry graphite-metal
Layer, dispersion liquid B is filtered, dry sulphur layer.
According to above-mentioned steps, different every preparation parameters is respectively adopted and is prepared, the preparation parameter of each embodiment is such as
Shown in table 7 below；Preparation-obtained lithium sulfur battery anode material is subjected to coherent detection, such as the number of plies, gross thickness, sulphur thickness
Specific discharge capacity/the mAhg of 150 times is circulated under degree, graphite-metal thickness degree, sulphur aspect density, 0.2C-1, circulate under 0.5C
Specific discharge capacity/the mAhg of 190 times-1Deng；Acquired results see the table below 8.
Table 7
| Embodiment | x | m | l1 | l2 | y | l 3 |
| 46 | 1:1 | Absolute ethyl alcohol | 0.05 | 20 | 1:0.1 | 0.05 |
| 47 | 1:2 | Absolute ethyl alcohol | 2.0 | 50 | 1:0.09 | 2.0 |
| 48 | 1:3 | Absolute ethyl alcohol | 0.1 | 30 | 1:0.08 | 0.1 |
| 49 | 1:4 | Absolute ethyl alcohol | 0.5 | 35 | 1:0.07 | 0.5 |
| 50 | 1:5 | Absolute ethyl alcohol | 1.0 | 40 | 1:0.05 | 1.0 |
| 51 | 1:1 | Acetone | 0.05 | 20 | 1:0.1 | 0.05 |
| 52 | 1:2 | Acetone | 2.0 | 50 | 1:0.09 | 2.0 |
| 53 | 1:3 | Acetone | 0.1 | 30 | 1:0.08 | 0.1 |
| 54 | 1:4 | Acetone | 0.5 | 35 | 1:0.07 | 0.5 |
| 55 | 1:5 | Acetone | 1.0 | 40 | 1:0.05 | 1.0 |
| 56 | 1:1 | Ethylene glycol | 0.05 | 20 | 1:0.1 | 0.05 |
| 57 | 1:2 | Ethylene glycol | 2.0 | 50 | 1:0.09 | 2.0 |
| 58 | 1:3 | Ethylene glycol | 0.1 | 30 | 1:0.08 | 0.1 |
| 59 | 1:4 | Ethylene glycol | 0.5 | 35 | 1:0.07 | 0.5 |
| 60 | 1:5 | Ethylene glycol | 1.0 | 40 | 1:0.05 | 1.0 |
Table 8
As can be seen from the above table, nano-graphene is graphene nano used by one-embodiment of embodiment three
Volume, used nano-metal-oxide is the nano wire or nanobelt of manganese dioxide, vanadic anhydride or molybdenum trioxide respectively,
The specific discharge capacity of gained positive electrode is above embodiment four, and especially embodiment one is compared with embodiment four.
In addition, preparation parameter is different used by each embodiment in one-embodiment of embodiment three, and final gained
Positive electrode in certain structural features there is also difference, also therefore the difference of each parameter and architectural feature result in each positive pole
The specific discharge capacity that material prepares gained lithium-sulfur cell has differences.
In addition, for the lithium sulfur battery anode material of the application and preparation method is better described, present invention also provides phase
The detection collection of illustrative plates of pass, such as shown in Fig. 1-Fig. 6, Fig. 1 is the graphene nano volume that in embodiment of the present invention one prepared by embodiment 1
The ESEM and distribution diagram of element for the double-layer structure positive pole modified with manganese dioxide nanowire or nanobelt；Fig. 2 is the present invention
Graphene nano volume and manganese dioxide nanowire that in embodiment one prepared by embodiment 2 or the three-decker that nanobelt is modified are just
The scanning electron microscope (SEM) photograph of pole；Fig. 3 is the graphene nano volume and manganese dioxide nano that in embodiment of the present invention one prepared by embodiment 2
The scanning of line or the three-decker positive pole of nanobelt modification and distribution diagram of element；Fig. 4 is embodiment 2 in embodiment of the present invention one
Prepare the circulation signal of graphene nano volume and manganese dioxide nanowire or the three-decker positive pole of nanobelt modification under 0.2C
Figure；Fig. 5 is the graphene nano volume and vanadium pentoxide nanowires prepared in embodiment of the present invention two in embodiment 17 or received
The ESEM and distribution diagram of element of three-decker positive pole of the rice with modification；Fig. 6 is embodiment 17 in embodiment of the present invention two
Circulation of the three-decker positive pole that the graphene nano volume and vanadium pentoxide nanowires or nanobelt of preparation are modified under 0.5C
Schematic diagram.Fig. 7 is the graphene nano volume and the modification of molybdenum trioxide nano band that in embodiment of the present invention three prepared by embodiment 32
Circulation schematic diagram of the three-decker positive pole under 0.5C.It can be drawn from Fig. 2 and Fig. 5, in embodiment 2 and embodiment 17
Shape that graphene nano in first layer and third layer is rolled up and manganese dioxide, vanadium pentoxide nanowires or nanobelt mutually interweave
Into the tridimensional network of UNICOM, namely the three-dimensional netted of UNICOM is intertwined to form between the graphite-metal layer for illustrating to be separated by
Structure.
It the above is only the preferred embodiment of the present invention, it is noted that above-mentioned preferred embodiment is not construed as pair
The limitation of the present invention, protection scope of the present invention should be defined by claim limited range.For the art
For those of ordinary skill, without departing from the spirit and scope of the present invention, some improvements and modifications can also be made, these change
Enter and retouch and also should be regarded as protection scope of the present invention.
Claims (10)
- A kind of 1. lithium sulfur battery anode material, it is characterised in that：Formed by N layer graphite-metal layers and sulphur layer alternative stacked, it is described Graphite-metal layer includes nano-graphene and nano-metal-oxide, and the sulphur layer includes sulphur and nano-graphene；N>1, and N is natural number；The thickness of the lithium sulfur battery anode material is 1-200 μm, and the thickness of graphite-metal layer or sulphur layer is 0.5-50 μm；Phase Every graphite-metal layer between be intertwined to form the tridimensional network of UNICOM.
- 2. lithium sulfur battery anode material according to claim 1, it is characterised in that：N=2,3,4 or 5.
- 3. lithium sulfur battery anode material according to claim 1, it is characterised in that：In graphite metal layer nano-graphene and The part by weight of nano-metal-oxide is 1:(1-5).
- 4. lithium sulfur battery anode material according to claim 1, it is characterised in that：Nano-metal-oxide be manganese, vanadium or The nano-oxide of molybdenum.
- 5. lithium sulfur battery anode material according to claim 1, it is characterised in that：Nano-graphene is graphene nano Volume.
- 6. lithium sulfur battery anode material according to claim 1, it is characterised in that：Nano-metal-oxide is metal oxidation Thing nano wire or metal oxide nano band.
- 7. lithium sulfur battery anode material according to claim 1, it is characterised in that：The weight of sulphur and nano-graphene in sulphur layer Amount ratio is 1：(0.05-0.1).
- 8. weigh the preparation method of 7 any described lithium sulfur battery anode material of 1- power, it is characterised in that：Comprise the following steps,(1) proportionally nano-graphene and nano-metal-oxide are scattered in water or organic solvent, that is, obtain dispersion liquid A, be divided into more parts it is stand-by；(2) sulphur is dissolved in ethylenediamine solution, and the concentration for obtaining sulphur is 20-50mg/mL sulphur-ethylenediamine solution, then by described in The nano-graphene of ratio is immersed in the sulphur-ethylenediamine solution, and hydrochloric acid solution is added dropwise thereto and adjusts pH to 5-6, is persistently stirred It is centrifuged after mixing 2-10min, it is neutrality to wash to solution, and the material after washing is finally scattered in into water or organic again In solvent, obtain dispersion liquid B, be divided into more parts it is stand-by；(3) more parts of dispersion liquid A and dispersion liquid B are alternately filtered into same container successively respectively, the suitable number of plies to be obtained Afterwards to filtration cakes torrefaction, 7 any described lithium sulfur battery anode material of 1- power must be weighed；Dispersion liquid A is filtered, dry graphite-metal Layer, dispersion liquid B is filtered, dry sulphur layer.
- 9. preparation method according to claim 8, it is characterised in that：Dispersion liquid A and dispersion liquid B concentration are 0.05- 2.0mg/mL。
- 10. preparation method according to claim 8, it is characterised in that：The organic solvent is absolute ethyl alcohol, acetone, second At least one of glycol.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108615933A (en) * | 2018-05-16 | 2018-10-02 | 东莞市振华新能源科技有限公司 | A kind of aluminium ion battery and preparation method thereof based on novel anode material |
| CN108630889A (en) * | 2018-04-17 | 2018-10-09 | 西安交通大学 | A kind of lithium-sulfur cell and its anode and preparation method using nitride/graphene as interlayer |
| CN109378459A (en) * | 2018-10-22 | 2019-02-22 | 江西烯牛石墨烯科技有限公司 | A kind of lithium sulfur battery anode material and preparation method thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103972467A (en) * | 2013-02-06 | 2014-08-06 | 中国科学院金属研究所 | Lithium-sulfur battery multilayer composite positive electrode and preparation method thereof |
| CN104143630A (en) * | 2013-05-09 | 2014-11-12 | 中国科学院大连化学物理研究所 | Application of graphene-nanometer metal oxide composite material in lithium sulfur battery |
| CN104377355A (en) * | 2014-11-13 | 2015-02-25 | 华南师范大学 | Curved graphene ribbon/sulfur composite cathode material and preparation method and application thereof |
| CN104638246A (en) * | 2015-03-03 | 2015-05-20 | 哈尔滨工业大学 | Graphene-based flexible lithium-sulfur battery positive electrode material, preparation method of positive electrode material and preparation method of positive electrode |
| CN105047882A (en) * | 2015-09-09 | 2015-11-11 | 哈尔滨工业大学 | Method for preparing lithium-sulfur battery positive pole material |
| CN106058150A (en) * | 2016-08-15 | 2016-10-26 | 柔电（武汉）科技有限公司 | Electrode of lithium sulfur battery and preparation method thereof |
| CN106169573A (en) * | 2016-10-06 | 2016-11-30 | 电子科技大学 | A kind of preparation method of the composite of graphene coated sulfur family simple substance |
| CN106374087A (en) * | 2016-09-30 | 2017-02-01 | 上海空间电源研究所 | Cathode material for long-circulation lithium-sulfur battery and preparation method thereof |
| CN106450245A (en) * | 2016-12-23 | 2017-02-22 | 合肥工业大学 | Flexible cathode material of chargeable/dischargeable lithium-sulfur battery and preparation method thereof |
| US20170098856A1 (en) * | 2015-10-02 | 2017-04-06 | Aruna Zhamu | Process for producing lithium batteries having an ultra-high energy density |
| CN106876670A (en) * | 2016-12-28 | 2017-06-20 | 广东工业大学 | The metal oxide of a kind of flexible self-supporting/graphene nano composite membrane and its preparation method and application |
-
2017
- 2017-11-12 CN CN201711109993.6A patent/CN107863520A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103972467A (en) * | 2013-02-06 | 2014-08-06 | 中国科学院金属研究所 | Lithium-sulfur battery multilayer composite positive electrode and preparation method thereof |
| CN104143630A (en) * | 2013-05-09 | 2014-11-12 | 中国科学院大连化学物理研究所 | Application of graphene-nanometer metal oxide composite material in lithium sulfur battery |
| CN104377355A (en) * | 2014-11-13 | 2015-02-25 | 华南师范大学 | Curved graphene ribbon/sulfur composite cathode material and preparation method and application thereof |
| CN104638246A (en) * | 2015-03-03 | 2015-05-20 | 哈尔滨工业大学 | Graphene-based flexible lithium-sulfur battery positive electrode material, preparation method of positive electrode material and preparation method of positive electrode |
| CN105047882A (en) * | 2015-09-09 | 2015-11-11 | 哈尔滨工业大学 | Method for preparing lithium-sulfur battery positive pole material |
| US20170098856A1 (en) * | 2015-10-02 | 2017-04-06 | Aruna Zhamu | Process for producing lithium batteries having an ultra-high energy density |
| CN106058150A (en) * | 2016-08-15 | 2016-10-26 | 柔电（武汉）科技有限公司 | Electrode of lithium sulfur battery and preparation method thereof |
| CN106374087A (en) * | 2016-09-30 | 2017-02-01 | 上海空间电源研究所 | Cathode material for long-circulation lithium-sulfur battery and preparation method thereof |
| CN106169573A (en) * | 2016-10-06 | 2016-11-30 | 电子科技大学 | A kind of preparation method of the composite of graphene coated sulfur family simple substance |
| CN106450245A (en) * | 2016-12-23 | 2017-02-22 | 合肥工业大学 | Flexible cathode material of chargeable/dischargeable lithium-sulfur battery and preparation method thereof |
| CN106876670A (en) * | 2016-12-28 | 2017-06-20 | 广东工业大学 | The metal oxide of a kind of flexible self-supporting/graphene nano composite membrane and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 马晶晶 等: "适用于智能电网的石墨烯基能源材料", 《智能电网》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108630889A (en) * | 2018-04-17 | 2018-10-09 | 西安交通大学 | A kind of lithium-sulfur cell and its anode and preparation method using nitride/graphene as interlayer |
| CN108615933A (en) * | 2018-05-16 | 2018-10-02 | 东莞市振华新能源科技有限公司 | A kind of aluminium ion battery and preparation method thereof based on novel anode material |
| CN109378459A (en) * | 2018-10-22 | 2019-02-22 | 江西烯牛石墨烯科技有限公司 | A kind of lithium sulfur battery anode material and preparation method thereof |
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