CN109256564A - Carbon nanotube-graphite composite material, lithium sulfur battery anode material and lithium-sulfur cell - Google Patents
Carbon nanotube-graphite composite material, lithium sulfur battery anode material and lithium-sulfur cell Download PDFInfo
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- CN109256564A CN109256564A CN201811051020.6A CN201811051020A CN109256564A CN 109256564 A CN109256564 A CN 109256564A CN 201811051020 A CN201811051020 A CN 201811051020A CN 109256564 A CN109256564 A CN 109256564A
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
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- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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Abstract
The invention belongs to lithium ion battery material technical fields, and in particular to carbon nanotube-graphite composite material, lithium sulfur battery anode material and lithium-sulfur cell.The present invention provides a kind of carbon nanotube-graphite composite materials to be successively made through molding, charing, graphitization and roll-in by including carbon nanotube, polyimides chopped strand, shaping assistant, the raw material for preparing for discongesting agent, dispersing agent and polar organic solvent；Carbon nanotube-the graphite composite material has hole.Embodiment the result shows that, using composite material provided by the invention prepare lithium sulfur battery anode material, can be prepared under 1C multiplying power, recycle the lithium-sulfur cell that 200 specific capacities are still 470mAh/g.
Description
Technical field
The invention belongs to lithium ion battery material technical fields, and in particular to carbon nanotube-graphite composite material and its system
Preparation Method, lithium sulfur battery anode material and preparation method thereof and lithium-sulfur cell.
Background technique
Sulphur rich reserves in the earth, it is environmental-friendly, it is pollution-free, and its theoretical specific capacity with higher and energy are close
Degree, therefore can be used as battery anode active material.When sulphur is as active material, it is typically supported on collector and forms positive plate,
It is assembled into lithium-sulfur cell jointly with cathode and electrolyte.The lithium-sulphur cell positive electrode prepared at present is mostly aluminum foil material with collector,
The capacitance fall-off for the lithium-sulfur cell being prepared using the material is rapid, and the cyclical stability of battery is unsatisfactory.
Summary of the invention
The purpose of the present invention is to provide a kind of carbon nanotube-graphite composite materials, can prepare in this, as collector
Obtain the preferable lithium-sulfur cell of cyclical stability.
To achieve the goals above, the invention provides the following technical scheme:
The present invention provides a kind of carbon nanotube-graphite composite materials, by including carbon nanotube, the chopped fibre of polyimides
Dimension, shaping assistant, the raw material for preparing for discongesting agent, dispersing agent and polar organic solvent, successively through molding, charing, graphitization and roller
It is pressed into；
Carbon nanotube-the graphite composite material has hole.
Preferably, the mass ratio of the carbon nanotube and polyimides chopped strand is 1:1~7；
Polyimides chopped strand is 1:0.005~0.01 with the mass ratio for discongesting agent；
The mass ratio of carbon nanotube and dispersing agent is 1:0.005~0.01；
The mass ratio of the gross mass and shaping assistant of carbon nanotube and polyimides chopped strand is 1:0.004~0.01.
Preferably, the shaping assistant includes binder and flocculant；
The binder includes polyacrylate and/or polyvinyl alcohol；
The flocculant includes cationic polyacrylamide and/or anionic polyacrylamide.
Preferably, the carbon nanotube-graphite composite material hole aperture be 3~100nm, specific surface area be 15~
30m2/ g, porosity are 50~60%, and sheet resistance is 3~15 Ω/.
The present invention provides carbon nanotube-graphite composite material preparation method described in above-mentioned technical proposal, including it is following
Step:
It (1) will include carbon nanotube, polyimides chopped strand, the mixing for discongesting agent, dispersing agent and polar organic solvent
Material is sheared, and mixed slurry is obtained；
(2) it after mixing the mixed slurry of the step (1) with shaping assistant, is formed, obtains carbon nanotube-polyamides
Imines non-woven fabrics；
(3) carbon nanotube-polyimide nonwoven fabric of the step (2) successively carbonized, be graphitized and roll-in, obtained
To carbon nanotube-graphite composite material.
Preferably, in the step (3), the temperature of charing is 1000~1200 DEG C, and the time of charing is 3~8h；
Graphited temperature is 2800~3000 DEG C, and the graphited time is 24~48h；
The pressure of roll-in is 100~120kN/m.
The present invention provides a kind of lithium sulfur battery anode material, including collector, polysulfide barrier layer and it is located at described
Active material between collector and polysulfide barrier layer；
The collector is described in carbon nanotube-graphite composite material described in above-mentioned technical proposal or above-mentioned technical proposal
Carbon nanotube-graphite composite material that preparation method is prepared；
The active material includes sulphur simple substance；
The polysulfide barrier layer includes carbon nanotube-aramid nonwoven.
Preferably, the active material accounts for the 10~30% of lithium sulfur battery anode material gross mass.
The present invention provides the preparation methods of lithium sulfur battery anode material described in above-mentioned technical proposal, comprising:
By include active material slurry be coated in above-mentioned technical proposal described in carbon nanotube-graphite composite material or on
Carbon nanotube-graphite composite material single side that preparation method described in technical solution is prepared is stated, then by carbon nanotube-virtue
Synthetic fibre nonwoven layer is layered on the surface of pulp layer, obtains lithium sulfur battery anode material using hot pressing.
The present invention provides a kind of lithium-sulfur cells, including anode cover, anode, diaphragm, cathode, negative electrode casing and electrolyte；Institute
State just that extremely preparation method described in lithium sulfur battery anode material or above-mentioned technical proposal described in above-mentioned technical proposal is prepared
Lithium sulfur battery anode material.
The present invention provides a kind of carbon nanotube-graphite composite materials, by including carbon nanotube, the chopped fibre of polyimides
Dimension, shaping assistant, the raw material for preparing for discongesting agent, dispersing agent and polar organic solvent, successively through molding, charing, graphitization and roller
It is pressed into；Carbon nanotube-the graphite composite material has hole.The present invention is using polyimides chopped strand as raw material, through charcoal
After changing and being graphitized, polyimides chopped strand is first carbonized, graphite is then converted to, is cooperatively formed with carbon nanotube with hole
The composite material of gap structure, is attached to active component in the surface and hole of composite material, while improving load capacity,
The stability combined between active component and composite material is improved, lithium-sulfur cell cyclical stability is advantageous to improving.Embodiment
The result shows that the lithium sulfur battery anode material prepared using composite material provided by the invention, can be prepared under 1C multiplying power,
Recycle the lithium-sulfur cell that 200 specific capacities are still 470mAh/g.
Detailed description of the invention
Fig. 1 provides the structural schematic diagram of lithium sulfur battery anode material for the present invention；Wherein 1 is compound for carbon nanotube-graphite
Material；2 be positive electrode active materials；3 be polysulfide barrier layer；
Fig. 2 is 1 lithium-sulfur cell cycle performance comparison diagram of embodiment 1 and comparative example.
Specific embodiment
The present invention provides a kind of carbon nanotube-graphite composite materials, by including carbon nanotube, the chopped fibre of polyimides
Dimension, shaping assistant, the raw material for preparing for discongesting agent, dispersing agent and polar organic solvent, successively through molding, charing, graphitization and roller
It is pressed into；
Carbon nanotube-the graphite composite material has hole.
The raw material for preparing of carbon nanotube-graphite composite material provided by the invention includes carbon nanotube, the carbon nanotube
Preferably multi-walled carbon nanotube, the diameter of the carbon nanotube are preferably 30~150nm, more preferably 45~125nm, further preferably
For 50~100nm；The length of carbon nanotube is preferably 5~10 μm, and more preferably 6~9 μm, be further preferably 7~8 μm.
The raw material for preparing of carbon nanotube-graphite composite material provided by the invention includes polyimides chopped strand, described
The diameter of polyimides chopped strand is preferably 10~14 μm, and more preferably 11~13 μm, be further preferably 12 μm；Length is preferably
3~5mm, more preferably 3~4mm are further preferably 4mm.
The raw material for preparing of carbon nanotube-graphite composite material provided by the invention includes shaping assistant, the shaping assistant
Binder and flocculant are preferably included, the binder preferably includes polyacrylate and/or polyvinyl alcohol, and more preferably poly- third
Olefin(e) acid ester.The flocculant preferably includes cationic polyacrylamide and/or anionic polyacrylamide, more preferably cationic
Polyacrylamide.The binder and the mass ratio of flocculant are preferably 1:0.8~1.2, more preferably 1:0.9~1.1, optimal
It is selected as 1:1.
The raw material for preparing of carbon nanotube-graphite composite material provided by the invention includes discongesting agent, and described to discongest agent preferred
Including polyethylene glycol oxide or dodecyl sodium sulfate (SDBS).
The raw material for preparing of carbon nanotube-graphite composite material provided by the invention includes dispersing agent, and the dispersing agent is preferred
Including lauryl sodium sulfate (SDS) or polyvinylpyrrolidone (PVP).
The raw material for preparing of carbon nanotube-graphite composite material provided by the invention includes polar organic solvent, the polarity
Organic solvent preferably includes ethyl alcohol or dimethylformamide (DMF).
In the present invention, the mass ratio of the carbon nanotube and polyimides chopped strand is preferably 1:1~7, more preferably
It is further preferably 1:3~5 for 1:2~6.The polyimides chopped strand and the mass ratio for discongesting agent be preferably 1:0.005~
0.01；More preferably 1:0.006~0.009 is further preferably 1:0.007~0.008.The quality of the carbon nanotube and dispersing agent
Than being preferably 1:0.005~0.01；More preferably 1:0.006~0.009 is further preferably 1:0.007~0.008.The carbon is received
The mass ratio of the gross mass and shaping assistant of mitron and polyimides chopped strand is preferably 1:0.004~0.01, more preferably
1:0.005~0.009 is further preferably 1:0.006~0.008.
Carbon nanotube-graphite composite material provided by the invention has a hole, and the aperture of the hole is preferably 3~
100nm, more preferably 3~80nm are further preferably 3~75nm；The specific surface area of the carbon nanotube-graphite composite material is preferred
For 15~30m2/ g, more preferably 18~27m2/ g is further preferably 20~25m2/g.Carbon nanotube-the graphite composite material
Porosity is preferably 50~60%, and more preferably 52~58%, it is further preferably 54~55%.Carbon nanotube-the graphite is compound
The sheet resistance of material is preferably 3~15 Ω/, more preferably 3~10 Ω/, is further preferably 3~6 Ω/.The carbon is received
Mitron-graphite composite material intensity is 0.12~0.18kg/mm2。
In the present invention, the thickness of the carbon nanotube-graphite composite material is preferably 0.03~0.1mm, more preferably
0.05~0.08mm is further preferably 0.06~0.07mm.
The present invention provides carbon nanotube-graphite composite material preparation method described in above-mentioned technical proposal, including it is following
Step:
It (1) will include carbon nanotube, polyimides chopped strand, the mixing for discongesting agent, dispersing agent and polar organic solvent
Material is sheared, and mixed slurry is obtained；
(2) it after mixing the mixed slurry of the step (1) with shaping assistant, is formed, obtains carbon nanotube-polyamides
Imines non-woven fabrics；
(3) carbon nanotube-polyimide nonwoven fabric of the step (2) successively carbonized, be graphitized and roll-in, obtained
To carbon nanotube-graphite composite material.
The present invention will include carbon nanotube, polyimides chopped strand, discongest the mixed of agent, dispersing agent and polar organic solvent
It closes material to be sheared, obtains mixed slurry.In the present invention, the preparation method of the mixed slurry preferably includes:
The mixture of polyimides chopped strand dispersion liquid and carbon nano tube dispersion liquid is sheared, mixing slurry is obtained
Material.
In the present invention, the polyimides chopped strand dispersion liquid includes polyimides chopped strand, discongests agent and pole
The mass ratio of property organic solvent, the polyimides chopped strand and polar organic solvent is preferably 1:100~200, more preferably
It is further preferably 1:130~170 for 1:120~180.
In the present invention, the preparation method of the polyimides chopped strand dispersion liquid preferably includes for polyimides to be chopped
Fiber discongests agent and polar organic solvent mixing, is then allowed to stand.The time of the standing is preferably 10~30min, more preferably
15~25min.
In the present invention, including carbon nanotube alcohol dispersion liquid includes carbon nanotube, dispersing agent and polar organic solvent, described
The mass ratio of carbon nanotube and polar organic solvent is preferably 1:200~300, more preferably 1:230~280, is further preferably 1:
240~275.The present invention does not have particular/special requirement to the preparation method of the carbon nanotube alcohol dispersion liquid, is by said components mixing
It can.
The present invention is not special to the hybrid mode of the polyimides chopped strand dispersion liquid and carbon nano tube dispersion liquid
It is required that using well known to those skilled in the art.In the present invention, the rate of the shearing is preferably 1200~2000r/
Min, more preferably 1400~1800r/min are further preferably 1500~1700r/min；The time of the shearing is preferably 30~
60min, more preferably 40~55min are further preferably 45~50min.The present invention preferably prepares mixed slurry under the above conditions,
Each component can be made to be sufficiently mixed, and then obtain the preferable carbon nanotube-graphite composite material of electric conductivity.
After obtaining mixed slurry, after the present invention preferably mixes the mixed slurry with shaping assistant, is formed, obtained
Carbon nanotube-polyimide nonwoven fabric.The present invention does not have particular/special requirement to the hybrid mode of the mixed slurry and shaping assistant,
Using mode well known to those skilled in the art.In the present invention, the molding mode is preferably filtered by vacuum, described
The pressure of vacuum filtration is preferably 0.08~0.12MPa, more preferably 0.08~0.1MPa.
After obtaining carbon nanotube-polyimide nonwoven fabric, the present invention by the carbon nanotube-polyimide nonwoven fabric successively
It carbonized, be graphitized and roll-in, obtain carbon nanotube-graphite composite material.
In the present invention, the temperature of the charing is preferably 1000~1200 DEG C, and more preferably 1050~1180 DEG C, then it is excellent
It is selected as 1100~1150 DEG C；The time of charing is preferably 3~8h, more preferably 4~7h, is further preferably 5~6h.The charing is excellent
Choosing carries out under anaerobic, and the oxygen free condition is preferably realized under nitrogen protection.In the present invention, it is warming up to charing institute
The rate for needing temperature is preferably 100~200 DEG C/h, and more preferably 120~180 DEG C, be further preferably 125~175 DEG C/h.The present invention
Carbon nanotube-the polyimide nonwoven fabric is carbonized, makes the polyimides chopped strand in non-woven fabrics in hot conditions
Lower decomposition removes hydrogen atom and oxygen atom therein, obtains carbon component.
After charing, the present invention is graphitized the material after charing.In the present invention, the graphited temperature is preferred
It is 2800~3000 DEG C, more preferably 2850~2970 DEG C, is further preferably 2900~2950 DEG C；The graphited time is preferably 24
~48h, more preferably 28~46h, more preferably 30~42h.In the present invention, it is described graphitization preferably under nitrogen protection into
Row.In the present invention, being warming up to the rate of graphitization required temperature by above-mentioned carbonization temperature is preferably 100~200 DEG C/h, more excellent
It is selected as 120~180 DEG C/h, is further preferably 125~175 DEG C/h.The present invention is graphitized the material after charing, and carbon can be improved
The electric conductivity of nanotube-graphene composite material.
After graphitization, the present invention carries out roll-in to the material after graphitization, to improve the compactness and intensity of material structure.
In the present invention, the pressure of the roll-in is preferably 100~120kN/m, more preferably 105~118kN/m, is further preferably 108
~115kN/m.The present invention does not have particular/special requirement to the time of the roll-in and number, can obtain the carbon nanometer of the thickness
Pipe-graphite composite material.
The present invention provides a kind of lithium sulfur battery anode material, including collector, polysulfide barrier layer and it is located at described
Active material between collector and polysulfide barrier layer；
The collector is described in carbon nanotube-graphite composite material described in above-mentioned technical proposal or above-mentioned technical proposal
Carbon nanotube-graphite composite material that preparation method is prepared；
The active material includes sulphur simple substance；
The polysulfide barrier layer includes carbon nanotube-aramid nonwoven.
Active material provided by the invention includes sulphur simple substance, and the sulphur simple substance is preferably sulphur powder, and the partial size of the sulphur powder is excellent
It is selected as 30~80nm, more preferably 40~60nm；The purity of the sulphur powder is preferably >=99%.
In the present invention, for the active material it is also preferable to include carbon black and Kynoar, the carbon black is preferably super
Carbon black.The present invention does not have particular/special requirement to the mass ratio of the sulphur simple substance, carbon black and Kynoar, using those skilled in the art
Known to member, in embodiments of the present invention, the mass ratio of the sulphur simple substance, carbon black and Kynoar is preferably 1:(0.1
~0.2): (0.08~0.15), more preferably 1:(0.12~0.15): (0.1~0.12).In the present invention, the active material
Material preferably accounts for the 10~30% of lithium sulfur battery anode material gross mass, more preferably 15~25%, is further preferably 20~25%.
Active material of the present invention is between collector and polysulfide barrier layer, since the carbon as collector is received
Mitron-graphite composite material has pore structure, therefore active material can be attached in the surface and hole of collector.
Lithium sulfur battery anode material provided by the invention includes polysulfide barrier layer, and the polysulfide barrier layer includes
Carbon nanotube-aramid nonwoven.In the present invention, the carbon nanotube-aramid nonwoven has pore structure, the hole
Aperture is preferably 2~110nm, more preferably 2~80nm, is further preferably 2~50nm.Carbon nanotube-the aramid nonwoven
Thickness is preferably 0.01~0.1mm, more preferably 0.03~0.08mm, is further preferably 0.05~0.07mm.The present invention preferably with
Carbon nanotube-aramid nonwoven can effectively inhibit the shuttle effect of sulphur as polysulfide barrier layer.
The present invention provides the preparation methods of lithium sulfur battery anode material described in above-mentioned technical proposal, comprising:
It will include that the slurry of active material is coated in carbon nanotube-graphite composite material or above-mentioned described in above-mentioned technical proposal
Carbon nanotube-graphite composite material single side that preparation method described in technical solution is prepared, then by carbon nanotube-aramid fiber
Nonwoven layer is layered on the surface of pulp layer, obtains lithium sulfur battery anode material using hot pressing.
In the present invention, the slurry preferably includes active material and solvent, and the solvent preferably includes N- methylpyrrole
Alkanone.The present invention does not have particular/special requirement to the dosage of the solvent, can obtain the slurry suitable for coating.The present invention is to described
The preparation method of slurry does not have particular/special requirement, after preferably active material and solvent are mixed, ball milling.In the present invention
In, the speed of the ball milling is preferably 200~300r/min, more preferably 220~250r/min；The time of ball milling is preferably 6
~10h, more preferably 7~8h.
The present invention does not have particular/special requirement to coating method, the coated weight of the slurry, using known to those skilled in the art
Mode, mass percentage of the active material in lithium sulfur battery anode material can be made to reach model described in above-mentioned technical proposal
It encloses.
After coating, carbon nanotube-aramid nonwoven layer is layered on the surface of pulp layer by the present invention.In the present invention, described
Carbon nanotube-aramid nonwoven preparation method preferably includes:
It will include that carbon nanotube, aramid fiber, the mixture for discongesting agent, dispersing agent and polar organic solvent are sheared,
Obtain carbon nanotube-aramid fiber mixed slurry；
It after the carbon nanotube-aramid fiber mixed slurry is mixed with shaping assistant, is formed, obtains carbon nanotube-virtue
Synthetic fibre non-woven fabrics.
In the present invention, the carbon nanotube-aramid fiber mixed slurry preparation method preferably includes:
It is beaten after p-aramid fiber chopped strand dispersion liquid is mixed with para-aramid pulp fiber dispersion, obtains aramid fiber fibre
Tie up slurry；
The aramid fiber slurry is mixed with carbon nanotube alcohol dispersion liquid and dodecyl sodium sulfate, obtains carbon nanometer
Pipe-aramid fiber mixed slurry.
In the present invention, the p-aramid fiber chopped strand dispersion liquid preferably includes p-aramid fiber chopped strand, dodecane
The mass ratio of base benzene sulfonic acid sodium salt and water, the p-aramid fiber chopped strand, neopelex and water is preferably 1:
(0.005~0.01): (200~400), more preferably 1:(0.006~0.009): (220~360) are further preferably 1:(0.007
~0.008): (240~320).
In the present invention, the diameter of the p-aramid fiber chopped strand is preferably 10~14 μm, and more preferably 11~13 μm,
It is further preferably 12 μm；Length is preferably 3~5mm, more preferably 3~4mm, is further preferably 4mm.The p-aramid fiber chopped strand
For commercial product well known to those skilled in the art.
In the present invention, the generation type of the p-aramid fiber chopped strand dispersion liquid preferably includes following steps:
P-aramid fiber chopped strand is mixed with water, neopelex then is added to mixed material and is dredged
Solution, obtains p-aramid fiber chopped strand dispersion liquid.
In the present invention, the temperature discongested is preferably 40~60 DEG C, and more preferably 45~55 DEG C, further preferably for 48~
52℃；The time discongested is preferably 15~30min, more preferably 17~28min, is further preferably 20~25min.It is described to dredge
Solution preferably carries out under agitation, and the stirring uses mode well known to those skilled in the art.
In the present invention, the para-aramid pulp fiber dispersion preferably includes para-aramid pulp fiber, polyoxygenated
Ethylene and ethyl alcohol, the mass ratio of the para-aramid pulp fiber, polyethylene glycol oxide and ethyl alcohol be preferably 1:(0.005~
0.01): (200~400), more preferably 1:(0.006~0.009): (220~360), further preferably for 1:(0.007~
0.008): (240~320).
In the present invention, the length of the para-aramid pulp fiber is preferably 1.2~2mm, more preferably 1.4~
1.8mm is further preferably 1.5~1.6mm.The para-aramid pulp fiber is commercial product well known to those skilled in the art.
In the present invention, the generation type of the para-aramid pulp fiber dispersion preferably includes following steps:
Para-aramid pulp fiber is mixed with water, is then discongested, is obtained to mixed material addition polymerization ethylene oxide (PEO)
To para-aramid pulp fiber dispersion.
In the present invention, the temperature discongested is preferably 40~60 DEG C, and more preferably 45~55 DEG C, further preferably for 48~
52℃；The time discongested is preferably 15~30min, more preferably 17~28min, is further preferably 20~25min.It is described to dredge
Solution preferably carries out under agitation, and the stirring uses mode well known to those skilled in the art.
After obtaining p-aramid fiber chopped strand dispersion liquid and p-aramid fiber slurry cypress fiber dispersion, the present invention is by the contraposition
It is beaten after aramid short fiber dispersion liquid and p-aramid fiber slurry cypress fiber dispersion mixing, obtains aramid fiber slurry.In this hair
In bright, when preparing aramid fiber slurry, the mass ratio of p-aramid fiber chopped strand and para-aramid pulp fiber is preferably 1:(1
~7), more preferably 1:(2~6), be further preferably 1:(3~5)；The beating degree of the fibre stuff is preferably 40~60 ° of SR, more
Preferably 45~58 ° of SR are further preferably 47~55 ° of SR.The present invention does not have particular/special requirement to the specific embodiment of the mashing,
It can obtain above-mentioned beating degree.
After obtaining aramid fiber slurry, the present invention is by the aramid fiber slurry and carbon nanotube alcohol dispersion liquid and dodecane
The mixing of base sodium sulfonate, obtains carbon nanotube-aramid fiber mixture.In the present invention, the carbon nanotube alcohol dispersion liquid includes that carbon is received
The mass ratio of mitron, lauryl sodium sulfate and ethyl alcohol, the carbon nanotube, lauryl sodium sulfate and ethyl alcohol is preferably 1:
(0.005~0.01): (200~300), more preferably 1:(0.006~0.009): (220~285) are further preferably 1:(0.007
~0.008): (240~275).
In the present invention, the carbon nanotube is preferably multi-walled carbon nanotube, and the diameter of the carbon nanotube is preferably 30
~150nm, more preferably 45~125nm are further preferably 50~100nm；The length of carbon nanotube is preferably 5~10 μm, more excellent
6~9 μm are selected as, is further preferably 7~8 μm.The carbon nanotube is commercial product well known to those skilled in the art.
In the present invention, when preparing carbon nanotube-aramid fiber mixed slurry, the quality of carbon nanotube and aramid short fiber and
The total mass ratio of ppta-pulp fibre is preferably 1:(0.5~2), more preferably 1:(0.8~1.8).Further preferably for 1:(1.0~
1.5)。
In the present invention, mixed between the aramid fiber slurry and carbon nanotube alcohol dispersion liquid and dodecyl sodium sulfate
Conjunction preferably carries out in a shear condition, and the rate of the shearing is preferably 1200~2000r/min, more preferably 1500~
1800r/min；The time of the shearing is preferably 30~60min, more preferably 40~55min.
After obtaining carbon nanotube-aramid fiber slurry, the present invention mixes the carbon nanotube-aramid fiber mixed slurry with shaping assistant
It after conjunction, is formed, obtains carbon nanotube-polyimide nonwoven fabric.In the present invention, the shaping assistant preferably includes to bond
Agent and flocculant, the binder preferably include polyacrylate and/or polyvinyl alcohol, more preferably polyacrylate.It is described
Flocculant preferably includes cationic polyacrylamide and/or anionic polyacrylamide, more preferably anionic polyacrylamide.
The binder and the mass ratio of flocculant are preferably 1:0.8~1.2, more preferably 1:0.9~1.1, most preferably 1:1.?
In the present invention, the mass ratio of the gross mass and shaping assistant of the carbon nanotube and aramid fiber is preferably 1:0.004~0.01,
More preferably 1:0.005~0.009 is further preferably 1:0.006~0.008.
The present invention does not have particular/special requirement to the hybrid mode of the carbon nanotube-aramid fiber mixed slurry and shaping assistant, adopts
With mode well known to those skilled in the art.In the present invention, the molding mode is preferably filtered by vacuum, described true
The pressure of empty pump filter is preferably 0.08~0.12MPa, more preferably 0.08~0.1MPa.Tool of the present invention to the vacuum filtration
Body embodiment does not have particular/special requirement, can obtain carbon nanotube-aramid nonwoven of thickness described in above scheme.
The present invention does not have particular/special requirement to the layer paving mode of the carbon nanotube-aramid nonwoven, and non-woven fabrics can be made smooth
It is covered on the surface of active slurry layer.
After layer paving, the present invention includes carbon nanotube-graphite composite material, active slurry and carbon nanotube-virtue to what is obtained
The compound material of synthetic fibre non-woven fabrics carries out hot pressing, obtains lithium-sulfur cell material.In the present invention, the temperature of the hot pressing is preferably
300~320 DEG C, more preferably 305~315 DEG C are further preferably 310~315 DEG C；The time of the hot pressing is preferably 2~5min,
More preferably 3~4min；The pressure of the hot pressing is preferably 8~10MPa, more preferably 8.5~10MPa, further preferably for 8.5~
9.5MPa.In embodiments of the present invention, the hot pressing is preferably completed by vulcanizing press.
The present invention is by hot pressing, by carbon nanotube-graphite composite material, active slurry and carbon nanotube-aramid nonwoven
Integration is carried out, the preferable lithium sulfur battery anode material of chemical property is obtained.
The present invention also provides a kind of lithium-sulfur cells, including anode cover, anode, diaphragm, cathode, negative electrode casing and electrolyte；
It is described that just extremely preparation method described in lithium sulfur battery anode material or above-mentioned technical proposal described in above-mentioned technical proposal is prepared into
The lithium sulfur battery anode material arrived；
The cathode preferably includes lithium piece；
The diaphragm preferably includes polypropylene porous film；
The electrolyte preferably includes LiPF6。
The present invention does not have a particular/special requirement to the assemble method of the lithium-sulfur cell, preferably according to anode cover, anode, diaphragm,
The sequence of cathode, negative electrode casing and electrolyte assembles.
In embodiment of above, unless otherwise specified, agents useful for same of the present invention is city well known to those skilled in the art
Sell product.
In order to further illustrate the present invention, with reference to the accompanying drawings and examples to carbon nanotube-graphite provided by the invention
Composite material, lithium sulfur battery anode material and lithium-sulfur cell are described in detail, but they cannot be interpreted as to the present invention
The restriction of protection scope.
Embodiment 1
The preparation of carbon nanotube-graphite composite material:
0.5g polyimides chopped strand is dissolved in 100g ethyl alcohol, 0.005g polyethylene glycol oxide (PEO) conduct is added
Agent is discongested, discongests polyimides chopped strand sufficiently, polyimides chopped strand slurry is made.
It weighs 0.5g carbon nanotube and 0.005gSDS is dissolved in 100g ethyl alcohol, it is then super under the conditions of frequency is 80KHz
Then sound 20min shears 30min under conditions of revolving speed is 1000r/min, carbon nano tube dispersion liquid is made.
After the carbon nano tube dispersion liquid of polyimides chopped strand slurry is mixed under conditions of 1500r/min, pass through
High-speed shearing machine shears 30min, and the mixed slurry of carbon nanotube-polyimides chopped strand is made.
0.008g polyacrylate and 0.005g sun are added in carbon nanotube-polyimides chopped strand mixed slurry
Cationic polyacrylamide obtains carbon nanotube-polyimide nonwoven fabric by way of vacuum filtration.
Under nitrogen protection, 1200 DEG C are warming up to the rate of 100 DEG C/h, make carbon nanotube-polyimide nonwoven fabric into
Row charing, after being then warming up to 2800 DEG C according to the heating rate of 100 DEG C/h, after being graphitized, by pricking machine repeatedly to roller
After rolling, carbon nanotube-graphite composite material is made.
The preparation of carbon nanotube-aramid nonwoven:
It weighs 0.5g para-aramid pulp fiber and 0.005g polyethylene glycol oxide (PEO) is dispersed in liquid, be standing and soaking, into
Row is discongested；It weighs 0.5g p-aramid fiber chopped strand and 0.005g dodecyl sodium sulfate is dissolved in ethanol solution, stirring is dredged
Solution carries out mashing processing after mixing two kinds of fibers after above-mentioned discongest in beater, and aramid fiber slurry is made.
Weigh 0.5g carbon nanotube and 0.005gSDS dissolution in ethanol, frequency 80KHz, ultrasonic 20min, speed is
30min is sheared under the conditions of 1500r/min, and carbon nano tube dispersion liquid is made.
30min is sheared by high-speed shearing machine after aramid fiber slurry and carbon nano tube dispersion liquid are mixed, obtained carbon is received
Mitron-aramid fiber mixed slurry.
0.08g anionic polyacrylamide is added in carbon nanotube-aramid fiber mixed slurry, passes through the side of vacuum filtration
Formula obtains carbon nanotube/aramid nonwoven.
The preparation of the multi-functional anode of lithium-sulfur cell:
1.4g active material sulphur, the super carbon black of 0.4g and 0.2g Kynoar are weighed in appropriate N-Methyl pyrrolidone
In, shearing dispersion obtains positive-active slurry；
Positive-active slurry obtained is homogeneously applied to carbon nanotube-graphite composite material by way of coating
Single side.
Carbon nanotube-the graphite composite material for applying positive-active slurry and carbon nanotube-aramid nonwoven are attached to one
Rising through vulcanizing press in temperature is 300 DEG C, and lithium-sulphur cell positive electrode is made in hot pressing 3min under pressure 10MPa.
The preparation of lithium-sulfur cell:
According to the sequence of anode cover, anode, diaphragm, cathode, negative electrode casing, lithium-sulfur cell is assembled into after electrolyte is added dropwise.
Embodiment 2~3
Prepare carbon nanotube-graphite composite material, lithium sulfur battery anode material and lithium sulphur respectively in the way of embodiment 1
Battery, the difference is that raw material dosage and technological parameter, are specifically listed in Table 1.
Comparative example 1
Using aluminium foil as collector, remaining prepares positive electrode and battery in the way of embodiment 1.
1 Examples 1 to 3 raw material dosage of table and technological parameter
Performance characterization and result
Using four probe resistance instrument testing example, 1~3 gained carbon nanotube-graphite composite material sheet resistance, survey
Test result is listed in table 2；
Carbon nanotube-graphite composite material specific surface area and aperture are tested using specific surface area analysis instrument, using in list
The tensile strength of the method test material of counterweight is hung under the sectional area of position, test result is listed in table 2；
Carbon nanotube-graphite composite material structure obtained by 2 Examples 1 to 3 of table and performance parameter
By 2 test result of table it is found that carbon nanotube-graphite composite material provided by the invention has preferable mechanical property
And electric property, it is suitable for the collector of positive electrode；In addition, the pore structure that carbon nanotube-graphite composite material has,
Positive electrode active materials can be made to be embedded, it is advantageous to the load capacity for improving positive electrode active materials.
Under conditions of charge-discharge magnification is 1C, the circulation of 1 gained lithium-sulfur cell of testing example 1~3 and comparative example is steady
Qualitative, test result is shown in that Fig. 2 and table 3, Fig. 2 are the cycle performance comparison diagram of 1 gained battery of embodiment 1 and comparative example, can by figure
Know, recycle 250 times under the multiplying power of 1C, battery capacity conservation rate made from embodiment 1 is about 88%, hence it is evident that be higher than comparative example 1
The conservation rate of obtained battery capacity 65%.
The electrochemical property test result of lithium-sulfur cell obtained by 3 Examples 1 to 3 of table
By 3 test result of table it is found that being prepared using carbon nanotube-graphite composite material provided by the invention as collector
Lithium sulfur battery anode material can reduce the rate of decay of battery specific capacity, improve the cyclical stability of lithium-sulfur cell.
As seen from the above embodiment, carbon nanotube-graphite composite material provided by the invention have good pore structure,
Intensity and toughness can inhibit Volumetric expansion, and carbon nanotube-graphite composite material also has excellent electric conductivity,
And then the problem of improving sulphur simple substance poorly conductive.In addition, lithium-sulphur cell positive electrode is also using carbon nanotube-aramid nonwoven as more sulphur
Compound barrier layer can inhibit the shuttle effect of sulphur, further improve the cyclical stability of lithium-sulfur cell.
The present invention coats lithium fluoride passivating film in lithium belt surface, can prevent the oxidation of lithium；Lithium fluoride passivating film can also be
In battery charge and discharge process, effectively prevents excessive lithium and be electrolysed the problem of qualitative response forms Li dendrite, and then improve lithium ion
The cyclical stability of battery.
The preparation method of flexible lithium ion battery provided by the invention is simple, easily-controllable, and cost is relatively low, is suitable for popularization and application.
Although above-described embodiment is made that detailed description to the present invention, it is only a part of the embodiment of the present invention,
Rather than whole embodiments, people can also obtain other embodiments under the premise of without creativeness according to the present embodiment, these
Embodiment belongs to the scope of the present invention.
Claims (10)
1. a kind of carbon nanotube-graphite composite material, by including carbon nanotube, polyimides chopped strand, shaping assistant, discongesting
Agent, dispersing agent and polar organic solvent prepare raw material, are successively made through molding, charing, graphitization and roll-in；
Carbon nanotube-the graphite composite material has hole.
2. carbon nanotube-graphite composite material as described in claim 1, which is characterized in that the carbon nanotube and polyamides are sub-
The mass ratio of amine chopped strand is 1:1~7；
Polyimides chopped strand is 1:0.005~0.01 with the mass ratio for discongesting agent；
The mass ratio of carbon nanotube and dispersing agent is 1:0.005~0.01；
The mass ratio of the gross mass and shaping assistant of carbon nanotube and polyimides chopped strand is 1:0.004~0.01.
3. carbon nanotube-graphite composite material as claimed in claim 1 or 2, which is characterized in that the shaping assistant includes viscous
Tie agent and flocculant；
The binder includes polyacrylate and/or polyvinyl alcohol；
The flocculant includes cationic polyacrylamide and/or anionic polyacrylamide.
4. carbon nanotube-graphite composite material as described in claim 1, which is characterized in that the carbon nanotube-graphite is compound
The aperture of material hole is 3~100nm, and specific surface area is 15~30m2/ g, porosity be 50~60%, sheet resistance be 3~
15Ω/□。
5. the preparation method of any one of Claims 1 to 4 carbon nanotube-graphite composite material, comprising the following steps:
(1) will include carbon nanotube, polyimides chopped strand, discongest the mixture of agent, dispersing agent and polar organic solvent into
Row shearing, obtains mixed slurry；
(2) it after mixing the mixed slurry of the step (1) with shaping assistant, is formed, obtains carbon nanotube-polyimides
Non-woven fabrics；
(3) carbon nanotube-polyimide nonwoven fabric of the step (2) successively carbonized, be graphitized and roll-in, obtain carbon
Nanotube-graphene composite material.
6. preparation method as claimed in claim 5, which is characterized in that in the step (3),
The temperature of charing is 1000~1200 DEG C, and the time of charing is 3~8h；
Graphited temperature is 2800~3000 DEG C, and the graphited time is 24~48h；
The pressure of roll-in is 100~120kN/m.
7. a kind of lithium sulfur battery anode material, including collector, polysulfide barrier layer and it is located at the collector and more vulcanizations
Active material between object barrier layer；
The collector is the described in any item carbon nanotube-graphite composite materials of Claims 1 to 4 or claim 5 or 6 institutes
State carbon nanotube-graphite composite material that preparation method is prepared；
The active material includes sulphur simple substance；
The polysulfide barrier layer includes carbon nanotube-aramid nonwoven.
8. lithium sulfur battery anode material as claimed in claim 7, which is characterized in that the active material accounts for lithium-sulphur cell positive electrode
The 10~30% of material gross mass.
9. the preparation method of the lithium sulfur battery anode material of claim 7 or 8, comprising:
By include active material slurry be coated in the described in any item carbon nanotube-graphite composite materials of Claims 1 to 4 or
Carbon nanotube-graphite composite material single side that the preparation method of claim 5 or 6 is prepared, then by carbon nanotube-
Aramid nonwoven layer is layered on the surface of pulp layer, obtains lithium sulfur battery anode material using hot pressing.
10. a kind of lithium-sulfur cell, including anode cover, anode, diaphragm, cathode, negative electrode casing and electrolyte；It is characterized in that, described
The just extremely lithium sulphur that is prepared of preparation method described in lithium sulfur battery anode material or claim 9 described in claim 7 or 8
Cell positive material.
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