CN109461909A - Lithium sulfur battery anode material and preparation method thereof - Google Patents
Lithium sulfur battery anode material and preparation method thereof Download PDFInfo
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- CN109461909A CN109461909A CN201811189810.0A CN201811189810A CN109461909A CN 109461909 A CN109461909 A CN 109461909A CN 201811189810 A CN201811189810 A CN 201811189810A CN 109461909 A CN109461909 A CN 109461909A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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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
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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
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- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H—ELECTRICITY
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
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Abstract
The present invention provides a kind of lithium sulfur battery anode materials, including base layer, coat the polymeric layer of the base layer, and the sandwich layer in base layer.The present invention also provides the preparation methods of above-mentioned lithium sulfur battery anode material.Lithium sulfur battery anode material provided by the present invention, in base layer outer cladding conductive polymer coating, sandwich layer is filled in base layer, the suction-operated of the physical limit effect and chemical component of the one-dimensional pipeline of base layer is utilized simultaneously, it solves in the prior art, the shuttle effect of the more sulphions of intermediate product generated in lithium-sulfur cell sulphur anode charge and discharge process can make battery capacity, circulation conservation rate lower, the low problem of whole chemical property.Base layer is galapectite layer, and more sulphions can not only be inhibited to shuttle in terms of physical limit and chemisorption two, and for galapectite as cheap natural minerals, the cost of anode can also be reduced by using it as matrix, is conducive to promote and apply.
Description
Technical field
The invention belongs to battery material technical fields, and in particular to lithium sulfur battery anode material and preparation method thereof.
Background technique
With the rapid development of new-energy automobile and mobile electronic device, there is an urgent need to the higher batteries of energy density.?
In new energy system, lithium-sulfur cell is with its high theoretical specific energy (2600Wh/kg), elemental sulfur is cheap and environmental-friendly etc. special
Property, become one of next-generation most potential secondary cell system.
Typical lithium-sulfur cell generally uses elemental sulfur as anode, and metal lithium sheet is as cathode.However, lithium-sulfur cell master
There are problems that three: (1) substance of elemental sulfur and discharging product lithium sulfide as non-conductive or low conduction, electric conductivity is very
Difference；(2) in charge and discharge process, volume can expand and reduce sulphur, it is possible to lead to cell damage；(3) intermediate product vulcanizes more
The shuttle effect of lithium, i.e., in charge and discharge process, the polysulfide (Li of anode generation2Sx) intermediate is dissolved into electrolyte,
And diaphragm is passed through, it spreads to cathode, directly reacts with the lithium metal of cathode, ultimately caused in battery active principle not
Reversible loss, the decaying of battery life and low coulombic efficiency.The more lithium sulfides of above three problem, especially intermediate product
Shuttle effect, hinder the commercialization of lithium-sulfur cell.To solve this problem, the prior art is mainly inhaled from physical limit and chemistry
Attached two aspect is started with.In terms of physical limit, mainly in carrier (such as graphite with pore structure of positive high-specific surface area
Alkene, carbon pipe etc.) physical absorption and confinement are carried out to sulphur and polysulfide；It is mainly further to load in terms of chemisorption
Body is chemically modified, modification activities site, to realize chemisorption.
As CN107403916A discloses a kind of lithium-sulfur cell anode with the more lithium sulfides of graphene conductive network constraint
Material, the positive electrode vulcanize lithium powder, polyimide solution and organic carbon source aqueous solution by graphene microchip, more and are made, should
The graphene microchip of invention has the characteristics that good dispersion and conductivity are high, modified to advantageously reduce between graphene sheet layer
It stacks again.Graphene microchip can hinder the polysulfide generated to be dissolved in electrolyte after mixing carbonization with organic carbon source aqueous solution
In, be conducive to the electric conductivity for improving anode and the fixation of more lithium sulfides, that is, improve the cycle-index of electrode, also improve electrode
Multiplying power property.CN103490027B discloses a kind of lithium-sulfur cell diaphragm and preparation method thereof, the lithium-sulfur cell with every
Film is made of common batteries diaphragm with the Porous barriers loaded thereon, and Porous barriers can permit lithium ion and pass through, but right
More lithium sulfide intermediates that sulphur anode is formed in charge and discharge process have blocking and suction-operated, so as to limit active material sulphur
System prevents sulphur anode from irreversible appearance occurs because the more lithium sulfide intermediates formed in cyclic process are dissolved in electrolyte in positive side
Amount decaying, improves the cycle performance of sulphur anode.Meanwhile the diaphragm can also weaken shuttle effect of the polysulfide to cathode of lithium,
It prevents circulating battery from forming sulfur-bearing passivation layer on cathode of lithium surface in the process, improves the cycle performance of cathode of lithium.The invention is also public
The lithium-sulfur cell using the diaphragm is opened, the invention lithium-sulfur cell is simple with diaphragm preparation method, and raw material is easy to get, and is suitable for
Large-scale production.However, shuttle effect problem of the existing technology still without the more lithium sulfides of adequate solution intermediate product.
Summary of the invention
To solve in the prior art, the shuttle effect of the more lithium sulfides of sulphur anode intermediate product, leads to battery in lithium-sulfur cell
Specific capacity, circulation conservation rate are lower, the low problem of whole chemical property, and an object of the present invention is to provide a kind of lithium sulphur electricity
Pond positive electrode.
The second object of the present invention is to provide the preparation method of above-mentioned lithium sulfur battery anode material.
To achieve the above object, the invention adopts the following technical scheme:
Lithium sulfur battery anode material, including base layer coat the polymeric layer of the base layer, and are located in base layer
Sandwich layer.
Preferably, the base layer is galapectite.
Preferably, the polymer is polypyrrole (PPy), polyaniline (PANI) and poly- 3,4-rthylene dioxythiophene
One of (PEDOT).
Preferably, the sandwich layer is sulphur simple substance layer.
The preparation method of above-mentioned lithium sulfur battery anode material, which is characterized in that step includes:
(1) it is heat-treated after mentioning the base layer with acidleach；
(2) in a solvent by the dispersion of step (1) treated base layer, polymer monomer and oxidant are added into solvent
Semi-finished product are obtained after polymerization；
(3) sandwich layer is loaded into semi-finished product obtained by step (2).
The purpose that step (1) acidleach mentions is to remove the impurity in base layer.
Preferably, acid described in step (1) is one of hydrochloric acid, sulfuric acid or oxalic acid.
It is further preferred that the mass fraction of the hydrochloric acid is 30~40%.
Preferably, the temperature of step (1) described extraction is 60~70 DEG C, and the time of the extraction is 100~150min.
Preferably, the temperature of step (1) described heat treatment is 200~500 DEG C, and the time of the heat treatment is 2~6h.
Preferably, solvent described in step (2) is water, and the oxidant is FeCl3, ammonium persulfate, potassium peroxydisulfate and
One of sodium peroxydisulfate.
It is further preferred that the mass ratio of base layer and polymer monomer is 1:(0.5~3 in step (2)), polymer list
The mass ratio of body and oxidant is 1:(1~5).
Preferably, the temperature of step (2) described polymerization be 20~30 DEG C, the time be 12~for 24 hours.
Preferably, the carrying method of step (3) described sandwich layer is hot fusion method, specifically: step (2) will be obtained half at
Product are uniformly mixed with sulphur, are placed in tube furnace, under Ar atmosphere, 150~200 DEG C of 10~16h of heat preservation.
Galapectite is a kind of natural silicate minerals, has unique hollow tubular structure, and pipe outer wall is by silicon oxygen four sides
Body composition, inside pipe wall is alumina octahedral.For the shuttle effect problem for solving more lithium sulfides, the one of galapectite can be utilized simultaneously
Dimension pipeline and chemical component play physical limit and chemisorption to more lithium sulfides, to finally improve battery performance.
In the prior art, having scholar to first pass through acid etch increases the lumen diameter of galapectite, then uses liquid phase chemical
Sulphur is filled into the lumen of galapectite by sedimentation and heat treatment two-step method, is formed galapectite/sulphur composite material, is used further to prepare
Obtain the lithium-sulphur cell positive electrode piece based on galapectite.However, the limitation handled in this way is, since galapectite does not have conduction
Property, it is unfavorable for electron-transport, therefore battery capacity, circulation conservation rate are lower, whole chemical property is to be improved.
Beneficial effects of the present invention
1, lithium sulfur battery anode material provided by the present invention, in base layer outer cladding conductive polymer coating, in base layer
Middle filling sandwich layer, while the suction-operated of the physical limit effect and chemical component of the one-dimensional pipeline of base layer is utilized, it solves
In the prior art, the shuttle effect of the more sulphions of intermediate product generated in lithium-sulfur cell sulphur anode charge and discharge process can make
Battery specific capacity, circulation conservation rate are lower, the low problem of whole chemical property；
2, in lithium sulfur battery anode material provided by the present invention, base layer is galapectite layer, can not only be limited from physics
More sulphions are inhibited to shuttle in terms of system and chemisorption two, galapectite uses it as matrix also as cheap natural minerals
The cost of anode can be reduced, is conducive to promote and apply；
3, preparation method provided by the present invention first carries out the cladding of conducting polymer on galapectite surface, then comes again
Sulfur loaded is ingenious to solve the problems, such as that galapectite is nonconducting；
4, the lithium sulfur battery anode material being prepared using method of the invention, discharge specific volume for the first time under 0.1C multiplying power
Amount is 786.9mAh g-1, after 100 circulations, circulation conservation rate is up to 71.8%.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of lithium sulfur battery anode material.
Fig. 2 is the scanning electron microscope (SEM) photograph of untreated galapectite.
Fig. 3 is the scanning electron microscope (SEM) photograph for the lithium sulfur battery anode material that embodiment 2 is prepared.
Fig. 4 is the battery high rate performance test result of embodiment 2.
Fig. 5 is the battery high rate performance test result of embodiment 5.
Fig. 6 is the battery high rate performance test result of comparative example 1.
Fig. 7 is the cycle performance of battery test result of embodiment 2.
Fig. 8 is the cycle performance of battery test result of embodiment 5.
Fig. 9 is the cycle performance of battery test result of comparative example 1.
Specific embodiment
The following is specific embodiments of the present invention, and is described with reference to the drawings and further retouches to technical solution of the present invention work
It states, however, the present invention is not limited to these examples.
Embodiment 1
Lithium sulfur battery anode material, including base layer coat the polymeric layer of the base layer, and are located in base layer
Sandwich layer.As shown in Figure 1, wherein 1 be base layer, 2 be polymeric layer, and 3 be sandwich layer.
Base layer is galapectite, and polymer is polypyrrole (PPy), polyaniline (PANI) and poly- 3,4-rthylene dioxythiophene
One of (PEDOT), sandwich layer is sulphur simple substance layer.
Fig. 2 is scanning electron microscope (SEM) figure of untreated galapectite, and galapectite has smooth as we can see from the figure
Outer wall and hollow pipeline.
Embodiment 2
Lithium sulfur battery anode material, preparation method include:
(1) it is heat-treated after mentioning galapectite with acidleach, specifically:
The natural galapectite solid powder of 10g is added to the concentrated hydrochloric acid and 7ml deionization that are 38% by 28ml mass fraction
In the solution of water composition, 120min is reacted at 70 DEG C, is then centrifuged for washing, solid is obtained by filtration, is placed in 80 DEG C of baking ovens dry
For 24 hours, the galapectite powder after obtaining acidleach purification under an argon atmosphere by the galapectite powder after purification is placed in tube furnace,
300 DEG C of heat preservation 3h, heating rate are 5 DEG C/min, cooling up to heat treated galapectite powder.
(2) in a solvent by the dispersion of step (1) treated galapectite, the polymer and oxidant are added into solvent
Semi-finished product are obtained after polymerization, specifically:
By step (1), treated that 0.1g galapectite is added in 90ml deionized water, is added after ultrasound 10min at room temperature
100 μ L pyrroles stir 10min, obtain suspension, take 0.15g FeCl3After being dissolved in 10ml deionized water, by FeCl3Solution instills outstanding
In supernatant liquid, stir at room temperature for 24 hours, by liquid centrifuge separation, washing, the galapectite powder obtained by drying to PPy cladding.
(3) sandwich layer is loaded into semi-finished product obtained by step (2), specifically:
The galapectite powder of PPy cladding obtained by 0.07g distillation sulphur powder and 0.03g step (2) is uniformly mixed, tubular type is placed in
In furnace, under argon atmosphere, the 155 DEG C plus heat preservation 12h galapectite mixing materials coated to get S/PPy, scanning electron microscope result is as schemed
Shown in 3, the outer wall of galapectite otherwise smooth is roughening from the figure not difficult to find, is attached with a large amount of additional substance thereon, simultaneously
It is filled full in pipeline.
The mass ratio of galapectite, polymer and sulphur is 1:1:(7/3 in this example).
Embodiment 3
Lithium sulfur battery anode material, preparation method include:
(1) it is heat-treated after mentioning galapectite with acidleach, specifically:
The natural galapectite solid powder of 10g is added to the concentrated hydrochloric acid and 7ml deionization that are 38% by 28ml mass fraction
In the solution of water composition, 120min is reacted at 70 DEG C, is then centrifuged for washing, solid is obtained by filtration, is placed in 80 DEG C of baking ovens dry
For 24 hours, the galapectite powder after obtaining acidleach purification under an argon atmosphere by the galapectite powder after purification is placed in tube furnace,
300 DEG C of heat preservation 3h, heating rate are 5 DEG C/min, cooling up to heat treated galapectite powder.
(2) in a solvent by the dispersion of step (1) treated galapectite, the polymer and oxidant are added into solvent
Semi-finished product are obtained after polymerization, specifically:
By step (1), treated that 0.1g galapectite is added in 90ml deionized water, is added after ultrasound 10min at room temperature
120 μ L aniline stir 10min, obtain suspension, take 0.1mol L-1240 μ L of HCl is added in suspension, then takes 0.2g ammonium persulfate
After being dissolved in 5mL water, ammonium persulfate solution is instilled in suspension, is stirred at room temperature for 24 hours, by liquid centrifuge separation, washing, drying
Obtain the galapectite powder of PANI cladding.
(3) sandwich layer is loaded into semi-finished product obtained by step (2), specifically:
The galapectite powder of PANI cladding obtained by 0.07g distillation sulphur powder and 0.03g step (2) is uniformly mixed, pipe is placed in
In formula furnace, under argon atmosphere, the 155 DEG C plus heat preservation 12h galapectite mixing materials coated to get S/PANI.
The mass ratio of galapectite, polymer and sulphur is 1:1:(7/3 in this example).
Embodiment 4
Lithium sulfur battery anode material, preparation method include:
(1) it is heat-treated after mentioning galapectite with acidleach, specifically:
The natural galapectite solid powder of 10g is added to the concentrated hydrochloric acid and 7ml deionization that are 38% by 28ml mass fraction
In the solution of water composition, 120min is reacted at 70 DEG C, is then centrifuged for washing, solid is obtained by filtration, is placed in 80 DEG C of baking ovens dry
For 24 hours, the galapectite powder after obtaining acidleach purification under an argon atmosphere by the galapectite powder after purification is placed in tube furnace,
300 DEG C of heat preservation 3h, heating rate are 5 DEG C/min, cooling up to heat treated galapectite powder.
(2) in a solvent by the dispersion of step (1) treated galapectite, the polymer and oxidant are added into solvent
Semi-finished product are obtained after polymerization, specifically:
By step (1), treated that 0.1g galapectite is added in 90ml deionized water, is added after ultrasound 10min at room temperature
120 μ LPEDOT stir 10min, obtain suspension, are added in suspension after taking 0.12g camphorsulfonic acid to be dissolved in 5mL water, then take 0.6g
After ammonium persulfate is dissolved in 5mL water, ammonium persulfate solution is instilled in suspension, is stirred at room temperature for 24 hours, liquid is centrifugated,
Washing, the galapectite powder obtained by drying to PEDOT cladding.
(3) sandwich layer is loaded into semi-finished product obtained by step (2), specifically:
The galapectite powder of PEDOT cladding obtained by 0.07g distillation sulphur powder and 0.03g step (2) is uniformly mixed, pipe is placed in
In formula furnace, under argon atmosphere, the 155 DEG C plus heat preservation 12h galapectite mixing materials coated to get S/PEDOT.
The mass ratio of galapectite, polymer and sulphur is 1:1:(7/3 in this example).
Embodiment 5
Lithium sulfur battery anode material, preparation method include:
(1) it is heat-treated after mentioning galapectite with acidleach, specifically:
The natural galapectite solid powder of 10g is added to the concentrated hydrochloric acid and 7ml deionization that are 38% by 28ml mass fraction
In the solution of water composition, 120min is reacted at 70 DEG C, is then centrifuged for washing, solid is obtained by filtration, is placed in 80 DEG C of baking ovens dry
For 24 hours, the galapectite powder after obtaining acidleach purification under an argon atmosphere by the galapectite powder after purification is placed in tube furnace,
300 DEG C of heat preservation 3h, heating rate are 5 DEG C/min, cooling up to heat treated galapectite powder.
(2) in a solvent by the dispersion of step (1) treated galapectite, the polymer and oxidant are added into solvent
Semi-finished product are obtained after polymerization, specifically:
By step (1), treated that 0.1g galapectite is added in 90ml deionized water, is added after ultrasound 10min at room temperature
200 μ L pyrroles stir 10min, obtain suspension, take 0.3gFeCl3After being dissolved in 10ml deionized water, FeCl3 solution is instilled and is suspended
In liquid, stir at room temperature for 24 hours, by liquid centrifuge separation, washing, the galapectite powder obtained by drying to PPy cladding.
(3) sandwich layer is loaded into semi-finished product obtained by step (2), specifically:
The galapectite powder of PPy cladding obtained by 0.07g distillation sulphur powder and 0.03g step (2) is uniformly mixed, tubular type is placed in
In furnace, under argon atmosphere, the 155 DEG C plus heat preservation 12h galapectite mixing materials coated to get S/PPy.
The mass ratio of galapectite, polymer and sulphur is 1:2:(7/3 in this example).
Embodiment 6
Lithium sulfur battery anode material, preparation method include:
(1) it is heat-treated after mentioning galapectite with acidleach, specifically:
The natural galapectite solid powder of 10g is added to the concentrated hydrochloric acid and 7ml deionization that are 38% by 28ml mass fraction
In the solution of water composition, 120min is reacted at 70 DEG C, is then centrifuged for washing, solid is obtained by filtration, is placed in 80 DEG C of baking ovens dry
For 24 hours, the galapectite powder after obtaining acidleach purification under an argon atmosphere by the galapectite powder after purification is placed in tube furnace,
300 DEG C of heat preservation 3h, heating rate are 5 DEG C/min, cooling up to heat treated galapectite powder.
(2) in a solvent by the dispersion of step (1) treated galapectite, the polymer and oxidant are added into solvent
Semi-finished product are obtained after polymerization, specifically:
By step (1), treated that 0.1g galapectite is added in 90ml deionized water, is added after ultrasound 10min at room temperature
240 μ L aniline stir 10min, obtain suspension, take 0.1mol L-1480 μ L of HCl is added in suspension, then takes 0.4g ammonium persulfate
After being dissolved in 5mL water, ammonium persulfate solution is instilled in suspension, is stirred at room temperature for 24 hours, by liquid centrifuge separation, washing, drying
Obtain the galapectite powder of PANI cladding.
(3) sandwich layer is loaded into semi-finished product obtained by step (2), specifically:
The galapectite powder of PANI cladding obtained by 0.07g distillation sulphur powder and 0.03g step (2) is uniformly mixed, pipe is placed in
In formula furnace, under argon atmosphere, the 155 DEG C plus heat preservation 12h galapectite mixing materials coated to get S/PANI.
The mass ratio of galapectite, polymer and sulphur is 1:2:(7/3 in this example).
Embodiment 7
Lithium sulfur battery anode material, preparation method include:
(1) it is heat-treated after mentioning galapectite with acidleach, specifically:
The natural galapectite solid powder of 10g is added to the concentrated hydrochloric acid and 7ml deionization that are 38% by 28ml mass fraction
In the solution of water composition, 120min is reacted at 70 DEG C, is then centrifuged for washing, solid is obtained by filtration, is placed in 80 DEG C of baking ovens dry
For 24 hours, the galapectite powder after obtaining acidleach purification under an argon atmosphere by the galapectite powder after purification is placed in tube furnace,
300 DEG C of heat preservation 3h, heating rate are 5 DEG C/min, cooling up to heat treated galapectite powder.
(2) in a solvent by the dispersion of step (1) treated galapectite, the polymer and oxidant are added into solvent
Semi-finished product are obtained after polymerization, specifically:
By step (1), treated that 0.1g galapectite is added in 90ml deionized water, is added after ultrasound 10min at room temperature
240 μ LPEDOT stir 10min, obtain suspension, are added in suspension after taking 0.24g camphorsulfonic acid to be dissolved in 5mL water, then take 1.2g
After ammonium persulfate is dissolved in 5mL water, ammonium persulfate solution is instilled in suspension, is stirred at room temperature for 24 hours, liquid is centrifugated,
Washing, the galapectite powder obtained by drying to PEDOT cladding.
(3) sandwich layer is loaded into semi-finished product obtained by step (2), specifically:
The galapectite powder of PEDOT cladding obtained by 0.07g distillation sulphur powder and 0.03g step (2) is uniformly mixed, pipe is placed in
In formula furnace, under argon atmosphere, the 155 DEG C plus heat preservation 12h galapectite mixing materials coated to get S/PEDOT.
The mass ratio of galapectite, polymer and sulphur is 1:2:(7/3 in this example).
Embodiment 8
Application of the lithium sulfur battery anode material in cell positive material, this example provides the preparation method of electrode material,
Specifically: after lithium sulfur battery anode material and conductive agent 7:2 in mass ratio grinding uniformly, binder is added, stirs at room temperature
Slurry is made afterwards for 24 hours, then slurry is uniformly coated on aluminium foil by rubbing method, is sliced after drying up to galapectite positive electrode.
Conductive agent is Super-P, and binder is 250 μ L of PVDF/NMP and NMP.
Comparative example 1
Lithium sulfur battery anode material, preparation method include:
(1) it is heat-treated after mentioning galapectite with acidleach, specifically:
The natural galapectite solid powder of 10g is added to the concentrated hydrochloric acid and 7ml deionization that are 38% by 28ml mass fraction
In the solution of water composition, 120min is reacted at 70 DEG C, is then centrifuged for washing, solid is obtained by filtration, is placed in 80 DEG C of baking ovens dry
For 24 hours, the galapectite powder after obtaining acidleach purification under an argon atmosphere by the galapectite powder after purification is placed in tube furnace,
300 DEG C of heat preservation 3h, heating rate are 5 DEG C/min, cooling up to heat treated galapectite powder.
(2) sandwich layer is loaded into semi-finished product obtained by step (1), specifically:
Semi-finished product powder obtained by 0.07g distillation sulphur powder and 0.03g step (1) is uniformly mixed, is placed in tube furnace, argon gas
Under atmosphere, 155 DEG C plus heat preservation 12h to get S/ galapectite mixing material.
The mass ratio of galapectite, polymer and sulphur is 1:(7/3 in this example).
Detect example
The lithium sulfur battery anode material prepared with embodiment 2,4 and comparative example 1,2, the electrode material provided by embodiment 8
The electrode material of reference numeral is prepared in preparation method for material.
Electrode material and lithium metal are matched, using Celgard diaphragm, with 1mol L-1LiTFSI/(DOL+DME)(V/V
=1:1)/1%LiNO3For electrolyte, it is assembled into 2016 button cells and carries out multiplying power, cycle performance test.As a result such as 1 institute of table
Show.
1 battery testing data of table
As shown in Table 1, when the PPy/ galapectite mixing material that pyrroles's additive amount is 50% synthesis, under 0.1C multiplying power for the first time
Specific discharge capacity is 786.9mAh g-1, recycled by 100 times, circulation conservation rate is 71.8%；When pyrroles's additive amount is 67% conjunction
At PPy/ galapectite mixing material, under 0.1C multiplying power first discharge specific capacity be 947.8mAh g-1, it is recycled by 100 times,
Capacity retention ratio is 53.2%.Compared to galapectite, the battery of the galapectite mixing material preparation of conducting polymer cladding is for the first time
Specific discharge capacity and circulation conservation rate be all improved, illustrate coated with conductive polymer keep galapectite original structure and
On the basis of chemical constituent, the electric conductivity of galapectite is improved, to improve battery performance.
Fig. 4~6 are the battery high rate performance test result of embodiment 2, embodiment 5 and comparative example 1 respectively, it can be seen that real
The high rate performance of example 2,5 is applied better than battery discharge prepared by comparative example, the galapectite mixing material by conducting polymer cladding
Capacity restoration is good.
Fig. 7~9 are the cycle performance of battery test result of embodiment 2, embodiment 5 and comparative example 1 respectively, it can be seen that real
The cycle performance of example 2,5 is applied better than circulating battery prepared by comparative example, the galapectite mixing material by conducting polymer cladding
Curve is stablized, and capacity retention ratio is high.
The above main feature and advantage that detailed description of the preferred embodimentsthe present invention has been described.The technical staff of the industry should
Solution, the present invention is not limited to the above embodiments, under the premise of not departing from spirit and scope of the present invention, the change of the invention done
Change and improves all in the scope of the present invention.The claimed scope of the invention is by appended claims and its equivalent circle
It is fixed.
Claims (10)
1. lithium sulfur battery anode material, which is characterized in that including base layer, coat the polymeric layer of the base layer, Yi Jiwei
Sandwich layer in base layer.
2. lithium sulfur battery anode material according to claim 1, which is characterized in that the base layer is galapectite.
3. lithium sulfur battery anode material according to claim 1, which is characterized in that the polymer be polypyrrole (PPy),
One of polyaniline (PANI) and poly- 3,4-rthylene dioxythiophene (PEDOT).
4. lithium sulfur battery anode material according to claim 1, which is characterized in that the sandwich layer is sulphur simple substance layer.
5. the preparation method of lithium sulfur battery anode material as described in any one of Claims 1 to 4, which is characterized in that step includes:
(1) it is heat-treated after mentioning the base layer with acidleach；
(2) in a solvent by the dispersion of step (1) treated base layer, polymer monomer and oxidant polymerization are added into solvent
Semi-finished product are obtained afterwards；
(3) sandwich layer is loaded into semi-finished product obtained by step (2).
6. the preparation method of lithium sulfur battery anode material according to claim 5, which is characterized in that described in step (1)
Acid is one of hydrochloric acid, sulfuric acid and oxalic acid.
7. the preparation method of lithium sulfur battery anode material according to claim 5, which is characterized in that step (1) described leaching
The temperature mentioned is 60~70 DEG C, and the time of the extraction is 100~150min.
8. the preparation method of lithium sulfur battery anode material according to claim 5, which is characterized in that step (1) described heat
The temperature of processing is 200~500 DEG C, and the time of the heat treatment is 2~6h.
9. the preparation method of lithium sulfur battery anode material according to claim 5, which is characterized in that described in step (2)
Solvent is water, and the oxidant is FeCl3, ammonium persulfate, one of potassium peroxydisulfate and sodium peroxydisulfate.
10. the preparation method of lithium sulfur battery anode material according to claim 5, which is characterized in that step (2) is described poly-
The temperature of conjunction be 20~30 DEG C, the time be 12~for 24 hours.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102626649A (en) * | 2012-03-21 | 2012-08-08 | 重庆大学 | Oxygen reduction non-noble metal catalyst and preparation method thereof |
| CN103647104A (en) * | 2013-12-18 | 2014-03-19 | 中国科学院上海硅酸盐研究所 | Lithium-sulfur battery |
| DE102015101450A1 (en) * | 2014-02-05 | 2015-08-06 | GM Global Technology Operations LLC (n. d. Gesetzen des Staates Delaware) | Sulfur-based active material for a positive electrode |
| CN105789575A (en) * | 2016-03-08 | 2016-07-20 | 北京理工大学 | Silicon dioxide carbon composite negative electrode material, modified silicon dioxide carbon composite negative electrode material and preparation methods and application of silicon dioxide carbon composite negative electrode material and modified silicon dioxide carbon composite negative electrode material |
-
2018
- 2018-10-12 CN CN201811189810.0A patent/CN109461909B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102626649A (en) * | 2012-03-21 | 2012-08-08 | 重庆大学 | Oxygen reduction non-noble metal catalyst and preparation method thereof |
| CN103647104A (en) * | 2013-12-18 | 2014-03-19 | 中国科学院上海硅酸盐研究所 | Lithium-sulfur battery |
| DE102015101450A1 (en) * | 2014-02-05 | 2015-08-06 | GM Global Technology Operations LLC (n. d. Gesetzen des Staates Delaware) | Sulfur-based active material for a positive electrode |
| CN105789575A (en) * | 2016-03-08 | 2016-07-20 | 北京理工大学 | Silicon dioxide carbon composite negative electrode material, modified silicon dioxide carbon composite negative electrode material and preparation methods and application of silicon dioxide carbon composite negative electrode material and modified silicon dioxide carbon composite negative electrode material |
Non-Patent Citations (1)
| Title |
|---|
| 张勇: "埃洛石改性锂硫电池正极材料的研究", 《中国优秀硕士学位论文全文数据库工程科技II辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110534742A (en) * | 2019-07-16 | 2019-12-03 | 江汉大学 | A kind of preparation method of anode composite material of lithium sulfur battery |
| CN110534742B (en) * | 2019-07-16 | 2021-05-28 | 江汉大学 | Preparation method of lithium-sulfur battery positive electrode composite material |
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