CN109301223A - Anode composite material of lithium sulfur battery and preparation method thereof - Google Patents
Anode composite material of lithium sulfur battery and preparation method thereof Download PDFInfo
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The present invention provides a kind of anode composite material of lithium sulfur battery, including base layer, coat the carbon-coating of the base layer, and the sandwich layer in base layer.The present invention also provides the preparation methods of above-mentioned anode composite material of lithium sulfur battery.Anode composite material of lithium sulfur battery provided by the present invention, in base layer outer cladding conductive carbon layer, 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 anode composite material of lithium sulfur battery 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；In terms of chemisorption, mainly further to carrier into
Row chemical modification, 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, both improved the cycle-index of electrode, and also improved 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 anode composite material.
The second object of the present invention is to provide the preparation method of above-mentioned anode composite material of lithium sulfur battery.
To achieve the above object, the invention adopts the following technical scheme:
Anode composite material of lithium sulfur battery, including base layer coat the carbon-coating of the base layer, and are located at described matrix
Sandwich layer in layer.
Preferably, the base layer is galapectite.
Preferably, the sandwich layer is sulphur simple substance layer.
The preparation method of above-mentioned anode composite material of lithium sulfur battery, step include:
(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, it is carbonized after polymerization reaction, obtains semi-finished product；
(3) sandwich layer is loaded into semi-finished product obtained by step (2).
Preferably, acid described in step (1) is hydrochloric acid, and the mass fraction of the hydrochloric acid is 30~40%, the extraction
Temperature 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 dopamine hydrochloride solution.
It is further preferred that the dopamine hydrochloride solution is buffered with tris (three (methylol) aminomethane hydrochlorides)
It is 8~12 that solution, which is adjusted to pH,.
It is further preferred that the buffer concentration is 0.2~2mol L-1。
It is further preferred that the dopamine hydrochloride quality is 0.05~10 times of galapectite quality.
Preferably, the temperature of step (2) described polymerization be 25~40 DEG C, polymerization time be 6~for 24 hours.
Preferably, the temperature of step (2) described charing is 700~900 DEG C, and the time of charing is 2~6h.
Preferably, the method for step (3) described load is hot fusion method, and the temperature of the hot fusion method is 150~200 DEG C, is protected
The warm time is 10~16h.
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, anode composite material of lithium sulfur battery provided by the present invention is filled out in base layer in base layer outer cladding carbon-coating
Sandwich layer is filled, while the suction-operated of the physical limit effect and chemical component of the one-dimensional pipeline of base layer is utilized, is solved existing
Have in technology, 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 are lower, the low problem of whole chemical property；
2, in anode composite material of lithium sulfur battery provided by the present invention, base layer is galapectite layer, not only can be from object
More sulphions are inhibited to shuttle in terms of reason limitation and chemisorption two, galapectite uses it as base as cheap natural minerals
Body can also reduce the cost of anode, be conducive to promote and apply；
3, preparation method provided by the present invention first carries out the cladding of carbon-coating on galapectite surface, then carrys out sulfur loaded again,
It is ingenious to solve the problems, such as that galapectite is nonconducting；
4, the anode composite material of lithium sulfur battery being prepared using method of the invention is discharged for the first time under 0.1C multiplying power
Specific capacity is 803.4mAh g-1, after 100 circulations, circulation conservation rate is up to 79.3%.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of anode composite material of lithium sulfur battery；
Fig. 2 is scanning electron microscope (SEM) figure of untreated galapectite；
Fig. 3 is that poly-dopamine (PDA) prepared by embodiment 4 coats halloysite composite material infrared absorption light map；
Fig. 4 is that poly-dopamine (PDA) prepared by embodiment 5 coats halloysite composite material infrared absorption light map；
Fig. 5 is the infrared absorption light map of galapectite prepared by comparative example；
Fig. 6 is galapectite/carbon composite XRD spectrum prepared by embodiment 5；
Fig. 7 is the XRD spectrum of the galapectite of comparative example preparation；
Fig. 8 is lithium-sulfur cell high rate performance figure prepared by embodiment 4；
Fig. 9 is lithium-sulfur cell cycle performance figure prepared by embodiment 4；
Figure 10 is lithium-sulfur cell high rate performance figure prepared by embodiment 5；
Figure 11 is lithium-sulfur cell cycle performance figure prepared by embodiment 5；
Figure 12 is lithium-sulfur cell high rate performance figure prepared by comparative example；
Figure 13 is lithium-sulfur cell cycle performance figure prepared by comparative example；
Figure 14 is anode composite material of lithium sulfur battery scanning electron microscope (SEM) figure prepared by embodiment 5；
Figure 15 is anode composite material of lithium sulfur battery transmission electron microscope (TEM) figure prepared by embodiment 5.
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
Anode composite material of lithium sulfur battery, including base layer coat the carbon of the base layer, and in base layer
Sandwich layer.As shown in Figure 1, wherein 1 be base layer, 2 be carbon-coating, and 3 be sandwich layer.
Base layer is galapectite, and it is sulphur simple substance layer in base layer that base layer, which is coated with carbon-coating,.
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
Anode composite material of lithium sulfur battery, 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, it is carbonized after polymerization reaction, specifically:
1. 0.02g dopamine hydrochloride is added in 100ml deionized water, with tris buffer solution tune pH to 8.5；
2. step is added 1. in acquired solution in 0.3g step (1) treated galapectite, stirred for 24 hours at 40 DEG C；
3. liquid centrifuge separation, washing, drying after reaction, are obtained the galapectite powder of poly-dopamine (PDA) cladding
End；
4. the step galapectite powder that 3. gained PDA is coated is placed in tube furnace, under argon atmosphere, 900 DEG C of heat preservations
2h is to get carbon-coated galapectite.
(3) sandwich layer is loaded into semi-finished product obtained by step (2), specifically:
0.07g is distilled carbon-coated galapectite powder mixing obtained by sulphur powder and 0.03g step (2) by 7:3 in proportion
It is even, it is placed in tube furnace, under argon atmosphere, 155 DEG C of heat preservation 12h are to get anode composite material of lithium sulfur battery.
Embodiment 3
Anode composite material of lithium sulfur battery, 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, it is carbonized after polymerization reaction, specifically:
1. 0.1g dopamine hydrochloride is added in 100ml deionized water, with tris buffer solution tune pH to 8.5；
2. step is added 1. in acquired solution in 1g step (1) treated galapectite, stirred for 24 hours at 40 DEG C；
3. liquid centrifuge separation, washing, drying after reaction, are obtained the galapectite powder of PDA cladding；
4. the step galapectite powder that 3. gained PDA is coated is placed in tube furnace, under argon atmosphere, 900 DEG C of heat preservations
2h is to get carbon-coated galapectite.
(3) sandwich layer is loaded into semi-finished product obtained by step (2), specifically:
0.07g is distilled carbon-coated galapectite powder mixing obtained by sulphur powder and 0.03g step (2) by 7:3 in proportion
It is even, it is placed in tube furnace, under argon atmosphere, 155 DEG C of heat preservation 12h are to get anode composite material of lithium sulfur battery.
Embodiment 4
Anode composite material of lithium sulfur battery, 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, it is carbonized after polymerization reaction, specifically:
1. 0.1g dopamine hydrochloride is added in 100ml deionized water, with tris buffer solution tune pH to 9；
2. step is added 1. in acquired solution in 0.5g step (1) treated galapectite, stirred for 24 hours at 40 DEG C；
3. liquid centrifuge separation, washing, drying after reaction, are obtained the galapectite powder of PDA cladding；
4. the step galapectite powder that 3. gained PDA is coated is placed in tube furnace, under argon atmosphere, 900 DEG C of heat preservations
2h is to get carbon-coated galapectite.
(3) sandwich layer is loaded into semi-finished product obtained by step (2), specifically:
0.07g is distilled carbon-coated galapectite powder mixing obtained by sulphur powder and 0.03g step (2) by 7:3 in proportion
It is even, it is placed in tube furnace, under argon atmosphere, 155 DEG C of heat preservation 12h are to get anode composite material of lithium sulfur battery.
Embodiment 5
Anode composite material of lithium sulfur battery, 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, it is carbonized after polymerization reaction, specifically:
1. 0.5g dopamine hydrochloride is added in 100ml deionized water, with tris buffer solution tune pH to 9；
2. step is added 1. in acquired solution in 0.5g step (1) treated galapectite, stirred for 24 hours at 40 DEG C；
3. liquid centrifuge separation, washing, drying after reaction, are obtained the galapectite powder of PDA cladding；
4. the step galapectite powder that 3. gained PDA is coated is placed in tube furnace, under argon atmosphere, 900 DEG C of heat preservations
2h is to get carbon-coated galapectite.
(3) sandwich layer is loaded into semi-finished product obtained by step (2), specifically:
0.07g is distilled carbon-coated galapectite powder mixing obtained by sulphur powder and 0.03g step (2) by 7:3 in proportion
It is even, it is placed in tube furnace, under argon atmosphere, 155 DEG C of heat preservation 12h are to get anode composite material of lithium sulfur battery.
Embodiment 6
Anode composite material of lithium sulfur battery, 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, it is carbonized after polymerization reaction, specifically:
1. 1g dopamine hydrochloride is added in 100ml deionized water, with tris buffer solution tune pH to 8.5；
2. step is added 1. in acquired solution in 0.1g step (1) treated galapectite, stirred for 24 hours at 40 DEG C；
3. liquid centrifuge separation, washing, drying after reaction, are obtained the galapectite powder of PDA cladding；
4. the step galapectite powder that 3. gained PDA is coated is placed in tube furnace, under argon atmosphere, 900 DEG C of heat preservations
2h is to get carbon-coated galapectite.
(3) sandwich layer is loaded into semi-finished product obtained by step (2), specifically:
0.07g is distilled carbon-coated galapectite powder mixing obtained by sulphur powder and 0.03g step (2) by 7:3 in proportion
It is even, it is placed in tube furnace, under argon atmosphere, 155 DEG C of heat preservation 12h are to get anode composite material of lithium sulfur battery.
Embodiment 7
This example be the application of anode composite material of lithium sulfur battery in the battery, battery anode slice the preparation method comprises the following steps: press lithium
The mass ratio of sulphur cell positive electrode composite material, conductive agent and binder is 7:2:1, takes anode composite material of lithium sulfur battery 0.07g
After Super-P0.02g grinding uniformly, the 250 μ L of PVDF/NMP 0.2g and NMP of mass fraction 5% is added, stirs at room temperature
For 24 hours, slurry is made, slurry is uniformly coated on aluminium foil by rubbing method, is dried, slice obtains battery anode slice.
Comparative example
Anode composite material of lithium sulfur battery, 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:
Galapectite powder obtained by 0.07g distillation sulphur powder and 0.03g step (1) is uniformly mixed, is placed in pipe by 7:3 in proportion
In formula furnace, under argon atmosphere, 155 DEG C of heat preservation 12h are to get anode composite material of lithium sulfur battery.
Detect example
The anode composite material of lithium sulfur battery prepared with embodiment 4,5 and comparative example, the battery provided by embodiment 7 is just
The battery anode slice of reference numeral is prepared in pole piece preparation method.
Battery anode slice 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
Fig. 3, Fig. 4 are the infrared absorption of the cladding halloysite composite material of PDA prepared by embodiment 4 and embodiment 5 respectively
Light map, Fig. 5 are the infrared absorption light maps of galapectite prepared by comparative example.Comparison diagram 5 is as can be seen that Fig. 3, Fig. 4 exist
3132~3197cm-1There are the stretching vibration peak of N-H key, 1488cm in place-1There are N-H bond bending vibration peak, 1396cm at left and right-1It is left
Right place is the superposition peak of C=C and N-H key scissoring vibration in phenyl ring, illustrates that PDA is successfully coated on galapectite.
Fig. 6 is XRD spectrum prepared by embodiment 5, and Fig. 7 is the XRD diagram of galapectite prepared by comparative example.By Fig. 7
As it can be seen that in 12 ° and 20 ° or so the characteristic diffraction peaks with obvious galapectite；25 ° or so are quartzy characteristic diffraction peak, 26 ° of left sides
Right is the characteristic diffraction peak of cristobalite, 30 ° or so be then alunite feature diffraction.Paired observation Fig. 6 is it is found that by 900
After DEG C charing, the characteristic diffraction peak of galapectite weakens, and occurs the undefined structure sial oxidation of disperse between 20 °~30 °
The characteristic diffraction peak of object shows that galapectite tube wall crystal structure changes, and forms undefined structure；At 23 ° and 44.5 ° or so
There are two Bao Feng, (002) and (10) diffraction maximum of corresponding carbon illustrates that the galapectite material of PDA cladding obtains after carbonizing.
Fig. 8~13 are the battery performance test result of embodiment 4, embodiment 5 and comparative example respectively, it can be seen that embodiment
4,5 high rate performance and cycle performance are better than comparative example, in terms of high rate performance, the lithium-sulfur cell that is prepared using poly-dopamine as carbon source
Anode composite material discharge capacity of the cell restores preferable；In terms of cycle performance, the electricity of anode composite material of lithium sulfur battery preparation
Pond cyclic curve is stablized, and capacity retention ratio is high.For more intuitively comparative analysis, the cycle performance number of three examples is summarized
According to being shown in Table 1.It can be obtained by table 1: when dopamine additive amount is 17% anode composite material of lithium sulfur battery synthesized, in 0.1C multiplying power
Lower first discharge specific capacity is 803.4mAh g-1, recycled by 100 times, capacity retention ratio 79.3%；When dopamine additive amount
For the anode composite material of lithium sulfur battery of 50% synthesis, first discharge specific capacity is 827.1mAh g under 0.1C multiplying power-1, pass through
100 circulations, capacity retention ratio 67.7%.Compared to galapectite, using poly-dopamine as carbon source lithium-sulphur cell positive electrode composite wood
The battery first discharge specific capacity and circulation conservation rate for expecting preparation are all improved, and illustrate keeping by carbon source of poly-dopamine
On the basis of the original structure of galapectite, the electric conductivity of galapectite is improved, to improve battery performance.
Figure 14 is anode composite material of lithium sulfur battery scanning electron microscope (SEM) figure prepared by embodiment 5, it can be seen that Ai Luo
The reservation of stone pattern is more complete, and there is substance cladding on surface, and serious agglomeration phenomenon does not occur；Figure 15 is prepared by embodiment 5
Anode composite material of lithium sulfur battery transmission electron microscope (TEM) figure, can be clearly seen galapectite tubular structure and not be destroyed, in lumen
There is substance filling, there is substance cladding on tube wall.
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. anode composite material of lithium sulfur battery, which is characterized in that including base layer, coat the carbon-coating of the base layer, Yi Jiwei
Sandwich layer in the base layer.
2. anode composite material of lithium sulfur battery according to claim 1, which is characterized in that the base layer is galapectite.
3. anode composite material of lithium sulfur battery according to claim 1, which is characterized in that the sandwich layer is sulphur simple substance layer.
4. the preparation method of anode composite material of lithium sulfur battery as described in any one of claims 1 to 3, which is characterized in that step
Include:
(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, it is carbonized after polymerization reaction, obtains semi-finished product；
(3) sandwich layer is loaded into semi-finished product obtained by step (2).
5. the preparation method of anode composite material of lithium sulfur battery according to claim 4, which is characterized in that step (1) institute
The acid stated is hydrochloric acid, and the mass fraction of the hydrochloric acid is 30~40%, and the temperature of the extraction is 60~70 DEG C, the extraction
Time is 100~150min.
6. the preparation method of anode composite material of lithium sulfur battery according to claim 4, which is characterized in that step (1) institute
The temperature for stating heat treatment is 200~500 DEG C, and the time of the heat treatment is 2~6h.
7. the preparation method of anode composite material of lithium sulfur battery according to claim 4, which is characterized in that step (2) institute
The solvent stated is dopamine hydrochloride solution, and the pH of the dopamine hydrochloride solution is 8~12.
8. the preparation method of anode composite material of lithium sulfur battery according to claim 4, which is characterized in that step (2) institute
State polymerization temperature be 25~40 DEG C, polymerization time be 6~for 24 hours.
9. the preparation method of anode composite material of lithium sulfur battery according to claim 4, which is characterized in that step (2) institute
The temperature for stating charing is 700~900 DEG C, and the time of charing is 2~6h.
10. the preparation method of anode composite material of lithium sulfur battery according to claim 4, which is characterized in that step (3) institute
The method for stating load is hot fusion method, and the temperature of the hot fusion method is 150~200 DEG C, and soaking time is 10~16h.
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