CN109473639A - A kind of redox graphene/carbon nano-tube/poly aniline/sulphur composite material preparation method and application - Google Patents
A kind of redox graphene/carbon nano-tube/poly aniline/sulphur composite material preparation method and application 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 relates to the technical field of the preparation of lithium-sulfur rechargeable battery material more particularly to a kind of redox graphene/carbon nano-tube/poly aniline/sulphur composite material preparation method and as the application of lithium sulfur battery anode material.The present invention is using the method being spray-dried, the compound of polyaniline/sulphur and graphene and carbon nanotube by spraying simultaneously, improve the cycle life of sulfur electrode material, preparation method is simple, controllable, conductive network is provided for graphene with good conductivity, conductive polymer polyanaline coats sulphur nano particle, not only improve the electric conductivity of sulphur, and the dissolution of discharging product polysulfide can be prevented and alleviate volume expansion, using the composite material as the anode of lithium-sulfur rechargeable battery, have the characteristics that capacity height, stable cycle performance.
Description
Technical field
The present invention relates to the technical field of the preparation of lithium-sulfur rechargeable battery material more particularly to a kind of reduction-oxidation graphite
Alkene/carbon nano-tube/poly aniline/sulphur composite material preparation method and the application as lithium sulfur battery anode material.
Background technique
With the rapid development of society, demand of the mankind to the energy is increasing.But not with people's living standard
It is disconnected to improve, some main fossil energies, such as coal, petroleum, natural gas increasingly shortage.At the same time, some fossil energies
Burning, bring environmental pollution and destruction be unrepairable.As the excessive discharge of carbon dioxide results in greenhouse effect
It answers, and this results in the continuous rising on sea level, meanwhile, the continuous discharge of vehicle exhaust also leads to the increasingly evil of haze
Change, this by it is serious threaten the mankind health and living environment.So studying novel renewable and clean energy resource and energy storage device
It is extremely urgent.Wind energy, although the new energies cleanliness without any pollution such as solar energy and tide energy, the limitation by energy sources
It is that vehicle etc. provides the stable energy that internal combustion engine, which can not be replaced,.Battery is as a kind of novel, high energy, free of contamination chemical-electrical
Source has been widely used in the energy storage fields such as portable electronic device, electric car and hybrid-electric car, has as one kind
The energy storage device of height ratio capacity and long circulation life enters the visual field of people and receives extensive attention and study.Currently, quotient
The lithium ion battery theoretical specific capacity of industry is that 300 mAh/g are limited by itself theoretical specific capacity, it is clear that is not able to satisfy to lithium
The requirement of ion battery practical application quality, and the theoretical specific capacity of novel lithium-sulfur cell is about commercial Li-ion batteries theory ratio
Five times (theoretical specific capacity 1675mAh/g, specific energy be 2500 Wh/kg) of capacity, it is considered to be most development potentiality
One of high-energy battery.
However, but there are many obstacles in practical applications in lithium-sulfur cell.First, bright sulfur is insulator at room temperature, electricity
Son and transmission of the ion in the anode using sulphur as positive electrode are extremely difficult.Second, in formed in the charge and discharge process
Between the more lithium sulfides of product be soluble in electrolyte solution, so as to cause on anode electroactive material powder of detached and dissolution damage
Lose, and dissolve the lithium sulfide that more lithium sulfides in the electrolytic solution are diffused on lithium an- ode, and react generation be deposited in it is negative
The surface of pole causes the internal resistance of battery to increase, eventually leads to the capacity attenuation of battery.Third, sulphur and final product Li2S's is close
Degree is different, and volume expansion can occur for sulphur anode and fragmentation (expansion ratio 76%), these can all lead to lithium-sulfur cell cyclical stability
It is deteriorated.
Graphene it is conductive it is excellent, chemical stability is high, large specific surface area, the strong and unique two dimension of mechanical performance are more
The feature of the brilliance such as pore network geometry, what can simply and easily be carried out forms nucleocapsid clad structure with sulphur, utilizes graphene
Modified lithium-sulfur cell, can be improved the electro-chemical activity of sulphur simple substance, shortens electronics and ion transmission path, limits polysulfide
Dissolution, and then improve lithium-sulfur cell overall performance.Graphene is a kind of carbon material with 2D planar structure, due in its structure
There is excellent electric conductivity there are the big pi bond of the delocalization of long-range.Reduced graphene (rGO) is considered equally having preferable conductive
Property.Meanwhile the oxidation of precursor graphene of redox graphene is due to having oxygen-containing group (such as hydroxyl abundant in its structure
Base, epoxy group, carboxyl and carbonyl) and there is chemical modifiability well.Redox graphene provides for composite material
Preferable electric conductivity.Meanwhile carbon receives the accumulation again occurred when the introducing of nanotube can prevent GO to be reduced to rGO, this
Composite material is considered to have biggish specific surface area.Further, since rGO has preferable toughness and flexible, draw
Enter to alleviate material structure collapses caused by volume change in charge and discharge process, so as to improve the stable circulation of material
Property.
Undeniable grapheme material effectively limits the granular size of sulphur simple substance, while redox graphene electric conductivity
Good material improve the conductivity of elemental sulfur but sulphur/graphene composite material in middle discharge process the volume expansion of sulphur and
It shrinks, falls off if sulfur granules surface layer without other coatings, necessarily will appear sulfur granules and cause Capacity fading phenomenon.
Summary of the invention
It is an object of that present invention to provide a kind of redox graphene/carbon nano-tube/poly aniline/sulphur composite material preparations
Method and application as lithium sulfur battery anode material improve the cycle life of sulfur electrode material, and preparation method is simple, controllable,
Conductive network is provided for graphene with good conductivity, conductive polymer polyanaline coats sulphur nano particle, not only improves sulphur
Electric conductivity, and the dissolution of discharging product polysulfide can be prevented and alleviate volume expansion, using the composite material as lithium sulphur
The anode of secondary cell has the characteristics that capacity height, stable cycle performance.
For achieving the above object, the technical scheme is that
A kind of redox graphene/carbon nano-tube/poly aniline/sulphur composite material preparation method, steps are as follows:
Step 1: preparing polyaniline/sulfur compound
It measures 0.1-0.5g aniline and is dissolved into formation aniline salting liquid in the hydrochloric acid that 10-50mL concentration is 35%, weigh 5-10g sulphur
Sodium thiosulfate solid, which is dissolved into water, forms hypo solution, is gradually added drop-wise in aniline salting liquid, stirs at 70-90 DEG C
18-24 h collects powder, obtains polyaniline/sulfur compound then by after obtained washing of precipitate drying.
Step 2: preparing redox graphene/carbon nano-tube/poly aniline/sulphur composite material
Polyaniline/sulfur compound prepared by the above-mentioned first step is added in a mixed solution, 1-2 hours ultrasonic, is stirred for 10-
Then 20h is spray-dried at 200-220 DEG C；The powder for being spray-dried out is collected, redox graphene/carbon is obtained and receives
Mitron/polyaniline/sulphur composite material.
The features of the present invention is also:
Preferably, in the first step, the concentration of aniline salting liquid is 5%-50%.
Preferably, in the first step, the concentration of hypo solution is 20%-50%.
Preferably, in the first step, rate of addition is 20-50 drop/min.
Preferably, in second step, for spray drying device using common air pressure, intake is 5 cubes/point
Clock, 5 ml/min of charging rate, cleansing pin rate are 30 seconds every 5 times.
Wherein, the solute of a mixed solution is graphene powder and carbon nanotube powder, the quality of graphene and carbon nanotube
Than for 1:1-1:2；The mixed-powder of every milliliter of a mixed solution graphene containing 2-10mg and carbon nanotube.
1-2g polyaniline/sulfur compound is added in every 200-500mLa mixed solution.
Many conventionally known technologies can be used in heretofore described graphene preparation process, and (such as hummers method is consolidated
Phase/liquid phase removing etc.), wherein involved raw material are commercially available, equipment used and technique are this technologies
Known to the technical staff in field.
A kind of redox graphene/carbon nano-tube/poly aniline/sulphur composite material is answered as lithium sulfur battery anode material
With.
Beneficial effects of the present invention are as follows:
The present invention is using the method being spray-dried, while the compound of polyaniline/sulphur and graphene and carbon nanotube by spraying.Graphite
Alkene and carbon nanotube synergistic effect can more enhance the electric conductivity of active material, and can be very good to avoid the group of molybdenum disulfide
Poly- phenomenon.
The present invention is the simplest in the method employed in polyaniline/sulphur/redox graphene/carbon nanotube material for preparing
Just with the synthesizing mean of high yield, it is easy to commercially produce.High theoretical capacity, composite material have big specific surface area, favorably
In the infiltration of electrolyte and the transmission of ion, conductive polymer polyanaline coats sulphur nano particle, not only improves the electric conductivity of sulphur,
And the dissolution of discharging product polysulfide can be prevented and alleviate volume expansion, using the composite material as lithium-sulfur rechargeable battery
Anode, have the characteristics that capacity is high, stable cycle performance.Since composite graphite alkene is received with carbon by way of spray drying for it
Mitron, this just greatly reinforces its electric conductivity, and graphene and the compound of carbon nanotube can be very good prevention and treatment polyaniline
With the agglomeration of sulfur compound, active material in battery is avoided well, and avalanche phenomenon occurs in cyclic process.Always
It, the solution of the present invention passes through ingenious and meticulous design, breaks through suffering, and experimental program is simple, yield is big, has industrial production
Prospect.
Detailed description of the invention
Present invention will be further explained below with reference to the attached drawings and examples.
Fig. 1 is redox graphene/carbon nano-tube/poly aniline/sulphur composite material charge and discharge obtained by embodiment 1
Curve.
Fig. 2 is redox graphene/carbon nano-tube/poly aniline/sulphur composite material cyclicity obtained by embodiment 2
Energy.
Fig. 3 be 1 polyaniline of comparative example/sulfur compound as lithium sulfur battery anode material when in 0.2C, 0.4C, 1C, 2C,
High rate performance.
Fig. 4 be 2 redox graphenes of comparative example/carbon nanotube/sulphur composite material as lithium sulfur battery anode material when
In 0.2C, 0.4C, 1C, 2C, high rate performance.
Specific embodiment
Below in conjunction with specific embodiments of the present invention, apparent and completion is carried out to technical solution of the present invention and is explained
It states.Described embodiment is only a part of the embodiments of the present invention, and is not whole, all in spirit and original of the invention
Within then, any modification, equivalent substitution, improvement and etc. done be should all be included in the protection scope of the present invention.
Embodiment 1:
Step 1: preparing polyaniline/sulfur compound
It measures 0.1 g aniline and is dissolved into formation aniline salting liquid in the hydrochloric acid (concentration 35%) of 15mL.Weigh sodium thiosulfate
6 g of solid is dissolved into formation hypo solution in 20 g water and is gradually added drop-wise in aniline salting liquid, rate of addition 20-
50 drops/min stir 18 h at 90 DEG C.Then by after obtained washing of precipitate drying, powder is collected, it is multiple to obtain polyaniline/sulphur
Close object.
Step 2: preparing redox graphene/carbon nano-tube/poly aniline/sulphur composite material
The graphene powder and carbon of powder (1g) and 200mL after polyaniline prepared by the above-mentioned first step/sulfur compound drying
Nanotube powder a mixed solution (quality is than graphene: carbon nanotube=1:1, every milliliter of a mixed solution graphene containing 2mg and
The mixed-powder of carbon nanotube) it is admixed together.Ultrasound 1 hour, and 10h is stirred, then spray drying is (spraying at 200 DEG C
For drying equipment using common air pressure, intake is 5 cubes/minute, 5 ml/min of charging rate, cleansing pin rate
It is 30 seconds every for 5 times).The powder for being spray-dried out is collected, it is compound to obtain redox graphene/carbon nano-tube/poly aniline/sulphur
Material, and prepare as lithium sulfur battery anode material.
Using redox graphene obtained/carbon nano-tube/poly aniline/sulphur as active material, carbon dust is conductive agent, is gathered
Vinylidene (PVDF) is adhesive, and presses redox graphene/carbon nano-tube/poly aniline/sulphur: C: Kynoar=8:
Mixing, grinding uniformly, then instill N-methyl pyrrolidinone solvent (NMP) and are ground to pulpous state in the weight ratio merging mortar of 1:1,
Slurry is uniformly applied on aluminium foil, load capacity 2mg, is then put into 60 DEG C of thermostatic drying chamber dry 12h, drying to constant weight
Flakiness is pushed in 5MPa pressure using tablet press machine afterwards, redox graphene/carbon nano-tube/poly aniline/sulphur lithium is thus made
Sulphur cell positive electrode piece；It is to electrode and reference electrode with lithium metal, lithium sulphur electrolyte is electrolyte, and porous polypropylene is diaphragm,
CR2025 button cell is assembled in the glove box full of argon gas.
Fig. 1 is redox graphene/carbon nano-tube/poly aniline/sulphur composite material charge and discharge obtained by embodiment 1
Curve.Such as Fig. 1, the charging and discharging curve of first lap can be seen that initial discharge capacity and reach 1682 mAh/g, high charge and discharge
Performance gains can prevent the dissolution of discharging product polysulfide and alleviate volume in the good electric conductivity of its positive electrode
Expansion.
Embodiment 2:
Step 1: preparing polyaniline/sulfur compound
It measures 0.2 g aniline and is dissolved into formation aniline salting liquid in the hydrochloric acid (concentration 35%) of 20mL.Weigh sodium thiosulfate
7 g of solid is dissolved into formation hypo solution in 25 g water and is gradually added drop-wise in aniline salting liquid, stirs 20 at 80 DEG C
h .Then by after obtained washing of precipitate drying, powder is collected, polyaniline/sulfur compound is obtained.
Step 2: preparing redox graphene/carbon nano-tube/poly aniline/sulphur composite material
Specific step is as follows:
The graphene powder of powder (1.2g) and 200mL after the drying of polyaniline prepared by the above-mentioned first step/sulfur compound with
(quality is than graphene: carbon nanotube=1:1, every milliliter of a mixed solution graphene containing 2mg for a mixed solution of carbon nanotube powder
With the mixed-powder of carbon nanotube) it is admixed together.Ultrasound 1 hour, and 10h is stirred, the then spray drying (spray at 200 DEG C
For mist drying equipment using common air pressure, intake is 5 cubes/minute, 5 ml/min of charging rate, cleansing pin speed
Rate is 30 seconds every 5 times).The powder for being spray-dried out is collected, it is multiple to obtain redox graphene/carbon nano-tube/poly aniline/sulphur
Condensation material, and prepare as lithium sulfur battery anode material.
Using redox graphene obtained/carbon nano-tube/poly aniline/sulphur as active material, carbon dust is conductive agent, is gathered
Vinylidene (PVDF) is adhesive, and presses redox graphene/carbon nano-tube/poly aniline/sulphur: C: Kynoar=8:
Mixing, grinding uniformly, then instill N-methyl pyrrolidinone solvent (NMP) and are ground to pulpous state in the weight ratio merging mortar of 1:1,
Slurry is uniformly applied on aluminium foil, load capacity 2mg, is then put into 60 DEG C of thermostatic drying chamber dry 12h, drying to constant weight
Flakiness is pushed in 5MPa pressure using tablet press machine afterwards, redox graphene/carbon nano-tube/poly aniline/sulphur material is thus made
Material is used as lithium-sulphur cell positive electrode piece;It is to electrode and reference electrode with lithium metal, lithium sulphur electrolyte is electrolyte, porous polypropylene
For diaphragm, CR2025 button cell is assembled in the glove box full of argon gas.
Fig. 2 is redox graphene/carbon nano-tube/poly aniline/sulphur composite material cyclicity obtained by embodiment 2
Energy.As seen in Figure 2, redox graphene/carbon nano-tube/poly aniline/sulphur composite electrode is after the circle of circulation 100
The capacity for still maintaining 800 mAh/g has absolutely proved the cyclical stability of this positive electrode.
Embodiment 3:
Step 1: preparing polyaniline/sulfur compound
It measures 0.3g aniline and is dissolved into formation aniline salting liquid in the hydrochloric acid (concentration 35%) of 25mL.Weigh sodium thiosulfate
Solid 8g is dissolved into formation hypo solution in 30 g water and is gradually added drop-wise in aniline salting liquid, and 24 h are stirred at 70 DEG C
, then by after obtained washing of precipitate drying, powder is collected, polyaniline/sulfur compound is obtained.
Step 2: preparing redox graphene/carbon nano-tube/poly aniline/sulphur composite material
The graphene powder of powder (1.5g) and 200mL after the drying of polyaniline prepared by the above-mentioned first step/sulfur compound with
(quality is than graphene: carbon nanotube=1:1, every milliliter of a mixed solution graphene containing 2mg for a mixed solution of carbon nanotube powder
With the mixed-powder of carbon nanotube) it is admixed together.Ultrasound 1 hour, and 10h is stirred, then the spray drying ((spray at 200 DEG C
For mist drying equipment using common air pressure, intake is 5 cubes/minute, 5 ml/min of charging rate, cleansing pin speed
Rate is 30 seconds every 5 times).The powder for being spray-dried out is collected, it is multiple to obtain redox graphene/carbon nano-tube/poly aniline/sulphur
Condensation material, and prepare as lithium sulfur battery anode material.
Using redox graphene obtained/carbon nano-tube/poly aniline/sulphur as active material, carbon dust is conductive agent, is gathered
Vinylidene (PVDF) is adhesive, and presses redox graphene/carbon nano-tube/poly aniline/sulphur: C: Kynoar=8:
Mixing, grinding uniformly, then instill N-methyl pyrrolidinone solvent (NMP) and are ground to pulpous state in the weight ratio merging mortar of 1:1,
Slurry is uniformly applied on aluminium foil, load capacity 2mg, is then put into 60 DEG C of thermostatic drying chamber dry 12h, drying to constant weight
Flakiness is pushed in 5MPa pressure using tablet press machine afterwards, redox graphene/carbon nano-tube/poly aniline/sulphur lithium is thus made
Sulphur cell positive electrode piece；It is to electrode and reference electrode with lithium metal, lithium sulphur electrolyte is electrolyte, and porous polypropylene is diaphragm,
CR2025 button cell is assembled in the glove box full of argon gas.
Comparative example 1
Compare polyaniline/sulfur compound and redox graphene of the invention/carbon nano-tube/poly aniline/sulphur composite material
Performance.
Prepare polyaniline/sulfur compound
0.1 g aniline, which is dissolved into the hydrochloric acid (concentration 35%) of 15mL, forms aniline salting liquid.Weigh sodium thiosulfate solid
6 g are dissolved into formation hypo solution in 20 g water and are gradually added drop-wise in aniline salting liquid, and 18 h are stirred at 90 DEG C.
Then by after obtained washing of precipitate drying, powder is collected, polyaniline/sulfur compound is obtained.
Using polyaniline/sulphur obtained as active material, carbon dust is conductive agent, and Kynoar (PVDF) is adhesive,
And press polyaniline/sulphur: C: Kynoar=8:1:1 weight ratio is placed in mixing in mortar, grinding uniformly, then instills n-formyl sarcolysine
Base pyrrolidinone solvent (NMP) is ground to pulpous state, and slurry is uniformly applied on aluminium foil, and load capacity 2mg is then put into 60 DEG C
Dry 12h in thermostatic drying chamber pushes flakiness in 5MPa pressure using tablet press machine after drying to constant weight, polyphenyl is thus made
Amine/sulphur lithium-sulphur cell positive electrode piece；It is to electrode and reference electrode with lithium metal, lithium sulphur electrolyte is electrolyte, porous polypropylene
For diaphragm, CR2025 button cell is assembled in the glove box full of argon gas.
From figure 3, it can be seen that using polyaniline/sulfur compound as lithium sulfur battery anode material when in 0.2C, 0.4C,
1C, 2C, high rate performance.As can be seen that without adding the material initial capacity of redox graphene and carbon nanotube to only have
600mAh/g or so, and in 0.4C, 1C, 2C, capacity attenuation is very fast.
Comparative example 2 compares redox graphene/carbon nanotube/sulphur composite material and reduction-oxidation graphite of the invention
Alkene/carbon nano-tube/poly aniline/sulphur composite material performance.
Prepare redox graphene/carbon nanotube/sulphur composite material
The a mixed solution of the graphene powder and carbon nanotube powder of sulphur powder (1.5g) and 200mL (quality is than graphene: receive by carbon
Mitron=1:1, the mixed-powder of every milliliter of a mixed solution graphene containing 2mg and carbon nanotube) it is admixed together.Ultrasound 1 hour,
And 10h is stirred, then ((spray drying device is using common air pressure, intake 5 for spray drying at 200 DEG C
Cube/minute, 5 ml/min of charging rate, cleansing pin rate are 30 seconds every 5 times).The powder for being spray-dried out is collected, is obtained
Redox graphene/carbon nanotube/sulphur composite material, and prepare as lithium sulfur battery anode material.
Figure 4, it is seen that using redox graphene/carbon nanotube/sulphur composite material as lithium-sulfur cell just
In 0.2C, 0.4C, 1C, 2C when the material of pole, high rate performance.As can be seen that without adding redox graphene and carbon nanometer
The material initial capacity of pipe only has 500mAh/g or so, and capacity attenuation is very fast in 0.4C, 1C, 2C.
Claims (8)
1. a kind of redox graphene/carbon nano-tube/poly aniline/sulphur composite material preparation method, steps are as follows:
Step 1: preparing polyaniline/sulfur compound
It measures 0.1-0.5g aniline and is dissolved into formation aniline salting liquid in the hydrochloric acid that 10-50mL concentration is 35%, weigh 5-10g sulphur
Sodium thiosulfate solid, which is dissolved into water, forms hypo solution, is gradually added drop-wise in aniline salting liquid, stirs at 70-90 DEG C
18-24 h collects powder, obtains polyaniline/sulfur compound then by after obtained washing of precipitate drying；
Step 2: preparing redox graphene/carbon nano-tube/poly aniline/sulphur composite material
Polyaniline/sulfur compound prepared by the above-mentioned first step is added in a mixed solution, 1-2 hours ultrasonic, is stirred for 10-
Then 20h is spray-dried at 200-220 DEG C；The powder for being spray-dried out is collected, redox graphene/carbon is obtained and receives
Mitron/polyaniline/sulphur composite material.
2. redox graphene according to claim 1/carbon nano-tube/poly aniline/sulphur composite material preparation method,
It is characterized in that, the concentration of aniline salting liquid is 5%-50% in the first step.
3. redox graphene according to claim 1/carbon nano-tube/poly aniline/sulphur composite material preparation method,
It is characterized in that, the concentration of hypo solution is 20%-50% in the first step.
4. redox graphene according to claim 1/carbon nano-tube/poly aniline/sulphur composite material preparation method,
It is characterized in that, rate of addition is 20-50 drop/min in the first step.
5. redox graphene according to claim 1/carbon nano-tube/poly aniline/sulphur composite material preparation method,
It is characterized in that, for spray drying device using common air pressure, intake is 5 cubes/minute in second step, into
Expect that 5 ml/min of speed, cleansing pin rate are 30 seconds every 5 times.
6. redox graphene according to claim 1/carbon nano-tube/poly aniline/sulphur composite material preparation method,
It is characterized in that, wherein, the solute of a mixed solution is graphene powder and carbon nanotube powder, graphene and carbon nanotube
Mass ratio is 1:1-1:2；The mixed-powder of every milliliter of a mixed solution graphene containing 2-10mg and carbon nanotube.
7. redox graphene according to claim 6/carbon nano-tube/poly aniline/sulphur composite material preparation method,
It is characterized in that, 1-2g polyaniline/sulfur compound is added in every 200-500mLa mixed solution.
8. the resulting redox graphene of -7 any claims/carbon nano-tube/poly aniline/sulphur is compound according to claim 1
Application of the material as lithium sulfur battery anode material.
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| CN111554931A (en) * | 2020-05-11 | 2020-08-18 | 中科廊坊过程工程研究院 | Composite positive electrode material, preparation method thereof and application thereof in zinc ion battery |
| CN112164771A (en) * | 2020-08-25 | 2021-01-01 | 合肥国轩高科动力能源有限公司 | Sulfur/polyaniline nanotube/reduced graphene oxide composite material and preparation method and application thereof |
| CN112436114A (en) * | 2020-11-16 | 2021-03-02 | 扬州大学 | Three-dimensional graphene/carbon nanotube/phosphotungstic acid/sulfur composite material, preparation method and application thereof |
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| CN114497499A (en) * | 2022-01-26 | 2022-05-13 | 中汽创智科技有限公司 | Lithium sulfide/carbon composite material with multilevel structure and preparation method and application thereof |
| CN114497499B (en) * | 2022-01-26 | 2023-11-21 | 中汽创智科技有限公司 | Multi-stage structure lithium sulfide/carbon composite material and preparation method and application thereof |
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