CN108923026A - A kind of preparation method of the rich nitrogen material of porous carbon nanosheet filling hollow carbon sphere - Google Patents

A kind of preparation method of the rich nitrogen material of porous carbon nanosheet filling hollow carbon sphere Download PDF

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CN108923026A
CN108923026A CN201810658111.XA CN201810658111A CN108923026A CN 108923026 A CN108923026 A CN 108923026A CN 201810658111 A CN201810658111 A CN 201810658111A CN 108923026 A CN108923026 A CN 108923026A
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microballoon
preparation
rich nitrogen
porous carbon
nanosheet
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CN108923026B (en
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张凤祥
朱伟丽
杨贺
李攀月
王芳
李永鹏
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Dalian University of Technology
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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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E60/10—Energy storage using batteries

Abstract

A kind of preparation method of the rich nitrogen material of porous carbon nanosheet filling hollow carbon sphere belongs to electrochemical energy source domain, and step is：1) using Dopamine hydrochloride as carbon source coated nano calcium carbonate；2) using tetrabutyl silicate as silicon source, CTAB is surfactant, coats layer of silicon dioxide again outside coated nano calcium carbonate；3) it after coating a strata dopamine again outside step 2 product, keeps performing etching after carbonization treatment for 2 hours at 800~900 DEG C；4) sulphur and above-mentioned material ground and mixed is uniform, it is put into after being sealed in ampoule bottle, both obtains S-C composite material after heating melting perfusion in vacuum drying oven.For the present invention compared with traditional hollow carbon sphere, the carbon ball for filling carbon nanosheet has biggish specific surface area, increases the effect that physics consolidates sulphur；Moreover, the problem of material is using dopamine as carbon source, and higher nitrogen content improves the chemical captured sulfur result of material, while highly conductive carbon material has neutralized sulphur poorly conductive.2) micropore and the mesoporous infiltration for being conducive to absorption polysulfide and electrolyte that activation is formed.

Description

A kind of preparation method of the rich nitrogen material of porous carbon nanosheet filling hollow carbon sphere
Technical field
The invention belongs to lithium-sulfur cell fields, are related to a kind of system of the rich nitrogen material of porous carbon nanosheet filling hollow carbon sphere Preparation Method prepares porous carbon nanosheet and fills out specifically using dopamine as carbon source, using nanometer calcium carbonate as template and functional activation agent The rich nitrogen material of hollow carbon sphere is filled, and is used for lithium-sulphur cell positive electrode.
Background technique
As people are to energy crisis, the portable electronic devices such as the concern of environmental pollution and Shou Ji ﹑ computer are electronic The development of automobile, the lithium secondary battery of high-energy density increasingly become the emphasis of people's research.With traditional lithium ion battery It compares, lithium-sulfur cell theoretical specific capacity 1675mAh/g with higher and higher theoretical specific energy 2600Wh/kg, and simple substance The rich reserves of sulphur, it is cheap, it is environmental-friendly pollution-free.Therefore lithium-sulfur cell becomes the emphasis of people's research.
However, there is also much restrict its development and promote lithium-sulfur cell：(1) elemental sulfur is by 8 sulphur originals The coronal S that son is connected to form8Molecule is the insulator (5*10 of electronics and ion-30S/cm), therefore, S8As electrode activity thing When material, activation difficulty is big, and utilization rate is low.(2) intermediate product of exoelectrical reaction can be largely dissolved in electrolyte, largely Poly- lithium sulfide dissolves and is spread in the loss that will lead to positive active material in electrolyte, to reduce the cycle life of battery. (3) about 80% volume expansion can be generated in charge and discharge process, it is likely that will lead to collapsing of anode structure etc..
In view of the above problems, numerous scholars' research has shown that, the design of positive electrode can well solve three above and ask Topic.Carbon material be with its excellent electric conductivity, the good stability for modifying performance of control and skeleton structure, it is extensive Applied in lithium sulfur battery anode material.
Summary of the invention
In view of the problems of the existing technology, the present invention provides a kind of porous carbon nanosheet filling hollow carbon sphere of rich nitrogen Lithium sulfur battery anode material.The material, using nanometer calcium carbonate as template and functional activation agent, is received using the dopamine of rich nitrogen as carbon source The CO2 gas that rice calcium carbonate pyrolytic generates activates internal carbon-coating, generates porous carbon nanosheet, improves the ratio table of material Area increases physics captured sulfur result, and the nitrogen of high-content has stronger chemical captured sulfur result, carbon material to polysulfide Superior electrical conductivity neutralized the non-conductive property of sulphur.Porous nano-sheet after activation is encapsulated in silicon shell by the cladding of silica It is interior, play the role of to the maintenance of material structure vital.
In order to achieve the above object, the technical solution adopted by the present invention is：
A kind of preparation method of the rich nitrogen material of porous carbon nanosheet filling hollow carbon sphere, the richness nitrogen material is as lithium sulphur electricity Pond positive electrode, preparation method include the following steps：
The first step：Prepare poly-dopamine coated nano calcium carbonate microballoon A
The nanometer calcium carbonate of 0.9~3g is dispersed in 10~20ml ethyl alcohol, 140~280ml deionized water is added, is surpassed The trishydroxymethylaminomethane (tris) and Dopamine hydrochloride that concentration is 2mg/mL, room temperature are separately added into after 20~30min of sound Stirring 20~for 24 hours.Centrifugation uses deionized water, ethanol washing three times respectively, is placed in 40~80 DEG C of dry 12h in baking oven and obtains Microballoon A.
The mass ratio of the trishydroxymethylaminomethane and Dopamine hydrochloride is 1:1；The Dopamine hydrochloride and carbon The mass ratio of sour calcium is 1:3~1:5.
Second step：Prepare the microballoon B of coated with silica A
The A microballoon that the first step obtains is dispersed in ethyl alcohol and the mixed solution of deionized water, after ultrasonic disperse is uniform, is added Enter appropriate NH3·H2O(0.91g/cm3) and CTAB, 30min is stirred, a certain amount of tetrabutyl silicate (TEOS is added； 0.899g/cm3), 6h is stirred at room temperature, filters, with ethyl alcohol, deionized water is washed three times respectively, and it is placed in baking oven and dries completely, Obtain the microballoon B of coated with silica A.The porous carbon nanosheet generated after activation can be encapsulated in packet by the cladding of silica The inside of coating plays the role of the holding of material structure vital.
The A microballoon, NH3H2O, the mass ratio of CTAB, TEOS are 1:(5~6):(1~2):(1~2).Described is mixed Closing the volume ratio of ethyl alcohol and deionized water in solution is 3:4.
Third step：Prepare the microballoon C of poly-dopamine cladding B
It is identical as first step step, 0.9~3.0g microballoon B is dispersed in 10~20mL ethyl alcohol, add 140~ After 20~30min of ultrasound, the trishydroxymethylaminomethane (tris) and salt that concentration is 2mg/mL is added in 280mL deionized water Sour dopamine, it is stirred at room temperature 20~for 24 hours；Centrifugation uses deionized water respectively, ethanol washing three times, is placed in baking oven and has dried Microballoon C is obtained entirely
The mass ratio of the trishydroxymethylaminomethane and Dopamine hydrochloride is 1:1；The Dopamine hydrochloride with it is micro- The mass ratio of ball B is 1:3~1:5.
4th step：Prepare the hollow carbon sphere of porous carbon nanosheet filling
The product that third step is obtained is placed in tube furnace, N2800 DEG C~900 DEG C (nanometer calcium carbonates are warming up in environment Complete, the CO of generation in 760 DEG C of basic decomposition2Gas activates the hole knot for generating carbon nanosheet and layering to inner most carbon-coating Structure), after keeping 2~3h, it is down to the product after room temperature is carbonized, it is the dilute of 1mol/L that the product after carbonization, which is added to concentration, In hydrochloric acid solution, 6~12h is stirred at room temperature, filtering and washing to neutrality is redispersed in the HF solution of mass fraction 10%~20% In, 6~12h is stirred at room temperature, filtering and washing to neutrality places drying in baking oven and completely, finally obtains porous carbon nanosheet filling Hollow carbon sphere D.The heating rate is 5 DEG C/min.
5th step：Prepare carbon sulphur composite material
By carbon material D and sublimed sulfur with 1:1~4 mass ratio is added in peace times bottle, is sealed with alcohol blast burner, is placed in baking oven In, it is kept for 10~12 hours at 155~160 DEG C, then be warming up to 200~300 DEG C and kept for 1~2 hour, makes to remain in material appearance The sulphur in face volatilizees and makes the sulphur being impregnated into inside material D volatilization a part to ensure the formation of internal voids to alleviate volume expansion Problem obtains the rich nitrogen material that can be used as lithium sulfur battery anode material.
Above-mentioned rich nitrogen material is applied to lithium-sulfur cell field and prepares lithium-sulfur cell, is included the following steps：
(1) positive pole plate of lithium-sulfur cell is prepared
At room temperature, rich nitrogen material, superconduction carbon black (super P), Kynoar (PVDF) are pressed 70%~80%:10% ~20%:10%~20% quality is more uniform than mixed grinding, and appropriate nmp solvent stirring 12~be uniformly mixed system for 24 hours is added Anode sizing agent is obtained, anode sizing agent is coated in aluminum foil current collector with coating machine and is fixed on a flat glass plate, vacuum is dry It is dry complete in dry case, it is pressed into the disk of diameter 12mm with tablet machine drift, obtains anode pole piece.
(2) assembled battery
Step (1) is prepared into anode pole piece obtained and polypropylene micropore diaphragm, cathode lithium piece are subsequently assembled into battery And appropriate electrolyte is added dropwise：Electrolyte is that the bis- trifluoromethanesulfonimide lithiums (LiTFSI) of 1M and 0.2M LiNO3 are dissolved in 1,3- Dioxolanes (DOL)/glycol dimethyl ether (DME) (volume ratio 1:1).
Of the invention has following beneficial effect：
The material is using the dopamine of rich nitrogen as carbon source, using nanometer calcium carbonate as template and functional activation agent, silica Cladding plays the role of maintaining structure, and the nitrogen of high-content increases captured sulfur result, and the superior electrical conductivity of carbon material has neutralized sulphur Nonconducting problem, and this hollow carbon sphere for being filled with porous carbon nanosheet not only has biggish specific surface area, Er Qiejing It crosses pore structure (micropore and mesoporous) that the activation of CO2 gas generates and porous carbon nanosheet is conducive to physics suction to polysulfide It is attached, conducive to the infiltration of electrolyte, increase the cyclical stability of battery.
Detailed description of the invention
Fig. 1 (a) is the scanning electron microscope (SEM) photograph of the poly-dopamine coated nano calcium carbonate (PDA@CaCO3) of case study on implementation 1；
Fig. 1 (b) is nanometer calcium carbonate (the SiO2@PDA@that the coated with silica poly-dopamine of case study on implementation 1 coats CaCO3 scanning electron microscope (SEM) photograph)；
Fig. 2 is the carbon ball transmission electron microscope picture that case study on implementation 4 fills carbon nanosheet；
Fig. 3 (a) is charging and discharging curve of the case study on implementation 1 at 0.1C；
Fig. 3 (b) is cyclic curve of the case study on implementation 1 at 1C；
Fig. 4 is the thermal gravimetric analysis curve of 1 carbon sulphur compound of case study on implementation.
Specific embodiment
Pass through the preparation method and property of the following case study on implementation sulphur carbon composite that present invention be described in more detail is related to Can, but do not constitute any limitation of the invention.
Embodiment 1
1.2g nanometer calcium carbonate is dispersed in 10ml ethyl alcohol, is added 140ml deionized water, is added after ultrasonic 20min 0.3g trishydroxymethylaminomethane (tris), 0.3g Dopamine hydrochloride are stirred at room temperature for 24 hours.Deionized water, second are used in centrifugation respectively Alcohol washs three times, is placed in 60 DEG C of dry 12h in baking oven, obtains the calcium carbonate microspheres A of poly-dopamine cladding.
1.0g A microballoon is dispersed in 60ml ethyl alcohol and the mixed solution of 80ml deionized water, ultrasonic 20min, and 6ml is added NH3·H2O and 1.4g CTAB stirs 30min, adds 2.0ml tetrabutyl silicate (TEOS), 6h is stirred at room temperature, and filters, uses second Alcohol, deionized water are washed three times respectively, are placed in 60 DEG C of dry 12h in baking oven, are obtained the microballoon B of coated with silica A.
1.2g B microballoon is dispersed in 20ml ethyl alcohol, adds 180ml deionized water, 0.4g tri- is added after ultrasonic 20min Hydroxymethyl aminomethane (tris), 0.4g Dopamine hydrochloride are stirred at room temperature for 24 hours.Deionized water, ethanol washing are used in centrifugation respectively Three times, 60 DEG C of dry 12h in baking oven are placed in, obtain the microballoon C of poly-dopamine cladding B.
Microballoon C is placed in tube furnace, and 5 DEG C/min rises to 900 DEG C in N2 environment, is kept 2h, room temperature is down to, after carbonization Product is added in the dilute hydrochloric acid solution of 1mol/L, and 4h is stirred at room temperature, and filtering and washing to neutrality is redispersed in 20% HF solution In, 6h is stirred at room temperature, filtering and washing to neutrality places 60 DEG C of dry 12h in baking oven, obtains porous carbon nanosheet and fills hollow carbon Carbon material in ball.
0.104g carbon material and 0.244g elemental sulfur, which are uniformly mixed, to be placed in peace times bottle, and 155 DEG C are kept for 12 hours, then heated up It is kept for 2 hours to 200 DEG C, obtains carbon sulphur composite material.
The lithium sulfur battery anode material of this example preparation is used to prepare lithium-sulfur cell, and concrete operation step is：
A：The preparation of anode pole piece：
Above-mentioned cell positive material 0.288g, super P 0.036g, PVDF 0.038g are taken, grinding is uniform and is dispersed in It in suitable NMP, is stirred at room temperature 12 hours, anode sizing agent is made, anode sizing agent is coated in aluminum foil current collector with coating machine, 60 DEG C of vacuum drying 12h, the disk of diameter 12mm is pressed into tablet machine drift, obtains anode pole piece；
B:The preparation of lithium-sulfur cell：
Anode pole piece made from step A, polypropylene micropore diaphragm, cathode lithium piece are subsequently assembled into battery and are added dropwise suitable Measure electrolyte：Electrolyte is that the bis- trifluoromethanesulfonimide lithiums (LiTFSI) of 1M and 0.2M LiNO3 are dissolved in 1,3- dioxolanes (DOL)/glycol dimethyl ether (DME) (volume ratio 1:1).
Embodiment 2
0.9g nanometer calcium carbonate is dispersed in 10ml ethyl alcohol, is added 140ml deionized water, is added after ultrasonic 20min 20h is stirred at room temperature in 0.3g trishydroxymethylaminomethane (tris), 0.3g Dopamine hydrochloride.Deionized water, second are used in centrifugation respectively Alcohol washs three times, is placed in 70 DEG C of dry 12h in baking oven, obtains A microballoon.
0.9g A microballoon is dispersed in 60ml ethyl alcohol and the mixed solution of 80ml deionized water, ultrasonic 20min, and 5ml is added NH3·H2O and 1.26g CTAB stirs 30min, adds 1.8ml tetrabutyl silicate (TEOS), 6h is stirred at room temperature, and filters, and uses Ethyl alcohol, deionized water are washed three times respectively, are placed in 60 DEG C of dry 12h in baking oven, are obtained microballoon B.
1.2g B microballoon is dispersed in 20ml ethyl alcohol, adds 180ml deionized water, 0.4g tri- is added after ultrasonic 20min Hydroxymethyl aminomethane (tris), 0.4g Dopamine hydrochloride are stirred at room temperature for 24 hours.Deionized water, ethanol washing are used in centrifugation respectively Three times, 50 DEG C of dry 12h in baking oven are placed in, microballoon C is obtained.
Microballoon C is placed in tube furnace, N25 DEG C/min rises to 900 DEG C in environment, keeps 2h, room temperature is down to, after carbonization Product is added in the dilute hydrochloric acid solution of 1mol/L, and 4h is stirred at room temperature, and filtering and washing to neutrality is redispersed in 20% HF solution In, 6h is stirred at room temperature, filtering and washing to neutrality places 60 DEG C of dry 12h in baking oven, obtains porous carbon nanosheet and fills hollow carbon Carbon material in ball.
0.096g carbon material and 0.231g elemental sulfur, which are uniformly mixed, to be placed in peace times bottle, and 155 DEG C are kept for 12 hours, then heated up It is kept for 1 hour to 300 DEG C, obtains carbon sulphur composite material.
The lithium sulfur battery anode material of this example preparation is used to prepare lithium-sulfur cell, and concrete operation step is：
A：The preparation of anode pole piece：
Above-mentioned cell positive material 0.286g, super P 0.037g, PVDF 0.041g are taken, grinding is uniform and is dispersed in It in suitable NMP, is stirred at room temperature 12 hours, anode sizing agent is made, anode sizing agent is coated in aluminum foil current collector with coating machine, 60 DEG C of vacuum drying 12h, the disk of diameter 12mm is pressed into tablet machine drift, obtains anode pole piece；
B:The preparation of lithium-sulfur cell：
Anode pole piece made from step A, polypropylene diaphragm, cathode lithium piece are subsequently assembled into battery and electrolysis is added dropwise Liquid：Electrolyte is the bis- trifluoromethanesulfonimide lithiums (LiTFSI) of 1M and 0.2M LiNO3 to be dissolved in volume ratio be 1:1 1,3- In dioxolanes (DOL)/glycol dimethyl ether (DME) solution.
Embodiment 3
3.0g nanometer calcium carbonate is dispersed in 20ml ethyl alcohol, is added 280ml deionized water, is added after ultrasonic 30min 20h is stirred at room temperature in 0.6g trishydroxymethylaminomethane (tris), 0.6g Dopamine hydrochloride.Deionized water, second are used in centrifugation respectively Alcohol washs three times, is placed in 80 DEG C of dry 12h in baking oven, obtains A microballoon.
1.2g A microballoon is dispersed in 60ml ethyl alcohol and the mixed solution of 80ml deionized water, ultrasonic 20min, and 7ml is added NH3·H2O and 1.68g CTAB stirs 30min, adds 2.4ml tetrabutyl silicate (TEOS), 6h is stirred at room temperature, and filters, and uses Ethyl alcohol, deionized water are washed three times respectively, are placed in 60 DEG C of dry 12h in baking oven, are obtained microballoon B.
1.2g B microballoon is dispersed in 20ml ethyl alcohol, adds 180ml deionized water, 0.4g tri- is added after ultrasonic 20min Hydroxymethyl aminomethane (tris), 0.4g Dopamine hydrochloride are stirred at room temperature for 24 hours.Deionized water, ethanol washing are used in centrifugation respectively Three times, 60 DEG C of dry 12h in baking oven are placed in, microballoon C is obtained.
Microballoon C is placed in tube furnace, N25 DEG C/min rises to 800 DEG C in environment, keeps 2h, room temperature is down to, after carbonization Product is added in the dilute hydrochloric acid solution of 1mol/L, and 4h is stirred at room temperature, and filtering and washing to neutrality is redispersed in 20% HF solution In, 6h is stirred at room temperature, filtering and washing to neutrality places 60 DEG C of dry 12h in baking oven, obtains porous carbon nanosheet and fills hollow carbon Carbon material in ball.
0.12g carbon material and 0.28g elemental sulfur, which are uniformly mixed, to be placed in peace times bottle, and 160 DEG C are kept for 12 hours, then are warming up to 250 DEG C are kept for 1.5 hours, obtain carbon sulphur composite material.
The lithium sulfur battery anode material of this example preparation is used to prepare lithium-sulfur cell, and concrete operation step is：
A：The preparation of anode pole piece：
Above-mentioned cell positive material 0.32g, super P 0.04g, PVDF 0.041g are taken, grinding is uniform and is dispersed in suitable It in the NMP of amount, is stirred at room temperature 12 hours, anode sizing agent is made, anode sizing agent is coated in aluminum foil current collector with coating machine, 60 DEG C vacuum drying 12h, the disk of diameter 12mm is pressed into tablet machine drift, obtains anode pole piece；
B:The preparation of lithium-sulfur cell：
Anode pole piece made from step A, polypropylene diaphragm, cathode lithium piece are subsequently assembled into battery and electrolysis is added dropwise Liquid：Electrolyte is the bis- trifluoromethanesulfonimide lithiums (LiTFSI) of 1M and 0.2M LiNO3 to be dissolved in volume ratio be 1:1 1,3- In dioxolanes (DOL)/glycol dimethyl ether (DME) solution.
Embodiment 4
2.4g nanometer calcium carbonate is dispersed in 20ml ethyl alcohol, is added 280ml deionized water, is added after ultrasonic 20min 0.6g trishydroxymethylaminomethane (tris), 0.6g Dopamine hydrochloride are stirred at room temperature for 24 hours.Deionized water, second are used in centrifugation respectively Alcohol washs three times, is placed in 50 DEG C of dry 12h in baking oven, obtains A microballoon.
1.28g A microballoon is dispersed in 60ml ethyl alcohol and the mixed solution of 80ml deionized water, ultrasonic 20min, and 7ml is added NH3·H2O and 2g CTAB stirs 30min, adds 2.4ml tetrabutyl silicate (TEOS), 6h is stirred at room temperature, and filters, uses second Alcohol, deionized water are washed three times respectively, are placed in 60 DEG C of dry 12h in baking oven, are obtained microballoon B.
1.2g B microballoon is dispersed in 20ml ethyl alcohol, adds 280ml deionized water, 0.6g tri- is added after ultrasonic 20min Hydroxymethyl aminomethane (tris), 0.6g Dopamine hydrochloride are stirred at room temperature for 24 hours.Deionized water, ethanol washing are used in centrifugation respectively Three times, 60 DEG C of dry 12h in baking oven are placed in, microballoon C is obtained.
Microballoon C is placed in tube furnace, N25 DEG C/min rises to 900 DEG C in environment, keeps 2h, room temperature is down to, after carbonization Product is added in the dilute hydrochloric acid solution of 1mol/L, and 6h is stirred at room temperature, and filtering and washing to neutrality is redispersed in 20% HF solution In, 6h is stirred at room temperature, filtering and washing to neutrality places 60 DEG C of dry 12h in baking oven, obtains porous carbon nanosheet and fills hollow carbon Carbon material in ball.
0.1376g carbon material and 0.2064g elemental sulfur, which are uniformly mixed, to be placed in peace times bottle, and 160 DEG C are kept for 10 hours, then risen Temperature to 200 DEG C keep 2 hours, obtain carbon sulphur composite material.
The lithium sulfur battery anode material of this example preparation is used to prepare lithium-sulfur cell, and concrete operation step is：
A：The preparation of anode pole piece：
Above-mentioned cell positive material 0.227g, super P 0.029g, PVDF 0.030g are taken, grinding is uniform and is dispersed in It in suitable NMP, is stirred at room temperature 12 hours, anode sizing agent is made, anode sizing agent is coated in aluminum foil current collector with coating machine, 60 DEG C of vacuum drying 12h, the disk of diameter 12mm is pressed into tablet machine drift, obtains anode pole piece；
B:The preparation of lithium-sulfur cell：
Anode pole piece made from step A, polypropylene diaphragm, cathode lithium piece are subsequently assembled into battery and electrolysis is added dropwise Liquid：Electrolyte is the bis- trifluoromethanesulfonimide lithiums (LiTFSI) of 1M and 0.2M LiNO3 to be dissolved in volume ratio be 1:1 1,3- In dioxolanes (DOL)/glycol dimethyl ether (DME) solution.
Embodiments of the present invention above described embodiment only expresses, but it cannot be understood as special to the present invention The limitation of the range of benefit, it is noted that for those skilled in the art, without departing from the inventive concept of the premise, Various modifications and improvements can be made, these are all belonged to the scope of protection of the present invention.

Claims (10)

1. a kind of preparation method of the rich nitrogen material of porous carbon nanosheet filling hollow carbon sphere, it is characterised in that following steps：
The first step：Prepare poly-dopamine coated nano calcium carbonate microballoon A
The nanometer calcium carbonate of 0.9~3g is dispersed in 10~20ml ethyl alcohol, adds 140~280ml deionized water, at ultrasound It is 1 that mass ratio is added after reason:1 trishydroxymethylaminomethane and Dopamine hydrochloride, be stirred at room temperature 20~for 24 hours after, be centrifuged, wash It washs, is placed in drying in baking oven and obtains microballoon A completely；The mass ratio of the Dopamine hydrochloride and calcium carbonate is 1:3~1:5；
Second step：Prepare the microballoon B of coated with silica A
The A microballoon that the first step obtains is dispersed in ethyl alcohol and the mixed solution of deionized water, after ultrasonic disperse is uniform, is added NH3·H2O and CTAB adds tetrabutyl silicate TEOS after stirring 30min, and 6h is stirred at room temperature, and filters, is placed in baking after washing It is dry complete in case, obtain the microballoon B of coated with silica A；The A microballoon, NH3H2O, the mass ratio of CTAB, TEOS are 1: (5~6):(1~2):(1~2)；
Third step：Prepare the microballoon C of poly-dopamine cladding B
It is identical as first step step, 0.9~3.0g microballoon B is dispersed in 10~20mL ethyl alcohol, 140~280mL is added and goes Ionized water, after ultrasonic treatment, it is 1 that mass ratio, which is added,:1 trishydroxymethylaminomethane and Dopamine hydrochloride, it is stirred at room temperature 20~ 24h；Centrifugation, washing are placed in drying in baking oven and obtain microballoon C completely；The mass ratio of the Dopamine hydrochloride and microballoon B is 1:3~1:5；
4th step：Prepare the hollow carbon sphere of porous carbon nanosheet filling
The product that third step is obtained is placed in tube furnace, N2After being warming up to 800 DEG C~900 DEG C 2~3h of holding in environment, it is down to By in the product addition dilute hydrochloric acid solution after carbonization 6~12h is stirred at room temperature, filtering and washing is extremely in product after room temperature is carbonized Neutrality is redispersed in HF solution, and 6~12h is stirred at room temperature, and filtering and washing to neutrality is placed in baking oven and obtained after drying completely The hollow carbon sphere D of porous carbon nanosheet filling；
5th step：Prepare carbon sulphur composite material
Carbon material D and sublimed sulfur are pressed 1:1~4 mass ratio is added in peace times bottle, is kept for 10~12 hours at 155~160 DEG C, It is warming up to 200~300 DEG C again to be kept for 1~2 hour, so that the sulphur for remaining in outer surface is volatilized and makes to be impregnated into inside material D Sulphur a part of volatilizing ensure to form internal voids, obtain the rich nitrogen material that can be used as lithium sulfur battery anode material.
2. a kind of preparation method of the rich nitrogen material of porous carbon nanosheet filling hollow carbon sphere according to claim 1, It is characterized in that, the concentration of trishydroxymethylaminomethane described in the first step and third step and Dopamine hydrochloride is 2mg/mL.
3. a kind of preparation method of the rich nitrogen material of porous carbon nanosheet filling hollow carbon sphere according to claim 1 or 2, It is characterized in that, drying temperature described in the first step and third step is 40~80 DEG C, drying time 12h.
4. a kind of preparation method of the rich nitrogen material of porous carbon nanosheet filling hollow carbon sphere according to claim 1 or 2, It is characterized in that, the volume ratio of ethyl alcohol and deionized water is 3 in mixed solution described in second step:4.
5. a kind of preparation method of the rich nitrogen material of porous carbon nanosheet filling hollow carbon sphere according to claim 3, It is characterized in that, the volume ratio of ethyl alcohol and deionized water is 3 in mixed solution described in second step:4.
6. a kind of preparation side of the rich nitrogen material of porous carbon nanosheet filling hollow carbon sphere described according to claim 1 or 2 or 5 Method, which is characterized in that dilute hydrochloric acid solution concentration described in the 4th step is 1mol/L；The mass fraction of HF solution be 10%~ 20%.
7. a kind of preparation method of the rich nitrogen material of porous carbon nanosheet filling hollow carbon sphere according to claim 3, It is characterized in that, dilute hydrochloric acid solution concentration described in the 4th step is 1mol/L；The mass fraction of HF solution is 10%~20%.
8. a kind of preparation method of the rich nitrogen material of porous carbon nanosheet filling hollow carbon sphere according to claim 4, It is characterized in that, dilute hydrochloric acid solution concentration described in the 4th step is 1mol/L；The mass fraction of HF solution is 10%~20%.
9. a kind of rich nitrogen material of porous carbon nanosheet filling hollow carbon sphere described according to claim 1 or 2 or 5 or 7 or 8 Preparation method, which is characterized in that heating rate described in the 4th step is 5 DEG C/min.
10. a kind of preparation method of the rich nitrogen material of porous carbon nanosheet filling hollow carbon sphere according to claim 6, It is characterized in that, heating rate described in the 4th step is 5 DEG C/min.
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