CN109346689A - A kind of preparation method of the hollow Nano carbon balls combination electrode material of N doping multi-pore channel - Google Patents

A kind of preparation method of the hollow Nano carbon balls combination electrode material of N doping multi-pore channel Download PDF

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CN109346689A
CN109346689A CN201811132838.0A CN201811132838A CN109346689A CN 109346689 A CN109346689 A CN 109346689A CN 201811132838 A CN201811132838 A CN 201811132838A CN 109346689 A CN109346689 A CN 109346689A
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pore channel
nano carbon
carbon balls
hollow nano
electrode material
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王克坚
张奎博
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CH Auto Technology Co Ltd
Beijing Changcheng Huaguan Automobile Technology Development Co Ltd
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Beijing Changcheng Huaguan Automobile Technology Development Co Ltd
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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
    • H01M4/62—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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention provides a kind of preparation methods of the hollow Nano carbon balls combination electrode material of N doping multi-pore channel, and main technical solution is: by by SiO2Porous microsphere is as template, polymerization reaction is occurred into for p-phenylenediamine and terephthalaldehyde etc., the hollow Nano carbon balls composite material of N doping multi-pore channel is made, and as the carbon material of sulphur carbon composite electrode, it is compound fill sulphur to N doping Porous hollow carbon ball composite material by melting diffusion method, obtains the hollow Nano carbon balls composite material/S of N doping multi-pore channel.When the hollow Nano carbon balls combination electrode material of the N doping multi-pore channel of method provided by the invention preparation, its hollow structure can provide cushion space for bulk strain of the elemental sulfur in lithium-sulfur cell in charge and discharge process, the doping of nitrogen provides more free electrons, is conducive to the electric conductivity for enhancing lithium-sulphur cell positive electrode piece.

Description

A kind of preparation method of the hollow Nano carbon balls combination electrode material of N doping multi-pore channel
Technical field
The present invention relates to lithium-sulfur cell technical fields, in particular to a kind of hollow Nano carbon balls of N doping multi-pore channel The preparation method of combination electrode material.
Background technique
Since the 21th century, chemical energy source is just petered out, and the energy conservation and environmental awareness of people are gradually increased, lithium-ion electric It has been used widely in social all trades and professions as the rechargeable secondary cell of environmental protection portable, high-energy density in pond.But with This simultaneously, the rapid development in the fields such as portable electronic device, the energy, communication, traffic, military affairs, space flight is to lithium ion battery Energy density proposes higher and higher application requirement.And existing commercial Li-ion battery is limited to its positive electrode itself Theoretical specific capacity, energy density is limited, is temporarily unable to satisfy these requirements.In recent years, lithium-sulfur cell is up to 1675mAh/g with it Theoretical specific capacity, the theoretical specific energy of 2600Wh/kg (with lithium metal form battery) become research hotspot, theoretical specific capacity About an order of magnitude is higher by than current commercial lithium battery.Meanwhile sulphur has the characteristics that rich reserves, asepsis environment-protecting, has high Application potential.The research of lithium-sulfur cell is achieved many theoretical in decades and is actually answered since the 1970s With progress.However, there are still many more scabrous technical problems and deficiencies for lithium-sulfur cell for state-of-the art Place, for example, as polysulfide dissolution migration caused by shuttle effect and cause the coulombic efficiency of sulphur carbon electrode is lower to ask Topic.
Summary of the invention
In consideration of it, the invention proposes a kind of preparation sides of the hollow Nano carbon balls combination electrode material of N doping multi-pore channel Method, it is intended to solve the problems, such as that existing sulphur carbon electrode coulombic efficiency is lower.
Specifically, the invention proposes a kind of preparation sides of the hollow Nano carbon balls combination electrode material of N doping multi-pore channel Method, comprising the following steps:
(1) continue under the first preset temperature after mixing p-phenylenediamine with terephthalaldehyde, DMAC N,N' dimethyl acetamide After stirring a period of time, hydroquinone is added, until obtaining as clear as crystal precursor solution；Meanwhile by SiO2Template dispersion Into n,N-dimethylacetamide, and dispersing agent is added and is uniformly dispersed, the precursor solution is added dropwise to scattered SiO2In template suspension, PH to 4.6-4.8 is adjusted, is then persistently stirred under the second preset temperature after a period of time to product Be centrifuged, washed and after dry a period of time, product is warming up to certain temperature with default heating rate, be carbonized one section when Between after, etch, be centrifuged and wash to neutrality, dry a period of time, is made N doping Porous hollow carbon under third preset temperature Ball composite material.
Specifically, select it to be polymerize with terephthalaldehyde and hydroquinone since p-phenylenediamine nitrogen content is higher, The doping rate of nitrogen-atoms can be improved, and the doping of nitrogen-atoms can provide more free electrons, be conducive to improve carbon material Electric conductivity.Precursor solution in the step is polymerizeing of generating of hydroquinone, the effect of terephthalaldehyde and p-phenylenediamine Object phenolic resin.
In the step, SiO2Template, p-phenylenediamine, terephthalaldehyde and hydroquinone molar ratio be (1~3): (1~ 6): (1~2): (1~2)；Wherein, it is preferred that the molar ratio of p-phenylenediamine and terephthalaldehyde is 1:(3~6), more preferably 1:3.Such as the dosage of p-phenylenediamine can be 1.26g, 3.78g, 7.56g etc.；The dosage of terephthalaldehyde can for 1.34g, 2.68g waiting；The dosage of DMAC N,N' dimethyl acetamide can be 10ml, 20ml etc.；The dosage of hydroquinone can be 1.1g, 2.2g Deng.
SiO2The preparation process of template, which can be such that, mixes ethyl alcohol with deionized water, ethyl orthosilicate is added, stirring is extremely After solution stable homogeneous, it is slowly added to ammonium hydroxide, continues stirring a period of time, by product centrifugation, dry, obtained SiO2Template.This The addition sequence of sample can prevent reactant ethyl orthosilicate from reacting with ammonia water and be not enough and complex reaction generation occur and sinks It forms sediment.
Specifically, ethyl orthosilicate, ethyl alcohol, deionized water and ammonium hydroxide molar ratio can be (6~6.15): (70~ 80): (10~12): (3.10~3.20), preferably 6:75:10:3.15.In the step, when separation product, high speed can be selected Centrifuge is separated, and isolated product is washed with deionized water and ethyl alcohol respectively, product is dried Temperature can preferably (55~60) DEG C, such as 60 DEG C；The dry time can be (10-12) h, such as 12h.SiO obtained2 The partial size of porous microsphere template is (200-400) nm, such as 300nm.In the step, room temperature can be according to specific external environment It determines, generally can be 20~25 DEG C, not do any restriction herein.
In the step, SiO2The microstructure of template is in porous for microspheroidal, dispersion SiO2Dispersing agent when template can be Neopelex, methyl anyl alcohol, polyvinyl lactam or triethyl group hexyl phosphoric acid.Adjusting regulator used in PH can be Do not have the weak acid of oxidisability and reproducibility, such as glacial acetic acid.
First preset temperature is (75~90) DEG C, it is preferred that first preset temperature is (75~85) DEG C；? Mixing time under one preset temperature can be (10~30) min, for example, 20min；Second preset temperature be (50~ 60) DEG C, preferably (50~55) DEG C, (30-60) min can be stirred at such a temperature；Default heating rate be (1-8) DEG C/ Min, preferably (1-5) DEG C/min, further preferably 3 DEG C/min；Carburizing temperature is (700~780) DEG C, preferably (700~ 750)℃；Carbonization time is (2-8) h, preferably (4-6) h；Etch period is (2-9) h, further preferably 6h；The third Preset temperature is (50~65) DEG C, preferably (55~60) DEG C.
Etching agent used in etching process can be the alcohol solution of HF aqueous solution or sodium hydroxide.Preferably, the HF The concentration of aqueous solution is (10-20) wt%, such as mass concentration is the HF aqueous solution of 10wt%；The alcohol solution of sodium hydroxide In, the concentration of sodium hydroxide is (0.5-1) mol/L, and the volume ratio of second alcohol and water is 1:1 in solvent.
In the embodiment of the present invention, by SiO2Porous microsphere surface is by p-phenylenediamine, hydroquinone and terephthaldehyde Aldehyde occurs polymerization reaction and generates uniform phenolic resin, then carries out high temperature cabonization, by the aqueous solution of HF or sodium hydroxide Alcohol solution is to SiO2Further etching obtains N doping Porous hollow carbon ball composite material to layer, and it is more to represent N doping with NPHCN The hollow Nano carbon balls composite material in duct.
(2) the hollow Nano carbon balls composite material of the N doping multi-pore channel and sublimed sulfur mixed grinding are uniformly sealed afterwards, Mixture is heated to a period of time under the 4th preset temperature, is finally warming up to the 5th preset temperature heat preservation a period of time for appearance The sulphur in face evaporates, and obtains the hollow Nano carbon balls of N doping multi-pore channel/S combination electrode material.
Specifically, the mass ratio of the hollow Nano carbon balls composite material of N doping multi-pore channel and sublimed sulfur can for 7:(3~ 3.2)；Preferably 7:3.4th preset temperature is (140~160) DEG C, preferably (150~155) DEG C, more preferably 155 DEG C；Add The hot time is (10~14) h, preferably (10~12) h, more preferably 12h；5th preset temperature is (160~220) DEG C, preferably For (180~200) DEG C, more preferably 200 DEG C；Soaking time be (0.2~1) h, preferably (0.4~0.6) h, more preferably 0.5h.In the embodiment of the present invention, the hollow Nano carbon balls of N doping multi-pore channel/S combination electrode material is represented with NPHCN/S.
When it is implemented, due to the easy distillation of sulphur simple substance under high temperature, in order to guarantee that sulphur can be hollow with N doping multi-pore channel The progress of Nano carbon balls composite material is compound, is here placed in glass container the two at room temperature, then passes through alcohol blast burner It is sealed again after the corresponding site of glass container is melted.
The hollow Nano carbon balls combination electrode material of N doping multi-pore channel provided by the invention, passes through ethyl orthosilicate and second SiO is prepared in alcohol, deionized water and ammonium hydroxide effect2Porous microsphere template；In SiO2Porous microsphere surface is by p-phenylenediamine, right Benzenediol and terephthalaldehyde occur polymerization reaction and generate uniform phenolic resin, then carry out pyrocarbon to above-mentioned product Change, pass through HF aqueous solution or sodium hydroxide alcohol solution to SiO2It carries out the operation such as washing after performing etching, it is more to obtain N doping Hole hollow carbon balls composite material NPHCN；By melt diffusion method pair the hollow Nano carbon balls composite material of N doping multi-pore channel into The capable sulphur that fills is compound, finally obtains the hollow Nano carbon balls of N doping multi-pore channel/S combination electrode material.Whole preparation process operation letter It is single, it is low for equipment requirements, it is easily operated.
Further, the hollow Nano carbon balls combination electrode material of N doping multi-pore channel of the method preparation provided through the invention When material, hollow structure can provide cushion space, nitrogen for bulk strain of the elemental sulfur in lithium-sulfur cell in charge and discharge process The doping of element provides more free electrons, is conducive to the electric conductivity for enhancing lithium-sulphur cell positive electrode piece.
Detailed description of the invention
Fig. 1 is SiO in the embodiment of the present invention2The scanning electron microscope (SEM) photograph of porous microsphere；
Fig. 2 is the scanning electron microscope (SEM) photograph of the hollow Nano carbon balls composite material NPHCN of N doping multi-pore channel in the embodiment of the present invention；
Fig. 3 a is the transmission electron microscope of the hollow Nano carbon balls composite material NPHCN of N doping multi-pore channel in the embodiment of the present invention Figure；
Fig. 3 b is the transmission electron microscope picture of the hollow Nano carbon balls composite material NPHCN of N doping multi-pore channel in the embodiment of the present invention Enlarged drawing；
Fig. 4 a is the scanning electron microscope (SEM) photograph of NPHCN/S combination electrode material in the embodiment of the present invention 1；
Fig. 4 b-f is the distribution map of C, N, O, S each element in NPHCN/S combination electrode material in the embodiment of the present invention 1；
Fig. 5 is the TGA curve graph of NPHCN/S combination electrode material in the embodiment of the present invention；
Fig. 6 is that the battery that the NPHCN/S combination electrode material prepared in embodiment 1-3 in the embodiment of the present invention is assembled into exists Stable circulation comparison diagram under 0.4C.
Specific embodiment
The following is a preferred embodiment of the present invention, it is noted that for those skilled in the art For, without departing from the principle of the present invention, some improvements and modifications can also be made, these improvement and modification are also considered as Protection scope of the present invention.
Embodiment 1
75ml ethyl alcohol, 25ml deionized water are poured into beaker, 6ml ethyl orthosilicate is added, is stirred continuously, it is equal to solution It is slowly added to 3ml ammonium hydroxide after even, is stirred at room temperature 2 hours.Products therefrom is subjected to high speed centrifugation, and constantly spends ionized water And ethanol washing until solution PH be 7, by product 60 DEG C vacuum oven 24 hours, obtain product SiO2Template；
By 6.48g p-phenylenediamine and 1.34g terephthalaldehyde, 10mlN, held at 70 DEG C after the mixing of N- dimethyl acetamide Continuous stirring 20 minutes, is then added 1.1g hydroquinone, until obtaining as clear as crystal precursor solution.Meanwhile it is 1.89g is more Hole SiO2It is distributed in deionized water, and a small amount of neopelex is added, 1h is stirred by ultrasonic.By above-mentioned precursor solution Scattered SiO is added dropwise under vigorous stirring2In suspension, PH to 4.6-4.8 is adjusted with glacial acetic acid, then at 60 DEG C Product is centrifuged using supercentrifuge after persistently stirring 1h, and is washed with deionized twice.By the product after washing In a vacuum drying oven at 60 DEG C it is dry for 24 hours after, 800 DEG C are risen under tube furnace nitrogen atmosphere with the heating rate of 5 DEG C/min Be carbonized 9h.Finally with 10% HF solution etches 6h, be centrifuged with supercentrifuge, and be washed with deionized to neutrality, true Drying obtains NPHCN afterwards for 24 hours at 60 DEG C in empty drying box；
By the sublimed sulfur of NPHCN made from 0.7g and 0.3g after mixed grinding is uniform in agate mortar, puts into glass and hold Sealing, heats 12h for mixture therewith at 155 DEG C in device, finally by temperature rise to 200 DEG C keep 30 minutes by outer surface Sulphur evaporation, obtains the hollow Nano carbon balls of N doping multi-pore channel/S combination electrode material.
Embodiment 2
70ml ethyl alcohol, 20ml deionized water are poured into beaker, 5ml ethyl orthosilicate is added, is stirred continuously, it is equal to solution It is slowly added to 2.5ml ammonium hydroxide after even, is stirred at room temperature 2 hours.Products therefrom is subjected to high speed centrifugation, and constantly spends ion Water and ethanol washing are 7 until solution PH, by product 65 DEG C vacuum oven 24 hours, obtain product SiO2Template；
After 6.48g p-phenylenediamine is mixed with 2.68g terephthalaldehyde, 10ml DMAC N,N' dimethyl acetamide at 60 DEG C It persistently stirs 10 minutes, 2.2g hydroquinone is then added, until obtaining as clear as crystal precursor solution.Meanwhile by 1.22g Porous SiO2It is distributed in deionized water, and a small amount of methyl anyl alcohol is added, 0.5h is stirred by ultrasonic.By above-mentioned precursor solution strong Scattered SiO is added dropwise under strong stirring2In suspension, PH to 4.6-4.8 is adjusted with glacial acetic acid, is then continued at 50 DEG C Product is centrifuged using supercentrifuge after stirring 1h, and is washed with deionized twice.By the product after washing true 850 DEG C of carbonizations are risen under tube furnace nitrogen atmosphere with the heating rate of 3 DEG C/min after dry 12h at 50 DEG C in empty drying box 6h.Finally with 15% HF solution etches 9h, be centrifuged with supercentrifuge, and be washed with deionized to neutrality, it is dry in vacuum Drying obtains NPHCN afterwards for 24 hours at 65 DEG C in dry case；
NPHCN mixed grinding in agate mortar by the sublimed sulfur of NPHCN composite material and 0.6g made from 1.4g wt% After uniformly, sealing in glass container is put into, therewith mixture 12h is heated at 140 DEG C, temperature is finally risen into 180 DEG C of guarantors It holds the 36 minutes sulphur by outer surface to evaporate, obtains the hollow Nano carbon balls of N doping multi-pore channel/S combination electrode material.
Embodiment 3
75ml ethyl alcohol, 25ml deionized water are poured into beaker, 8ml ethyl orthosilicate is added, is stirred continuously, it is equal to solution It is slowly added to 4ml ammonium hydroxide after even, is stirred at room temperature 2 hours.Products therefrom is subjected to high speed centrifugation, and constantly spends ionized water And ethanol washing until solution PH be 7, by product 60 DEG C vacuum oven 24 hours, obtain product SiO2Template.
After 1.08g p-phenylenediamine is mixed with 1.34g terephthalaldehyde, 10ml DMAC N,N' dimethyl acetamide (DMAC) It is persistently stirred at 70 DEG C 20 minutes, 0.73g hydroquinone is then added, until obtaining as clear as crystal precursor solution.Meanwhile By the porous SiO of 0.61g2It is distributed in deionized water, and a small amount of polyvinyl lactam is added, 1h is stirred by ultrasonic.By above-mentioned presoma Scattered SiO is added dropwise in solution under vigorous stirring2In suspension, PH to 4.6-4.8 is adjusted with glacial acetic acid, then 60 Product is centrifuged using supercentrifuge after persistently stirring 1h at DEG C, and is washed with deionized twice.After washing Product in a vacuum drying oven at 60 DEG C it is dry for 24 hours after, risen under tube furnace nitrogen atmosphere with the heating rate of 1 DEG C/min 850 DEG C of carbonization 6h.Finally with 10% HF solution etches 9h, be centrifuged with supercentrifuge, and be washed with deionized to neutrality, Drying obtains NPHCN afterwards for 24 hours at 60 DEG C in a vacuum drying oven；
By the sublimed sulfur of NPHCN composite material and 0.32g made from 0.7g after mixed grinding is uniform in agate mortar, dress It is sealed in into glass container, mixture is heated into 12h at 160 DEG C therewith, temperature is finally risen to 220 DEG C of holdings 10 minutes will The sulphur of outer surface evaporates, and obtains the hollow Nano carbon balls of N doping multi-pore channel/S combination electrode material.
Experimental example
The molar ratio (F/M) of p-phenylenediamine and terephthalaldehyde is respectively 6:1,3:1,1:1 in embodiment 1-3, with NPHCN-1, NPHCN-2, NPHCN-3 respectively represent NPHCN made from embodiment 1- embodiment 3, and each NPHCN sample is passed through member Result such as the following table 1 of element analysis:
The elemental analysis result of 1 NPHCN of table
It can be seen that with the reduction of F/M ratio, nitrogen content is continuously increased.As F/M=1, nitrogen content is up to 14.93%.
Since the electric conductivity of positive electrode has important influence to the chemical property of sulphur anode, the embodiment of the present invention is adopted Four electrode contact methods are taken to test the conductivity of the NPHCN material of different F/M ratios, as a result such as table 2:
The Conductivity Results of the NPHCN of the different nitrogen contents of table 2
Material Surface resistance (Ω/cm2) Resistivity (Ω cm) Conductivity (Scm)
NPHCN-1 (F/M=6) 156.0 0.58 1.7
NPHCN-2 (F/M=3) 61.8 0.23 4.3
NPHCN-3 (F/M=1) 72.6 0.27 3.6
It can be seen that the conductivity of NPHCN-2 is by NPHCN-1's when itrogen content of getter with nitrogen doped increases to 10.28% by 7.9% 1.7S/cm is increased to 4.3S/cm；When itrogen content of getter with nitrogen doped increases to 14.93%, the conductivity of NPHCN-3 is 3.6S/cm, is dropped It is low；This can may destroy to a certain extent the connection structure between graphite flake layer due to excessive nitrating, tend to graphite flake layer It is unordered, to affect the quick conduction of electronics.
In order to verify SiO obtained in the embodiment of the present invention2The appearance structure and crystalline substance of porous microsphere, NPHCN and NPHCN/S The features such as body structure have carried out dependence test, test result such as Fig. 1-to the NPHCN and NPHCN/S that prepare in embodiment 3 respectively 5:
SiO as shown in Figure 12Template is porous microsphere shape structure, and diameter is about 300nm, and surface is smooth, thus may be used Know, SiO2The structure of template is relatively stable.
NPHCN is chondritic as shown in Figure 2, and roughened state is presented in outer surface.After being coated, calcine, etching, NPHCN The enlarged-diameter of microballoon is to about 350nm.Thus the shell thickness for inferring hollow NPHCN microballoon is about 25nm.
Fig. 3 is the transmission electron microscope picture of NPHCN, it can be seen that the really hollow knot of NPHCN microballoon from transmission electron microscope picture Structure, shell thickness are about 25nm, are consistent with surface sweeping Electronic Speculum result.The spherical shell of hollow microsphere and rough simultaneously, coarse surface is deposited In many unordered holes, be conducive to the absorption of sulphur simple substance.
The pore structure property of NPHCN material is measured by the adsorption/desorption experiment of nitrogen, specific surface area is 1281m2g-1, pore volume difference 3.88cm3g-1.Illustrate that it, with biggish reference area, is conducive to the absorption to sulphur simple substance.
Fig. 4 a is the STEM picture of NPHCN/S, it can be seen that after filling sulphur, sulphur and the entire cavity of underfill exist NPHCN Internal voids, to battery, good buffer function is played in the bulk strain of sulphur anode in charge and discharge process for this.Fig. 4 b-f is pair The distribution diagram of element answered, wherein Fig. 4 d represents the distribution of nitrogen；Fig. 4 f represents the distribution of element sulphur, it can be seen that N element and S element is evenly distributed on NPHCN microballoon.
As seen from Figure 5, the content of sulphur is 71.0wt%, NPHCN/S combination electrode in NPHCN/S combination electrode material The sulphur sublimation temperature of material is 150~350 DEG C, illustrates that the binding force between NPHCN and S is stronger.
It, first will be positive in order to verify the chemical property of NPHCN/S combination electrode material prepared by 1-3 of the embodiment of the present invention Material is made after anode pole piece and is assembled into button cell with the metal lithium sheet as cathode.Specific step is as follows: by the nitrogen of preparation Doping Porous hollow carbon ball/S combination electrode material, second block are black, PVDF is uniformly mixed with the mass ratio of 14:3:3, and are added appropriate NMP, magnetic agitation 12h mixes them thoroughly into the slurry with certain viscosity.It is later that slurry is uniform with automatic coating instrument It on the aluminium foil being coated in, and is dried in vacuo for 24 hours at 60 DEG C, is then washed into the round pole that diameter is 12mm manually with slicer Piece.Battery is assembled using CR2016 button cell shell, following assembling process carries out in glove box, it is filled with high-purity argon gas, Water, oxygen content are respectively less than 0.1ppm.Using electrode slice obtained be anode, microporous polyethylene and polyacrylic composite membrane as diaphragm, Metal lithium sheet is cathode, and above-mentioned positive plate, diaphragm and negative electrode tab are sequentially placed into battery case, injects the bis- fluoroform Huang acyls of 1M Imine lithium (LiTFSI), 2wt%LiNO31,3- dioxolanes DOL:1,2- dimethoxy-ethane DME (volume ratio 1:1) it is molten Then assembled battery is compressed sealing by liquid in hand seamer, seal the battery standing 12h finished.
To above-mentioned button cell carry out cyclical stability test, as a result as shown in fig. 6, under 0.4C current density NPHCN- The first discharge specific capacity of the battery of tri- kinds of composite materials of 1/S, NPHCN-2/S and NPHCN-3/S assembling is close, respectively 1205mAh/g,1197mAh/g,1235mAh/g.The composite material battery that nitrogen content is the NPHCN-2/S of 10.28wt% is stablized Property it is optimal, especially 10 circle (1030mAh/g) after, after 90 charging cycles, specific capacity is able to maintain in 910mAh/g, Capacity retention ratio is 88%, and capacitance loss rate is only 0.13%.NPHCN-1/S (NPHCN/S prepared by embodiment 1) and NPHCN- 3/S (NPHCN/S prepared by embodiment 3) capacity after 100 circle charge and discharge cycles is kept at 809mAh/g, 751mAh/ G, capacity retention ratio are respectively 79%, 73%, and capacitance loss rate is respectively 0.23%/circle, 0.30%/circle.NPHCN/S compound electric The stability of pole material can sum up are as follows: the doping of nitrogen-atoms changes the surface chemical property and electronic structure of carbon atom, promotees The generation for making coordinate bond between Li-N limits the shuttle effect of polysulfide in such a way that chemisorption is in conjunction with physical absorption It answers, to improve the coulombic efficiency of sulphur carbon electrode.
To sum up, the N doping Porous hollow carbon ball combination electrode material of method preparation provided by the invention, hollow structure Cushion space can be provided for bulk strain of the elemental sulfur in lithium-sulfur cell in charge and discharge process, the doping of nitrogen provides More free electrons are conducive to the electric conductivity for enhancing lithium-sulphur cell positive electrode piece.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously Limitations on the scope of the patent of the present invention therefore cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention Protect range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.

Claims (10)

1. a kind of hollow Nano carbon balls combination electrode material of N doping multi-pore channel, which comprises the following steps:
(1) it is persistently stirred under the first preset temperature after mixing p-phenylenediamine with terephthalaldehyde, DMAC N,N' dimethyl acetamide After a period of time, hydroquinone is added, until obtaining as clear as crystal precursor solution；Meanwhile by the SiO2Template dispersion Into n,N-dimethylacetamide, and dispersing agent is added and is uniformly dispersed, the precursor solution is added dropwise to scattered SiO2In template suspension, PH to 4.6-4.8 is adjusted, is then persistently stirred under the second preset temperature after a period of time to product Be centrifuged, washed and after dry a period of time, product is warming up to certain temperature with default heating rate, be carbonized one section when Between after, etch, be centrifuged and wash to neutrality, dry a period of time, it is hollow to be made N doping multi-pore channel under third preset temperature Nano carbon balls composite material；
(2) the hollow Nano carbon balls composite material of the N doping multi-pore channel and sublimed sulfur mixed grinding are uniformly sealed afterwards, will be mixed It closes object and heats a period of time under the 4th preset temperature, be finally warming up to the 5th preset temperature heat preservation a period of time for outer surface Sulphur evaporation, obtains the hollow Nano carbon balls of N doping multi-pore channel/S combination electrode material.
2. the hollow Nano carbon balls combination electrode material of N doping multi-pore channel according to claim 1, which is characterized in that described In step (1), SiO2Template, p-phenylenediamine, terephthalaldehyde and hydroquinone molar ratio be (1~3): (1~2): (1~ 6): (1~2).
3. the hollow Nano carbon balls combination electrode material of N doping multi-pore channel according to claim 2, which is characterized in that described In step (1), the molar ratio of p-phenylenediamine and terephthalaldehyde is 1:3.
4. the hollow Nano carbon balls combination electrode material of N doping multi-pore channel according to claim 1, which is characterized in that described In step (2), the mass ratio of the hollow Nano carbon balls composite material of N doping multi-pore channel and sublimed sulfur is 7:(3~3.2).
5. the hollow Nano carbon balls combination electrode material of N doping multi-pore channel according to claim 1, which is characterized in that described Dispersing agent is neopelex, methyl anyl alcohol, polyvinyl lactam or triethyl group hexyl phosphoric acid.
6. the hollow Nano carbon balls combination electrode material of N doping multi-pore channel according to claim 1, which is characterized in that described In step (1), etching agent used in etching process is the alcohol solution of HF aqueous solution or sodium hydroxide.
7. the hollow Nano carbon balls combination electrode material of N doping multi-pore channel according to claim 1, which is characterized in that described In step (1), first preset temperature is (75~90) DEG C；Second preset temperature is (50~60) DEG C；Default heating Rate is (1-8) DEG C/min, carburizing temperature is (700~780) DEG C, carbonization time is (2-8) h, etch period is (3-12) h； The third preset temperature is (50~65) DEG C.
8. the hollow Nano carbon balls combination electrode material of N doping multi-pore channel according to claim 7, which is characterized in that
In the step (2), first preset temperature is (75~85) DEG C；Second preset temperature is (50~55) DEG C； Default heating rate is (1-5) DEG C/min, carburizing temperature is (700~750) DEG C, carbonization time is (4-6) h, etch period is (6-9)h；The third preset temperature is (55~60) DEG C.
9. the hollow Nano carbon balls combination electrode material of N doping multi-pore channel according to claim 1, which is characterized in that described In step (2), the 4th preset temperature is (140~160) DEG C, heating time is (10~14) h；5th preset temperature It is (0.2~1) h for (160~220) DEG C, the soaking time.
10. the hollow Nano carbon balls combination electrode material of N doping multi-pore channel according to claim 9, which is characterized in that institute It states in step (2), the 4th preset temperature is (150~155) DEG C, heating time is (10~12) h；Described 5th default temperature Degree is (180~200) DEG C, the soaking time is (0.4~0.6) h.
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