CN106927498A - A kind of zinc sulfide nano-belt, preparation and its application in lithium sulfur battery anode material is prepared - Google Patents

A kind of zinc sulfide nano-belt, preparation and its application in lithium sulfur battery anode material is prepared Download PDF

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CN106927498A
CN106927498A CN201710149058.6A CN201710149058A CN106927498A CN 106927498 A CN106927498 A CN 106927498A CN 201710149058 A CN201710149058 A CN 201710149058A CN 106927498 A CN106927498 A CN 106927498A
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sulphur
zinc
preparation
nitrogen
source
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CN106927498B (en
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赖延清
张治安
王鹏
张志帅
孙学文
郭靖
王军言
韩兴璞
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Guangdong Mic Power New Energy Co Ltd
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Central South University
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Abstract

The invention discloses a kind of method for preparing nano strip zinc sulphide, and nitrogen-doped carbon/sulphur composite positive pole and its preparation method and application is prepared as template.Nano strip zinc sulphide is to carry out hydro-thermal reaction under conditions of zinc source, sulphur source and surfactant and obtain；Nitrogen-doped carbon/sulphur composite positive pole is that N doping nitrogen cladding sulphur is constituted; its preparation method is that poly-dopamine is coated on into vulcanization zinc surface; it is carbonized under the conditions of protective atmosphere; add molysite; solid-liquor separation; solid product is by freeze-drying; nitrogen-doped carbon/sulphur composite positive pole is obtained final product, the N doping amount of the composite positive pole is big, and sulphur load capacity is controllable; and Load Balanced; the utilization rate of active material sulphur is high, and with height ratio capacity, energy density is high; the advantages of high stability, the cycle performance of lithium-sulfur cell can be substantially improved.

Description

A kind of zinc sulfide nano-belt, preparation and its in lithium sulfur battery anode material is prepared Using
Technical field
The present invention relates to the preparation of zinc sulfide nano-belt, and in particular to its preparation method, and using obtained vulcanization Zinc nanobelt is applied to prepare the application of lithium sulfur battery anode material.
Background technology
With lithium ion battery extensively should in portable type electronic product, electric automobile and instant-plugging hybrid electric vehicle With the battery in the urgent need to developing higher energy density.It is restricted because anode material for lithium-ion batteries specific capacity is improved, lithium The energy density of ion battery is difficult to further increase considerably.Simultaneously energy is improved by increasing the voltage platform of positive electrode Density can bring safety issue again.Positive electrode is gone to " conversion reaction chemism " from " deintercalation mechanism ", it is expected to obtain The material of height ratio capacity and specific energy.Elemental sulfur is one of most promising positive electrode, and sulphur reacts generation with lithium metal completely Li2S, cell reaction is S+2Li=Li2S, is bielectron course of reaction, is not related to the deintercalation of lithium ion to react.Due to dividing for sulphur Son amount is low, and the theoretical specific capacity of sulphur is up to 1675mAh/g (almost LiFePO410 times), and theoretical specific energy is then up to 2600Wh/Kg.Additionally, elemental sulfur is in nature rich reserves, low toxicity, cheap, therefore elemental sulfur is that one kind has suction very much The positive electrode of gravitation.
But, sulphur positive electrode also faces some challenges, mainly includes：(1) many lithium sulfides of intermediate product are in the electrolytic solution Dissolving.In cyclic process, intermediate product long-chain lithium polysulphides (Li2S4To Li2S8) can easily be dissolved into ether electrolyte In.Active material is persistently reduced during this phenomenon will cause electrode, and a portion will still be dissolved in electrolysis in electric discharge terminal Positive electrode surface can not be deposited again in liquid.Therefore, this is by guiding discharge capacity is low and capacity rapid decay.The dissolving of many lithium sulfides The reason for still causing shuttle effect simultaneously, a large amount of self discharges, coulombic efficiency and cycle performance reduction are caused, irreversible appearance occur Amount decay.(2) elemental sulfur is low with the electrical conductivity of discharging product lithium sulfide.S electrical conductivity (5 × 10-30S/cm, 25 DEG C), Li2S/ Li2S2Electrical conductivity (~10-30S/cm), the utilization rate of sulphur is caused there was only 50-70% or so.(3) sulphur is produced during physics and chemistry Enormousness deformation.From orthorhombic system α-S (ρ1=2.03g/cm3) it is converted into the Li of antifluorite structure2S(ρ2=1.66g/cm3), Volumetric expansion is big, destroys electrode structure, have impact on cyclical stability.
In order to solve these problems of sulfur electrode, at present typically by elemental sulfur load (filling, attachment, mixing, extension life Long, cladding etc.) in the carbon class material with high-specific surface area, high porosity and excellent conductive performance feature, form compound Positive electrode, to limit the various negative effects that polysulfide in cyclic process dissolves in electrolyte and thus causes.Wherein, nitrogen is mixed Miscellaneous carbon material strengthens the advantage of the electric conductivity of carbon material due to N doping, while the adsorptivity strong to polysulfide, in addition, nitrogen is first Element has stronger chemical adsorptivity to polysulfide, can effectively suppress the migration of polysulfide.
For example, the Chinese patent literature of Publication No. CN103746098A discloses a kind of rich sulphur of nitrogen multimode honeycomb carbon one answering The preparation method of positive electrode is closed, this composite largely improves the chemical property of lithium-sulfur cell really, but It is due to obtaining carbon sulphur composite by heat melting method, still having part sulphur simple substance to cannot be introduced into in duct, causing composite wood On the one hand load sulfur content is low for material, is on the other hand constantly flowed out from open cavity along with circulation sulphur simple substance, causes cycle performance Decline；Simultaneously because this honeycomb carbon can not form the conductive network of long-range, it is unfavorable for the performance of lithium-sulfur cell performance, therefore close It is necessary into a kind of generated in-situ material of sulphur simple substance while banding.
Existing lithium sulfur battery anode material is generally ball-type core-shell structure copolymer, and the defect of this structure is：Sphere material is unfavorable for Long-range is conductive, and spherical inside zinc sulphide is difficult to dissolve, and is unfavorable for improving the sulfur content of sulphur carbon material.But made To become band but be possible to and overcome two above defect.
Existing banding zinc sulphide is mainly prepared using vapour deposition process, the preparation method high cost, is yielded poorly, is difficult to industry Metaplasia is produced；In addition, the homogeneity of obtained product is poor, it is difficult to be adapted to lithium-sulfur cell field.
Therefore, how a kind of banding will be prepared, sulphur simple substance is fixed on inside carbon material, will improve and improve its current-carrying capacity, Improving combination process makes compound rear sulphur content cloth more uniform while making it be not easily runed off when circulating, and improves the ratio energy of lithium-sulfur cell Amount, high rate performance and cycle life, are the problems for still needing to make great efforts to solve at present.
The content of the invention
To overcome the defect of prior art, an object of the present disclosure to be to provide a kind of preparation method of zinc sulfide nano-belt.
It is a second object of the invention to provide a kind of preparing lithium-sulfur cell just using obtained zinc sulfide nano-belt The method of pole material.
Sulfur doping and load capacity for nitrogen-doped carbon of the prior art/sulphur positive electrode generally existing is relatively low, energy Density is low, and cycle performance is poor, and the shortcomings of preparation flow is long, the third object of the present invention is using the positive pole of the lithium-sulfur cell Lithium sulfur battery anode material obtained in the preparation method of material.It is intended to lifting sulfur doping amount greatly, load capacity is controllable, and load is equal Even, stabilization nano strip positive electrode.
A kind of preparation method of zinc sulfide nano-belt, is obtained by the solution hydro-thermal reaction of zinc source, sulphur source, surfactant.
The inventors discovered that, in the presence of surfactant, nano level tool is obtained by a step by hydro-thermal reaction There is the zinc sulphide of banded structure.The inventive method step is simple, flow is short, low cost, can be mass-produced.
The inventors discovered that, surfactant can be as a nuclearing centre, while the introducing of surfactant can be with Banding zinc sulphide is set more to be uniformly dispersed, it is to avoid undue reunion, this is extremely closed to it as carbon sulphur composite prepared by template It is important.Use the positive electrode obtained in template of zinc sulfide nano-belt obtained in methods described be more beneficial for electrolyte infiltration and The transmission of electric charge.
Preferably, described surfactant is anion surfactant.
The species and usage amount of surfactant can to a certain degree influence the pattern of banding zinc sulphide, and then influence positive pole material The performance of material.
Further preferably, described surfactant be lauryl sodium sulfate, neopelex at least It is a kind of.
Preferably, the weight of the surfactant is 0.1~0.5 times of zinc source weight.
Described zinc source is Zn2+Water soluble salt.
For example, described zinc source is Zn2+Sulfate, nitrate, chlorate, acetate etc..
Preferably, described zinc source is zinc nitrate and its hydrate, zinc sulfate and its hydrate, zinc chloride and its hydration At least one in thing.
Described sulphur source is low price, water-soluble organic sulfur compound or inorganic sulphide with reproducibility.
Preferably, described sulphur source is at least one in thiocarbamide, thioacetamide.
Described sulphur source and zinc source add weight so that Zn in zinc source2+It is sufficiently converted into ZnS.
The mol ratio of the zinc in sulphur and zinc source in described sulphur source is 1~5 times.It is also contemplated that described sulphur source is added Weight is make the theoretical amount of zinc ion reaction in zinc source 1~5 times.
Further preferably, the mol ratio of the sulphur in described sulphur source and the zinc in zinc source is 1~1.8 times.
Preferably, described hydrothermal temperature is 120~220 DEG C.
Under described hydrothermal temperature, preferred the hydro-thermal reaction time is 6~12h.
A kind of preparation method of preferred zinc sulfide nano-belt of the present invention, described zinc source, sulphur source, surfactant is molten Solve and/or be dispersed in water, obtain mixed liquor；Described mixed liquor is placed in closed container, described 120~220 are warming up to 6~12h of hydro-thermal reaction at DEG C, after hydro-thermal reaction terminates, the reaction solution to hydro-thermal reaction carries out separation of solid and liquid treatment；Collect solid Part, and wash, be dried to obtain described zinc sulfide nano-belt.
Present invention also offers a kind of preparation method of lithium sulfur battery anode material, in described zinc sulfide nano belt surface Cladding carbon source or C/N sources；Material after cladding is carbonized under the conditions of protective atmosphere again；The product of carbonization is anti-through ferric iron source again Should, solid-liquor separation, drying, obtain final product described lithium sulfur battery anode material.
In method for preparing anode material of the present invention, using nano strip zinc sulphide as template, in its Surface coating carbon source or C/N sources, and be carbonized, then carbonized product and iron ion (ferric iron source) are reacted, make elemental sulfur in-situ deposition in carbon source or C/N sources Inside carbon skeleton after carbonization, sulphur simple substance core is formed.Described carbon skeleton has the carbon structure of micropore with close and surface, makes It has porosity and bigger specific surface area higher, considerably increase elemental sulfur load capacity (weight content reaches 50~ 90%) and with elemental sulfur contact area, improve electron transfer rate and response area.And the carbon skeleton that carbonization is formed constitutes conduction Network, is conducive to that electronics conducts and lithium ion spreads, and leads to for whole positive pole provides effective conductive network and lithium ion mobility Road.Sulphur simple substance is closed in the carbon shell (shell, carbon skeleton) of micropore, and the pore network of nanoscale inhibits many lithium sulfides Dissolving diffusion be lost in.Using banded structure zinc sulfide nano-belt obtained in the present invention as template, can be obtained with bar-shaped knot The nucleocapsid positive electrode of structure, described bar-shaped positive electrode is more conducive to conductive and electrolyte the infiltration of long-range, improves lithium-sulfur cell The utilization rate of sulphur, and then lift the performance of positive electrode.
The preparation method of described lithium sulfur battery anode material, the length of described zinc sulfide nano-belt is received for 20~300 Rice, diameter (or width) is 20~60nm nanometers；Diameter is more preferably 20~30nm nanometers.
Described carbon source is material that can be well known in the art, for example, water soluble organic substance.
In the present invention, in zinc sulfide nano-belt surface recombination carbon source, being then carbonized forms carbon shell cladding zinc sulfide nano-belt Composite (C-ZnS)；The positive electrode (C-S) of carbon coating sulphur is then obtained with ferric iron source reaction again.
Preferably, described carbon source is 2~10: 1 with the mass ratio of zinc sulfide nano-belt.
Described C/N sources are itrogenous organic substance；Preferably polymer with nitrogen and conducting polymer.
Preferably, described C/N sources are poly-dopamine, polypyrrole, polyaniline, polypyridine etc..
Preferably, described C/N sources are poly-dopamine
Described C/N sources are 2~10: 1 with the mass ratio of zinc sulfide nano-belt.
Preferred embodiments of the present invention, in described zinc sulfide nano-belt Surface coating C/N sources.
Preferably, in described zinc sulfide nano belt surface deposition C/N sources, through carbonization treatment, being obtained and being received in zinc sulphide The shell (N/C-ZnS) of the carbon of rice belt surface cladding N doping；Then reacted through ferric iron source again, N/C-S is obtained, and (N adulterates Carbon-S) it is combined the lithium sulfur battery anode material of core shell structure.
Preferably, the temperature of carbonisation is 600~1100 DEG C.
Further preferably, the temperature of described carbonisation is 800~1000 DEG C.
Under described carburizing temperature, insulation carbonization, preferred carbonization time is 1~12 hour.
Described protective atmosphere is nitrogen atmosphere and/or rare gas atmosphere.
Described rare gas is, for example, helium, argon gas etc..
Described ferric iron source includes ferric ion compound；More preferably Fe3+Water soluble salt.
Preferably, described ferric iron source is at least in ferric nitrate and its hydrate, iron chloride, ferric sulfate etc. Kind.
When in use, described ferric iron source can be configured to source of iron solution in advance, then adds described C-ZnS or N/ C-ZnS；Stirring reaction, subsequent separation of solid and liquid, washing, dry described positive electrode (C-S；Or N/C-S).
C-ZnS or N/C-ZnS is preferably 12~24h with the ferric iron source stirring reaction time.
In described source of iron solution, the mass percent of molysite solute is 10~50%.
The invention also discloses a kind of lithium sulphur of preferred nitrogen-doped carbon/sulphur (N/C-S) composite Nano banding core shell structure The preparation method of cell positive material, surface deposition, carbonization in described zinc sulfide nano-belt, iron salt solutions reaction, is obtained Nitrogen/carbon coating sulphur positive electrode (N/C-S)；Specifically include following steps：
Step (1)：The preparation of zinc sulfide nano-belt：
The solution of zinc source, sulphur source, surfactant is carried out into hydro-thermal reaction；Hydro-thermal reaction product through separation of solid and liquid, washing, It is dried to obtain described zinc sulfide nano-belt；
Step (2)：C/N is coated：
Zinc sulfide nano-belt is scattered in deionized water, Dopamine hydrochloride monomer is added, regulation system pH is 8~9 simultaneously Kept for 6~24 hours, the zinc sulfide nano carrying material (N/C- of C/N sources cladding is obtained by freeze-drying through solid product after ZnS)；
Step (3)：Carbonization：
The covering material of step (2) is being carbonized under protective atmosphere；Obtain N doping carbon-coating cladding zinc sulfide nano-belt Core-shell material；
Step (4)：Sulphur in-situ deposition：
The carbonized product of step (3) is mixed with iron salt solutions, stirring reaction, subsequent separation of solid and liquid, washing, dry institute The N doping carbon-coating stated coats the positive electrode (N/C-S) of sulphur.
Preferably, in step (1), described zinc source is zinc nitrate, zinc sulfate, at least one of zinc chloride.
Preferably, in step (1), described sulphur source is thiocarbamide, at least one in thioacetamide.
Preferably, in step (1), surfactant be in lauryl sodium sulfate, neopelex extremely Few one kind.
Preferably, in step (1), the weight of the surfactant for zinc source (in terms of zinc ion) weight 0.1~ 0.5 times.
Preferably, in step (1), the mol ratio of the zinc in sulphur and zinc source in described sulphur source is 1~1.8 times.
Preferably, in step (1), hydrothermal temperature is 120~220 DEG C.
Preferably, in step (1), the hydro-thermal reaction time is 6~12h.
In step (2), it is preferred to use the described pH of Tris-buffer regulations.
The carbonisation of step (3) is carried out preferably in atmosphere furnace.
Preferably, in step (2), added Dopamine hydrochloride monomer is 2~10: 1 with zinc sulfide nano-belt mass ratio.
Preferably, in step (3), under argon gas protective condition, 600~1100 DEG C of carbonizations, under described carburizing temperature 1~12h of insulation carbonization.
Preferably, in step (3), the solute of iron salt solutions includes：In iron chloride, ferric nitrate, ferric sulfate at least one Kind, the concentration of iron salt solutions is 10~50%.
In step (4), the stirring reaction time is preferably 12~24h.
Lithium sulfur battery anode material, described lithium-sulphur cell positive electrode material obtained in also a kind of described preparation method of the present invention Material is in bar-shaped nucleocapsid structure, wherein, Shell Materials are carbon, or are nitrogen-doped carbon；Described core is that in-situ oxidation reaction is heavy Long-pending elemental sulfur.
Preferably, in described lithium sulfur battery anode material, quality percentage fraction shared by core (sulphur) for 50%~ 90%；Balance of carbon shell or nitrogen-doped carbon shell.
A kind of preferred lithium sulfur battery anode material of the present invention, the shell of the nitrogen-doped carbon with club shaped structure is described The enclosure in-situ deposition of nitrogen-doped carbon has sulphur simple substance.
In preferred nitrogen-doped carbon/sulphur composite positive pole (being labeled as N/C-S), N doping and deposition not only improve carbon Electrical conductivity, improves material high rate performance, and forms chemical bond between many lithium sulfides, and the shuttle to suppressing polysulfide has pole It is big to help, be conducive to the raising of lithium-sulfur cell cyclical stability, the utilization ratio of active substances in cathode materials sulphur is substantially increased, Be conducive to the raising of lithium-sulfur cell cyclical stability.
Preferably, in described lithium sulfur battery anode material, the quality percentage fraction shared by core is 50%~90%；It is remaining It is nitrogen-doped carbon shell to measure, and in the nitrogen-doped carbon shell, on the basis of nitrogen-doped carbon shell weight, N doping amount is 0.5%~6%.
Preferred scheme, the nano-zinc sulfide band is nanoscale, in nano strip nitrogen-doped carbon/sulphur composite positive pole The mass percentage content of element sulphur is 50%~90%.Sulfur loaded in nano strip nitrogen-doped carbon/sulphur composite positive pole Amount is controllable, and can reach load capacity higher, can reach 90% or so, solves existing nitrogen-doped carbon/sulphur compound just Low-sulfur content problem in the material of pole.
More preferably scheme, the nano strip nitrogen-doped carbon/sulphur composite, in nitrogen-doped carbon the doping of nitrogen compared with Height, far above level of the prior art.
Technical scheme, to it is critical only that and synthesized zinc sulfide nano-belt using hydro-thermal method, is vulcanized with nano strip Zinc nanobelt is that template coats poly-dopamine, and sulphur simple substance is changed into after iron ion reaction after carbonization, sulphur simple substance is directly sunk Product is inside nitrogen-doped carbon.Poly-dopamine after carbonization is conducive to the infiltration of electrolyte by microcellular structure, while can limit many The migration of sulfide and diffusion.
The solution of the present invention can rapidly and effectively prepare nano strip N doping/sulphur composite positive pole, relatively existing There is technology to enormously simplify processing step.
Present invention also offers a kind of application of described lithium sulfur battery anode material.
Preferably, the nano strip nitrogen-doped carbon/sulphur composite positive pole of preparation is applied to prepare lithium-sulfur cell Positive pole.
Nano strip sulfur doping nitrogen-doped carbon/sulphur composite positive pole of the invention is used as positive active material and conductive charcoal Black, Kynoar (PVDF) etc. uniformly mixes, and adds appropriate NMP and is made slurry (solid content is 80wt%), is coated in aluminium On paper tinsel collector, after vacuum drying, lithium-sulphur cell positive electrode piece is obtained；Lithium sulphur electricity is further assembled into negative pole, electrolyte etc. Pond.
Compared with the prior art, the Advantageous Effects that technical scheme is brought：
1st, the present invention originally selects surfactant, and the zinc sulphide with banding pattern is obtained by hydro-thermal reaction； Obtained banding zinc sulphide is uniformly dispersed, and is difficult to reunite；With good homogeneity；In addition, described zinc sulfide nano-belt Draw ratio is controllable；
2nd, the regulation and control of proportion are added by the species of Surfactant and, can the further homogeneous material of pattern；
3rd, the preparation method is simple of zinc sulfide nano-belt of the invention；
4th, the core with club shaped structure can be obtained as template using banded structure zinc sulfide nano-belt obtained in the present invention Shell positive electrode, the bar-shaped positive electrode is conducive to long-range conductive and infiltration and the transmission of electric charge of electrolyte, is more conducive to carry The utilization rate of lithium-sulfur cell sulphur high；Lift the performance of positive electrode.
5th, deposited by the surface of described zinc sulfide nano-belt, carbonization forms clad, then again through ferric iron source Reaction, an in situ, step is obtained with nano strip and with sulphur as core, with the core shell structure of carbon or the shell of nitrogen-doped carbon Positive electrode, described positive electrode can effectively suppress polysulfide dissolving in the electrolytic solution, and active material utilization efficiency is high.
6th, the N doping amount and sulphur load capacity of currently preferred nano strip nitrogen-doped carbon sulphur composite positive pole it is big and Controllable, and Load Balanced, overcoming nitrogen-doped carbon/sulphur composite positive pole in the prior art, to carry sulfur content low, and loads uneven Shortcoming.
7th, when nano strip nitrogen-doped carbon/sulphur composite positive pole of the invention is as lithium sulfur battery anode material, activity Material utilization efficiency is high, and with height ratio capacity, energy density is high, the advantages of high stability, can substantially improve following for lithium-sulfur cell Ring performance.
8th, nano strip nitrogen-doped carbon/sulphur composite positive pole of the invention, processing step is greatly simplified, it is possible to achieve sulphur And load capacity is controllable, without using organic solvent, be conducive to environmental protection, the raw material sources of use are wide, and inexpensively, low cost is adapted to Industrialized production.
Brief description of the drawings
Fig. 1 schemes for the SEM of a- zinc sulfide nano-belts, b- nano strips nitrogen-doped carbon/sulphur composite；Can from figure Go out, sulphur is evenly distributed in whole composite positive pole.
Fig. 2 is the discharge curve first of nano strip nitrogen-doped carbon/sulphur composite positive pole that embodiment 1 is obtained.
Fig. 3 is the nano strip nitrogen-doped carbon/sulphur composite positive pole that obtains of embodiment 1 under 0.5C current densities 100 circle cycle performance figures.
Fig. 4 is the discharge curve first of nano strip nitrogen-doped carbon/sulphur composite positive pole that embodiment 2 is obtained.
Fig. 5 is the nano strip nitrogen-doped carbon/sulphur composite positive pole that obtains of embodiment 2 under 0.5C current densities 100 circle cycle performance figures.
Fig. 6 is the discharge curve first of nano strip nitrogen-doped carbon/sulphur composite positive pole that embodiment 3 is obtained.
Fig. 7 is the nano strip nitrogen-doped carbon/sulphur composite positive pole that obtains of embodiment 3 under 0.5C current densities 100 circle cycle performance figures.
Fig. 8 is the discharge curve first of nano strip nitrogen-doped carbon/sulphur composite positive pole that embodiment 4 is obtained.
Fig. 9 is the nano strip nitrogen-doped carbon/sulphur composite positive pole that obtains of embodiment 4 under 0.5C current densities 100 circle cycle performance figures.
Figure 10 is the discharge curve first of nano strip nitrogen-doped carbon/sulphur composite positive pole that comparative example 1 is obtained.
Figure 11 is the nano strip nitrogen-doped carbon/sulphur composite positive pole that obtains of comparative example 1 under 0.5C current densities 100 circle cycle performance figures.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but is not limited to the protection domain of invention.
Embodiment 1
By 0.2 gram of zinc chloride and 0.2 gram of thioacetamide (S/Zn mol ratios are 1.8), 0.08 gram of lauryl sodium sulfate Well mixed to be transferred in water heating kettle, 120 DEG C are incubated 6 hours, and separation of solid and liquid is and can be prepared by zinc sulfide nano-belt after drying； Zinc sulfide nano strip length is 120nm, diameter 30nm.
Obtained zinc sulfide nano-belt is scattered in 500mL ionized waters, 1 gram of Dopamine hydrochloride monomer is added, added Tris-buffer adjusts pH to 8.5, and is kept for 6 hours, solid product by freeze-drying, in transferring them to atmosphere furnace, in argon 600 DEG C are heated under the conditions of gas shielded, and are incubated 1 hour.By 200 milliliters of liquor ferri trichloridis that product addition concentration is 10% In and be stirred overnight (12h), by the drying of 60 DEG C of products obtained therefrom.By thermogravimetric test its actual sulfur content be 50wt.%. The composite positive pole of gained, conductive black, Kynoar (PVDF) uniformly mix according to 8: 1: 1 mass ratio, and disperse Slurry (solid content is 80wt%) is made in the NMP of certain mass, is then coated with aluminum foil current collector, the vacuum at 60 DEG C It is dried to obtain a kind of lithium-sulphur cell positive electrode piece.
Battery assembling test is：Positive plate is struck out the electrode slice of a diameter of 10mm, with metal lithium sheet as negative pole, electrolysis Liquid is 1M LiTFSI/DOL: DME (1: 1), and the button cells of CR 2025 are assembled into the glove box full of argon gas.At room temperature (25 DEG C) carry out constant current charge-discharge test with the current density of 0.5C (837mA/g), and discharge and recharge blanking voltage is 1.5~3.0V. As shown in Figures 2 and 3,1180mAh/g, specific capacity keeps 950mAh/g after 100 circulations, and 80.5% capacity is maintained respectively Conservation rate.
Embodiment 2
By 0.2 gram of zinc chloride and 0.4 gram of thioacetamide (S/Zn mol ratios are 3.6), 0.1 gram of lauryl sodium sulfate is mixed Conjunction uniformly is transferred in water heating kettle, and 180 DEG C are incubated 6 hours, and separation of solid and liquid is and zinc sulfide nano-belt can be obtained after drying, and it is grown It is 150nm to spend, diameter 60nm.
Obtained zinc sulfide nano-belt is scattered in 500mL ionized waters, 3 grams of Dopamine hydrochloride monomers are added, added Tris-buffer adjusts pH to 8.8, and is kept for 6 hours, solid product by freeze-drying, in transferring them to atmosphere furnace, in argon 800 DEG C are heated under the conditions of gas shielded, and are incubated 5 hours.By 500 milliliters of liquor ferri trichloridis that product addition concentration is 15% In and be stirred overnight (12h), by the drying of 60 DEG C of products obtained therefrom.The composite positive pole of gained, conductive black, polyvinylidene fluoride Alkene (PVDF) uniformly mixes according to 8: 1: 1 mass ratio, and is dispersed in the NMP of certain mass and makes slurry (solid content is 80wt%), it is then coated with aluminum foil current collector, a kind of lithium-sulphur cell positive electrode piece is obtained after being vacuum dried at 60 DEG C.It is logical Overheat resurvey try its actual sulfur content be 52.1wt.%.The composite positive pole of gained, conductive black, Kynoar (PVDF) uniformly mix according to 8: 1: 1 mass ratio, and be dispersed in the NMP of certain mass and make slurry (solid content is 80wt%), it is then coated with aluminum foil current collector, a kind of lithium-sulphur cell positive electrode piece is obtained after being vacuum dried at 60 DEG C.
Battery assembling test is：Positive plate is struck out the electrode slice of a diameter of 10mm, with metal lithium sheet as negative pole, electrolysis Liquid is 1M LiTFSI/DOL: DME (1: 1), and the button cells of CR 2025 are assembled into the glove box full of argon gas.At room temperature (25 DEG C) carry out constant current charge-discharge test with the current density of 0.5C (837mA/g), and discharge and recharge blanking voltage is 1.5~3.0V. As shown in Figure 4 and Figure 5,1066mAh/g, specific capacity keeps 830mAh/g after 100 circulations, and 80.95% appearance is maintained respectively Amount conservation rate.
Embodiment 3
By 0.2 gram of zinc chloride and 0.5 gram of thioacetamide (S/Zn mol ratios are 4.5), 0.1 gram of lauryl sodium sulfate is mixed Conjunction uniformly is transferred in water heating kettle, and 200 DEG C are incubated 10 hours, separation of solid and liquid be and after drying by obtain zinc sulfide nano-belt, its Length 180nm, diameter 40nm.
Obtained zinc sulfide nano-belt is scattered in 500mL ionized waters, 4 grams of Dopamine hydrochloride monomers are added, added Tris-buffer adjusts pH to 8.5, and is kept for 12 hours, solid product by freeze-drying, in transferring them to atmosphere furnace, 800 DEG C are heated under argon gas protective condition, and are incubated 5 hours.By 500 milliliters of vulcanization ferrous solutions that product addition concentration is 30% In and be stirred overnight (12h), by the drying of 60 DEG C of products obtained therefrom.By thermogravimetric test its actual sulfur content is 70.8wt.%.The composite positive pole of gained, conductive black, Kynoar (PVDF) are uniformly mixed according to 8: 1: 1 mass ratio Close, and be dispersed in the NMP of certain mass and make slurry (solid content is 80wt%), be then coated with aluminum foil current collector, A kind of lithium-sulphur cell positive electrode piece is obtained after being vacuum dried at 60 DEG C.
Battery assembling test is：Positive plate is struck out the electrode slice of a diameter of 10mm, with metal lithium sheet as negative pole, electrolysis Liquid is 1M LiTFSI/DOL: DME (1: 1), and the button cells of CR 2025 are assembled into the glove box full of argon gas.At room temperature (25 DEG C) carry out constant current charge-discharge test with the current density of 0.5C (837mA/g), and discharge and recharge blanking voltage is 1.5~3.0V. As shown in Figure 6 and Figure 7,959mAh/g, specific capacity keeps 712mAh/g after 100 circulations, and 74.2% capacity is maintained respectively Conservation rate.
Embodiment 4
0.2 gram of zinc chloride and 0.5 gram of thioacetamide, 0.1 gram of lauryl sodium sulfate are well mixed and are transferred to hydro-thermal In kettle, 200 DEG C are incubated 12 hours, and separation of solid and liquid is and can obtain zinc sulfide nano-belt, its zinc sulfide nano strip length after drying It is 100nm, diameter 50nm.
Obtained zinc sulfide nano-belt is scattered in 500mL ionized waters, 8 grams of Dopamine hydrochloride monomers are added, add Tris-buffer adjusts pH to 8.5, and is kept for 12 hours, solid product by freeze-drying, in transferring them to atmosphere furnace, 1100 DEG C are heated under argon gas protective condition, and are incubated 12 hours.500 milliliters of ferric nitrates for adding concentration to be 40% product are molten In liquid and it is stirred overnight (12h), by 60 DEG C of drying of products obtained therefrom.By thermogravimetric test its actual sulfur content is 83.8wt.%.The composite positive pole of gained, conductive black, Kynoar (PVDF) are uniformly mixed according to 8: 1: 1 mass ratio Close, and be dispersed in the NMP of certain mass and make slurry (solid content is 80wt%), be then coated with aluminum foil current collector, A kind of lithium-sulphur cell positive electrode piece is obtained after being vacuum dried at 60 DEG C.
Battery assembling test is：Positive plate is struck out the electrode slice of a diameter of 10mm, with metal lithium sheet as negative pole, electrolysis Liquid is 1M LiTFSI/DOL: DME (1: 1), and CR2025 button cells are assembled into the glove box full of argon gas.At room temperature (25 DEG C) carry out constant current charge-discharge test with the current density of 0.5C (837mA/g), and discharge and recharge blanking voltage is 1.5~3.0V. As shown in Figure 8 and Figure 9,691mAh/g, specific capacity keeps 442mAh/g after 100 circulations, and 63.8% capacity is maintained respectively Conservation rate.
Comparative example 1
0.2 gram of zinc chloride is well mixed with 0.2 gram of thioacetamide and is transferred in water heating kettle, 120 DEG C are incubated 6 hours, Separation of solid and liquid be and after drying by zinc sulphide ball, its a diameter of 1 micron.
Obtained zinc sulfide nano-sphere is scattered in 500mL ionized waters, 1 gram of Dopamine hydrochloride monomer is added, added Tris-buffer adjusts pH to 8.5, and is kept for 6 hours, solid product by freeze-drying, in transferring them to atmosphere furnace, in argon 600 DEG C are heated under the conditions of gas shielded, and are incubated 1 hour.By 200 milliliters of liquor ferri trichloridis that product addition concentration is 10% In and be stirred overnight, by the drying of 60 DEG C of products obtained therefrom.By thermogravimetric test its actual sulfur content be 40wt.%.Gained Composite positive pole, conductive black, Kynoar (PVDF) uniformly mix according to 8: 1: 1 mass ratio, and be dispersed in one Slurry (solid content is 80wt%) is made in the NMP for determining quality, is then coated with aluminum foil current collector, be vacuum dried at 60 DEG C Afterwards obtain a kind of lithium-sulphur cell positive electrode piece.
Battery assembling test is：Positive plate is struck out the electrode slice of a diameter of 10mm, with metal lithium sheet as negative pole, electrolysis Liquid is 1M LiTFSI/DOL: DME (1: 1), and the button cells of CR 2025 are assembled into the glove box full of argon gas.At room temperature (25 DEG C) carry out constant current charge-discharge test with the current density of 0.5C (837mA/g), and discharge and recharge blanking voltage is 1.5~3.0V. As shown in Figure 10 and Figure 11,680mAh/g, specific capacity keeps 410mAh/g after 100 circulations, and 60.1% appearance is maintained respectively Amount conservation rate.

Claims (10)

1. a kind of preparation method of zinc sulfide nano-belt, it is characterised in that by zinc source, sulphur source, the solution hydro-thermal of surfactant Reaction is obtained.
2. the preparation method of zinc sulfide nano-belt as claimed in claim 1, it is characterised in that described surfactant is the moon Ionic surface active agent.
3. the preparation method of zinc sulfide nano-belt as claimed in claim 2, it is characterised in that described surfactant is ten At least one in sodium dialkyl sulfate, neopelex.
4. the preparation method of the zinc sulfide nano-belt as described in any one of claims 1 to 3, it is characterised in that live on the surface Property agent weight be 0.1~0.5 times of zinc source weight；
Described zinc source is Zn2+Water soluble salt；
Described sulphur source is low price, water-soluble organic sulfur compound or inorganic sulphide with reproducibility；
The mol ratio of the zinc in sulphur and zinc source in described sulphur source is 1~5 times；
Hydrothermal temperature is 120~220 DEG C；The hydro-thermal reaction time is 6~12.
5. a kind of preparation method of lithium sulfur battery anode material, it is characterised in that in Claims 1 to 4 any one methods described Obtained zinc sulfide nano-belt Surface coating carbon source or C/N sources；Material after cladding is carbonized under the conditions of protective atmosphere again；Carbonization Product again through ferric iron source reaction, solid-liquor separation, drying, obtain final product described lithium sulfur battery anode material.
6. the preparation method of lithium sulfur battery anode material as claimed in claim 5, it is characterised in that described zinc sulfide nano The length of band is 20~300 nanometers, a diameter of 20~60 nanometers.
7. the preparation method of lithium sulfur battery anode material as claimed in claim 5, it is characterised in that
Described C/N sources are poly-dopamine, polypyrrole, polyaniline, at least one in polypyridine；
Described carbon source is 2~10: 1 with the mass ratio of zinc sulfide nano-belt；
Described C/N sources are 2~10: 1 with the mass ratio of zinc sulfide nano-belt.
8. the preparation method of the lithium sulfur battery anode material as described in any one of claim 5~7, it is characterised in that be carbonized The temperature of journey is 600~1100 DEG C, and carbonization time is 1~12 hour；Described protective atmosphere is nitrogen atmosphere and/or rare gas Body atmosphere.
9. lithium sulfur battery anode material obtained in the preparation method described in a kind of any one of claim 5~8, it is characterised in that Described lithium sulfur battery anode material is in bar-shaped nucleocapsid structure, wherein, Shell Materials are carbon, or are nitrogen-doped carbon；It is described Core for in-situ oxidation reactive deposition elemental sulfur.
10. lithium sulfur battery anode material as claimed in claim 9, it is characterised in that in described lithium sulfur battery anode material, Quality percentage fraction shared by sulphur is 50%~90%；Balance of carbon shell or nitrogen-doped carbon shell；
In the nitrogen-doped carbon shell, on the basis of nitrogen-doped carbon shell weight, N doping amount is 0.5%~6%.
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107381620A (en) * 2017-08-07 2017-11-24 中国科学技术大学 A kind of zinc sulphide/diethylenetriamine hydridization and zinc sulphide ultrathin nanometer band and preparation method thereof
CN109301213A (en) * 2018-09-30 2019-02-01 肇庆市华师大光电产业研究院 A kind of lithium ion battery negative material and preparation method thereof
CN109326786A (en) * 2018-10-25 2019-02-12 济南大学 A kind of zinc sulphide containing sulphur vacancy/rGO composite material and preparation method and application
CN110817844A (en) * 2019-12-19 2020-02-21 南昌大学 Preparation method of nitrogen-sulfur co-doped porous carbon nano-microspheres
CN111584858A (en) * 2020-05-06 2020-08-25 电子科技大学 Lithium-sulfur battery with hollow hexagonal rod-shaped structure zinc sulfide loaded sulfur elementary substance as positive electrode material and preparation method thereof
CN112952096A (en) * 2021-02-18 2021-06-11 广东佳纳能源科技有限公司 Nitrogen-doped carbon-coated lithium ion battery positive electrode material and preparation method thereof
CN113460971A (en) * 2021-07-23 2021-10-01 安徽壹石通材料科技股份有限公司 Preparation method of sulfide for pigment

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101249982A (en) * 2008-03-27 2008-08-27 中国建筑材料科学研究总院 Method for preparing zinc blende nano particle and zinc blende nano particle prepared thereby
CN101486487A (en) * 2008-01-16 2009-07-22 中国科学院合肥物质科学研究院 Zinc sulfide micron hollow sphere and preparation method thereof
CN101519223A (en) * 2009-04-10 2009-09-02 武汉理工大学 One-step template-free method for preparing a great amount of monodisperse ZnS hollow nanospheres
CN102867963A (en) * 2012-09-29 2013-01-09 上海空间电源研究所 Anode active material of lithium sulfur battery and preparation method of anode active material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101486487A (en) * 2008-01-16 2009-07-22 中国科学院合肥物质科学研究院 Zinc sulfide micron hollow sphere and preparation method thereof
CN101249982A (en) * 2008-03-27 2008-08-27 中国建筑材料科学研究总院 Method for preparing zinc blende nano particle and zinc blende nano particle prepared thereby
CN101519223A (en) * 2009-04-10 2009-09-02 武汉理工大学 One-step template-free method for preparing a great amount of monodisperse ZnS hollow nanospheres
CN102867963A (en) * 2012-09-29 2013-01-09 上海空间电源研究所 Anode active material of lithium sulfur battery and preparation method of anode active material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MA YOUMEI ET AL.: "A Simple and Controllable Preparation of PbS Nanobelts", 《应用化学》 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107381620A (en) * 2017-08-07 2017-11-24 中国科学技术大学 A kind of zinc sulphide/diethylenetriamine hydridization and zinc sulphide ultrathin nanometer band and preparation method thereof
CN109301213A (en) * 2018-09-30 2019-02-01 肇庆市华师大光电产业研究院 A kind of lithium ion battery negative material and preparation method thereof
CN109301213B (en) * 2018-09-30 2021-07-13 肇庆市华师大光电产业研究院 Lithium ion battery cathode material and preparation method thereof
CN109326786A (en) * 2018-10-25 2019-02-12 济南大学 A kind of zinc sulphide containing sulphur vacancy/rGO composite material and preparation method and application
CN110817844A (en) * 2019-12-19 2020-02-21 南昌大学 Preparation method of nitrogen-sulfur co-doped porous carbon nano-microspheres
CN110817844B (en) * 2019-12-19 2021-07-23 南昌大学 Preparation method of nitrogen-sulfur co-doped porous carbon nano-microspheres
CN111584858A (en) * 2020-05-06 2020-08-25 电子科技大学 Lithium-sulfur battery with hollow hexagonal rod-shaped structure zinc sulfide loaded sulfur elementary substance as positive electrode material and preparation method thereof
CN112952096A (en) * 2021-02-18 2021-06-11 广东佳纳能源科技有限公司 Nitrogen-doped carbon-coated lithium ion battery positive electrode material and preparation method thereof
CN113460971A (en) * 2021-07-23 2021-10-01 安徽壹石通材料科技股份有限公司 Preparation method of sulfide for pigment

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