CN106927498B - A kind of zinc sulfide nano-belt, preparation and its preparing the application in lithium sulfur battery anode material - Google Patents

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

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CN106927498B
CN106927498B CN201710149058.6A CN201710149058A CN106927498B CN 106927498 B CN106927498 B CN 106927498B CN 201710149058 A CN201710149058 A CN 201710149058A CN 106927498 B CN106927498 B CN 106927498B
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sulphur
belt
zinc
zinc sulfide
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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 methods for preparing nano strip zinc sulphide, and prepare nitrogen-doped carbon/sulphur composite positive pole and its preparation method and application 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; preparation method is that poly-dopamine is coated on to vulcanization zinc surface; it is carbonized under the conditions of protective atmosphere; add molysite; solid-liquor separation; solid product is by freeze-drying; up to nitrogen-doped carbon/sulphur composite positive pole, 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, has height ratio capacity, and energy density is high; the advantages that high stability, can substantially improve the cycle performance of lithium-sulfur cell.

Description

A kind of zinc sulfide nano-belt, preparation and its in preparing lithium sulfur battery anode material Using
Technical field
The present invention relates to the preparations of zinc sulfide nano-belt, and in particular to preparation method, and use obtained vulcanization Zinc nanobelt is applied to prepare the application of lithium sulfur battery anode material.
Background technique
With lithium ion battery answering in portable electronic product, electric car and instant-plugging hybrid electric vehicle extensively With there is an urgent need to develop the batteries of higher energy density.Since the raising of anode material for lithium-ion batteries specific capacity is restricted, lithium The energy density of ion battery is difficult to further increase considerably.Energy is improved by increasing the voltage platform of positive electrode simultaneously Density can bring safety issue again.Positive electrode is gone into " 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 S+2Li=Li2S is bielectron reaction process, is not related to the deintercalation reaction of lithium ion.Due to point of 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.In addition, elemental sulfur is in nature rich reserves, low toxicity, cheap, therefore elemental sulfur is that a kind of have very much suction The positive electrode of gravitation.
But sulphur positive electrode also faces some challenges, specifically includes that the more lithium sulfides of (1) intermediate product in the electrolytic solution Dissolution.In cyclic process, intermediate product long-chain lithium polysulphides (Li2S4To Li2S8) it can be dissolved into ether electrolyte easily In.This phenomenon will lead to active material in electrode and persistently reduce, and a portion will still be dissolved in electrolysis in electric discharge terminal It positive electrode surface cannot be deposited again in liquid.Therefore, this will lead to that discharge capacity is low and capacity rapid decay.The dissolution of more lithium sulfides The reason of still causing shuttle effect simultaneously causes a large amount of self discharges, and coulombic efficiency and cycle performance reduce, and irreversible appearance occurs Amount decaying.(2) elemental sulfur is low with the conductivity of discharging product lithium sulfide.S conductivity (5 × 10-30S/cm, 25 DEG C), Li2S/ Li2S2Conductivity (~10-30S/cm), the utilization rate of sulphur is caused there was only 50-70% or so.(3) sulphur generates 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), Volume expansion is big, destroys electrode structure, affects cyclical stability.
It is at present usually that (filling, attachment, mixing, extension are raw by elemental sulfur load to solve these problems of sulfur electrode Long, cladding etc.) into the carbon class material with high-specific surface area, high porosity and excellent conductive performance feature, it is formed compound Positive electrode dissolves in electrolyte and thus caused various negative effects to limit polysulfide in cyclic process.Wherein, nitrogen is mixed Miscellaneous carbon material enhances the advantages of 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 inhibit the migration of polysulfide.
For example, to disclose a kind of rich one sulphur of nitrogen multimode honeycomb carbon multiple for the Chinese patent literature of Publication No. CN103746098A The preparation method of positive electrode is closed, this composite material largely improves the chemical property of lithium-sulfur cell really, but It is still to there is part sulphur simple substance to cannot be introduced into duct due to obtaining carbon sulphur composite material by heat melting method, lead to composite wood On the one hand load sulfur content is low for material, on the other hand constantly flows out from open cavity along with circulation sulphur simple substance, causes cycle performance Decline；Simultaneously because this honeycomb carbon cannot form the network of long-range conduction, it is unfavorable for the performance of lithium-sulfur cell performance, therefore close At it is a kind of band-like while the generated in-situ material of sulphur simple substance it is necessary.
Existing lithium sulfur battery anode material is mostly 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 it is made Become band and is but possible to overcome two above defect.
Existing band-like zinc sulphide mainly uses vapour deposition process to prepare, and the preparation method is at high cost, low output, is difficult to industry Metaplasia produces；In addition, the homogeneity of product obtained is poor, it is difficult to be suitble to lithium-sulfur cell field.
Therefore, how will prepare a kind of band-like, sulphur simple substance is fixed on inside carbon material, its current-carrying capacity is improved and improves, Improving combination process keeps compound rear sulphur content cloth more uniform while making to not easily run off when its circulation, improves the ratio energy of lithium-sulfur cell Amount, high rate performance and cycle life are to still need to make great efforts to solve the problems, such as at present.
Summary of the invention
To overcome the shortcomings of existing technologies, an object of the present disclosure is 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.
Relatively low, the energy for nitrogen-doped carbon in the prior art/generally existing sulfur doping of sulphur positive electrode and load capacity The disadvantages of density is low, poor circulation, preparation flow is long, the third object of the present invention are the anode using the lithium-sulfur cell Lithium sulfur battery anode material made from the preparation method of material.It is intended to be promoted that sulfur doping amount is big, and load capacity is controllable, and loads equal Even, stable nano strip positive electrode.
A kind of preparation method of zinc sulfide nano-belt, You Xinyuan, sulphur source, the solution hydro-thermal reaction of surfactant are made.
The inventors discovered that under the action of surfactant, it can the obtained nanoscale tool of a step by hydro-thermal reaction There is the zinc sulphide of banded structure.The method of the present invention step is simple, process is short, it is at low cost, can be mass-produced.
The inventors discovered that surfactant can be used as a nuclearing centre, while the introducing of surfactant can be with So that band-like zinc sulphide is more uniformly dispersed, avoid excessive reunion, this extremely closes its carbon sulphur composite material as template preparation It is important.Use zinc sulfide nano-belt made from the method for positive electrode made from template be more advantageous to electrolyte infiltration and The transmission of charge.
Preferably, the surfactant is anionic surfactant.
The type and usage amount of surfactant can influence the pattern of band-like zinc sulphide to a certain degree, and then influence positive material The performance of material.
Further preferably, the surfactant be lauryl sodium sulfate, in neopelex at least It is a kind of.
Preferably, the weight of the surfactant is 0.1~0.5 times of zinc source weight.
The zinc source is Zn2+Water soluble salt.
For example, the zinc source is Zn2+Sulfate, nitrate, chlorate, acetate etc..
Preferably, the zinc source is zinc nitrate and its hydrate, zinc sulfate and its hydrate, zinc chloride and its hydration At least one of object.
The sulphur source is low price, the water soluble organic sulfide with reproducibility or inorganic sulphide.
Preferably, the sulphur source is at least one of thiocarbamide, thioacetamide.
The sulphur source and zinc source add weight so that Zn in zinc source2+It is sufficiently converted into ZnS.
The molar ratio of the zinc in sulphur and zinc source in the sulphur source is 1~5 times.It is also contemplated that the sulphur source adds Weight is 1~5 times for making the theoretical amount of zinc ion reaction in zinc source.
Further preferably, the molar ratio of the sulphur in the sulphur source and the zinc in zinc source is 1~1.8 times.
Preferably, the hydrothermal temperature is 120~220 DEG C.
Under the 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, the zinc source, sulphur source, surfactant is molten It solves and/or is dispersed in water, obtain mixed liquor；The 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, carries out solid-liquid separation treatment to the reaction solution of hydro-thermal reaction；Collect solid Part, and wash, be dried to obtain the zinc sulfide nano-belt.
The present invention also provides a kind of preparation methods of lithium sulfur battery anode material, in the zinc sulfide nano belt surface Coat carbon source or the source C/N；Material after cladding is carbonized under the conditions of protective atmosphere again；The product of carbonization is anti-through ferric iron source again It answers, solid-liquor separation, dry to get the lithium sulfur battery anode material.
In method for preparing anode material of the present invention, using nano strip zinc sulphide as template, in its coated with carbon source or The source C/N, and be carbonized, then carbonized product is reacted with iron ion (ferric iron source), make elemental sulfur in-situ deposition in carbon source or the source C/N Inside carbon skeleton after carbonization, sulphur simple substance core is formed.There is the carbon skeleton closed and surface to have the carbon structure of micropore, make Its with higher porosity and bigger specific surface area, 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 electronics conduction and lithium ion diffusion, provides effective conductive network for entire anode and lithium ion mobility is logical Road.Sulphur simple substance is closed in the carbon shell (shell, carbon skeleton) of micropore, and the pore network of nanoscale inhibits more lithium sulfides Dissolution spread be lost.Using banded structure zinc sulfide nano-belt produced by the present invention as template, can be made with rodlike knot The nucleocapsid positive electrode of structure, the rodlike positive electrode are more conducive to the infiltration of long-range conduction and electrolyte, improve lithium-sulfur cell The utilization rate of sulphur, and then promote the performance of positive electrode.
The length of the preparation method of the lithium sulfur battery anode material, the zinc sulfide nano-belt is received for 20~300 Rice, diameter (or width) are 20~60nm nanometers；Diameter is more preferably 20~30nm nanometers.
The 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, then carbonization forms carbon shell cladding zinc sulfide nano-belt Composite material (C-ZnS)；The positive electrode (C-S) that carbon coating sulphur is made then is reacted with ferric iron source again.
Preferably, the mass ratio of the carbon source and zinc sulfide nano-belt is 2~10: 1.
The source C/N is itrogenous organic substance；Preferably polymer with nitrogen and conducting polymer.
Preferably, the source C/N is poly-dopamine, polypyrrole, polyaniline, polypyridine etc..
Preferably, the source C/N is poly-dopamine
The mass ratio in the source C/N and zinc sulfide nano-belt is 2~10: 1.
Preferred embodiments of the present invention coat the source C/N in the zinc sulfide nano belt surface.
Preferably, depositing the source C/N in the zinc sulfide nano belt surface, through carbonization treatment, it is made and is received in zinc sulphide The shell (N/C-ZnS) of the carbon of rice belt surface cladding N doping；It is then reacted again through ferric iron source, N/C-S is made, and (N is adulterated Carbon-S) compound core-shell structure lithium sulfur battery anode material.
Preferably, the temperature of carbonisation is 600~1100 DEG C.
Further preferably, the temperature of the carbonisation is 800~1000 DEG C.
Under the carburizing temperature, heat preservation carbonization, preferred carbonization time is 1~12 hour.
The protective atmosphere is nitrogen atmosphere and/or rare gas atmosphere.
The rare gas is, for example, helium, argon gas etc..
The ferric iron source includes ferric ion compound；Further preferably Fe3+Water soluble salt.
Preferably, the ferric iron source is at least one in ferric nitrate and its hydrate, iron chloride, ferric sulfate etc. Kind.
When in use, the ferric iron source source of iron solution be can be configured in advance, the C-ZnS or N/ then added C-ZnS；It is stirred to react, is then separated by solid-liquid separation, washing, dry the positive electrode (C-S；Or N/C-S).
C-ZnS or N/C-ZnS and ferric iron source be stirred to react the time be preferably 12~for 24 hours.
In the source of iron solution, the mass percent of molysite solute is 10~50%.
The invention also discloses a kind of lithium sulphur of the band-like core-shell structure of preferred nitrogen-doped carbon/sulphur (N/C-S) composite Nano The preparation method of cell positive material, on the surface of the zinc sulfide nano-belt, deposition, carbonization, iron salt solutions reaction, are made Nitrogen/carbon coating sulphur positive electrode (N/C-S)；Specifically includes the following steps:
Step (1): the preparation of zinc sulfide nano-belt:
The solution of zinc source, sulphur source, surfactant is subjected to hydro-thermal reaction；Hydro-thermal reaction product through separation of solid and liquid, washing, It is dried to obtain the zinc sulfide nano-belt；
Step (2): C/N cladding:
It disperses zinc sulfide nano-belt in deionized water, Dopamine hydrochloride monomer is added, regulation system pH is 8~9 simultaneously It is kept for 6~24 hours, obtains the zinc sulfide nano carrying material (N/C- of the source C/N cladding by being freeze-dried through solid product after ZnS)；
Step (3): carbonization:
The covering material of step (2) is 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, is stirred to react, is then separated by solid-liquid separation, washing, dry institute The positive electrode (N/C-S) for the N doping carbon-coating cladding sulphur stated.
Preferably, the zinc source is at least one of zinc nitrate, zinc sulfate, zinc chloride in step (1).
Preferably, the sulphur source is thiocarbamide, at least one of thioacetamide in step (1).
Preferably, in step (1), surfactant be lauryl sodium sulfate, in neopelex extremely Few one kind.
Preferably, in step (1), the weight of the surfactant be zinc source (in terms of zinc ion) weight 0.1~ 0.5 times.
Preferably, the molar ratio of the zinc in sulphur and zinc source in the sulphur source is 1~1.8 times in step (1).
Preferably, hydrothermal temperature is 120~220 DEG C in step (1).
Preferably, the hydro-thermal reaction time is 6~12h in step (1).
In step (2), it is preferred to use Tris-buffer adjusts the pH.
The carbonisation of step (3) carries out preferably in atmosphere furnace.
Preferably, added Dopamine hydrochloride monomer and zinc sulfide nano-belt mass ratio are 2~10: 1 in step (2).
Preferably, in step (3), under argon gas protective condition, 600~1100 DEG C of carbonizations, under the carburizing temperature 1~12h of heat preservation carbonization.
Preferably, in step (3), the solute of iron salt solutions includes: iron chloride, ferric nitrate, at least one in ferric sulfate Kind, the concentration of iron salt solutions is 10~50%.
In step (4), be stirred to react the time be preferably 12~for 24 hours.
Lithium sulfur battery anode material made from preparation method described in the present invention also one kind, the lithium-sulphur cell positive electrode material Material is in rodlike nucleocapsid structure, wherein Shell Materials are carbon, or are nitrogen-doped carbon；The core is that in-situ oxidation reaction is heavy Long-pending elemental sulfur.
Preferably, in the lithium sulfur battery anode material, quality percentage score shared by core (sulphur) is 50%~ 90%；Surplus is 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 are described The interior of shell 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 Conductivity improves material high rate performance, and forms chemical bond between more lithium sulfides, has pole to the shuttle for inhibiting polysulfide It is big to help, be conducive to the raising of lithium-sulfur cell cyclical stability, substantially increase the utilization efficiency of active substances in cathode materials sulphur, Be conducive to the raising of lithium-sulfur cell cyclical stability.
Preferably, quality percentage score shared by core is 50%~90% in the lithium sulfur battery anode material；It is remaining Measuring is nitrogen-doped carbon shell, 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 achieve higher load capacity, can reach 90% or so, it is compound just to solve existing nitrogen-doped carbon/sulphur Low-sulfur content problem in the material of pole.
More preferably scheme, the nano strip nitrogen-doped carbon/sulphur composite material, in nitrogen-doped carbon the doping of nitrogen compared with Height is much higher than level in the prior art.
Technical solution of the present invention, key are to have synthesized zinc sulfide nano-belt using hydro-thermal method, be vulcanized with nano strip Zinc nanobelt is that template coats poly-dopamine, is changed into sulphur simple substance after iron ion reaction after carbonization, keeps sulphur simple substance directly heavy Product is inside nitrogen-doped carbon.Poly-dopamine after carbonization is conducive to the infiltration of electrolyte by microcellular structure, while can limit more The migration and diffusion of sulfide.
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.
The present invention also provides the applications of the lithium sulfur battery anode material described in one kind.
Preferably, nano strip nitrogen-doped carbon/sulphur composite positive pole of preparation is applied to prepare lithium-sulfur cell Anode.
Nano strip sulfur doping nitrogen-doped carbon/sulphur composite positive pole of the invention as a positive electrode active material with conductive charcoal Black, Kynoar (PVDF) etc. uniformly mixes, and adds suitable NMP and slurry (solid content 80wt%) is made, and is coated in aluminium On foil collector, after vacuum drying, lithium-sulphur cell positive electrode piece is obtained；Lithium sulphur electricity is further assembled into cathode, electrolyte etc. Pond.
Compared with the prior art, technical solution of the present invention bring advantageous effects:
1, the present invention originally selects surfactant, and the zinc sulphide with band-like pattern is made by hydro-thermal reaction； Band-like zinc sulphide obtained is uniformly dispersed, not easy to reunite；With good homogeneity；In addition, the zinc sulfide nano-belt Draw ratio is controllable；
2, by the type of Surfactant and the regulation of specific gravity is added, it can the further uniform material of pattern；
3, the preparation method of zinc sulfide nano-belt of the invention is easy；
4, the core with club shaped structure can be made as template using banded structure zinc sulfide nano-belt produced by the present invention Shell positive electrode, the rodlike positive electrode are conducive to the infiltration of long-range conduction and electrolyte and the transmission of charge, are more conducive to mention The utilization rate of high lithium-sulfur cell sulphur；Promote the performance of positive electrode.
5, by forming clad in the surface of zinc sulfide nano-belt deposition, carbonization, then again through ferric iron source Reaction, an in situ, step be made with nano strip and using sulphur as core, with the core-shell structure of carbon or the shell of nitrogen-doped carbon Positive electrode, the positive electrode can effectively inhibit the dissolution of polysulfide in the electrolytic solution, and active material utilization efficiency is high.
6, the N doping amount and sulphur load capacity of currently preferred nano strip nitrogen-doped carbon sulphur composite positive pole it is big and Controllably, and Load Balanced, overcoming nitrogen-doped carbon/sulphur composite positive pole in the prior art, to carry sulfur content low, and loads uneven The shortcomings that.
7, when nano strip of the invention nitrogen-doped carbon/sulphur composite positive pole is as lithium sulfur battery anode material, activity Substance utilization efficiency is high, has the advantages that height ratio capacity, energy density is high, high stability, can substantially improve following for lithium-sulfur cell Ring performance.
8, nano strip of the invention nitrogen-doped carbon/sulphur composite positive pole, processing step greatly simplify, and sulphur may be implemented And load capacity is controllable, without organic solvent, is good for the environment, and the raw material sources of use are wide, and it is inexpensively, at low cost, it is suitble to Industrialized production.
Detailed description of the invention
Fig. 1 is that the SEM of a- zinc sulfide nano-belt schemes, b- nano strip nitrogen-doped carbon/sulphur composite material；It can from figure Out, sulphur is evenly distributed in entire composite positive pole.
Fig. 2 is nano strip nitrogen-doped carbon/sulphur composite positive pole discharge curve for the first time that embodiment 1 obtains.
Fig. 3 is the obtained nano strip nitrogen-doped carbon/sulphur composite positive pole of embodiment 1 under 0.5C current density 100 circle cycle performance figures.
Fig. 4 is nano strip nitrogen-doped carbon/sulphur composite positive pole discharge curve for the first time that embodiment 2 obtains.
Fig. 5 is the obtained nano strip nitrogen-doped carbon/sulphur composite positive pole of embodiment 2 under 0.5C current density 100 circle cycle performance figures.
Fig. 6 is nano strip nitrogen-doped carbon/sulphur composite positive pole discharge curve for the first time that embodiment 3 obtains.
Fig. 7 is the obtained nano strip nitrogen-doped carbon/sulphur composite positive pole of embodiment 3 under 0.5C current density 100 circle cycle performance figures.
Fig. 8 is nano strip nitrogen-doped carbon/sulphur composite positive pole discharge curve for the first time that embodiment 4 obtains.
Fig. 9 is the obtained nano strip nitrogen-doped carbon/sulphur composite positive pole of embodiment 4 under 0.5C current density 100 circle cycle performance figures.
Figure 10 is nano strip nitrogen-doped carbon/sulphur composite positive pole discharge curve for the first time that comparative example 1 obtains.
Figure 11 is the obtained nano strip nitrogen-doped carbon/sulphur composite positive pole of comparative example 1 under 0.5C current density 100 circle cycle performance figures.
Specific embodiment
Below with reference to embodiment, invention is further described in detail, but is not limited to the protection scope of invention.
Embodiment 1
By 0.2 gram of zinc chloride and 0.2 gram of thioacetamide (S/Zn molar ratio is 1.8), 0.08 gram of lauryl sodium sulfate It is uniformly mixed and is transferred in water heating kettle, 120 DEG C keep the temperature 6 hours, are separated by solid-liquid separation i.e. and can be prepared by zinc sulfide nano-belt after drying； Zinc sulfide nano strip length is 120nm, diameter 30nm.
It disperses zinc sulfide nano-belt obtained in 500mL ionized water, 1 gram of Dopamine hydrochloride monomer is added, adds Tris-buffer tune pH to 8.5, and kept for 6 hours, solid product transfers them in atmosphere furnace, by freeze-drying in argon It is heated to 600 DEG C under the conditions of gas shielded, and keeps the temperature 1 hour.200 milliliters of liquor ferri trichloridis that concentration is 10% are added in product In and be stirred overnight (12h), by 60 DEG C of products obtained therefrom dry.By thermogravimetric test its practical sulfur content be 50wt.%. Resulting composite positive pole, conductive black, Kynoar (PVDF) uniformly mix according to 8: 1: 1 mass ratio, and disperse It is made into slurry (solid content 80wt%) in the NMP of certain mass, is then coated in aluminum foil current collector, the vacuum at 60 DEG C A kind of lithium-sulphur cell positive electrode piece is obtained after drying.
Battery assembly test are as follows: positive plate is struck out into the electrode slice that diameter is 10mm, using metal lithium sheet as cathode, electrolysis Liquid is 1M LiTFSI/DOL: DME (1: 1), is assembled into 2025 button cell of CR in 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 charge and discharge blanking voltage is 1.5~3.0V. As shown in Figures 2 and 3,1180mAh/g, 100 times circulation after specific capacity keep 950mAh/g, maintain 80.5% capacity respectively Conservation rate.
Embodiment 2
By 0.2 gram of zinc chloride and 0.4 gram of thioacetamide (S/Zn molar ratio is 3.6), 0.1 gram of lauryl sodium sulfate is mixed Conjunction is uniformly transferred in water heating kettle, and 180 DEG C keep the temperature 6 hours, is separated by solid-liquid separation i.e. and can be obtained zinc sulfide nano-belt after drying, grows Degree is 150nm, diameter 60nm.
It disperses zinc sulfide nano-belt obtained in 500mL ionized water, 3 grams of Dopamine hydrochloride monomers is added, add Tris-buffer tune pH to 8.8, and kept for 6 hours, solid product transfers them in atmosphere furnace, by freeze-drying in argon It is heated to 800 DEG C under the conditions of gas shielded, and keeps the temperature 5 hours.500 milliliters of liquor ferri trichloridis that concentration is 15% are added in product In and be stirred overnight (12h), by 60 DEG C of products obtained therefrom dry.Resulting composite positive pole, conductive black, polyvinylidene fluoride Alkene (PVDF) is uniformly mixed according to 8: 1: 1 mass ratio, and is dispersed in the NMP of certain mass and is made into slurry (solid content is 80wt%), it is then coated in aluminum foil current collector, obtains a kind of lithium-sulphur cell positive electrode piece after being dried in vacuo at 60 DEG C.It is logical Overheat resurvey try its practical sulfur content be 52.1wt.%.Resulting composite positive pole, conductive black, Kynoar (PVDF) it is uniformly mixed according to 8: 1: 1 mass ratio, and is dispersed in the NMP of certain mass and is made into slurry (solid content is 80wt%), it is then coated in aluminum foil current collector, obtains a kind of lithium-sulphur cell positive electrode piece after being dried in vacuo at 60 DEG C.
Battery assembly test are as follows: positive plate is struck out into the electrode slice that diameter is 10mm, using metal lithium sheet as cathode, electrolysis Liquid is 1M LiTFSI/DOL: DME (1: 1), is assembled into 2025 button cell of CR in 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 charge and discharge blanking voltage is 1.5~3.0V. As shown in Figure 4 and Figure 5,1066mAh/g, 100 times circulation after specific capacity keep 830mAh/g, maintain 80.95% appearance respectively Measure conservation rate.
Embodiment 3
By 0.2 gram of zinc chloride and 0.5 gram of thioacetamide (S/Zn molar ratio is 4.5), 0.1 gram of lauryl sodium sulfate is mixed Conjunction is uniformly transferred in water heating kettle, and 200 DEG C keep the temperature 10 hours, is separated by solid-liquid separation i.e. and can be obtained zinc sulfide nano-belt after drying, Length 180nm, diameter 40nm.
It disperses zinc sulfide nano-belt obtained in 500mL ionized water, 4 grams of Dopamine hydrochloride monomers is added, add Tris-buffer tune pH to 8.5, and kept for 12 hours, solid product transfers them in atmosphere furnace by freeze-drying, It is heated to 800 DEG C under argon gas protective condition, and keeps the temperature 5 hours.500 milliliters of vulcanization ferrous solutions that concentration is 30% are added in product In and be stirred overnight (12h), by 60 DEG C of products obtained therefrom dry.By thermogravimetric test its practical sulfur content is 70.8wt.%.Resulting composite positive pole, conductive black, Kynoar (PVDF) are uniformly mixed according to 8: 1: 1 mass ratio It closes, and is dispersed in the NMP of certain mass and is made into slurry (solid content 80wt%), be then coated in aluminum foil current collector, A kind of lithium-sulphur cell positive electrode piece is obtained after being dried in vacuo at 60 DEG C.
Battery assembly test are as follows: positive plate is struck out into the electrode slice that diameter is 10mm, using metal lithium sheet as cathode, electrolysis Liquid is 1M LiTFSI/DOL: DME (1: 1), is assembled into 2025 button cell of CR in 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 charge and discharge blanking voltage is 1.5~3.0V. As shown in Figure 6 and Figure 7,959mAh/g, 100 times circulation after specific capacity keep 712mAh/g, maintain 74.2% capacity respectively Conservation rate.
Embodiment 4
By 0.2 gram of zinc chloride and 0.5 gram of thioacetamide, 0.1 gram of lauryl sodium sulfate, which is uniformly mixed, is transferred to hydro-thermal In kettle, 200 DEG C keep the temperature 12 hours, are separated by solid-liquid separation i.e. and can obtain zinc sulfide nano-belt, zinc sulfide nano strip length after drying For 100nm, diameter 50nm.
It disperses zinc sulfide nano-belt obtained in 500mL ionized water, 8 grams of Dopamine hydrochloride monomers is added, it adds Tris-buffer tune pH to 8.5, and kept for 12 hours, solid product transfers them in atmosphere furnace by freeze-drying, It is heated to 1100 DEG C under argon gas protective condition, and keeps the temperature 12 hours.It is molten that 500 milliliters of ferric nitrates that concentration is 40% are added in product It in liquid and is stirred overnight (12h), 60 DEG C of products obtained therefrom is dried.By thermogravimetric test its practical sulfur content is 83.8wt.%.Resulting composite positive pole, conductive black, Kynoar (PVDF) are uniformly mixed according to 8: 1: 1 mass ratio It closes, and is dispersed in the NMP of certain mass and is made into slurry (solid content 80wt%), be then coated in aluminum foil current collector, A kind of lithium-sulphur cell positive electrode piece is obtained after being dried in vacuo at 60 DEG C.
Battery assembly test are as follows: positive plate is struck out into the electrode slice that diameter is 10mm, using metal lithium sheet as cathode, electrolysis Liquid is 1M LiTFSI/DOL: DME (1: 1), is assembled into CR2025 button cell in 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 charge and discharge blanking voltage is 1.5~3.0V. As shown in Figure 8 and Figure 9,691mAh/g, 100 times circulation after specific capacity keep 442mAh/g, maintain 63.8% capacity respectively Conservation rate.
Comparative example 1
0.2 gram of zinc chloride is uniformly mixed with 0.2 gram of thioacetamide and is transferred in water heating kettle, 120 DEG C keep the temperature 6 hours, It is separated by solid-liquid separation i.e. and can obtain after drying zinc sulphide ball, a diameter of 1 micron.
It disperses zinc sulfide nano-sphere obtained in 500mL ionized water, 1 gram of Dopamine hydrochloride monomer is added, adds Tris-buffer tune pH to 8.5, and kept for 6 hours, solid product transfers them in atmosphere furnace, by freeze-drying in argon It is heated to 600 DEG C under the conditions of gas shielded, and keeps the temperature 1 hour.200 milliliters of liquor ferri trichloridis that concentration is 10% are added in product In and be stirred overnight, by 60 DEG C of products obtained therefrom dry.By thermogravimetric test its practical 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 Determine to be made into slurry (solid content 80wt%) in the NMP of quality, be then coated in aluminum foil current collector, is dried in vacuo at 60 DEG C Afterwards obtain a kind of lithium-sulphur cell positive electrode piece.
Battery assembly test are as follows: positive plate is struck out into the electrode slice that diameter is 10mm, using metal lithium sheet as cathode, electrolysis Liquid is 1M LiTFSI/DOL: DME (1: 1), is assembled into 2025 button cell of CR in 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 charge and discharge blanking voltage is 1.5~3.0V. As shown in Figure 10 and Figure 11,680mAh/g, 100 times circulation after specific capacity keep 410mAh/g, maintain 60.1% appearance respectively Measure conservation rate.

Claims (11)

1. a kind of preparation method of zinc sulfide nano-belt, which is characterized in that You Xinyuan, sulphur source, the solution hydro-thermal of surfactant Reaction is made；
The surfactant is lauryl sodium sulfate；
The weight of the surfactant is 0.1 ~ 0.4 times or 0.5 times of zinc source weight；
The zinc source is Zn2+Water soluble salt；
The sulphur source is low price, the water soluble organic sulfide with reproducibility or inorganic sulphide；
The molar ratio of the zinc in sulphur and zinc source in the sulphur source is 1 ~ 5 times；
Hydrothermal temperature is 120 ~ 220 DEG C；The hydro-thermal reaction time is 6 ~ 12h.
2. the preparation method of zinc sulfide nano-belt as described in claim 1, which is characterized in that by 0.2 gram of zinc chloride and 0.2 gram Thioacetamide, 0.08 gram of lauryl sodium sulfate, which is uniformly mixed, to be transferred in water heating kettle, and 120 DEG C keep the temperature 6 hours, solid-liquid point From i.e. and after drying can be prepared by zinc sulfide nano-belt；Zinc sulfide nano strip length is 120 nm, 30 nm of diameter.
3. the preparation method of zinc sulfide nano-belt as described in claim 1, which is characterized in that by 0.2 gram of zinc chloride and 0.4 gram Thioacetamide, 0.1 gram of lauryl sodium sulfate, which is uniformly mixed, to be transferred in water heating kettle, and 180 DEG C keep the temperature 6 hours, is separated by solid-liquid separation Zinc sulfide nano-belt i.e. and after drying can be obtained, the length is 150 nm, 60 nm of diameter.
4. the preparation method of zinc sulfide nano-belt as described in claim 1, which is characterized in that by 0.2 gram of zinc chloride and 0.5 gram Thioacetamide, 0.1 gram of lauryl sodium sulfate, which is uniformly mixed, to be transferred in water heating kettle, and 200 DEG C keep the temperature 10 hours, solid-liquid point From i.e. and after drying zinc sulfide nano-belt, 180 nm of length, 40 nm of diameter can be obtained.
5. the preparation method of zinc sulfide nano-belt as described in claim 1, which is characterized in that by 0.2 gram of zinc chloride and 0.5 gram Thioacetamide, 0.1 gram of lauryl sodium sulfate, which is uniformly mixed, to be transferred in water heating kettle, and 200 DEG C keep the temperature 12 hours, solid-liquid point From that i.e. and after drying can obtain zinc sulfide nano-belt, zinc sulfide nano strip length is 100 nm, 50 nm of diameter.
6. a kind of preparation method of lithium sulfur battery anode material, which is characterized in that in any one of claim 1 ~ 5 the method system The zinc sulfide nano-belt coated with carbon source or the source C/N obtained；Material after cladding is carbonized under the conditions of protective atmosphere again；Carbonization Product is again through ferric iron source reaction, solid-liquor separation, drying to get the lithium sulfur battery anode material.
7. the preparation method of lithium sulfur battery anode material as claimed in claim 6, which is characterized in that the zinc sulfide nano The length of band is 20 ~ 300 nanometers, and diameter is 20 ~ 60 nanometers.
8. the preparation method of lithium sulfur battery anode material as claimed in claim 7, which is characterized in that
The source C/N is poly-dopamine, polypyrrole, polyaniline, at least one of polypyridine；
The mass ratio of the carbon source and zinc sulfide nano-belt is 2 ~ 10:1；
The mass ratio in the source C/N and zinc sulfide nano-belt is 2 ~ 10:1.
9. such as the preparation method of the described in any item lithium sulfur battery anode materials of claim 6 ~ 8, which is characterized in that carbonisation Temperature be 600 ~ 1100 DEG C, carbonization time be 1 ~ 12 hour；The protective atmosphere is nitrogen atmosphere and/or rare gas Atmosphere.
10. lithium sulfur battery anode material made from a kind of described in any item preparation methods of claim 6 ~ 9, which is characterized in that The lithium sulfur battery anode material is in rodlike nucleocapsid structure, wherein Shell Materials are carbon, or are nitrogen-doped carbon；It is described Core be in-situ oxidation reactive deposition elemental sulfur.
11. lithium sulfur battery anode material as claimed in claim 10, which is characterized in that the lithium sulfur battery anode material In, quality percentage score shared by sulphur is 50% ~ 90%；Surplus is 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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