CN105883940B - Preparation method of block NiS2 and application of block NiS2 to sodium-ion battery - Google Patents

Preparation method of block NiS2 and application of block NiS2 to sodium-ion battery Download PDF

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CN105883940B
CN105883940B CN201610239755.6A CN201610239755A CN105883940B CN 105883940 B CN105883940 B CN 105883940B CN 201610239755 A CN201610239755 A CN 201610239755A CN 105883940 B CN105883940 B CN 105883940B
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block
nis
nickel
nis2
sodium
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CN201610239755.6A
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Chinese (zh)
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CN105883940A (en
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刘军
朱坤杰
杨浩然
王浩
何鹏辉
谢天
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中南大学
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00Compounds of nickel
    • C01G53/11Sulfides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/054Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581Chalcogenides or intercalation compounds thereof
    • H01M4/5815Sulfides
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00Crystal-structural characteristics
    • C01P2002/70Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/01Particle morphology depicted by an image
    • C01P2004/03Particle morphology depicted by an image obtained by SEM
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/01Particle morphology depicted by an image
    • C01P2004/04Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/64Nanometer sized, i.e. from 1-100 nanometer
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention discloses a preparation method of block NiS2 and an application of the block NiS2 to a sodium-ion battery. According to the method, a 2-methylimidazole alcohol solution is added to a nickel salt alcohol solution, the mixture is evenly mixed, left to stand, subjected to centrifugal separation and dried, and nickel precursors are obtained; the nickel precursors and sulfur powder are ground and mixed, the mixture is placed in a vacuum environment for heat treatment, and a block NiS2 material comprising high-purity NiS2 nano spherical small particles is obtained. The material is used as an anode material to be applied to the sodium-ion battery and shows excellent electrochemical properties such as the high specific capacity, the long cycle life and the like; the preparation method of the block NiS2 material is simple, the cost is low, and industrial production requirements are met.

Description

A kind of block NiS2Preparation method and its application in sodium-ion battery

Technical field

The present invention relates to a kind of block NiS2Preparation method and application, more particularly to a kind of block NiS2As negative pole material Application of the material in sodium-ion battery;Belong to sodium-ion battery field.

Background technology

Into 21st century since, population, grain, the energy, resource and environment be it has been recognized that the hang-up of the world five, Wherein, energy problem is the most important difficult problem that people have to consider to solve immediately.With demand of the mankind to the energy It is continuously increased, fossil energy is limited due to content on earth, and non-renewable and environmental pollution, people can not have been met The needs of class.Then the mankind can be and seek various clean energy resourcies, such as the lithium ion battery of commercial applications.But It is can not to meet aboundresources, cost in addition to excellent chemical property as the lithium resource of lithium ion battery material Cheap economic results in society etc. are required.In this case, people are received with the sodium for there are similar physicochemical properties of main group with lithium Favor, and sodium-ion battery is basically identical with the charge-discharge principle of lithium ion battery.

By sodium-ion battery charge-discharge principle we can draw, limit sodium-ion battery large-scale commercial bottleneck It is not find the positive and negative pole material for being suitable to the stable deintercalation of sodium ion at present.In terms of positive electrode, more predominantly layer is studied Shape material NaxMO2With polyanionic material etc.;The alloy types such as embedded category, tin and the phosphorus such as material with carbon element are mainly in terms of negative material Material and oxide or sulfide etc. convert class material (Xingde Xiang, Kai Zhang, Jun Chen. [J] .Advanced Materials,2015,27(36).).In recent years, people are with going deep into for studying sodium-ion battery, used as negative material Sulfide is increasingly paid close attention to by people.The 2D material MoS of document report2Through 100 under the current density of 1000mA/g Capacity can reach 484mAh/g (Zhu C, Mu X, van Aken P A, et after secondary cycle charge-discharge al.Angew.Chem.Int.Ed.2014,53:2152-2156).The ball-type FeS of Zhe Hu et al. reports2It is negative as sodium ion Pole material still can reach after the circulation of 20000 times under the current density of 1A/g 200mAh/g (Hu Z, Zhu Z,Cheng F,et al.[J].Energy&Environmental Science,2015,8(4):1309-1316.)。 The sodium ion negative material CoS of Zulipiya Shadike et al. reports2With carbon nano tube compound material 100mA/g electric current Still can reach after 100 cycle charge-discharges under density 631mAh/g specific capacity (Shadike Z, Cao M H, Ding F,et al.[J].Chemical Communications,2015,51(52):10486-10489.)。

In sum, sulfide as sodium ion negative material because its excellent chemical property has attracted people very big Interest, but up to the present, not with regard to NiS2As the report of anode material of lithium-ion battery.

The content of the invention

For the defect of prior art, it is to provide one kind to prepare by high purity N iS that the purpose of the present invention is2Nanometer is spherical The block NiS that little particle is constituted2The method of material, the method is simple, flow process is short, low cost, meets industrialization production requirements.

Further object is that providing described block NiS2Application, as sodium-ion battery negative pole Material, specific capacity is high and the excellent chemical property such as have extended cycle life to show sodium-ion battery.

In order to realize above-mentioned technical purpose, the invention provides a kind of block NiS2Preparation method, the preparation method is 2-methylimidazole alcoholic solution is added to after being well mixed in nickel salt alcoholic solution, is stood, centrifugation, drying obtain nickel forerunner Body;The nickel presoma after ground and mixed, in being placed in vacuum environment, carries out hot place with sulphur powder at a temperature of 400~800 DEG C Reason, obtains final product.

Preferred scheme, 2-methylimidazole is with the mol ratio of nickel ion in nickel salt alcoholic solution in 2-methylimidazole alcoholic solution 2~6:1.

More preferably scheme, 2-methylimidazole alcoholic solution concentration is 0.3~1mol/L.

More preferably scheme, the concentration of nickel salt is 0.1~0.3mol/L in nickel salt alcoholic solution.

More preferably scheme, the solvent adopted in 2-methylimidazole alcoholic solution and nickel salt alcoholic solution is for methyl alcohol.

Preferred scheme, standing is carried out at ambient temperature, and time of repose is 12~24h.

Preferred scheme, the ground and mixed time is 10~60min.

Preferred scheme, heat treatment time is 1~6h.

Preferred scheme, nickel salt is nickel nitrate and/or nickel chloride.

Preferred scheme, nickel presoma is 1~3 with the mass ratio of sulphur powder:1.

More preferably scheme, block NiS2By NiS2Nano particle is piled up and is constituted.

Present invention also offers block NiS prepared by described method2Application, by block NiS2Should as negative material For sodium-ion battery.

Block NiS prepared by the present invention2By highly purified Ni nanoparticle S2Particle is constituted, Ni nanoparticle S2Grain diameter size is about For 10nm, its small volume, specific surface area is very big, considerably increases the contact area of electrode material and battery electrolyte, reduces Path of the ion in particle internal motion, and the transfer rate of ion can be improved, the electrode potential of battery is reduced, improve The speed of electrochemical reaction, thus bulk NiS2With excellent sodium-ion battery chemical property.

Hinge structure, the beneficial effect that technical solution of the present invention is brought:

1st, NiS prepared by the present invention2Material has block structure, and microstructure by highly purified NiS2Nanometer little particle Constitute;

2nd, block NiS of the invention2Material preparation method is simple, and low cost, environmental protection is suitable to large-scale industry metaplasia Produce;

3rd, graininess NiS prepared by the present invention2First Application makes sodium-ion battery charge and discharge cycles steady in sodium-ion battery Qualitative good, capability retention is high.

4th, technical scheme promotes the coordination dispersion of nickel ion, favorably using 2-methylimidazole as complexing agent In the generation of nano nickel particles;And the 2-methylimidazole complex of nickel is conducive to block NiS into floccule body2Generation.

Description of the drawings

【Fig. 1】For NiS prepared by embodiment 12X-ray collection of illustrative plates;

【Fig. 2】In A and B be respectively embodiment 1 preparation NiS2ESEM and transmission electron microscope photo;

【Fig. 3】For NiS prepared by embodiment 12Cyclic voltammetric (CV) figure of sodium-ion battery;

【Fig. 4】For NiS prepared by embodiment 12Sodium-ion battery is in 100mAg-1Current density under charge and discharge electrograph.

Specific embodiment

It is intended to further illustrate the present invention with reference to embodiments, and the protection domain of unrestricted the claims in the present invention.

Embodiment 1

1. by the Ni (NO of the commercialization of 5mmol3)2·4H2O is dissolved in 30mL methyl alcohol, is stirred the appropriate time and is treated that its is complete Dissolving;2. the 2-methylimidazole of 20mmol is dissolved among 30mL methyl alcohol, is stirred, treat that it is completely dissolved.In 2. pouring into 1., so Stand 24h under room temperature afterwards.Then with after methyl alcohol centrifuge washing three times, as 12h is dried in 50 DEG C of drying boxes, obtain containing Ni Presoma, then take appropriate presoma and sulphur powder in mass ratio 2:1 grinds in agate mortar, afterwards vacuum sealing tube, Product is thermally treated resulting in tube furnace in 600 degrees Celsius.SEM (Fig. 2A) and TEM (Fig. 2 B) result show, the NiS of synthesis2To receive The bulk morphologies of rice grain composition, and XRD (Fig. 1) result shows that its purity is high, good crystallinity is single pure phase.

The NiS for preparing2Active material, conductive agent Super P, binding agent CMC are with mass ratio 7:2:1 ratio is in mortar In at least grind 30 minutes, in being then transferred to 5mL vials, the mixed liquor of appropriate water and absolute ethyl alcohol, stirring is added dropwise 24h, is coated on Cu paper tinsels, and more than 10h is dried in vacuum drying chamber, the pole piece of a diameter of 12mm is gone out with sheet-punching machine, in hand Casing (fills the battery of model 2016 in (Mbraun, Garching, Germany).Specially:Negative pole is sodium piece, and barrier film is glass Glass fibre diaphragm, electrolyte is with volume ratio 1:1 dimethyl carbonate (DMC) and ethylene carbonate (EC) solution, per 100 milliliters In containing one mole of sodium perchlorate, 0.05 milliliter of ethylene fluoride carbonic ester (FEC).

Embodiment 2

1. by the Ni (NO of the commercialization of 5mmol3)2·4H2O is dissolved in 30mL methyl alcohol, is stirred the appropriate time and is treated that its is complete Dissolving;2. the 2-methylimidazole of 15mmol is dissolved among 30mL methyl alcohol, is stirred, treat that it is completely dissolved.In 2. pouring into 1., so Stand 2h under room temperature afterwards.Then with after methyl alcohol centrifuge washing three times, as 12h is dried in 50 DEG C of drying boxes, obtain containing Ni Presoma, then take appropriate presoma and sulphur powder in mass ratio 4:1 grinds in agate mortar, afterwards vacuum sealing tube, Product is thermally treated resulting in tube furnace in 400 degrees Celsius.Jing SEM and TEM detection, as a result shows the NiS of synthesis2For nano particle The bulk morphologies of composition, and XRD results show that its purity is high, are single NiS2Crystalline phase.

The method such as embodiment 1 of sodium-ion battery is prepared, the sodium-ion battery of preparation shows good charge and discharge cycles Stability and high power capacity conservation rate.

Embodiment 3

1. by the Ni (NO of the commercialization of 5mmol3)2·4H2O is dissolved in 30mL methyl alcohol, is stirred the appropriate time and is treated that its is complete Dissolving;2. the 2-methylimidazole of 25mmol is dissolved among 30mL methyl alcohol, is stirred, treat that it is completely dissolved.In 2. pouring into 1., so Stand 18h under room temperature afterwards.Then with after methyl alcohol centrifuge washing three times, as 12h is dried in 50 DEG C of drying boxes, obtain containing Ni Presoma, then take appropriate presoma and sulphur powder in mass ratio 1:1 grinds in agate mortar, afterwards vacuum sealing tube, Product is thermally treated resulting in tube furnace in 800 degrees Celsius.Jing SEM and TEM detection, as a result shows the NiS of synthesis2For nano particle The bulk morphologies of composition, and XRD results show that its purity is high, are single NiS2Crystalline phase.

The method such as embodiment 1 of sodium-ion battery is prepared, the sodium-ion battery of preparation shows good charge and discharge cycles Stability and high power capacity conservation rate.

Claims (8)

1. a kind of block NiS2Preparation method, it is characterised in that:2-methylimidazole alcoholic solution is added in nickel salt alcoholic solution and is mixed After closing uniformly, stand, centrifugation, drying obtain nickel presoma;The nickel presoma and sulphur powder in mass ratio 1~3:1 passes through After ground and mixed, in being placed in vacuum environment, it is heat-treated at a temperature of 400~800 DEG C, is obtained final product.
2. block NiS according to claim 12Preparation method, it is characterised in that:2- first in 2-methylimidazole alcoholic solution Base imidazoles is 2~6 with the mol ratio of nickel ion in nickel salt alcoholic solution:1.
3. block NiS according to claim 1 and 22Preparation method, it is characterised in that:Described 2-methylimidazole alcohol is molten Liquid concentration is 0.3~1mol/L;The concentration of nickel salt is 0.1~0.3mol/L in described nickel salt alcoholic solution.
4. block NiS according to claim 12Preparation method, it is characterised in that:Described standing is at ambient temperature Carry out, time of repose is 12~24h.
5. block NiS according to claim 12Preparation method, it is characterised in that:The ground and mixed time be 10~ 60min。
6. block NiS according to claim 12Preparation method, it is characterised in that:Heat treatment time is 1~6h.
7. block NiS according to claim 12Preparation method, it is characterised in that:Described nickel salt be nickel nitrate and/or Nickel chloride.
8. the block NiS according to claim 1,2,4,5,6 or 72Preparation method, it is characterised in that:Described bulk NiS2By NiS2Nano particle is piled up and is constituted.
CN201610239755.6A 2016-04-18 2016-04-18 Preparation method of block NiS2 and application of block NiS2 to sodium-ion battery CN105883940B (en)

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CN107344732A (en) * 2017-03-29 2017-11-14 武汉理工大学 A kind of controllable three-dimensional porous NiS of hole2Microballoon and its preparation method and application
CN107140699B (en) * 2017-05-31 2018-12-11 武汉理工大学 NiS2Meso-porous nano ball material and its preparation method and application
CN107658459B (en) * 2017-09-30 2020-05-05 哈尔滨工业大学 Preparation method and application of iron oxide, ferrous disulfide and sulfur composite material
CN107785548B (en) * 2017-09-30 2020-07-28 哈尔滨工业大学 FeS2Preparation method and application of S-S composite material
CN108666540B (en) * 2018-04-02 2020-10-27 中南大学 Carbon-coated nickel disulfide material, preparation method thereof and application of carbon-coated nickel disulfide material as sodium ion battery cathode material
CN109277104A (en) * 2018-10-16 2019-01-29 陕西科技大学 A kind of NiS of sulfur-rich vanadium modification2Elctro-catalyst and preparation method thereof
CN110182860B (en) * 2019-07-11 2020-08-14 昆明理工大学 Method for preparing nano nickel-sulfur compound by eutectic solvent one-step synthesis method

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JPS6161229B2 (en) * 1979-07-24 1986-12-24 Hitachi Maxell
KR100406979B1 (en) * 2001-05-11 2003-11-28 한국과학기술원 Fabrication Method of An Electrode for the Lithium Secondary Batteries Using Nickel Sulfide Compound
CN102633309A (en) * 2012-01-13 2012-08-15 沈阳理工大学 Hydrothermal preparation method for NiS2 with controllable shape
CN104261491B (en) * 2014-10-10 2019-03-26 湘潭大学 A kind of synthetic method of high-purity curing nickel

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