CN105280887B - A kind of preparation method of negative electrode of lithium ion battery - Google Patents
A kind of preparation method of negative electrode of lithium ion battery Download PDFInfo
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- CN105280887B CN105280887B CN201510583283.1A CN201510583283A CN105280887B CN 105280887 B CN105280887 B CN 105280887B CN 201510583283 A CN201510583283 A CN 201510583283A CN 105280887 B CN105280887 B CN 105280887B
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- molybdenum
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- disulfide nano
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection 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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of preparation method of negative electrode of lithium ion battery, including：It is 1 by the molybdenum in molybdenum source, the sulphur mol ratio in sulphur source using thiocarbamide as sulphur source using one or both of ammonium molybdate, sodium molybdate mixture as molybdenum source:(1.8~2.5), and be 1 by the molybdenum in molybdenum source and NaCl mol ratio:(150~600) count, molybdenum source, sulphur source and NaCl are dissolved, then freeze and be dried in vacuo, obtain mixture；By obtained mixture grind into powder, it is placed in tube furnace flat-temperature zone and is calcined and chemical vapor deposition, obtain product A；Wash and be dried in vacuo, obtain molybdenum disulfide nano sheet.The present invention prepares molybdenum disulfide nano sheet using raw material cheap and easy to get, and cost is cheap, and course of reaction is simple, controllability is strong.Molybdenum disulfide nano sheet, which is used for negative electrode of lithium ion battery, has certain specific capacity and cycle performance.
Description
Technical field
The present invention relates to a kind of method for making negative electrode of lithium ion battery.
Background technology
With 21 century scientific and technological and industrial continuous development, World Economics has marched toward a brand-new epoch, but with
The consumption of resource and the pollution of environment, disruption of ecological balance, energy nowadays but occurs in human material, cultural life extreme enrichment
The exhausted stem reality in source, we are badly in need of, and exploitation one kind had not only cleaned but also the efficient energy is non-renewable to substitute oil, colliery etc.
Resource.And lithium ion battery is as a kind of emerging chemical energy source, with its cost is cheap, operating voltage is high, it is higher than energy, from
Discharge rate is low, high conversion efficiency, the advantage such as have extended cycle life, be environment-friendly, has received the widely studied of people and has applied
In the various equipment of production and living.
Although the business development of lithium ion battery has tended to ripe, in some high-grade, precision and advanced fields, such as electric automobile, army
Work, Aero-Space etc., its energy-storage property using energy density and power density as representative are but far from reaching desirable level, therefore
The tip application of lithium electricity is limited by larger.It is exactly to find newly to improve one of Main Means of lithium ion battery chemical property
Type electrode material, make battery that there is higher lithium embedded quantity and outstanding lithium deintercalation invertibity.At present, commercial is most
Negative material is graphite-like carbon material, and its theoretical reversible specific capacity is only 372mAh/g, far from the needs for meeting modernization, and
The destructible layer structure during fast charging and discharging, cyclical stability is poor, while also with compatibility of electrolyte, electrode safety
The problems such as property.Molybdenum disulfide possesses the close-packed hexagonal knot similar to graphene as a kind of typical transition metal dichalcogenide
Structure and lamella way of stacking, broader (002) interplanar distance make it have bigger storage lithium space, calculate the theory of gained
Specific capacity is up to 669mAh/g；Moreover, in first circle discharge process, MoS2React to form SEI films to activity with electrolyte
The consumption of material in itself makes it have higher coulombic efficiency first also than relatively limited.Therefore, MoS2As a kind of active material
Material is used for preparing before negative electrode of lithium ion battery has much application for the capacity for improving current commercial Li-ion battery negative pole
Scape.
The content of the invention
It is an object of the invention to provide a kind of method using molybdenum disulfide nano sheet making as negative electrode of lithium ion battery.
The present invention makees template using NaCl, with reference to a step chemical vapor deposition, freeze-dried, calcining, suction filtration, can be obtained with matter after drying
Amount height, size uniformity, the number of plies is relatively controllable, yield is higher, prepares the molybdenum disulfide nano sheet of the features such as advantage of lower cost, then
Using prepared molybdenum disulfide nano sheet as active material, conductive carbon black, PVDF and NMP are added, homogenate coating is made in stirring
In on copper foil, obtained using the molybdenum disulfide nano sheet as the negative electrode of lithium ion battery for storing up lithium active material after drying.
The present invention is to be realized by the following technical programs,
A kind of preparation method of negative electrode of lithium ion battery, comprises the following steps：
(1) using one or both of ammonium molybdate, sodium molybdate mixture as molybdenum source, using thiocarbamide as sulphur source, by molybdenum source
Sulphur mol ratio in molybdenum, sulphur source is 1:(1.8~2.5), and be 1 by the molybdenum in molybdenum source and NaCl mol ratio:(150~600)
Meter, molybdenum source, sulphur source and NaCl are added in deionized water and dissolved, stir wiring solution-forming, then ultrasonic mixing is uniformly after cold at 0 DEG C
Freeze, be dried in vacuo after solution freeze over, obtain mixture；
(2) by mixture grind into powder made from step (1), it is laid on after crossing 100-300 mesh sieves in Noah's ark, is placed in tubular type
Calcined stove flat-temperature zone：With N2, He and Ar a kind of gas or mixed gas as inert gas source, first using flow as 200-
400ml/min is passed through inert gas 10-30 minutes to exclude air；Again using Ar as protection gas, protection air-flow amount is fixed as
50-300ml/min, 600-750 DEG C being warming up to 1-10 DEG C/min programming rate, insulation 1-3h carries out chemical vapor deposition,
Reaction cools to room temperature with the furnace after terminating, and obtains product A；
(3) powder product A made from collection step (2), is washed to untill not having NaCl in calcined product, after washing
Product, which is placed in, to be dried in vacuo, and obtains molybdenum disulfide nano sheet；
(4) it is 1285 according to mass ratio：1338：16 proportioning, by molybdenum disulfide nano sheet, PVDF and conductive carbon black mixing
Uniform stirring is applied to copper sheet as negative pole after slurry is made, with LiPF6As electrolyte, using lithium piece as positive pole, half electricity is made
Pond.
The present invention has advantages below：The present invention prepares molybdenum disulfide nano sheet using raw material cheap and easy to get, and cost is low
Honest and clean, course of reaction is simple, controllability is strong.This kind of material crystalline degree is high simultaneously, and quality is good, and structure is homogeneous, and pattern is excellent, performance is excellent
Different, molybdenum disulfide nano sheet, which is used for negative electrode of lithium ion battery, has certain specific capacity and cycle performance, in 100mA/g electric current
Remain to keep more than 250mAh/g specific capacity under density after circulating 50 times.
Brief description of the drawings
Fig. 1 is the SEM photograph of molybdenum disulfide nano sheet made from the embodiment of the present invention 1.From this view it is apparent that curing
The pattern and size of molybdenum nanometer sheet.
Fig. 2 is the FE-SEM photos of molybdenum disulfide nano sheet made from the embodiment of the present invention 1.From this view it is apparent that two sulphur
Change the thickness of molybdenum nanometer sheet.
Fig. 3 is the TEM photos of molybdenum disulfide nano sheet made from the embodiment of the present invention 1.From this view it is apparent that curing
The overall structure of molybdenum nanometer sheet.
Fig. 4 is the TEM photos of molybdenum disulfide nano sheet made from the embodiment of the present invention 1.From this view it is apparent that curing
The piece number of layers and lattice dot matrix of molybdenum nanometer sheet.
Fig. 5 is the XRD spectrum of molybdenum disulfide nano sheet made from the embodiment of the present invention 1.
Fig. 6 is charge and discharge cycles of the embodiment of the present invention 1 using negative electrode of lithium ion battery made from molybdenum disulfide nano sheet
Performance map.
Embodiment
The particular content of the present invention is described as follows with reference to specific embodiment：
Embodiment 1：
0.3531g ammonium molybdates, 0.3654g thiocarbamides and 35.1g sodium chloride are weighed, mixture is dissolved in 200ml deionization
In water, with mixing speed 300r/min magnetic stirring apparatus, stirring and dissolving wiring solution-forming, the then ultrasound using power as 400W again
Device ultrasound 15min, it is well mixed.Mixed liquor is put into 12h in refrigerator to freeze, is placed in -50 DEG C of vacuum in freeze drier afterwards
Dry, until drying obtains mixture.Milled mixtures simultaneously cross 150 mesh sieves, take 10g powder to be placed in Noah's ark, Noah's ark is put into
In tube furnace, the Ar inert gases for being passed through 200ml/min exclude air, then with 200ml/min Ar inert gases and with 10
DEG C/min programming rate is warming up to 750 DEG C of temperature, insulation 2h carries out chemical vapor deposition, reaction terminate after in Ar atmosphere protections
Under be cooled to room temperature, obtain calcined product A, collect, it is finely ground, be washed to untill there is no NaCl in product, in freeze drier
Vacuum drying 8h is carried out at -50 DEG C, obtains molybdenum disulfide nano sheet, how triangular in shape the molybdenum disulfide nano sheet is and six sides
Shape, the length of single nanometer sheet is 0.1-40um, and thickness 0.6-100.0nm, the molybdenum disulfide nano sheet number of plies is 1-40 layers.
0.1285g molybdenum disulfide nano sheets, 0.1338gPVDF (Kynoar), the mixing of 0.0161g conductive carbon blacks is equal
Even stirring is applied to copper sheet as negative pole after slurry is made, with 1M LiPF6As electrolyte, using lithium piece as positive pole, half is made
Battery, it circulates the specific capacity that 50 circles still protect more than 250mAh/g under 100mA/g current density, as shown in Figure 6.
Claims (2)
1. a kind of preparation method of negative electrode of lithium ion battery, comprises the following steps：
(1) using one or both of ammonium molybdate, sodium molybdate mixture as molybdenum source, using thiocarbamide as sulphur source, by the molybdenum in molybdenum source and
Sulphur mol ratio in sulphur source is 1:(1.8~2.5), and be 1 by the molybdenum in molybdenum source and NaCl mol ratio:(150~600) count,
Molybdenum source, sulphur source and NaCl are added in deionized water and dissolved, stirs wiring solution-forming, then ultrasonic mixing uniformly freezes after at 0 DEG C,
It is dried in vacuo after solution freeze over, obtains mixture；
(2) by mixture grind into powder made from step (1), it is laid on after crossing 100-300 mesh sieves in Noah's ark, is placed in tube furnace perseverance
Warm area is calcined：With N2, He and Ar a kind of gas or mixed gas as inert gas source, first using flow as 200-
400mL/min is passed through inert gas 10-30 minutes to exclude air；Again using Ar as protection gas, protection air-flow amount is fixed as
50-300mL/min, 600-750 DEG C being warming up to 1-10 DEG C/min programming rate, insulation 1-3h carries out chemical vapor deposition,
Reaction cools to room temperature with the furnace after terminating, and obtains product A；
(3) powder product A made from collection step (2), is washed to untill not having NaCl in calcined product, by the product after washing
It is placed in and is dried in vacuo, obtains molybdenum disulfide nano sheet；
(4) it is 1285 according to mass ratio：1338：16 proportioning, by molybdenum disulfide nano sheet, PVDF and conductive carbon black are well mixed
Stirring is applied to copper sheet as negative pole after slurry is made, with LiPF6As electrolyte, using lithium piece as positive pole, half-cell is made.
2. preparation method according to claim 1, it is characterised in that the product after washing is placed in freeze drier
Vacuum drying 8h is carried out at a temperature of -50 DEG C~-30 DEG C, obtains molybdenum disulfide nano sheet.
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| CN201510583283.1A CN105280887B (en) | 2015-09-14 | 2015-09-14 | A kind of preparation method of negative electrode of lithium ion battery |
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| CN105280887B true CN105280887B (en) | 2017-11-21 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106058200A (en) * | 2016-07-25 | 2016-10-26 | 天津大学 | Method for modifying titanium-dioxide lithium-ion battery negative pole material simultaneously by using carbon and monolayer molybdenum disulfide |
| WO2020124394A1 (en) * | 2018-12-18 | 2020-06-25 | 深圳先进技术研究院 | Transition metal chalcogenide nanosheet material, preparation method thereof, negative electrode material for battery, secondary battery and use thereof |
| CN111785928B (en) * | 2019-04-04 | 2021-11-16 | 中南大学 | Solid electrolyte interface material, negative electrode precursor material and negative electrode of lithium metal battery, and preparation and application thereof |
| CN112899704B (en) * | 2020-11-25 | 2022-04-29 | 武汉大学 | Electrochemical method for preparing high-purity molybdenum disulfide nanosheet from molybdenite |
| CN113140803A (en) * | 2021-04-29 | 2021-07-20 | 天能帅福得能源股份有限公司 | Based on lamella MoS2Preparation method of high-rate lithium ion battery as anode |
| CN115092959B (en) * | 2022-06-16 | 2024-03-26 | 西安理工大学 | Manganese/sodium vanadate material prepared by salt template-assisted solid-phase sintering method, and preparation method and application thereof |
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| CN103715430A (en) * | 2013-12-23 | 2014-04-09 | 天津大学 | Three-dimensional graphene reticular structure loaded carbon-coated tin nanometer material as well as preparation method and application thereof |
| CN104393294A (en) * | 2014-11-27 | 2015-03-04 | 江苏理工学院 | Preparation method of flower-shaped molybdenum disulfide microspheres |
| CN104409706A (en) * | 2014-12-22 | 2015-03-11 | 湖南大学 | Molybdenum disulfide/sulfur-and-nitrogen-doped graphene nanosheet composite material as well as preparation method and application thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103715430A (en) * | 2013-12-23 | 2014-04-09 | 天津大学 | Three-dimensional graphene reticular structure loaded carbon-coated tin nanometer material as well as preparation method and application thereof |
| CN104393294A (en) * | 2014-11-27 | 2015-03-04 | 江苏理工学院 | Preparation method of flower-shaped molybdenum disulfide microspheres |
| CN104409706A (en) * | 2014-12-22 | 2015-03-11 | 湖南大学 | Molybdenum disulfide/sulfur-and-nitrogen-doped graphene nanosheet composite material as well as preparation method and application thereof |
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Address after: 300350 District, Jinnan District, Tianjin Haihe Education Park, 135 beautiful road, Beiyang campus of Tianjin University Patentee after: Tianjin University Address before: 300072 Tianjin City, Nankai District Wei Jin Road No. 92 Patentee before: Tianjin University |
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