CN109428079A - A kind of preparation method of lithium sulfur battery anode material - Google Patents
A kind of preparation method of lithium sulfur battery anode material Download PDFInfo
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- CN109428079A CN109428079A CN201710784307.9A CN201710784307A CN109428079A CN 109428079 A CN109428079 A CN 109428079A CN 201710784307 A CN201710784307 A CN 201710784307A CN 109428079 A CN109428079 A CN 109428079A
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- 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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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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
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- 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 invention discloses a kind of preparation methods of lithium sulfur battery anode material: first passing through liquid phase deposition and heat treating process and sulphur is filled into the lumen of galapectite, form galapectite/sulphur composite material, then PPy-HNT@S composite material is formed in galapectite/one layer of sulphur composite material surface in-situ polymerization electric polypyrrole, is used further to that lithium-sulphur cell positive electrode piece is prepared.Galapectite is that a kind of material of tubular macroporous structure with adsorptivity has biggish specific surface area, with good mechanical, heat, chemical stability, halloysite nanotubes inner surface has positive charge, outer surface has negative electrical charge, polysulfide can be adsorbed, inhibit the dissolution of polysulfide, but the electric conductivity of galapectite itself is very poor.Polypyrrole is a kind of conducting polymer, has excellent electric conductivity and chemical property, one strata pyrroles can significantly improve its electric conductivity in galapectite surface aggregate, significantly improve battery capacity and cyclical stability.Many advantages, such as preparation process of the present invention is simple, and environmentally protective and environmental stability is high.
Description
Technical field
The present invention relates to a kind of preparation methods of lithium sulfur battery anode material, belong to lithium-sulfur cell Material Field.
Background technique
With the continuous development of science and technology with the raising of living standards of the people, people propose the development of serondary lithium battery
Higher demand, especially in terms of high-performance electric motor-car, pole need to possess high energy storage and energy output system, lithium-sulfur cell be with
Lithium metal is as cathode, the composite material conduct anode of elemental sulfur or sulfur-bearing, the electricity that ethers organic matter is assembled into for electrolyte
Pond, the system battery have the theoretical specific energy of up to 2600Wh/kg, the secondary electricity of ion in significantly larger than commercially using at present
Pond.Lithium-sulfur cell is due to having the characteristics that high-energy-density, low cost and environmental-friendly and have received widespread attention.However, in reality
Border application road on, still have it is some challenge it is urgently to be resolved, cycle life it is short it is low with sulphur load capacity be most sharp problem.S member
Element is the most common positive electrode in lithium-sulfur cell, and hindering it as the main reason for electro-chemical activity element is lower conductance
Rate (is 5 × 10 at 25 DEG C-30 S cm-1), it can tissue S and lithium sulfide (Li2S) solid-solid conversion at room temperature.
One side cell reaction intermediate product polysulfide can be migrated to negative side in cyclic process and be reacted with lithium metal, be caused tight
The battery device service life is significantly lost in the shuttle effect of weight, corrosion cathode；The slow problem system of another aspect cell reaction dynamics
About depth and high power charging-discharging, so that chemical energy is difficult to make full use of.Lithium-sulfur cell system reaction process is related to polyelectron
Multiphase converts between reaction and solid-liquid, wherein complicated chemical reaction and physics mass transport process increases the difficulty of lithium-sulfur cell research
Degree.In order to solve this slow kinetic reaction, the suitable electronic conductor (conductive carbon or conducting polymer) of addition is connect, allows electricity
Sub- conductor is uniformly dispersed with active material, and interface therebetween forms electron propagation ducts.In view of electronics and ion
The limitation of transport, characteristic diffusion length of the nano material due to reducing carrier, reduces obstacle kinetically, while again
A large amount of reactivity site can be provided on the surface, therefore by as preferred material in rechargeable battery.
Halloysite nanotubes have the hollow nanotube structure of both ends open, have certain draw ratio, mainly by silicon, aluminium,
Four kinds of elements of oxygen and hydrogen and a small amount of impurity composition, have good crystal structure, are formed by several laminate element stacks, often
A layered structure unit is double-layer structure.Halloysite nanotubes are made of external oxygen-octahedron and internal alumina octahedral, it
Periodic arrangement, separated by single layer hydrone between lamella, it is excellent that unique tubular structure and stratiform tube wall have it
Physicochemical property: thermal stability with higher, high specific surface area, the presence of intermediary water expand galapectite interlamellar spacing, have
Conducive to the intercalation and ion exchange etc. to galapectite.
Summary of the invention
It is lacked for current lithium-sulfur cell reaction intermediate polysulfide shuttle effect is low with active sulphur simple substance electric conductivity
It falls into, galapectite (HNT) is a kind of material of tubular macroporous structure with adsorptivity, has biggish specific surface area, good
Mechanical, heat, chemical stability, halloysite nanotubes inner surface have positive charge, and outer surface has negative electrical charge, can adsorb more sulphur
Compound inhibits the dissolution of polysulfide, one layer of electric polypyrrole (PPy) of halloysite nanotubes surface aggregate after carrying sulphur, can
To reach the shuttle effect for inhibiting polysulfide in lithium-sulfur cell, and the purpose of active material electric conductivity can be effectively improved, from
And improve the cycle performance and coulombic efficiency of lithium-sulfur cell.
To achieve the goals above, the present invention provides a kind of preparation methods of lithium-sulfur cell cell positive material, including
Following steps:
(1) dry halloysite nanotubes and sublimed sulfur the preparation of galapectite/sulphur (HNT@S) composite material: are weighed in mortar
It is transferred to after being fully ground in hydrothermal reaction kettle and keeps the temperature 12h at 155 DEG C -160 DEG C, then naturally cool to room temperature, obtained
HNT@S composite material；
(2) preparation of polypyrrole-galapectite/sulphur (PPy-HNT@S) composite material: the HNT@S for being 25-85% by above-mentioned sulfur content
Composite material is added in the hydrochloric acid solution of 0.2-0.5mol/L, obtains mixed solution A, by mixed solution A magnetic agitation 10-
30min, then ultrasonic disperse 10-30min is handled 3-5 times repeatedly；A certain amount of pyrroles is measured to be added in above-mentioned mixed liquor A,
By the mixed solution A magnetic agitation 12-24h after addition pyrroles；It weighs a certain amount of ammonium persulfate (APS) and is added to 0.1mol/L
Hydrochloric acid solution in, the mixed solution B newly prepared, by the mixed solution B newly prepared be added to be added pyrroles after mixing
Mixed solution C is obtained in solution A, by obtained mixed solution C under condition of ice bath magnetic agitation 12-15h, by solution in room temperature
Lower suction filtration is simultaneously washed with water to neutrality, and PPy-HNT@S composite material can be obtained in obtained product drying；
(3) preparation of electrode material: PPy-HNT@S composite material, conductive carbon and binder are stirred evenly and applied in a solvent
It is layed on aluminium foil, dries tabletting after 12-24h in an oven, obtain lithium-sulphur cell positive electrode piece.
The internal diameter of the halloysite nanotubes is 20-80nm, length 100-500nm；
The content of sulphur is 25-85% in the HNT@S composite material.
The percentage of HNT@S composite material and hydrochloric acid solution is 0.2-1%, the volume of pyrroles in the mixed solution A system
Score is 0.1-0.5%.
The mass percent of APS and hydrochloric acid solution is 2.27-11.35% in the mixed solution B.
The volume ratio of solution A and solution B is 20-25% in the mixed solution C.
The drying is to be put into 50-80 DEG C of dry 12-24h in vacuum drying oven.
The solvent is N-Methyl pyrrolidone or deionized water；The conductive agent be acetylene black, Ketjen black,
One or more of Super P, graphene；The binder is Kynoar (PVDF), carboxymethyl cellulose
(CMC), one or both of butadiene-styrene rubber (SBR).
The invention has the following advantages that
1, for halloysite nanotubes as clay mineral, stability is stronger, and because it is higher in the presence of having with one-dimensional nano shape
Thermal stability and high specific surface area, the volume expansion for charge and discharge process sulphur space is provided；
2, the meso-hole structure inner surface of halloysite nanotubes has positive charge, and outer surface has negative electrical charge, strong to polysulfide
Absorption property can adsorb polysulfide, inhibit the dissolution of polysulfide；
3, halloysite nanotubes are natural minerals, eliminate processing preparation process, cheap and easy to get, are conducive to lithium-sulfur cell
Industrialization.
Detailed description of the invention
The hot weight curve of composite positive pole obtained in Fig. 1 embodiment.
The lithium-sulfur cell first charge-discharge platform figure that Fig. 2 embodiment 3 obtains.
The cycle performance test chart of lithium-sulfur cell prepared by Fig. 3 embodiment and comparative example.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, to this
Invention is further elaborated.It should be appreciated that described herein, specific examples are only used to explain the present invention, without structure
At limitation of the present invention.
Embodiment 1:
(1) dry 0.15g halloysite nanotubes and 0.85g distillation the preparation of galapectite/sulphur (HNT@S) composite material: are weighed
Sulphur is transferred in hydrothermal reaction kettle after being fully ground in mortar and keeps the temperature 12h at 155 DEG C, then naturally cools to room temperature, obtains
To HNT@S composite material；
(2) it the preparation of polypyrrole-galapectite/sulphur (PPy-HNT@S) composite material: weighs 0.8g HNT@S composite material and is added to
In the hydrochloric acid solution of 400ml 0.2mol/L, mixed solution A is obtained, by mixed solution A magnetic agitation 10min, then ultrasound is divided
Scattered 10min is handled 3 times repeatedly；It measures 0.5ml pyrroles to be added in above-mentioned mixed liquor A, by the mixed solution A magnetic after addition pyrroles
Power stirs 12h；It weighs 2.27g ammonium persulfate (APS) to be added in the hydrochloric acid solution of 100ml 0.1mol/L, newly be prepared
Mixed solution B, the mixed solution B for taking 80ml newly to prepare are added in the mixed solution A after pyrroles is added and obtain mixed solution C,
By obtained mixed solution C under condition of ice bath magnetic agitation 12h, solution is filtered at normal temperature and is washed with water to neutrality, is obtained
To product drying PPy-HNT@S composite material can be obtained；
(3) preparation of electrode material: by PPy-HNT@S composite material, acetylene black and Kynoar according to mass ratio be 7: 2
: 1 mixing, with N-Methyl pyrrolidone dispersion and ball milling obtains anode sizing agent, and anode sizing agent is coated in aluminium collector
On, 60 DEG C of vacuum drying are for 24 hours to get anode pole piece;The anode pole piece of preparation, diaphragm, cathode lithium are subsequently assembled into battery
；Diaphragm is PP/PE/PP composite diaphragm；Electrolyte is that 1M bis trifluoromethyl sulfimide lithium is dissolved in glycol dimethyl ether and two
The in the mixed solvent (volume ratio 1: 1) at oxygen five rings；Electrolysis additive is lithium nitrate, additive amount 0.2M.
Embodiment 2:
(1) dry 0.15g halloysite nanotubes and 0.85g distillation the preparation of galapectite/sulphur (HNT@S) composite material: are weighed
Sulphur is transferred in hydrothermal reaction kettle after being fully ground in mortar and keeps the temperature 12h at 155 DEG C, then naturally cools to room temperature, obtains
To HNT@S composite material；
(2) it the preparation of polypyrrole-galapectite/sulphur (PPy-HNT@S) composite material: weighs 4g HNT@S composite material and is added to
In the hydrochloric acid solution of 400ml 0.2mol/L, mixed solution A is obtained, by mixed solution A magnetic agitation 30min, then ultrasound is divided
Scattered 30min is handled 3 times repeatedly；It measures 2ml pyrroles to be added in above-mentioned mixed liquor A, by the mixed solution A magnetic force after addition pyrroles
Stir 12h；It weighs 11.35g ammonium persulfate (APS) to be added in the hydrochloric acid solution of 100ml 0.1mol/L, newly be prepared
Mixed solution B, the mixed solution B for taking 100ml newly to prepare are added in the mixed solution A after pyrroles is added and obtain mixed solution C,
By obtained mixed solution C, magnetic agitation for 24 hours, solution is filtered at normal temperature and is washed with water to neutrality, is obtained under condition of ice bath
To product drying PPy-HNT@S composite material can be obtained；
(3) preparation of electrode material: by PPy-HNT@S composite material, acetylene black and Kynoar according to mass ratio be 7: 2
: 1 mixing, with N-Methyl pyrrolidone dispersion and ball milling obtains anode sizing agent, and anode sizing agent is coated in aluminium collector
On, 60 DEG C of vacuum drying are for 24 hours to get anode pole piece;The anode pole piece of preparation, diaphragm, cathode lithium are subsequently assembled into battery
；Diaphragm is PP/PE/PP composite diaphragm；Electrolyte is that 1M bis trifluoromethyl sulfimide lithium is dissolved in glycol dimethyl ether and two
The in the mixed solvent (volume ratio 1: 1) at oxygen five rings；Electrolysis additive is lithium nitrate, additive amount 0.2M.
Embodiment 3:
(1) dry 0.15g halloysite nanotubes and 0.85g distillation the preparation of galapectite/sulphur (HNT@S) composite material: are weighed
Sulphur is transferred in hydrothermal reaction kettle after being fully ground in mortar and keeps the temperature 12h at 155 DEG C, then naturally cools to room temperature, obtains
To HNT@S composite material；
(2) it the preparation of polypyrrole-galapectite/sulphur (PPy-HNT@S) composite material: weighs 2g HNT@S composite material and is added to
In the hydrochloric acid solution of 400ml 0.2mol/L, mixed solution A is obtained, by mixed solution A magnetic agitation 20min, then ultrasound is divided
Scattered 20min is handled 3 times repeatedly；It measures 1ml pyrroles to be added in above-mentioned mixed liquor A, by the mixed solution A magnetic force after addition pyrroles
Stir 12h；It weighs 5.54g ammonium persulfate (APS) to be added in the hydrochloric acid solution of 100ml 0.1mol/L, that is newly prepared is mixed
Solution B is closed, the mixed solution B for taking 80ml newly to prepare is added in the mixed solution A after pyrroles is added and obtains mixed solution C, will
Solution is filtered at normal temperature and is washed with water to neutrality, obtained by obtained mixed solution C magnetic agitation 12h under condition of ice bath
Product drying PPy-HNT@S composite material can be obtained；
(3) preparation of electrode material: by PPy-HNT@S composite material, acetylene black and Kynoar according to mass ratio be 7: 2
: 1 mixing, with N-Methyl pyrrolidone dispersion and ball milling obtains anode sizing agent, and anode sizing agent is coated in aluminium collector
On, 60 DEG C of vacuum drying are for 24 hours to get anode pole piece;The anode pole piece of preparation, diaphragm, cathode lithium are subsequently assembled into battery
；Diaphragm is PP/PE/PP composite diaphragm；Electrolyte is that 1M bis trifluoromethyl sulfimide lithium is dissolved in glycol dimethyl ether and two
The in the mixed solvent (volume ratio 1: 1) at oxygen five rings；Electrolysis additive is lithium nitrate, additive amount 0.2M.
The battery assembled in above-described embodiment carries out constant current charge-discharge test, voltage range under the current density of 0.2C
For 1.8-2.8V.Test result is listed in table 1.
Table 1
| Serial number | First discharge specific capacity (mAh/g) | 150 specific discharge capacities (mAh/g) | Capacity retention ratio |
| Embodiment 1 | 968.91 | 587.5 | 60.6% |
| Embodiment 2 | 1360.87 | 650.32 | 47.7% |
| Embodiment 3 | 1204.17 | 743.49 | 61.7% |
Claims (8)
1. a kind of preparation method of lithium sulfur battery anode material, it is characterised in that the following steps are included:
The preparation of galapectite/sulphur (HNT@S) composite material: it is abundant in mortar that dry halloysite nanotubes and sublimed sulfur are weighed
It is transferred to after grinding in hydrothermal reaction kettle and keeps the temperature 12h at 155 DEG C -160 DEG C, then naturally cool to room temperature, it is multiple to obtain HNT@S
Condensation material；
The preparation of polypyrrole-galapectite/sulphur (PPy-HNT@S) composite material: above-mentioned sulfur content is compound for the HNT@S of 25-85%
Material is added in the hydrochloric acid solution of 0.2-0.5mol/L, magnetic agitation 10-30min, and then ultrasonic disperse 10-30min is repeatedly
Processing 3-5 times, obtains mixed solution A；A certain amount of pyrroles is measured to be added in above-mentioned mixed liquor A, it will be mixed after addition pyrroles
Close solution A magnetic agitation 12-24h；It weighs a certain amount of ammonium persulfate (APS) to be added in the hydrochloric acid solution of 0.1mol/L, obtain
To the mixed solution B newly prepared, the mixed solution B newly prepared is added in the mixed solution A after pyrroles is added and is mixed
Solution C, by obtained mixed solution C under condition of ice bath magnetic agitation 12-15h, solution is filtered and is washed with water at normal temperature
To neutrality, PPy-HNT@S composite material is can be obtained in obtained product drying；
The preparation of electrode material: PPy-HNT@S composite material, conductive carbon and binder are stirred evenly and is coated in a solvent
On aluminium foil, tabletting after 12-24h is dried in an oven, obtains lithium-sulphur cell positive electrode piece.
2. a kind of preparation method of lithium sulfur battery anode material according to claim 1, it is characterised in that the galapectite
The internal diameter of nanotube is 20-80nm, length 100-500nm.
3. a kind of preparation method of lithium sulfur battery anode material according to claim 1, it is characterised in that the HNT@S is multiple
The content of sulphur is 25-85% in condensation material.
4. a kind of preparation method of lithium sulfur battery anode material according to claim 1, it is characterised in that the mixing is molten
The mass percent of HNT@S composite material and hydrochloric acid solution is 0.2-1% in liquid A system, and the volume fraction of pyrroles is 0.1-
0.5%。
5. a kind of preparation method of lithium sulfur battery anode material according to claim 1, it is characterised in that the mixing is molten
The mass percent of APS and hydrochloric acid solution is 2.27-11.35% in liquid B.
6. a kind of preparation method of lithium sulfur battery anode material according to claim 1, it is characterised in that the mixing is molten
The volume ratio of solution A and solution B is 20-25% in liquid C.
7. a kind of preparation method of lithium sulfur battery anode material according to claim 1, it is characterised in that the drying
To be put into 50-80 DEG C of dry 12-24h in vacuum drying oven.
8. a kind of preparation method of lithium sulfur battery anode material according to claim 1, it is characterised in that the solvent
For N-Methyl pyrrolidone or deionized water；The conductive agent is one of acetylene black, Ketjen black, Super P, graphene
Or it is several；The binder is one of Kynoar (PVDF), carboxymethyl cellulose (CMC), butadiene-styrene rubber (SBR)
Or two kinds.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110620235A (en) * | 2019-09-16 | 2019-12-27 | 安徽师范大学 | Polypyrrole-coated hollow porous cobalt manganate-loaded sulfur composite material, preparation method thereof, lithium-sulfur battery positive electrode and lithium-sulfur battery |
| CN111952594A (en) * | 2020-08-25 | 2020-11-17 | 中南大学 | Lithiated halloysite lithium-sulfur battery positive electrode material and preparation method thereof |
| CN112234172A (en) * | 2020-09-29 | 2021-01-15 | 江汉大学 | Carbon-coated tubular halloysite sulfur-loaded active material and preparation method thereof |
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| CN110620235A (en) * | 2019-09-16 | 2019-12-27 | 安徽师范大学 | Polypyrrole-coated hollow porous cobalt manganate-loaded sulfur composite material, preparation method thereof, lithium-sulfur battery positive electrode and lithium-sulfur battery |
| CN111952594A (en) * | 2020-08-25 | 2020-11-17 | 中南大学 | Lithiated halloysite lithium-sulfur battery positive electrode material and preparation method thereof |
| CN112234172A (en) * | 2020-09-29 | 2021-01-15 | 江汉大学 | Carbon-coated tubular halloysite sulfur-loaded active material and preparation method thereof |
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Application publication date: 20190305 |