CN109755446A - A kind of lithium-sulfur cell diaphragm and preparation method thereof - Google Patents
A kind of lithium-sulfur cell diaphragm and preparation method thereof Download PDFInfo
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- CN109755446A CN109755446A CN201811501892.8A CN201811501892A CN109755446A CN 109755446 A CN109755446 A CN 109755446A CN 201811501892 A CN201811501892 A CN 201811501892A CN 109755446 A CN109755446 A CN 109755446A
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- lithium
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- carragheen
- sulfur cell
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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
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Abstract
The present invention provides a kind of lithium-sulfur cell diaphragms and preparation method thereof, by the method for electrostatic spinning by OK a karaoke club glue gel with conventional separator is compound that a kind of novel lithium sulphur battery diaphragm has been prepared, have the advantages that good electrolyte wellability, heat-resistant fireproof, more effective inhibition shuttle effect and lithium dendrite growth, improves cyclical stability and the safety of lithium-sulfur cell；Lithium-sulfur cell composite diaphragm of the invention has excellent thermal stability simultaneously, can high temperature resistant, be able to maintain normal operating conditions in the high temperature environment, can further greatly improve the operating temperature and safety of battery.This method cost of material is low, simple process, is easy to be mass produced.
Description
Technical field
The present invention relates to a kind of lithium batteries and preparation method thereof, more particularly to a kind of lithium-sulfur cell diaphragm and its preparation side
Method.
Background technique
Lithium-sulfur cell energy density with higher can be applied in individual soldier's power supply, unmanned plane and passenger car field.Lithium sulphur electricity
Using lithium metal as cathode, when use, there are security risks in pond.Due to the inhomogeneities on lithium metal surface, cyclic process is easy life
At Li dendrite, make inside battery that short circuit, catching fire occur.The energy density of lithium-sulfur cell is about 3-5 times of common batteries,
It generates heat in charge and discharge process serious, battery overheat itself is easy to cause battery thermal runaway, causes on fire or even explosion.Use function
Energy property diaphragm can inhibit the generation of internal short-circuit of battery and thermal runaway, promote the security performance of lithium-sulfur cell, can be to a certain degree
Shuttle effect in upper weakening cyclic process.
Relative to conventional lithium ion battery, the polyelectron reaction intrinsic property of sulfur molecule forms electrode material high capacity
Feature, but it is more complicated to also result in lithium-sulfur cell system, is primarily present following problem: (1) safety issue.Lithium anode table
Face is uneven, out-of-flatness, causes lithium ion to be deposited in negative terminal surface and generates dendrite, dendrite can pierce through diaphragm and cause battery plus-negative plate
Short circuit leads to cells burst and explosion；(2) sulfide problems of dissolution.Sulfur electrode generates soluble more sulphur in charge and discharge process
On the one hand compound causes across the diaphragm diffusion of high-order polysulfide directly to be reacted with lithium anode and generates low order polysulfide, band
Come the side reaction circulation in lithium-sulfur cell, i.e. shuttle effect, reduces the coulombic efficiency of lithium-sulfur cell；On the other hand also lead to battery
Middle sulfur component loss, makes battery performance rapid decay.
Problem above is the key reason for causing lithium-sulfur cell security performance poor, can be had to the diagram modification of lithium-sulfur cell
Effect alleviates the overall performance for even being eliminated the above problem, and then promoting lithium-sulfur cell, especially security performance and cycle performance.
Summary of the invention
The purpose of the present invention is to provide a kind of lithium-sulfur cell diaphragms and preparation method thereof, and the present invention can effectively improve lithium sulphur
The problem of Li dendrite present in battery and shuttle effect, while the heat-resisting quantity of diaphragm can also be promoted.
The purpose of the present invention is what is be achieved through the following technical solutions:
A kind of lithium-sulfur cell diaphragm is applied in the OK a karaoke club glue gel that the conventional separator both side surface of different-thickness is coated with anti-flammability
Layer, is prepared into a kind of compound lithium-sulfur cell diaphragm comprising three-decker using electrostatic spinning and sol-gel combined method.
Wherein, preferred embodiment are as follows: the thickness of the carragheen gel coat with anti-flammability is between 1-20 μm.
Wherein, preferred embodiment are as follows: described its porosity of carragheen gel coat is 70-99.9%, and the size of hole is 10-
50nm, specific surface area 400-1200m2/g。
Wherein, preferred embodiment are as follows: the carragheen gel coat is by K-type carragheen, I type carragheen, L-type carragheen
One or more of be composed.
Wherein, preferred embodiment are as follows: the conventional separator of the different-thickness is 5-30 μm of polyethylene diagrams, 5-30 μm of polypropylene
Any one in diaphragm, 5-30 μm of Kynoar diaphragm, 5-35 μm of nylon membrane or nonwoven cloth diaphragm.
Wherein, preferred embodiment are as follows: the following steps are included:
Step 1: 20-40 parts of carragheen powder is taken to be immersed in 50-300 parts of concentration as 3-6mol/L's in parts by weight
In NaOH solution, magnetic agitation (250-320rpm) 30-50 minutes, obtain the molten of clear in 50-70 DEG C of water-bath
Obtained solution is centrifuged 5 minutes by liquid at 3500rpm, is taken supernatant that dehydrated alcohol is added and is adjusted concentration to 10-12%, preparation
Obtain electrostatic spinning solution.
Step 2: the electrostatic spinning solution that step 1 is obtained is packed into spinning head, by conventional separator wound on reception roller
On, drum rotation speed 400-600rpm is received, the distance of spinning head to receiver roller is 12-18cm, defeated in high-voltage DC power supply
Volume 15-20kV electrostatic pressure out, temperature are 30-40 DEG C, and humidity is spinning in the environment of 20-25%, fltting speed 0.002-
The diaphragm of single side coating carragheen gel coat is prepared in 0.005mm/s.
Step 3: the membrane winding for the single side coating carragheen gel coat that step 2 is obtained connects on receiving roller
Drum rotation speed 400-600rpm is received, the distance of spinning head to receiver roller is 12-18cm, in high-voltage DC power supply amount of exports
15-20kV electrostatic pressure, temperature are 30-40 DEG C, and humidity is spinning in the environment of 20-25%, fltting speed 0.002-0.005mm/
S obtains the diaphragm of coated on both sides OK a karaoke club glue gel, is placed in 50-60 DEG C of baking oven dry 20-24h, that is, lithium sulphur electricity is prepared
Pond diaphragm.
The advantages and effects of the present invention are:
The present invention by OK a karaoke club glue gel by electrostatic-spinning with conventional separator is compound that compound carragheen lithium-sulfur cell is prepared
Diaphragm has good electrolyte wellability, heat-resistant fireproof, more effective inhibition shuttle effect and Li dendrite compared to conventional separator materials
The advantages of growth, improves cyclical stability and the safety of lithium-sulfur cell；Cost of material of also having simultaneously is low, spy of simple process
Point provides a kind of new scheme for the preparation of lithium-sulfur cell diaphragm, is suitble to industrial applications.Specifically, the present invention has
Following advantages: (1) carragheen is from a wealth of sources, cheap, is conducive to the utilization rate for improving resource, after electrostatic spinning, card
Draw glue gel formed the uniform tridimensional network of hole, facilitate lithium ion uniformly through to delay the life of Li dendrite
It is long；(2) carragheen surface has sulfate ion abundant, and this structure can obstruct the more of sulfur electrode charge and discharge process generation
Sulphur object inhibits shuttle effect, promotes the cycle efficieny of battery by diaphragm；(3) carragheen has the advantages that resistant to high temperature, the present invention
Lithium-sulfur cell composite diaphragm have excellent thermal stability, can high temperature resistant, be able to maintain normal work shape in the high temperature environment
State can further greatly improve the operating temperature and safety of battery.
Detailed description of the invention
Fig. 1 is conventional separator and lithium-sulfur cell diaphragm mechanism of action comparison diagram of the present invention.
Specific embodiment
The following describes the present invention in detail with reference to examples.
Embodiment one:
Step 1: taking the K-type carragheen powder of 20g to be immersed in the concentration of 50g is in the NaOH solution of 3mol/L, in 50 DEG C of water
Magnetic agitation (250rpm) 30 minutes, obtain the solution of clear in bath, and obtained solution is centrifuged 5 at 3500rpm
Minute, it takes supernatant that dehydrated alcohol is added and adjusts concentration to 10%, electrostatic spinning solution is prepared.
Step 2: the electrostatic spinning solution that step 1 is obtained is packed into spinning head, by 5 μm of polyethylene diagrams wound on reception
On roller, drum rotation speed 400rpm is received, the distance of spinning head to receiver roller is 12cm, in high-voltage DC power supply amount of exports
15kV electrostatic pressure, temperature are 30 DEG C, and humidity is spinning in the environment of 20%, and single side is prepared in fltting speed 0.002mm/s
Coat the polyethylene diagrams of carragheen gel coat.
Step 3: the polyethylene diagrams for the single side coating carragheen gel coat that step 2 is obtained are wound on reception roller
On, drum rotation speed 400rpm is received, the distance of spinning head to receiver roller is 12cm, in high-voltage DC power supply amount of exports 15kV
Electrostatic pressure, temperature are 30 DEG C, and humidity is spinning in the environment of 20%, and fltting speed 0.002mm/s obtains coated on both sides OK a karaoke club
The polyethylene diagrams of glue gel are placed in 50 DEG C of baking oven dry 20h, that is, lithium-sulfur cell diaphragm are prepared.
Embodiment two:
Step 1: taking the L-type carragheen powder of 30g to be immersed in the concentration of 200g is in the NaOH solution of 5mol/L, at 60 DEG C
Magnetic agitation (280rpm) 40 minutes, obtain the solution of clear in water-bath, and obtained solution is centrifuged at 3500rpm
It 5 minutes, takes supernatant that dehydrated alcohol is added and adjusts concentration to 11%, electrostatic spinning solution is prepared.
Step 2: the electrostatic spinning solution that step 1 is obtained is packed into spinning head, by 15 μm of Kynoar membrane windings
On receiving roller, drum rotation speed 500rpm is received, the distance of spinning head to receiver roller is 15cm, in high-voltage DC power supply
Amount of exports 18kV electrostatic pressure, temperature are 35 DEG C, and humidity is spinning in the environment of 22%, and fltting speed 0.003mm/s is prepared into
To the Kynoar diaphragm of single side coating carragheen gel coat.
Step 3: the Kynoar membrane winding for the single side coating carragheen gel coat that step 2 obtains is being received
On roller, drum rotation speed 500rpm is received, the distance of spinning head to receiver roller is 15cm, in high-voltage DC power supply amount of exports
18kV electrostatic pressure, temperature are 35 DEG C, and humidity is spinning in the environment of 22%, and fltting speed 0.003mm/s obtains coated on both sides
The Kynoar diaphragm of OK a karaoke club glue gel is placed in 55 DEG C of baking oven dry 20h, that is, lithium-sulfur cell diaphragm is prepared.
Embodiment three:
Step 1: the concentration that the I type carragheen powder of the K-type carragheen powder and 20g that take 20g is immersed in 300g is 6mol/L's
In NaOH solution, magnetic agitation (320rpm) 50 minutes, obtain the solution of clear in 70 DEG C of water-bath, by what is obtained
Solution is centrifuged 5 minutes at 3500rpm, is taken supernatant that dehydrated alcohol is added and is adjusted concentration to 12%, it is molten that electrostatic spinning is prepared
Liquid.
Step 2: the electrostatic spinning solution that step 1 is obtained is packed into spinning head, and 20 μm of non-woven fabrics membrane windings are being connect
It receives on roller, receives drum rotation speed 600rpm, the distance of spinning head to receiver roller is 18cm, is exported in high-voltage DC power supply
Volume 20kV electrostatic pressure, temperature are 40 DEG C, and humidity is spinning in the environment of 25%, and list is prepared in fltting speed 0.005mm/s
The nonwoven cloth diaphragm of face coating carragheen gel coat.
Step 3: the non-woven fabrics membrane winding for the single side coating carragheen gel coat that step 2 is obtained is receiving roller
On, drum rotation speed 600rpm is received, the distance of spinning head to receiver roller is 18cm, in high-voltage DC power supply amount of exports 20kV
Electrostatic pressure, temperature are 40 DEG C, and humidity is spinning in the environment of 25%, and fltting speed 0.005mm/s obtains coated on both sides OK a karaoke club
The nonwoven cloth diaphragm of glue gel is placed in drying in 60 DEG C of baking oven and for 24 hours, that is, lithium-sulfur cell diaphragm is prepared.
Comparative example one
Using commercialization polypropylene diaphragm as a comparison, to illustrate the correlation performance parameters of lithium-sulfur cell diaphragm in this patent.
To the different diaphragms in above-described embodiment one, embodiment two, embodiment three and comparative example one be tested for the property with
Characterization, the data result of detection are shown in Table 1.
Table 1
By testing result it is found that using the lithium-sulfur cell diaphragm porosity with higher of method provided by the invention preparation, suction
Liquid rate and limit oxygen index value, and there is very low shrinking percentage, meet the requirement of lithium battery diaphragm, and further can substantially mention
The operating temperature and safety of high battery.
Using lithium metal as cathode, sulphur is as anode, and diaphragm is using embodiment one, embodiment two, embodiment three and right
Diaphragm in ratio one forms lithium-sulfur cell group.Different diaphragms are respectively 1.0mA cm in charging and discharging currents density-2、2.0mA
cm-2、3.0mA cm-2Average coulombic efficiency after lower 120 circle of circulation is shown in Table 2.
Table 2
By testing result it is found that lithium-sulfur cell diaphragm of the invention shows height under low current density and high current density
Coulombic efficiency, it was demonstrated that diaphragm of the invention can effectively inhibit lithium dendrite growth and shuttle effect, improve lithium-sulfur cell
Cyclical stability.
Claims (3)
1. a kind of lithium-sulfur cell diaphragm, which is characterized in that be coated with anti-flammability in the conventional separator both side surface of different-thickness
Carragheen gel coat is prepared into a kind of compound lithium-sulfur cell diaphragm comprising three-decker using electrospinning process；Tool
There is the thickness of carragheen gel coat of anti-flammability between 1-20 μm；Its porosity of carragheen gel coat is 70-99.9%,
The size of hole is 10-50nm, specific surface area 400-1200m2/g；Carragheen gel coat is by K-type carragheen, I type
One or more of carragheen, L-type carragheen are composed.
2. a kind of lithium-sulfur cell diaphragm as described in claim 1, which is characterized in that the conventional separator of the different-thickness is 5-
30 μm of polyethylene diagrams, 5-30 μm of polypropylene diaphragm, 5-30 μm of Kynoar diaphragm, 5-35 μm of nylon membrane or nonwoven cloth diaphragm
In any one.
3. a kind of preparation method of lithium-sulfur cell diaphragm, which comprises the following steps:
Step 1: 20-40 parts of carragheen powder is taken to be immersed in 50-300 parts of concentration as 3-6mol/L's in parts by weight
In NaOH solution, magnetic agitation (250-320rpm) 30-50 minutes, obtain the molten of clear in 50-70 DEG C of water-bath
Obtained solution is centrifuged 5 minutes by liquid at 3500rpm, is taken supernatant that dehydrated alcohol is added and is adjusted concentration to 10-12%, preparation
Obtain electrostatic spinning solution；
Step 2: the electrostatic spinning solution that step 1 is obtained is packed into spinning head, by conventional separator wound on receiving on roller, connects
Drum rotation speed 400-600rpm is received, the distance of spinning head to receiver roller is 12-18cm, in high-voltage DC power supply amount of exports
15-20kV electrostatic pressure, temperature are 30-40 DEG C, and humidity is spinning in the environment of 20-25%, fltting speed 0.002-0.005mm/
The diaphragm of single side coating carragheen gel coat is prepared in s；
Step 3: the membrane winding for the single side coating carragheen gel coat that step 2 is obtained receives rolling on receiving roller
The distance of cylinder revolving speed 400-600rpm, spinning head to receiver roller are 12-18cm, in high-voltage DC power supply amount of exports 15-
20kV electrostatic pressure, temperature be 30-40 DEG C, humidity be 20-25% in the environment of spinning, fltting speed 0.002-0.005mm/s,
The diaphragm of coated on both sides OK a karaoke club glue gel is obtained, dry 20-24h is placed in 50-60 DEG C of baking oven, that is, lithium-sulfur cell is prepared
Diaphragm.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811501892.8A CN109755446B (en) | 2018-12-10 | 2018-12-10 | Lithium-sulfur battery diaphragm and preparation method thereof |
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| CN201811501892.8A CN109755446B (en) | 2018-12-10 | 2018-12-10 | Lithium-sulfur battery diaphragm and preparation method thereof |
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| CN109755446B CN109755446B (en) | 2021-11-23 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110592807A (en) * | 2019-09-18 | 2019-12-20 | 宁波大学 | Thin film material for inhibiting growth of lithium dendrite and preparation method thereof |
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