CN110098375A - A kind of modification of cyano sulphur anode and its high-performance lithium-sulfur cell that constitutes - Google Patents
A kind of modification of cyano sulphur anode and its high-performance lithium-sulfur cell that constitutes Download PDFInfo
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- CN110098375A CN110098375A CN201910415995.0A CN201910415995A CN110098375A CN 110098375 A CN110098375 A CN 110098375A CN 201910415995 A CN201910415995 A CN 201910415995A CN 110098375 A CN110098375 A CN 110098375A
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Abstract
The invention belongs to lithium-sulfur cell technical field more particularly to a kind of cyano the sulphur anode modified and its high-performance lithium-sulfur cells of composition.The main component of sulphur anode coating of the present invention is cyano, is modified cyano to sulphur positive electrode surface, then through being dried to obtain using knife coating (or spin-coating method, spray coating method, transfer printing etc.).Method provided by the present invention is easy to operate, convenient for application, and the polymer coating can effectively adsorb polysulfide, inhibit " the shuttle effect " of polysulfide, to significantly improve the long circulating stability energy and specific discharge capacity of lithium-sulfur cell, a kind of new method is provided for the development of long-life lithium-sulfur cell.
Description
Technical field
The present invention relates to lithium-sulfur cells；The invention further relates to the sulphur anode of cyano modification and its high-performance of composition
Lithium-sulfur cell.
Background technique
In past 20 years, the progress of lithium ion battery technology is greatly promoted the development of portable electronic device.
In recent years, with the exploitation and application of mobile intelligent terminal equipment and new-energy automobile, that there is an urgent need to develop costs is lower by people
And the higher secondary cell technology of energy density.Lithium-sulfur cell based on two electron reactions has 1675 mAh g-1Theory
Specific capacity and 2600 Wh kg-1Theoretical specific energy, and sulphur is widely present in the Nature, it is at low cost.Therefore lithium-sulfur cell has
Hope the next-generation high-performance energy-storage battery for becoming substitution lithium ion battery.
The charging and discharging reaction process of sulfur electrode is more complicated, and there are a series of reversible more sulphion intermediate products.
In typical liquid lithium sulphur battery system, the discharge process of sulfur electrode mainly includes two steps, and it is flat to respectively correspond two electric discharges
Platform: (1) discharge platform in the section the V of 2.4 V ~ 2.1, corresponding S8Cyclic structure become Sn 2-The chain of (4≤n≤8) ion
Structure, and and Li+In conjunction with generation Li2Sn；(2) the 2.1 longer discharge platforms in the section the V of V ~ 1.8, corresponding Sn 2-Ion
Chain structure becomes S2-With Li+In conjunction with generation Li2S, the platform are the main discharge regions of lithium-sulfur cell.Conversely, sulphur when charging
Li in electrode2S is gradually oxidized to S by this inverse process8.But since ion/electronics of sulphur and its discharging product lithium sulfide is led
It is electrically poor, cause the utilization rate of sulphur low.And the intermediate product polysulfide generated is soluble in liquid electrolyte, and is worn
Shuttle is reacted to cathode with lithium piece, causes the reduction of active loss and coulombic efficiency, this " shuttle effect " always present in
During the long circulating of liquid lithium-sulfur cell, the continuous decaying of capacity is in turn resulted in.Therefore, it can say in this way, " shuttle effect "
It is the maximum stumbling-block for hindering lithium-sulfur cell to run business big and strong with the following extensive development.In order to solve problem above, researcher
By designing various carbon materials, including carbon nanotube (CN106663797A), graphene (CN106159209A) and hetero atom
(CN105609772A) etc. is adulterated, to improve the electric conductivity and constraint polysulfide of anode, these methods can be in certain journey
Degree inhibits " shuttle effect " and improves the long circulating stability of lithium-sulfur cell.But the carbon material of specific morphology is mass produced
Technology is complicated, with high costs, is unfavorable for the commercialization of lithium-sulfur cell.Research paper (ACS Macro Lett. 2016,5,
471) it reports the anode of polymer overmold and is used for lithium-sulfur cell, after 100 circle of circulation, there are also 800 mAh g for battery-1It is reversible
Specific capacity, Cui Yi (ACS. Nano. 2011,5,9187) reports a kind of mode of PEDOT:PSS cladding sulphur anode, such
Method makes the performance of lithium-sulfur cell be significantly improved, but its cost is too high.In Chinese patent CN104485449A, by sulphur with
Polymer containing unsaturated bond carbon-carbon double bond is added in solution, and ultraviolet initiator is added, under the irradiation of ultraviolet light, hair
Raw polymerization, elemental sulfur is coated, and obtains the sulphur anode of polymer overmold, and after 500 circles recycle, reversible capacity is 430 mAh g-1,
Capacity attenuation is very fast.Chinese patent CN103515646A reports a kind of conducting polymer barrier layer and for lithium-sulfur cell, and 100
There are 900 mAh g after circle circulation-1Capacity, but the thickness of conductive layer is thicker, can reduce the energy density of battery entirety.China
Patent CN102664264A discloses the sulfur-containing polymer positive electrode of a kind of polysulfide rubber and the preparation of sulphur co-sintering, this method
It is prepared for positive electrode and is unable to get higher sulfur content.Other related patents further include CN105826534A,
CN105845965A、CN104332600A、CN106432726A、CN104051695A、CN105161722A、CN103700859A
Deng.In conclusion these methods can improve to a certain extent the utilization rate of sulphur, but fail fundamentally to solve more lithium sulfides molten
The problem of solution shuttles, the performance of lithium-sulfur cell is still to be improved.
Based on high-performance lithium sulphur discussed above, coating sulphur anode the invention proposes a kind of cyano and its constitute
Battery.This method can effectively inhibit the shuttle of polysulfide, improve the long circulating performance and specific discharge capacity of lithium-sulfur cell,
And it is easy to operate, it is at low cost, be conducive to the large-scale production of lithium-sulfur cell.
Summary of the invention
The purpose of the present invention is to provide a kind of sulphur anode of cyano modification, the long circulatings of Lai Tigao lithium-sulfur cell
Stability.
Another object of the present invention is to provide the height of the preparation method of the sulphur anode of cyano modification and its composition
Performance lithium-sulfur cell.
To achieve the above object, the method that the present invention takes is to modify the solution of cyano to the sulphur prepared just
Pole piece, experimental procedure are as follows:
(1) positive active material, binder solution and conductive agent common sulphur anode preparation: are scraped into collection according to a certain percentage
On fluid；
(2), it prepares cyano solution: cyano being dissolved in organic solvent, it is molten to be configured to certain density polymer
Liquid eliminates bubble, stand for standby use；
(3), the polymer solution for obtaining above-mentioned steps passes through knife coating, spin-coating method, spray coating method or transfer printing modification to preparation
It on good sulphur positive plate, dries at a certain temperature, obtains the sulphur anode of cyano modification.
The positive active material is elemental sulfur, sulphur/carbon composite, sulfurized polyacrylonitrile, vulcanization polyaniline, vulcanizes and gather
One of pyrroles, ferrous disulfide, molybdenum disulfide, vanadium disulfide, cobalt disulfide, curing nickel, curing copper and iron sulfide or
It is a variety of；The binder is Kynoar, polytetrafluoroethylene (PTFE), polyacrylic acid, sodium carboxymethylcellulose, butadiene-styrene rubber, propylene
One of nitrile multiple copolymer, sodium alginate, alginic acid magnesium and lithium alginate are a variety of；The conductive agent be conductive black,
One of acetylene black, Ketjen black and graphene are a variety of；The collector is aluminium foil, nickel foil, stainless steel, titanium foil, carbon nanometer
One of film and cracking graphite film are a variety of.
The cyano has the structure as shown in general formula 1:
General formula 1
Wherein the value of n is 50-10000；R1For hydrogen or ester group；R2For (CH2)m, the value of m is 1-10.
Organic solvent is acetonitrile, dimethyl sulfoxide, sulfolane, dimethyl sulfite, sulfurous acid diethyl ester, acetone, tetrahydro
One or more of furans, chloroform, ethyl acetate, N,N-dimethylformamide and DMAC N,N' dimethyl acetamide；Matched
The mass percent for the cyano solution set is 0.1 %-50 %.
The drying temperature is 30 DEG C to 100 DEG C.
A kind of high-performance lithium-sulfur cell, including anode, cathode, diaphragm and electrolyte between positive and negative anodes, it is described just
The extremely sulphur anode of cyano modification；Negative electrode active material is in lithium metal, lithium-aluminium alloy, lithium-copper alloy and lithium indium alloy
It is one or more；Diaphragm be polypropylene, polyethylene, polypropylene, polyethylene, polypropylene, polyethylene/polypropylene, glass fibre,
One or more of cellulose and bacteria cellulose；Electrolyte solvent is glycol dimethyl ether, diethylene glycol dimethyl ether, three second
One or more of glycol dimethyl ether, tetraethyleneglycol dimethyl ether, 1,3- dioxolanes, dimethyl sulfoxide and tetrahydrofuran mix
It closes；Electrolyte lithium salt is double trifluoromethanesulfonimide lithiums, lithium hexafluoro phosphate, LiBF4, lithium perchlorate, hexafluoroarsenate
One of lithium, dioxalic acid lithium borate, difluorine oxalic acid boracic acid lithium and double fluoromethane sulfimide lithiums are a variety of.
A kind of preparation method of high-performance lithium-sulfur cell, the sulphur anode that above-mentioned cyano is modified, cathode, diaphragm and
Electrolyte seals to obtain high-performance lithium-sulfur cell.
Detailed description of the invention
Fig. 1 is the transmission electron microscope for the cyanacrylate cladding sulphur anode that the embodiment of the present invention 1 provides.
Fig. 2 is the lithium-sulfur cell long circulating curve for the cyanopropionate cladding sulphur carbon anode that the embodiment of the present invention 2 provides.
Fig. 3 is that the charge and discharge of the lithium-sulfur cell for the Methyl 2-cyanoacrylate cladding sulphur anode that the embodiment of the present invention 3 provides are bent
Line.
Specific embodiment
Be above to generality description of the invention, below we will be by specific embodiment to claim of the invention
It is further explained.
Embodiment 1
The sodium alginate soln that configuration quality score is 5%, weighs sulphur carbon composite, conduction according to the mass ratio of 8:1:1 respectively
Carbon black and sodium alginate soln (5%) prepare anode sizing agent.Then slurry is scratched to above aluminium collector, 35oC is dried, is obtained
To positive plate.0.1 g cyanacrylate is weighed, is added into the bottle equipped with 10 g acetone, is stirred evenly, seal up for safekeeping,
It is spare.On the cyanacrylate prepared blade coating to sulphur anode, the sulphur anode of poly- cyanacrylate coating will be obtained.
Embodiment 2
The acrylonitrile copolymer solution that mass fraction is 15% is prepared, weighs elemental sulfur, section according to the ratio that mass ratio is 7:2:1
Qin is black and acrylonitrile copolymer solution (15%) prepares sulphur anode sizing agent, using nickel foil as collector, 50oC drying, weighs 0.5
G cyanacrylate is added into the bottle equipped with 10 g acetone, and magnetic agitation is uniform, seals up for safekeeping, spare.It will prepare
Cyanacrylate blade coating to sulphur anode on, obtain the sulphur anode of poly- cyanacrylate coating.
Embodiment 3
The sodium alginate soln that configuration quality score is 10%, weighs sulphur carbon composite wood in mass ratio for the ratio of 6:3:1 respectively
Material, graphene, sodium alginate soln (10%) prepare sulphur anode sizing agent, using aluminium foil as collector, 60oC drying, weighs 0.7
G cyanacrylate is added into the bottle equipped with 10 g n,N-dimethylacetamide, and magnetic agitation is uniform, is sealed up for safekeeping,
It is spare.Just by the sulphur by poly- cyanacrylate coating on the Methyl 2-cyanoacrylate prepared blade coating to sulphur anode, is obtained
Pole.
Embodiment 4
The carboxymethylcellulose sodium solution that configuration quality score is 15% weighs sulphur carbon according to the ratio that mass ratio is 8:1:1 respectively
Composite material, graphene, carboxymethylcellulose sodium solution (15%) prepare sulphur anode sizing agent, using aluminium foil as collector, 70oC
Drying, weighs 0.2 g polyacrylonitrile, is added into the bottle equipped with 20 g acetonitriles, magnetic agitation is uniform, seals up for safekeeping, spare.
It scratches by by the polyacrylonitrile prepared onto sulphur anode, obtains the sulphur anode of polyacrylonitrile coating.
Embodiment 5
The Kynoar solution that configuration quality score is 4%, weighs ferrous disulfide in mass ratio for the ratio of 7:2:1 respectively, leads
Electric carbon black, Kynoar solution (4%) prepare anode sizing agent and scrape on cracking graphite film, are prepared positive electrode, and 80oC drying.0.01 g Methyl 2-cyanoacrylate is weighed, is dissolved in 10 g acetone, is stirred evenly, seal up for safekeeping, it is spare.It presses
On the methyl acrylate prepared blade coating to sulphur anode, the sulphur anode of poly- Methyl 2-cyanoacrylate coating will be obtained.
Embodiment 6
Prepare mass fraction be 5% Kynoar solution, in mass ratio for 7:2:1 ratio weigh respectively sulphur carbon composite,
Conductive black, Kynoar solution (5%) prepare anode sizing agent, and scrape on cracking graphite film, and positive electrode is prepared,
45 oC drying.0.01 g cyanoacrylate propyl propionate is weighed, is dissolved in 10 g acetone, is stirred evenly, seal up for safekeeping, it is spare.
By on the cyanoacrylate propyl propionate blade coating to sulphur anode that will be prepared, the sulphur anode of paracyanogen base propyl acrylate coating is obtained.
Embodiment 7
The Kynoar solution that mass fraction is 5% is prepared, weighs sulphur carbon composite wood respectively in mass ratio for the ratio of 7:2:1
Material, conductive black, Kynoar solution (5%) prepare anode sizing agent, scrape on cracking graphite film, positive electrode is prepared,
50 oC drying.1 g polyacrylonitrile multiple copolymer (LA133) is weighed, is dissolved in 10 g deionized waters, stirring is equal
It is even, it seals up for safekeeping, it is spare.By on the LA133 solution blade coating to sulphur anode that will be prepared, the sulphur anode of LA133 coating is obtained.
Embodiment 8
The Kynoar solution that mass fraction is 5% is prepared, weighs sulphur, conductive charcoal respectively in mass ratio for the ratio of 6:3:1
Black, Kynoar solution (5%) prepares anode sizing agent and scrapes on aluminium foil, is prepared positive electrode, and 40oC drying.It weighs
1g polyacrylonitrile multiple copolymer (LA133), is dissolved in 10g deionized water, stirs evenly, seal up for safekeeping, spare.By general
On the LA132 solution blade coating to sulphur anode prepared, the sulphur anode of LA132 coating, using lithium indium alloy as cathode, assembling are obtained
Battery is tested.
Embodiment 9
The alginic acid magnesium solution that mass fraction is 3% is prepared, weighs sulphur, acetylene black, sea respectively in mass ratio for the ratio of 6:3:1
Alginic acid magnesium solution (3%) prepares anode sizing agent, scrapes on nickel foil, is prepared positive electrode, and 65oC drying.Weigh 1 g cyano
Cellulose is dissolved in 10 g n,N-Dimethylformamide, stirs evenly, seal up for safekeeping, spare.By the cyano prepared is fine
It ties up on plain solution blade coating to sulphur anode, obtains the sulphur anode of cyanocelluloses coating, using lithium indium alloy as cathode, assembled battery
It is tested.
Embodiment 10
The polytetrafluoroethylsolution solution that mass fraction is 5% is prepared, weighs sulphur, conductive charcoal respectively in mass ratio for the ratio of 6:3:1
Black, polytetrafluoroethylsolution solution (5%) prepares anode sizing agent, scrapes on nickel foil, is prepared positive electrode, and 75oC drying.Weigh 1
G cyano polyvinyl alcohol is dissolved in 8 g n,N-dimethylacetamide, stirs evenly, seal up for safekeeping, spare.By what will be prepared
Cyano poly-vinyl alcohol solution blade coating to sulphur anode on, obtain cyano polyvinylalcohol coats sulphur anode, using lithium-aluminium alloy as bear
Pole, assembled battery are tested.
Claims (8)
1. a kind of high-performance lithium-sulfur cell with sulphur anode, it is characterised in that: the sulphur just extremely cyano modification sulphur just
Pole.
2. a kind of high-performance lithium-sulfur cell sulphur anode as described in claim 1, the cyano have such as 1 institute of general formula
The structure shown:
General formula 1
Wherein the value of n is 50-10000；R1For hydrogen or ester group；R2For (CH2)m, the value of m is 1-10.
3. a kind of preparation method of high-performance lithium-sulfur cell sulphur anode as claimed in claim 1 or 2, which is characterized in that packet
Include following steps:
(1) preparation of common sulphur anode: positive active material, binder solution and conductive agent are scraped according to a certain percentage
On collector；
(2) it prepares cyano solution: cyano being dissolved in organic solvent, it is molten to be configured to certain density polymer
Liquid eliminates bubble, stand for standby use；
(3) by polymer solution that above-mentioned steps obtain by knife coating, spin-coating method, spray coating method or transfer printing modification to preparing
Sulphur positive plate on, dry at a certain temperature, obtain cyano modification sulphur anode.
4. a kind of preparation method of high-performance lithium-sulfur cell sulphur anode as claimed in claim 3, it is characterised in that: anode is living
Property substance be elemental sulfur, sulphur/carbon composite, sulfurized polyacrylonitrile, vulcanization polyaniline, vulcanization polypyrrole, ferrous disulfide, two sulphur
Change one of molybdenum, vanadium disulfide, cobalt disulfide, curing nickel, curing copper and iron sulfide or a variety of；Binder is to gather inclined fluorine
Ethylene, polytetrafluoroethylene (PTFE), polyacrylic acid, sodium carboxymethylcellulose, butadiene-styrene rubber, acrylonitrile multiple copolymer, sodium alginate, sea
One of alginic acid magnesium and lithium alginate are a variety of；Conductive agent is one of conductive black, acetylene black, Ketjen black and graphene
Or it is a variety of；Collector is one of aluminium foil, nickel foil, stainless steel, titanium foil, carbon nanocapsule thin film and cracking graphite film or a variety of.
5. a kind of preparation method of high-performance lithium-sulfur cell sulphur anode as claimed in claim 3, it is characterised in that: preparation step
Suddenly cyano described in (2) has the structure as shown in general formula 1:
General formula 1
Wherein the value of n is 50-10000；R1For hydrogen or ester group；R2For (CH2)m, the value of m is 1-10；Organic solvent be acetonitrile,
Dimethyl sulfoxide, sulfolane, dimethyl sulfite, sulfurous acid diethyl ester, acetone, tetrahydrofuran, chloroform, ethyl acetate,
One or more of N,N-dimethylformamide and DMAC N,N' dimethyl acetamide；The matter of the cyano solution configured
Amount percentage is 0.1 %-50 %.
6. a kind of preparation method of high-performance lithium-sulfur cell sulphur anode as claimed in claim 3, it is characterised in that: step
(3) drying temperature described in is 30 DEG C to 100 DEG C.
7. a kind of high-performance lithium-sulfur cell, including anode, cathode, diaphragm and electrolyte between positive and negative anodes, feature exist
In: the sulphur anode of the cyano modification just extremely described in claim 1；Negative electrode active material is lithium metal, lithium aluminium
One of alloy, lithium-copper alloy and lithium indium alloy are a variety of；Diaphragm is polypropylene, polyethylene, polypropylene, polyethylene, poly- third
One or more of alkene/polyethylene/polypropylene, glass fibre, cellulose and bacteria cellulose；Electrolyte solvent is ethylene glycol
Dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether, 1,3- dioxolanes, dimethyl sulfoxide and four
The mixing of one or more of hydrogen furans；Electrolyte lithium salt is double trifluoromethanesulfonimide lithiums, lithium hexafluoro phosphate, tetrafluoro boron
In sour lithium, lithium perchlorate, hexafluoroarsenate lithium, dioxalic acid lithium borate, difluorine oxalic acid boracic acid lithium and double fluoromethane sulfimide lithiums
It is one or more.
8. a kind of preparation of high-performance lithium-sulfur cell as claimed in claim 7, it is characterised in that: will be described in claim 1
Sulphur anode, cathode, diaphragm and the electrolyte of cyano modification, seal to obtain high-performance lithium-sulfur cell.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116003942A (en) * | 2022-12-29 | 2023-04-25 | 重庆硕盈峰新能源科技有限公司 | NiS (nickel-zinc sulfide) 2 SPAN composite material, preparation method and application |
| CN116053407A (en) * | 2023-03-31 | 2023-05-02 | 宁德新能源科技有限公司 | Secondary battery and electronic device |
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