CN105304861B - A kind of lithium-sulfur cell electrode and its preparation and application - Google Patents
A kind of lithium-sulfur cell electrode and its preparation and application Download PDFInfo
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- CN105304861B CN105304861B CN201410307000.6A CN201410307000A CN105304861B CN 105304861 B CN105304861 B CN 105304861B CN 201410307000 A CN201410307000 A CN 201410307000A CN 105304861 B CN105304861 B CN 105304861B
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Abstract
The present invention relates to a kind of lithium-sulfur cell electrode and its preparation and application, including carbon-sulfur compound, the binding agent being mutually mixed, quaternary ammonium anion exchange resin is also added with electrode, the addition of resin is the 1 15% of carbon-sulfur compound quality.Quaternary ammonium salt cationic is conducive to stablizing intermediate product polysulfide, therefore suppression polysulfide is conducive to be deposited or deposit to from electrolyte solution in the hole of barrier film, be conducive to keeping the activity of active material, ultimately facilitate the decay for suppressing lithium-sulfur cell capacity.Anion exchange resin has micropore and big mesh, is added to as adsorbent in electrode, absorption that can be reversible and release polysulfide, the effect with polysulfide cistern.And then be conducive to stablizing polysulfide, be conducive to improving the coulombic efficiency of battery.
Description
Technical field
The invention belongs to a kind of technology of preparing of lithium-sulphur cell positive electrode, belong to technical field of energy material.
Background technology
Nowadays it is increasingly serious the problems such as world environments pollution, greenhouse effects, energy crisis.With the secondary of high-energy-density
Battery has very important significance for solving the energy and environmental problem of protrusion.During wherein lithium ion battery is secondary cell
One of specific energy highest battery.But in lithium rechargeable battery system, the specific capacity of positive electrode, cycle performance are all needed
Further to optimize.Traditional positive electrode such as LiCoO2/ graphite and LiFePO4The theoretical energy density of/graphite system is each about
400Wh/kg.Due to the limitation of its theoretical energy density, these positive electrodes are constituted and process aspect even if determining
Improvement be also difficult to make lithium ion battery make a breakthrough in energy density.Therefore, what exploitation was new has high-energy close
The low energy storage material of degree, long circulation life, cost is imperative.Wherein elemental sulfur has highest theoretical discharge specific capacity：
1675mAh/g, and by positive pole of elemental sulfur, lithium metal can reach for the theoretical energy density of the lithium-sulfur cell of negative pole
2600Wh/kg, its theoretical energy density is LiCoO2/ graphite and LiFePO4More than 6 times of/graphite system, are far longer than at this stage
Used commercialized secondary cell.In addition sulphur simple substance also has the excellent of the great commercial value such as with low cost, environment-friendly
Gesture.
However, the cycle performance of lithium-sulfur cell presence seriously hinders its commercialization process the problem of poor.Followed in battery
It is mainly what following several factors were caused present in ring process the problem of capacity rapid decay：(1) lithium-sulfur cell is in discharge and recharge
During many lithium sulfide (Li of intermediate product that produce2Sx, 4≤x≤8) be soluble in organic electrolyte makes the active material on positive pole
Gradually decrease, and due to shuttle effect, many lithium sulfides of dissolving can be diffused into the negative pole lithium piece of battery through barrier film, it is raw
Into Li2S2And Li2S precipitates poorly conductive, so as to cause the corrosion of GND and the increase of the internal resistance of cell.And shuttle
Effect also results in Li2S2And Li2S is deposited on positive electrode surface, so as to cause significantly changing for electrode pattern.And then cause capacity
Rapid decay.(2) in cyclic process, the cubical expansivity of sulfur electrode is up to 80% in lithium-sulfur cell, and this is likely to result in
Cracked inside sulfur electrode, the presence of this crackle and nonconducting Li2S2And Li2S is destroyed just in the generation of cracks
The globality of pole, ultimately results in the rapid decay of capacity.(3) polysulfide solubility of elemental sulfur and short chain is low, therefore they
It can be deposited or can even deposit in the hole of barrier film from electrolyte solution, and then lose activity, ultimately result in lithium sulphur
The decay of battery capacity.
The content of the invention
In order to solve the problem of lithium-sulfur cell cyclicity is poor, the invention provides a kind of lithium-sulfur cell binding agent and its electricity
The preparation method of pole.The present invention adds quaternary ammonium anion exchange resin as solid in lithium-sulphur cell positive electrode preparation process
Sulfur additives, play stable polysulfide, suppress the effect of battery capacity decay.Because the polysulfide of elemental sulfur and short chain is molten
Xie Du is low, therefore they can be deposited from electrolyte solution or can even deposit in the hole of barrier film, and then loses work
Property, ultimately result in the decay of lithium-sulfur cell capacity., should in lithium-sulfur cell in order to effectively improve the utilization rate of active sulfur materials
This, which is tried one's best, minimizes the disproportionated reaction of polysulfide.According to " hsab theory ", Li+It is hard acid, polysulfide anion is
Soft base, this combination is unstable.Therefore, polysulfide is intended to the polysulfide for the short chain that disproportionation generation is more stablized.
The present invention is by introducing quaternary ammonium cation (soft acid), to stablize polysulfide intermediate product, and then plays suppression battery capacity and decline
The effect subtracted.
Anion exchange resin is embedded in carbon-sulfur compound, by weak by the present invention according to medicament slow release principle simultaneously
Chemical bond adsorbs polysulfide.And this process can accomplish reversible to be adsorbed in release.Anion exchange resin has
Micropore and big mesh, and redox reaction is not involved in, it is added to as adsorbent in electrode, with polysulfide retaining
The effect in pond.And then be conducive to stablizing polysulfide, be conducive to improving the coulombic efficiency of battery.
Specific technical scheme of the invention is as follows：
Quaternary ammonium is also added with a kind of lithium-sulfur cell electrode, including carbon-sulfur compound, the binding agent being mutually mixed, electrode
Salt form anion exchange resin, the addition of resin is the 1-15% of carbon-sulfur compound quality.
The mass ratio of carbon-sulfur compound and binding agent is 7~9.6：0.4~3.
Sulphur mass content is 40-90% in carbon-sulfur compound.
Specifically preparation process is：(1) resin is pre-processed：By quaternary ammonium anion exchange resin under 100-300rpm,
Ball milling 1-5h, sieving, obtains the toner of 100-300 mesh.(2) slurry is prepared：By the pretreated tree described in step (1)
Fat, carbon-sulfur compound, binding agent, solvent, three mix and slurry are made.The mass ratio of carbon-sulfur compound and binding agent is 7
~9.6：0.4~3.The addition of resin is the preparation of 1-15% (3) electrode of carbon-sulfur compound quality：Slurry is uniformly applied
Cover on a current collector, be dried in vacuo 1-72h at 30-70 DEG C, obtain lithium-sulphur cell positive electrode.
Anion exchange resin described in step 1 is：Resin matrix be by one kind in styrene, divinylbenzene or
Two kinds of lists are poly- or copolymerization and obtain.Resin surface group be quaternary ammonium, the other groups being connected with nitrogen-atoms in quaternary ammonium (R1, R2,
R3 it is) one or more in methyl, ethyl, propyl group, isopropyl.Counter ion (M-) it is F-、Cl-、Br-、I-、HSO4 -。
Binding agent described in step 2 is oil-soluble binding agent：PVDF.Water-soluble binder is polytetrafluoroethylene (PTFE), polycyclic oxygen
Ethane, LA132, polymethyl methacrylate, beta-schardinger dextrin, agar, starch, sodium carboxymethylcellulose, polybutadiene rubber, fourth
Benzene rubber, ethylene propylene diene rubber.When binding agent is oil-soluble binding agent, solvent is NMP；When binding agent is water-soluble binder
When, solvent is water.
Collector described in step 3 is metal foil, foam metal, foamy carbon, carbon paper, carbon felt or carbon cloth.
Described metal foil is aluminium foil, iron foil, nickel foil.
Electrode effect lithium-sulphur cell positive electrode is applied in lithium-sulfur cell.
This additive for sulfur capture and its preparation method of electrode that the present invention is designed can solve the problem that many of elemental sulfur and short chain
Sulfide solubility is low, is easily deposited or can even deposit in the hole of barrier film from electrolyte solution, and then loses work
Property, the problem of ultimately resulting in the decay of lithium-sulfur cell capacity.Therefore, it is possible to solve the problem of lithium-sulfur cell cyclicity is poor.
Beneficial effect：
1. lithium-sulfur cell positive pole of the present invention is used as additive for sulfur capture by adding quaternary ammonium anion exchange resin, rise
To polysulfide is stablized, suppress the effect of battery capacity decay.Because the polysulfide solubility of elemental sulfur and short chain is low, therefore
They can be deposited from electrolyte solution or can even deposit in the hole of barrier film, and then lose activity, and ultimately result in
The decay of lithium-sulfur cell capacity., should be as far as possible minimum in lithium-sulfur cell in order to effectively improve the utilization rate of active sulfur materials
Change the disproportionated reaction of polysulfide.According to " hsab theory ", Li+It is hard acid, polysulfide anion is soft base, this group
Conjunction is unstable.Therefore, polysulfide is intended to the polysulfide for the short chain that disproportionation generation is more stablized.
Quaternary ammonium salt anionic is conducive to stablizing intermediate product polysulfide, therefore is conducive to suppressing polysulfide from electrolyte
In the hole that barrier film is deposited or deposited in solution, be conducive to keeping the activity of active material, ultimately facilitate suppression lithium
The decay of sulphur battery capacity.
2. anion exchange resin is embedded in carbon-sulfur compound according to medicament slow release principle, passes through weak change by the present invention
Key is learned to adsorb polysulfide.And this process can accomplish reversible to be adsorbed in release.Anion exchange resin has micro-
Pore and big mesh, and be not involved in redox reaction, are added in electrode as adsorbent, absorption that can be reversible and release
Polysulfide is put, the effect with polysulfide cistern.And then be conducive to stablizing polysulfide, be conducive to improving the storehouse of battery
Human relations efficiency.
Brief description of the drawings
Fig. 1 adds respectively to the addition of the electrode (embodiment 4) of additive for sulfur capture of the present invention and be not added with solid sulphur
Plus the electrode (comparative example 1) of agent is assembled into the discharge curve comparison diagram of button cell.
Fig. 2 is quaternary ammonium anion exchange resin, and resin matrix is by one kind in styrene, divinylbenzene or two
Plant single poly- or copolymerization and obtain.Resin surface group be quaternary ammonium group, the other groups being connected with nitrogen-atoms in quaternary ammonium (R1, R2,
R3 it is) one or more in methyl, ethyl, propyl group, isopropyl.Counter ion (M-) it is F-、Cl-、Br-、I-Or HSO4 -。
Embodiment
Detailed introduction is done to the present invention below in conjunction with embodiment, but the invention is not limited in described in following examples
Content.
The anion exchange resin structural formula of selection is
Wherein n=2000
Embodiment 1：
A resins are pre-processed：By quaternary ammonium anion exchange resin at 200 rpm, ball milling 4h, sieving, obtains 200 mesh
Toner.
B prepares slurry：By pretreated resin, carbon-sulfur compound, binding agent, solvent, three mixes and slurry is made
Material.The mass ratio of carbon-sulfur compound and binding agent is 9：1.The addition of resin is the 1% of carbon-sulfur compound quality, stock quality
Solid content 20%.
The preparation of c electrodes：Slurry is uniformly coated on a current collector, 72h is dried in vacuo at 60 DEG C, obtain lithium sulphur
Anode.
The binding agent is：PVDF.Solvent is NMP.
The collector is aluminium foil.
Embodiment 2：
A resins are pre-processed：By quaternary ammonium anion exchange resin at 200 rpm, ball milling 4h, sieving, obtains 200 mesh
Toner.
B prepares slurry：By pretreated resin, carbon-sulfur compound, binding agent, solvent, three mixes and slurry is made
Material.The mass ratio of carbon-sulfur compound and binding agent is 9：1.The addition of resin is the 2% of carbon-sulfur compound quality, stock quality
Solid content 20%.
The preparation of c electrodes：Slurry is uniformly coated on a current collector, 72h is dried in vacuo at 60 DEG C, obtain lithium sulphur
Anode.
The binding agent is：PVDF.Solvent is NMP.
The collector is aluminium foil.
Embodiment 3：
A resins are pre-processed：By quaternary ammonium anion exchange resin at 200 rpm, ball milling 4h, sieving, obtains 200 mesh
Toner.
B prepares slurry：By pretreated resin, carbon-sulfur compound, binding agent, solvent, three mixes and slurry is made
Material.The mass ratio of carbon-sulfur compound and binding agent is 9：1.The addition of resin is the 5% of carbon-sulfur compound quality, stock quality
Solid content 20%.
The preparation of c electrodes：Slurry is uniformly coated on a current collector, 72h is dried in vacuo at 60 DEG C, obtain lithium sulphur
Anode.
The binding agent is：PVDF.Solvent is NMP.
The collector is aluminium foil.
Embodiment 4：
A resins are pre-processed：By quaternary ammonium anion exchange resin at 200 rpm, ball milling 4h, sieving, obtains 200 mesh
Toner.
B prepares slurry：By pretreated resin, carbon-sulfur compound, binding agent, solvent, three mixes and slurry is made
Material.The mass ratio of carbon-sulfur compound and binding agent is 9：1.The addition of resin is the 10% of carbon-sulfur compound quality, slurry matter
Measure solid content 20%.
The preparation of c electrodes：Slurry is uniformly coated on a current collector, 72h is dried in vacuo at 60 DEG C, obtain lithium sulphur
Anode.
The binding agent is：PVDF.Solvent is NMP.
The collector is aluminium foil.
Embodiment 5：
A resins are pre-processed：By quaternary ammonium anion exchange resin at 200 rpm, ball milling 4h, sieving, obtains 200 mesh
Toner.
B prepares slurry：By pretreated resin, carbon-sulfur compound, binding agent, solvent, three mixes and slurry is made
Material.The mass ratio of carbon-sulfur compound and binding agent is 9：1.The addition of resin is the 15% of carbon-sulfur compound quality, slurry matter
Measure solid content 20%.
The preparation of c electrodes：Slurry is uniformly coated on a current collector, 72h is dried in vacuo at 60 DEG C, obtain lithium sulphur
Anode.
The binding agent is：PVDF.Solvent is NMP.
The collector is aluminium foil.
Comparative example 1：
Carbon-sulfur compound, PVDF, NMP, stirring are mixed and made into slurry by a.Carbon-sulfur compound and PVDF mass ratio are 9:
1。
The preparation of b electrodes：Slurry is uniformly coated in collector metal foil using knife coating, the vacuum at 60 DEG C
72h is dried, lithium-sulphur cell positive electrode is obtained.
The metal foil is aluminium foil.
The preparation of battery：
Argon gas protection, water content for below 1ppm glove box in, with the above-mentioned electrode slice prepared as positive pole,
Metal lithium sheet is as negative pole, using Guotai Huarong Chemical New Material Co., Ltd., Zhangjiagang City's lithium battery electrolytes：1mol/L
LiClO4/DOL+DME(1：1, by volume), Celgard2325 barrier films are assembled into CR2016 type button cells, and filled
Discharge test.
Charge-discharge test is carried out at room temperature to the battery made in embodiment 4 and comparative example 1.
The electrode assembled battery in the same fashion that embodiment 4 and comparative example 1 are obtained, and survey in the same fashion
Determine the cell performance curve of battery.
As shown in Figure 1：In the case of the loading of identical sulphur, it is respectively adopted and with the addition of solid sulphur addition of the present invention
The electrode (embodiment 4) of agent is assembled into after button cell, and specific discharge capacity conservation rate is apparently higher than being not added with additive for sulfur capture
Battery (comparative example 1).
Claims (8)
1. a kind of lithium-sulfur cell electrode, including carbon-sulfur compound, the binding agent being mutually mixed, it is characterised in that：In electrode also
Added with quaternary ammonium anion exchange resin, the addition of resin is the 1-15% of carbon-sulfur compound quality, the quaternary ammonium salt
The resin matrix of type anion exchange resin be by a kind of list in styrene, divinylbenzene is poly- or two kinds of copolymerization and obtain；Tree
Fat matrix surface is bonded with quaternary ammonium, other three groups being connected with nitrogen-atoms in quaternary ammonium be R1, R2 and R3, wherein R1,
R2, R3 are one kind in methyl, ethyl, propyl group, isopropyl or two kinds or three kinds；Counter ion (the M of quaternary ammonium salt-) it is F-、Cl-、
Br-、I-Or HSO4 -；Its chemical structural formula is：
2. according to electrode described in claim 1, it is characterised in that：The mass ratio of carbon-sulfur compound and binding agent is 7~9.6：0.4
~3.
3. according to electrode described in claim 1, it is characterised in that：Sulphur mass content is 40-90% in carbon-sulfur compound.
4. according to any electrodes of claim 1-3, it is characterised in that preparation process is：(1) resin is pre-processed：By quaternary ammonium
Salt form anion exchange resin is under 100-300rpm, ball milling 1-5h, sieving, obtains the toner of 100-300 mesh；
(2) slurry is prepared：By pretreated toner, carbon-sulfur compound, binding agent, solvent, slurry is made in mixing；
The mass ratio of carbon-sulfur compound and binding agent is 7~9.6：0.4~3；The addition of resin is the 1- of carbon-sulfur compound quality
15%；The quality solid content of slurry is 5-40%；
(3) preparation of electrode：Slurry is uniformly coated on a current collector, be dried in vacuo 1-72h at 30-70 DEG C, obtain lithium
Sulphur cell positive electrode.
5. electrode according to claim 4, it is characterised in that：The binding agent is oil-soluble binding agent or water-soluble bonding
Agent；Oil-soluble binding agent is Kynoar (PVDF)；Water-soluble binder be polytetrafluoroethylene (PTFE), PEO, LA132,
Polymethyl methacrylate, beta-schardinger dextrin, agar, starch, sodium carboxymethylcellulose, polybutadiene rubber, butadiene-styrene rubber, ternary
One or two or more kinds in EP rubbers.
6. electrode according to claim 4, it is characterised in that：When binding agent is oil-soluble binding agent, solvent is N- first
Base -2-Pyrrolidone (NMP)；When binding agent is water-soluble binder, solvent is water.
7. electrode according to claim 4, it is characterised in that：Described collector is metal foil, foam metal, foam
Carbon, carbon paper, carbon felt or carbon cloth；Described metal foil is aluminium foil, iron foil, nickel foil.
8. a kind of any described electrode effect lithium-sulphur cell positive electrodes of claim 1-3 are applied in lithium-sulfur cell.
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| CN201410307000.6A CN105304861B (en) | 2014-06-30 | 2014-06-30 | A kind of lithium-sulfur cell electrode and its preparation and application |
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| CN111613795B (en) * | 2020-04-26 | 2021-11-12 | 中山大学 | Multifunctional binder for lithium-sulfur battery anode and preparation method thereof |
| CN112072067B (en) * | 2020-09-18 | 2022-10-14 | 北京理工大学 | Carbon-sulfur composite positive electrode for lithium-sulfur battery and preparation method thereof |
| CN112928331B (en) * | 2021-02-20 | 2022-07-01 | 集美大学 | Electrolyte for lithium-sulfur battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1285085A (en) * | 1997-12-19 | 2001-02-21 | 摩尔科技公司 | Electrochemical cells composite cathodes comprising cationic polymers and electroactive polysulfide compounds |
| CN1467865A (en) * | 2002-07-10 | 2004-01-14 | 三星Sdi株式会社 | Positive electrode for lithium-sulfur battery and lithium-sulfur battery fabricated using same |
| CN1717834A (en) * | 2002-11-29 | 2006-01-04 | 株式会社汤浅 | Nonaqueous electrolyte and nonaqueous electrolyte battery |
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- 2014-06-30 CN CN201410307000.6A patent/CN105304861B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1285085A (en) * | 1997-12-19 | 2001-02-21 | 摩尔科技公司 | Electrochemical cells composite cathodes comprising cationic polymers and electroactive polysulfide compounds |
| CN1467865A (en) * | 2002-07-10 | 2004-01-14 | 三星Sdi株式会社 | Positive electrode for lithium-sulfur battery and lithium-sulfur battery fabricated using same |
| CN1717834A (en) * | 2002-11-29 | 2006-01-04 | 株式会社汤浅 | Nonaqueous electrolyte and nonaqueous electrolyte battery |
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