CN102208599B - Positive pole piece of lithium-sulphur battery and preparation method thereof - Google Patents
Positive pole piece of lithium-sulphur battery and preparation method thereof Download PDFInfo
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- CN102208599B CN102208599B CN201110124658XA CN201110124658A CN102208599B CN 102208599 B CN102208599 B CN 102208599B CN 201110124658X A CN201110124658X A CN 201110124658XA CN 201110124658 A CN201110124658 A CN 201110124658A CN 102208599 B CN102208599 B CN 102208599B
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- lithium
- pole piece
- positive pole
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- 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 invention relates to a positive pole piece of a lithium-sulfur battery based on an L-cysteine or L-cystine agent as an additive and a preparation method thereof. According to the method, based on gelatin as a binder, the L-cysteine or L-cystine additive is introduced, thus the redox property of a sulphur electrode is obviously improved, and the electrochemistry reversibility and circulation stability of the lithium-sulfur battery are significantly improved.
Description
Technical field:
The present invention relates to a kind of positive pole piece of lithium-sulphur battery take Cys or CYSTINE as additive and preparation method thereof.
Background technology:
The theoretical specific capacity of elemental sulfur is 1672mAh/g, and theoretical specific energy is 2600W/kg, and is the highest in all known anode material of lithium battery.Simultaneously, the elemental sulfur produce are abundant, environmental sound, make lithium-sulfur rechargeable battery become the focus of Recent study.
The positive electrode of general lithium-sulfur cell is comprised of active material, conductive agent and binder.Traditional binder such as PEO, butadiene-styrene rubber or Kynoar (PVDF) etc., is dissolved in the nonaqueous solvents, is mixed and made into slurries with sulphur and conductive agent again.The addition of these binders in positive electrode is large, and made slurries are poor in the collection liquid surface spreadability.Vacuumize removes that active material and conductive agent easily come off from collector behind the residual solvent, and poor stability in charge and discharge process becomes the serious major reason of capacity attenuation of lithium-sulfur cell.Gelatin is the collagen in the mammal connective tissue, through the macro-molecular protein that appropriateness is hydrolyzed and thermal denaturation obtains.Early-stage Study proves that gelatin has obvious advantage as the anodal binder of lithium-sulfur cell, and battery capacity and cycle performance all are significantly improved.The present inventor discloses in the ZL200710122444.2 patent and has a kind ofly prepared porous anode by freeze-drying, makes the lithium-sulfur cell chemical property obtain certain raising.
Cys is a kind of amino acid with physiological function, plays an important role in vital movement.It is uniquely in 20 several amino acids of constitutive protein matter to have reproducibility group sulfydryl (amino acid SH).As a kind of reducing agent, in medicine, food additives and cosmetics, be widely used.The function that promotes body cell oxidation and reduction is pharmaceutically arranged, increase white blood cell and stop the pathogen growth to wait effect.In view of its excellent electro-chemical activity, research is active aspect electrochemical analysis and electro-catalysis.Mainly concentrate on two aspects: the one, as the main path of producing mercaptan in the industry, by the synthetic cysteine of electrochemical reduction cystine; Another is the electrochemical analysis by cysteine, studies its biologically active.
Cys is water-soluble, ethanol, acetic acid and ammoniacal liquor, is insoluble to ether, acetone, ethyl acetate, benzene, carbon disulfide and carbon tetrachloride.In neutral and weakly alkaline solution, be oxidised with air to CYSTINE.At present, there is not yet Cys, CYSTINE or other kinds amino acid are applied to report in the lithium-sulfur cell.
Summary of the invention:
The preparation method who the purpose of this invention is to provide a kind of positive pole piece of lithium-sulphur battery, take gelatin on the binder basis, improve the oxidation-reduction quality of electrode by introducing Cys or CYSTINE additive, thereby further improve electrochemical reversibility and the cyclical stability of battery.
Positive pole piece of lithium-sulphur battery of the present invention, formed by the collector of conduction current and active material, conductive agent, binder and the additive that is coated on the collector, it is characterized in that: described binder is gelatin, and additive is Cys or CYSTINE.The mass ratio of positive active material, conductive agent, binder and additive is 50-80: 20-40: 5-15: 0.1-0.2.
Described collector is aluminium foil or aluminium net.
Described positive active material is S
8, Li
2S
n(1≤n≤8) or organosulfur compound, wherein organic sulfur compound is preferably carbon sulphur polymer (C
2S
x)
m(wherein x is 2.5-50, and m 〉=2).
Described conductive agent is carbon-based conductive agent, such as conductive black, acetylene black or graphite powder etc.
Described gelatin can be that the whole bag of tricks makes, and is divided into skin gelatin or bone gelatin according to its source difference.
The present invention also provides above-mentioned positive pole piece of lithium-sulphur battery preparation method, and the preparation mass percentage concentration is the aqueous gelatin solution of 1-6%; Add Cys or CYSTINE additive, regulating the pH value with alkali lye is 7-10, and alkali lye can be the aqueous solution of 0.5-1.0mol/L potassium hydroxide, NaOH or lithium hydroxide.Then add positive active material, conductive agent evenly mixes, wherein, the mass ratio of positive active material, conductive agent, gelatin binder and additive is 50-80: 20-40: 5-15: 0.1-0.2.The method of mixing can be mechanical ball-milling method, physical grinding method or mechanical mixing method.The anode sizing agent of making is coated in collection liquid surface, makes positive pole piece of lithium-sulphur battery after the drying.
The dry run of above-mentioned positive electrode material slurry can adopt boulton process or other drying means, such as the solvent dehydration seasoning.
The prepared lithium-sulfur cell take Cys or CYSTINE as additive of the present invention is anodal, and circulation volume and cycle life all are improved.In the sulphur positive electrode, add Cys or CYSTINE additive, can form stable solid/dielectric film on anodal surface and effectively improve the anodal chemical property of sulphur.Cys or CYSTINE additive have significantly improved electrochemical reversibility and the oxidation-reduction quality of lithium-sulfur cell, and battery discharge specific capacity, cyclical stability all are significantly improved.
Cooperate with anode pole piece of the present invention to be assembled into CR2025 type button cell, negative material is the alloys such as the alloy of lithium or lithium and otheralkali metal or alkaline-earth metal and Li/Al, Li/Si, Li/Pb, Li/Sn, Li/Sb, Li/Bi, Li/Zn, Li/Cd, Li/C.Electrolytical range of choice is liquid state, gel, solid-state electrolyte system, liquid electrolyte can be selected a kind of and organic solvent among DME (glycol dimethyl ether), DOL (1,3-dioxolane) and the THF (oxolane) or the mixture of several organic solvents.Supporting electrolyte salt can be lithium perchlorate, trifluoromethyl sulfonic acid lithium, hexafluoro phosphorus lithium etc.Carry out the constant current charge-discharge performance test under the room temperature environment, deboost is 1.5～2.8V, and charging and discharging currents density is respectively 0.4mAh/cm
2And 1mAh/cm
2
At first, among the embodiment 1, the mass ratio of sublimed sulfur, acetylene black, gelatin, Cys is 60: 30: 10: 0.1, and mixed solution pH=7, the pole piece of preparation are anodal, and negative pole is the simple substance lithium, and liquid electrolyte is the LiClO of 1mol/L
4DME/DOL (V/V=1/1) is assembled into battery, carries out the charge-discharge performance test.The result shows that its first discharge specific capacity is 1018mAh/g, and specific discharge capacity is 709mAh/g after 30 circulations.
Secondly, among the embodiment 2, the mass ratio of sublimed sulfur, acetylene black, gelatin, Cys is 60: 30: 10: 0.1, and mixed solution pH=10, the pole piece of preparation are anodal, and negative pole is lithium metal, and liquid electrolyte is the LiClO of 1mol/L
4DME/DOL (V/V=1/1) is assembled into battery, carries out the charge-discharge performance test.The result shows that its first discharge specific capacity is 1119mAh/g, and specific discharge capacity is 719mAh/g after 30 circulations.
Again, embodiment 3, and the mass ratio of sublimed sulfur, acetylene black, gelatin, Cys is 60: 40: 15: 0.2, and mixed solution pH=7, the pole piece of preparation are anodal, and negative pole is lithium metal, and liquid electrolyte is the LiClO of 1mol/L
4DME/DOL (V/V=1/1) is assembled into battery, carries out the charge-discharge performance test.The result shows that its first discharge specific capacity is 1063mAh/g, and specific discharge capacity is 815mAh/g after 30 circulations.
At last, among the embodiment 4, the mass ratio of sublimed sulfur, acetylene black, gelatin, Cys is 60: 40: 15: 0.2, and mixed solution pH=10, the pole piece of preparation are anodal, and negative pole is lithium metal, and liquid electrolyte is the LiClO of 1mol/L
4DME/DOL (V/V=1/1) is assembled into battery, carries out the charge-discharge performance test.The result shows that its first discharge specific capacity is 1087mAh/g, and specific discharge capacity is 830mAh/g after 30 circulations.
Description of drawings:
Fig. 1 is the units activity material sulphur weight of the anode pole piece assembled batteries of adopting the embodiment of the invention 1,2,3 and 4 preparations discharge characteristic curve figure first.
The first discharge specific capacity of the battery of four embodiment making in the comparison diagram 1, the first discharge specific capacity of embodiment 2 is the highest.
Fig. 2 is units activity material sulphur weight cycle performance and the efficiency chart that adopts the anode pole piece assembled battery of the embodiment of the invention 3 preparations.Wherein, the top curve is the efficiency for charge-discharge curve of battery among the figure, the specific discharge capacity curve when lower curve is different cycle-index.
The anode pole piece assembled battery of embodiment 3 preparations has excellent cycle performance, and efficiency for charge-discharge is about 100%.After showing the adding Cys, the oxidation-reduction quality of sulfur electrode is significantly improved, and has obviously improved electrochemical reversibility and the cyclical stability of battery.
Embodiment:
Below be exemplary embodiments of the present invention, the invention is not restricted to these embodiment but should understand.
Embodiment 1:
The preparation mass percentage concentration is 2% aqueous gelatin solution, then adds Cys, and the mass ratio of Cys and gelatin is 0.1: 10.KOH solution with 1mol/L is transferred pH=7, and is for subsequent use.
The preparation of anode pole piece: add in above-mentioned Cys and the gelatin mixed solution after grinding sublimed sulfur, acetylene black evenly.The mass ratio of sublimed sulfur, acetylene black, gelatin, cysteine is 60: 30: 10: 0.1, continue to grind, and make even anode sizing agent, be coated on the aluminum foil current collector with scraping the skill in using a kitchen knife in cookery, after room temperature was air-dry, dry 10h in vacuum drying chamber was pressed into the disk of diameter 1.2cm.
Use the pole piece of above-mentioned preparation to make positive pole, negative pole is lithium metal, and barrier film is selected polypropylene screen, and electrolyte is the LiClO of 1mol/L
4Solution, solvent are DME (glycol dimethyl ether), DOL (1,3-dioxolane) (V/V=1/1), (humidity is less than 1%) is assembled into CR2025 type button cell in the argon shield glove box.At room temperature carry out charge-discharge test, charging and discharging currents density is respectively 0.4mAh/cm
2And 1mAh/cm
2, deboost is 2.8 to 1.5V.The first discharge specific capacity of battery is 1018mAh/g, specific discharge capacity 709mAh/g after 30 circulations.
Embodiment 2:
The preparation mass percentage concentration is 2% aqueous gelatin solution, then adds Cys, and the mass ratio of Cys and gelatin is 0.1: 10.KOH solution with 1mol/L is transferred pH=10, and is for subsequent use.
The preparation of anode pole piece: add above-mentioned Cys and gelatin mixed solution after grinding sublimed sulfur, acetylene black evenly.The mass ratio of sublimed sulfur, acetylene black, gelatin, cysteine is 60: 30: 10: 0.1, continue to grind, and make even anode sizing agent, be coated on the aluminum foil current collector with scraping the skill in using a kitchen knife in cookery, after room temperature was air-dry, dry 10h in vacuum drying chamber was pressed into the disk of diameter 1.2cm.
Use the pole piece of above-mentioned preparation to make positive pole, negative pole is lithium metal, and barrier film is selected polypropylene screen, and electrolyte is the LiClO of 1mol/L
4Solution, solvent are DME (glycol dimethyl ether), DOL (1,3-dioxolane) (V/V=1/1), after (humidity is less than 1%) is assembled into CR2025 type button cell in the argon shield glove box.At room temperature carry out charge-discharge test, charging and discharging currents density is respectively 0.4mAh/cm
2And 1mAh/cm
2, deboost is 2.8 to 1.5V.The first discharge specific capacity of battery is 1119mAh/g, and specific discharge capacity remains on 719mAh/g after 30 circulations.
Embodiment 3:
The preparation mass percentage concentration is 3% aqueous gelatin solution, then adds Cys, and the mass ratio of Cys and gelatin is 0.2: 15.LiOH solution with 0.1mol/L is transferred pH=7, and is for subsequent use.
The preparation of anode pole piece: the preparation of anode pole piece: add in above-mentioned Cys and the gelatin mixed solution after grinding sublimed sulfur, acetylene black evenly.The mass ratio of sublimed sulfur, acetylene black, gelatin, cysteine is 60: 40: 15: 0.2, continue to grind, and make even anode sizing agent, be coated on the aluminum foil current collector with scraping the skill in using a kitchen knife in cookery, after room temperature was air-dry, dry 10h in vacuum drying chamber was pressed into the disk of diameter 1.2cm.
Use the pole piece of above-mentioned preparation to make positive pole, negative pole is lithium metal, and barrier film is selected polypropylene screen, and electrolyte is the LiClO of 1mol/L
4Solution, solvent are DME (glycol dimethyl ether), DOL (1,3-dioxolane) (V/V=1/1), (humidity is less than 1%) is assembled into CR2025 type button cell in the argon shield glove box.At room temperature carry out charge-discharge test, charging and discharging currents density is respectively 0.4mAh/cm
2And 1mAh/cm
2, deboost is 2.8 to 1.5V.The first discharge specific capacity of battery is 1063mAh/g, and after 30 circulations, specific discharge capacity is 815mAh/g.
Embodiment 4:
The preparation mass percentage concentration is 3% aqueous gelatin solution, then adds Cys, and the mass ratio of Cys and gelatin is 0.2: 15.LiOH solution with 0.1mol/L is transferred pH=10, and is for subsequent use.
The preparation of anode pole piece: the preparation of anode pole piece: add in above-mentioned Cys and the gelatin mixed solution after grinding sublimed sulfur, acetylene black evenly.The mass ratio of sublimed sulfur, acetylene black, gelatin, cysteine is 60: 40: 15: 0.2, continue to grind, and make even anode sizing agent, be coated on the aluminum foil current collector with scraping the skill in using a kitchen knife in cookery, after room temperature was air-dry, dry 10h in vacuum drying chamber was pressed into the disk of diameter 1.2cm.
Use the pole piece of above-mentioned preparation to make positive pole, negative pole is lithium metal, and barrier film is selected polypropylene screen, and electrolyte is the LiClO of 1mol/L
4Solution, solvent are DME (glycol dimethyl ether), DOL (1,3-dioxolane) (V/V=1/1), (humidity is less than 1%) carries out electro-chemical test after being assembled into CR2025 type button cell in the argon shield glove box.At room temperature carry out charge-discharge test, charging and discharging currents density is respectively 0.4mAh/cm
2And 1mAh/cm
2, deboost is 2.8 to 1.5V.Battery first discharge specific capacity 1087mAh/g, specific discharge capacity is 830mAh/g after 30 circulations.
Claims (8)
1. positive pole piece of lithium-sulphur battery, formed by the collector of conduction current and positive active material, conductive agent, binder and the additive that is coated on the collector, it is characterized in that: described binder is gelatin, and additive is Cys or CYSTINE; The mass ratio of positive active material, conductive agent, binder and additive is 50-80:20-40:5-15:0.1-0.2.
2. positive pole piece of lithium-sulphur battery according to claim 1, it is characterized in that: described collector is aluminium foil or aluminium net.
3. positive pole piece of lithium-sulphur battery according to claim 1, it is characterized in that: described positive active material is S
8, organosulfur compound or Li
2S
n, 1≤n≤8 wherein.
4. positive pole piece of lithium-sulphur battery according to claim 3, it is characterized in that: organic sulfur compound is carbon sulphur polymer (C
2S
x)
m, wherein x is 2.5-50, and m 〉=2.
5. positive pole piece of lithium-sulphur battery according to claim 1, it is characterized in that: described conductive agent is carbon-based conductive agent.
6. positive pole piece of lithium-sulphur battery according to claim 5, it is characterized in that: described carbon-based conductive agent is conductive black, acetylene black or graphite powder.
7. the preparation method of any positive pole piece of lithium-sulphur battery of claim 1-6, the preparation mass percentage concentration is the aqueous gelatin solution of 1-6%; Add Cys or CYSTINE; Regulating the pH value with alkali lye is 7-10, and alkali lye is the aqueous solution of potassium hydroxide, NaOH or the lithium hydroxide of 0.5-1.0mol/L; Then add positive active material, conductive agent evenly mixes, wherein, the mass ratio of positive active material, conductive agent, gelatin binder and additive is 50-80:20-40:5-15:0.1-0.2, and the anode sizing agent of making is coated in collection liquid surface, makes positive pole piece of lithium-sulphur battery after the drying.
8. the preparation method of described positive pole piece of lithium-sulphur battery according to claim 7, it is characterized in that: the dry run of described positive electrode material slurry adopts boulton process or solvent dehydration seasoning.
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Cited By (1)
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|---|---|---|---|---|
| EP3706210A4 (en) * | 2017-10-31 | 2021-08-04 | Adeka Corporation | Slurry composition, and electrode using slurry composition |
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| KR101984716B1 (en) * | 2015-06-25 | 2019-05-31 | 주식회사 엘지화학 | Binder for lithium secondary battery, and electrode and lithium secondary battery comprising the same |
| CN114373988A (en) * | 2020-11-20 | 2022-04-19 | 扬州大学 | Lithium metal battery electrolyte containing amino acid additive and preparation method thereof |
| CN113321485B (en) * | 2021-05-28 | 2022-06-24 | 湖南恩捷前沿新材料科技有限公司 | Preparation method of chalcogenide solid electrolyte |
| WO2023218638A1 (en) * | 2022-05-13 | 2023-11-16 | 日本電信電話株式会社 | Secondary battery |
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| KR100477987B1 (en) * | 2002-09-11 | 2005-03-23 | 삼성에스디아이 주식회사 | Positive electrode for lithium-sulfur battery, and lithium-sulfur battery comprising same |
| ITRM20090161A1 (en) * | 2009-04-08 | 2010-10-09 | Jusef Hassoun | LITHIUM-SULFUR ACCUMULATORS |
| CN201536138U (en) * | 2009-08-25 | 2010-07-28 | 苏州宝时得电动工具有限公司 | Lithium-sulfur battery |
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