CN110416612A - A kind of novel electrolyte and battery of secondary lithium-sulfur battery - Google Patents
A kind of novel electrolyte and battery of secondary lithium-sulfur battery Download PDFInfo
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- CN110416612A CN110416612A CN201910676761.1A CN201910676761A CN110416612A CN 110416612 A CN110416612 A CN 110416612A CN 201910676761 A CN201910676761 A CN 201910676761A CN 110416612 A CN110416612 A CN 110416612A
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- lithium
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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
- H01M10/00—Secondary cells; Manufacture thereof
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a kind of novel electrolytes of secondary lithium-sulfur battery, including solvent, lithium salts and additive, the mass fraction of the additive in the electrolytic solution is 0.5%~15% comprising the combination of one or both of mononitriles, two nitriles, unsaturated nitrile and cyclic annular nitrile.Battery using above-mentioned electrolyte is also disclosed in the present invention.Additive in electrolyte provided by the invention uses nitriles substance, can be with positive electrode active materials complex reaction because nitriles substance contains tri- key of C ≡ N; form protective film; the dissolution and shuttle of polysulfide are hindered, thus improves cycle life, the application being commercialized.
Description
Technical field
The present invention relates to electrolyte more particularly to a kind of novel electrolytes of secondary lithium-sulfur battery.The present invention uses the electricity
Solve the battery of liquid.
Background technique
In known cell negative electrode material, the current potential of lithium metal is most negative, specific capacity is larger.In known positive electrode
In, the current potential of elemental sulfur is moderate, specific capacity is also larger.When the elemental sulfur of unit mass is completely transformed into S2-When generated theory
Specific capacity is up to 1675mAh/g.Lithium-sulfur cell is by lithium metal and elemental sulfur composition battery, and theoretical specific energy can achieve
2600Wh/kg is 3-5 times of current commercial lithium-ion batteries theory specific energy.After being made into battery core product, the reality of lithium-sulfur cell
Border energy density still can achieve the higher level of 300-900Wh/kg, and the energy density of lithium-ion-power cell is commercialized
Only 100-200Wh/kg.Even if changing the cathode of lithium ion battery into lithium metal, energy density is still substantially lower than lithium sulphur
Battery.And sulphur has many advantages, such as that environmental pollution is small, big, at low cost in nature reserves, and therefore, lithium-sulfur cell has very big
Technology attraction, be the important research direction of current energy storage field.
Typical lithium-sulfur cell generally uses elemental sulfur as anode, and metal lithium sheet is as cathode, its reaction mechanism is not
It is same as the ion deinsertion mechanism of lithium ion battery, but electrochemical mechanism.Negative reaction, which loses electronics for lithium, when electric discharge becomes lithium
Ion, it is that sulphur and lithium ion and electron reaction generate sulfide that anode, which reacts, and the potential difference of anode and negative reaction is lithium sulphur
Discharge voltage provided by battery.Under applied voltage effect, the anode and negative reaction of lithium-sulfur cell are inversely carried out, and are as filled
Electric process.But current lithium-sulfur cell cycle life and high rate performance are very poor, are not able to satisfy the demand of commercialization, it is main former
Because being the shuttle effect and the Li dendrite side reaction of cathode of positive more lithium sulfides.
Summary of the invention
One of the object of the invention is intended to provide a kind of novel electrolyte of secondary lithium-sulfur battery.
The two of the object of the invention are intended to provide a kind of lithium battery using above-mentioned electrolyte.
In order to realize the first purpose, the present invention the following technical schemes are provided: a kind of novel electrolyte of secondary lithium-sulfur battery,
Including solvent, lithium salts and additive, the mass fraction of the additive in the electrolytic solution is 0.5%~15% comprising mononitrile
The combination of one or both of class, two nitriles, unsaturated nitrile and cyclic annular nitrile.
The mononitrile includes but is not limited to one of Arneel SD and aromatic nitriles or combination.The Arneel SD includes but unlimited
In acetonitrile, butyronitrile etc.；The aromatic nitriles include but is not limited to benzonitrile etc..Two nitrile include but is not limited to succinonitrile, oneself
Dintrile etc..The unsaturated nitrile includes but is not limited to acrylonitrile etc..The ring-type nitrile includes but is not limited to pyrroles etc..
The solvent includes but is not limited to ethers, such as dimethyl ether (DME), 4- methyl-1,3- dioxolanes (DOL) etc..
As an embodiment of the present invention, the solvent is dimethyl ether (DME) and 4- methyl-1, and 3- dioxolanes (DOL) form,
The mass fraction of the two in the electrolytic solution is respectively 10%~90%.
The ingredient of the lithium salts is lithium hexafluoro phosphate (LiPF6), bis- (fluoroform sulphonyl) imine lithiums (LiTFSi), nitric acid
Lithium (LiNO3), the combination of one or more of bis- (fluorine sulphonyl) imine lithiums (LIFSI) and dioxalic acid lithium borate (LIBOB).No
The mass fraction of same compound in the electrolytic solution is different.Wherein, lithium hexafluoro phosphate (LiPF6) 10%~16%, bis- (fluoroforms
Alkane sulphonyl) imine lithium (LiTFSi) 0.2%~5%, bis- (fluorine sulphonyl) imine lithiums (LIFSI) 0.2%~5%, lithium nitrate
(LiNO3) 0.2%~5% and dioxalic acid lithium borate (LIBOB) 0.2%~5%, the above components content is its each comfortable electricity
Solve the mass fraction in liquid.
The second object of the present invention is achieved through the following technical solutions: a kind of lithium battery, specially lithium-sulfur cell, including
Anode, cathode, diaphragm and electrolyte, including solvent, lithium salts and additive, the mass fraction of the additive in the electrolytic solution are
0.5%~15% comprising the combination of one or both of mononitriles, two nitriles, unsaturated nitrile and cyclic annular nitrile.
The mononitrile includes but is not limited to one of Arneel SD and aromatic nitriles or combination.The Arneel SD includes but unlimited
In acetonitrile, butyronitrile etc.；The aromatic nitriles include but is not limited to benzonitrile etc..Two nitrile include but is not limited to succinonitrile, oneself
Dintrile etc..The unsaturated nitrile includes but is not limited to acrylonitrile etc..The ring-type nitrile includes but is not limited to pyrroles etc..
The solvent includes but is not limited to ethers, such as dimethyl ether (DME), 4- methyl-1,3- dioxolanes (DOL) etc..
As an embodiment of the present invention, the solvent is dimethyl ether (DME) and 4- methyl-1, and 3- dioxolanes (DOL) form,
The mass fraction of the two in the electrolytic solution is respectively 10%~90%.
The ingredient of the lithium salts is lithium hexafluoro phosphate (LiPF6), bis- (fluoroform sulphonyl) imine lithiums (LiTFSi), nitric acid
Lithium (LiNO3), the combination of one or more of bis- (fluorine sulphonyl) imine lithiums (LIFSI) and dioxalic acid lithium borate (LIBOB).No
The mass fraction of same compound in the electrolytic solution is different.Wherein, lithium hexafluoro phosphate (LiPF6) 10%~16%, bis- (fluoroforms
Alkane sulphonyl) imine lithium (LiTFSi) 0.2%~5%, bis- (fluorine sulphonyl) imine lithiums (LIFSI) 0.2%~5%, lithium nitrate
(LiNO3) 0.2%~5% and dioxalic acid lithium borate (LIBOB) 0.2%~5%, the above components content is its each comfortable electricity
Solve the mass fraction in liquid.
The anode is made of for anode sulphur powder, conductive agent, bonding agent.The cathode is lithium metal.The diaphragm is poly-
Propylene (PP) or polyethylene (PE).
The battery further includes outer packing, using aluminum plastic film, metal or plastics.
The beneficial effects of the present invention are:
1. the additive in electrolyte provided by the invention uses nitriles substance, because nitriles substance contains tri- key of C ≡ N,
Protective film can be formed with positive active material complex reaction, hinder the dissolution and shuttle of polysulfide, thus improve circulation
Service life, the application being commercialized.
2. electrolyte provided by the invention can be used for secondary lithium-sulfur battery, the circulation of secondary lithium-sulfur battery equally can be improved
Service life, the application being commercialized.
Specific embodiment
With reference to embodiment, claim of the invention is described in further detail, but do not constituted pair
Any restrictions of the invention, any limited times modification made in the claims in the present invention protection scope, still of the invention
In claims.
In embodiment of the present invention, solvent includes but is not limited to ethers, such as dimethyl ether (DME), 4- methyl-1,3- dioxy ring
Pentane (DOL) etc..As an embodiment of the present invention, the solvent is dimethyl ether (DME) and 4- methyl-1,3- dioxy ring penta
Alkane (DOL) composition, the mass fraction of the two in the electrolytic solution is respectively 10%~90%.The ingredient of lithium salts is lithium hexafluoro phosphate
(LiPF6), bis- (fluoroform sulphonyl) imine lithiums (LiTFSi), lithium nitrate (LiNO3), bis- (fluorine sulphonyl) imine lithiums (LIFSI) and
The combination of one or more of dioxalic acid lithium borate (LIBOB).The mass fraction of different compounds in the electrolytic solution is different.
Wherein, lithium hexafluoro phosphate (LiPF6) 10%~16%, it is bis- (fluoroform sulphonyl) imine lithiums (LiTFSi) 0.2%~5%, double
(fluorine sulphonyl) imine lithium (LIFSI) 0.2%~5%, lithium nitrate (LiNO3) 0.2%~5% and dioxalic acid lithium borate (LIBOB)
0.2%~5%, the above components content is its mass fraction respectively in the electrolytic solution.
Embodiment one
Lithium battery is made of anode, cathode, diaphragm, electrolyte and outer packing.Outer packing is aluminum plastic film.
Wherein, anode sulphur powder, conductive agent and bonding agent by being made of.Conductive agent is SUPER-P, and content is 3%, bonding agent
For PVDF, for content 3.5%, remaining is sulphur powder.
Cathode is lithium metal, and diaphragm PE, capacity is that 350mAh electrolyte is made of solvent, lithium salts and additive.Solvent,
The mass fraction of additive and lithium salts is as follows:
Solvent: DME/DOL=40%/40% (WT)
Additive: acetonitrile 3%
Lithium salts: LiPF613%, LiTFSi 1% and LINO33%
Gained lithium-sulfur cell is recycled through 0.2C, and charge and discharge 200 times, capacity keeps 80%.
Embodiment two
Unlike embodiment one:
Solvent: DME/DOL=40%/40% (WT)
Additive: adiponitrile 3%
Lithium salts: LiPF613%, LiTFSi 1% and LINO33%
Gained lithium-sulfur cell is recycled through 0.3C, and charge and discharge 250 times, capacity keeps 80%.
Embodiment three
Unlike embodiment one:
Solvent: DME/DOL=40%/40% (WT)
Additive: acrylonitrile 3%
Lithium salts: LiPF613%, LiTFSi 1% and LINO33%.
Gained lithium battery is recycled through 0.5C, and charge and discharge 300 times, capacity keeps 80%.
Example IV
Unlike embodiment one:
Solvent: DME/DOL=40%/40% (WT)
Additive: pyrroles 3%
Lithium salts: LiPF613%, LiTFSi 1% and LiNO33%.
Gained lithium battery is recycled through 0.8C, and charge and discharge 350 times, capacity keeps 80%.
Embodiment five
Unlike embodiment one:
Solvent: DME/DOL=35%/35% (WT)
Additive: pyrroles 15%
Lithium salts: LiPF611%, LiTFSi 1% and LiNO33%.
Gained lithium battery is recycled through 0.8C, and charge and discharge 350 times, capacity keeps 85%.
Claims (10)
1. a kind of novel electrolyte of secondary lithium-sulfur battery, including solvent, lithium salts and additive, characterized in that the additive
Mass fraction in the electrolytic solution is 0.5%~15%, including in mononitriles, two nitriles, unsaturated nitrile and cyclic annular nitrile
One or two kinds of combinations.
2. the novel electrolyte of secondary lithium-sulfur battery according to claim 1, characterized in that the mononitrile includes but is not limited to
One of Arneel SD and aromatic nitriles or combination；Two nitrile includes but is not limited to succinonitrile or adiponitrile；The unsaturation
Nitrile includes but is not limited to acrylonitrile；The ring-type nitrile includes but is not limited to pyrroles.
3. the novel electrolyte of secondary lithium-sulfur battery according to claim 2, characterized in that the Arneel SD includes but unlimited
In one or both of acetonitrile and butyronitrile；The aromatic nitriles include but is not limited to benzonitrile.
4. the novel electrolyte of secondary lithium-sulfur battery according to claim 1, characterized in that the solvent includes but is not limited to
Ethers.
5. the novel electrolyte of secondary lithium-sulfur battery according to claim 4, characterized in that the solvent is by dimethyl ether and 4-
Methyl-1,3- dioxolanes composition, the mass fraction of the two in the electrolytic solution is respectively 10%~90%.
6. the novel electrolyte of secondary lithium-sulfur battery according to claim 1, characterized in that the ingredient of the lithium salts is hexafluoro
Lithium phosphate, bis- (fluoroform sulphonyl) imine lithiums, lithium nitrate, bis- (fluorine sulphonyl) one of imine lithiums and dioxalic acid lithium borate.
7. the novel electrolyte of secondary lithium-sulfur battery according to claim 6, characterized in that the lithium salts is following quality point
Several compounds: lithium hexafluoro phosphate 10%~16%, bis- (fluoroform sulphonyl) imine lithiums 0.2%~5%, bis- (fluorine sulphonyl) are sub-
Amine lithium 0.2%~5%, lithium nitrate 0.2%~5% or dioxalic acid lithium borate 0.2%~5%.
8. a kind of lithium battery, including anode, cathode, diaphragm and electrolyte, including solvent, lithium salts and additive, characterized in that institute
Stating the mass fraction of additive in the electrolytic solution is 0.5%~15% comprising mononitriles, two nitriles, unsaturated nitrile and ring
The combination of one or both of shape nitrile.
9. lithium battery according to claim 8, characterized in that the mononitrile includes but is not limited in Arneel SD and aromatic nitriles
A kind of or combination；Two nitrile includes but is not limited to succinonitrile or adiponitrile；The unsaturated nitrile includes but is not limited to propylene
Nitrile；The ring-type nitrile includes but is not limited to pyrroles.
10. lithium battery according to claim 8 or claim 9, characterized in that the anode is anode by sulphur powder, conductive agent, bonding agent
Composition；The cathode is lithium metal；The diaphragm is polypropylene or polyethylene.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910676761.1A CN110416612A (en) | 2019-07-25 | 2019-07-25 | A kind of novel electrolyte and battery of secondary lithium-sulfur battery |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111244492A (en) * | 2020-02-29 | 2020-06-05 | 同济大学 | High-specific-energy primary lithium-sulfur battery and application thereof |
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