CN109411817A - A kind of lithium ion battery or lithium-sulfur cell electrolyte - Google Patents
A kind of lithium ion battery or lithium-sulfur cell electrolyte Download PDFInfo
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- CN109411817A CN109411817A CN201811275581.4A CN201811275581A CN109411817A CN 109411817 A CN109411817 A CN 109411817A CN 201811275581 A CN201811275581 A CN 201811275581A CN 109411817 A CN109411817 A CN 109411817A
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- sulfur cell
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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
- H01M10/052—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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M10/42—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
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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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 invention discloses a kind of lithium ion battery or lithium-sulfur cell electrolyte, and it includes organic supermolecular additives；The organic supermolecular has the ring inner hole structure of the subspace containing short of electricity.Lithium ion battery or lithium-sulfur cell electrolyte make full use of the short of electricity subspace of organic supermolecular to capture the anion of electron rich in electrolyte, anion and supramolecular structured synthetic macromolecule, the ionization of lithium salts is promoted, conductivity improves, simultaneously, the migration of anion is restricted, and the transport number of lithium ion becomes larger, and the high rate performance of lithium ion battery or lithium-sulfur cell may be significantly promotion.
Description
Technical field
The present invention relates to a kind of lithium ion battery or lithium-sulfur cell electrolyte more particularly to a kind of utilize to have containing short of electricity
The organic supermolecular of the ring inner hole structure of subspace is as lithium ion battery or lithium-sulfur cell additive, effectively enhancing conductance
Rate improves lithium ion transference number and promotes battery high rate performance；Belong to technical field of lithium batteries.
Background technique
The mankind rely on traditional fossil energy development for a long time, start to be faced with many problems (shortage of resource and environment
Pollution), seek to can satisfy human demand and the new energy of sustainable development is very urgent.In new energy, lithium battery has
More clear advantage.Lithium battery has been obtained in our daily life field and is widely applied.The height of society now
Speed development proposes more requirements to lithium battery.Many lithium ion battery enterprises have turned to tertiary cathode material and silicon-carbon
Negative electrode material, while many enterprises start to be laid out the fields such as lithium-sulfur cell.In lithium ion battery, NCM (811) high-nickel material and
Although the promotion of entire battery energy density may be implemented, the charging under high current still faces very big silicon-carbon cathode
The problem of.The fast development of new-energy automobile industry, to the fast charge ability of lithium battery, more stringent requirements are proposed.Power-performance
Promotion can by using the better positive and negative pole material of high rate performance, reduce electrode coating weight, reduce compacted density, battery
The methods of structure design is realized.Meanwhile electrolyte influences also very greatly the performance of fast charge lithium ion battery.Lithium battery electrolysis
Liquid plays the role of transmitting ion in the battery.Generally it is made of lithium salts and organic solvent.Different electrolyte constituents,
The conductivity and lithium ion transference number of electrolyte have very big difference, to have an impact to the performance of entire battery.Electrolyte
Conductivity be to be collectively constituted by lithium ion and anion.Li+Transport number t+It is closer big, then migrated in electrolyte
Li+Accounting is higher, then electrolyte charge efficiency is transmitted between positive and negative anodes will be higher.Studies have shown that works as Li+Migration
Number is increased to about 0.7 or so, can be obviously improved the rate capability of lithium battery.
Therefore, influence highly significant of the electrolyte properties to battery high rate performance, the optimization pair of electrolyte composition and performance
The high rate performance for improving lithium battery has very important significance.
Summary of the invention
For lithium ion battery in the prior art or lithium-sulfur cell electrolyte, that there are conductivity is low low with lithium ion transference number
The problems such as, the purpose of the invention is to provide a kind of organic supermoleculars with the ring inner hole structure with the subspace containing short of electricity
It, can be bright by adding a small amount of organic supermolecular in the electrolytic solution as lithium ion battery or lithium-sulfur cell electrolysis additive
It is aobvious to improve conductivity, the migration of anion is limited, the transport number of lithium ion is increased, improves lithium ion or lithium-sulfur cell battery
High rate performance.
In order to achieve the above technical purposes, the present invention provides a kind of lithium ion battery or lithium-sulfur cell electrolyte, packets
Additive containing organic supermolecular；The organic supermolecular has the ring inner hole structure of the subspace containing short of electricity.
Organic supermolecular of the invention has the ring inner hole structure of the subspace containing short of electricity.Its short of electricity subspace can be effective
The anion for capturing electron rich in electrolyte, is substantially reduced the transport number of anion, and the transport number of lithium ion becomes larger,
Meanwhile anion and supramolecular structured synthetic macromolecule, the ionization of lithium salts electrolyte can be promoted, conductivity improves, therefore,
Addition has the organic supermolecular of the ring inner hole structure of the subspace containing short of electricity in electrolyte, so that lithium ion battery or lithium sulphur electricity
The available promotion of the high rate performance in pond.
Preferred scheme, the pore size of the ring inner hole structure of the organic supermolecular are 0.1nm~20nm.It is organic super
The ring inner hole structure of molecule has the ring inner hole in suitable aperture, can effectively capture anion, and aperture is too small, and anion is difficult
To enter ring inner hole, and aperture is excessive, then anion cannot be by organic supermolecular stable bond.
The ring inner hole structure of preferred scheme, the subspace containing short of electricity is made of cyclic conjugated system.Cyclic conjugated body
System is singly-bound and the cyclic structure that double bond is alternatively formed.Conjugated system shows short of electricity daughter, cricoid conjugated system electronics trip
Delocalization is big, shows higher electron deficient, is more advantageous in conjunction with anion.
Preferred scheme, the cyclic conjugated system contain polar substituent group.Polar substituent group is mainly electron deficient
Highly polar substituent group, such as cyano, nitro can be improved machine supermolecule to the combination stability of anion.
Preferred scheme, the organic supermolecular have 1 structure of formula.Its synthetic method can be with bibliography: Lee, S.；
Chen,C.-H.；Flood,A.H.Nat.Chem.2013,5(8),704-710.
Preferred scheme, the mass percent concentration of the organic supermolecular additive in the electrolytic solution be 0.001~
5%；Preferably 1~5%.Model of the mass percent concentration of organic supermolecular additive in the electrolytic solution 0.001~5%
Certain promotion conductivity is all had in enclosing, and is limited the migration of anion, is increased the effect of the transport number of lithium ion, and concentration is got over
Greatly, effect is more obvious.
Preferred scheme, lithium ion battery or lithium-sulfur cell electrolyte also include lithium salts electrolyte and organic solvent.
More preferably scheme, the lithium salts electrolyte is the inorganic lithium salt of this field routine, common such as bis- (fluoroforms
Alkane sulphonyl) imine lithium LiN (SO2CF3)2, double fluorine sulfimide lithium LiN (SO2F)2, double trifluorosulfonimide lithium LiN (SO2F3)2、
Lithium hexafluoro phosphate LiPF6, lithium perchlorate LiClO4, LiBF4 LiBF4, hexafluoroarsenate lithium LiAsF6, di-oxalate lithium borate
LiBC4O8, trifluoromethyl sulfonic acid lithium (LiCF3SO3) etc..
More preferably scheme, the solvent is this field common organic solvent, common such as ethers, sulfone class, carbonic ester
Class (cyclic annular and chain), carboxylate etc..Lithium-ion battery electrolytes generally use carbonates (cyclic annular and chain), lithium sulphur electricity
Pond electrolyte generally uses ethers, sulfone class.
Compared with the prior art, bring of the present invention the utility model has the advantages that
For fast charge problem existing for existing lithium ion battery or lithium-sulfur cell, technical solution of the present invention will have for the first time
The organic supermolecular of special molecular structure improves such case as electrolysis additive.Organic oversubscription that the present invention uses
Son has the ring inner hole structure of the subspace containing short of electricity, can make full use of the characteristic to capture lithium ion battery or lithium-sulfur cell
Anion in electrolyte, is combined into macromolecular, and so as to promote the ionization of lithium salts in the electrolytic solution, conductivity becomes larger, together
When lithium ion transport number improve, charge transfer charge efficiency gets higher, the high rate performance enhancing of battery.
Specific embodiment
In order to preferably explain the present invention, in order to understand, below by specific embodiment, to the solution of the present invention
And technical effect is described in detail.Obviously, described embodiments are some of the embodiments of the present invention, rather than whole realities
Apply example.Based on the embodiments of the present invention, those of ordinary skill in the art are obtained without creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.
Comparative example 1
Lithium-ion battery electrolytes formula common in the art exemplified below:
(1) by cyclic carbonate solvents ethylene carbonate (EC) and linear carbonate solvent diethyl carbonate (DEC), carbon
Sour methyl ethyl ester (EMC) mixes according to volume ratio 1:1:1.
(2) under room temperature, by lithium salts LiPF6It is dissolved in solvent obtained in step 1, so that concentration is 1.0mol/L,
It stirs evenly, obtains general electrolytic liquid.
(3) conductivity and lithium ion transference number of the electrolyte are tested.Lithium ion transference number is 0.4.Conductivity is
12.45mS/cm。
Comparative example 2
Lithium-sulfur cell electrolyte prescription common in the art exemplified below:
(1) it by 1,3 dioxolanes of solvent ethylene glycol dimethyl ether DME and solvent, is mixed according to volume ratio 1:1.
(2) under room temperature, lithium salts bis trifluoromethyl sulfimide lithium LiTFSI is dissolved in molten obtained in step 1
Agent stirs evenly so that concentration is 1.0mol/L, obtains general electrolytic liquid.
(3) conductivity and lithium ion transference number of the electrolyte are tested.Lithium ion transference number is 0.4.Conductivity is
12.47mS/cm。
Following example 1~4 enumerate common in the prior art lithium-ion battery electrolytes or lithium-sulfur cell electrolyte
Supermolecule additive is added in formula.
Embodiment 1
(1) by cyclic carbonate solvents ethylene carbonate (EC) and linear carbonate solvent diethyl carbonate (DEC), carbon
Sour methyl ethyl ester (EMC) mixes according to volume ratio 1:1:1.
(2) under room temperature, by lithium salts LiPF6It is dissolved in solvent obtained in step 1, so that concentration is 1.0mol/L,
It stirs evenly, while supermolecule CS is added as additive.
(3) mass percent shared in lithium battery electrolytes of supermolecule CS is 0.1wt%.
(4) conductivity and lithium ion transference number of the electrolyte are tested.Lithium ion transference number is 0.44.Conductivity is higher than
Conductivity in comparative example 1 is 13.21mS/cm.
Embodiment 2
(1) by cyclic carbonate solvents ethylene carbonate (EC) and linear carbonate solvent diethyl carbonate (DEC), carbon
Sour methyl ethyl ester (EMC) mixes according to volume ratio 1:1:1.
(2) under room temperature, by lithium salts LiPF6It is dissolved in solvent obtained in step 1, so that concentration is 1.0mol/L,
It stirs evenly, while supermolecule CS is added as additive.
(3) mass percent shared in the electrolytic solution of supermolecule CS is 2wt%.
(4) conductivity and lithium ion transference number of the electrolyte are tested.Lithium ion transference number is 0.6.Conductivity be higher than pair
Conductivity in ratio 1 is 15mS/cm.
Embodiment 3
(1) by cyclic carbonate solvents ethylene carbonate (EC) and linear carbonate solvent diethyl carbonate (DEC), carbon
Sour methyl ethyl ester (EMC) mixes according to volume ratio 1:1:1.
(2) under room temperature, by lithium salts LiPF6It is dissolved in solvent obtained in step 1, so that concentration is 1.0mol/L,
It stirs evenly, while supermolecule CS is added as additive.
(3) mass percent shared in the electrolytic solution of supermolecule CS is 5wt%.
(4) conductivity and lithium ion transference number of the electrolyte are tested.Conductivity is higher than the conductivity in comparative example 1.Lithium
Transference number of ions is 0.7.Conductivity is higher than the conductivity in comparative example 1, is 16mS/cm.
Embodiment 4
(4) it by 1,3 dioxolanes of solvent ethylene glycol dimethyl ether DME and solvent, is mixed according to volume ratio 1:1.
(5) under room temperature, lithium salts bis trifluoromethyl sulfimide lithium LiTFSI is dissolved in molten obtained in step 1
Agent stirs evenly, while supermolecule CS is added as additive so that concentration is 1.0mol/L.
(6) mass percent shared in the electrolytic solution of supermolecule CS is 4wt%.
(7) conductivity and lithium ion transference number of the electrolyte are tested.Conductivity is higher than the conductivity in comparative example 2.Lithium
Transference number of ions is 0.65.Conductivity is higher than the conductivity in comparative example 1, is 15.32mS/cm.
1 comparative example 1~2 of table and Examples 1 to 4 electrolyte composition table
Claims (9)
1. a kind of lithium ion battery or lithium-sulfur cell electrolyte, it is characterised in that: include organic supermolecular additive；It is described organic
Supermolecule has the ring inner hole structure of the subspace containing short of electricity.
2. a kind of lithium ion battery according to claim 1 or lithium-sulfur cell electrolyte, it is characterised in that: described organic super
The pore size of the ring inner hole structure of molecule is 0.1nm~20nm.
3. a kind of lithium ion battery according to claim 1 or lithium-sulfur cell electrolyte, it is characterised in that: described to contain short of electricity
The ring inner hole structure of subspace is made of cyclic conjugated system.
4. a kind of lithium ion battery according to claim 3 or lithium-sulfur cell electrolyte, it is characterised in that: described cyclic annular total
Yoke system contains polar substituent group.
5. a kind of lithium ion battery according to any one of claims 1 to 4 or lithium-sulfur cell electrolyte, it is characterised in that:
The organic supermolecular has 1 structure of formula:
6. a kind of described in any item lithium ion batteries or lithium-sulfur cell electrolyte according to claim 1~5, it is characterised in that:
The mass percent concentration of the organic supermolecular additive in the electrolytic solution is 0.001~5%.
7. a kind of described in any item lithium ion batteries or lithium-sulfur cell electrolyte according to claim 1~5, it is characterised in that:
It also include lithium salts electrolyte and organic solvent.
8. a kind of lithium ion battery according to claim 7 or lithium-sulfur cell electrolyte, it is characterised in that: the lithium salts electricity
Solving matter includes bis- (fluoroform sulphonyl) imine lithiums, double fluorine sulfimide lithiums, double trifluorosulfonimide lithiums, lithium hexafluoro phosphate, height
At least one of lithium chlorate, LiBF4, hexafluoroarsenate lithium, di-oxalate lithium borate, trifluoromethyl sulfonic acid lithium.
9. a kind of lithium ion battery according to claim 7 or lithium-sulfur cell electrolyte, it is characterised in that: when electrolyte is
When lithium-ion battery electrolytes, the solvent includes at least one of ethers, sulfone class, carbonates, carboxylate；
When electrolyte is lithium-sulfur cell electrolyte, the solvent includes at least one of ethers, sulfone class.
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