CN109256587A - Lithium metal secondary battery electrolyte and the lithium metal secondary battery for using the electrolyte - Google Patents
Lithium metal secondary battery electrolyte and the lithium metal secondary battery for using the electrolyte Download PDFInfo
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- CN109256587A CN109256587A CN201810791112.1A CN201810791112A CN109256587A CN 109256587 A CN109256587 A CN 109256587A CN 201810791112 A CN201810791112 A CN 201810791112A CN 109256587 A CN109256587 A CN 109256587A
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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
- H01M10/42—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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
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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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Abstract
The invention discloses a kind of lithium metal secondary battery electrolyte containing sulfur-bearing conjugated structure additive and use the lithium metal secondary battery of the electrolyte.The lithium metal secondary battery is made of with electrolyte lithium salts, nonaqueous solvents and sulfur-bearing conjugated structure additive, and the quality of the sulfur-bearing conjugated structure additive is 0.01-100mg/mL relative to the ratio of nonaqueous solvents volume.The present invention can effectively inhibit the growth of Li dendrite in lithium metal secondary battery by the electrolyte of special additive ingredient of the selection containing specific quantity, to play the role of improving lithium metal secondary battery cycle performance and safety.
Description
Technical field
The invention belongs to battery technology fields, and in particular to a kind of lithium metal containing sulfur-bearing conjugated structure additive is secondary
Battery electrolytic solution and the lithium metal secondary battery for having used the electrolyte.
Background technique
In recent years, the haze of environmental pollution and its initiation has become the major hidden danger for threatening national health, wherein quite
Burning of a part pollution from fossil fuel.To solve the environmental problem that fossil fuel generates, various green energy resources are gradually
Come into the visual field of people.Wherein, green energy resource lithium battery due to the features such as its energy density is high, self discharge is small energy storage,
Communication and traffic and transport field are used widely.In lithium battery, traditional negative electrode material graphite is because of lower capacity density
(372mA h g-1), the trend that restricted lithium battery further develops.Therefore, it is close to seek higher energy one after another by enterprise and scholars
The negative electrode material of degree.
A kind of negative electrode material (3860mA h g of the lithium metal as high capacity density-1), in serondary lithium battery, lithium air electricity
There is very big application potential in pond.But lithium metal works as lithium also due to its chemical property vivaciously has very big safety problem
It is influenced to be easy to growth dendrite puncture diaphragm by concentration polarization and electric field when deposition, causes a series of safety problems.
In order to enhance the safety of the lithium metal secondary battery with lithium anode, current method has focused largely on lithium
The modification of metal surface, i.e., cathode of lithium surface formed one layer it is stable, there is height to lead the interface protective film of lithium ion ability
(SEI (Solid electrolyte interphase) film).As a kind of method be formed in situ in lithium electrode surface it is inorganic
The SEI film rich in LiF for leading ion energy height, high mechanical strength accelerates the deposition solvability of lithium and inhibits lithium dendrite growth,
For example add fluorinated ethylene carbonate (Angew.Chem.Int.Ed.2018,57,1-6) etc. in the electrolytic solution to be formed rich in F
The inorganic SEI film of element, thus stablize cathode of lithium, dendrite inhibition growth.For another example, another method is gone using organic film
Lithium metal is protected, for example forms protective film dendrite inhibition in metallic lithium surface using compounds such as pyrroles and grows, enhancing anode is steady
Qualitative (patent document: CN102315420A).But method mentioned above all can not fundamentally solve concentration ladder in solution
Spend caused by nonuniform deposition, while be formed by film also be easy with metal surface deformation deform, current density compared with
It is difficult to preferably protect anode surface when big, to generate dendrite.Namely the growth result for inhibiting Li dendrite can only be played, without
It can fundamentally go to prevent the formation of Li dendrite.
In addition, being the macromolecular additive that other complexity are added there are also method, the insertion eliminating efficiency of lithium is promoted, thus anti-
The only short-circuit behavior under high current density.However the synthesis of the additive molecule of this complexity is difficult, preparation process is cumbersome, and cost is high
It is expensive, it is very difficult to practical application (patent document: CN108054429A).
Summary of the invention
In order to fundamentally overcome the problems, such as existing lithium metal surface dendritic growth, the present invention provides one kind and contains small point
Son sulfur-bearing conjugated structure additive lithium metal secondary battery electrolyte and used the lithium metal of the electrolyte secondary
Battery, can prevent at lower cost, which can fill lithium metal battery, generates dendrite.
Of the invention is a kind of lithium metal secondary battery electrolyte, is conjugated and ties containing lithium salts, nonaqueous solvents and sulfur-bearing
Structure additive, wherein the concentration of the lithium salts is 0.5-10mol/L, and the quality of sulfur-bearing conjugated structure additive is relative to non-aqueous
The ratio of solvent volume is 0.01-100mg/mL.
In the lithium metal secondary battery electrolyte of the invention, it is preferred that the lithium salts is LiPF6, LiTFSI and
LiClO4One of or it is a variety of.
In the lithium metal secondary battery electrolyte of the invention, as nonaqueous solvents, 1,3-dioxolane can be selected from
(DOL), glycol dimethyl ether (DME), ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), carbonic acid third
One of enester (PC) is a variety of.
In the lithium metal secondary battery electrolyte of the invention, it is preferred that the nonaqueous solvents is 1,3- dioxy penta
The mixing of the mixed solvent of ring (DOL) and glycol dimethyl ether (DME), ethylene carbonate (EC) and diethyl carbonate (DEC) is molten
Agent, the mixed solvent of ethylene carbonate (EC) and dimethyl carbonate (DMC) or propene carbonate (PC).
In the lithium metal secondary battery electrolyte of the invention, it is preferred that the sulfur-bearing conjugated structure additive is
One of carbonyl sulfur class, thioether class and sulfone class are a variety of.
In the lithium metal secondary battery electrolyte of the invention, it is preferred that the sulfur-bearing conjugated structure additive is
Dithiooxamide, thioacetamide, thiocarbamide, thiophene, carbon disulfide, diphenyl sulfide or thiambutosine.
In the lithium metal secondary battery electrolyte of the invention, it is preferred that the sulfur-bearing conjugated structure additive is not
Contain phenyl ring.
In the lithium metal secondary battery electrolyte of the invention, it is preferred that the sulfur-bearing conjugated structure additive
Quality is 0.05-50mg/mL relative to the ratio of nonaqueous solvents volume.
In the lithium metal secondary battery electrolyte of the invention, it is preferred that the sulfur-bearing conjugated structure additive
Quality is 0.1-10mg/mL relative to the ratio of nonaqueous solvents volume.
Another aspect of the present invention is a kind of lithium metal secondary batteries, have lithium metal secondary battery of the invention and use
Electrolyte, the positive electrode, the negative electrode and the separator.
In the present invention, the active component in sulfur-bearing conjugated structure additive is the molecule that sulphur head base is connected with conjugated structure
Segment, entire effect partial exist using molecular forms or are connected in macromolecular and substrate as active group.Further, sulphur head
In metallic lithium surface adsoption catalysis can occur for base in the case where conjugated structure is stablized, and promote the deposition of lithium and play the role of leveling.Its
Middle sulphur head base is adsorbed on metallic lithium surface, and subsequent conjugation group containing double bonds is stablized sulphur head base and formed with other organic structures
Solvophilic ingredient gives certain solvability.Sulphur head base gives the growing point of lithium deposition, reduces the energy barrier of its growth, this point
Different from performance of the sulfur-containing additive in traditional copper, zinc plating.The sulfur-bearing conjugated structure additive is suitable for ethers, ester
A variety of electrolyte systems such as class, ionic liquid and gel electrolyte, i.e., in liquid, condensed state lithium secondary battery and lithium-air battery
In have application.
Detailed description of the invention
Fig. 1 shows scanning electron microscope (SEM) figure without the lithium piece of any processing under different amplification.
Fig. 2 a is the scanning electron microscope (SEM) photograph of the lithium electrode surface in conventional ethers electrolyte after long circulating；Fig. 2 b is normal
Under warm (25 DEG C), long circulating performance curve of the lithium lithium Symmetrical cells in conventional ethers electrolyte.The electricity of charging and electric discharge
Current density is 2mA cm-2, the amount control of the lithium metal of circulation is 1mAh cm-2。
Fig. 3 a is the scanning electron microscope of the lithium electrode surface in the ethers electrolyte containing dithiooxamide after long circulating
Figure.Fig. 3 b is the sulfur-bearing conjugated structure additive using dithiooxamide as electrolyte, and under room temperature (25 DEG C), lithium lithium is symmetrical
Long circulating performance curve of the battery in the ethers electrolyte containing dithiooxamide.Charging and the current density discharged are
2mA cm-2, the amount control of the lithium metal of circulation is 1mAh cm-2。
Fig. 4 a is that lithium lithium Symmetrical cells recycle 20 weeks in conventional electrolyte one step ahead, after generating Li dendrite, dismantles electricity
Two lithium pieces are taken out in pond, later again in the ethers electrolyte containing dithiooxamide assembled battery and recycle 20 weeks after
The scanning electron microscope (SEM) photograph of lithium electrode surface.Fig. 4 b and Fig. 4 c are that the lithium lithium Symmetrical cells after dismantling assembling again are not containing respectively
Long circulating performance in the ethers electrolyte of dithiooxamide and the ethers electrolyte containing dithiooxamide.Charging and
The current density of electric discharge is 2mA cm-2, the amount control of the lithium metal of circulation is 1mAh cm-2。
Specific embodiment
Description of specific embodiments of the present invention below.
One embodiment of the present invention is a kind of lithium metal secondary battery electrolyte, contains following lithium salts, non-aqueous
Agent and sulfur-bearing conjugated structure additive.
(1) lithium salts
As lithium salts, LiCl, LiF, LiFSI, LiPF can be selected from6、LiTFSI、LiClO4One of or it is a variety of, preferably
It is to be selected from LiPF6、LiTFSI、LiClO4One of or it is a variety of.When use LiPF6、LiTFSI、LiClO4When, the present invention in
The surface smoothness of cathode of lithium and the cycle performance of lithium lithium Symmetrical cells are substantially better than other lithium salts.
The additive amount of the lithium salts is 0.5-10mol/L, preferably 1-5mol/L, further preferably 1-3mol/L.When
When the additive amount of the lithium salts is lower than 1mol/L, it will lead to the lithium ion mobility ability decline of solution, influence electrical conductivity of solution, from
And the cycle performance under lithium battery high current density is influenced, when the additive amount of the lithium salts is higher than 10mol/L, can be confined to
The solubility of lithium salts, in addition, the viscosity of electrolyte becomes very high, to affect electrolysis again when the adding too much of lithium salts
Liquid further will affect the cycle performance of battery to the wellability of cathode of lithium.By using the above-mentioned lithium salts of specific quantity, the present invention
The growth for inhibiting Li dendrite improves the flatness on cathode of lithium surface, further improves the cycle life of lithium battery.
(2) nonaqueous solvents
As nonaqueous solvents, 1,3-dioxolane (DOL), glycol dimethyl ether (DME), ethylene carbonate can be selected from
(EC), one of diethyl carbonate (DEC), dimethyl carbonate (DMC), propene carbonate (PC) or a variety of, preferably 1,3-
The mixed solvent of dioxolanes (DOL) and glycol dimethyl ether (DME), ethylene carbonate (EC) and diethyl carbonate (DEC)
Mixed solvent, the mixed solvent of ethylene carbonate (EC) and dimethyl carbonate (DMC) or propene carbonate (PC).When use 1,3-
When the mixed solvent of dioxolanes (DOL) and glycol dimethyl ether (DME), the surface smoothness of lithium is high in the present invention, lithium lithium pair
Battery is claimed to have longest cycle life.
The volume ratio of mixed solvent is 1:5-5:1, preferably 1:1, when the 1,3-dioxolane for the use of volume ratio being 1:1
(DOL) and when the mixed solvent of glycol dimethyl ether (DME), inhibit the effect of Li dendrite best in the present invention, the surface of lithium is most
To be smooth, the cycle life highest of lithium lithium Symmetrical cells.
(3) sulfur-bearing conjugated structure additive
It, can be for selected from one of carbonyl sulfur class, thioether class or a variety of, preferably as sulfur-bearing conjugated structure additive
It is to be selected from one of carbonyl sulfur class, thioether class and sulfone class or a variety of, most preferably carbonyl sulfur class.Wherein, the preferably described sulfur-bearing
Conjugated structure additive does not contain phenyl ring.When using carbonyl sulfur class, in the present invention, cathode of lithium obtained one it is more smooth
Surface without dendrite, and the cycle performance of lithium lithium Symmetrical cells has obtained big promotion.It is conjugated when using the sulfur-bearing containing phenyl ring
When structural additives, it will lead to the surface more out-of-flatness of cathode of lithium, there is the protrusion of height, in subsequent further cyclic process
In, the behaviors such as short circuit are easy to cause, the cycle life of lithium lithium Symmetrical cells is reduced.
As carbonyl sulfur class, carbon disulfide, thiocarbamide, dithiooxamide, thioacetamide, thiambutosine etc. can be enumerated.
As thioether class, thiophene, diphenyl sulfide etc. can be enumerated.
As the additive amount of sulfur-bearing conjugated structure additive, the volume relative to the nonaqueous solvents is 0.01-100mg/
ML, preferably 0.05-50mg/mL, further preferably 0.1-10mg/mL.When the addition of the sulfur-bearing conjugated structure additive
When amount is lower than 0.01mg/mL, the knot of leveling cathode of lithium surface topography well can not be had because the concentration of additive is too low
Fruit, so that the effect for inhibiting Li dendrite to generate is not achieved, when the additive amount of the sulfur-bearing conjugated structure additive is higher than 100mg/
When mL, then it can be confined to the influence of additive solubility, to increase the viscosity of electrolyte and influence lithium by electrolyte
Wetting ability increases cost in addition, will cause the waste of additive again.By using the above-mentioned sulfur-bearing conjugated structure of specific quantity
Additive, the present invention have successfully obtained the smooth cathode of lithium without dendrite, have largely improved following for lithium battery
The ring service life.
(4) other additives
Other can also be added as needed in lithium metal secondary battery electrolyte of the invention commonly used in the art to add
Add agent, such as lithium nitrate, lithium sulfide, fluorinated ethylene carbonate, vinylene carbonate etc..
Another embodiment of the invention is a kind of lithium metal secondary battery, has above-mentioned lithium metal two of the invention
Primary cell electrolyte, following the positive electrode, the negative electrode and the separators.
(1) positive
Anode is the electrode in anode current collector with positive electrode active material layer.As in positive electrode active material layer
Positive active material, the substance that can absorb and release lithium ion during charge and discharge, such as layered-type lithium manganese can be used
Hydrochlorate such as LiMnO2Or LixMn2O4(0 < x < 2), spinel type lithium manganate, LiCoO2、LiNiO2, be wherein present in above-mentioned chemical combination
A part of transition metal in object is by the substance of other metal replacements, olivine compound such as LiFePO4And LiMnPO4、
Li2MSiO4(M is selected from least one of Mn, Fe and Co), activity are nonmetallic such as S, I2And its various active load forms etc..
They can be used alone or are used in a manner of two or more combinations.
(2) cathode
Cathode is lithium piece or the carrier containing lithium, such as nickel foam, foam copper carrier.
(3) diaphragm
Any diaphragm can be used, if its inhibit positive electrode and negative electrode contact, make electric charge carrier can pass through and
There is durability in electrolyte.Specific material suitable for diaphragm may include that polyolefin such as polypropylene or polyethylene kind are micro-
Pore membrane, cellulose, polyethylene terephthalate, polyimides, polyvinylidene fluoride etc..They can be used as such as porous
The form of film, fabric or non-woven fabrics uses.
Lithium metal secondary battery electrolyte according to the present invention and the gold for having used the lithium metal secondary battery electrolyte
Belong to lithium secondary battery, the result tested by charge-discharge test, SEM is it is found that lithium metal secondary battery electrolyte of the invention makes
Lithium an- ode surfacing fundamentally solves the problems, such as Li dendrite without protrusion, improves the cycle life of lithium battery.It fills
Discharge test and SEM test are as follows:
Charge-discharge test: the generation of the lithium battery as caused by Li dendrite is characterized using lithium lithium Symmetrical cells recognized within the industry
Short-circuit behavior, and then influence the cycle life problem of battery.Test condition are as follows: using blue electric battery test system, when carrying out long
Between charge and discharge cycles test, until short circuit occurs for battery, circulation time for having carried out when short circuit occurs for record battery.Charging
And the current density of electric discharge is 2mA cm-2, the amount control of the lithium metal of circulation is 1mAh cm-2, test temperature control is 25
℃。
SEM test: the observation of the surface topography of lithium is carried out using the Hitachi S-4800 scanning electron microscope of Japan's production, is surveyed
Examination voltage is 10kV, and electric current is 10 microamperes, obtains the evaluation of leveling effect, evaluation criterion are as follows: ◎: surfacing by observation result
It spends excellent；Zero: surface smoothness is good；△: surface smoothness is bad；×: surface smoothness is poor.
Embodiment
With reference to embodiments, the present invention is further explained.But these embodiments be only limitted to illustrate the present invention rather than
It limits the scope of the invention.It is to be appreciated that the lithium piece for test is cathode lithium below as not specified
Piece.
Comparative example 1
SEM test is carried out before assembled battery to the lithium piece without any processing, as a result as shown in Figure 1.By double trifluoros
Sulfonyl methane imine lithium (LiTFSI) is added to 1,3- dioxolanes (DOL)-glycol dimethyl ether (DME) in the mixed solvent
(DOL and DME volume ratio be 1:1), is configured to the electrolyte of 1mol/L, and stirring and dissolving is to forming uniform solution.With above-mentioned
Electrolyte assembles lithium Symmetrical cells in pairs, and carries out charge-discharge test to battery.Testing current density is 2mA cm-2, circulation
Lithium metal amount control be 1mAh cm-2.Cycle performance is as shown in Figure 2 b, and the cathode lithium piece of battery is dismantled within 20 weeks after circulation
SEM figure is as shown in Figure 2 a.
Comparative example 2
By lithium hexafluoro phosphate (LiPF6) it is added to the in the mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC)
(EC and DEC volume ratio be 1:1), is configured to the electrolyte of 1mol/L, and stirring and dissolving is to forming uniform solution.With above-mentioned electricity
It solves liquid and assembles lithium Symmetrical cells in pairs, and charge-discharge test is carried out to battery.Current density is 2mA cm-2, the lithium gold of circulation
The amount control of category is 1mAh cm-2。
Comparative example 3
By lithium hexafluoro phosphate (LiPF6) it is added to the in the mixed solvent of ethylene carbonate (EC) and dimethyl carbonate (DMC)
(EC and DMC volume ratio be 1:1), is configured to the electrolyte of 1mol/L, and stirring and dissolving is to forming uniform solution.With above-mentioned electricity
It solves liquid and assembles lithium Symmetrical cells in pairs, and charge-discharge test is carried out to battery.Current density is 2mA cm-2, the lithium gold of circulation
The amount control of category is 1mAh cm-2。
Comparative example 4
By lithium perchlorate (LiClO4) be added in propene carbonate (PC) solvent, it is configured to the electrolyte of 1mol/L, is stirred
It mixes and is dissolved to form uniform solution.Lithium Symmetrical cells in pairs are assembled with above-mentioned electrolyte, and charge and discharge are carried out to battery
Test.Current density is 2mA cm-2, the amount control of the lithium metal of circulation is 1mAh cm-2。
Embodiment 1
Double trifluoromethanesulfonimide lithiums (LiTFSI) are added to 1,3- dioxolanes (DOL)-glycol dimethyl ether
(DME) in the mixed solvent (DOL and DME volume ratio is 1:1), is configured to the electrolyte of 1mol/L, adds two thio oxalyl
Amine, to uniform solution is formed, (concentration of dithiooxamide is that (concentration is that sulfur-bearing conjugation adds to 0.1mg/mL to stirring and dissolving
Add the quality of agent relative to the ratio of nonaqueous solvents volume, the same below)).Lithium Symmetrical cells in pairs are assembled with above-mentioned electrolyte,
And charge-discharge test is carried out to battery.Current density is 2mA cm-2, the amount control of the lithium metal of circulation is 1mAh cm-2。
Embodiment 2
Double trifluoromethanesulfonimide lithiums (LiTFSI) are added to 1,3- dioxolanes (DOL)-glycol dimethyl ether
(DME) in the mixed solvent (DOL and DME volume ratio is 1:1), is configured to the electrolyte of 1mol/L, adds two thio oxalyl
Amine, to uniform solution is formed, (concentration of dithiooxamide is 1mg/mL) to stirring and dissolving.It is assembled into above-mentioned electrolyte
Double lithium Symmetrical cells, and charge-discharge test is carried out to battery.Current density is 2mA cm-2, the amount control of the lithium metal of circulation
For 1mAh cm-2.Cycle performance is as shown in Figure 3b, and the SEM figure for dismantling the lithium piece of battery for 20 weeks after circulation is as shown in Figure 3a.
Embodiment 3
Double trifluoromethanesulfonimide lithiums (LiTFSI) are added to 1,3- dioxolanes (DOL)-glycol dimethyl ether
(DME) in the mixed solvent (DOL and DME volume ratio is 1:1), is configured to the electrolyte of 1mol/L, adds two thio oxalyl
Amine, to uniform solution is formed, (concentration of dithiooxamide is 5mg/mL) to stirring and dissolving.It is assembled into above-mentioned electrolyte
Double lithium Symmetrical cells, and charge-discharge test is carried out to battery.Current density is 2mA cm-2, the amount control of the lithium metal of circulation
For 1mAh cm-2。
Embodiment 4
Double trifluoromethanesulfonimide lithiums (LiTFSI) are added to 1,3- dioxolanes (DOL)-glycol dimethyl ether
(DME) in the mixed solvent (DOL and DME volume ratio is 1:1), is configured to the electrolyte of 1mol/L, adds two thio oxalyl
Amine, to uniform solution is formed, (concentration of dithiooxamide is 10mg/mL) to stirring and dissolving.It is assembled into above-mentioned electrolyte
Double lithium Symmetrical cells, and charge-discharge test is carried out to battery.Current density is 2mA cm-2, the amount control of the lithium metal of circulation
For 1mAh cm-2。
Embodiment 5
By lithium hexafluoro phosphate (LiPF6) it is added to the in the mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC)
(EC and DEC volume ratio is 1:1), is configured to the electrolyte of 1mol/L, adds dithiooxamide, and stirring and dissolving is equal to being formed
One solution (concentration of dithiooxamide is 0.1mg/mL).Lithium Symmetrical cells in pairs are assembled with above-mentioned electrolyte, and
Charge-discharge test is carried out to battery.Current density is 2mAcm-2, the amount control of the lithium metal of circulation is 1mAh cm-2。
Embodiment 6
By lithium hexafluoro phosphate (LiPF6) it is added to the in the mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC)
(EC and DEC volume ratio is 1:1), is configured to the electrolyte of 1mol/L, adds dithiooxamide, and stirring and dissolving is equal to being formed
One solution (concentration of dithiooxamide is 10mg/mL).Lithium Symmetrical cells in pairs are assembled with above-mentioned electrolyte, and right
Battery carries out charge-discharge test.Current density is 2mAcm-2, the amount control of the lithium metal of circulation is 1mAh cm-2。
Embodiment 7
By lithium hexafluoro phosphate (LiPF6) it is added to the in the mixed solvent of ethylene carbonate (EC) and dimethyl carbonate (DMC)
(EC and DMC volume ratio is 1:1), is configured to the electrolyte of 1mol/L, adds dithiooxamide, and stirring and dissolving is equal to being formed
One solution (concentration of dithiooxamide is 0.1mg/mL).Lithium Symmetrical cells in pairs are assembled with above-mentioned electrolyte, and
Charge-discharge test is carried out to battery.Current density is 2mAcm-2, the amount control of the lithium metal of circulation is 1mAh cm-2。
Embodiment 8
By lithium hexafluoro phosphate (LiPF6) it is added to the in the mixed solvent of ethylene carbonate (EC) and dimethyl carbonate (DMC)
(EC and DMC volume ratio is 1:1), is configured to the electrolyte of 1mol/L, adds dithiooxamide, and stirring and dissolving is equal to being formed
One solution (concentration of dithiooxamide is 10mg/mL).Lithium Symmetrical cells in pairs are assembled with above-mentioned electrolyte, and right
Battery carries out charge-discharge test.Current density is 2mAcm-2, the amount control of the lithium metal of circulation is 1mAh cm-2。
Embodiment 9
By lithium perchlorate (LiClO4) be added in PC solvent, it is configured to the electrolyte of 1mol/L, adds two thio grass
Amide, to uniform solution is formed, (concentration of dithiooxamide is 0.1mg/mL) to stirring and dissolving.With above-mentioned electrolyte group
Double lithium Symmetrical cells are dressed up, and charge-discharge test is carried out to battery.Current density is 2mA cm-2, the amount of the lithium metal of circulation
Control is 1mAh cm-2。
Embodiment 10
By lithium perchlorate (LiClO4) be added in PC solvent, it is configured to the electrolyte of 1mol/L, adds two thio grass
Amide, to uniform solution is formed, (concentration of dithiooxamide is 10mg/mL) to stirring and dissolving.It is assembled with above-mentioned electrolyte
Lithium Symmetrical cells in pairs, and charge-discharge test is carried out to battery.Current density is 2mA cm-2, the amount control of the lithium metal of circulation
It is made as 1mAh cm-2。
Embodiment 11-14
Embodiment 1-4 is copied to prepare electrolyte, it is (thio that dithiooxamide therein is only replaced with thioacetamide
The concentration of acetamide is followed successively by 0.1,1,5,10mg/mL).Lithium Symmetrical cells in pairs are assembled with above-mentioned electrolyte, and to electricity
Pond carries out charge-discharge test.Current density is 2mA cm-2, the amount control of the lithium metal of circulation is 1mAh cm-2。
Embodiment 15-16
Embodiment 5-6 is copied to prepare electrolyte, it is (thio that dithiooxamide therein is only replaced with thioacetamide
The concentration of acetamide is followed successively by 0.1,10mg/mL).Assemble lithium Symmetrical cells in pairs with above-mentioned electrolyte, and to battery into
Row charge-discharge test.Current density is 2mA cm-2, the amount control of the lithium metal of circulation is 1mAh cm-2。
Embodiment 17-18
Embodiment 7-8 is copied to prepare electrolyte, it is (thio that dithiooxamide therein is only replaced with thioacetamide
The concentration of acetamide is followed successively by 0.1,10mg/mL).Assemble lithium Symmetrical cells in pairs with above-mentioned electrolyte, and to battery into
Row charge-discharge test.Current density is 2mA cm-2, the amount control of the lithium metal of circulation is 1mAh cm-2。
Embodiment 19-20
It copies embodiment 9-10 to prepare electrolyte, dithiooxamide therein is only replaced with into thioacetamide (sulphur
0.1,10mg/mL is followed successively by for the concentration of acetamide).Lithium Symmetrical cells in pairs are assembled with above-mentioned electrolyte, and to battery
Carry out charge-discharge test.Current density is 2mA cm-2, the amount control of the lithium metal of circulation is 1mAh cm-2。
Embodiment 21-24
It copies embodiment 1-4 to prepare electrolyte, dithiooxamide therein is only replaced with into the thiocarbamide (concentration of thiocarbamide
It is followed successively by 0.1,1,5,10mg/mL).Lithium Symmetrical cells in pairs are assembled with above-mentioned electrolyte, and charge and discharge are carried out to battery
Test.Current density is 2mA cm-2, the amount control of the lithium metal of circulation is 1mAh cm-2。
Embodiment 25-26
It copies embodiment 5-6 to prepare electrolyte, dithiooxamide therein is only replaced with into the thiocarbamide (concentration of thiocarbamide
It is followed successively by 0.1,10mg/mL).Lithium Symmetrical cells in pairs are assembled with above-mentioned electrolyte, and charge-discharge test is carried out to battery.
Current density is 2mA cm-2, the amount control of the lithium metal of circulation is 1mAhcm-2。
Embodiment 27-28
It copies embodiment 7-8 to prepare electrolyte, dithiooxamide therein is only replaced with into the thiocarbamide (concentration of thiocarbamide
It is followed successively by 0.1,10mg/mL).Lithium Symmetrical cells in pairs are assembled with above-mentioned electrolyte, and charge-discharge test is carried out to battery.
Current density is 2mA cm-2, the amount control of the lithium metal of circulation is 1mAhcm-2。
Embodiment 29-30
Copy embodiment 9-10 to prepare electrolyte, only by dithiooxamide therein replace with thiocarbamide (thiocarbamide it is dense
Degree is followed successively by 0.1,10mg/mL).Lithium Symmetrical cells in pairs are assembled with above-mentioned electrolyte, and charge and discharge electrical measurement is carried out to battery
Examination.Current density is 2mA cm-2, the amount control of the lithium metal of circulation is 1mAh cm-2。
Embodiment 31-34
It copies embodiment 1-4 to prepare electrolyte, dithiooxamide therein is only replaced with into the thiophene (concentration of thiophene
It is followed successively by 0.1,1,5,10mg/mL).Lithium Symmetrical cells in pairs are assembled with above-mentioned electrolyte, and charge and discharge are carried out to battery
Test.Current density is 2mA cm-2, the amount control of the lithium metal of circulation is 1mAh cm-2。
Embodiment 35-36
It copies embodiment 5-6 to prepare electrolyte, dithiooxamide therein is only replaced with into the thiophene (concentration of thiophene
It is followed successively by 0.1,10mg/mL).Lithium Symmetrical cells in pairs are assembled with above-mentioned electrolyte, and charge-discharge test is carried out to battery.
Current density is 2mA cm-2, the amount control of the lithium metal of circulation is 1mAh cm-2。
Embodiment 37-38
It copies embodiment 7-8 to prepare electrolyte, dithiooxamide therein is only replaced with into the thiophene (concentration of thiophene
It is followed successively by 0.1,10mg/mL).Lithium Symmetrical cells in pairs are assembled with above-mentioned electrolyte, and charge-discharge test is carried out to battery.
Current density is 2mA cm-2, the amount control of the lithium metal of circulation is 1mAh cm-2。
Embodiment 39-40
Copy embodiment 9-10 to prepare electrolyte, only by dithiooxamide therein replace with thiophene (thiophene it is dense
Degree is followed successively by 0.1,10mg/mL).Lithium Symmetrical cells in pairs are assembled with above-mentioned electrolyte, and charge and discharge electrical measurement is carried out to battery
Examination.Current density is 2mA cm-2, the amount control of the lithium metal of circulation is 1mAh cm-2。
Embodiment 41-44
It copies embodiment 1-4 to prepare electrolyte, dithiooxamide therein is only replaced with into carbon disulfide (curing
The concentration of carbon is followed successively by 0.1,1,5,10mg/mL).Assemble lithium Symmetrical cells in pairs with above-mentioned electrolyte, and to battery into
Row charge-discharge test.Current density is 2mA cm-2, the amount control of the lithium metal of circulation is 1mAh cm-2。
Embodiment 45-46
It copies embodiment 5-6 to prepare electrolyte, dithiooxamide therein is only replaced with into carbon disulfide (curing
The concentration of carbon is followed successively by 0.1,10mg/mL).Lithium Symmetrical cells in pairs are assembled with above-mentioned electrolyte, and battery is filled
Discharge test.Current density is 2mA cm-2, the amount control of the lithium metal of circulation is 1mAh cm-2。
Embodiment 47-48
It copies embodiment 7-8 to prepare electrolyte, dithiooxamide therein is only replaced with into carbon disulfide (curing
The concentration of carbon is followed successively by 0.1,10mg/mL).Lithium Symmetrical cells in pairs are assembled with above-mentioned electrolyte, and battery is filled
Discharge test.Current density is 2mA cm-2, the amount control of the lithium metal of circulation is 1mAh cm-2。
Embodiment 49-50
It copies embodiment 9-10 to prepare electrolyte, dithiooxamide therein is only replaced with into carbon disulfide (two sulphur
The concentration for changing carbon is followed successively by 0.1,10mg/mL).Lithium Symmetrical cells in pairs are assembled with above-mentioned electrolyte, and battery is carried out
Charge-discharge test.Current density is 2mA cm-2, the amount control of the lithium metal of circulation is 1mAh cm-2。
Embodiment 51-54
It copies embodiment 1-4 to prepare electrolyte, dithiooxamide therein is only replaced with into diphenyl sulfide (diphenyl sulfide
The concentration of ether is followed successively by 0.1,1,5,10mg/mL).Assemble lithium Symmetrical cells in pairs with above-mentioned electrolyte, and to battery into
Row charge-discharge test.Current density is 2mA cm-2, the amount control of the lithium metal of circulation is 1mAh cm-2。
Embodiment 55-56
It copies embodiment 5-6 to prepare electrolyte, dithiooxamide therein is only replaced with into diphenyl sulfide (diphenyl sulfide
The concentration of ether is followed successively by 0.1,10mg/mL).Lithium Symmetrical cells in pairs are assembled with above-mentioned electrolyte, and battery is filled
Discharge test.Current density is 2mA cm-2, the amount control of the lithium metal of circulation is 1mAh cm-2。
Embodiment 57-58
It copies embodiment 7-8 to prepare electrolyte, dithiooxamide therein is only replaced with into diphenyl sulfide (diphenyl sulfide
The concentration of ether is followed successively by 0.1,10mg/mL).Lithium Symmetrical cells in pairs are assembled with above-mentioned electrolyte, and battery is filled
Discharge test.Current density is 2mA cm-2, the amount control of the lithium metal of circulation is 1mAh cm-2。
Embodiment 59-60
It copies embodiment 9-10 to prepare electrolyte, dithiooxamide therein is only replaced with into diphenyl sulfide (hexichol
The concentration of thioether is followed successively by 0.1,10mg/mL).Lithium Symmetrical cells in pairs are assembled with above-mentioned electrolyte, and battery is carried out
Charge-discharge test.Current density is 2mA cm-2, the amount control of the lithium metal of circulation is 1mAh cm-2。
Embodiment 61-64
It copies embodiment 1-4 to prepare electrolyte, dithiooxamide therein is only replaced with into thiambutosine (diphenyl sulfide
The concentration of urea is followed successively by 0.1,1,5,10mg/mL).Assemble lithium Symmetrical cells in pairs with above-mentioned electrolyte, and to battery into
Row charge-discharge test.Current density is 2mA cm-2, the amount control of the lithium metal of circulation is 1mAh cm-2。
Embodiment 65-66
It copies embodiment 5-6 to prepare electrolyte, dithiooxamide therein is only replaced with into thiambutosine (diphenyl sulfide
The concentration of urea is followed successively by 0.1,10mg/mL).Lithium Symmetrical cells in pairs are assembled with above-mentioned electrolyte, and battery is filled
Discharge test.Current density is 2mA cm-2, the amount control of the lithium metal of circulation is 1mAh cm-2。
Embodiment 67-68
It copies embodiment 7-8 to prepare electrolyte, dithiooxamide therein is only replaced with into thiambutosine (diphenyl sulfide
The concentration of urea is followed successively by 0.1,10mg/mL).Lithium Symmetrical cells in pairs are assembled with above-mentioned electrolyte, and battery is filled
Discharge test.Current density is 2mA cm-2, the amount control of the lithium metal of circulation is 1mAh cm-2。
Embodiment 69-70
It copies embodiment 9-10 to prepare electrolyte, dithiooxamide therein is only replaced with into thiambutosine (hexichol
The concentration of thiocarbamide is followed successively by 0.1,10mg/mL).Lithium Symmetrical cells in pairs are assembled with above-mentioned electrolyte, and battery is carried out
Charge-discharge test.Current density is 2mA cm-2, the amount control of the lithium metal of circulation is 1mAh cm-2。
The charge-discharge test result of comparative example 1-4 and embodiment 1-70 and leveling effect are shown in the following table 1.
Table 1
Effect example 1
Double trifluoromethanesulfonimide lithiums (LiTFSI) are added to 1,3- dioxolanes (DOL)-glycol dimethyl ether
(DME) in the mixed solvent (DOL and DME volume ratio is 1:1), is configured to the electrolyte of 1mol/L, is denoted as electrolyte 1.Later,
Dithiooxamide is added into electrolyte 1, (concentration of dithiooxamide is 1mg/ to stirring and dissolving to uniform solution is formed
ML), it is denoted as electrolyte 2.Lithium Symmetrical cells in pairs are assembled with electrolyte 1, and charge-discharge test, current density are carried out to battery
It is 2mA cm-2, the amount control of the lithium metal of circulation is 1mAh cm-2.After 20 weeks circulations, electricity is dismantled in glove box
The lithium piece being circulated throughout is carried out charge-discharge test, electric current is close respectively with electrolyte 1,2 assembled battery of electrolyte again by pond again
Degree is 2mA cm-2, the amount control of the lithium metal of circulation is 1mAh cm-2.Cycle performance comparison is as shown in Figure 4 b, prior to electrolyte
Recycled 20 weeks in 1, after recycled in electrolyte 2 20 weeks after dismantle battery lithium piece SEM figure as shown in fig. 4 a.
From the above results:
1. other conditions are consistent in controlling lithium-ion battery electrolytes, sulfur-bearing conjugated structure additive is added
Dithiooxamide, thioacetamide, thiocarbamide, carbon disulfide, thiophene, thiambutosine, diphenyl sulfide embodiment 1-70 in, it is double
The cycle life of lithium Symmetrical cells is all than the circulation longevity of double lithium Symmetrical cells under the same terms in comparative example 1-4 without additive
It orders much longer.
2. sulfur-bearing conjugated structure additive, which is added, can be improved the cycle life of lithium lithium battery within the scope of a certain concentration,
Expected effect is then not achieved below or above this concentration range, when the concentration of the sulfur-bearing conjugated structure additive of addition is low
In 0.01mg/mL, the effect of leveling lithium electrode surface will not be had, if being higher than 100mg/mL, during the long circulating of battery,
Along with the decomposition of electrolyte, lithium surface locally has the precipitation of additive granules, and will affect the cycle life of battery.
3. being found after the electrical property loop-around data (i.e. circulation time) of embodiment and comparative example 1 is compared, mentioned in the present invention
To electrolyte for lithium secondary batteries used in sulfur-bearing conjugated structure additive, the additive containing carbonyl sulfur class is improving
Effect in double lithium Symmetrical cells cycle lives is apparently higher than the additive of thioether class.Moreover, in comparative example it is several containing
The leveling effect and chemical property of the additive of carbonyl sulfur class, additive molecule of the discovery containing big phenyl ring class is in leveling effect
And improve effect in the cycle life of battery and be not so good as small additive molecule, this is because the big phenyl ring etc. of steric hindrance will affect and add
Add the combination of S atom and lithium electrode surface in agent molecule.
4. cycle performance Fig. 2 of comparison diagram 1, comparative example 1 and cycle performance Fig. 3 of embodiment 2, discovery electrolyte is not having
Have that when dithiooxamide is added, the cycle life of battery is very short, and after 20 weeks recycle lithium surface have it is many small
The further growth in subsequent long circulating is formed Li dendrite, pierces through diaphragm, influence following for lithium battery by protrusion, these protrusions
Ring service life and security performance.On the contrary, in the electrolyte containing dithiooxamide additive, being followed by 20 weeks in embodiment 2
After ring, the surface of cathode of lithium is very smooth, cleans, and not any raised phenomenon, this effectively improves the circulation longevity of battery
Life and security performance, this illustrates dithiooxamide in the effect of leveling electrode surface.Compare macrocyclic battery testing knot
Fruit finds that in the electrolyte containing sulfur-bearing conjugated structure additive, the cycle life of double lithium Symmetrical cells has obtained very big
Raising.
5. Fig. 4 of comparison diagram 2 and effect example 1, it is found that battery will form small protrusion under pure electrolyte,
That is dendrite, after long circulation, lithium preferential deposition is in high spot, so that dendrite infinitely amplifies growth, however it is thio being added two
In the circulation of oxamides, the dendritic crystalline lithium piece of protrusion, after 20 weeks are recycled in the environment of dithiooxamide, lithium piece have been generated
Surface occur it is apparent leveling and reparation phenomenon.This bright and clean lithium surface, it was demonstrated that additive dithiooxamide can be with
The out-of-flatness dendrite phenomenon for repairing lithium piece surface, fundamentally inhibits the generation of dendrite, to effectively raise lithium battery
Cycle life.
Above-described embodiment is only the preferred embodiments of the invention, but the present invention is not limited in above-described embodiment, not
The phase strain type carried out under the premise of being detached from the principle of the invention, is also considered as protection scope of the present invention.
Claims (10)
1. a kind of lithium metal secondary battery electrolyte, containing lithium salts, nonaqueous solvents and sulfur-bearing conjugated structure additive,
In, the concentration of the lithium salts is 0.5-10mol/L, ratio of the quality of sulfur-bearing conjugated structure additive relative to nonaqueous solvents volume
Value is 0.01-100mg/mL.
2. lithium metal secondary battery electrolyte according to claim 1, wherein the sulfur-bearing conjugated structure additive is
One of carbonyl sulfur class, thioether class and sulfone class are a variety of.
3. lithium metal secondary battery electrolyte according to claim 1, wherein the sulfur-bearing conjugated structure additive is
One of dithiooxamide, thioacetamide, thiocarbamide, thiophene, carbon disulfide, diphenyl sulfide and thiambutosine are a variety of.
4. lithium metal secondary battery electrolyte described in any one of claim 1 to 3, wherein the sulfur-bearing conjugation
Structural additives do not contain phenyl ring.
5. lithium metal secondary battery electrolyte described in any one of claim 1 to 3, wherein the sulfur-bearing conjugation
The quality of structural additives is 0.05-50mg/mL relative to the ratio of nonaqueous solvents volume.
6. lithium metal secondary battery electrolyte described in any one of claim 1 to 3, wherein the sulfur-bearing conjugation
The quality of structural additives is 0.1-10mg/mL relative to the ratio of nonaqueous solvents volume.
7. lithium metal secondary battery electrolyte according to claim 1, wherein the lithium salts is LiPF6, LiTFSI and
LiClO4One of or it is a variety of.
8. lithium metal secondary battery electrolyte according to claim 1, wherein the nonaqueous solvents is selected from 1,3- bis-
Butyl oxide link (DOL), glycol dimethyl ether (DME), ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC),
One of propene carbonate (PC) is a variety of.
9. lithium metal secondary battery electrolyte according to claim 1 or 8, wherein the nonaqueous solvents is 1,3- bis-
The mixed solvent of butyl oxide link (DOL) and glycol dimethyl ether (DME), ethylene carbonate (EC) and diethyl carbonate (DEC) it is mixed
Bonding solvent, the mixed solvent of ethylene carbonate (EC) and dimethyl carbonate (DMC) or propene carbonate (PC).
10. a kind of lithium metal secondary battery has lithium metal secondary battery electricity consumption according to any one of claims 1 to 9
Solve liquid, the positive electrode, the negative electrode and the separator.
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| CN201810791112.1A CN109256587A (en) | 2018-07-18 | 2018-07-18 | Lithium metal secondary battery electrolyte and the lithium metal secondary battery for using the electrolyte |
| PCT/CN2018/112571 WO2020015234A1 (en) | 2018-07-18 | 2018-10-30 | Electrolyte for metal lithium secondary battery and metal lithium secondary battery using same |
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| CN110148787A (en) * | 2019-06-17 | 2019-08-20 | 中南大学 | A kind of electrolyte and lithium-sulfur cell improving lithium-sulfur cell capacity |
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