CN108054429B - A kind of lithium an- ode protection electrolysis additive and its preparation method and application - Google Patents

A kind of lithium an- ode protection electrolysis additive and its preparation method and application Download PDF

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CN108054429B
CN108054429B CN201711234286.XA CN201711234286A CN108054429B CN 108054429 B CN108054429 B CN 108054429B CN 201711234286 A CN201711234286 A CN 201711234286A CN 108054429 B CN108054429 B CN 108054429B
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lithium battery
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CN108054429A (en
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李长明
邓雯雯
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Suzhou University of Science and Technology
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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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
    • C07C255/33—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring with cyano groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by saturated carbon chains
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
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    • C07B2200/13—Crystalline forms, e.g. polymorphs
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    • 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 an- ode protection electrolysis additive and its preparation method and application, electrolysis additive is formula (1) compound represented:

Description

A kind of lithium an- ode protection electrolysis additive and its preparation method and application
Technical field
The invention belongs to new energy materials fields, and in particular to a kind of lithium an- ode protection electrolysis additive and its Preparation method and application.
Background technique
At this stage, LiFePO is used in commodity electrochemical cell4,LiCoO2, Li2MnO3Equal transistion metal compounds do anode, stone Ink or hard carbon do cathode.Either transistion metal compound anode or graphite cathode, their theoretical specific capacity are no more than The energy density of 400mAh/g, battery are limited.With the development of vehicle technology, requirement of the people to battery energy density is more next Higher, the battery being commercialized at present can no longer meet requirement of the power battery to energy density.Then, Li-S, Li- in recent years O2The high energy density cells system such as battery receives very big concern.It is different from commercial lithium-ion batteries, Li-S, Li-O2Battery Directly use lithium metal as cathode.Lithium anode has the theoretical specific capacity of 3860mAh/g, is the 10 of commodity graphite Times, it can greatly improve lithium battery energy density.However, being primarily present the following problem: (1) metal in the application of restriction lithium The activity of lithium is higher, almost reacts with most of organic solvent, to be formed at the interface of lithium metal and electrolyte SEI film, with the progress of reaction, SEI film progressive additive, interface impedance is continuously increased, and coulombic efficiency reduces, and battery capacity declines Subtract；(2) SEI film is unstable, and-falling off-is constantly ruptured during removal lithium embedded and is regenerated, and consumes lithium metal and electrolyte；(3) Lithium deposits-deviates from process current density and is unevenly distributed, and causes deposition uneven, forms Li dendrite, causes security risk and " dead Lithium " causes the loss of irreversible capacity.Therefore, the application of Yao Shixian cathode of lithium, the protection of lithium anode are urgently to be solved Problem.
Currently, solid electrolyte interface layer (SEI film) can play down to a certain degree in the report protected about cathode of lithium The effect of dendrite inhibition growth.It and include manually manufacturing SEI film and being formed in situ using the method that SEI film carries out cathode of lithium protection Two kinds of SEI film, artificial SEI embrane method is referred specifically to polymer dielectric film such as PEO, the PVDF for leading ionic good, non-conductive son Film etc. is coated on lithium anode in advance, is then tested with the metal lithium sheet that polymer film has coated.This method has Certain effect, but since artificial synthesized polymer dielectric film is difficult to accomplish that enough thin, relatively thick boundary layer can generate Very big internal resistance, and over time, it makes a big impact in practical application to the chemical property of battery.It is formed in situ SEI embrane method refers to is added a certain amount of electrolysis additive in the electrolytic solution, and additive can be formed in situ one in metallic lithium surface Interfacial layer, to play the purpose of protection cathode of lithium.
Present inventor's innovation proposes a kind of novel electrolysis additive, and such electrolysis additive can be in lithium Solid dielectric interface is formed in situ in negative terminal surface, and the effective growth for inhibiting Li dendrite improves lithium and deposits dissolved efficiency, thus Improve cyclical stability and the safety of lithium battery.
Summary of the invention
The technical problem to be solved by the present invention is to overcome deficiency in the prior art, a kind of novel lithium metal cathode is provided Protection electrolysis additive, can effectively inhibit lithium dendrite growth, improve lithium and deposit dissolved efficiency, and then can promote lithium electricity The performances such as the cyclical stability in pond and safety.
The present invention also provides a kind of preparation methods of electrolysis additive.
The present invention also provides a kind of lithium battery electrolytes.
The present invention also provides a kind of lithium batteries.
In order to solve the above technical problems, a kind of technical solution that the present invention takes is as follows:
A kind of lithium an- ode protection electrolysis additive, the electrolysis additive are formula (1) compound represented (it is easy that the following are descriptions, also referred to as LiTCNQ):
The purity of some preferred aspects according to the present invention, formula (1) compound represented is more than or equal to 98%.Purification Method conventional method in the prior art can be selected, obtained using recrystallization or dissolubility difference etc..For example, using second The method that ether, methylene chloride equal solvent are recrystallized realizes the purifying of formula (1) compound represented；
Alternatively, selecting suitable organic solvent, dissolution, filtering, and then remove shown in formula (1) using the difference of solubility Compound in micro TCNQ, LiI and I that may be present2Simple substance.
A specific aspect according to the present invention, the X ray diffracting spectrum of formula (1) compound represented is in 2theta Value is 10.5 ° ± 0.2 °, 17 ° ± 0.2 °, 26 ° ± 0.2 °, 28 ° ± 0.2 °, 15.2 ° ± 0.2 °, 29 ° ± 0.2 ° and 31.5 ° There is characteristic peak at ± 0.2 °.
Further, the X-ray diffractogram of formula (1) compound represented also 2theta value be 34 ° ± 0.2 °, One or more in 36.5 ° ± 0.2 ° are with characteristic peak.
A specific aspect according to the present invention, the X-ray diffractogram of formula (1) compound represented substantially with figure 2 is consistent.
A kind of another technical solution provided by the invention: lithium an- ode protection electrolysis additive described above Preparation method, the preparation method include: to make reproducibility lithium salts and 7, and 7,8,8- four cyano benzoquinone bismethanes are organic molten Reaction is in agent to get the formula (1) compound represented.
Preferably, the reaction is carried out at 60~80 DEG C.
In certain specific embodiments of the invention, the organic solvent is in acetonitrile, ethyl alcohol, acetone and chloroform One or more combinations；Preferably, the organic solvent is acetonitrile.
In certain specific embodiments of the invention, the reproducibility lithium salts is selected from LiI, Li2S and Li2C2O4In One or more combinations.Preferably, the reproducibility lithium salts is LiI.
Some preferred aspects according to the present invention, described 7,7,8,8- four cyano benzoquinone bismethanes, the reproducibility The mass ratio that feeds intake of lithium salts and the organic solvent is 1 ︰, 0.9~1.1 ︰ 35~45.It is highly preferred that described 7,7,8,8- four cyanos The mass ratio that feeds intake of benzoquinone's bismethane, the reproducibility lithium salts and the organic solvent is 1 ︰, 0.95~1.07 ︰ 38~43. It is further preferred that described 7,7,8,8- four cyano benzoquinone bismethanes, the reproducibility lithium salts and the organic solvent The mass ratio that feeds intake is 1 ︰, 1~1.03 ︰ 39~41.
Another technical solution provided by the invention: a kind of lithium battery electrolytes, the lithium battery electrolytes include additive, The additive includes formula described above (1) compound represented.
Some preferred aspects according to the present invention, the formula (1) compound represented account for the lithium battery electrolytes Mass percentage is 0.1%~0.5%.It is highly preferred that described formula (1) compound represented accounts for the lithium battery electrolytes Mass percentage be 0.1%~0.3%.A specific aspect according to the present invention, the formula (1) compound represented The mass percentage for accounting for the lithium battery electrolytes is 0.2%~0.25%.
The lithium battery electrolytes are that formula (1) compound represented is dissolved in conventional electrolysis liquid to be made.Conventional electrolysis Liquid can be LiPF containing 1M6The organosilane ester electrolyte of electrolytic salt, wherein based organic solvent can be ethylene carbonate (EC), diethyl carbonate (DEC) according to isometric than mixing, be also possible to EC, DEC and methyl ethyl ester (EMC) by etc. Volume ratio mixing；Lithium battery electrolytes can also be the ethers electrolyte of the electrolytic salt of LiTFSI containing 1M, wherein ethers has Solvent can be 1,3-dioxolane (DOL) and glycol dimethyl ether (DME) and mix by equal proportion, be also possible to diethylene glycol Dimethyl ether (DEGDME).
Another technical solution provided by the invention: a kind of lithium battery, the lithium battery include electrolyte, and the electrolyte is Lithium battery electrolytes described above.
Due to the use of above technical scheme, the invention has the following advantages over the prior art:
The carbon radicals that the Novel electrolytic solution additive of the application can be contained under voltage stimulation using it are in lithium metal The intermolecular polymerization reaction of LiTCNQ occurs for negative terminal surface, to form one layer of uniform, stable and thin packet in metallic lithium surface Coating is conducive to the uniform deposition of lithium ion, to effectively inhibit the growth of Li dendrite, it is short to prevent or even avoid battery generation The case where road, and then the safety of lithium battery is improved, and improve the deposition dissolved efficiency of lithium ion, with circulation time Passage, stable electrochemical properties such as coulombic efficiency, capacity of lithium battery and conservation rate is higher, while its preparation are simple and in lithium electricity Additive amount is few in the electrolyte of pond, has saved cost, can be conducive to the big application of industrialization.
Detailed description of the invention
Fig. 1 is the infrared spectrum comparative diagram of LiTCNQ and 7,7,8,8- four cyano benzoquinone bismethane (TCNQ)；
Fig. 2 is the X-ray diffraction spectrogram of LiTCNQ；
Fig. 3 is the stability test figure of lithium in Li/Cu battery (using the 1M LiPF for not adding LiTCNQ6EC/DEC electrolysis Liquid)；
Fig. 4 is the deposition solubility curve test chart of lithium in Li/Cu battery (using the 1M LiPF for not adding LiTCNQ6 EC/ DEC electrolyte)；
Fig. 5 is the stability test figure of lithium in Li/Cu battery (using the 1M LiPF of addition LiTCNQ6EC/DEC electrolysis Liquid)；
Fig. 6 is the deposition solubility curve test chart of lithium in Li/Cu battery (using the 1M LiPF of addition LiTCNQ6 EC/ DEC electrolyte)；
Fig. 7, (the 1M LiPF for not adding LiTCNQ is used for the stability test figure of lithium in Li/Cu battery6 EC/EMC/DMC Electrolyte)；
Fig. 8 is the deposition solubility curve test chart of lithium in Li/Cu battery (using the 1M LiPF for not adding LiTCNQ6 EC/ EMC/DMC electrolyte)；
Fig. 9 is the stability test figure of lithium in Li/Cu battery (using the 1M LiPF of addition LiTCNQ6 EC/EMC/DMC Electrolyte)；
Figure 10 is the deposition solubility curve test chart of lithium in Li/Cu battery (using the 1M LiPF of addition LiTCNQ6 EC/ EMC/DMC electrolyte)；
Figure 11 is the stability test figure of lithium in Li/Cu battery (using the 1M LiTFSI DOL/DME electricity for not adding LiTCNQ Solve liquid)；
Figure 12 is the deposition solubility curve test chart of lithium in Li/Cu battery (using the 1M LiTFSI for not adding LiTCNQ DOL/DME electrolyte)；
Figure 13 is the stability test figure of lithium in Li/Cu battery (using the 1M LiTFSI DOL/DME electricity of addition LiTCNQ Solve liquid)；
Figure 14 is the deposition solubility curve test chart of lithium in Li/Cu battery (using the 1M LiTFSI of addition LiTCNQ DOL/DME electrolyte)；
Figure 15 is the stability test figure of lithium in Li/Cu battery (using the 1M LiTFSIG DEGDME electricity for not adding LiTCNQ Solve liquid)；
Figure 16 is the deposition solubility curve test chart of lithium in Li/Cu battery (using the 1M LiTFSIG for not adding LiTCNQ DEGDME electrolyte)；
Figure 17 is the stability test figure of lithium in Li/Cu battery (using the 1M LiTFSIG DEGDME electricity of addition LiTCNQ Solve liquid)；
Figure 18 is the deposition solubility curve test chart of lithium in Li/Cu battery (using the 1M LiTFSIG of addition LiTCNQ DEGDME electrolyte)；
Figure 19 is in the 1M LiPF for not summing it up addition LiTCNQ6It sinks on copper foil after respectively being recycled in EC/DEC electrolyte 25 weeks The XPS spectrum figure (N1s) of long-pending metallic lithium surface N element.
Specific embodiment
The present invention provides a kind of electrolysis additives with cathode of lithium protecting effect.In the present invention, by normal LiTCNQ is added in rule electrolyte, so that the carbon radicals that the LiTCNQ described in charge and discharge process contains lure under voltage stimulation Lead that LiTCNQ is intermolecular to be polymerize, so as to form one layer of uniform, stable and thin polymer in cathode of lithium surface in situ Protective film is conducive to the uniform deposition of lithium ion, plays the effect for inhibiting lithium dendrite growth, protecting cathode of lithium, improves lithium Dissolved efficiency and stability are deposited, minimum to the Electrochemical Performances of lithium battery in cyclic process (made lithium is negative Although pole surface protective film can play the role of inhibiting lithium dendrite growth, the internal resistance of cell, shadow can be significantly greatly increased under normal circumstances Ring the performance of battery).Simultaneously because the ready dissolution of LiTCNQ in organic solvent, then be easy to be prepared containing LiTCNQ's Lithium battery electrolytes, and electrolysis additive additive amount in lithium battery electrolytes is few, has saved cost, is more applicable in work Industry mass production.
The test condition for the X-ray diffraction that the present invention is carried out is as follows:
Instrument: Shimadzu XRD-6000 diffractometer
X-ray source: Cu, K α
Scanning speed: 2 θ=4 °/min
Above scheme is described further below in conjunction with specific embodiment；It should be understood that these embodiments are for illustrating The basic principles, principal features and advantages of the present invention, and the present invention is not by the scope limitation of following embodiment；It is used in embodiment Implementation condition can select or do further adjustment according to specific requirement, the implementation condition being not specified is usually routine experiment In condition.Such as 200mL round-bottomed flask can be used in consersion unit, recrystallization can use crystallization culture dish etc.；Drying equipment can For such as vacuum drying oven.Other are not specifically limited, as long as can implement the preparation step and belong to known to those skilled in the art simultaneously The equipment of effect of the present invention can be reached.
In the following embodiments, unless otherwise specified, all raw materials are both from routine that is commercially available or passing through this field Method obtains.Li/Cu battery in embodiment is using lithium metal as cathode, copper foil as anode.Preferably, copper foil is before use 30min can be impregnated with dilute hydrochloric acid, then be cleaned with clear water and carry out drying and processing.
For convenience of description, 7,7,8,8- four cyano benzoquinone's bismethanes are indicated with TCNQ in following embodiments, structural formula It is as follows:
Embodiment 1
LiTCNQ preparation:
1g TCNQ and 1.02gLiI are weighed, grinding uniformly, is then respectively adding in 50mL acetonitrile solution and stirs 40min.In It is reacted at 60-80 DEG C, when the color of solid product becomes purple from yellow, reaction terminates, filtering, cleans gained with acetonitrile and produces Object finally recrystallizes in ethanol solution, and by obtained solid, to get LiTCNQ, purity is dry 12h in 80 DEG C of vacuum drying ovens 98.5%~99.5%.
LiTCNQ characterization:
IR test is done to gained LiTCNQ, and is compared with the IR spectrogram of raw material TCNQ, as shown in Figure 1, can from the figure See, formula (I) compound represented (LiTCNQ) successfully synthesizes.
XRD test is carried out to gained LiTCNQ, XRD diagram is as shown in Figure 2, the results showed that the LiTCNQ of preparation is crystal shape Formula, X-ray diffractogram are to have feature at 10.5 °, 15.2 °, 17 °, 26 °, 28 °, 29 °, 31.5 °, 34 °, 36.5 ° in 2theta Peak.
LiTCNQ application:
0.005g LiTCNQ is weighed, 1mL 1M LiPF is added to6EC/DEC electrolyte (is purchased from Zhangjiagang Cathay Huarong New chemical materials Co., Ltd) in, small magneton stirring 30min is to dissolution completely to get lithium battery electrolytes of the invention (it is 0.2%-0.25% that LiTCNQ, which accounts for the mass percentage of lithium battery electrolytes).
To LiPF6Stability and lithium metal of the lithium metal on copper foil are in copper foil in the Li/Cu battery of EC/DEC electrolyte On deposition solubility curve be tested, be embodied in capacity (charge and discharge 2h under 0.5mA electric current) and coulombic efficiency, as a result Ginseng is seen figures 3 and 4.
To stability and lithium metal of the lithium metal on copper foil in the Li/Cu battery of lithium battery electrolytes of the invention in copper Deposition solubility curve on foil is tested, and is embodied in capacity (charge and discharge 2h under 0.5mA electric current) and coulombic efficiency, knot Fruit is referring to Figures 5 and 6.
The result shows that in 1M LiPF6In EC/DEC electrolyte, the efficiency (showing as coulombic efficiency) of lithium deposition dissolution is about It is 88%, circulation 30h behind efficiency drops to about 55%, while its volume change is very big, is reduced to from initial 0.9mAh or so 0.42mAh or so.In the 1M LiPF for having added LiTCNQ additive6In EC/DEC electrolyte, the efficiency of lithium deposition dissolution is about 95%, circulation 100h behind efficiency keeps about 93%, and capacity is kept almost at 0.9mAh or so, excellent stability.
Respectively in LiPF6The lithium battery after 25 weeks is recycled in EC/DEC electrolyte and lithium battery electrolytes of the invention It is dismantled, metal lithium sheet DMC solvent cleaning, drying is taken out under inert atmosphere, the XPS analysis of N element is done to lithium surface.Ginseng See Figure 19, the results showed that, in the 1M LiPF for not adding LiTCNQ6Lithium surface is without N element signal after recycling in EC/DEC electrolyte, And N element signal can be detected in lithium surface after recycling in the lithium battery electrolytes that the present invention is added to LiTCNQ, it was demonstrated that LiTCNQ occurs polymerization and is covered on lithium surface.
Embodiment 2
LiTCNQ application:
The LiTCNQ 0.005g prepared as described in Example 1 is weighed, 1mL 1M LiPF is added to6 EC/EMC/DMC In electrolyte (be purchased from Zhangjiagang Cathay Huarong new chemical materials Co., Ltd), small magneton stirring 30min to dissolution completely to get Lithium battery electrolytes of the invention (it is 0.2%-0.25% that LiTCNQ, which accounts for the mass percentage of lithium battery electrolytes).
To LiPF6Stability and lithium metal of the lithium metal on copper foil exist in the Li/Cu battery of EC/EMC/DMC electrolyte Deposition solubility curve on copper foil is tested, and is embodied in capacity (charge and discharge 2h under 0.5mA electric current) and coulombic efficiency, As a result referring to Fig. 7 and 8.
To stability and lithium metal of the lithium metal on copper foil in the Li/Cu battery of lithium battery electrolytes of the invention in copper Deposition solubility curve on foil is tested, and is embodied in capacity (charge and discharge 2h under 0.5mA electric current) and coulombic efficiency, knot Fruit is referring to Fig. 9 and 10.
The result shows that in 1M LiPF6In EC/EMC/DMC electrolyte, the efficiency of lithium deposition dissolution (shows as coulomb effect Rate) it is about 60%, circulation 30h behind efficiency is about 65%, while capacity also declines quickly, almost only has after a period of time 0.28mAh or so.In the 1mL 1M LiPF for having added LiTCNQ additive6In EC/EMC/DMC electrolyte, lithium deposition dissolution Efficiency is 95%, and circulation 80h behind efficiency is maintained at 90% or so, and capacity is kept almost at 0.9mAh or so, excellent stability.
Embodiment 3
LiTCNQ application:
The LiTCNQ 0.005g prepared as described in Example 1 is weighed, 1mL 1M LiTFSI DOL/DME electricity is added to It solves in liquid (being purchased from Zhangjiagang Cathay Huarong new chemical materials Co., Ltd), small magneton stirring 30min to dissolution is completely to get this The lithium battery electrolytes of invention (it is 0.2%-0.25% that LiTCNQ, which accounts for the mass percentage of lithium battery electrolytes).
To stability and lithium metal of the lithium metal on copper foil in the Li/Cu battery of LiTFSI DOL/DME electrolyte in copper Deposition solubility curve on foil is tested, and is embodied in capacity (charge and discharge 2h under 0.5mA electric current) and coulombic efficiency, knot Fruit is referring to Figure 11 and 12.
To stability and lithium metal of the lithium metal on copper foil in the Li/Cu battery of lithium battery electrolytes of the invention in copper Deposition solubility curve on foil is tested, and is embodied in capacity (charge and discharge 2h under 0.5mA electric current) and coulombic efficiency, knot Fruit is referring to Figure 13 and 14.
The result shows that in 1M LiTFSI DOL/DME electrolyte, the efficiency (showing as coulombic efficiency) of lithium deposition dissolution About 60%, circulation 15h behind efficiency drops to about 5%, and variation is very big, while its capacity is dropped to from initial 0.8mAh or so 0.5mAh or so is changed greatly.In the 1M LiTFSI DOL/DME electrolyte for having added LiTCNQ additive, lithium deposition dissolution Efficiency be about 95%, circulation 80h behind efficiency is maintained at 88% or so, capacity from start to finish substantially remain in 0.85mAh~ Between 0.95mAh, excellent stability.
Embodiment 4
LiTCNQ application:
The LiTCNQ 0.005g prepared as described in Example 1 is weighed, 1mL 1M LiTFSIG DEGDME electricity is added to It solves in liquid (being purchased from Yichuan Jin Hui new energy materials Co., Ltd), small magneton stirring 30min is to dissolution completely to get addition Lithium battery electrolytes of the invention (it is 0.2%-0.25% that LiTCNQ, which accounts for the mass percentage of lithium battery electrolytes).
To stability and lithium metal of the lithium metal on copper foil in the Li/Cu battery of LiTFSIG DEGDME electrolyte in copper Deposition solubility curve on foil is tested, and is embodied in capacity (charge and discharge 2h under 0.5mA electric current) and coulombic efficiency, knot Fruit is referring to Figure 15 and 16.
To stability and lithium metal of the lithium metal on copper foil in the Li/Cu battery of lithium battery electrolytes of the invention in copper Deposition solubility curve on foil is tested, and is embodied in capacity (charge and discharge 2h under 0.5mA electric current) and coulombic efficiency, knot Fruit is referring to Figure 17 and 18.
The result shows that in 1M LiTFSIG DEGDME electrolyte, the efficiency (showing as coulombic efficiency) of lithium deposition dissolution About 80%, circulation 20h behind efficiency is 120%, and deposition solubility curve polarization is very big, while its capacity and extremely unstable, change Change larger.In the 1M LiTFSIG DEGDME electrolyte for having added LiTCNQ additive, the efficiency of lithium deposition dissolution is 95%, Circulation 60h behind efficiency is maintained at 90% or so, while its capacity maintains essentially in 0.9mAh or so, excellent stability.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art Scholar cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention, it is all according to the present invention Equivalent change or modification made by Spirit Essence, should be covered by the protection scope of the present invention.

Claims (9)

1. a kind of lithium battery electrolytes, the lithium battery electrolytes include additive, which is characterized in that the additive is formula (1) compound represented:
2. lithium battery electrolytes according to claim 1, which is characterized in that the purity of formula (1) compound represented More than or equal to 98%.
3. lithium battery electrolytes according to claim 1, which is characterized in that the X-ray of formula (1) compound represented Diffraction pattern 2theta value be 10.5 ° ± 0.2 °, 15.2 ° ± 0.2 °, 17 ° ± 0.2 °, 26 ° ± 0.2 °, 28 ° ± 0.2 °, 29 ° ± There is characteristic peak at 0.2 ° and 31.5 ° ± 0.2 °.
4. lithium battery electrolytes according to claim 1, which is characterized in that the preparation of formula (1) compound represented Method includes: to make reproducibility lithium salts and 7, and 7,8,8- four cyano benzoquinone bismethanes are reacted in organic solvent to get described Formula (1) compound represented.
5. lithium battery electrolytes according to claim 4, which is characterized in that carry out the reaction at 60~80 DEG C.
6. lithium battery electrolytes according to claim 4, which is characterized in that the organic solvent be selected from acetonitrile, ethyl alcohol, One of acetone and chloroform or a variety of combinations；The reproducibility lithium salts is selected from LiI, Li2S and Li2C2O4One of or A variety of combinations.
7. lithium battery electrolytes according to claim 4, which is characterized in that described 7,7,8,8- four cyano benzoquinones two The mass ratio that feeds intake of methane, the reproducibility lithium salts and the organic solvent is 1 ︰, 0.9~1.1 ︰ 35~45.
8. lithium battery electrolytes according to claim 1, which is characterized in that described formula (1) compound represented accounts for institute The mass percentage for stating lithium battery electrolytes is 0.1%~0.5%.
9. a kind of lithium battery, the lithium battery includes electrolyte, which is characterized in that the electrolyte is to appoint in claim 1-8 Lithium battery electrolytes described in one claim.
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