CN108054429A - 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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CN108054429A
CN108054429A CN201711234286.XA CN201711234286A CN108054429A CN 108054429 A CN108054429 A CN 108054429A CN 201711234286 A CN201711234286 A CN 201711234286A CN 108054429 A CN108054429 A CN 108054429A
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lithium
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lithium battery
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CN108054429B (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
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/13—Crystalline forms, e.g. polymorphs
    • 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 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 technology
At this stage, LiFePO is used in commodity electrochemical cell4,LiCoO2, Li2MnO3Transistion metal compounds is waited to 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 400mAh/g, the energy density of battery are limited.With the development of vehicle technology, requirement of the people to battery energy density is more next Higher, the battery of commercialization at present can not 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 Lithium metal is directly used 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, it is primarily present the following problem in the application of restriction lithium：(1) metal The activity of lithium is higher, almost reacts with most of organic solvent, so as to be formed at the interface of lithium metal and electrolyte SEI films, with the progress of reaction, SEI film progressive additives, interface impedance is continuously increased, and coulombic efficiency reduces, and battery capacity declines Subtract；(2) SEI films are unstable, constantly ruptured during removal lithium embedded, and-coming off-regenerates, and consumes lithium metal and electrolyte；(3) Lithium deposits-deviates from process electric current distribution unevenness, causes to deposit uneven, forms Li dendrite, causes security risk and " dead Lithium " causes the loss of irreversible capacity.Therefore, the application of cathode of lithium is realized, the protection of lithium anode is to be badly in need of solving Problem.
At present, in the report of cathode of lithium protection, solid electrolyte interface layer (SEI films) can play down to a certain degree The effect of dendrite inhibition growth.And the method that cathode of lithium protection is carried out using SEI films includes manually manufacturing SEI films and being formed in situ Two kinds of SEI films, artificial SEI embrane methods are 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, and the metal lithium sheet then coated with polymer film is tested.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, make a big impact in practical application to the chemical property of battery.It is formed in situ SEI embrane methods refer to add in a certain amount of electrolysis additive in the electrolytic solution, and additive can be formed in situ one in metallic lithium surface Interfacial layer, so as to play the purpose of protection cathode of lithium.
A kind of new electrolysis additive of proposition of present inventor's innovation, such electrolysis additive can be in lithium Negative terminal surface is formed in situ solid dielectric interface, the effective growth for inhibiting Li dendrite, improves lithium deposition dissolved efficiency, so as to Improve the cyclical stability and security of lithium battery.
The content of the invention
The technical problems to be solved by the invention are to overcome deficiency of the prior art, provide a kind of novel lithium metal cathode Protection electrolysis additive can effectively inhibit lithium dendrite growth, improve lithium deposition dissolved efficiency, and then can promote lithium electricity The performances such as the cyclical stability in pond and security.
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.
For solution more than technical problem, 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 (following easy for description, to be also referred to as LiTCNQ)：
Some preferred aspects according to the present invention, the purity of formula (1) compound represented are 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, use second The method that ether, dichloromethane equal solvent are recrystallized realizes the purifying of formula (1) compound represented；
Alternatively, using the difference of solubility, suitable organic solvent, dissolving, filtering are selected, and then is removed shown in formula (1) 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 It is worth for 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 values for 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.
Another technical solution provided by the invention：A kind of lithium an- ode protection electrolysis additive described above Preparation method, the preparation method include：Make reproducibility lithium salts with 7,7,8,8- four cyano benzoquinone bismethanes organic molten Reaction is to get the formula (1) compound represented in agent.
Preferably, the reaction is made to be 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 (1) compound represented described above.
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 made for formula (1) compound represented is dissolved in conventional electrolysis liquid.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) is mixed according to isometric ratio or EC, DEC and methyl ethyl ester (EMC) are pressed etc. Volume ratio mixes；Lithium battery electrolytes can also be the ethers electrolyte of the electrolytic salts of LiTFSI containing 1M, wherein, ethers has Solvent can be 1,3-dioxolane (DOL) and glycol dimethyl ether (DME) by equal proportion mixing or 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 present invention has the following advantages that compared with 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 polymerisations of LiTCNQ occur for negative terminal surface, so as to form one layer of uniform, stable and thin bag in metallic lithium surface Coating is conducive to the uniform deposition of lithium ion, and so as to effectively inhibit the growth of Li dendrite, it is short to prevent or even avoid battery generation The situation on road, and then the security of lithium battery is improved, and the deposition dissolved efficiency of lithium ion is improved, with circulation time Passage, stable electrochemical properties such as coulombic efficiency, capacity of lithium battery and conservation rate is higher, while its prepare it is simple and in lithium electricity Additive amount is few in the electrolyte of pond, has saved cost, can be beneficial to the big application of industrialization.
Description of the drawings
Fig. 1 is the infrared spectrum compares figure of LiTCNQ and 7,7,8,8- four cyano benzoquinone bismethanes (TCNQ)；
Fig. 2 is the X-ray diffraction spectrogram of LiTCNQ；
Fig. 3 is the stability test figure of lithium in Li/Cu batteries (using the 1M LiPF for not adding LiTCNQ6EC/DEC is electrolysed Liquid)；
Fig. 4 is the deposition solubility curve test chart of lithium in Li/Cu batteries (using the 1M LiPF for not adding LiTCNQ6 EC/ DEC electrolyte)；
Fig. 5 is the stability test figure of lithium in Li/Cu batteries (using the 1M LiPF of addition LiTCNQ6EC/DEC is electrolysed Liquid)；
Fig. 6 is the deposition solubility curve test chart of lithium in Li/Cu batteries (using the 1M LiPF of addition LiTCNQ6 EC/ DEC electrolyte)；
Fig. 7, (the 1M LiPF for not adding LiTCNQ are used for the stability test figure of lithium in Li/Cu batteries6 EC/EMC/DMC Electrolyte)；
Fig. 8 is the deposition solubility curve test chart of lithium in Li/Cu batteries (using the 1M LiPF for not adding LiTCNQ6 EC/ EMC/DMC electrolyte)；
Fig. 9 is the stability test figure of lithium in Li/Cu batteries (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 batteries (using the 1M LiPF of addition LiTCNQ6 EC/ EMC/DMC electrolyte)；
Figure 11 is the stability test figure of lithium in Li/Cu batteries (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 batteries (using the 1M LiTFSI for not adding LiTCNQ DOL/DME electrolyte)；
Figure 13 is the stability test figure of lithium in Li/Cu batteries (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 batteries (using the 1M LiTFSI of addition LiTCNQ DOL/DME electrolyte)；
Figure 15 is the stability test figure of lithium in Li/Cu batteries (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 batteries (using the 1M LiTFSIG for not adding LiTCNQ DEGDME electrolyte)；
Figure 17 is the stability test figure of lithium in Li/Cu batteries (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 batteries (using the 1M LiTFSIG of addition LiTCNQ DEGDME electrolyte)；
Figure 19 is not sum it up the 1M LiPF of addition LiTCNQ6It sinks after respectively being cycled in EC/DEC electrolyte 25 weeks on copper foil 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 born Although pole surface protection 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 dissolutions 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 The big production of industryization.
The test condition for the X-ray diffraction that the present invention is carried out is as follows：
Instrument：Shimadzu XRD-6000 diffractometers
X-ray source：Cu, K α
Sweep speed：2 θ=4 °/min
Said program is described further below in conjunction with specific embodiment；It is to be understood that these embodiments are for illustrating The basic principles, principal features and advantages of the present invention, and the present invention limits from the scope 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 flasks 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 process 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 batteries in embodiment are 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 represented with TCNQ in following embodiments, structural formula It is as follows：
Embodiment 1
It is prepared by LiTCNQ：
1g TCNQ and 1.02gLiI are weighed, grinding is uniform, is then respectively adding in 50mL acetonitrile solutions and stirs 40min. It is reacted at 60-80 DEG C, when the color of solid product becomes purple from yellow, reaction terminates, filtering, and gained production is cleaned with acetonitrile 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 is characterized：
IR tests are done to gained LiTCNQ, and are compared with the IR spectrograms of raw material TCNQ, as shown in Figure 1, can from the figure See, formula (I) compound represented (LiTCNQ) successfully synthesizes.
XRD tests are 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 have feature at 2theta is 10.5 °, 15.2 °, 17 °, 26 °, 28 °, 29 °, 31.5 °, 34 °, 36.5 ° Peak.
LiTCNQ is applied：
0.005g LiTCNQ are weighed, are added to 1mL 1M LiPF6EC/DEC electrolyte (is purchased from Zhangjiagang Cathay Huarong New chemical materials Co., Ltd) in, small magneton stirring 30min to dissolving is completely to get the lithium battery electrolytes of the present invention (mass percentage that LiTCNQ accounts for lithium battery electrolytes is 0.2%-0.25%).
To LiPF6Stability and lithium metal of the lithium metal on copper foil are in copper foil in the Li/Cu batteries of EC/DEC electrolyte On deposition solubility curve be tested, be embodied in capacity (charge and discharge 2h under 0.5mA electric currents) and coulombic efficiency, as a result Referring to Fig. 3 and 4.
To stability and lithium metal of the lithium metal on copper foil in the Li/Cu batteries of the lithium battery electrolytes of the present invention in copper Deposition solubility curve on paper tinsel is tested, and is embodied in capacity (charge and discharge 2h under 0.5mA electric currents) 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 dissolving is about For 88%, cycle 30h behind efficiencies drop to about 55%, while its volume change is very big, is reduced to from initial 0.9mAh or so 0.42mAh or so.Adding the 1M LiPF of LiTCNQ additives6In EC/DEC electrolyte, the efficiency of lithium deposition dissolving is about 95%, Xun Huan 100h behind efficiency keep about 93%, and capacity is kept almost at 0.9mAh or so, excellent stability.
Respectively in LiPF6The lithium battery after 25 weeks is cycled in EC/DEC electrolyte and the lithium battery electrolytes of the present invention It is dismantled, metal lithium sheet DMC solvent cleaning, dryings is taken out under inert atmosphere, the XPS analysis of N element are done to lithium surface.Ginseng See Figure 19, the results showed that, do not adding the 1M LiPF of LiTCNQ6Lithium surface is without N element signal after being cycled in EC/DEC electrolyte, And lithium surface can detect N element signal after the present invention is with the addition of and is cycled in the lithium battery electrolytes of LiTCNQ, it was demonstrated that LiTCNQ occurs polymerization and is covered in lithium surface.
Embodiment 2
LiTCNQ is applied：
The LiTCNQ 0.005g prepared as described in Example 1 are weighed, are added to 1mL 1M LiPF6 EC/EMC/DMC In electrolyte (be purchased from Huarong new chemical materials Co., Ltd of Zhangjiagang Cathay), small magneton stirring 30min to dissolve completely to get The lithium battery electrolytes of the present invention (mass percentage that LiTCNQ accounts for lithium battery electrolytes is 0.2%-0.25%).
To LiPF6Stability and lithium metal of the lithium metal on copper foil exist in the Li/Cu batteries 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 currents) 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 batteries of the lithium battery electrolytes of the present invention in copper Deposition solubility curve on paper tinsel is tested, and is embodied in capacity (charge and discharge 2h under 0.5mA electric currents) 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 dissolving (shows as coulomb effect Rate) it is about 60%, Xun Huan 30h behind efficiencies are about 65%, while capacity also declines quickly, almost only has after a period of time 0.28mAh or so.Adding the 1mL 1M LiPF of LiTCNQ additives6In EC/EMC/DMC electrolyte, lithium deposition dissolving Efficiency is 95%, and Xun Huan 80h behind efficiencies are maintained at 90% or so, and capacity is kept almost at 0.9mAh or so, excellent stability.
Embodiment 3
LiTCNQ is applied：
The LiTCNQ 0.005g prepared as described in Example 1 are weighed, are added to 1mL 1M LiTFSI DOL/DME electricity It solves in liquid (being purchased from Huarong new chemical materials Co., Ltd of Zhangjiagang Cathay), small magneton stirring 30min to dissolving is completely to get this The lithium battery electrolytes of invention (mass percentage that LiTCNQ accounts for lithium battery electrolytes is 0.2%-0.25%).
To stability and lithium metal of the lithium metal on copper foil in the Li/Cu batteries of LiTFSI DOL/DME electrolyte in copper Deposition solubility curve on paper tinsel is tested, and is embodied in capacity (charge and discharge 2h under 0.5mA electric currents) 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 batteries of the lithium battery electrolytes of the present invention in copper Deposition solubility curve on paper tinsel is tested, and is embodied in capacity (charge and discharge 2h under 0.5mA electric currents) 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 dissolving About 60%, Xun Huan 15h behind efficiencies drop 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 additives, lithium deposition dissolving Efficiency be about 95%, cycle 80h behind efficiencies are maintained at 88% or so, capacity from start to finish substantially remain in 0.85mAh~ Between 0.95mAh, excellent stability.
Embodiment 4
LiTCNQ is applied：
The LiTCNQ 0.005g prepared as described in Example 1 are weighed, are added to 1mL 1M LiTFSIG DEGDME electricity It solves in liquid (being purchased from Yichuan Jin Hui new energy materials Co., Ltd), small magneton stirring 30min is to dissolving completely to get addition The lithium battery electrolytes of the present invention (mass percentage that LiTCNQ accounts for lithium battery electrolytes is 0.2%-0.25%).
To stability and lithium metal of the lithium metal on copper foil in the Li/Cu batteries of LiTFSIG DEGDME electrolyte in copper Deposition solubility curve on paper tinsel is tested, and is embodied in capacity (charge and discharge 2h under 0.5mA electric currents) 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 batteries of the lithium battery electrolytes of the present invention in copper Deposition solubility curve on paper tinsel is tested, and is embodied in capacity (charge and discharge 2h under 0.5mA electric currents) 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 dissolving About 80%, Xun Huan 20h behind efficiency are 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 additives, the efficiency of lithium deposition dissolving is 95%, Xun Huan 60h behind efficiencies are 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 can understand present disclosure and implement according to this, and it is not intended to limit the scope of the present invention, it is all according to the present invention The equivalent change or modification that Spirit Essence is made, should be covered by the protection scope of the present invention.

Claims (10)

1. a kind of lithium an- ode protection electrolysis additive, which is characterized in that the electrolysis additive is shown in formula (1) Compound：
2. lithium an- ode protection electrolysis additive according to claim 1, which is characterized in that formula (1) institute The purity for the compound shown is more than or equal to 98%.
3. lithium an- ode protection electrolysis additive according to claim 1, which is characterized in that formula (1) institute The X-ray diffractogram for the compound shown 2theta values for 10.5 ° ± 0.2 °, 15.2 ° ± 0.2 °, 17 ° ± 0.2 °, 26 ° ± There is characteristic peak at 0.2 °, 28 ° ± 0.2 °, 29 ° ± 0.2 ° and 31.5 ° ± 0.2 °.
4. the preparation of the lithium an- ode protection electrolysis additive described in a kind of any one of claim 1-3 claim Method, which is characterized in that the preparation method includes：Reproducibility lithium salts is made to exist with 7,7,8,8- four cyano benzoquinone's bismethanes Reaction is to get the formula (1) compound represented in organic solvent.
5. preparation method according to claim 4, which is characterized in that the reaction is made to be carried out at 60~80 DEG C.
6. preparation method according to claim 4, which is characterized in that the organic solvent is selected from acetonitrile, ethyl alcohol, acetone With one or more combinations in chloroform；The reproducibility lithium salts is selected from LiI, Li2S and Li2C2O4In one or more Combination.
7. preparation method according to claim 4, which is characterized in that described 7,7,8,8- four cyano benzoquinone's diformazans The mass ratio that feeds intake of alkane, the reproducibility lithium salts and the organic solvent is 1 ︰, 0.9~1.1 ︰ 35~45.
8. a kind of lithium battery electrolytes, the lithium battery electrolytes include additive, which is characterized in that the additive includes power Profit requires formula (1) compound represented described in any one of 1-3 claims.
9. lithium battery electrolytes according to claim 8, 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%.
10. a kind of lithium battery, the lithium battery includes electrolyte, which is characterized in that the electrolyte is 8 or 9 institute of claim The lithium battery electrolytes stated.
CN201711234286.XA 2017-11-30 2017-11-30 A kind of lithium an- ode protection electrolysis additive and its preparation method and application Active CN108054429B (en)

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CN109900756A (en) * 2019-01-23 2019-06-18 苏州科技大学 A kind of MXene/ manganese phosphate composite material and preparation method and application

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CN109900756A (en) * 2019-01-23 2019-06-18 苏州科技大学 A kind of MXene/ manganese phosphate composite material and preparation method and application
CN109879754A (en) * 2019-02-11 2019-06-14 李金铃 A kind of compound, non-aqueous electrolyte for lithium ion cell and lithium ion battery

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