CN109980286A - A kind of effective lithium-ion battery electrolytes for inhibiting organic solvent reduction decomposition - Google Patents
A kind of effective lithium-ion battery electrolytes for inhibiting organic solvent reduction decomposition Download PDFInfo
- Publication number
- CN109980286A CN109980286A CN201910351002.8A CN201910351002A CN109980286A CN 109980286 A CN109980286 A CN 109980286A CN 201910351002 A CN201910351002 A CN 201910351002A CN 109980286 A CN109980286 A CN 109980286A
- Authority
- CN
- China
- Prior art keywords
- lithium
- ionic liquid
- lithium salts
- ion battery
- electrolyte
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M10/0568—Liquid materials characterised by the solutes
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a kind of lithium-ion battery electrolytes for effectively inhibiting organic solvent reduction decomposition, including solute, organic solvent, the solute is the mixture of ionic liquid and lithium salts, the organic solvent is carbonic ester, the lithium salts is LiTFSI, and the anion of the ionic liquid is identical as the lithium salts anion.The invention also discloses the preparation method and application of the electrolyte.Preparation method of electrolyte of the invention is simple, compares with the electrolyte formed when using the ionic liquid and organic solvent as cosolvent, can more efficiently inhibit the reduction decomposition of electrolyte, while the SEI film properties that graphite electrode surface is formed are more preferable.
Description
Technical field
The invention belongs to battery electrolyte technical fields, and in particular to ionic liquid forms new electrolyte as cosolute
System and its preparation and application.
Background technique
Commercialized lithium-ion battery electrolytes are made of lithium salts and carbonate solvent, in order to improve the electrochemistry of electrolyte
Some additives are usually added in performance and high temperature performance.But main solvent composition carbonate solvent steam forces down, it is inflammable
It burns, electrochemical window is narrow, is difficult to meet the requirement to lithium ion battery high-energy density, high safety performance at present.
Ionic liquid is since it is good, non-volatile with thermal stability, do not burn, ionic conductivity is high, electrochemical window mouth width
The advantages that, by the concern of numerous researchers, application in the electrolytic solution has also been widely studied.There is researcher will be from
Sub- liquid studies the compatibility of itself and various electrode materials as pure solvent, but since ionic liquid itself is with higher viscous
It spends, capacity attenuation is than very fast in cyclic process, especially in high magnification, so the high rate performance of such electrolyte system
It is all poor with cryogenic property.In order to solve this problem, researcher mixes ionic liquid and traditional carbonate solvent, should
Electrolyte system has converted into the advantage of ionic liquid and carbonate solvent respectively, but its for the first time coulombic efficiency, reversible capacity and
The conservation rate of circulation volume is also less desirable.The advantages of to make full use of ionic liquid, explores ionic liquid in lithium ion
New application is also necessary in battery electrolyte.
Summary of the invention
The present invention is on the basis of existing research, it is contemplated that is the ionic liquid of liquid under room temperature, has solute and solvent
Double grading, provide a kind of lithium-ion battery electrolytes for effectively inhibiting organic solvent reduction decomposition, and provide ion
The preparation method and the application in graphite/Li half-cell of the new application of liquid and this electrolyte system.The present invention selects tool
The ionic liquid and lithium salts for having identical anion structure reduce the type of anion in electrolyte, further as cosolute
Reduce the reduction of graphite electrode surface electrolyte, effectively inhibit the reduction decomposition of electrolyte, while can effectively improve graphite
The SEI film properties of electrode surface.
Technical scheme is as follows:
In a first aspect, the present invention provides novel electrolyte system, including solute salt and organic solvent.
The solute salt is mixed by lithium salts and ionic liquid by different mol ratio, and the lithium salts is that bis trifluoromethyl sulphonyl is sub-
The anion of amine lithium (LiTFSI), the ionic liquid is identical as lithium salts anion.
Preferably, the ionic liquid is bis- (trimethyl fluoride sulfonyl) imines (PP13* of N- methyl-N- propylene phenylpiperidines
TFSI), shown in cationic structural such as formula (I), shown in anion structure such as formula (II).
Preferably, the total mol concentration of the lithium salts and ionic liquid is 2-3.5molL-1
Preferably, the total mol concentration of the lithium salts and ionic liquid is 3molL-1。
Preferably, the molar ratio between the lithium salts and ionic liquid is 3:1-1:1.
It is furthermore preferred that the molar ratio between the lithium salts and ionic liquid is 3:1 or 2:1.
It is furthermore preferred that the molar ratio between the lithium salts and ionic liquid is 3:1,2:1 or 1:1.
Preferably, the organic solvent is carbonic ester.
Preferably, the organic solvent is propene carbonate.
Second aspect, the present invention relates to the preparation method of Novel electrolytic liquid system above-mentioned, the preparation method includes such as
Lower step:
Step 1 takes required lithium salts and ionic liquid；
The desired amount of ionic liquid is put into centrifuge tube by step 2, and the desired amount of organic solvent is added, and is uniformly mixed,
It stands；
The desired amount of lithium salts is dissolved in mixed solution described in step 2, shakes up by step 3, stands, keeps lithium salts complete
Fully dissolved；Up to required electrolyte.
The above operation carries out under inert gas protection, and the further inert gas is argon gas.
Preferably, molar concentration of the mixture of the lithium salts and ionic liquid in carbonate solvent is 3molL-1。
Preferably, it is liquid under the ionic liquid room temperature, prepares Shi Yingxian according between required lithium salts and ionic liquid
Molar ratio calculate the quality of lithium salts and ionic liquid, the carbonic ester for first taking the amount of required ionic liquid to be dissolved in required volume is molten
In agent, required lithium salts is finally weighed again and is dissolved in the mixed solution of foregoing ion liquid and carbonate solvent.
The third aspect, the invention further relates to application of the aforementioned Novel electrolytic liquid system in graphite/Li half-cell.
Fourth aspect, the present invention also provides a kind of lithium ion batteries, with above-mentioned electrolyte system.
Compared with the prior art, the present invention has the advantage that
(1) reduction decomposition for effectively inhibiting electrolyte, extends battery life.
(2) compatibility of PC base electrolyte and graphite cathode, the SEI film properties that graphite electrode surface is formed are effectively improved
More preferably.
(3) viscosity of electrolyte increases without the addition because of ionic liquid, and conductivity dramatically increases, and improves electricity
Solve the physical property of liquid.
(4) electrolyte quota method of the invention breaches the conventional application method of ionic liquid, and matches in this approach
The electrolyte set can more effectively improve the physical property and chemical property of carbonate solvent PC base electrolyte.
Certainly, implement product of the invention not needing to reach all the above advantage simultaneously.
Detailed description of the invention
Fig. 1 .1 be 2 ionic liquid of the embodiment of the present invention as cosolute when CV curve；
Fig. 1 .2 be 3 ionic liquid of comparative example as cosolvent when CV curve carry out；
Fig. 1 .3 is 5 ionic liquid of comparative example as cosolute, lithium salts anion and the asynchronous CV of ionic liquid anion
Curve；
Fig. 2 .1 is embodiment 1-3 and 1 graphite electrode of comparative example is electrolyte of the present invention and ionic liquid as cosolvent
The long-term cycle performance of electrolyte compares；
Fig. 2 .2 is that embodiment 2 and 3 graphite electrode intermediate ion liquid of comparative example are followed with the long-term of the electrolyte that PC is cosolvent
Ring performance compares；
Fig. 3 is that (longitudinal axis is conductance to conductivity Arrhenius figure at different temperatures for embodiment 1-3 and 1 electrolyte of comparative example
The logarithm of rate, inverse of the horizontal axis for thermodynamic temperature, Arrhenius formula:Both sides take logarithm up to horizontal in figure
Ordinate).
Specific embodiment
Herein, the range indicated by " numerical value to another numerical value ", is that one kind avoids enumerating in the description
The summary representation of all numerical value in the range.Therefore, the record of a certain special value range, covers the numberical range
Interior any number and the relatively fractional value range defined by any number in the numberical range, as bright in the description
Text writes out any number as should be compared with fractional value range.
The present invention on the basis of existing technology, by ionic liquid PP13*TFSI replaces the portion in PC solution as solute salt
Divide lithium salts, actually reduce lithium salt, selects LiTFSI as lithium salts, the anion phase of anion and ionic liquid
It together, is all TFSI-, so what is mainly adjusted after ionic liquid substitution part lithium salts is the ligancy of lithium ion, lead to electrolyte
Become two electronics and an electron reduction from two electron reductions in the reduction reaction that graphite surface occurs while occurring, is i.e. reduzate
By Li2CO3Based on become Li2CO3Based on LODP.Electrolyte can more effectively be inhibited with the two SEI film as main component
Reduction decomposition improves the chemical property of electrolyte so the SEI film properties that graphite electrode surface is formed are more preferable.
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate this hair
It is bright, rather than limit the scope of protection of the present invention.What those skilled in the art made according to the present invention in practical applications changes
Into and adjustment, still fall within protection scope of the present invention.Unless otherwise defined, the term as used herein and one skilled in the art institute
Known meaning is identical.PC: propene carbonate；PP13*TFSI:N- methyl-N- propylene phenylpiperidines bis- (trimethyl fluoride sulfonyls) are sub-
Amine.
Embodiment 1
The lithium-ion battery electrolytes in the present invention are prepared in glove box, main component includes lithium salts, ionic liquid, has
Solvent.The lithium salts is LiTFSI, and ionic liquid is bis- (trimethyl fluoride sulfonyl) imines of N- methyl-N- propylene phenylpiperidines
(PP13*TFSI), organic solvent is propene carbonate, and the molar ratio of lithium salts and ionic liquid is 3:1, lithium salts and ionic liquid
Total mol concentration is 3molL-1。
The preparation method of above-mentioned electrolyte is:
The quality of lithium salts and ionic liquid needed for calculating according to the molar ratio of lithium salts and ionic liquid first claims in centrifuge tube
The desired amount of ionic liquid is taken, the desired amount of PC solvent is added, sufficiently shakes up；The desired amount of lithium salts dissolution is weighed again wherein, is shaken
It is even, stand at least 24 hours to get required electrolyte solution.
The performance test of electrolyte: the lithium-ion battery electrolytes that the present embodiment is obtained are used to assemble graphite-lithium button
Half-cell tests 0.01-2V, 0.1C rate charge-discharge cycle performance under graphite-lithium half-cell room temperature.Test result are as follows: for the first time
Coulombic efficiency 84.2%, capacity retention ratio is about 91% after 200 circles recycle, and long-term cycle performance as shown in Fig. 2 .1, survey by conductivity
Examination as shown in figure 3, the present embodiment sample in the various figures label be13*TFSI(3:1)/PC。
Embodiment 2
The lithium-ion battery electrolytes in the present invention are prepared in glove box, main component includes lithium salts, ionic liquid, has
Solvent.The lithium salts is LiTFSI, and ionic liquid is bis- (trimethyl fluoride sulfonyl) imines of N- methyl-N- propylene phenylpiperidines
(PP13*TFSI), organic solvent is propene carbonate, and the molar ratio of lithium salts and ionic liquid is 2:1, lithium salts and ionic liquid
Total mol concentration is 3molL-1。
The preparation method of above-mentioned electrolyte is:
The quality of lithium salts and ionic liquid needed for calculating according to the molar ratio of lithium salts and ionic liquid first claims in centrifuge tube
The desired amount of ionic liquid is taken, the desired amount of organic solvent PC is added, sufficiently shakes up；The desired amount of lithium salts is weighed again dissolves it
In, it shakes up, stand at least 24 hours to get required electrolyte solution.
The performance test of electrolyte: the lithium-ion battery electrolytes that the present embodiment is obtained are used to assemble graphite-lithium button
Half-cell tests 0.01-2V, 0.1C rate charge-discharge cycle performance under graphite-lithium half-cell room temperature.Test result are as follows: for the first time
Coulombic efficiency 86.8%, capacity retention ratio is about 101% after 200 circles recycle；CV curve is as shown in Fig. 1 .1, two curve difference
To recycle 1 time and recycling gained twice；Long-term cycle performance is as shown in Fig. 2 .1, and long-term cycle performance is as shown in Fig. 2 .2, conductance
Rate test is as shown in figure 3, the present embodiment sample marks in Fig. 1 .1, Fig. 2 .1, Fig. 3 is13*TFSI (2:1)/PC,
Label is in Fig. 2 .213*TFSI=2:1 (m/m).
Embodiment 3
The lithium-ion battery electrolytes in the present invention are prepared in glove box, main component includes lithium salts, ionic liquid, has
Solvent.The lithium salts is LiTFSI, and ionic liquid is bis- (trimethyl fluoride sulfonyl) imines of N- methyl-N- propylene phenylpiperidines
(PP13*TFSI), organic solvent is propene carbonate (PC), and the molar ratio of lithium salts and ionic liquid is 1:1, lithium salts and ionic liquid
The total mol concentration of body is 3molL-1。
The preparation method of above-mentioned electrolyte is:
The quality of lithium salts and ionic liquid needed for calculating according to the molar ratio of lithium salts and ionic liquid first claims in centrifuge tube
The desired amount of ionic liquid is taken, the desired amount of organic solvent PC is added, sufficiently shakes up；The desired amount of lithium salts is weighed again dissolves it
In, it shakes up, stand at least 24 hours to get required electrolyte solution.
The performance test of electrolyte: the lithium-ion battery electrolytes that the present embodiment is obtained are used to assemble graphite-lithium button
Half-cell tests 0.01-2V, 0.1C rate charge-discharge cycle performance under graphite-lithium half-cell room temperature.Test result are as follows: for the first time
Coulombic efficiency 75.9%, capacity retention ratio is about 80% after 200 circles recycle；Long-term cycle performance is as shown in Fig. 2 .1, the present embodiment
Sample marks in figure13*TFSI(1:1)/PC；Conductivity is tested as shown in figure 3, the present embodiment sample is being schemed
Middle label is13*TFSI(1:1)/PC。
Comparative example 1
The lithium-ion battery electrolytes in the present invention are prepared in glove box, main component includes lithium salts, organic solvent.Institute
Stating lithium salts is LiTFSI, and organic solvent is cyclic carbonate solvents propene carbonate (PC), mole of lithium salts in organic solvent
Concentration is 3molL-1。
The preparation method of above-mentioned electrolyte is:
The lithium salts of the quality, is dissolved in the PC of a predetermined amount by the quality of lithium salts needed for calculating according to the molar concentration of lithium salts
It in solvent, sufficiently shakes up, stands at least 24 hours, form uniform, stable electrolyte solution.
The performance test of electrolyte: the lithium-ion battery electrolytes that the present embodiment is obtained are used to assemble graphite-lithium button
Half-cell tests 0.01-2V, 0.1C rate charge-discharge cycle performance under graphite-lithium half-cell room temperature.Test result are as follows: for the first time
Coulombic efficiency 48.9%, capacity retention ratio is about 80% after 200 circles recycle.Long-term cycle performance as shown in Fig. 2 .1, survey by conductivity
Examination as shown in figure 3, this comparative example in the various figures label be.
Comparative example 2
It is a kind of inhibit organic solvent reduction decomposition lithium-ion battery electrolytes, main component include lithium salts, ionic liquid,
Organic solvent.The lithium salts is LiTFSI, and ionic liquid is bis- (trimethyl fluoride sulfonyl) imines of N- methyl-N- propylene phenylpiperidines
(PP13*TFSI), organic solvent is propene carbonate (PC), PC and PP13*The volume ratio of TFSI is 7:3, the molar concentration of lithium salts
For 1molL-1。
The preparation method of above-mentioned electrolyte is:
The quality of lithium salts needed for calculating according to the molar concentration of lithium salts, first weighs the desired amount of lithium salts in centrifuge tube, adds
Enter the desired amount of organic solvent PC, sufficiently shakes up；The desired amount of ionic liquid is measured again to be added thereto, and is shaken up, is stood at least 24
Hour is to get required electrolyte solution.
The performance test of electrolyte: the lithium-ion battery electrolytes that the present embodiment is obtained are used to assemble graphite-lithium button
Half-cell, for the first time coulombic efficiency 66.81%.
Comparative example 3
It is a kind of inhibit organic solvent reduction decomposition lithium-ion battery electrolytes, main component include lithium salts, ionic liquid,
Organic solvent.The lithium salts is LiTFSI, and ionic liquid is bis- (trimethyl fluoride sulfonyl) imines of N- methyl-N- propylene phenylpiperidines
(PP13*TFSI), organic solvent is propene carbonate (PC), PC and PP13*The volume ratio of TFSI is 6:4, the molar concentration of lithium salts
For 1molL-1。
The preparation method of above-mentioned electrolyte is:
The quality of lithium salts needed for calculating according to the molar concentration of lithium salts, first weighs the desired amount of lithium salts in centrifuge tube, adds
Enter the desired amount of organic solvent PC, sufficiently shakes up；The desired amount of ionic liquid is measured again to be added thereto, and is shaken up, is stood at least 24
Hour is to get required electrolyte solution.
The performance test of electrolyte: the lithium-ion battery electrolytes that the present embodiment is obtained are used to assemble graphite-lithium button
Half-cell tests the CV curve under graphite-lithium half-cell room temperature, voltage range 0-2.5V, sweep speed 0.05mVs-1.Test
As a result are as follows: coulombic efficiency 70.1% for the first time.As are shown in figure 1.2, this comparative example is labeled as PC:PP to CV curve13*TFSI=6:
4；For long-term cycle performance as shown in Fig. 2 .2, this comparative example is labeled as PC:PP13*TFSI=6:4 (v:v).
Comparative example 4
It is a kind of inhibit organic solvent reduction decomposition lithium-ion battery electrolytes, main component include lithium salts, ionic liquid,
Organic solvent.The lithium salts is LiTFSI, and ionic liquid is bis- (trimethyl fluoride sulfonyl) imines of N- methyl-N- propylene phenylpiperidines
(PP13*TFSI), organic solvent is cyclic carbonate solvents propene carbonate (PC), PC and PP13*The volume ratio of TFSI is 5:5,
The molar concentration of lithium salts is 1molL-1。
The preparation method of above-mentioned electrolyte is:
The quality of lithium salts needed for calculating according to the molar concentration of lithium salts, first weighs the desired amount of lithium salts in centrifuge tube, adds
Enter the desired amount of organic solvent PC, sufficiently shakes up；The desired amount of ionic liquid is measured again to be added thereto, and is shaken up, is stood at least 24
Hour is to get required electrolyte solution.
The performance test of electrolyte: the lithium-ion battery electrolytes that the present embodiment is obtained are used to assemble graphite-lithium button
Half-cell, for the first time coulombic efficiency 63.39%.
Comparative example 5
The electrolyte in the present invention is prepared in glove box, main component has: organic solvent, lithium salts, ionic liquid.It is described
Organic solvent is propene carbonate (PC), lithium salts LiPF6, ionic liquid PP13*TFSI, LiPF6And PP13*Mole of TFSI
Than for 4:1, the total mol concentration of lithium salts and ionic liquid in organic solvent is 2.5mol/L.
The preparation method of above-mentioned lithium-ion battery electrolytes:
Step 1, stoichiometry is weighed according to the molar ratio of the molar concentration of electrolyte and lithium salts and ionic liquid
PP13*TFSI is dissolved in the PC solvent of certain volume；
Step 2, stoichiometry is weighed according to the molar ratio of the molar concentration of electrolyte and lithium salts and ionic liquid
LiPF6, it is dissolved in mixed solution 1)；
Step 3, above-mentioned solution is sufficiently shaken up, is stood for 24 hours.
The lithium-ion battery electrolytes that the present embodiment is obtained are used to assemble graphite-lithium button half-cell, test graphite-lithium
CV curve under half-cell room temperature, voltage range 0-2.5V, sweep speed 0.05mVs-1, as shown in Fig. 1 .3.After 100 circle circulations
Capacity retention ratio is 107% or more.
Fig. 1 .1 and Fig. 1 .2 is CV curve, statistics indicate that: with ionic liquid PP13*TFSI is as cosolvent (PC:PP13*
TFSI=6:4 it) compares, ionic liquid is as cosolute (LiTFSI:PP13* TFSI=2:1) when 0.7V or so electrolyte
Reduction peak is smaller, and the reduction decomposition of electrolyte can more be effectively inhibited by illustrating the ionic liquid as cosolute.Fig. 1 .1, figure
1.3CV curve compares, (LiTFSI:PP when ionic liquid anion is identical as lithium salts anion13*TFSI=2:1), at 0.7V also
Parent peak is smaller；In terms of the deintercalation Li electric current of 0V or so, the current peak in Fig. 1 .1 is stronger, illustrates SEI film of the invention to lithium ion
Obstruction it is smaller, Li deviates from from graphite linings and insertion is easier, and SEI film properties improve significant.Therefore ionic liquid of the present invention
The reduction decomposition of electrolyte, the SEI film that graphite electrode surface is formed can be more effectively inhibited as solute salt substitution part lithium salts
Performance is more preferable.
Compared with Fig. 2 .1 is long-term cycle performance with Fig. 2 .2, from Fig. 2 .1 as can be seen that when solute salt is free of ionic liquid
(LiTFSI/PC), specific capacity straight line declines after circulation counts to 13 circles；And ionic liquid as cosolute when (LiTFSI+PP13*
TFSI(3:1)/PC；LiTFSI+PP13*TFSI(2:1)/PC；LiTFSI+PP13*TFSI (1:1)/PC), with the increase of recurring number,
Specific capacity variation is smaller, wherein LiTFSI:PP13*Long-term cycle performance is preferably also more stable when TFSI=2:1 (m/m).Fig. 2 .2
It is to choose in comparative example the best 3 (PC:PP of comparative example of capacity retention ratio after 200 circle circulations13*TFSI=6:4 (V/V)), with reality
Apply 2 electrolyte LiTFSI:PP of example13*The long-term cycle performance of TFSI=2:1 (m/m) compares, the long-term cyclicity of electrolyte of the invention
Can be more excellent, the compatibility of PC base electrolyte and graphite cathode can be more effectively improved, to can also illustrate the stone in this electrolyte
The SEI film properties that electrode ink surface is formed are more preferable.
Fig. 3 be the conductivity of embodiment 1-3 and 1 electrolyte of comparative example at different temperatures, from experimental result as can be seen that
Although ionic liquid itself has very high viscosity, the addition of the ionic liquid does not influence the conductivity of electrolyte, instead
And with the addition of ionic liquid, conductivity increases, and the physical property of electrolyte also makes moderate progress.
It is found that ionic liquid is as cosolute from the data of coulombic efficiency for the first time that embodiment 1-3 and comparative example 1-4 is provided
When, coulombic efficiency significantly improves for the first time, and up to 86.8%.In conjunction with the test of long-term cycle performance, conductivity test, ionic liquid
Electrolyte when body is as cosolute can more effectively improve the compatibility of PC base electrolyte and graphite cathode, and electrolyte is in electrode
The reduction decomposition on surface is obviously reduced；The SEI film formed by electrolyte reduction decomposition in electrode surface is thin and compact, stability
More preferably.
In conclusion electrolyte configuration method of the invention breaches the conventional application method of ionic liquid, ionic liquid
PP13*When TFSI is as cosolute, the reduction decomposition of electrolyte can be significantly inhibited, is effectively improved the SEI of graphite electrode surface formation
Film properties, and the electrolyte configured in this approach can more effectively improve the electrochemistry of carbonate solvent PC base electrolyte
Energy.
Under the teaching of the present invention and the above embodiments, those skilled in the art are easy to it is envisioned that cited by the present invention
Or each raw material enumerated or its equivalent alterations, each processing method or its equivalent alterations can realize the present invention and each original
The parameter bound value of material and processing method, interval value can realize the present invention, embodiment numerous to list herein.
Claims (10)
1. a kind of lithium-ion battery electrolytes, including solute, organic solvent, the solute is the mixing of ionic liquid and lithium salts
Object, the organic solvent be carbonic ester, it is characterised in that: the lithium salts be LiTFSI, the anion of the ionic liquid with
The anion of the lithium salts is identical.
2. lithium-ion battery electrolytes according to claim 1, it is characterised in that: the ionic liquid is N- methyl-N-
Bis- (trimethyl fluoride sulfonyl) imines of propylene phenylpiperidines.
3. lithium-ion battery electrolytes according to claim 1, it is characterised in that: the lithium salts and ionic liquid always rub
Your concentration is 2-3.5molL-1。
4. lithium-ion battery electrolytes according to claim 1, it is characterised in that: between the lithium salts and ionic liquid
Molar ratio is 3:1-1:1.
5. lithium-ion battery electrolytes according to claim 1, it is characterised in that: between the lithium salts and ionic liquid
Molar ratio is 3:1 or 2:1.
6. lithium-ion battery electrolytes according to claim 1, it is characterised in that: the carbonate solvent is propylene carbonate
Ester.
7. lithium-ion battery electrolytes according to claim 1, it is characterised in that: it is made with the following method, it first will be from
Sub- liquid and organic solvent mix, and add lithium salts, dissolve, mix, stand to obtain the final product.
8. a kind of prepare the method such as the described in any item lithium-ion battery electrolytes of claim 1-7, it is characterised in that: including
Step:
Step 1 takes required lithium salts and ionic liquid；
The desired amount of ionic liquid is put into centrifuge tube by step 2, and the desired amount of organic solvent is added, and is uniformly mixed, and is stood；
The desired amount of lithium salts is dissolved in mixed solution described in step 2, shakes up by step 3, stands, keeps lithium salts completely molten
Solution；Up to required electrolyte.
The above operation carries out under inert gas protection.
9. lithium-ion battery electrolytes described in -7 any one are preparing the application in graphite/Li half-cell according to claim 1.
10. a kind of lithium ion battery, it is characterised in that: with the electrolyte any in claim 1-7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910351002.8A CN109980286A (en) | 2019-04-28 | 2019-04-28 | A kind of effective lithium-ion battery electrolytes for inhibiting organic solvent reduction decomposition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910351002.8A CN109980286A (en) | 2019-04-28 | 2019-04-28 | A kind of effective lithium-ion battery electrolytes for inhibiting organic solvent reduction decomposition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109980286A true CN109980286A (en) | 2019-07-05 |
Family
ID=67086797
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910351002.8A Pending CN109980286A (en) | 2019-04-28 | 2019-04-28 | A kind of effective lithium-ion battery electrolytes for inhibiting organic solvent reduction decomposition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109980286A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101087035A (en) * | 2006-06-06 | 2007-12-12 | 比亚迪股份有限公司 | An electrolyte for secondary lithium battery and secondary lithium battery using this electrolyte |
| CN101271989A (en) * | 2008-04-30 | 2008-09-24 | 深圳新宙邦科技股份有限公司 | Lithium ion battery room temperature ionic liquid electrolyte and method for producing the same |
| CN103618111A (en) * | 2013-12-13 | 2014-03-05 | 东莞市凯欣电池材料有限公司 | Ion liquid electrolytic solution and secondary lithium battery containing electrolytic solution |
| US20140087214A1 (en) * | 2012-03-14 | 2014-03-27 | Glenn G. Amatucci | Electrochemical Devices and Methods of Fabrication |
| US20160240840A1 (en) * | 2015-02-18 | 2016-08-18 | Hui He | Alkali metal-sulfur secondary battery containing a pre-sulfurized cathode and production process |
| WO2017081182A1 (en) * | 2015-11-10 | 2017-05-18 | Grabat Energy S.L. | Carbon composites |
| CN106876787A (en) * | 2016-12-08 | 2017-06-20 | 盐城利庞新型材料科技有限公司 | A kind of il electrolyte and the serondary lithium battery containing the electrolyte |
| CN107799826A (en) * | 2017-11-01 | 2018-03-13 | 上海应用技术大学 | Improve electrolyte of graphite electrode surface solid electrolyte film properties and preparation method thereof |
-
2019
- 2019-04-28 CN CN201910351002.8A patent/CN109980286A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101087035A (en) * | 2006-06-06 | 2007-12-12 | 比亚迪股份有限公司 | An electrolyte for secondary lithium battery and secondary lithium battery using this electrolyte |
| CN101271989A (en) * | 2008-04-30 | 2008-09-24 | 深圳新宙邦科技股份有限公司 | Lithium ion battery room temperature ionic liquid electrolyte and method for producing the same |
| US20140087214A1 (en) * | 2012-03-14 | 2014-03-27 | Glenn G. Amatucci | Electrochemical Devices and Methods of Fabrication |
| CN103618111A (en) * | 2013-12-13 | 2014-03-05 | 东莞市凯欣电池材料有限公司 | Ion liquid electrolytic solution and secondary lithium battery containing electrolytic solution |
| US20160240840A1 (en) * | 2015-02-18 | 2016-08-18 | Hui He | Alkali metal-sulfur secondary battery containing a pre-sulfurized cathode and production process |
| WO2017081182A1 (en) * | 2015-11-10 | 2017-05-18 | Grabat Energy S.L. | Carbon composites |
| CN106876787A (en) * | 2016-12-08 | 2017-06-20 | 盐城利庞新型材料科技有限公司 | A kind of il electrolyte and the serondary lithium battery containing the electrolyte |
| CN107799826A (en) * | 2017-11-01 | 2018-03-13 | 上海应用技术大学 | Improve electrolyte of graphite electrode surface solid electrolyte film properties and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| HONGHE ZHENG等: "Film-Forming Properties of Propylene Carbonate in the Presence of a Quaternary Ammonium Ionic Liquid on Natural Graphite Anode", 《J. PHYS. CHEM. C》 * |
| XIMEI GAO等: "Optimizing solid electrolyte interphase on graphite anode by adjusting the electrolyte solution structure with ionic liquid", 《ELECTROCHIMICA ACTA》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lane et al. | The electrochemistry of lithium in ionic liquid/organic diluent mixtures | |
| CN107293789B (en) | Lithium ion battery with good circulation effect and electrolyte thereof | |
| Zhang et al. | From lithium to emerging mono-and multivalent-cation-based rechargeable batteries: non-aqueous organic electrolyte and interphase perspectives | |
| Mizrahi et al. | Electrolyte solutions with a wide electrochemical window for rechargeable magnesium batteries | |
| CN103972588B (en) | Non-aqueous electrolyte and lithium ion battery | |
| Sirisopanaporn et al. | New, ionic liquid-based membranes for lithium battery application | |
| Yoshida et al. | Change from glyme solutions to quasi-ionic liquids for binary mixtures consisting of lithium bis (trifluoromethanesulfonyl) amide and glymes | |
| Sauvage et al. | Study of the insertion/deinsertion mechanism of sodium into Na0. 44MnO2 | |
| CN103765663B (en) | Ionic liquid nanoscale ionic material compositionss, methods and applications | |
| Kubota et al. | Novel inorganic ionic liquids possessing low melting temperatures and wide electrochemical windows: Binary mixtures of alkali bis (fluorosulfonyl) amides | |
| Lee et al. | Lithium salt solutions in mixed sulfone and sulfone-carbonate solvents: A Walden plot analysis of the maximally conductive compositions | |
| US5874185A (en) | Polymer electrolyte material for use in lithium and lithium ion batteries | |
| Ma et al. | Pseudoconcentrated electrolyte with high ionic conductivity and stability enables high-voltage lithium-ion battery chemistry | |
| Matsumoto et al. | Thermal, physical, and electrochemical properties of Li [N (SO2F) 2]-[1-ethyl-3-methylimidazolium][N (SO2F) 2] ionic liquid electrolytes for li secondary batteries operated at room and intermediate temperatures | |
| Wu et al. | Study of the electrochemical characteristics of sulfonyl isocyanate/sulfone binary electrolytes for use in lithium-ion batteries | |
| Li et al. | Determining the absolute anodic stability threshold of polymer electrolytes: a capacity-based electrochemical method | |
| Hofmann et al. | Electrolyte Mixtures Based on Ethylene Carbonate and Dimethyl Sulfone for Li‐Ion Batteries with Improved Safety Characteristics | |
| CN108539257A (en) | Lithium secondary cell electrolyte and its lithium secondary battery | |
| Biernacka et al. | Development of new solid-state electrolytes based on a hexamethylguanidinium plastic crystal and lithium salts | |
| CN105938918A (en) | Liquid electrolyte for fluoride ion battery and fluoride ion battery | |
| Grundy et al. | Impact of frictional interactions on conductivity, diffusion, and transference number in ether-and perfluoroether-based electrolytes | |
| Salem et al. | Non-flammable electrolyte mixtures of ringed ammonium-based ionic liquids and ethylene carbonate for high voltage Li-ion batteries | |
| CN108767318A (en) | A kind of lithium salt electrolyte containing additive | |
| CN106876787A (en) | A kind of il electrolyte and the serondary lithium battery containing the electrolyte | |
| Zhao et al. | Thermally and oxidatively stable polymer electrolyte for lithium batteries enabled by phthalate plasticization |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190705 |