CN107863558A - Electrolyte and its application for lithium ion battery - Google Patents
Electrolyte and its application for lithium ion battery Download PDFInfo
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- CN107863558A CN107863558A CN201711012280.8A CN201711012280A CN107863558A CN 107863558 A CN107863558 A CN 107863558A CN 201711012280 A CN201711012280 A CN 201711012280A CN 107863558 A CN107863558 A CN 107863558A
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- Prior art keywords
- electrolyte
- lithium
- ion battery
- additive
- lithium salt
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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
- H01M10/0568—Liquid materials characterised by the solutes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—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
- H01M10/0569—Liquid materials characterised by the solvents
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0037—Mixture of solvents
- H01M2300/004—Three solvents
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a kind of electrolyte for lithium ion battery, and it includes the electrolyte lithium salt and additive of organic solvent dissolving；Wherein, the concentration of electrolyte lithium salt is 1.0mol/L；It is 1 that electrolyte lithium salt, which includes the ratio between amount of material,:1~9:1 double (trifluorosulfonimide) lithiums and difluorine oxalic acid boracic acid lithium；The concentration of additive is 0.01mol/L~0.4mol/L, and additive is lithium hexafluoro phosphate；Organic solvent is that mass ratio is 1~2:1~2:3~5 ethylene carbonate, propylene carbonate acid esters and methyl ethyl carbonate.Li dendrite can be reduced according to the electrolyte of the present invention in use, belong to one kind and have high temperature resistant, low temperature resistant and there is high-tension Novel electrolytic liquid system concurrently.The invention also discloses application of the above-mentioned electrolyte in lithium ion battery.
Description
Technical field
The invention belongs to technical field of lithium ion, it relates in particular to a kind of electrolyte for lithium ion battery,
And its application in lithium ion battery.
Background technology
Lithium ion battery have operating voltage is high, have extended cycle life, self discharge is small, memory-less effect bigger than energy, without dirt
The advantages that dye, thus it is widely used in the numerous areas such as notebook computer, portable dam, mobile communication, electric automobile.Electricity
Important component of the liquid as lithium ion battery is solved, the research to it has great meaning to the performance for improving lithium ion battery
Justice.
The common electrolyte system for lithium ion battery is made up of lithium hexafluoro phosphate and carbonate-based solvent, carbonic ester
Class solvent includes dimethyl carbonate, ethylene carbonate, propene carbonate etc..Lithium hexafluoro phosphate has higher solubility and conductance
Rate, but its heat endurance is poor, it is strong to water sensitivity, easily decompose and produce LiF and PF5, and aggravation is reacted under high temperature；Caused PF5
With very strong acidity, not only make the cyclic carbonate in solvent that ring-opening reaction occur, or decompose some linear carbonates, also
Reacted with minor amount of water and produce HF, further corroded positive electrode, battery capacity is decayed rapidly.
Therefore, it is that technology urgently to be resolved hurrily is asked to explore a kind of Novel electrolytic liquid system that can be overcome or avoid above mentioned problem
Topic.
The content of the invention
To solve the above-mentioned problems of the prior art, the invention provides a kind of electrolyte for lithium ion battery,
It can reduce Li dendrite in use, belong to one kind and have high temperature resistant, low temperature resistant and have high-tension Novel electrolytic concurrently
Liquid system.
In order to reach foregoing invention purpose, present invention employs following technical scheme：
A kind of electrolyte for lithium ion battery, include the electrolyte lithium salt and additive of organic solvent dissolving；Wherein,
The concentration of the electrolyte lithium salt is 1.0mol/L；It is 1 that the electrolyte lithium salt, which includes the ratio between amount of material,:1~9:1 pair
(trifluorosulfonimide) lithium and difluorine oxalic acid boracic acid lithium；The concentration of the additive is 0.01mol/L~0.4mol/L；It is described to add
It is lithium hexafluoro phosphate to add agent；The organic solvent is that mass ratio is 1~2:1~2:3~5 ethylene carbonate, propylene carbonate
Acid esters and methyl ethyl carbonate.
Further, it is 3 that the electrolyte lithium salt, which includes the ratio between amount of material,:2 double (trifluorosulfonimide) lithiums and two
Fluorine Lithium bis (oxalate) borate.
Further, the organic solvent is that mass ratio is 1:1:3 ethylene carbonate, propylene carbonate acid esters and carbonic acid
Methyl ethyl ester.
Another object of the present invention is to provide application of a kind of as above any described electrolyte in lithium ion battery.
Further, the positive electrode of the lithium ion battery is LiNi0.5Co0.2Mn0.3O2, negative material is lithium metal.
The present invention by with the ratio between amount of material be 1:1~9:1 double (trifluorosulfonimide) lithiums and difluoro oxalate boric acid
Lithium is as electrolyte lithium salt, formation matrix electrolyte, then adds the additive lithium hexafluoro phosphate of scheduled volume thereto, finally by
The organic solvent dissolved dilution said components of predetermined composition can obtain the electrolyte of the present invention；The electrolyte can be up to 60
DEG C to as little as being used in -20 DEG C of temperature range, and compared with prior art in conventional lithium ion battery 2.5V~3.7V
Operating voltage range, its operating voltage range is 2.7V~4.3V, is a kind of high temperature resistant, low temperature resistant and with high-tension
Novel electrolyte, also, the electrolyte can reduce Li dendrite in use, embody more preferable application effect.
Brief description of the drawings
The following description carried out in conjunction with the accompanying drawings, above and other aspect, feature and the advantage of embodiments of the invention
It will become clearer, in accompanying drawing：
Fig. 1 is SEM of the pole piece under different multiplying after the copper lithium half-cell test in 11 according to an embodiment of the invention
Picture；
Fig. 2 is SEM picture of the pure copper foil in 11 under different multiplying according to an embodiment of the invention；
Fig. 3 is that SEM of the pole piece under different multiplying after the copper lithium half-cell test in the comparative example 1 according to the present invention schemes
Piece；
Fig. 4 is that SEM of the pole piece under different multiplying after the copper lithium half-cell test in the comparative example 2 according to the present invention schemes
Piece.
Embodiment
Hereinafter, with reference to the accompanying drawings to embodiments of the invention are described in detail.However, it is possible to come in many different forms real
Apply the present invention, and the specific embodiment of the invention that should not be construed as limited to illustrate here.Conversely, there is provided these implementations
Example is in order to explain the principle and its practical application of the present invention, so that others skilled in the art are it will be appreciated that the present invention
Various embodiments and be suitable for the various modifications of specific intended application.
The invention provides a kind of electrolyte for lithium ion battery, and it includes the electrolyte lithium salt of organic solvent dissolving
And additive.
Specifically, in the electrolyte, the concentration of electrolyte lithium salt is 1.0mol/L；The concentration of additive is 0.01mol/
L~0.4mol/L.
Specifically, it is 1 that electrolyte lithium salt, which includes the ratio between amount of material,:1~9:1 double (trifluorosulfonimide) lithiums are (following
Abbreviation LiTFSI) and difluorine oxalic acid boracic acid lithium (hereinafter referred to as LiDFOB), the ratio between amount of preferred substance is 3:2；Additive is six
Lithium fluophosphate (hereinafter referred to as LiPF6)；Organic solvent is that mass ratio is 1~2:1~2:3~5 ethylene carbonate (following letter
Claim EC), propylene carbonate acid esters (hereinafter referred to as PC) and methyl ethyl carbonate (hereinafter referred to as EMC), the ratio between preferred mass is 1:1:3.
In the above-mentioned electrolyte of the present invention, the above-mentioned organic solvent with specific components and fixed composition can ensure electricity
Solution liquid has relatively low freezing point, while makes the electrolyte also high temperature resistant；Additive LiPF6With the collective effect of electrolyte lithium salt
It is to strengthen electrolyte in use to the interface stability of negative pole, reduces Li dendrite；And above-mentioned particular electrolyte lithium salts
Composition LiTFSI can improve the ionic conductance of electrolyte, and another composition LiDFOB can suppress LiTFSI to collector aluminium
Corrosion, while improve the resistance to elevated temperatures of the electrolyte.Thus, according to the present invention electrolyte have concurrently it is low temperature resistant (it is minimum can to-
20 DEG C), the characteristic of high temperature resistant (up to 60 DEG C), and it can suppress electrolyte to negative material metal in use
Li dendrite caused by lithium, so as to improve the high voltage capability of electrolyte.
It will be made up of below specific embodiment to embody the specific proportioning of the above-mentioned electrolyte of the present invention, but following realities
Apply the specific example of the proportioning composition for the electrolyte that example is only the present invention, the proportioning composition not limited to this of electrolyte of the invention.
Embodiment 1
Solvent is that mass ratio is 1 in the electrolyte of the present embodiment:1:3 EC, PC and EMC, electrolyte lithium salt are material
The ratio between amount be 3:2 LiTFSI and LiDFOB；The total concentration of electrolyte lithium salt is 1.0mol/L, additive LiPF6Concentration
For 0.02mol/L.
Embodiment 2
Solvent is that mass ratio is 1 in the electrolyte of the present embodiment:1:3 EC, PC and EMC, electrolyte lithium salt are material
The ratio between amount be 3:2 LiTFSI and LiDFOB；The total concentration of electrolyte lithium salt is 1.0mol/L, additive LiPF6Concentration
For 0.05mol/L.
Embodiment 3
Solvent is that mass ratio is 1 in the electrolyte of the present embodiment:1:3 EC, PC and EMC, electrolyte lithium salt are material
The ratio between amount be 3:2 LiTFSI and LiDFOB；The total concentration of electrolyte lithium salt is 1.0mol/L, additive LiPF6Concentration
For 0.1mol/L.
Embodiment 4
Solvent is that mass ratio is 1 in the electrolyte of the present embodiment:1:3 EC, PC and EMC, electrolyte lithium salt are material
The ratio between amount be 3:2 LiTFSI and LiDFOB；The total concentration of electrolyte lithium salt is 1.0mol/L, additive LiPF6Concentration
For 0.2mol.
Embodiment 5
Solvent is that mass ratio is 1 in the electrolyte of the present embodiment:1:3 EC, PC and EMC, electrolyte lithium salt are material
The ratio between amount be 4:1 LiTFSI and LiDFOB；The total concentration of electrolyte lithium salt is 1.0mol/L, additive LiPF6Concentration
For 0.02mol/L.
Embodiment 6
Solvent is that mass ratio is 1 in the electrolyte of the present embodiment:1:3 EC, PC and EMC, electrolyte lithium salt are material
The ratio between amount be 7:3 LiTFSI and LiDFOB；The total concentration of electrolyte lithium salt is 1.0mol/L, additive LiPF6Concentration
For 0.1mol/L.
Embodiment 7
Solvent is that mass ratio is 1 in the electrolyte of the present embodiment:1:3 EC, PC and EMC, electrolyte lithium salt are material
The ratio between amount be 1:1 LiTFSI and LiDFOB；The total concentration of electrolyte lithium salt is 1.0mol/L, additive LiPF6Concentration
For 0.2mol/L.
In order to verify the performance of above-mentioned electrolyte, it is applied in lithium ion battery and is accordingly tested.Below will
Application of the above-mentioned electrolyte of the present invention in lithium ion battery is illustrated by specific embodiment.
Embodiment 8
With LiNi0.5Co0.2Mn0.3O2For positive electrode, using lithium metal as negative material, respectively with above-described embodiment 1-7
Electrolyte of the electrolyte as lithium ion battery, it is corresponding to obtain seven kinds of lithium ion batteries；To seven kinds of lithium-ion electrics of acquisition
Pond carries out charge and discharge cycles test under room temperature (25 DEG C), and test voltage scope is 2.7V~4.3V, with 0.5C multiplying power charge and discharge
Electricity, the discharge capacity and capability retention of battery after comparison loop 100 is enclosed；1~battery of battery 7 is denoted as individually below, and it is tested
As a result it is as shown in table 1.
The electrochemical property test result of 1 seven kinds of lithium ion batteries of table at room temperature
As it can be seen from table 1 electrolyte provided by the present invention shows good cycle performance at room temperature.
Embodiment 9
Under high temperature (60 DEG C) discharge and recharge is carried out to 1~battery of battery 7 using with method of testing similar in embodiment 8
Loop test, test voltage scope is 2.7V~4.3V, and with 0.5C rate charge-discharge, battery puts after comparison loop 100 is enclosed
Capacitance and capability retention；Its test result is as shown in table 2.
The electrochemical property test result of 2 seven kinds of lithium ion batteries of table at high temperature
From table 2 it can be seen that electrolyte provided by the present invention shows good cycle performance at high temperature, have resistance to
The characteristic of high temperature.
Embodiment 10
Under low temperature (- 20 DEG C) charge and discharge is carried out to 1~battery of battery 7 using with method of testing similar in embodiment 8
Electric loop test, test voltage scope are 2.7V~4.3V, with 0.2C rate charge-discharge, battery after comparison loop 100 is enclosed
Discharge capacity and capability retention；Its test result is as shown in table 3.
The electrochemical property test result of 3 seven kinds of lithium ion batteries of table at low temperature
From table 3 it can be seen that electrolyte provided by the present invention shows good cycle performance at low temperature, have resistance to
The characteristic of low temperature.
In conjunction with the embodiments 9, the test result of embodiment 10, it can be seen that electrolyte provided by the present invention, applied
By with more wide in range application temperature in lithium ion battery, there is wide warm nature energy.
In order to determine interface stability of the additive to negative pole, copper lithium half-cell is assembled, pole piece is entered after constant-current charge
Scanning electron microscope test (SEM) is gone；The above-mentioned electrolyte pair of the present invention will be illustrated by specific embodiment below
The stability of cathode interface.
Embodiment 11
Using copper foil as negative material, using lithium metal as positive electrode, lithium is used as using the electrolyte in above-described embodiment 2
The electrolyte of ion battery, assembling obtain a kind of copper lithium half-cell.
After control electric current size is 0.05mA constant-current charges 7d, SEM tests are carried out to pole piece, test result is as shown in Figure 1.
At the same time, the beneficial effect of the electrolyte in the application is embodied for convenience, and SEM has been carried out to pure copper foil in advance
Test, test result are as shown in Figure 2；Meanwhile assemble two kinds of copper lithiums as electrolyte using following two kinds of solution formed respectively
Half-cell is as a comparison case.
Comparative example 1
Electrolyte composition is used by this comparative example：Solvent is that mass ratio is 1:1:3 EC, PC and EMC, electrolyte
Lithium salts is that the ratio between amount of material is 3:2 LiTFSI and LiDFOB；The total concentration of electrolyte lithium salt is 1.0mol/L.In other words
Say, the difference of the composition of electrolyte and the composition of electrolyte in above-described embodiment 11 is to eliminate additive in this comparative example
LiPF6。
Operated using with the copper lithium half-cell in identical method of testing this comparative example of embodiment 11, the SEM tests of pole piece
As a result it is as shown in Figure 3.
Comparative example 2
Electrolyte composition is used by this comparative example：Solvent is that mass ratio is 1:1:3 EC, PC and EMC, additive
LiPF6Concentration be 0.02mol/L.In other words, the composition of electrolyte and electrolyte in above-described embodiment 11 in this comparative example
The difference of composition be to eliminate electrolyte lithium salt.
Operated using with the copper lithium half-cell in identical method of testing this comparative example of embodiment 11, the SEM tests of pole piece
As a result it is as shown in Figure 4.
1~Fig. 4 of comparison diagram, it can be seen that：, can be in copper foil using the electrolyte of comparative example 1 and comparative example 2 compared with Fig. 2
Obvious Li dendrite is shown on surface；And use the electrolyte of the present invention there is no Li dendrite on surfaces of the copper foil then, show root
According under the electrolyte of the invention wherein collective effect of electrolyte lithium salt and additive, it can substantially suppress lithium during use
The generation of dendrite.
Although the present invention has shown and described with reference to specific embodiment, it should be appreciated by those skilled in the art that：
In the case where not departing from the spirit and scope of the present invention limited by claim and its equivalent, can carry out herein form and
Various change in details.
Claims (5)
- A kind of 1. electrolyte for lithium ion battery, it is characterised in that including organic solvent dissolving electrolyte lithium salt and add Add agent；Wherein, the concentration of the electrolyte lithium salt is 1.0mol/L；It is 1 that the electrolyte lithium salt, which includes the ratio between amount of material,:1~ 9:1 double (trifluorosulfonimide) lithiums and difluorine oxalic acid boracic acid lithium；The concentration of the additive is 0.01mol/L~0.4mol/L, and the additive is lithium hexafluoro phosphate；The organic solvent is that mass ratio is 1~2:1~2:3~5 ethylene carbonate, propylene carbonate acid esters and methyl ethyl carbonate Ester.
- 2. electrolyte according to claim 1, it is characterised in that it is 3 that the electrolyte lithium salt, which includes the ratio between amount of material,: 2 double (trifluorosulfonimide) lithiums and difluorine oxalic acid boracic acid lithium.
- 3. electrolyte according to claim 1, it is characterised in that the organic solvent is that mass ratio is 1:1:3 carbon Vinyl acetate, propylene carbonate acid esters and methyl ethyl carbonate.
- 4. application of the electrolyte as described in claim 1-3 is any in lithium ion battery.
- 5. application according to claim 4, it is characterised in that the positive electrode of the lithium ion battery is LiNi0.5Co0.2Mn0.3O2, negative material is lithium metal.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711012280.8A CN107863558A (en) | 2017-10-26 | 2017-10-26 | Electrolyte and its application for lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711012280.8A CN107863558A (en) | 2017-10-26 | 2017-10-26 | Electrolyte and its application for lithium ion battery |
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Family
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109888394A (en) * | 2019-04-08 | 2019-06-14 | 黄杜斌 | A kind of novel serondary lithium battery electrolyte |
| CN110994032A (en) * | 2019-12-30 | 2020-04-10 | 上海交通大学 | Lithium ion battery safety electrolyte with excellent cycle performance and lithium ion battery |
| CN112186255A (en) * | 2019-07-03 | 2021-01-05 | 万向一二三股份公司 | Lithium ion battery electrolyte and preparation method of rate type NMC lithium ion battery |
| CN112271328A (en) * | 2020-09-21 | 2021-01-26 | 东莞市创明电池技术有限公司 | Lithium ion battery electrolyte and lithium ion battery |
| CN114373991A (en) * | 2021-12-31 | 2022-04-19 | 远景动力技术(江苏)有限公司 | Non-aqueous electrolyte for lithium battery and lithium ion battery |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109888394A (en) * | 2019-04-08 | 2019-06-14 | 黄杜斌 | A kind of novel serondary lithium battery electrolyte |
| CN112186255A (en) * | 2019-07-03 | 2021-01-05 | 万向一二三股份公司 | Lithium ion battery electrolyte and preparation method of rate type NMC lithium ion battery |
| CN110994032A (en) * | 2019-12-30 | 2020-04-10 | 上海交通大学 | Lithium ion battery safety electrolyte with excellent cycle performance and lithium ion battery |
| CN112271328A (en) * | 2020-09-21 | 2021-01-26 | 东莞市创明电池技术有限公司 | Lithium ion battery electrolyte and lithium ion battery |
| CN114373991A (en) * | 2021-12-31 | 2022-04-19 | 远景动力技术(江苏)有限公司 | Non-aqueous electrolyte for lithium battery and lithium ion battery |
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Application publication date: 20180330 |