CN104393342A - Method for reducing electrochemical impedance of lithium-ion battery - Google Patents
Method for reducing electrochemical impedance of lithium-ion battery Download PDFInfo
- Publication number
- CN104393342A CN104393342A CN201410642399.3A CN201410642399A CN104393342A CN 104393342 A CN104393342 A CN 104393342A CN 201410642399 A CN201410642399 A CN 201410642399A CN 104393342 A CN104393342 A CN 104393342A
- Authority
- CN
- China
- Prior art keywords
- lithium
- ion battery
- carbonate
- battery
- impedance
- 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
- H01M10/056—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
-
- 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
-
- 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
-
- 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)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a method for reducing the electrochemical impedance of a lithium-ion battery. The method is characterized in that butanedioic anhydride is added to a lithium-ion battery electrolyte liquid. An electrolyte liquid solvent is selected from two or more of ethylene carbonate, propene carbonate, methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate and fluoroethylene carbonate, and the solvent accounts for 80-90 wt% of the lithium-ion battery electrolyte liquid. The butanedioic anhydride can form a thin, dense and stable solid electrolyte interfacial film on the surface of an electrode. The interfacial film has small impedance and good stability, restrains the catalyzed oxidation separation of the electrolyte liquid solvent on the surface of the electrode, effectively reduces the impedance of the battery, and increases the battery capacity retention ratio and the battery cycle life.
Description
Technical field
The invention belongs to technical field of lithium ion, relate to the method for the lithium ion battery electrochemical impedance that a kind of reduction is positive pole with lithium manganate material, ternary material or nickel ion doped material.
Background technology
It is high that lithium ion battery has operating voltage, and volume is little, and energy efficiency is high, has extended cycle life and the feature such as non-environmental-pollution, be widely used in the every field of daily life.In battery use procedure, lithium ion battery constantly carries out discharge and recharge, and the impedance of battery can increase.This is mainly due in charge and discharge process, and some active site place local voltage of electrode surface are too high, cause the decomposition of electrolyte and the destruction of electrode material.The catabolite of electrolyte constantly can be accumulated at electrode and electrolyte contacts face, thus causes the increase of whole battery impedance.
Therefore, improve the character at active electrode and electrolyte contacts interface, the increase reducing impedance is necessary.Succinic anhydride, as electrolysis additive, at the battery charging and discharging initial stage, can form the thin and interface diaphragm of densification.Along with the increase of charge and discharge cycles number of times, the impedance of interfacial film increases hardly.Meanwhile, the interfacial film that succinic anhydride is formed can protect electrolyte directly not contact with electrode, and the battery impedance preventing electrolyte decomposition from causing increases.
Summary of the invention
Main purpose of the present invention is the problem increased for current lithium ion cell charging process middle impedance, proposes to add the method for succinic anhydride as additive in the electrolytic solution, for improving the interface stability of electrode and electrolyte.
For achieving the above object, present invention employs following technical scheme:
The present invention is a kind of method reducing lithium ion battery electrochemical impedance, it is characterized in that, in lithium-ion battery electrolytes, add the functional additive reducing lithium ion battery electrochemical impedance, described functional additive is 0.1%-5% in the mass percent of lithium-ion battery electrolytes.
According to method of the present invention, wherein said functional additive is succinic anhydride.
According to method of the present invention, the lithium ion battery that wherein said lithium ion battery is is positive pole with spinel lithium manganate, ternary material or nickel ion doped material.
According to the method for reduction lithium ion battery electrochemical impedance of the present invention, the electrolyte lithium salt in described lithium-ion battery electrolytes is LiPF
6, LiBF
4with one or more in LiTFSI, electrolyte solvent is two or more mixture of ethylene carbonate, propene carbonate, methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate and fluorinated ethylene carbonate; Described electrolyte concentration is in the electrolytic solution 0.8-1.5mol/L, and described electrolyte solvent accounts for 80 ~ 90wt% of lithium-ion battery electrolytes.
Succinic anhydride is as electrolysis additive in lithium-ion battery electrolytes for the inventive method, and succinic anhydride can decompose when the preliminary discharge and recharge of battery, forms stable electrode and electrolyte interface film, reduces the generation of side reaction in inside battery charge and discharge process.
The total impedance of battery is mainly by the body impedance R of battery
b, SEI membrane impedance R
sEIwith Charge-transfer resistance R
ctthree part compositions.Wherein, R
band R
sEIbe the resistance of ohm character, they combine and are also called ohmage.R
ctthe corresponding electrochemical reaction of electrode material and electrolyte surface, is also called Faradaic impedance.What succinic anhydride was decomposed to form stablizes and the interfacial film of densification, has less R
sEIimpedance, this impedance can not carrying out and increase with battery charging and discharging circulation.Meanwhile, this battery also has less R
ctimpedance.Therefore, relative to the lithium ion battery not adding succinic anhydride, the lithium ion battery total impedance employing succinic anhydride additive reduces.
The invention has the beneficial effects as follows, the present invention by adding the method for succinic anhydride in electrolyte, the stable interfacial film of one deck is formed at electrode surface, interfacial film inhibits electrolyte solvent to decompose at the catalytic oxidation of electrode surface, effectively reduce the impedance of battery, improve capability retention and the cycle life of battery.
Accompanying drawing explanation
Fig. 1 is the electrochemical impedance curve after embodiment of the present invention 1-3 and comparative example 1 change into.
Fig. 2 is that embodiment of the present invention 1-3 and comparative example 1 circulate the electrochemical impedance curve after 50 times.
Fig. 3 is circulation volume and the efficiency for charge-discharge curve of embodiments of the invention 2 and comparative example 1 battery.
Embodiment
Being formulated in the glove box being full of high-purity argon gas of electrolyte is carried out, H
2o≤1ppm, temperature is at 25 DEG C.LiPF selected by electrolyte lithium salts
6.Solvent contains ethylene carbonate (EC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC) and vinylene carbonate (VC) additive.The functional additive reducing lithium ion battery electrochemical impedance selects succinic anhydride (SA).
The electrolyte prescription of specific embodiment and comparative example is as shown in table 1.
The electrolyte prescription of table 1 embodiment 1-3 and comparative example 1
In table: the mass percent of VC and succinic anhydride is for 100% in electrolyte gross mass.
Application performance test
With LiMn
2o
4for positive pole, lithium sheet is negative pole, is assembled into CR2032 button cell, evaluates prepared electrolyte.Battery adopts 0.2C electric current to change into, and adopt 1C electric current to carry out cycle performance test, charging/discharging voltage interval is 3.5-4.95V.
Adopt PAR2273 electrochemical workstation to carry out ac impedance measurement to the battery changed into, EIS frequency range is 100kHz-10mHz, and disturbing signal is 5mV.
The ac impedance spectroscopy of embodiment 1-3 and comparative example 1 as shown in Figure 1 and Figure 2.
After embodiment 2 and comparative example 1 battery circulate for 100 times, capability retention is as shown in table 2.The capacity circulating figure of embodiment 2 and comparative example 1 as shown in Figure 3.
Capability retention after 100 circulations of table 2 battery
| Embodiment 2 | Comparative example 1 | |
| Conservation rate (25 DEG C) | 99.12％ | 95.26％ |
As seen from Figure 1, after the Battery formation of embodiment 1-3 and comparative example 1, the R that the battery adopting the electrolyte adding SA to be assembled into is formed
sEIthe battery that membrane impedance is assembled slightly larger than the electrolyte not adding SA, illustrates and adopts the battery of SA to define interfacial film when changing into.Fig. 2 can find out, after 50 circulations terminate, adopts the R of the battery adding SA electrolyte
sEImembrane impedance is than the battery R adopting basic electrolyte
sEIimpedance is little.Result shows, succinic anhydride joins in electrolyte as additive, can form stable, fine and close and that impedance is little interfacial film, stable in charge and discharge process of guard electrode.The SA content characteristic impedance best performance of embodiment 2.
As seen from Figure 3, add the battery of the electrolyte assembling of SA, efficiency for charge-discharge is close to 100%, and discharge capacity, along with the carrying out of circulation, does not almost decay.And adopt the increase of battery capacity along with cycle-index of basic electrolyte, in attenuation trend.After 50 circle circulations, adopt the battery capacity of adding SA electrolyte to be 103.24mAh/g, capability retention is 99.49%; The discharge capacity of the cell adopting basic electrolyte is 102.31mAh/g, and capability retention is 98.58%.
Claims (4)
1. one kind is reduced the method for lithium ion battery electrochemical impedance, it is characterized in that, in lithium-ion battery electrolytes, add the functional additive reducing lithium ion battery electrochemical impedance, described functional additive is 0.1%-5% in the mass percent of lithium-ion battery electrolytes.
2. method according to claim 1, is characterized in that, described functional additive is succinic anhydride.
3. method according to claim 1, is characterized in that, the lithium ion battery that described lithium ion battery is is positive pole with spinel lithium manganate, ternary material or nickel ion doped material.
4. method according to claim 1, is characterized in that, the electrolyte lithium salt in described lithium-ion battery electrolytes is LiPF
6, LiBF
4with one or more in LiTFSI, electrolyte solvent is two or more mixture of ethylene carbonate, propene carbonate, methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate and fluorinated ethylene carbonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410642399.3A CN104393342A (en) | 2014-11-07 | 2014-11-07 | Method for reducing electrochemical impedance of lithium-ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410642399.3A CN104393342A (en) | 2014-11-07 | 2014-11-07 | Method for reducing electrochemical impedance of lithium-ion battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104393342A true CN104393342A (en) | 2015-03-04 |
Family
ID=52611204
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410642399.3A Pending CN104393342A (en) | 2014-11-07 | 2014-11-07 | Method for reducing electrochemical impedance of lithium-ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104393342A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113594546A (en) * | 2021-08-19 | 2021-11-02 | 蜂巢能源科技有限公司 | Electrolyte and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101276936A (en) * | 2007-03-28 | 2008-10-01 | 三洋电机株式会社 | Non-aqueous electrolyte secondary cell |
| CN101841065A (en) * | 2010-05-21 | 2010-09-22 | 东莞新能源科技有限公司 | Lithium-ion secondary battery and electrolyte thereof |
| CN101847752A (en) * | 2010-05-26 | 2010-09-29 | 惠州市德赛聚能电池有限公司 | Additive of electrolytic solution of lithium ion battery |
| CN104134818A (en) * | 2014-08-18 | 2014-11-05 | 奇瑞汽车股份有限公司 | High-energy-density lithium ion battery and preparation method thereof |
-
2014
- 2014-11-07 CN CN201410642399.3A patent/CN104393342A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101276936A (en) * | 2007-03-28 | 2008-10-01 | 三洋电机株式会社 | Non-aqueous electrolyte secondary cell |
| CN101841065A (en) * | 2010-05-21 | 2010-09-22 | 东莞新能源科技有限公司 | Lithium-ion secondary battery and electrolyte thereof |
| CN101847752A (en) * | 2010-05-26 | 2010-09-29 | 惠州市德赛聚能电池有限公司 | Additive of electrolytic solution of lithium ion battery |
| CN104134818A (en) * | 2014-08-18 | 2014-11-05 | 奇瑞汽车股份有限公司 | High-energy-density lithium ion battery and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113594546A (en) * | 2021-08-19 | 2021-11-02 | 蜂巢能源科技有限公司 | Electrolyte and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103078140B (en) | Lithium ion secondary battery and electrolyte thereof | |
| CN104269576B (en) | A kind of electrolyte and the lithium ion battery using the electrolyte | |
| CN110600804B (en) | Lithium ion battery electrolyte suitable for NCM811 and SiO-C material system and preparation method thereof | |
| CN105226324B (en) | A kind of high-voltage electrolyte and the lithium ion battery using the electrolyte | |
| CN109346760A (en) | A kind of electrolyte and high-voltage lithium ion batteries of high-voltage lithium ion batteries | |
| CN107017433B (en) | Nonaqueous electrolytic solution and lithium ion battery | |
| CN106159325B (en) | A kind of low temperature electrolyte for lithium ion battery and low-temperature lithium ion battery | |
| CN103078141A (en) | Lithium-ion secondary battery and electrolyte thereof | |
| CN105336984B (en) | Lithium ion battery and its electrolyte | |
| CN105406124B (en) | A kind of electrolyte improving high-temperature lithium ion battery and high voltage capability and its application in lithium ion battery | |
| CN102569889A (en) | Non-aqueous electrolyte for lithium ion battery, and lithium ion battery | |
| CN104979586B (en) | Lithium ion secondary battery and electrolyte thereof | |
| CN109935908B (en) | Low-concentration lithium salt electrolyte and lithium secondary battery comprising same | |
| CN102593512B (en) | Lithium ion battery and electrolyte solution thereof | |
| CN102255105B (en) | The lithium ion battery of secondary fluid injection | |
| CN107069087A (en) | It is a kind of to be applicable high/low temperature electrolyte of lithium iron phosphate dynamic battery and preparation method thereof | |
| EP3930066A1 (en) | Solid-liquid battery | |
| CN109659615A (en) | Match the lithium-ion battery electrolytes of silicon-carbon cathode material and its battery of preparation | |
| CN106410272A (en) | Electrolyte for high-voltage lithium ion battery and high-voltage lithium ion battery | |
| CN105633465A (en) | Ethylene sulfate additive contained high-voltage functional electrolyte and preparation method and application therefor | |
| CN105789685A (en) | Lithium ion battery and electrolyte thereof | |
| CN109786832A (en) | Electrolysis additive, electrolyte and lithium ion secondary battery | |
| CN114784381A (en) | Electrolyte, preparation method thereof and lithium ion battery | |
| CN108390098A (en) | A kind of high-voltage lithium-ion battery electrolyte and high-voltage lithium ion batteries | |
| CN105119017A (en) | Nonaqueous electrolyte solution for high-voltage lithium ion secondary battery and high-voltage lithium secondary battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20150304 |