CN109980277A - A kind of nonaqueous electrolytic solution and secondary cell - Google Patents
A kind of nonaqueous electrolytic solution and secondary cell Download PDFInfo
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- CN109980277A CN109980277A CN201711444497.6A CN201711444497A CN109980277A CN 109980277 A CN109980277 A CN 109980277A CN 201711444497 A CN201711444497 A CN 201711444497A CN 109980277 A CN109980277 A CN 109980277A
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- electrolytic solution
- nonaqueous electrolytic
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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
-
- 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
- H01M10/42—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
-
- 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)
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- General Chemical & Material Sciences (AREA)
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- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The present invention relates to a kind of nonaqueous electrolytic solutions; including lithium salts, solvent and additive, the additive includes difluorophosphate and contains sulfonyl compound, and described is chemical compounds I and/or compound ii containing sulfonyl compound; wherein, the structural formula of chemical compounds I are as follows:The structural formula of compound ii are as follows:
Description
Technical field
The invention belongs to electrochemical technology fields, and in particular to a kind of nonaqueous electrolytic solution and secondary cell.
Background technique
In recent years, the universal of the portable electronic devices such as mobile phone, laptop promotes high-energy density secondary battery
Demand.In numerous secondary cells, realize that the lithium ion secondary battery of energy conversion has with the insertion of lithium ion and abjection
Energy density more higher than lead-acid battery and nickel-metal hydride battery has developed especially rapidly since emerging, and application field covers number
Code product, electric tool, electric car, communication base station and power grid energy storage etc..
Secondary cell mainly includes anode, cathode, diaphragm and electrolyte.Medium of the electrolyte as discharge and recharge reaction, it is right
The performance of secondary cell has an important influence.
Use carbon, silicon materials as in the lithium ion secondary battery of negative electrode active material, cathode is living in charge and discharge process
Property substance be easy to react with electrolyte, lead to the decomposition of electrolyte, it is general to make electrolyte in negative terminal surface by additive
It is formed solid electrolyte interface film (SEI), the decomposition reaction of solvent molecule in electrolyte can be inhibited.By adding into electrolyte
Add vinylene carbonate (VC), can play the role of to carbon, silicium cathode surface filming, however when battery is in hot environment
When, skin covering of the surface can decompose and regenerate, and protective effect weakens therewith, and will lead to internal resistance of cell increase.
Using lithium-transition metal composite oxide (such as LiMn containing manganese2O4、LiNi1/3Co1/3Mn1/3O2Deng) living as anode
In the lithium ion secondary battery of property substance, the dissolution due to manganese ion and the deposition in negative terminal surface will lead to battery performance
Deteriorate.Using LiCoO2Or LiNi0.5Co0.2Mn0.3O2When as a positive electrode active material, in order to obtain higher battery capacity, have
When can set 4.3V or more for charge cutoff voltage, under this high voltage environment, oxidative decomposition easily occurs for electrolyte.
Therefore, it should also draw attention to the protection on anode surface.
Patent document JP3439085B2 is disclosed through difluorophosphate in battery plus-negative plate surface filming, improves battery
Storage performance.
Patent document CN1280942C, which is disclosed, forms passivation layer at battery electrode interface by cyclic sulfonic acid ester, prevents molten
Agent is decomposed, and improves cycle performance of battery, and the internal resistance of cell is inhibited to increase.
Patent document CN100544108C is disclosed by being added in the electrolytic solution containing sulfonyl compound, can be in anode
Surface forms protective film, inhibits the side reaction between anode and electrolyte, so as to improve the high-temperature storage performance of battery.
It includes lithium that patent document CN107093765A, which discloses a kind of nonaqueous electrolytic solution and secondary cell, nonaqueous electrolytic solution,
Salt, organic solvent and additive, the additive includes containing sulfonyl compound, described to be containing sulfonyl compoundAnd/orBy using the compound containing vinyl containing sulfonyl as addition
Agent, the additive of two kinds of structures facilitate battery electrode surface and form protective film, in battery charging and discharging circulation and high temperature storage
In the process, which has very high stability, can inhibit the decomposition of solvent molecule in electrolyte, reduces decomposition product and exists
The internal resistance of cell caused by electrode surface is accumulated increases, and improves battery storage performance.But found by practice, only with containing
Battery made from the electrolyte of sulfonyl compound is easy inflatable at high temperature, and then influences the performance of battery.
Summary of the invention
Technical problem to be solved by the invention is to provide one kind can preferably improve the high-temperature storage performance of battery
Nonaqueous electrolytic solution and secondary cell.
In order to achieve the above objectives, the technical solution adopted by the present invention is that:
A kind of nonaqueous electrolytic solution, including lithium salts, solvent and additive, the additive include difluorophosphate and containing sulphur
Acyl compounds, described is chemical compounds I and/or compound ii containing sulfonyl compound, wherein the structural formula of chemical compounds I are as follows:The structural formula of compound ii are as follows:
The quality that feeds intake of the difluorophosphate accounts for the 0.2~1.5% of nonaqueous electrolytic solution gross mass.
Preferably, the quality that feeds intake of the difluorophosphate accounts for the 0.2~1.5% of nonaqueous electrolytic solution gross mass, into one
Step preferably 0.5~1%.
Specifically, it is described containing sulfonyl compound be the chemical compounds I and the compound ii when, the matter of the two
Amount is than being arbitrary proportion, it is further preferred that the mass ratio of the chemical compounds I and the compound ii is 1:1~3.
Specifically, the quality that feeds intake containing sulfonyl compound account for the nonaqueous electrolytic solution gross mass 0.1~
5%.
Preferably, the quality that feeds intake containing sulfonyl compound account for the nonaqueous electrolytic solution gross mass 1~
4%.
Specifically, the additive further includes dioxalic acid lithium borate.
Preferably, the quality that feeds intake of the dioxalic acid lithium borate account for the nonaqueous electrolytic solution gross mass 0.1~
2%.
Preferably, the quality that feeds intake of the dioxalic acid lithium borate account for the nonaqueous electrolytic solution gross mass 0.2~
1.5%.
Lithium salts in the present invention is selected from lithium hexafluoro phosphate, LiBF4, hexafluoroarsenate lithium, Lithium perchlorate anhydrous, two
(trifluoromethane sulfonic acid acyl) imine lithium, trifluoromethyl sulfonic acid lithium, dioxalic acid lithium borate, single oxalic acid double lithium fluoroborates, double fluorine sulphonyl
One of imine lithium is several, preferably lithium hexafluoro phosphate, concentration 0.9-1.1mol/L.
Solvent in the present invention is selected from ethylene carbonate, propene carbonate, gamma-butyrolacton, dimethyl carbonate, carbonic acid two
Ethyl ester, methyl ethyl carbonate, methyl propyl carbonate, methyl propionate, ethyl propionate, propyl propionate, methyl acetate, ethyl acetate, acetic acid
One of propyl ester, methyl butyrate, ethyl butyrate, propyl butyrate, sulfolane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether
Or it is several.
Preferably, the solvent is the mixed solvent of ethylene carbonate and diethyl carbonate that mass ratio is 1:2~3.
A kind of secondary cell uses the nonaqueous electrolytic solution.
Preferably, the anode of the secondary cell and cathode being capable of absorption and desorption lithium ions.
The positive active material of battery is LiCoO in the present invention2, negative electrode active material is graphite.
Due to the above technical solutions, the present invention has the following advantages over the prior art:
Nonaqueous electrolytic solution of the invention by using difluorophosphate and chemical compounds I and/or compound ii as additive, this
The synergistic effect of two or three of additive can improve the high temperature inflatable and storage performance of battery.
Specific embodiment
The application is described in detail below with reference to embodiment, but the application is not limited to these embodiments.If not special herein
Illustrate, " % " representation quality percentage.
Embodiment 1:
[positive manufacture]
LiCoO is weighed according to mass ratio 90:5:52, conductive black and PVDF, appropriate NMP is added, is sufficiently stirred, obtains just
Pole slurry.Anode sizing agent is coated on aluminium foil, roll-in is carried out after dry, cuts to obtain anode.
[manufacture of cathode]
Graphite, butadiene-styrene rubber and carboxymethyl cellulose are weighed according to mass ratio 95:3:2, appropriate amount of deionized water is added, sufficiently
Stirring, obtains negative electrode slurry.Negative electrode slurry is coated on copper foil, roll-in is carried out after dry, cuts to obtain cathode.
[preparation of electrolyte]
Mixed solvent is obtained according to mass ratio 3:7 mixed carbonic acid vinyl acetate (EC), diethyl carbonate (DEC), by hexafluoro phosphorus
Sour lithium is dissolved in wherein with the concentration of 1 mol/L.Add 0.2wt%LiPO2F2With 1.0wt% chemical compounds I to obtain electrolyte.
[manufacture of battery]
Using above-mentioned anode, cathode, electrolyte, 20 microns of thickness of PE diaphragm is selected, is manufactured using winding process at soft
Packet battery, model 053048.
[battery performance test]
Battery charging and discharging test carries out under the conditions of 25 DEG C, and voltage range is 3.0~4.4V.By battery with 0.1C multiplying power
Cheng Hou is recycled 5 weeks in advance with 0.2C multiplying power.Then storage performance test is carried out.
Storage performance test is by battery with 0.5C circulation 3 weeks, and then 0.5C charges to 4.4V, is placed in 60 degrees Celsius of baking
In case, store 7 days.Test the thickness before and after battery storage.Thickness change=[(thickness before internal resistance-storage after storage)/
Thickness before storage] * 100%.Then battery is discharged with 0.5C.Test the capacity retention ratio of battery.Capacity retention ratio=(deposit
The discharge capacity before discharge capacity/storage after storage) * 100%.
Embodiment 2:
In addition to electrolyte adds 1.0wt%LiPO2F2With 1.0wt% chemical compounds I, battery is in the same manner as example 1
Manufacture.Battery performance test is tested in the same manner as example 1.
Embodiment 3:
In addition to electrolyte adds 1.5wt%LiPO2F2With 3.0wt% chemical compounds I, battery is in the same manner as example 1
Manufacture.Battery performance test is tested in the same manner as example 1.
Embodiment 4:
In addition to electrolyte adds 0.2wt%LiPO2F2With 1.0wt% compound ii, battery is with side same as Example 1
Formula manufacture.Battery performance test is tested in the same manner as example 1.
Embodiment 5:
In addition to electrolyte adds 1.0wt%LiPO2F2With 4.0wt% compound ii, battery is with side same as Example 1
Formula manufacture.Battery performance test is tested in the same manner as example 1.
Embodiment 6:
In addition to electrolyte adds 1.0wt%LiPO2F2, 1.0wt% chemical compounds I and 2.0wt% compound ii, battery with
The identical mode of embodiment 1 manufactures.Battery performance test is tested in the same manner as example 1.
Embodiment 7:
In addition to electrolyte adds 1.0wt%LiPO2F2, 1.0wt% chemical compounds I and 0.2wt%LiBOB, battery with implementation
The identical mode of example 1 manufactures.Battery performance test is tested in the same manner as example 1.
Embodiment 8:
In addition to electrolyte adds 0.5wt%LiPO2F2, 1.0wt% chemical compounds I and 1.5wt%LiBOB, battery with implementation
The identical mode of example 1 manufactures.Battery performance test is tested in the same manner as example 1.
Comparative example 1:
In addition to electrolyte is free of additive, battery manufactures in the same manner as example 1.Battery performance test with reality
The identical mode of example 1 is applied to be tested.
Comparative example 2:
In addition to electrolyte does not add LiPO2F2, battery manufactures in the same manner as example 1.Battery performance test with
The identical mode of embodiment 1 is tested.
Comparative example 3:
In addition to electrolyte adds 1.0wt%LiPO2F2, battery manufactures in the same manner as example 1.Battery performance is surveyed
Examination is tested in the same manner as example 1.
The results are shown in Table 1 for the battery performance test of Examples 1 to 8 and comparative example 1~3.
Table 1
The thickness change and appearance of the battery of nonaqueous electrolytic solution preparation by each embodiment and comparative example in table 1 containing additive
Conservation rate data explanation is measured, by LiPO containing additive of the invention2F2With containing vinyl containing sulfonyl compound (chemical compounds I and/
Or compound ii) voltage range of battery of nonaqueous electrolytic solution preparation associated with collaboration is 3.0~4.4V, 0.5C rate charge-discharge
Battery thickness change and capacity retention ratio be substantially better than the secondary cell prepared by comparative example nonaqueous electrolytic solution, i.e. battery
With superior storage performance；Also, embodiment 8 therein is even more to have in terms of cell thickness change rate and capacity retention ratio
There is extremely apparent advantage.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention, it is all according to the present invention
Equivalent change or modification made by Spirit Essence, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of nonaqueous electrolytic solution, including lithium salts, solvent and additive, it is characterised in that: the additive includes difluoro phosphorus
Sour lithium and contain sulfonyl compound, described containing sulfonyl compound is chemical compounds I and/or compound ii, wherein chemical compounds I
Structural formula are as follows:The structural formula of compound ii are as follows:
The quality that feeds intake of the difluorophosphate accounts for the 0.1~2% of the nonaqueous electrolytic solution gross mass.
2. nonaqueous electrolytic solution according to claim 1, it is characterised in that: the quality that feeds intake of the difluorophosphate accounts for non-
The 0.2~1.5% of water electrolysis liquid gross mass.
3. nonaqueous electrolytic solution according to claim 1, it is characterised in that: the quality that feeds intake containing sulfonyl compound
Account for the 0.1~5% of the nonaqueous electrolytic solution gross mass.
4. nonaqueous electrolytic solution according to claim 3, it is characterised in that: the quality that feeds intake containing sulfonyl compound
Account for the 1~4% of the nonaqueous electrolytic solution gross mass.
5. nonaqueous electrolytic solution according to claim 1, it is characterised in that: the additive further includes dioxalic acid boric acid
Lithium.
6. nonaqueous electrolytic solution according to claim 5, it is characterised in that: the quality that feeds intake of the dioxalic acid lithium borate accounts for
The 0.1~2% of the nonaqueous electrolytic solution gross mass.
7. nonaqueous electrolytic solution according to claim 6, it is characterised in that: the quality that feeds intake of the dioxalic acid lithium borate accounts for
The 0.2~1.5% of the nonaqueous electrolytic solution gross mass.
8. nonaqueous electrolytic solution according to claim 1, it is characterised in that: the solvent is the carbon that mass ratio is 1:2~3
The mixed solvent of vinyl acetate and diethyl carbonate.
9. a kind of secondary cell, it is characterised in that: it uses nonaqueous electrolytic solution described in any item of the claim 1 to 8.
10. secondary cell according to claim 9, it is characterised in that: the anode and the equal energy of cathode of the secondary cell
Enough absorption and desorption lithium ions.
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| CN201711444497.6A CN109980277A (en) | 2017-12-27 | 2017-12-27 | A kind of nonaqueous electrolytic solution and secondary cell |
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| CN201711444497.6A CN109980277A (en) | 2017-12-27 | 2017-12-27 | A kind of nonaqueous electrolytic solution and secondary cell |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1167270A (en) * | 1997-08-21 | 1999-03-09 | Sanyo Electric Co Ltd | Nonaqueous electrolyte secondary battery |
| CN102820483A (en) * | 2011-06-07 | 2012-12-12 | 索尼公司 | Nonaqueous electrolyte battery, battery pack, electronic device, and electric vehicle |
| CN103035949A (en) * | 2011-10-07 | 2013-04-10 | 索尼公司 | Electrolytic solution, secondary battery, battery pack, electric vehicle, electric power storage system, electric power tool, and electronic device |
| CN105098242A (en) * | 2015-07-31 | 2015-11-25 | 宁德新能源科技有限公司 | Electrolyte and lithium ion battery comprising the same |
| CN106025359A (en) * | 2016-07-08 | 2016-10-12 | 珠海市赛纬电子材料股份有限公司 | Lithium ion power battery non-water electrolyte |
| CN106099171A (en) * | 2016-07-13 | 2016-11-09 | 东莞市凯欣电池材料有限公司 | A kind of lithium ion power battery electrolyte and lithium-ion-power cell |
| CN106602140A (en) * | 2015-10-23 | 2017-04-26 | 天津金牛电源材料有限责任公司 | Electrolytic solution for improving high temperature performance of polymer lithium ion secondary battery |
| CN107093765A (en) * | 2017-04-28 | 2017-08-25 | 张家港市国泰华荣化工新材料有限公司 | A kind of nonaqueous electrolytic solution and secondary cell |
-
2017
- 2017-12-27 CN CN201711444497.6A patent/CN109980277A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1167270A (en) * | 1997-08-21 | 1999-03-09 | Sanyo Electric Co Ltd | Nonaqueous electrolyte secondary battery |
| CN102820483A (en) * | 2011-06-07 | 2012-12-12 | 索尼公司 | Nonaqueous electrolyte battery, battery pack, electronic device, and electric vehicle |
| CN103035949A (en) * | 2011-10-07 | 2013-04-10 | 索尼公司 | Electrolytic solution, secondary battery, battery pack, electric vehicle, electric power storage system, electric power tool, and electronic device |
| CN105098242A (en) * | 2015-07-31 | 2015-11-25 | 宁德新能源科技有限公司 | Electrolyte and lithium ion battery comprising the same |
| CN106602140A (en) * | 2015-10-23 | 2017-04-26 | 天津金牛电源材料有限责任公司 | Electrolytic solution for improving high temperature performance of polymer lithium ion secondary battery |
| CN106025359A (en) * | 2016-07-08 | 2016-10-12 | 珠海市赛纬电子材料股份有限公司 | Lithium ion power battery non-water electrolyte |
| CN106099171A (en) * | 2016-07-13 | 2016-11-09 | 东莞市凯欣电池材料有限公司 | A kind of lithium ion power battery electrolyte and lithium-ion-power cell |
| CN107093765A (en) * | 2017-04-28 | 2017-08-25 | 张家港市国泰华荣化工新材料有限公司 | A kind of nonaqueous electrolytic solution and secondary cell |
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Application publication date: 20190705 |