CN108091933B - Application of the fluosulfonic acid ester type compound in battery electrolyte - Google Patents
Application of the fluosulfonic acid ester type compound in battery electrolyte Download PDFInfo
- Publication number
- CN108091933B CN108091933B CN201711313228.6A CN201711313228A CN108091933B CN 108091933 B CN108091933 B CN 108091933B CN 201711313228 A CN201711313228 A CN 201711313228A CN 108091933 B CN108091933 B CN 108091933B
- Authority
- CN
- China
- Prior art keywords
- acid ester
- type compound
- ester type
- fluosulfonic acid
- 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.)
- Active
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
- H01M10/05—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
-
- 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
Abstract
Application of the fluosulfonic acid ester type compound in battery electrolyte, belong to the technical field of battery electrolyte, fluosulfonic acid ester type compound is added in battery electrolyte as additive, additive amount is the 0.1-10% of battery electrolyte quality, and the fluosulfonic acid ester type compound is the combination of one or more of Formulas I, Formula II, formula III, formula IV；
Description
Technical field
The invention belongs to the technical fields of battery electrolyte, are related to a kind of additive of battery electrolyte, and in particular to will
Fluosulfonic acid ester type compound is applied in battery electrolyte.By the way that fluosulfonic acid ester type compound is added into lithium battery electrolytes,
Make battery cryogenic discharging characteristic and life cycle good drawing property；Even if battery be stored under fully charged state high temperature or just into
Row charge/discharge process, the decomposition reaction of the organic solvent based on carbonic ester also will receive inhibition, ask to solve expansion
Topic, the high temperature service life cyclophysis of battery also obtain improvement.
Background technique
Recently, the concern of energy storage technologies is continuously increased.With energy storage technologies to such as mobile phone, can take
The extension of the equipment such as formula video camera, laptop, PC and electric vehicle, to the energy for being used as this class of electronic devices
The demand of the high energy density cells in source is also increasing.Lithium ion secondary battery is one of optimal battery, at present
It is actively being implemented a variety of to its improved research.
In secondary cell used at present, the lithium secondary battery of early 1990s exploitation includes one by can be embedding
Enter or deviate from anode made of the carbon material of lithium ion, a cathode made of lithium-containing oxides and a kind of by by appropriate lithium
Salt is dissolved in mixed organic solvents and the non-aqueous electrolytic solution of preparation.As energy density of the people to lithium ion battery proposes
Increasingly higher demands, traditional lithium-ion battery are no longer satisfied the demand of people.
Currently in order to improving the energy density of lithium ion battery, researcher generallys use exploitation high capacity, high working voltage
Positive electrode solve the problems, such as this, such as improve the operating voltage of lithium cobalt composite oxide, complex Li-Mn-oxide, develop senior engineer
Make the lithium nickel manganese composite oxide etc. of voltage.However, solvent recurring structure changes these positive electrodes under high voltages, transition gold
Category is easy to happen dissolution, and can deposit on cathode, in addition, common electrolyte, it will usually issue in the voltage higher than 4V
Solution estranged produces gas, to will lead to the reduction of battery performance.In order to solve problem above, researcher would generally be to positive electrode
Surface protection cladding or doping are carried out to improve the cycle performance under high voltage, but these methods are often along with battery
Can capacity loss, and manufacture craft is cumbersome, and manufacturing cost increases.Replaced by exploitation novel high voltage electrolyte normal at present
Electrolyte system is to realize one of commercialized improvement approach of high-voltage lithium ion batteries.
Summary of the invention
Fluosulfonic acid ester type compound is used in battery electrolyte by the present invention to solve the above problems, proposing, to change
High temperature, the room temperature, low-temperature circulating performance of kind battery, improve the service life of battery.
The present invention be realize its purpose the technical solution adopted is that:
Application of the fluosulfonic acid ester type compound in battery electrolyte, fluosulfonic acid ester type compound are added to as additive
In battery electrolyte, additive amount be battery electrolyte quality 0.1-10%, the fluosulfonic acid ester type compound be Formulas I, Formula II,
The combination of one or more of formula III, formula IV；
The battery electrolyte includes that mass ratio is (15-20): (60-80): (0.1-10) lithium salts, organic solvent and fluorine
Sulfonates compounds.
The organic solvent be selected from ethylene carbonate, propene carbonate, gamma-butyrolacton, gamma-valerolactone, dimethyl carbonate,
Methyl ethyl carbonate, diethyl carbonate, methyl propionate, ethyl propionate, propyl propionate, trifluoro-acetate, Trifluoroacetic Acid Ethyl Ester, three
One of fluoroacetic acid butyl ester is a variety of.
The lithium salts is selected from LiPF6、LiBF4、LiSO3CF3、LiClO4、LiN(CF3SO2)2、LiC(CF3SO2)3In one
Kind is a variety of.
The beneficial effects of the present invention are:
The battery electrolyte of fluosulfonic acid ester type compound is added, charge and discharge is high-efficient, good cycle, is able to satisfy 45 DEG C of conditions
Under the charge and discharge requirement with 600 capacity retention ratios of 1C charge and discharge cycles greater than 80%, the high temperature that can especially improve lithium battery follows
Ring performance；The storge quality of battery can be increased, do not influence other performances of lithium battery.Cycle life of lithium ion battery length, inflatable
Rate low and high temperature is functional, and battery operating voltage can be higher than 4.5V.
Specific embodiment
The present invention is further illustrated combined with specific embodiments below.
One, specific embodiment
Embodiment 1
Battery electrolyte includes that mass ratio is 15:84.9:0.1 lithium salts, organic solvent and fluosulfonic acid ester type compound.It is described
Organic solvent is ethylene carbonate, the trifluoro-acetate of volume ratio 40:60.The lithium salts is LiPF6, concentration 1mol/L.
Additive is fluorine sulfonyloxy benzene (Formulas I).
Embodiment 2
Battery electrolyte includes that mass ratio is 16:74:10 lithium salts, organic solvent and fluosulfonic acid ester type compound.It is described to have
Solvent is propene carbonate, the methyl propionate, butyl trifluoroacetate of volume ratio 30:40:30.The lithium salts is LiBF4, dense
Spend 1mol/L.Additive is fluorosulfonyl oxygroup ethane (Formula II).
Embodiment 3
Battery electrolyte includes that mass ratio is 17:81:2 lithium salts, organic solvent and fluosulfonic acid ester type compound.It is described organic
Solvent is gamma-butyrolacton, the diethyl carbonate of volume ratio 50:50.The lithium salts is LiPF6, concentration 1mol/L.Additive is
Fluorosulfonyl oxygroup propylene (formula III).
Embodiment 4
Battery electrolyte includes that mass ratio is 18:79:3 lithium salts, organic solvent and fluosulfonic acid ester type compound.It is described organic
Solvent is dimethyl carbonate, trifluoro-acetate, the ethyl propionate of volume ratio 40:30:30.The lithium salts is LiSO3F3, dense
Spend 1mol/L.Additive is fluorosulfonyl oxygroup pentyne (formula IV).
Embodiment 5
Battery electrolyte includes that mass ratio is 19:77:4 lithium salts, organic solvent and fluosulfonic acid ester type compound.It is described organic
Solvent is gamma-valerolactone, the methyl ethyl carbonate of volume ratio 60:40.The lithium salts is Li (CF3SO2)3, concentration 1mol/L.Add
Adding agent is fluorine sulfonyloxy benzene (Formulas I).
Embodiment 6
Battery electrolyte includes that mass ratio is 20:75:5 lithium salts, organic solvent and fluosulfonic acid ester type compound.It is described organic
Solvent is the propyl propionate of volume ratio 40:60, butyl trifluoroacetate.The lithium salts is LiPF6, concentration 1mol/L.Additive
For fluorosulfonyl oxygroup ethane (Formula II).
Embodiment 7
Battery electrolyte includes that mass ratio is 16.5:77.5:6 lithium salts, organic solvent and fluosulfonic acid ester type compound.It is described
Organic solvent is ethylene carbonate, the trifluoro-acetate of volume ratio 40:60.The lithium salts is Li (CF3SO2)N2, concentration
1mol/L.Additive is fluorine sulfonyloxy benzene (Formulas I).
Embodiment 8
Battery electrolyte includes that mass ratio is 17.5:75.5:7 lithium salts, organic solvent and fluosulfonic acid ester type compound.It is described
Organic solvent is methyl ethyl carbonate, diethyl carbonate, the methyl propionate of volume ratio 20:50:30.The lithium salts is LiClO4,
Concentration 1mol/L.Additive is fluorosulfonyl oxygroup propylene (formula III).
Embodiment 9
Battery electrolyte includes that mass ratio is 18.5:73.5:8 lithium salts, organic solvent and fluosulfonic acid ester type compound.It is described
Organic solvent is ethylene carbonate, the trifluoro-acetate of volume ratio 40:60.The lithium salts is LiBF4, concentration 1mol/L.
Additive is fluorine sulfonyloxy benzene (Formulas I).
Embodiment 10
Battery electrolyte includes that mass ratio is 19.5:71.5:9 lithium salts, organic solvent and fluosulfonic acid ester type compound.It is described
Organic solvent is ethylene carbonate, the trifluoro-acetate of volume ratio 40:60.The lithium salts is LiSO3F, concentration 1mol/L.
Additive is fluorosulfonyl oxygroup pentyne (formula IV).
Two, application test
By electrolyte of the invention be not added with fluosulfonic acid ester type compound basic electrolyte distinguish assembled battery it is laggard
Row cycle performance test, the method is as follows: using cobalt acid lithium as positive electrode, cathode uses carbonaceous mesophase spherules, positive and negative anodes collector
It is distributed as aluminium foil and copper foil, diaphragm forms soft-package battery using ceramic diaphragm, after injecting electrolyte, is assembled into glove box soft
Packet battery is tested after standing 8 hours.
1, normal-temperature circulating performance
Normal temperature circulation test result is shown in Table 1.
Table 1
| Processing | Capacity retention ratio after normal temperature circulation 600 weeks |
| It is not added with the basic electrolyte of fluosulfonic acid ester type compound | 73.8% |
| Embodiment 1 | 88.2% |
| Embodiment 2 | 89.1% |
| Embodiment 3 | 88.5% |
| Embodiment 4 | 91.3% |
| Embodiment 5 | 92.8% |
| Embodiment 6 | 88.4% |
| Embodiment 7 | 89.3% |
| Embodiment 8 | 88.6% |
| Embodiment 9 | 90.7% |
| Embodiment 10 | 90.3% |
2, high temperature cyclic performance
Charge and discharge are carried out respectively under 25 DEG C of constant temperature of room temperature with 1/10C 3.0V to 4.5V or more to activate battery, with
Circulation under the conditions of 45 DEG C is with 1C charge and discharge afterwards.High temperature circulation test result is shown in Table 2.
Table 2
3, high and low temperature storge quality
85 DEG C/7D tests high-temperature storage performance；- 40 DEG C are shelved time 240min, test low-temperature storage performance.Test result
It is shown in Table 3.
Table 3
4, conductivity, internal resistance detection
With the internal resistance of battery Inner Resistance Tester in Virtual Instrument test battery, to be not added with the basic electrolyte of fluosulfonic acid ester type compound
Internal resistance is 1, investigates the variation of internal resistance after addition fluosulfonic acid ester type compound；To be not added with the basis electricity of fluosulfonic acid ester type compound
The conductivity for solving liquid is 1, investigates the variation of conductivity after addition fluosulfonic acid ester type compound.Investigation the results are shown in Table 4.
Table 4
| Processing | Conductivity | Internal resistance |
| Embodiment 1 | - 18.6% | + 20.1% |
| Embodiment 2 | - 17.3% | + 18.3% |
| Embodiment 3 | - 17.8% | + 17.6% |
| Embodiment 4 | - 18.2% | + 19.2% |
| Embodiment 5 | - 18.1% | + 19.8% |
| Embodiment 6 | - 17.6% | + 18.7% |
| Embodiment 7 | - 17.5% | + 17.6% |
| Embodiment 8 | - 17.4% | + 17.3% |
| Embodiment 9 | - 18.4% | + 18.2% |
| Embodiment 10 | - 17.7% | + 19.4% |
Note :+indicate to increase ,-indicate to reduce.
By above-mentioned table 1-4 it is found that the high temperature of battery, room temperature, low-temperature circulating performance obtain after fluosulfonic acid ester type compound is added
To greatly improving, while the storge quality of high/low temperature is also improved, but conductivity and the decline of internal resistance performance, in this way to this hair
The application of bright fluosulfonic acid ester type compound causes to limit, to solve the above problems, exploring through long-term research and development into electrolyte
1,3,6- hexane, three nitrile and benzene sulfonic acid sodium salt of electrolyte quality 3-5% is added, can improve because fluosulfonic acid ester type compound is added
The problem of decline of conductivity caused by and and internal resistance increase, the mass ratio that need to control 1,3,6- hexane, three nitrile and benzene sulfonic acid sodium salt is
0.5:(1-2).Performance detection after three nitrile of 1,3,6- hexane and benzene sulfonic acid sodium salt is added is as follows:
Table 5
Table 6
By above-mentioned table 5, table 6 it can be seen that other no for influencing battery of the addition of three nitrile of 1,3,6- hexane and benzene sulfonic acid sodium salt
Performance, but significantly improve the conductivity and internal resistance performance of battery because caused by being added fluosulfonic acid ester type compound and ask
Topic.
Claims (4)
1. application of the fluosulfonic acid ester type compound in battery electrolyte, it is characterised in that: fluosulfonic acid ester type compound, which is used as, to be added
Agent is added to be added in battery electrolyte, additive amount is the 0.1-10% of battery electrolyte quality, the fluosulfonic acid ester type compound
For the combination of one or more of Formulas I, Formula II, formula III, formula IV；
1,3,6- hexane, three nitrile and benzene sulfonic acid sodium salt that quality 3-5% is added in electrolyte, control 1,3,6- hexane, three nitrile and benzene sulphur
The mass ratio of sour sodium is 0.5:(1-2).
2. application of the fluosulfonic acid ester type compound according to claim 1 in battery electrolyte, it is characterised in that: described
Battery electrolyte include mass ratio be (15-20): (60-80): (0.1-10) lithium salts, organic solvent and fluosulfonic acid esters chemical combination
Object.
3. application of the fluosulfonic acid ester type compound according to claim 2 in battery electrolyte, it is characterised in that: described
Organic solvent be selected from ethylene carbonate, propene carbonate, gamma-butyrolacton, gamma-valerolactone, dimethyl carbonate, methyl ethyl carbonate,
Diethyl carbonate, methyl propionate, ethyl propionate, propyl propionate, trifluoro-acetate, Trifluoroacetic Acid Ethyl Ester, butyl trifluoroacetate
One of or it is a variety of.
4. application of the fluosulfonic acid ester type compound according to claim 2 in battery electrolyte, it is characterised in that: described
Lithium salts be selected from LiPF6、LiBF4、LiSO3CF3、LiClO4、LiN(CF3SO2)2、LiC(CF3SO2)3One of or it is a variety of.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711313228.6A CN108091933B (en) | 2017-12-12 | 2017-12-12 | Application of the fluosulfonic acid ester type compound in battery electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711313228.6A CN108091933B (en) | 2017-12-12 | 2017-12-12 | Application of the fluosulfonic acid ester type compound in battery electrolyte |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108091933A CN108091933A (en) | 2018-05-29 |
| CN108091933B true CN108091933B (en) | 2019-11-12 |
Family
ID=62173883
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711313228.6A Active CN108091933B (en) | 2017-12-12 | 2017-12-12 | Application of the fluosulfonic acid ester type compound in battery electrolyte |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108091933B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3985774A1 (en) * | 2020-10-13 | 2022-04-20 | Hyundai Motor Company | Electrolyte for lithium secondary battery and lithium secondary battery comprising the same |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109980282B (en) * | 2019-04-09 | 2021-01-15 | 杉杉新材料（衢州）有限公司 | Low-temperature-resistant non-aqueous electrolyte for lithium ion battery and lithium ion battery |
| CN110429336B (en) * | 2019-07-24 | 2022-07-12 | 江苏国泰超威新材料有限公司 | Non-aqueous electrolyte and lithium ion battery |
| CN111029652A (en) * | 2019-12-20 | 2020-04-17 | 杉杉新材料（衢州）有限公司 | Lithium ion battery electrolyte and lithium ion battery containing same |
| CN111313090A (en) * | 2020-02-18 | 2020-06-19 | 白银科奥夫化学科技有限公司 | Lithium ion battery electrolyte and lithium ion secondary battery containing same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5125379B2 (en) * | 2007-10-04 | 2013-01-23 | 宇部興産株式会社 | Electrolytic solution for lithium secondary battery containing benzenesulfonic acid ester, and lithium secondary battery using the same |
| CN105074994B (en) * | 2013-03-27 | 2018-10-19 | 三菱化学株式会社 | Nonaqueous electrolytic solution and the nonaqueous electrolyte battery for using the nonaqueous electrolytic solution |
| CN105047995B (en) * | 2015-09-22 | 2018-05-08 | 宁德新能源科技有限公司 | Lithium ion battery of electrolyte including the electrolyte and preparation method thereof |
-
2017
- 2017-12-12 CN CN201711313228.6A patent/CN108091933B/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3985774A1 (en) * | 2020-10-13 | 2022-04-20 | Hyundai Motor Company | Electrolyte for lithium secondary battery and lithium secondary battery comprising the same |
| US11830979B2 (en) | 2020-10-13 | 2023-11-28 | Hyundai Motor Company | Electrolyte for lithium secondary battery and lithium secondary battery comprising same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108091933A (en) | 2018-05-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108091933B (en) | Application of the fluosulfonic acid ester type compound in battery electrolyte | |
| CN105914399B (en) | A kind of electrolyte and the lithium ion battery containing the electrolyte | |
| CN110867613A (en) | Silicon-carbon negative electrode lithium ion battery electrolyte and lithium battery | |
| CN103972588A (en) | Non-aqueous electrolyte and lithium ion battery | |
| CN104022310B (en) | Lithium rechargeable battery and the lithium ion battery containing this electrolyte | |
| CN103107355B (en) | Lithium ion battery and electrolyte thereof | |
| CN107591557B (en) | A kind of non-aqueous electrolyte for lithium ion cell and the lithium ion battery using the electrolyte | |
| CN106410279A (en) | Electrolyte and secondary battery | |
| CN105098244A (en) | Electrolyte and lithium ion battery comprising same | |
| CN104051786A (en) | Electrolyte, preparation method for same and high-voltage lithium ion battery | |
| CN108258311A (en) | Non-aqueous electrolyte for lithium ion cell and lithium ion battery | |
| CN103515651B (en) | A kind of lithium ion battery high-voltage carbonate group electrolyte and preparation method and application | |
| CN112310473A (en) | High-low temperature lithium ion battery electrolyte and lithium ion battery | |
| CN105762410B (en) | A kind of nonaqueous electrolytic solution and the lithium ion battery using the nonaqueous electrolytic solution | |
| CN105789685A (en) | Lithium ion battery and electrolyte thereof | |
| CN103956517A (en) | High-voltage lithium ion battery electrolyte, preparation method and application of electrolyte | |
| CN112331914A (en) | Non-aqueous electrolyte of lithium ion battery without ethylene carbonate solvent and battery | |
| CN108110322A (en) | A kind of nonaqueous electrolytic solution and lithium ion battery for lithium ion battery | |
| CN112635835A (en) | Non-aqueous electrolyte and lithium ion battery with high and low temperature consideration | |
| CN113451653A (en) | Non-aqueous electrolyte and lithium ion battery comprising same | |
| US20200136183A1 (en) | Electrolyte and lithium ion battery | |
| CN106450462B (en) | The wide temperature lithium-ion battery electrolytes of high voltage | |
| CN109473717A (en) | A kind of electrolyte and the high nickel-based battery of high voltage suitable for the high nickel power battery of high voltage | |
| CN108987806A (en) | Application of the cyclic boronic anhydride in battery electrolyte | |
| CN114188606B (en) | Electrolyte and application thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 051430 douyu Industrial Zone, Luancheng District, Shijiazhuang City, Hebei Province Patentee after: Hebei Shengtai Materials Co.,Ltd. Address before: 051430 douyu Industrial Zone, Luancheng District, Shijiazhuang City, Hebei Province Patentee before: SHIJIAZHUANG SHENGTAI CHEMICAL Co.,Ltd. |
|
| CP01 | Change in the name or title of a patent holder |