CN106920991A - A kind of lithium battery electrolytes and lithium battery for improving wellability - Google Patents
A kind of lithium battery electrolytes and lithium battery for improving wellability Download PDFInfo
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- CN106920991A CN106920991A CN201510991526.5A CN201510991526A CN106920991A CN 106920991 A CN106920991 A CN 106920991A CN 201510991526 A CN201510991526 A CN 201510991526A CN 106920991 A CN106920991 A CN 106920991A
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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
- H01M10/052—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
- H01M10/0569—Liquid materials characterised by the 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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Abstract
The present invention relates to a kind of lithium battery electrolytes for improving wellability, including lithium salts, organic solvent and additive, described additive includes additive A, and described additive A is selected from the combination of one or more in following structural formula：, in formula, R1、R2、R3、R4、R5The one kind in hydrogen, hydroxyl, alkyl, alkoxy, alkenyl, ketone group, phenyl, phenoxy group, fluoro-alkyl, fluoroalkyl, fluoro alkenyl, fluoro ketone group, difluorophenyl, fluorinated phenoxy independently is, wherein：Fluoro is part substitution or full substitution.The present invention in lithium battery electrolytes by adding additive A so that the wetting property of electrolyte is obviously improved, and has good high temperature output characteristics, multiplying power and cycle performance using the lithium battery of the electrolyte.
Description
Technical field
The invention belongs to electrochemical technology field, and in particular to lithium battery electrolytes and the lithium electricity of a kind of raising wellability
Pond.
Background technology
Lithium ion battery is deep into the middle of the production and living of people more and more widely, and this causes that its safety problem turns into
The main points of concern, solution route of the lithium battery safety problem in terms of electrolyte has two, approach one：All-solid lithium-ion battery electricity
Solution Quality Research, at present also in development, also immature, industrialization distance is also very very long；Approach two：To existing lithium-ion electric
The improvement of pond electrolyte system, i.e., be to solve current lithium using fire retardant or even non-ignitable solvent (fluorine-containing solvent) or fire retardant
One of most promising approach of the inflammable problem of ion battery electrolyte, they damage smaller to battery performance, suppress electrolyte combustion
The effect of burning is obvious.But the fire retardant or even non-ignitable general viscosity of solvent is all larger, battery imbibition difficulty is, it is necessary to add a certain amount of
Surfactant is size.
Fluorine-containing surfactant has high surface, heat-resistant stability high, low combustible and high chemical stability etc. excellent
Point.Fluorine-containing surfactants are that active highest is a kind of so far in all surface activating agent, this be fluorine-containing surfactant most
Important properties, when concentration is very low just the surface tension of solution can significantly reduce for it；General fluorine-containing surfactant heating
Will not be decomposed to more than 400 DEG C, this is sufficiently stable with C-F keys relevant, C-F keys make it have anti-strong acid very high, highly basic, strong oxygen
The ability of agent, can use in more harsh environment；The liquid wetting power and penetration for adding fluorine-containing surfactant are big
To improve, after other surfaces activating agent compounding, the ability with reduction surface tension higher.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of lithium battery electrolytes and lithium battery for improving wellability, make
There is good high temperature output characteristics, multiplying power and cycle performance with the lithium battery of the electrolyte.
To reach above-mentioned purpose, the technical solution adopted by the present invention is：
A kind of lithium battery electrolytes for improving wellability, including lithium salts, organic solvent and additive, described additive include additive
A, described additive A is selected from the combination of one or more in following structural formula：
In formula, R1、R2、R3、R4、R5Independently be hydrogen, hydroxyl, alkyl, alkoxy, alkenyl, ketone group, phenyl, phenoxy group, fluoro-alkyl,
One kind in fluoroalkyl, fluoro alkenyl, fluoro ketone group, difluorophenyl, fluorinated phenoxy, wherein：Fluoro replaces for part
Or full substitution.
Specifically, described R1It is the perfluoroalkyl that carbon number is 6~10, described R2、R3It independently is carbon atom
Number is 1~3 alkyl, described R4It is the alkyl that carbon number is 1~3 or the ketone group that carbon number is 1~3, described R5For
Carbon number is 2~5 alkenyl or hydroxyl.
More specifically, described additive A is 2- [ethyl [(17 fluorine octyl group) sulphonyl] amino] ethanol APEO
Or methacrylic acid N- ethylperfluoro perfluorooctane sulfonyl aminoethyls.
Specifically, mass percent of the described additive A in described lithium battery electrolytes is 0.001~2%.
Preferably, mass percent of the described additive A in described lithium battery electrolytes is 0.005~1%.
Specifically, described lithium salts is selected from lithium hexafluoro phosphate LiPF6, LiBF4 LiBF4, hexafluoroarsenate lithium
LiAsF6, Lithium perchlorate anhydrous LiClO4, two (trifluoromethane sulfonic acid acyl) imine lithium LiN (SO2CF3)2, trifluoromethyl sulfonic acid lithium
LiSO3CF3, dioxalic acid lithium borate LiC2O4BC2O4, the double lithium fluoroborate LiF of single oxalic acid2BC2O4, double fluorine sulfimide lithium LiN
(SO2F)2In the combination of one or more, the molar concentration of described lithium salts in described lithium battery electrolytes is 0.001
~2 mol/Ls.
Specifically, described organic solvent is cyclic carbonates organic solvent, linear carbonate class organic solvent, fluoro
The combination of one or more in organic solvent.
More specifically, described cyclic carbonates organic solvent is selected from gamma-butyrolacton (GBL), ethylene carbonate
(EC), the combination of one or more in propene carbonate (PC)；
Described linear carbonate class organic solvent is selected from dimethyl carbonate (DMC), methyl ethyl carbonate (EMC), carbonic acid
Diethylester (DEC), methyl propyl carbonate (MPC), propyl methyl (MP), ethyl propionate (EP), propyl propionate (PP), methyl acetate
(MA), one kind in ethyl acetate (EA), propyl acetate (PA), methyl butyrate (MB), ethyl butyrate (EB), propyl butyrate (PB)
Or several combinations；
Described fluorinated organic solvent is the fluoro ethyl -2,2,3,3- tetrafluoros propyl ethers of 1,1,2,2- tetra- or fluoro ethylene carbonate
Ester (FEC).
Specifically, described additive also includes other functions additive, and described other functions additive is described
Mass percent in lithium battery electrolytes is 0.01~20%.
More specifically, described additive also includes other functions additive, described other functions additive is described
Lithium battery electrolytes in mass percent be 0.1~5%.
More specifically, described other functions additive is selected from vinylene carbonate (VC), 1,3 propane sultones
(PS), vinylethylene carbonate (VEC), biphenyl (BP), cyclohexyl benzene (CHB), sulfuric acid propylene (TSA), trioctyl phosphate
(TOP) combination of one or more in.
A kind of lithium battery, including positive pole, negative pole and electrolyte, described electrolyte are described lithium battery electrolytes, institute
The negative pole stated is that, selected from the combination of one or more in lithium titanate, Delanium, native graphite, described is just extremely selected from cobalt
The combination of one or more in sour lithium, ternary material, nickel ion doped.
Because above-mentioned technical proposal is used, the present invention has following advantages compared with prior art：
The present invention in lithium battery electrolytes by adding additive A so that the wetting property of electrolyte is obviously improved, and adopts
There is good high temperature output characteristics, multiplying power and cycle performance with the lithium battery of the electrolyte.
Brief description of the drawings
Accompanying drawing 1 is the graph of a relation of the cycle-index of battery and discharge capacity obtained in embodiment 1；
Accompanying drawing 2 is the relation of embodiment 2, comparative example 1 and the cycle-index of battery and battery capacity obtained in comparative example 2
Figure；
Accompanying drawing 3 is the relation of embodiment 3, comparative example 3 and the cycle-index of battery and battery capacity obtained in comparative example 4
Figure；
Accompanying drawing 4 is the cycle-index and the graph of a relation of battery capacity of battery obtained in embodiment 4,5,6.
Specific embodiment
The present invention is elaborated below in conjunction with specific embodiment：
Embodiment 1
(the H in the glove box of applying argon gas2O<10ppm), with EC/PC/DMC/LIPF6/ VC/PS=35/10/35/15/2/3
Mass ratio be well mixed, then to added respectively in the electrolyte electrolyte total amount 0%, 0.05%, 0.1%, 0.3%,
0.5%th, 1% and 2% 2- [ethyl [(17 fluorine octyl group) sulphonyl] amino] ethanol APEO.
Battery is melted into 0.1C discharge and recharges from ternary graphite cell, battery normal-temperature circulating performance is tested.Test
Result is as shown in Figure 1.
Comparative example 1
(the H in the glove box of applying argon gas2O<10ppm), with FEC/1,1,2,2- tetra- fluoro ethyl -2,2,3,3- tetra- fluoropropyls
Ether=1/1 mass ratio is well mixed, and then dissolves the lithium hexafluoro phosphate (LiPF of 1.0mol/L6) in wherein, in the electrolyte
The vinylene carbonate of addition electrolyte total amount 1%.
From cobalt acid lithium graphite cell, battery is melted into 0.1C discharge and recharges, surveys its first charge-discharge efficiency, and do
Normal temperature circulation.Test result is as shown in table 1 and Fig. 2.
Comparative example 2
(the H in the glove box of applying argon gas2O<10ppm), with FEC/1,1,2,2- tetra- fluoro ethyl -2,2,3,3- tetra- fluoropropyls
Ether=1/1 mass ratio is well mixed, and then dissolves the lithium hexafluoro phosphate (LiPF of 1.0mol/L6) in wherein, in the electrolyte
The trioctyl phosphate and the vinylene carbonate of electrolyte total amount 1% of addition electrolyte total amount 0.5%.
From cobalt acid lithium graphite cell, battery is melted into 0.1C discharge and recharges, surveys its first charge-discharge efficiency, and do
Normal temperature circulation.Test result is as shown in table 1 and Fig. 2.
Embodiment 2
(the H in the glove box of applying argon gas2O<10ppm), with FEC/1,1,2,2- tetra- fluoro ethyl -2,2,3,3- tetra- fluoropropyls
Ether=1/1 mass ratio is well mixed, and then dissolves the lithium hexafluoro phosphate (LiPF of 1.0mol/L6) in wherein, in the electrolyte
2- [ethyl [(17 fluorine octyl group) sulphonyl] amino] the ethanol APEOs and electrolyte of addition electrolyte total amount 0.5% are total
Measure 1% vinylene carbonate.
From cobalt acid lithium graphite cell, battery is melted into 0.1C discharge and recharges, surveys its first charge-discharge efficiency, and do
Normal temperature circulation.Test result is as shown in table 1 and Fig. 2.
Table 1
Comparative example 3
(the H in the glove box of applying argon gas2O<10ppm), it is well mixed with DMC/EC=2/1 mass ratioes, then dissolve
Lithium hexafluoro phosphate (the LiPF of 1.2mol/L6) in wherein, to the vinylene carbonate of addition electrolyte total amount 1% in the electrolyte.
From cobalt acid lithium graphite cell, battery is melted into 0.1C discharge and recharges, surveys its first charge-discharge efficiency, and do
Normal temperature and high temperature circulation and 85 DEG C of high temperature shelve 4H.Test result is as shown in table 2,3,4 and Fig. 3.
Comparative example 4
(the H in the glove box of applying argon gas2O<10ppm), it is well mixed with DMC/EC=2/1 mass ratioes, then dissolve
Lithium hexafluoro phosphate (the LiPF of 1.2mol/L6) in wherein, it is pungent to the tricresyl phosphate that electrolyte total amount 0.05% is added in the electrolyte
Ester and the vinylene carbonate of electrolyte total amount 1%.
From cobalt acid lithium graphite cell, battery is melted into 0.1C discharge and recharges, surveys its first charge-discharge efficiency, and do
Normal temperature and high temperature circulation and 85 DEG C of high temperature shelve 4H.Test result is as shown in table 2,3,4 and Fig. 3.
Embodiment 3
(the H in the glove box of applying argon gas2O<10ppm), it is well mixed with DMC/EC=2/1 mass ratioes, then dissolve
Lithium hexafluoro phosphate (the LiPF of 1.2mol/L6) in wherein, to the 2- [ethyls that electrolyte total amount 0.05% is added in the electrolyte
[(17 fluorine octyl group) sulphonyl] amino] ethanol APEO and the vinylene carbonate of electrolyte total amount 1%.
From cobalt acid lithium graphite cell, battery is melted into 0.1C discharge and recharges, surveys its first charge-discharge efficiency, and do
Normal temperature and high temperature circulation and 85 DEG C of high temperature shelve 4H.Test result as shown in table 2,3,4 and Fig. 3, wherein, table 2 and table 3 are 85 DEG C
High temperature shelves the test result of 4H, and table 4 is normal temperature 45C multiplying power test results.
Table 2
Table 3
Table 4
Embodiment 4
(the H in the glove box of applying argon gas2O<10ppm), it is well mixed with GBL/EC=2/1 mass ratioes, then dissolve
Lithium hexafluoro phosphate (the LiPF of 0.9mol/L6) in wherein, to the methacrylic acid that electrolyte total amount 0.3% is added in the electrolyte
N- ethylperfluoro perfluorooctane sulfonyl aminoethyls and the vinylene carbonate of electrolyte total amount 1%.
From cobalt acid lithium graphite cell, battery is melted into 0.1C discharge and recharges, surveys its first charge-discharge efficiency, and do
Normal temperature.Test result is as shown in table 5 and Fig. 4.
Embodiment 5
(the H in the glove box of applying argon gas2O<10ppm), it is well mixed with GBL/EC=2/1 mass ratioes, then dissolve
Lithium hexafluoro phosphate (the LiPF of 0.9mol/L6) in wherein, to the methacrylic acid that electrolyte total amount 0.5% is added in the electrolyte
N- ethylperfluoro perfluorooctane sulfonyl aminoethyls and the vinylene carbonate of electrolyte total amount 1%.
From cobalt acid lithium graphite cell, battery is melted into 0.1C discharge and recharges, surveys its first charge-discharge efficiency, and do
Normal temperature.Test result is as shown in table 5 and Fig. 4.
Embodiment 6
(the H in the glove box of applying argon gas2O<10ppm), it is well mixed with GBL/EC=2/1 mass ratioes, then dissolve
Lithium hexafluoro phosphate (the LiPF of 0.9mol/L6) in wherein, to the methacrylic acid that electrolyte total amount 0.1% is added in the electrolyte
N- ethylperfluoro perfluorooctane sulfonyl aminoethyls and the vinylene carbonate of electrolyte total amount 1%.
From cobalt acid lithium graphite cell, battery is melted into 0.1C discharge and recharges, surveys its first charge-discharge efficiency, and do
Normal temperature.Test result is as shown in table 5 and Fig. 4.
Comparative example 5
(the H in the glove box of applying argon gas2O<10ppm), it is well mixed with GBL/EC=2/1 mass ratioes, then dissolve
Lithium hexafluoro phosphate (the LiPF of 0.9mol/L6) in wherein, to the vinylene carbonate of addition electrolyte total amount 1% in the electrolyte.
From cobalt acid lithium graphite cell, battery is melted into 0.1C discharge and recharges, surveys its first charge-discharge efficiency, and do
Normal temperature.Test result is as shown in table 5 and Fig. 4.
Table 5
The above embodiments merely illustrate the technical concept and features of the present invention, its object is to allow person skilled in the art
Scholar will appreciate that present disclosure and implement according to this that it is not intended to limit the scope of the present invention, all according to the present invention
The equivalent change or modification that Spirit Essence is made, should all be included within the scope of the present invention.
Claims (10)
1. a kind of lithium battery electrolytes for improving wellability, including lithium salts, organic solvent and additive, it is characterised in that：It is described
Additive include additive A, described additive A is selected from the combination of one or more in following structural formula：, in formula, R1、R2、R3、R4、R5It independently is hydrogen, hydroxyl, alkyl, alkoxy, alkene
Base, ketone group, phenyl, phenoxy group, fluoro-alkyl, fluoroalkyl, fluoro alkenyl, fluoro ketone group, difluorophenyl, fluorinated phenoxy
In one kind, wherein：Fluoro is part substitution or full substitution.
2. lithium battery electrolytes according to claim 1, it is characterised in that：Described R1For carbon number for 6 ~ 10 it is complete
Fluoro-alkyl, described R2、R3It independently is the alkyl that carbon number is 1 ~ 3, described R4It is the alkyl that carbon number is 1 ~ 3
Or carbon number is 1 ~ 3 ketone group, described R5It is alkenyl or hydroxyl that carbon number is 2 ~ 5.
3. lithium battery electrolytes according to claim 2, it is characterised in that：Described additive A is 2- [ethyls [(17
Fluorine octyl group) sulphonyl] amino] ethanol APEO or methacrylic acid N- ethylperfluoro perfluorooctane sulfonyl aminoethyls.
4. lithium battery electrolytes according to any one of claim 1 to 3, it is characterised in that：Described additive A is in institute
Mass percent in the lithium battery electrolytes stated is 0.001 ~ 2%.
5. lithium battery electrolytes according to claim 1, it is characterised in that：Described lithium salts is selected from LiPF6、LiBF4、
LiAsF6、LiClO4、LiN(SO2CF3)2、LiSO3CF3、LiC2O4BC2O4、LiF2BC2O4、LiN(SO2F)2In one or more
Combination, the molar concentration of described lithium salts in described lithium battery electrolytes is 0.001 ~ 2 mol/L.
6. lithium battery electrolytes according to claim 1, it is characterised in that：Described organic solvent is cyclic carbonates
The combination of one or more in organic solvent, linear carbonate class organic solvent, fluorinated organic solvent.
7. lithium battery electrolytes according to claim 6, it is characterised in that：Described cyclic carbonates organic solvent is
Selected from the combination of one or more in gamma-butyrolacton, ethylene carbonate, propene carbonate；
Described linear carbonate class organic solvent is selected from dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, carbonic acid first third
Ester, propyl methyl, ethyl propionate, propyl propionate, methyl acetate, ethyl acetate, propyl acetate, methyl butyrate, ethyl butyrate, fourth
The combination of one or more in propyl propionate；
Described fluorinated organic solvent is the fluoro ethyl -2,2,3,3- tetrafluoros propyl ethers of 1,1,2,2- tetra- or fluorinated ethylene carbonate.
8. lithium battery electrolytes according to claim 1, it is characterised in that：Described additive also adds including other functions
Plus agent, the mass percent of described other functions additive in described lithium battery electrolytes is 0.01 ~ 20%.
9. lithium battery electrolytes according to claim 8, it is characterised in that：Described other functions additive is selected from carbon
In sour vinylene, 1,3 propane sultones, vinylethylene carbonate, biphenyl, cyclohexyl benzene, sulfuric acid propylene, trioctyl phosphate
The combination of one or more.
10. a kind of lithium battery, including positive pole, negative pole and electrolyte, it is characterised in that：Described electrolyte is claim 1 to 9
Any one of lithium battery electrolytes, described negative pole be selected from the one kind in lithium titanate, Delanium, native graphite or
Several combinations, the described combination of one or more being just extremely selected from cobalt acid lithium, ternary material, nickel ion doped.
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| CN110870126A (en) * | 2017-08-03 | 2020-03-06 | 三星Sdi株式会社 | Electrolyte for lithium battery and lithium battery including the same |
| US20210246098A1 (en) * | 2018-01-30 | 2021-08-12 | Daikin Industries, Ltd. | Electrolyte, electrochemical device, lithium ion secondary battery, and module |
| US11945776B2 (en) * | 2018-01-30 | 2024-04-02 | Daikin Industries, Ltd. | Electrolyte, electrochemical device, lithium ion secondary battery, and module |
| CN110247116A (en) * | 2019-06-24 | 2019-09-17 | 珠海市赛纬电子材料股份有限公司 | A kind of non-aqueous electrolyte for lithium ion cell and the lithium ion battery using the electrolyte |
| CN110247116B (en) * | 2019-06-24 | 2022-04-05 | 珠海市赛纬电子材料股份有限公司 | Non-aqueous electrolyte of lithium ion battery and lithium ion battery using same |
| US11888115B2 (en) | 2019-09-09 | 2024-01-30 | Contemporary Amperex Technology Co., Limited | Electrolytic solution and lithium metal battery containing the same, battery module, battery pack, and device |
| CN112467207A (en) * | 2019-09-09 | 2021-03-09 | 宁德时代新能源科技股份有限公司 | Electrolyte and lithium metal battery containing same |
| CN112820941A (en) * | 2019-11-15 | 2021-05-18 | 浙江中蓝新能源材料有限公司 | Composition for electrolyte |
| CN112820941B (en) * | 2019-11-15 | 2022-10-28 | 浙江中蓝新能源材料有限公司 | Composition for electrolyte |
| CN110838596A (en) * | 2019-11-19 | 2020-02-25 | 凌帕新能源科技(上海)有限公司 | Lithium battery electrolyte and lithium battery |
| CN113764728A (en) * | 2020-06-01 | 2021-12-07 | 比亚迪股份有限公司 | Electrolyte and lithium metal battery |
| CN113764728B (en) * | 2020-06-01 | 2023-11-14 | 比亚迪股份有限公司 | Electrolyte and lithium metal battery |
| CN113488696A (en) * | 2021-06-04 | 2021-10-08 | 天津市捷威动力工业有限公司 | High-wettability electrolyte for cylindrical lithium ion battery |
| CN113488696B (en) * | 2021-06-04 | 2022-08-02 | 天津市捷威动力工业有限公司 | High-wettability electrolyte for cylindrical lithium ion battery |
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