CN108199076A - A kind of lithium ion battery high-voltage electrolyte and lithium ion battery - Google Patents
A kind of lithium ion battery high-voltage electrolyte and lithium ion battery Download PDFInfo
- Publication number
- CN108199076A CN108199076A CN201711448337.9A CN201711448337A CN108199076A CN 108199076 A CN108199076 A CN 108199076A CN 201711448337 A CN201711448337 A CN 201711448337A CN 108199076 A CN108199076 A CN 108199076A
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- lithium
- ion battery
- lithium ion
- additive
- carbonate
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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
-
- 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
The invention discloses a kind of lithium ion battery high-voltage electrolyte and lithium ion battery, electrolyte includes following raw material：Lithium salts, nonaqueous solvents, additive A and additive B, nonaqueous solvents are linear carbonate and the mixed solvent of cyclic carbonate, and additive A is benzothiophene or dibenzothiophenes class solvent, and additive B is 1,3 sultones of acrylic；This lithium ion battery high-voltage electrolyte and lithium ion battery can reduce oxygenolysis of the carbonate-based solvent in electrode surface using the solvent of element sulphur is contained as the high pressure additive of lithium-ion electrolyte；1,3 sultones of acrylic has good cathode film formation performance, can effectively coat negative material, can substantially improve the room temperature cycles performance under high voltage.
Description
Technical field
The present invention relates to technical field of lithium ion, specially a kind of lithium ion battery high-voltage electrolyte and lithium from
Sub- battery.
Background technology
Lithium ion battery has that operating voltage is high, specific capacity is big, have extended cycle life, memory-less effect and environmentally friendly
The advantages that, be widely used in various electronic equipments, with extensive use of the lithium ion battery on electric vehicle, people couple
The energy density of battery proposes requirements at the higher level, and the positive electrodes such as ternary material, LiFePO4 for using at present can be very
The deintercalation reaction of lithium ion is carried out under high voltage, the energy density for people's raising battery provides new approach, but mesh
The lithium ion cell electrode liquid of preceding conventional organic carbonate system easy oxygenolysis at high temperature, generates a large amount of gases, makes
The internal pressure of battery increases, and the cycle performance and security performance to battery generate very negative impact, constrain high voltage lithium from
The further development of sub- battery, therefore propose a kind of lithium ion battery high-voltage electrolyte and lithium ion battery.
Invention content
The purpose of the present invention is to provide a kind of lithium ion battery high-voltage electrolyte and lithium ion battery, carbonates
Solvent is difficult to the oxygenolysis in electrode surface, substantially improves the room temperature cycles performance under high voltage, to solve above-mentioned background skill
The problem of being proposed in art.
To achieve the above object, the present invention provides following technical solution：A kind of lithium ion battery high-voltage electrolyte, packet
Include following raw material：Lithium salts, nonaqueous solvents, additive A and additive B, nonaqueous solvents are linear carbonate and cyclic carbonate
Mixed solvent, additive A are propenyl-1,3-sulfonic acid lactone for benzothiophene or dibenzothiophenes class solvent, additive B；
Benzothiophene structural formula is：
Dibenzothiophenes class structure in solvent formula is：
Wherein R is phosphate-based or boric acid ester group, and carbon atom number is the straight chained alkyl of 2- 8, and part hydrogen or whole hydrogen are taken by halogen
The carbon atom number in generation is the straight chained alkyl of 2-8, and carbon atom number is the linear carbonate base of 1-6；
Propenyl-1,3-sulfonic acid lactone, structural formula are：
Preferably, it is 0.5~1.5% that additive A occupies mass ratio in the electrolytic solution, and additive B occupies mass ratio in the electrolytic solution
It is 0.5~1.5%.
Preferably, lithium salts for lithium hexafluoro phosphate, hexafluoroarsenate lithium, lithium perchlorate, LiBF4, dioxalic acid lithium borate,
In difluorine oxalic acid boracic acid lithium, pyrovinic acid lithium, trifluoromethyl sulfonic acid lithium, bis trifluoromethyl sulfimide lithium any one or
Several mixture therein, wherein lithium salt are 1.0M.
Preferably, nonaqueous solvents for organic solvent under nitrogen or inert gas shielding, by vacuum distillation purify and point
Son sieve dehydration is made, and non-aqueous organic solvent is ethylene carbonate, propene carbonate, butylene, gamma-butyrolacton, carbonic acid two
Propyl ester, dimethyl sulfite, vinylene carbonate, methyl propyl carbonate, ethyl acetate, methyl acetate, methyl butyrate, butyric acid second
Any one in ester, methyl propionate, ethyl propionate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, propyl acetate or
The mixture of several compositions.
A kind of lithium ion battery, lithium ion battery use the high-voltage electrolyte for containing electrolysis additive as electrolyte.
Preferably, anode material for lithium-ion batteries is ternary material（LixNiyCozMnaMeO2, wherein, 0.95≤x≤1.1,
0≤y≤0.9,0≤z≤0.5,0≤d≤0.5；In 0.001≤e≤0.1, Me Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V extremely
A kind of few element）, cobalt acid lithium（LiCoO2）, lithium nickelate（LiNiO2）, layered lithium manganate（LiMnO2）, spinelle shape LiMn2O4
（LiMn2O4）, LiFePO4（LiFePO4）, rich lithium manganese xLi2MnO3•（1-x）LiMO2One kind or more in (M=Ni, Co, Mn)
Kind.
Preferably, lithium ion battery negative material for carbonaceous material, Si, SiOx, Si alloy, Si carbon composites, Sn,
SnOx, Sn alloys, at least one of Sn carbon composites；Wherein, 0 ＜ x<2.
Compared with prior art, the beneficial effects of the invention are as follows：
This lithium ion battery high-voltage electrolyte and lithium ion battery use the benzothiophene containing element sulphur or dibenzo thiophene
High pressure additive of the fen class solvent as lithium-ion electrolyte can form one layer of form compact and stable interfacial film in positive electrode surface,
Reduce oxygenolysis of the carbonate-based solvent in electrode surface；Acrylic -1,3- sultones has good cathode film formation
Can, negative material can be effectively coated, the room temperature cycles performance under high voltage can be substantially improved.
Specific embodiment
The embodiment of the present invention is will be detailed below, however, the embodiment of the present invention is not limited thereto.Based in the present invention
Embodiment, those of ordinary skill in the art's all other embodiments obtained without making creative work,
It shall fall within the protection scope of the present invention.
In the present invention：A kind of lithium ion battery high-voltage electrolyte, including following raw material：Lithium salts, nonaqueous solvents, addition
Agent A and additive B, nonaqueous solvents are linear carbonate and the mixed solvent of cyclic carbonate, and additive A is benzothiophene or two
Benzothiophene kind solvent, additive B are propenyl-1,3-sulfonic acid lactone；
Benzothiophene structural formula is：
Dibenzothiophenes class structure in solvent formula is：
Wherein R is phosphate-based or boric acid ester group, and carbon atom number is the straight chained alkyl of 2- 8, and part hydrogen or whole hydrogen are taken by halogen
The carbon atom number in generation is the straight chained alkyl of 2-8, and carbon atom number is the linear carbonate base of 1-6；
Propenyl-1,3-sulfonic acid lactone, structural formula are：
In the electrolytic solution, it is 0.5~1.5% that additive A, which occupies mass ratio, and it is 0.5 that additive B occupies mass ratio in the electrolytic solution
~1.5%；Lithium salts is lithium hexafluoro phosphate, hexafluoroarsenate lithium, lithium perchlorate, LiBF4, dioxalic acid lithium borate, difluoro oxalate
In lithium borate, pyrovinic acid lithium, trifluoromethyl sulfonic acid lithium, bis trifluoromethyl sulfimide lithium any one or it is therein several
The mixture of kind, wherein lithium salt are 1.0M；Nonaqueous solvents for organic solvent under nitrogen or inert gas shielding, through over-subtraction
Pressure distilation and molecular sieve dehydration be made, non-aqueous organic solvent for ethylene carbonate, propene carbonate, butylene, γ-
Butyrolactone, dipropyl carbonate, dimethyl sulfite, vinylene carbonate, methyl propyl carbonate, ethyl acetate, methyl acetate, butyric acid
Appoint in methyl esters, ethyl butyrate, methyl propionate, ethyl propionate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, propyl acetate
The mixture of the one or several kinds of compositions of meaning；Lithium ion battery uses the high-voltage electrolyte for containing electrolysis additive as electrolysis
Liquid；Anode material for lithium-ion batteries is ternary material（LixNiyCozMnaMeO2, wherein, 0.95≤x≤1.1,0≤y≤0.9,0
≤ z≤0.5,0≤d≤0.5；At least one of 0.001≤e≤0.1, Me Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V members
Element）, cobalt acid lithium（LiCoO2）, lithium nickelate（LiNiO2）, layered lithium manganate（LiMnO2）, spinelle shape LiMn2O4（LiMn2O4）, phosphorus
Sour iron lithium（LiFePO4）, rich lithium manganese xLi2MnO3•（1-x）LiMO2It is one or more in (M=Ni, Co, Mn)；Lithium ion battery
Negative material is carbonaceous material, Si, SiOx, Si alloy, Si carbon composites, Sn, SnOx, Sn alloys, in Sn carbon composites
It is at least one；Wherein, 0 ＜ x<2.
Embodiment one：
A kind of lithium ion battery high-voltage electrolyte and lithium ion battery, electrolyte include a kind of dibenzo containing borate
Thiophene additive, structural formula are：
For high voltage additive when in for lithium-ion battery electrolytes, shared mass percent is 0.8% in the electrolytic solution,
The mass fraction of acrylic -1,3- sultones is 1.2%；Organic solvent in electrolyte is ethylene carbonate (EC), carbonic acid two
The mixture of methyl esters (DMC) and methyl ethyl carbonate (EMC), the wherein mass ratio of EC, DMC and EMC are 1：1：1；Lithium ion
The electrolyte of battery is respectively the LiPF of 1M6, it is denoted as electrolyte 1.
Embodiment two：
A kind of lithium ion battery high-voltage electrolyte and lithium ion battery, electrolyte include a kind of dibenzothiophenes of phosphate
Additive, structural formula are：
For high voltage additive when in for lithium-ion battery electrolytes, shared mass percent is 0.8% in the electrolytic solution,
The mass fraction of acrylic -1,3- sultones is 1.2%；Organic solvent in electrolyte is ethylene carbonate (EC), carbonic acid two
The mixture of methyl esters (DMC) and methyl ethyl carbonate (EMC), the wherein mass ratio of EC, DMC and EMC are 1：1：1；Lithium ion
The electrolyte of battery is respectively the LiPF of 1M6, it is denoted as electrolyte 2.
Embodiment three：
A kind of lithium ion battery high-voltage electrolyte and lithium ion battery, electrolyte is including hydrogen atom on a kind of methyl by part
Substituted methyl benzothiophene additive, structural formula are：
For high voltage additive when in for lithium-ion battery electrolytes, shared mass percent is 0.7% in the electrolytic solution,
The mass fraction of acrylic -1,3- sultones is 1.3%；Organic solvent in electrolyte is ethylene carbonate (EC), carbonic acid two
The mixture of methyl esters (DMC) and methyl ethyl carbonate (EMC), the wherein mass ratio of EC, DMC and EMC are 1：1：1；Lithium ion
The electrolyte of battery is respectively the LiPF of 1M6, it is denoted as electrolyte 3.
Example IV：
A kind of lithium ion battery high-voltage electrolyte and lithium ion battery, electrolyte are added including a kind of ethane benzothiophene
Agent, structural formula are：
For high voltage additive when in for lithium-ion battery electrolytes, shared mass percent is 0.7% in the electrolytic solution,
The mass fraction of acrylic -1,3- sultones is 1.3%；Organic solvent in electrolyte is ethylene carbonate (EC), carbonic acid two
The mixture of methyl esters (DMC) and methyl ethyl carbonate (EMC), the wherein mass ratio of EC, DMC and EMC are 1：1：1；Lithium ion
The electrolyte of battery is respectively the LiPF of 1M6, it is denoted as electrolyte 4.
Comparative example one：
The electrolyte that additive is not added in embodiment one is denoted as electrolyte 5.
Note：Electrolyte uses the mass ratio of solvent EC, DMC and EMC electrolyte lithium salts is dense for 1: 1: 1 in table
It spends for 1.0 M.
Table 1
| Electrolyte | Additive A（wt. %） | Additive B（wt. %） | Cycle-index | Capacity retention ratio（%） |
| 1 | 0.8 | 1.2 | 500 | 83 |
| 2 | 0.8 | 1.2 | 500 | 84 |
| 3 | 0.7 | 1.3 | 500 | 79 |
| 4 | 0.7 | 1.3 | 500 | 81 |
| 5 | 0 | 0 | 500 | 72 |
As can be seen that electrolyte 1 adds the addition of the dibenzothiophenes containing borate for accounting for that mass percent is 0.8% in table 1
Agent and account for mass percent be 1.2% propenyl-1,3-sulfonic acid lactone, cycle 500 times after capacity retention ratio be 83%, electrolyte
2 additions account for the dibenzothiophenes additive of the phosphate of mass percent 0.8% and account for acrylic -1 of mass percent 1.2%,
3- sultones, capacity retention ratio is 84 after recycling 500 times；It is former that electrolyte 3 adds hydrogen on the methyl for accounting for mass percent 0.7%
Son is by partially substituted methyl benzothiophene additive and the propenyl-1,3-sulfonic acid lactone for accounting for mass percent 1.3%, cycle
Capacity retention ratio is 79 after 500 times；Electrolyte 4 adds the ethane benzothiophene additive for accounting for mass percent 0.7% and accounts for matter
The propenyl-1,3-sulfonic acid lactone of percentage 1.3% is measured, capacity retention ratio is 81, the wherein hexichol of borate after recycling 500 times
Bithiophene additive, the dibenzothiophenes additive of phosphate, hydrogen atom is added by partially substituted methyl benzothiophene on methyl
Add in agent and ethane benzothiophene additive and contain element sulphur；When being not added with additive, capacity retention ratio after recycling 500 times
It is 72, the above-mentioned capacity retention ratio added with additive and without adding during additive of comparison, capacity when obtaining addition additive
Conservation rate is greatly improved.
In summary：This lithium ion battery high-voltage electrolyte and lithium ion battery use the benzo thiophene containing element sulphur
It is steady can to form one layer of densification in positive electrode surface for the high pressure additive of fen or dibenzothiophenes class solvent as lithium-ion electrolyte
Fixed interfacial film reduces oxygenolysis of the carbonate-based solvent in electrode surface；Secondly, propenyl-1,3-sulfonic acid lactone has
Good cathode film formation performance, can effectively coat negative material, substantially improve high voltage（More than 4.5V）Under room temperature cycles
Performance.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
Understanding without departing from the principles and spirit of the present invention can carry out these embodiments a variety of variations, modification, replace
And modification, the scope of the present invention is defined by the appended.
Claims (7)
1. a kind of lithium ion battery high-voltage electrolyte, which is characterized in that including following raw material：Lithium salts, nonaqueous solvents, addition
Agent A and additive B, nonaqueous solvents are linear carbonate and the mixed solvent of cyclic carbonate, and additive A is benzothiophene or two
Benzothiophene kind solvent, additive B are propenyl-1,3-sulfonic acid lactone；
Benzothiophene structural formula is：
Dibenzothiophenes class structure in solvent formula is：
Wherein R is phosphate-based or boric acid ester group, and carbon atom number is the straight chained alkyl of 2- 8, and part hydrogen or whole hydrogen are taken by halogen
The carbon atom number in generation is the straight chained alkyl of 2-8, and carbon atom number is the linear carbonate base of 1-6；
Propenyl-1,3-sulfonic acid lactone, structural formula are：
。
A kind of 2. lithium ion battery high-voltage electrolyte according to claim 1, which is characterized in that the additive A
It is 0.5~1.5% to occupy mass ratio in the electrolytic solution, and it is 0.5~1.5% that additive B occupies mass ratio in the electrolytic solution.
3. a kind of lithium ion battery high-voltage electrolyte according to claim 1, which is characterized in that the lithium salts is six
Lithium fluophosphate, hexafluoroarsenate lithium, lithium perchlorate, LiBF4, dioxalic acid lithium borate, difluorine oxalic acid boracic acid lithium, pyrovinic acid
Any one in lithium, trifluoromethyl sulfonic acid lithium, bis trifluoromethyl sulfimide lithium or several mixture therein, wherein
Lithium salt is 1.0M.
A kind of 4. lithium ion battery high-voltage electrolyte according to claim 1, which is characterized in that the nonaqueous solvents
It is organic solvent under nitrogen or inert gas shielding, is made by vacuum distillation purification and molecular sieve dehydration, it is non-aqueous organic molten
Agent is ethylene carbonate, propene carbonate, butylene, gamma-butyrolacton, dipropyl carbonate, dimethyl sulfite, carbonic acid are sub-
Vinyl acetate, methyl propyl carbonate, ethyl acetate, methyl acetate, methyl butyrate, ethyl butyrate, methyl propionate, ethyl propionate, carbonic acid
The mixture of any one in dimethyl ester, diethyl carbonate, methyl ethyl carbonate, propyl acetate or several compositions.
5. a kind of lithium ion battery, which is characterized in that the lithium ion battery uses the high-pressure electrolysis containing electrolysis additive
Liquid is as electrolyte.
6. a kind of lithium ion battery according to claim 5, which is characterized in that the anode material for lithium-ion batteries is three
First material（LixNiyCozMnaMeO2, wherein, 0.95≤x≤1.1,0≤y≤0.9,0≤z≤0.5,0≤d≤0.5；0.001≤
At least one of e≤0.1, Me Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V elements）, cobalt acid lithium（LiCoO2）, lithium nickelate
（LiNiO2）, layered lithium manganate（LiMnO2）, spinelle shape LiMn2O4（LiMn2O4）, LiFePO4（LiFePO4）, rich lithium manganese
xLi2MnO3•（1-x）LiMO2It is one or more in (M=Ni, Co, Mn).
7. a kind of lithium ion battery according to claim 5, which is characterized in that the lithium ion battery negative material is carbon
Material, Si, SiOx, Si alloy, Si carbon composites, Sn, SnOx, Sn alloys, at least one of Sn carbon composites；Its
In, 0 ＜ x<2.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109192984A (en) * | 2018-08-24 | 2019-01-11 | 宁波科力安新能源技术有限公司 | A kind of lithium battery |
| CN110459804A (en) * | 2019-07-18 | 2019-11-15 | 河南平煤国能锂电有限公司 | A kind of lithium-ion battery electrolytes |
| CN111490292A (en) * | 2020-04-18 | 2020-08-04 | 东莞东阳光科研发有限公司 | Non-aqueous electrolyte functional additive, non-aqueous electrolyte and lithium ion battery |
| CN112635827A (en) * | 2020-12-04 | 2021-04-09 | 上海应用技术大学 | Electrolyte additive, electrolyte containing additive and lithium ion battery |
| CN113193231A (en) * | 2021-05-06 | 2021-07-30 | 江西理工大学 | High-voltage electrolyte for lithium ion battery and preparation method thereof |
| CN113394461A (en) * | 2021-07-26 | 2021-09-14 | 天目湖先进储能技术研究院有限公司 | High-voltage additive for lithium battery electrolyte, electrolyte and lithium battery |
| CN113937358A (en) * | 2021-09-29 | 2022-01-14 | 广东工业大学 | Lithium ion battery electrolyte additive, preparation method thereof and lithium battery electrolyte |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109192984A (en) * | 2018-08-24 | 2019-01-11 | 宁波科力安新能源技术有限公司 | A kind of lithium battery |
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| CN111490292A (en) * | 2020-04-18 | 2020-08-04 | 东莞东阳光科研发有限公司 | Non-aqueous electrolyte functional additive, non-aqueous electrolyte and lithium ion battery |
| CN112635827A (en) * | 2020-12-04 | 2021-04-09 | 上海应用技术大学 | Electrolyte additive, electrolyte containing additive and lithium ion battery |
| CN113193231A (en) * | 2021-05-06 | 2021-07-30 | 江西理工大学 | High-voltage electrolyte for lithium ion battery and preparation method thereof |
| CN113193231B (en) * | 2021-05-06 | 2022-07-05 | 江西理工大学 | High-voltage electrolyte for lithium ion battery and preparation method thereof |
| CN113394461A (en) * | 2021-07-26 | 2021-09-14 | 天目湖先进储能技术研究院有限公司 | High-voltage additive for lithium battery electrolyte, electrolyte and lithium battery |
| CN113394461B (en) * | 2021-07-26 | 2022-06-17 | 天目湖先进储能技术研究院有限公司 | High-voltage additive for lithium battery electrolyte, electrolyte and lithium battery |
| CN113937358A (en) * | 2021-09-29 | 2022-01-14 | 广东工业大学 | Lithium ion battery electrolyte additive, preparation method thereof and lithium battery electrolyte |
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Application publication date: 20180622 |