CN109786839A - A kind of lithium-ion battery electrolytes and its additive - Google Patents
A kind of lithium-ion battery electrolytes and its additive Download PDFInfo
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- CN109786839A CN109786839A CN201910235489.3A CN201910235489A CN109786839A CN 109786839 A CN109786839 A CN 109786839A CN 201910235489 A CN201910235489 A CN 201910235489A CN 109786839 A CN109786839 A CN 109786839A
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a kind of lithium-ion battery electrolytes, including solvent, lithium salts and additive, in the component of the additive comprising 2,4,6- trimethoxy boroxin and its derivative, in additive 2,4,6- trimethoxy boroxin and its derivative account for the 0.5%-5% of electrolyte quality percentage.The present invention by being added into lithium-ion battery electrolytes containing 2,4, the additive of 6- trimethoxy boroxin and its derivative, effectively reduce the internal resistance of lithium ion battery, capacity of lithium ion battery conservation rate is significantly increased, the cycle performance of lithium ion battery is improved.
Description
Technical field
The present invention relates to technical field of lithium ion, especially it is a kind of produce electrolyte that lithium ion battery uses and its
Additive.
Background technique
Since lithium ion battery has excellent energy density, longer cycle life compared to other secondary rechargeable batteries
The advantages that with higher voltage, has been widely used in portable electronic device (such as mobile phone, computer) and power-equipment (such as electricity
Electrical automobile etc.).It is enough that lithium ion battery service life is applied to electronic equipment, but is applied to electric car or power grid storage
Can aspect seem awkward, be mainly manifested in that capacity retention ratio is low and battery impedance is larger, so the circulation of lithium ion battery
Service life is still to be improved.
Lithium ion battery is mainly made of anode, cathode, electrolyte, diaphragm and five part of shell.Its positive active material
The transition metal oxide containing lithium ion is mostly used, plays the role of providing lithium ion, is the base of lithium ion battery energy density
Plinth can be divided into layer structure (such as cobalt acid lithium), spinel structure (such as LiMn2O4) and olivine structural (such as by textural classification
LiFePO4 etc.).Its negative electrode active material is based on carbon material, such as natural graphite, artificial graphite, in addition, silica-base material and
Metal or alloy class can also be used as negative electrode material, play the role of reversible storage lithium ion, when charging embeddable lithium ion, put
Deviate from lithium ion when electric.
Electrolyte is also one of important component of lithium ion battery, plays the role of transmitting ion in inside battery,
The performance of electrolyte largely influences the performance of lithium ion battery.Nonaqueous lithium ion battery electrolyte is had by carbonates
Solvent, lithium salts and additive composition.There are commonly solvents cyclic carbonate (such as ethylene carbonate, propene carbonate, carbon
Sour ethyl etc.), linear carbonate (such as dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate), cyclic annular esters (such as γ-fourth
Lactone etc.) and chain esters (such as methyl acetate).Key component of the lithium salts as electrolyte, there are commonly LiPF6、LiBF4、
LiClO4、LiN(CF3SO2)2Deng wherein being commercialized most mature lithium salts is LiPF6, the comprehensive performances such as stability and dissolubility
Better than other lithium salts.Electrolysis additive is for improving the most common means of battery performance, as VC, LiBOB add as film forming
Agent is added to improve battery high-temperature behavior, CHB, BP improvement battery safety etc..
Currently, the addition of conventional electrolysis solution additive can all cause lithium battery internal resistance to increase, with battery performance requirements
It is higher and higher, it reduces internal resistance and becomes to improve one of the effective means of battery performance.In consideration of it, for enough improvement lithium ion batteries
Cycle life, internal resistance is effectively reduced, the electrolyte and its additive for finding a kind of suitable lithium ion battery are a kind of succinct
Efficient mode.
Summary of the invention
The technical problem to be solved by the invention is to provide a kind of electrolyte for lithium ion battery and its additives, to reduce
The internal resistance of cell increases capacity of lithium ion battery conservation rate, improves the cycle life of battery.
In order to solve the above technical problems, the technical solution used in the present invention is as follows.
A kind of lithium-ion battery electrolytes, including solvent, lithium salts and additive, in the component of the additive comprising 2,4,
6- trimethoxy boroxin and its derivative, 2,4, the chemical structural formula of 6- trimethoxy boroxin and its derivative such as
Under:
In formula, n1, n2, n3 0,1,2,3.
A kind of above-mentioned lithium-ion battery electrolytes, in the additive 2,4,6- trimethoxy boroxin and its derivative
Object accounts for the 0.5%-5% of electrolyte quality percentage.
A kind of above-mentioned lithium-ion battery electrolytes, the solvent be ethylene carbonate, propene carbonate, methyl ethyl carbonate,
One of dimethyl carbonate, diethyl carbonate, gamma-butyrolacton, methyl formate, Ethyl formate, propyl acetate, tetrahydrofuran or
Several combinations.
A kind of lithium-ion battery electrolytes additive includes 2,4,6- trimethoxy basic ring boron in the component of the additive
Oxygen alkane and its derivative, 2,4, the chemical structural formula of 6- trimethoxy boroxin and its derivative it is as follows:
In formula, n1, n2, n3 0,1,2,3.
Due to using above technical scheme, the invention technological progress is as follows.
The present invention into lithium-ion battery electrolytes by being added containing 2,4,6- trimethoxy boroxin and its derivative
The additive of object effectively reduces the internal resistance of lithium ion battery, significantly increases capacity of lithium ion battery conservation rate, improves lithium
The cycle performance of ion battery.
Specific embodiment
A kind of lithium-ion battery electrolytes, including solvent, lithium salts and additive, the main component of lithium salts are LiPF6.
Since LiPF6 is easily decomposed as the electrolyte of lithium salts, as shown in formula (1).Wherein LiF participates in forming SEI film,
PF5 continues to be decomposed into HF, and as shown in formula (2), HF is as electrolyte impurity to the stability and battery performance of electrolyte itself
Influence is very big, is mainly manifested in: catalysis lithium salts (such as LiPF6) hydrolysis, to accelerate the rotten of electrolyte；Organic Solvents are poly-
It closes, to increase electrolysis fluid viscosity, reduce electrolyte conductivity；HF impurity can also consume the lithium ion in electrolyte, and
LiF is generated, as shown in formula (3), when LiF content is more in the SEI film of negative terminal surface, will lead to internal resistance of cell increase；It is rotten
SEI film is lost, leads in cyclic process that SEI film is unstable, the effect of protection cathode is lost, eventually leads to capacity attenuation.
LiPF6——LiF+PF5 (1)
PF5+H2O——HF+X (2)
HF+Li+e-——LiF+1/2H2 (3)
If HF can be captured, the HF in electrolyte is eliminated, the cycle performance of lithium ion battery can be improved.Based on this
Principle, the present invention provide a kind of additive, include 2,4,6- trimethoxy boroxin and its derivative, additive in component
In 2,4,6- trimethoxy boroxin and its derivative account for the 0.5%-5% of electrolyte quality percentage.
2,4, the chemical structural formula of 6- trimethoxy boroxin and its derivative (TMOBX) is as follows:
In formula, n1, n2, n3 0,1,2,3.
Solvent in the present invention is ethylene carbonate, propene carbonate, methyl ethyl carbonate, dimethyl carbonate, carbonic acid diethyl
The combination of one or more of ester, gamma-butyrolacton, methyl formate, Ethyl formate, propyl acetate, tetrahydrofuran.
Below in conjunction with specific embodiment, the present invention will be described in further detail.In following embodiment and comparative example
Percentage refer to the mass percent of respective substance in the electrolytic solution.
Embodiment 1
A kind of lithium-ion battery electrolytes, including 1mol/L LiPF6, solvent and additive.
Solvent is the mixture of the EC:DMC:PC of 1:1:1.
Additive includes that total mass fraction is 2% vinylene carbonate (VC) and 0.5% TMOBX.
It handles to obtain the battery core to be injected of moisture removal by process before stirring, coating, winding etc., wherein just extremely cobalt acid lithium
(LiCoO2), cathode is graphite.Electrolyte is cast in and is wherein prepared into lithium ion battery.
Embodiment 2
A kind of lithium-ion battery electrolytes, including 1mol/L LiPF6, solvent and additive.
Solvent is the mixture of the EC:DMC:PC of 1:1:1.
Additive includes that total mass fraction is 2% vinylene carbonate (VC) and 1% TMOBX.
It handles to obtain the battery core to be injected of moisture removal by process before stirring, coating, winding etc., wherein just extremely cobalt acid lithium
(LiCoO2), cathode is graphite.Electrolyte is cast in and is wherein prepared into lithium ion battery.
Embodiment 3
A kind of lithium-ion battery electrolytes, including 1mol/L LiPF6, solvent and additive.
Solvent is the mixture of the EC:DMC:PC of 1:1:1.
Additive includes that total mass fraction is 2% vinylene carbonate (VC) and 3% TMOBX.
It handles to obtain the battery core to be injected of moisture removal by process before stirring, coating, winding etc., wherein just extremely cobalt acid lithium
(LiCoO2), cathode is graphite.Electrolyte is cast in and is wherein prepared into lithium ion battery.
Embodiment 4
A kind of lithium-ion battery electrolytes, including 1mol/L LiPF6, solvent and additive.
Solvent is the mixture of the EC:DMC:PC of 1:1:1.
Additive includes that total mass fraction is 2% vinylene carbonate (VC) and 5% TMOBX.
It handles to obtain the battery core to be injected of moisture removal by process before stirring, coating, winding etc., wherein just extremely cobalt acid lithium
(LiCoO2), cathode is graphite.Electrolyte is cast in and is wherein prepared into lithium ion battery.
Comparative example 1
A kind of lithium-ion battery electrolytes, including 1mol/L LiPF6, solvent and additive.
Solvent is the mixture of the EC:DMC:PC of 1:1:1.
Additive includes the vinylene carbonate (VC) that total mass fraction is 2%.
It handles to obtain the battery core to be injected of moisture removal by process before stirring, coating, winding etc., wherein just extremely cobalt acid lithium
(LiCoO2), cathode is graphite.Electrolyte is cast in and is wherein prepared into lithium ion battery.
Embodiment 5
A kind of lithium-ion battery electrolytes, including 1mol/L LiPF6, solvent and additive.
Solvent is the mixture of the EC:DMC:PC of 1:1:1.
Additive includes that total mass fraction is 2% vinylene carbonate (VC) and 0.5% TMOBX.
It handles to obtain the battery core to be injected of moisture removal by process before stirring, coating, winding etc., wherein just extremely ferric phosphate
Lithium (LiFePO4), cathode is graphite.Electrolyte is cast in and is wherein prepared into lithium ion battery.
Embodiment 6
A kind of lithium-ion battery electrolytes, including 1mol/L LiPF6, solvent and additive.
Solvent is the mixture of the EC:DMC:PC of 1:1:1.
Additive includes that total mass fraction is 2% vinylene carbonate (VC) and 1% TMOBX.
It handles to obtain the battery core to be injected of moisture removal by process before stirring, coating, winding etc., wherein just extremely ferric phosphate
Lithium (LiFePO4), cathode is graphite.Electrolyte is cast in and is wherein prepared into lithium ion battery.
Embodiment 7
A kind of lithium-ion battery electrolytes, including 1mol/L LiPF6, solvent and additive.
Solvent is the mixture of the EC:DMC:PC of 1:1:1.
Additive includes that total mass fraction is 2% vinylene carbonate (VC) and 3% TMOBX.
It handles to obtain the battery core to be injected of moisture removal by process before stirring, coating, winding etc., wherein just extremely ferric phosphate
Lithium (LiFePO4), cathode is graphite.Electrolyte is cast in and is wherein prepared into lithium ion battery.
Embodiment 8
A kind of lithium-ion battery electrolytes, including 1mol/L LiPF6, solvent and additive.
Solvent is the mixture of the EC:DMC:PC of 1:1:1.
Additive includes that total mass fraction is 2% vinylene carbonate (VC) and 5% TMOBX.
It handles to obtain the battery core to be injected of moisture removal by process before stirring, coating, winding etc., wherein just extremely ferric phosphate
Lithium (LiFePO4), cathode is graphite.Electrolyte is cast in and is wherein prepared into lithium ion battery.
Comparative example 2
A kind of lithium-ion battery electrolytes, including 1mol/L LiPF6, solvent and additive.
Solvent is the mixture of the EC:DMC:PC of 1:1:1.
Additive includes the vinylene carbonate (VC) that total mass fraction is 2%.
It handles to obtain the battery core to be injected of moisture removal by process before stirring, coating, winding etc., wherein just extremely ferric phosphate
Lithium (LiFePO4), cathode is graphite.Electrolyte is cast in and is wherein prepared into lithium ion battery.
Embodiment 9
A kind of lithium-ion battery electrolytes, including 1mol/L LiPF6, solvent and additive.
Solvent is the mixture of the EC:DMC:PC of 1:1:1.
Additive includes that total mass fraction is 2% vinylene carbonate (VC) and 0.5% TMOBX.
It handles to obtain the battery core to be injected of moisture removal by process before stirring, coating, winding etc., wherein just extremely ternary material
Expect (NCM523), cathode is graphite.Electrolyte is cast in and is wherein prepared into lithium ion battery.
Embodiment 10
A kind of lithium-ion battery electrolytes, including 1mol/L LiPF6, solvent and additive.
Solvent is the mixture of the EC:DMC:PC of 1:1:1.
Additive includes that total mass fraction is 2% vinylene carbonate (VC) and 1% TMOBX.
It handles to obtain the battery core to be injected of moisture removal by process before stirring, coating, winding etc., wherein just extremely ternary material
Expect (NCM523), cathode is graphite.Electrolyte is cast in and is wherein prepared into lithium ion battery.
Embodiment 11
A kind of lithium-ion battery electrolytes, including 1mol/L LiPF6, solvent and additive.
Solvent is the mixture of the EC:DMC:PC of 1:1:1.
Additive includes that total mass fraction is 2% vinylene carbonate (VC) and 3% TMOBX.
It handles to obtain the battery core to be injected of moisture removal by process before stirring, coating, winding etc., wherein just extremely ternary material
Expect (NCM523), cathode is graphite.Electrolyte is cast in and is wherein prepared into lithium ion battery.
Embodiment 12
A kind of lithium-ion battery electrolytes, including 1mol/L LiPF6, solvent and additive.
Solvent is the mixture of the EC:DMC:PC of 1:1:1.
Additive includes that total mass fraction is 2% vinylene carbonate (VC) and 5% TMOBX.
It handles to obtain the battery core to be injected of moisture removal by process before stirring, coating, winding etc., wherein just extremely ternary material
Expect (NCM523), cathode is graphite.Electrolyte is cast in and is wherein prepared into lithium ion battery.
Comparative example 3
A kind of lithium-ion battery electrolytes, including 1mol/L LiPF6, solvent and additive.
Solvent is the mixture of the EC:DMC:PC of 1:1:1.
Additive includes the vinylene carbonate (VC) that total mass fraction is 2%.
It handles to obtain the battery core to be injected of moisture removal by process before stirring, coating, winding etc., wherein just extremely ternary material
Expect (NCM523), cathode is graphite.Electrolyte is cast in and is wherein prepared into lithium ion battery.
Experiment 1
The test of capacity retention ratio, test result such as table are carried out to lithium ion battery prepared by above-described embodiment and comparative example
Shown in 1.
Table 1
From table 1 it follows that being substantially better than pair using the capacity retention ratio of lithium ion battery cell prepared by the present invention
The battery of ratio preparation, significantly improves the cycle performance of lithium ion battery.
Experiment 2
The test of battery core internal resistance, test result such as table 2 are carried out to lithium ion battery prepared by above-described embodiment and comparative example
It is shown.
Table 2
| Number | Internal resistance |
| Comparative example 1 | 32.2 |
| Embodiment 1 | 27.4 |
| Embodiment 2 | 27.6 |
| Embodiment 3 | 27.4 |
| Embodiment 4 | 26.9 |
| Comparative example 2 | 56.3 |
| Embodiment 5 | 49.9 |
| Embodiment 6 | 49.7 |
| Embodiment 7 | 49.6 |
| Embodiment 8 | 49.4 |
| Comparative example 3 | 36.8 |
| Embodiment 9 | 30.8 |
| Embodiment 10 | 29.9 |
| Embodiment 11 | 29.4 |
| Embodiment 12 | 29.3 |
2 the data obtained of table is the internal resistance measured after being melted under 25.As can be seen from Table 2, using lithium prepared by the present invention
The internal resistance of ion battery battery core is significantly lower than the internal resistance of cell of contrast groups, greatly reduces the internal resistance of lithium ion battery.
Claims (4)
1. a kind of lithium-ion battery electrolytes, including solvent, lithium salts and additive, which is characterized in that the component of the additive
In comprising 2,4,6- trimethoxy boroxin and its derivative, 2,4, the chemistry of 6- trimethoxy boroxin and its derivative
Structural formula is as follows:
In formula, n1, n2, n3 0,1,2,3.
2. a kind of lithium-ion battery electrolytes according to claim 1, which is characterized in that in the additive 2,4,6-
Trimethoxy boroxin and its derivative account for the 0.5%-5% of electrolyte quality percentage.
3. a kind of lithium-ion battery electrolytes according to claim 1, which is characterized in that the solvent is ethylene carbonate
Ester, propene carbonate, methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, gamma-butyrolacton, methyl formate, Ethyl formate, second
The combination of one or more of propyl propionate, tetrahydrofuran.
4. a kind of lithium-ion battery electrolytes additive, which is characterized in that include 2,4,6- tri- in the component of the additive
Methoxy boroxines and its derivative, 2,4, the chemical structural formula of 6- trimethoxy boroxin and its derivative it is as follows:
In formula, n1, n2, n3 0,1,2,3.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111883830A (en) * | 2020-07-24 | 2020-11-03 | 香河昆仑化学制品有限公司 | Lithium ion battery electrolyte, battery cathode and electrochemical energy storage device |
| CN112803069A (en) * | 2020-12-30 | 2021-05-14 | 珠海冠宇电池股份有限公司 | Non-aqueous electrolyte for lithium ion battery and lithium ion battery comprising same |
| CN113851712A (en) * | 2021-08-26 | 2021-12-28 | 合肥国轩高科动力能源有限公司 | High-voltage lithium ion battery electrolyte and lithium ion battery |
| CN114430065A (en) * | 2020-10-13 | 2022-05-03 | 中国石油化工股份有限公司 | Lithium ion battery electrolyte and lithium ion battery using same |
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| US5891592A (en) * | 1997-01-31 | 1999-04-06 | Nec Moli Energy (Canada) Limited | Additives for improving cycle life of non-aqueous rechargeable lithium batteries |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111883830A (en) * | 2020-07-24 | 2020-11-03 | 香河昆仑化学制品有限公司 | Lithium ion battery electrolyte, battery cathode and electrochemical energy storage device |
| CN111883830B (en) * | 2020-07-24 | 2023-05-12 | 香河昆仑新能源材料股份有限公司 | Lithium ion battery electrolyte, battery cathode and electrochemical energy storage device |
| CN114430065A (en) * | 2020-10-13 | 2022-05-03 | 中国石油化工股份有限公司 | Lithium ion battery electrolyte and lithium ion battery using same |
| CN112803069A (en) * | 2020-12-30 | 2021-05-14 | 珠海冠宇电池股份有限公司 | Non-aqueous electrolyte for lithium ion battery and lithium ion battery comprising same |
| CN113851712A (en) * | 2021-08-26 | 2021-12-28 | 合肥国轩高科动力能源有限公司 | High-voltage lithium ion battery electrolyte and lithium ion battery |
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Application publication date: 20190521 |