CN101853963A - Over-charge prevention lithium ion battery electrolyte and lithium ion battery prepared by using same - Google Patents
Over-charge prevention lithium ion battery electrolyte and lithium ion battery prepared by using same Download PDFInfo
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- CN101853963A CN101853963A CN200910029650A CN200910029650A CN101853963A CN 101853963 A CN101853963 A CN 101853963A CN 200910029650 A CN200910029650 A CN 200910029650A CN 200910029650 A CN200910029650 A CN 200910029650A CN 101853963 A CN101853963 A CN 101853963A
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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 an over-charge prevention lithium ion battery electrolyte having an over-charge prevention function and small adverse impacts on a lithium ion battery and a lithium ion battery prepared by using the electrolyte. The over-charge prevention lithium ion battery electrolyte contains an additive shown as a structural formula disclosed in the specification, and the weight ratio of the additive in the over-charge prevention lithium ion battery electrolyte is 0.01-53.6 percent. In the structural formula, X, Y, Z and A are respectively selected from halogens or hydroxyl groups, or alkyl groups, alkoxyl groups, alkyl halide groups, sulfonic acid groups, aromatic groups, carboxyl groups or aether-oxyl groups with a carbon atom number between 0 and 12, and D is selected from elements of C, S, O, N, P, B or Si. The lithium ion battery electrolyte and the lithium ion battery have better over-charge resistance and higher charge and discharge cycle efficiency and can meet the requirement on application.
Description
Technical field
The invention belongs to technical field of electrochemistry, relate to a kind of anti-overcharge lithium-ion battery electrolytes and lithium ion battery prepared therefrom.
Background technology
Along with the minimizing day by day of earth energy resource and the continuous increase of people's environmental consciousness, force the continuous utilance that improves resource of people, the various advantages of secondary chargeable battery, especially lithium ion battery make it become one of strong energy reserves instrument.Characteristics such as energy density height, power density are big because lithium ion battery has, good cycle, memory-less effect, environmental protection, lithium ion battery is widely used in various electronic products such as mobile communication equipment such as mobile phone, mobile camera, notebook computer, also is one of strong candidate of following hybrid electric vehicle dynamical system simultaneously.The organic solvent that uses in the lithium ion battery has usually: diethyl carbonate, dimethyl carbonate, Methylethyl carbonic ester, vinylene carbonate, butylene, ethylene carbonate, propene carbonate, gamma-butyrolacton, diformazan malonate etc. and their two or more mixtures, the electrolyte lithium salt of use has usually: lithium hexafluoro phosphate, lithium perchlorate, LiBF4, dioxalic acid close lithium borate, trifluoromethyl sulfonic acid lithium, lithium trifluoromethanesulp,onylimide etc. and their two kinds or more of mixtures.But, the safety problem that lithium ion battery exists, becoming large-scale lithium ion battery can't business-like maximum one of hinder.Danger such as a lot of explosions, on fire, blast are all because overcharging of lithium ion battery causes that these accidents all out of controlly cause violent exothermic reaction to cause because inside battery is voltage-controlled fundamentally.In order to solve these safety problems, traditional solution is gas pressure detection unit, explosion relief valve to be installed in the safety cap of battery or to prevent overcharging of battery by adding special-purpose overcharge protection circuit.But these methods have increased battery cost and complexity, and safe effect is also undesirable.Realize that by additive the inside battery over-charge protective just solves these problems.The kind of additive is confined to derivative and the ferrocene and the derivative thereof of biphenyl, cyclohexylbenzene, halobenzene (bromobenzene, chlorobenzene), furans substantially, because after adding such additive, can have influence on the normal battery charge and discharge ability, influence its cycle performance, configuration of surface to battery material has certain negative effect simultaneously, battery has produced a large amount of gas in charging and discharging process, thereby makes cell expansion cause the decreased performance of lithium ion battery.
Summary of the invention
First technical problem to be solved by this invention is: a kind of have anti-overcharge function and the anti-overcharge lithium-ion battery electrolytes little to the lithium ion battery negative effect are provided; Second technical problem that the present invention will solve is: a kind of lithium ion battery by above-mentioned electrolyte preparation will be provided.
For solving above-mentioned first technical problem, the technical solution used in the present invention is: contain the additive that following structural formula is represented in the described anti-overcharge lithium-ion battery electrolytes, and this additive shared part by weight in lithium-ion battery electrolytes is: 0.01%-53.6%.
In the said structure formula, X, Y, Z, A are selected from halogen or hydroxyl or carbon atom number alkyl, alkoxyl, haloalkyl, sulfonic group, aromatic group, carboxyl or the ether oxygen base between 0～12 respectively; D is selected from C, S, O, N, P, B or Si element.
Contain the solvent ethylene carbonate in the above-mentioned lithium-ion battery electrolytes, and ethylene carbonate accounts for the 0.01%-98.5% of lithium-ion battery electrolytes total weight.
For solving the further technical scheme that above-mentioned first technical problem the present invention adopts be: described additive is at least a in the following material: the N-phenylimidazole, 2-perfluorophenyl imidazoles, 4-(3,4-two trifluoromethylbenzenes) imidazoles, 4-(4-methoxyl group-3-tert-butyl benzene) imidazoles, 4-(2,5-di-t-butyl-4-methoxyphenyl) imidazoles, the 4-phenylimidazole, the perfluor imidazoles, 2-perfluorophenyl pyrroles, the perfluor pyrroles, the 3-tert-butyl group-4-(2,5-dipropyl-4-(trifluoromethyl) phenyl)-1H-pyrroles, the 3-tert-butyl group-4-(4-tert-butyl group-2,5-two trifluoromethyls)-1-nitrogen 3-silicon pentamethylene, 2-(2,3,4,5-tetrafluoro phenyl)-4-(2,4,5-three fluoro-3, the 6-dimethoxy benzene)-1-nitrogen-3-boron-pentamethylene.
For solving above-mentioned second technical problem, the technical solution used in the present invention is to include any lithium-ion battery electrolytes recited above in the described lithium ion battery.
The invention has the beneficial effects as follows: in lithium-ion battery electrolytes, added described additive, can improve the overcharging resisting performance of electrolyte effectively, improved the cycle efficieny that discharges and recharges; Lithium ion battery by the lithium-ion battery electrolytes preparation that contains this additive has possessed these advantages equally, and is very little to the performance impact of normal lithium ion battery, can satisfy the needs of application.
Description of drawings
Fig. 1 is the voltage-time curve figure that the lithium ion battery of embodiment 1 gained overcharged under the multiplying power condition of 0.5C 20 hours;
Fig. 2 is the voltage-time curve figure that the lithium ion battery of Comparative Examples gained overcharged under the multiplying power condition of 0.5C 20 hours.
Embodiment
The present invention is described in further detail below in conjunction with specific embodiment.But the present invention is not limited in these embodiment.
Comparative Examples
With ethylene carbonate, dimethyl carbonate, Methylethyl carbonic ester mixed with 1: 1: 1, make its electrolyte that is formulated as 1mol/L to wherein adding a certain amount of lithium hexafluoro phosphate, make its dissolving prepare the electrolyte of this comparative example.
Anodal preparation: with a certain amount of LiCoO
2Be dispersed in by Kynoar (be called for short PVDF) with acetylene black and be dissolved in the solvent in the N-N-methyl-2-2-pyrrolidone N-(being called for short NMP), obtain uniform slurry, be coated on the aluminium foil and in 120 ℃ of vacuum, dry 12h, obtain anode pole piece after the calendering.
The preparation of negative pole: a certain amount of carbonaceous mesophase spherules (be called for short CMS) and acetylene black is dispersed in by PVDF is dissolved in the solvent among the NMP, obtain uniform slurry, be coated on the Copper Foil and in 120 ℃ of vacuum, dry 12h, obtain cathode pole piece after the calendering.
The preparation of lithium ion battery: above-mentioned positive pole and cathode pole piece and celgand 2400 barrier films are assembled into button cell, simultaneously the resulting electrolyte in front are added in this battery, sealing makes lithium ion battery.
The relevant test result of overcharging is seen Fig. 2.As can be seen from this figure, after battery overcharged experiment, voltage was raised to 5.45V soon, and voltage becomes 0 then, and entire cell lost efficacy.
With ethylene carbonate, dimethyl carbonate, Methylethyl carbonic ester mixed with 1: 1: 1, to wherein adding lithium hexafluoro phosphate, be formulated as the electrolyte of 1mol/L, to wherein adding the 4-phenylimidazole, prepare electrolyte of the present invention then as additive, dissolving.Weight with electrolyte is benchmark, and the composition of this additive is:
4-phenylimidazole 1wt.%.
Anodal preparation: with a certain amount of LiCoO
2Be dispersed in by PVDF with acetylene black and be dissolved in the solvent among the NMP, obtain uniform slurry, be coated on the aluminium foil and in 120 ℃ of vacuum, dry 12h, obtain anode pole piece after the calendering.
The preparation of negative pole: a certain amount of CMS and acetylene black is dispersed in by PVDF is dissolved in the solvent among the NMP, obtain uniform slurry, be coated on the Copper Foil and in 120 ℃ of vacuum, dry 12h, obtain cathode pole piece after the calendering.
The preparation of lithium ion battery: above-mentioned positive pole and cathode pole piece and celgand 2400 barrier films are assembled into button cell, simultaneously the resulting electrolyte in front are added in this battery, sealing makes lithium ion battery.
The relevant test result of overcharging is seen accompanying drawing 1.As can be seen from this figure, after battery overcharged 20 hours, voltage maintained 5.26V, and when normally discharging and recharging then, entire cell also shows good invertibity.
With ethylene carbonate, dimethyl carbonate, Methylethyl carbonic ester mixed with 3: 1: 3, close lithium borate to wherein adding dioxalic acid, be formulated as the electrolyte of 0.8mol/L,, make its dissolving prepare electrolyte of the present invention then to wherein adding additive perfluorophenyl pyrroles.Weight with electrolyte is benchmark, and the composition of this additive is:
Perfluorophenyl pyrroles 3wt.%.
Prepare lithium ion battery according to the electrolyte that the same procedure of embodiment 1 adopts present embodiment to obtain.Adopt the method identical with embodiment 1, lithium ion battery was overcharged 30 hours, when normally discharging and recharging then, entire cell also shows good invertibity.
With ethylene carbonate, diethyl carbonate, Methylethyl carbonic ester mixed with 4: 2: 4, to wherein adding lithium trifluoromethanesulp,onylimide, be formulated as the electrolyte of 1mol/L, to wherein adding additive N-phenylimidazole, make its dissolving prepare electrolyte of the present invention then.Weight with electrolyte is benchmark, and the composition of this additive is:
N-phenylimidazole 5wt.%.
Prepare lithium ion battery according to the electrolyte that the same procedure of embodiment 1 adopts present embodiment to obtain.Adopt the method identical with embodiment 1, lithium ion battery was overcharged 10 hours, when normally discharging and recharging then, entire cell also shows good invertibity.
Embodiment 4
With ethylene carbonate, dimethyl carbonate, Methylethyl carbonic ester mixed with 1: 1: 1, to wherein adding a certain amount of lithium hexafluoro phosphate, be formulated as the electrolyte of 1mol/L, then to wherein adding additive 2-(2,3,4,5-tetrafluoro phenyl)-and 4-(2,4,5-three fluoro-3, the 6-dimethoxy benzene)-and 1-nitrogen-3-boron-pentamethylene, make its dissolving prepare electrolyte of the present invention.Weight with electrolyte is benchmark, and the composition of this additive is:
2-(2,3,4,5-tetrafluoro phenyl)-4-(2,4,5-three fluoro-3,6-dimethoxy benzene)-1-nitrogen-3-boron-pentamethylene 1wt.%.
Prepare lithium ion battery according to the electrolyte that the same procedure of embodiment 1 adopts present embodiment to obtain.Adopt the method identical with embodiment 1, lithium ion battery was overcharged 15 hours, when normally discharging and recharging then, entire cell also shows good invertibity.
With ethylene carbonate, dimethyl carbonate, Methylethyl carbonic ester mixed with 1: 1: 1, to wherein adding lithium hexafluoro phosphate, be formulated as the electrolyte of 1mol/L, then to wherein adding 2-(2,3,4,5-tetrafluoro phenyl)-and 4-(2,4,5-three fluoro-3, the 6-dimethoxy benzene)-mixture of 1-nitrogen-3-boron-pentamethylene and N-phenylimidazole makes its dissolving prepare electrolyte of the present invention as additive.Weight with electrolyte is benchmark, and the composition of this additive is:
2-(2,3,4,5-tetrafluoro phenyl)-4-(2,4,5-three fluoro-3,6-dimethoxy benzene)-1-nitrogen-3-boron-pentamethylene 1.5wt.%, N-phenylimidazole 1.5wt.%.
Prepare lithium ion battery according to the electrolyte that the same procedure of embodiment 1 adopts present embodiment to obtain.Adopt the method identical with embodiment 1, lithium ion battery was overcharged 40 hours, when normally discharging and recharging then, entire cell also shows good invertibity.
With ethylene carbonate, dimethyl carbonate, Methylethyl carbonic ester mixed with 1: 1: 1, to wherein adding lithium hexafluoro phosphate, be formulated as the electrolyte of 1mol/L, then to wherein adding 2-(2,3,4,5-tetrafluoro phenyl)-and 4-(2,4,5-three fluoro-3, the 6-dimethoxy benzene)-mixture of 1-nitrogen-3-boron-pentamethylene and 4-phenylimidazole prepares electrolyte of the present invention as additive, dissolving.Weight with electrolyte is benchmark, and the composition of this additive is:
2-(2,3,4,5-tetrafluoro phenyl)-4-(2,4,5-three fluoro-3,6-dimethoxy benzene)-1-nitrogen-3-boron-pentamethylene 3wt.%, 4-phenylimidazole 2wt.%.
Prepare lithium ion battery according to the electrolyte that the same procedure of embodiment 1 adopts present embodiment to obtain.Adopt the method identical with embodiment 1, lithium ion battery was overcharged 50 hours, when normally discharging and recharging then, entire cell also shows good invertibity.
Claims (4)
1. anti-overcharge lithium-ion battery electrolytes is characterized in that: contain the additive that following structural formula is represented in the described lithium-ion battery electrolytes, and this additive shared part by weight in lithium-ion battery electrolytes is: 0.01%-53.6%.
In the said structure formula, X, Y, Z, A are selected from halogen or hydroxyl or carbon atom number alkyl, alkoxyl, haloalkyl, sulfonic group, aromatic group, carboxyl or the ether oxygen base between 0～12 respectively; D is selected from C, S, O, N, P, B or Si element.
2. anti-overcharge lithium-ion battery electrolytes according to claim 1 is characterized in that: contain the solvent ethylene carbonate in the described lithium-ion battery electrolytes, and ethylene carbonate accounts for the 0.01%-98.5% of lithium-ion battery electrolytes total weight.
3. anti-overcharge lithium-ion battery electrolytes according to claim 1 and 2, it is characterized in that: described additive is at least a in the following material: the N-phenylimidazole, 2-perfluorophenyl imidazoles, 4-(3,4-two trifluoromethylbenzenes) imidazoles, 4-(4-methoxyl group-3-tert-butyl benzene) imidazoles, 4-(2,5-di-t-butyl-4-methoxyphenyl) imidazoles, the 4-phenylimidazole, the perfluor imidazoles, 2-perfluorophenyl pyrroles, the perfluor pyrroles, the 3-tert-butyl group-4-(2,5-dipropyl-4-(trifluoromethyl) phenyl)-1H-pyrroles, the 3-tert-butyl group-4-(4-tert-butyl group-2,5-two trifluoromethyls)-1-nitrogen 3-silicon pentamethylene, 2-(2,3,4,5-tetrafluoro phenyl)-4-(2,4,5-three fluoro-3, the 6-dimethoxy benzene)-1-nitrogen-3-boron-pentamethylene.
4. lithium ion battery is characterized in that including the described lithium-ion battery electrolytes of arbitrary claim in the claim 1 to 3.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910029650A CN101853963A (en) | 2009-03-30 | 2009-03-30 | Over-charge prevention lithium ion battery electrolyte and lithium ion battery prepared by using same |
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| CN200910029650A CN101853963A (en) | 2009-03-30 | 2009-03-30 | Over-charge prevention lithium ion battery electrolyte and lithium ion battery prepared by using same |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9221756B2 (en) | 2011-12-05 | 2015-12-29 | University Of Leicester | Pyrrole derivatives |
| CN107240716A (en) * | 2016-03-28 | 2017-10-10 | 比亚迪股份有限公司 | A kind of electrolyte, positive pole and preparation method thereof and a kind of lithium ion battery |
| CN114600295A (en) * | 2020-06-15 | 2022-06-07 | 株式会社Lg新能源 | Electrolyte solution additive for lithium secondary battery, non-aqueous electrolyte solution for lithium secondary battery comprising same, and lithium secondary battery |
-
2009
- 2009-03-30 CN CN200910029650A patent/CN101853963A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9221756B2 (en) | 2011-12-05 | 2015-12-29 | University Of Leicester | Pyrrole derivatives |
| CN107240716A (en) * | 2016-03-28 | 2017-10-10 | 比亚迪股份有限公司 | A kind of electrolyte, positive pole and preparation method thereof and a kind of lithium ion battery |
| CN107240716B (en) * | 2016-03-28 | 2019-12-20 | 比亚迪股份有限公司 | Electrolyte, positive electrode and preparation method thereof, and lithium ion battery |
| CN114600295A (en) * | 2020-06-15 | 2022-06-07 | 株式会社Lg新能源 | Electrolyte solution additive for lithium secondary battery, non-aqueous electrolyte solution for lithium secondary battery comprising same, and lithium secondary battery |
| CN114600295B (en) * | 2020-06-15 | 2024-03-01 | 株式会社Lg新能源 | Electrolyte solution additive for lithium secondary battery, nonaqueous electrolyte solution for lithium secondary battery comprising same, and lithium secondary battery |
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Application publication date: 20101006 |