CN102306835B - High voltage resistant and high temperature resistant safety type electrolyte for lithium ion battery adopting manganese material as anode, and use thereof - Google Patents
High voltage resistant and high temperature resistant safety type electrolyte for lithium ion battery adopting manganese material as anode, and use thereof Download PDFInfo
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Abstract
The invention relates to high voltage resistant and high temperature resistant safety type electrolyte for a lithium ion battery adopting a manganese material as an anode, and a use thereof, specifically to high voltage resistant and high temperature resistant safety type electrolyte for a lithium ion battery adopting a manganese material as an anode. The electrolyte comprises a non-aqueous organic solvent, a lithium salt, a film forming additive and a stabilizing additive. The electrolyte further comprises: a high voltage resistant and high temperature resistant additive, wherein the high voltage resistant and high temperature resistant additive comprises one selected from Li2B12F12-XHX ( the X is an integer more than or equal to zero and less than or equal to 11), Li2B12Cl12-XHX (the X is an integer more than or equal to zero and less than or equal to 11), or a mixture formed through mixing the Li2B12F12-XHX and the Li2B12Cl12-XHX according to any ratio, the use amount of the high voltage resistant and high temperature resistant additive is 1-15% of the total mass of the electrolyte; a high voltage resistant overcharge-proof additive, wherein the high voltage resistant overcharge-proof additive comprises fluorinated anisole, fluorinated diphenyl sulfide or a mixture formed through mixing the fluorinated anisole and the fluorinated diphenyl sulfide according to any ratio, the use amount of the high voltage resistant overcharge-proof additive is 1-10% of the total mass of the electrolyte. With the present invention, the lithium ion battery adopting the manganese material has performances of high temperature resistance, safety and high voltage resistance, the charging voltage of the manganese material can be increased to more than 4.5 V.
Description
Technical field
The present invention relates to a kind of lithium-ion battery electrolytes, particularly relate to the high voltage withstanding high temperature safe type electrolyte of lithium ion battery that a kind of manganese based material is positive pole.
Background technology
Lithium ion battery is due to a series of advantages such as its operating voltage is high, energy density is high, power density is large, self discharge is little, memory-less effect, excellent charge-discharge performance, long circulation life, environmental friendliness, be widely used in the portable type electronic products such as mobile communication, digital camera, MP3 at present, and progressively in national defence, military aspect application.In recent years, along with the whole world is to the attention of environmental problem, new-energy automobile fast development, lithium ion battery is considered to the most potential current Vehicular dynamic battery.
Along with market and social development, lithium ion battery is had higher requirement, require in price more cheap on the one hand, require higher energy density on the other hand.In price, as everyone knows, apply or formed by the transition metal oxide of the positive electrode applied primarily of lithium, wherein, transition metal is the most cheap with manganese and iron, and ferrous iron is easily oxidized causes ferrous material price does not have advantage, therefore, manganese based material (refers to meet Li
xmn
ym
zthe positive electrode of O general formula, wherein M is any one or multiple transition metal, y>=z, z can be 0) become the positive electrode that price comparatively has superiority, but its have a serious defect to be that the dissolving of manganese causes that the high-temperature behavior of battery is undesirable, high temperature and safety is difficult to take into account.In lifting energy density, one is improve battery process as improved pole piece compaction density, and two is the materials using gram volume high, and another kind of effective approach is the operating voltage promoting battery.Fact proved, in manganese based material, relative 4.2V, LiMn
2o
4battery charges to the capacity that 4.35V can promote more than 10%, charges to the capacity that 4.5V can promote more than 15%; LiMnO
2actual gram volume reaches more than 200mAh, and charging voltage raises can bring considerable capacity; And LiNi
0.5mn
1.5o
2the discharge platform of itself is just at more than 4.6V.
The high temperature of manganese based material, safety, high voltage withstanding performance, propose higher challenge to its supporting electrolyte.
In high-temperature behavior improvement, application number is 200810218809.6, denomination of invention is the Chinese patent of " a kind of electrolyte of lithium manganate battery ", it discloses a kind of electrolyte of lithium manganate battery, this electrolyte comprises lithium salts, non-aqueous organic solvent, film for additive and stabilization additives heptamethyldisilazane, this invention, by the stabilization of stabilization additives heptamethyldisilazane to acidity in electrolyte, improves the high-temperature behavior of lithium manganate battery electrolyte.Application number is 200810030369.1, the Chinese patent that denomination of invention is " improving the electrolyte of lithium manganate lithium ion battery performance ", it discloses a kind of manganate lithium ion battery electrolyte, it adds 1 in the electrolytic solution, 3-propane sultone (PS) or two oxalic acid borate lithium (LiBOB) do film for additive, certain improvement is had to the high-temperature behavior of lithium manganate battery, but it is well-known, PS widely uses in the electrolytic solution, and though LiBOB is conducive to being formed resistant to elevated temperatures SEI film, but the electrolyte containing LiBOB often acidity is too high, and it improves limited efficiency.
In security performance lifting, in electrolyte mostly with the alkyl of the benzene such as biphenyl, cyclohexyl benzene, methyl phenyl ethers anisole, toluene, alkoxyl derivatives for safe additive, and these additives have fatal negative effect to the high-temperature behavior of manganese based material battery and cycle performance.
In high voltage withstanding performance improvement, application number is 201010225533.1, denomination of invention is the Chinese patent of " under more than 4.2V high voltage Undec lithium-ion battery electrolytes ", it discloses a kind of high pressure resistant electrolyte, a kind of sulfate derivative is comprised in electrolyte, can improve the high voltage cycle performance of battery preferably, but it does not solve the high voltage safety problem of battery.Application number is 200680010988.3, denomination of invention is the Chinese patent of " electrolyte ", containing the linear carbonate with fluorine-containing ether in its electrolyte, this electrolyte has flame retardancy, low-temperature characteristics, proof voltage excellence, but does not solve the high-temperature behavior of electrolyte.
Above-mentioned invention does not all solve the high temperature of manganese based material lithium ion battery, safety and high voltage withstanding performance simultaneously.
Summary of the invention
Institute of the present invention object is to provide a kind of manganese based material to be the electrolyte for lithium ion battery of positive pole, and this electrolyte can solve the high temperature of manganese based material lithium ion battery, safety and high voltage withstanding performance simultaneously.
Technical solution of the present invention is: this electrolyte comprises: non-aqueous organic solvent, lithium salts, film for additive, stabilization additives, also containing high voltage withstanding high temperature additive Li
2b
12f
12-Xh
x(0≤x≤11), Li
2b
12cl
12-Xh
x(0≤x≤11) or both arbitrary proportions mix, and its use amount accounts for 1 ~ 15% of electrolyte gross mass; High voltage withstanding anti-overcharge additive fluorobenzene methyl ether, fluorobenzene thioether or both arbitrary proportions mix, and its use amount accounts for 1 ~ 10% of electrolyte gross mass.
Described high voltage withstanding high temperature additive accounts for 0.3% ~ 15% of electrolyte gross mass.
Described high voltage withstanding anti-overcharge additive accounts for 2% ~ 15% of electrolyte gross mass.
Described non-aqueous organic solvent is carbonic ester, the one of carboxylate, ether, fluoro carbonic ester, alpha-fluorocarboxylate ester, fluoro-ether or mix arbitrarily, accounts for 65% ~ 90% of electrolyte gross mass, preferably 70% ~ 88%, more preferably 75% ~ 88%.
Described lithium salts is LiPF
6, LiBF
4, LiODFB, LiCF
3sO
3, LiN (CF
3sO
2)
2, LiN (C
2f
5sO
2)
2one or mix arbitrarily, account for 0.5% ~ 17% of electrolyte gross mass, preferably 5% ~ 15%.
Described film for additive is vinylene carbonate, vinyl ethylene carbonate, PS, Isosorbide-5-Nitrae-butyl sultone, 1, the one of 3-propene sultone or mix arbitrarily, account for 0.5% ~ 8% of electrolyte gross mass, preferably 0.5% ~ 5%, more preferably 1% ~ 3%.
Described stabilization additives is one or more of organic amine or alkyl silicon azane class, accounts for 0.01% ~ 1% of electrolyte gross mass, preferably 0.02% ~ 0.5%, more preferably 0.02% ~ 0.2%.Described organic amine is preferably C1-C8 alkyl amine, two C1-C8 alkyl amines, or three C1-C8 alkyl amines, or is preferably alcamines, as carbinolamine, monoethanolamine or Propanolamine.Described silazane class is preferably hexamethyldisiloxane, hexaethyl disilazine or six propyl group disilazanes.
Described electrolyte injects with LiMn
2o
4, LiNi
0.5mn
1.5o
2or LiMnO
2in soft-package battery for the nominal capacity 10Ah of positive electrode active materials.
Advantage of the present invention and the good effect brought: on the basis of reasonably optimizing non-aqueous organic solvent, lithium salts, film for additive, stabilization additives, adopt Li
2b
12f
12-Xh
x(0≤x≤11), Li
2b
12cl
12-Xh
x(0≤x≤11) or its mixing are as high voltage withstanding high temperature additive; Fluorobenzene methyl ether, fluorobenzene thioether or its mixing, as high voltage withstanding anti-overcharge additive, solve the high temperature of manganese based material lithium ion battery, safety and high voltage withstanding performance, the charging voltage of manganese based material lithium ion battery can be made to be promoted to more than 4.5V.
Accompanying drawing explanation
Fig. 1 is LiMn prepared by the electrolyte of comparative example and embodiment 1
2o
4battery is at the cycle performance figure of 25 DEG C of normal temperature environment 1C multiplying power 2.75 ~ 4.5V discharge and recharge.
Fig. 2 is LiMn prepared by the electrolyte of comparative example and embodiment 1
2o
4battery is at the cycle performance figure of 60 DEG C of hot environment 1C multiplying power 2.75 ~ 4.5V discharge and recharge.
Fig. 3 is LiNi prepared by the electrolyte of comparative example and embodiment 1
0.5mn
1.5o
2battery is at the cycle performance figure of 25 DEG C of normal temperature environment 1C multiplying power 2.75 ~ 4.8V discharge and recharge.
Fig. 4 is LiNi prepared by the electrolyte of comparative example and embodiment 1
0.5mn
1.5o
2battery is at the cycle performance figure of 60 DEG C of hot environment 1C multiplying power 2.75 ~ 4.8V discharge and recharge.
Fig. 5 is LiMnO prepared by the electrolyte of comparative example and embodiment 1
2battery is at the cycle performance figure of 25 DEG C of normal temperature environment 1C multiplying power 2.5 ~ 4.6V discharge and recharge.
Fig. 6 is LiMnO prepared by the electrolyte of comparative example and embodiment 1
2battery is at the cycle performance figure of 60 DEG C of hot environment 1C multiplying power 2.5 ~ 4.6V discharge and recharge.
Embodiment
Be described further the present invention below in conjunction with embodiment, enforcement of the present invention includes but not limited to lower routine execution mode.
Comparative example
By lithium salts LiPF
6be dissolved in the mixed solvent of ethylene carbonate/propylene carbonate/methyl ethyl carbonate/diethyl carbonate (mass ratio is 35/5/10/50) and obtain solution, wherein LiPF
6account for 12.5% of electrolyte gross mass, press in this solution electrolyte gross mass calculate the vinylene carbonate of interpolation 2%, the monoethanolamine of 0.1%, 1, the 3-propane sultone of 2% and 3% biphenyl, obtain contrast electrolyte.
Embodiment 1
By lithium salts LiPF
6be dissolved in the mixed solvent of ethylene carbonate/propylene carbonate/methyl ethyl carbonate/diethyl carbonate (mass ratio is 35/5/10/50) and obtain solution, wherein LiPF
6account for 12.5% of electrolyte gross mass, in this solution, press vinylene carbonate, the monoethanolamine of 0.1%, the Li of 2% that electrolyte gross mass calculates interpolation 2%
2b
12f
8h
4fluorobenzene methyl ether with 8%, obtains electrolyte of the present invention.
Embodiment 2
By lithium salts LiPF
6be dissolved in the mixed solvent of ethylene carbonate/fluorinated ethylene carbonate/methyl ethyl carbonate/diethyl carbonate (mass ratio is 30/10/10/50) and obtain solution, wherein LiPF
6account for 10.5% of electrolyte gross mass, in this solution, press electrolyte gross mass calculate the vinyl ethylene carbonate of interpolation 3%, PS, the ethylenediamine of 0.1%, the Li of 1% of 2%
2b
12f
7h
5fluorobenzene thioether with 5%, obtains electrolyte of the present invention.
Embodiment 3
By lithium salts LiBF
4be dissolved in the mixed solvent of ethylene carbonate/propylene carbonate/fluoro methyl ethyl carbonate/diethyl carbonate (mass ratio is 35/5/10/50) and obtain solution, wherein LiBF
4account for 14.5% of electrolyte gross mass, in this solution, press vinylene carbonate, the hexamethyldisiloxane of 1%, the Li of 4% that electrolyte gross mass calculates interpolation 1%
2b
12cl
6h
6, the fluorobenzene methyl ether of 3% and the fluorobenzene thioether of 3%, obtain electrolyte of the present invention.
Embodiment 4
Lithium salts LiODFB is dissolved in the mixed solvent of ethylene carbonate/ethyl butyrate/methyl ethyl carbonate/diethyl carbonate (mass ratio is 35/10/10/45) and obtains solution, wherein LiODFB accounts for 9.5% of electrolyte gross mass, in this solution, press electrolyte gross mass calculate the vinyl ethylene carbonate of interpolation 3%, 1,3-propene sultone, the heptamethyldisilazane of 0.5%, the Li of 1% of 3%
2b
12f
10h
2, 2% Li
2b
12cl
12fluorobenzene methyl ether with 10%, obtains electrolyte of the present invention.
Embodiment 5
By lithium salts LiPF
6with LiN (C
2f
5sO
2)
21:1 is dissolved in the mixed solvent of fluorinated ethylene carbonate/ethyl butyrate/ethyl propionate/diethyl carbonate (mass ratio is 40/10/10/40) and obtains solution in mass ratio, wherein lithium salts accounts for 7.5% of electrolyte gross mass, in this solution, press electrolyte gross mass calculate the vinyl ethylene carbonate of interpolation 2%, Isosorbide-5-Nitrae-butyl sultone, the ethamine of 0.2%, the Li of 8% of 4%
2b
12f
10h
2fluorobenzene thioether with 6%, obtains electrolyte of the present invention.
Embodiment 6
By lithium salts LiPF
6with LiCF
3sO
37:3 is dissolved in the mixed solvent of ethylene carbonate/ethyl butyrate/fluoropropionic acid ethyl ester/diethyl carbonate (mass ratio is 40/10/10/40) and obtains solution in mass ratio, wherein lithium salts accounts for 15.5% of electrolyte gross mass, presses vinylene carbonate, the ethamine of 0.2%, the Li of 2% that electrolyte gross mass calculates interpolation 2% in this solution
2b
12cl
5h
7fluorobenzene methyl ether with 6%, obtains electrolyte of the present invention.
Embodiment 7
By lithium salts LiPF
6be dissolved in the mixed solvent of ethylene carbonate/gamma-butyrolacton/methyl ethyl carbonate/diethyl carbonate (mass ratio is 20/5/20/55) and obtain solution, wherein LiPF
6account for 11% of electrolyte gross mass, in this solution, press electrolyte gross mass calculate the vinyl ethylene carbonate of interpolation 2%, PS, the ethylenediamine of 0.1%, the Li of 1% of 2%
2b
12f
5h
7fluorobenzene methyl ether with 4%, obtains electrolyte of the present invention.
Embodiment 8
By lithium salts LiN (CF
3sO
2)
2be dissolved in ethylene carbonate/1, in the mixed solvent of 2-dimethoxy-ethane/methyl ethyl carbonate/diethyl carbonate (mass ratio is 30/10/30/30), obtain solution, wherein LiN (CF
3sO
2)
2account for 12% of electrolyte gross mass, in this solution, press vinyl ethylene carbonate, the monoethanolamine of 0.3%, the Li of 2% that electrolyte gross mass calculates interpolation 5%
2b
12f
9h
3, 1% Li
2b
12cl
9h
3, the fluorobenzene methyl ether of 8% and the fluorobenzene thioether of 3%, obtain electrolyte of the present invention.
Embodiment 9
By lithium salts LiBF
4with LiCF
3sO
34:1 is dissolved in the mixed solvent of ethylene carbonate/propylene carbonate/methyl ethyl carbonate/diethyl carbonate (mass ratio is 35/5/10/50) and obtains solution in mass ratio, wherein lithium salts accounts for 11.5% of electrolyte gross mass, in this solution, press electrolyte gross mass calculate the vinylene carbonate of interpolation 1%, Isosorbide-5-Nitrae-butyl sultone, the monoethanolamine of 0.1%, the Li of 6% of 4%
2b
12f
10the fluorobenzene thioether of H and 6%, obtains electrolyte of the present invention.
Embodiment 10
By lithium salts LiPF
6be dissolved in the mixed solvent of ethylene carbonate/propylene carbonate/fluoro dimethyl carbonate/diethyl carbonate (mass ratio is 30/10/10/50) and obtain solution, wherein LiPF
6account for 15.5% of electrolyte gross mass, in this solution, press vinyl ethylene carbonate, the ethylenediamine of 0.1%, the Li of 2% that electrolyte gross mass calculates interpolation 2%
2b
12cl
6h
6fluorobenzene methyl ether with 6%, obtains electrolyte of the present invention.
Embodiment 11
By lithium salts LiPF
6be dissolved in the mixed solvent of ethylene carbonate/fluoropropylene carbonate/methyl ethyl carbonate/diethyl carbonate (mass ratio is 35/5/10/50) and obtain solution, wherein LiPF
6account for 4.5% of electrolyte gross mass, in this solution, press electrolyte gross mass calculate the vinyl ethylene carbonate of interpolation 4%, 1,3-propene sultone, the hexamethyldisiloxane of 1%, the Li of 13% of 3%
2b
12f
9h
3fluorobenzene methyl ether with 5%, obtains electrolyte of the present invention.
Result of the test:
The electrolyte of comparative example and all embodiments is injected same batch respectively with LiMn
2o
4, LiNi
0.5mn
1.5o
2and LiMnO
2in soft-package battery for the nominal capacity 10Ah of positive electrode active materials, test battery is in the high voltage cycle performance of normal temperature environment and 60 DEG C of hot environments and security performance.
Accompanying drawing 1 is LiMn prepared by the electrolyte of comparative example and embodiment 1
2o
4battery is at the cycle performance figure of 25 DEG C of normal temperature environment 1C multiplying power 2.75 ~ 4.5V discharge and recharge; Accompanying drawing 2 is LiMn prepared by the electrolyte of comparative example and embodiment 1
2o
4battery is at the cycle performance figure of 60 DEG C of hot environment 1C multiplying power 2.75 ~ 4.5V discharge and recharge; Accompanying drawing 3 is LiNi prepared by the electrolyte of comparative example and embodiment 1
0.5mn
1.5o
2battery is at the cycle performance figure of 25 DEG C of normal temperature environment 1C multiplying power 2.75 ~ 4.8V discharge and recharge; Accompanying drawing 4 is LiNi prepared by the electrolyte of comparative example and embodiment 1
0.5mn
1.5o
2battery is at the cycle performance figure of 60 DEG C of hot environment 1C multiplying power 2.75 ~ 4.8V discharge and recharge; Accompanying drawing 5 is LiMnO prepared by the electrolyte of comparative example and embodiment 1
2battery is at the cycle performance figure of 25 DEG C of normal temperature environment 1C multiplying power 2.5 ~ 4.6V discharge and recharge; Accompanying drawing 6 is LiMnO prepared by the electrolyte of comparative example and embodiment 1
2battery is at the cycle performance figure of 60 DEG C of hot environment 1C multiplying power 2.5 ~ 4.6V discharge and recharge.As seen from the figure, the high voltage withstanding normal-temperature circulating performance of manganese based material lithium ion battery prepared of electrolyte of the present invention and high temperature cyclic performance are obviously better than comparative example.
LiMn prepared by comparative example and all embodiment electrolyte
2o
4battery at the circulation of 4.5V normal temperature and the Data Comparison of 60 DEG C of high temperature circulation as following table 1:
| Example | Comparative example | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Normal temperature 300 weeks conservation rates | 0% | 84.0% | 85.9% | 86.6% | 85.7% |
| 60 DEG C of 200 weeks conservation rates | 0% | 73.1% | 73.0% | 73.7% | 73.6% |
| Example | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 |
| Normal temperature 300 weeks conservation rates | 84.5% | 83.9% | 86.7% | 83.1% | 84.7% |
| 60 DEG C of 200 weeks conservation rates | 72.80% | 72.9% | 73.8% | 72.3% | 73.1% |
| Example | Embodiment 10 | Embodiment 11 | ? | ? | ? |
| Normal temperature 300 weeks conservation rates | 85.6% | 84.9% | ? | ? | ? |
| 60 DEG C of 200 weeks conservation rates | 71.3% | 72.5% | ? | ? | ? |
LiNi prepared by comparative example and all embodiment electrolyte
0.5mn
1.5o
2battery at the circulation of 4.8V normal temperature and the Data Comparison of 60 DEG C of high temperature circulation as following table 2:
| Example | Comparative example | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Normal temperature 300 weeks conservation rates | 20.1% | 86.2% | 84.9% | 86.4% | 85.9% |
| 60 DEG C of 200 weeks conservation rates | 0% | 75.7% | 72.0% | 72.5% | 74.7% |
| Example | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 |
| Normal temperature 300 weeks conservation rates | 86.3% | 85.5% | 84.9% | 85.6% | 85.2% |
| 60 DEG C of 200 weeks conservation rates | 75.6% | 73.2% | 72.8% | 74.1% | 74.4% |
| Example | Embodiment 10 | Embodiment 11 | ? | ? | ? |
| Normal temperature 300 weeks conservation rates | 84.6% | 85.9% | ? | ? | ? |
| 60 DEG C of 200 weeks conservation rates | 72.1% | 73.3% | ? | ? | ? |
LiMnO prepared by comparative example and all embodiment electrolyte
2battery at the circulation of 4.6V normal temperature and the Data Comparison of 60 DEG C of high temperature circulation as following table 3:
| Example | Comparative example | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Normal temperature 300 weeks conservation rates | 4.8% | 84.1% | 85.2% | 84.5% | 84.9% |
| 60 DEG C of 200 weeks conservation rates | 0% | 72.4% | 73.3% | 74.1% | 72.3% |
| Example | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 |
| Normal temperature 300 weeks conservation rates | 83.6% | 85.7% | 84.9% | 86.7% | 85.8% |
| 60 DEG C of 200 weeks conservation rates | 71.9% | 74.3% | 73.2% | 74.5% | 73.6% |
| Example | Embodiment 10 | Embodiment 11 | ? | ? | ? |
| Normal temperature 300 weeks conservation rates | 85.4% | 86.9% | ? | ? | ? |
| 60 DEG C of 200 weeks conservation rates | 72.3% | 74.6% | ? | ? | ? |
From above table, embodiments of the invention are in normal temperature circulation or high temperature circulation is all obviously better than comparative example.
LiMn prepared by comparative example and all embodiment electrolyte
2o
4the safety test result of battery is as following table 4:
| Example | Comparative example | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| 3C10V overcharges | OK | OK | OK | OK | OK |
| 4.5V acupuncture | Smolder | OK | OK | OK | OK |
| 4.5V extruding | On fire from explosion | OK | OK | OK | OK |
| Example | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 |
| 3C10V overcharges | OK | OK | OK | OK | OK |
| 4.5V acupuncture | OK | OK | OK | OK | OK |
| 4.5V extruding | OK | OK | OK | OK | OK |
| Example | Embodiment 10 | Embodiment 11 | ? | ? | ? |
| 3C10V overcharges | OK | OK | ? | ? | ? |
| 4.5V acupuncture | OK | OK | ? | ? | ? |
| 4.5V extruding | OK | OK | ? | ? | ? |
LiNi prepared by comparative example and all embodiment electrolyte
0.5mn
1.5o
2the safety test result of battery is as following table 5:
| Example | Comparative example | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| 3C10V overcharges | OK | OK | OK | OK | OK |
| 4.8V acupuncture | On fire from explosion | OK | OK | OK | OK |
| 4.8V extruding | On fire from explosion | OK | OK | OK | OK |
| Example | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 |
| 3C10V overcharges | OK | OK | OK | OK | OK |
| 4.8V acupuncture | OK | OK | OK | OK | OK |
| 4.8V extruding | OK | OK | OK | OK | OK |
| Example | Embodiment 10 | Embodiment 11 | ? | ? | ? |
| 3C10V overcharges | OK | OK | ? | ? | ? |
| 4.8V acupuncture | OK | OK | ? | ? | ? |
| 4.8V extruding | OK | OK | ? | ? | ? |
LiMnO prepared by comparative example and all embodiment electrolyte
2the safety test result of battery is as following table 6:
| Example | Comparative example | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| 3C10V overcharges | OK | OK | OK | OK | OK |
| 4.6V acupuncture | Blast | OK | OK | OK | OK |
| 4.6V extruding | Blast is smoldered | OK | OK | OK | OK |
| Example | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 |
| 3C10V overcharges | OK | OK | OK | OK | OK |
| 4.6V acupuncture | OK | OK | OK | OK | OK |
| 4.6V extruding | OK | OK | OK | OK | OK |
| Example | Embodiment 10 | Embodiment 11 | ? | ? | ? |
| 3C10V overcharges | OK | OK | ? | ? | ? |
| 4.6V acupuncture | OK | OK | ? | ? | ? |
| 4.6V extruding | OK | OK | ? | ? | ? |
From above table, there is potential safety hazard in battery prepared by comparative example electrolyte, and battery prepared by embodiments of the invention can meet security performance under high voltages.
Claims (2)
1. manganese based material is the high voltage withstanding high temperature safe type electrolyte of lithium ion battery of positive pole, it is characterized in that lithium salts LiN (CF
3sO
2)
2be dissolved in ethylene carbonate/1, obtain solution in the mixed solvent of 2-dimethoxy-ethane/methyl ethyl carbonate/diethyl carbonate, the mass ratio of described solvent is 30/10/30/30, wherein LiN (CF
3sO
2)
2account for 12% of electrolyte gross mass, in this solution, press vinyl ethylene carbonate, the monoethanolamine of 0.3%, the Li of 2% that electrolyte gross mass calculates interpolation 5%
2b
12f
9h
3, 1% Li
2b
12cl
9h
3, the fluorobenzene methyl ether of 8% and the fluorobenzene thioether of 3%, obtain electrolyte.
2. used for electrolyte in injecting with LiMn described in claim 1
2o
4, LiNi
0.5mn
1.5o
2or LiMnO
2in soft-package battery for the nominal capacity 10Ah of positive electrode active materials.
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|---|---|---|---|
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|---|---|---|---|
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101777668A (en) * | 2010-02-05 | 2010-07-14 | 九江天赐高新材料有限公司 | Electrolyte for lithium manganese battery |
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