CN102306835A - 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, relate in particular to a kind of manganese based material for anodal lithium ion battery with high voltage withstanding high temperature safe type electrolyte.
Background technology
Lithium ion battery is because a series of advantages such as its operating voltage is high, energy density is high, power density is big, self discharge is little, memory-less effect, good charge-discharge performance, long circulation life, environmental friendliness; Be widely used in portable type electronic products such as mobile communication, digital camera, MP3 at present, and progressively use at national defence, military aspect.In recent years, along with the attention of the whole world to environmental problem, the new-energy automobile fast development, lithium ion battery is considered to the most potential current Vehicular dynamic battery.
Along with the development of market with society, lithium ion battery to be had higher requirement, one side requires on the price more cheap, requires to have higher energy density on the other hand.In price, well-known, the positive electrode of having used or soon having used mainly is made up of the transition metal oxide of lithium; Wherein, transition metal is the most cheap with manganese and iron, and easy oxidized causing of ferrous iron do not have advantage on the ferrous material price; Therefore, the 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 has superiority on the price, but its dissolving that serious defective is arranged is manganese causes the high-temperature behavior of battery undesirable, high temperature and safety are difficult to take into account.Aspect the lifting energy density, the one, improve battery process as improving the pole piece compacted density, two are to use the high material of gram volume, and another kind of valid approach is the operating voltage that promotes battery.Fact proved, in the manganese based material, relative 4.2V, LiMn
2O
4Battery charge can promote the capacity more than 10% to 4.35V, charges to 4.5V and can promote the capacity more than 15%; LiMnO
2Actual gram volume reaches more than the 200mAh, and charging voltage raises can bring considerable capacity; And LiNi
0.5Mn
1.5O
2The discharge platform of itself is just more than 4.6V.
The high temperature of manganese based material, safety, high voltage withstanding performance have proposed higher challenge for its supporting electrolyte.
Aspect high-temperature behavior improves; 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 improves the high-temperature behavior of lithium manganate battery electrolyte through the stabilization of stabilization additives heptamethyldisilazane to acidity in the electrolyte.Application number is 200810030369.1; Denomination of invention is the Chinese patent of " improving the electrolyte of lithium manganate lithium ion battery performance "; It discloses a kind of manganate lithium ion battery electrolyte; It adds 1 in electrolyte; 3-propane sultone (PS) or two oxalic acid borate lithiums (LiBOB) are done film for additive; High-temperature behavior to lithium manganate battery has certain improvement; But it is well-known; PS is widely used in electrolyte; Though and LiBOB helps forming resistant to elevated temperatures SEI film; Often acidity is too high but contain the electrolyte of LiBOB, and it is limited that it improves effect.
Aspect the security performance lifting; In the electrolyte mostly alkyl, the alkoxyl derivatives with benzene such as biphenyl, cyclohexyl benzene, methyl phenyl ethers anisole, toluene be safe additive, and these additives have fatal negative effect to the high-temperature behavior and the cycle performance of manganese based material battery.
Aspect high voltage withstanding performance improvement; Application number is 201010225533.1; Denomination of invention is the Chinese patent of " Undec lithium-ion battery electrolytes under the above high voltage of 4.2V "; It discloses a kind of high pressure resistant electrolyte; Comprise a kind of sulfate derivative in the 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 "; Contain 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 high temperature, safety and the high voltage withstanding performance of manganese based material lithium ion battery simultaneously.
Summary of the invention
Institute of the present invention purpose is to provide a kind of manganese based material to be anodal electrolyte for lithium ion battery, and this electrolysis fluid power solves high temperature, safety and the high voltage withstanding performance of manganese based material lithium ion battery simultaneously.
Technical solution of the present invention is: this electrolyte comprises: non-aqueous organic solvent, lithium salts, film for additive, stabilization additives, also contain 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-overcharging 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-overcharging additive accounts for 2%～15% of electrolyte gross mass.
Described non-aqueous organic solvent is a kind of or any mixing of carbonic ester, carboxylate, ether, fluoro carbonic ester, alpha-fluorocarboxylate ester, fluoro-ether, accounts for 65%～90% of electrolyte gross mass, and is preferred 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)
2A kind of or any mixing, account for 0.5%～17% of electrolyte gross mass, preferred 5%～15%.
Described film for additive is vinylene carbonate, vinyl ethylene carbonate, 1,3-N-morpholinopropanesulfonic acid lactone, 1,4-butyl sultone, 1; A kind of or any mixing of 3-propene sulfonic acid lactone; Account for 0.5%～8% of electrolyte gross mass, preferred 0.5%～5%, more preferably 1%～3%.
Described stabilization additives is one or more of organic amine or alkyl silazane class, accounts for 0.01%～1% of electrolyte gross mass, and is preferred 0.02%～0.5%, more preferably 0.02%～0.2%.Described organic amine is the C1-C8 alkyl amine preferably, and two C1-C8 alkyl amines, or three C1-C8 alkyl amines, or alcamines preferably are like carbinolamine, monoethanolamine or Propanolamine.Said silazane class is hexamethyldisiloxane, hexaethyl disilazine or six propyl group disilazanes preferably.
Said electrolyte injects with LiMn
2O
4, LiNi
0.5Mn
1.5O
2Or LiMnO
2In the soft-package battery for the nominal capacity 10Ah of positive electrode active materials.
Advantage of the present invention and the good effect that brings: 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 mix as high voltage withstanding high temperature additive; Fluorobenzene methyl ether, fluorobenzene thioether or its mixing have solved high temperature, safety and the high voltage withstanding performance of manganese based material lithium ion battery as high voltage withstanding anti-overcharging additive, and the charging voltage of manganese based material lithium ion battery is promoted to more than the 4.5V.
Description of drawings
Fig. 1 is the LiMn of the electrolyte preparation of Comparative Examples and embodiment 1
2O
4The cycle performance figure that battery discharges and recharges at 25 ℃ of normal temperature environment 1C multiplying power 2.75～4.5V.
Fig. 2 is the LiMn of the electrolyte preparation of Comparative Examples and embodiment 1
2O
4The cycle performance figure that battery discharges and recharges at 60 ℃ of hot environment 1C multiplying power 2.75～4.5V.
Fig. 3 is the LiNi of the electrolyte preparation of Comparative Examples and embodiment 1
0.5Mn
1.5O
2The cycle performance figure that battery discharges and recharges at 25 ℃ of normal temperature environment 1C multiplying power 2.75～4.8V.
Fig. 4 is the LiNi of the electrolyte preparation of Comparative Examples and embodiment 1
0.5Mn
1.5O
2The cycle performance figure that battery discharges and recharges at 60 ℃ of hot environment 1C multiplying power 2.75～4.8V.
Fig. 5 is the LiMnO of the electrolyte preparation of Comparative Examples and embodiment 1
2The cycle performance figure that battery discharges and recharges at 25 ℃ of normal temperature environment 1C multiplying power 2.5～4.6V.
Fig. 6 is the LiMnO of the electrolyte preparation of Comparative Examples and embodiment 1
2The cycle performance figure that battery discharges and recharges at 60 ℃ of hot environment 1C multiplying power 2.5～4.6V.
Embodiment
Below in conjunction with embodiment the present invention is done to further describe, enforcement of the present invention includes but not limited to down routine execution mode.
Comparative Examples
With 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 the electrolyte gross mass calculate to add 2% vinylene carbonate, 0.1% monoethanolamine, 2% 1,3-propane sultone and 3% biphenyl must contrast electrolyte.
Embodiment 1
With 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 the calculating of electrolyte gross mass and add 2% vinylene carbonate, 0.1% monoethanolamine, 2% Li
2B
12F
8H
4Fluorobenzene methyl ether with 8% gets electrolyte of the present invention.
Embodiment 2
With 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 the electrolyte gross mass calculate to add 3% vinyl ethylene carbonate, 2% 1,3-N-morpholinopropanesulfonic acid lactone, 0.1% ethylenediamine, 1% Li
2B
12F
7H
5Fluorobenzene thioether with 5% gets electrolyte of the present invention.
Embodiment 3
With 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 the calculating of electrolyte gross mass and add 1% vinylene carbonate, 1% hexamethyldisiloxane, 4% Li
2B
12Cl
6H
6, 3% fluorobenzene methyl ether and 3% fluorobenzene thioether, 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 the electrolyte gross mass calculate to add 3% vinyl ethylene carbonate, 3% 1,3-propene sulfonic acid lactone, 0.5% heptamethyldisilazane, 1% Li
2B
12F
10H
2, 2% Li
2B
12Cl
12Fluorobenzene methyl ether with 10% gets electrolyte of the present invention.
Embodiment 5
With lithium salts LiPF
6With LiN (C
2F
5SO
2)
2Be dissolved in by mass ratio 1:1 in the mixed solvent of fluorinated ethylene carbonate/ethyl butyrate/ethyl propionate/diethyl carbonate (mass ratio is 40/10/10/40) and obtain solution; Wherein lithium salts accounts for 7.5% of electrolyte gross mass; In this solution, press the electrolyte gross mass calculate to add 2% vinyl ethylene carbonate, 4% 1,4-butyl sultone, 0.2% ethamine, 8% Li
2B
12F
10H
2Fluorobenzene thioether with 6% gets electrolyte of the present invention.
Embodiment 6
With lithium salts LiPF
6With LiCF
3SO
3Be dissolved in by mass ratio 7:3 in the mixed solvent of ethylene carbonate/ethyl butyrate/fluoropropionic acid ethyl ester/diethyl carbonate (mass ratio is 40/10/10/40) and obtain solution; Wherein lithium salts accounts for 15.5% of electrolyte gross mass, in this solution, presses the calculating of electrolyte gross mass and adds 2% vinylene carbonate, 0.2% ethamine, 2% Li
2B
12Cl
5H
7Fluorobenzene methyl ether with 6% gets electrolyte of the present invention.
Embodiment 7
With 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 the electrolyte gross mass calculate to add 2% vinyl ethylene carbonate, 2% 1,3-N-morpholinopropanesulfonic acid lactone, 0.1% ethylenediamine, 1% Li
2B
12F
5H
7Fluorobenzene methyl ether with 4% gets electrolyte of the present invention.
Embodiment 8
With 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 (mass ratio is 30/10/30/30), wherein LiN (CF
3SO
2)
2Account for 12% of electrolyte gross mass, in this solution, press the calculating of electrolyte gross mass and add 5% vinyl ethylene carbonate, 0.3% monoethanolamine, 2% Li
2B
12F
9H
3, 1% Li
2B
12Cl
9H
3, 8% fluorobenzene methyl ether and 3% fluorobenzene thioether, electrolyte of the present invention.
Embodiment 9
With lithium salts LiBF
4With LiCF
3SO
3Be dissolved in by mass ratio 4:1 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 lithium salts accounts for 11.5% of electrolyte gross mass; In this solution, press the electrolyte gross mass calculate to add 1% vinylene carbonate, 4% 1,4-butyl sultone, 0.1% monoethanolamine, 6% Li
2B
12F
10H and 6% fluorobenzene thioether, electrolyte of the present invention.
Embodiment 10
With 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 the calculating of electrolyte gross mass and add 2% vinyl ethylene carbonate, 0.1% ethylenediamine, 2% Li
2B
12Cl
6H
6Fluorobenzene methyl ether with 6% gets electrolyte of the present invention.
Embodiment 11
With lithium salts LiPF
6Be dissolved in the mixed solvent of ethylene carbonate/fluoro propene 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 the electrolyte gross mass calculate to add 4% vinyl ethylene carbonate, 3% 1,3-propene sulfonic acid lactone, 1% hexamethyldisiloxane, 13% Li
2B
12F
9H
3Fluorobenzene methyl ether with 5% gets electrolyte of the present invention.
Result of the test:
The electrolyte of Comparative Examples and all embodiment is injected same batch respectively with LiMn
2O
4, LiNi
0.5Mn
1.5O
2And LiMnO
2In the soft-package battery for the nominal capacity 10Ah of positive electrode active materials, test battery is in the high voltage cycle performance and the security performance of normal temperature environment and 60 ℃ of hot environments.
Accompanying drawing 1 is the LiMn of the electrolyte preparation of Comparative Examples and embodiment 1
2O
4The cycle performance figure that battery discharges and recharges at 25 ℃ of normal temperature environment 1C multiplying power 2.75～4.5V; Accompanying drawing 2 is the LiMn of the electrolyte preparation of Comparative Examples and embodiment 1
2O
4The cycle performance figure that battery discharges and recharges at 60 ℃ of hot environment 1C multiplying power 2.75～4.5V; Accompanying drawing 3 is the LiNi of the electrolyte preparation of Comparative Examples and embodiment 1
0.5Mn
1.5O
2The cycle performance figure that battery discharges and recharges at 25 ℃ of normal temperature environment 1C multiplying power 2.75～4.8V; Accompanying drawing 4 is the LiNi of the electrolyte preparation of Comparative Examples and embodiment 1
0.5Mn
1.5O
2The cycle performance figure that battery discharges and recharges at 60 ℃ of hot environment 1C multiplying power 2.75～4.8V; Accompanying drawing 5 is the LiMnO of the electrolyte preparation of Comparative Examples and embodiment 1
2The cycle performance figure that battery discharges and recharges at 25 ℃ of normal temperature environment 1C multiplying power 2.5～4.6V; Accompanying drawing 6 is the LiMnO of the electrolyte preparation of Comparative Examples and embodiment 1
2The cycle performance figure that battery discharges and recharges at 60 ℃ of hot environment 1C multiplying power 2.5～4.6V.Can know that by figure the high voltage withstanding normal-temperature circulating performance of manganese based material lithium ion battery and the high temperature cyclic performance of electrolyte preparation of the present invention obviously are better than Comparative Examples.
The LiMn of Comparative Examples and all embodiment electrolyte preparations
2O
4Battery contrasts like following table 1 in the data of the circulation of 4.5V normal temperature and 60 ℃ of high temperature circulation:
| Instance | Comparative Examples | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| |
0% | 84.0% | 85.9% | 86.6% | 85.7% |
| 60 ℃ of 200 all |
0% | 73.1% | 73.0% | 73.7% | 73.6% |
| Instance | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 |
| |
84.5% | 83.9% | 86.7% | 83.1% | 84.7% |
| 60 ℃ of 200 all conservation rate | 72.80% | 72.9% | 73.8% | 72.3% | 73.1% |
| Instance | Embodiment 10 | Embodiment 11 | ? | ? | ? |
| |
85.6% | 84.9% | ? | ? | ? |
| 60 ℃ of 200 all conservation rate | 71.3% | 72.5% | ? | ? | ? |
The LiNi of Comparative Examples and all embodiment electrolyte preparations
0.5Mn
1.5O
2Battery contrasts like following table 2 in the data of the circulation of 4.8V normal temperature and 60 ℃ of high temperature circulation:
| Instance | Comparative Examples | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| |
20.1% | 86.2% | 84.9% | 86.4% | 85.9% |
| 60 ℃ of 200 all |
0% | 75.7% | 72.0% | 72.5% | 74.7% |
| Instance | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 |
| |
86.3% | 85.5% | 84.9% | 85.6% | 85.2% |
| 60 ℃ of 200 all conservation rate | 75.6% | 73.2% | 72.8% | 74.1% | 74.4% |
| Instance | Embodiment 10 | Embodiment 11 | ? | ? | ? |
| |
84.6% | 85.9% | ? | ? | ? |
| 60 ℃ of 200 all conservation rate | 72.1% | 73.3% | ? | ? | ? |
The LiMnO of Comparative Examples and all embodiment electrolyte preparations
2Battery contrasts like following table 3 in the data of the circulation of 4.6V normal temperature and 60 ℃ of high temperature circulation:
| Instance | Comparative Examples | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| |
4.8% | 84.1% | 85.2% | 84.5% | 84.9% |
| 60 ℃ of 200 all |
0% | 72.4% | 73.3% | 74.1% | 72.3% |
| Instance | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 |
| |
83.6% | 85.7% | 84.9% | 86.7% | 85.8% |
| 60 ℃ of 200 all conservation rate | 71.9% | 74.3% | 73.2% | 74.5% | 73.6% |
| Instance | Embodiment 10 | Embodiment 11 | ? | ? | ? |
| |
85.4% | 86.9% | ? | ? | ? |
| 60 ℃ of 200 all conservation rate | 72.3% | 74.6% | ? | ? | ? |
Can know that by above table embodiments of the invention are in the normal temperature circulation or high temperature circulation all obviously is better than Comparative Examples.
The LiMn of Comparative Examples and all embodiment electrolyte preparations
2O
4The safety test result of battery such as following table 4:
| Instance | Comparative Examples | 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 |
| Instance | 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 |
| Instance | Embodiment 10 | Embodiment 11 | ? | ? | ? |
| 3C10V overcharges | OK | OK | ? | ? | ? |
| 4.5V acupuncture | OK | OK | ? | ? | ? |
| 4.5V extruding | OK | OK | ? | ? | ? |
The LiNi of Comparative Examples and all embodiment electrolyte preparations
0.5Mn
1.5O
2The safety test result of battery such as following table 5:
| Instance | Comparative Examples | 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 |
| Instance | 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 |
| Instance | Embodiment 10 | Embodiment 11 | ? | ? | ? |
| 3C10V overcharges | OK | OK | ? | ? | ? |
| 4.8V acupuncture | OK | OK | ? | ? | ? |
| 4.8V extruding | OK | OK | ? | ? | ? |
The LiMnO of Comparative Examples and all embodiment electrolyte preparations
2The safety test result of battery such as following table 6:
| Instance | Comparative Examples | 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 |
| Instance | 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 |
| Instance | Embodiment 10 | Embodiment 11 | ? | ? | ? |
| 3C10V overcharges | OK | OK | ? | ? | ? |
| 4.6V acupuncture | OK | OK | ? | ? | ? |
| 4.6V extruding | OK | OK | ? | ? | ? |
Can be known that by above table there is potential safety hazard in the battery of Comparative Examples electrolyte preparation, the battery of embodiments of the invention preparation can satisfy security performance under high voltage.
Claims (8)
- A manganese based material be anodal lithium ion battery with high voltage withstanding high temperature safe type electrolyte, it is characterized in that electrolyte comprises: non-aqueous organic solvent, lithium salts, film for additive, stabilization additives, also contain 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-overcharging additive fluorobenzene methyl ether, fluorobenzene thioether or both arbitrary proportions mix, and its use amount accounts for 1 ~ 10% of electrolyte gross mass.
- 2. electrolyte according to claim 1 is characterized in that described high voltage withstanding high temperature additive accounts for 0.3%～15% of electrolyte gross mass.
- 3. electrolyte according to claim 1 is characterized in that described high voltage withstanding anti-overcharging additive accounts for 2%～15% of electrolyte gross mass.
- 4. electrolyte according to claim 1; It is characterized in that described non-aqueous organic solvent is a kind of or any mixing of carbonic ester, carboxylate, ether, fluoro carbonic ester, alpha-fluorocarboxylate ester, fluoro-ether; Account for 65%～90% of electrolyte gross mass, preferred 70%～88%, more preferably 75%～88%.
- 5. electrolyte according to claim 1 is characterized in that described lithium salts is LiPF 6, LiBF 4, LiODFB, LiCF 3SO 3, LiN (CF 3SO 2) 2, LiN (C 2F 5SO 2) 2A kind of or any mixing, account for 0.5%～17% of electrolyte gross mass, preferred 5%～15%.
- 6. electrolyte according to claim 1; It is characterized in that described film for additive is vinylene carbonate, vinyl ethylene carbonate, 1; 3-N-morpholinopropanesulfonic acid lactone, 1; 4-butyl sultone, 1; A kind of or any mixing of 3-propene sulfonic acid lactone; Account for 0.5%～8% of electrolyte gross mass, preferred 0.5%～5%, more preferably 1%～3%.
- 7. electrolyte according to claim 1 is characterized in that described stabilization additives is one or more of organic amine or alkyl silazane class, accounts for 0.01%～1% of electrolyte gross mass, and is preferred 0.02%～0.5%, more preferably 0.02%～0.2%; Described organic amine is the C1-C8 alkyl amine preferably, and two C1-C8 alkyl amines, or three C1-C8 alkyl amines, or alcamines preferably are like carbinolamine, monoethanolamine or Propanolamine; Said silazane class is hexamethyldisiloxane, hexaethyl disilazine or six propyl group disilazanes preferably.
- 8. each said used for electrolyte of claim 1 to 7 is in injecting with LiMn 2O 4, LiNi 0.5Mn 1.5O 2Or LiMnO 2In the soft-package battery for the nominal capacity 10Ah of positive electrode active materials.
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