CN103094613A - Electrolyte used for high-voltage power battery and power battery containing electrolyte - Google Patents
Electrolyte used for high-voltage power battery and power battery containing electrolyte Download PDFInfo
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- CN103094613A CN103094613A CN2013100172785A CN201310017278A CN103094613A CN 103094613 A CN103094613 A CN 103094613A CN 2013100172785 A CN2013100172785 A CN 2013100172785A CN 201310017278 A CN201310017278 A CN 201310017278A CN 103094613 A CN103094613 A CN 103094613A
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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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to the technical field of power batteries, and particularly relates to electrolyte used for a high-voltage power battery. The electrolyte is prepared from a non-aqueous organic solvent, lithium salt, an additive, and a siloxane sulphone derivant, wherein the siloxane sulphone derivant accounts for 0.1%-10% of the total mass of the electrolyte. Compared with the prior art, the electrolyte has the advantages that corrosive substances of HF (Hydrogn Fluoride) and the like in an electrolyte system or dissociating on the surface of a positive electrode can effectively eliminated by adding the siloxane sulphone derivant into the electrolyte, and meanwhile, an SEI (Solid Electrolyte Interface) film can be formed on an interface of the positive electrode during the formation process of the added siloxane sulphone derivant, and the SEI film contains groups swallowing the HF, so that the HF reacting with active materials of the positive electrode on an interface of the positive electrode can be effectively eliminated, and the function of protecting the active components of the positive electrode can be played; and further, the high-voltage and high-temperature cycling performance of a battery containing the electrolyte can be obviously enhanced. In addition, the invention also discloses a power battery containing the electrolyte.
Description
Technical field
The invention belongs to the power battery technology field, the electrokinetic cell that relates in particular to a kind of high voltage power battery electrolytic solution and comprise this electrolyte.
Background technology
Lithium ion battery due to have energy density high, have extended cycle life and the characteristics such as environmental friendliness, the traditional secondary batteries such as nickel-cadmium cell and Ni-MH battery have progressively been replaced, in consumption electronic product market, be widely used at present, but course continuation mileage is short, fast charging and discharging ability and cost is higher etc. that shortcoming has hindered the development of lithium ion battery in widespread adoption fields such as electric automobile and hybrid vehicles.
Composite transition metal oxide LiNi
1/3co
1/3mn
1/3o
2possess high reversible charge/discharge capacity, security performance and the lower advantages such as use cost preferably, be expected to promote the further application of lithium ion battery in fields such as electric automobile, hybrid vehicle and energy-accumulating power stations.Wherein, the LiNi of high nickel content
1-xco
xmn
yo
2(1-x>=0.5) positive electrode (being rich nickel type tri compound positive electrode) is more preponderated with characteristics cheaply owing to having high power capacity, therefore has been subject to people's special concern.But discharge and recharge under condition high price Ni high-tension
4+ion has strong oxidizing property, easily causes the decay of battery capacity.
In former studies, the chemical property of material is at room temperature tested mostly, and the report of the cyclical stability of relevant rich nickel type tri compound positive electrode under the high temperature high voltage few.PARK B C[Journal of Power Sources wherein, 2008,178 (2): 826-831] etc. studied employing AlF
3clad anode material, the capacity attenuation erosion of positive electrode caused to reduce HF in cyclic process, improved the cycle life of battery; The Japanese Patent Application Publications such as Unexamined Patent 2001-057237 and Unexamined Patent 2000-243440 a kind of quaternary silicon ether additive, by silicon ether additive, with HF, react, control the content of HF in electrolyte, weaken the destruction of HF to active material, thereby improve the cycle performance of battery.Yet, at LiNi
1-xco
xmn
yo
2in the ternary high pressure system, for the battery that makes electric automobile can be 55 ℃ of high temperature (>) use in situation, need a large amount of additives that add containing F, to improve the high temperature cyclic performance of battery, this has just caused battery to produce a large amount of HF in the high temperature circulation process, and then makes the high temperature cyclic performance of battery become the bottleneck that limits battery applications.By active material (AlF
3, Al
2o
3deng) although coating can improve to a certain extent the high temperature cyclic performance of battery, the sharply rising of the internal resistance of cell due to coat inhomogeneous and after coating, make the utilization of the method in this field be subject to larger restriction.
On the other hand, by add a certain amount of additive in electrolyte, can play the effect of the high temperature cyclic performance that improves preferably battery.But, it should be noted that, can remove the HF in electrolyte although add the silicon ether material, reach the function of stablizing electrolyte, yet, as the application number described silicon ether material of patent application that is CN200710195959, can only realize " contact reaction " (the contact reaction can be understood as the silicon ether material and contacts and produce HF with reactant), yet the generation of the HF characteristics that the amount of possessing is large and randomness is strong usually under hot conditions, and be easy to be diffused on positive electrode and be in contact with it the corrosion that causes active material, and can not isolate timely contacting of HF and positive electrode, continuity along with reaction, battery can be at lower cycle life scope inward dive, thereby can not well realize the function of cycle life protection.
In view of this, the necessary electrokinetic cell that a kind of high voltage power battery electrolytic solution is provided and comprises this electrolyte, by add silicon ether sulfone derivative in electrolyte, can be at anodal interface formation SEI film in formation process, there is the composition group that can " engulf " HF on this SEI film, can effectively eliminate the HF reacted with active material on anodal interface, and then weaken the destruction of HF to positive electrode active materials, thus the high temperature cyclic performance of raising battery.
Summary of the invention
One of purpose of the present invention is: for the deficiencies in the prior art, and provide a kind of high voltage power battery electrolytic solution, by add silicon ether sulfone derivative in electrolyte, can be at anodal interface formation SEI film in formation process, there is the composition group that can " engulf " HF on this SEI film, can effectively eliminate the HF reacted with active material on anodal interface, and then weaken the destruction of HF to positive electrode active materials, thus the high temperature cyclic performance of raising battery.
In order to achieve the above object, the present invention adopts following technical scheme:
A kind of high voltage power battery electrolytic solution, described electrolyte comprises non-aqueous organic solvent, lithium salts and additive, also comprises the silicon ether sulfone derivatives meaned by chemical formula (1):
Wherein, R
1,r
2and R
3the alkyl that is respectively aromatic group or contains 1-10 carbon atom, and R
1, R
2and R
3identical or not identical; R
4for the alkyl of 1-10 carbon atom, R
5for alkylene, the mass percent that described silicon ether sulfone derivatives accounts for described electrolyte gross mass is 0.1% ~ 10%.If the too high levels of silicon ether sulfone derivatives, the SEI film that can make at anodal interface formation is blocked up, makes anodal impedance become large, finally causes the cycle performance of battery to reduce; And if the content of silicon ether sulfone derivatives is too low, can not reach again the effect of good raising battery high-temperature cycle performance.
As a kind of improvement of high voltage power battery electrolytic solution of the present invention, the mass percent that described silicon ether sulfone derivatives accounts for described electrolyte gross mass is 0.5% ~ 5%, and this is preferred scope.
As a kind of improvement of high voltage power battery electrolytic solution of the present invention, the mass percent that described silicon ether sulfone derivatives accounts for described electrolyte gross mass is 2%, and this is preferably to select.
A kind of improvement as high voltage power battery electrolytic solution of the present invention, described silicon ether sulfone derivatives is the silica-based ethyl vinyl sulfone of trimethoxy, the silica-based methylpropenyl sulfone of trimethoxy, the silica-based propyl group cyclobutenyl of triethoxy sulfone, the silica-based butyl acrylic of tripropoxy sulfone, the silica-based methyl ethylene sulfone of methoxy ethoxy propoxyl group, the silica-based ethyl propylene base of triple phenoxyl sulfone, the silica-based ethyl vinyl sulfone of three benzyloxies or the silica-based allyl ethyl sulfone of dimethoxy phenoxy group, these are preferred materials, because they are than being easier to synthetic and preparation.
As a kind of improvement of high voltage power battery electrolytic solution of the present invention, described additive is at least two kinds in vinylene carbonate, fluorinated ethylene carbonate and vinylethylene carbonate.These several additives can form in negative terminal surface the SEI film of one deck densification, thereby the protection negative pole is not damaged, and extends the cycle life of battery.
As a kind of improvement of high voltage power battery electrolytic solution of the present invention, the mass percent that described additive accounts for described electrolyte gross mass is 1-5%.If the content of additive is too low too thin at the SEI of negative pole interface formation film, the protective effect of anticathode is not obvious; The content Ruo Taigao of additive, because of the passivation of its anticathode, cause internal battery impedance to increase, and battery capacity reduces.
As a kind of improvement of high voltage power battery electrolytic solution of the present invention, described lithium salts is LiPF
6, LiBF
4, LiAsF
6, LiClO
4, LiBOB, LiDFOB, LiCF
3sO
3, LiC
4f
9sO
3, Li (CF
3sO
2)
2n and Li (C
2f
5sO
2)
2at least one in N, and the concentration of described lithium salts is 0.8-1.7mol/L.Lithium salt is too low, and the conductivity of electrolyte is low, can affect multiplying power and the cycle performance of whole battery system; Lithium salt is too high, and electrolyte viscosity is excessive, affects equally the multiplying power of whole battery system.Wherein, lithium salts is preferably LiPF
6.
As a kind of improvement of high voltage power battery electrolytic solution of the present invention, described non-aqueous organic solvent comprises carbonic ester, and described carbonic ester comprises cyclic carbonate and linear carbonate.
Described cyclic carbonate is at least one in ethylene carbonate, propene carbonate and butylene.
Described linear carbonate is at least one in dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, dipropyl carbonate, methyl propyl carbonate, carbonic acid first isopropyl ester, carbonic acid first butyl ester and butylene carbonate.
The mass ratio of described cyclic carbonate and described linear carbonate is 4:1 ~ 1:20.
As a kind of improvement of high voltage power battery electrolytic solution of the present invention, described non-aqueous organic solvent also comprises at least one in carboxylate, ether compound and aromatic compound.
Wherein, described carboxylate comprises non-substituted carboxylate and halogenated carboxylic ester, and described non-substituted carboxylate is at least one in methyl formate, Ethyl formate, formic acid n-propyl, isopropyl formate, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, gamma-butyrolacton, gamma-valerolactone and caprolactone; Described halogenated carboxylic ester is fluoro methyl formate, fluoro Ethyl formate, single fluoro methyl acetate, two fluoro methyl acetates, single fluoro ethyl acetate, two fluoro ethyl acetate, three fluoro ethyl acetate, fluoro propyl formate, 3-fluorine methyl propionate, 3,3-difluoro methyl propionate, 3,3,3-trifluoroacetic acid methyl esters, 3-fluorine ethyl propionate, 3,3-difluoro ethyl propionate and 3, at least one in 3,3-trifluoroacetic acid ethyl ester.
Described ether compound is at least one in butyl oxide, dimethoxymethane, dimethoxy-ethane, diethoxymethane, diethoxyethane, oxolane, dimethyl-tetrahydrofuran, single fluorine dimethoxymethane, single fluorine dimethoxy-ethane, single fluorine diethoxymethane and single fluorine diethoxyethane.
Described aromatic compound is toluene, fluorobenzene, adjacent fluorotoluene, benzotrifluoride, 4-toluene fluoride, at least one in fluorine methoxybenzene, adjacent fluorine methoxybenzene, adjacent difluoromethoxy phenyl, the fluoro-4-tert-butyl benzene of 1-and fluorodiphenyl.
With respect to prior art; the present invention by adding silicon ether sulfone derivative in electrolyte; in can more effective removing electrolyte system and dissociate to the corrosive substances such as HF on anodal surface; the silicon ether sulfone derivative added can form the SEI film in formation process on anodal interface; there is the composition group of " engulfing " HF on this SEI film simultaneously; can effectively eliminate on anodal interface the HF with the positive electrode active material qualitative response; thereby play the effect of the anodal active component of protection, thereby significantly improve the high temperature cyclic performance of battery under high voltage that contains this electrolyte.Its reaction mechanism (wherein, R as follows
5take vinyl as example).
Facts have proved: adopt the electrokinetic cell of electrolyte of the present invention to circulate under 60 ℃ after 2000 times, capability retention is still higher than 85%.This shows: can effectively protect positive pole by adding silicon ether sulfone derivative, make the electrokinetic cell that comprises this electrolyte show superior cycle performance under hot conditions.
Another object of the present invention is to provide a kind of electrokinetic cell, comprise electrode assemblie, for holding the metal shell of described electrode assemblie, be injected into the electrolyte in described metal shell and be fixedly connected on the top cover on described metal shell, described electrode assemblie comprises positive plate, negative plate and be interval in described positive plate and described negative plate between barrier film, described positive plate comprises plus plate current-collecting body and is arranged at the anodal diaphragm of described anode collection surface, described anodal diaphragm comprises positive active material, bonding agent and conductive agent, described positive active material is LiNi
1-x-yco
xm
yo
2, wherein M is Mn or Al, 0≤x≤1,0≤y≤1,0≤x+y≤1, and described electrolyte is high voltage power battery electrolytic solution of the present invention.
With respect to prior art; the present invention is owing to having adopted the electrolyte that is added with silicon ether sulfone derivative; this silicon ether sulfone derivative can be in formation process; form interfacial film at positive pole; this interfacial film can be well and the HF effect in cyclic process simultaneously; remove timely HF, thereby effectively protection is anodal, makes electrokinetic cell of the present invention show superior cycle performance under high voltage and hot conditions.
Embodiment
Below in conjunction with embodiment, the present invention and beneficial effect thereof are described further, but the present invention is not limited to this.
The invention provides a kind of high voltage power battery electrolytic solution.
Embodiment 1: the high voltage power battery electrolytic solution that the present embodiment provides, comprise non-aqueous organic solvent, lithium salts and additive, and also comprise that the silica-based ethyl vinyl sulfone of trimethoxy (is the R in chemical formula (1)
1, R
2and R
3be methyl, R
4for ethyl, R
5for vinyl), the mass percent that the silica-based ethyl vinyl sulfone of trimethoxy accounts for the electrolyte gross mass is 1%.Wherein, non-aqueous organic solvent is ethylene carbonate, dimethyl carbonate and propene carbonate (three's volume ratio is 2:2:1); Lithium salts is LiPF
6, and the concentration of described lithium salts is 1mol/L; The mixture that additive is vinylene carbonate and fluorinated ethylene carbonate, the two mass percent that accounts for the electrolyte gross mass is respectively 2% and 3%.
Embodiment 2: the high voltage power battery electrolytic solution that the present embodiment provides, comprise non-aqueous organic solvent, lithium salts and additive, and also comprise that the silica-based methylpropenyl sulfone of trimethoxy (is the R in chemical formula (1)
1, R
2and R
3be methyl, R
4for methyl, R
5for acrylic), the mass percent that the silica-based methylpropenyl sulfone of trimethoxy accounts for the electrolyte gross mass is 2%.Wherein, non-aqueous organic solvent is ethylene carbonate, fluorobenzene and propene carbonate (three's volume ratio is 10:1:7); Lithium salts is LiBF
4, and the concentration of described lithium salts is 1.2mol/L; The mixture that additive is fluorinated ethylene carbonate and vinylethylene carbonate, the two mass percent that accounts for the electrolyte gross mass is respectively 3% and 2%.
Embodiment 3: the high voltage power battery electrolytic solution that the present embodiment provides, comprise non-aqueous organic solvent, lithium salts and additive, and also comprise that the silica-based propyl group cyclobutenyl of triethoxy sulfone (is the R in chemical formula (1)
1, R
2and R
3be ethyl, R
4for propyl group, R
5for cyclobutenyl), the mass percent that the silica-based propyl group cyclobutenyl of triethoxy sulfone accounts for the electrolyte gross mass is 5%.Wherein, non-aqueous organic solvent is ethylene carbonate, benzotrifluoride and diethyl carbonate (three's volume ratio is 5:1:5); Lithium salts is LiAsF
6, and the concentration of described lithium salts is 0.9mol/L; The mixture that additive is fluorinated ethylene carbonate and vinylethylene carbonate, the two mass percent that accounts for the electrolyte gross mass is respectively 1% and 1%.
Embodiment 4: the high voltage power battery electrolytic solution that the present embodiment provides, comprise non-aqueous organic solvent, lithium salts and additive, and also comprise that the silica-based butyl acrylic of tripropoxy sulfone (is the R in chemical formula (1)
1, R
2and R
3be propyl group, R
4for butyl, R
5for acrylic), the mass percent that the silica-based butyl acrylic of tripropoxy sulfone accounts for the electrolyte gross mass is 7%.Wherein, non-aqueous organic solvent is ethylene carbonate, butylene, oxolane and diethyl carbonate (four volume ratio is 5:3:1:5); Lithium salts is LiPF
6with the LiBOB(di-oxalate lithium borate) mixture (mass ratio of the two is 1:1), and the concentration of described lithium salts is 1.1mol/L; The mixture that additive is vinylene carbonate and vinylethylene carbonate, the two mass percent that accounts for the electrolyte gross mass is respectively 1.5% and 1.5%.
Embodiment 5: the high voltage power battery electrolytic solution that the present embodiment provides, comprise non-aqueous organic solvent, lithium salts and additive, and also comprise that the silica-based methyl ethylene sulfone of methoxy ethoxy propoxyl group (is the R in chemical formula (1)
1for methyl, R
2for ethyl, R
3be propyl group, R
4for methyl, R
5for vinyl), the mass percent that the silica-based methyl ethylene sulfone of methoxy ethoxy propoxyl group accounts for the electrolyte gross mass is 10%.Wherein, non-aqueous organic solvent is propene carbonate, butylene, fluoro methyl formate and diethyl carbonate (four volume ratio is 3:7:1:5); Lithium salts is LiPF
6with the LiDFOB(difluorine oxalic acid boracic acid lithium) mixture (mass ratio of the two is 5:1), and the concentration of described lithium salts is 0.8mol/L; The mixture that additive is vinylene carbonate and vinylethylene carbonate, the two mass percent that accounts for the electrolyte gross mass is respectively 2% and 2%.
Embodiment 6: the high voltage power battery electrolytic solution that the present embodiment provides, comprise non-aqueous organic solvent, lithium salts and additive, and also comprise that the silica-based ethyl propylene base of triple phenoxyl sulfone (is the R in chemical formula (1)
1, R
2and R
3be phenyl, R
4for ethyl, R
5for acrylic), the mass percent that the silica-based ethyl propylene base of triple phenoxyl sulfone accounts for the electrolyte gross mass is 0.1%.Wherein, non-aqueous organic solvent is propene carbonate, methyl formate and methyl ethyl carbonate (three's volume ratio is 10:2:8); Lithium salts is LiPF
6and Li (CF
3sO
2)
2the mixture of N (mass ratio of the two is 20:1), and the concentration of described lithium salts is 1.5mol/L; The mixture that additive is vinylene carbonate, fluorinated ethylene carbonate and vinylethylene carbonate, the mass percent that the three accounts for the electrolyte gross mass is respectively 1%, 1% and 1%.
Embodiment 7: the high voltage power battery electrolytic solution that the present embodiment provides, comprise non-aqueous organic solvent, lithium salts and additive, and also comprise that the silica-based ethyl vinyl sulfone of three benzyloxies (is the R in chemical formula (1)
1, R
2and R
3be benzyl, R
4for ethyl, R
5for vinyl), the mass percent that the silica-based ethyl vinyl sulfone of three benzyloxies accounts for the electrolyte gross mass is 0.5%.Wherein, non-aqueous organic solvent is ethylene carbonate, fluoro methyl formate and dipropyl carbonate (three's volume ratio is 9:1:4); Lithium salts is LiPF
6, and the concentration of described lithium salts is 1.7mol/L; The mixture that additive is vinylene carbonate, fluorinated ethylene carbonate and vinylethylene carbonate, the mass percent that the three accounts for the electrolyte gross mass is respectively 0.5%, 1.5% and 0.5%.
Embodiment 8: the high voltage power battery electrolytic solution that the present embodiment provides, comprise non-aqueous organic solvent, lithium salts and additive, and also comprise that the silica-based allyl ethyl sulfone of dimethoxy phenoxy group (is the R in chemical formula (1)
1and R
2be methyl, R
3be phenyl, R
4for ethyl, R
5for pi-allyl), the mass percent that the silica-based allyl ethyl sulfone of dimethoxy phenoxy group accounts for the electrolyte gross mass is 2.5%.Wherein, non-aqueous organic solvent is ethylene carbonate, dimethoxy-ethane and methyl propyl carbonate (three's volume ratio is 8:1:6); Lithium salts is LiPF
6, and the concentration of described lithium salts is 1.3mol/L; The mixture that additive is vinylene carbonate, fluorinated ethylene carbonate and vinylethylene carbonate, the mass percent that the three accounts for the electrolyte gross mass is respectively 2%, 0.7% and 0.3%.
Comparative example 1 is not both with embodiment 1: the electrokinetic cell that this comparative example provides does not contain the silica-based ethyl vinyl sulfone of trimethoxy with electrolyte, and all the other,, with embodiment 1, repeat no more here.
The present invention also provides a kind of electrokinetic cell.
Embodiment 9: the electrokinetic cell that the present embodiment provides, comprise electrode assemblie, for the metal shell of hold electrodes assembly, be injected into the electrolyte in metal shell and be fixedly connected on the top cover on metal shell, electrode assemblie comprise positive plate, negative plate and be interval in positive plate and negative plate between barrier film, positive plate comprises plus plate current-collecting body and is arranged at the anodal diaphragm of anode collection surface, anodal diaphragm comprises positive active material, bonding agent and conductive agent, and positive active material is LiNi
0.5co
0.2mn
0.3o
2, the high voltage power battery electrolytic solution that electrolyte provides for embodiment 1.
Embodiment 10, and as different from Example 9: positive active material is LiNi
0.6co
0.2mn
0.2o
2, the high voltage power battery electrolytic solution that electrolyte provides for embodiment 2.All the other,, with embodiment 9, repeat no more here.
Embodiment 11, and as different from Example 9: positive active material is LiNi
0.7co
0.2al
0.1o
2, the high voltage power battery electrolytic solution that electrolyte provides for embodiment 3.All the other,, with embodiment 9, repeat no more here.
Embodiment 12, and as different from Example 9: positive active material is LiNi
0.8co
0.15mn
0.15o
2, the high voltage power battery electrolytic solution that electrolyte provides for embodiment 4.All the other,, with embodiment 9, repeat no more here.
Embodiment 13, and as different from Example 9: positive active material is LiNi
0.9co
0.05mn
0.05o
2, the high voltage power battery electrolytic solution that electrolyte provides for embodiment 5.All the other,, with embodiment 9, repeat no more here.
Embodiment 14, and as different from Example 9: positive active material is LiNi
0.3co
0.3mn
0.4o
2, the high voltage power battery electrolytic solution that electrolyte provides for embodiment 6.All the other,, with embodiment 9, repeat no more here.
Embodiment 15, and as different from Example 9: positive active material is LiNi
0.4co
0.4mn
0.2o
2, the high voltage power battery electrolytic solution that electrolyte provides for embodiment 7.All the other,, with embodiment 9, repeat no more here.
Embodiment 16, and as different from Example 9: positive active material is LiNi
0.2co
0.5mn
0.3o
2, the high voltage power battery electrolytic solution that electrolyte provides for embodiment 8.All the other,, with embodiment 9, repeat no more here.
Comparative example 2, as different from Example 9: the electrolyte that electrolyte provides for comparative example 1.All the other,, with embodiment 9, repeat no more here.
Electrokinetic cell to embodiment 9-16 and comparative example 2 carries out following high temperature circulation test: under 60 ℃, by the electrokinetic cell in the electrokinetic cell of embodiment 9-16 and comparative example 2, with the 0.5C constant current charge to 4.8V, then constant voltage charge to electric current is 0.05C, then use the 0.5C constant current discharge to 3.0V, so charge/discharge is 400 times and 2000 times.Calculate capacity and the capability retention of battery.Acquired results is in Table 1.
Table 1: the high temperature circulation test result of the electrokinetic cell of embodiment 9-16 and comparative example 2.
| Group | 60 ℃ discharge and recharge capability retention after 400 circulations | 60 ℃ discharge and recharge capability retention after 400 circulations |
| Embodiment 9 | 92.1% | 88.1% |
| Embodiment 10 | 93.7% | 89.3% |
| Embodiment 11 | 95.7% | 90.1% |
| Embodiment 12 | 97.4% | 91.2% |
| Embodiment 13 | 95.1% | 85.5% |
| Embodiment 14 | 93.1% | 85.0% |
| Embodiment 15 | 92.1% | 86.5% |
| Embodiment 16 | 92.5% | 89.9% |
| Comparative example 2 | 40.3% | 1.2% |
As can be seen from Table 1: electrolyte of the present invention has silicon ether sulfone derivative owing to having added; this silicon ether sulfone derivative can be in formation process; form interfacial film at positive pole; this interfacial film can be well and the HF effect in cyclic process simultaneously; remove timely HF, thereby effectively protection is anodal, makes electrokinetic cell of the present invention show superior cycle performance under high voltage and hot conditions; even under 60 ℃ the circulation 2000 times after, the capability retention of battery is still higher than 85%.
The announcement of book and enlightenment according to the above description, those skilled in the art in the invention can also be changed and be revised above-mentioned execution mode.Therefore, the present invention is not limited to embodiment disclosed and described above, to modifications and changes more of the present invention, also should be included in the protection range of claim of the present invention.In addition, although used some specific terms in this specification, these terms just for convenience of description, do not form any restriction to the present invention.
Claims (10)
1. a high voltage power battery electrolytic solution, described electrolyte comprises non-aqueous organic solvent, lithium salts and additive, it is characterized in that, also comprises the silicon ether sulfone derivatives meaned by chemical formula (1):
Wherein, R
1,r
2and R
3the alkyl that is respectively aromatic group or contains 1-10 carbon atom, and R
1, R
2and R
3identical or not identical; R
4for the alkyl of 1-10 carbon atom, R
5for alkylene, the mass percent that described silicon ether sulfone derivatives accounts for described electrolyte gross mass is 0.1% ~ 10%.
2. high voltage power battery electrolytic solution according to claim 1, it is characterized in that: the mass percent that described silicon ether sulfone derivatives accounts for described electrolyte gross mass is 0.5% ~ 5%.
3. high voltage power battery electrolytic solution according to claim 2, it is characterized in that: the mass percent that described silicon ether sulfone derivatives accounts for described electrolyte gross mass is 2%.
4. high voltage power battery electrolytic solution according to claim 1, it is characterized in that: described silicon ether sulfone derivatives is the silica-based ethyl vinyl sulfone of trimethoxy, the silica-based methylpropenyl sulfone of trimethoxy, the silica-based propyl group cyclobutenyl of triethoxy sulfone, the silica-based butyl acrylic of tripropoxy sulfone, the silica-based methyl ethylene sulfone of methoxy ethoxy propoxyl group, the silica-based ethyl propylene base of triple phenoxyl sulfone, the silica-based ethyl vinyl sulfone of three benzyloxies or the silica-based allyl ethyl sulfone of dimethoxy phenoxy group.
5. high voltage power battery electrolytic solution according to claim 1, it is characterized in that: described additive is at least two kinds in vinylene carbonate, fluorinated ethylene carbonate and vinylethylene carbonate.
6. high voltage power battery electrolytic solution according to claim 5, it is characterized in that: the mass percent that described additive accounts for described electrolyte gross mass is 1-5%.
7. high voltage power battery electrolytic solution according to claim 1, it is characterized in that: described lithium salts is LiPF
6, LiBF
4, LiAsF
6, LiClO
4, LiBOB, LiDFOB, LiCF
3sO
3, LiC
4f
9sO
3, Li (CF
3sO
2)
2n and Li (C
2f
5sO
2)
2at least one in N, and the concentration of described lithium salts is 0.8-1.7mol/L.
8. high voltage power battery electrolytic solution according to claim 1, it is characterized in that: described non-aqueous organic solvent comprises carbonic ester, described carbonic ester comprises cyclic carbonate and linear carbonate;
Described cyclic carbonate is at least one in ethylene carbonate, propene carbonate and butylene;
Described linear carbonate is at least one in dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, dipropyl carbonate, methyl propyl carbonate, carbonic acid first isopropyl ester, carbonic acid first butyl ester and butylene carbonate;
The mass ratio of described cyclic carbonate and described linear carbonate is 4:1 ~ 1:20.
9. high voltage power battery electrolytic solution according to claim 8, it is characterized in that: described non-aqueous organic solvent also comprises at least one in carboxylate, ether compound and aromatic compound.
10. an electrokinetic cell, comprise electrode assemblie, for the metal shell that holds described electrode assemblie, be injected into the electrolyte in described metal shell and be fixedly connected on the top cover on described metal shell, described electrode assemblie comprise positive plate, negative plate and be interval in described positive plate and described negative plate between barrier film, described positive plate comprises plus plate current-collecting body and is arranged at the anodal diaphragm of described anode collection surface, described anodal diaphragm comprises positive active material, bonding agent and conductive agent, it is characterized in that: described positive active material is LiNi
1-x-yco
xm
yo
2, wherein M is Mn or Al, 0≤x≤1,0≤y≤1,0≤x+y≤1, and described electrolyte is the described high voltage power battery electrolytic solution of claim 1-9 any one.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310017278.5A CN103094613B (en) | 2013-01-17 | 2013-01-17 | High voltage power battery electrolytic solution and comprise the electrokinetic cell of this electrolyte |
Applications Claiming Priority (1)
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| CN106532106A (en) * | 2016-12-21 | 2017-03-22 | 远东福斯特新能源有限公司 | Lithium-ion battery, electrolyte and preparation method of electrolyte |
| CN107069088A (en) * | 2016-12-20 | 2017-08-18 | 中国科学院成都有机化学有限公司 | A kind of linear siloxane additive and its for high-temperature electrolyte of lithium ion battery |
| CN110957528A (en) * | 2018-09-27 | 2020-04-03 | 深圳市比克动力电池有限公司 | Additive for battery electrolyte, lithium ion battery electrolyte and lithium ion battery |
| CN112290092A (en) * | 2020-09-22 | 2021-01-29 | 合肥国轩高科动力能源有限公司 | High-voltage additive and preparation method and application thereof |
| EP3771014A4 (en) * | 2018-03-23 | 2021-11-03 | Tomiyama Pure Chemical Industries, Limited | Nonaqueous electrolyte solution for power storage devices |
| CN113646943A (en) * | 2019-04-29 | 2021-11-12 | 株式会社Lg新能源 | Nonaqueous electrolyte for lithium secondary battery and lithium secondary battery comprising same |
| CN116487708A (en) * | 2023-06-20 | 2023-07-25 | 东莞市楷德精密机械有限公司 | Electrolyte and lithium ion battery using same |
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| CN116487708A (en) * | 2023-06-20 | 2023-07-25 | 东莞市楷德精密机械有限公司 | Electrolyte and lithium ion battery using same |
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