CN102569890A - Lithium ion secondary battery and electrolyte thereof - Google Patents
Lithium ion secondary battery and electrolyte thereof Download PDFInfo
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- CN102569890A CN102569890A CN2012100310583A CN201210031058A CN102569890A CN 102569890 A CN102569890 A CN 102569890A CN 2012100310583 A CN2012100310583 A CN 2012100310583A CN 201210031058 A CN201210031058 A CN 201210031058A CN 102569890 A CN102569890 A CN 102569890A
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Abstract
The invention, belonging to the technical field of lithium ion secondary battery, particularly relates to an electrolyte for a lithium ion secondary battery, comprising a non-aqueous solvent, lithium salts and additives, wherein the additives comprise a fluorinated cyclotriphosphazene derivative of formula (I), R1 represents aromatic group or aromatic group containing halogen substituent group, R2 represents alkyl, alkylene or halogen substituted alkyl, alkylene, R3 represents hydrogen, halogen, alkyl or alkyloxy, halogenated alkyl groups or halogenated alkyloxy, and the fluorinated cyclotriphosphazene derivative accounts for 0.1-20 wt% of the total weight of the electrolyte. Compared with the prior art, by using the fire resistance function of fluorinated cyclotriphosphazene derivative, the decomposition of the electrolyte on the anode surface can be effectively prevented, the decomposition and gas generation of the electrolyte are reduced, and the high temperature storage thickness expansion ratio of the battery is greatly reduced. In addition, the invention further discloses a lithium ion secondary battery containing the electrolyte.
Description
Technical field
The invention belongs to technical field of lithium ion secondary, relate in particular to a kind of electrolyte that can significantly improve the lithium rechargeable battery high-temperature storage performance, have excellent thermal stability, and the lithium ion battery that comprises this electrolyte.
Background technology
Lithium rechargeable battery can be described as state-of-the-art in the world at present commercialization secondary cell, along with the development of various electronic products, on the market demand as the lithium rechargeable battery of the energy supply element of these electronic products is presented the situation that increases rapidly.And, make it obtain application, like power vehicle, electric bicycle and energy-accumulating power station etc. in growing field because lithium rechargeable battery has high discharge voltage, high-energy-density and good plurality of advantages such as low self-discharge characteristic.
The production process of lithium rechargeable battery generally comprises stirring, is coated with, colds pressing, reels, changes into and capacity etc.; Wherein, The purpose of formation process is solid electrolyte film (SEI film) densification in order to form stable at the anode membrane surface, and this SEI film only allows lithium ion to pass through.The SEI film can effectively be protected anode material, makes it avoid the destruction of the solvent molecule (like ethylene carbonate, propylene carbonate ester, diethyl carbonate, methyl ethyl carbonate and dimethyl carbonate etc.) in the electrolyte.Yet in the forming process and the use at battery of SEI film, the solvent in the electrolyte can decompose, and produces CO
2, CO, CH
4, C
2H
2, C
2H
4, C
2H
6, C
3H
6, C
3H
8Deng gas, and LiF, Li
2CO
3, ROCO
2Solid matters such as Li cause cell thickness to expand, and serious if aerogenesis expands, even possibly cause danger such as battery explosion.In addition, battery uses under hot conditions or stores, or long-term under the situation that sunlight is exposed to the sun, use or during storage; The SEI film of battery will be destroyed; Electrolyte and anode/cathode reaction then with reparation SEI film, thereby produces a large amount of gas; Cause the expansion of cell thickness, and then possibly cause danger such as battery explosion.Therefore, necessary a kind of electrolyte with excellent thermal stability is provided.
In order to address the above problem; Application number is that 200910133674.8 Chinese patent proposes to use trimerization to fluoridize phosphonitrile as improving the additive that battery high-temperature expands; But its effect is very desirable, even be not too obvious to the thickness swelling improvement effect under 60 ℃.
In view of this, the necessary electrolyte solution for lithium ion secondary battery that provides a kind of and can significantly improve the lithium rechargeable battery high-temperature storage performance, has excellent thermal stability, and the lithium rechargeable battery that comprises this electrolyte.
Summary of the invention
One of the object of the invention is: to the deficiency of prior art, and the electrolyte solution for lithium ion secondary battery that provides a kind of and can significantly improve the lithium rechargeable battery high-temperature storage performance, have excellent thermal stability.
In order to achieve the above object, the present invention adopts following technical scheme:
A kind of electrolyte solution for lithium ion secondary battery comprises nonaqueous solvents, lithium salts and additive, and said additive comprises that fluoridizing of formula (I) expression encircles three phosphazene derivatives:
Formula (I)
Wherein, R
1For aromatic group or contain the aromatic group of halogenic substituent, R
2Be the substituted alkyl of alkyl, alkylene or halogen, alkylene, R
3Be hydrogen, halogen, alkyl or alkoxyl, haloalkyl or halogenated alkoxy, said to fluoridize the mass percent that ring three phosphazene derivatives account for the electrolyte gross mass be 0.1wt%～20wt%.
As a kind of improvement of electrolyte solution for lithium ion secondary battery of the present invention, said to fluoridize the mass percent that ring three phosphazene derivatives account for the electrolyte gross mass be 1wt%～10wt%.
As a kind of improvement of electrolyte solution for lithium ion secondary battery of the present invention, said to fluoridize the mass percent that ring three phosphazene derivatives account for the electrolyte gross mass be 3wt%.
As a kind of improvement of electrolyte solution for lithium ion secondary battery of the present invention, said fluoridize the ring three phosphazene derivatives be 2,4; 6-three fluoro-2-phenoxy groups-4; 6-dipropoxy-ring three phosphonitriles or 2,4,6-three fluoro-2-(3-4-trifluoromethylphenopendant)-6-ethyoxyl-ring three phosphonitriles.
As a kind of improvement of electrolyte solution for lithium ion secondary battery of the present invention, said additive also comprises vinylene carbonate, vinylethylene carbonate, fluorinated ethylene carbonate, 1, in the 3-propane sultone at least two kinds.
As a kind of improvement of electrolyte solution for lithium ion secondary battery of the present invention, the mass percent that the total weight of said additive accounts for the electrolyte gross mass is 1wt%～30wt%.
As a kind of improvement of electrolyte solution for lithium ion secondary battery of the present invention, said nonaqueous solvents comprises at least a in carbonic ester, carboxylate, ether compound and the aromatic compound.
As a kind of improvement of electrolyte solution for lithium ion secondary battery of the present invention, said carbonic ester comprises cyclic carbonate and linear carbonate, and the mass ratio of said cyclic carbonate and linear carbonate is 3: 1～1: 10.
A kind of improvement as electrolyte solution for lithium ion secondary battery of the present invention; Said cyclic carbonate is at least a in ethylene carbonate, propene carbonate, the butylene, and said linear carbonate is at least a in dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, dipropyl carbonate, carbonic acid first propyl ester, carbonic acid first isopropyl ester, carbonic acid first butyl ester, the butylene carbonate.
Said carboxylate comprises non-substituted carboxylic acid ester and halogenated carboxylic ester.Non-substituted carboxylic acid ester is selected from: at least a 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 the caprolactone; Halogenated carboxylic ester is selected from: 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, 3; 3, at least a in the 3-trifluoroacetic acid ethyl ester.
Described ether compound comprises non-substituent ether compound and halogen ether compounds, and said non-substituent ether compound is selected from: one or more in butyl oxide, dimethoxymethane, dimethoxy-ethane, diethoxymethane, diethoxyethane, oxolane, the dimethyl-tetrahydrofuran; The halogen ether compounds is selected from: single fluorine dimethoxymethane, single fluorine dimethoxy-ethane, single fluorine diethoxymethane, single fluorine diethoxyethane.
Described aromatic compound is selected from: toluene, fluorobenzene, adjacent fluorotoluene, benzotrifluoride, 4-toluene fluoride, to fluorine methoxybenzene, adjacent fluorine methoxybenzene, adjacent difluoromethoxy phenyl, 1-fluoro-4-tert-butyl benzene, fluorodiphenyl.
Said lithium salts is selected from LiPF
6, LiBF
4, LiAsF
6, LiClO
4, LiBOB (dioxalic acid lithium borate), LiDFOB (difluorine oxalic acid boracic acid lithium), LiCF
3SO
3, LiC
4F
9SO
3, Li (CF
3SO
2)
2N and Li (C
2F
5SO
2)
2At least a among the N etc.The molar concentration of lithium salts is 0.85mol/L～1.3mol/L.
With respect to prior art; Beneficial effect of the present invention is: ring three phosphazene derivatives of fluoridizing that the present invention adopts have fire-retardant function, containing substituting groups such as oxygen aromatic group or alkoxyl and can effectively promote to fluoridize the acid HF in the ring three phosphonitrile Electolyte-absorptives wherein, and promote to fluoridize ring three phosphonitriles and at high temperature form fine and close SEI film at anode surface; Thereby imitate and prevent that metal ion is (like Mn in the active material of cathode; Fe, the Ni plasma) in the anode surface deposition, effectively stop the decomposition of electrolyte at anode surface; Reduce the decomposition and the aerogenesis of electrolyte, significantly reduce the high temperature storage thickness swelling of battery.
Than hexafluoro ring three phosphonitriles; Contain substituting groups such as oxygen aromatic group or alkoxyl and replaced the part fluorine element; Broken the fluoridized symmetrical structure of fluoridizing ring three phosphonitriles, made it be easier to form free radical, be easier to form fine and close more SEI film at anode surface; Therefore, of the present invention fluoridize ring three phosphazene derivatives than hexafluoro ring three phosphonitriles to the high-temperature storage performance of lithium rechargeable battery to improve effect more remarkable.
Another object of the present invention is to provide a kind of lithium rechargeable battery, and comprise cathode sheets, anode strip, be interval in the barrier film between cathode sheets and the anode strip, and electrolyte, said electrolyte is the described electrolyte solution for lithium ion secondary battery of above-mentioned paragraph.
Wherein, the active material that adopts in the cathode sheets is selected from least a in the following material:
LiCoO
2, LiNiO
2, LiNi
1-x-yCo
xM
yO
2, wherein M is Mn or Al, 0≤x≤1,0≤y≤1,0≤x+y≤1; LiFePO
4, LiVPO
4, LiMnPO
4, LiFe
1-a-bV
aMn
bPO
4, wherein, 0≤a≤1,0≤b≤1,0≤a+b≤1; Li
2FeSiO
4, Li
2MnSiO
4, Li
2Fe
2Mn
1-zSiO
4, wherein, 0＜z＜1.
Active material in the anode strip is selected from least a in the following material:
Graphite-based material: native graphite, Delanium, hard carbon, soft carbon and amorphous graphite etc.; Alloy anode materials such as Sn, Si base; Lithium titanate.
Barrier film is polyethylene (PE), polypropylene (PP) or PP/PE/PP composite diaphragm, or surperficial PE, PP or the PP/PE/PP composite diaphragm that adopts ceramic powder or Kynoar (PVDF) or polymethyl methacrylate (PMMA) etc. to handle.
With respect to prior art, lithium ion battery of the present invention also has excellent high-temperature storage performance when having excellent cycle performance.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but execution mode of the present invention is not limited thereto.
Embodiment 1
The preparation of cathode sheets:
With positive active material cobalt acid lithium (LiCoO
2), conductive carbon (Super-P) and Kynoar (PVDF) be blended in the solvent according to 95: 2: 3 mass ratio, stirs, and obtains cathode slurry.Slurry is coated on the aluminium foil of 9 μ m, drying is colded pressing, and obtaining compacted density is 1.6g/cm
3Pole piece, pass through cut-parts, soldering polar ear again, obtain cathode sheets.
The preparation of anode strip:
Negative electrode active material native graphite, conductive carbon (Super-P) and sodium carboxymethylcellulose (CMC) mass ratio according to 95: 2: 3 is blended in the solvent, stirs, obtain anode slurry.Slurry is coated on the Copper Foil of 9 μ m, drying is colded pressing, and obtaining compacted density is 1.7g/cm
3Pole piece, pass through cut-parts, soldering polar ear again, obtain anode strip.
It is polypropylene (PP) perforated membrane of 16 μ m that barrier film adopts thickness.
The preparation of electrolyte:
Nonaqueous solvents ethylene carbonate, diethyl carbonate, propene carbonate are mixed by mass ratio at 1: 2: 1, leave standstill 30min, add mass percent then and be 2% and 3% vinylethylene carbonate and fluorinated ethylene carbonate, add lithium salts LiPF again
6, it is fully dissolved, and makes LiPF
6Concentration be 1M.Add 2,4 at last, 6-three fluoro-2-phenoxy groups-4,6-dipropoxy-ring three phosphonitriles, making its quality percentage composition in electrolyte is 1%, mixes, and promptly accomplishes the preparation of electrolyte.
The preparation of lithium ion battery:
The cathode sheets that obtains, anode strip and barrier film are wound into electric core in order, with electric core closedtop and side seal, stay liquid injection port with aluminium plastic membrane.Then from liquid injection port perfusion electrolyte, again through changing into, operation such as capacity makes lithium ion battery.
Embodiment 2
Different with embodiment 1 is that positive active material is nickle cobalt lithium manganate (LiNi
0.4Co
0.3Mn
0.3O
2) and lithium nickelate (LiNiO
2) mixture, the mass ratio of the two is 1: 1; Negative electrode active material is the mixture of hard carbon and soft carbon, and the mass ratio of the two is 3: 1; It is polyethylene (PE) perforated membrane of 16 μ m that barrier film adopts thickness.
The preparation of electrolyte is following:
With nonaqueous solvents butylene, dimethyl carbonate, Ethyl formate and fluorobenzene by mass ratio 3: 1: 0.1: 0.2 mixes; Leave standstill 30min; Add mass percent then and be 2% and 3% 1; 3-propane sultone and vinylene carbonate add lithium salts (difluorine oxalic acid boracic acid lithium (LiDFOB) and LiBF again
4Mixture, the mass ratio of the two is 4: 1), it is fully dissolved, and to make the concentration of lithium salts be 0.85M.Add people 2,4 at last, 6-three fluoro-2-(3-4-trifluoromethylphenopendant)-6-ethyoxyl-ring three phosphonitriles, making its quality percentage composition in electrolyte is 10%, mixes, and promptly accomplishes the preparation of electrolyte.
All the other repeat no more with embodiment 1 here.
Embodiment 3
Different with embodiment 1 is that positive active material is LiFePO4 (LiFePO
4) and phosphoric acid vanadium lithium (LiVPO
4) mixture, the mass ratio of the two is 6: 1; Negative electrode active material is an elementary silicon; It is the PP/PE/PP composite membrane of 20 μ m that barrier film adopts thickness.
The preparation of electrolyte is following:
With nonaqueous solvents propene carbonate, methyl ethyl carbonate, 3; 3-difluoro methyl propionate and oxolane were by mass ratio 2: 10: 0.5: 0.5 mixes, and leaves standstill 30min, add mass percent then and be 4% and 5% 1; 3-propane sultone and fluorinated ethylene carbonate; Add Lithium Salt LiBOB again, it is fully dissolved, and to make the concentration of lithium salts be 1.3M.Add 2,4 at last, 6-three fluoro-2-(3-4-trifluoromethylphenopendant)-4-chloro-6-methoxyl group-ring three phosphonitriles, making its quality percentage composition in electrolyte is 20%, mixes, and promptly accomplishes the preparation of electrolyte.
All the other repeat no more with embodiment 1 here.
Embodiment 4
Different with embodiment 1 is that positive active material is LiFePO4 (LiFePO
4) and ferric metasilicate lithium (Li
2FeSiO
4) mixture, the mass ratio of the two is 3: 1; Negative electrode active material is lithium titanate (Li
4Ti
5O
12); Barrier film adopts surface treatment that titanium dioxide (TiO is arranged
2) thickness of ceramic powder is the PP/PE/PP composite membrane of 20 μ m.
The preparation of electrolyte is following:
With nonaqueous solvents ethylene carbonate, carbonic acid first propyl ester, gamma-valerolactone and diethoxymethane by mass ratio 3: 10: 1: 0.5 mixes; Leave standstill 30min; Add mass percent then and be 3% and 1% 1; 3-propane sultone and fluorinated ethylene carbonate add lithium salts (TFMS lithium (LiCF again
3SO
3) and the mixture of LiBOB, the mass ratio of the two is 3: 1), it is fully dissolved, and to make the concentration of lithium salts be 1.1M.Add 2,4 at last, 6-three fluoro-2-methylphenoxy-4-methyl-6-ethyleneoxy-ring three phosphonitriles, making its quality percentage composition in electrolyte is 15%, mixes, and promptly accomplishes the preparation of electrolyte.
All the other repeat no more with embodiment 1 here.
Embodiment 5
Different with embodiment 1 is that positive active material is LiMn2O4 (LiMnO
4) and nickel cobalt lithium aluminate (LiNi
0.4Co
0.4Al
0.2O
2) mixture, the mass ratio of the two is 4: 1; Negative electrode active material is the mixture of native graphite and Delanium, and the mass ratio of the two is 2: 3; It is the PP perforated membrane of 20 μ m that barrier film adopts surface treatment that the thickness of Kynoar (PVDF) is arranged.
The preparation of electrolyte is following:
With nonaqueous solvents propene carbonate, carbonic acid first isopropyl ester, gamma-butyrolacton and single fluorine dimethoxy-ethane by mass ratio 5: 10: 1: 0.1 mixes; Leave standstill 30min; Add mass percent then and be 2% and 2% 1,3-propane sultone and fluorinated ethylene carbonate add lithium salts (LiPF again
6With the mixture of LiBOB, the mass ratio of the two is 2: 1), it is fully dissolved, and to make the concentration of lithium salts be 0.9M.Add 2,4 at last, 6-three fluoro-2-ethyl phenoxy group-4-trifluoromethoxy-6-propenyloxy group-ring three phosphonitriles, making its quality percentage composition in electrolyte is 5%, mixes, and promptly accomplishes the preparation of electrolyte.
All the other repeat no more with embodiment 1 here.
Embodiment 6
Different with embodiment 1 is that positive active material is LiMn2O4 (LiMnO
4) and cobalt acid lithium (LiCoO
2) mixture, the mass ratio of the two is 1: 1; Negative electrode active material is the mixture of soft carbon and Delanium, and the mass ratio of the two is 1: 6; It is the PE perforated membrane of 20 μ m that barrier film adopts surface treatment that the thickness of polymethyl methacrylate (PMMA) is arranged.
The preparation of electrolyte is following:
With nonaqueous solvents ethylene carbonate, carbonic acid first butyl ester, caprolactone and adjacent difluoromethoxy phenyl by mass ratio 2: 1: 0.5: 0.2 mixes; Leave standstill 30min; Add mass percent then and be 1% and 3% 1,3-propane sultone and vinylene carbonate add Lithium Salt LiBOB again; It is fully dissolved, and to make the concentration of lithium salts be 1.2M.Add 2,4 at last, 6-three fluoro-2-n-pro-pyl phenoxy group-4-perfluor ethyoxyl-6-n-butoxy-ring three phosphonitriles, making its quality percentage composition in electrolyte is 3%, mixes, and promptly accomplishes the preparation of electrolyte.
All the other repeat no more with embodiment 1 here.
Embodiment 7
Different with embodiment 1 is that positive active material is LiMn2O4 (LiMnO
4) and nickle cobalt lithium manganate (LiNi
0.5Co
0.3Mn
0.2O
2) mixture, the mass ratio of the two is 3: 1; Negative electrode active material is the mixture of hard carbon and native graphite, and the mass ratio of the two is 1: 2; It is the PE perforated membrane of 20 μ m that barrier film adopts surface treatment that the thickness of alundum (Al ceramic powders is arranged.
The preparation of electrolyte is following:
With nonaqueous solvents ethylene carbonate, methyl ethyl carbonate, two fluoro ethyl acetate and fluorodiphenyl by mass ratio 2: 1: 0.5: 0.1 mixes; Leave standstill 30min; Add mass percent then and be 1% and 3% 1; 3-propane sultone and vinylene carbonate add lithium salts (LiBOB and the Li (CF of certain mass again
3SO
2)
2The mixture of N, the mass ratio of the two are 4: 1), it is fully dissolved, and to make the concentration of lithium salts be 1M.Add 2,4 at last, 6-three fluoro-2-isopropyl phenoxy group-4-n-pro-pyl-6-methoxyl group-ring three phosphonitriles, making its quality percentage composition in electrolyte is 0.1%, mixes, and promptly accomplishes the preparation of electrolyte.
All the other repeat no more with embodiment 1 here.
Embodiment 8
Different with embodiment 1 is that positive active material is LiMn2O4 (LiMnO
4) and nickel cobalt lithium aluminate (LiNi
0.5Co
0.4Al
0.1O
2) mixture, the mass ratio of the two is 3: 1; Negative electrode active material is a kamash alloy; It is the PE perforated membrane of 20 μ m that barrier film adopts surface treatment that the thickness of alundum (Al ceramic powders is arranged.
The preparation of electrolyte is following:
With nonaqueous solvents ethylene carbonate, methyl ethyl carbonate, two fluoro ethyl acetate and fluorodiphenyl by mass ratio 2: 1: 0.5: 0.1 mixes; Leave standstill 30min; Add mass percent then and be 1% and 3% 1; 3-propane sultone and vinylene carbonate add lithium salts (LiBOB and Li (C again
2F
5SO
2)
2The mixture of N, the mass ratio of the two are 4: 1), it is fully dissolved, and to make the concentration of lithium salts be 1M.Add 2,4 at last, 6-three fluoro-2-isopropyl phenoxy group-4-n-pro-pyl-6-ethyoxyl-ring three phosphonitriles, making its quality percentage composition in electrolyte is 7%, mixes, and promptly accomplishes the preparation of electrolyte.
All the other repeat no more with embodiment 1 here.
Embodiment 9
Different with embodiment 1 is, 2,4, and 6-three fluoro-2-phenoxy groups-4, the 6-dipropoxy-quality percentage composition of ring three phosphonitriles in electrolyte is 2%.
All the other repeat no more with embodiment 1 here.
Embodiment 10
Different with embodiment 1 is, 2,4, and 6-three fluoro-2-phenoxy groups-4, the 6-dipropoxy-quality percentage composition of ring three phosphonitriles in electrolyte is 12%.
All the other repeat no more with embodiment 1 here.
Comparative Examples 1
Different with embodiment 1 is to add in the electrolyte and fluoridize ring three phosphazene derivatives.
All the other repeat no more with embodiment 1 here.
Comparative Examples 2
Different with embodiment 1 is that what to add in the electrolyte is not 2,4,6-three fluoro-2-phenoxy groups-4,6-dipropoxy-ring three phosphonitriles, but hexafluoro ring three phosphonitriles.
All the other repeat no more with embodiment 1 here.
Embodiment 1 to 10 is tested with the lithium rechargeable battery of Comparative Examples 1 and 2 as follows:
The high temperature storage test:
With the battery of preparation in embodiment 1 to 10 and the Comparative Examples 1 and 2, with the multiplying power constant current charge of 0.5C to 4.2V, then at 85 ℃ of held 4h, and 60 ℃ of held 30 days, the thickness swelling of mensuration battery, the result is shown in table 1.
The method of testing of thickness swelling is following
A: thickness before the test; B:85 ℃ of held 4 hours or the thickness of 60 ℃ of held after 30 days
Thickness swelling=(B-A)/A * 100%.
The cycle life test:
At room temperature; With the battery for preparing in embodiment 1 to 10 and the Comparative Examples 1 and 2, to 4.2V, constant voltage charge to electric current is 0.05C then with the multiplying power constant current charge of 0.5C; Use the 0.5C constant current discharge to 3.0V then; So charge/discharge is 300 times, the capability retention of counting cell, and the result is shown in table 1.
The calculating of capability retention:
The capability retention of corresponding circulation=(discharge capacity of corresponding circulation/discharge capacity of circulation) first * 100%
The high temperature storage and the The cyclic lifetime test results of table 1: the embodiment 1 to 10 and the lithium rechargeable battery of comparative example 1 and 2
Can know by table 1; After ring three phosphazene derivatives are fluoridized in interpolation in electrolyte; Can the thickness swelling of 60 ℃ of following storages after 30 days be reduced to from about 15% (seeing Comparative Examples 1) and (see embodiment) below 3%; With 85 ℃ down 4 hours thickness swelling of storage and compare from being reduced to about 12% (seeing embodiment) greater than 80% (seeing Comparative Examples 1) with Comparative Examples 1, the interpolation of fluoridizing ring three phosphazene derivatives does not influence the charge-discharge performance of battery; And with Comparative Examples 2 in add hexafluoro ring three phosphonitriles and compare; Lithium ion battery of the present invention has excellent more high-temperature storage performance; This be because, contain substituting groups such as oxygen aromatic group or alkoxyl and replaced the part fluorine element, broken fluoridized fluoridize the ring three phosphonitriles symmetrical structure; Make it be easier to form free radical; Be easier to form fine and close more SEI film at anode surface, therefore, of the present invention fluoridize ring three phosphazene derivatives than hexafluoro ring three phosphonitriles to the high-temperature storage performance of lithium rechargeable battery to improve effect more remarkable.
According to the announcement and the instruction of above-mentioned specification, those skilled in the art in the invention can also change and revise above-mentioned execution mode.Therefore, the embodiment that discloses and describe above the present invention is not limited to also should fall in the protection range of claim of the present invention modifications more of the present invention and change.In addition, although used some specific terms in this specification, these terms are explanation for ease just, the present invention is not constituted any restriction.
Claims (10)
1. an electrolyte solution for lithium ion secondary battery comprises nonaqueous solvents, lithium salts and additive, it is characterized in that: said additive comprises that fluoridizing of formula (I) expression encircles three phosphazene derivatives:
Formula (I)
Wherein, R
1For aromatic group or contain the aromatic group of halogenic substituent, R
2Be the substituted alkyl of alkyl, alkylene or halogen, alkylene, R
3Be hydrogen, halogen, alkyl or alkoxyl, haloalkyl or halogenated alkoxy, said to fluoridize the mass percent that ring three phosphazene derivatives account for the electrolyte gross mass be 0.1wt%～20wt%.
2. electrolyte solution for lithium ion secondary battery according to claim 1 is characterized in that: said to fluoridize the mass percent that ring three phosphazene derivatives account for the electrolyte gross mass be 1wt%～10wt%.
3. electrolyte solution for lithium ion secondary battery according to claim 2 is characterized in that: said to fluoridize the mass percent that ring three phosphazene derivatives account for the electrolyte gross mass be 3wt%.
4. electrolyte solution for lithium ion secondary battery according to claim 1 is characterized in that: said fluoridize the ring three phosphazene derivatives be 2,4; 6-three fluoro-2-phenoxy groups-4; 6-dipropoxy-ring three phosphonitriles or 2,4,6-three fluoro-2-(3-4-trifluoromethylphenopendant)-6-ethyoxyl-ring three phosphonitriles.
5. electrolyte solution for lithium ion secondary battery according to claim 1 is characterized in that: said additive also comprises vinylene carbonate, vinylethylene carbonate, fluorinated ethylene carbonate, 1, in the 3-propane sultone at least two kinds.
6. electrolyte solution for lithium ion secondary battery according to claim 5 is characterized in that: the mass percent that the total weight of said additive accounts for the electrolyte gross mass is 1wt%～30wt%.
7. electrolyte solution for lithium ion secondary battery according to claim 1 is characterized in that: said nonaqueous solvents comprises at least a in carbonic ester, carboxylate, ether compound and the aromatic compound.
8. electrolyte solution for lithium ion secondary battery according to claim 7 is characterized in that: said carbonic ester comprises cyclic carbonate and linear carbonate, and the mass ratio of said cyclic carbonate and linear carbonate is 3: 1～1: 10.
9. electrolyte solution for lithium ion secondary battery according to claim 8; It is characterized in that: said cyclic carbonate is at least a in ethylene carbonate, propylene carbonate ester, the butylene, and said linear carbonate is at least a in dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, dipropyl carbonate, carbonic acid first propyl ester, carbonic acid first isopropyl ester, carbonic acid first butyl ester, the butylene carbonate.
10. a lithium rechargeable battery comprises cathode sheets, anode strip, is interval in the barrier film between cathode sheets and the anode strip, and electrolyte, it is characterized in that: said electrolyte is 9 each described electrolyte solution for lithium ion secondary battery of claim 1.
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Cited By (27)
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|---|---|---|---|---|
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