CN103401019A - Silazane additive and lithium ion battery electrolyte prepared by using same and capable of preventing corrosion of steel shell - Google Patents
Silazane additive and lithium ion battery electrolyte prepared by using same and capable of preventing corrosion of steel shell Download PDFInfo
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- CN103401019A CN103401019A CN2013103434949A CN201310343494A CN103401019A CN 103401019 A CN103401019 A CN 103401019A CN 2013103434949 A CN2013103434949 A CN 2013103434949A CN 201310343494 A CN201310343494 A CN 201310343494A CN 103401019 A CN103401019 A CN 103401019A
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- lithium
- ion battery
- additive
- silazane
- battery electrolytes
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 76
- 239000003792 electrolyte Substances 0.000 title claims abstract description 73
- 230000007797 corrosion Effects 0.000 title claims abstract description 55
- 238000005260 corrosion Methods 0.000 title claims abstract description 55
- 239000000654 additive Substances 0.000 title claims abstract description 43
- 230000000996 additive effect Effects 0.000 title claims abstract description 40
- 229910000831 Steel Inorganic materials 0.000 title abstract 5
- 239000010959 steel Substances 0.000 title abstract 5
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 12
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 239000003112 inhibitor Substances 0.000 claims abstract description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 37
- 229910052744 lithium Inorganic materials 0.000 claims description 37
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 33
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 21
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims description 18
- 229910019142 PO4 Inorganic materials 0.000 claims description 18
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 18
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 18
- 239000010452 phosphate Substances 0.000 claims description 18
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 18
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 14
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 11
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 11
- 229960002645 boric acid Drugs 0.000 claims description 11
- 235000010338 boric acid Nutrition 0.000 claims description 11
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims description 11
- 235000006408 oxalic acid Nutrition 0.000 claims description 11
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 10
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 150000002466 imines Chemical class 0.000 claims description 8
- HIMXYMYMHUAZLW-UHFFFAOYSA-N [[[dimethyl(phenyl)silyl]amino]-dimethylsilyl]benzene Chemical compound C=1C=CC=CC=1[Si](C)(C)N[Si](C)(C)C1=CC=CC=C1 HIMXYMYMHUAZLW-UHFFFAOYSA-N 0.000 claims description 7
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- GJWAPAVRQYYSTK-UHFFFAOYSA-N [(dimethyl-$l^{3}-silanyl)amino]-dimethylsilicon Chemical compound C[Si](C)N[Si](C)C GJWAPAVRQYYSTK-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- ZSMNRKGGHXLZEC-UHFFFAOYSA-N n,n-bis(trimethylsilyl)methanamine Chemical compound C[Si](C)(C)N(C)[Si](C)(C)C ZSMNRKGGHXLZEC-UHFFFAOYSA-N 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- DSMUTQTWFHVVGQ-UHFFFAOYSA-N 4,5-difluoro-1,3-dioxolan-2-one Chemical compound FC1OC(=O)OC1F DSMUTQTWFHVVGQ-UHFFFAOYSA-N 0.000 claims description 5
- AVTOEKKTKXLWDL-UHFFFAOYSA-N acetylene;1,3-dioxolan-2-one Chemical group C#C.O=C1OCCO1 AVTOEKKTKXLWDL-UHFFFAOYSA-N 0.000 claims description 5
- 239000001273 butane Substances 0.000 claims description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 claims description 4
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 4
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 3
- JOOMLFKONHCLCJ-UHFFFAOYSA-N N-(trimethylsilyl)diethylamine Chemical group CCN(CC)[Si](C)(C)C JOOMLFKONHCLCJ-UHFFFAOYSA-N 0.000 claims description 3
- GXGDLEBZHWVDTF-UHFFFAOYSA-N 1-[[[butyl(dimethyl)silyl]amino]-dimethylsilyl]butane Chemical compound CCCC[Si](C)(C)N[Si](C)(C)CCCC GXGDLEBZHWVDTF-UHFFFAOYSA-N 0.000 claims description 2
- MHRNQQUEUYMEEH-UHFFFAOYSA-N [[[ethyl(dimethyl)silyl]amino]-dimethylsilyl]ethane Chemical compound CC[Si](C)(C)N[Si](C)(C)CC MHRNQQUEUYMEEH-UHFFFAOYSA-N 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 239000003518 caustics Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 description 37
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 20
- 229910052786 argon Inorganic materials 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 235000015097 nutrients Nutrition 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- QRMHDYCPNIVCBO-UHFFFAOYSA-N [SH2]=N.[F] Chemical compound [SH2]=N.[F] QRMHDYCPNIVCBO-UHFFFAOYSA-N 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- FANANXQSVYPRCQ-UHFFFAOYSA-N azane;silicon Chemical compound N.[Si] FANANXQSVYPRCQ-UHFFFAOYSA-N 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- IDGCBXSROJHVOG-UHFFFAOYSA-N [Li].[SH2]=N.[F] Chemical compound [Li].[SH2]=N.[F] IDGCBXSROJHVOG-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- -1 ethylene carbonate vinylene, vinylene carbonate Chemical compound 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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 specifically relates to a silazane additive and a lithium ion battery electrolyte prepared by using the same and capable of preventing corrosion of a steel shell, belonging to the technical field of additives for lithium ion battery electrolytes. The silazane additive provided by the invention is used as a steel shell corrosion inhibitor in the lithium ion battery electrolyte and can continuously react with moderately strong corrosive substances in the lithium ion battery electrolyte, thereby enabling the steel shell to maintain shining even after long time storage in the lithium ion battery electrolyte. The lithium ion battery electrolyte prepared by using the silazane additive and capable of preventing corrosion of the steel shell is directed at respective physicochemical characteristics of a solvent, a lithium salt and the additive and allows the solvent, the lithium salt and the silazane additive to perform respective advantages and mutually inhibit respective disadvantages after appropriate proportioning of the solvent, the lithium salt and the silazane additive; through the synergistic effect of the solvent, the lithium salt and the silazane additive, the anticorrosion effect of the lithium ion battery electrolyte provided by the invention is far better than that of conventional lithium ion battery electrolytes, and a preparation process for the lithium ion battery electrolyte is simple and easily practicable and has good market prospects.
Description
Technical field
The invention belongs to lithium-ion battery electrolytes additive technology field, be specifically related to the silazane additive and apply the lithium-ion battery electrolytes that prevents the box hat corrosion of its preparation.
Background technology
Lithium ion battery has the advantages such as energy density is high, self-discharge rate is little, environmental protection and is widely used in various electronic equipments.In the production process of lithium ion battery, the battery liquid-filling rear surface inevitably has residual electrolyte and exists, if remaining in the electrolyte of battery surface can not in time wipe or fail to wipe totally, battery produces glove box and is positioned over open environment lower time, residual electrolyte will be rapidly and air reaction generate the deep-etching material, thereby the existence of strong corrosive material will cause the appearance of box hat battery corrosion to cause the battery bad order even to be scrapped.
Prior art mainly reaches by the method for wiping box hat remained on surface electrolyte and by cleaning agent, clean the purpose that prevents electrolyte corrosivity box hat.If but wipe not in time or fluid injection long to the scavenging period interval, corrosion still inevitably produces, and will waste a large amount of manpower and materials.
Existing lithium-ion battery electrolytes additive has the purposes such as the cycle life that improves lithium ion battery and high temperature performance, but does not find that it possesses the purposes that prevents the box hat corrosion.
Therefore, need badly a kind of the deficiencies in the prior art that overcome are provided, provide a kind of and can prevent the additive of box hat corrosion and apply the lithium-ion battery electrolytes of its preparation.
Summary of the invention
, for addressing the above problem, the invention provides a kind of lithium-ion battery electrolytes that prevents the box hat corrosion.
The object of the present invention is achieved like this.
The silazane additive, described silazane additive is as the application of box hat corrosion inhibitor in lithium-ion battery electrolytes.
Wherein, described silazane additive has the described silazane additive of (1) structural formula for comprising,
（1）
Wherein, R
1～R
3For 1～2 hydrocarbon amino that hydrogen atom is replaced by C1～C4 alkyl in methyl, ethyl, propyl group, butyl, the tert-butyl group, phenyl, vinyl, amino or amino; R
4～R
5The hydrocarbon that is replaced by C1～C4 alkyl for 1～2 hydrogen atom in hydrogen atom, methyl, ethyl, propyl group, butyl, the tert-butyl group, phenyl, vinyl, amino or amino is amino or have
The described group of structural formula (2),
（2）
Wherein, R
6～R
8For 1～2 hydrocarbon amino that hydrogen atom is replaced by C1～C4 alkyl in methyl, ethyl, propyl group, butyl, the tert-butyl group, phenyl, vinyl, amino or amino.
Wherein, described silazane additive is for comprising the two or more described silazane additives of structural formula (1) that have.
Wherein, described silazane additive is TMSDEA, tetramethyl-disilazane, hexamethyldisiloxane, heptamethyldisilazane, 1,3-diethyl-1,1,3,3-tetramethyl-disilazane, 1,3-diphenyl tetramethyl-disilazane, 1,3-two (tert-butyl group is amino)-2-tert-butyl group disilazane, 1,3-dibutyl-1,1,3,3-tetramethyl-disilazane, 1,1,3,3-tetramethyl-1, a kind of or two or more in any proportion the mixtures in 3-divinyl silazane.
The lithium-ion battery electrolytes that prevents the box hat corrosion of applying silicon azane additive preparation, the described lithium-ion battery electrolytes that prevents that box hat from corroding comprises solvent, lithium salts and silazane additive, and described silazane additive accounts for the 0.01wt%～2.00wt% of the lithium-ion battery electrolytes total content that prevents the box hat corrosion.
Wherein, described solvent is two or more mixture in any proportion in dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, propene carbonate, ethylene carbonate, methyl propyl carbonate, gamma-butyrolacton.
Preferably, described solvent accounts for the 83wt%～94.0wt% of the total content of the lithium-ion battery electrolytes that prevents the box hat corrosion.
Wherein, described lithium salts is a kind of or two or more in any proportion the mixtures in lithium hexafluoro phosphate, LiBF4, di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium, two (trimethyl fluoride sulfonyl) imine lithium.
Preferably, described lithium salts accounts for the 5.0wt%～18.0wt% of the total content of the lithium-ion battery electrolytes that prevents the box hat corrosion.
Wherein, described additive also comprises vinylene carbonate, ethylene carbonate vinylene, 1,3-propane sultone, Isosorbide-5-Nitrae-butane sultones, fluorinated ethylene carbonate, difluoroethylene carbonate, 1, a kind of or two or more in any proportion the mixtures in 3-propene sulfonic acid lactone; It accounts for the 1.0wt%～5.0wt% of the total content of the lithium-ion battery electrolytes that prevents the box hat corrosion.
Beneficial effect of the present invention is:Silazane additive of the present invention can be constantly and strong corrosive material reaction in lithium-ion battery electrolytes, makes box hat deposit the state that still can keep light for a long time at lithium-ion battery electrolytes; The lithium-ion battery electrolytes that prevents the box hat corrosion of applying silicon azane additive preparation, materialization characteristics separately for solvent, lithium salts and additive, make silazane additive and solvent, lithium salts after suitable proportioning, advantage separately can be brought into play and shortcoming separately can be mutually suppressed again, make anticorrosion ability of the present invention be far superior to prior art by the synergy between the three, and preparation technology of the present invention is simple and easy to and implements, and has market prospects preferably.
Embodiment
The invention will be further described below by embodiment, but practical range of the present invention is not limited to this.
Comparative Examples.
Be full of the glove box (moisture＜10ppm of argon gas, in nutrient＜1ppm), get the organic mixed solution of dimethyl carbonate, methyl ethyl carbonate, ethylene carbonate that accounts for lithium-ion battery electrolytes gross mass 86.0%, the mass ratio of dimethyl carbonate, methyl ethyl carbonate, ethylene carbonate is 1:1:1, add the vinylene carbonate that accounts for lithium-ion battery electrolytes gross mass 2.0% in mixed solution, slowly add the lithium hexafluoro phosphate that accounts for lithium-ion battery electrolytes gross mass 12.0% in the most backward mixed solution, obtain the lithium-ion battery electrolytes of Comparative Examples after stirring.
Embodiment 1.
be full of the glove box (moisture＜10ppm of argon gas, in nutrient＜1ppm), get the dimethyl carbonate that accounts for the lithium-ion battery electrolytes gross mass 85.0% that prevents the box hat corrosion, methyl ethyl carbonate, the organic mixed solution of ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate, the mass ratio of ethylene carbonate is 1:1:1, add in mixed solution and account for gross mass 2.0% vinylene carbonate, slowly add the lithium hexafluoro phosphate that accounts for gross mass 12.0% in mixed solution, being stirred to lithium hexafluoro phosphate dissolves fully, add the hexamethyldisiloxane that accounts for gross mass 1.0% to obtain the lithium-ion battery electrolytes that prevents the box hat corrosion of embodiment 1 in the most backward mixed solution.
Embodiment 2.
be full of the glove box (moisture＜10ppm of argon gas, in nutrient＜1ppm), get the methyl ethyl carbonate that accounts for the lithium-ion battery electrolytes gross mass 85.0% that prevents the box hat corrosion, the organic mixed solution of ethylene carbonate, methyl ethyl carbonate, the mass ratio of ethylene carbonate is 7:3, add in mixed solution and account for gross mass 2.0% ethylene carbonate vinylene and 1, the mixture of 3-propane sultone, the ethylene carbonate vinylene, 1, the mass ratio of 3-propane sultone is 1:1, slowly add the LiBF4 that accounts for gross mass 12.0% in mixed solution, being stirred to LiBF4 dissolves fully, add the heptamethyldisilazane that accounts for gross mass 1.0% in the most backward mixed solution, 1, 3-butyl-1, 1, 3, the 3-tetramethyl-disilazane, 1, 1, 3, 3-tetramethyl-1, the mixture of 3-divinyl silazane, heptamethyldisilazane, 1, 3 dibutyl-1, 1, 3, the 3-tetramethyl-disilazane, 1, 1, 3, 3-tetramethyl-1, the mass ratio of 3-divinyl silazane is 1:2:2, obtain the lithium-ion battery electrolytes that prevents the box hat corrosion of embodiment 2.
Embodiment 3.
(in moisture＜10ppm, nutrient＜1ppm), get the dimethyl carbonate that accounts for the lithium-ion battery electrolytes gross mass 85.0% that prevents the box hat corrosion being full of the glove box of argon gas, diethyl carbonate, methyl ethyl carbonate, propene carbonate, the organic mixed solution of ethylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, propene carbonate, the mass ratio of ethylene carbonate is 1:1:1:0.5:1.5, adds the Isosorbide-5-Nitrae that accounts for gross mass 2.0%-butane sultones in mixed solution, slowly adds the di-oxalate lithium borate that accounts for gross mass 12.0% in mixed solution, difluorine oxalic acid boracic acid lithium, the mixture of two (trimethyl fluoride sulfonyl) imine lithium, di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium, the mass ratio of two (trimethyl fluoride sulfonyl) imine lithium is 1:2:1, is stirred to di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium, the mixture of two (trimethyl fluoride sulfonyl) imine lithium dissolves fully, adds the tetramethyl-disilazane that accounts for gross mass 1.0% in the most backward mixed solution, hexamethyldisiloxane, heptamethyldisilazane, 1,3-diethyl-1,1,3, the mixture of 3-tetramethyl-disilazane, tetramethyl-disilazane, hexamethyldisiloxane, heptamethyldisilazane, 1,3-diethyl-1,1,3, the mass ratio of 3-tetramethyl-disilazane is 2:1.5:0.5:1, obtains the lithium-ion battery electrolytes that prevents the box hat corrosion of embodiment 3.
Embodiment 4.
be full of the glove box (moisture＜10ppm of argon gas, in nutrient＜1ppm), get the dimethyl carbonate that accounts for the lithium-ion battery electrolytes gross mass 85.0% that prevents the box hat corrosion, methyl ethyl carbonate, the organic mixed solution of ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate, the mass ratio of ethylene carbonate is 1:1:1, add in mixed solution and account for gross mass 2.0% vinylene carbonate, slowly add the lithium hexafluoro phosphate that accounts for gross mass 12.0% in mixed solution, being stirred to lithium hexafluoro phosphate dissolves fully, add in the most backward mixed solution 1.0% 1, 3-diethyl-1, 1, 3, the 3-tetramethyl-disilazane obtains the lithium-ion battery electrolytes that prevents the box hat corrosion of embodiment 4.
Embodiment 5.
be full of the glove box (moisture＜10ppm of argon gas, in nutrient＜1ppm), get the dimethyl carbonate that accounts for the lithium-ion battery electrolytes gross mass 85.0% that prevents the box hat corrosion, methyl ethyl carbonate, the organic mixed solution of ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate, the mass ratio of ethylene carbonate is 1:1:1, add in mixed solution and account for gross mass 2.0% vinylene carbonate, slowly add the lithium hexafluoro phosphate that accounts for gross mass 12.0% in mixed solution, being stirred to lithium hexafluoro phosphate dissolves fully, add in the most backward mixed solution 1.0% 1, 3-diphenyl tetramethyl-disilazane obtains the lithium-ion battery electrolytes that prevents the box hat corrosion of embodiment 5.
Embodiment 6.
(in moisture＜10ppm, nutrient＜1ppm), get the dimethyl carbonate that accounts for the lithium-ion battery electrolytes gross mass 93.0% that prevents the box hat corrosion being full of the glove box of argon gas, ethylene carbonate, the organic mixed solution of gamma-butyrolacton, dimethyl carbonate, ethylene carbonate, the gamma-butyrolacton mass ratio is 2:1:2, adds in mixed solution and accounts for 1 of gross mass 1.9%, the 3-propane sultone, Isosorbide-5-Nitrae-butane sultones, fluorinated ethylene carbonate, the mixture of difluoroethylene carbonate, 1,3-propane sultone, Isosorbide-5-Nitrae-butane sultones, fluorinated ethylene carbonate, the mass ratio of difluoroethylene carbonate is 1:0.2:0.3:0.5, slowly adds the lithium hexafluoro phosphate that accounts for gross mass 5% in mixed solution, LiBF4, the mixture of di-oxalate lithium borate, lithium hexafluoro phosphate, LiBF4, the mass ratio of di-oxalate lithium borate is 1.5:2.5:1, is stirred to lithium hexafluoro phosphate, LiBF4, di-oxalate lithium borate dissolves fully, add in the most backward mixed solution 0.1% 1,3-dibutyl-1,1,3, the 3-tetramethyl-disilazane, obtain the lithium-ion battery electrolytes that prevents box hat corrosion of embodiment 6.
Embodiment 7.
be full of the glove box (moisture＜10ppm of argon gas, in nutrient＜1ppm), get the methyl ethyl carbonate that accounts for the lithium-ion battery electrolytes gross mass 83.0% that prevents the box hat corrosion, ethylene carbonate, methyl ethyl carbonate, the ethylene carbonate mass ratio is that then 7:3 adds and account for gross mass 1.0% difluoroethylene carbonate and account for gross mass 0.5%1, 3-propene sulfonic acid lactone, slowly add the difluorine oxalic acid boracic acid lithium that accounts for gross mass 15.0% in mixed solution, two (trimethyl fluoride sulfonyl) imine lithium, two fluorine sulfimide lithium mixtures, difluorine oxalic acid boracic acid lithium, two (trimethyl fluoride sulfonyl) imine lithium, the mass ratio of two fluorine sulfimide lithiums is 5:7:3, be stirred to difluorine oxalic acid boracic acid lithium, two (trimethyl fluoride sulfonyl) imine lithium, two fluorine sulfimide lithiums dissolve fully, add in the most backward mixed solution and account for 1 of gross mass 0.5%, 1, 3, 3-tetramethyl-1, 3 divinyl silazane, 1, 3-diphenyl tetramethyl-disilazane, 1, the mixture of 3-two (tert-butyl group is amino)-2-tert-butyl group disilazane, 1, 1, 3, 3-tetramethyl-1, 3 divinyl silazane, 1, 3-diphenyl tetramethyl-disilazane, 1, the mass ratio of 3-two (tert-butyl group is amino)-2-tert-butyl group disilazane is 2:1:2, obtain the lithium-ion battery electrolytes that prevents the box hat corrosion of embodiment 7.
Embodiment 8.
(in moisture＜10ppm, nutrient＜1ppm), get the dimethyl carbonate that accounts for the lithium-ion battery electrolytes gross mass 88.0% that prevents the box hat corrosion being full of the glove box of argon gas, methyl propyl carbonate, the organic mixed solution of ethylene carbonate, dimethyl carbonate, methyl propyl carbonate, the ethylene carbonate mass ratio is 3:3:4, adds the vinylene carbonate that accounts for gross mass 2.0% in mixed solution, the mixture of ethylene carbonate vinylene, vinylene carbonate, the mass ratio of ethylene carbonate vinylene is 1:1, slowly adds the lithium hexafluoro phosphate that accounts for gross mass 8.0% in mixed solution, LiBF4, di-oxalate lithium borate, the mixture of difluorine oxalic acid boracic acid lithium, lithium hexafluoro phosphate, LiBF4, di-oxalate lithium borate, the mass ratio of difluorine oxalic acid boracic acid lithium is 2:1:3:2, is stirred to lithium hexafluoro phosphate, LiBF4, di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium dissolves fully, adds the tetramethyl-disilazane that accounts for gross mass 2% in the most backward mixed solution, hexamethyldisiloxane, 1,3-diethyl-1,1,3, the 3-tetramethyl-disilazane, 1,3-diphenyl tetramethyl-disilazane, the mixture of 1,3-two (tert-butyl group is amino)-2-tert-butyl group disilazane, tetramethyl-disilazane, hexamethyldisiloxane, 1,3-diethyl-1,1,3, the 3-tetramethyl-disilazane, 1,3-diphenyl tetramethyl-disilazane, the mass ratio of 1,3-two (tert-butyl group is amino)-2-tert-butyl group disilazane is 1:2.5:3:1.5:2, obtains the lithium-ion battery electrolytes that prevents the box hat corrosion of embodiment 8.
Embodiment 9.
be full of the glove box (moisture＜10ppm of argon gas, in nutrient＜1ppm), get the dimethyl carbonate that accounts for the lithium-ion battery electrolytes gross mass 90.0% that prevents the box hat corrosion, methyl ethyl carbonate, the organic mixed solution of ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate, the mass ratio of ethylene carbonate is 1:1:1, add in mixed solution and account for gross mass 4.7% vinylene carbonate, slowly add the lithium hexafluoro phosphate that accounts for gross mass 5.0% in mixed solution, the mixture of two fluorine sulfimide lithiums, lithium hexafluoro phosphate, the mass ratio of two fluorine sulfimide lithiums is 2:3, be stirred to lithium hexafluoro phosphate, two fluorine sulfimide lithiums dissolve fully, add 0.3% TMSDEA in the most backward mixed solution, obtain the lithium-ion battery electrolytes that prevents the box hat corrosion of embodiment 9.
18650 lithium ion battery box hats are weighed in the lithium-ion battery electrolytes that prevents the box hat corrosion of the rear lithium-ion battery electrolytes that immerses respectively above-mentioned Comparative Examples and embodiment 1 ~ 9, the lithium-ion battery electrolytes that prevents the box hat corrosion of the lithium-ion battery electrolytes of 18650 lithium ion battery box hats, Comparative Examples and embodiment 1 ~ 9 opens wide and is positioned under room temperature environment, observe 18650 lithium ion battery box hat situations after 7 hours and 96 hours, result is as shown in table 1; After 96 hours, 18650 lithium ion battery box hats are cleaned oven dry and weigh, calculate the rate of weight loss of 18650 lithium ion battery box hats, result is as shown in table 2.
Table 1
| Numbering | 7 hours corrosion conditions | 96 hours corrosion conditions |
| Comparative Examples | Slightly | Seriously |
| Embodiment 1 | Nothing | Nothing |
| Embodiment 2 | Nothing | Nothing |
| Embodiment 3 | Nothing | Slightly |
| Embodiment 4 | Nothing | Nothing |
| Embodiment 5 | Nothing | Slightly |
| Embodiment 6 | Nothing | Nothing |
| Embodiment 7 | Nothing | Nothing |
| Embodiment 8 | Nothing | Nothing |
| Embodiment 9 | Nothing | Slightly |
Table 2
| Numbering | Front heavy | Rear heavy | Rate of weight loss/% |
| Comparative Examples | 7.3525 | 7.0905 | 3.563 |
| Embodiment 1 | 7.7598 | 7.7585 | 0.017 |
| Embodiment 2 | 7.7429 | 7.7420 | 0.012 |
| Embodiment 3 | 7.7598 | 7.7542 | 0.072 |
| Embodiment 4 | 7.6628 | 7.6616 | 0.016 |
| Embodiment 5 | 7.2497 | 7.2412 | 0.117 |
| Embodiment 6 | 7.7110 | 7.7085 | 0.033 |
| Embodiment 7 | 7.3968 | 7.3958 | 0.014 |
| Embodiment 8 | 7.7318 | 7.7296 | 0.029 |
| Embodiment 9 | 7.3535 | 7.3486 | 0.066 |
Can see from the result of table 1, table 2, the lithium-ion battery electrolytes that prevents the box hat corrosion of the embodiment of the present invention 1 ~ 9 will be significantly less than the corrosion of the lithium-ion battery electrolytes of Comparative Examples to box hat to the corrosion of 18650 box hats.
Hence one can see that, of the present inventionly prevents that the anticorrosion ability of the lithium-ion battery electrolytes of box hat corrosion is far superior to the lithium-ion battery electrolytes of prior art.
The above is only preferred embodiments of the present invention,, therefore all equivalences of doing according to the described structure of patent claim of the present invention, feature and principle change or modify, is included in patent claim of the present invention.
Claims (10)
1. silazane additive, it is characterized in that: described silazane additive is as the application of box hat corrosion inhibitor in lithium-ion battery electrolytes.
2. silazane additive according to claim 1, it is characterized in that: described silazane additive has the described silazane additive of (1) structural formula for comprising,
（1）
Wherein, R
1～R
3For 1～2 hydrocarbon amino that hydrogen atom is replaced by C1～C4 alkyl in methyl, ethyl, propyl group, butyl, the tert-butyl group, phenyl, vinyl, amino or amino; R
4～R
5The hydrocarbon that is replaced by C1～C4 alkyl for 1～2 hydrogen atom in hydrogen atom, methyl, ethyl, propyl group, butyl, the tert-butyl group, phenyl, vinyl, amino or amino is amino or have
The described group of structural formula (2),
（2）
Wherein, R
6～R
8For 1～2 hydrocarbon amino that hydrogen atom is replaced by C1～C4 alkyl in methyl, ethyl, propyl group, butyl, the tert-butyl group, phenyl, vinyl, amino or amino.
3. silazane additive according to claim 1, it is characterized in that: described silazane additive is for comprising the two or more described silazane additives of structural formula (1) that have.
4. silazane additive according to claim 1, it is characterized in that: described silazane additive is TMSDEA, tetramethyl-disilazane, hexamethyldisiloxane, heptamethyldisilazane, 1,3-diethyl-1,1,3,3-tetramethyl-disilazane, 1,3-diphenyl tetramethyl-disilazane, 1,3-two (tert-butyl group is amino)-2-tert-butyl group disilazane, 1,3-dibutyl-1,1,3,3-tetramethyl-disilazane, 1,1,3,3-tetramethyl-1, a kind of or two or more in any proportion the mixtures in 3-divinyl silazane.
5. application rights requires the lithium-ion battery electrolytes that prevents the box hat corrosion of the silazane additive preparation of 1 ~ 4 any one, it is characterized in that: the described lithium-ion battery electrolytes that prevents that box hat from corroding comprises solvent, lithium salts and silazane additive, and described silazane additive accounts for the 0.01wt%～2.00wt% of the lithium-ion battery electrolytes total content that prevents the box hat corrosion.
6. the lithium-ion battery electrolytes that prevents box hat corrosion according to claim 5, it is characterized in that: described solvent is two or more mixture in any proportion in dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, propene carbonate, ethylene carbonate, methyl propyl carbonate, gamma-butyrolacton.
7. the lithium-ion battery electrolytes that prevents box hat corrosion according to claim 5, it is characterized in that: described solvent accounts for the 83wt%～94.0wt% of the total content of the lithium-ion battery electrolytes that prevents the box hat corrosion.
8. the lithium-ion battery electrolytes that prevents box hat corrosion according to claim 5 is characterized in that: described lithium salts is a kind of or two or more in any proportion the mixtures in lithium hexafluoro phosphate, LiBF4, di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium, two (trimethyl fluoride sulfonyl) imine lithium.
9. the lithium-ion battery electrolytes that prevents box hat corrosion according to claim 5, it is characterized in that: described lithium salts accounts for the 5.0wt%～18.0wt% of the total content of the lithium-ion battery electrolytes that prevents the box hat corrosion.
10. the described lithium-ion battery electrolytes that prevents box hat corrosion of according to claim 5～8 any one, it is characterized in that: described additive also comprises vinylene carbonate, ethylene carbonate vinylene, 1,3-propane sultone, 1,4-butane sultones, fluorinated ethylene carbonate, difluoroethylene carbonate, 1, a kind of or two or more in any proportion the mixtures in 3-propene sulfonic acid lactone; It accounts for the 1.0wt%～5.0wt% of the total content of the lithium-ion battery electrolytes that prevents the box hat corrosion.
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