CN102082292A - High-temperature lithium ion battery electrolyte and lithium ion battery - Google Patents
High-temperature lithium ion battery electrolyte and lithium ion battery Download PDFInfo
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- CN102082292A CN102082292A CN2010106036189A CN201010603618A CN102082292A CN 102082292 A CN102082292 A CN 102082292A CN 2010106036189 A CN2010106036189 A CN 2010106036189A CN 201010603618 A CN201010603618 A CN 201010603618A CN 102082292 A CN102082292 A CN 102082292A
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 120
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 119
- 238000002156 mixing Methods 0.000 claims abstract description 97
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 87
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 87
- 239000012266 salt solution Substances 0.000 claims abstract description 86
- 239000000654 additive Substances 0.000 claims abstract description 71
- 230000000996 additive effect Effects 0.000 claims abstract description 69
- 239000002608 ionic liquid Substances 0.000 claims abstract description 52
- 150000003839 salts Chemical class 0.000 claims abstract description 48
- 239000011356 non-aqueous organic solvent Substances 0.000 claims abstract description 39
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims abstract description 17
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000012986 modification Methods 0.000 claims description 63
- 230000004048 modification Effects 0.000 claims description 63
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 54
- 229910052744 lithium Inorganic materials 0.000 claims description 54
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 40
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 claims description 39
- 229910013188 LiBOB Inorganic materials 0.000 claims description 38
- 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 37
- 229910019142 PO4 Inorganic materials 0.000 claims description 37
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 37
- 239000010452 phosphate Substances 0.000 claims description 37
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 34
- 239000000463 material Substances 0.000 claims description 32
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 claims description 21
- 239000000126 substance Substances 0.000 claims description 20
- 230000004888 barrier function Effects 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 239000010941 cobalt Substances 0.000 claims description 13
- 229910017052 cobalt Inorganic materials 0.000 claims description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 13
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 8
- 230000005764 inhibitory process Effects 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- 238000012856 packing Methods 0.000 claims description 5
- 229920000098 polyolefin Polymers 0.000 claims description 5
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 abstract description 23
- 238000013461 design Methods 0.000 abstract description 10
- 230000002401 inhibitory effect Effects 0.000 abstract 3
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical group B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 36
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 34
- 229910013870 LiPF 6 Inorganic materials 0.000 description 31
- 239000002904 solvent Substances 0.000 description 25
- 238000004519 manufacturing process Methods 0.000 description 21
- 238000000034 method Methods 0.000 description 20
- 239000007789 gas Substances 0.000 description 18
- 229910052786 argon Inorganic materials 0.000 description 17
- 238000011056 performance test Methods 0.000 description 13
- 238000003860 storage Methods 0.000 description 12
- 238000007600 charging Methods 0.000 description 9
- 125000004122 cyclic group Chemical group 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 7
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 238000004513 sizing Methods 0.000 description 6
- 229910013872 LiPF Inorganic materials 0.000 description 5
- 101150058243 Lipf gene Proteins 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- 238000010281 constant-current constant-voltage charging Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 3
- 229910015645 LiMn Inorganic materials 0.000 description 3
- -1 Methylethyl Chemical group 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 230000000712 assembly Effects 0.000 description 2
- 238000000429 assembly Methods 0.000 description 2
- 239000007767 bonding agent Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 210000005069 ears Anatomy 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000011712 cell development Effects 0.000 description 1
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
Images
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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
- 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
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Abstract
The invention discloses a high-temperature lithium ion battery electrolyte and a lithium ion battery. The electrolyte is prepared by uniformly mixing electrolyte salts, a nonaqueous organic solvent, a high-temperature film-forming additive and high-temperature gas generation inhibiting additives, wherein the high-temperature film-forming additive is lithium bis(oxalate) borate (LiBOB); the LiBOB accounts for 0.2-3% by mass of the mixed lithium salt solution formed by the electrolyte salts and the nonaqueous organic solvent; the high-temperature gas generation inhibiting additive is one or two of ionic liquid and phthalic anhydride, and accounts for 0.8-9% by mass of the mixed lithium salt solution; and the total content of the added high-temperature film-forming additive and high-temperature gas generation inhibiting additives accounts for 1-11% by mass of the mixed lithium salt solution. The lithium ion battery comprises a cathode, an anode, a diaphragm and the high-temperature lithium ion battery electrolyte. The invention has the advantage of reasonable design, the steps in the preparation processes are simple and convenient to implement, and the prepared electrolyte and the lithium ion battery have excellent comprehensive performance.
Description
Technical field
The present invention relates to a kind of lithium-ion battery electrolytes and use the lithium ion battery of this electrolyte, especially relate to a kind of high temperature modification lithium-ion battery electrolytes and lithium ion battery.
Background technology
In recent years, because the pressure of environmental pollution and energy shortage forces each state all at the energy of seeking new green, environmental protection and sustainable development.The high-capacity environment-protecting lithium ion battery that occurs the nineties in 20th century because the energy density height that it had, have extended cycle life, the operating voltage advantages of higher, make it become one of electrical source of power that attracts most attention.Yet, along with people deepen continuously to the understanding of battery service condition, find that the use of battery under a lot of situations all is being higher than under the condition of normal temperature, when moving, battery is because heating can cause temperature to rise to about 45 ℃ as notebook computer; And the GPS battery, because long term exposure in the sun, temperature tends to reach about 80 ℃, working under the hot conditions or storing requires harshlyer to the job stability of battery system and storage stability, make to have caused attention to improving the electrical property and the high temperature storage performance of battery under hot conditions in the industry.
Under hot environment, a series of variations can take place in lithium-ion battery system.Positive electrode is because active higher, together with electrolyte generation oxidation reaction, thereby influences the performance of lithium ion battery.When negative material changed at lithium ion battery, the surface can form the SEI film, and when being in hot environment, the SEI film can dissolve and be destroyed, thereby influenced the cycle performance of battery and capacity performance etc.Particularly the lithium manganate material of one of popular positive electrode of power lithium battery because the dissolving of Mn aggravation causes the decay of circulation volume to accelerate, is the bottleneck that limits its large-scale application under hot conditions always.Simultaneously, when battery stored for a long time in hot environment, volatilization or reduction decomposition can take place in electrolyte, cause battery " inflatable ", may cause safety problems such as battery explosion.
Therefore, face to face during Lingao temperature service condition, the design of lithium-ion battery electrolytes must be considered the compatibility between the lithium ion battery plus-negative plate material and electrolyte under the hot environment, reduce the probability that electrolyte reacts with both positive and negative polarity, and improve the stability of SEI film.The researcher is arranged by adding a certain amount of special additive in the industry at present, can solve the inflatable problem of battery to a certain extent, but but seriously influenced the electrical property of battery at normal temperature and high temperature.
In addition, ionic liquid has lot of advantages: most of ionic liquids all exist with liquid form in wider temperature range, are applied in the serviceability temperature scope that can enlarge battery in the battery; Ion liquid vapour pressure is zero, and is also non-volatile under higher temperature, can solve the problem of electrokinetic cell high temperature inflatable; Viscosity is low, and thermal capacitance is big, and some ionic liquid is all stable to water, air, easily handles; Preparation is than being easier to, and cost of material is cheap etc.
Summary of the invention
Technical problem to be solved by this invention is at above-mentioned deficiency of the prior art, provides that a kind of processing and preparing is easy, cost is low and high temperature performance and electrical property equal excellent high-temperature type lithium-ion battery electrolytes and lithium ion battery.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of high temperature modification lithium-ion battery electrolytes and lithium ion battery, comprise the mixing lithium salt solution that forms by electrolytic salt and the even mixed preparing of non-aqueous organic solvent, it is characterized in that: also comprise the high temperature film for additive that evenly is blended in the described mixing lithium salt solution and suppress high temperature aerogenesis additive, described high temperature film for additive is biethyl diacid lithium borate LiBOB, and biethyl diacid lithium borate LiBOB is 0.2%～3% with described mass percent of mixing between the lithium salt solution; Described inhibition high temperature aerogenesis additive is one or both in ionic liquid and the phthalic anhydride, and described inhibition high temperature aerogenesis additive is 0.8%～9% with described mass percent of mixing between the lithium salt solution, and described ion liquid chemical formula is
R=CH wherein
2CH
3, CH
2CH
2CH
3Or CH
2CH
2CH
2CH
3And described ionic liquid should be ionic liquid EMI-TFSI, ionic liquid PMI-TFSI or ionic liquid BMI-TFSI mutually; The gross mass of adding the high temperature film for additive and suppressing high temperature aerogenesis additive be 1%～11% with mass percent between the described solution quality that mixes lithium salt solution.
Above-mentioned a kind of high temperature modification lithium-ion battery electrolytes, it is characterized in that: described electrolytic salt is one or both in lithium hexafluoro phosphate, LiBF4, biethyl diacid lithium borate and the lithium trifluoromethanesulp,onylimide, and described electrolytic salt and the described non-aqueous organic solvent amount of substance concentration of mixing lithium salt solution that forms that evenly is mixed is 0.8mol/L～1.4mol/L.
Above-mentioned a kind of high temperature modification lithium-ion battery electrolytes, it is characterized in that: the mixed solvent of described non-aqueous organic solvent for evenly mixing by ethylene carbonate, propene carbonate and diethyl carbonate, and the volume ratio of ethylene carbonate, propene carbonate and diethyl carbonate ratio is 2～5: 1～3: 3～6.
Above-mentioned a kind of high temperature modification lithium-ion battery electrolytes is characterized in that: described electrolytic salt is a lithium hexafluoro phosphate.
Simultaneously, the present invention also provides a kind of high comprehensive performance and has had the lithium ion battery of good high-temperature storage performance, high temperature cyclic performance and low temperature performance, comprise positive pole, negative pole and barrier film, it is characterized in that: also comprise the high temperature modification lithium-ion battery electrolytes.
Above-mentioned a kind of high temperature modification lithium ion battery is characterized in that: described positive pole is made by cobalt acid lithium or lithium manganate material, and described negative pole is made by material with carbon element, and described barrier film is made by the porous polyolefin material.
Above-mentioned a kind of high temperature modification lithium ion battery is characterized in that: described lithium ion battery is square flexible packing lithium ion battery.
The present invention compared with prior art has the following advantages:
1, the manufacture method step of electrolyte and lithium ion battery is simple and workable, makes easily the high comprehensive performance of prepared electrolyte and lithium ion battery.The lithium ion battery of making is as positive pole by cobalt acid lithium material or lithium manganate material, native graphite, carbonaceous mesophase spherules material with carbon elements such as (MCMB) are as negative pole, the porous polyolefin compound is as barrier film, and adopts lamination or winding method to make the square flexible packing lithium ion battery.
2, prepared electrolyte has excellent low temperature performance, has the discharge capability that carries out regular picture under-30 ℃ of temperature conditions.
3, prepared electrolyte has higher high temperature discharge performance, has 98.3% discharge ratio under high temperature (55 ℃, the 0.2C discharge) condition.
4, prepared electrolyte has the high temperature storage performance of superelevation, the gas that electrolyte volatilization or reduction decomposition produce when storing in order to suppress the battery long term high temperature effectively, the present invention has used the good ionic liquid of thermal stability as high temperature additive, utilize its higher boiling point of 300 ℃, almost do not have advantages such as vapour pressure, no combustibility and high conductivity, and add an amount of phthalic anhydride, by the collaborative use of the two, improved the high temperature storage performance of battery under this electrolyte system effectively.The battery that uses electrolyte that this invention is prepared is being shelved 48h and after shelving 4h under 100 ℃ under 85 ℃, battery is inflatable not all, and has higher capability retention and capacity restoration rate, is respectively 85% and 95%, and the internal resistance rate of change of battery is also less in addition.
5, prepared electrolyte has excellent normal-temperature circulating performance.
6, reasonable in design, manner of formulation is flexible and practical value is high, popularizing application prospect is extensive, it is the main body solvent that its solvent adopts higher boiling point, high-flash, high-k and low viscous ring-type or linear carbonate class, burning-point, boiling point, the decomposition temperature of electrolyte system be can improve so greatly, and then the thermal stability and the fail safe of electrolyte system improved.Simultaneously, be LiPF in order to improve main salt
6The stability of base electrolyte system, the present invention has introduced novel electrolytes salt LiBOB as film for additive.At present, one of problem of restriction LiMn2O4 electrokinetic cell development is that battery inducing capacity fading under hot environment is very fast, and K.Amine studies show that the mechanism of high temperature inducing capacity fading mainly is LiPF
6Decomposition has produced HF acid, and sour environment has been accelerated Mn
3+Disproportionation and the dissolving of Mn, destroyed the composition structure of SEI film simultaneously, and used LiBOB base electrolyte can improve the stability of SEI film greatly, reduce the output of HF simultaneously, improve the high temperature cyclic performance of battery.To sum up, the present invention efficiently solves the high temperature capacity attenuation problem of lithium manganate battery, has high temperature cyclic performance preferably.
In sum, the present invention is reasonable in design, preparation method's step is simple, realize convenient and prepared electrolyte and lithium ion battery high comprehensive performance, it adopts higher boiling point, high-k and low viscous solvent are base solvent, adopt the good electrolytic salt LiBOB of high temperature cyclic performance and thermal stability as film for additive, adopt outstanding ionic liquid of thermal stability and phthalic anhydride as high temperature additive, suppressed the aerogenesis phenomenon in the battery high-temperature storage process effectively, make the lithium ion battery that uses electrolyte of the present invention on the basis that does not influence the normal temperature electrical property, have 100 ℃ high temperature storage performance and 60 ℃ high temperature cyclic performance, and take into account-30 ℃ of low temperature performances under the temperature conditions.
Below by drawings and Examples, technical scheme of the present invention is described in further detail.
Description of drawings
Fig. 1 is for going out the test result schematic diagram that cobalt acid lithium battery carries out the test of normal temperature 1C cycle performance to the present invention is prepared.
Fig. 2 is for going out the test result schematic diagram that cobalt acid lithium battery carries out the test of high temperature 1C cycle performance to the present invention is prepared.
Fig. 3 is for going out the test result schematic diagram that the manganese cobalt acid lithium battery carries out the test of high temperature 1C cycle performance to the present invention is prepared.
Fig. 4 is for going out the test result schematic diagram that cobalt acid lithium battery carries out high low temperature performance test to the present invention is prepared.
Embodiment
The invention discloses a kind of high temperature modification lithium-ion battery electrolytes, comprise the mixing lithium salt solution that forms by electrolytic salt and the even mixed preparing of non-aqueous organic solvent, also comprise the high temperature film for additive that evenly is blended in the described mixing lithium salt solution and suppress high temperature aerogenesis additive, described high temperature film for additive is biethyl diacid lithium borate LiBOB, and biethyl diacid lithium borate LiBOB is 0.2%～3% with described mass percent of mixing between the lithium salt solution; Described inhibition high temperature aerogenesis additive is one or both in ionic liquid and the phthalic anhydride, and described inhibition high temperature aerogenesis additive is 0.8%～9% with described mass percent of mixing between the lithium salt solution, and described ion liquid chemical formula is
R=CH wherein
2CH
3, CH
2CH
2CH
3Or CH
2CH
2CH
2CH
3And described ionic liquid should be ionic liquid EMI-TFSI, ionic liquid PMI-TFSI or ionic liquid BMI-TFSI mutually; The gross mass of adding the high temperature film for additive and suppressing high temperature aerogenesis additive be 1%～11% with mass percent between the described solution quality that mixes lithium salt solution, described ion liquid purity is pure for analysis.
In the actual fabrication process, described electrolytic salt is one or both in lithium hexafluoro phosphate, LiBF4, biethyl diacid lithium borate and the lithium trifluoromethanesulp,onylimide, and described electrolytic salt and the described non-aqueous organic solvent amount of substance concentration of mixing lithium salt solution that forms that evenly is mixed is 0.8mol/L～1.4mol/L.The mixed solvent of described non-aqueous organic solvent for evenly mixing by ethylene carbonate, propene carbonate and diethyl carbonate, and the ratio of the volume ratio between ethylene carbonate, propene carbonate and the diethyl carbonate is 2～5: 1～3: 3～6.
In addition, high temperature modification lithium ion battery disclosed in this invention comprises positive pole, negative pole and barrier film, also comprises the high temperature modification lithium-ion battery electrolytes simultaneously.
Embodiment 1
In the present embodiment, during preparation electrolyte: (the H in being full of the glove box of argon gas of elder generation
2O content＜10ppm), is that 3: 1: 3 mixed is evenly made non-aqueous organic solvent with solvent ethylene carbonate (EC), propene carbonate (PC) and diethyl carbonate (DEC) according to volume ratio, and the electrolytic salt that adds respective quality again in made non-aqueous organic solvent (specifically is lithium hexafluoro phosphate LiPF
6), be mixed with the mixing lithium salt solution that amount of substance concentration is 1mol/L after evenly mixing.Simultaneously, in described mixing lithium salt solution, add earlier biethyl diacid lithium borate LiBOB as the high temperature film for additive and to add biethyl diacid lithium borate LiBOB be 1% with the be made into mass percent of mixing between the lithium salt solution, can according to actual needs biethyl diacid lithium borate LiBOB be adjusted accordingly in 0.2%～3% scope with described mass percent of mixing between the lithium salt solution in the actual fabrication process; Add ionic liquid EMI-TFSI again as suppressing high temperature aerogenesis additive, and to add ionic liquid EMI-TFSI be 3% with the be made into mass percent of mixing between the lithium salt solution, can described inhibition high temperature aerogenesis additive be adjusted accordingly in 0.8%～9% scope with described mass percent of mixing between the lithium salt solution according to the concrete needs of reality in the actual fabrication process, and interpolation high temperature film for additive and the gross mass that suppresses high temperature aerogenesis additive are controlled in 1%～11% scope with mass percent between the described solution quality that mixes lithium salt solution.Treat that electrolytic salt (is lithium hexafluoro phosphate LiPF
6) fully after the dissolving, leave standstill 24h, promptly obtain the high temperature modification lithium-ion battery electrolytes.
In the present embodiment, the electrolytic salt that is adopted (specifically is lithium hexafluoro phosphate LiPF
6During actual fabrication, can be according to the concrete needs of reality, select for use in lithium hexafluoro phosphate, LiBF4, biethyl diacid lithium borate and the lithium trifluoromethanesulp,onylimide one or both as electrolytic salt, wherein the performance of lithium hexafluoro phosphate is the most excellent, it is commercialization lithium ion battery lithium salts commonly used, therefore, select lithium hexafluoro phosphate LiPF in the present embodiment for use
6Be main salt.Simultaneously, during actual fabrication, can be according to actual needs, select for use in ionic liquid and the phthalic anhydride one or both as suppressing high temperature aerogenesis additive.
When the high temperature modification lithium-ion battery electrolytes that utilization is mixed with is made cobalt acid lithium ion battery, should make the positive pole, negative pole and the barrier film that constitute lithium ion battery respectively.In the present embodiment, described positive pole is made by cobalt acid lithium material, described negative pole is made by material with carbon element, described barrier film is made by the porous polyolefin material, described lithium ion battery is that square flexible packing lithium ion battery and its are formed by a plurality of lamination closed assemblies, also can adopt conventional winding method to make during the actual fabrication lithium ion battery.
When making positive pole, be solvent with N-dimethyl pyrrolidone (NMP), active material is cobalt acid lithium (LiCoO
2), conductive agent is super conductive carbon black (Super P), the NMP adding proportion is between 40%～65%.In the present embodiment, the mass percent of making used each raw material of anode sizing agent should be mutually: LiCoO
2: Super P: PVDF (Kynoar): NMP=94: 3: 3: 60.At first with LiCoO
2, Super P, PVDF and NMP be mixed with anode sizing agent according to design proportion, again the anode sizing agent for preparing is uniformly coated on the collector aluminium foil afterwards and drying, roll-in and die-cut after, just finish the making of positive plate.
When making negative pole, the preparation of cathode size is consistent with anodal preparation steps, is solvent with water, and active material is a modified graphite, and conductive agent is super conductive carbon black (Super P), and bonding agent is the mixture of SBR and CMC, and the water adding proportion is between 90%～120%.Thereby preparation is during cathode size, with modified graphite, Super P, SBR, CMC and H
2O is mixed with cathode size according to design proportion, again the cathode size for preparing is coated on afterwards on the copper foil of affluxion body and drying, roll-in and die-cut after, just finish the making of negative plate.Among the embodiment, the mass percent of making used each raw material of cathode size should be mutually: modified graphite: Super P: SBR: CMC: H
2O=93: 3: 2: 2: 110.
At last, die-cut good positive plate, negative plate and barrier film stacked gradually by the order of barrier film, negative plate, barrier film, positive plate, barrier film and negative plate from the bottom to top be combined into electric core, the electric core that is combined into utilizes aluminium pole ears and nickel lug to carry out ultrasonic bonding, the electric core that has welded is put in the aluminum-plastic packaged shell of square, with electric core after injecting above-mentioned high temperature modification lithium-ion battery electrolytes for preparing and sealing behind 80 ℃ of baking 24h, just making battery size is the cobalt acid lithium ion battery of 403465S, and the design capacity of battery is 1000mAh.
In addition, when utilizing the high temperature modification lithium-ion battery electrolytes that is mixed with to make manganate lithium ion battery, should make the positive pole, negative pole and the barrier film that constitute lithium ion battery respectively.In the present embodiment, described positive pole is made by lithium manganate material, and described negative pole is made by material with carbon element, and described barrier film is made by the porous polyolefin material, and described lithium ion battery is that square flexible packing lithium ion battery and its are formed by a plurality of lamination closed assemblies.
When making positive pole, be solvent with N-dimethyl pyrrolidone (NMP), active material is spinel lithium manganate (LiMn
2O
4), conductive agent is super conductive carbon black (Super P) and anodal graphite agent (KS6), the NMP adding proportion is between 40%～65%.In the present embodiment, the mass percent of making used each raw material of anode sizing agent should be mutually: LiMn
2O
4: Super P: KS6: PVDF: NMP=91: 3: 2: 4: 60.At first with LiMn
2O
4, Super P, KS6, PVDF and NMP be mixed with anode sizing agent according to design proportion, again the anode sizing agent for preparing is uniformly coated on the collector aluminium foil afterwards and drying, roll-in and die-cut after, just finish the making of positive plate.
When making negative pole, the preparation of cathode size is consistent with anodal preparation steps, is solvent with water, and active material is a modified graphite, and conductive agent is super conductive carbon black (Super P), and bonding agent is the mixture of SBR and CMC, and the water adding proportion is between 90%～120%.Thereby preparation is during cathode size, with modified graphite, Super P, SBR, CMC and H
2O is mixed with cathode size according to design proportion, again the cathode size for preparing is coated on afterwards on the copper foil of affluxion body and drying, roll-in and die-cut after, just finish the making of negative plate.Among the embodiment, the mass percent of making used each raw material of cathode size should be mutually: modified graphite: Super P: SBR: CMC: H
2O=93: 3: 2: 2: 110.
At last, die-cut good positive plate, negative plate and barrier film stacked gradually by the order of barrier film, negative plate, barrier film, positive plate, barrier film and negative plate from the bottom to top be combined into electric core, the electric core that is combined into utilizes aluminium pole ears and nickel lug to carry out ultrasonic bonding, the electric core that has welded is put in the aluminum-plastic packaged shell of square, with electric core after injecting above-mentioned high temperature modification lithium-ion battery electrolytes for preparing and sealing behind 80 ℃ of baking 24h, just make the manganate lithium ion battery that battery size is 553465MS, and the design capacity of battery is 1000mAh.
Embodiment 2
In the present embodiment, as different from Example 1: during preparation electrolyte: be full of the glove box (H of argon gas
2In the O content＜10ppm), is that 3: 1: 5 mixed is evenly made non-aqueous organic solvent with solvent ethylene carbonate (EC), propene carbonate (PC) and diethyl carbonate (DEC) according to volume ratio, and the electrolytic salt that adds respective quality again in made non-aqueous organic solvent (specifically is lithium hexafluoro phosphate LiPF
6), be mixed with the mixing lithium salt solution that amount of substance concentration is 1.1mol/L after evenly mixing.Simultaneously, in described mixing lithium salt solution, add earlier biethyl diacid lithium borate LiBOB as the high temperature film for additive and to add biethyl diacid lithium borate LiBOB be 0.5% with the be made into mass percent of mixing between the lithium salt solution; Add ionic liquid BMI-TFSI again as suppressing high temperature aerogenesis additive, and to add ionic liquid BMI-TFSI be 5% with the be made into mass percent of mixing between the lithium salt solution.Treat that electrolytic salt (is lithium hexafluoro phosphate LiPF
6) fully after the dissolving, leave standstill 24h, promptly obtain the high temperature modification lithium-ion battery electrolytes.
In the present embodiment, utilize the manufacture method step of the high temperature modification lithium-ion battery electrolytes making lithium ion battery that is mixed with all identical with embodiment 1 with material requested.
Embodiment 3
In the present embodiment, as different from Example 1: during preparation electrolyte: (the H in being full of the glove box of argon gas of elder generation
2O content＜10ppm), is that 1: 1: 1 mixed is evenly made non-aqueous organic solvent with solvent ethylene carbonate (EC), propene carbonate (PC) and diethyl carbonate (DEC) according to volume ratio, and the electrolytic salt that adds respective quality again in made non-aqueous organic solvent (specifically is lithium hexafluoro phosphate LiPF
6), be mixed with the mixing lithium salt solution that amount of substance concentration is 0.8mol/L after evenly mixing.Simultaneously, in described mixing lithium salt solution, add earlier biethyl diacid lithium borate LiBOB as the high temperature film for additive and to add biethyl diacid lithium borate LiBOB be 2% with the be made into mass percent of mixing between the lithium salt solution; Add additive package that ionic liquid PMI-TFSI and phthalic anhydride mix again as suppressing high temperature aerogenesis additive, and to add ionic liquid PMI-TFSI be 5% with the be made into mass percent of mixing between the lithium salt solution, to add phthalic anhydride be 4% with the be made into mass percent of mixing between the lithium salt solution.Treat that electrolytic salt (is lithium hexafluoro phosphate LiPF
6) fully after the dissolving, leave standstill 24h, promptly obtain the high temperature modification lithium-ion battery electrolytes.
In the present embodiment, utilize the manufacture method step of the high temperature modification lithium-ion battery electrolytes making lithium ion battery that is mixed with all identical with embodiment 1 with material requested.
Embodiment 4
In the present embodiment, as different from Example 1: during preparation electrolyte: (the H in being full of the glove box of argon gas of elder generation
2O content＜10ppm), is that 3: 2: 5 mixed is evenly made non-aqueous organic solvent with solvent ethylene carbonate (EC), propene carbonate (PC) and diethyl carbonate (DEC) according to volume ratio, and the electrolytic salt that adds respective quality again in made non-aqueous organic solvent (specifically is lithium hexafluoro phosphate LiPF
6), be mixed with the mixing lithium salt solution that amount of substance concentration is 1mol/L after evenly mixing.Simultaneously, in described mixing lithium salt solution, add earlier biethyl diacid lithium borate LiBOB as the high temperature film for additive and to add biethyl diacid lithium borate LiBOB be 1% with the be made into mass percent of mixing between the lithium salt solution; Add additive package that ionic liquid EMI-TFSI and phthalic anhydride mix again as suppressing high temperature aerogenesis additive, and to add ionic liquid EMI-TFSI be 5% with the be made into mass percent of mixing between the lithium salt solution, to add phthalic anhydride be 3% with the be made into mass percent of mixing between the lithium salt solution.Treat that electrolytic salt (is lithium hexafluoro phosphate LiPF
6) fully after the dissolving, leave standstill 24h, promptly obtain the high temperature modification lithium-ion battery electrolytes.
In the present embodiment, utilize the manufacture method step of the high temperature modification lithium-ion battery electrolytes making lithium ion battery that is mixed with all identical with embodiment 1 with material requested.
Embodiment 5
In the present embodiment, as different from Example 1: during preparation electrolyte: (the H in being full of the glove box of argon gas of elder generation
2O content＜10ppm), is that 1: 1: 1 mixed is evenly made non-aqueous organic solvent with solvent ethylene carbonate (EC), propene carbonate (PC) and diethyl carbonate (DEC) according to volume ratio, and the electrolytic salt that adds respective quality again in made non-aqueous organic solvent (specifically is lithium hexafluoro phosphate LiPF
6), be mixed with the mixing lithium salt solution that amount of substance concentration is 1mol/L after evenly mixing.Simultaneously, in described mixing lithium salt solution, add earlier biethyl diacid lithium borate LiBOB as the high temperature film for additive and to add biethyl diacid lithium borate LiBOB be 2% with the be made into mass percent of mixing between the lithium salt solution; Add additive package that ionic liquid EMI-TFSI and phthalic anhydride mix again as suppressing high temperature aerogenesis additive, and to add ionic liquid EMI-TFSI be 3% with the be made into mass percent of mixing between the lithium salt solution, to add phthalic anhydride be 2% with the be made into mass percent of mixing between the lithium salt solution.Treat that electrolytic salt (is lithium hexafluoro phosphate LiPF
6) fully after the dissolving, leave standstill 24h, promptly obtain the high temperature modification lithium-ion battery electrolytes.
In the present embodiment, utilize the manufacture method step of the high temperature modification lithium-ion battery electrolytes making lithium ion battery that is mixed with all identical with embodiment 1 with material requested.
Embodiment 6
In the present embodiment, as different from Example 1: during preparation electrolyte: (the H in being full of the glove box of argon gas of elder generation
2O content＜10ppm), is that 3: 2: 3 mixed is evenly made non-aqueous organic solvent with solvent ethylene carbonate (EC), propene carbonate (PC) and diethyl carbonate (DEC) according to volume ratio, and the electrolytic salt that adds respective quality again in made non-aqueous organic solvent (specifically is lithium hexafluoro phosphate LiPF
6), be mixed with the mixing lithium salt solution that amount of substance concentration is 1.2mol/L after evenly mixing.Simultaneously, in described mixing lithium salt solution, add earlier biethyl diacid lithium borate LiBOB as the high temperature film for additive and to add biethyl diacid lithium borate LiBOB be 1% with the be made into mass percent of mixing between the lithium salt solution; Add additive package that ionic liquid PMI-TFSI, ionic liquid BMI-TFSI and phthalic anhydride mix again as suppressing high temperature aerogenesis additive, and to add ionic liquid PMI-TFSI be 3% with the be made into mass percent of mixing between the lithium salt solution, to add ionic liquid BMI-TFSI be 2% with the be made into mass percent of mixing between the lithium salt solution, to add phthalic anhydride be 2% with the be made into mass percent of mixing between the lithium salt solution.Treat that electrolytic salt (is lithium hexafluoro phosphate LiPF
6) fully after the dissolving, leave standstill 24h, promptly obtain the high temperature modification lithium-ion battery electrolytes.
In the present embodiment, utilize the manufacture method step of the high temperature modification lithium-ion battery electrolytes making lithium ion battery that is mixed with all identical with embodiment 1 with material requested.
During actual fabrication, go out the good characteristic of high temperature modification lithium-ion battery electrolytes for checking the present invention is prepared, also done following three contrast tests simultaneously:
Contrast test one, in being full of the glove box of argon gas (H
2O＜10ppm), solvent ethylene carbonate (EC) and Methylethyl carbonic ester (EMC) are that 1: 1 mixed is even according to volume ratio, and add the LiPF of certain mass
6, be mixed with the electrolyte that concentration is 1mol/L, add mass percent simultaneously and be 2% vinylene carbonate (VC), treat electrolytic salt LiPF
6Fully after the dissolving, leave standstill 24h, promptly obtain contrasting electrolyte one.
Contrast test two, in being full of the glove box of argon gas (H
2O＜10ppm) is that 1: 1: 1 mixed is even with solvent ethylene carbonate (EC), dimethyl carbonate (DMC) and Methylethyl carbonic ester (EMC) according to volume ratio, and adds the LiPF of certain mass
6, be mixed with the electrolyte that concentration is 1mol/L, add mass percent simultaneously and be 1% film for additive vinylene carbonate (VC) and mass percent and be 2% 1.3-propane sultone (PS), leave standstill 24h, promptly obtain contrasting electrolyte two.
Contrast test three, in being full of the glove box of argon gas (H
2O＜10ppm) is that 1: 1: 1 mixed is even with solvent ethylene carbonate (EC), propene carbonate (PC) and Methylethyl carbonic ester (EMC) according to volume ratio, and adds the LiPF of certain mass
6, be mixed with the electrolyte that concentration is 1mol/L, adding mass percent simultaneously and be 2% film for additive vinylene carbonate (VC) and mass percent is 3%1.3-propane sultone (PS), leaves standstill 24h, promptly obtains contrasting electrolyte three.
At first, three kinds of electrolyte that make in six kinds of high temperature modification lithium-ion battery electrolytes being made among the embodiment 1-6 and three contrast tests are carried out the test of normal temperature 1C cycle performance:
Tester: Neware charge-discharge test instrument;
Probe temperature: ambient temperature is a room temperature, is specially 25 ℃;
Charging modes: constant-current constant-voltage charging is to 4.2V, cut-off current 0.03CmA;
Discharge mode: constant-current discharge is to 3.0V;
Charging and discharging currents: 1.0C.
Finally draw the six kinds of high temperature modification lithium-ion battery electrolytes being made among the embodiment 1-6 and the normal-temperature circulating performance test result of three contrast test electrolyte and see Table 1:
Table 1 electrolyte normal-temperature circulating performance test result contrast table
Secondly, three kinds of electrolyte that make in six kinds of high temperature modification lithium-ion battery electrolytes being made among the embodiment 1-6 and three contrast tests are carried out the test of high temperature 1C cycle performance:
Tester: Neware charge-discharge test instrument;
Probe temperature: 60 ℃;
Test battery: cobalt acid lithium battery;
Charging modes: constant-current constant-voltage charging is to 4.2V, cut-off current 0.03CmA;
Discharge mode: constant-current discharge is to 3.0V;
Charging and discharging currents: 1.0C;
Finally draw the six kinds of high temperature modification lithium-ion battery electrolytes being made among the embodiment 1-6 and the high temperature cyclic performance test result of three contrast test electrolyte and see Table 2:
Table 2 electrolyte high temperature cyclic performance test result contrast table
Afterwards, two kinds of electrolyte that make in six kinds of high temperature modification lithium-ion battery electrolytes being made among the embodiment 1-3 and contrast test one and 2 two contrast tests of contrast test are carried out the test of high temperature 1C cycle performance:
Tester: Neware charge-discharge test instrument;
Probe temperature: 60 ℃;
Test battery: lithium manganate battery;
Charging modes: constant-current constant-voltage charging is to 4.2V, cut-off current 0.03CmA;
Discharge mode: constant-current discharge is to 3.0V;
Charging and discharging currents: 1.0C;
The high temperature cyclic performance test result that finally draws two kinds of electrolyte that make in six kinds of high temperature modification lithium-ion battery electrolytes being made among the embodiment 1-3 and contrast test one and 2 two contrast tests of contrast test sees Table 3:
Table 3 electrolyte high temperature cyclic performance test result contrast table
Then, three kinds of high temperature modification lithium-ion battery electrolytes that made in embodiment 3,5 and 6 are carried out the high temperature storage performance test:
The storage condition: under the full power state, shelve the regular hour in certain temperature, specific as follows:
Shelve under 60 ℃ of temperature conditions 60 days, shelving 48h under 85 ℃ of temperature conditions and under 100 ℃ of temperature conditions, shelving 4h three times test;
Test battery: cobalt acid lithium battery;
Test mode: storage is cooled to room temperature after finishing, and it is carried out the 1.0C discharge, and its discharge capacity is the maintenance capacity, carries out 1.0C three weeks circulation again, and the 3rd all discharge capacities are designated as the recovery capacity; Conservation rate=maintenance capacity/initial capacity, recovery rate=recovery capacity/initial capacity;
The high temperature storage The performance test results that finally draws two kinds of electrolyte that make in three kinds of high temperature modification lithium-ion battery electrolytes being made in embodiment 3,5 and 6 and contrast test one and 2 two contrast tests of contrast test sees Table 4:
Table 4 electrolyte high temperature storage The performance test results contrast table
At last, three kinds of high temperature modification lithium-ion battery electrolytes that made among the embodiment 1-3 are carried out high low temperature performance test:
Tester: climatic chamber;
Probe temperature: 55 ℃/-10 ℃/-30 ℃;
Test battery: cobalt acid lithium battery;
Charging modes: after room temperature left standstill 2h, constant-current constant-voltage charging was to 4.2V, cut-off current 0.03CmA;
Discharge mode: leave standstill 8h under probe temperature after, constant-current discharge is to 3.0V;
Charging and discharging currents: charging 1.0C/ discharge 0.2C.
The high low temperature performance test result that finally draws three kinds of high temperature modification lithium-ion battery electrolytes that made among the embodiment 1-3 sees Table 5:
The high low temperature performance test result of table 5 electrolyte contrast table
Embodiment 7
In the present embodiment, as different from Example 1: during preparation electrolyte: (the H in being full of the glove box of argon gas of elder generation
2O content＜10ppm), is that 3: 3: 4 mixed is evenly made non-aqueous organic solvent with solvent ethylene carbonate (EC), propene carbonate (PC) and diethyl carbonate (DEC) according to volume ratio, and the electrolytic salt that adds respective quality again in made non-aqueous organic solvent (specifically is lithium hexafluoro phosphate LiPF
6), be mixed with the mixing lithium salt solution that amount of substance concentration is 2mol/L after evenly mixing.Simultaneously, in described mixing lithium salt solution, add earlier biethyl diacid lithium borate LiBOB as the high temperature film for additive and to add biethyl diacid lithium borate LiBOB be 0.2% with the be made into mass percent of mixing between the lithium salt solution; Add additive package that ionic liquid PMI-TFSI and phthalic anhydride mix again as suppressing high temperature aerogenesis additive, and to add ionic liquid PMI-TFSI be 1% with the be made into mass percent of mixing between the lithium salt solution, to add phthalic anhydride be 0.5% with the be made into mass percent of mixing between the lithium salt solution.Treat that electrolytic salt (is lithium hexafluoro phosphate LiPF
6) fully after the dissolving, leave standstill 24h, promptly obtain the high temperature modification lithium-ion battery electrolytes.
In the present embodiment, utilize the manufacture method step of the high temperature modification lithium-ion battery electrolytes making lithium ion battery that is mixed with all identical with embodiment 1 with material requested.
Embodiment 8
In the present embodiment, as different from Example 1: during preparation electrolyte: (the H in being full of the glove box of argon gas of elder generation
2O content＜10ppm), is that 3: 1: 5 mixed is evenly made non-aqueous organic solvent with solvent ethylene carbonate (EC), propene carbonate (PC) and diethyl carbonate (DEC) according to volume ratio, and the electrolytic salt that adds respective quality again in made non-aqueous organic solvent (specifically is lithium hexafluoro phosphate LiPF
6), be mixed with the mixing lithium salt solution that amount of substance concentration is 1.6mol/L after evenly mixing.Simultaneously, in described mixing lithium salt solution, add earlier biethyl diacid lithium borate LiBOB as the high temperature film for additive and to add biethyl diacid lithium borate LiBOB be 0.4% with the be made into mass percent of mixing between the lithium salt solution; Add ionic liquid EMI-TFSI again as suppressing high temperature aerogenesis additive, and to add ionic liquid EMI-TFSI be 3% with the be made into mass percent of mixing between the lithium salt solution.Treat that electrolytic salt (is lithium hexafluoro phosphate LiPF
6) fully after the dissolving, leave standstill 24h, promptly obtain the high temperature modification lithium-ion battery electrolytes.
In the present embodiment, utilize the manufacture method step of the high temperature modification lithium-ion battery electrolytes making lithium ion battery that is mixed with all identical with embodiment 1 with material requested.
Embodiment 9
In the present embodiment, as different from Example 1: during preparation electrolyte: (the H in being full of the glove box of argon gas of elder generation
2O content＜10ppm), is that 3: 3: 5 mixed is evenly made non-aqueous organic solvent with solvent ethylene carbonate (EC), propene carbonate (PC) and diethyl carbonate (DEC) according to volume ratio, and the electrolytic salt that adds respective quality again in made non-aqueous organic solvent (specifically is lithium hexafluoro phosphate LiPF
6), be mixed with the mixing lithium salt solution that amount of substance concentration is 1.4mol/L after evenly mixing.Simultaneously, in described mixing lithium salt solution, add earlier biethyl diacid lithium borate LiBOB as the high temperature film for additive and to add biethyl diacid lithium borate LiBOB be 0.2% with the be made into mass percent of mixing between the lithium salt solution; Add ionic liquid EMI-TFSI again as suppressing high temperature aerogenesis additive, and to add ionic liquid EMI-TFSI be 0.8% with the be made into mass percent of mixing between the lithium salt solution.Treat that electrolytic salt (is lithium hexafluoro phosphate LiPF
6) fully after the dissolving, leave standstill 24h, promptly obtain the high temperature modification lithium-ion battery electrolytes.
In the present embodiment, utilize the manufacture method step of the high temperature modification lithium-ion battery electrolytes making lithium ion battery that is mixed with all identical with embodiment 1 with material requested.
In the present embodiment, as different from Example 1: during preparation electrolyte: (the H in being full of the glove box of argon gas of elder generation
2O content＜10ppm), is that 2: 1: 3 mixed is evenly made non-aqueous organic solvent with solvent ethylene carbonate (EC), propene carbonate (PC) and diethyl carbonate (DEC) according to volume ratio, and the electrolytic salt that adds respective quality again in made non-aqueous organic solvent (specifically is lithium hexafluoro phosphate LiPF
6), be mixed with the mixing lithium salt solution that amount of substance concentration is 1.4mol/L after evenly mixing.Simultaneously, in described mixing lithium salt solution, add earlier biethyl diacid lithium borate LiBOB as the high temperature film for additive and to add biethyl diacid lithium borate LiBOB be 1.5% with the be made into mass percent of mixing between the lithium salt solution; Add ionic liquid EMI-TFSI again as suppressing high temperature aerogenesis additive, and to add ionic liquid EMI-TFSI be 4% with the be made into mass percent of mixing between the lithium salt solution.Treat that electrolytic salt (is lithium hexafluoro phosphate LiPF
6) fully after the dissolving, leave standstill 24h, promptly obtain the high temperature modification lithium-ion battery electrolytes.
In the present embodiment, utilize the manufacture method step of the high temperature modification lithium-ion battery electrolytes making lithium ion battery that is mixed with all identical with embodiment 1 with material requested.
Embodiment 11
In the present embodiment, as different from Example 1: during preparation electrolyte: (the H in being full of the glove box of argon gas of elder generation
2O content＜10ppm), is that 5: 3: 6 mixed is evenly made non-aqueous organic solvent with solvent ethylene carbonate (EC), propene carbonate (PC) and diethyl carbonate (DEC) according to volume ratio, and the electrolytic salt that adds respective quality again in made non-aqueous organic solvent (specifically is lithium hexafluoro phosphate LiPF
6), be mixed with the mixing lithium salt solution that amount of substance concentration is 1.2mol/L after evenly mixing.Simultaneously, in described mixing lithium salt solution, add earlier biethyl diacid lithium borate LiBOB as the high temperature film for additive and to add biethyl diacid lithium borate LiBOB be 1% with the be made into mass percent of mixing between the lithium salt solution; Add ionic liquid EMI-TFSI again as suppressing high temperature aerogenesis additive, and to add ionic liquid EMI-TFSI be 4% with the be made into mass percent of mixing between the lithium salt solution.Treat that electrolytic salt (is lithium hexafluoro phosphate LiPF
6) fully after the dissolving, leave standstill 24h, promptly obtain the high temperature modification lithium-ion battery electrolytes.
In the present embodiment, utilize the manufacture method step of the high temperature modification lithium-ion battery electrolytes making lithium ion battery that is mixed with all identical with embodiment 1 with material requested.
Embodiment 12
In the present embodiment, as different from Example 1: during preparation electrolyte: (the H in being full of the glove box of argon gas of elder generation
2O content＜10ppm), is that 4: 3: 4 mixed is evenly made non-aqueous organic solvent with solvent ethylene carbonate (EC), propene carbonate (PC) and diethyl carbonate (DEC) according to volume ratio, and the electrolytic salt that adds respective quality again in made non-aqueous organic solvent (specifically is lithium hexafluoro phosphate LiPF
6), be mixed with the mixing lithium salt solution that amount of substance concentration is 1.2mol/L after evenly mixing.Simultaneously, in described mixing lithium salt solution, add earlier biethyl diacid lithium borate LiBOB as the high temperature film for additive and to add biethyl diacid lithium borate LiBOB be 1% with the be made into mass percent of mixing between the lithium salt solution; Add ionic liquid EMI-TFSI again as suppressing high temperature aerogenesis additive, and to add ionic liquid EMI-TFSI be 4% with the be made into mass percent of mixing between the lithium salt solution.Treat that electrolytic salt (is lithium hexafluoro phosphate LiPF
6) fully after the dissolving, leave standstill 24h, promptly obtain the high temperature modification lithium-ion battery electrolytes.
In the present embodiment, utilize the manufacture method step of the high temperature modification lithium-ion battery electrolytes making lithium ion battery that is mixed with all identical with embodiment 1 with material requested.
Embodiment 13
In the present embodiment, as different from Example 1: during preparation electrolyte: (the H in being full of the glove box of argon gas of elder generation
2O content＜10ppm), is that 4: 2: 5 mixed is evenly made non-aqueous organic solvent with solvent ethylene carbonate (EC), propene carbonate (PC) and diethyl carbonate (DEC) according to volume ratio, and the electrolytic salt that adds respective quality again in made non-aqueous organic solvent (specifically is lithium hexafluoro phosphate LiPF
6), be mixed with the mixing lithium salt solution that amount of substance concentration is 1.2mol/L after evenly mixing.Simultaneously, in described mixing lithium salt solution, add earlier biethyl diacid lithium borate LiBOB as the high temperature film for additive and to add biethyl diacid lithium borate LiBOB be 1% with the be made into mass percent of mixing between the lithium salt solution; Add ionic liquid EMI-TFSI again as suppressing high temperature aerogenesis additive, and to add ionic liquid EMI-TFSI be 4% with the be made into mass percent of mixing between the lithium salt solution.Treat that electrolytic salt (is lithium hexafluoro phosphate LiPF
6) fully after the dissolving, leave standstill 24h, promptly obtain the high temperature modification lithium-ion battery electrolytes.
In the present embodiment, utilize the manufacture method step of the high temperature modification lithium-ion battery electrolytes making lithium ion battery that is mixed with all identical with embodiment 1 with material requested.
Embodiment 14
In the present embodiment, as different from Example 1: during preparation electrolyte: (the H in being full of the glove box of argon gas of elder generation
2O content＜10ppm), is that 5: 2: 6 mixed is evenly made non-aqueous organic solvent with solvent ethylene carbonate (EC), propene carbonate (PC) and diethyl carbonate (DEC) according to volume ratio, and the electrolytic salt that adds respective quality again in made non-aqueous organic solvent (specifically is lithium hexafluoro phosphate LiPF
6), be mixed with the mixing lithium salt solution that amount of substance concentration is 1.2mol/L after evenly mixing.Simultaneously, in described mixing lithium salt solution, add earlier biethyl diacid lithium borate LiBOB as the high temperature film for additive and to add biethyl diacid lithium borate LiBOB be 1% with the be made into mass percent of mixing between the lithium salt solution; Add ionic liquid EMI-TFSI again as suppressing high temperature aerogenesis additive, and to add ionic liquid EMI-TFSI be 4% with the be made into mass percent of mixing between the lithium salt solution.Treat that electrolytic salt (is lithium hexafluoro phosphate LiPF
6) fully after the dissolving, leave standstill 24h, promptly obtain the high temperature modification lithium-ion battery electrolytes.
In the present embodiment, utilize the manufacture method step of the high temperature modification lithium-ion battery electrolytes making lithium ion battery that is mixed with all identical with embodiment 1 with material requested.
The above; it only is preferred embodiment of the present invention; be not that the present invention is imposed any restrictions, everyly any simple modification that above embodiment did, change and equivalent structure changed, all still belong in the protection range of technical solution of the present invention according to the technology of the present invention essence.
Claims (7)
1. high temperature modification lithium-ion battery electrolytes, comprise the mixing lithium salt solution that forms by electrolytic salt and the even mixed preparing of non-aqueous organic solvent, it is characterized in that: also comprise the high temperature film for additive that evenly is blended in the described mixing lithium salt solution and suppress high temperature aerogenesis additive, described high temperature film for additive is biethyl diacid lithium borate LiBOB, and biethyl diacid lithium borate LiBOB is 0.2%～3% with described mass percent of mixing between the lithium salt solution; Described inhibition high temperature aerogenesis additive is one or both in ionic liquid and the phthalic anhydride, and described inhibition high temperature aerogenesis additive is 0.8%～9% with described mass percent of mixing between the lithium salt solution, and described ion liquid chemical formula is
R=CH wherein
2CH
3, CH
2CH
2CH
3Or CH
2CH
2CH
2CH
3And described ionic liquid should be ionic liquid EMI-TFSI, ionic liquid PMI-TFSI or ionic liquid BMI-TFSI mutually; The gross mass of adding the high temperature film for additive and suppressing high temperature aerogenesis additive be 1%～11% with mass percent between the described solution quality that mixes lithium salt solution.
2. according to the described a kind of high temperature modification lithium-ion battery electrolytes of claim 1, it is characterized in that: described electrolytic salt is one or both in lithium hexafluoro phosphate, LiBF4, biethyl diacid lithium borate and the lithium trifluoromethanesulp,onylimide, and described electrolytic salt and the described non-aqueous organic solvent amount of substance concentration of mixing lithium salt solution that forms that evenly is mixed is 0.8mol/L～1.4mol/L.
3. according to claim 1 or 2 described a kind of high temperature modification lithium-ion battery electrolytes, it is characterized in that: the mixed solvent of described non-aqueous organic solvent for evenly mixing by ethylene carbonate, propene carbonate and diethyl carbonate, and the volume ratio of ethylene carbonate, propene carbonate and diethyl carbonate ratio is 2～5: 1～3: 3～6.
4. according to claim 1 or 2 described a kind of high temperature modification lithium-ion battery electrolytes, it is characterized in that: described electrolytic salt is a lithium hexafluoro phosphate.
5. a lithium ion battery that utilizes high temperature modification lithium-ion battery electrolytes as claimed in claim 1 to make comprises positive pole, negative pole and barrier film, it is characterized in that: also comprise the high temperature modification lithium-ion battery electrolytes.
6. according to the described a kind of high temperature modification lithium ion battery of claim 5, it is characterized in that: described positive pole is made by cobalt acid lithium or lithium manganate material, and described negative pole is made by material with carbon element, and described barrier film is made by the porous polyolefin material.
7. according to claim 5 or 6 described a kind of high temperature modification lithium ion batteries, it is characterized in that: described lithium ion battery is square flexible packing lithium ion battery.
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Cited By (22)
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| CN102952058A (en) * | 2011-08-30 | 2013-03-06 | 海洋王照明科技股份有限公司 | Maleimide ionic liquid, and preparation method and application thereof |
| CN103187595A (en) * | 2013-03-18 | 2013-07-03 | 常州大学 | Maintenance method for capacity recovery type lithium ion battery |
| CN103618106A (en) * | 2013-10-14 | 2014-03-05 | 厦门大学 | Electrolyte for preventing lithium titanate battery flatulence, and lithium titanate battery |
| CN103988357A (en) * | 2011-11-24 | 2014-08-13 | 丰田自动车株式会社 | Manufacturing method of non-aqueous electrolyte secondary battery |
| CN104953164A (en) * | 2014-03-26 | 2015-09-30 | 丰田自动车株式会社 | Nonaqueous electrolyte secondary battery |
| CN105206796A (en) * | 2012-02-29 | 2015-12-30 | 新神户电机株式会社 | Lithium ion battery |
| CN105355889A (en) * | 2015-11-28 | 2016-02-24 | 西安瑟福能源科技有限公司 | High-voltage high-magnification lithium ion battery |
| CN106299324A (en) * | 2016-10-17 | 2017-01-04 | 广州天赐高新材料股份有限公司 | A kind of electrolyte for high-capacity lithium ion cell, preparation method and lithium ion battery |
| CN106848401A (en) * | 2017-01-11 | 2017-06-13 | 长兴天晟能源科技有限公司 | A kind of lithium ion battery high temperature from the preparation method for blocking electrolyte |
| CN106935911A (en) * | 2017-03-07 | 2017-07-07 | 欣旺达电子股份有限公司 | Reduce the method that nickelic battery high-temperature stores aerogenesis |
| CN107887647A (en) * | 2017-10-26 | 2018-04-06 | 广州天赐高新材料股份有限公司 | A kind of 5V high voltages electrolyte for lithium secondary batteries and the lithium secondary battery containing the electrolyte |
| CN107910587A (en) * | 2017-12-08 | 2018-04-13 | 广州天赐高新材料股份有限公司 | Lithium secondary cell electrolyte and lithium secondary battery |
| CN108112276A (en) * | 2015-06-22 | 2018-06-01 | 野猫技术开发公司 | For the electrolyte preparations of lithium ion battery |
| CN109428110A (en) * | 2017-09-05 | 2019-03-05 | 三星Sdi株式会社 | Lithium rechargeable battery |
| CN109559903A (en) * | 2017-09-27 | 2019-04-02 | 太阳诱电株式会社 | Electrochemical device electrolyte and electrochemical device |
| CN109935908A (en) * | 2019-04-02 | 2019-06-25 | 合肥工业大学 | Low-concentration lithium salt electrolyte and lithium secondary battery containing the same |
| CN110161174A (en) * | 2019-05-28 | 2019-08-23 | 中南大学 | A kind of detection device and method of manganese containing materials modifying interface integrity degree |
| CN111463487A (en) * | 2018-12-20 | 2020-07-28 | 杨霞 | Processing technology of lithium ion battery electrolyte |
| CN114006125A (en) * | 2021-10-29 | 2022-02-01 | 河北金力新能源科技股份有限公司 | High-temperature-storage-resistant oil-based lithium ion battery diaphragm and preparation method thereof |
| CN114243110A (en) * | 2021-12-16 | 2022-03-25 | 惠州市惠德瑞锂电科技股份有限公司 | High-temperature-resistant bulging lithium-manganese dioxide soft package battery |
| CN114976239A (en) * | 2022-05-31 | 2022-08-30 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） | High-safety lithium ion battery electrolyte suitable for full sea depth |
| WO2024011620A1 (en) * | 2022-07-15 | 2024-01-18 | 宁德时代新能源科技股份有限公司 | Secondary battery, battery module, battery pack and electric device |
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| WO2010007223A1 (en) * | 2008-06-25 | 2010-01-21 | Commissariat A L'energie Atomique | Non-aqueous electrolyte for a high-voltage lithium battery |
| CN101640291A (en) * | 2008-07-29 | 2010-02-03 | 三星Sdi株式会社 | Electrolyte and lithium ion secondary battery including the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2010007223A1 (en) * | 2008-06-25 | 2010-01-21 | Commissariat A L'energie Atomique | Non-aqueous electrolyte for a high-voltage lithium battery |
| CN101640291A (en) * | 2008-07-29 | 2010-02-03 | 三星Sdi株式会社 | Electrolyte and lithium ion secondary battery including the same |
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| CN102952058B (en) * | 2011-08-30 | 2015-05-06 | 海洋王照明科技股份有限公司 | Maleimide ionic liquid, and preparation method and application thereof |
| CN102952058A (en) * | 2011-08-30 | 2013-03-06 | 海洋王照明科技股份有限公司 | Maleimide ionic liquid, and preparation method and application thereof |
| CN103988357A (en) * | 2011-11-24 | 2014-08-13 | 丰田自动车株式会社 | Manufacturing method of non-aqueous electrolyte secondary battery |
| CN103988357B (en) * | 2011-11-24 | 2017-09-26 | 丰田自动车株式会社 | The manufacture method of nonaqueous electrolytic solution secondary battery |
| US9559350B2 (en) | 2011-11-24 | 2017-01-31 | Toyota Jidosha Kabushiki Kaisha | Method for producing nonaqueous electrolyte secondary battery |
| CN105206796A (en) * | 2012-02-29 | 2015-12-30 | 新神户电机株式会社 | Lithium ion battery |
| CN103187595A (en) * | 2013-03-18 | 2013-07-03 | 常州大学 | Maintenance method for capacity recovery type lithium ion battery |
| CN103187595B (en) * | 2013-03-18 | 2016-01-06 | 常州大学 | A kind of maintaining method of capacity recovery type lithium ion battery |
| CN103618106A (en) * | 2013-10-14 | 2014-03-05 | 厦门大学 | Electrolyte for preventing lithium titanate battery flatulence, and lithium titanate battery |
| CN104953164B (en) * | 2014-03-26 | 2017-06-06 | 丰田自动车株式会社 | Rechargeable nonaqueous electrolytic battery |
| CN104953164A (en) * | 2014-03-26 | 2015-09-30 | 丰田自动车株式会社 | Nonaqueous electrolyte secondary battery |
| CN108112276B (en) * | 2015-06-22 | 2021-01-08 | 野猫技术开发公司 | Electrolyte formulation for lithium ion batteries |
| CN108112276A (en) * | 2015-06-22 | 2018-06-01 | 野猫技术开发公司 | For the electrolyte preparations of lithium ion battery |
| CN105355889B (en) * | 2015-11-28 | 2018-02-23 | 西安瑟福能源科技有限公司 | A kind of high voltage high multiplying power lithium ion battery |
| CN105355889A (en) * | 2015-11-28 | 2016-02-24 | 西安瑟福能源科技有限公司 | High-voltage high-magnification lithium ion battery |
| CN106299324A (en) * | 2016-10-17 | 2017-01-04 | 广州天赐高新材料股份有限公司 | A kind of electrolyte for high-capacity lithium ion cell, preparation method and lithium ion battery |
| CN106848401A (en) * | 2017-01-11 | 2017-06-13 | 长兴天晟能源科技有限公司 | A kind of lithium ion battery high temperature from the preparation method for blocking electrolyte |
| CN106935911A (en) * | 2017-03-07 | 2017-07-07 | 欣旺达电子股份有限公司 | Reduce the method that nickelic battery high-temperature stores aerogenesis |
| CN106935911B (en) * | 2017-03-07 | 2019-02-19 | 欣旺达电子股份有限公司 | Reduce the method that nickelic battery high-temperature storage produces gas |
| CN109428110A (en) * | 2017-09-05 | 2019-03-05 | 三星Sdi株式会社 | Lithium rechargeable battery |
| US11342586B2 (en) | 2017-09-05 | 2022-05-24 | Samsung Sdi Co., Ltd. | Rechargeable lithium battery |
| CN109428110B (en) * | 2017-09-05 | 2022-04-29 | 三星Sdi株式会社 | Rechargeable lithium battery |
| CN109559903A (en) * | 2017-09-27 | 2019-04-02 | 太阳诱电株式会社 | Electrochemical device electrolyte and electrochemical device |
| CN107887647B (en) * | 2017-10-26 | 2020-08-11 | 广州天赐高新材料股份有限公司 | Electrolyte for 5V high-voltage lithium secondary battery and lithium secondary battery containing electrolyte |
| CN107887647A (en) * | 2017-10-26 | 2018-04-06 | 广州天赐高新材料股份有限公司 | A kind of 5V high voltages electrolyte for lithium secondary batteries and the lithium secondary battery containing the electrolyte |
| CN107910587A (en) * | 2017-12-08 | 2018-04-13 | 广州天赐高新材料股份有限公司 | Lithium secondary cell electrolyte and lithium secondary battery |
| CN111463487A (en) * | 2018-12-20 | 2020-07-28 | 杨霞 | Processing technology of lithium ion battery electrolyte |
| CN111463486A (en) * | 2018-12-20 | 2020-07-28 | 杨霞 | Lithium ion battery electrolyte |
| CN111463487B (en) * | 2018-12-20 | 2023-05-30 | 安徽巡鹰新材料科技有限公司 | Processing technology of lithium ion battery electrolyte |
| CN111463486B (en) * | 2018-12-20 | 2023-08-01 | 江西普瑞森新能源科技有限公司 | Lithium ion battery electrolyte |
| CN109935908A (en) * | 2019-04-02 | 2019-06-25 | 合肥工业大学 | Low-concentration lithium salt electrolyte and lithium secondary battery containing the same |
| CN110161174B (en) * | 2019-05-28 | 2021-08-24 | 中南大学 | A detection device and method for the integrity of interface modification of manganese-containing materials |
| CN110161174A (en) * | 2019-05-28 | 2019-08-23 | 中南大学 | A kind of detection device and method of manganese containing materials modifying interface integrity degree |
| CN114006125A (en) * | 2021-10-29 | 2022-02-01 | 河北金力新能源科技股份有限公司 | High-temperature-storage-resistant oil-based lithium ion battery diaphragm and preparation method thereof |
| CN114243110A (en) * | 2021-12-16 | 2022-03-25 | 惠州市惠德瑞锂电科技股份有限公司 | High-temperature-resistant bulging lithium-manganese dioxide soft package battery |
| CN114976239A (en) * | 2022-05-31 | 2022-08-30 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） | High-safety lithium ion battery electrolyte suitable for full sea depth |
| WO2024011620A1 (en) * | 2022-07-15 | 2024-01-18 | 宁德时代新能源科技股份有限公司 | Secondary battery, battery module, battery pack and electric device |
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