CN109336918A - A kind of organosiloxane fire retardant and its preparation method and application - Google Patents
A kind of organosiloxane fire retardant and its preparation method and application Download PDFInfo
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- CN109336918A CN109336918A CN201811189566.8A CN201811189566A CN109336918A CN 109336918 A CN109336918 A CN 109336918A CN 201811189566 A CN201811189566 A CN 201811189566A CN 109336918 A CN109336918 A CN 109336918A
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- Prior art keywords
- organosiloxane
- fire retardant
- carbonate
- fire
- electrolyte
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 58
- 125000005375 organosiloxane group Chemical group 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000003792 electrolyte Substances 0.000 claims abstract description 64
- 239000000654 additive Substances 0.000 claims abstract description 26
- 230000000996 additive effect Effects 0.000 claims abstract description 26
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 22
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 18
- -1 sulfuric acid acrylic ester Chemical class 0.000 claims description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 9
- 229910003002 lithium salt Inorganic materials 0.000 claims description 9
- 159000000002 lithium salts Chemical class 0.000 claims description 9
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 7
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 2
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 claims description 2
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910013188 LiBOB Inorganic materials 0.000 claims description 2
- 229910000552 LiCF3SO3 Inorganic materials 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 150000004651 carbonic acid esters Chemical class 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 2
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 239000013538 functional additive Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- 238000011403 purification operation Methods 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical class [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 claims description 2
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 claims 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims 1
- 150000001350 alkyl halides Chemical class 0.000 claims 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims 1
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims 1
- 238000012360 testing method Methods 0.000 description 32
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 229910052744 lithium Inorganic materials 0.000 description 10
- 229910052710 silicon Inorganic materials 0.000 description 10
- 239000010703 silicon Substances 0.000 description 10
- 239000002253 acid Substances 0.000 description 8
- 239000010941 cobalt Substances 0.000 description 8
- 229910017052 cobalt Inorganic materials 0.000 description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 8
- 239000010439 graphite Substances 0.000 description 8
- 229910002804 graphite Inorganic materials 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 229920001296 polysiloxane Polymers 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- NOKUWSXLHXMAOM-UHFFFAOYSA-N hydroxy(phenyl)silicon Chemical compound O[Si]C1=CC=CC=C1 NOKUWSXLHXMAOM-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- RSNQKPMXXVDJFG-UHFFFAOYSA-N tetrasiloxane Chemical compound [SiH3]O[SiH2]O[SiH2]O[SiH3] RSNQKPMXXVDJFG-UHFFFAOYSA-N 0.000 description 3
- 235000009161 Espostoa lanata Nutrition 0.000 description 2
- 240000001624 Espostoa lanata Species 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- BIFQHCGLXZWNLN-UHFFFAOYSA-N 2,2,6-trifluoro-4-methyl-4-propyl-1,3,5,2,4,6-trioxatrisilinane Chemical class CCC[Si]1(C)O[SiH](F)O[Si](F)(F)O1 BIFQHCGLXZWNLN-UHFFFAOYSA-N 0.000 description 1
- DDJYSYJBTTYOBJ-UHFFFAOYSA-N CC=1C=C(C=C(C1)C)[SiH2]C=C Chemical class CC=1C=C(C=C(C1)C)[SiH2]C=C DDJYSYJBTTYOBJ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- ZSTLPJLUQNQBDQ-UHFFFAOYSA-N azanylidyne(dihydroxy)-$l^{5}-phosphane Chemical class OP(O)#N ZSTLPJLUQNQBDQ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- FHHHXDQAWOUGAT-UHFFFAOYSA-N ethenyl-dimethyl-(trifluoromethyl)silane Chemical compound C=C[Si](C)(C)C(F)(F)F FHHHXDQAWOUGAT-UHFFFAOYSA-N 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001535 kindling effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
- C07F7/0872—Preparation and treatment thereof
- C07F7/0889—Reactions not involving the Si atom of the Si-O-Si sequence
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Secondary Cells (AREA)
- Silicon Polymers (AREA)
Abstract
The invention discloses a kind of organosiloxane fire retardants, and the invention also discloses the preparation method and applications of the organosiloxane fire retardant, and further, the invention also discloses a kind of high-fire-resistance lithium-ion battery electrolytes.By adding the organosiloxane flame-retardant additive, not only flame retardant property is good for obtained lithium-ion battery electrolytes, has self-gravitation characteristic, and conductivity is higher, the lithium ion battery charge-discharge performance of assembling also increases.
Description
Technical field
The present invention relates to a kind of organosiloxane fire retardants, and in particular to one kind can be used for high-fire-resistance lithium ion battery
Organosiloxane fire retardant in electrolyte, belongs to electrochemical technology field.
Background technique
Lithium ion battery is high with open-circuit voltage, specific capacity is big, self discharge is small, has extended cycle life, has a safety feature, without note
Recall effect, it is pollution-free the advantages that, be widely used in each class of electronic devices, also become nearly ten years obtain great development it is novel
One of energy.However, lithium-ion battery electrolytes are this kind of molten generally based on the carbonate based organic solvent dissolved with lithium salts at present
Agent has the shortcomings that flash-point is low and inflammable, and when battery releases amount of heat or short circuit, easily kindling, burning are even quick-fried
It is fried, the security performance of lithium ion battery is affected, the large-scale commercial development of lithium ion battery is constrained.
For the security performance for improving lithium ion battery, traditional solution is to install explosion relief valve in inside battery,
But these attachment devices increase the cost of battery.Currently, being considered most effective method is to be electrolysed in lithium ion battery
Flame-retardant additive is added in liquid, keeps organic electrolyte fire retardant using its fire retardation or even non-ignitable.Wherein, most widely used resistance
It includes phosphate, phosphite ester, halogenated phosphate, ring phosphorus nitrile compounds etc. that combustion additive, which is mainly organic phosphorus compound, such as
The patent of invention of Publication No. CN105870503A reports halogenated phosphate based flame retardant, adds the electrolyte of the based flame retardant
Anti-flammability with higher;A kind of fire retardant of phosphonitrile class of the patent report of Publication No. CN106711505A, the fire retardant
Good flame retardation effect, and it is good with positive/negative plate and diaphragm wetability.Although these reported organic phosphates fire retardants can be improved
The flame retardant property of electrolyte, but that there are stability is not high, viscosity is big, additive amount leads to greatly conductivity and charge and discharge cycles after being added
The disadvantages of equal electrical properties decline, and combustion product is harmful to environment, thus limit its application to a certain extent.
Organosiloxane has good anti-flammability, thermal stability, low viscosity, low toxicity, pollution-free as new flame retardant
The advantages that, and become the hot spot studied at present.In recent years, also there is the report being applied to siloxanes in electrolyte, such as
The Chinese invention patent of Publication No. CN104380518A just reports chain and annular siloxane containing Si-O-Si key, though
So its flame retardant property is not reported, but this kind of siloxanes can greatly improve the stability of electrolyte and the cycle performance of battery;
In addition, a kind of trifluoro propyl methyl cyclotrisiloxanes flame-retardant additive of the patent report of Publication No. CN107293785A,
When the siloxanes additive amount is 6%-7%, electrolyte just has self-gravitation characteristic, furthermore can also improve the stable circulation of battery
Property and capacity retention ratio.Although siloxanes in above-mentioned two example can be improved the stability and anti-flammability of electrolyte, but tie
Silicone content is relatively low (15%-18%) in structure, does not make full use of the anti-flammability of element silicon, and causes additive amount larger, electricity
Conductance decline, cost also will increase.
It therefore, can be using organosiloxane as the flame-retardant additive of lithium-ion battery electrolytes, by improving silicone content
The flame retardant property of electrolyte is improved, and the electrolytic conductivity guaranteed on this basis and charge and discharge cycles etc. are electrically
It can be unaffected.
Summary of the invention
An object of the present invention is to synthesize new organosiloxane flame-retardant additive by improving silicon content, only
A small amount of additive need to be added in electrolyte, under conditions of not influencing electrical property, electrolyte can have excellent
Anti-flammability, also improves the utilization rate of this ignition-proof element of silicon at the shortcomings that not only avoiding phosphorus flame retardant.In addition, also having
Other functional groups are introduced in organic siloxane flame-retardant additive structure, by the synergistic effect with element silicon, are further increased fire-retardant
Performance, and avoid influence of the common flame-retardant additive to electrical properties such as conductivity, charge and discharge cycles.
Contain the fire-retardant or even complete of above-mentioned organosiloxane flame-retardant additive it is a further object of the present invention to provide a kind of
Non-ignitable flame-retardant lithium ion battery electrolyte.
To achieve the above object, the technical solution adopted by the present invention is that:
A kind of organosiloxane fire retardant has following structure:
Wherein, m > 0, n >=0, R1、R2、R3For halogen, alkyl, alkoxy, alkylene, phenyl, xenyl, phenylate base, halogen
Substituted alkyl, halogenated alkoxy, haloalkene alkyl, halogenophenyl, halogenated biphenyl base etc., in which: halogen F, Cl or Br.
Preferably, 0 < m≤3,0 n≤6 <.
It is further preferred that the organosiloxane fire retardant is
Wherein, 0 < m≤3,0 n≤6 <.
Invention further provides the preparation method of the organosiloxane fire retardant, specifically:
By hydrogen-containing siloxane and vinyl silanes with molar ratio for 1:1 amount under the effect of the catalyst, at 30-100 DEG C
1-6h is reacted, and carries out purifying after the completion of reaction and except miscellaneous operation, finally obtains required flame-retardant additive.
More specifically, the catalyst is Karsted or Spiere catalyst.
More specifically, the purification operations are rectifying;The miscellaneous operation that removes is activated carbon adsorption.
It is to be applied to prepare high-fire-resistance lithium-ion electric the present invention also provides the application of the organosiloxane fire retardant
Pond electrolyte.
Concrete application method is:
By lithium salts, organic solvent, organosiloxane fire retardant and other functional additives mix, obtain high-fire-resistance lithium from
Sub- battery electrolyte.
Preferably, the additive amount of the organosiloxane fire retardant is the 0.5-20% of electrolyte gross mass, further
Preferably 0.5-5%.
Preferably, the organic solvent includes cyclic carbonates solvent and/or linear carbonate class solvent, described
Cyclic carbonates solvent is selected from one of ethylene carbonate, propene carbonate, gamma-butyrolacton and butylene carbonate or several
Kind;The linear carbonate is selected from dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, dipropyl carbonate and carbon
Number is one or more of the carbonic acid ester derivative that the linear chain or branched chain aliphatic monool of 3-8 is synthesized with carbonic acid.
Preferably, the lithium salts is selected from LiPF6、LiBF4、LiAsF6、LiClO4、LiBOB、LiCF3SO3、
LiCH3SO3、LiN(CF3SO2)2、LiN(C2F5SO2)2One or more of mixture, further preferably LiPF6。
Preferably, the lithium salt is 0.1-1.5mol/L, further preferably 1mol/L.
Preferably, other function additive is at least one of following compounds: vinylene carbonate, ethylene carbonate are sub-
Ethyl ester, fluorinated ethylene carbonate, 1,3- propane sultone, 1,4- butyl sultone, sulfuric acid acrylic ester, ethylene sulfite, fourth
Dintrile, further preferably vinylene carbonate or fluorinated ethylene carbonate.
Preferably, the additive amount of other function additive is the 0.01-20%, further preferably 1- of electrolyte gross mass
10%.
The present invention be also claimed by the high-fire-resistance lithium that is prepared of application of the organosiloxane fire retardant from
Sub- battery electrolyte.
Compared with prior art, the invention has the benefit that
(1) fire retardant improves silicone content, is effectively utilized the flame retardant property of element silicon, while also introducing fluorine original
Son, phenyl etc. have the function functional group of synergistic effect with element silicon, further improve flame retarding efficiency;(2) the fire retardant viscosity
Small, additional amount is few, influences on electrical properties such as conductivity, charge and discharge cycles small.
Specific embodiment
The present invention provides a kind of organosiloxane fire retardants and preparation method thereof, and are prepared using the fire retardant
High-fire-resistance lithium-ion battery electrolytes, wherein the performance of high-fire-resistance lithium-ion battery electrolytes is mainly from electrolyte
It is evaluated in terms of anti-flammability, conductivity and charge-discharge performance three:
1. anti-flammability
The anti-flammability of the electrolyte is evaluated using self-gravitation time test (SET), concrete operations are as follows: by quality be m1,
Diameter is that the glass fibre cotton balls of 5mm is immersed in prepared electrolyte to be measured, and it is m that its weight is weighed up after sufficiently infiltrating2,
The cotton balls is placed on iron wire loop, is lighted with igniter, record is denoted as T from the time for removing fire source to fray-out of flame, counts
The self-gravitation time t of unit mass electrolyte is calculated as the standard for measuring electrolyte flame-retardant performance, t=T/ (m2-m1), comparative example 1
And each sample tests take the average value tested three times, related data such as table 1 in embodiment 1-6.
2. conductivity
Conductance is carried out using the electrolyte that 731 conductivity meter of plum Teller InLab configures comparative example 1 and embodiment 1-6
The test of rate, test temperature are 25 DEG C, and the measurement result of each sample takes the average value measured three times, test result such as table 1.
3. charge-discharge performance
Each electrolyte sample carries out to the assembling of battery, assembled cobalt acid lithium graphite electrode be placed in 25 DEG C of thermostatic chambers into
Row test, is first melted into 0.1C electric current, is then carried out 200 circle charge and discharge cycles tests with 0.2C multiplying power, will be recycled result
It compares, the battery testing data assembled using comparative example 1 and embodiment 1-6 electrolyte are as shown in table 2.
Here is preparation example, comparative example and embodiment:
Preparation example 1: the preparation of phenyl siloxane
Using 3,5-dimethylphenyl vinyl silanes as raw material, in molar ratio for 1:1 respectively with prestox dihydro tetrasiloxane, ten
Five siloxanes of methyl dihydro, ten dimethyl dihydros, six siloxanes, the mixing of ten hexamethyl dihydros, eight siloxanes, are added Karsted and urge
Agent is warming up to 80 DEG C under nitrogen protection, obtains crude product after reacting 4h.Rectifying is then carried out, the complete raw material of unreacted is removed,
It is subsequently added into 10% activated carbon adsorption catalyst, heat filtering after 10h is stirred at 70 DEG C, active carbon is removed, obtains different silicon
The phenyl siloxane sterling of content.It will be with prestox dihydro tetrasiloxane, five siloxanes of decamethyl dihydro, ten dimethyl dihydros six
The phenyl siloxane product that siloxanes, ten hexamethyl dihydros, eight siloxane reactions obtain is denoted as A, B, C, D respectively, calculates silicone content
It is respectively as follows: 27.7%, 28.8%, 29.7%, 30.5%.
Preparation example 2: the preparation of fluorosilicone
Using vinyl (trifluoromethyl) dimethylsilane as raw material, in molar ratio for 1:1 respectively with four silicon of prestox dihydro
Oxygen alkane, five siloxanes of decamethyl dihydro, ten dimethyl dihydros, six siloxanes, the mixing of ten hexamethyl dihydros, eight siloxanes, are added
Karsted catalyst is warming up to 90 DEG C under nitrogen protection, obtains crude product after reacting 4h.Rectifying is then carried out, unreacted is removed
Complete raw material is subsequently added into 10% activated carbon adsorption catalyst, and heat filtering after 10h is stirred at 70 DEG C, active carbon is removed, obtains
To the fluorosilicone sterling of different silicone contents.It will be with prestox dihydro tetrasiloxane, five siloxanes of decamethyl dihydro, ten diformazans
The phenyl siloxane product that six siloxanes of base dihydro, ten hexamethyl dihydros, eight siloxane reactions obtain is denoted as E, F, G, H, silicon respectively
Content is respectively as follows: 28.5%, 29.5%, 30.4%, 31.1%.
Comparative example 1:
(the H in the glove box full of argon gas20 < 10ppm), by ethylene carbonate (EC), propene carbonate (PC), carbonic acid
Dimethyl ester (DMC) is uniformly mixed with volume ratio 1:1:1, is then slowly added to LiPF6, quality point is added after lithium salts is completely dissolved
The vinylene carbonate (VC) that number is 1%, obtains electrolyte 1 after mixing evenly, and wherein lithium salt is 1mol/L.
Prepared electrolyte is subjected to SET and conductivity test, as a result such as table 1;Then electrolyte 1 is injected into cobalt acid lithium
The test of room temperature charge and discharge cycles is carried out in graphite cell, test result is as shown in table 2.
Embodiment 1:
(the H in the glove box full of argon gas20 < 10ppm) 4 parts of electrolyte as described in comparative example 1 is prepared, then by benzene
Radical siloxane A, B, C, D with mass fraction be 1% amount be added separately in 4 parts of electrolyte, be made electrolyte 2A, 2B, 2C,
2D。
Prepared electrolyte 2A, 2B, 2C, 2D are subjected to SET and conductivity test respectively, as a result such as table 1;Then will
It is as shown in table 2 that 2A, 2B, 2C, 2D are injected separately into progress room temperature charge and discharge cycles test, test result in cobalt acid lithium graphite cell.
Embodiment 2:
(the H in the glove box full of argon gas20 < 10ppm) 4 parts of electrolyte as described in comparative example 1 is prepared, then by benzene
Radical siloxane A, B, C, D with mass fraction be 3% amount be added separately in 4 parts of electrolyte, be made electrolyte 3A, 3B, 3C,
3D。
Prepared electrolyte 3A, 3B, 3C, 3D are subjected to SET and conductivity test respectively, as a result such as table 1;Then will
It is as shown in table 2 that 3A, 3B, 3C, 3D are injected separately into progress room temperature charge and discharge cycles test, test result in cobalt acid lithium graphite cell.
Embodiment 3:
(the H in the glove box full of argon gas20 < 10ppm) 4 parts of electrolyte as described in comparative example 1 is prepared, then by benzene
Radical siloxane A, B, C, D with mass fraction be 5% amount be added separately in 4 parts of electrolyte, be made electrolyte 4A, 4B, 4C,
4D。
Prepared electrolyte 4A, 4B, 4C, 4D are subjected to SET and conductivity test respectively, as a result such as table 1;Then will
It is as shown in table 2 that 4A, 4B, 4C, 4D are injected separately into progress room temperature charge and discharge cycles test, test result in cobalt acid lithium graphite cell.
Embodiment 4:
(the H in the glove box full of argon gas20 < 10ppm) 4 parts of electrolyte as described in comparative example 1 is prepared, then by fluorine
For siloxanes E, F, G, H with mass fraction be 1% amount be added separately in 4 parts of electrolyte, be made electrolyte 2E, 2F, 2G,
2H。
Prepared electrolyte 2E, 2F, 2G, 2H are subjected to SET and conductivity test respectively, as a result such as table 1;Then will
It is as shown in table 2 that 2E, 2F, 2G, 2H are injected separately into progress room temperature charge and discharge cycles test, test result in cobalt acid lithium graphite cell.
Embodiment 5:
(the H in the glove box full of argon gas20 < 10ppm) 4 parts of electrolyte as described in comparative example 1 is prepared, then by fluorine
For siloxanes E, F, G, H with mass fraction be 3% amount be added separately in 4 parts of electrolyte, be made electrolyte 3E, 3F, 3G,
3H。
Prepared electrolyte 3E, 3F, 3G, 3H are subjected to SET and conductivity test respectively, as a result such as table 1;Then will
It is as shown in table 2 that 3E, 3F, 3G, 3H are injected separately into progress room temperature charge and discharge cycles test, test result in cobalt acid lithium graphite cell.
Embodiment 6:
(the H in the glove box full of argon gas20 < 10ppm) 4 parts of electrolyte as described in comparative example 1 is prepared, then by fluorine
For siloxanes E, F, G, H with mass fraction be 5% amount be added separately in 4 parts of electrolyte, be made electrolyte 4E, 4F, 4G,
4H。
Prepared electrolyte 4E, 4F, 4G, 4H are subjected to SET and conductivity test respectively, as a result such as table 1;Then will
It is as shown in table 2 that 4E, 4F, 4G, 4H are injected separately into progress room temperature charge and discharge cycles test, test result in cobalt acid lithium graphite cell.
The anti-flammability and conductivity test data of 1 electrolyte of table
As shown in Table 1, silicone content is higher, and flame retardant effect is better, and wherein silicone content highest D and H is 3% in additive amount
When, electrolyte can achieve the effect that non-ignitable.In addition, though with the increase of silicon content, conductivity decreases, but 5%
Additive amount in, influence of the addition of additive to conductivity is little.
2 battery charging and discharging loop test data of table
As shown in Table 2, the sample of each embodiment charge and discharge cycles test in, result without especially rule variation,
But compared with comparative example 1, all increase in terms of battery capacity and conservation rate.
Although reference be made herein to invention has been described for explanatory embodiment of the invention, and above-described embodiment is only this hair
Bright preferable embodiment, embodiment of the present invention are not limited by the above embodiments, it should be appreciated that those skilled in the art
Member can be designed that a lot of other modification and implementations, these modifications and implementations will fall in principle disclosed in the present application
Within scope and spirit.
Claims (10)
1. a kind of organosiloxane fire retardant, it is characterised in that have following structure:
Wherein, m > 0, n >=0, R1、R2、R3For halogen, alkyl, alkoxy, alkylene, phenyl, xenyl, phenylate base, alkyl halide
Base, halogenated alkoxy, haloalkene alkyl, halogenophenyl or halogenated biphenyl base, in which: halogen F, Cl or Br.
2. organosiloxane fire retardant according to claim 1, it is characterised in that:
0 < m≤3,0 n≤6 <.
3. organosiloxane fire retardant according to claim 1, it is characterised in that:
The organosiloxane fire retardant are as follows:
4. the preparation method of organosiloxane fire retardant described in claims 1 to 3 any claim, it is characterised in that:
By hydrogen-containing siloxane and vinyl silanes with molar ratio for 1:1 amount under the effect of the catalyst, reacted at 30-100 DEG C
1-6h, and carry out purifying after the completion of reaction and except miscellaneous operation, finally obtain required flame-retardant additive.
5. the preparation method of organosiloxane fire retardant according to claim 4, it is characterised in that:
The catalyst is Karsted or Spiere catalyst;
The purification operations are rectifying;The miscellaneous operation that removes is activated carbon adsorption.
6. the application of organosiloxane fire retardant described in claims 1 to 3 any claim is to be applied to prepare high-fire-resistance
Lithium-ion battery electrolytes are to mix lithium salts, organic solvent, organosiloxane fire retardant and other functional additives, obtain
High-fire-resistance lithium-ion battery electrolytes.
7. the application of organosiloxane fire retardant according to claim 6, it is characterised in that:
The additive amount of the organosiloxane fire retardant is the 0.5-20% of electrolyte gross mass.
8. the application of organosiloxane fire retardant according to claim 6, it is characterised in that:
The organic solvent includes cyclic carbonates solvent and/or linear carbonate class solvent, the cyclic carbonate
Class solvent is selected from one or more of ethylene carbonate, propene carbonate, gamma-butyrolacton and butylene carbonate;Described
It is 3-8's that linear carbonate, which is selected from dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, dipropyl carbonate and carbon number,
One or more of the carbonic acid ester derivative that linear chain or branched chain aliphatic monool is synthesized with carbonic acid;
The lithium salts is selected from LiPF6、LiBF4、LiAsF6、LiClO4、LiBOB、LiCF3SO3、LiCH3SO3、LiN
(CF3SO2)2、LiN(C2F5SO2)2One or more of mixture, lithium salt 0.1-1.5mol/L.
9. the application of organosiloxane fire retardant according to claim 6, it is characterised in that:
Other function additive is at least one of following compounds: vinylene carbonate, vinylethylene carbonate, fluoro carbon
Vinyl acetate, 1,3-propane sultone, Isosorbide-5-Nitrae-butyl sultone, sulfuric acid acrylic ester, ethylene sulfite, succinonitrile, other function
The additive amount of energy additive is the 0.01-20% of electrolyte gross mass.
10. the high fire-retardance being prepared according to the application of organosiloxane fire retardant described in claim 6 to 9 any claim
Type lithium-ion battery electrolytes.
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