CN108017669A - A kind of preparation method of phosphinate, phosphinate and nonaqueous electrolytic solution - Google Patents
A kind of preparation method of phosphinate, phosphinate and nonaqueous electrolytic solution Download PDFInfo
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- CN108017669A CN108017669A CN201610946254.1A CN201610946254A CN108017669A CN 108017669 A CN108017669 A CN 108017669A CN 201610946254 A CN201610946254 A CN 201610946254A CN 108017669 A CN108017669 A CN 108017669A
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- Prior art keywords
- phosphinate
- preparation
- reaction
- small
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- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000008151 electrolyte solution Substances 0.000 title claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 129
- 239000002904 solvent Substances 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 150000002367 halogens Chemical class 0.000 claims abstract description 10
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 9
- 239000011737 fluorine Substances 0.000 claims abstract description 9
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 6
- QCJQWJKKTGJDCM-UHFFFAOYSA-N [P].[S] Chemical compound [P].[S] QCJQWJKKTGJDCM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 5
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 5
- 239000000460 chlorine Substances 0.000 claims abstract description 5
- 230000002140 halogenating effect Effects 0.000 claims abstract description 5
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 5
- 239000011630 iodine Substances 0.000 claims abstract description 5
- 239000007818 Grignard reagent Substances 0.000 claims abstract description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000005864 Sulphur Substances 0.000 claims abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000004795 grignard reagents Chemical class 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052796 boron Inorganic materials 0.000 claims abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- 125000000962 organic group Chemical group 0.000 claims abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 3
- 239000011574 phosphorus Substances 0.000 claims abstract description 3
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 3
- 239000010703 silicon Substances 0.000 claims abstract description 3
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- -1 2- ethoxyethyl groups Chemical group 0.000 claims description 30
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
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- GUNJVIDCYZYFGV-UHFFFAOYSA-K Antimony trifluoride Inorganic materials F[Sb](F)F GUNJVIDCYZYFGV-UHFFFAOYSA-K 0.000 claims description 12
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
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- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
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- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IYPQZXRHDNGZEB-UHFFFAOYSA-N cobalt sodium Chemical compound [Na].[Co] IYPQZXRHDNGZEB-UHFFFAOYSA-N 0.000 description 1
- 238000000205 computational method Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-N hydroperoxyl Chemical compound O[O] OUUQCZGPVNCOIJ-UHFFFAOYSA-N 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- ZTWBEOCMVOSCSU-UHFFFAOYSA-N lithium;oxotitanium Chemical compound [Li].[Ti]=O ZTWBEOCMVOSCSU-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- IKULXUCKGDPJMZ-UHFFFAOYSA-N sodium manganese(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Na+] IKULXUCKGDPJMZ-UHFFFAOYSA-N 0.000 description 1
- 238000006561 solvent free reaction Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000011366 tin-based material Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/32—Esters thereof
- C07F9/3258—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/32—Esters thereof
- C07F9/3258—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/3264—Esters with hydroxyalkyl compounds
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6568—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms
- C07F9/65681—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms the ring phosphorus atom being part of a (thio)phosphinic acid or ester thereof
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
Abstract
The present invention provides a kind of preparation method of phosphinate, phosphinate and its nonaqueous electrolytic solution.A kind of preparation method of phosphinate, comprises the following steps：(1) Grignard Reagent R is passed through1MgX and three halogen sulphur phosphorus X3P=S reacts in a solvent, obtains the first intermediate；(2) halogenating agent M ' X are passed throughaReacted with first intermediate, obtain the second intermediate；(3) R is passed through2OH, water and second intermediate reaction, obtain phosphinate；Wherein, R1、R2It is respectively selected from alkyl or the organic group containing at least one of boron, silicon, nitrogen, phosphorus, oxygen, sulphur, fluorine, chlorine, bromine and iodine element；X represents halogen；M ' represents metallic element；A represents the chemical valence of metallic element M '.The electrolyte prepared using phosphinate of the present invention can lift the high temperature circulation stability of secondary cell；Also there are non-ignitable, fire-retardant or self extinguishment characteristics at the same time, secondary battery safety can be lifted.
Description
Technical field
The present invention relates to a kind of preparation method of phosphinate, phosphinate and nonaqueous electrolytic solution.
Background technology
In lithium rechargeable battery application field, security performance is one " stumbling-block " all the time, such as electric automobile field
Event on fire.Electric automobile event on fire is main reason is that its lithium rechargeable battery for using, and the original of battery catches fire
One of cause is the flammable nonaqueous electrolytic solution that it is used.In addition, under the service life of lithium rechargeable battery, especially hot conditions
Capacity retention ratio, can not meet current practice demand.
So far, phosphinate is used as film for additive, the flame-retardant additive of electrolyte by existing more document report
Or non-ignitable solvent is to lift the hot properties of lithium/sodium ion secondary battery and security performance.Chinese patent CN102916223A
A kind of nonaqueous electrolytic solution is disclosed, which includes at least one organophosphor such as phosphine oxide, phosphonate ester and phosphinate
Compound.It is it has been recognised by the inventors that phosphinate can form a coating at least one electrode surface of cathode and/or anode
(SEI), which can improve the High temperature storage characteristic and high temperature cyclic performance of battery.Chinese patent CN1685556A is disclosed
A kind of electrolyte containing phosphinate can prevent electrolyte decomposed metamorphic during high trickle charge or high-temperature storage, from
And improve the high-temperature stability of secondary cell.Japan Patent JP1998228928A and JP1999233141A, which are individually disclosed, to be passed through
Add 5~100% contents phosphonate ester and/or phosphinate to lift the non-flame properties method of electrolyte.This method not only can be with
The security for lifting secondary cell does not damage other performances of battery again at the same time.The application value of phosphinate is increasingly subject to people
Concern, but the research to its synthetic method is fewer and fewer.
The content of the invention
To solve the above-mentioned problems, the present invention provides a kind of preparation method of phosphinate, comprise the following steps：
(1) Grignard Reagent R is passed through1MgX and three halogen sulphur phosphorus X3P=S reacts in a solvent, obtains the first intermediate
(2) halogenating agent M ' X are passed throughaReacted with first intermediate, obtain the second intermediate
(3) R is passed through2- OH, water and second intermediate reaction, obtain phosphinate
Wherein, R1、R2It is respectively selected from alkyl or containing at least one of boron, silicon, nitrogen, phosphorus, oxygen, sulphur, fluorine, chlorine, bromine and iodine
The organic group of element；X represents halogen；M ' represents metallic element；A represents the chemical valence of metallic element M '.
In the first step of the present invention, Grignard Reagent R1MgX three halogen sulphur phosphorus X with Halogen group elements in anhydrous conditions3P=S is anti-
Should, obtain R1First intermediate of base substitutionReaction equation is as follows：
Second step, the first intermediateWith halogenating agent M ' Xa(the two substitution halogenations of the second intermediate of reaction generation
Thing)Reaction equation is as follows：
Second step reaction of the present invention can react in a solvent, can not also use solvent.
3rd step, R2- OH, water and the second intermediateProduct phosphinate is obtained by single step reaction.Reaction equation
It is as follows：
In three-step reaction, the oxygen in the hydroxyl oxygen and water of alcohol is in electron rich, nucleophilic attack P elements.Occur
Alcoholysis and hydrolysis, halogen group are substituted.Water can be moisture in air in the present invention, can also additionally add；In the present invention
Water be preferably deionized water.
In three-step reaction, because the second intermediate easily hydrolyzes, therefore when the addition of the second intermediate is less than etc.
When 2mol, three-step reaction can react under air atmosphere obtains product phosphinate, i.e., the moisture in air can expire
To the demand of water content in sufficient reactant, added without adding water as reactant.So on the one hand can save preparation into
This, it is often more important that it can prevent that addition and addition speed due to water from not having to control violent hydrolysis that is suitable and producing
The danger of initiation；The water for adding excess can also be avoided to increase during purification (such as extraction, distillation, rectifying, drying) at the same time
Addition sheet.Method of purification is included by published methods in this area such as extraction, distillation, rectifying, dryings.
Among three-step reaction, when the second intermediate dosage is more than 2mol, water is needed as reactant volume in the present invention
Outer addition.Because when reaction feeds intake it is larger when, water loading of the air is not enough to that the reaction was complete with the second intermediate and alcohol.But
Water content cannot be excessive, because commercialized electrolyte is pure organic solvent system, it is very sensitive to moisture, so water content
The excessive cost that can make purification increases.
Meanwhile three-step reaction is solvent-free reaction, reaction raw materials are environmentally protective, therefore this reaction belongs to environmentally protective section
About type reacts.Purification (such as extraction, distillation, rectifying, drying) cost of reaction is also greatly reduced at the same time, because the present invention's is anti-
Product is answered to be used as electrolysis additive, and purity requirement of the electrolyte to its additive is very high.In addition, this reaction is not required to
Anhydrous and oxygen-free is wanted to operate, this has fully provided for advantage for expanding production.
As a kind of embodiment, the R1For saturation chain-like alkyl or saturation chain alkoxy.Preferably, R1It is selected from
Methyl, ethyl, butyl, iso-octyl, 2- methoxy ethyls, 2- ethoxyethyl groups or methoxy.
As a kind of embodiment, the R1For the unsaturated chain-like groups containing alkenyl, non-end alkynyl or nitro.Make
To be preferred, R1Selected from vinyl, 1- methylpropynyls, pi-allyl, 2- nitro-ethyls or nitromethyla.
As a kind of embodiment, the R1Saturated cyclic group for saturated cyclic alkyls or containing ether.As excellent
Choosing, R1Selected from cyclohexyl, cyclopenta or 3- methoxycyclohexyls.
As a kind of embodiment, the R1For the unsaturated cyclic group containing alkenyl, alkynyl or nitro；Or R1For benzene
Base, phenyl derivatives group or heterocyclic group；Preferably, the R1Selected from cyclopentenyl, 3- alkynyls cyclohexyl, 3- nitro rings
Hexyl, phenyl, 4- aminomethyl phenyls, 4- methoxyphenyls, diphenyl methyl, naphthyl, furans, thiophene or imidazoles.
As a kind of embodiment, the R2The saturation chain-like alkyl for being 1~8 for carbon number.Preferably, the R2
For methyl, ethyl, propyl group, isopropyl, butyl or the tert-butyl group.
As a kind of embodiment, the R2The fluoro-alkyl for being 1~8 for carbon number.Preferably, the R2It is selected from
2,2,2- trifluoroethyls, hexafluoro isopropyl, seven fluorine isobutyl groups or perfluoro butyl.
As a kind of embodiment, the R2For the aryl of halogen substituent.Preferably, the R2For pentafluorophenyl group,
Fluorotoluene base, trifluoromethyl, three (2,2,2- trifluoroethyls) phenyl or three (2,2,2- trifluoro ethoxies) phenyl.
As a kind of embodiment, the three halogen sulphur phosphorus is phosphorus thiochloride；The M ' is selected from arsenic or antimony；The X be selected from fluorine,
At least one of chlorine, bromine and iodine.
As a kind of embodiment, the solvent of the step (1) be selected from aliphatic hydrocarbon compound, arene compound,
At least one of ether compound and ketone compounds.Preferably, the solvent of the step (1) be selected from n-hexane, hexamethylene,
At least one of benzene, toluene, tetrahydrofuran and ether.
As a kind of embodiment, reaction temperature is -30~60 DEG C in the step (1)；Reaction time is small for 2~48
When.Preferably, reaction temperature -10~25 DEG C in step (1)；When reaction time is 6~24 small.As a kind of embodiment,
Reaction temperature is 25~200 DEG C in the step (2), when the reaction time is 0.2~10 small.Preferably, reaction in step (2)
Temperature is 50~150 DEG C；When reaction time is 0.5~5 small.As a kind of embodiment, reaction temperature is in the step (3)
0~80 DEG C；When reaction time is 1~48 small.Preferably, reaction temperature is 20 DEG C~40 DEG C in step (3)；Reaction time is
5~24 it is small when.
As a kind of embodiment, the second intermediate and H in step (3)2The molar ratio of O is 1:(0.5~1)；As excellent
Select, the second intermediate and H in step (3)2The molar ratio of O is 1:(0.5~0.8).Second intermediate and R in step (3)2OH's
Molar ratio is 1:(1~1.5).Preferably, the second intermediate and R in step (3)2The molar ratio of OH is 1:(1~1.2).
In step (3), the second intermediate and water reaction generation intermediate productThe intermediate productCan be after
It is continuous to react to obtain the phosphinate of the present invention with alcoholThe present inventor passes through following three kinds by the discovery that studies for a long period of time
At least one of method can improve the phosphinate obtained in step (3) reactionYield；In addition, three kinds of sides
Method can select at least one use, and when selecting two or three, effect is more preferable, and especially three kinds effects when being used together are most
It is good.
The present invention improves phosphinateThe first method of yield is：Control rubbing for the second intermediate and water
You are than being 1:(0.5~1).Since when reactants water is excessive, which part water and the second intermediate reaction generation intermediate productAnd remaining water then may proceed to the intermediate product with generationReaction generation accessory substanceSo cause
With the intermediate product of alcohol reactionContent is reduced, even if the phosphinate reacted with alcoholYield reduces.
Therefore, in order to improve yield, the control of the molar ratio of the second intermediate and water is 1 by the present invention:(0.5~1)；Preferably, second
The control of the molar ratio of intermediate and water is 1:(0.5~0.8).
In addition, commercialized electrolyte is essentially pure organic solvent system at present, and it is very sensitive to moisture, so of the invention
Middle control H2The amount of O is very important.
The present invention improves phosphinateThe second method of yield is：Control the second intermediate and R2OH's
Molar ratio is 1:(1~1.5), preferable second intermediate and R2The molar ratio of OH is 1:(1~1.2).This proportioning can ensure
Alcohol and intermediate productEven if fully reaction intermediate productThe reaction was complete.
In addition, purification (such as extraction, distillation, rectifying, drying) fairly simple and recoverable of excessive alcohol.
The present invention improves phosphinateThe third method of yield is：Step of the present invention (3) is put into
The sequential control of reactant is：Second intermediate and water first adds in reaction vessel to (the second intermediate and water can add at the same time
Entering to be separately added into), then alcohol is added in reaction vessel, to ensure that water is first reacted with the second intermediate.If first add alcohol
With the second intermediate, water is added, the yield of phosphinate can be reduced substantially.
It is a further object to provide a kind of phosphinate, using the preparation method of the above-mentioned phosphinate of the present invention
It is prepared.
It is a further object to provide a kind of nonaqueous electrolytic solution, including the phosphinate that the present invention is above-mentioned.The electricity
Solution liquid can lift the high temperature circulation stability of secondary cell, while also have non-ignitable, fire-retardant or self extinguishment characteristics, can lift two
Secondary battery safety.
As a kind of embodiment, the quality of the phosphinate is the 5~90% of nonaqueous electrolytic solution quality.As excellent
Choosing, the quality of the phosphinate are the 10~80% of nonaqueous electrolytic solution quality.As further preferred, the phosphinate
Quality is the 25~60% of nonaqueous electrolytic solution quality.
The present invention also provides a kind of nonaqueous electrolytic solution secondary battery, including cathode, anode, membrane and of the present invention non-
Water electrolysis liquid.
Preferably, the positive electrode is selected from lithium nickel cobalt manganese oxide, sodium cobalt-nickel-manganese oxide compound, sodium nickel
Cobalt composite oxide, lithium nickel cobalt aluminium composite oxide, li-mn-ni compound oxide, olivine-type lithium iron phosphate oxide, lithium cobalt oxide
At least one of compound, sodium cobalt/cobalt oxide, lithium manganese oxide and sodium manganese oxide.But it is not limited to above-mentioned material.
Preferably, the negative material is selected from graphite, carbonaceous mesophase spherules, agraphitic carbon, lithium titanium oxygen compound, lithium
At least one of oxyvanadium compound, silica-base material, tin-based material and transition metal oxide.The graphite include Delanium and
Native graphite；The non-type carbon includes hard carbon and soft carbon.But it is not limited to above-mentioned material.
Preferably, the membrane is selected from polyolefin fusion drawn membrane；Or the membrane is selected from PET (poly- terephthaldehydes
Sour glycol ester), Kynoar, the membrane that at least one of aramid fiber and polyamide are base material；It is or porous selected from high softening-point
The membrane of polyolefin is coated with basis material.Polyolefins fusion drawn membrane of the present invention can be polypropylene single-layer septum or gather
Ethylene single-layer membrane, or three layers of composite diaphragm of polypropylene, polyethylene/polypropylene etc..High softening-point of the present invention it is porous
Basis material refers to that softening point is higher than 150 DEG C of porous matrix material.But it is not limited to above-mentioned material.
Nonaqueous electrolytic solution secondary battery of the present invention, except the active matter using heretofore described positive electrode
Outside matter, the active material of negative material, membrane and nonaqueous electrolytic solution, it is constructed and is not construed as limiting, to its process for machining and manufacturing
Also it is not especially limited, can be identical with common lithium-ion secondary cell.As cathode, anode, membrane can be made with the following method
Standby, battery can assemble with the following method：
(a) cathode
The nonaqueous electrolytic solution secondary battery can be manufactured with cathode with method as described below.
First, mixing powdery positive active material, conductive agent and bonding agent, and solvent is added, slurry is made.Cathode is starched
The mixing ratio of each material in material, often determines the chemical property of lithium rechargeable battery.Usually, each solid in anode sizing agent
The gross mass of material composition is similar with the cathode of common lithium rechargeable battery as 100 mass parts, preferably by active anode compartment
Material content be set as 80~95 mass parts, conductive material content be set as 2~15 mass parts, bonding agent content be set as 1~
18 mass parts.
The anode sizing agent obtained is coated on to the surface of made with aluminum foil collector, and is dried so that solvent volatilizees.Root
According to needs, can also be pressurizeed by roll-in method etc., to improve electrode density.Thus, sheet-like anode can be manufactured.Can be according to mesh
Battery is marked, sheet-like anode is cut with appropriate size.The manufacture method of cathode is not limited to illustrated method, can also adopt
With other methods.When manufacturing anode pole piece, as conductive agent, such as carbon can be used, can be that amorphous carbon can also be
Crystalline carbon, including it is charcoal, coke, bone black, sugar charcoal, activated carbon, carbon black, coke, graphitized intermediate-phase carbosphere (MCMB), soft
Carbon, hard carbon and graphite etc.；Divide from microstructure, the carbon can be carbon nanotubes, graphite flake, fullerene, stone
Black alkene etc.；Divide from microscopic appearance, the carbon can be carbon fiber, carbon pipe, carbon ball etc..It is preferred that highly electron conductive, knot
The good carbon material of structure intensity.
Bonding agent serves the connection fixation of positive active material particle, including hydrophilic polymer, that is, carboxymethyl cellulose
Plain (CMC), methylcellulose (MC), cellulose acetate-phthalate (CAP), HYDROXY PROPYL METHYLCELLULOSE (HPMC), hydroxyl
Propyl methocel phthalic acid ester (HPMCP), polyvinyl alcohol (PVA), polyethylene glycol oxide (PEO) etc. and hydrophobicity are gathered
Compound material such as polytetrafluoroethylene (PTFE) (PTFE), tetrafluoroethene perfluoroalkyl vinyl ether copolymer (FEP), Kynoar
(PVDF), the fluorine resin such as polyethylene-TFE copolymer (ETFE) and acetate ethylene copolymer, styrene-butadiene
At least one in rubbers such as block copolymer (SBR), acrylic acid modified SBR resins (SBR systems latex), acacia gum etc.
Kind.Wherein, preferably using fluorine resins such as PTFE, PVDF.Lead electronic polymer has obviously advantage as binding agent,
It is the developing direction for the binding agent in electrochemical device.
Made an addition in appropriate solvent, and made by positive electrode active materials and foregoing illustrative conductive agent and bonding agent etc.
It disperses or dissolves and is mixed, and slurry is thus made.
The slurry modulated is coated on plus plate current-collecting body, and after making solvent volatile dry, carries out roll-in.As representative
The example of property, can use apparatus for coating (coating machine), with defined thickness in collection liquid surface coating sizing-agent.To coating thickness simultaneously
There is no particular limitation, can suitably be set according to the shape or purposes of Anode and battery.It is dry to remove solvent after coating,
The positive electrode active material layer of specific thickness is formed in collection liquid surface, then carries out roller process as needed, it is thick to obtain target
The anode pole piece of degree.
(b) anode
Heretofore described cathode pole piece, by active material of the present invention and conductive agent, adhesive, solvent
It is mixed in a certain ratio after slurry is made and is evenly applied on copper foil, then is made through dry and rolling.
The description of the above-mentioned manufacture to battery pole piece be based on current conventional mass production process, but be not precluded from
Plasma spraying technology, 3D printing technique for being expected to realize afterwards etc. is applied to the manufacture of lithium ion secondary battery pole piece.
(c) membrane
Membrane is one of key components of battery, between the positive and negative electrode of battery, for isolating positive and negative electricity
Pole, avoids internal short-circuit of battery, while ensures that ion can be passed through in discharge and recharge again.Membrane for battery is a kind of
The electronic insulating film of loose structure, has high ionic conduction performance and good mechanical strength, can grow in the electrolytic solution
Phase is stabilized, and does not chemically react.In the secondary battery, the quality of membrane properties directly affects the internal resistance of battery, holds
Amount, charging and discharging currents density, cycle life and safety etc. key performance.
Battery of the present invention is not particularly limited the material of membrane, structure.Polyolefins melting can be selected to draw
Membrane is stretched, predominantly polypropylene, polyethylene single-layer septum, or three layers of composite diaphragm of polypropylene, polyethylene/polypropylene；Also may be used
To select using PET (polyethylene terephthalate) non-woven fabrics as membrane.
(d) shape of battery, structure
A kind of heretofore described long-life can fast charge nonaqueous electrolyte battery, by above-mentioned cathode, anode, membrane with
Can be that cylindrical type, square etc. are variously-shaped, outer packing can be that metal-back can also be plastic-aluminum and non-aqueous electrolyte is formed
Film, can need to design according to practical application.
Brief description of the drawings
Fig. 1 is the charging and discharging curve of battery in the embodiment of the present invention 1 and comparative example 1；
Fig. 2 is the capacity circulating curve of battery in the embodiment of the present invention 1 and comparative example 1；
Fig. 3 is the energy efficiency cyclic curve of the embodiment of the present invention 1 and comparative example 1；
Fig. 4 is the charging and discharging curve of the embodiment of the present invention 2；
Fig. 5 is the capacity circulating curve of the embodiment of the present invention 2；
Fig. 6 is the energy efficiency cyclic curve of the embodiment of the present invention 2.
Embodiment
The present invention is described in detail in following specific embodiment, but the present invention is not restricted to following implementation
Example.
Embodiment 1：
The first step is reacted：The phosphorus thiochloride and 1.5L solvents tetrahydrofuranes of 170.0g is added into reaction vessel, and in room
Stirred evenly under temperature, then add the magnesium bromide of normal-butyl containing 191.0g tetrahydrofuran solution continue stir 18h obtain reaction solution.
Reaction solution is poured into the sulfuric acid solution of 500mL10wt%, with ether extraction and isolated organic layer, the anhydrous sulphur of organic layer
Vacuum distillation removes solvent and obtains solid mixture after sour magnesium drying.Solid mixture is obtained with toluene and ethyl alcohol recrystallization white
Color solid, obtains 74.0g products after vacuum drying
Second step reacts：The above-mentioned products of 70.0g are transferred in single necked round bottom flask, are opened after adding 85.9g antimony trifluorides
Begin to stir, and single necked round bottom flask is connected into vacuum distillation apparatus, 165 DEG C of reaction 1h are heated under decompression and obtain colourless liquid
40.2g.Colourless liquid is evaporated under reduced pressure to purifying again and obtains 34.4g colorless liquid products
Three-step reaction：The above-mentioned colorless liquid products of 30.0g are transferred in two mouthfuls of round-bottomed flasks, keep reaction vessel with
Air is connected, so as to using the moisture in air, be slowly stirred at 27 DEG C 0.5 it is small when after, when 0.5 is small it is interior be slowly stirred plus
Enter 14.9g trifluoroethanols, and the reaction was continued 10 it is small when terminate, by vacuum distillation obtain 34.5g (yield about 89%) product
Nonaqueous electrolytic solution is prepared：Prepare ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC)
Non- water mixed solvent, EC：EMC：The volume ratio of DMC is 30:50:20, then add thereto(content
For the 15.0wt% of nonaqueous electrolytic solution quality) and film for additive vinylene carbonate (VC, content are nonaqueous electrolytic solution weight
The 2.0wt% of quality).It is slowly added to electrolytic salt LiPF6And cooled down, form LiPF6Concentration is the non-water power of 12.5wt%
Solve liquid.
Battery makes：11.5Ah is laminated aluminum plastic film flexible-packed battery, and positive electrode uses LiNi0.6Co0.2Mn0.2O2
(NCM622), negative material uses hard carbon, when room temperature 1C discharges, energy density about 150Wh/kg.
Battery performance test：Under 45 DEG C of environment temperatures, by above-mentioned flexible-packed battery in 2.00~4.20V voltage ranges
Discharge and recharge, i.e. constant current (rate of charge 2C) charge to 4.20V, then 4.20V constant-voltage charges (multiplying power 0.1C), then constant current
(discharge-rate 2C) is discharged to 2.00V.The constant current ratio of battery charging is between 94~98%.The efficiency of discharge and recharge is basically stable at
100% or so.Discharge capacity can reach 10.85Ah first, and circulation 150 weeks can be using discharge capacity as 10.64Ah, and capacity is kept
Rate 98.06%.Battery core can reach 142.10Wh/Kg than energy first, and circulation can reach 139.50Wh/Kg in 150 weeks.Battery
Energy conversion efficiency be basically stable at 95% or so.Energy conversion efficiency is discharge energy and the ratio of rechargeable energy.Specifically
Test result is see Fig. 1, Fig. 2 and Fig. 3.
Embodiment 2：
The first step and second step are reacted with embodiment 1, unlike, three-step reaction is by 36g colorless liquid productsIt is transferred in two mouthfuls of round-bottomed flasks, keeps reaction vessel and air to connect, so as to using the moisture in air, 27 DEG C
Under be slowly stirred 0.5 it is small when after, when 0.5 is small, interior be slowly stirred adds 15.8g n-butanols, reacts 1h extremely at 27 DEG C of room temperature
Reaction terminates.33.3g (yield 80%) product is obtained by vacuum distillation
Nonaqueous electrolytic solution is prepared：Prepare ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC)
Non- water mixed solvent, EC：EMC：The volume ratio of DMC is 30:50:20, then add thereto(content is
The 5.0wt% of nonaqueous electrolytic solution quality) and film for additive vinylene carbonate (VC, content are non-aqueous solution electrolysis liquid heavy
The 2.0wt% of amount).It is slowly added to electrolytic salt LiPF6And cooled down, form the nonaqueous electrolytic solution that concentration is 12.5wt%.
Battery makes：10Ah is laminated aluminum plastic film flexible-packed battery, and positive electrode uses LiNi0.6Co0.2Mn0.2O2
(NCM622), negative material uses hard carbon, and battery energy density is higher, when room temperature 1C discharges, energy density about 130Wh/kg.
Battery performance test performance：Under 45 DEG C of environment temperatures, by above-mentioned flexible-packed battery in 2.00~4.20V voltage models
Interior discharge and recharge is enclosed, i.e. constant current (rate of charge 2C) charges to 4.20V, then 4.20V constant-voltage charges (multiplying power 0.1C), then
Constant current (discharge-rate 2C) is discharged to 2.00V.The constant current ratio of battery charging is between 94~98%.The efficiency of discharge and recharge is basicly stable
100% or so.Discharge capacity can reach 10.98Ah first, and circulation 150 weeks can be using discharge capacity as 10.88Ah, and capacity is protected
Holdup 99.09%.Battery core can reach 138.20Wh/Kg than energy first, and circulation can reach 135.20Wh/Kg in 150 weeks.Electricity
The energy conversion efficiency in pond is between 94~95%.Energy conversion efficiency is discharge energy and the ratio of rechargeable energy.It is specific to survey
Test result is see Fig. 4, Fig. 5 and Fig. 6.
Embodiment 3：
The first step is reacted：170.0g phosphorus thiochlorides and 1.5L solvents tetrahydrofuranes are added into reaction vessel, and in room temperature
Stirred evenly under (25 DEG C).Then (399.1g refers to ethylmagnesium bromide to the tetrahydrofuran solution of addition 399.1g ethylmagnesium bromides
Quality) continue to obtain reaction solution when 25 DEG C of stirrings are small to reaction 48.Reaction solution is poured into the sulfuric acid solution of 500mL10wt%,
With ether extraction and isolated organic layer, after organic layer is dried with anhydrous magnesium sulfate vacuum distillation remove solvent and obtain solid and mix
Compound.Solid mixture is obtained into white solid with toluene and ethyl alcohol recrystallization, 69.0g products are obtained after vacuum drying
Second step reacts：The above-mentioned products of 69.0g are transferred in single necked round bottom flask, are opened after adding 108.0g antimony trifluorides
Begin to stir.And single necked round bottom flask is connected into vacuum distillation apparatus, is heated to obtaining when 144 DEG C of reactions 2 are small under decompression colourless
Liquid 57.0g.Colourless liquid is evaporated under reduced pressure to purifying again and obtains 52.5g colorless liquid products
Three-step reaction：The above-mentioned colorless liquid products of 50.0g are transferred in two mouthfuls of round-bottomed flasks, keep reaction vessel with
Air is connected, so as to using the moisture in air, be slowly stirred at 0 DEG C 0.5 it is small when after, it is interior when 0.5 is small to be slowly added to
25.2g n-butanols, and continue to terminate when reaction 48 is small at 0 DEG C, 52.4g (yield about 86%) product is obtained by vacuum distillation
Embodiment 4：
The first step is reacted：500.0g phosphorus thiochlorides and 1.6L solvents tetrahydrofuranes are added into reaction vessel, and in room temperature
Under stir evenly.Then (779.2g refers to fourth diyl magnesium bromide to the tetrahydrofuran solution of the addition positive fourth diyl magnesium bromides of 779.2g
Quality) continue at 60 DEG C stirring to reaction 2 it is small when obtain reaction solution, with ether extraction and isolated organic layer, organic layer
Vacuum distillation removes solvent and obtains solid mixture after being dried with anhydrous magnesium sulfate.Solid mixture is tied again with toluene and ethanol
Crystalline substance obtains white solid, and 182.0g (yield about 52%) product is obtained after vacuum drying
Second step reacts：The above-mentioned products of 180.0g are transferred in single necked round bottom flask, after adding 328.3g antimony trifluorides
Start to stir.And single necked round bottom flask is connected into vacuum distillation apparatus, is heated to obtaining when 167 DEG C of reactions 3.6 are small under decompression
Colourless liquid 163.6g.Colourless liquid is evaporated under reduced pressure to purifying again and obtains 154.6g colorless liquid products(repeat this
Experiment is twice).
Three-step reaction：The above-mentioned colorless liquid products of 300.0g are transferred in two mouthfuls of round-bottomed flasks, in 30min at 27 DEG C
Interior addition 19.0g deionized waters and continue stirring 0.5 it is small when after, 0.7 when small it is interior be slowly stirred add 104.0g ethanol, and
60 DEG C the reaction was continued 6 it is small when terminate, by vacuum distillation obtain 281.0g (yield about 91%) product
Embodiment 5：
The first step is reacted：500.0g phosphorus thiochlorides and 3.0L solvents tetrahydrofuranes are added into reaction vessel, and in room temperature
Under stir evenly.Then the tetrahydrofuran solution (1.6kg refers to the quality of phenyl-magnesium-bromide) for adding 1.6kg phenyl-magnesium-bromides continues
Stirring obtains reaction solution when extremely reaction 36 is small at 45 DEG C.Reaction solution is poured into the sulfuric acid solution of 1.5L 10wt%, is extracted with ether
Take and isolated organic layer, organic layer are evaporated under reduced pressure removing solvent and obtain solid mixture after being dried with anhydrous magnesium sulfate.Will
Solid mixture obtains white solid with toluene and ethyl alcohol recrystallization, and 274.4g products are obtained after vacuum drying
Second step reacts：The above-mentioned products of 160.0g are transferred in single necked round bottom flask, after adding 291.8g antimony trifluorides
Start to stir.And single necked round bottom flask is connected into vacuum distillation apparatus, is heated to obtaining when 167 DEG C of reactions 3.6 are small under decompression
Colourless liquid 132.9g.Colourless liquid is evaporated under reduced pressure to purifying again and obtains 126.7g colorless liquid products
Three-step reaction：The above-mentioned colorless liquid products of 120.0g are transferred in two mouthfuls of round-bottomed flasks, 0.7 is interior slow when small
Stirring adds 34.1g ethanol, and at 60 DEG C the reaction was continued 8 it is small when terminate, obtain 111.0g by vacuum distillation (yield be about
91%) product
Embodiment 6：
The first step is reacted：500.0g phosphorus thiochlorides and 3.0L solvents tetrahydrofuranes are added into reaction vessel, and in room temperature
Under stir evenly.Then add the tetrahydrofuran solution of 1.6kg allylic bromination magnesium (1.6kg refers to the quality of allylic bromination magnesium)
Continue the stirring at 45 DEG C and obtain reaction solution to 36h is reacted.Reaction solution is poured into the sulfuric acid solution of 1.5L 10wt%, uses ether
Extract and isolated organic layer, organic layer are evaporated under reduced pressure removing solvent and obtain solid mixture after being dried with anhydrous magnesium sulfate.
Solid mixture is obtained into white solid with toluene and ethyl alcohol recrystallization, 274.4 products are obtained after vacuum drying
Second step reacts：By 160.0g, the product is transferred in single necked round bottom flask, is opened after adding 291.8g antimony trifluorides
Begin to stir.And single necked round bottom flask is connected into vacuum distillation apparatus, is heated to obtaining nothing when 167 DEG C of reactions 3.6 are small under decompression
Color liquid 137.8g.Colourless liquid is evaporated under reduced pressure to purifying again and obtains 126.7g colorless liquid products
Three-step reaction：By 120.0g, the colorless liquid product is transferred in two mouthfuls of round-bottomed flasks, and 0.7 interior when small slowly stirs
Mix and add 41.6g ethanol, and at 60 DEG C the reaction was continued 8 it is small when terminate, obtain 111.0g by vacuum distillation (yield be about
91%) product
Embodiment 7：
The first step is reacted：500.0g phosphorus thiochlorides and 3.0L solvents tetrahydrofuranes are added into reaction vessel, and in room temperature
Under stir evenly.Then 1.6kg is addedTetrahydrofuran solution (1.6kg refers toQuality) continue at 45 DEG C
Lower stirring obtains reaction solution when extremely reaction 36 is small.Reaction solution is poured into the sulfuric acid solution of 1.5L 10wt%, is extracted and divided with ether
From organic layer is obtained, vacuum distillation removing solvent obtains solid mixture after organic layer is dried with anhydrous magnesium sulfate.Solid is mixed
Compound obtains white solid with toluene and ethyl alcohol recrystallization, and 274.4g (yield about 41%) product is obtained after vacuum drying
Second step reacts：The above-mentioned products of 160.0g are transferred in single necked round bottom flask, after adding 291.8g antimony trifluorides
Start to stir.And single necked round bottom flask is connected into vacuum distillation apparatus, be heated under decompression 167 DEG C reaction 3.6h obtain it is colourless
Liquid 133.3g.Colourless liquid is evaporated under reduced pressure to purifying again and obtains 126.7g colorless liquid products
Three-step reaction：By the above-mentioned second step products of 100gIt is transferred in two mouthfuls of round-bottomed flasks, 0.7 is interior when small
Be slowly stirred and add 18.2g ethanol, and at 60 DEG C the reaction was continued 13 it is small when, obtain 85.3g by vacuum distillation (yield be about
84%) product
Embodiment 8：
The first step is reacted：500.0g phosphorus thiochlorides and 3.0L solvents tetrahydrofuranes are added into reaction vessel, and in room temperature
Under stir evenly.Then (1.6kg refers to the matter of benzene diyl magnesium bromide to the tetrahydrofuran solution of addition 1.6kg p-fluorophenyl magnesium bromides
Amount) continue at 45 DEG C stirring to reaction 36 it is small when obtain reaction solution.Reaction solution is poured into cut-and-dried 1.5L 10wt%'s
Sulfuric acid solution, with ether extraction and isolated organic layer, vacuum distillation removing solvent is consolidated after being dried with anhydrous magnesium sulfate
Body mixture.Solid mixture is obtained into white solid with toluene and ethyl alcohol recrystallization, 274.4g products are obtained after vacuum drying
Second step reacts：The above-mentioned products of 160.0g are transferred in single necked round bottom flask, after adding 291.8g antimony trifluorides
Start to stir.And single necked round bottom flask is connected into vacuum distillation apparatus, is heated to obtaining when 167 DEG C of reactions 3.6 are small under decompression
Colourless liquid 130.7g.Colourless liquid is evaporated under reduced pressure to purifying again and obtains 126.7g colorless liquid products(repeat this
Experiment five times).
Three-step reaction：By the above-mentioned second step products of 600gBe transferred in two mouthfuls of round-bottomed flasks, at 27 DEG C
21.8g deionized waters are added in 30min and continue stirring 0.5 it is small when after, 0.7 interior be slowly stirred when small adds 133.5g second
Alcohol, and at 60 DEG C the reaction was continued 13 it is small when terminate, by vacuum distillation obtain 511.8g (yield about 84%) product
Embodiment 9：
The first step is reacted：170.0g phosphorus thiochlorides and 1.5L solvents tetrahydrofuranes are added into reaction vessel, and at -30 DEG C
Under stir evenly.Then add 399.1g ethylmagnesium bromides tetrahydrofuran solution (399.1g refers to the quality of ethylmagnesium bromide) after
Continue and obtain reaction solution when -30 DEG C of stirrings are small to reaction 48.Reaction solution is poured into the sulfuric acid solution of 500mL 10wt%, uses ether
Extract and isolated organic layer, organic layer are evaporated under reduced pressure removing solvent and obtain solid mixture after being dried with anhydrous magnesium sulfate.
Solid mixture is obtained into white solid with toluene and ethyl alcohol recrystallization, 53.1g products are obtained after vacuum drying
Second step reacts：The above-mentioned products of 50.0g are transferred in single necked round bottom flask, are opened after adding 78.3g antimony trifluorides
Begin to stir.And single necked round bottom flask is connected into vacuum distillation apparatus, is heated to obtaining when 25 DEG C of reactions 10 are small under decompression colourless
Liquid 27.8g.Colourless liquid is evaporated under reduced pressure to purifying again and obtains 22.4g colorless liquid products(repeat this experiment
20 times).
Three-step reaction：The above-mentioned colorless liquid products of 438.0g are transferred in two mouthfuls of round-bottomed flasks, in 30min at 27 DEG C
Interior addition 48.6g deionized waters and continue stirring 0.5 it is small when after, it is interior when 0.5 is small to be slowly added to 222.0g n-butanols, and
Continue to terminate when reaction 48 is small at 0 DEG C, 422.7g (yield about 79%) product is obtained by vacuum distillation
Embodiment 10：
With embodiment 2, the difference is that the reaction temperature of step (3) is 80 DEG C, when the reaction time is 2 small, product is obtained39.1g (yield about 94%).
Embodiment 11：
The first step is reacted：250.0g phosphorus thiochlorides and 1.6L solvents tetrahydrofuranes are added into reaction vessel, and in room temperature
Under stir evenly.Then (389.6g refers to fourth diyl magnesium bromide to the tetrahydrofuran solution of the addition positive fourth diyl magnesium bromides of 389.6g
Quality) continue at 60 DEG C stirring to reaction 2 it is small when obtain reaction solution.Reaction solution is poured into the sulfuric acid solution of 540mL10wt%,
With ether extraction and isolated organic layer, after organic layer is dried with anhydrous magnesium sulfate vacuum distillation remove solvent and obtain solid and mix
Compound.Solid mixture is obtained into white solid with toluene and ethyl alcohol recrystallization, 91.0g is obtained after vacuum drying, and (yield is about
52%) product
Second step reacts：The above-mentioned products of 80.0g are transferred in single necked round bottom flask, are opened after adding 145.9g antimony trifluorides
Begin to stir.And single necked round bottom flask is connected into vacuum distillation apparatus, is heated to obtaining nothing when 200 DEG C of reactions 0.2 are small under decompression
Color liquid 49.5g.Colourless liquid is evaporated under reduced pressure to purifying again and obtains 43.8g colorless liquid products
Three-step reaction：The above-mentioned colorless liquid products of 30.0g are transferred in two mouthfuls of round-bottomed flasks, in 30min at 27 DEG C
Interior addition 2.5g deionized waters and continue stirring 0.5 it is small when after, 0.7 interior be slowly stirred when small adds 10.4g ethanol, and 60
DEG C the reaction was continued 6 it is small when terminate, 27.4g (yield about 89%) product is obtained by vacuum distillation
Comparative example 1：
Nonaqueous electrolytic solution is prepared：Prepare ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC)
Non- water mixed solvent, EC：EMC：The volume ratio of DMC is 30:50:20, film for additive carbonic acid Asia second is then added thereto
Enester (VC, content are the 2.0wt% of nonaqueous electrolytic solution weight quality).It is slowly added to electrolytic salt LiPF6And cooled down, shape
Into the nonaqueous electrolytic solution that concentration is 12.5wt%.
Battery makes：11.5Ah is laminated aluminum plastic film flexible-packed battery, and positive electrode uses LiNi0.6Co0.2Mn0.2O2
(NCM622), negative material uses hard carbon, when room temperature 1C discharges, energy density about 130Wh/kg.
Battery performance test：Under 45 DEG C of environment temperatures, by above-mentioned flexible-packed battery in 2.00V~4.20V voltage ranges
Interior discharge and recharge, i.e. constant current (rate of charge 2C) charge to 4.20V, then 4.20V constant-voltage charges (multiplying power 0.1C), Ran Houheng
Stream (discharge-rate 2C) is discharged to 2.00V.The constant current ratio of battery charging at circulation initial stage 93.00% or so, after decay to
86.00% or so.The efficiency of discharge and recharge is basically stable at 100% or so.Discharge capacity is 9.57Ah first, and circulation 150 weeks can
Using discharge capacity as 9.26Ah, capacity retention ratio 96.76%.Battery core can reach 115.80Wh/Kg than energy first, circulation
150 weeks are 112.30Wh/Kg.Specific test result is see Fig. 1, Fig. 2 and Fig. 3.
Comparative example 2：
With embodiment 8, the difference is that in three-step reaction, by 600g second step productsAddition reactor, 0.7
Hour in be slowly stirred add 133.5g ethanol, and 60 DEG C the reaction was continued 8 it is small when after recover to 27 DEG C, then just in 30min
Inside it is slowly added to react when 21.8g deionized waters stirring 0.5 is small and terminates, 249.8g (yield about 41%) is obtained by vacuum distillation
Product
Comparative example 3：
With embodiment 8, the difference is that the amount that deionized water is added in three-step reaction is 58.05g, reaction 53.3g is obtained
(yield about 53%) productAnd accessory substanceAmount (i.e. 28% raw material is converted to the by-product for 25.4g
Thing).
Comparative example 4：
The first step is reacted：250.0g phosphorus thiochlorides and 1.6L solvents tetrahydrofuranes are added into reaction vessel, and in room temperature
Under stir evenly.Then (389.6g refers to fourth diyl magnesium bromide to the tetrahydrofuran solution of the addition positive fourth diyl magnesium bromides of 389.6g
Quality) continue at 70 DEG C stirring to reaction 1 it is small when obtain reaction solution.Reaction solution is poured into the sulfuric acid solution of 540mL10wt%,
With ether extraction and isolated organic layer, after organic layer is dried with anhydrous magnesium sulfate vacuum distillation remove solvent and obtain solid and mix
Compound.Solid mixture is obtained into white solid with toluene and ethyl alcohol recrystallization, 36.8g is obtained after vacuum drying, and (yield is about
21%) product
Second step reacts：The above-mentioned products of 35.0g are transferred in single necked round bottom flask, are opened after adding 63.8g antimony trifluorides
Begin to stir.And single necked round bottom flask is connected into vacuum distillation apparatus, is heated to obtaining nothing when 200 DEG C of reactions 0.2 are small under decompression
Color liquid 27.2g.Colourless liquid is evaporated under reduced pressure to purifying again and obtains 21.6g colorless liquid products
Three-step reaction：The above-mentioned colorless liquid products of 20.0g are transferred in two mouthfuls of round-bottomed flasks, 0.5 is interior slow when small
Stirring adds 6.9g ethanol, and 60 DEG C the reaction was continued 6 it is small when terminate, obtain 20.3g by vacuum distillation (yield be about
97.1%) product
Comparative example 5：
The first step is reacted：With embodiment 9, product is obtainedCommon 53.1g.
Second step reacts：The above-mentioned products of 50.0g are transferred in single necked round bottom flask, are opened after adding 78.3g antimony trifluorides
Begin to stir.And single necked round bottom flask is connected into vacuum distillation apparatus, is heated to obtaining when 10 DEG C of reactions 12 are small under decompression colourless
Liquid 9.6g.Colourless liquid is evaporated under reduced pressure to purifying again and obtains 7.1g colorless liquid products
Three-step reaction：The above-mentioned colorless liquid products of 7.0g are transferred in two mouthfuls of round-bottomed flasks, it is interior slow when 0.5 is small
3.5g n-butanols are added, and continue to terminate when reaction 48 is small at 0 DEG C, 5.9g (yield about 69%) product is obtained by vacuum distillation
The yield computational methods of all embodiments of the invention and comparative example are：(product quality/the theoretical product actually obtained
Quality) × 100%.
It was found from from embodiment 1 and comparative example 1：The capacity retention ratio of comparative example 1 is not only lower than embodiment 1 and comparative example 1
Discharge capacity with test environment change fluctuation it is larger；In addition, the capacity performance of comparative example 1 is relatively low, it is only embodiment 1
88.20%.Finally, the energy conversion efficiency of the battery of comparative example 1 is floated change between 88%-91%, far below embodiment 1.
It was found from from embodiment 8 and comparative example 2：When other reaction conditions are identical in three-step reaction, embodiment 8 is (first
Add water and the second intermediate, then add the reactant addition sequence of alcohol) obtained product yield apparently higher than comparative example 2 (first plus alcohol
With the second intermediate, the reactant addition sequence added water).
It was found from embodiment 8 and comparative example 3：In three-step reaction, when the amount and the amount of the second intermediate of addition that add water
Molar ratio be more than 1.5:When 1, the yield of phosphinate can be reduced substantially.
It was found from embodiment 8 and comparative example 4：When the reaction time is 1 small in first step reaction, reaction temperature is 70 DEG C, i.e.,
Reaction time and reaction temperature in step (1) not when in the range of application claims, obtained first step products collection efficiency
It is very low.
It was found from embodiment 9 and comparative example 5：Reaction temperature is 10 DEG C in second step reacts, when the reaction time is 12 small,
Reaction time and reaction temperature i.e. in step (2), obtained second step product produced not when in the range of application claims
Rate is very low.
Claims (31)
1. a kind of preparation method of phosphinate, comprises the following steps：
(1) Grignard Reagent R is passed through1MgX and three halogen sulphur phosphorus X3P=S reacts in a solvent, obtains the first intermediate
(2) halogenating agent M ' X are passed throughaReacted with first intermediate, obtain the second intermediate
(3) R is passed through2OH, water and second intermediate reaction, obtain phosphinate
Wherein, R1、R2It is respectively selected from alkyl, or R1、R2It is respectively selected from containing in boron, silicon, nitrogen, phosphorus, oxygen, sulphur, fluorine, chlorine, bromine and iodine
The organic group of at least one element；X represents halogen；M ' represents metallic element；A represents the chemical valence of metallic element M '.
2. the preparation method of phosphinate as claimed in claim 1, it is characterised in that：The R1For saturation chain-like alkyl or saturation
Chain alkoxy.
3. the preparation method of phosphinate as claimed in claim 2, it is characterised in that：The R1Selected from methyl, ethyl, butyl, different
Octyl group, 2- methoxy ethyls, 2- ethoxyethyl groups or methoxy.
4. the preparation method of phosphinate as claimed in claim 1, it is characterised in that：The R1To contain alkenyl, non-end alkynyl
Or the unsaturated chain-like groups of nitro.
5. the preparation method of phosphinate as claimed in claim 4, it is characterised in that：The R1Selected from vinyl, 1- methyl propine
Base, pi-allyl, 2- nitro-ethyls or nitromethyla.
6. the preparation method of phosphinate as claimed in claim 1, it is characterised in that：The R1For saturated cyclic alkyls or contain
The saturated cyclic group of ether.
7. the preparation method of phosphinate as claimed in claim 6, it is characterised in that：The R1Selected from cyclohexyl, cyclopenta or 3-
Methoxycyclohexyl.
8. the preparation method of phosphinate as claimed in claim 1, it is characterised in that：The R1To contain alkenyl, alkynyl or nitro
Unsaturated cyclic group；Or R1For phenyl, phenyl derivatives group or heterocyclic group.
9. the preparation method of phosphinate as claimed in claim 8, it is characterised in that：The R1Selected from cyclopentenyl, 3- alkynyl rings
Hexyl, 3- nitrocyclohexes base, phenyl, 4- aminomethyl phenyls, 4- methoxyphenyls, diphenyl methyl, naphthyl, furans, thiophene or miaow
Azoles.
10. the preparation method of phosphinate as claimed in claim 1, it is characterised in that：The R2For carbon number be 1~8 it is full
And chain-like alkyl.
11. the preparation method of phosphinate as claimed in claim 10, it is characterised in that：The R2For methyl, ethyl, propyl group, different
Propyl group, butyl or the tert-butyl group.
12. the preparation method of phosphinate as claimed in claim 10, it is characterised in that：The R2It is 1~8 for carbon number
Fluoro-alkyl.
13. the preparation method of phosphinate as claimed in claim 12, it is characterised in that：The R2Selected from 2,2,2- trifluoroethyls,
Hexafluoro isopropyl, seven fluorine isobutyl groups or perfluoro butyl.
14. the preparation method of phosphinate as claimed in claim 1, it is characterised in that：The R2For fluorinated aryl.
15. the preparation method of phosphinate as claimed in claim 14, it is characterised in that：The R2For pentafluorophenyl group, fluorotoluene
Base, trifluoromethyl, three (2,2,2- trifluoroethyls) phenyl or three (2,2,2- trifluoro ethoxies) phenyl.
16. the preparation method of phosphinate as claimed in claim 1, it is characterised in that：The three halogen sulphur phosphorus is phosphorus thiochloride.
17. the preparation method of phosphinate as claimed in claim 1, it is characterised in that：The M ' is selected from arsenic or antimony.
18. the preparation method of phosphinate as claimed in claim 1, it is characterised in that：The X is in fluorine, chlorine, bromine and iodine
It is at least one.
19. the preparation method of phosphinate as claimed in claim 1, it is characterised in that：The halogenating agent be selected from arsenic trifluoride or
Antimony trifluoride.
20. the preparation method of phosphinate as claimed in claim 1, it is characterised in that：The solvent of the step (1) is selected from fat
At least one of race's hydrocarbon compound, arene compound, ether compound and ketone compounds.
21. the preparation method of phosphinate as claimed in claim 20, it is characterised in that：The solvent of the step (1) is selected from just
At least one of hexane, hexamethylene, benzene, toluene, tetrahydrofuran and ether.
22. the preparation method of phosphinate as claimed in claim 1, it is characterised in that：In step (1) reaction temperature for -30~
60℃；When reaction time is 2~48 small.
23. the preparation method of phosphinate as claimed in claim 1, it is characterised in that：In step (2) reaction temperature for 25~
200℃；When reaction time is 0.2~10 small.
24. the preparation method of phosphinate as claimed in claim 1, it is characterised in that：Reaction temperature is 0~80 in step (3)
℃；When reaction time is 1~48 small.
25. the preparation method of phosphinate as claimed in claim 1, it is characterised in that：Second intermediate and H in step (3)2O's
Molar ratio is 1:(0.5~1).
26. the preparation method of phosphinate as claimed in claim 25, it is characterised in that：Second intermediate and H in step (3)2O
Molar ratio be 1:(0.5~0.8).
27. the preparation method of phosphinate as claimed in claim 1, it is characterised in that：Second intermediate and R in step (3)2OH
Molar ratio be 1:(1~1.5).
28. the preparation method of phosphinate as claimed in claim 27, it is characterised in that：Second intermediate and R in step (3)2OH
Molar ratio be 1:(1~1.2).
29. a kind of phosphinate, is prepared using the preparation method of phosphinate as claimed in claim 1.
30. a kind of nonaqueous electrolytic solution, including phosphinate as claimed in claim 29.
31. nonaqueous electrolytic solution as claimed in claim 30, it is characterised in that：The quality of the phosphinate is nonaqueous electrolytic solution
The 5~90% of quality.
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| CN112745348A (en) * | 2021-03-15 | 2021-05-04 | 兰州大学 | Preparation method of dialkyl dithiophosphinate |
| JP7508321B2 (en) | 2020-09-24 | 2024-07-01 | 三菱ケミカル株式会社 | Non-aqueous electrolyte secondary battery |
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| Publication number | Publication date |
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| CN108017669B (en) | 2020-07-28 |
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