CN111690002A - Lithium salt compound, preparation method thereof and lithium ion battery electrolyte containing lithium salt compound - Google Patents
Lithium salt compound, preparation method thereof and lithium ion battery electrolyte containing lithium salt compound Download PDFInfo
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- CN111690002A CN111690002A CN202010358039.6A CN202010358039A CN111690002A CN 111690002 A CN111690002 A CN 111690002A CN 202010358039 A CN202010358039 A CN 202010358039A CN 111690002 A CN111690002 A CN 111690002A
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- -1 Lithium salt compound Chemical class 0.000 title claims abstract description 61
- 229910003002 lithium salt Inorganic materials 0.000 title claims abstract description 57
- 239000003792 electrolyte Substances 0.000 title claims abstract description 51
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 239000002253 acid Substances 0.000 claims abstract description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims abstract description 19
- 229940126062 Compound A Drugs 0.000 claims abstract description 17
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims abstract description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000003586 protic polar solvent Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 125000005250 alkyl acrylate group Chemical group 0.000 claims abstract description 10
- 238000010992 reflux Methods 0.000 claims abstract description 9
- 238000005886 esterification reaction Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 23
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 23
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 17
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 17
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 16
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 11
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003729 cation exchange resin Substances 0.000 claims description 8
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 8
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 8
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 8
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 7
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 7
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 7
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims 2
- 239000000243 solution Substances 0.000 description 32
- 239000000203 mixture Substances 0.000 description 13
- 230000035484 reaction time Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 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 description 9
- 239000003063 flame retardant Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 239000004744 fabric Substances 0.000 description 7
- 239000003365 glass fiber Substances 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- 229960000583 acetic acid Drugs 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000006245 Carbon black Super-P Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- NSSMTQDEWVTEKN-UHFFFAOYSA-N diethoxy(methyl)phosphane Chemical compound CCOP(C)OCC NSSMTQDEWVTEKN-UHFFFAOYSA-N 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 229940021013 electrolyte solution Drugs 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- HECJPIQDURBJBX-UHFFFAOYSA-M [Li+].P([O-])(O)=O Chemical compound [Li+].P([O-])(O)=O HECJPIQDURBJBX-UHFFFAOYSA-M 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000001394 phosphorus-31 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- 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)]
- C07F9/301—Acyclic saturated acids which can have further substituents on alkyl
-
- 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
- H01M10/0568—Liquid materials characterised by the solutes
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- 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
- H01M10/058—Construction or manufacture
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- 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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention provides a preparation method of a lithium salt compound, which comprises the following steps: adding dialkyl alkylphosphonous acid into a protic solvent, uniformly mixing, and then adding alkyl acrylate while stirring for reaction to obtain a compound A; adding an acid solution A into the compound A, heating and refluxing for reaction, adding acetone after the reaction is finished, and crystallizing to obtain a compound B; adding an alcoholic solution and an acid solution B into the compound B for esterification reaction to obtain a compound C; and adding an alcohol solution into the compound C, uniformly stirring, then adding a lithium source, stirring for reaction, and concentrating and crystallizing after the reaction is finished to obtain the lithium salt compound. The invention also provides a lithium ion battery electrolyte containing the lithium salt compound. The lithium salt compound prepared by the method has flame retardance and good conductivity, and the lithium ion battery electrolyte formed by the lithium salt compound has stable performance, safety and reliability.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a lithium salt compound, a preparation method thereof and a lithium ion battery electrolyte containing the lithium salt compound.
Background
The lithium ion battery has the advantages of high working voltage, high energy density, low self-discharge rate, no memory effect, long cycle life, environmental friendliness and the like, and is widely applied to various fields such as mobile phones, digital cameras, notebook computers, pure electric vehicles and hybrid electric vehicles.
Currently, a liquid electrolyte applied to a lithium ion battery generally uses flammable and explosive Ethylene Carbonate (EC) and dimethyl carbonate (DMC) as electrolyte solvents, and is matched with corresponding lithium salts to form an electrolyte system. However, the high flammability of the electrolyte inside the lithium ion battery is an important cause of the safety problem of the battery, and particularly, under the condition of being heated or being improperly used, the internal temperature of the battery rises, and the exothermic reactions such as the reaction between the electrode material inside the battery and the electrolyte, the decomposition of the electrolyte itself, and the like are very likely to occur, so that the temperature of the battery rises rapidly, and the "thermal runaway" is caused, and finally the combustion and the explosion are caused. Therefore, the safety is a bottleneck problem restricting the commercialization application of the high-capacity lithium ion battery.
The lithium salt applied to the electrolyte at present is relatively few in types, less in flame retardant and conductive performance and not easy to prepare on a large scale. Therefore, there is a need to design and develop new lithium salt varieties having both good flame retardant properties and electrical conductivity.
Disclosure of Invention
In view of this, the present invention provides a novel lithium salt compound having good flame retardant properties and electrical conductivity, a preparation method of the novel lithium salt compound, and a lithium ion battery electrolyte containing the novel lithium salt compound.
The invention provides a preparation method of a lithium salt compound, which comprises the following steps:
step S101, adding dialkyl alkylphosphonous acid into a protic solvent, uniformly mixing, and then adding alkyl acrylate while stirring for reaction to obtain a compound A;
step S102, adding an acid solution A into the compound A, heating and refluxing for reaction, adding acetone after the reaction is finished, and crystallizing to obtain a compound B;
step S103, adding an alcohol solution and an acid solution B into the compound B to perform selective mono-esterification reaction to obtain a compound C;
step S104, adding an alcohol solution into the compound C, uniformly stirring, then adding a lithium source, stirring for reaction, and concentrating and crystallizing after the reaction is finished to obtain a lithium salt compound; the structural formula of the lithium salt compound is shown as the formula (I):
in formula (I): r1Is any one of methyl, ethyl, n-propyl and isopropyl; r4Is methyl or ethyl.
Further, the dialkyl alkylphosphonous acid has the structural formula shown in formula (II):
in formula (II): r1Is any one of methyl, ethyl, n-propyl and isopropyl; r2Is methyl, ethyl, n-propyl or isopropylAny of a group, n-butyl, isobutyl, and tert-butyl.
Further, the alkyl acrylate has a structural formula shown in formula (III):
in the formula (III): r3Is any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl. Preferably, the substituent R in the formula (III)3With the substituent R in formula (II)2Are the same substituents.
Further, the structural formula of the compound A is shown as the formula (IV):
in the formula (IV): r1Is any one of methyl, ethyl, n-propyl and isopropyl; r2Is any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl; r3Is any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl.
Further, the structural formula of compound B is shown in formula (v):
in formula (V): r1Is any one of methyl, ethyl, n-propyl and isopropyl.
Further, the structural formula of the compound C is shown as the formula (VI):
in formula (VI): r1Is any one of methyl, ethyl, n-propyl and isopropyl; r4Is methyl or ethyl.
Further, in step S101, the reaction temperature is 0-80 ℃ and the reaction time is 2-10 h. Preferably, in step S101, the reaction temperature is 5-60 deg.C and the reaction time is 2-6 h.
Further, in step S101, the protic solvent is any one of methanol, ethanol, formic acid, and acetic acid. Preferably, the protic solvent is acetic acid.
Further, in step S101, the molar ratio of protic solvent to dialkylalkylphosphonous acid ester is from 1:1 to 1: 1.2. Preferably, the molar ratio of protic solvent to dialkyl alkylphosphonous acid is from 1:1 to 1: 1.05.
Further, in step S101, the molar ratio of the dialkyl alkylphosphonous acid ester to the alkyl acrylate ester is 1:1 to 1: 1.2. Preferably, the molar ratio of dialkyl alkylphosphonous acid to alkyl acrylate is from 1:1 to 1: 1.05.
Further, in step S102, the reaction temperature of the heating reflux reaction is 80-120 ℃, and the reaction time is 4-12 h. Preferably, in step S102, the reaction temperature of the heating reflux reaction is 100 ℃ to 110 ℃, and the reaction time is 6-10 h.
Further, in step S102, the acid solution a is concentrated sulfuric acid or a strong acid cation exchange resin, and the molar amount of the acid solution a is 0.5% to 5% of the molar amount of the compound a. Preferably, the molar amount of acid solution a is 0.5% to 1.5% of the molar amount of compound a.
Further, in step S103, the reaction temperature of the esterification reaction is 0-40 ℃ and the reaction time is 6-24 h. Preferably, in step S103, the reaction temperature of the esterification reaction is 10-30 ℃ and the reaction time is 6-12 h.
Further, in step S103, the mass ratio of the compound B to the alcohol solution is 1:1-1:1.5, the acid solution B is concentrated sulfuric acid or a strong acid cation exchange resin, and the molar amount of the acid solution B is 0.5-5% of the molar amount of the compound B. Preferably, the molar amount of the acid solution B is 0.5% to 1.5% of the molar amount of the compound B.
Further, the alcohol solution used in step S103 and step S104 is methanol or ethanol. Preferably, the alcohol solution used in step S103 and step S104 is methanol.
Further, in step S104, the reaction temperature is 0-50 ℃ and the reaction time is 1-5 h. Preferably, in step S104, the reaction temperature is 0-25 deg.C and the reaction time is 1-2 h.
Further, in step S104, the mass ratio of the compound C to the alcoholic solution is 1:1-1: 1.5.
Further, the lithium source used in step S104 is lithium carbonate or lithium hydroxide. Preferably, the lithium source used in step S104 is lithium carbonate.
Further, in step S104, the molar ratio of the lithium source to the compound C is 1:2 to 1: 2.2. Preferably, the molar ratio of the lithium source to compound C is 1:2.
The invention also provides a lithium salt compound prepared by the preparation method, and the structure of the lithium salt compound is shown as the formula (I):
in formula (I): r1Is any one of methyl, ethyl, n-propyl and isopropyl; r4Is methyl or ethyl.
The invention also provides a lithium ion battery electrolyte containing the lithium salt compound.
Further, the lithium ion battery electrolyte consists of the lithium salt compound prepared by the invention and an organic solvent; wherein the molar concentration of the lithium salt compound in the lithium ion battery electrolyte is 1.0mol/L, and the organic solvent is formed by mixing dimethyl carbonate (DMC) and Ethylene Carbonate (EC) according to the mass ratio of 1:1 or is formed by mixing dimethyl carbonate (DMC) and Propylene Carbonate (PC) according to the mass ratio of 1:1.
The reaction mechanism of the preparation method provided by the invention is as follows: the method comprises the following steps of carrying out Michael-Abuzov reaction on alkyl phosphonous acid dialkyl ester and alkyl acrylate in an anhydrous protic solvent to obtain a compound A, hydrolyzing with strong acid to obtain a compound B, carrying out selective esterification again by using the strong acid and alcohol to obtain an organic phosphonate carboxylate compound C, and finally carrying out salt formation in a system of a lithium source and alcohol to obtain the organic phosphonate carboxylate mono-lithium salt compound.
The technical scheme provided by the invention has the beneficial effects that: the method provided by the invention overcomes the defect that phosphonate ester and carboxylate coexist, phosphonate monolithium salt cannot be prepared by a conventional method and carboxylate is reserved; the method provided by the invention has the advantages of high reaction yield, simple and convenient operation, no need of special equipment, sufficient and reliable raw material source, low cost, environmental protection and suitability for industrial production; the lithium salt compound prepared by the method has flame retardance and good conductivity, and the lithium ion battery electrolyte formed by the lithium salt compound has stable performance, safety and reliability.
Drawings
Fig. 1 is a schematic view of a reaction process for preparing a lithium salt compound according to the present invention.
FIG. 2 is a hydrogen spectrum of the lithium salt compound obtained in example 1 of the present invention.
FIG. 3 is a phosphorus spectrum of the lithium salt compound obtained in example 1 of the present invention.
FIG. 4 is a carbon spectrum diagram of a lithium salt compound obtained in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be further described with reference to the accompanying drawings.
An embodiment of the present invention provides a method of preparing a lithium salt compound, including the steps of:
step S101, adding dialkyl alkylphosphonous acid into a protic solvent, uniformly mixing, adding alkyl acrylate while stirring, and reacting for 2-10h at the temperature of 0-80 ℃ to obtain a compound A; wherein the protic solvent is any one of methanol, ethanol, formic acid and acetic acid, the molar ratio of the protic solvent to the dialkyl alkylphosphonous acid is 1:1-1:1.2, and the molar ratio of the dialkyl alkylphosphonous acid to the alkyl acrylate is 1:1-1: 1.2;
step S102, adding an acid solution A into the compound A, heating and refluxing for reaction for 4-12h at 80-120 ℃, adding acetone after the reaction is finished, and crystallizing to obtain a compound B; wherein, the acid solution A is concentrated sulfuric acid or strong acid cation exchange resin, and the molar amount of the acid solution A is 0.5 to 5 percent of the molar amount of the compound A;
step S103, adding an alcohol solution and an acid solution B into the compound B, and carrying out esterification reaction for 6-24h at the temperature of 0-40 ℃ to obtain a compound C; wherein the mass ratio of the compound B to the alcoholic solution is 1:1-1:1.5, the acid solution B is concentrated sulfuric acid or strong acid cation exchange resin, the molar amount of the acid solution B is 0.5-5% of the molar amount of the compound B, and the alcoholic solution is methanol or ethanol;
step S104, adding an alcohol solution into the compound C, uniformly stirring, then adding a lithium source, stirring and reacting for 1-5h at the temperature of 0-50 ℃, and concentrating and crystallizing after the reaction is finished to obtain a lithium salt compound; wherein the mass ratio of the compound C to the alcoholic solution is 1:1-1:1.5, the lithium source is lithium carbonate or lithium hydroxide, and the molar ratio of the lithium source to the compound C is 1:2-1: 2.2.
The reaction processes of steps S101-S104 are shown in FIG. 1, formula (II) is a structural formula of dialkyl alkylphosphonous acid ester, formula (III) is a structural formula of alkyl acrylate ester, formula (IV) is a structural formula of compound A, formula (V) is a structural formula of compound B, formula (VI) is a structural formula of compound C, and formula (I) is a structural formula of lithium salt compound; in the formula (I) -formula (VI), R1Is any one of methyl, ethyl, n-propyl and isopropyl, R2Is any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl, R3Is any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl, R4Is methyl or ethyl; preferably, the substituent R3With a substituent R2Are the same substituents.
Preferably, in step S101, the reaction temperature is 5-60 deg.C and the reaction time is 2-6 h.
Preferably, the protic solvent is acetic acid.
Preferably, the molar ratio of protic solvent to dialkyl alkylphosphonous acid is from 1:1 to 1: 1.05.
Preferably, the molar ratio of dialkyl alkylphosphonous acid to alkyl acrylate is from 1:1 to 1: 1.05.
Preferably, in step S102, the reaction temperature of the heating reflux reaction is 100 ℃ to 110 ℃, and the reaction time is 6-10 h.
Preferably, the molar amount of acid solution a is 0.5% to 1.5% of the molar amount of compound a.
Preferably, in step S103, the reaction temperature of the esterification reaction is 10-30 ℃ and the reaction time is 6-12 h.
Preferably, the molar amount of the acid solution B is 0.5% to 1.5% of the molar amount of the compound B.
Preferably, the alcohol solution used in step S103 and step S104 is methanol, and the alcohol solution used in step S103 and step S104 may be different.
Preferably, in step S104, the reaction temperature is 0-25 deg.C and the reaction time is 1-2 h.
Preferably, the lithium source used in step S104 is lithium carbonate.
Preferably, the molar ratio of the lithium source to compound C is 1:2.
The embodiment of the invention also provides a lithium ion battery electrolyte containing the lithium salt compound, which consists of the lithium salt compound prepared by the invention and an organic solvent; wherein the molar concentration of the lithium salt compound in the lithium ion battery electrolyte is 1.0mol/L, and the organic solvent is formed by mixing dimethyl carbonate (DMC) and Ethylene Carbonate (EC) according to the mass ratio of 1:1 or is formed by mixing dimethyl carbonate (DMC) and Propylene Carbonate (PC) according to the mass ratio of 1:1.
The lithium salt compound provided by the present invention, the preparation method thereof, and the lithium ion battery electrolyte comprising the same will be described in detail below with reference to examples.
Example 1:
preparation of lithium salt compound:
adding 408g (3mol) of diethyl methylphosphonite and 180g (3mol) of glacial acetic acid into a 1L four-neck bottle, reducing the temperature to 5 ℃, dropwise adding 300g (3mol) of ethyl acrylate under the protection of nitrogen and mechanical stirring, keeping the temperature at not more than 25 ℃ at the dropwise adding speed, keeping the temperature at 25 ℃ after about 1.5h of dropwise adding, keeping the temperature at 25 ℃ for 1h of reaction, and evaporating low-boiling-point substances after the reaction is finished to obtain a compound A592.8g of a colorless oily liquid, wherein the yield of the compound A is 95 percent and the GC purity is 97 percent; 592.8g (2.85mol) of the compound A is added into a 2L three-necked bottle, 500g of water and 5g of concentrated sulfuric acid are added, the mixture is stirred and heated under the condition of 100 ℃ for refluxing for 6 hours, then the water and the generated ethanol are evaporated, the mixture is cooled to room temperature, 500g of acetone is added, the mixture is stirred, dispersed and filtered, the obtained filter cake is washed by a small amount of acetone, and then the obtained filter cake is dried to obtain the compound B424.5g of white solid powder, wherein the yield of the compound B is 98 percent, and the HPLC purity is 98.5 percent; 424.5g (2.79mol) of the compound B is added into a 2L three-necked bottle, then 500g of methanol and 3g of concentrated sulfuric acid are added, the mixture is stirred and reacted for 18 hours at room temperature, 1.3g of sodium bicarbonate is added after the reaction is finished to remove sulfuric acid, the mixture is filtered, and the filtrate is evaporated to dryness to obtain a compound C463g which is colorless oily liquid; 231.5g (1.395mol) of the compound C and 250g of methanol were added to a 1L three-necked flask, and after the mixture was stirred to be homogeneous, 51.6g (0.697mol) of anhydrous lithium carbonate was added in portions at room temperature, and after the addition was completed, the mixture was stirred for 2 hours, and then the methanol was concentrated to the original half, the temperature was cooled to 0 ℃ to precipitate a large amount of solid after 1 hour, and the solid was filtered, and the filter cake was washed with a small amount of cold methanol, and vacuum-dried at 50 ℃ to obtain 235.4g of a white solid lithium salt compound.
Hydrogen spectra of lithium salt compound obtained in example 1: (1H-NMR spectrum is shown in FIG. 2, phosphorus spectrum: (31P-NMR spectrum is shown in FIG. 3, carbon spectrum: (13C-NMR) spectrum is shown in FIG. 4.
Preparing the lithium ion battery electrolyte:
weighing a proper amount of the prepared lithium salt compound, 200g of dimethyl carbonate (DMC) and 200g of Ethylene Carbonate (EC), and uniformly mixing at 25 ℃ to obtain the lithium ion battery electrolyte, wherein the molar concentration of the lithium salt compound in the lithium ion battery electrolyte is controlled to be 1.0 mol/L.
Example 2:
preparation of lithium salt compound:
204g (1.5mol) of diethyl methylphosphonite and 90g (1.5mol) of glacial acetic acid are added into a 1L four-neck flask, 192g (1.5mol) of tert-butyl acrylate are dropwise added under the protection of nitrogen and mechanical stirring at room temperature, the dropping speed is maintained at 70 ℃ or less, after 1h of dropwise addition, the temperature is kept at 75 ℃ for 3h of heat preservation reaction, low-boiling substances are distilled off after the reaction is finished, and the compound A in colorless oily liquid, namely 345.6g, is obtained, the yield of the compound A is 97.6%, and the GC purity is 97.5%; 345.6g (1.46mol) of compound A is added into a 2L three-necked flask, 500g of water and 2g of strong acid cation exchange resin are added, the mixture is stirred and heated to reflux for 4 hours at the temperature of 110 ℃, water and generated ethanol are evaporated, the mixture is cooled to room temperature, the resin is recovered by filtration, 500g of acetone is added, the mixture is stirred, dispersed and filtered, a filter cake obtained by washing with a small amount of acetone is obtained, and the compound B is dried to obtain 220.3g of compound B in white solid powder form, wherein the yield of the compound B is 99.3 percent and the HPLC purity is 98.8 percent; adding 212.3g (1.395mol) of the compound B into a 1L three-necked flask, adding 250g of methanol and 1.5g of strong-acid cation exchange resin, stirring at room temperature for reaction for 13h, filtering after the reaction is finished, recovering the resin, and evaporating the filtrate to dryness to obtain 231.5g of a compound which is colorless oily liquid; 115.8g (0.698mol) of the compound C and 120g of methanol were added into a 1L three-necked flask, after the mixture was stirred uniformly, 25.85g (0.349mol) of anhydrous lithium carbonate was added in portions at room temperature, after the addition was completed, the mixture was stirred for 1 hour, then the methanol was concentrated to the original half, the temperature was cooled to 0 ℃, a large amount of solid was precipitated after 2 hours, the solid was filtered, the filter cake was washed with a small amount of cold methanol, and the solid was dried under vacuum at 50 ℃ to obtain 118.3g of a white solid lithium salt compound.
Preparing the lithium ion battery electrolyte:
weighing a proper amount of the prepared lithium salt compound, 100g of dimethyl carbonate (DMC) and 100g of Propylene Carbonate (PC) and uniformly mixing at 25 ℃ to obtain the lithium ion battery electrolyte, wherein the molar concentration of the lithium salt compound in the lithium ion battery electrolyte is controlled to be 1.0 mol/L.
Comparative example 1:
200g of dimethyl carbonate (DMC) and 200g of Ethylene Carbonate (EC) were weighed and mixed, 1.0mol/L of lithium hexafluorophosphate was added thereto, and the mixture was uniformly mixed at 25 ℃ to prepare the electrolyte for lithium ion battery of comparative example 1.
And (3) testing the flammability of the electrolyte:
the lithium ion battery electrolytes prepared in example 1, example 2 and comparative example 1 were subjected to flame retardancy and conductivity tests by a self-extinguishing time method. The method comprises the following specific steps:
twelve pieces of glass fiber cloth (size: 6cm long × 2cm wide × 1.5cm thick) were taken and equally divided into three groups, four of each group were designated as a first group, a second group, and a third group, the glass fiber cloth of the first group was immersed in the electrolyte prepared in example 1, the glass fiber cloth of the second group was immersed in the electrolyte prepared in example 2, the glass fiber cloth of the third group was immersed in the electrolyte prepared in comparative example 1, so that each piece of glass fiber cloth absorbed about 5g of electrolyte, then the glass fiber cloth immersed with the electrolyte was hung in a case of a vertical combustion tester, and was rapidly ignited with a propane lamp in an air environment for an ignition time of 2s, the time from the removal of the ignition device to the automatic extinction of the flame was recorded, and this time was divided by the total time of the electrolyte that had been immersed on the glass fiber cloth, to obtain the self-extinction time per unit mass of electrolyte, this time is called Self-extinguishing time (SET) in seconds/gram (s/g). The flame retardant property of the electrolyte is expressed by a flame retardant rate F, and the calculation formula of the flame retardant rate F is as follows:
in the formula, SETiI is the average self-extinguishing time of the electrolyte, 1,2,3, SET1Average self-extinguishing time, SET, for the electrolyte prepared in example 12Average self-extinguishing time, SET, for the electrolyte prepared in example 23Mean self-extinguishing time, SET, for the electrolyte prepared in comparative example 10For the self-extinguishing time of electrolytes not having flame-retardant properties, the definition when 1/3<F<2/3, the electrolyte has flame retardancy, when 2/3<F<1, the electrolyte was nonflammable, and the calculation results are shown in table 1. as can be seen from table 1, the lithium ion battery electrolytes obtained in examples 1 and 2 were flame retardant, and the lithium ion battery electrolyte obtained in comparative example 1 was nonflammable.
And (3) compatibility testing:
the electrolyte solutions obtained in comparative example 1, example 1 and example 2 were left at 25 ℃ for 30 days, and the state of the electrolyte solution was observed, and the results are shown in table 1.
And (3) conductivity test:
the conductivity test was carried out at 25 ℃ using a Cond7400 test bench type conductivity tester using the electrolytes prepared in comparative example 1, example 1 and example 2, and the results are shown in Table 1.
And (3) testing discharge capacity:
the electrolytes prepared in comparative example 1, example 1 and example 2 were assembled into 2016 type button type positive/lithium and negative/half cells in a glove box, and the half cells were subjected to charge and discharge experiments.
The positive electrode material is prepared by mixing lithium iron phosphate, super-P conductive carbon black and PVDF binder according to the mass ratio of 8:1:1, and the preparation process of the positive electrode material comprises the following steps: firstly, preparing 6 mass percent NMP solution of PVDF, then weighing lithium iron phosphate powder into a mortar, grinding for 20min, adding super-P conductive carbon black, further grinding for 20min, then placing into a vacuum oven at 60 ℃ for drying for 2h, taking out, then grinding for 20min, rapidly adding PVDF solution for grinding, scraping the ground slurry on an aluminum foil by a doctor blade (100 mu m), drying in a blast drying oven at 60 ℃, compacting an electrode by a tablet press under the pressure of 10MPa, and then stamping the electrode into a pole piece with the diameter of 14 mm. And finally, weighing the pole piece, and continuously drying for 6 hours in vacuum at 120 ℃.
The electric negative electrode is formed by mixing graphite and PVDF according to the mass ratio of 9: 1.
The electrolytes prepared in comparative example 1, example 1 and example 2 were assembled into Li/C half-cells and Li/LiFePO, respectively, using Celgard2400 as a separator4And (5) carrying out constant current charge and discharge test on the half cell at a current multiplying power of 0.2C or 0.5C. The first discharge capacity of the positive electrode/lithium half cell and the results of the 80 cycle capacity retention test are shown in table 1.
Table 1: test results of electrochemical properties and flame retardant properties
As can be seen from table 1, the lithium ion battery electrolytes prepared in examples 1 and 2 have better flame retardancy and electrical conductivity.
The features of the embodiments and embodiments described herein above may be combined with each other without conflict.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A method for preparing a lithium salt compound, comprising the steps of:
s101, adding dialkyl alkylphosphonous acid into a protic solvent, uniformly mixing, and then adding alkyl acrylate while stirring for reaction to obtain a compound A;
s102, adding an acid solution A into the compound A, heating and refluxing for reaction, adding acetone after the reaction is finished, and crystallizing to obtain a compound B;
s103, adding an alcoholic solution and an acid solution B into the compound B for esterification reaction to obtain a compound C;
s104, adding an alcohol solution into the compound C, uniformly stirring, adding a lithium source, stirring for reaction, and concentrating and crystallizing after the reaction is finished to obtain a lithium salt compound; the structural formula of the lithium salt compound is shown as the formula (I):
in formula (I): r1Is any one of methyl, ethyl, n-propyl and isopropyl; r4Is methyl or ethyl.
2. The method of claim 1, wherein the dialkyl alkylphosphonous acid has the formula (II):
in formula (II): r2Is any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl.
3. The method of preparing a lithium salt compound according to claim 1, wherein the alkyl acrylate has a structural formula represented by formula (iii):
in the formula (III): r3Is any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl.
4. The method for preparing a lithium salt compound according to claim 1, wherein the protic solvent is any one of methanol, ethanol, formic acid, and acetic acid in step S101.
5. The method of preparing a lithium salt compound according to claim 1, wherein in step S102, the acid solution a is concentrated sulfuric acid or a strongly acidic cation exchange resin; in step S103, the acid solution B is concentrated sulfuric acid or a strongly acidic cation exchange resin.
6. The method of claim 1, wherein the alcohol solution used in step S103 and step S104 is methanol or ethanol.
7. The method of preparing a lithium salt compound according to claim 1, wherein the lithium source used in step S104 is lithium carbonate or lithium hydroxide.
8. A lithium salt compound obtained by the method of claim 1, wherein the lithium salt compound has a structural formula represented by formula (i):
in formula (I): r1Is any one of methyl, ethyl, n-propyl and isopropyl; r4Is methyl or ethyl.
9. A lithium ion battery electrolyte, characterized in that it comprises the lithium salt compound of claim 8.
10. The lithium ion battery electrolyte of claim 9, further comprising an organic solvent consisting of dimethyl carbonate and ethylene carbonate mixed in a mass ratio of 1:1 or dimethyl carbonate and propylene carbonate mixed in a mass ratio of 1:1.
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|---|---|---|---|---|
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008071738A1 (en) * | 2006-12-14 | 2008-06-19 | Solvay Pharmaceuticals B.V. | Selective inhibitors of neurotensin degrading enzymes |
| US20080188598A1 (en) * | 2006-12-12 | 2008-08-07 | Clariant International Ltd. | Salts of alkyl esters of carboxyethyl(Alkyl)phosphinic acid |
| CN101641363A (en) * | 2007-03-23 | 2010-02-03 | 明治制果株式会社 | Process for production of phosphorus-containing alpha-keto acid |
| CN103342718A (en) * | 2013-07-22 | 2013-10-09 | 重庆紫光化工股份有限公司 | Method for preparing 3-(methyl alkoxy phosphoryl group) propionate compound |
| CN107799841A (en) * | 2017-10-19 | 2018-03-13 | 江汉大学 | Dialkyl phosphinic acid fat fire retardant, lithium-ion battery electrolytes and lithium ion battery containing the fire retardant |
-
2020
- 2020-04-29 CN CN202010358039.6A patent/CN111690002A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080188598A1 (en) * | 2006-12-12 | 2008-08-07 | Clariant International Ltd. | Salts of alkyl esters of carboxyethyl(Alkyl)phosphinic acid |
| WO2008071738A1 (en) * | 2006-12-14 | 2008-06-19 | Solvay Pharmaceuticals B.V. | Selective inhibitors of neurotensin degrading enzymes |
| CN101641363A (en) * | 2007-03-23 | 2010-02-03 | 明治制果株式会社 | Process for production of phosphorus-containing alpha-keto acid |
| CN103342718A (en) * | 2013-07-22 | 2013-10-09 | 重庆紫光化工股份有限公司 | Method for preparing 3-(methyl alkoxy phosphoryl group) propionate compound |
| CN107799841A (en) * | 2017-10-19 | 2018-03-13 | 江汉大学 | Dialkyl phosphinic acid fat fire retardant, lithium-ion battery electrolytes and lithium ion battery containing the fire retardant |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113717224A (en) * | 2021-07-28 | 2021-11-30 | 南通江山农药化工股份有限公司 | MPP microchannel reaction preparation process and MPP |
| CN113717224B (en) * | 2021-07-28 | 2023-08-01 | 南通江山农药化工股份有限公司 | MPP microchannel reaction preparation process and MPP |
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