CN110845380A - Lithium ion battery electrolyte, additive and preparation method of additive - Google Patents
Lithium ion battery electrolyte, additive and preparation method of additive Download PDFInfo
- Publication number
- CN110845380A CN110845380A CN201911217907.2A CN201911217907A CN110845380A CN 110845380 A CN110845380 A CN 110845380A CN 201911217907 A CN201911217907 A CN 201911217907A CN 110845380 A CN110845380 A CN 110845380A
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- CN
- China
- Prior art keywords
- lithium ion
- ion battery
- additive
- mercaptan
- trithiocarbonate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000000654 additive Substances 0.000 title claims abstract description 24
- 230000000996 additive effect Effects 0.000 title claims abstract description 24
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 24
- 239000003792 electrolyte Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- HIZCIEIDIFGZSS-UHFFFAOYSA-L trithiocarbonate Chemical group [S-]C([S-])=S HIZCIEIDIFGZSS-UHFFFAOYSA-L 0.000 claims abstract description 17
- 239000012989 trithiocarbonate Substances 0.000 claims abstract description 16
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 150000001728 carbonyl compounds Chemical class 0.000 claims abstract description 6
- 238000006845 Michael addition reaction Methods 0.000 claims abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000002000 Electrolyte additive Substances 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 239000005457 ice water Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 238000001953 recrystallisation Methods 0.000 claims description 5
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 4
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 4
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 4
- VSKYJOJQOKKIPN-UHFFFAOYSA-N 3-methylbut-3-ene-1-thiol Chemical compound CC(=C)CCS VSKYJOJQOKKIPN-UHFFFAOYSA-N 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- -1 -unsaturated hydrocarbyl compound Chemical class 0.000 claims description 2
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- NKKMVIVFRUYPLQ-NSCUHMNNSA-N crotononitrile Chemical compound C\C=C\C#N NKKMVIVFRUYPLQ-NSCUHMNNSA-N 0.000 claims description 2
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohex-2-enone Chemical compound O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 claims description 2
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 2
- MCVVUJPXSBQTRZ-ONEGZZNKSA-N methyl (e)-but-2-enoate Chemical compound COC(=O)\C=C\C MCVVUJPXSBQTRZ-ONEGZZNKSA-N 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- 125000002560 nitrile group Chemical group 0.000 claims description 2
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000002585 base Substances 0.000 claims 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims 1
- 150000007944 thiolates Chemical class 0.000 abstract description 2
- 239000007787 solid Substances 0.000 description 18
- 239000000203 mixture Substances 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- ULIKDJVNUXNQHS-UHFFFAOYSA-N 2-Propene-1-thiol Chemical compound SCC=C ULIKDJVNUXNQHS-UHFFFAOYSA-N 0.000 description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 208000013883 Blast injury Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a lithium ion battery electrolyte, an additive and a preparation method of the additive, wherein the additive is trithiocarbonate, the preparation method of the additive comprises the following steps of (1) putting mercaptan and a solvent into a reaction container, adding alkali for pre-reaction to obtain thiolate, and gradually dropwise adding carbon disulfide to generate trithiocarbonate, (2) carrying out Michael addition reaction on the trithiocarbonate and α -unsaturated carbonyl compound under the action of alkali, and (3) finally acidifying to obtain a trithiocarbonate fine product.
Description
[ technical field ]
The invention relates to the technical field of lithium ion battery electrolyte additives, in particular to a lithium ion battery electrolyte, an additive and a preparation method of the additive.
[ background art ]
Electrolyte additives (electrolyte additive agents) refer to some natural or synthetic organic or inorganic compounds added to improve the physical and electrochemical properties of an electrolyte. The electrolyte additive does not participate in the electrode process reaction generally, but can improve the physical properties of the electrolyte or the interface contact tissue of the electrolyte and the material, thereby influencing the performance of an electrochemical system. The electrolyte additives are generally used in small amounts but are an integral part of the electrolyte system.
Lithium ion batteries are widely used in portable electronic devices due to their characteristics of high energy density, high voltage, long life, no memory effect, no pollution, etc., and are also widely used in new energy powered vehicles as the traditional energy sources such as petroleum become increasingly deficient and the environmental problems become more prominent. However, in recent years, explosion injury events of lithium ion batteries have frequently occurred, so that safety and high efficiency of lithium ion batteries are always important in industrial research, and a novel special lithium ion electrolyte additive is a main research direction for solving the problem.
[ summary of the invention ]
In view of the above problems, the present invention provides an electrolyte for lithium ion batteries, an additive and a method for preparing the additive, aiming at improving the efficiency and safety problems of the existing electrolyte.
On one hand, the additive is trithiocarbonate, and the structural general formula of the additive is as follows:
structural formula I;
wherein R is1、R2Respectively select C1-C8Containing or not containing any unsaturated bond, carbonyl group, nitrile group, or ester group.
The structural formula I is any one of the following structural formulas:
in another aspect, the method for preparing the lithium ion battery electrolyte comprises the following steps:
and (1) placing a solvent, alkali and mercaptan into a reaction container, and slowly dropwise adding carbon disulfide under an ice-water bath.
And (2) adding α -unsaturated carbonyl compound to carry out Michael addition reaction after the reaction is finished, and preparing a crude trithiocarbonate.
And (3) adding acid for acidification, washing with a solvent, drying, and recrystallizing to obtain a refined trithiocarbonate.
Further, the solvent in the step (1) is any one or more of acetonitrile, propionitrile, butyronitrile, N-dimethylformamide and tetrahydrofuran.
Further, the alkali in the step (1) is any one of sodium hydroxide, potassium hydroxide, sodium ethoxide, sodium methoxide, DBU and triethylamine.
Further, the mercaptan in the step (1) is methyl mercaptan, ethyl mercaptan, thiophenol, 2-propylene-1-mercaptan,2-first 2-propen-1-thiolAnd isopentenyl mercaptan.
Further, the molar ratio of the mercaptan to the alkali in the step (1) is 1:1-1:1.3, preferably 1:1.05-1: 1.1; the reaction time for generating the thiolate is 25-50 minutes;
further, the carbon disulfide is dripped in the step (1) for 10-60 minutes at the temperature of 0-10 ℃.
Further, the α -unsaturated carbonyl compound in the step (2) is one of methyl acrylate, methyl methacrylate, acrylonitrile, methyl vinyl ketone, acrylamide, methyl crotonate, 2-butenenitrile and cyclohexenone.
Further, the molar ratio of the mercaptan to the carbon disulfide and the α -unsaturated carbonyl compound in the step (2) is 1:1.2: 1-1: 1.5:1, preferably 1:1.25: 1-1: 1.35:1, and the reaction time for generating the trithiocarbonate is 24-36 h.
Further, the acid in the step (3) is any one of dilute hydrochloric acid, dilute sulfuric acid and dilute phosphoric acid.
Further, the washing solvent in the step (3) is any one or more of deionized water, ethanol and methanol.
Further, the recrystallization reagent in the step (3) is any one of n-butane, n-pentane, n-hexane, n-heptane, tert-butane, n-octane, diethyl ether, dimethyl ether, diethyl ether, methyl ethyl ether, dipropyl ether, petroleum ether, anisole, phenetole, benzene, toluene, xylene and trimethylbenzene.
In a third aspect, a lithium ion battery electrolyte is provided, wherein the lithium ion battery electrolyte comprises the trithiocarbonate additive or the electrolyte contains the trithiocarbonate additive prepared by the method.
In the preparation method, the solvent obtained by extraction and recrystallization can be recovered, rectified and separated, and recycled.
The novel sulfur-containing electrolyte additive disclosed by the invention is high in purity and low in cost, after the additive is added into an electrolyte, trithiocarbonate groups in the additive can absorb oxygen radicals generated by structural change of a positive electrode material under high voltage or high temperature, so that oxidative decomposition of the electrolyte under high voltage is avoided, and an SEI film on the surfaces of a positive electrode and a negative electrode has high stability and high conductivity and can be used as an RAFT (reversible addition-fragmentation chain transfer) reagent to regulate and control the molecular weight of a VC (vinyl chloride) polymer, thereby reducing impedance and improving the cycle performance of a battery.
Meanwhile, the preparation method of the additive has the advantages of easily available raw materials, low cost, simple process, high production efficiency and high product purity, and lays a good foundation for the application of the additive in the lithium ion battery electrolyte.
[ detailed description of the invention ]
The present invention will be described in detail with reference to examples, which are provided only for the purpose of facilitating understanding of the present invention and are not intended to limit the scope of the present invention.
Example 1:
10.12g (100mmol) of isopentenyl thiol and 4.6g (115mmol) of sodium hydroxide solid were dissolved in a 250ml three-neck flask containing 30ml of DMF, a stirrer was added, the three-neck flask was immersed in an ice-water bath at 5 ℃, and a magnetic stirrer was started to stir well. Slowly dripping 9.51g (125mmol) of carbon disulfide into a three-neck flask, leading the reaction solution to become turbid, controlling the dripping speed, continuing stirring for 30min after dripping, removing the ice water bath when the temperature is constant, dripping 10.01g (100mmol) of methyl methacrylate within 10min, and reacting for 24h at room temperature.
And (3) adding 20ml of deionized water into the mixed solution after the reaction, and dropwise adding dilute hydrochloric acid under the ice bath condition until all solids are separated out. Suction filtration was performed, and the solid was washed with ice, deionized water, and recrystallized from n-hexane to obtain 17.2g (yield 62.0%, purity 99.5%) of a bright yellow solid.
Example 2:
4.81g (100mmol) of methyl mercaptan and 7.0g (103mmol) of sodium ethoxide solid are dissolved in a 250ml three-neck flask containing 30ml of DMF, a stirrer is added, the three-neck flask is immersed in an ice-water bath at the temperature of 3 ℃, a magnetic stirrer is started, and the mixture is fully stirred uniformly. 9.8g (129mmol) of carbon disulfide is slowly dripped into the three-neck flask, the reaction solution becomes turbid, the dripping speed is controlled, the mixture is continuously stirred for 45min after the dripping is finished, when the temperature is constant, the ice water bath is removed, 86.09g (100mmol) of methyl acrylate is dripped within 10min, and the reaction is carried out for 30h at room temperature.
And (3) adding 20ml of deionized water into the mixed solution after the reaction, and dropwise adding dilute sulfuric acid under the ice bath condition until all solids are separated out. Suction filtration and washing of the solid with ice ethanol followed by recrystallization from n-heptane gave 15.3g of a white solid (68.2% yield, 99.8% purity).
Example 3:
6.21g (100mmol) of ethanethiol and 11.1g (110mmol) of triethylamine liquid are dissolved in a 250ml three-neck flask containing 30ml of DMSO, a stirrer is added, the three-neck flask is immersed in an ice-water bath at 1 ℃, a magnetic stirrer is started, and the mixture is stirred fully and uniformly. Slowly dripping 10.28g (135mmol) of carbon disulfide into a three-neck flask, leading the reaction solution to become turbid, controlling the dripping speed, continuing stirring for 30min after dripping is finished, removing the ice water bath when the temperature is constant, dripping 10.01g (100mmol) of methyl methacrylate within 10min, and reacting for 28h at room temperature.
And (3) adding 20ml of deionized water into the mixed solution after the reaction, and dropwise adding dilute phosphoric acid under the ice bath condition until all solids are separated out. Suction filtration and washing of the solid with ice in deionized water followed by recrystallization from petroleum ether gave 16.7g of a white solid (70.1% yield, 98.5% purity).
Example 4:
11.02g (100mmol) of thiophenol and 7.0g (103mmol) of solid sodium ethoxide are dissolved in a 250ml three-neck flask containing 30ml of acetonitrile, a stirrer is added, the three-neck flask is immersed in an ice-water bath at the temperature of 2 ℃, a magnetic stirrer is started, and the mixture is fully stirred uniformly. 9.8g (129mmol) of carbon disulfide is slowly dripped into the three-neck flask, the reaction solution becomes turbid, the dripping speed is controlled, the mixture is continuously stirred for 45min after the dripping is finished, when the temperature is constant, the ice water bath is removed, 5.3g (100mmol) of acrylonitrile is dripped within 10min, and the mixture reacts for 32h at room temperature.
And (3) adding 20ml of deionized water into the mixed solution after the reaction, and dropwise adding dilute hydrochloric acid under the ice bath condition until all solids are separated out. Suction filtration was performed, and the solid was washed with ice-cold ethanol and recrystallized from ether to obtain 18.3g (yield 76.5%, purity 97.9%) of a white solid.
Example 5:
7.42g (100mmol) of 2-propene-1-thiol and 7.0g (103mmol) of triethylamine liquid are dissolved in a 250ml three-neck flask containing 30ml of propionitrile, a stirrer is added, the three-neck flask is immersed in an ice water bath at 3 ℃, a magnetic stirrer is started, and the mixture is fully stirred uniformly. Slowly dripping 9.8g (129mmol) of carbon disulfide into a three-neck flask, leading the reaction solution to become turbid, controlling the dripping speed, continuing stirring for 45min after dripping is finished, removing the ice water bath when the temperature is constant, dripping 7.11g (100mmol) of acrylamide within 10min, and reacting for 25h at room temperature.
And (3) adding 20ml of deionized water into the mixed solution after the reaction, and dropwise adding dilute hydrochloric acid under the ice bath condition until all solids are separated out. The solid was filtered with suction, washed with ice-cold ethanol and recrystallized from toluene to give 16.1g (yield 72.7%, purity 99.9%) of a bright yellow solid.
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 and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The additive for the electrolyte of the lithium ion battery is characterized by being trithiocarbonate, and the structural general formula of the additive is shown as I:
wherein R is1、R2Respectively select C1-C8Containing or not containing any unsaturated bond, carbonyl group, nitrile group, or ester group.
2. The lithium ion battery electrolyte additive of claim 1 wherein the structural formula I is any one of the following structural formulas:
3. a method of preparing the lithium ion battery electrolyte additive of claim 1 or 2, comprising the steps of:
step 1: the solvent, alkali and mercaptan are placed in a reaction vessel, and carbon disulfide is slowly dropped under an ice-water bath.
And 2, adding α -unsaturated carbonyl compound to carry out Michael addition reaction after the reaction is finished, and preparing a crude trithiocarbonate.
And step 3: acidifying with acid, washing with solvent, recrystallizing, and drying to obtain refined trithiocarbonate.
4. The method for preparing the lithium ion battery electrolyte additive according to claim 3, wherein the solvent in the step 1 is any one or more of acetonitrile, propionitrile, butyronitrile, dimethyl sulfoxide, N-dimethylformamide and tetrahydrofuran.
5. The method for preparing the lithium ion battery electrolyte additive according to claim 3, wherein the base in the step 1 is any one of sodium hydroxide, potassium hydroxide, sodium ethoxide, sodium methoxide, DBU and triethylamine.
6. The method for preparing the lithium ion battery electrolyte additive according to claim 3, wherein the mercaptan in the step 1 is any one of methyl mercaptan, ethyl mercaptan, thiophenol, 2-propylene-1-mercaptan, 2-methyl-2-propylene-1-mercaptan and isopentenyl mercaptan.
7. The method for preparing the lithium ion battery electrolyte additive according to claim 3, wherein the α -unsaturated carbonyl compound in the step 3 is any one of methyl acrylate, methyl methacrylate, acrylonitrile, methyl vinyl ketone, acrylamide, methyl crotonate, 2-butenenitrile and cyclohexenone, and the acid in the step 3 is any one of dilute hydrochloric acid, dilute sulfuric acid and dilute phosphoric acid.
8. The preparation method of the lithium ion battery electrolyte additive according to claim 3, wherein the molar ratio of the mercaptan to the alkali is 1:1-1:1.3, the molar ratio of the mercaptan to the carbon disulfide, α -unsaturated hydrocarbyl compound is 1:1.2: 1-1: 1.5:1, the reaction time for generating the trithiocarbonate is 24-36 h, and the reaction temperature is controlled at 0-10 ℃.
9. The method for preparing the lithium ion battery electrolyte additive according to claim 3, wherein the washing solvent in the step 3 is any one or more of deionized water, ethanol and methanol; the recrystallization reagent is any one or more of n-butane, n-pentane, n-hexane, n-heptane, tert-butane, n-octane, diethyl ether, dimethyl ether, diethyl ether, methyl ethyl ether, dipropyl ether, petroleum ether, anisole, phenetole, benzene, toluene, xylene and trimethylbenzene.
10. A lithium ion battery electrolyte comprising the trithiocarbonate additive of any of claims 1-2 or an electrolyte comprising the trithiocarbonate additive prepared by the method of any of claims 3-9.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130096219A1 (en) * | 2011-08-05 | 2013-04-18 | Christopher Bowman | Reducing polymerization-induced shrinkage stress by reversible addition-fragmentation chain transfer |
| CN104221196A (en) * | 2012-04-13 | 2014-12-17 | 阿科玛股份有限公司 | Battery based on organosulfur species |
| CN107180997A (en) * | 2017-06-09 | 2017-09-19 | 张家港市国泰华荣化工新材料有限公司 | A kind of lithium battery electrolytes and lithium battery |
| CN107880161A (en) * | 2017-11-27 | 2018-04-06 | 中山大学 | A kind of stabilized hyperbranched free radical polyalcohol of Photocrosslinkable and its preparation method and application |
| JP2019137799A (en) * | 2018-02-13 | 2019-08-22 | 株式会社日本触媒 | Polycarboxylic acid copolymer and method for producing the same, and additive for inorganic particles and cement composition including the same |
| CN110305269A (en) * | 2019-04-03 | 2019-10-08 | 华南理工大学 | A kind of rubber-modified (AB) Z type multi-block copolymer and its preparation method and application |
-
2019
- 2019-12-03 CN CN201911217907.2A patent/CN110845380A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130096219A1 (en) * | 2011-08-05 | 2013-04-18 | Christopher Bowman | Reducing polymerization-induced shrinkage stress by reversible addition-fragmentation chain transfer |
| CN104221196A (en) * | 2012-04-13 | 2014-12-17 | 阿科玛股份有限公司 | Battery based on organosulfur species |
| CN107180997A (en) * | 2017-06-09 | 2017-09-19 | 张家港市国泰华荣化工新材料有限公司 | A kind of lithium battery electrolytes and lithium battery |
| CN107880161A (en) * | 2017-11-27 | 2018-04-06 | 中山大学 | A kind of stabilized hyperbranched free radical polyalcohol of Photocrosslinkable and its preparation method and application |
| JP2019137799A (en) * | 2018-02-13 | 2019-08-22 | 株式会社日本触媒 | Polycarboxylic acid copolymer and method for producing the same, and additive for inorganic particles and cement composition including the same |
| CN110305269A (en) * | 2019-04-03 | 2019-10-08 | 华南理工大学 | A kind of rubber-modified (AB) Z type multi-block copolymer and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 程传杰等: "一锅法合成三硫代碳酸酯", 《合成化学》 * |
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