CN109575067A - A kind of silicon-containing organic compound and its application - Google Patents
A kind of silicon-containing organic compound and its application Download PDFInfo
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- CN109575067A CN109575067A CN201811401995.7A CN201811401995A CN109575067A CN 109575067 A CN109575067 A CN 109575067A CN 201811401995 A CN201811401995 A CN 201811401995A CN 109575067 A CN109575067 A CN 109575067A
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- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 39
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000010703 silicon Substances 0.000 title claims abstract description 28
- 150000002894 organic compounds Chemical class 0.000 title claims abstract description 24
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 52
- 239000003792 electrolyte Substances 0.000 claims abstract description 50
- 239000002904 solvent Substances 0.000 claims abstract description 40
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims abstract description 26
- -1 ether modified silicon alkanes Chemical class 0.000 claims abstract description 24
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 21
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims abstract description 16
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 11
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims abstract description 10
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 10
- 239000010452 phosphate Substances 0.000 claims abstract description 10
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 claims abstract description 9
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims description 25
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 8
- 229910000077 silane Inorganic materials 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 150000001721 carbon Chemical group 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 239000000654 additive Substances 0.000 abstract description 6
- 230000000996 additive effect Effects 0.000 abstract description 6
- 150000004649 carbonic acid derivatives Chemical class 0.000 abstract description 4
- 150000003961 organosilicon compounds Chemical class 0.000 abstract 2
- 230000004087 circulation Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000011056 performance test Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910018557 Si O Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910001453 nickel ion Inorganic materials 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 4
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 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 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1896—Compounds having one or more Si-O-acyl linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/04—Esters of silicic acids
-
- 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
- H01M10/0569—Liquid materials characterised by the solvents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
-
- 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)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a kind of silicon-containing organic compound and its applications.Organo-silicon compound of the invention mainly include silicone carbonate class, silicone carboxylates' class, ether modified silicon alkanes；Silicon-containing organic compound of the present invention can be applied to lithium-ion battery electrolytes, solvent as lithium-ion battery electrolytes, also comprising ethylene carbonate, propene carbonate, methyl ethyl carbonate and diethyl carbonate as basic solvent in the lithium-ion battery electrolytes, and lithium hexafluoro phosphate, vinylene carbonate, 1,3-propane sultone and fluorinated ethylene carbonate are as additive.Organo-silicon compound electrolyte solvent of the invention has higher oxygenolysis current potential, it can be good at improving the high temperature resistant and high pressure resistant stability of lithium ion battery, and its preferable wellability and low viscosity, it can be good at improving lithium ion conductivity, high rate performance and the safety for improving battery are a kind of novel two generations solvent for lithium.
Description
Technical field
The present invention relates to field of lithium ion battery, it is specifically related to a kind of silicon-containing organic compound and its application.
Background technique
Four big main materials one of of the electrolyte as lithium ion battery, have very strong suitability, it is important that one
Feature is exactly to customize, and end formulation is needed according to positive electrode type, cell shapes, battery performance of lithium battery etc. certainly
It is fixed.Organic solvent low boiling point in conventional lithium ion battery electrolyte, flash-point is low, inflammable volatile, and poor radiation, is easy band
Carry out security risk；Ordinary high pressure electrolyte, which introduces high pressure additive, can get 4.4~4.7V electrolyte, but still is unable to satisfy and is based on
The power lithium battery 4.8V of the high-voltage positive electrode material of new generation even requirement of 5V potential window.The five-year, according to power lithium battery industry
Layout, the research and development of electrolyte and industrialization direction will be and the matched height of positive electrode of new generation such as nickelic, lithium-rich manganese-based
Voltage, high security novel high-pressure electrolyte.
Currently, be mostly to widen the electrochemical window of electrolyte by changing solvent type, solvent burden ratio or lithium salts type,
Wherein most feasibility be change solvent.Several high pressure solvents of current research and concern at most mainly have fluorinated solvents, sulfone
Class solvent and nitrile solvents.In addition, introducing silicon atom in traditional carbonic ester, carboxylate or ether compound obtains organosilicon
Class compound has very big development prospect in high-voltage lithium-ion battery electrolyte application.
Summary of the invention
The present invention provides a kind of silicon-containing organic compounds, including silicone carbonate class, silicone carboxylates' class, ether to change
Property silanes.In silicon-containing organic compound of the present invention, silicon atom has lower electronegativity, with oxygen atom bonding
Afterwards, Si-O key has the characteristic of part ion key, has biggish bond energy, therefore the compound after silicon of the present invention generation is with higher
Oxidation resistance, can be used as high-voltage electrolyte solvent, the addition of such electrolyte solvent improves lithium ion well
The high temperature resistant of battery and high pressure resistant stability improve high rate performance and the safety of battery, are a kind of novel two generations lithium ions
Battery solvent.
To achieve the object of the present invention, silicon-containing organic compound of the present invention includes organosilicon carbonic acid shown in formula (I)
Ether modified silicon alkyl compound shown in silicone carboxylates' class compound shown in ester type compound, formula (II) and formula (III):
In formula (I), M1And M2Respectively indicate the alkyl containing 1-6 carbon atom or silane or silicon oxygen containing 1-4 silicon atom
Alkane；Wherein, M1And M2At least one is silane or siloxanes containing 1-4 silicon atom；
In formula (II), X1And X2Respectively indicate the alkyl containing 1-6 carbon atom or silane or silicon containing 1-4 silicon atom
Oxygen alkane；Wherein, X1And X2At least one is silane or siloxanes containing 1-4 silicon atom；
In formula (III), R indicates the alkyl containing 1-6 carbon atom；X indicates the short chain ethers containing 1-8 oxygen atom；M is
Any one numerical value in 0-3.
An embodiment according to the present invention, the compound that the formula (I) indicates include:
Wherein compound (1)-(7) usage amount accounts for the 5-50% of electrolyte quality percentage；Preferably 5-20%.
An embodiment according to the present invention, the compound that the formula (II) indicates include:
Wherein compound (8)-(17) usage amount accounts for the 5-50% of electrolyte quality percentage；Preferably 5-20%.
An embodiment according to the present invention, the compound that the formula (III) indicates include:
Wherein compound (18)-(21) usage amount accounts for the 5-50% of electrolyte quality percentage；Preferably 5-20%.
Silicon-containing organic compound of the present invention can be applied to lithium-ion battery electrolytes, be electrolysed as lithium ion battery
The solvent of liquid.
It further, also include ethylene carbonate (EC), propene carbonate (PC), carbon in the lithium-ion battery electrolytes
Sour methyl ethyl ester (EMC) and diethyl carbonate (DEC) are used as basic solvent and lithium hexafluoro phosphate, vinylene carbonate (VC), 1,
3- propane sultone (1,3-PS) and fluorinated ethylene carbonate (FEC) are used as additive.
Preferably, in the lithium-ion battery electrolytes, ethylene carbonate (EC), propene carbonate (PC), methyl ethyl carbonate
The weight ratio of ester (EMC) and diethyl carbonate (DEC) is 25:5:50:20.
Preferably, in the lithium-ion battery electrolytes, the content of lithium hexafluoro phosphate is 12.5wt%.
Preferably, in the lithium-ion battery electrolytes, the mass fraction of vinylene carbonate (VC) is 0.5%, 1,3-
The mass fraction of propane sultone (1,3-PS) is 1.5%, and the mass fraction of fluorinated ethylene carbonate (FEC) is 2%.
It is further preferred that the lithium-ion battery electrolytes the preparation method comprises the following steps: by ethylene carbonate (EC), carbonic acid third
Enester (PC), methyl ethyl carbonate (EMC) and diethyl carbonate (DEC) are mixed according to the ratio of weight ratio 25:5:50:20,
Then silicone carboxylates shown in silicone carbonate class compound shown in formula (I) or formula (II) are added in the mixed solvent
Ether modified silicon alkyl compound shown in class compound or formula (III), and it is slowly added to the lithium hexafluoro phosphate of 12.5wt%, it
Afterwards, it is 0.5% vinylene carbonate (VC), 1.5% 1,3-propane sultone (1,3- that mass fraction is added into electrolyte
PS), 2% fluorinated ethylene carbonate (FEC).
Preferably, the usage amount of the silicon-containing compound accounts for the 5-50% of electrolyte quality percentage；Further preferably
5-20%.
The present invention also provides a kind of lithium ion battery, which has been used using the siliceous organic compound of the present invention
The lithium-ion battery electrolytes of object preparation.
Further, the preparation method of the lithium ion battery include the lithium for preparing silicon-containing organic compound of the present invention from
Sub- battery electrolyte is injected into the LiNi by sufficiently dry 4.7V0.5Mn1.5O4/ AG soft-package battery is shelved by 45 DEG C, is high
Warm fixture chemical conversion and secondary sealing process.
The present invention provides the silicon-containing organic compounds of a new generation as high-voltage electrolyte solvent, and this kind of solvent mainly wraps
Including silicone carbonate class, silicone carboxylates' class and ether modified silicon alkanes, wherein silicon atom has lower electronegativity,
After oxygen atom bonding, Si-O key have part ion key characteristic, have biggish bond energy, therefore silicon generation after carbonic ester,
Carboxylate or ether compound have higher oxidation resistance；On the other hand, Si-O key bond distance is longer, compared to C-O key,
Si-O key has very low interior Rotational Barriers, therefore after silicon generation the chain flexibility of former compound is increased, and reduces former compound
Viscosity.Advantage possessed by the silicon-containing organic compound solvent of a new generation of the invention mainly has:
(1) oxidation resistance and chemical stability for increasing original carbonates, carboxylic acid esters and ether compound, mention
The high high-temperature behavior of lithium battery, the lithium battery system suitable for higher voltage；
(2) viscosity for reducing original solvent improves the shuttling performance of lithium ion in a solvent, can largely improve
The cryogenic property and high rate performance of lithium battery；
(3) combustibility for reducing former solvent, improves flame retardant effect and the safety of lithium ion battery；
(4) silicon is environmentally friendly compound for solvent, is of great significance for Green Development, safety and environmental protection.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated.Additional aspect and advantage of the invention will be set forth in part in the description, partially will be under
Become obvious in the description in face, or practice through the invention is recognized.It is only used to explain this hair it should be appreciated that being described below
It is bright, it is not intended to limit the present invention.
Term "comprising" used herein, " comprising ", " having ", " containing " or its any other deformation, it is intended that covering
Non-exclusionism includes.For example, composition, step, method, product or device comprising listed elements are not necessarily limited to those and want
Element, but may include not expressly listed other elements or such composition, step, method, product or device it is intrinsic
Element.
Conjunction " Consists of " excludes any element that do not point out, step or component.If in claim, this
Phrase will make claim closed, so that it is not included the material in addition to the material of those descriptions, but relative normal
Except rule impurity.When being rather than immediately following after theme in the clause that phrase " Consists of " appears in claim main body,
It is only limited to element described in the clause；Other elements are not excluded except the claim as a whole.
Equivalent, concentration or other values or parameter are excellent with range, preferred scope or a series of upper limit preferred values and lower limit
When the Range Representation that choosing value limits, this should be understood as specifically disclosing by any range limit or preferred value and any range
Any pairing of lower limit or preferred value is formed by all ranges, regardless of whether the range separately discloses.For example, when open
When range " 1 to 5 ", described range should be interpreted as including range " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to
5 ", " 1 to 3 and 5 " etc..When numberical range is described herein, unless otherwise stated, otherwise the range is intended to include its end
Value and all integers and score in the range.
Singular includes that plural number discusses object, unless the context clearly dictates otherwise." optional " or it is " any
It is a kind of " refer to that the item described thereafter or event may or may not occur, and the description include situation that event occurs and
The situation that event does not occur.
Approximate term in specification and claims is used to modify quantity, and it is specific to indicate that the present invention is not limited to this
Quantity further includes the acceptable modified part without will lead to the change of dependency basis this function close with the quantity.Phase
It answers, modifies a numerical value with " about ", " about " etc., mean that the present invention is not limited to the exact numericals.In some examples, approximate
Term likely corresponds to the precision of the instrument of measurement numerical value.In present specification and claims, range limits can be with
Combination and/or exchange, these ranges if not stated otherwise include all subranges contained therebetween.
Indefinite article "an" before element or component of the present invention (goes out the quantitative requirement of element or component with "one"
Occurrence number) unrestriction.Therefore "one" or "an" should be read as including one or at least one, and singular
Element or component also include plural form, unless the quantity obviously only refers to singular.
Moreover, technical characteristic involved in each embodiment of the present invention as long as they do not conflict with each other can
To be combined with each other.
Performance of lithium ion battery test
Normal-temperature circulating performance test: under the conditions of room temperature (25 DEG C), lithium ion battery obtained by the embodiment of the present invention is existed
0.2C constant current constant voltage is charged to 4.7V, is then discharged to 3.0V under 0.2C constant current conditions.After charge and discharge 100 circulations, the is calculated
Capacity retention ratio after 100 circulations:
High-temperature storage performance test: under the conditions of room temperature (25 DEG C), a 0.5C/0.5C charging is carried out to lithium ion battery
(discharge capacity is denoted as DC with electric discharge0), battery is then charged into 4.7V under the conditions of 0.5C constant current constant voltage；By lithium ion battery
It is placed in 65 DEG C of high-temperature cabinets and saves 7 days, after taking-up, carrying out 0.5C electric discharge under normal temperature conditions, (discharge capacity is denoted as DC1)；Then
Carrying out 0.5C/0.5C charging and discharging under normal temperature conditions, (discharge capacity is denoted as DC2), lithium-ion electric is calculated using following formula
The capacity retention ratio and capacity restoration rate in pond:
Cryogenic property test: under the conditions of low temperature (0 DEG C), above-mentioned lithium ion battery is charged in 0.2C constant current constant voltage
Then 4.7V is discharged to 3.0V under 0.5C constant current conditions.After charge and discharge 10 circulations, the capacity after calculating the 10th circulation is protected
Holdup:
Embodiment 1-1
Electrolyte quota step: full of argon gas glove box in, by ethylene carbonate (EC), propene carbonate (PC),
Methyl ethyl carbonate (EMC) and diethyl carbonate (DEC) are mixed according to the ratio of weight ratio 25:5:50:20, then to mixing
Organic silicon solvent shown in the compound (1) based on solvent gross mass 5wt% is added in solvent, and is slowly added to 12.5wt%'s
Lithium hexafluoro phosphate, later, it is 0.5% vinylene carbonate (VC), 1.5% 1,3- third that mass fraction is added into electrolyte
Alkane sultone (1,3-PS), 2% fluorinated ethylene carbonate (FEC), obtain the lithium ion battery of embodiment 1-1 after mixing evenly
Electrolyte.
Prepared lithium ion battery is injected into nonaqueous electrolytic solution by sufficiently dry 4.7V's
LiNi0.5Mn1.5O4/ AG soft-package battery is shelved by 45 DEG C, after the processes such as high-temperature clamp chemical conversion and secondary sealing, carries out battery
Performance test obtains battery used in embodiment 1-1.
Embodiment 1-2 to embodiment 1-14 and comparative example 1 arrive comparative example 2
It is other other than being added shown in each ingredient composition and ratio according to the form below of electrolyte in embodiment 1-2 to embodiment 1-14
It is identical as embodiment 1-1, reference can be made to table 1.
Comparative example 1 is compared with embodiment 1-1, other than not adding containing siloxane solvent, not comprising 1.5% in electrolysis additive
1,3-propane sultone (1,3-PS) and 2% fluorinated ethylene carbonate (FEC), other are identical as embodiment 1-1；Comparative example 2
Compared with embodiment 1-1, other than not adding containing siloxane solvent, other conditions are identical, reference can be made to table 1.
The compound that 1 formula of table (I) represents is as the effect after solvent addition
Embodiment 2-1
Electrolyte quota step: full of argon gas glove box in, by ethylene carbonate (EC), propene carbonate (PC),
Methyl ethyl carbonate (EMC) and diethyl carbonate (DEC) are mixed according to the ratio of weight ratio 25:5:50:20, then to mixing
Silicone carboxylates' solvent shown in the compound (8) based on solvent gross mass 5wt% is added in solvent, and is slowly added to
The lithium hexafluoro phosphate of 12.5wt%, later, into electrolyte be added mass fraction be 0.5% vinylene carbonate (VC),
1.5% 1,3-propane sultone (1,3-PS), 2% fluorinated ethylene carbonate (FEC), obtain embodiment 2- after mixing evenly
1 lithium-ion battery electrolytes.
Prepared lithium ion battery is injected into nonaqueous electrolytic solution by sufficiently dry 4.7V's
LiNi0.5Mn1.5O4/ AG soft-package battery is shelved by 45 DEG C, after the processes such as high-temperature clamp chemical conversion and secondary sealing, carries out battery
Performance test obtains battery used in embodiment 2-1.
Embodiment 2-2 to embodiment 2-20
It is other other than being added shown in each ingredient composition and ratio according to the form below of electrolyte in embodiment 2-2 to embodiment 2-20
It is identical as embodiment 2-1.
The compound that 2 formula of table (II) represents is as the effect after solvent addition
Embodiment 3-1
Electrolyte quota step: full of argon gas glove box in, by ethylene carbonate (EC), propene carbonate (PC),
Methyl ethyl carbonate (EMC) and diethyl carbonate (DEC) are mixed according to the ratio of weight ratio 25:5:50:20, then to mixing
Ether modified silicon alkanes solvent shown in the compound (18) based on solvent gross mass 5wt% is added in solvent, and is slowly added to
The lithium hexafluoro phosphate of 12.5wt%, later, into electrolyte be added mass fraction be 0.5% vinylene carbonate (VC),
1.5% 1,3-propane sultone (1,3-PS), 2% fluorinated ethylene carbonate (FEC), obtain embodiment 3- after mixing evenly
1 lithium-ion battery electrolytes.
Prepared lithium ion battery is injected into nonaqueous electrolytic solution by sufficiently dry 4.7V's
LiNi0.5Mn1.5O4/ AG soft-package battery is shelved by 45 DEG C, after the processes such as high-temperature clamp chemical conversion and secondary sealing, carries out battery
Performance test obtains battery used in embodiment 3-1.
Embodiment 3-2 to embodiment 3-8
It is other other than being added shown in each ingredient composition and ratio according to the form below of electrolyte in embodiment 3-2 to embodiment 3-8
It is identical as embodiment 3-1.
The compound that 3 formula of table (III) represents is as the effect after solvent addition
According to Electrochemical results, it is as follows that conclusion can be obtained:
1. siliceous organic solvent stability with higher and oxidation resistance, high added with being conducive to improve nickel ion doped
The high-temperature storage performance of voltage lithium ion battery；Silicone carbonate and silicone carboxylates' class solvent viscosity it is lower, to interface
Wellability is preferable, is of great significance to the room temperature and low-temperature circulating performance that improve nickel ion doped high-voltage lithium ion batteries；
2. when siliceous organic solvent additive amount less (5%), to the normal temperature circulation of nickel ion doped high-voltage lithium ion batteries
It is more preferable with high temperature storage effect；With the increase (20%) of additive amount, the normal temperature circulation and high temperature storage effect of lithium ion battery
It is gradually deteriorated, especially normal-temperature circulating performance, but still has certain improvement to normal temperature circulation and high temperature storage；
3. ether modified silicon alkanes solvent viscosity is relatively large, addition can deteriorate the normal of lithium ion battery to a certain extent
Warm cycle performance；It but may be since its wellability at interface is excellent, in the normal of nickel ion doped high-voltage lithium ion batteries
Temperature circulation still has a degree of promotion；
4. on the whole, siliceous organic solvent of the invention all has the cryogenic property of high-voltage lithium ion batteries certain
Improve, from result after the dismantling of the electrode of lithium ion battery as it can be seen that it has certain improvement to battery analysis lithium, has to low-temperature circulating performance
Very big promotion.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of silicon-containing organic compound, which is characterized in that the silicon-containing organic compound includes organic silicon-carbon shown in formula (I)
Ether modified silicon alkanes chemical combination shown in silicone carboxylates' class compound shown in acid esters compound, formula (II) and formula (III)
Object:
In formula (I), M1And M2Respectively indicate the alkyl containing 1-6 carbon atom or silane or siloxanes containing 1-4 silicon atom；
Wherein, M1And M2At least one is silane or siloxanes containing 1-4 silicon atom；
In formula (II), X1And X2Respectively indicate the alkyl containing 1-6 carbon atom or silane or siloxanes containing 1-4 silicon atom；
Wherein, X1And X2At least one is silane or siloxanes containing 1-4 silicon atom；
In formula (III), R indicates the alkyl containing 1-6 carbon atom；X indicates the short chain ethers containing 1-8 oxygen atom；M is 0-3
In any one numerical value.
2. silicon-containing organic compound according to claim 1, which is characterized in that the compound that the formula (I) indicates includes:
3. silicon-containing organic compound according to claim 1, which is characterized in that the compound packet that the formula (II) indicates
It includes:
4. silicon-containing organic compound according to claim 1, which is characterized in that the compound packet that the formula (III) indicates
It includes:
5. a kind of application of the described in any item silicon-containing organic compounds of claim 1-4, which is characterized in that described siliceous organic
Compound is applied to lithium-ion battery electrolytes, the solvent as lithium-ion battery electrolytes.
6. the application of silicon-containing organic compound according to claim 5, which is characterized in that the lithium-ion battery electrolytes
In also include ethylene carbonate, propene carbonate, methyl ethyl carbonate and diethyl carbonate and lithium hexafluoro phosphate, carbonic acid Asia second
Enester, 1,3- propane sultone and fluorinated ethylene carbonate.
7. the application of silicon-containing organic compound according to claim 6, which is characterized in that the lithium-ion battery electrolytes
In, ethylene carbonate, propene carbonate, methyl ethyl carbonate and diethyl carbonate weight ratio be 25:5:50:20；Preferably, institute
It states in lithium-ion battery electrolytes, the content of lithium hexafluoro phosphate is 12.5wt%；Preferably, the lithium-ion battery electrolytes
In, the mass fraction of vinylene carbonate is 0.5%, and the mass fraction of 1,3-propane sultone is 1.5%, fluoro ethylene carbonate
The mass fraction of ester is 2%.
8. the application of silicon-containing organic compound according to claim 5, which is characterized in that the lithium-ion battery electrolytes
The preparation method comprises the following steps: by ethylene carbonate, propene carbonate, methyl ethyl carbonate and diethyl carbonate according to weight ratio 25:5:50:
20 ratio is mixed, and silicone carbonate class compound or formula (II) shown in formula (I) then is added in the mixed solvent
Shown in ether modified silicon alkyl compound shown in silicone carboxylates' class compound or formula (III), and be slowly added to
The vinylene carbonate, 1.5% that mass fraction is 0.5% are added into electrolyte later for the lithium hexafluoro phosphate of 12.5wt%
1,3- propane sultone, 2% fluorinated ethylene carbonate.
9. according to the application of the described in any item silicon-containing organic compounds of claim 5-8, which is characterized in that the siliceous chemical combination
The usage amount of object accounts for the 5-50% of electrolyte quality percentage；Further preferably 5-20%.
10. a kind of lithium ion battery, which is characterized in that the lithium ion battery used the lithium in claim any one of 5-9 from
Sub- battery electrolyte.
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| CN109888393A (en) * | 2019-04-08 | 2019-06-14 | 珠海冠宇电池有限公司 | A kind of lithium-ion battery electrolytes and the lithium ion battery using the electrolyte |
| CN111106388A (en) * | 2020-01-18 | 2020-05-05 | 湖南大学 | Electrolyte and lithium ion battery |
| CN112652818A (en) * | 2021-01-12 | 2021-04-13 | 东莞维科电池有限公司 | Electrolyte for lithium ion battery and lithium ion battery |
| CN113394459A (en) * | 2021-06-21 | 2021-09-14 | 深圳市比克动力电池有限公司 | Additive for battery electrolyte, electrolyte and lithium ion battery |
| CN113921907A (en) * | 2021-09-28 | 2022-01-11 | 湖南立方新能源科技有限责任公司 | Additive for sodium ion battery electrolyte, electrolyte and sodium ion battery |
| CN114284557A (en) * | 2021-12-17 | 2022-04-05 | 上海瑞浦青创新能源有限公司 | Electrolyte for battery and battery using same |
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| CN113921907A (en) * | 2021-09-28 | 2022-01-11 | 湖南立方新能源科技有限责任公司 | Additive for sodium ion battery electrolyte, electrolyte and sodium ion battery |
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Application publication date: 20190405 |