CN115010151B - Lithium salt for preparing lithium ion electrolyte and lithium ion electrolyte - Google Patents
Lithium salt for preparing lithium ion electrolyte and lithium ion electrolyte Download PDFInfo
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- CN115010151B CN115010151B CN202210723461.6A CN202210723461A CN115010151B CN 115010151 B CN115010151 B CN 115010151B CN 202210723461 A CN202210723461 A CN 202210723461A CN 115010151 B CN115010151 B CN 115010151B
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 127
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 96
- 229910003002 lithium salt Inorganic materials 0.000 title claims abstract description 72
- 159000000002 lithium salts Chemical class 0.000 title claims abstract description 72
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims abstract description 28
- 239000000654 additive Substances 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000000996 additive effect Effects 0.000 claims abstract description 10
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 9
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims abstract description 6
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims abstract description 6
- 229910013075 LiBF Inorganic materials 0.000 claims abstract description 3
- 229910013188 LiBOB Inorganic materials 0.000 claims abstract description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims abstract description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 28
- WIORFJNMBGEUGT-UHFFFAOYSA-K lithium magnesium trifluoride Chemical compound [Li+].[F-].[F-].[F-].[Mg++] WIORFJNMBGEUGT-UHFFFAOYSA-K 0.000 claims description 24
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 17
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 13
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 12
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 11
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 8
- 229910013872 LiPF Inorganic materials 0.000 claims description 7
- 101150058243 Lipf gene Proteins 0.000 claims description 7
- USOPFYZPGZGBEB-UHFFFAOYSA-N calcium lithium Chemical compound [Li].[Ca] USOPFYZPGZGBEB-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 4
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 4
- 239000004305 biphenyl Substances 0.000 claims description 4
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- 229940014800 succinic anhydride Drugs 0.000 claims description 4
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims description 2
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 claims description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 2
- 235000015598 salt intake Nutrition 0.000 claims 2
- ZQXCQTAELHSNAT-UHFFFAOYSA-N 1-chloro-3-nitro-5-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC(Cl)=CC(C(F)(F)F)=C1 ZQXCQTAELHSNAT-UHFFFAOYSA-N 0.000 claims 1
- 229910052790 beryllium Inorganic materials 0.000 claims 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims 1
- 230000007062 hydrolysis Effects 0.000 abstract description 9
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 9
- 238000013508 migration Methods 0.000 abstract description 6
- 230000005012 migration Effects 0.000 abstract description 6
- 229910013870 LiPF 6 Inorganic materials 0.000 abstract description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract description 2
- 150000001342 alkaline earth metals Chemical class 0.000 abstract description 2
- 229910052729 chemical element Inorganic materials 0.000 abstract description 2
- 230000000737 periodic effect Effects 0.000 abstract description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005979 thermal decomposition reaction Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 101100091149 Rattus norvegicus Rnf39 gene Proteins 0.000 description 1
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
-
- 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
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0563—Liquid materials, e.g. for Li-SOCl2 cells
-
- 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
- H01M2300/002—Inorganic electrolyte
-
- 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
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
-
- 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
-
- 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
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a lithium salt for preparing a lithium ion electrolyte and the lithium ion electrolyte, wherein the lithium salt has the structural formula:r is any one of alkaline earth metals of a second group of the periodic table of chemical elements, the lithium ion electrolyte comprises electrolyte lithium salt I, electrolyte lithium salt II, a nonaqueous solvent and an additive, wherein the electrolyte lithium salt I is the lithium salt for preparing the lithium ion electrolyte, and the electrolyte lithium salt II is lithium hexafluorophosphate (LiPF 6 ) Lithium hexafluoroarsenate (LiAsF) 6 ) Lithium perchlorate (LiClO) 4 ) Lithium tetrafluoroborate (LiBF) 4 ) Any one or a mixture of a plurality of lithium oxalato borate (LiBOB). According to the technical scheme, the prepared lithium ion electrolyte has higher conductivity and lithium ion migration number, the novel lithium salt is compounded with lithium hexafluorophosphate for use, the hydrolysis of the lithium hexafluorophosphate is inhibited, the hydrolysis resistance and stability of the electrolyte are improved, and the cycle performance of the lithium ion battery can be remarkably improved.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a lithium salt for preparing a lithium ion electrolyte and the lithium ion electrolyte.
Background
As one of the most important electrochemical energy storage devices at present, the application range of the lithium ion battery is gradually expanded from the application of a small-capacity battery to consumer electronics and electric tools to the emerging fields of new energy electric automobiles, electric ships, electric airplanes, robots and the like, and the lithium ion battery also has higher requirements. In the related art, lithium hexafluorophosphate is generally used as an electrolyte lithium salt of the lithium ion electrolyte, the thermal decomposition temperature is low, the lithium ion electrolyte is easy to hydrolyze after the service time is long, the safety performance of a lithium battery is seriously affected, and meanwhile, the development and the use of the lithium ion battery are seriously restricted due to low performances such as conductivity.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art or related art.
Therefore, the invention aims to provide the lithium salt for preparing the lithium ion electrolyte and the lithium ion electrolyte, wherein the lithium salt has good conductivity in a nonaqueous solvent, the thermal decomposition temperature exceeds 260 ℃, the stability is strong, meanwhile, the lithium salt has higher conductivity and lithium ion migration number, has better oxidation resistance, can be compatible with widely applied electrode materials, and meets the use requirement of a lithium ion battery. The water content and acidity value of the lithium ion electrolyte prepared by the lithium salt can meet the standard, and the conductivity is higher, and the lithium salt is compounded with lithium hexafluorophosphate for use, so that the hydrolysis of the lithium hexafluorophosphate is inhibited, the hydrolysis resistance and stability of the electrolyte are improved, and the cycle performance of the lithium ion battery can be remarkably improved.
In order to achieve the above purpose, the technical scheme of the invention provides a lithium salt for preparing lithium ion electrolyte, wherein the structural formula of the lithium salt is as follows:
wherein R is any one of alkaline earth metals of the second group of the periodic table of the chemical elements.
In the technical scheme, the novel lithium salt structure applied to the lithium ion electrolyte is provided, the lithium salt has higher thermal stability and water resistance, and the thermal decomposition graduation is higher than 300 ℃ and is far higher than that of the traditional lithium hexafluorophosphate.
In the above technical scheme, preferably, the lithium salt is magnesium lithium trifluoride (LiMgF 3 ) The lithium magnesium trifluoride (LiMgF) 3 ) The total amount of lithium salt in the lithium ion electrolyte is 8% -100% when the lithium ion electrolyte is prepared.
In the above technical solution, preferably, the lithium salt is lithium calcium trifluorocalcium (LiCaF) 3 ) The lithium calcium trifluoro (LiCaF) 3 ) When preparing the lithium ion electrolyte, the lithium ion electrolyte accounts for 8% -100% of the total consumption of lithium salt in the lithium ion electrolyte; or the lithium salt is lithium trifluoroberyllium (LiBeF) 3 ) The lithium trifluoroberyllium (LiBeF 3 ) The total amount of lithium salt in the lithium ion electrolyte is 8% -100% when the lithium ion electrolyte is prepared.
In the technical proposal, the lithium magnesium trifluoride (LiMgF 3 ) Lithium calcium trifluoro (LiCaF) 3 ) Lithium trifluoroberyllium (LiBeF) 3 ) The electrolyte lithium salt in the lithium ion electrolyte can be used as main salt or additive, and can effectively inhibit the hydrolysis of traditional lithium hexafluorophosphate when used as additive, and adopts magnesium lithium trifluoride (LiMgF 3 ) The conductivity of the electrolyte can reach 9.5ms cm -1 The performance of the lithium ion electrolyte is improved.
The technical scheme of the invention also provides a lithium ion electrolyte, which comprises an electrolyte lithium salt I, an electrolyte lithium salt II, a nonaqueous solvent and an additive, wherein the electrolyte lithium salt I is the lithium salt for preparing the lithium ion electrolyte provided in any one of the technical schemes; the electrolyte lithium salt II is lithium hexafluorophosphate (LiPF) 6 ) Lithium hexafluoroarsenate (LiAsF) 6 ) Lithium perchlorate (LiClO) 4 ) Lithium tetrafluoroborate (LiBF) 4 ) Any one or a mixture of a plurality of lithium dioxalate borate (LiBOB); the additive is any one or a mixture of more of ethylene carbonate (VC), biphenyl (BP), triphenyl phosphite (TPP), 1, 3-Propane Sultone (PS), 1, 4-Butane Sultone (BS), succinic Anhydride (SA) and fluoroethylene carbonate (FEC).
In the technical scheme, the lithium ion electrolyte adopts compound lithium salt, liRF 3 The addition of the lithium ion electrolyte can not only improve the conductivity and the migration number of lithium ions of the electrolyte, but also well inhibit the hydrolysis of the electrolyte lithium salt II, thereby being beneficial to improving the performance of the lithium ion battery.
In the above technical scheme, preferably, the ratio of the amounts of the substances of the electrolyte lithium salt i and the electrolyte lithium salt ii is (1-4): (8-11), and the dosage of the electrolyte lithium salt I and the electrolyte lithium salt II is 1-30% of the total mass of the electrolyte.
In the technical scheme, the ratio of the amounts of the electrolyte lithium salt I and the electrolyte lithium salt II in the lithium ion electrolyte is further limited, and under the ratio, the conductivity and the lithium ion migration number of the lithium ion electrolyte are improved, the hydrolysis of the electrolyte lithium salt II is well inhibited, the performance of the lithium ion battery is improved, and after 500 weeks of circulation, the capacity retention rate can still reach more than 90%.
In any one of the above embodiments, preferably, the electrolyte lithium salt i is lithium magnesium trifluoride (LiMgF 3 ) The electrolyte lithium salt II is lithium hexafluorophosphate (LiPF) 6 ) The ratio of the amounts of the substances is 4:8.
In the technical scheme, the proportion of the amount of the electrolyte lithium salt I, the amount of the electrolyte lithium salt II and the amount of the substance in the lithium ion electrolyte is further optimized, the performance of the lithium ion battery is further improved, the acidity and the water can meet the standards, the conductivity is higher, the capacity retention rate is higher after 500 weeks circulation, the thermal stability of the lithium ion electrolyte is greatly improved, and the safety performance of the lithium battery is obviously improved. In addition, the compatibility of all substances in the lithium ion electrolyte is good, and the performance of the lithium ion battery is further guaranteed.
In any of the above technical solutions, preferably, the additives are Vinylene Carbonate (VC) and 1, 3-Propane Sultone (PS), and the amount thereof is 0.01% -5% of the total mass of the electrolyte.
In any of the above embodiments, preferably, the additive is 1.5wt% Vinylene Carbonate (VC) and 2wt%1, 3-Propane Sultone (PS).
In any one of the above embodiments, preferably, the nonaqueous solvent is any one or a mixture of several of dimethyl carbonate (DMC), ethylene Carbonate (EC), ethylmethyl carbonate (EMC), diethyl carbonate (DEC), propylene Carbonate (PC) and methylpropyl carbonate (MPC).
In any of the above technical solutions, preferably, the nonaqueous solvent is a mixture of dimethyl carbonate (DMC), ethylene Carbonate (EC) and ethylmethyl carbonate (EMC), the volume ratio is 2:3:5, and the amount of the nonaqueous solvent is 60% -80% of the total mass of the electrolyte.
In the technical scheme, the preparation of the lithium ion electrolyte is further optimized, the thermal stability of the lithium ion electrolyte is greatly improved, and meanwhile, the lithium ion electrolyte has higher conductivity and lithium ion migration number, higher oxidation resistance and lithium hexafluorophosphate (LiPF) 6 ) Is well inhibited by adding 3000ppm of water to the lithium ion electrolyte, and no LiPF is detected after 70 hours 6 And (5) hydrolyzing.
The technical scheme of the invention also provides a lithium ion battery, and the lithium ion electrolyte adopting any one of the technical schemes has all the beneficial technical effects of the lithium ion electrolyte adopting any one of the technical schemes, and is not repeated here.
The lithium salt for preparing the lithium ion electrolyte and the lithium ion electrolyte have the following beneficial technical effects:
(1) The lithium salt for preparing the lithium ion electrolyte provided by the invention can be compatible with widely applied electrode materials, has thermal decomposition graduation of more than 260 ℃, has high conductivity and lithium ion migration number and better oxidation resistance when being applied to the lithium ion electrolyte, and can meet the use requirement of the current lithium ion battery.
(2) The lithium salt for preparing the lithium ion electrolyte provided by the invention can be used as a conductive main salt of the lithium ion electrolyte, can also be used as an additive of the traditional electrolyte lithium salt, and can well inhibit lithium hexafluorophosphate (LiPF 6 ) Even if 3000ppm of water was added to the electrolyte system, no LiPF was detected for 70 hours 6 And (5) hydrolyzing.
(3) The lithium ion electrolyte provided by the invention has the advantages that the electrolyte lithium salt I and the electrolyte lithium salt II are compounded, meanwhile, the materials and the dosage of a nonaqueous solvent and an additive are optimized, the compatibility of the lithium ion electrolyte is good, the hydrolysis resistance and the thermal stability are high, and the first charging efficiency and the capacity retention rate after 600 weeks of circulation are high.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
The invention discloses a lithium salt for preparing a lithium ion electrolyte and the lithium ion electrolyte, and a person skilled in the art can refer to the content of the lithium salt and the lithium ion electrolyte, and the method is realized by properly improving process parameters. It is expressly noted that all such similar substitutions and modifications will be apparent to those skilled in the art, and are deemed to be included in the present invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those skilled in the relevant art that variations and modifications can be made in the methods and applications described herein, and in the practice and application of the techniques of this invention, without departing from the spirit or scope of the invention.
The invention is further illustrated by the following examples:
for lithium salt LiMgF 3 、LiBeF 3 、LiCaF 3 Conventional LiPF 6 Thermal performance testing was performed and the test results are shown in table 1 below.
TABLE 1 lithium salt thermal performance test results
Example 1
Maintaining the water content of the glove box at about 0.1ppm and the oxygen content at about 0.1ppm, sequentially adding dimethyl carbonate (DMC), ethylene Carbonate (EC) and methyl ethyl carbonate (EMC) into a beaker according to the volume ratio of 2:3:5, cooling, slowly adding lithium hexafluorophosphate at the temperature of not higher than 10 ℃, regulating the concentration to 1.1mol/L, adding 1.5wt% of ethylene carbonate (VC), 2wt% of 1, 3-Propane Sultone (PS), and adding lithium magnesium trifluoride (LiMgF) 3 )0.1mol/L。
Example 2
Maintaining the glove box at about 0.1ppm of water and about 0.1ppm of oxygen, and mixing dimethyl carbonate (DMC) and ethylene carbonateSequentially adding Ester (EC) and methyl ethyl carbonate (EMC) into a beaker according to a volume ratio of 2:3:5, cooling, slowly adding lithium hexafluorophosphate at a temperature not higher than 10 ℃, adjusting the concentration to 1.0mol/L, adding 1.5wt% of Vinylene Carbonate (VC) and 2wt% of 1, 3-Propane Sultone (PS), and adding lithium magnesium trifluoride (LiMgF) 3 )0.2mol/L。
Example 3
Maintaining the water content of the glove box at about 0.1ppm and the oxygen content at about 0.1ppm, sequentially adding dimethyl carbonate (DMC), ethylene Carbonate (EC) and methyl ethyl carbonate (EMC) into a beaker according to the volume ratio of 2:3:5, cooling, slowly adding lithium hexafluorophosphate at the temperature of not higher than 10 ℃, regulating the concentration to 0.9mol/L, adding 1.5wt% of ethylene carbonate (VC), 2wt% of 1, 3-Propane Sultone (PS), and adding lithium magnesium trifluoride (LiMgF) 3 )0.3mol/L。
Example 4
Maintaining the water content of the glove box at about 0.1ppm and the oxygen content at about 0.1ppm, sequentially adding dimethyl carbonate (DMC), ethylene Carbonate (EC) and methyl ethyl carbonate (EMC) into a beaker according to the volume ratio of 2:3:5, cooling, slowly adding lithium hexafluorophosphate at the temperature of not higher than 10 ℃, regulating the concentration to 0.8mol/L, adding 1.5wt% of ethylene carbonate (VC), 2wt% of 1, 3-Propane Sultone (PS), and adding lithium magnesium trifluoride (LiMgF) 3 )0.4mol/L。
Example 5
Maintaining the water content of the glove box at about 0.1ppm and the oxygen content at about 0.1ppm, sequentially adding dimethyl carbonate (DMC), ethylene Carbonate (EC) and methyl ethyl carbonate (EMC) into a beaker according to the volume ratio of 2:3:5, cooling, slowly adding lithium hexafluorophosphate at the temperature of not higher than 10 ℃, regulating the concentration to 0.8mol/L, adding 1.5wt% of ethylene carbonate (VC), 2wt% of 1, 3-Propane Sultone (PS), and adding lithium trifluoroberyllium (LiBeF) 3 )0.4mol/L。
Example 6
Maintaining the glove box at water content of about 0.1ppm and oxygen content of about 0.1ppm, sequentially adding dimethyl carbonate (DMC), ethylene Carbonate (EC) and methyl ethyl carbonate (EMC) into a beaker at volume ratio of 2:3:5, and coolingCooling, slowly adding lithium hexafluorophosphate at a temperature not higher than 10deg.C, regulating concentration to 0.8mol/L, adding 1.5wt% of Vinylene Carbonate (VC) and 2wt% of 1, 3-Propane Sultone (PS)), and adding calcium lithium trifluoro (LiCaF) 3 )0.4mol/L。
Comparative example
The water content of the glove box is kept to be about 0.1ppm, the oxygen content is about 0.1ppm, dimethyl carbonate (DMC), ethylene Carbonate (EC) and methyl ethyl carbonate (EMC) are sequentially added into a beaker according to the volume ratio of 2:3:5, cooling is carried out, lithium hexafluorophosphate is slowly added at the temperature of not higher than 10 ℃, the concentration is regulated to be 1.2mol/L, and then 1.5wt% of ethylene carbonate (VC) and 2wt% of 1, 3-Propane Sultone (PS) are added.
The lithium ion electrolytes prepared in examples 1 to 6 and comparative examples were subjected to moisture, acidity, conductivity, thermal stability, water resistance, test results shown in table 2 below,
TABLE 2 lithium ion electrolyte Performance test results
From tables 1 and 2, it can be seen that the lithium salt for preparing lithium ion electrolyte provided by the invention has higher thermal stability, and the thermal decomposition temperature is higher than 300 ℃ and is far higher than that of the traditional LiPF 6 . The water content and the acidity of the lithium ion electrolyte prepared by the invention meet the standards, the water content in the electrolyte is relatively low, the oxidation resistance of the electrolyte is improved, the hydrolysis resistance and the thermal stability of the electrolyte are high, and the lithium magnesium trifluoride (LiMgF) 3 ) Can effectively inhibit LiPF 6 Is beneficial to guaranteeing the safety performance of the lithium ion battery. Example 4 has better effect, and the conductivity of the electrolyte can reach 9.5 mS.cm -1 HF was not detected in the water resistance, and the thermal stability could reach 322 ℃.
The lithium ion electrolytes prepared in examples 1 to 6 and comparative example were respectively injected into lithium iron batteries for cycle test, and the initial charge efficiency and the capacity retention after 600 weeks of cycle are shown in table 3 below.
Table 3 cyclic test results for lithium ion batteries
As can be seen from table 3, the cycle performance of the lithium ion battery adopting the lithium ion electrolyte provided by the invention is obviously improved, the first charge efficiency and the capacity retention rate after 600 weeks of cycle are high, the electrolyte compatibility is good, the safety performance is higher, and the use requirement of the current lithium ion battery can be met.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (7)
1. The lithium ion electrolyte is characterized by comprising electrolyte lithium salt I, electrolyte lithium salt II, a nonaqueous solvent and an additive, wherein the structural formula of the electrolyte lithium salt I is as follows:
the electrolyte lithium salt I is magnesium lithium trifluoride (LiMgF) 3 ) The lithium magnesium trifluoride (LiMgF) 3 ) The lithium ion electrolyte accounts for 8% -100% of the total lithium salt consumption in the lithium ion electrolyte and does not contain 100%;
or the electrolyte lithium salt I is lithium calcium trifluoro (LiCaF) 3 ) The lithium calcium trifluoro (LiCaF) 3 ) The lithium ion electrolyte accounts for 8% -100% of the total lithium salt consumption in the lithium ion electrolyte and does not contain 100%;
or the electrolyte lithium salt I is lithium beryllium trifluoride (LiBeF) 3 ) The lithium trifluoroberyllium (LiBeF 3 ) When the lithium ion electrolyte is prepared, the lithium ion electrolyte accounts for 8 to 100 percent of the total dosage of lithium salt in the lithium ion electrolyte and does not contain 100 percent,
the electrolyte lithium salt II is lithium hexafluorophosphate (LiPF) 6 ) Lithium hexafluoroarsenate (LiAsF) 6 ) Lithium perchlorate (LiClO) 4 ) Lithium tetrafluoroborate (LiBF) 4 ) Any one or a mixture of a plurality of lithium dioxalate borate (LiBOB);
the additive is any one or a mixture of more of ethylene carbonate (VC), biphenyl (BP), triphenyl phosphite (TPP), 1, 3-Propane Sultone (PS), 1, 4-Butane Sultone (BS), succinic Anhydride (SA) and fluoroethylene carbonate (FEC).
2. The lithium ion electrolyte according to claim 1, wherein the ratio of the amounts of the substances of the electrolyte lithium salt i and the electrolyte lithium salt ii is (1-4): (8-11), and the dosage of the electrolyte lithium salt I and the electrolyte lithium salt II is 1-30% of the total mass of the electrolyte.
3. The lithium ion electrolyte of claim 2, wherein the electrolyte lithium salt i is lithium magnesium trifluoride (LiMgF 3 ) The electrolyte lithium salt II is lithium hexafluorophosphate (LiPF) 6 ) The ratio of the amounts of the substances is 4:8.
4. A lithium-ion electrolyte according to any one of claims 1 to 3, characterized in that the additives are Vinylene Carbonate (VC) and 1, 3-Propane Sultone (PS) in an amount of 0.01% -5% of the total mass of the electrolyte.
5. The lithium-ion electrolyte according to claim 4, wherein,
the nonaqueous solvent is any one or mixture of several of dimethyl carbonate (DMC), ethylene Carbonate (EC), ethylmethyl carbonate (EMC), diethyl carbonate (DEC), propylene Carbonate (PC) and Methyl Propyl Carbonate (MPC).
6. The lithium-ion electrolyte according to claim 5, wherein,
the nonaqueous solvent is a mixture of dimethyl carbonate (DMC), ethylene Carbonate (EC) and methyl ethyl carbonate (EMC) with a volume ratio of 2:3:5, and the dosage of the nonaqueous solvent is 60-80% of the total mass of the electrolyte.
7. A lithium ion battery characterized in that the lithium ion electrolyte according to any one of the preceding claims 1 to 6 is used.
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