WO2021223181A1 - 一种电解液及电化学装置 - Google Patents
一种电解液及电化学装置 Download PDFInfo
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- WO2021223181A1 WO2021223181A1 PCT/CN2020/089041 CN2020089041W WO2021223181A1 WO 2021223181 A1 WO2021223181 A1 WO 2021223181A1 CN 2020089041 W CN2020089041 W CN 2020089041W WO 2021223181 A1 WO2021223181 A1 WO 2021223181A1
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- H—ELECTRICITY
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- 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
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
Definitions
- This application relates to the field of energy storage technology, and in particular to an electrolyte and an electrochemical device containing the electrolyte.
- Electrochemical devices for example, lithium-ion batteries
- Lithium-ion batteries have been widely used in new energy electric vehicles, electronic products such as cameras, digital cameras, and 3C products due to their high energy density, high working voltage, long life, and environmental protection.
- Lithium-ion batteries generally consist of a positive electrode, a negative electrode, a separator and an electrolyte. As an important component, the electrolyte plays a role in transferring lithium ions between the positive and negative electrodes. An important guarantee for high security and other performance.
- Lithium-ion batteries are prone to deterioration in battery performance at high temperatures, causing problems such as high-temperature storage gas production and circulating gas production. At the same time, lithium-ion batteries also have problems such as large film-forming resistance and poor storage performance. Therefore, how to develop lithium-ion batteries with excellent performance has become an urgent problem in the industry.
- the present invention provides an electrolyte and an electrochemical device with excellent high-temperature cycle performance and over-discharge storage performance.
- One aspect of the present invention provides an electrochemical device, comprising a positive electrode, a negative electrode, an electrolyte, and a separator.
- the positive electrode includes a positive electrode current collector and a positive electrode active material layer disposed on the positive electrode current collector.
- the X-ray photoelectron spectrum of the material layer has a peak from 164 eV to 175 eV, and the electrolyte retention of the electrochemical device is 1.0 g/Ah to 4.0 g/Ah.
- the positive electrode active material layer includes first particles, and the cross section perpendicular to the positive electrode current collector in the positive electrode is tested by scanning electron microscopy, and the gray scale of the first particles is not less than 115RGB, and the The cross-sectional area of the first particles is less than 20 square microns, and the total area of the first particles occupies a proportion of 5% to 50% based on the area of the cross section of the positive electrode perpendicular to the positive electrode current collector.
- the positive electrode active material layer includes second particles, and a cross section perpendicular to the positive electrode current collector in the positive electrode is tested by scanning electron microscopy.
- the gray level of the second particles is less than 115RGB, and the second particle
- the cross-sectional area of the two particles is greater than or equal to 20 square microns, and the total area of the second particles occupies a proportion of 10% to 60% based on the area of the cross section of the positive electrode perpendicular to the positive electrode current collector.
- the first particles comprise Li a Ni x Co y Mn z M m O 2 , wherein 0.9 ⁇ a ⁇ 1.1, 0.3 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 0.7, 0 ⁇ z ⁇ 0.4, x+y+z ⁇ 1, 0 ⁇ m ⁇ 0.1
- the M element includes at least one of Al, Ti, Mg, W, Zr, Nb, In, Ru, Sb, Sr, Y, or F; wherein The content of the M element is 0 to 1% based on the total weight of the positive active material.
- the second particles include Li b Mn 2-n Me n O 4 , wherein the Me element includes at least one of Mg, Ti, Cr, Al, B, Fe, Zr, Na, F, or S One, 0.9 ⁇ b ⁇ 1.1, 0 ⁇ n ⁇ 0.1, wherein the content of the Me element is 0% to 1% based on the total weight of the positive electrode active material.
- the electrolyte includes additive A, and the additive A includes at least one of a compound of formula I, a compound of formula II, a compound of formula III, or a compound of formula IV:
- R 1 is selected from H, C 1-6 alkyl or C 2-6 alkenyl
- R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each independently selected from H, halogen, unsubstituted or substituted with one or more halogens C 1-6 alkyl, or unsubstituted or C 2-6 alkenyl substituted with one or more halogens;
- n is an integer from 1 to 3;
- the mass fraction of the additive A is 0.01% to 5%.
- the additive A includes at least one of the following compounds:
- the electrolyte includes at least one of a compound of formula I, a compound of formula II, or a compound of formula III and a compound of formula IV.
- the electrolyte includes additive B
- the additive B includes lithium difluorophosphate, lithium 4,5-dicyano-2-trifluoromethylimidazolium, or difluorobis(oxalate) At least one of lithium phosphate; based on the total weight of the electrolyte, the mass fraction of the additive B is 0.01% to 3%.
- the electrolyte includes additive C, and the additive C includes at least one of the following phosphate compounds:
- the mass fraction of the additive C is 0.01% to 5%.
- the electrolyte includes additive D
- the additive D includes at least one of the following compounds: vinylene carbonate, vinyl ethylene carbonate, 1,4-butane sultone, sulfuric acid Vinyl ester, succinonitrile, glutaronitrile, adiponitrile, 2-methyleneglutaronitrile, dipropylmalononitrile, 1,3,6-hexamethylenetricarbonitrile, 1,2,6-hexamethylenetricarbonitrile , 1,3,5-pentatricarbonitrile or 1,2-bis(cyanoethoxy)ethane; based on the total weight of the electrolyte, the total amount of the additive D accounts for 0.01% to 10% of the total amount of the electrolyte .
- the electrolyte includes: additive A, and one, two, or three of additive B, additive C, and additive D; wherein, the additive A, the additive B, and the Additive C and said additive D are as defined in this application.
- Another aspect of the present invention provides an electronic device, which includes any one of the electrochemical devices described above.
- Figure 1 X-ray photoelectron spectroscopy test results of an embodiment of the present application.
- Figure 2 Scanning electron microscopy test results of an embodiment of the present application.
- the term "about” is used to describe and illustrate small variations.
- the term may refer to an example in which the event or situation occurs precisely and an example in which the event or situation occurs very closely.
- the term can refer to a range of variation less than or equal to ⁇ 10% of the stated value, such as less than or equal to ⁇ 5%, less than or equal to ⁇ 4%, less than or equal to ⁇ 3%, Less than or equal to ⁇ 2%, less than or equal to ⁇ 1%, less than or equal to ⁇ 0.5%, less than or equal to ⁇ 0.1%, or less than or equal to ⁇ 0.05%.
- a list of items connected by the term "one of” may mean any one of the listed items. For example, if items A and B are listed, then the phrase “one of A and B” means only A or only B. In another example, if items A, B, and C are listed, then the phrase "one of A, B, and C" means only A; only B; or only C.
- Project A can contain a single element or multiple elements.
- Project B can contain a single element or multiple elements.
- Project C can contain a single element or multiple elements.
- a list of items connected by the terms “at least one of”, “at least one of” or other similar terms can mean any combination of the listed items. For example, if items A and B are listed, then the phrase “at least one of A and B" or “at least one of A or B” means only A; only B; or A and B. In another example, if items A, B, and C are listed, then the phrase “at least one of A, B, and C” or “at least one of A, B, or C” means only A; or only B; C only; A and B (exclude C); A and C (exclude B); B and C (exclude A); or all of A, B, and C.
- Project A can contain a single element or multiple elements.
- Project B can contain a single element or multiple elements.
- Project C can contain a single element or multiple elements.
- the number after the capital letter “C”, such as “C 1 -C 10 ", “C 3 -C 10 “, etc., after the "C” indicates the number of carbons in a specific functional group. That is, the functional groups may include 1-10 carbon atoms and 3-10 carbon atoms, respectively.
- C 1 -C 4 alkyl or “C 1-4 alkyl” refers to an alkyl group having 1 to 4 carbon atoms, such as CH 3 -, CH 3 CH 2 -, CH 3 CH 2 CH 2 -, (CH 3 ) 2 CH-, CH 3 CH 2 CH 2 CH 2 -, CH 3 CH 2 CH(CH 3 )- or (CH 3 ) 3 C-.
- alkyl refers to a linear saturated hydrocarbon structure having 1 to 6 carbon atoms.
- Alkyl is also expected to be a branched or cyclic hydrocarbon structure having 3 to 6 carbon atoms.
- the alkyl group may be an alkyl group of 1 to 4 carbon atoms.
- butyl means to include n-butyl, sec-butyl, isobutyl, and tert-butyl And cyclobutyl;
- propyl includes n-propyl, isopropyl and cyclopropyl.
- alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, Isopentyl, neopentyl, cyclopentyl, methylcyclopentyl, ethylcyclopentyl, n-hexyl, isohexyl, cyclohexyl, cyclopropyl, cyclobutyl, etc.
- the alkyl group may be optionally substituted.
- alkenyl refers to a monovalent unsaturated hydrocarbon group that can be straight or branched and has at least one and usually 1, 2, or 3 carbon-carbon double bonds. Unless otherwise defined, the alkenyl group usually contains 2-6 carbon atoms, and may be, for example, an alkenyl group of 2-4 carbon atoms. Representative alkenyl groups include, for example, vinyl, n-propenyl, isopropenyl, n-but-2-enyl, but-3-enyl, n-hex-3-enyl, and the like. In addition, alkenyl groups may be optionally substituted.
- halogen encompasses F, Cl, Br, and I, preferably F or Cl.
- the content of each component in the electrolyte is calculated based on the total weight of the electrolyte.
- Some embodiments of the present invention provide an electrolyte.
- the electrolyte includes additive A, and the additive A includes at least one of a compound of formula I, a compound of formula II, a compound of formula III, or a compound of formula IV:
- R 1 is selected from H, C 1-6 alkyl or C 2-6 alkenyl
- R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each independently selected from H, halogen, unsubstituted or substituted with one or more halogens C 1-6 alkyl, or unsubstituted or C 2-6 alkenyl substituted with one or more halogens;
- n is an integer from 1 to 3;
- the mass fraction of the additive A is 0.01% to 5%.
- R 1 is selected from H, C 1-4 alkyl, or C 2-4 alkenyl.
- R 1 is selected from H, methyl, or ethyl.
- m is 1 or 2.
- R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each independently selected from H, F, the following groups that are unsubstituted or substituted with one or more F: C 1-4 alkyl or C 2-4 alkenyl.
- R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each independently selected from H, F, methyl, ethyl, propyl, isopropyl, vinyl, -CH 2 F, -CHF 2 , or -CF 3 .
- the mass fraction of the additive A is 0.2% to 4% or 0.5% to 3%. In some embodiments, based on the total weight of the electrolyte, the mass fraction of the additive A is about 0.01%, about 0.05%, about 0.1%, about 0.2%, about 0.3%, about 0.4%, about 0.5%, about 0.6%, about 0.7%, about 0.8%, about 0.9%, about 1%, about 1.2%, about 1.4%, about 1.6%, about 1.8%, about 2.0%, about 2.2%, about 2.4%, about 2.6% , About 2.8%, about 3%, about 3.2%, about 3.4%, about 3.6%, about 3.8%, about 4%, about 4.2%, about 4.4%, about 4.6%, about 4.8%, or about 5% .
- the additive A includes at least one of the following compounds:
- the additive A includes at least one of methylene methane disulfonate, propenyl-1,3-sultone, or 1,3-propane disulfonic anhydride.
- the formula IV comprises:
- the electrolyte includes at least one of a compound of formula I, a compound of formula II, or a compound of formula III and a compound of formula IV.
- the electrolyte includes additive B
- the additive B includes lithium difluorophosphate, lithium 4,5-dicyano-2-trifluoromethylimidazolium, or difluorobis(oxalate) At least one of lithium phosphate; based on the total weight of the electrolyte, the mass fraction of the additive B is 0.01% to 3%.
- the mass fraction of the additive B is 0.3% to 3% or 0.5% to 3%. In some embodiments, based on the total weight of the electrolyte, the mass fraction of the additive B is about 0.01%, about 0.05%, about 0.1%, about 0.2%, about 0.3%, about 0.4%, about 0.5%, about 0.6%, about 0.7%, about 0.8%, about 0.9%, about 1%, about 1.2%, about 1.4%, about 1.6%, about 1.8%, about 2.0%, about 2.2%, about 2.4%, about 2.6% , About 2.8% or about 3%.
- the electrolyte includes additive C, and the additive C includes at least one of the following phosphate compounds:
- the mass fraction of the additive C is 0.01% to 5%.
- the mass fraction of the additive C is 0.2% to 4% or 0.5% to 3%. In some embodiments, based on the total weight of the electrolyte, the mass fraction of the additive C is about 0.01%, about 0.05%, about 0.1%, about 0.2%, about 0.3%, about 0.4%, about 0.5%, about 0.6%, about 0.7%, about 0.8%, about 0.9%, about 1%, about 1.2%, about 1.4%, about 1.6%, about 1.8%, about 2.0%, about 2.2%, about 2.4%, about 2.6% , About 2.8%, about 3%, about 3.2%, about 3.4%, about 3.6%, about 3.8%, about 4%, about 4.2%, about 4.4%, about 4.6%, about 4.8%, or about 5%.
- the electrolyte includes additive D
- the additive D includes at least one of the following compounds: vinylene carbonate, vinyl ethylene carbonate, 1,4-butane sultone, sulfuric acid Vinyl ester, succinonitrile, glutaronitrile, adiponitrile, 2-methyleneglutaronitrile, dipropylmalononitrile, 1,3,6-hexamethylenetricarbonitrile, 1,2,6-hexamethylenetricarbonitrile , 1,3,5-pentatricarbonitrile or 1,2-bis(cyanoethoxy)ethane; based on the total weight of the electrolyte, the total amount of the additive D accounts for 0.01% to 10% of the total amount of the electrolyte .
- the additive D includes at least one of the following compounds: vinylene carbonate, 1,3-propane sultone, vinyl sulfate, or 1,3,6-hexamethylenetricarbonitrile.
- the mass fraction of the additive D is 0.5% to 8% or 1% to 5%. In some embodiments, based on the total weight of the electrolyte, the mass fraction of the additive D is about 0.01%, about 0.05%, about 0.1%, about 0.5%, about 1%, about 1.5%, about 2.0%, about 2.5%, about 3%, about 3.5%, about 4%, about 4.5%, about 5%, about 5.5%, about 6%, about 6.5%, about 7%, about 7.5%, about 8%, about 8.5% , About 9%, about 9.5%, or about 10%.
- the electrolyte includes: additive A, and one, two, or three of additive B, additive C, and additive D; wherein, the additive A, the additive B, and the Additive C and said additive D are as defined in this application.
- the electrolyte includes two or more of additive A, additive B, additive C, and additive D. In some embodiments, the electrolyte includes additive A and additive B. In some embodiments, the electrolyte includes additive A, additive B, and additive C. In some embodiments, the electrolyte includes additive A, additive B, additive C, and additive D.
- the electrolyte solution further includes a salt and an organic solvent.
- the salt includes at least one of a lithium salt, a sodium salt, or a potassium salt.
- the lithium salt is optionally selected from at least one of an organic lithium salt or an inorganic lithium salt.
- the lithium salt contains at least one of fluorine, boron, and phosphorus.
- the lithium salt comprises lithium hexafluorophosphate LiPF 6 , lithium bistrifluoromethanesulfonimide LiN (CF 3 SO 2 ) 2 (abbreviated as LiTFSI), lithium bis(fluorosulfonyl)imide Li(N (SO 2 F) 2 ) (abbreviated as LiFSI), lithium bisoxalate borate LiB (C 2 O 4 ) 2 (abbreviated as LiBOB), lithium difluorooxalate borate LiBF 2 (C 2 O 4 ) (abbreviated as LiDFOB), At least one of lithium hexafluoroarsenate LiAsF 6 , lithium perchlorate LiClO 4 , or lithium trifluoromethanesulfonate
- the concentration of the lithium salt is 0.5 mol/L to 1.5 mol/L, or 0.8 mol/L to 1.2 mol/L.
- the sodium salt comprises sodium hexafluorophosphate NaPF 6 , sodium bistrifluoromethanesulfonimide NaN(CF 3 SO 2 ) 2 (abbreviated as NaTFSI), sodium bis(fluorosulfonyl)imide Na(N(SO 2 F) 2 ) (abbreviated as NaFSI), sodium bisoxalate borate NaB(C 2 O4) 2 (abbreviated as NaBOB), sodium difluorooxalate borate NaBF 2 (C 2 O 4 ) (abbreviated as NaDFOB) ), at least one of sodium hexafluoroarsenate NaAsF 6 , sodium perchlorate NaClO 4 , or sodium trifluoromethanesulfonate NaCF 3 SO 3
- NaTFSI sodium bistrifluoromethanesulfonimide NaN(CF 3 SO 2 ) 2
- NaFSI sodium bis(fluorosulfonyl)imide Na(N(SO
- the potassium salt comprises potassium hexafluorophosphate KPF 6 , potassium bistrifluoromethanesulfonimide KN(CF 3 SO 2 ) 2 (abbreviated as KTFSI), potassium bis(fluorosulfonyl)imide K(N(SO 2 F) 2 ) (abbreviated as KFSI), potassium bisoxalate borate KB (C 2 O 4 ) 2 (abbreviated as KBOB), potassium difluorooxalate borate KBF 2 (C 2 O 4 ) (abbreviated as KDFOB), at least one of potassium hexafluoroarsenate KAsF 6 , potassium perchlorate KClO 4 , or potassium triflate KCF 3 SO 3.
- KTFSI potassium bistrifluoromethanesulfonimide KN(CF 3 SO 2 ) 2
- KFSI potassium bis(fluorosulfonyl)imide K(N(SO 2 F) 2 )
- the organic solvent includes a cyclic ester and a chain ester, and the mass ratio of the cyclic ester to the chain ester is 1:9 to 7:3, and the cyclic ester includes ethylene carbonate (EC), At least one of propylene carbonate (PC), ⁇ -butyrolactone (BL), ethylene carbonate substituted with fluorine-containing groups, or propylene carbonate; chain esters include dimethyl carbonate (DMC), diethyl carbonate Ester (DEC), ethyl methyl carbonate (EMC), ethyl acetate (EA), methyl formate (MF), ethyl formate (MA), ethyl propionate (EP), propyl propionate (PP), At least one of methyl butyrate (MB) fluoro ethyl methyl carbonate, or fluoro ethyl propionate.
- DMC dimethyl carbonate
- DEC diethyl carbonate Ester
- EMC ethyl
- the organic solvent accounts for 70% to 95% by weight of the electrolyte solution.
- the electrochemical device of the present application includes any device that undergoes an electrochemical reaction, and specific examples thereof include all kinds of primary batteries, secondary batteries, fuel cells, solar cells, or capacitors.
- the electrochemical device is a lithium secondary battery, including a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery, or a lithium ion polymer secondary battery.
- the electrochemical device of the present application is an electrochemical device having a positive electrode with a positive electrode active material capable of occluding and releasing metal ions and a negative electrode having a negative electrode active material capable of occluding and releasing metal ions, including Positive electrode, negative electrode, separator, and any electrolyte solution mentioned above in this application.
- the positive electrode of the electrochemical device includes a current collector and a positive electrode active material layer provided on the current collector.
- the positive electrode active material layer includes a positive electrode active material, and the positive electrode active material includes a compound that reversibly intercalates and deintercalates lithium ions (ie, a lithiated intercalation compound).
- the positive electrode active material may include one or more of lithium cobaltate, lithium nickel cobalt manganate, lithium nickel cobalt aluminate, lithium manganate, and the like.
- the positive electrode includes a positive electrode current collector and a positive electrode active material layer, and the positive electrode active material layer may include a mixture of lithium nickel cobalt manganate (NCM) and lithium manganate (LMO).
- NCM lithium nickel cobalt manganate
- LMO lithium manganate
- the positive electrode includes a positive electrode current collector and a positive electrode active material layer disposed on the positive electrode current collector, the X-ray photoelectron spectrum of the positive electrode active material layer has a peak in the range of 164 eV to 175 eV, and the electrochemical The electrolyte holding capacity of the device is 1.0g/Ah to 4.0g/Ah.
- the electrolyte retention of the electrochemical device is 1.5 g/Ah to 4 g/Ah. In some embodiments, the electrolyte retention of the electrochemical device is about 1.0g/Ah, about 1.5g/Ah, about 2.0g/Ah, about 2.3g/Ah, about 2.5g/Ah, about 3.0g /Ah, about 3.5g/Ah, or about 4.0g/Ah.
- the positive electrode active material layer includes first particles, and the cross section perpendicular to the positive electrode current collector in the positive electrode is tested by scanning electron microscopy, and the gray scale of the first particles is not less than 115RGB, and the The cross-sectional area of the first particles is less than 20 square microns, and the total area of the first particles occupies a proportion of 5% to 50% based on the area of the cross section of the positive electrode perpendicular to the positive electrode current collector.
- the positive electrode active material layer includes second particles, and a cross section perpendicular to the positive electrode current collector in the positive electrode is tested by scanning electron microscopy.
- the gray level of the second particles is less than 115RGB, and the second particle
- the cross-sectional area of the two particles is greater than or equal to 20 square microns, and the total area of the second particles occupies a proportion of 10% to 60% based on the area of the cross section of the positive electrode perpendicular to the positive electrode current collector.
- the porosity of the positive active material layer is 15% to 23%.
- the proportion of the positive electrode current collector is 5% to 25%.
- the first particles comprise Li a Ni x Co y Mn z M m O 2 , wherein 0.9 ⁇ a ⁇ 1.1, 0.3 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 0.7, 0 ⁇ z ⁇ 0.4, x+y+z ⁇ 1, 0 ⁇ m ⁇ 0.1
- the M element includes at least one of Al, Ti, Mg, W, Zr, Nb, In, Ru, Sb, Sr, Y, or F; wherein Based on the total weight of the positive active material, the content of the M element is 0% to 1%.
- the first particles comprise LiNi 0.5 Co 0.3 Mn 0.2 O 2 , LiNi 0.5 Co 0.3 Mn 0.198 Zr 0.002 O 2 , LiNi 0.5 Co 0.3 Mn 0.198 Mg 0.002 O 2 , LiNi 0.5 Co 0.3 Mn 0.198 Zr At least one of 0.001 Ti 0.001 O 2 , LiNi 0.6 Co 0.2 Mn 0.198 Mg 0.001 Al 0.001 O 2 , or LiNi 0.8 Co 0.1 Mn 0.098 Zr 0.001 Ti 0.001 O 2 .
- the second particles include Li b Mn 2-n Me n O 4 , wherein the Me element includes at least one of Mg, Ti, Cr, Al, B, Fe, Zr, Na, F, or S One, 0.9 ⁇ b ⁇ 1.1, 0 ⁇ n ⁇ 0.1, wherein the content of the Me element is 0% to 1% based on the total weight of the positive electrode active material.
- the second particles include at least one of LiMn 2 O 4 , LiMn 1.998 Mg 0.002 O 4 , or LiMn 1.98 Mg 0.02 O 4.
- the positive active material layer further includes a binder, and optionally a conductive material.
- the binder improves the bonding of the positive electrode active material particles to each other, and also improves the bonding of the positive electrode active material to the current collector.
- binders include polyvinyl alcohol, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, ethylene oxide-containing polymers, polyvinyl chloride Vinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene butadiene rubber, acrylic (ester) styrene butadiene rubber, epoxy resin, nylon, etc.
- the positive electrode active material layer includes a conductive material, thereby imparting conductivity to the electrode.
- the conductive material may include any conductive material as long as it does not cause a chemical change.
- Non-limiting examples of conductive materials include carbon-based materials (e.g., natural graphite, artificial graphite, carbon black, acetylene black, Ketjen black, carbon fiber, etc.), metal-based materials (e.g., metal powder, metal fiber, etc., including For example, copper, nickel, aluminum, silver, etc.), conductive polymers (for example, polyphenylene derivatives), and mixtures thereof.
- the current collector may be aluminum (Al), but is not limited thereto.
- the negative electrode of the electrochemical device includes a current collector and a negative active material layer formed on the current collector.
- the negative active material layer includes a negative active material.
- the negative active material may include a reversible intercalation/deintercalation of lithium ions. Materials, lithium metal, lithium metal alloys, materials capable of doping/undoping lithium, or transition metal oxides.
- the material that reversibly intercalates/deintercalates lithium ions may be a carbon material.
- the carbon material may be any carbon-based negative active material commonly used in lithium ion rechargeable electrochemical devices. Examples of carbon materials include crystalline carbon, amorphous carbon, and combinations thereof.
- the crystalline carbon may be amorphous or plate-shaped, flake-shaped, spherical or fiber-shaped natural graphite or artificial graphite.
- Amorphous carbon can be soft carbon, hard carbon, mesophase pitch carbonization products, burnt coke, and the like. Both low crystalline carbon and high crystalline carbon can be used as the carbon material.
- soft carbon and hard carbon may generally be included.
- As a high crystalline carbon material it may generally include natural graphite, crystalline graphite, pyrolysis carbon, mesophase pitch-based carbon fiber, mesophase carbon microbeads, mesophase pitch, and high-temperature calcined carbon (such as petroleum or coke derived from coal tar pitch) ).
- the negative electrode active material of the electrochemical device of the present invention is not subject to specific restrictions, and can be selected according to requirements.
- the negative electrode active material is selected from natural graphite, artificial graphite, mesophase micro-carbon spheres (MCMB for short), hard carbon, soft carbon, silicon, silicon-carbon composite, Li-Sn alloy, Li-Sn- One or more of O alloy, Sn, SnO, SnO2, spinel structure lithiated TiO 2 -Li 4 Ti 5 O 12 , and Li-Al alloy.
- the negative active material layer contains a binder
- the binder may include various binder polymers, such as vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinylidene fluoride, poly Acrylonitrile, polymethyl methacrylate, polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, polymers containing ethylene oxide, Polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyethylene, polypropylene, styrene butadiene rubber, acrylic (ester) styrene butadiene rubber, epoxy resin, nylon, etc., but not limited to these.
- PVDF-co-HFP vinylidene fluoride-hexafluoropropylene copolymer
- PVDF-co-HFP polyvinylidene
- the negative active material layer also includes a conductive material to improve electrode conductivity.
- Any conductive material can be used as the conductive material as long as it does not cause a chemical change.
- Examples of conductive materials include: carbon-based materials, such as natural graphite, artificial graphite, carbon black, acetylene black, Ketjen black, carbon fibers, etc.; metal-based materials, such as metal powders or metal fibers including copper, nickel, aluminum, silver, etc. ; Conductive polymers, such as polyphenylene derivatives, etc.; or their mixtures.
- the current collector can be copper foil, nickel foil, stainless steel foil, titanium foil, foamed nickel, foamed copper, polymer substrate coated with conductive metal, or a combination thereof.
- the current collector includes, but is not limited to: copper foil, nickel foil, stainless steel foil, titanium foil, foamed nickel, foamed copper, conductive metal-coated polymer substrates, and any combination thereof.
- the negative electrode can be prepared by a preparation method known in the art.
- the negative electrode can be obtained by mixing an active material, a conductive material, and a binder in a solvent to prepare an active material composition, and coating the active material composition on a current collector.
- the electrochemical device of the present application is provided with a separator between the positive electrode and the negative electrode to prevent short circuits.
- the material and shape of the isolation membrane used in the electrochemical device of the present application are not particularly limited, and it may be any technology disclosed in the prior art.
- the isolation membrane includes a polymer or an inorganic substance formed of a material that is stable to the electrolyte of the present application.
- the separator may include a substrate layer and a surface treatment layer.
- the substrate layer is a non-woven fabric, film or composite film with a porous structure, and the material of the substrate layer is selected from at least one of polyethylene, polypropylene, polyethylene terephthalate and polyimide.
- a polypropylene porous film, a polyethylene porous film, a polypropylene non-woven fabric, a polyethylene non-woven fabric, or a polypropylene-polyethylene-polypropylene porous composite film can be selected.
- a surface treatment layer is provided on at least one surface of the substrate layer.
- the surface treatment layer may be a polymer layer or an inorganic substance layer, or a layer formed by a mixed polymer and an inorganic substance.
- the inorganic layer includes inorganic particles and a binder.
- the inorganic particles are selected from alumina, silica, magnesium oxide, titanium oxide, hafnium dioxide, tin oxide, ceria, nickel oxide, zinc oxide, calcium oxide, zirconium oxide, One or a combination of yttrium oxide, silicon carbide, boehmite, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, and barium sulfate.
- the binder is selected from polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, polyvinyloxy , Polymethyl methacrylate, polytetrafluoroethylene and polyhexafluoropropylene or a combination of several.
- the polymer layer contains a polymer, and the material of the polymer is selected from polyamide, polyacrylonitrile, acrylate polymer, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, polyvinyloxy, polyvinylidene fluoride, At least one of poly(vinylidene fluoride-hexafluoropropylene)
- the isolation membrane of the electrochemical device of the embodiments of the present application includes a polyolefin-based microporous membrane and a coating.
- the coating includes an organic coating and an inorganic coating, wherein the organic coating is selected from Polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, polyacrylonitrile, polyimide, acrylonitrile-butadiene copolymer, acrylonitrile-styrene-butadiene copolymer, polymethylmethacrylate At least one of ester, polymethyl acrylate, polyethyl acrylate, acrylic-styrene copolymer, polydimethylsiloxane, sodium polyacrylate, sodium carboxymethyl cellulose, and the inorganic coating is selected from SiO 2 One or more of Al 2 O 3 , CaO, TiO 2 , ZnO 2 , MgO, ZrO 2 and SnO 2 ; the polyviny
- the membrane is selected from polyethylene (PE), ethylene-propylene copolymer, polypropylene (PP), ethylene-butene copolymer, ethylene-hexene copolymer , A single-layer or multi-layer polyolefin microporous film composed of one or more of ethylene-methyl methacrylate copolymers.
- the electrolyte according to the embodiments of the present application can improve the high-temperature cycle performance, high-temperature storage performance and kinetics of the electrochemical device, and has higher safety, so that the electrochemical device manufactured thereby is suitable for electronic equipment in various fields .
- the use of the electrochemical device of the present application is not particularly limited, and it can be used for various well-known uses.
- notebook computers pen-input computers, mobile computers, e-book players, portable phones, portable fax machines, portable copiers, portable printers, headsets, video recorders, LCD TVs, portable cleaners, portable CD players , Mini discs, transceivers, electronic notebooks, calculators, memory cards, portable recorders, radios, backup power supplies, motors, cars, motorcycles, assisted bicycles, bicycles, lighting equipment, toys, game consoles, clocks, power tools, Flashlights, cameras, large household storage batteries or lithium-ion capacitors, etc.
- the negative electrode slurry The solid content is 54% by weight; the negative electrode slurry is uniformly coated on the negative electrode current collector copper foil; the copper foil is dried at 85 degrees Celsius, and then cold pressed to obtain the negative electrode active material layer, after cutting and slitting , Dried for 12 hours under a vacuum condition of 120 degrees Celsius to obtain a negative electrode.
- the positive electrode active material lithium nickel cobalt manganese oxide (LiNi 0.5 Co 0.3 Mn 0.2 O 2 ) and lithium manganese oxide (LiMn 2 O 4 ) were mixed in a mass ratio of 3:7, and then the mixed positive electrode active material,
- the conductive agent Super P and the binder polyvinylidene fluoride (PVDF) are mixed in a weight ratio of 96:2:2, and N-methylpyrrolidone (NMP) is added, and stirred evenly under the action of a vacuum mixer to obtain a positive electrode slurry , Wherein the solid content of the positive electrode slurry is 72% by weight.
- the positive electrode slurry is uniformly coated on the positive electrode current collector aluminum foil; the coated aluminum foil is dried at 85 degrees Celsius, and then cold pressed to obtain the positive electrode active material layer. It was dried for 4 hours under vacuum to obtain a positive electrode.
- the preparation method of the positive electrode is similar to Example 4, except that the area ratio of lithium nickel cobalt manganate and lithium manganate in the positive electrode active material is different.
- the particle size of lithium cobalt manganate and lithium manganate particles can be achieved as long as the technical solution can be realized.
- the preparation method of the positive electrode is similar to that of Example 4, except that the positive electrode active material is different.
- the preparation method of the positive electrode is similar to Example 4, except that the positive electrode active material is not exactly the same and the area ratio of lithium nickel cobalt manganate and lithium manganate is different.
- the difference in area ratio is achieved by controlling the quality of lithium nickel cobalt manganese oxide and lithium manganate. Compared with the particle size of lithium nickel cobalt manganate and lithium manganate particles, as long as the technical solution can be realized.
- the preparation method of the positive electrode is exactly the same as in Example 18.
- the electrode assembly prepared in the above manner is placed in the outer packaging foil aluminum-plastic film, a certain amount of electrolyte is injected into the electrode assembly, vacuum-encapsulated, formed, and drawn out after exhaust A certain amount of electrolyte can be used to obtain a battery with a specific amount of electrolyte.
- the lithium-ion battery that reaches a constant temperature is charged at a constant current of 1C to a voltage of 4.35V, then charged at a constant voltage of 4.35V to a current of 0.05C, and then discharged at a constant current of 1C to a voltage of 2.8V.
- This is a charge-discharge cycle. Record the discharge capacity this time and record it as the capacity of the first discharge; at the same time, test the battery thickness and record it as the initial battery thickness.
- Capacity retention rate (capacity when cycled to 500 weeks/capacity at first discharge) x 100%
- Thickness expansion ratio (thickness when cycled to 500 weeks/initial battery thickness) x 100%
- Over-discharge storage thickness expansion rate (%) (thickness after 30 days storage/initial battery thickness) x 100%
- the amount of electrolyte retained in the battery the mass of electrolyte in the battery (g) / battery capacity (Ah), unit: g/Ah.
- Battery capacity test method The battery is charged at a constant current of 0.2C to a voltage of 4.35V, then charged at a constant voltage of 4.35V to a current of 0.05C, and then discharged at a constant current of 0.2C to a voltage of 2.8V, and the battery capacity is recorded.
- Disassemble the battery discharged to 2.8V remove the positive electrode from the battery, take the area of the positive electrode active material layer on both sides of the positive electrode current collector with a size of 1.5cm ⁇ 1.0cm, and put the flat and clean sample into the analysis room for testing. Maintain the ultra-high vacuum state of the analysis chamber, select the sample analysis position through the video device, X-rays excite the sample analysis position, collect photoelectrons, and the electron neutralization system ejects slow electrons to neutralize the residual charge in the analysis position to obtain a spectrum.
- the porosity P of the positive electrode active material layer was measured by the gas displacement method.
- V (V-V0)/V ⁇ 100%, where V0 is the true volume and V is the apparent volume.
- test method is "GB/T 24586-2009 Determination of apparent density, true density and porosity of iron ore”.
- JEOL scanning electron microscope JSM-6390LV was used for testing. Test method: disassemble the battery discharged to 2.8V and take out the positive electrode. After the positive electrode is dried, cut a sample of appropriate size into the sample chamber, magnification: 1000 to 30K, resolution: 3.0 to 10nm, select the vertical in the positive electrode Test on the cross section of the positive electrode current collector.
- the total area of the cross section of the positive electrode is S
- the total area of the second particles is S 2
- the area of the positive electrode current collector is S 3
- the porosity is P
- the area ratio of the conductive agent and the bonding is ignored.
- the gray scale of the second particles is less than 115RGB
- the cross-sectional area of the second particles is greater than or equal to 20 square microns.
- the proportion of the total area of the first particles (SS 2 -S 3 )/S ⁇ 100%-P;
- the proportion of the total area of the second particles S 2 /S ⁇ 100%.
- Substance name Molecular formula or abbreviation
- Substance name Molecular formula or abbreviation
- Lithium Difluorophosphate LiPO 2 F 2 Methylene disulfonate MMDS 4,5-dicyano-2-trifluoromethylimidazolium lithium LiTDI Propenyl-1,3-sultone PES Lithium difluorobis(oxalate)phosphate LiDFOP 1,3-propane disulfonic anhydride
- PA Tris(trimethylsilyl) phosphate
- TMSP 1,3-propane sultone
- Triphenyl phosphate TPPA Vinylene carbonate
- VC Tris(trimethylsilyl) phosphite
- TMSPi Vinyl Sulfate
- DTD Triphenyl phosphite TPPi 1,3,6-Hexanetricarbonitrile
- the X-ray photoelectron spectroscopy test result of the positive electrode active material layer of Example 1 is shown in FIG.
- the XPS spectrum has no peak at 164 to 175 eV (that is, its XPS spectrum shows a baseline at 164 to 175 eV).
- Example 2 As shown in Table 2, similar to Example 1, the XPS spectra of the positive electrode active material layers of Examples 2 to 9 and Comparative Examples 1 to 2 have peaks at 164 to 175 eV.
- Example 1 to Example 9 Comparative Example 1 to Comparative Example 2
- the battery has an improved high temperature cycle. Performance and over-discharge storage performance.
- the improvement effect is particularly obvious when the holding amount of the electrolyte is 1.5g/Ah to 4g/Ah.
- the above improvement may be due to the sulfur-containing protective layer can be formed when sulfur-containing additive A is added to the electrolyte.
- the sulfur-containing substance has excellent stability, thus improving the high-temperature cycle performance of the battery;
- controlling the amount of electrolyte to be within an appropriate range can not only ensure the required amount of electrolyte during the cycle, but also make the battery have a good interface and consume less additives, so it can inhibit high-temperature cycle performance and/or over-discharge storage. Performance deteriorates.
- Example 4 Prepare the electrolytes and lithium ion batteries of Example 4 and Examples 10 to 19 according to the above methods. Please refer to Table 3 for the components of the positive electrode, SEM test and battery performance test results.
- the electrolyte composition of each battery sample is the same as in Example 4, and the electrolyte holding amount of each battery sample is 2.3 g/Ah.
- the area ratio of the first particles and the second particles in Table 3 is controlled by controlling the mass ratio of the first particles and the second particles.
- Figure 2 shows the SEM image of the positive electrode of Example 11.
- Example 4 Comparing Example 4 with Example 10 to Example 19, it can be seen that under the action of the electrolyte of the present invention, the first particles and the second particles in the positive electrode material are mixed in different proportions within an appropriate range, and better effects can be obtained. Effect.
- the above improvement may be mainly because the additive A can form a sulfur-containing protective layer on the positive electrode.
- the sulfur-containing material has excellent stability and therefore improves the high temperature cycle performance of the battery;
- the additive B can form a lower impedance
- the solid electrolyte interface membrane (SEI) protects the negative electrode interface, thereby improving the high temperature cycle performance;
- Additive C can improve the thermal stability of the electrolyte, alleviate the transition metal ions of the positive electrode caused by the decomposition of LiPF 6 and produce HF, and improve the stability of the positive electrode.
- the additive A and the additive B and/or the additive C act synergistically to improve the circulation and gas production problems without increasing the impedance, and improve the stability of the SEI.
- Example 42 and Examples 52 to 55 Prepare the electrolytes and lithium ion batteries of Example 42 and Examples 52 to 55 according to the above method. See Table 5 for electrolyte composition and test results. The electrolyte retention of each battery sample in Table 5 is 2.3 g/Ah.
- additive D for example, at least one of VC, DTD, HTCN, etc.
- the above improvement may be mainly due to the fact that the additive D further forms a film on the negative electrode, stabilizes the transition metal ions of the positive electrode, and slows down the reaction of the electrolyte on the positive electrode.
- the combined use of the above additives A, B, C and D improves the stability of the positive electrode of the lithium ion battery, thereby improving the safety performance of the battery.
- the above examples show that the electrolyte provided by the present invention can improve the cycle performance and over-discharge storage performance of an electrochemical device.
- references to “some embodiments”, “partial embodiments”, “one embodiment”, “another example”, “examples”, “specific examples” or “partial examples” throughout the specification mean At least one embodiment or example in this application includes the specific feature, structure, material, or characteristic described in the embodiment or example. Therefore, descriptions appearing in various places throughout the specification, such as: “in some embodiments”, “in embodiments”, “in one embodiment”, “in another example”, “in an example “In”, “in a specific example” or “exemplary”, which are not necessarily quoting the same embodiment or example in this application.
- the specific features, structures, materials or characteristics herein can be combined in one or more embodiments or examples in any suitable manner.
Abstract
Description
物质名称 | 分子式或简称 | 物质名称 | 分子式或简称 |
二氟磷酸锂 | LiPO 2F 2 | 甲烷二磺酸亚甲酯 | MMDS |
4,5-二氰基-2-三氟甲基咪唑锂 | LiTDI | 丙烯基-1,3-磺酸内酯 | PES |
二氟双(草酸根)合磷酸锂 | LiDFOP | 1,3-丙烷二磺酸酐 | PA |
三(三甲基硅基)磷酸酯 | TMSP | 1,3-丙烷磺酸内酯 | PS |
三苯基磷酸酯 | TPPA | 碳酸亚乙烯酯 | VC |
三(三甲基硅基)亚磷酸酯 | TMSPi | 硫酸乙烯酯 | DTD |
三苯基亚磷酸酯 | TPPi | 1,3,6-己三甲腈 | HTCN |
Claims (12)
- 一种电化学装置,包含正极、负极、电解液和隔离膜,所述正极包括正极集流体和设置于所述正极集流体上的正极活性材料层,所述正极活性材料层的X射线光电子能谱在164eV至175eV有峰,且所述电化学装置的电解液保有量为1.0g/Ah至4.0g/Ah。
- 根据权利要求1所述的电化学装置,其中所述正极活性材料层包含第一颗粒,采用扫描电镜测试在所述正极中垂直于所述正极集流体的截面,所述第一颗粒的灰度不小于115RGB,所述第一颗粒的截面面积小于20平方微米,以所述正极中垂直于所述正极集流体的所述截面的面积计,所述第一颗粒的总面积所占比例为5%至50%。
- 根据权利要求1所述的电化学装置,其中所述正极活性材料层包含第二颗粒,采用扫描电镜测试在所述正极中垂直于所述正极集流体的截面,所述第二颗粒的灰度小于115RGB,所述第二颗粒的截面面积大于或等于20平方微米,以所述正极中垂直于所述正极集流体的所述截面的面积计,所述第二颗粒的总面积所占比例为10%至60%。
- 根据权利要求2所述的电化学装置,其中所述第一颗粒包含Li aNi xCo yMn zM mO 2,其中0.9≤a<1.1,0.3≤x<1,0<y<0.7,0<z≤0.4,x+y+z≤1,0≤m≤0.1,所述M元素包含Al、Ti、Mg、W、Zr、Nb、In、Ru、Sb、Sr、Y、或F中的至少一种;其中基于所述正极活性材料的总重量,所述M元素的含量为0%至1%。
- 根据权利要求3所述的电化学装置,其中所述第二颗粒包含Li bMn 2-nMe nO 4,其中Me元素包含Mg、Ti、Cr、Al、B、Fe、Zr、Na、F、或S中的至少一种,0.9≤b<1.1,0≤n≤0.1,其中基于所述正极活性材料的总重量,所述Me元素的含量为0%至1%。
- 根据权利要求1所述电化学装置,其中所述电解液包含添加剂B,所述添加剂B包含二氟磷酸锂、4,5-二氰基-2-三氟甲基咪唑锂、或二氟双(草酸根)合磷酸锂中的至少一种;以电解液总重量计,所述添加剂B的质量分数为0.01%至3%。
- 根据权利要求1所述电化学装置,所述电解液包括添加剂D,所述添加剂D包含如下化合物中的至少一种:碳酸亚乙烯酯、乙烯基碳酸乙烯酯、1,4-丁烷磺酸内酯、硫酸乙烯酯、丁二腈、戊二腈、己二腈、2-亚甲基戊二腈、二丙基丙二腈、1,3,6-已三甲腈、1,2,6-已三甲腈、1,3,5-戊三甲腈或1,2-双(氰乙氧基)乙烷;以电解液总重量计,所述添加剂D的总量占电解液总量的0.01%至10%。
- 根据权利要求1至5中任一权利要求所述的电化学装置,其中所述电解液包括:添加剂A,及添加剂B、添加剂C及添加剂D之中的一者、两者或三者;其中,所述添加剂A根据权利要求6或7所定义,所述添加剂B根据权利要求8所定义、所述添加剂C根据权利要求9所定义,所述添加剂D根据权利要求10所定义。
- 一种电子装置,其包括根据权利要求1-11中任一权利要求所述的电化学装置。
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CN107004911A (zh) * | 2014-11-28 | 2017-08-01 | 三洋电机株式会社 | 非水电解质二次电池 |
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US20210351438A1 (en) | 2021-11-11 |
EP3933996A4 (en) | 2022-05-11 |
BR112022022488A2 (pt) | 2022-12-13 |
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