CN114450834A - Electrochemical device and electronic device - Google Patents
Electrochemical device and electronic device Download PDFInfo
- Publication number
- CN114450834A CN114450834A CN202180005430.0A CN202180005430A CN114450834A CN 114450834 A CN114450834 A CN 114450834A CN 202180005430 A CN202180005430 A CN 202180005430A CN 114450834 A CN114450834 A CN 114450834A
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- China
- Prior art keywords
- positive electrode
- electrolyte
- mass
- present application
- electrochemical device
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- 239000007774 positive electrode material Substances 0.000 claims description 27
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 13
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- 239000008151 electrolyte solution Substances 0.000 claims description 6
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- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- LEGITHRSIRNTQV-UHFFFAOYSA-N carbonic acid;3,3,3-trifluoroprop-1-ene Chemical compound OC(O)=O.FC(F)(F)C=C LEGITHRSIRNTQV-UHFFFAOYSA-N 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229940105329 carboxymethylcellulose Drugs 0.000 description 1
- 239000006257 cathode slurry Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- SNQXJPARXFUULZ-UHFFFAOYSA-N dioxolane Chemical compound C1COOC1 SNQXJPARXFUULZ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010325 electrochemical charging Methods 0.000 description 1
- 238000010326 electrochemical discharging Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- JBTUPCMIRXTEFB-UHFFFAOYSA-N ethenyl trifluoromethyl carbonate Chemical compound FC(F)(F)OC(=O)OC=C JBTUPCMIRXTEFB-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- KLKFAASOGCDTDT-UHFFFAOYSA-N ethoxymethoxyethane Chemical compound CCOCOCC KLKFAASOGCDTDT-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229920005614 potassium polyacrylate Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000004759 spandex Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- WMOVHXAZOJBABW-UHFFFAOYSA-N tert-butyl acetate Chemical compound CC(=O)OC(C)(C)C WMOVHXAZOJBABW-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- 238000009461 vacuum packaging Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
An electrochemical device includes a positive electrode, a negative electrode, a separator, and an electrolyte including phosphorus oxychloride and a polycyano compound including at least two cyano groups. The electrolyte can form a compact and stable protective film on the surface of the positive electrode, and inhibit the decomposition reaction of the electrolyte under high voltage. The electrochemical device containing the electrolyte has good high-temperature safety performance and cycle performance.
Description
Technical Field
The present application relates to the field of electrochemistry, and in particular, to an electrochemical device and an electronic device.
Background
The lithium ion battery has the advantages of high energy storage density, high open circuit voltage, low self-discharge rate, long cycle life, good safety and the like, and is widely applied to electronic products such as cameras, mobile phones, unmanned aerial vehicles, notebook computers, smart watches and the like as a power supply. At present, the charge cut-off voltage of the lithium ion battery is improved to improve the lithium removal amount of the anode material, and the method is an effective means for improving the energy density of the lithium ion battery.
However, the increase in the charge cut-off voltage of the lithium ion battery is likely to cause the safety problems of the lithium ion battery such as swelling, rapid deterioration of the cycle capacity at high temperatures, and thermal runaway at high temperatures. This is because the surface of the positive electrode of the lithium ion battery has a strong electrochemical oxidation activity under a high voltage, and once the surface exceeds the electrochemical window of the electrolyte, the electrolyte is oxidized and decomposed, thereby causing phenomena such as capacity fading, gas generation, heat release and the like. In view of the above, developing a suitable lithium ion battery is a technical problem to be solved by those skilled in the art.
Disclosure of Invention
An object of the present application is to provide an electrochemical device and an electronic device to improve high-temperature safety performance and cycle performance of the electrochemical device.
In a first aspect, the present application provides an electrochemical device comprising a positive electrode, a negative electrode, a separator, and an electrolyte, the positive electrode comprising a positive electrode current collector and a positive electrode active material layer disposed on at least one surface of the positive electrode current collector, the positive electrode active material layer comprising a positive electrode active material; the electrolyte includes phosphorus oxychloride and a polycyano compound including at least two cyano groups.
According to some embodiments of the present application, the phosphorus oxychloride comprises 0.001 to 5% by mass a, based on the total mass of the electrolyte.
According to some embodiments of the present application, the phosphorus oxychloride is present in an amount of 0.001 to 3% by mass, based on the total mass of the electrolyte.
According to some embodiments of the present application, the polycyano compound B is 0.1% to 10% by mass based on the total mass of the electrolyte.
According to some embodiments of the present application, the polycyano compound content B is 2% to 8% by mass, based on the total mass of the electrolyte.
According to some embodiments of the present application, the mass percentage of the phosphorus oxychloride is a and the mass percentage of the polycyano compound is B, based on the total mass of the electrolyte, satisfy: a and B are more than or equal to 0.15% and less than or equal to 11%.
According to some embodiments of the present application, the polycyano compound includes at least one of the compounds of structural formula (I):
wherein R is selected from C1To C15A chain alkyl group of C1To C15Alkenyl or C1To C15An alkynylene group of (a); a and c are each independently 0 or a positive integer and a and c are not simultaneously 0, 2. ltoreq. a + c. ltoreq.7, 0. ltoreq. b.ltoreq.6, the number b of alkylene groups to which each cyano group is bonded may be the same or different.
According to some embodiments of the present application, the polycyano compound includes any one of the following formulas (1) to (62):
according to some embodiments of the present application, the electrolyte further includes at least one of a fluorinated ester compound, a cyclic sulfonate ester, or a cyclic carbonate ester containing an unsaturated bond.
According to some embodiments of the present application, the fluorinated ester compound has a mass percentage content C of 0.1% to 15% based on the total mass of the electrolyte.
According to some embodiments of the present application, the cyclic sulfonic acid ester is present in an amount D of 0.1 to 5% by mass based on the total mass of the electrolyte.
According to some embodiments of the present application, the unsaturated bond-containing cyclic carbonate is present in an amount E of 0.01 to 2% by mass, based on the total mass of the electrolyte.
According to some embodiments of the present application, the mass percentage of the phosphorus oxychloride a and the mass percentage of the cyclic sulfonate ester D satisfy: a and D are more than or equal to 0.1 percent and less than or equal to 20 percent.
According to some embodiments of the present application, the fluorinated ester compound comprises at least one of fluoroethylene carbonate, difluoroethylene carbonate, fluoroethyl carbonate, dimethyl fluorocarbonate, diethyl fluorocarbonate, ethyl fluoropropionate, propyl fluoropropionate, methyl fluoropropionate, ethyl fluoroacetate, methyl fluoroacetate, propyl fluoroacetate, fluoroethylene carbonate, vinyl difluorocarbonate, and vinyl trifluoromethyl carbonate.
According to some embodiments of the present application, the cyclic sulfonate ester comprises at least one of 1, 3-propane sultone or 1, 4-butane sultone.
According to some embodiments of the present application, the cyclic carbonate containing an unsaturated bond comprises at least one of vinylene carbonate or vinyl ethylene carbonate.
According to some embodiments of the present application, the electrolyte includes a fluorinated ester compound and a cyclic sulfonate ester.
According to some embodiments of the present application, the electrolyte includes a fluorinated ester compound, a cyclic sulfonate ester, or a cyclic carbonate ester having an unsaturated bond.
According to some embodiments of the present application, a mass percentage content F of the metal element other than lithium in the positive electrode active material and a mass percentage content a of the phosphorus oxytrifluoride in the electrolytic solution satisfy: 600 > F/A > 10.
According to some embodiments of the present application, the metallic element other than lithium comprises at least one of Fe, Co, Ni, Mn, Ti, Mg, Al, Zr, La, Y, V, Cr, Ge, Ru, Sn, Ti, Nb, Mo.
In a second aspect, the present application provides an electronic device comprising an electrochemical device according to the first aspect of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the present application will be further described in detail below with reference to examples. It is to be understood that the embodiments described are only a few embodiments of the present application and not all embodiments. All other technical solutions obtained by a person of ordinary skill in the art based on the embodiments in the present application belong to the scope of protection of the present application.
In the present application, the present application is explained by taking a lithium ion battery as an example of an electrochemical device, but the electrochemical device of the present application is not limited to a lithium ion battery. The specific technical scheme is as follows:
a first aspect of the present application provides an electrochemical device comprising a positive electrode, a negative electrode, a separator, and an electrolyte, the positive electrode comprising a positive electrode current collector and a positive electrode active material layer disposed on at least one surface of the positive electrode current collector, the positive electrode active material layer comprising a positive electrode active material; the electrolyte includes phosphorus oxychloride and a polycyano compound including at least two cyano groups.
In one embodiment of the present application, the electrolyte comprises phosphorus oxide trifluoride (POF)3) And the multicyano compound, wherein the phosphorus oxide trifluoride can perform a passivation reaction on the positive electrode to form a compact protective film, the multicyano compound can form stable adsorption coordination on the surface of the positive electrode, the phosphorus oxide trifluoride and the multicyano compound can form a compact and stable protective film under the synergistic action, and the oxidative decomposition reaction of the electrolyte under high voltage is inhibited to avoid the phenomena of capacity attenuation, gas generation, heat release and the like, so that the safety problems of the lithium ion battery such as gas expansion, rapid cycle capacity attenuation at high temperature and thermal runaway at high temperature are effectively prevented, and the high-temperature safety performance and the cycle performance of the lithium ion battery are obviously improved.
Phosphorus oxide trifluoride (POF) in one embodiment of the present application3) May be generated by decomposition of an additive in the electrolyte, such as lithium hexafluorophosphate.
The present application does not specifically limit the number of cyano groups in the polycyano compound as long as it contains at least two cyano groups, which can achieve the object of the present application. For example, the polycyano compound may contain 2, 3, 4, 5, 6, or 7 cyano groups. Different polycyano compound molecules have different spatial structures, and have different improvement effects on lithium ion batteries.
The application provides an electrochemical device, contains positive pole, negative pole, barrier film and electrolyte, and the positive pole contains the anodal mass flow body and sets up the anodal active material layer on the anodal mass flow body at least one surface, and this anodal active material layer contains anodal active material. Wherein the electrolyte comprises phosphorus oxychloride and a polycyano compound, and the polycyano compound comprises at least two cyano groups. The electrolyte can form a compact and stable protective film on the surface of the anode, inhibit the oxidative decomposition of the electrolyte under high voltage, and greatly reduce the phenomena of capacity attenuation, gas generation, heat release and the like of the lithium ion battery caused by the decomposition reaction of the electrolyte under high voltage, thereby effectively improving the high-temperature safety performance and the cycle performance of the electrochemical device.
In one embodiment of the present application, the phosphorus oxychloride content a is from 0.001 to 5% by mass, based on the total mass of the electrolyte. In one embodiment of the present application, the mass percentage of phosphorus oxychloride a is from 0.01% to 3% based on the total mass of the electrolyte. In one embodiment of the present application, the phosphorus oxychloride content a is from 0.01% to 0.95% by mass, based on the total mass of the electrolyte. In one embodiment of the present application, the multicyano compound is present in an amount B of 0.1 to 10% by mass, based on the total mass of the electrolyte. In one embodiment of the present application, the mass percentage B of the polycyano compound is 2% to 8% based on the total mass of the electrolyte. For example, the lower limit of the phosphorus oxychloride mass percentage a may include the following values: 0.001%, 0.2%, 0.5% or 1%; the upper limit value of the mass percent content A of the phosphorus oxychloride can comprise the following numerical values: 3% or 5%. The lower limit of the percentage by mass B of the polycyano compound may include the following values: 0.1%, 0.5%, 1%, 2% or 3%; the upper limit value of the mass percentage content B of the polycyano compound can be included in the following numerical values: 5%, 7%, 8% or 10%. Without being limited to any theory, the phosphorus trifluoride oxide can fully exert the effect when the positive electrode is lithiated to make up for the protection defect by controlling the mass percentage content A of the phosphorus trifluoride oxide within the range. By controlling the mass percentage B of the polycyano compound within the above range, the polycyano compound forms stable adsorption coordination on the surface of the positive electrode. By controlling the mass percentage content a of phosphorus oxychloride and the mass percentage content B of the polycyano compound within the above preferable ranges, it is possible to obtain correspondingly more excellent effects.
In one embodiment of the present application, the mass percentage of phosphorus oxychloride a and the mass percentage of polycyano compound B satisfy: a and B are more than or equal to 0.15% and less than or equal to 11%. In one embodiment of the present application, 2.5% by mass or more and 10% by mass or less of A + B are satisfied between A, the phosphorus oxytrifluoride and B, the polycyano compound. For example, the lower limit of the sum of a and B may be included in the following values: 0.15%, 1.5%, 2%, 2.2%, 2.5%, 3%, 4% or 5%; the upper limit of the sum of a and B may be included in the following values: 6%, 7%, 8%, 9% or 10%. Without being limited to any theory, by controlling the sum of A and B within the above range, the synergistic adsorption reaction of phosphorus oxytrifluoride and a polycyano compound has high film forming efficiency, and a compact, stable and low-impedance interface protective film can be quickly formed.
In one embodiment of the present application, the polycyano compounds include at least one of the compounds of structural formula (I):
wherein R is selected from C1To C15A chain alkyl group of C1To C15Alkenyl or C1To C15An alkynylene group of (a); a and c are each independently 0 or a positive integer, and a and c are not simultaneously 0, 2. ltoreq. a + c. ltoreq.7, 0. ltoreq. b.ltoreq.6, and the number b of alkylene groups to which each cyano group is bonded may be the same or different.
Preferably, the compound represented by structural formula (I) includes any one of the following formulae (1) to (62):
in one embodiment of the present application, the electrolyte comprises at least one of formula (1) to formula (9), and comprises at least one of formula (10) to formula (62). The multicyano compounds with different structures act together, so that the high-temperature safety performance and the cycle performance of the lithium ion battery can be further improved without affecting other performances.
In one embodiment of the present application, the total content of the at least one polycyano compound of formulae (1) to (9) is B1% and the total content of the at least one polycyano compound of formulae (10) to (62) is B2%, based on the total mass of the electrolyte, satisfying B1 > B2. When the content meets the range, the electrolyte has a relatively proper viscosity value, and the comprehensive performance of the lithium ion battery is better.
In one embodiment of the present application, the electrolyte comprises at least one of formula (1) to formula (9), and comprises at least one of formula (14) to formula (23).
In one embodiment of the present application, the electrolyte comprises at least one of formulas (1) to (9), at least one of formulas (14) to (23), and at least one of formulas (38) to (48). The multicyano compound having an ether bond and the multicyano compound having no ether bond act together, and the performance of the lithium ion battery can be improved.
In one embodiment of the present application, the electrolyte further includes at least one of a fluorinated ester compound, a cyclic sulfonate ester, or a cyclic carbonate ester containing an unsaturated bond. When at least one of the fluorinated ester compound, the cyclic sulfonate or the cyclic carbonate containing an unsaturated bond is contained in the electrolyte, the electrolyte can form a stable protective layer on both the positive electrode and the negative electrode, and the high-temperature safety performance and the cycle performance of the lithium ion battery can be more effectively improved.
In one embodiment of the present application, the fluorinated ester compound is present in an amount of 0.1 to 15% by mass C, and/or the cyclic sulfonic acid ester is present in an amount of 0.1 to 5% by mass D, and/or the unsaturated bond-containing cyclic carbonate is present in an amount of 0.01 to 2% by mass E, based on the total mass of the electrolyte. For example, the lower limit of the fluorinated ester compound in mass percent C may include the following values: 0.1%, 5% or 7.6%; the upper limit value of the fluorinated ester compound in percentage by mass C may include the following values: 8%, 10% or 15%. The lower limit of the cyclic sulfonic acid ester content D may be included in the following values: 0.1%, 1% or 2.5%; the upper limit of the cyclic sulfonic acid ester content D may be included in the following values: 3% or 5%. The lower limit value of the unsaturated bond-containing cyclic carbonate content E in mass% may include the following values: 0.01%, 0.1% or 0.5%; the upper limit value of the unsaturated bond-containing cyclic carbonate content E by mass percentage may include the following values: 1.4% or 2%. Without being limited to any theory, the stability of the electrolyte under high voltage can be further improved and the decomposition reaction of the electrolyte under high voltage can be more effectively avoided by controlling the mass percentage content C of the fluorinated ester compound, the mass percentage content D of the cyclic sulfonic acid ester and the mass percentage content E of the cyclic carbonate containing unsaturated bonds within the above ranges, so that the high-temperature safety performance and the cycle performance of the lithium ion battery are further remarkably improved.
In one embodiment of the present application, the mass percentage of phosphorus oxychloride a and the mass percentage of cyclic sulfonate D satisfy: a and D are more than or equal to 0.1 percent and less than or equal to 20 percent. For example, the lower limit of the sum of a and D may be included in the following values: 0.1%, 1%, 3.001%, 3.05%, 3.2%, 3.5%, 4%, 6% or 8%; the upper limit of the sum of a and D may be included in the following values: 10%, 15% or 20%. Without being limited to any theory, by controlling the sum of A and D within the range, the cyclic sulfonic acid ester and the phosphorus oxychloride act synergistically to improve the composition of the cathode protective film, so that the reaction passivation of the phosphorus oxychloride at the cathode can be more effectively enhanced to make up for the protection defect.
In one embodiment of the present application, there is no particular limitation on the kind of the fluorinated ester compound as long as the object of the present application can be achieved. For example, the fluorinated ester compound may include at least one of fluoroethylene carbonate (FEC), difluoroethylene carbonate, fluoroethyl carbonate, fluorodimethyl carbonate, fluoroethyl carbonate, fluoropropionic acid ethyl ester, fluoropropionic acid propyl ester, fluoropropionic acid methyl ester, fluoroethyl acetate, fluoroacetic acid methyl ester, fluoroacetic acid propyl ester, fluoroethylene carbonate, difluoroethylene carbonate, and trifluoromethyl ethylene carbonate.
In another embodiment of the present application, there is no particular limitation on the kind of the cyclic sulfonic acid ester as long as the object of the present application can be achieved. For example, the cyclic sulfonate ester can comprise at least one of 1, 3-Propane Sultone (PS) or 1, 4-butane sultone.
In still another embodiment of the present application, the kind of the unsaturated bond-containing cyclic carbonate is not particularly limited as long as the object of the present application can be achieved. For example, the unsaturated bond-containing cyclic carbonate may contain at least one of Vinylene Carbonate (VC) or vinyl ethylene carbonate (vinylcarbonate).
In one embodiment of the present application, the electrolyte includes a fluorinated ester compound and a cyclic sulfonate ester.
In one embodiment of the present application, 0.2 ≦ C + D ≦ 15. For example, the sum of C and D may be 0.3, 0.5, 1.5, 2, 4, 5, 7, 9, 11, 12, or 15, or a range of any two of these values.
In one embodiment of the present application, the electrolyte solution includes a fluorinated ester compound, a cyclic sulfonate ester, and a cyclic carbonate ester having an unsaturated bond. When the electrolyte contains the substances, the cathode can be better protected, and the performance of the lithium ion battery is improved.
In one embodiment of the present application, a mass percentage content F of a metal element other than lithium in the positive electrode active material and a mass percentage content a of phosphorus oxychloride in the electrolyte satisfy: 600 > F/A > 10. For example, the lower limit of F/A may be included in the following values: 12. 20, 60, 120 or 300; the upper limit of F/A may be included in the following values: 400. 500 or 600. In the present application, the kind of the metal element other than lithium is not particularly limited as long as the object of the present application can be achieved. For example, at least one of Fe, Co, Ni, Mn, Ti, Mg, Al, Zr, La, Y, V, Cr, Ge, Ru, Sn, Ti, Nb, Mo may be included. Without being limited to any theory, the passivation protection effect of the phosphorus oxyfluoride on the surface of the positive electrode can be better exerted by limiting the relation between the mass percentage content F of the transition metal element in the positive electrode active material and the mass percentage content A of the phosphorus oxyfluoride in the electrolyte.
The electrolyte of the present application further includes a lithium salt and a nonaqueous solvent. The lithium salt is not particularly limited as long as the object of the present application can be achieved. For example, the lithium salt may comprise lithium hexafluorophosphate (LiPF)6)、LiBF4、LiB(C6H5)4、LiCH3SO3、LiCF3SO3、LiN(SO2CF3)2、LiC(SO2CF3)3、LiSiF6At least one of LiBOB or lithium difluoroborate. Preferably, the lithium salt may include LiPF6Because of LiPF6Can give high ionic conductivity and improve the cycle performance of the lithium ion battery. The nonaqueous solvent is not particularly limited in the present application as long as the object of the present application can be achieved. For example, the nonaqueous solvent may contain at least one of a carbonate compound, a carboxylate compound, an ether compound, or other organic solvent. The carbonate compound may be at least one of a chain carbonate compound and a cyclic carbonate compound. Examples of the above chain carbonate compound are at least one of dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), Methyl Propyl Carbonate (MPC), Ethyl Propyl Carbonate (EPC) or Methyl Ethyl Carbonate (MEC). Examples of the cyclic carbonate compound are at least one of Ethylene Carbonate (EC), Propylene Carbonate (PC), or Butylene Carbonate (BC). Examples of fluorine above-mentioned carboxylic ester compounds are ethyl acetate, n-propyl acetate, t-butyl acetate, propylAt least one of methyl propionate, ethyl propionate and propyl propionate. Examples of the above ether compounds are at least one of dibutyl ether, tetraglyme, diglyme, 1, 2-dimethoxyethane, 1, 2-diethoxyethane, ethoxymethoxyethane, 2-methyltetrahydrofuran, or tetrahydrofuran. Examples of the above-mentioned other organic solvent are at least one of dimethyl sulfoxide, 1, 2-dioxolane, sulfolane, methylsulfolane, 1, 3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone, formamide, dimethylformamide, acetonitrile, trimethyl phosphate, triethyl phosphate, trioctyl phosphate, or a phosphate ester.
The positive electrode of the present application includes a positive electrode current collector and a positive electrode active material layer disposed on at least one surface of the positive electrode current collector. The positive electrode current collector is not particularly limited as long as the object of the present invention can be achieved. For example, the positive electrode current collector may include an aluminum foil, an aluminum alloy foil, a composite current collector, or the like. The positive electrode active material layer of the present application contains a positive electrode active material. The kind of the positive electrode active material is not particularly limited as long as the object of the present application can be achieved. For example, the positive electrode active material may include at least one of lithium nickel cobalt manganese oxide (811, 622, 523, 111), lithium nickel cobalt aluminate, lithium iron phosphate, a lithium rich manganese based material, lithium cobalt oxide, lithium manganese oxide, lithium iron manganese phosphate, lithium titanate, or the like. In the present application, the positive electrode active material may further include non-metallic elements, such as fluorine, phosphorus, boron, chlorine, silicon, sulfur, and the like, which can further improve the stability of the positive electrode active material. In the present application, the thickness of the positive electrode current collector and the positive electrode active material layer is not particularly limited as long as the object of the present application can be achieved. For example, the thickness of the positive electrode current collector is 5 μm to 20 μm, or 6 μm to 18 μm. The thickness of the single-sided positive electrode active material layer is 30 μm to 120 μm. In the present application, the positive electrode active material layer may be provided on one surface (first surface) in the thickness direction of the positive electrode current collector, and may also be provided on both surfaces (first surface and second surface) in the thickness direction of the positive electrode current collector. The "surface" herein may be the entire region of the positive electrode current collector or a partial region of the positive electrode current collector, and the present application is not particularly limited as long as the object of the present application can be achieved. Optionally, the positive electrode sheet may further include a conductive layer between the positive electrode current collector and the positive electrode active material layer. The composition of the conductive layer is not particularly limited, and may be a conductive layer commonly used in the art. The conductive layer includes a conductive agent and a binder.
The negative electrode of the present application is not particularly limited as long as the object of the present application can be achieved. For example, the negative electrode includes a negative electrode current collector and a negative electrode active material layer. The present application is not particularly limited as long as the object of the present application can be achieved. For example, the negative electrode current collector may include a copper foil, a copper alloy foil, a nickel foil, a stainless steel foil, a titanium foil, a nickel foam, a copper foam, a composite current collector, or the like. The anode active material layer of the present application contains an anode active material. The present application does not particularly limit the kind of the anode active material as long as the object of the present application can be achieved. For example, the negative active material may include natural graphite, artificial graphite, mesophase micro carbon spheres (MCMB), hard carbon, soft carbon, silicon-carbon composite, SiOx(0<x<2) Li-Sn alloy, Li-Sn-O alloy, Sn, SnO2Lithium titanate Li of spinel structure4Ti5O12At least one of Li-Al alloy and metallic lithium. In the present application, the thickness of the anode current collector and the anode active material layer is not particularly limited as long as the object of the present application can be achieved. For example, the thickness of the negative electrode current collector is 6 to 10 μm, and the thickness of the negative electrode active material layer is 30 to 120 μm. In the present application, the negative electrode active material layer may be provided on one surface (first surface) in the thickness direction of the negative electrode current collector, and may also be provided on both surfaces (first surface and second surface) in the thickness direction of the negative electrode current collector. The "surface" herein may be the entire region of the negative electrode current collector or a partial region of the negative electrode current collector, and the present application is not particularly limited as long as the object of the present application can be achieved. Optionally, the negative electrode tab may further include a conductive layer between the negative electrode current collector and the negative active material layer. The composition of the conductive layer is not particularly limited, and may beConductive layers commonly used in the art. The conductive layer includes a conductive agent and a binder.
The conductive agent is not particularly limited as long as the object of the present application can be achieved. For example, the conductive agent may include at least one of conductive carbon black (Super P), Carbon Nanotubes (CNTs), carbon nanofibers, flake graphite, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, or graphene. For example, the binder may include at least one of polyvinyl alcohol, sodium polyacrylate, potassium polyacrylate, lithium polyacrylate, polyimide, polyamideimide, styrene-butadiene rubber (SBR), polyvinyl alcohol (PVA), polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE), polyvinyl butyral (PVB), aqueous acrylic resin, carboxymethyl cellulose (CMC), sodium carboxymethyl cellulose (CMC-Na), or the like.
The lithium ion battery further comprises an isolating membrane used for separating the positive electrode from the negative electrode, preventing short circuit inside the lithium ion battery, allowing electrolyte ions to freely pass through, and completing the effect of an electrochemical charging and discharging process. The separator in the present application is not particularly limited as long as the object of the present application can be achieved. For example, at least one of Polyolefin (PO) type separators mainly composed of Polyethylene (PE) and polypropylene (PP), polyester films (for example, polyethylene terephthalate (PET) films), cellulose films, polyimide films (PI), polyamide films (PA), spandex or aramid films, woven films, nonwoven films (nonwoven fabrics), microporous films, composite films, separator papers, roll-pressed films, and spun films. For example, the release film may include a base material layer and a surface treatment layer. The substrate layer may be a non-woven fabric, a film or a composite film having a porous structure, and the material of the substrate layer may include at least one of polyethylene, polypropylene, polyethylene terephthalate, polyimide, and the like. Optionally, a polypropylene porous film, a polyethylene porous film, a polypropylene nonwoven fabric, a polyethylene nonwoven fabric, or a polypropylene-polyethylene-polypropylene porous composite film may be used. Optionally, a surface treatment layer is disposed on at least one surface of the substrate layer, and the surface treatment layer may be a polymer layer or an inorganic layer, or a layer formed by mixing a polymer and an inorganic substance. For example, the inorganic layer includes inorganic particles and a binder, and the inorganic particles are not particularly limited and may be, for example, at least one selected from the group consisting of alumina, silica, magnesia, titania, hafnia, tin oxide, ceria, nickel oxide, zinc oxide, calcium oxide, zirconia, yttria, silicon carbide, boehmite, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, barium sulfate, and the like. The binder is not particularly limited, and may be, for example, one or a combination of several selected from polyvinylidene fluoride, a copolymer of vinylidene fluoride-hexafluoropropylene, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene, and polyhexafluoropropylene. The polymer layer contains a polymer, and the material of the polymer comprises at least one of polyamide, polyacrylonitrile, acrylate polymer, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, polyvinyl ether, polyvinylidene fluoride, poly (vinylidene fluoride-hexafluoropropylene), and the like.
The electrochemical device of the present application is not particularly limited, and may include any device in which electrochemical reactions occur. In some embodiments, the electrochemical device may include, but is not limited to: a lithium metal secondary battery, a lithium ion secondary battery (lithium ion battery), a lithium polymer secondary battery, a lithium ion polymer secondary battery, or the like.
The process for preparing the electrochemical device is well known to those skilled in the art, and the present application is not particularly limited as long as the object of the present application can be achieved. For example, the electrochemical device may be manufactured by the following process: the method comprises the steps of putting an isolating film between a positive pole piece and a negative pole piece, winding or stacking the isolating film according to needs, putting the isolating film into a shell, injecting electrolyte into the shell, and sealing the shell, wherein the isolating film is the isolating film provided by the application. In addition, an overcurrent prevention element, a guide plate, or the like may be placed in the case as necessary to prevent a pressure rise and overcharge/discharge inside the electrochemical device.
A second aspect of the present application provides an electronic device comprising the electrochemical device described in the embodiments of the present application, which has good high-temperature safety performance and cycle performance.
The electronic device of the present application is not particularly limited, and may be any electronic device known in the art. In some embodiments, the electronic device may include, but is not limited to, a notebook computer, a pen-input computer, a mobile computer, an electronic book player, a portable phone, a portable facsimile, a portable copier, a portable printer, a headphone, a video recorder, a liquid crystal television, a handheld cleaner, a portable CD player, a mini-disc, a transceiver, an electronic organizer, a calculator, a memory card, a portable recorder, a radio, a backup power source, an electric motor, an automobile, a motorcycle, a moped, a bicycle, a lighting fixture, a toy, a game machine, a clock, an electric tool, a flashlight, a camera, a large household battery, a lithium ion capacitor, and the like.
An electrochemical device includes a positive electrode, a negative electrode, a separator, and an electrolyte including phosphorus oxychloride and a polycyano compound including at least two cyano groups. The electrolyte can form a compact and stable protective film on the surface of the positive electrode, and inhibit the decomposition reaction of the electrolyte under high voltage. The electrochemical device containing the electrolyte has good high-temperature safety performance and cycle performance.
Examples
Hereinafter, embodiments of the present application will be described in more detail with reference to examples and comparative examples. Various tests and evaluations were carried out according to the following methods. Unless otherwise specified, "part" and "%" are based on mass.
The test method and the test equipment are as follows:
and (3) testing the cycle performance:
the method comprises the steps of standing the lithium ion battery for 30min at 25 ℃, then carrying out constant current charging to 4.45V at a rate of 1C, then carrying out constant voltage charging to 0.05C at a voltage of 4.45V, standing for 5min, and then carrying out constant current discharging to 3.0V at a rate of 0.5C, wherein the discharge capacity is the first discharge capacity of the lithium ion battery, and then carrying out 500 charge-discharge cycle processes.
The capacity retention (%) after N charge and discharge cycles of the lithium ion battery is equal to the discharge capacity at the N-th cycle/the first discharge capacity × 100%.
And (3) testing the high-temperature resistant safety performance:
standing the lithium ion battery for 30min at 25 ℃, and then charging the lithium ion battery to 4.45V at a constant current of 1C multiplying power, and then charging the lithium ion battery to 0.05C at a constant voltage of 4.45V; and (3) placing the fully charged lithium ion battery in an oven, heating the oven at the heating rate of 5 ℃/min, monitoring the surface temperature of the lithium ion battery, and recording the temperature of the oven when the lithium ion battery is subjected to thermal runaway combustion.
< preparation of electrolyte solution >
Ethylene Carbonate (EC), Propylene Carbonate (PC), diethyl carbonate (DEC) and Ethyl Propionate (EP) were mixed in a mass ratio EC: PC: DEC: EP of 20:10:40:30 under a dry argon atmosphere to obtain a nonaqueous organic solvent. Addition of LiPF to non-aqueous organic solvent6And optionally adding POF3A polycyano compound, a fluoro ester compound, a cyclic sulfonic acid ester and a cyclic carbonic ester containing unsaturated bonds to obtain LiPF6The concentration is 1.1mol/L, POF3The contents of the polycyano compound, the fluoro-ester compound, the cyclic sulfonic acid ester and the cyclic carbonate ester having an unsaturated bond are shown in Table 1.
< preparation of Positive electrode >
Weighing 2kg of solvent N-methyl-2-pyrrolidone (NMP), 1.5kg of binder polyvinylidene fluoride solvent (PVDF, the mass percentage of polyvinylidene fluoride is 10%), 0.15kg of conductive agent conductive carbon black (Super P) and 9.7kg of positive electrode active material lithium cobaltate (LiCoO)2) And fully mixing and stirring to obtain the anode slurry. Wherein the cobalt element in the positive electrode active material is LiCoO2The mass percentage content F in the composition is 60 percent. And uniformly coating the positive electrode slurry on the first surface of a positive electrode current collector aluminum foil with the thickness of 12 mu m, and baking for 1h at the temperature of 120 ℃ to obtain the positive electrode with the single-side coated with the positive electrode slurry. And then, repeating the steps on the second surface of the positive electrode to obtain the positive electrode with the positive electrode slurry coated on the two sides. After coating, compacting and cutting are carried out to obtain the anode with the specification of 74mm multiplied by 867mm for later use.
< preparation of negative electrode >
Weighing 2.0kg of thickener carboxymethylcellulose sodium (CMC, the mass percentage of the carboxymethylcellulose sodium is 1.5%), 0.2kg of binder styrene-butadiene rubber emulsion (the mass percentage of styrene-butadiene rubber is 50%) and 4.8kg of negative electrode active material graphite powder (the average particle size Dv50 is 11.5 mu m), and uniformly mixing to obtain negative electrode slurry. And uniformly coating the negative electrode slurry on the first surface of a negative electrode current collector copper foil with the thickness of 8 mu m, and baking for 1h at the temperature of 120 ℃ to obtain the negative electrode with the single-side coated with the negative electrode slurry. And then, repeating the steps on the second surface of the cathode to obtain the cathode with the cathode slurry coated on the two sides. After coating, compacting and cutting are carried out to obtain the cathode with the specification of 76mm multiplied by 851mm for later use.
< preparation of separator >
Alumina and polyvinylidene fluoride were mixed in a mass ratio of 90:10 and dissolved in deionized water to form a ceramic slurry with 50% solids. Then, the ceramic slurry was uniformly coated on one side of a porous substrate (polypropylene, thickness 7 μm, average pore diameter 0.073 μm, porosity 26%) by a gravure coating method, and dried to obtain a two-layer structure of a ceramic coating layer and the porous substrate, the ceramic coating layer having a thickness of 50 μm.
Polyvinylidene fluoride (PVDF) was mixed with polyacrylate in a mass ratio of 96:4 and dissolved in deionized water to form a polymer slurry with 50% solids. And then, uniformly coating the polymer slurry on two surfaces of the double-layer structure of the ceramic coating and the porous substrate by adopting a micro-gravure coating method, and drying to obtain the isolating membrane, wherein the thickness of a single-layer coating formed by the polymer slurry is 2 mu m.
< preparation of lithium ion Battery >
And (3) stacking the prepared positive electrode, the prepared isolating membrane and the prepared negative electrode in sequence to enable the isolating membrane to be positioned between the positive electrode and the negative electrode to play an isolating role, and winding to obtain the electrode assembly. And (3) packaging the electrode assembly into an aluminum foil packaging bag, baking at 80 ℃ to remove water, injecting the prepared electrolyte, and performing vacuum packaging, standing, formation, shaping and other processes to obtain the lithium ion battery.
Examples 1 to 57, comparative examples 1 to 6, the production steps of < electrolyte preparation >, < positive electrode preparation >, < negative electrode preparation >, < separator preparation > and < lithium ion battery preparation > were the same as the above-described production steps, and the changes in the relevant production parameters were as shown in table 1:
it can be seen from examples 1 to 9 and comparative examples 1 and 5 that the high-temperature safety performance and cycle performance of the lithium ion battery vary with the mass percentage a of phosphorus oxychloride in the electrolyte. The lithium ion battery with the mass percentage content A of the phosphorus oxide trifluoride in the electrolyte in the content range has obviously better high-temperature safety performance and cycle performance.
As can be seen from example 7, example 19 to example 23, and comparative example 2, the high-temperature safety performance and cycle performance of the lithium ion battery were varied according to the mass percentage B of the polycyano compound in the electrolyte. The lithium ion battery with the multicyano compound in the electrolyte and the mass percentage content B in the range of the application has obviously better high-temperature safety performance and cycle performance.
The types and mass percentages of the fluorinated ester compound, the cyclic sulfonate compound and the unsaturated bond-containing cyclic carbonate in the electrolyte generally affect the high-temperature safety performance and the cycle performance of the lithium ion battery. As can be seen from examples 39 to 51, a lithium ion battery having good high-temperature safety performance and cycle performance can be obtained as long as the kind and content of the fluorinated ester compound, the cyclic sulfonate compound, and the cyclic carbonate having an unsaturated bond in the electrolytic solution are within the ranges of the present application.
The sum A + B of the mass percent of the phosphorus oxychloride A and the mass percent of the polycyano compound B, and the sum A + D of the mass percent of the phosphorus oxychloride A and the mass percent of the cyclic sulfonate D also generally influence the high-temperature safety performance and the cycle performance of the lithium ion battery. As can be seen from Table 1, the lithium ion battery with good high-temperature safety performance and cycle performance can be obtained when A + B or A + D is within the range of the application.
The ratio F/A of the mass percentage content F of the transition metal element in the positive active material to the mass percentage content A of the phosphorus oxychloride in the electrolyte generally affects the high-temperature safety performance and the cycle performance of the lithium ion battery. As can be seen from example 7 and examples 53 to 57, the F/a was within the range of the present application, and a lithium ion battery having excellent high-temperature safety performance and cycle performance was obtained.
In summary, the present application provides an electrochemical device including a positive electrode, a negative electrode, a separator, and an electrolyte solution including phosphorus oxychloride and a polycyano compound including at least two cyano groups. The electrolyte can form a compact and stable protective film on the surface of the positive electrode, and inhibit the decomposition reaction of the electrolyte under high voltage. The electrochemical device containing the electrolyte has good high-temperature safety performance and cycle performance.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (11)
1. An electrochemical device comprising a positive electrode, a negative electrode, a separator, and an electrolyte, the positive electrode comprising a positive electrode current collector and a positive electrode active material layer disposed on at least one surface of the positive electrode current collector, the positive electrode active material layer comprising a positive electrode active material; the electrolyte includes phosphorus oxychloride and a polycyano compound including at least two cyano groups.
2. The electrochemical device according to claim 1, wherein the phosphorus oxychloride is contained in an amount of 0.001 to 5% by mass, and the polycyano compound is contained in an amount of 0.1 to 10% by mass, based on the total mass of the electrolyte.
3. The electrochemical device according to claim 1, wherein the mass percentage of the phosphorus oxychloride is a and the mass percentage of the polycyano compound is B, based on the total mass of the electrolyte, satisfy: a and B are more than or equal to 0.15% and less than or equal to 11%.
4. The electrochemical device of claim 1, wherein the polycyano compound includes at least one of the compounds of structural formula (I):
wherein R is selected from C1To C15A chain alkyl group of C1To C15Alkenyl or C1To C15An alkynylene group of (a); a and c are each independently 0 or a positive integer, and a and c are not simultaneously 0, 2. ltoreq. a + c. ltoreq.7, 0. ltoreq. b.ltoreq.6, and the number b of alkylene groups to which each cyano group is bonded may be the same or different.
5. The electrochemical device according to claim 1, wherein the polycyano compound includes any one of the following formulas (1) to (62):
6. the electrochemical device according to claim 1, wherein the electrolyte further comprises at least one of a fluorinated ester compound, a cyclic sulfonate ester, or a cyclic carbonate ester containing an unsaturated bond.
7. The electrochemical device according to claim 6, wherein the fluorinated ester compound is 0.1 to 15% by mass, and/or the cyclic sulfonic acid ester is 0.1 to 5% by mass, and/or the unsaturated bond-containing cyclic carbonate is 0.01 to 2% by mass, based on the total mass of the electrolyte.
8. The electrochemical device according to claim 7, wherein the mass percentage of the phosphorus oxychloride a and the mass percentage of the cyclic sulfonate ester D satisfy: a and D are more than or equal to 0.1 percent and less than or equal to 20 percent.
9. The electrochemical device according to claim 6, wherein the fluorinated ester compound comprises at least one of fluoroethylene carbonate, difluoroethylene carbonate, fluoroethyl carbonate, dimethyl fluorocarbonate, diethyl fluorocarbonate, ethyl fluoropropionate, propyl fluoropropionate, methyl fluoropropionate, ethyl fluoroacetate, methyl fluoroacetate, propyl fluoroacetate, fluoroethylene carbonate, ethylene difluorocarbonate, and ethylene trifluoromethylcarbonate;
the cyclic sulfonate ester comprises at least one of 1, 3-propane sultone or 1, 4-butane sultone;
the unsaturated bond-containing cyclic carbonate contains at least one of vinylene carbonate or vinyl ethylene carbonate.
10. The electrochemical device according to any one of claims 1 to 9, wherein a mass percentage content F of a metal element other than lithium in the positive electrode active material and a mass percentage content a of the phosphorus oxytrifluoride in the electrolytic solution satisfy: 600 > F/A > 10.
11. An electronic device comprising the electrochemical device of any one of claims 1 to 10.
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