WO2023087937A1 - 一种电化学装置及电子装置 - Google Patents

一种电化学装置及电子装置 Download PDF

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Publication number
WO2023087937A1
WO2023087937A1 PCT/CN2022/122164 CN2022122164W WO2023087937A1 WO 2023087937 A1 WO2023087937 A1 WO 2023087937A1 CN 2022122164 W CN2022122164 W CN 2022122164W WO 2023087937 A1 WO2023087937 A1 WO 2023087937A1
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Prior art keywords
lithium
electrolyte
electrochemical device
mass percentage
positive electrode
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PCT/CN2022/122164
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English (en)
French (fr)
Inventor
徐春瑞
许艳艳
周邵云
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Ningde Amperex Technology Ltd
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Ningde Amperex Technology Ltd
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Priority to EP22894475.7A priority Critical patent/EP4394945A4/en
Priority to KR1020237006569A priority patent/KR20230035681A/ko
Priority to JP2024516343A priority patent/JP7771368B2/ja
Publication of WO2023087937A1 publication Critical patent/WO2023087937A1/zh
Priority to US18/620,055 priority patent/US20240282943A1/en
Anticipated expiration legal-status Critical
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • 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
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • 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
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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

  • the invention relates to the technical field of energy storage, in particular to an electrochemical device and an electronic device.
  • lithium-ion batteries have been widely used in electric vehicles, consumer electronics, energy storage devices and other fields, and have gradually become the mainstream batteries in the above fields due to their advantages such as high energy density and no memory effect.
  • Co-containing lithium cobaltate and nickel-cobalt lithium manganese oxide have high volumetric energy density, and have become an inevitable choice for high-energy-density materials.
  • the present application provides an electrochemical device and an electronic device to improve the performance of the electrochemical device at high temperature.
  • the inventors of the present application have found that by synergistically controlling the mass percentage of the Co element in the positive electrode active material and the mass percentage of the polynitrile compound within the above range, the effect of the polynitrile compound on the positive electrode active material can be effectively brought into play. protection, while avoiding the damage of the polynitrile compound to the negative electrode interface, and significantly improving the performance of the electrochemical device at high temperature.
  • the mass percentage b% of the polynitrile compound satisfies: 0 ⁇ b ⁇ 7, for example, b can be 0.01, 0.5, 1, 2, 3, 4, 5, 6, 7 or any range in between.
  • the polynitrile compound comprises a dinitrile compound and/or a trinitrile compound, based on the total mass of the electrolyte, the mass percentage of the dinitrile compound is b1%, so The mass percentage of the trinitrile compound is b2%, b1 and b2 meet: 0 ⁇ b1/b2 ⁇ 4, for example, b1/b2 can be 0, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0 or any range in between.
  • the applicant found that by synergistically controlling the mass percentages of dinitrile compounds and trinitrile compounds to satisfy the above relational formula, the performance of electrochemical devices at high temperatures can be further improved.
  • the dinitrile compound includes succinonitrile (SN), adiponitrile (AND), 1,2-bis(cyanoethoxy)ethane (DENE) or 1,4 - at least one of dicyano-2-butene (HEDN),
  • the trinitrile compounds include 1,3,6-hexanetrinitrile (HTCN) or 1,2,3-tris(2-cyanooxy base) propane (TCEP) at least one.
  • the electrolyte meets at least one of the following conditions:
  • the electrolyte also contains ethylene carbonate (EC), based on the total mass of the electrolyte, the mass percentage of the ethylene carbonate is c%, and c satisfies: 0.5 ⁇ c/b ⁇ 20, 3 ⁇ c ⁇ 30, for example, c/b can be 0.5, 1.5, 3.5, 5.5, 7.5, 9.5, 11.5, 13.5, 15.5, 17.5, 19.5, 20 or any range in between, and c can be 3, 5, 7, 9, 12, 15, 18, 21, 24, 27, 30 or any range in between, when the mass percentage of EC is too low, EC cannot form a good solid electrolyte interface (SEI) film on the negative electrode , cannot prevent the damage of polynitrile compounds to the SEI film.
  • SEI solid electrolyte interface
  • the mass percentage of EC When the mass percentage of EC is too high, the mass percentage of polynitrile compounds is too low to effectively complex the active sites of positive electrode active materials.
  • the mass percentage of ethylene carbonate is within the above range, which can improve the performance of the electrochemical device at high temperature;
  • the electrolyte contains lithium difluorophosphate, based on the total mass of the electrolyte, the mass percentage of lithium difluorophosphate is d%, and d satisfies: 0.01 ⁇ d ⁇ 1, for example, d can 0.01, 0.05, 0.1, 0.2, 0.3, 0.4, 0.6, 0.8, 1.0 or any range in between, by controlling the mass percentage of lithium difluorophosphate in the electrolyte within the above range, a stable
  • the SEI film prevents the Co dissolving from the positive electrode from damaging the SEI film, thereby improving the performance of the electrochemical device at high temperature;
  • the electrolyte contains lithium difluorophosphate, based on the total mass of the electrolyte, the mass percentage of the lithium difluorophosphate is d%, and d satisfies: 0.015 ⁇ d/a, through coordinated control of two
  • the mass percentage of Co element in lithium fluorophosphate and the positive electrode active material satisfies the above relational formula, which can form a stable SEI film on the negative electrode and prevent the destruction of the SEI film by the dissolved Co from the positive electrode, thereby improving the performance of the electrochemical device at high temperature ;
  • the electrolyte contains fluoroethylene carbonate (FEC), vinylene carbonate (VC), propylene sulfite (PS), ethylene sulfate (DTD), lithium difluorooxalate borate (LiDFOB) or At least one of bisoxalate lithium borate (LiBOB), by selecting the above-mentioned additives, a stable positive electrode electrolyte interface (CEI) and SEI film can be formed on the surface of the positive electrode and the negative electrode, the positive electrode and the negative electrode are stable, and the gap between the positive electrode, the negative electrode and the electrolyte is inhibited. side reactions, thereby improving the performance of electrochemical devices at high temperatures.
  • FEC fluoroethylene carbonate
  • VC vinylene carbonate
  • PS propylene sulfite
  • DTD ethylene sulfate
  • LiDFOB lithium difluorooxalate borate
  • LiBOB bisoxalate lithium borate
  • the applicant found that by controlling the electrolyte to satisfy one, two or a combination of more than two of the above conditions, the performance of the electrochemical device at high temperature can be further improved.
  • the electrolyte solution comprises a lithium salt
  • the lithium salt comprises at least one of an inorganic lithium salt or an organic lithium salt, based on the total mass of the electrolyte solution, the lithium salt
  • the mass percentage content is 7.5% to 25%, for example, the mass percentage content of lithium salt can be 7.5%, 10.0%, 12.5%, 15.0%, 17.5%, 20.0%, 22.5%, 25% or any in between scope.
  • the lithium salt includes lithium hexafluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium perchlorate, lithium bisfluorosulfonyl imide, lithium bistrifluoromethanesulfonyl imide at least one of the Without being bound by any theory, the applicants have found that by selecting the lithium salts described above, the performance of electrochemical devices at high temperatures can be further improved.
  • the electrolyte solution also contains dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propylene carbonate, ethyl acetate, ethyl propionate, propyl propionate at least one of .
  • the mass percentage of the above-mentioned non-aqueous solvent is 10% to 70%, for example, it can be 10%, 20%, 30%, 40%, 50%, 60%, 70% or any range in between.
  • the differential scanning calorimetry (DSC) curve of the positive electrode sheet contains at least one exothermic main peak, and when the above-mentioned at least one exothermic main peak appears in the DSC test of the positive electrode sheet, it can be detected by electrolysis
  • the adjustment of the liquid composition obtains a higher decomposition temperature (higher stability), wherein, the main exothermic peak is an exothermic peak with a heat release>2mW/mg during the DSC test.
  • T can be 200, 220, 240, 260, 280, 300, 320, 340, 360 or any range in between, when the exothermic main peak temperature and the mass percentage of polynitrile compounds meet the above relationship
  • the positive electrode current collector is not particularly limited, as long as the purpose of the present application can be achieved, for example, it may include but not limited to aluminum foil, aluminum alloy foil, or a composite current collector.
  • the thickness of the positive electrode current collector there is no particular limitation on the thickness of the positive electrode current collector, as long as the purpose of the present application can be achieved, for example, the thickness is 4 ⁇ m to 12 ⁇ m.
  • the positive electrode material layer may be provided on one surface in the thickness direction of the positive electrode current collector, or on two surfaces in the thickness direction of the positive electrode current collector. It should be noted that the "surface” here may refer to the entire area of the positive electrode collector or a partial area of the positive electrode collector. This application is not particularly limited, as long as the purpose of this application can be achieved.
  • the positive electrode material layer includes the positive electrode active material in any of the foregoing embodiments of the present application, and the positive electrode active material may include a composite oxide containing lithium and at least one selected from cobalt, manganese and nickel. kind of element.
  • the specific type of positive electrode active material is not particularly limited, as long as the purpose of the present application can be achieved.
  • the positive electrode active material is selected from lithium cobalt oxide (LiCoO 2 ), lithium nickel manganese cobalt ternary material, lithium manganese oxide (LiMn 2 O 4 ), lithium nickel manganese oxide (LiNi 0.5 Mn 1.5 O 4 ), phosphoric acid One or more of iron lithium (LiFePO 4 ).
  • the thickness of the positive electrode active material layer is not particularly limited, as long as the purpose of the present application can be achieved, for example, the thickness is 30 ⁇ m to 120 ⁇ m.
  • the positive electrode material layer may also include a binder, and the present application has no particular limitation on the binder, as long as the purpose of the present application can be achieved, for example, it may include but not limited to polyacrylic acid, sodium polyacrylate, potassium polyacrylate, lithium polyacrylate, At least one of polyimide, polyvinyl alcohol, carboxymethyl cellulose, sodium carboxymethyl cellulose, polyimide, polyamideimide, styrene-butadiene rubber or polyvinylidene fluoride.
  • a conductive agent may also be included in the positive electrode material layer, and the present application has no special limitation on the conductive agent, as long as the purpose of the application can be realized, for example, it may include but not limited to conductive carbon black (Super P), carbon nanotubes (CNTs), carbon fiber, flake graphite, Ketjen black, graphene, metal material or conductive polymer.
  • the aforementioned carbon nanotubes may include, but are not limited to, single-walled carbon nanotubes and/or multi-walled carbon nanotubes.
  • the aforementioned carbon fibers may include, but are not limited to, vapor grown carbon fibers (VGCF) and/or carbon nanofibers.
  • the above metal material may include but not limited to metal powder and/or metal fiber, specifically, the metal may include but not limited to at least one of copper, nickel, aluminum or silver.
  • the aforementioned conductive polymer may include but not limited to at least one of polyphenylene derivatives, polyaniline, polythiophene, polyacetylene or polypyrrole.
  • the positive electrode may further include a conductive layer located between the positive electrode current collector and the positive electrode material layer.
  • the present application has no particular limitation on the composition of the conductive layer, which may be a commonly used conductive layer in the field, for example, may include but not limited to the above-mentioned conductive agent and the above-mentioned binder.
  • the negative electrode sheet in the present application is not particularly limited, as long as the purpose of the application can be achieved, for example, the negative electrode sheet usually includes a negative electrode collector and a negative electrode material layer.
  • the negative electrode material layer may be provided on one surface in the thickness direction of the negative electrode current collector, or on two surfaces in the thickness direction of the negative electrode current collector. It should be noted that the "surface” here may be the entire area of the negative electrode collector, or a partial area of the negative electrode collector. This application is not particularly limited, as long as the purpose of this application can be achieved.
  • the negative electrode current collector is not particularly limited, as long as the purpose of this application can be achieved, for example, it may include but not limited to copper foil, copper alloy foil, nickel foil, stainless steel foil, titanium foil, nickel foam, copper foam or composite Collectors, etc.
  • the thickness of the current collector of the negative electrode is 4 ⁇ m to 12 ⁇ m.
  • the negative electrode material layer includes negative electrode active materials, wherein the negative electrode active material is not particularly limited, as long as the purpose of the application can be achieved, for example, it can include but not limited to natural graphite, artificial graphite, mesophase micro carbon spheres, hard Carbon, soft carbon, silicon, silicon-carbon composite, Li-Sn alloy, Li-Sn-O alloy, Sn, SnO, SnO 2 , lithiated TiO 2 -Li 4 Ti 5 O 12 or Li with spinel structure - at least one of Al alloys.
  • the negative electrode active material is not particularly limited, as long as the purpose of the application can be achieved, for example, it can include but not limited to natural graphite, artificial graphite, mesophase micro carbon spheres, hard Carbon, soft carbon, silicon, silicon-carbon composite, Li-Sn alloy, Li-Sn-O alloy, Sn, SnO, SnO 2 , lithiated TiO 2 -Li 4 Ti 5 O 12 or Li with spinel structure
  • the negative electrode material layer may also include a conductive agent.
  • the present application has no special limitation on the conductive agent, as long as the purpose of the present application can be achieved, for example, it may include but not limited to at least one of the above-mentioned conductive agents.
  • the negative electrode material layer may also include a binder.
  • the present application has no special limitation on the binder, as long as the purpose of the present application can be achieved, for example, it may include but not limited to at least one of the above-mentioned binders.
  • the negative electrode may further include a conductive layer located between the negative electrode current collector and the negative electrode material layer.
  • the present application has no particular limitation on the composition of the conductive layer, which may be a commonly used conductive layer in the field, and the conductive layer may include but not limited to the above-mentioned conductive agent and the above-mentioned binder.
  • This application has no special restrictions on the separator, as long as the purpose of this application can be achieved, for example, it can include but not limited to polyethylene (PE), polypropylene (PP), polytetrafluoroethylene-based polyolefin (PO) separators , polyester film (such as polyethylene terephthalate (PET) film), cellulose film, polyimide film (PI), polyamide film (PA), spandex, aramid film, woven film, non At least one of woven film (non-woven fabric), microporous film, composite film, separator paper, laminated film or spun film, preferably PP.
  • PET polyethylene terephthalate
  • PI polyimide film
  • PA polyamide film
  • aramid film woven film
  • woven film non At least one of woven film (non-woven fabric), microporous film, composite film, separator paper, laminated film or spun film, preferably PP.
  • the separator of the present application may have a porous structure, and the pore size is not particularly limited as long as the purpose of the present application can be achieved, for example, the pore size may be 0.01 ⁇ m to 1 ⁇ m.
  • the thickness of the isolation film is not particularly limited, as long as the purpose of the present application can be achieved, for example, the thickness may be 5 ⁇ m to 500 ⁇ m.
  • a separator may include a substrate layer and a surface treatment layer.
  • the substrate layer can be a non-woven fabric, film or composite film with a porous structure, and the material of the substrate layer can include but not limited to polyethylene, polypropylene, polyethylene terephthalate or polyimide at least one.
  • a polypropylene porous film, polyethylene porous film, polypropylene nonwoven fabric, polyethylene nonwoven fabric, or polypropylene-polyethylene-polypropylene porous composite film may be used.
  • at least one surface of the substrate layer is provided with a surface treatment 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 material.
  • the inorganic material layer may include but not limited to inorganic particles and inorganic material layer binder, and the present application has no special limitation on inorganic particles, for example, may include but not limited to aluminum oxide, silicon oxide, magnesium oxide, titanium oxide, hafnium dioxide, At least one of tin oxide, cerium oxide, nickel oxide, zinc oxide, calcium oxide, zirconium oxide, yttrium oxide, silicon carbide, boehmite, aluminum hydroxide, magnesium hydroxide, calcium hydroxide or barium sulfate.
  • the present application has no particular limitation on the inorganic layer binder, for example, it may include but not limited to polyvinylidene fluoride, copolymer of vinylidene fluoride-hexafluoropropylene, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, At least one of polyacrylate, polyvinylpyrrolidone, polyvinyl ether, polymethylmethacrylate, polytetrafluoroethylene or polyhexafluoropropylene.
  • polyvinylidene fluoride copolymer of vinylidene fluoride-hexafluoropropylene
  • polyamide polyacrylonitrile
  • polyacrylate polyacrylic acid
  • the polymer layer contains a polymer, and the polymer material may include but not limited to polyamide, polyacrylonitrile, acrylate polymer, polyacrylic acid, polyacrylate, polyvinyl pyrrolidone, polyvinyl ether, polyvinylidene fluoride At least one of ethylene or poly(vinylidene fluoride-hexafluoropropylene).
  • the electrochemical device of the present application is not particularly limited, and it may include any device that undergoes an electrochemical reaction.
  • 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, or a lithium ion polymer secondary battery, among others.
  • the preparation process of electrochemical devices is well known to those skilled in the art, and the present application is not particularly limited.
  • it may include but not limited to the following steps: stack the positive electrode sheet, separator and negative electrode sheet in sequence, and as required Winding, folding, etc. to obtain an electrode assembly with a winding structure, put the electrode assembly into a packaging bag, inject electrolyte into the packaging bag and seal it to obtain an electrochemical device; or, put the positive electrode, separator and negative electrode in order Stacking, and then fixing the four corners of the entire laminated structure with adhesive tape to obtain the electrode assembly of the laminated structure, putting the electrode assembly into a packaging bag, injecting electrolyte into the packaging bag and sealing it to obtain an electrochemical device.
  • overcurrent prevention elements, guide plates, etc. can also be placed in the packaging bag as needed, so as to prevent pressure rise and overcharge and discharge inside the electrochemical device.
  • the second aspect of the present application provides an electronic device, which includes the electrochemical device provided in the first aspect of the present application.
  • the electrochemical device provided by the present application has good high-temperature performance, so the electronic device provided by the present application has a long service life and good performance.
  • the electronic device of the present application is not particularly limited, and it may be used in any electronic device known in the prior art.
  • electronic devices may include, but are not limited to, notebook computers, pen-based computers, mobile computers, e-book players, cellular phones, portable fax machines, portable copiers, portable printers, headsets, VCRs, LCD TVs, portable cleaners, portable CD players, mini discs, transceivers, electronic organizers, calculators, memory cards, portable tape recorders, radios, backup power supplies, motors, cars, motorcycles, power-assisted bicycles, bicycles, Lighting appliances, toys, game consoles, clocks, electric tools, flashlights, cameras, large household storage batteries and lithium-ion capacitors, etc.
  • the mass percentage of the polynitrile compound is adjusted, and further through the coordination and complexation of the polynitrile compound, Co and other additives
  • the combined use of these materials can significantly improve the structural stability of the positive electrode material after highly delithiated, inhibit the dissolution of Co, reduce the oxidation of the active material to the electrolyte, and inhibit related side reactions, thereby effectively improving the performance of the electrochemical device at high temperature.
  • a lithium-ion battery is used as an example of an electrochemical device to explain the present application, but the electrochemical device of the present application is not limited to the lithium-ion battery.
  • Thickness expansion ratio (thickness after cycle-initial thickness)/initial thickness ⁇ 100%.
  • Thickness expansion rate [(thickness stored for 24 hours-initial thickness)/initial thickness] ⁇ 100%.
  • Thickness expansion rate [(thickness after cycle-initial thickness)/initial thickness] ⁇ 100%.
  • Thickness expansion rate [(60-day floating thickness - initial thickness) / initial thickness] ⁇ 100%.
  • Negative electrode active material artificial graphite, conductive agent Super P, sodium carboxymethylcellulose (CMC), and styrene-butadiene rubber (SBR) are mixed according to the mass ratio of 96.4:1.5:0.5:1.6, and then deionized water is added as a solvent to prepare A slurry with a solid content of 54wt%, and stirred evenly.
  • the slurry is evenly coated on one surface of a copper foil with a thickness of 8 ⁇ m, dried at 110° C., and cold-pressed to obtain a negative electrode sheet with a negative active material layer coated on one side with a negative active material layer thickness of 150 ⁇ m.
  • a 7 ⁇ m thick polyethylene porous polymer film was used as the isolation membrane.
  • the Co element and polynitrile compounds in the positive electrode active material usually affect the high-temperature cycle performance and high-temperature cycle performance of lithium-ion batteries.
  • the mass percentage a of the Co element in the positive electrode active material and the mass percentage b% of the polynitrile compound are selected within the scope of the present application, while b and a satisfy the lithium ion battery of the relational formula of claim 1 of the present application, Due to the complexation between the cyano group and Co in the polynitrile compound, the structural stability is enhanced, and the fabricated Li-ion battery has good ITC, high-temperature cycle and high-temperature storage performance.
  • Example 2-1 to Example 2-10 the type and mass percentage of the polyophthalic compound generally also affect the high-temperature performance of the lithium-ion battery.
  • the mass percentage content of polynitrile compound, and the ratio (b1/b2) of the mass percentage content of dinitrile compound and the mass percentage content of trinitrile compound, can affect the high-temperature cycle performance and high-temperature storage performance of lithium-ion battery, from From Examples 2-1 to 2-5, it can be seen that as the proportion of trinitrile compounds in polynitrile compounds increases, the high-temperature cycle performance and high-temperature storage performance of lithium-ion batteries are better improved.
  • Example 3 Except that the relevant preparation parameters and performance parameters are shown in Table 3, all the other are the same as in Example 1-3, wherein, in the process of changing the mass percentage of EC, the mass percentage of EC and the mass percentage of PC are kept The sum of the contents is 40%.
  • Example 3-1 to Example 3-8 and Comparative Example 3-1 it can be seen that polynitrile compounds and EC usually also affect the high-temperature cycle performance and high-temperature storage performance of lithium-ion batteries.
  • the ratio (c/b) of the mass percent content of the polynitrile compound to the mass percent content of EC is within the scope of the application, the lithium-ion battery has better high-temperature cycle performance and high-temperature storage performance.
  • LiPO 2 F 2 usually also affects the high-temperature cycle performance and high-temperature storage performance of lithium-ion batteries.
  • LiPO 2 F 2 mass percentage due to LiPO 2 F 2 forms a low-resistance positive electrode-electrolyte interface (CEI) on the surface of the positive electrode, inhibits the dissolution of Co, and forms a stable SEI film on the negative electrode, which effectively improves the high-temperature cycle and ITC performance of lithium-ion batteries, and because LiPO 2
  • CEI positive electrode-electrolyte interface
  • the strong water absorption of F2 used in conjunction with polynitrile compounds, can better play the role of polynitrile compounds and improve the high-temperature storage and high-temperature cycle performance of lithium-ion batteries.
  • lithium-ion batteries prepared in Examples 1-4 to 1-7 were fully charged and disassembled to obtain positive pole pieces, and DSC tests were performed on the positive pole pieces, and the performance test results obtained are shown in Table 5.
  • Example 5-1 to Example 5-7 a stable CEI and SEI film can be formed on the surface of the positive and negative electrodes by selecting a lithium-ion battery containing FEC, VC, PS, DTD, LiDFOB, and LiBOB as additives.

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Abstract

本申请提供了一种电化学装置及电子装置，其中，电化学装置包括正极极片、负极极片、隔离膜及电解液，正极极片包含正极活性材料，正极活性材料包含Co元素，电解液包含多腈化合物，根据正极活性材料中Co元素的含量，调节多腈化合物的含量，进一步通过多腈化合物和Co的配位络合作用及其他添加剂的组合使用，显著提升正极材料高度脱锂后的结构稳定性，抑制Co的溶出，降低正极活性材料对电解液的氧化，抑制相关副反应，从而有效改善电化学装置在高温下的性能。

Description

一种电化学装置及电子装置
本申请要求于2021年11月18日提交中国专利局、申请号为202111372370.4发明名称为“一种电化学装置及电子装置”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及储能技术领域，特别是涉及一种电化学装置及电子装置。
背景技术
目前，锂离子电池已广泛应用于电动汽车、消费电子产品、储能装置等领域，并凭借其高能量密度、无记忆效应等优势逐渐成为上述领域的主流电池。在目前众多成熟正极材料中，含Co的钴酸锂、镍钴锰酸锂等材料具有较高的体积能量密度，成为高能量密度材料的必然选择。为了进一步提升能量密度，不断提升充电截至电压，随之而来的是对其高温性能的严峻挑战。
有鉴于此，在储能技术领域，进一步提升锂离子电池的高温性能成为了各大锂离子电池厂商和相关工作者研究的重中之重。
发明内容
本申请提供了一种电化学装置及电子装置，以提高电化学装置在高温下的性能。
本申请的第一方面提供了一种电化学装置，其包括正极极片、负极极片、隔离膜及电解液，其中，所述正极极片包含正极活性材料，所述正极活性材料包含Co元素，基于所述正极活性材料的总质量，所述Co元素的质量百分含量为a；所述电解液包含多腈化合物，基于所述电解液的总质量，所述多腈化合物的质量百分含量为b％，所述多腈化合物的质量百分含量b％与所述Co元素的质量百分含量a满足关系：b＝9.7a-0.07+C，-1.5<C≤1.5，0<a≤0.65，例如，C可以为-1.4、-1.0、-0.5、0、0.5、1.0、1.5或为其间的任何范围，a可以为0.001、0.25、0.30、0.35、0.40、0.45、0.50、0.55、0.60、0.65或为其间的任何范围。通过深入研究，本申请的发明人发现，通过协同控制正极活性材料中Co元素的质量百分含量和多腈化合物的质量百分含量在上述范围内，可以有效发挥多腈化合物对正极活性材料的保护，同时避免多腈化合物对负极界面的破坏，显著改善电化学装置在高温下的性能。
在本申请的一种实施方案中，基于所述电解液的总质量，所述多腈化合物的质量百分含量b％满足：0<b≤7，例如，b可以为0.01、0.5、1、2、3、4、5、6、7或为其间的任何 范围。通过控制多腈化合物的质量百分含量在上述范围内，可以强化正极结构稳定性，从而改善电化学装置在高温下的性能。
在本申请的一种实施方案中，所述多腈化合物包含二腈化合物和/或三腈化合物，基于所述电解液的总质量，所述二腈化合物的质量百分含量为b1％，所述三腈化合物的质量百分含量为b2％，b1和b2满足：0≤b1/b2≤4，例如，b1/b2可以为0、0.5、1.0、1.5、2.0、2.5、3.0、3.5、4.0或为其间的任何范围。不限于任何理论，本申请人发现，通过协同控制二腈化合物和三腈化合物的质量百分含量满足上述关系式，可以进一步改善电化学装置在高温下的性能。
在本申请的一种实施方案中，所述二腈化合物包括丁二腈(SN)、己二腈(AND)、1,2-双(氰乙氧基)乙烷(DENE)或1,4-二氰基-2-丁烯(HEDN)中的至少一种，所述三腈化合物包括1,3,6-己烷三腈(HTCN)或1,2,3-三(2-氰氧基)丙烷(TCEP)中的至少一种。不限于任何理论，本申请人发现，通过选择上述二腈化合物和三腈化合物可以进一步改善电化学装置高温下的性能。
在本申请的一种实施方案中，所述电解液满足以下条件的至少一者：
(1)所述电解液还包含碳酸亚乙酯(EC)，基于所述电解液的总质量，所述碳酸亚乙酯的质量百分含量为c％，c满足：0.5≤c/b≤20，3≤c≤30，例如，c/b可以为0.5、1.5、3.5、5.5、7.5、9.5、11.5、13.5、15.5、17.5、19.5、20或为其间的任何范围，c可以为3、5、7、9、12、15、18、21、24、27、30或为其间的任何范围，当EC质量百分含量过低时，EC无法在负极形成良好的固体电解质界面(SEI)膜，无法阻止多腈化合物对SEI膜的破坏，当EC质量百分含量过高时，多腈化合物的质量百分含量过低，无法有效络合正极活性材料的活性位点，通过控制电解液中碳酸亚乙酯的质量百分含量在上述范围内，可以提升电化学装置的高温下的性能；
(2)所述电解液包含二氟磷酸锂，基于所述电解液的总质量，所述二氟磷酸锂的质量百分含量为d％，d满足：0.01≤d≤1，例如，d可以为0.01、0.05、0.1、0.2、0.3、0.4、0.6、0.8、1.0或为其间的任何范围，通过控制电解液中二氟磷酸锂的质量百分含量在上述范围内，可以在负极表面形成稳定的SEI膜，阻止正极溶出的Co对SEI膜的破坏，从而提高电化学装置在高温下的性能；
(3)所述电解液包含二氟磷酸锂，基于所述电解液的总质量，所述二氟磷酸锂的质量百分含量为d％，d满足：0.015≤d/a，通过协同控制二氟磷酸锂和正极活性材料中Co 元素的质量百分含量满足上述关系式，能够在负极形成稳定的SEI膜，阻止正极溶出的Co对SEI膜的破坏，从而提高电化学装置在高温下的性能；
(4)所述电解液包含氟代碳酸乙烯酯(FEC)、碳酸亚乙烯酯(VC)、亚硫酸丙烯酯(PS)、硫酸亚乙酯(DTD)、二氟草酸硼酸锂(LiDFOB)或双草酸硼酸锂(LiBOB)中的至少一种，通过选择上述添加剂可以在正极和负极表面形成稳定的正极电解质界面(CEI)和SEI膜，稳定正极和负极，抑制正极、负极和电解液之间的副反应，从而提高电化学装置在高温下的性能。
不限于任何理论，本申请人发现，通过控制电解液满足上述条件中的一种、两种或两种以上的组合，可以进一步提高电化学装置在高温下的性能。
在本申请的一种实施方案中，所述电解液包含锂盐，所述锂盐包含无机锂盐或有机锂盐中的至少一种，基于所述电解液的总质量，所述锂盐的质量百分含量为7.5％至25％，例如，锂盐的质量百分含量可以为7.5％、10.0％、12.5％、15.0％、17.5％、20.0％、22.5％、25％或为其间的任何范围。通过选择上述锂盐并控制锂盐的质量百分含量在上述范围内，可以使电解液的离子电导率提高，从而改善电化学装置在高温下的性能。
在本申请的一种实施方案中，所述锂盐包括六氟磷酸锂、四氟硼酸锂、六氟砷酸锂、高氯酸锂、双氟磺酰亚胺锂、双三氟甲烷磺酰亚胺锂中的至少一种。不限于任何理论，本申请人发现，通过选择上述锂盐，可以进一步改善电化学装置在高温下的性能。
在本申请的一种实施方案中，所述电解液还包含碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸亚丙酯、乙酸乙酯、丙酸乙酯、丙酸丙酯中的至少一种。本申请中，基于电解液的总质量，上述非水溶剂的质量百分含量为10％至70％，例如可以为10％、20％、30％、40％、50％、60％、70％或为其间的任何范围。不限于任何理论，本申请人发现，通过选择上述溶剂，可以进一步改善电化学装置在高温下的性能。
在本申请的一种实施方案中，正极极片的差示扫描量热(DSC)曲线包含至少一个放热主峰，当正极极片的DSC测试中出现上述至少一个放热主峰时，可以通过电解液成分的调整获得较高的分解温度(较高的稳定性)，其中，所述放热主峰为DSC测试过程中放热量>2mW/mg的放热峰。
在本申请的一种实施方案中，在DSC曲线上，所述放热主峰温度为T℃，T满足：T＝10b+267+X，-20≤X≤20，0<b≤7，200≤T≤360，例如T可以为200、220、240、260、280、300、320、340、360或为其间的任何范围，当放热主峰温度与多腈化合物的质量百 分含量满足上述关系式时，由于多腈化合物可以与含Co正极材料实现良好的配位，提升正极材料表面结构稳定性，进而可以改善电化学装置在高温下的性能。
在本申请中，正极集流体没有特别限制，只要能够实现本申请目的即可，例如可以包括但不限于铝箔、铝合金箔或复合集流体等。在本申请中，对正极集流体的厚度没有特别限制，只要能够实现本申请目的即可，例如厚度为4μm至12μm。在本申请中，正极材料层可以设置于正极集流体厚度方向上的一个表面上，也可以设置于正极集流体厚度方向上的两个表面上。需要说明，这里的“表面”可以是正极集流体的全部区域，也可以是正极集流体的部分区域，本申请没有特别限制，只要能实现本申请目的即可。
在本申请中，正极材料层中包括本申请前述任一实施方案中的正极活性材料，正极活性材料可以包括复合氧化物，该复合氧化物含有锂以及从钴、锰和镍中选择的至少一种元素。正极活性材料的具体种类没有特别限制，只要能够实现本申请目的即可。具体地，所述正极活性材料选自钴酸锂(LiCoO 2)、锂镍锰钴三元材料、锰酸锂(LiMn 2O 4)、镍锰酸锂(LiNi 0.5Mn 1.5O 4)、磷酸铁锂(LiFePO 4)中的一种或几种。在本申请中，正极活性材料层的厚度没有特别限制，只要能够实现本申请目的即可，例如厚度为30μm至120μm。
正极材料层还可以包括粘结剂，本申请对粘结剂没有特别限制，只要能够实现本申请目的即可，例如可以包括但不限于聚丙烯酸、聚丙烯酸钠、聚丙烯酸钾、聚丙烯酸锂、聚酰亚胺、聚乙烯醇、羧甲基纤维素、羧甲基纤维素钠、聚酰亚胺、聚酰胺酰亚胺、丁苯橡胶或聚偏氟乙烯中的至少一种。
在本申请中，正极材料层中还可以包括导电剂，本申请对导电剂没有特别限制，只要能够实现本申请目的即可，例如可以包括但不限于导电炭黑(Super P)、碳纳米管(CNTs)、碳纤维、鳞片石墨、科琴黑、石墨烯、金属材料或导电聚合物中的至少一种。上述碳纳米管可以包括但不限于单壁碳纳米管和/或多壁碳纳米管。上述碳纤维可以包括但不限于气相生长碳纤维(VGCF)和/或纳米碳纤维。上述金属材料可以包括但不限于金属粉和/或金属纤维，具体地，金属可以包括但不限于铜、镍、铝或银中的至少一种。上述导电聚合物可以包括但不限于聚亚苯基衍生物、聚苯胺、聚噻吩、聚乙炔或聚吡咯中的至少一种。
任选地，正极还可以包括导电层，导电层位于正极集流体和正极材料层之间。本申请对导电层的组成没有特别限制，可以是本领域常用的导电层，例如可以包括但不限于上述导电剂和上述粘结剂。
本申请中的负极极片没有特别限制，只要能实现本申请的目的即可，例如负极极片通 常包括负极集流体和负极材料层。在本申请中，负极材料层可以设置于负极集流体厚度方向上的一个表面上，也可以设置于负极集流体厚度方向上的两个表面上。需要说明，这里的“表面”可以是负极集流体的全部区域，也可以是负极集流体的部分区域，本申请没有特别限制，只要能实现本申请目的即可。
本申请中，负极集流体没有特别限制，只要能够实现本申请目的即可，例如，可以包括但不限于铜箔、铜合金箔、镍箔、不锈钢箔、钛箔、泡沫镍、泡沫铜或复合集流体等。在本申请中，对负极的集流体的厚度没有特别限制，只要能够实现本申请目的即可，例如厚度为4μm至12μm。
本申请中，负极材料层包括负极活性材料，其中，负极活性材料没有特别限制，只要能实现本申请的目的即可，例如可以包括但不限于天然石墨、人造石墨、中间相微碳球、硬碳、软碳、硅、硅-碳复合物、Li-Sn合金、Li-Sn-O合金、Sn、SnO、SnO 2、尖晶石结构的锂化TiO 2-Li 4Ti 5O 12或Li-Al合金中的至少一种。
本申请中，负极材料层中还可以包括导电剂，本申请对导电剂没有特别限制，只要能够实现本申请目的即可，例如可以包括但不限于上述导电剂中的至少一种。
本申请中，负极材料层中还可以包括粘结剂，本申请对粘结剂没有特别限制，只要能够实现本申请目的即可，例如可以包括但不限于上述粘结剂中的至少一种。
任选地，负极还可以包括导电层，导电层位于负极集流体和负极材料层之间。本申请对导电层的组成没有特别限制，可以是本领域常用的导电层，导电层可以包括但不限于上述导电剂和上述粘结剂。
本申请对隔离膜没有特别限制，只要能够实现本申请目的即可，例如可以包括但不限于聚乙烯(PE)、聚丙烯(PP)、聚四氟乙烯为主的聚烯烃(PO)类隔膜、聚酯膜(例如聚对苯二甲酸二乙酯(PET)膜)、纤维素膜、聚酰亚胺膜(PI)、聚酰胺膜(PA)、氨纶、芳纶膜、织造膜、非织造膜(无纺布)、微孔膜、复合膜、隔膜纸、碾压膜或纺丝膜中的至少一种，优选为PP。本申请的隔离膜可以具有多孔结构，孔径的尺寸没有特别限制，只要能实现本申请的目的即可，例如，孔径的尺寸可以为0.01μm至1μm。在本申请中，隔离膜的厚度没有特别限制，只要能实现本申请的目的即可，例如厚度可以为5μm至500μm。
例如，隔离膜可以包括基材层和表面处理层。基材层可以为具有多孔结构的无纺布、膜或复合膜，基材层的材料可以包括但不限于聚乙烯、聚丙烯、聚对苯二甲酸乙二醇酯或聚酰亚胺中的至少一种。任选地，可以使用聚丙烯多孔膜、聚乙烯多孔膜、聚丙烯无纺布、 聚乙烯无纺布或聚丙烯-聚乙烯-聚丙烯多孔复合膜。任选地，基材层的至少一个表面上设置有表面处理层，表面处理层可以是聚合物层或无机物层，也可以是混合聚合物与无机物所形成的层。
无机物层可以包括但不限于无机颗粒和无机物层粘结剂，本申请对无机颗粒没有特别限制，例如，可以包括但不限于氧化铝、氧化硅、氧化镁、氧化钛、二氧化铪、氧化锡、二氧化铈、氧化镍、氧化锌、氧化钙、氧化锆、氧化钇、碳化硅、勃姆石、氢氧化铝、氢氧化镁、氢氧化钙或硫酸钡中的至少一种。本申请对无机物层粘结剂没有特别限制，例如，可以包括但不限于聚偏氟乙烯、偏氟乙烯-六氟丙烯的共聚物、聚酰胺、聚丙烯腈、聚丙烯酸酯、聚丙烯酸、聚丙烯酸盐、聚乙烯呲咯烷酮、聚乙烯醚、聚甲基丙烯酸甲酯、聚四氟乙烯或聚六氟丙烯中的至少一种。聚合物层中包含聚合物，聚合物的材料可以包括但不限于聚酰胺、聚丙烯腈、丙烯酸酯聚合物、聚丙烯酸、聚丙烯酸盐、聚乙烯呲咯烷酮、聚乙烯醚、聚偏氟乙烯或聚(偏氟乙烯-六氟丙烯)中的至少一种。
本申请的电化学装置没有特别限制，其可以包括发生电化学反应的任何装置。在一些实施方案中，电化学装置可以包括但不限于：锂金属二次电池、锂离子二次电池(锂离子电池)、锂聚合物二次电池或锂离子聚合物二次电池等。
电化学装置的制备过程为本领域技术人员所熟知的，本申请没有特别的限制，例如，可以包括但不限于以下步骤：将正极极片、隔离膜和负极极片按顺序堆叠，并根据需要将其卷绕、折叠等操作得到卷绕结构的电极组件，将电极组件放入包装袋内，将电解液注入包装袋并封口，得到电化学装置；或者，将正极、隔离膜和负极按顺序堆叠，然后用胶带将整个叠片结构的四个角固定好得到叠片结构的电极组件，将电极组件置入包装袋内，将电解液注入包装袋并封口，得到电化学装置。此外，也可以根据需要将防过电流元件、导板等置于包装袋中，从而防止电化学装置内部的压力上升、过充放电。
本申请的第二方面提供了一种电子装置，其包含本申请第一方面提供的电化学装置。本申请提供的电化学装置具有良好的高温性能，从而本申请提供的电子装置具有较长的使用寿命和良好的性能。
本申请的电子装置没有特别限定，其可以是用于现有技术中已知的任何电子装置。在一些实施例中，电子装置可以包括，但不限于，笔记本电脑、笔输入型计算机、移动电脑、电子书播放器、便携式电话、便携式传真机、便携式复印机、便携式打印机、头戴式立体声耳机、录像机、液晶电视、手提式清洁器、便携CD机、迷你光盘、收发机、电子记事 本、计算器、存储卡、便携式录音机、收音机、备用电源、电机、汽车、摩托车、助力自行车、自行车、照明器具、玩具、游戏机、钟表、电动工具、闪光灯、照相机、家庭用大型蓄电池和锂离子电容器等。
本申请提供的电化学装置及电子装置，根据正极活性材料中Co元素的质量百分含量，调节多腈化合物的质量百分含量，进一步通过多腈化合物、Co的配位络合作用及其他添加剂的组合使用，显著提升正极材料高度脱锂后的结构稳定性，抑制Co的溶出，降低活性材料对电解液的氧化，抑制相关副反应，从而有效改善电化学装置在高温下的性能。
当然，实施本申请的任一产品或方法并不一定需要同时达到以上所述的所有优点。
具体实施方式
为使本申请的目的、技术方案、及优点更加清楚明白，以下参照实施例，对本申请进一步详细说明。显然，所描述的实施例仅仅是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员所获得的所有其他技术方案，都属于本申请保护的范围。
需要说明的是，本申请的具体实施方式中，以锂离子电池作为电化学装置的例子来解释本申请，但是本申请的电化学装置并不仅限于锂离子电池。
测试方法和设备：
高温循环性能测试:
将锂离子电池置于45℃恒温箱中，静置30min，使锂离子电池达到恒温。将达到恒温的锂离子电池以1C恒流充电至电压为4.45V，然后以4.45V恒压充电至电流为0.05C，接着以1C恒流放电至电压为2.8V，此为一个充放电循环。以首次放电的容量为100％，反复进行充放电循环，至放电容量衰减至80％时，停止测试，记录循环圈数和锂离子电池厚度膨胀率，作为评价锂离子电池循环性能的指标。
厚度膨胀率＝(循环结束后厚度-初始厚度)/初始厚度×100％。
高温存储性能测试:
将锂离子电池置于25℃恒温箱中，静置30min，使锂离子电池达到恒温。以1C恒流充电至4.45V，恒压充电至电流为0.05C，然后用1C恒流放电至2.8V，记录放电容量，作为锂离子电池初始容量。之后以0.5C恒流充电至4.45V，恒压充电至电流为0.05C，用千分尺测试并记录电池的厚度。将测试锂离子电池转至60℃恒温箱中进行存储90天，期间每隔3天测试并记录电池厚度一次，90天存储结束后将电池转移至25℃恒温箱中，静置 1h，以1C恒流放电至2.8V，记录放电容量，作为锂离子电池剩余容量。以1C恒流充电至4.45V，恒压充电至电流为0.05C，然后用1C恒流放电至2.8V，记录放电容量，作为锂离子电池可恢复容量。测试电池的厚度(THK)，计算锂离子电池存储厚度膨胀率，并作为评价锂离子电池高温存储产气量的指标。
厚度膨胀率＝[(存储24小时厚度-初始厚度)/初始厚度]×100％。
0℃直流阻抗(DCR)测试：
将锂离子电池置于0℃低温箱中，静置4h，使锂离子电池达到恒温。以0.1C恒流充电至电压为4.45V，恒压充电至电流为0.05C，静置10min。然后用0.1C恒流放电至3.4V，记录此容量为实际放电容量D 0。随后静置5min，以0.1C恒流充电至4.45V，恒压充电至电流为0.05C(电流以D 0对应容量计算)。静置10min，用0.1C恒流放电3h(电流以D 0对应容量计算)，记录此时电压V1。接着，用1C恒流放电1s(10ms采点，电流以电芯标注容量对应计算)，记录此时电压V2。然后计算电芯70％剩余电量(SOC)状态对应直流阻抗，计算公式如下：
70％SOC DCR＝(V2-V1)/1C。
过充测试：
将锂离子电池在25℃下以0.5C放电至2.8V，再以2C恒流充电至5V，再恒压充电3h，监控电芯表面温度变化，通过标准为电芯不起火、不燃烧、不爆炸。
日历寿命(ITC)测试：
将锂离子电池置于45℃恒温箱中，静置30min，使锂离子电池达到恒温。将达到恒温的锂离子电池以1C恒流充电至电压为4.45V，以4.45V恒压充电至电流为0.05C，用千分尺测试并记录电池的初始厚度，在45℃下静置24h，接着以1C恒流放电至电压为2.8V，此为一个充放电循环。以首次放电的容量为100％，反复进行充放电循环，至放电容量衰减至80％时，停止测试。停止测试前，将锂离子电池放入25℃恒温箱中，静置30min，使锂离子电池达到恒温。将达到恒温的锂离子电池以1C恒流充电至电压为4.45V，以4.45V恒压充电至电流为0.05C(用千分尺测试并记录电池的循环后厚度)，并记录循环圈数，作为评价锂离子电池日历寿命的指标。
厚度膨胀率＝[(循环结束后厚度-初始厚度)/初始厚度]×100％。
浮充性能测试(CV测试)：
将锂离子电池置于25℃恒温箱中，静置30min，使锂离子电池达到恒温。以1C恒流 充电至电压为4.45V，恒压充电至电流为0.05C，用千分尺测试并记录电池的初始厚度。将测试锂离子电池转至45℃恒温箱中以1C的电流持续充电60天，结束后将电池转移至25℃恒温箱中，测试并记录电池厚度为浮充60天厚度。计算锂离子电池浮充测试过程中厚度膨胀率，并作为评价锂离子电池浮充性能的指标。
厚度膨胀率＝[(浮充60天厚度-初始厚度)/初始厚度]×100％。
正极极片热稳定性测试(DSC测试)：
将锂离子电池置于25℃恒温箱中，静置30min，使锂离子电池达到恒温。以1C恒流充电至4.45V，恒压充电至电流为0.05C。拆下电池正极极片后，放入碳酸二甲酯(DMC)中浸泡24h后，采用差示扫描量热仪进行DSC测试，以2℃/min的速率加热至400℃，并记录正极极片的主要热反应峰及对应温度T。
实施例1-1
(1)正极极片的制备
将正极活性材料锂镍锰钴三元材料(NCM613)、导电剂Super P、粘结剂聚偏二氟乙烯按照重量比97:1.4:1.6进行混合，加入N-甲基吡咯烷酮(NMP)，在真空搅拌机作用下搅拌至体系成均一透明状，固含量为72wt％的正极浆料；将正极浆料均匀涂覆于厚度为12μm的正极集流体铝箔上；将铝箔在85℃下烘干，冷压后得到正极活性材料层厚度为100μm的正极极片，然后在该正极极片的另一个表面上重复以上步骤，得到双面涂布有正极活性材料层的正极极片。将正极极片裁切成74mm×867mm的规格并焊接极耳后待用。
(2)负极极片的制备
将负极活性材料人造石墨、导电剂Super P、羧甲基纤维素钠(CMC)、丁苯橡胶(SBR)按质量比96.4:1.5:0.5:1.6混合，然后加入去离子水作为溶剂，调配成固含量为54wt％的浆料，并搅拌均匀。将浆料均匀涂布在厚度为8μm的铜箔的一个表面上，110℃条件下烘干，冷压后得到负极活性材料层厚度为150μm的单面涂布负极活性材料层的负极极片，然后在该负极极片的另一个表面上重复以上涂布步骤，得到双面涂布有负极活性材料层的负极极片。将负极极片裁切成(74mm×867mm)的规格并焊接极耳后待用。
(3)电解液的制备
在含水量<10ppm的氩气气氛手套箱中，将碳酸亚乙酯(EC)、碳酸亚丙酯(PC)、碳酸甲乙酯(EMC)、碳酸二乙酯(DEC)按照质量比为EC:PC:EMC:DEC＝10:30:30:30均匀混合，形成基础溶剂，然后按表1加入多腈化合物和锂盐LiPF 6，溶解并搅拌均匀，得到 电解液，其中多腈化合物包括己二腈(AND)、1,2-双(氰乙氧基)乙烷(DENE)和1,3,6-己烷三腈(HTCN)，上述多腈化合物的质量比为AND:DENE:HTCN＝1:1:1，其中，LiPF 6的质量百分含量为12.5％。
(4)隔离膜
以7μm厚的聚乙烯多孔聚合物薄膜为隔离膜。
(5)锂离子电池的制备
将正极片、隔离膜、负极片按顺序叠好，使隔离膜处于正、负极片之间起到隔离的作用，然后卷绕得到裸电芯；焊接极耳后将裸电芯置于外包装箔铝塑膜中，将铝箔袋边缘封装，然后放置在85℃真空烘箱中干燥12h，将干电芯中的水分去除，最后将上述制备好的电解液注入到干燥后的裸电芯中，经过真空封装、静置、化成、成形等工序，完成锂离子电池的制备(厚度3.3mm、宽度39mm、长度96mm)。
实施例1-2至实施例1-13
除了相关制备参数和性能参数如表1所示以外，其余与实施例1-1相同。
对比例1-1至对比例1-7
除了相关制备参数和性能参数如表1所示以外，其余与实施例1-1相同。
表1
Figure PCTCN2022122164-appb-000001
Figure PCTCN2022122164-appb-000002
从实施例1-1至实施例1-13和对比例1-1至对比例1-7可以看出，正极活性材料中Co元素和多腈化合物通常会影响锂离子电池的高温循环性能和高温存储性能，选用正极活性材料中Co元素的质量百分含量a和多腈化合物的质量百分含量b％在本申请范围内，同时b和a满足本申请权利要求1关系式的锂离子电池，由于多腈化合物中的氰基与Co之间的络合作用，强化了结构的稳定性，所制备的锂离子电池具有良好的ITC、高温循环和高温存储性能。
实施例2-1至实施例2-10
除了相关制备参数和性能参数如表2所示以外，其余与实施例1-5相同。
表2
Figure PCTCN2022122164-appb-000003
Figure PCTCN2022122164-appb-000004
表2中，“/”表示不存在相应的制备参数。
从实施例2-1至实施例2-10中可以看出，多睛化合物的种类和质量百分含量通常也会影响锂离子电池的高温性能。多腈化合物的质量百分含量，以及二腈化合物的质量百分含量和三腈化合物的质量百分含量的比值(b1/b2)，会影响锂离子电池的高温循环性能和高温存储性能，从实施例2-1至实施例2-5可以看出，随着多腈化合物中三腈化合物比例的增大，锂离子电池的高温循环性能和高温存储性能得到更好地改善。
实施例3-1至实施例3-8
除了相关的制备参数和性能参数如表3所示以外，其余与实施例1-3相同，其中，在变化EC的质量百分含量过程中，保持EC的质量百分含量与PC的质量百分含量之和为40％。
对比例3-1
除了相关的制备参数和性能参数如表3所示以外，其余与实施例1-3相同。
表3
Figure PCTCN2022122164-appb-000005
Figure PCTCN2022122164-appb-000006
从实施例3-1至实施例3-8和对比例3-1可以看出，多睛化合物和EC通常也会影响锂离子电池的高温循环性能和高温存储性能，选用含有多腈化合物和EC，同时多腈化合物的质量百分含量和EC的质量百分含量的比值(c/b)在本申请范围内的的锂离子电池，具有更好的高温循环性能和高温存储性能。
实施例4-1至实施例4-5
除了按照表4调整LiPO 2F 2的质量百分含量以外，其余与实施例1-4相同。
表4
Figure PCTCN2022122164-appb-000007
从实施例4-1至实施例4-5可以看出，LiPO 2F 2通常也会影响锂离子电池的高温循环性能和高温存储性能，随着LiPO 2F 2质量百分含量的提高，由于LiPO 2F 2在正极表面形成低阻抗的正极-电解质界面(CEI)，抑制Co的溶出，同时在负极形成稳定的SEI膜，有效改善了锂离子电池的高温循环和ITC性能，而且由于LiPO 2F 2的强吸水性，与多腈化合物协同使用，可以更好地发挥多腈化合物的作用，改善锂离子电池的高温存储和高温循环性能。
进一步对实施例1-4至实施例1-7制备的锂离子电池满充拆解后得到正极极片，对正极极片进行DSC测试，得到的性能测试结果如表5所示。
表5
Figure PCTCN2022122164-appb-000008
从实施例1-4至实施例1-7正极极片的DSC测试结果可以看出，由于多腈化合物对Co的配位络合作用，提升了正极活性材料的稳定性，正极脱锂的热失效温度随着多腈化合物加入而显著升高。
实施例5-1至实施例5-7
除了按照表6加入氟代碳酸乙烯酯(FEC)、碳酸亚乙烯酯(VC)、亚硫酸丙烯酯(PS)、硫酸亚乙酯(DTD)、二氟草酸硼酸锂(LiDFOB)或双草酸硼酸锂(LiBOB)并调整相应物质的质量百分含量以外，其余与实施例1-4相同。
表6
Figure PCTCN2022122164-appb-000009
Figure PCTCN2022122164-appb-000010
表6中，“/”表示不存在相应的制备参数。
从实施例5-1至实施例5-7可以看出，选用同时含有FEC、VC、PS、DTD、LiDFOB、LiBOB作为添加剂的锂离子电池，可以在正极和负极表面形成稳定的CEI和SEI膜，抑制正极、负极和电解液之间的副反应，同时由于添加剂与多腈化合物之间的协同作用，可以有效抑制多腈化合物在负极界面还原分解对SEI膜的破坏，能够更好地提升锂离子电池的高温循环性能、浮充性能、安全性能和高温存储性能，同时还能降低锂离子电池的直流阻抗。
以上所述仅为本申请的较佳实施例，并非用于限定本申请的保护范围。凡在本申请的精神和原则之内所作的任何修改、等同替换、改进等，均包含在本申请的保护范围内。

Claims (11)

  1. 一种电化学装置，其包括正极极片、负极极片、隔离膜及电解液，其中，所述正极极片包含正极活性材料，所述正极活性材料包含Co元素，基于所述正极活性材料的总质量，所述Co元素的质量百分含量为a；所述电解液包含多腈化合物，基于所述电解液的总质量，所述多腈化合物的质量百分含量为b％，所述多腈化合物的质量百分含量b％与所述Co元素的质量百分含量a满足关系：b＝9.7a-0.07+C，-1.5<C≤1.5，0<a≤0.65。
  2. 根据权利要求1所述的电化学装置，其中，基于所述电解液的总质量，所述多腈化合物的质量百分含量b％满足：0<b≤7。
  3. 根据权利要求1所述的电化学装置，其中，所述多腈化合物包含二腈化合物和/或三腈化合物，基于所述电解液的总质量，所述二腈化合物的质量百分含量为b1％，所述三腈化合物的质量百分含量为b2％，b1和b2满足：0≤b1/b2≤4。
  4. 根据权利要求3所述的电化学装置，其中，所述二腈化合物包括丁二腈、己二腈、1,2-双(氰乙氧基)乙烷或1,4-二氰基-2-丁烯中的至少一种，所述三腈化合物包括1,3,6-己烷三腈或1,2,3-三(2-氰氧基)丙烷中的至少一种。
  5. 根据权利要求1所述的电化学装置，其中，所述电解液满足以下条件的至少一者：
    (1)所述电解液还包含碳酸亚乙酯，基于所述电解液的总质量，所述碳酸亚乙酯的质量百分含量为c％，c满足：0.5≤c/b≤20，3≤c≤30；
    (2)所述电解液包含二氟磷酸锂，基于所述电解液的总质量，所述二氟磷酸锂的质量百分含量为d％，d满足：0.01≤d≤1；
    (3)所述电解液包含二氟磷酸锂，基于所述电解液的总质量，所述二氟磷酸锂的质量百分含量为d％，d满足：0.015≤d/a；
    (4)所述电解液包含氟代碳酸乙烯酯、碳酸亚乙烯酯、亚硫酸丙烯酯、硫酸亚乙酯、二氟草酸硼酸锂或双草酸硼酸锂中的至少一种。
  6. 根据权利要求1所述的电化学装置，其中，所述电解液包含锂盐，所述锂盐包含无机锂盐或有机锂盐中的至少一种，基于所述电解液的总质量，所述锂盐的质量百分含量为7.5％至25％。
  7. 根据权利要求6所述的电化学装置，其中，所述锂盐包括六氟磷酸锂、四氟硼酸锂、六氟砷酸锂、高氯酸锂、双氟磺酰亚胺锂、双三氟甲烷磺酰亚胺锂中的至少一种。
  8. 根据权利要求1所述的电化学装置，其中，所述电解液还包含碳酸二甲酯、碳酸甲 乙酯、碳酸二乙酯、碳酸亚丙酯、乙酸乙酯、丙酸乙酯、丙酸丙酯中的至少一种。
  9. 根据权利要求1所述的电化学装置，其中，所述正极极片的差式扫描量热曲线包含至少一个放热主峰。
  10. 根据权利要求9所述的电化学装置，其中，在所述差示扫描量热曲线上，所述放热主峰温度为T℃，T满足：T＝10b+267+X，-20≤X≤20，0<b≤7，200≤T≤360。
  11. 一种电子装置，其包含权利要求1-10中任一项所述的电化学装置。
PCT/CN2022/122164 2021-11-18 2022-09-28 一种电化学装置及电子装置 Ceased WO2023087937A1 (zh)

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