WO2023087223A1 - Électrolyte, dispositif électrochimique le contenant, et dispositif électronique - Google Patents

Électrolyte, dispositif électrochimique le contenant, et dispositif électronique Download PDF

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Publication number
WO2023087223A1
WO2023087223A1 PCT/CN2021/131558 CN2021131558W WO2023087223A1 WO 2023087223 A1 WO2023087223 A1 WO 2023087223A1 CN 2021131558 W CN2021131558 W CN 2021131558W WO 2023087223 A1 WO2023087223 A1 WO 2023087223A1
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formula
lithium
electrolyte
substituted
unsubstituted
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PCT/CN2021/131558
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English (en)
Chinese (zh)
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彭谢学
唐超
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宁德新能源科技有限公司
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Priority to PCT/CN2021/131558 priority Critical patent/WO2023087223A1/fr
Priority to CN202180007386.7A priority patent/CN114846668B/zh
Publication of WO2023087223A1 publication Critical patent/WO2023087223A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—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
    • 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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic 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

Definitions

  • the present application relates to the technical field of electrochemistry, and in particular to an electrolytic solution and electrochemical devices and electronic devices containing the electrolytic solution.
  • Lithium-ion batteries have the advantages of high energy storage density, high open circuit voltage, low self-discharge rate, long cycle life, and good safety. They have been widely used as power sources in cameras, mobile phones, drones, laptops, and smart watches product.
  • the purpose of the present application is to provide an electrolytic solution, an electrochemical device and an electronic device containing the electrolytic solution, so as to improve the high-temperature storage performance and cycle performance of the electrochemical device.
  • the first aspect of the present application provides an electrolyte, which includes the cyano compound represented by formula (I) and formula (II):
  • A is independently selected from formula (I-A) or formula (II-A),
  • n are each independently selected from 0 or 1;
  • R 1 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 are each independently selected from covalent single bonds, substituted or unsubstituted C 1 to C 10 Alkylene or heterocyclylene, substituted or unsubstituted C 2 to C 10 alkenylene or alkynylene, substituted or unsubstituted C 3 to C 10 allenylene or alicyclic hydrocarbon group, In the substituted or unsubstituted C6 to C10 arylene group, the substituents of each group are independently selected from fluorine, chlorine, bromine or iodine.
  • the compound represented by the formula (I) comprises at least one of the following compounds:
  • the compound represented by the formula (II) comprises at least one of the following compounds:
  • the mass percentage of the compound represented by formula (I) is W 1
  • the mass percentage of the compound represented by formula (II) is W 2 satisfies: 0.01% ⁇ W 1 ⁇ 5%, 0.001% ⁇ W 2 ⁇ 5%, 0.1% ⁇ W 1 +W 2 ⁇ 5%.
  • the electrolyte also includes polynitrile compounds, and the polynitrile compounds include at least one of the following compounds:
  • the mass percentage of the compound represented by the formula (I) is W 1
  • the mass percentage of the compound represented by the formula (II) The percentage content is W 2
  • the mass percentage content of the polynitrile compound is W 3 , satisfying: 0.5% ⁇ W 3 ⁇ 7%, 0.01 ⁇ (W 1 +W 2 )/W 3 ⁇ 1.
  • the electrolytic solution further includes a boron-based lithium salt compound
  • the boron-based lithium salt compound includes lithium tetrafluoroborate (LiBF 4 ), lithium dioxalate borate (LiBOB) or bis At least one of lithium fluorooxalate borate (LiDFOB).
  • the mass percentage W 4 of the boron-based lithium salt compound is 0.1% to 1%.
  • the electrolyte solution further includes a P-O bond compound
  • the P-O bond compound includes lithium difluorophosphate, lithium difluorobisoxalate phosphate, lithium tetrafluorooxalate phosphate, 1, 2-bis((difluorophosphino)oxy)ethane, trimethylphosphate, triphenylphosphate, triisopropylphosphate, 3,3,3-trifluoroethylphosphate, 3, 3,3-trifluoroethyl phosphite, tris(trimethylsilyl) phosphate, 2-(2,2,2-trifluoroethoxy)-1,3,2-dioxaphosphorane2 - at least one of oxides.
  • the mass percentage W 5 of the PO bond compound is 0.1% to 1%.
  • the electrolyte further includes a sulfur-oxygen double bond compound, and the sulfur-oxygen double bond compound includes at least one of the compounds represented by formula (IV):
  • A is selected from at least one of formula (IV-A), formula (IV-B), formula (IV-C), formula (IV-D), and formula (IV-E):
  • R 41 and R 42 are each independently selected from a covalent bond, a substituted or unsubstituted C 1 to C 5 alkyl or alkylene group, a substituted or unsubstituted C 1 to C 6 heterocyclic group, a substituted or unsubstituted Substituted C 2 to C 10 alkenyl or alkynyl, substituted or unsubstituted C 3 to C 10 alicyclic group, and R 41 and R 42 may be connected to form a ring;
  • R 43 is selected from a covalent bond, a substituted or unsubstituted C 1 to C 3 alkylene group, a substituted or unsubstituted C 2 to C 3 alkenylene or alkynylene group;
  • the substituent is selected from halogen, substituted or unsubstituted C1 to C3 alkyl, substituted or unsubstituted C2 to C3 alkenyl, substituted or unsubstituted C2 to C3 alkynyl;
  • heteroatom is selected from at least one of N, O or S;
  • the mass percentage W 6 of the compound represented by the formula (IV) is 0.1% to 8%.
  • the compound represented by formula (IV) comprises at least one of the following compounds:
  • the electrolyte also includes a cyclic carbonate compound, and the cyclic carbonate compound includes at least one of the following compounds:
  • the mass percentage W 7 of the cyclic carbonate compound is 0.1% to 10%
  • the electrolyte solution contains lithium salts, and the lithium salts include lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bisoxalate borate, lithium difluorooxalate borate, lithium hexafluoroantimonate, lithium hexafluoroarsenate, lithium perfluorobutyl sulfonate , lithium perchlorate, lithium aluminate, lithium tetrachloroaluminate, lithium bissulfonylimide (LiN(C x F 2x+1 SO 2 )(C y F 2y+1 SO 2 ), where x is 0 to 10, y is a natural number from 0 to 10), at least one of lithium chloride and lithium fluoride, based on the total mass of the electrolyte, the mass percentage W of the lithium salt is 10% to 8 20%.
  • the lithium salts include lithium hexafluorophosphate, lithium tetrafluoroborate, lithium biso
  • the second aspect of the present application provides an electrochemical device, which includes the electrolyte solution provided in the first aspect of the present application.
  • the third aspect of the present application provides an electronic device, which includes the electrochemical device provided in the second aspect of the present application.
  • the present application provides an electrolytic solution and an electrochemical device and an electronic device containing the electrolytic solution, wherein the electrolytic solution includes cyano compounds represented by formula (I) and formula (II).
  • the electrolytic solution includes cyano compounds represented by formula (I) and formula (II).
  • Adding the cyano compound represented by formula (I) and formula (II) to the electrolyte can not only stabilize the transition metal in the positive and extremely high valence state, but also absorb the oxygen released from the positive electrode and inhibit the continuous decomposition of the electrolyte; it can also be used on the positive and negative electrodes Form an interface protective film to protect the surface of the positive and negative electrodes, thereby significantly improving the high-temperature storage performance and cycle performance of the electrochemical device.
  • An electronic device including the electrochemical device also has good high-temperature storage performance and cycle performance.
  • 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. It should be understood by those skilled in the art that the following description is only for illustration and does not limit the protection scope of the present application.
  • the first aspect of the present application provides an electrolyte, which includes the cyano compound represented by formula (I) and formula (II):
  • A is independently selected from formula (I-A) or formula (II-A),
  • n are each independently selected from 0 or 1;
  • R 1 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 are each independently selected from covalent single bonds, substituted or unsubstituted C 1 to C 10 Alkylene or heterocyclylene, substituted or unsubstituted C 2 to C 10 alkenylene or alkynylene, substituted or unsubstituted C 3 to C 10 allenylene or alicyclic hydrocarbon group, In the substituted or unsubstituted C 6 to C 10 arylene group, the substituents of each group are independently selected from fluorine, chlorine, bromine or iodine.
  • the cyano compounds represented by formula (I) and formula (II) in the present application have different spatial structures of cyano compound molecules with different numbers of cyano groups, and thus have different improvement effects on electrochemical devices.
  • the cyano compound represented by formula (I) and formula (II) is added to the electrolyte, which can stabilize the transition metal in the positive high-valence state, absorb the oxygen released from the positive electrode, and inhibit the continuous decomposition of the electrolyte.
  • the negative electrode forms an interface protective film to protect the surface of the positive and negative electrodes, thereby improving the high-temperature storage performance and cycle performance of the electrochemical device.
  • the compound represented by the formula (I) comprises at least one of the following compounds:
  • the compound represented by the formula (II) comprises at least one of the following compounds:
  • the electrolyte contains at least one of the compounds of formula (I-1) to formula (I-9), so that the compounds represented by formula (I) with different structures act together, In order to further improve the cycle performance and high-temperature storage performance of the electrochemical device without affecting other performances.
  • the electrolyte contains at least one of the compounds of formula (II-1) to formula (II-16), so that the compounds represented by formula (II) with different structures act together, In order to further improve the cycle performance and high-temperature storage performance of the electrochemical device without affecting other performances.
  • the mass percentage of the compound represented by formula (I) is W 1
  • the mass percentage of the compound represented by formula (II) is W 2 satisfies: 0.01% ⁇ W 1 ⁇ 5%, 0.001% ⁇ W 2 ⁇ 5%, 0.1% ⁇ W 1 +W 2 ⁇ 5%.
  • the value of W1 can be 0.01%, 0.05%, 0.1%, 0.5%, 1.5%, 3%, 5% or any value between the above-mentioned any two numerical ranges;
  • the value of W2 can be 0.001%, 0.005%, 0.01%, 0.05%, 0.1%, 0.5%, 1.5%, 3%, 5%, or any value between any two value ranges above;
  • W 1 +W 2 must satisfy 0.1% ⁇ W 1 + W 2 ⁇ 5%
  • the value of W 1 +W 2 can be 0.1%, 0.15%, 0.2%, 0.5%, 1%, 2.1%, 2.5%, 3.5%, 4%, 4.5%, 5% or any of the above Any value between the two value ranges.
  • the electrolyte also includes polynitrile compounds, and the polynitrile compounds include at least one of the following compounds:
  • the cycle performance and high-temperature storage performance of the electrochemical device can be further improved.
  • the mass percentage of the compound represented by the formula (I) is W 1
  • the mass percentage of the compound represented by the formula (II) The percentage content is W 2
  • the mass percentage content of the polynitrile compound is W 3 , satisfying: 0.5% ⁇ W 3 ⁇ 7%, 0.01 ⁇ (W 1 +W 2 )/W 3 ⁇ 1.
  • the value of the mass percent content W of described polynitrile compound can be 0.5%, 1%, 1.5%, 2% , 3%, 4%, 4.5%, 5%, 5.5%, 6, 6.5%, 7% % or any value between any two value ranges above.
  • the electrolytic solution further includes a boron-based lithium salt compound
  • the boron-based lithium salt compound includes lithium tetrafluoroborate (LiBF 4 ), lithium dioxalate borate (LiBOB) or bis At least one of lithium fluorooxalate borate (LiDFOB).
  • LiBF 4 lithium tetrafluoroborate
  • LiBOB lithium dioxalate borate
  • LiDFOB bis At least one of lithium fluorooxalate borate
  • a stable solid electrolyte interface (SEI) film can also be formed on the negative electrode to prevent the transition metals dissolved in the positive electrode from damaging the negative electrode.
  • SEI solid electrolyte interface
  • the mass percentage W 4 of the boron-based lithium salt compound is 0.1% to 1%.
  • the value of W 4 may be 0.1%, 0.2%, 0.3%, 0.5%, 0.8%, 1%, or any value between any two value ranges mentioned above.
  • the mass percentage W of the boron-type lithium salt compound is too high (for example, higher than 1%), it is difficult to be completely consumed in the formation stage of the electrochemical device, and a large amount of gas is generated during the storage of the electrochemical device, which affects the electrochemical device. high temperature storage performance. By controlling the value of W4 within the above range, the cycle performance and high-temperature storage performance of the electrochemical device can be effectively improved.
  • the electrolyte solution further includes a PO bond compound
  • the PO bond compound includes lithium difluorophosphate (LiPO 2 F 2 ), lithium difluorobisoxalate phosphate (LiDFOP) , lithium tetrafluorooxalate phosphate (LiTFOP), 1,2-bis((difluorophosphino)oxy)ethane, trimethyl phosphate, triphenyl phosphate, triisopropyl phosphate, 3,3 ,3-Trifluoroethyl phosphate, 3,3,3-trifluoroethyl phosphite, tris(trimethylsilane) phosphate, 2-(2,2,2-trifluoroethoxy)- At least one of 1,3,2-dioxaphosphane 2-oxides.
  • the contact between the electrolyte and the positive and negative electrodes can be reduced, and gas production
  • the mass percentage W 5 of the PO bond compound is 0.1% to 1%.
  • the electrolyte further includes a sulfur-oxygen double bond compound, and the sulfur-oxygen double bond compound includes at least one of the compounds represented by formula (IV):
  • A is selected from at least one of formula (IV-A), formula (IV-B), formula (IV-C), formula (IV-D), and formula (IV-E):
  • R 41 and R 42 are each independently selected from a covalent bond, a substituted or unsubstituted C 1 to C 5 alkyl or alkylene group, a substituted or unsubstituted C 1 to C 6 heterocyclic group, a substituted or unsubstituted Substituted C 2 to C 10 alkenyl or alkynyl, substituted or unsubstituted C 3 to C 10 alicyclic group, and R 41 and R 42 may be connected to form a ring;
  • R 43 is selected from a covalent bond, a substituted or unsubstituted C 1 to C 3 alkylene group, a substituted or unsubstituted C 2 to C 3 alkenylene or alkynylene group;
  • the substituent is selected from halogen, substituted or unsubstituted C1 to C3 alkyl, substituted or unsubstituted C2 to C3 alkenyl, substituted or unsubstituted C2 to C3 alkynyl;
  • heteroatom is selected from at least one of N, O or S;
  • the mass percentage W 6 of the compound represented by the formula (IV) is 0.1% to 8%.
  • the value of W6 can be 0.1%, 0.3%, 0.5%, 1%, 1.5%, 2%, 3%, 5%, 6%, 7%, 7.5%, 8%, or any two of the above numerical ranges Any value in between, for example, can be 1.5% to 6%.
  • the mass percentage W of the compound represented by formula (IV) is too high (such as higher than 8%), and it is easy to form an acidic substance, corrode the positive electrode electrolyte interface (CEI) film and the positive electrode material layer, and affect the stability of the positive electrode material structure. And then affect the cycle performance of the electrochemical device.
  • CEI positive electrode electrolyte interface
  • the sulfur-oxygen double bond compound has strong anti-oxidation ability, can protect the stability of the positive electrode interface, and can also be reduced on the surface of the negative electrode to form a protective film, inhibit the decomposition of the electrolyte, and further enhance the stability of the interface. performance, thereby further improving the high-temperature storage performance and cycle performance of the electrochemical device.
  • the compound represented by formula (IV) comprises at least one of the following compounds:
  • the electrolyte solution of the present application contains at least one of the compound formula (IV-1) to formula (IV-41), so that the sulfur-oxygen double bond compounds with different structures can work together to further Improve cycle performance and high-temperature storage performance of electrochemical devices.
  • the electrolyte also includes a cyclic carbonate compound, and the cyclic carbonate compound includes at least one of the following compounds:
  • the mass percentage W 7 of the cyclic carbonate compound is 0.1% to 10%.
  • the value of W7 can be 0.1%, 0.5%, 1%, 1.5%, 2%, 3%, 5%, 6%, 7%, 8%, 8.5%, 9%, 10%, or any two of the above Any value within a range of values, for example, may be 1% to 6%.
  • the cyclic carbonate compounds can enhance the stability of SEI film formation, and the use of cyclic carbonate compounds can increase the flexibility of the SEI film, further increase the protective effect of the active material, and reduce the interaction between the active material and the electrolyte.
  • the probability of interfacial contact is improved, thereby improving the impedance growth caused by the accumulation of by-products during the cycle, and improving the cycle performance of the electrochemical device.
  • the electrolyte solution contains a lithium salt
  • the lithium salt includes lithium hexafluorophosphate (LiPF 6 ), lithium bissulfonylimide (LiN(C x F 2x+1 SO 2 ) ( C y F 2y+1 SO 2 ), where x is a natural number from 0 to 10, and y is a natural number from 0 to 10), lithium perchlorate (LiClO 4 ), lithium hexafluoroantimonate (LiSbF 6 ), hexafluoroarsenic At least one of lithium salts (LiAsF 6 ), the mass percentage W 8 of the lithium salt is 10% to 20%.
  • the electrolyte solution may contain LiPF 6 , because LiPF 6 can give high ion conductivity and improve the cycle performance of the lithium ion battery.
  • LiPF 6 can give high ion conductivity and improve the cycle performance of the lithium ion battery.
  • the inventors of the present application found that by adjusting the mass percentage of lithium salt within the above range, it is beneficial to improve the electrical conductivity during the cycle of the electrochemical device, thereby improving the cycle performance of the electrochemical device.
  • the electrolyte solution may also contain other non-aqueous solvents.
  • This application has no special restrictions on other non-aqueous solvents, as long as the purpose of this application can be achieved, for example, it may include but not limited to carboxylate compounds, ethers Compound or at least one of other organic solvents.
  • carboxylic acid ester compounds may include but not limited to methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, butyl Methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate, ⁇ -butyrolactone, 2,2-difluoroethyl acetate, valerolactone, butyrolactone, ethyl 2-fluoroacetate, At least one of ethyl 2,2-difluoroacetate or ethyl trifluoroacetate.
  • the aforementioned ether compounds may include, but are not limited to, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, dibutyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, bis(2,2, At least one of 2-trifluoroethyl) ether, 1,3-dioxane or 1,4-dioxane.
  • the above-mentioned other organic solvents may include but not limited to ethyl vinyl sulfone, methyl isopropyl sulfone, isopropyl sec-butyl sulfone, sulfolane, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methylpropyl carbonate At least one of ester, ethylene propyl carbonate, dipropyl carbonate, ethylene carbonate, propylene carbonate, butylene carbonate, bis(2,2,2-trifluoroethyl) carbonate.
  • the total content of the above-mentioned other non-aqueous solvents is 5% to 80%, such as 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50% %, 55%, 60%, 65%, 70%, 75%, 80%, or any range therebetween.
  • the second aspect of the present application provides an electrochemical device, which includes the electrolyte solution provided in the first aspect of the present application.
  • the electrochemical device has good cycle performance and high-temperature storage performance.
  • the electrochemical device of the present application also includes an electrode assembly, which may include a separator, a positive electrode, and a negative electrode.
  • the separator is used to separate the positive electrode and the negative electrode to prevent the internal short circuit of the electrochemical device, which allows the electrolyte ions to pass freely to complete the electrochemical charge and discharge process.
  • the present application has no particular limitation on the number of separators, positive electrodes and negative electrodes, as long as the purpose of the present application can be achieved.
  • the present application has no particular limitation on the structure of the electrode assembly, as long as the purpose of the present application can be achieved.
  • the structure of the electrode assembly may include a wound structure or a laminated structure.
  • the positive electrode of the present application is not particularly limited, as long as the purpose of the present application can be achieved.
  • the positive electrode includes a positive electrode current collector and a positive electrode material layer.
  • the present application has no special limitation on the positive electrode current collector, as long as the purpose of the present application can be achieved.
  • the positive electrode current collector may include aluminum foil, aluminum alloy foil, or a composite current collector.
  • the positive electrode material layer of the present application contains the positive electrode material.
  • the present application has no particular limitation on the type of positive electrode material, as long as the purpose of the present application can be achieved.
  • the positive electrode material may include lithium nickel cobalt manganate (811, 622, 523, 111), lithium nickel cobalt aluminate, lithium iron phosphate, lithium-rich manganese-based materials, lithium cobalt oxide, lithium manganate, lithium manganese iron phosphate or At least one of lithium titanate and the like.
  • the positive electrode material may also contain non-metallic elements, for example, non-metallic elements include at least one of fluorine, phosphorus, boron, chlorine, silicon, sulfur, etc., and these elements can further improve the stability of the positive electrode material.
  • there is no particular limitation on the thickness of the positive electrode current collector and the positive electrode material layer as long as the purpose of the present application can be achieved.
  • the thickness of the positive electrode collector is 5 ⁇ m to 20 ⁇ m, preferably 6 ⁇ m to 18 ⁇ m.
  • the thickness of the single-sided positive electrode material layer is 30 ⁇ m to 120 ⁇ 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 sheet may further include a conductive layer, and the conductive layer is located between the positive electrode current collector and the positive electrode material layer.
  • the composition of the conductive layer is not particularly limited, and may be a commonly used conductive layer in the field.
  • 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 purpose of the present application can be achieved.
  • the negative electrode includes a negative electrode current collector and a negative electrode material layer.
  • the present application has no particular limitation on the negative electrode collector, as long as the purpose of the present application can be achieved.
  • the negative electrode current collector may include copper foil, copper alloy foil, nickel foil, stainless steel foil, titanium foil, nickel foam, copper foam, or a composite current collector.
  • the negative electrode material layer of the present application contains the negative electrode material.
  • the present application has no particular limitation on the type of negative electrode material, as long as the purpose of the present application can be achieved.
  • the negative electrode material can include natural graphite, artificial graphite, mesophase microcarbon spheres (MCMB), hard carbon, soft carbon, silicon, silicon-carbon composite, SiO x (0 ⁇ x ⁇ 2), and metal lithium, etc. at least one of .
  • MCMB mesophase microcarbon spheres
  • the thickness of the negative electrode current collector and the negative electrode material layer there is no particular limitation on the thickness of the negative electrode current collector and the negative electrode material layer, as long as the purpose of the present application can be achieved.
  • the thickness of the negative electrode current collector is 6 ⁇ m to 10 ⁇ m
  • the thickness of the single-sided negative electrode material layer is 30 ⁇ m to 130 ⁇ m.
  • 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 sheet may further include a conductive layer, and the conductive layer is located between the negative electrode current collector and the negative electrode material layer.
  • the composition of the conductive layer is not particularly limited, and may be a commonly used conductive layer in the field.
  • the conductive layer includes a conductive agent and a binder.
  • the conductive agent mentioned above is not particularly limited, as long as the purpose of the present application can be achieved.
  • the conductive agent can 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 A sort of.
  • the binder may include polyacryl alcohol, sodium polyacrylate, potassium polyacrylate, lithium polyacrylate, polyimide, polyimide, polyamideimide, styrene-butadiene rubber (SBR), polyvinyl alcohol ( PVA), polyvinylidene fluoride, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl butyral (PVB), water-based acrylic resin, carboxymethyl cellulose (CMC) or carboxymethyl At least one of base cellulose sodium (CMC-Na) and the like.
  • SBR styrene-butadiene rubber
  • PVA polyvinyl alcohol
  • PVDF polyvinylidene fluoride
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • PVB polyvinyl butyral
  • water-based acrylic resin carboxymethyl cellulose (CMC) or carboxymethyl At least one of base cellulose sodium (CMC-
  • the lithium-ion battery of the present application also includes a separator, and the present application has no special limitation on the separator, as long as the purpose of the present application can be achieved.
  • 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 polyethylene (PE), polypropylene (PP), polyethylene terephthalate and polyimide at least one of amines and the like.
  • a polypropylene porous film, a polyethylene porous film, a polypropylene non-woven fabric, a polyethylene non-woven fabric, or a polypropylene-polyethylene-polypropylene porous composite film 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 layer includes inorganic particles and a binder
  • the inorganic particles are not particularly limited, for example, they can be selected from aluminum oxide, silicon oxide, magnesium oxide, titanium oxide, hafnium oxide, tin oxide, cerium oxide, nickel oxide, oxide At least one of zinc, calcium oxide, zirconia, yttrium oxide, silicon carbide, boehmite, aluminum hydroxide, magnesium hydroxide, calcium hydroxide and barium sulfate.
  • the binder is not particularly limited, for example, it can be selected from polyvinylidene fluoride, copolymer of vinylidene fluoride-hexafluoropropylene, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, polyvinylpyrrolidine At least one of ketone, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene and polyhexafluoropropylene.
  • the polymer layer comprises a polymer, and the polymer material includes polyamide, polyacrylonitrile, acrylate polymer, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, polyvinyl ether, polyvinylidene fluoride or poly( at least one of vinylidene fluoride-hexafluoropropylene) and the like.
  • 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, and the like.
  • the third aspect of the present application provides an electronic device, which includes the electrochemical device provided in the second aspect of the present application.
  • the electronic device has good cycle performance and high-temperature storage performance.
  • the electronic devices of the present application are not particularly limited, and may include but not limited to the following types: notebook computers, pen-input computers, mobile computers, e-book players, portable phones, portable fax machines, portable copiers, portable printers, head-mounted Stereo headphones, VCRs, LCD TVs, portable cleaners, portable CD players, mini-discs, transceivers, electronic organizers, calculators, memory cards, portable tape recorders, radios, backup power supplies, electric motors, automobiles, motorcycles, power-assisted bicycles , bicycles, lighting appliances, toys, game consoles, clocks, electric tools, flashlights, cameras, and large batteries for household use.
  • the storage thickness expansion rate (%) of the lithium-ion battery after high-temperature storage for 24 hours (thickness after storage - initial thickness)/initial thickness ⁇ 100%. If the storage thickness expansion rate exceeds 50%, it is dangerous, so stop the test.
  • Discharge the lithium-ion battery at 0.5C to 3.0V at 45°C, then charge it to 4.5V at 0.5C, and charge it to 0.05C at a constant voltage at 4.5V, test the thickness of the lithium-ion battery and record it as the initial thickness, and place it at 45 In an oven at °C, charge at a constant voltage of 4.5V for 30 days, monitor the thickness change, and record the thickness as the thickness after float charge, and the thickness expansion rate of the lithium ion battery after float charge (%) (thickness after float charge-initial thickness)/initial thickness ⁇ 100%, the float thickness expansion rate exceeding 50% is dangerous, stop the test.
  • the mass percentage of formula (I-1) is 0.1%, the mass percentage of (II-1) is 0.001%, and the mass percentage of lithium salt LiPF 6 is 12.5%.
  • the amount is the mass percentage of the base solvent.
  • the positive electrode material lithium cobaltate (LiCoO 2 ), conductive carbon black, conductive paste, and binder polyvinylidene fluoride (PVDF) in a weight ratio of 97.9:0.4:0.5:1.2, and add N-methyl Pyrrolidone (NMP) was used as a solvent, fully stirred and mixed, and prepared into a positive electrode slurry with a solid content of 75% by weight; the positive electrode slurry was evenly coated on both surfaces of a positive electrode current collector aluminum foil with a thickness of 10 ⁇ m, and baked at 90 ° C. After drying and cold pressing, a positive electrode sheet with a coating thickness of 100 ⁇ m on one side was obtained, and the compacted density of the positive electrode was 4.15 g/cm 3 . Cut the positive electrode sheet for use.
  • NMP N-methyl Pyrrolidone
  • a polyethylene (PE) porous polymer film with a thickness of 5 ⁇ m was used as the separator.
  • the storage thickness expansion rate (%) of the lithium-ion battery after high-temperature storage for 6 hours (thickness after storage - initial thickness)/initial thickness ⁇ 100%. If the storage thickness expansion rate is greater than 50%, it is dangerous, so stop the test.
  • the positive electrode material nickel cobalt lithium manganese oxide NCM811 (molecular formula LiNi 0.8 Mn 0.1 Co 0.1 O 2 ), the conductive agent acetylene black, and the binder polyvinylidene fluoride (PVDF) were mixed in a weight ratio of 96:2:2, and N -Methylpyrrolidone (NMP) is used as a solvent, fully stirred and mixed, and prepared into a positive electrode slurry with a solid content of 75wt%; the positive electrode slurry is coated on both surfaces of a positive electrode current collector aluminum foil with a thickness of 10 ⁇ m, and the condition is 90 ° C. After drying under the hood and cold pressing, a positive electrode sheet with a coating thickness of 100 ⁇ m on one side was obtained, and the compacted density of the positive electrode was 3.50 g/cm 3 . Cut the positive electrode sheet for use.
  • NMP N -Methylpyrrolidone
  • Example 1 From Example 1 to Example 17, Example 48, Comparative Example 1, and Comparative Example 2, it can be seen that the application of the cyano compound represented by formula (I) and formula (II) in the electrolyte can significantly improve the lithium The cycle performance, float charge performance and high temperature storage performance of ion batteries.
  • Example 18 to Example 47 it can be seen that adding at least one of different types of sulfur-oxygen double bond compounds or polynitrile compounds in the electrolyte of the present application can further improve the performance of lithium-ion batteries. Cycle performance, float charge performance and high temperature storage performance; adding different types of boron lithium salt compounds can improve the cycle performance of lithium-ion batteries.
  • Example 48 to Example 50 it can be seen that adding different mass percentages of lithium salts to the electrolyte of the present application can improve the cycle performance and high-temperature storage performance of lithium-ion batteries. It can be seen from Example 48, Example 51 to Example 66 that adding at least one of different types of sulfur-oxygen double bond compounds, P-O bond compounds or cyclic carbonate compounds into the electrolyte solution of the present application, all It can further improve the cycle performance and high-temperature storage performance of lithium-ion batteries.

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Abstract

L'invention concerne un électrolyte, un dispositif électrochimique le contenant, et un dispositif électronique, l'électrolyte comprenant des composés cyano représentés par la formule (I) et la formule (II).
PCT/CN2021/131558 2021-11-18 2021-11-18 Électrolyte, dispositif électrochimique le contenant, et dispositif électronique WO2023087223A1 (fr)

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CN202180007386.7A CN114846668B (zh) 2021-11-18 2021-11-18 一种电解液和包含该电解液的电化学装置、电子装置

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CN109786835A (zh) * 2019-01-25 2019-05-21 宁德新能源科技有限公司 电解液和使用其的电化学装置
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KR20210074393A (ko) * 2020-08-13 2021-06-21 닝더 엠프렉스 테크놀로지 리미티드 전해액 및 전해액을 포함하는 전기화학장치와 전자장치
KR20210080560A (ko) * 2020-12-23 2021-06-30 닝더 엠프렉스 테크놀로지 리미티드 전해액, 전기화학장치 및 전자장치

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105958120A (zh) * 2016-06-28 2016-09-21 宁德时代新能源科技股份有限公司 一种电解液及使用该电解液的锂离子电池
US20200144672A1 (en) * 2018-10-30 2020-05-07 Enevate Corporation Silicon-based energy storage devices with phosphorus containing electrolyte additives
CN109786835A (zh) * 2019-01-25 2019-05-21 宁德新能源科技有限公司 电解液和使用其的电化学装置
CN109786824A (zh) * 2019-01-25 2019-05-21 宁德新能源科技有限公司 电解液和使用其的电化学装置
KR20210074393A (ko) * 2020-08-13 2021-06-21 닝더 엠프렉스 테크놀로지 리미티드 전해액 및 전해액을 포함하는 전기화학장치와 전자장치
CN112670578A (zh) * 2020-12-23 2021-04-16 东莞新能源科技有限公司 电解液、电化学装置及电子装置
KR20210080560A (ko) * 2020-12-23 2021-06-30 닝더 엠프렉스 테크놀로지 리미티드 전해액, 전기화학장치 및 전자장치

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