WO2022174550A1 - 电化学装置及包括其的电子装置 - Google Patents

电化学装置及包括其的电子装置 Download PDF

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Publication number
WO2022174550A1
WO2022174550A1 PCT/CN2021/106704 CN2021106704W WO2022174550A1 WO 2022174550 A1 WO2022174550 A1 WO 2022174550A1 CN 2021106704 W CN2021106704 W CN 2021106704W WO 2022174550 A1 WO2022174550 A1 WO 2022174550A1
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Prior art keywords
positive electrode
active material
electrode active
electrochemical device
ether
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PCT/CN2021/106704
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English (en)
French (fr)
Inventor
崔辉
栗文强
唐超
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Ningde Amperex Technology Ltd
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Ningde Amperex Technology Ltd
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Priority to EP25215705.2A priority Critical patent/EP4679520A3/en
Priority to EP25215702.9A priority patent/EP4679519A3/en
Priority to EP21926266.4A priority patent/EP4297138A4/en
Publication of WO2022174550A1 publication Critical patent/WO2022174550A1/zh
Priority to US18/452,049 priority patent/US20230395859A1/en
Anticipated expiration legal-status Critical
Priority to US19/398,629 priority patent/US20260081226A1/en
Priority to US19/398,742 priority patent/US20260081227A1/en
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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
    • 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
    • H01M10/05—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
    • H01M10/056—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
    • H01M10/0569—Liquid materials characterised by the solvents
    • 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
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • 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 field of energy storage technology, and in particular, to electrochemical devices and electronic devices including the same.
  • Lithium-ion batteries are widely used in wearable devices, smart phones, drones, laptops and other fields due to their high operating voltage, high energy density, environmental friendliness, stable cycling, and safety. With the development of modern information technology and the expansion of lithium-ion battery applications, higher requirements have been placed on lithium-ion batteries—excellent cycle performance and low-temperature discharge performance.
  • the interaction between the electrolyte and the positive and negative electrodes has a huge impact on these properties, especially when the operating voltage is increased to 4.4V in order to improve its energy density, the instability of the electrolyte and the positive electrode interface is aggravated, and the cycle performance and low-temperature discharge performance are reduced. , which seriously restricts the performance of lithium-ion batteries.
  • the present application provides an electrochemical device in an attempt to solve, at least to some extent, at least one of the problems present in the related art.
  • Embodiments of the present application also provide an electronic device including an electrochemical device.
  • the present application provides an electrochemical device comprising a positive electrode 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, wherein the positive electrode active material layer comprises a positive electrode active material layer Material, the positive electrode active material contains Mg element, based on the total weight of the positive electrode active material, the weight of the Mg element is X ppm, and 300 ⁇ X ⁇ 30000; wherein the electrolyte contains carboxylate, based on the total weight of the electrolyte, the carboxylate is The weight percentage of is Y%, and Y ⁇ 60, wherein the electrochemical device satisfies 5 ⁇ X/Y ⁇ 6000.
  • the Dn50 of the positive electrode active material particles is A ⁇ m, and 2 ⁇ A ⁇ 25.
  • the electrochemical device satisfies 0.04 ⁇ A/Y ⁇ 6.25.
  • the positive electrode active material satisfies at least one of the conditions (a)-(d): (a) the specific surface area of the positive electrode active material is C m 2 /g, and 0.004 ⁇ C/Y ⁇ 0.1; (b) Dv10/Dn10 of the positive electrode active material particles is Z, and satisfies 1.5 ⁇ Z ⁇ 11; (c)
  • the positive electrode active material further comprises M1 element, and M1 element comprises Al, Mo, Zr, Ti, Fe, V, at least one of Cr, Ba, Sr, or Nb; (d) the positive electrode active material layer contains M2 element, and the M2 element contains at least one of F, B, Cl, S, or P.
  • the positive electrode active material particles satisfy at least one of the conditions (e) or (f): (e) the Dv10 of the positive electrode active material particles is in the range of 2.2 ⁇ m to 4.1 ⁇ m; (f) the positive electrode The Dn10 of the active material particles is in the range of 0.35 ⁇ m to 1.4 ⁇ m.
  • the compaction density of the positive electrode active material layer is greater than or equal to 4.0 g/cm 3 .
  • the carboxylate comprises ethyl acetate, propyl acetate, ethyl propionate, methyl propionate, propyl propionate, butyl propionate, pentyl propionate, ethyl butyrate, At least one of butyl butyrate, propyl butyrate or amyl butyrate.
  • the electrolyte further includes a polynitrile compound
  • the polynitrile compound includes at least one of an ether-free dinitrile compound, an ether-dinitrile compound, an ether-free trinitrile compound, or an ether trinitrile compound .
  • the above-mentioned polynitrile compound contained in the electrolyte satisfies at least one of the conditions (g) to (j):
  • the ether-free dinitrile compound comprises malononitrile, succinonitrile Nitrile, glutaronitrile, adiponitrile, pimeliconitrile, suberonitrile, azelonitrile, sundinitrile, methylmalononitrile, ethylmalononitrile, isopropylmalononitrile, tert-butylmalononitrile Nitrile, methylsuccinonitrile, 2-methyleneglutaronitrile, 1,4-dicyano-3-butene, 2,2-dimethylsuccinonitrile, 2,3-dimethylsuccinonitrile Nitrile, 2,3,3-trimethylsuccinonitrile, 2,2,3,3-tetramethylsuccinonitrile, 2,3-diethyl
  • ether-free trinitrile compounds include:
  • (j) ether trinitrile compounds include:
  • the weight percentage of the ether-free dinitrile compound is B % and satisfies 0.0001 ⁇ B/X ⁇ 0.02.
  • the polynitrile compound includes at least an ether dinitrile compound and a trinitrile compound
  • the trinitrile compound includes at least one of the ether-free trinitrile compound or the ether trinitrile compound
  • the polynitrile compound includes at least an ether-free dinitrile compound
  • the ether-free dinitrile compound includes a saturated dinitrile compound and an unsaturated dinitrile compound, wherein the saturated dinitrile compound is based on the total weight of the electrolyte.
  • the weight percent of the nitrile compound is Q%
  • the weight percent of the unsaturated dinitrile compound is V%
  • 0.05 ⁇ V/Q ⁇ 1 is satisfied.
  • Yet another aspect of the present application provides an electronic device, the electronic device comprising any one of the above electrochemical devices.
  • a term may refer to a range of variation less than or equal to ⁇ 10% of the numerical value, such as less than or equal to ⁇ 5%, less than or equal to ⁇ 4%, less than or equal to ⁇ 3%, Less than or equal to ⁇ 2%, less than or equal to ⁇ 1%, less than or equal to ⁇ 0.5%, less than or equal to ⁇ 0.1%, or less than or equal to ⁇ 0.05%.
  • the difference between two values is less than or equal to ⁇ 10% of the mean of the values (eg, less than or equal to ⁇ 5%, less than or equal to ⁇ 4%, less than or equal to ⁇ 3%, less than or equal to ⁇ 2%, less than or equal to ⁇ 1%, less than or equal to ⁇ 0.5%, less than or equal to ⁇ 0.1%, or less than or equal to ⁇ 0.05%), then the two values are considered to be "about" the same.
  • a list of items joined by the terms "at least one of,” “at least one of,” “at least one of,” or other similar terms may mean the listed items any combination of .
  • the phrase “at least one of A and B” means A only; B only; or A and B.
  • the phrase "at least one of A, B, and C” means A only; or B only; C only; A and B (excluding C); A and C (excluding B); B and C (excluding A); or all of A, B, and C.
  • Item A may contain a single component or multiple components.
  • Item B may contain a single component or multiple components.
  • Item C may contain a single component or multiple components.
  • the application provides an electrochemical device, which includes a positive electrode and an electrolyte, the positive active material in the positive electrode includes Mg element, and the electrolyte includes carboxylate.
  • the electrochemical device of the present application can meet the requirements of high-voltage charging (voltage greater than or equal to 4.4V), and still maintains good high-temperature cycle performance and low-temperature discharge performance when the working voltage is greater than or equal to 4.4V.
  • Carboxylic esters have lower viscosity, which can reduce the impedance of electrochemical devices and improve the charge-discharge performance, but will affect the stability of the interface.
  • the doping element Mg in the cathode active material can occupy Li sites after delithiation of the cathode, thereby stabilizing the cathode structure and alleviating the structural distortion during cycling.
  • This application studies the relationship between the content of carboxylate in the electrolyte and the content of the doping element Mg in the positive electrode active material, and optimizes the entire electrochemical device system, thereby improving the high-temperature cycle performance and low-temperature discharge performance of the electrochemical device.
  • the application provides an electrochemical device, which includes a positive electrode and an electrolyte, the positive electrode 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, wherein the positive electrode active material layer includes a positive electrode active material, and the positive electrode
  • the active material contains Mg element, based on the total weight of the positive electrode active material, the weight of the Mg element is X ppm, and 300 ⁇ X ⁇ 30000; wherein the electrolyte contains carboxylate, based on the total weight of the electrolyte, the weight percentage of the carboxylate is Y%, and Y ⁇ 60, wherein the electrochemical device satisfies 5 ⁇ X/Y ⁇ 6000.
  • the electrochemical device of the present application has excellent high temperature cycle performance and low temperature discharge performance.
  • X can be about 300, about 500, about 1000, about 2000, about 2500, about 3000, about 4000, about 5000, about 6000, about 7000, about 7500, about 10000, about 15000, about 20000 , about 25,000, about 30,000, or a range of any two of the above values, such as about 300 to about 1,000, about 300 to about 7,500, about 500 to about 10,000, about 100 to about 10,000, about 100 to about 20,000, or about 500 to about 30,000.
  • Y can be about 5, about 10, about 15, about 20, about 25, about 30, about 40, about 50, about 60, or can be a range of any two of the above, such as about 5 to About 10, about 10 to about 30, about 30 to about 60, or about 10 to about 60. If the carboxylate content is too high, it will lead to poor interfacial stability and affect the cycle performance of the electrochemical device.
  • X/Y can be about 5, about 100, about 125, about 500, about 1000, about 2000, about 3000, about 4000, about 5000, about 6000, or can be a range of any two of the above For example, about 5 to about 125, about 5 to about 500, about 5 to about 2000, about 125 to about 2000, about 125 to about 6000, or about 2000 to about 6000.
  • the Dn50 of the positive active material particles is A ⁇ m, and 2 ⁇ A ⁇ 25.
  • A can be about 2, about 2.4, about 5, about 10, about 15, about 17, about 20, about 25, or can be a range of any two of the above values, such as about 2 to about 10, About 5 to about 25, about 15 to about 25, or about 2.4 to about 25.
  • Dn50 represents the particle size corresponding to 50% of the cumulative distribution of the number of particles.
  • the particle size of the positive electrode active material particles of the present application is small, so the lithium ion transport path is short, and the high temperature stability of the system can be improved while ensuring excellent low temperature performance.
  • the electrochemical device further satisfies 0.04 ⁇ A/Y ⁇ 6.25.
  • A/Y can be about 0.04, about 0.1, about 0.2, about 0.25, about 0.5, about 0.57, about 1, about 1.5, about 2, about 2.5, about 3, about 3.5, about 4, About 5, about 6, about 6.25, or can be a range of any two of the above, such as about 0.04 to about 1.5, about 0.25 to about 1, about 0.25 to about 1.5, about 2 to about 6.25, or about 3 to about 6.25.
  • the electrochemical device satisfies both 5 ⁇ X/Y ⁇ 6000 and 0.04 ⁇ A/Y ⁇ 6.25, so that the electrochemical device further has excellent cycle performance and low-temperature discharge performance.
  • the positive electrode active material satisfies at least one of the conditions (a)-(d): (a) the specific surface area of the positive electrode active material is C m 2 /g, and 0.004 ⁇ C/Y ⁇ 0.1; (b) Dv10/Dn10 of the positive electrode active material particles is Z, and satisfies 1.5 ⁇ Z ⁇ 11; (c)
  • the positive electrode active material further includes M1 element, and the M1 element includes Al, Mo, Zr, At least one of Ti, Fe, V, Cr, Ba, Sr or Nb; (d) the positive electrode active material layer contains M2 element, the M2 element contains at least one of F, B, Cl, S or P kind.
  • the specific surface area of the positive electrode active material is C m 2 /g, and the electrochemical device satisfies 0.004 ⁇ C/Y ⁇ 0.1, so the high temperature cycle performance and low temperature discharge performance of the electrochemical device can be further improved. If the specific surface area is too large, the side reaction between the positive electrode active material particles and the electrolyte will intensify, which will deteriorate the cycle performance and discharge performance; if the specific surface area is too small, the number of positive electrode particles required to achieve the same capacity increases, and the lithium ion transmission path becomes longer, which affects the discharge performance.
  • C/Y may be about 0.004, about 0.01, about 0.015, about 0.02, about 0.05, about 0.08, about 0.1, or may be in a range of any two of the above, such as about 0.004 to about 0.01, about 0.01 to about 0.05, about 0.01 to about 0.1, or about 0.05 to about 0.1.
  • Dv10/Dn10 of the positive electrode active material particles is Z, and satisfies 1.5 ⁇ Z ⁇ 11.
  • Z can be about 1.5, about 2, about 3, about 4, about 5, about 5.5, about 6, about 7, about 8, about 9, about 10, about 11 or can be any two of the above Numerical composition ranges, for example, from about 1.5 to about 5.5, from about 5.5 to about 11, from about 3 to about 11.
  • Dv10 represents the particle size corresponding to 10% of the cumulative volume distribution of the particles.
  • Dn10 represents the particle size corresponding to 10% of the cumulative distribution of the number of particles.
  • the positive electrode active material further includes an M1 element including at least one of Al, Mo, Zr, Ti, Fe, V, Cr, Ba, Sr, or Nb.
  • the M1 element includes Al.
  • the M1 element includes Al and Ti.
  • the M1 element includes Al, Ti, and Zr.
  • the M1 element includes Cr and Ba. Further inclusion of M1 element in the cathode active material can further stabilize the cathode structure and improve the cycle performance of the electrochemical device. If the content of M1 element is too low, the improvement effect is not obvious; if the content of M1 element is too high, the actual discharge capacity will be affected due to the reduction of Li content.
  • the weight percent of the M1 element is D ppm, and 300 ⁇ D ⁇ 20000.
  • D can be about 300, about 350, about 500, about 1000, about 2000, about 3000, about 5000, about 6000, about 7000, about 8000, about 10000, about 15000, about 20000 or can be A range composed of any two of the above values, for example, about 350 to 5000, about 2000 to 5000, or about 5000 to 20000.
  • the positive electrode active material layer includes M2 element, and the M2 element includes at least one of F, B, Cl, S, or P. In some embodiments, the M2 element contains F and P.
  • M2 element is mainly a positive electrode interface component, which can come from the coating layer on the surface of the positive electrode active material particles, or from the protective film formed by the reaction of the electrolyte. M2 element can protect the reaction of the electrolyte at the positive electrode interface, thereby improving the electrochemical device. cycle performance.
  • the weight percent of the M2 element is about 0.01% to about 20% based on the total weight of the positive active material.
  • the weight percent of M2 may be about 0.01%, about 0.05%, about 0.1%, about 0.5%, about 1%, about 1.5%, about 2%, about 3%, about 4%, about 5% %, about 5.5%, about 6%, about 10%, about 15%, about 20% or can be a range of any two of the above values, such as about 0.01% to about 15%, about 1% to about 15%, about 0.1% to about 10% or about 1% to about 20%.
  • the cathode active material particles satisfy at least one of the conditions (e) or (f): (e) the Dv10 of the cathode active material particles is in the range of 2.2 ⁇ m to 4.1 ⁇ m; (f) the cathode active material The Dn10 of the particles was in the range of 0.35 ⁇ m to 1.4 ⁇ m.
  • the positive active material particles Dv10 are about 2.2 ⁇ m, about 2.5 ⁇ m, about 3 ⁇ m, about 3.5 ⁇ m, about 4 ⁇ m, about 4.1 ⁇ m, or can be in a range of any two of the above values, such as about 2.2 ⁇ m to about 3.5 ⁇ m, about 3 ⁇ m to about 4 ⁇ m, or about 2.5 ⁇ m to about 4.1 ⁇ m.
  • the positive electrode active material particle Dn10 is about 0.35 ⁇ m, about 0.5 ⁇ m, about 0.7 ⁇ m, about 0.8 ⁇ m, about 1.0 ⁇ m, about 1.2 ⁇ m, about 1.4 ⁇ m, or can be a range of any two of the above values, For example, about 0.35 ⁇ m to about 0.8 ⁇ m, about 0.5 ⁇ m to about 1.0 ⁇ m, or about 0.5 ⁇ m to about 1.4 ⁇ m.
  • the positive electrode active material particles satisfy at least one of the above conditions (a) to (f).
  • the compaction density of the positive electrode active material layer is greater than or equal to 4.0 g/cm 3 .
  • the compaction density of the positive active material layer may be 4.0 g/cm 3 , 4.10 g/cm 3 , 4.23 g/cm 3 , 4.5 g/cm 3 , 4.1 g/cm 3 or more, or greater than or equal to 4.1 g/cm 3 . 4.23 g/cm 3 or more and 4.0 g/cm 3 or more and 4.5 g/cm 3 or less.
  • the compaction density of the positive electrode active material layer is too small, the transport path between the positive electrode particles is long, which is not conducive to the cycle performance and high temperature storage performance of the electrochemical device.
  • the positive electrode active material in the positive electrode active material layer of the present application may include any material known in the art.
  • the positive active material includes lithium cobalt oxide (LiCoO 2 ), lithium nickel cobalt manganese (NCM) ternary material, lithium iron phosphate (LiFePO 4 ), lithium manganate (LiMn 2 O 4 ), or their combination random combination.
  • the positive active material layer further includes a binder, and optionally a conductive material.
  • the binder improves the bonding of the positive electrode active material particles to each other, and also improves the bonding of the positive electrode active material to the positive electrode current collector.
  • binders include, but are not limited to: polyvinyl alcohol, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, ethylene-containing Oxygen polymer, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylic (esterified) styrene-butadiene rubber, epoxy resin, Nylon etc.
  • conductive materials include, but are not limited to, carbon-based materials, metal-based materials, conductive polymers, and mixtures thereof.
  • the carbon-based material is selected from natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, carbon fiber, or any combination thereof.
  • the metal-based material is selected from metal powders, metal fibers, copper, nickel, aluminum, silver.
  • the conductive polymer is a polyphenylene derivative.
  • the positive electrode current collector may be aluminum, but is not limited thereto.
  • the positive electrode can be prepared by a preparation method known in the art.
  • a positive electrode can be obtained by mixing a positive electrode active material, a conductive material, and a binder in a solvent to prepare an active material composition, and coating the active material composition on a positive electrode current collector.
  • the solvent may include N-methylpyrrolidone and the like, but is not limited thereto.
  • the positive electrode is made by forming a positive electrode material on a positive electrode current collector using a positive electrode active material layer including a lithium transition metal-based compound powder and a binder.
  • the positive electrode active material layer can generally be fabricated by the following operations: dry mixing the positive electrode active material and a binder (conductive material and thickener, etc., as required) to form a sheet, The obtained sheet is press-bonded to the positive electrode current collector, or these materials are dissolved or dispersed in a liquid medium to prepare a slurry, which is applied on the positive electrode current collector and dried.
  • the carboxylate in the electrolyte comprises ethyl acetate, propyl acetate, ethyl propionate, methyl propionate, propyl propionate, butyl propionate, amyl propionate, ethyl butyrate ester, butyl butyrate, propyl butyrate or amyl butyrate.
  • the carboxylate can comprise ethyl propionate.
  • the carboxylate can comprise propyl propionate.
  • the carboxylate can comprise ethyl acetate.
  • the carboxylate can comprise ethyl propionate and ethyl acetate.
  • the carboxylate can include ethyl propionate and propyl propionate.
  • the electrolyte further includes a polynitrile compound including at least one of an ether-free dinitrile compound, an ether-dinitrile compound, an ether-free trinitrile compound, or an ether trinitrile compound.
  • the ether-free dinitrile compound comprises malononitrile, succinonitrile, glutaronitrile, adiponitrile, pimeliconitrile, suberonitrile, azelonitrile, sundinitrile, methylmalononitrile Nitrile, ethylmalononitrile, isopropylmalononitrile, tert-butylmalononitrile, methylsuccinonitrile, 2-methyleneglutaronitrile, 1,4-dicyano-3-butene, 2,2-dimethylsuccinonitrile, 2,3-dimethylsuccinonitrile, 2,3,3-trimethylsuccinonitrile, 2,2,3,3-tetramethylsuccinonitrile, 2,3-Diethyl-2,3-dimethylsuccinonitrile, 2,2-diethyl-3,3-dimethylsuccinonitrile, dicyclohexyl-1,1-dicarbonitrile, bi
  • ether dinitrile compounds include:
  • the ether-free trinitrile compound includes:
  • ether trinitrile compounds include:
  • the polynitrile compound can form an effective protective film on the surface of the positive electrode, effectively separate the easily oxidizable components in the electrolyte from the surface of the positive electrode, stabilize the structure of the positive electrode, reduce the dissolution of the transition metal of the positive electrode, thereby effectively improving the high-temperature cycle of the electrochemical device. Float performance.
  • the weight percentage of the ether-free dinitrile compound is B % and satisfies 0.0001 ⁇ B/X ⁇ 0.02.
  • B/X can be about 0.0001, about 0.00015, about 0.00025, about 0.0005, about 0.0007, about 0.0008, about 0.0009, about 0.001, about 0.0011, about 0.0015, about 0.005, about 0.01, about 0.02, or It can be a range of any two of the above values, for example, about 0.0001 to about 0.0005, about 0.0001 to about 0.001, about 0.0015 to about 0.01, or about 0.001 to about 0.02. If the B/X is too high, the impedance is large, which is not conducive to the cycle and discharge capacity; if the B/X is too low, the improvement effect is not obvious.
  • the polynitrile compound includes at least an ether-free dinitrile compound, and the ether-free dinitrile compound includes a saturated dinitrile compound and an unsaturated dinitrile compound.
  • the dinitrile compound contains CN group, which can be complexed with the transition metal of the positive electrode to improve the stability of the positive electrode interface under high voltage, but the saturated dinitrile compound has poor compatibility with the negative electrode; if the dinitrile compound contains unsaturated bonds, it can be preferentially polymerized in the negative electrode to form Stabilize the interface film, improve the stability of the negative electrode interface, and improve the overall performance.
  • V/Q can be about 0.05, about 0.08, about 0.1, about 0.15, about 0.25, about 0.5, about 0.75, about 1, or can be a range of any two of the above, such as about 0.05 to about 0.5, about 0.08 to about 1, about 0.1 to about 0.5, or about 0.5 to about 1.
  • the unsaturated dinitrile compound comprises 2-methyleneglutaronitrile, 1,4-dicyano-3-butene, 1,4-dicyano-2-butene, or fumarate at least one of dinitrile.
  • the polynitrile compound includes at least an ether dinitrile compound and a trinitrile compound
  • the trinitrile compound includes at least one of an ether-free trinitrile compound or an ether trinitrile compound.
  • the weight percent of the ether dinitrile compound is H%
  • the weight percent of the trinitrile compound is G%
  • H/G ⁇ 2 is satisfied.
  • H/G may be about 0.1, about 0.25, about 0.33, about 0.5, about 1, about 1.33, about 2, 0.5 or less, 1 or less, or 1.5 or less.
  • the trinitrile compound is mainly adsorbed on the surface of the positive electrode through the complexation of CN. During the cycle, the CN group falls off and the interface protection is insufficient; Protection mechanisms improve overall performance.
  • the electrolyte further includes a film-forming additive
  • the film-forming additive may include lithium tetrafluoroborate (LiBF 4 ), vinyl sulfate (DTD), fluoroethylene carbonate (FEC), vinylene carbonate At least one of (VC) and 1,3-propane sultone (PS).
  • the electrolyte further includes a lithium salt.
  • the lithium salt may include LiPF 6 , LiBF 4 , LiSO 3 F, LiN(FSO 2 ) 2 LiCF 3 SO 3 , LiN(FSO 2 )(CF 3 SO 2 ), LiN(CF 3 SO 2 ) 2 or at least one of LiN(C 2 F 5 SO 2 ) 2 .
  • the electrochemical device includes a negative electrode that includes a negative electrode current collector and a negative electrode active material layer.
  • the negative electrode active material layer includes negative electrode active materials, and the specific types of negative electrode active materials are not specifically limited, and can be selected according to requirements.
  • the negative electrode active material may include lithium metal, structured lithium metal, natural graphite, artificial graphite, mesophase microcarbon spheres (MCMB), hard carbon, soft carbon, silicon, silicon-carbon composite, Li- At least one of Sn alloy, Li-Sn-O alloy, Sn, SnO, SnO 2 , spinel structure lithiated TiO 2 -Li 4 Ti 5 O 12 , and Li-Al alloy.
  • the negative active material layer includes a binder.
  • binders include, but are not limited to: polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyfluoro Ethylene, ethylene oxide-containing polymers, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene Rubber, epoxy or nylon.
  • the anode active material layer includes a conductive material.
  • the conductive material includes, but is not limited to: natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, carbon fiber, metal powder, metal fiber, copper, nickel, aluminum, silver, or polyphenylene derivative.
  • the negative active material layer may further include conventional thickeners, fillers, and the like.
  • the negative electrode current collector includes, but is not limited to, copper foil, nickel foil, stainless steel foil, titanium foil, nickel foam, copper foam, or a conductive metal clad polymer substrate.
  • the negative electrode further includes a conductive layer.
  • the conductive material of the conductive layer may include, but is not limited to: carbon-based materials (eg, natural graphite, artificial graphite, carbon black, acetylene black, Ketjen black, carbon fiber, carbon nanotubes, graphene, etc.), metal-based materials (eg, metal powder, metal fibers, etc., such as copper, nickel, aluminum, silver, etc.), at least one of conductive polymers (eg, polyphenylene derivatives), and mixtures thereof.
  • carbon-based materials eg, natural graphite, artificial graphite, carbon black, acetylene black, Ketjen black, carbon fiber, carbon nanotubes, graphene, etc.
  • metal-based materials eg, metal powder, metal fibers, etc., such as copper, nickel, aluminum, silver, etc.
  • at least one of conductive polymers eg, polyphenylene derivatives
  • the electrochemical device of the present application is provided with a separator between the positive electrode and the negative electrode to prevent short circuits.
  • the material and shape of the separator used in the electrochemical device of the present application are not particularly limited, and it may be any technology disclosed in the prior art.
  • the separator includes a polymer or inorganic or the like formed from a material that is stable to the electrolyte of the present application.
  • the separator can include a porous substrate and a surface treatment layer.
  • the porous substrate is a non-woven fabric, membrane or composite membrane with a porous structure, and the material of the porous substrate is at least one selected from polyethylene (PE), polypropylene, polyethylene terephthalate or polyimide.
  • PE polyethylene
  • At least one surface of the porous substrate is provided with a surface treatment layer, and the surface treatment layer can be a polymer layer or an inorganic layer, or a layer formed by mixing polymers and inorganic substances.
  • the inorganic layer includes inorganic particles and a binder, and the inorganic particles are selected from aluminum oxide, silicon oxide, magnesium oxide, titanium oxide, hafnium oxide, tin oxide, ceria, nickel oxide, zinc oxide, calcium oxide, zirconium oxide, One or a combination of yttrium oxide, silicon carbide, boehmite, aluminum hydroxide, magnesium hydroxide, calcium hydroxide and barium sulfate.
  • the binder includes polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, polyvinyl ether, polyvinyl One or a combination of methyl methacrylate, polytetrafluoroethylene and polyhexafluoropropylene.
  • the polymer layer contains a polymer, and the material of the polymer includes polyamide, polyacrylonitrile, acrylate polymer, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, polyvinyl ether, polyvinylidene fluoride or poly( At least one of vinylidene fluoride-hexafluoropropylene).
  • the electrochemical device of the present application is a lithium ion battery
  • the positive electrode of the lithium ion battery includes a positive electrode current collector and a positive electrode active material layer coated on the positive electrode current collector
  • the negative electrode includes a negative electrode current collector and a coating Anode active material layer on the anode current collector.
  • the electrochemical device of the present application is a high-voltage rechargeable lithium-ion battery comprising a negative electrode, a positive electrode, an electrolyte, and a separator.
  • electrochemical devices described by this application are suitable for use in electronic devices in various fields.
  • the electrochemical device of the present application is not particularly limited, and it can be used for any use known in the art.
  • the electrochemical devices of the present application may be used in, but are not limited to, notebook computers, pen input computers, mobile computers, e-book players, portable telephones, portable fax machines, portable copiers, portable printers, headsets stereo headphones, VCRs, LCD TVs, portable cleaners, portable CD players, mini discs, transceivers, electronic notepads, calculators, memory cards, portable recorders, radios, backup power, motors, cars, motorcycles, power Bicycles, bicycles, lighting fixtures, toys, game consoles, clocks, power tools, flashlights, cameras, large household batteries and lithium-ion capacitors, etc.
  • the negative electrode active material graphite, styrene-butadiene rubber (SBR), and sodium carboxymethylcellulose (CMC) are fully stirred and mixed in an appropriate amount of deionized water solvent in a weight ratio of 97.4:1.2:1.4 to form a uniform negative electrode slurry. ; Coat the slurry on the copper foil of the negative electrode current collector, dry the copper foil, cold-press and weld the tabs to obtain the negative electrode.
  • Mg-containing lithium cobalt oxide, acetylene black, and polyvinylidene fluoride are fully stirred and mixed in an appropriate amount of N-methylpyrrolidone (NMP) solvent at a weight ratio of 96:2:2 to form a uniform positive electrode slurry.
  • NMP N-methylpyrrolidone
  • the slurry is coated on the aluminum foil of the positive electrode current collector, and the aluminum foil is dried, cold-pressed, and the tabs are welded to obtain the positive electrode.
  • the Mg element content is shown in the following table based on the total weight of the positive electrode active material.
  • a PE porous polymer film was used as the separator.
  • the positive electrode, the separator, and the negative electrode are stacked in sequence, so that the separator is placed between the positive electrode and the negative electrode to play a role of isolation, and then rolled to obtain a bare cell; the bare cell is placed in the outer packaging foil aluminum-plastic film, and the above prepared
  • the good electrolyte is injected into the dried battery, and the preparation of the lithium-ion battery is completed after vacuum packaging, standing, forming, shaping and other processes.
  • the lithium ion batteries of Examples 1 to 48 and Comparative Examples 1 to 2 were prepared according to the above preparation methods, and the following tests were performed on the prepared lithium ion batteries.
  • the compaction densities of the positive electrode active material layers of Examples 1 to 45 were the same, and the compaction densities of the positive electrode active material layers of Examples 2 and 46 to 48 are shown in Table 5.
  • the lithium ion battery is disassembled after being discharged, and the positive electrode active material in the positive electrode active material layer is taken out, and the particle size distribution test is carried out using a particle size analyzer.
  • the lithium-ion battery was disassembled after discharge, and the positive electrode active material in the positive electrode active material layer was taken for ICP test.
  • the lithium-ion battery was disassembled after discharge, and the positive electrode active material layer was taken for surface EDS test.
  • the test area was magnified by 3000 times, and the whole area was scanned by EDS.
  • the lithium-ion battery was discharged and centrifuged, and the liquid obtained after centrifugation was tested by GC-MS, and the percentage of each addition was detected.
  • the test method refers to the national standard GB/T 19587-2017 and uses the gas adsorption BET method to determine the specific surface area.
  • the compaction density of the positive electrode active material layer is obtained by the following methods: First, use an accurate measuring tool, such as a micrometer, and then take a certain area of the positive pole piece to test the thickness, area and weight of the positive pole piece; and calculate the compaction density by the following formula:
  • Compaction density (positive electrode piece weight - positive electrode current collector weight) / (positive electrode electrode piece area ⁇ (positive electrode electrode piece thickness - positive electrode current collector thickness));
  • the unit of the weight of the positive pole piece is mg; the unit of the positive pole piece area is mm 2 ; the thickness of the positive pole piece is mm;
  • the weight of the positive electrode sheet is the positive electrode sheet from which the electrolyte solution has been removed by drying.
  • Table 1 shows the lithium ion battery parameters and test results of Examples 1 to 15 and Comparative Examples 1 to 2.
  • the weight percentage of F element in the positive active material layer of Examples and Comparative Examples in Table 1 is 4%
  • the weight percentage of P element is 4%.
  • the weight percent is 0.3%.
  • Carboxylic acid esters can reduce impedance and improve low-temperature performance, but have poor interface stability and cause structural cracks;
  • positive doping element Mg can occupy the position of Li after the positive electrode is delithiated to stabilize the positive electrode structure, relieve structural distortion during cycling, and improve overall performance;
  • the lithium cobalt oxide particles have a certain particle size, and the small particles have a short lithium ion transmission path, which can ensure excellent low temperature performance and improve the high temperature stability of the system.
  • Table 2 shows the lithium ion battery parameters and test results of Example 2 and Examples 16 to 24.
  • a and X of Examples 16 to 24 are the same as those of Example 2, and the differences are shown in Table 2.
  • the positive electrode active material layer of the examples in Table 2 has a weight percent of F element of 4%, and a weight percent of P element of 0.3%.
  • Example 24 By comparing Example 24 and Examples 16 to 23, it can be seen that when the lithium ion battery further satisfies 0.004 ⁇ C/Y ⁇ 0.1 or 1.5 ⁇ Z ⁇ 11, the lithium ion battery can have better high temperature cycle performance and low temperature discharge performance.
  • the specific surface area of the positive active material affects the contact with the electrolyte.
  • the larger the specific surface area the more the area in contact with the electrolyte, and the more likely side reactions will occur.
  • carboxylate With a lower content of carboxylate, a more stable system can be obtained and cycle performance can be improved; but As the carboxylate content becomes lower, the low-temperature discharge performance is affected, so the carboxylate content and specific surface area must satisfy a certain relationship.
  • Small particle lithium cobalt oxide has a short lithium ion transport path and excellent low temperature performance. Too small or too large will affect processing; therefore, its particle size and distribution must satisfy a certain relationship to obtain the best overall performance.
  • Table 3 shows the lithium ion battery parameters and test results of Example 16, Example 24, and Examples 25 to 32.
  • A, X, Y and C of Example 25 to Example 29 are the same as Example 24,
  • A, X, Y and C of Example 30 to Example 32 are the same as Example 16, the differences are shown in Table 3 .
  • the addition of M1 elements (eg, Al, Ti, Zr) to the positive electrode active material can further increase the structure stably and improve the high-temperature cycle performance of the electrochemical device.
  • the surface of the positive electrode active material further contains M2 elements (eg, F, P), which can further stabilize the positive electrode interface and improve the high-temperature cycle performance of the lithium-ion battery.
  • M1 element has a strong binding energy with O, which can stabilize O after delithiation of the positive electrode, alleviate the structural distortion during the cycle process, and improve the performance; however, when the doping content is too high, it will affect the extraction of Li, which will greatly affect the capacity of lithium cobaltate. Unfavorable for cycle capacity.
  • M2 element exists on the surface of the positive electrode active material layer, which is conducive to isolating the contact between the electrolyte and the positive electrode material and protecting the positive electrode; however, when the content is too high, the polarization becomes large, which is unfavorable for cycling.
  • Table 4 shows the lithium ion battery parameters and test results of Example 2, Example 16 and Examples 33 to 45.
  • A, Y, C, and Z of Examples 33 to 45 are the same as those of Example 16, with the differences shown in Table 4.
  • the electrolyte further contains a polynitrile compound, which can further improve the high temperature cycle performance of the electrochemical device.
  • the impedance of the negative electrode will be too large, and the polarization will increase, which is not conducive to the cycle; if the content of unsaturated dinitrile is too low, the protection of the negative electrode will be insufficient; . Therefore, adjusting the weight percentage of the saturated dinitrile compound and the unsaturated dinitrile compound in the electrolyte to satisfy 0.05 ⁇ V/Q ⁇ 1 can make the lithium ion battery obtain excellent performance.
  • Table 5 shows the compaction density and test results of the positive electrode active material layers of Example 2, Example 46 to Example 48. Parameters such as A, Y, X, C, and Z of Examples 46 to 48 are the same as those of Example 2.
  • the compaction density of the positive electrode active material layer is less than 4.0 g/cm 3 , the inter-particle contact becomes larger, and electron transport becomes poor, which is not conducive to cycling.

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Abstract

本申请涉及一种电化学装置及包括其的电子装置。所述电化学装置包括正极和电解液，所述正极包括正极集流体和设置于所述正极集流体的至少一个表面上的正极活性材料层，其中所述正极活性材料层包含正极活性材料，所述正极活性材料包含Mg元素，基于所述正极活性材料的总重量，所述Mg元素的重量为X ppm，且300≤X≤30000；其中所述电解液包含羧酸酯，基于所述电解液的总重量，所述羧酸酯的重量百分比为Y％，且Y≤60，其中所述电化学装置满足5≤X/Y≤6000。本申请的电化学装置通过控制电解液与正极活性材料之间的关系，可以有效地改善电化学装置的高温循环性能和低温放电性能。

Description

电化学装置及包括其的电子装置 技术领域
本申请涉及储能技术领域，尤其涉及电化学装置及包括其的电子装置。
背景技术
锂离子电池因其具有工作电压高、能量密度高、环境友好、循环稳定、安全等优点，被广泛应用于穿戴设备、智能手机、无人机，笔记本电脑等领域。随着现代信息技术的发展及锂离子电池应用的拓展，对锂离子电池提出了更高的要求——优异的循环性能及低温放电性能。电解液与正负极之间的相互作用对这些性能影响巨大，特别是为改善其能量密度将工作电压提升至4.4V时，电解液及正极界面不稳定性加剧，循环性能及低温放电性能降低，严重制约了锂离子电池性能的发挥。
现有的锂离子电池技术往往单一优化电解液或正极，而缺少对整个体系的深入创新，导致无法实现性能的整体提升。
发明内容
本申请提供一种电化学装置以试图在至少某种程度上解决至少一个存在于相关领域中的问题。本申请实施例还提供了包括电化学装置的电子装置。
一方面，本申请提供了一种电化学装置，其包括正极和电解液，正极包括正极集流体和设置于正极集流体的至少一个表面上的正极活性材料层，其中正极活性材料层包含正极活性材料，正极活性材料包含Mg元素，基于正极活性材料的总重量，Mg元素的重量为X ppm，且300≤X≤30000；其中电解液包含羧酸酯，基于电解液的总重量，羧酸酯的重量百分比为Y％，且Y≤60，其中电化学装置满足5≤X/Y≤6000。
根据本申请的一些实施例，正极活性材料颗粒的Dn50为Aμm，且2≤A≤25。
根据本申请的一些实施例，电化学装置满足0.04≤A/Y≤6.25。
根据本申请的一些实施例，正极活性材料满足条件(a)-(d)中的至少一者：(a) 正极活性材料的比表面积为C m 2/g，且满足0.004≤C/Y≤0.1；(b)正极活性材料颗粒的Dv10/Dn10为Z，且满足1.5≤Z≤11；(c)正极活性材料进一步包含M1元素，M1元素包含Al、Mo、Zr、Ti、Fe、V、Cr、Ba、Sr或Nb中的至少一种；(d)正极活性材料层包含M2元素，M2元素包含F、B、Cl、S或P中的至少一种。
根据本申请的一些实施例，正极活性材料颗粒满足条件(e)或(f)中的至少一者：(e)正极活性材料颗粒的Dv10在2.2μm至4.1μm的范围内；(f)正极活性材料颗粒的Dn10在0.35μm至1.4μm的范围内。
根据本申请的一些实施例，正极活性材料层的压实密度大于等于4.0g/cm 3。
根据本申请的一些实施例，羧酸酯包含乙酸乙酯、乙酸丙酯、丙酸乙酯、丙酸甲酯、丙酸丙酯、丙酸丁酯、丙酸戊酯、丁酸乙酯、丁酸丁酯、丁酸丙酯或丁酸戊酯中的至少一种。
根据本申请的一些实施例，电解液进一步包含多腈化合物，多腈化合物包含不含醚的二腈化合物、醚二腈化合物、不含醚的三腈化合物或醚三腈化合物中的至少一种。
根据本申请的一些实施例，电解液中所包含的上述多腈化合物满足条件(g)至(j)中的至少一者：(g)不含醚的二腈化合物包含丙二腈、丁二腈、戊二腈、己二腈、庚二腈、辛二腈、壬二腈、葵二腈、甲基丙二腈、乙基丙二腈、异丙基丙二腈、叔丁基丙二腈、甲基丁二腈、2-亚甲基戊二腈、1,4-二氰基-3-丁烯、2,2-二甲基丁二腈、2,3-二甲基丁二腈、2,3,3-三甲基丁二腈、2,2,3,3-四甲基丁二腈、2,3-二乙基-2,3-二甲基丁二腈、2,2-二乙基-3,3-二甲基丁二腈、双环己基-1,1-二甲腈、双环己基-2,2-二甲腈、双环己基-3,3-二甲腈、2,5-二甲基-2,5-己烷二甲腈、2,3-二异丁基-2,3-二甲基丁二腈、2,2-二异丁基-3,3-二甲基丁二腈、2-甲基戊二腈、2,3-二甲基戊二腈、2,4-二甲基戊二腈、2,2,3,3-四甲基戊二腈、2,2,4,4-四甲基戊二腈、2,2,3,4-四甲基戊二腈、2,3,3,4-四甲基戊二腈、1,4-二氰基戊烷、2,6-二氰基庚烷、2,7-二氰基辛烷、2,8-二氰基壬烷、1,6-二氰基癸烷、1,2-二氰基苯、1,3-二氰基苯、1,4-二氰基苯、3,3'-(亚乙基二氧)二丙腈、3,3'-(亚乙基二硫)二丙腈、1,4-二氰基-2-丁烯或反丁烯二腈中的至少一种；
(h)醚二腈化合物包括：
Figure PCTCN2021106704-appb-000001
Figure PCTCN2021106704-appb-000002
中的至少一种；
(i)不含醚的三腈化合物包括：
Figure PCTCN2021106704-appb-000003
中的至少一种；
(j)醚三腈化合物包括：
Figure PCTCN2021106704-appb-000004
Figure PCTCN2021106704-appb-000005
中的至少一种。
根据本申请的一些实施例，基于电解液的总重量，不含醚的二腈化合物的重量百分比为B％，且满足0.0001≤B/X≤0.02。
根据本申请的一些实施例，多腈化合物至少包括醚二腈化合物和三腈化合物，所述三腈化合物包括所述不含醚的三腈化合物或所述醚三腈化合物中的至少一种，其中基于电解液的总重量，醚二腈化合物的重量百分比为H％，三腈化合物的重量百分比为G％，且满足H/G≤2。
根据本申请的一些实施例，多腈化合物至少包括不含醚的二腈化合物，不含醚的二腈化合物包括饱和二腈化合物和不饱和二腈化合物，其中基于电解液的总重量，饱和二腈化合物的重量百分比为Q％，不饱和二腈化合物的重量百分比为V％，且满足0.05≤V/Q≤1。
本申请的再一方面提供了一种电子装置，所述电子装置包括上述任意一种电化学装置。
本申请实施例的额外层面及优点将部分地在后续说明中描述、显示、或是经由本申请实施例的实施而阐释。
具体实施方式
本申请的实施例将会被详细的描示在下文中。在此所描述的实施例为说明性质的且用于提供对本申请的基本理解。本申请的实施例不应该被解释为对本申请的限制。
如本文中所使用，术语“约”用以描述及说明小的变化。当与事件或情形结合使用时，所述术语可指代其中事件或情形精确发生的例子以及其中事件或情形极近似地发生的例子。举例来说，当结合数值使用时，术语可指代小于或等于所述数值的±10％的变化范围，例如小于或等于±5％、小于或等于±4％、小于或等于±3％、小于或等于±2％、小于或等于±1％、小于或等于±0.5％、小于或等于±0.1％、或小于或等于±0.05％。举例来说，如果两个数值之间的差值小于或等于所述值的平均值的±10％(例如小于或等于±5％、小于或等于±4％、小于或等于±3％、小于或等于±2％、小于或等于±1％、小于或等于±0.5％、小于或等于±0.1％、或小于或等于±0.05％)，那么可认为所述两个数值“约”相同。
另外，有时在本文中以范围格式呈现量、比率和其它数值。应理解，此类范围格式是用于便利及简洁起见，且应灵活地理解，不仅包含明确地指定为范围限制的数值，而且包含涵盖于所述范围内的所有个别数值或子范围，如同明确地指定每一数值及子范围一般。
在具体实施方式及权利要求书中，由术语“中的至少一者”、“中的至少一个”、“中的至少一种”或其他相似术语所连接的项目的列表可意味着所列项目的任何组合。例如，如果列出项目A及B，那么短语“A及B中的至少一者”意味着仅A；仅B；或A及B。在另一实例中，如果列出项目A、B及C，那么短语“A、B及C中的至少一者”意味着仅A；或仅B；仅C；A及B(排除C)；A及C(排除B)；B及C(排除A)；或A、B及C的全部。项目A可包含单个组分或多个组分。项目B可包含单个组分或多个组分。项目C可包含单个组分或多个组分。
本申请提供了一种电化学装置，其包括正极和电解液，正极中的正极活性材料包括Mg元素，电解液包括羧酸酯。本申请的电化学装置可以满足高电压充电(电压大于等于4.4V)的需求，在工作电压大于等于4.4V时仍然保持良好的高温循环性能及低温放电性能。
羧酸酯具有较低粘度，可降低电化学装置的阻抗，提升充放电性能，但会影响界面的稳定性。
正极活性材料中的掺杂元素Mg可在正极脱锂后占据Li位，进而稳定正极结构，缓解循环过程结构畸变。
本申请研究了电解液中羧酸酯的含量与正极活性材料的掺杂元素Mg的含量关系，优化整个电化学装置体系，从而改善电化学装置的高温循环性能及低温放电性能。
一、电化学装置
本申请提供了一种电化学装置，其包括正极和电解液，正极包括正极集流体和设置于正极集流体的至少一个表面上的正极活性材料层，其中正极活性材料层包含正极活性材料，正极活性材料包含Mg元素，基于正极活性材料的总重量，Mg元素的重量为X ppm，且300≤X≤30000；其中电解液包含羧酸酯，基于电解液的总重量，羧酸酯的重量百分比为Y％，且Y≤60，其中电化学装置满足5≤X/Y≤6000。本申请的电化学装置具有优异的高温循环性能及低温放电性能。
在一些实施例中，X可以为约300、约500、约1000、约2000、约2500、约3000、约4000、约5000、约6000、约7000、约7500、约10000、约15000、约20000、约25000、约30000或可以为以上任意两数值组成的范围，例如约300至约1000、约300至约7500、约500至约10000、约100至约10000、约100至约20000或约500至约30000。
在一些实施例中，Y可以为约5、约10、约15、约20、约25、约30、约40、约50、约60或可以为以上任意两数值组成的范围，例如约5至约10、约10至约30、约30至约60或约10至约60。若羧酸酯含量过高，会导致界面稳定性差，影响电化学装置的循环性能。
在一些实施例中，X/Y可以为约5、约100、约125、约500、约1000、约2000、约3000、约4000、约5000、约6000或可以为以上任意两数值组成的范围，例如约5至约125、约5至约500、约5至约2000、约125至约2000、约125至约6000或约2000至约6000。
在一些实施例中，正极活性材料颗粒的Dn50为Aμm，且2≤A≤25。在一些实施例中，A可以为约2、约2.4、约5、约10、约15、约17、约20、约25或可以为以上任意两数值组成的范围，例如约2至约10、约5至约25、约15至约25或约2.4至约25。Dn50表示颗粒的数量累积分布50％对应的粒径。本申请的正极活性材料颗粒的粒径较小，因此锂离子传输路径短，在保证优异的低温性能同时可提升体系高温稳定性。
在一些实施例中，电化学装置进一步满足0.04≤A/Y≤6.25。在一些实施例中，A/Y 可以为约0.04、约0.1、约0.2、约0.25、约0.5、约0.57、约1、约1.5、约2、约2.5、约3、约3.5、约4、约5、约6、约6.25或可以为以上任意两数值组成的范围，例如约0.04至约1.5、约0.25至约1、约0.25至约1.5、约2至约6.25或约3至约6.25。
在一些实施例中，电化学装置同时满足5≤X/Y≤6000和0.04≤A/Y≤6.25，使得电化学装置进一步具有优异的循环性能及低温放电性能。
在一些实施例中，正极活性材料满足条件(a)-(d)中的至少一者：(a)所述正极活性材料的比表面积为C m 2/g，且满足0.004≤C/Y≤0.1；(b)所述正极活性材料颗粒的Dv10/Dn10为Z，且满足1.5≤Z≤11；(c)所述正极活性材料进一步包含M1元素，所述M1元素包含Al、Mo、Zr、Ti、Fe、V、Cr、Ba、Sr或Nb中的至少一种；(d)所述正极活性材料层包含M2元素，所述M2元素包含F、B、Cl、S或P中的至少一种。
在一些实施例中，正极活性材料的比表面积为C m 2/g，电化学装置满足0.004≤C/Y≤0.1，因此可以进一步改善电化学装置的高温循环性能及低温放电性能。比表面积过大正极活性材料颗粒与电解液副反应加剧，会恶化循环性能及放电性能；比表面积过小达到相同容量所需正极颗粒数量增加，锂离子传输路径变长，影响放电性能。在一些实施例中，C/Y可以为约0.004、约0.01、约0.015、约0.02、约0.05、约0.08、约0.1或可以为以上任意两数值组成的范围，例如约0.004至约0.01、约0.01至约0.05、约0.01至约0.1或约0.05至约0.1。
在一些实施例中，正极活性材料颗粒的Dv10/Dn10为Z，且满足1.5≤Z≤11。在一些实施例中，Z可以为约1.5、约2、约3、约4、约5、约5.5、约6、约7、约8、约9、约10、约11或可以为以上任意两数值组成的范围，例如约1.5至约5.5、约5.5至约11、约3至约11。Dv10表示颗粒的体积累积分布10％对应的粒径。Dn10表示颗粒的数量累积分布10％对应的粒径。
在一些实施例中，正极活性材料进一步包含M1元素，M1元素包含Al、Mo、Zr、Ti、Fe、V、Cr、Ba、Sr或Nb中的至少一种。在一些实施例中，M1元素包含Al。在一些实施例中，M1元素包含Al和Ti。在一些实施例中，M1元素包含Al、Ti和Zr。在一些实施例中，M1元素包含Cr和Ba。正极活性材料进一步包含M1元素可以进一步稳定正极结构，改善电化学装置的循环性能。M1元素的含量过低，改善效果不明显；M1元素的含量过高，会因Li含量降低而影响实际放电容量。
在一些实施例中，基于正极活性材料的总重量，M1元素的重量百分比为D ppm，且 300≤D≤20000。在一些实施例中，D可以为约300、约350、约500、约1000、约2000、约3000、约5000、约6000、约7000、约8000、约10000、约15000、约20000或可以为以上任意两数值组成的范围，例如约350至5000、约2000至5000或约5000至20000。
在一些实施例中，正极活性材料层包含M2元素，M2元素包含F、B、Cl、S或P中的至少一种。在一些实施例中，M2元素包含F和P。M2元素主要为正极界面成分，可来自于正极活性材料颗粒表面的包覆层，也可来自电解液反应生成的保护膜，M2元素可保护电解液在正极界面的反应，从而改善电化学装置的循环性能。
在一些实施例中，基于正极活性材料的总重量，M2元素的重量百分比为约0.01％至约20％。在一些实施例中，M2的重量百分比可以为约0.01％、约0.05％、约0.1％、约0.5％、约1％、约1.5％、约2％、约3％、约4％、约5％、约5.5％、约6％、约10％、约15％、约20％或可以为以上任意两数值组成的范围，例如约0.01％至约15％、约1％至约15％、约0.1％至约10％或约1％至约20％。
在一些实施例中，正极活性材料颗粒满足条件(e)或(f)中的至少一者：(e)正极活性材料颗粒的Dv10在2.2μm至4.1μm的范围内；(f)正极活性材料颗粒的Dn10在0.35μm至1.4μm的范围内。
在一些实施例中，正极活性材料颗粒Dv10为约2.2μm、约2.5μm、约3μm、约3.5μm、约4μm、约4.1μm或可以为以上任意两数值组成的范围，例如约2.2μm至约3.5μm、约3μm至约4μm或约2.5μm至约4.1μm。
在一些实施例中，正极活性材料颗粒Dn10为约0.35μm、约0.5μm、约0.7μm、约0.8μm、约1.0μm、约1.2μm、约1.4μm或可以为以上任意两数值组成的范围，例如约0.35μm至约0.8μm、约0.5μm至约1.0μm或约0.5μm至约1.4μm。
在一些实施例中，正极活性材料颗粒满足上述条件(a)至(f)中的至少一者。
在一些实施例中，正极活性材料层的压实密度大于等于4.0g/cm 3。在一些实施例中，正极活性材料层的压实密度可以为4.0g/cm 3、4.10g/cm 3、4.23g/cm 3、4.5g/cm 3、大于等于4.1g/cm 3、大于等于4.23g/cm 3或大于等于4.0g/cm 3且小于等于4.5g/cm 3。当正极活性材料层的压实密度过小时，则正极颗粒间传输路径长，不利于电化学装置的循环性能及高温存储性能。
本申请的正极活性材料层中的正极活性材料可以包括任何本领域公知的材料。在一些实施例中，正极活性材料包括钴酸锂(LiCoO 2)、锂镍钴锰(NCM)三元材料、磷酸 亚铁锂(LiFePO 4)、锰酸锂(LiMn 2O 4)或它们的任意组合。
在一些实施例中，正极活性材料层还包括粘合剂，并且可选地包括导电材料。粘合剂提高正极活性材料颗粒彼此间的结合，并且还提高正极活性材料与正极集流体的结合。
在一些实施例中，粘合剂包括，但不限于：聚乙烯醇、羟丙基纤维素、二乙酰基纤维素、聚氯乙烯、羧化的聚氯乙烯、聚氟乙烯、含亚乙基氧的聚合物、聚乙烯吡咯烷酮、聚氨酯、聚四氟乙烯、聚偏1,1-二氟乙烯、聚乙烯、聚丙烯、丁苯橡胶、丙烯酸(酯)化的丁苯橡胶、环氧树脂、尼龙等。
在一些实施例中，导电材料包括，但不限于：基于碳的材料、基于金属的材料、导电聚合物和它们的混合物。在一些实施例中，基于碳的材料选自天然石墨、人造石墨、碳黑、乙炔黑、科琴黑、碳纤维或其任意组合。在一些实施例中，基于金属的材料选自金属粉、金属纤维、铜、镍、铝、银。在一些实施例中，导电聚合物为聚亚苯基衍生物。
在一些实施例中，正极集流体可以是铝，但不限于此。
正极可以通过本领域公知的制备方法制备。例如，正极可以通过如下方法获得：在溶剂中将正极活性材料、导电材料和粘合剂混合，以制备活性材料组合物，并将该活性材料组合物涂覆在正极集流体上。在一些实施例中，溶剂可以包括N-甲基吡咯烷酮等，但不限于此。
在一些实施例中，正极通过在正极集流体上使用包括锂过渡金属系化合物粉体和粘结剂的正极活性材料层形成正极材料而制成。
在一些实施例中，正极活性材料层通常可以通过如下操作来制作：将正极活性材料和粘结剂(根据需要而使用的导电材料和增稠剂等)进行干式混合而制成片状，将得到的片压接于正极集流体，或者使这些材料溶解或分散于液体介质中而制成浆料状，涂布在正极集流体上并进行干燥。
在一些实施例中，电解液中的羧酸酯包含乙酸乙酯、乙酸丙酯、丙酸乙酯、丙酸甲酯、丙酸丙酯、丙酸丁酯、丙酸戊酯、丁酸乙酯、丁酸丁酯、丁酸丙酯或丁酸戊酯中的至少一种。在一些实施例中，羧酸酯可以包含丙酸乙酯。在一些实施例中，羧酸酯可以包含丙酸丙酯。在一些实施例中，羧酸酯可以包含乙酸乙酯。在一些实施例中，羧酸酯可以包含丙酸乙酯和乙酸乙酯。在一些实施例中，羧酸酯可以包含丙酸乙酯和丙酸丙酯。
在一些实施例中，电解液进一步包含多腈化合物，多腈化合物包含不含醚的二腈化 合物、醚二腈化合物、不含醚的三腈化合物或醚三腈化合物中的至少一种。
在一些实施例中，不含醚的二腈化合物包含丙二腈、丁二腈、戊二腈、己二腈、庚二腈、辛二腈、壬二腈、葵二腈、甲基丙二腈、乙基丙二腈、异丙基丙二腈、叔丁基丙二腈、甲基丁二腈、2-亚甲基戊二腈、1,4-二氰基-3-丁烯、2,2-二甲基丁二腈、2,3-二甲基丁二腈、2,3,3-三甲基丁二腈、2,2,3,3-四甲基丁二腈、2,3-二乙基-2,3-二甲基丁二腈、2,2-二乙基-3,3-二甲基丁二腈、双环己基-1,1-二甲腈、双环己基-2,2-二甲腈、双环己基-3,3-二甲腈、2,5-二甲基-2,5-己烷二甲腈、2,3-二异丁基-2,3-二甲基丁二腈、2,2-二异丁基-3,3-二甲基丁二腈、2-甲基戊二腈、2,3-二甲基戊二腈、2,4-二甲基戊二腈、2,2,3,3-四甲基戊二腈、2,2,4,4-四甲基戊二腈、2,2,3,4-四甲基戊二腈、2,3,3,4-四甲基戊二腈、1,4-二氰基戊烷、2,6-二氰基庚烷、2,7-二氰基辛烷、2,8-二氰基壬烷、1,6-二氰基癸烷、1,2-二氰基苯、1,3-二氰基苯、1,4-二氰基苯、3,3'-(亚乙基二氧)二丙腈、3,3'-(亚乙基二硫)二丙腈、1,4-二氰基-2-丁烯或反丁烯二腈中的至少一种。
在一些实施例中，醚二腈化合物包括：
Figure PCTCN2021106704-appb-000006
Figure PCTCN2021106704-appb-000007
中的至少一种。
在一些实施例中，不含醚的三腈化合物包括：
Figure PCTCN2021106704-appb-000008
中的至少一种。
在一些实施例中，醚三腈化合物包括：
Figure PCTCN2021106704-appb-000009
Figure PCTCN2021106704-appb-000010
中的至少一种。
多腈化合物可以在正极表面形成有效的保护膜，有效地将电解液中易氧化组份与正极表面隔开，稳定正极结构，降低正极过渡金属溶出，从而有效地改善电化学装置的高温循环和浮充性能。
在一些实施例中，基于所述电解液的总重量，不含醚的二腈化合物的重量百分比为B％，且满足0.0001≤B/X≤0.02。在一些实施例中，B/X可以为约0.0001、约0.00015、约0.00025、约0.0005、约0.0007、约0.0008、约0.0009、约0.001、约0.0011、约0.0015、约0.005、约0.01、约0.02或可以为以上任意两数值组成的范围，例如约0.0001至约0.0005、约0.0001至约0.001、约0.0015至约0.01或约0.001至约0.02。B/X过高，阻抗大，不利于循环及放电容量；B/X过低，改善效果不明显。
在一些实施例中，多腈化合物至少包括不含醚的二腈化合物，不含醚的二腈化合物包括饱和二腈化合物和不饱和二腈化合物。二腈化合物含CN基团，可与正极过渡金属络合，提高高电压下正极界面稳定性，但饱和二腈化合物与负极兼容性差；如二腈化合物含不饱和键，可优先在负极聚合形成稳定界面膜，改善负极界面稳定性，改善整体性能。基于电解液的总重量，饱和二腈化合物的重量百分比为Q％，不饱和二腈化合物的重量百分比为V％，且满足0.05≤V/Q≤1。在一些实施例中，V/Q可以为约0.05、约0.08、约0.1、约0.15、约0.25、约0.5、约0.75、约1或可以为以上任意两数值组成的范围，例如约0.05至约0.5、约0.08至约1、约0.1至约0.5或约0.5至约1。
在一些实施例中，不饱和二腈化合物包含2-亚甲基戊二腈、1,4-二氰基-3-丁烯、1,4-二氰基-2-丁烯或反丁烯二腈中的至少一种。
在一些实施例中，多腈化合物至少包括醚二腈化合物和三腈化合物，三腈化合物包括不含醚的三腈化合物或醚三腈化合物中的至少一种。基于电解液的总重量，醚二腈化合物的重量百分比为H％，三腈化合物的重量百分比为G％，且满足H/G≤2。在一些实施例中，H/G可以为约0.1、约0.25、约0.33、约0.5、约1、约1.33、约2、小于等于0.5、小于等于1或小于等于1.5。三腈化合物主要通过CN的络合作用吸附在正极表面，在循环过程中CN基团存在脱落，界面保护不足；醚二腈具有较低的氧化电位，可在正 极表面氧化形成界面膜，通过双重保护机制改善整体性能。
在一些实施例中，电解液进一步包含成膜添加剂，所述成膜添加剂可以包含四氟硼酸锂(LiBF 4)、硫酸乙烯酯(DTD)、氟代碳酸乙烯酯(FEC)、碳酸亚乙烯酯(VC)、1,3-丙烷磺酸内酯(PS)中的至少一种。
在一些实施例中，电解液进一步包括锂盐。在一些实施例中，锂盐可以包括LiPF 6、LiBF 4、LiSO 3F、LiN(FSO 2) 2LiCF 3SO 3、LiN(FSO 2)(CF 3SO 2)、LiN(CF 3SO 2) 2或LiN(C 2F 5SO 2) 2中的至少一种。
在一些实施例中，电化学装置包括负极，负极包括负极集流体和负极活性材料层。负极活性材料层包括负极活性材料，负极活性材料的具体种类均不受到具体的限制，可根据需求进行选择。具体地，所述负极活性材料可以包含锂金属、结构化的锂金属、天然石墨、人造石墨、中间相微碳球(MCMB)、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、Li-Al合金中的至少一种。
在一些实施例中，负极活性材料层包括粘合剂。在一些实施例中，粘合剂包括，但不限于：聚乙烯醇、羧甲基纤维素、羟丙基纤维素、二乙酰基纤维素、聚氯乙烯、羧化的聚氯乙烯、聚氟乙烯、含亚乙基氧的聚合物、聚乙烯吡咯烷酮、聚氨酯、聚四氟乙烯、聚偏1,1-二氟乙烯、聚乙烯、聚丙烯、丁苯橡胶、丙烯酸(酯)化的丁苯橡胶、环氧树脂或尼龙。
在一些实施例中，负极活性材料层包括导电材料。在一些实施例中，导电材料包括，但不限于：天然石墨、人造石墨、碳黑、乙炔黑、科琴黑、碳纤维、金属粉、金属纤维、铜、镍、铝、银或聚亚苯基衍生物。
在一些实施例中，负极活性材料层还可以包括常规的增稠剂和填料等。
在一些实施例中，负极集流体包括，但不限于：铜箔、镍箔、不锈钢箔、钛箔、泡沫镍、泡沫铜或覆有导电金属的聚合物基底。
在一些实施例中，负极进一步包括导电层。导电层的导电材料可以包括，但不限于：基于碳的材料(例如，天然石墨、人造石墨、碳黑、乙炔黑、科琴黑、碳纤维、碳纳米管、石墨烯等)、基于金属的材料(例如，金属粉、金属纤维等，例如铜、镍、铝、银等)、导电聚合物(例如，聚亚苯基衍生物)及其混合物中的至少一种。
在一些实施例中，本申请的电化学装置在正极与负极之间设有隔离膜以防止短路。本申请的电化学装置中使用的隔离膜材料和形状没有特别限制，其可为任何现有技术中公开的技术。在一些实施例中，隔离膜包括由对本申请的电解液稳定的材料形成的聚合物或无机物等。
例如隔离膜可包括多孔基材和表面处理层。多孔基材为具有多孔结构的无纺布、膜或复合膜，多孔基材的材料选自聚乙烯(PE)、聚丙烯、聚对苯二甲酸乙二醇酯或聚酰亚胺中的至少一种。具体的，可选用聚丙烯多孔膜、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。
多孔基材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。
无机物层包括无机颗粒和粘结剂，无机颗粒选自氧化铝、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、氢氧化钙和硫酸钡中的一种或几种的组合。粘结剂包含聚偏氟乙烯、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、聚四氟乙烯和聚六氟丙烯中的一种或几种的组合。聚合物层中包含聚合物，聚合物的材料包括聚酰胺、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。
在一些实施例中，本申请的电化学装置是锂离子电池，所述锂离子电池的正极包括正极集流体及涂布在正极集流体上的正极活性材料层，负极包括负极集流体及涂布在负极集流体上的负极活性材料层。
在一些实施例中，本申请的电化学装置是高电压充电型锂离子电池，所述高电压充电型锂离子电池包含负极、正极、电解液和隔离膜。
二、电子装置
由本申请所述的电化学装置适用于各种领域的电子装置。
本申请的电化学装置的用途没有特别限定，其可用于现有技术中已知的任何用途。在一个实施例中，本申请的电化学装置可用于，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。
三、实施例
以下，举出实施例和对比例对本申请进一步具体地进行说明，但只要不脱离其主旨，则本申请并不限定于这些实施例。
锂离子电池的制备
(1)负极的制备
将负极活性材料石墨、丁苯橡胶(SBR)、羧甲基纤维素钠(CMC)按照重量比97.4:1.2:1.4在适量的去离子水溶剂中充分搅拌混合，使其形成均匀的负极浆料；将此浆料涂覆于负极集流体铜箔上，将铜箔烘干、冷压、焊接极耳后，得到负极。
(2)电解液的制备
在含水量<10ppm的氩气气氛手套箱中，将碳酸乙烯酯(EC)、碳酸丙烯酯(PC)、碳酸二乙酯(DEC)按照1:1:1质量比混合，之后加入羧酸酯混合均匀，再将充分干燥的锂盐LiPF 6溶解于上述非水溶剂，加入5％的氟代碳酸乙烯酯，最后加入一定质量的添加剂，配成实施例中的电解液。基于所述电解液的总重量，LiPF 6的重量百分比为14％，实施例和对比例中的具体羧酸酯、添加剂及它们的重量百分比如下表所示。
(3)正极的制备
将含Mg的钴酸锂、乙炔黑、聚偏二氟乙烯按重量比96:2:2在适量的N-甲基吡咯烷酮(NMP)溶剂中充分搅拌混合，使其形成均匀的正极浆料。将此浆料涂覆于正极集流体铝箔上，将铝箔烘干、冷压、焊接极耳后，得到正极。基于正极活性材料的总重量，Mg元素含量如下表所示。
(4)隔离膜的制备
以PE多孔聚合物薄膜作为隔离膜。
(5)锂离子电池的制备
将正极、隔离膜、负极按顺序叠好，使隔离膜处于正极和负极之间起到隔离的作用，然后卷绕得到裸电池；将裸电池置于外包装箔铝塑膜中，将上述制备好的电解液注入到 干燥后的电池中，经过真空封装、静置、化成、整形等工序，即完成锂离子电池的制备。
按照上述制备方法制备实施例1至48以及对比例1至2的锂离子电池，并对制备好的锂离子电池进行下面测试。实施例1至45的正极活性材料层的压实密度相同，实施例2、46至48正极活性材料层的压实密度如表5所示。
测试方法
(1)高温循环测试
将制备好的锂离子电池放至45℃恒温箱中，以恒定电流1.5C充电至4.4V，在4.4V下恒压充电至电流为0.05C，再以1.0C恒流放电至3.0V，此次为一个充放电循环过程。按上述方式进行500次循环充放电测试，并监测初始放电容量及500次循环后的剩余放电容量。高温容量保持率＝剩余放电容量/初始放电容量×100％。
(2)低温放电测试
将制备好的锂离子电池放至在高低温箱中，将温度调整至25℃，以恒定电流0.7C充电至4.4V，在4.4V下恒压充电至0.05C，再以0.2C恒流放电至3.0V，此时的放电容量为D0。再以恒定电流0.7C充电至4.4V，在4.4V下恒压充电至0.05C，将高低温箱温度调整至-10℃，待温度稳定后保持1小时，再以0.2C恒流放电至3.0V，此时的放电容量为D1。低温放电容量保持率＝(D1/D0)×100％。
(3)正极活性材料颗粒的Dn和Dv测试
将锂离子电池放电后拆解，取出正极活性材料层中的正极活性材料，使用粒度分析仪进行颗粒度分布测试。
(4)正极活性材料中的Mg和M1元素的含量测试
将锂离子电池放电后拆解，取正极活性材料层中的正极活性材料进行ICP测试。
(5)正极活性材料层中的M2元素的含量测试
将锂离子电池放电后拆解，取正极活性材料层进行表面EDS测试，将测试区域放大倍数3000倍，全区域进行EDS扫描得到。
(6)电解液中成分含量测试
将锂离子电池放电后离心，离心后得到的液体进行GC-MS测试，检测出各添加量百分比。
(7)正极活性材料的比表面积测试(BET)
选取一定质量极片，通风橱常温干燥24h后进行BET测试。测试方法参考国标GB/T 19587-2017采用气体吸附BET法测定比表面积。
(8)正极活性材料层的压实密度测试
正极活性材料层压实密度通过如下方式获得：首先使用精确的量具，如万分尺，然后取一定面积的正极极片，测试正极极片厚度、面积和重量；并通过下式计算压实密度：
压实密度＝(正极极片重量-正极集流体重量)/(正极极片面积×(正极极片厚度-正极集流体厚度))；
正极极片重量的单位为mg；正极极片面积单位为mm 2；正极极片厚度为mm；
正极极片重量为干燥被去除电解液的正极片。
测试结果
表1是实施例1至15以及对比例1至2的锂离子电池参数及测试结果，在表1中的实施例和对比例的正极活性材料层F元素的重量百分比为4％，P元素的重量百分比为0.3％。
表1
Figure PCTCN2021106704-appb-000011
Figure PCTCN2021106704-appb-000012
根据表1中的实施例1至实施例15以及对比例1至对比例2可以得知，当锂离子电池满足5≤X/Y≤6000时，锂离子电池具有较高的高温循环容量保持率和低温放电容量保持率；当锂离子电池进一步满足0.04≤A/Y≤25时，锂离子电池具有更佳的性能。
羧酸酯可降低阻抗，改善低温性能，但界面稳定性差，引发结构破裂；正极掺杂元素Mg可在正极脱锂后占据Li的位置而稳定正极结构，缓解循环过程结构畸变，提升整体性能；钴酸锂颗粒具有一定粒径，小颗粒锂离子传输路径短，在保证优异的低温性能同时可提升体系高温稳定性。
表2是实施例2和实施例16至24的锂离子电池参数及测试结果。实施例16至实施例24的A与X与实施例2相同，不同之处如表2所示。在表2中的实施例的正极活性材料层F元素的重量百分比为4％，P元素的重量百分比为0.3％。
表2
Figure PCTCN2021106704-appb-000013
通过比较实施例24、实施例16至23可知，当锂离子电池进一步满足0.004≤C/Y≤0.1或1.5≤Z≤11时，锂离子电池可具有较优的高温循环性能及低温放电性能。
正极活性材料的比表面积影响与电解液的接触，比表面积越大，与电解液接触的面积越多，更易发生副反应，搭配含量更低的羧酸酯获得更稳定体系，改善循环性能；但由于羧酸酯含量变低，低温放电性能受到影响，因此羧酸酯含量与比表面积需满足一定关系。
小颗粒钴酸锂的锂离子传输路径短，具有优异的低温性能，过小或过大均影响加工；因此其颗粒大小与分布需满足一定关系获取最有的整体性能。
表3是实施例16、实施例24、实施例25至32的锂离子电池参数及测试结果。实施例25至实施例29的A、X、Y和C与实施例24相同，实施例30至实施例32的A、X、Y和C与实施例16相同，不同之处如表3所示。
表3
Figure PCTCN2021106704-appb-000014
根据表3可以得知，正极活性材料进一步增加M1元素(例如，Al、Ti、Zr)可进一步稳定增加结构，改善电化学装置的高温循环性能。并且，正极活性材料表面进一步包含M2元素(例如，F、P)可进一步稳定正极界面，改善锂离子电池的高温循环性能。
M1元素与O具有较强的结合能，正极脱锂后可稳定O，缓解循环过程结构畸变，改善性能；但掺杂含量过高时影响Li的脱出，会大大影响钴酸锂的容量发挥，于循环容量不利。
M2元素存在于正极活性材料层表面，有利于隔绝电解液与正极材料的接触，保护正极；但含量过高时极化变大，于循环不利。
表4是实施例2、实施例16和实施例33至45的锂离子电池参数及测试结果。实施例33至实施45的A、Y、C和Z与实施例16相同，不同之处见表4。
表4
Figure PCTCN2021106704-appb-000015
Figure PCTCN2021106704-appb-000016
根据表4可以得知，电解液进一步包含多腈化合物可以进一步改善电化学装置的高温循环性能。
不饱和二腈含量过高会使负极阻抗过大，极化增加，不利于循环；不饱和二腈含量过低对负极保护不足；饱和二腈对负极的不兼容作用明显，无法获得最优性能。因此，调节电解液中饱和二腈化合物和不饱和二腈化合物的重量百分比满足0.05≤V/Q≤1可以使锂离子电池获得优异的性能。
表5是实施例2、实施例46至实施例48的正极活性材料层的压实密度及测试结果。实施例46至实施例48的A、Y、X、C、Z等参数与实施例2相同。
表5
Figure PCTCN2021106704-appb-000017
根据表5可以得知，正极活性材料层的压实密度大于等于4.0g/cm 3时，可以使电化学装置的能量密度、高温循环性能和低温放电性能均能处于较优的状态。
正极活性材料层的压实密度小于4.0g/cm 3，颗粒间接触变大，电子传输变差，不利于循 环。
以上所述，仅是本发明的几个实施例，并非对本发明做任何形式的限制，虽然本发明以较佳实施例揭示如上，然而并非用以限制本发明，任何熟悉本专业的技术人员，在不脱离本发明技术方案的范围内，利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例，均属于技术方案范围内。
整个说明书中对“一些实施例”、“部分实施例”、“一个实施例”、“另一举例”、“举例”、“具体举例”或“部分举例”的引用，其所代表的意思是在本申请中的至少一个实施例或举例包含了该实施例或举例中所描述的特定特征、结构、材料或特性。因此，在整个说明书中的各处所出现的描述，例如：“在一些实施例中”、“在实施例中”、“在一个实施例中”、“在另一个举例中”，“在一个举例中”、“在特定举例中”或“举例“，其不必然是引用本申请中的相同的实施例或示例。此外，本文中的特定特征、结构、材料或特性可以以任何合适的方式在一个或多个实施例或举例中结合。
尽管已经演示和描述了说明性实施例，本领域技术人员应该理解上述实施例不能被解释为对本申请的限制，并且可以在不脱离本申请的精神、原理及范围的情况下对实施例进行改变，替代和修改。

Claims (13)

  1. 一种电化学装置，其包括正极和电解液，所述正极包括正极集流体和设置于所述正极集流体的至少一个表面上的正极活性材料层，
    其中所述正极活性材料层包含正极活性材料，所述正极活性材料包含Mg元素，基于所述正极活性材料的总重量，所述Mg元素的重量为X ppm，且300≤X≤30000；
    其中所述电解液包含羧酸酯，基于所述电解液的总重量，所述羧酸酯的重量百分比为Y％，Y≤60；
    其中所述电化学装置满足5≤X/Y≤6000。
  2. 根据权利要求1所述的电化学装置，其中所述正极活性材料颗粒的Dn50为A μm，且2≤A≤25。
  3. 根据权利要求2所述的电化学装置，其中所述电化学装置满足0.04≤A/Y≤6.25。
  4. 根据权利要求1所述的电化学装置，其中所述正极活性材料满足条件(a)-(d)中的至少一者：
    (a)所述正极活性材料的比表面积为C m 2/g，且满足0.004≤C/Y≤0.1；
    (b)所述正极活性材料颗粒的Dv10/Dn10为Z，且满足1.5≤Z≤11；
    (c)所述正极活性材料进一步包含M1元素，所述M1元素包含Al、Mo、Zr、Ti、Fe、V、Cr、Ba、Sr或Nb中的至少一种；
    (d)所述正极活性材料层包含M2元素，所述M2元素包含F、B、Cl、S或P中的至少一种。
  5. 根据权利要求1所述的电化学装置，其中所述正极活性材料颗粒满足条件(e)或(f)中的至少一者：
    (e)所述正极活性材料颗粒的Dv10在2.2μm至4.1μm的范围内；
    (f)所述正极活性材料颗粒的Dn10在0.35μm至1.4μm的范围内。
  6. 根据权利要求1所述的电化学装置，其中所述正极活性材料层的压实密度大于等于4.0g/cm 3。
  7. 根据权利要求1所述的电化学装置，其中所述羧酸酯包含乙酸乙酯、乙酸丙酯、丙酸乙酯、丙酸甲酯、丙酸丙酯、丙酸丁酯、丙酸戊酯、丁酸乙酯、丁酸丁酯、丁酸丙酯或丁酸戊酯中的至少一种。
  8. 根据权利要求1所述的电化学装置，其中所述电解液进一步包含多腈化合物，所述多腈化合物包含不含醚的二腈化合物、醚二腈化合物、不含醚的三腈化合物或醚三腈化合物中的至少一种。
  9. 根据权利要求8所述的电化学装置，其中所述电解液满足条件(g)至(j)中的至少一者：
    (g)所述不含醚的二腈化合物包含丙二腈、丁二腈、戊二腈、己二腈、庚二腈、辛二腈、壬二腈、葵二腈、甲基丙二腈、乙基丙二腈、异丙基丙二腈、叔丁基丙二腈、甲基丁二腈、2-亚甲基戊二腈、1,4-二氰基-3-丁烯、2,2-二甲基丁二腈、2,3-二甲基丁二腈、2,3,3-三甲基丁二腈、2,2,3,3-四甲基丁二腈、2,3-二乙基-2,3-二甲基丁二腈、2,2-二乙基-3,3-二甲基丁二腈、双环己基-1,1-二甲腈、双环己基-2,2-二甲腈、双环己基-3,3-二甲腈、2,5-二甲基-2,5-己烷二甲腈、2,3-二异丁基-2,3-二甲基丁二腈、2,2-二异丁基-3,3-二甲基丁二腈、2-甲基戊二腈、2,3-二甲基戊二腈、2,4-二甲基戊二腈、2,2,3,3-四甲基戊二腈、2,2,4,4-四甲基戊二腈、2,2,3,4-四甲基戊二腈、2,3,3,4-四甲基戊二腈、1,4-二氰基戊烷、2,6-二氰基庚烷、2,7-二氰基辛烷、2,8-二氰基壬烷、1,6-二氰基癸烷、1,2-二氰基苯、1,3-二氰基苯、1,4-二氰基苯、3,3'-(亚乙基二氧)二丙腈、3,3'-(亚乙基二硫)二丙腈、1,4-二氰基-2-丁烯或反丁烯二腈中的至少一种；
    (h)所述醚二腈化合物包括：
    Figure PCTCN2021106704-appb-100001
    Figure PCTCN2021106704-appb-100002
    中的至少一种；
    (i)所述不含醚的三腈化合物包括：
    Figure PCTCN2021106704-appb-100003
    中的至少一种；
    (j)所述醚三腈化合物包括：
    Figure PCTCN2021106704-appb-100004
    Figure PCTCN2021106704-appb-100005
    中的至少一种。
  10. 根据权利要求8所述的电化学装置，其中基于所述电解液的总重量，所述不含醚的二腈化合物的重量百分比为B％，且满足0.0001≤B/X≤0.02。
  11. 根据权利要求8所述的电化学装置，其中所述多腈化合物至少包括醚二腈化合物和三腈化合物，所述三腈化合物包括所述不含醚的三腈化合物或所述醚三腈化合物中的至少一种，其中基于所述电解液的总重量，所述醚二腈化合物的重量百分比为H％，所述三腈化合物的重量百分比为G％，且满足H/G≤2。
  12. 根据权利要求8所述的电化学装置，其中所述多腈化合物至少包括不含醚的二腈化合物，所述不含醚的二腈化合物包括饱和二腈化合物和不饱和二腈化合物，
    其中基于所述电解液的总重量，所述饱和二腈化合物的重量百分比为Q％，所述不饱和二腈化合物的重量百分比为V％，且满足0.05≤V/Q≤1。
  13. 一种电子装置，其包含如权利要求1至12任一项所述的电化学装置。
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