WO2022247929A1 - 一种电解液及其电化学装置和电子装置 - Google Patents

一种电解液及其电化学装置和电子装置 Download PDF

Info

Publication number
WO2022247929A1
WO2022247929A1 PCT/CN2022/095586 CN2022095586W WO2022247929A1 WO 2022247929 A1 WO2022247929 A1 WO 2022247929A1 CN 2022095586 W CN2022095586 W CN 2022095586W WO 2022247929 A1 WO2022247929 A1 WO 2022247929A1
Authority
WO
WIPO (PCT)
Prior art keywords
substituted
unsubstituted
group
negative electrode
electrolytic solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2022/095586
Other languages
English (en)
French (fr)
Inventor
王仁和
王子沅
余乐
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Envision Dynamics Technology Jiangsu Co Ltd
Envision Intelligent Innovation Dynamics Technology Shanghai Ltd
Original Assignee
Envision Dynamics Technology Jiangsu Co Ltd
Envision Intelligent Innovation Dynamics Technology Shanghai Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Envision Dynamics Technology Jiangsu Co Ltd, Envision Intelligent Innovation Dynamics Technology Shanghai Ltd filed Critical Envision Dynamics Technology Jiangsu Co Ltd
Priority to US18/009,991 priority Critical patent/US20230231191A1/en
Priority to EP22810653.0A priority patent/EP4350833A4/en
Priority to CN202280004040.6A priority patent/CN115606032A/zh
Priority to JP2022580451A priority patent/JP2024505315A/ja
Publication of WO2022247929A1 publication Critical patent/WO2022247929A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—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
    • 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
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M10/058—Construction or manufacture
    • 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
    • H01M4/134—Electrodes based on metals, Si 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
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • H01M2004/027—Negative electrodes
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the embodiments of the present application relate to the field of electrolyte technology, for example, an electrolyte and its electrochemical device and electronic device.
  • lithium-ion batteries Due to the important advantages of high voltage and high capacity, long cycle life and good safety performance, lithium-ion batteries have broad application prospects in portable electronic devices, electric vehicles, space technology, and defense industries.
  • the electrolyte is the "blood" of the lithium battery, one of the four key raw materials of the lithium battery, the carrier of ion transmission in the battery, and the role of conducting lithium ions between the positive and negative electrodes. Capacity, operating temperature range, cycle life, safety performance, etc. all have important influences.
  • An embodiment of the present application provides an electrolyte and its electrochemical device and electronic device.
  • the electrochemical device made of the electrolyte of the present application has excellent cycle performance at high temperature and room temperature, and has low internal resistance.
  • an embodiment of the present application provides an electrolyte, and an embodiment of the present application adopts the following technical solutions:
  • a kind of electrolytic solution comprises the compound shown in formula (I):
  • R 1 , R 3 , and R 4 are each independently selected from hydrogen, cyano, substituted or unsubstituted C 1-12 hydrocarbon groups, substituted or unsubstituted C 1-12 carbonoxy groups, substituted or unsubstituted C 6-26 aryl group, substituted or unsubstituted C 2-12 amide group, substituted or unsubstituted C 0-12 phosphate ester group, substituted or unsubstituted C 0-12 sulfonyl group, substituted Or unsubstituted C 0-12 silyloxy group or substituted or unsubstituted C 0-12 borate ester group, when substituted, the substituent includes a halogen atom;
  • R 2 is selected from C 1-12 substituted or unsubstituted Substituted hydrocarbon group, substituted or unsubstituted C 1-12 carbonoxy group, substituted or unsubstituted C 6-26 aryl group, substituted or unsubstituted C
  • a C 1-12 hydrocarbon group refers to a hydrocarbon group containing 1 to 12 carbon atoms.
  • Electrolyte of the present application by adding the compound shown in formula (I), can improve negative electrode film-forming, reach the effect of reducing the amount of negative electrode film-forming additives, improving internal resistance, the electrochemical device that the electrolyte of the present application is made has excellent Excellent high temperature, room temperature cycle performance, and low internal resistance.
  • the mass content of the compound represented by the formula (I) is 0.1% to 5%, such as 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6% %, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9% , 4%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9% or 5%. If the amount of compound shown in formula (I) is too little, less than 0.1%, the film-forming effect will not be obvious; if the amount of compound shown in formula (I) is too much, more than 5%, the impedance will be sharp increase.
  • the mass content of the compound represented by the formula (I) is 0.3% to 3%.
  • the carbonyl group includes one of ether group, ester group and carbonyl group.
  • R 1 , R 3 , and R 4 are each independently selected from hydrogen, substituted or unsubstituted C 1-12 hydrocarbon groups; as a preferred embodiment, R 2 is selected from substituted or unsubstituted C 1-12 Substituted Hydrocarbyl.
  • the compound shown in the formula (I) is dimethyl fumarate Methyl methacrylate Dimethyl maleate 1,1,1,3,3,3-Hexafluoroisopropyl methacrylate vinyl methacrylate Any one or a mixture of two or more of them.
  • the typical but non-limiting combination of the mixture is a mixture of two, three, four or five, such as a mixture of dimethyl fumarate and methyl methacrylate, dimethyl fumarate, cis-butyl Mixture of dimethyl alkeneate, mixture of dimethyl fumarate, 1,1,1,3,3,3-hexafluoroisopropyl methacrylate, dimethyl fumarate, vinyl methacrylate Mixture of esters, dimethyl fumarate, methyl methacrylate, mixture of dimethyl maleate, dimethyl fumarate, methyl methacrylate, methacrylic acid 1,1,1, Mixture of 3,3,3-hexafluoroisopropyl ester, mixture of dimethyl fumarate, methyl methacrylate, vinyl methacrylate, methyl methacrylate, dimethyl maleate, Mixture of 1,1,1,3,3,3-hexafluoroisopropyl methacrylate, mixture of methyl methacrylate, dimethyl maleate, dimalene Di
  • the electrolytic solution is formed at a temperature of 45°C and a hot-pressed pressure of 0.1 MPa to produce HF. Based on the quality of the electrolytic solution after the chemical formation, the mass content of the produced HF is 20ppm to 800ppm.
  • the mass content of HF is 20ppm, 30ppm, 40ppm, 50ppm, 60ppm, 70ppm, 80ppm, 90ppm, 100ppm, 110ppm, 120ppm, 130ppm, 140ppm, 150ppm, 160ppm, 170ppm, 180ppm, 190ppm, 200ppm, 250ppm, 300ppm, 35ppm 400ppm, 450ppm, 500ppm, 550ppm, 600ppm, 650ppm, 700ppm, 750ppm, 800ppm, etc.
  • a trace amount of HF is used as a reaction initiator. If the amount of HF is too much, more than 800ppm, the cycle performance of the electrochemical device will be poor and the impedance will increase. Therefore, the compound represented by formula (I) can inhibit the acidification of the electrolyte after forming a film, thereby improving the cycle performance of the electrochemical device.
  • an embodiment of the present application provides an electrochemical device, including a negative electrode, a positive electrode, and the electrolyte described in the first aspect.
  • the electrochemical device of the present application includes any device that undergoes an electrochemical reaction, and its specific examples include all kinds of primary batteries, secondary batteries, fuel cells, solar cells, or capacitors.
  • the electrochemical device is a lithium secondary battery, including a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery or a lithium ion polymer secondary battery.
  • the electrochemical device of the present application is an electrochemical device comprising a positive electrode having a positive electrode active material capable of storing and releasing metal ions and a negative electrode having a negative electrode active material capable of storing and releasing metal ions.
  • the negative electrode includes a negative electrode active material and a current collector, and the negative electrode active material includes graphite or silicon carbon negative electrode active material.
  • the silicon-carbon negative electrode active material is selected from any one or a mixture of two or more of silicon, silicon-oxygen compounds and silicon-based alloys.
  • the negative electrode also includes a carbon material selected from any one or a mixture of two or more of acetylene black, conductive carbon black, carbon fiber, carbon nanotube and Ketjen black.
  • the porosity of the negative electrode is 20% to 40%, such as 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30% %, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, etc. If the porosity of the negative electrode is too low, lower than 20%, the impedance will be large and the cycle performance will be affected. If the porosity of the negative electrode is too high, higher than 40%, the electrode will become thicker, the side reactions will increase, and the cycle and Capacity retention performance is affected.
  • the porosity of the negative electrode or the positive electrode described herein means the porosity of the negative electrode sheet or the positive electrode sheet.
  • the positive electrode includes a positive electrode active material, and the positive electrode active material is selected from any one or a mixture of two or more of lithium iron phosphate, lithium-nickel transition metal composite oxide, and lithium-nickel-manganese composite oxide with a spinel structure.
  • the electrochemical device also includes a positive electrode, the porosity of the positive electrode is 20% to 35%, such as 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, etc. If the porosity of the positive electrode is too low, lower than 20%, the impedance will be large and the cycle performance will be affected. If the porosity of the positive electrode is too high, higher than 35%, the electrode will become thicker, the side reactions will increase, and the cycle and Capacity retention performance is affected.
  • the porosity of the positive electrode is 20% to 35%, such as 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, etc. If the porosity of the positive electrode is too low, lower than 20%, the impedance will be large and the cycle performance will be affected. If the porosity of the positive
  • the lithium iron phosphate is nano lithium iron phosphate or lithium iron phosphate secondary balls.
  • the Dv50 particle size of the nano-lithium iron phosphate is 0.8 ⁇ m to 2.5 ⁇ m, for example, 0.8 ⁇ m, 0.9 ⁇ m, 1 ⁇ m, 1.1 ⁇ m, 1.2 ⁇ m, 1.3 ⁇ m, 1.4 ⁇ m, 1.5 ⁇ m, 1.6 ⁇ m, 1.7 ⁇ m, 1.8 ⁇ m , 1.9 ⁇ m, 2 ⁇ m, 2.1 ⁇ m, 2.2 ⁇ m, 2.3 ⁇ m, 2.4 ⁇ m, 2.5 ⁇ m, etc., wherein, Dv50 is the particle size corresponding to when the cumulative volume percentage of the positive electrode active material reaches 50%.
  • the Dv50 of the positive electrode active material can be tested by a Malvern 3000 laser particle size analyzer, and the average value of three tests is the test result.
  • the Dv50 particle size of the lithium iron phosphate secondary ball is 7 ⁇ m to 11 ⁇ m, for example, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m, 11 ⁇ m, etc.
  • the general formula of the lithium nickel transition metal composite oxide is Li 1+a Ni x Co y Mnz M b O 2-e X e , in the general formula, -0.2 ⁇ a ⁇ 0.2, 0.3 ⁇ x ⁇ 0.95 , 0.05 ⁇ y ⁇ 0.3, 0.03 ⁇ z ⁇ 0.4, 0 ⁇ b ⁇ 0.05, 0 ⁇ e ⁇ 0.1, M is selected from Al, Ti, Zr, Nb, Sr, Sc, Sb, Y, Ba, Co, Mn Any one or a combination of two or more, X is selected from F and/or Cl; It should be noted that the above chemical formula of the lithium nickel transition metal composite oxide is when the battery SOC (State of Charge) is 0 Chemical formula at %.
  • an embodiment of the present application provides an electronic device, the electronic device including the electrochemical device described in the second aspect.
  • Such electronic devices include, but are not limited to, types such as notebook computers, pen-input computers, mobile computers, electronic book players, cellular phones, portable fax machines, portable copiers, portable printers, headsets, video recorders, liquid crystal Televisions, 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, large household storage batteries or lithium-ion capacitors, etc.
  • types such as notebook computers, pen-input computers, mobile computers, electronic book players, cellular phones, portable fax machines, portable copiers, portable printers, headsets, video recorders, liquid crystal Televisions, portable cleaners, portable CD players, mini discs, transceivers, electronic organizers, calculators, memory cards, portable tape recorders, radios, backup power supplies, electric motors, automobiles, motorcycles,
  • the cycle performance of the electrochemical device at high temperature and room temperature can be improved, and the internal resistance of the electrochemical device can be reduced at the same time.
  • the electrolyte solution of the present application comprises the compound shown in formula (I):
  • R 1 , R 3 , and R 4 are each independently selected from hydrogen, cyano, substituted or unsubstituted C 1-12 hydrocarbon groups, substituted or unsubstituted C 1-12 carbonoxy groups, substituted or unsubstituted C 6-26 aryl group, substituted or unsubstituted C 2-12 amide group, substituted or unsubstituted C 0-12 phosphate ester group, substituted or unsubstituted C 0-12 sulfonyl group, substituted Or unsubstituted C 0-12 silyloxy group or substituted or unsubstituted C 0-12 borate ester group, when substituted, the substituent includes a halogen atom;
  • R 2 is selected from C 1-12 substituted or unsubstituted Substituted hydrocarbon group, substituted or unsubstituted C 1-12 carbonoxy group, substituted or unsubstituted C 6-26 aryl group, substituted or unsubstituted C
  • the electrochemical device is a lithium ion battery
  • the lithium ion battery is a primary lithium battery or a secondary lithium battery, including: a positive electrode, a negative electrode, a diaphragm between the positive electrode and the negative electrode, and an electrolyte.
  • the preparation method of the secondary lithium battery of the present application is as follows:
  • NMP N-methylpyrrolidone
  • the positive electrode active material LiNi 0.8 Co 0.1 Mn 0.1 O 2
  • polyvinylidene fluoride as a binder
  • Super P as a conductive agent
  • NMP N-methylpyrrolidone
  • the mass ratio is 96:1:1: 2.
  • CMC-Na sodium carboxymethylcellulose
  • SBR styrene-butadiene rubber
  • a polypropylene film (PP) with a thickness of 12 ⁇ m was used as a separator, and the positive electrode, separator, and negative electrode prepared above were sequentially stacked, so that the separator was placed between the positive and negative electrodes to play the role of isolation. Then wrap it with aluminum-plastic film, transfer it to a vacuum oven to dry at 120°C, inject the electrolyte solution prepared above at 3.0g/Ah, seal it, and carry out electrolyte formation, and finally prepare a soft-pack battery with a capacity of 1Ah (that is, a lithium-ion battery) .
  • PP polypropylene film
  • the formation conditions of the electrolyte solution in the ternary battery cell and the iron-lithium battery cell involved in the present application are respectively as follows.
  • the specific step of forming the electrolyte in the ternary battery is as follows: after injecting the electrolyte, maintain a hot pressure environment of 0.1 MPa, charge it to 3.05V at 0.02C at 45°C in a static state, and let it stand for 30min Then charge it to 3.4V at 0.05C, let it stand still for 30 minutes, and then charge it to 3.75V at 0.1C, then cut off the air bag and vacuum seal it, and let it stand at room temperature for 48 hours to complete the formation of the electrolyte.
  • the formation steps of the electrolyte in the iron-lithium battery cell are as follows: after injecting the electrolyte, maintain a hot-pressed environment of 0.1 MPa, charge it at 0.02C at 45°C for 17 minutes in a static state, and then charge it at 0.02C for 17 minutes after standing for 5 minutes. Charge at 0.02C to 0.3Ah, then cut off the air bag and vacuum seal it, and let it stand at room temperature for 48 hours to complete the formation of the electrolyte.
  • the compound shown in formula (I) adopts the following five kinds, compound 1 is methyl methacrylate, compound 2 is dimethyl fumarate, and compound 3 is dimethyl maleate ester, compound 4 is 1,1,1,3,3,3-hexafluoroisopropyl methacrylate, and compound 5 is vinyl methacrylate.
  • the secondary battery of the present application can be tested by the following methods:
  • cycle charge and discharge with a current of 1C within the specified potential range record the discharge capacity of each cycle, and end the test when the battery capacity reaches 80% of the first cycle capacity .
  • the ratio of its value to the 3C current value is the DC resistance of the battery.
  • the DCR test result after the battery is fully charged for the first time is the initial DCR of the battery.
  • the cut-off voltage of charging and discharging is as follows:
  • LFP-graphite is 2.5V to 3.65V
  • 811-graphite is 2.8V to 4.2V
  • 811-siloxane is 2.8V to 4.25V.
  • the electrolyte composition of Examples 1 to 7 of the present application and Comparative Example 1 are shown in Table 1-1.
  • the above preparation method was used to prepare a lithium-ion battery, and its performance was tested.
  • the test results are shown in Table 1-2.
  • the addition amount of the compound shown in formula (I) is 0.3 to 4%
  • the 80% cycle number of the room temperature cycle of embodiment 2-5 is 1250 to 2023
  • the high temperature cycle 80% cycle number is 1119 to 1810
  • the initial The DCR is 98mOhm (milliohm) to 105mOhm (milliohm)
  • the capacity retention rate is 95% to 98% when stored at 60°C for 30 days.
  • the test results are significantly improved compared to Comparative Example 1 without adding the compound.
  • the applicant also speculates further that the addition of the compound shown in formula (I) can be combined with The synergy between the electrodes makes the lithium battery have better high temperature, room temperature cycle performance, high temperature storage performance, and lower internal resistance.
  • composition of the electrolyte of Examples 8 to 10 of the present application is as shown in Table 2-1, and the lithium-ion battery is prepared by the above-mentioned preparation method, and its performance is tested, and the test results are as shown in Table 2-2.
  • the electrochemical device can have excellent high temperature, room temperature cycle performance, high temperature storage performance, and at the same time have Lower internal resistance.
  • the positive electrode material lithium iron phosphate in this embodiment and embodiment 3 are lithium iron phosphate secondary balls, and the only difference from embodiment 3 is that the Dv50 particle size of the lithium iron phosphate secondary balls in this embodiment is 7 ⁇ m.
  • Example 3 The Dv50 particle size of the lithium iron phosphate secondary ball is 9 ⁇ m, and the electrolyte composition and other compositions are the same as those in Example 3.
  • the positive electrode material lithium iron phosphate in this embodiment and embodiment 3 are lithium iron phosphate secondary balls, and the only difference from embodiment 3 is that the Dv50 particle size of the lithium iron phosphate secondary balls in this embodiment is 11 ⁇ m.
  • Example 3 The Dv50 particle size of the lithium iron phosphate secondary ball is 9 ⁇ m, and the electrolyte composition and other compositions are the same as those in Example 3.
  • the negative electrode of this application uses graphite
  • the positive electrode uses lithium iron phosphate secondary balls
  • the Dv50 particle size of the lithium iron phosphate secondary balls is 7 ⁇ m to 11 ⁇ m, which can better play the role of electrolyte in the electrolyte.
  • the synergistic effect between the compound and the pole piece makes the battery have better high temperature, room temperature cycle performance, high temperature storage performance, and lower internal resistance.
  • Example 3 The difference between this example and Example 3 is that the positive electrode uses nano-lithium iron phosphate, and the Dv50 particle size of nano-lithium iron phosphate is 0.8 ⁇ m, and the electrolyte composition and other compositions are the same as those in Example 3.
  • Example 3 The difference between this example and Example 3 is that the positive electrode uses nano-lithium iron phosphate, and the Dv50 particle size of nano-lithium iron phosphate is 1.6 ⁇ m, and the composition of the electrolyte and other compositions are the same as those of Example 3.
  • Example 3 The difference between this example and Example 3 is that the positive electrode uses nano-lithium iron phosphate, and the Dv50 particle size of nano-lithium iron phosphate is 2.5 ⁇ m, and the composition of the electrolyte and other compositions are the same as those of Example 3.
  • the negative electrode of this application uses graphite
  • the positive electrode uses nano-lithium iron phosphate
  • the Dv50 particle size of nano-lithium iron phosphate is 0.8 ⁇ m to 2.5 ⁇ m, which can better play the role of compounds in the electrolyte and
  • the synergy between the pole pieces makes the lithium battery have better high temperature, room temperature cycle performance, high temperature storage performance, and lower internal resistance.
  • the negative electrode materials of this embodiment and embodiment 3 are all graphite, and the difference with embodiment 3 is only that the porosity of graphite in this embodiment is 20%, and the porosity of graphite in embodiment 3 is 30%.
  • the liquid composition and other compositions are all the same as in Example 3.
  • the negative electrode material of this embodiment and embodiment 3 is graphite, and the only difference from embodiment 3 is that the porosity of the graphite in this embodiment is 40%, and the positive electrode, electrolyte composition and other compositions are the same as that of embodiment 3.
  • the negative electrode of the present application uses graphite, and when the porosity of the graphite material is 20% to 40%, the number of 80% cycles at room temperature is 1033 to 1826, and the number of cycles at 80% at high temperature is 989 to 1607.
  • the DCR is 99mOhm to 113mOhm, and the capacity retention rate is 92% to 96% when stored at 60°C for 30 days.
  • the cycle number of 80% at room temperature is 1749 to 1826
  • the high temperature cycle The number of 80% turns is 1449 to 1607.
  • the addition of the compound shown in the formula (I) in the electrolyte and by controlling the porosity of the graphite material can better exert the synergistic effect between the compound in the electrolyte and the pole piece , so that the lithium battery has better high temperature, room temperature cycle performance, high temperature storage performance, and lower internal resistance.
  • Example 18 The difference between this example and Example 18 is that the porosity of the positive electrode material is different.
  • the porosity of 811 in this example is 20%, the porosity of 811 in Example 18 is 28%, and the others are the same as in Example 18. same.
  • Example 18 The difference between this example and Example 18 is that the porosity of the positive electrode material is different.
  • the porosity of 811 in this example is 35%
  • the porosity of 811 in Example 18 is 28%
  • the others are the same as in Example 18. same.
  • the positive electrode of the present application adopts 811, and the porosity of the positive electrode is controlled at 20% to 35%, which can better exert the synergistic effect between the compound in the electrolyte and the pole piece, making the lithium battery more efficient.
  • Example 22 The electrolyte compositions of Example 22, Comparative Example 4, and Examples 23 to 24 are shown in Table 7-1. Lithium-ion batteries were prepared using the above preparation method, and their performance was tested. The test results are shown in Table 7-2.
  • Example 18 which uses graphite as the negative electrode
  • the negative electrodes of Examples 22 to 24 use a carbon-silicon system.
  • the synergistic effect can improve the capacity performance of the battery, further improve the energy density, and is more conducive to Meet the room temperature and high temperature cycle requirements of the battery.
  • Example 24 The difference between this example and Example 24 is that the content of SiO x in silicon carbon is different, wherein, the content of SiO x in silicon carbon in Example 25 is 1%, and the content of SiO x in silicon carbon in Example 24 is 10% , others are the same as in Example 24. Its performance was tested in Example 26.
  • Embodiment 24 lies in that the content of SiO x in silicon carbon is 5%, and the others are the same as Embodiment 24.
  • Embodiment 24 lies in that the content of SiO x in silicon carbon is 20%, and the others are the same as Embodiment 24.
  • lithium-ion batteries were prepared by the above-mentioned preparation method, and the performance of the batteries was tested. The test results are shown in Table 8.
  • the SiO x content in it is between 1 and 20%, which can better exert the synergistic effect between the compound in the electrolyte and the pole piece, so that the lithium battery has a large energy density. While improving, it maintains good high temperature, room temperature cycle performance, and high temperature storage performance, and can meet applications with high energy density and low cycle requirements.
  • Comparative Example 5 The only difference between Comparative Example 5 and Example 3 is the content of HF, which is 5000ppm in Comparative Example 5 and 100ppm in Example 3.
  • Comparative Example 5 a lithium-ion battery was prepared using the above preparation method, and its performance was tested. The test results are shown in Table 9.
  • the application illustrates the detailed process equipment and process flow of the present application through the above-mentioned examples, but the application is not limited to the above-mentioned detailed process equipment and process flow, that is, it does not mean that the application must rely on the above-mentioned detailed process equipment and process flow to be implemented .
  • Those skilled in the art should understand that any improvement to the present application, the equivalent replacement of each raw material of the product of the present application, the addition of auxiliary components, the selection of specific methods, etc., all fall within the scope of protection and disclosure of the present application.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Secondary Cells (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Primary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

一种电解液及其电化学装置和电子装置。一种电解液，包含式(I)所示的化合物，其中，R 1、R 3、R 4各自独立地选自氢、氰基、取代或未取代的C 1-12的烃基、取代或未取代的C 1-12的碳氧基、取代或未取代的C 6-26的芳基、取代或未取代的C 2-12的酰胺基、取代或未取代的C 0-12的磷酸酯基、取代或未取代的C 0-12的磺酰基、取代或未取代的C 0-12的硅氧基、取代或未取代的C 0-12的硼酸酯基，经取代时，取代基包括卤素原子。电解液可以改善电化学装置的高温、室温循环性能，同时降低电化学装置的内阻。

Description

一种电解液及其电化学装置和电子装置 技术领域
本申请实施例涉及电解液技术领域，例如涉及一种电解液及其电化学装置和电子装置。
背景技术
由于锂离子电池具有高电压、高容量的重要优点，且循环寿命长、安全性能好，使其在便携式电子设备、电动汽车、空间技术、国防工业等多方面具有广阔的应用前景。
电解液为锂电池的“血液”，是锂电池四大关键原材料之一，是电池中离子传输的载体，在正负极之间起到传导锂离子的作用，对锂电池的能量密度、比容量、工作温度范围、循环寿命、安全性能等均有重要影响。
但是，常用的VC等负极成膜添加剂在产生保护效果的同时具有高内阻的特点，因此难以兼顾高温和室温循环性能以及低电阻的特点。
发明内容
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。
本申请一实施例提供一种电解液及其电化学装置和电子装置，本申请的电解液制成的电化学装置具有优良的高温、室温循环性能，同时具有较低的内阻。
第一方面，本申请实施例提供一种电解液，本申请一实施例采用以下技术方案：
一种电解液，包含式(I)所示的化合物：
Figure PCTCN2022095586-appb-000001
其中，R 1、R 3、R 4各自独立地选自氢、氰基、取代或未取代的C 1-12的烃基、取代或未取代的C 1-12的碳氧基、取代或未取代的C 6-26的芳基、取代或未取代的C 2-12的酰胺基、取代或未取代的C 0-12的磷酸酯基、取代或未取代的C 0-12的磺酰 基、取代或未取代的C 0-12的硅氧基或取代或未取代的C 0-12的硼酸酯基，经取代时，取代基包括卤素原子；R 2选自C 1-12的取代或未取代的烃基、取代或未取代的C 1-12的碳氧基、取代或未取代的C 6-26的芳基、取代或未取代的C 2-12的酰胺基、取代或未取代的C 0-12的磷酸酯基、取代或未取代的C 0-12的磺酰基、取代或未取代的C 0-12的硅氧基或取代或未取代的C 0-12的硼酸酯基，经取代时，取代基包括卤素原子。
其中，作为说明，C 1-12的烃基，是指含有碳原子数为1至12的烃基。
本申请的电解液，通过添加式(I)所示的化合物，可改善负极成膜，达到减少负极成膜添加剂用量、改善内阻的效果，本申请的电解液制成的电化学装置具有优秀的高温、室温循环性能，同时具有较低的内阻。
本申请中，基于所述电解液的质量，所述式(I)所示的化合物的质量含量为0.1％至5％，例如为0.1％、0.2％、0.3％、0.4％、0.5％、0.6％、0.7％、0.8％、0.9％、1％、1.1％、1.2％、1.3％、1.4％、1.5％、1.6％、1.7％、1.8％、1.9％、2％、2.1％、2.2％、2.3％、2.4％、2.5％、2.6％、2.7％、2.8％、2.9％、3％、3.1％、3.2％、3.3％、3.4％、3.5％、3.6％、3.7％、3.8％、3.9％、4％、4.1％、4.2％、4.3％、4.4％、4.5％、4.6％、4.7％、4.8％、4.9％或5％等。如果式(I)所示的化合物的用量太少，少于0.1％，会使成膜效果不明显；如果式(I)所示的化合物的用量太多，多于5％，会使阻抗剧增。
作为优选方案，基于所述电解液的质量，所述式(I)所示的化合物的质量含量为0.3％至3％。
本申请中，所述碳氧基包含醚基、酯基、羰基中的一种。
作为本申请的优选方案，R 1、R 3、R 4各自独立地选自氢、取代或未取代的C 1-12的烃基；作为优选方案，R 2选自C 1-12的取代或未取代的烃基。
作为优选方案，所述式(I)所示的化合物为富马酸二甲酯
Figure PCTCN2022095586-appb-000002
甲基丙烯酸甲酯
Figure PCTCN2022095586-appb-000003
顺丁烯二酸二甲酯
Figure PCTCN2022095586-appb-000004
甲基丙烯酸1,1,1,3,3,3-六氟异丙酯
Figure PCTCN2022095586-appb-000005
甲 基丙烯酸乙烯酯
Figure PCTCN2022095586-appb-000006
中的任意一种或两种以上的混合物。所述混合物典型但非限制的组合为两种、三种、四种或5种的混合物，例如为富马酸二甲酯、甲基丙烯酸甲酯的混合物，富马酸二甲酯、顺丁烯二酸二甲酯的混合物，富马酸二甲酯、甲基丙烯酸1,1,1,3,3,3-六氟异丙酯的混合物，富马酸二甲酯、甲基丙烯酸乙烯酯的混合物，富马酸二甲酯、甲基丙烯酸甲酯、顺丁烯二酸二甲酯的混合物，富马酸二甲酯、甲基丙烯酸甲酯、甲基丙烯酸1,1,1,3,3,3-六氟异丙酯的混合物，富马酸二甲酯、甲基丙烯酸甲酯、甲基丙烯酸乙烯酯的混合物，甲基丙烯酸甲酯、顺丁烯二酸二甲酯、甲基丙烯酸1,1,1,3,3,3-六氟异丙酯的混合物，甲基丙烯酸甲酯、顺丁烯二酸二甲酯、甲基丙烯酸乙烯酯的混合物，顺丁烯二酸二甲酯、甲基丙烯酸1,1,1,3,3,3-六氟异丙酯、甲基丙烯酸乙烯酯的混合物，富马酸二甲酯、甲基丙烯酸甲酯、顺丁烯二酸二甲酯、甲基丙烯酸1,1,1,3,3,3-六氟异丙酯的混合物，富马酸二甲酯、甲基丙烯酸甲酯、顺丁烯二酸二甲酯、甲基丙烯酸乙烯酯的混合物，甲基丙烯酸甲酯、顺丁烯二酸二甲酯、甲基丙烯酸1,1,1,3,3,3-六氟异丙酯、甲基丙烯酸乙烯酯的混合物，富马酸二甲酯、甲基丙烯酸甲酯、顺丁烯二酸二甲酯、甲基丙烯酸1,1,1,3,3,3-六氟异丙酯、甲基丙烯酸乙烯酯的混合物。
本申请中，所述电解液在温度为45℃，热压压强为0.1MPa的环境下进行化成后产生HF，基于所述化成后电解液的质量，产生的HF的质量含量为20ppm至800ppm，例如HF的质量含量为20ppm、30ppm、40ppm、50ppm、60ppm、70ppm、80ppm、90ppm、100ppm、110ppm、120ppm、130ppm、140ppm、150ppm、160ppm、170ppm、180ppm、190ppm、200ppm、250ppm、300ppm、350ppm、400ppm、450ppm、500ppm、550ppm、600ppm、650ppm、700ppm、750ppm、800ppm等。痕量HF作为反应引发剂，若HF量太多，多于800ppm，会使电化学装置的循环性能差，阻抗变大。因此，式(I)所示的化合物成膜之后可以抑制电解液变酸，从而改善电化学装置的循环性能。
第二方面，本申请实施例提供一种电化学装置，包括负极、正极和第一方面所述的电解液。
本申请的电化学装置包括发生电化学反应的任何装置，它的具体实例包括 所有种类的一次电池、二次电池、燃料电池、太阳能电池或电容。特别地，该电化学装置是锂二次电池，包括锂金属二次电池、锂离子二次电池、锂聚合物二次电池或锂离子聚合物二次电池。
在一些实施例中，本申请的电化学装置是具备具有能够吸留、放出金属离子的正极活性物质的正极以及具有能够吸留、放出金属离子的负极活性物质的负极的电化学装置。
所述负极包括负极活性材料和集流体，所述负极活性材料包括石墨或硅碳负极活性材料。
所述硅碳负极活性材料选自硅、硅氧化合物和硅基合金中的任意一种或两种以上的混合物。
所述负极还包括碳材料，所述碳材料选自乙炔黑、导电炭黑、碳纤维、碳纳米管和科琴黑中的任意一种或两种以上的混合物。
本申请中，所述负极的孔隙率为20％至40％，例如为20％、21％、22％、23％、24％、25％、26％、27％、28％、29％、30％、31％、32％、33％、34％、35％、36％、37％、38％、39％、40％等。如果负极的孔隙率太低，低于20％，会使阻抗较大，循环性能受影响，如果负极的孔隙率太高，高于40％，会使电极变厚，副反应变多，循环和容量保持性能受影响。
本文所述的负极或正极的孔隙率表示负极极片或正极极片的孔隙率。其中，极片的孔隙率的计算公式为：孔隙率＝1-(压实密度/真密度)。
所述正极包含正极活性材料，所述正极活性材料选自磷酸铁锂、锂镍过渡金属复合氧化物、具有尖晶石结构的锂镍锰复合氧化物的任意一种或两种以上的混合物。
所述的电化学装置，还包含正极，所述正极的孔隙率为20％至35％，例如为20％、21％、22％、23％、24％、25％、26％、27％、28％、29％、30％、31％、32％、33％、34％、35％等。如果正极的孔隙率太低，低于20％，会使阻抗较大，循环性能受影响，如果正极的孔隙率太高，高于35％，会使电极变厚，副反应变多，循环和容量保持性能受影响。
所述磷酸铁锂为纳米磷酸铁锂或者磷酸铁锂二次球。
所述纳米磷酸铁锂的Dv50粒径为0.8μm至2.5μm，例如为0.8μm、0.9μm、1μm、1.1μm、1.2μm、1.3μm、1.4μm、1.5μm、1.6μm、1.7μm、1.8μm、1.9 μm、2μm、2.1μm、2.2μm、2.3μm、2.4μm、2.5μm等，其中，Dv50为正极活性材料累计体积百分数达到50％时所对应的粒径。正极活性材料的Dv50可通过马尔文3000激光粒度仪进行测试，测试三次取平均值即为测试结果。
所述磷酸铁锂二次球的Dv50粒径为7μm至11μm，例如为7μm、8μm、9μm、10μm、11μm等。
所述锂镍过渡金属复合氧化物的通式为Li 1+aNi xCo yMn zM bO 2-eX e，所述通式中，-0.2＜a＜0.2，0.3≤x≤0.95，0.05≤y≤0.3，0.03≤z≤0.4，0≤b≤0.05，0≤e≤0.1，M选自Al、Ti、Zr、Nb、Sr、Sc、Sb、Y、Ba、Co、Mn中的任意一种或两种以上的组合，X选自F和/或Cl；需要说明的是，所述锂镍过渡金属复合氧化物的上述化学式通式是在电池SOC(State of Charge)为0％时的化学式。
第三方面，本申请实施例提供一种电子装置，所述电子装置包括第二方面所述的电化学装置。
所述电子装置包括但不限于如下类型，例如笔记本电脑、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、家庭用大型蓄电池或锂离子电容器等。
与相关技术相比，本申请实施例的有益效果为：
本申请实施例的电解液，通过添加式(I)所示的化合物，可以改善电化学装置的高温、室温循环性能，同时降低电化学装置的内阻。
在阅读并理解了详细描述后，可以明白其他方面。
具体实施方式
下面通过具体实施方式来进一步说明本申请的技术方案。
如无具体说明，本申请的各种原料均可市售购得，或根据本领域的常规方法制备得到。
本申请的电解液，包含式(I)所示的化合物：
Figure PCTCN2022095586-appb-000007
其中，R 1、R 3、R 4各自独立地选自氢、氰基、取代或未取代的C 1-12的烃基、取代或未取代的C 1-12的碳氧基、取代或未取代的C 6-26的芳基、取代或未取代的C 2-12的酰胺基、取代或未取代的C 0-12的磷酸酯基、取代或未取代的C 0-12的磺酰基、取代或未取代的C 0-12的硅氧基或取代或未取代的C 0-12的硼酸酯基，经取代时，取代基包括卤素原子；R 2选自C 1-12的取代或未取代的烃基、取代或未取代的C 1-12的碳氧基、取代或未取代的C 6-26的芳基、取代或未取代的C 2-12的酰胺基、取代或未取代的C 0-12的磷酸酯基、取代或未取代的C 0-12的磺酰基、取代或未取代的C 0-12的硅氧基或取代或未取代的C 0-12的硼酸酯基，经取代时，取代基包括卤素原子。
本申请中，电化学装置为锂离子电池，锂离子电池为一次锂电池或二次锂电池，包括：正极、负极、位于正极和负极之间的隔膜以及电解液。
本申请的二次锂电池的制备方法如下：
(1)LFP(LiFePO 4)正极的制备：
将正极活性材料(LiFePO 4)、作为粘结剂的聚偏氟乙烯以及作为导电剂的Super P按照重量比97:2:1进行混合后，加入N-甲基吡咯烷酮(NMP)，在真空搅拌机作用下搅拌至体系呈均一透明状，获得正极浆料；将正极浆料均匀涂覆于铝箔上；将铝箔在室温晾干后转移至烘箱干燥，然后经过冷压、分切得到正极(极片)；
(2)811(LiNi 0.8Co 0.1Mn 0.1O 2)正极的制备：
将正极活性材料(LiNi 0.8Co 0.1Mn 0.1O 2)、作为粘结剂的聚偏氟乙烯以及作为导电剂的Super P按照重量比98:1:1进行混合，加入N-甲基吡咯烷酮(NMP)，在真空搅拌机作用下搅拌至体系呈均一透明状，获得正极浆料；将正极浆料均匀涂覆于铝箔上；将铝箔在室温晾干后转移至烘箱干燥，然后经过冷压、分切得到正极(极片)；
(3)石墨负极的制备：
将人造石墨作为负极活性材料、Super P作为导电剂、羧甲基纤维素钠(CMC-Na)作为增稠剂、丁苯橡胶(SBR)作为粘结剂，按质量比96:1:1:2进行混 合，加入去离子水，在真空搅拌机作用下获得负极浆料；将负极浆料均匀涂覆在负极集流体铜箔上；将铜箔在室温晾干后转移至烘箱干燥，然后经过冷压、分切得到负极(极片)；
(4)硅氧负极的制备：
将氧化亚硅与人造石墨按质量比1:9混合作为负极活性材料，与作为导电剂的SWCNT和作为粘结剂的聚丙烯酸(PAA)按质量比96:0.2:3.8进行混合，加入去离子水，在真空搅拌机作用下获得负极浆料；将负极浆料均匀涂覆在负极集流体铜箔上；将铜箔在室温晾干后转移至烘箱干燥，然后经过冷压、分切得到负极(极片)；
(5)电解液的制备：
在含水量<10ppm的氩气气氛手套箱中，将电池级碳酸乙烯酯(EC)与碳酸甲乙酯(EMC)按照质量比3:7进行混合，形成有机溶剂。按照后述表格所述电解液组成定量加入其他成分，混合均匀，得到电解液。表中各成分含量为基于电解液的总重量计算得到的重量百分数；
(6)隔离膜的制备：
以聚丙烯膜作为隔离膜；
(7)二次电池的制备：
以厚度12μm的聚丙烯薄膜(PP)作为隔离膜，将上述制得的正极、隔离膜、负极依次进行叠片，使隔离膜处于正、负极中间起到隔离的作用。然后外包铝塑膜，转移至真空烘箱中120℃干燥，注入上述制得的电解液3.0g/Ah之后封口，进行电解液化成，最终制备得容量为1Ah的软包电池(即锂离子电池)。
电解液在本申请涉及的三元电芯以及铁锂电芯中的化成条件分别如下所述。
所述电解液在三元电芯的化成步骤具体为：将电解液进行注液后，保持0.1MPa的热压环境，以静置状态在45℃下以0.02C充电至3.05V，静置30min后以0.05C充电到3.4V，再次静置30min后以0.1C充电到3.75V，之后割去气袋并真空封装，常温静置48h，从而使电解液完成化成。
所述电解液在铁锂电芯的化成步骤具体为：将电解液进行注液后，保持0.1MPa的热压环境，以静置状态在45℃下以0.02C充电17min，静置5min后再以0.02C充到0.3Ah，之后割去气袋并真空封装，常温静置48h，从而使电解 液完成化成。
其中，本申请的示例中，式(I)所示的化合物采用以下五种，化合物1为甲基丙烯酸甲酯，化合物2为富马酸二甲酯，化合物3为顺丁烯二酸二甲酯，化合物4为甲基丙烯酸1,1,1,3,3,3-六氟异丙酯，化合物5为甲基丙烯酸乙烯酯。
本申请的二次电池可以通过如下方法进行测试：
一、二次电池循环测试
在指定温度(室温25℃或高温45℃)的烘箱内，以1C的电流在指定电位区间内进行循环充放电，记录每一圈的放电容量，当电池容量到达首圈容量80％时结束测试。
二、二次电池直流电阻(DCR)测试
在指定温度下，将电池以1C电流放电至50％SOC(荷电状态，反映电池的剩余容量)时，将电流调高至4C，并保持30s，检测更新的稳定电压与原平台电压的差，其数值与3C电流值的比值即为电池的直流电阻。电池首次满充后进行的DCR测试结果为电池的初始DCR。
三、二次电池高温存储容量保持率测试
将二次电池充满电后放置在60℃的恒温箱中，30天后取出，待冷却到室温后以0.33C倍率放电至截止电压，对照其容量相对于初始放电容量的百分比。
其中，充放电的截止电压具体如下：
LFP-石墨是2.5V至3.65V，811-石墨是2.8V至4.2V，811-硅氧是2.8V至4.25V。
本申请的实施例1至7，对比例1的电解液组成如表1-1所示，采用上述制备方法制备锂离子电池，对其性能进行测试，测试结果如表1-2所示。
表1-1
Figure PCTCN2022095586-appb-000008
Figure PCTCN2022095586-appb-000009
注：“-”代表未添加，下同。
表1-2
Figure PCTCN2022095586-appb-000010
由表1-2的数据可以看出，正极采用磷酸铁锂，负极采用石墨时，相对于对比例1不加式(I)所示的化合物，本申请的电解液由于添加了式(I)所示的化合物，加入量为0.1至5％时，实施例1至实施例7的室温循环80％圈数为1021至2023，高温循环80％圈数为887至1810，初始DCR为98至109mOhm(毫欧姆)，60℃存储30天容量保持率为91至98％，该各项测试结果都不同程度的优于对比例1。特别是当式(I)所示的化合物的加入量在0.3至4％时，实施例2-5的室温循环80％圈数为1250至2023，高温循环80％圈数为1119至1810，初始DCR为98mOhm(毫欧姆)至105mOhm(毫欧姆)，60℃存储30天容量保持率为95％至98％，测试结果相对于未加入该化合物的对比例1显著提高，电解液的电化学特性得到了改善。申请人认为其原因在于，通过添加式(I)所示的化合物，能够使负极表面成膜得到改善，优化内阻，申请人还进一步推测，式(I)所示的化合物的添加，能够与电极极片之间产生协同作用，使得锂电池具有更好的高温、室温循环性能、高温存储性能，实现更低的内阻。
本申请的实施例8至10的电解液组成如表2-1所示，采用上述制备方法制 备锂离子电池，对其性能进行测试，测试结果如表2-2所示。
表2-1
Figure PCTCN2022095586-appb-000011
表2-2
Figure PCTCN2022095586-appb-000012
由表2-2的数据可以看出，电解液中加入的式(I)所示的化合物为不同组合时，均可以使电化学装置具有优秀的高温、室温循环性能、高温存储性能，同时具有较低的内阻。
实施例11
本实施例与实施例3的正极材料磷酸铁锂均为磷酸铁锂二次球，与实施例3的不同之处仅在于，本实施例磷酸铁锂二次球的Dv50粒径为7μm，实施例3磷酸铁锂二次球的Dv50粒径为9μm，电解液组成及其他组成与实施例3均相同。
实施例12
本实施例与实施例3的正极材料磷酸铁锂均为磷酸铁锂二次球，与实施例3的不同之处仅在于，本实施例磷酸铁锂二次球的Dv50粒径为11μm，实施例3磷酸铁锂二次球的Dv50粒径为9μm，电解液组成及其他组成与实施例3均相同。
对实施例11至12制得的锂离子电池的性能测试进行测试，测试结果如表 3-1所示。
表3-1
Figure PCTCN2022095586-appb-000013
由表3-1数据可以看出，本申请的负极采用石墨，正极采用磷酸铁锂二次球，且磷酸铁锂二次球的Dv50粒径为7μm至11μm，可以更好的发挥电解液中化合物与极片之间的协同作用，使制得的电池具有更好的高温、室温循环性能、高温存储性能，以及更低的内阻。
实施例13
本实施例与实施例3的区别之处在于，正极采用纳米磷酸铁锂，且纳米磷酸铁锂的Dv50粒径为0.8μm，电解液组成及其他组成与实施例3均相同。
实施例14
本实施例与实施例3的区别之处在于，正极采用纳米磷酸铁锂，且纳米磷酸铁锂的Dv50粒径为1.6μm，电解液组成及其他组成与实施例3均相同。
实施例15
本实施例与实施例3的区别之处在于，正极采用纳米磷酸铁锂，且纳米磷酸铁锂的Dv50粒径为2.5μm，电解液组成及其他组成与实施例3均相同。
对实施例13至15制得的锂离子电池的性能测试进行测试，测试结果如表3-2所示。
表3-2
Figure PCTCN2022095586-appb-000014
由表3-2数据可以看出，本申请的负极采用石墨，正极采用纳米磷酸铁锂，且纳米磷酸铁锂的Dv50粒径为0.8μm至2.5μm，可以更好的发挥电解液中化 合物与极片之间的协同作用，使得锂电池具有更好的高温、室温循环性能、高温存储性能，以及更低的内阻。
实施例16
本实施例与实施例3的负极材料均为石墨，与实施例3的不同之处仅在于，本实施例石墨的孔隙率为20％，实施例3石墨的孔隙率为30％，正极、电解液组成及其他组成与实施例3均相同。
实施例17
本实施例与实施例3负极材料均为石墨，与实施例3的不同之处仅在于，本实施例石墨的孔隙率为40％，正极、电解液组成及其他组成与实施例3均相同。
对实施例16至17制得的锂离子电池的性能测试进行测试，测试结果如表4所示。
表4
Figure PCTCN2022095586-appb-000015
由表4数据可以看出，本申请的负极采用石墨，石墨材料的孔隙率20％至40％时，室温循环80％圈数为1033至1826，高温循环80％圈数为989至1607，初始DCR为99mOhm至113mOhm，60℃存储30天容量保持率为92％至96％，特别的，石墨材料的孔隙率为30％至40％时，室温循环80％圈数为1749至1826，高温循环80％圈数为1449至1607，可见，电解液中式(I)所示的化合物的加入，同时通过控制石墨材料的孔隙率，可以更好的发挥电解液中化合物与极片之间的协同作用，使得锂电池具有更好的高温、室温循环性能、高温存储性能，以及更低的内阻。
实施例18至19、对比例2至3的电解液组成如表5-1所示，采用上述制备方法制备锂离子电池，对其性能进行测试，测试结果如表5-2所示。
表5-1
Figure PCTCN2022095586-appb-000016
Figure PCTCN2022095586-appb-000017
表5-2
Figure PCTCN2022095586-appb-000018
由表5-2数据可以看出，相对于对比例3不加式(I)所示的化合物，本申请实施例18、实施例19的电解液，通过添加式(I)所示的化合物，改善了负极成膜添加剂共聚，达到改善负极保护、改善内阻的效果，本申请的电解液制成的电化学装置具有优秀的高温、室温循环性能，同时具有较低的内阻。
实施例20
本实施例与实施例18的不同之处在于正极材料的孔隙率不同，本实施例的811的孔隙率为20％，实施例18的811的孔隙率为28％，其他的与实施例18均相同。
实施例21
本实施例与实施例18的不同之处在于正极材料的孔隙率不同，本实施例的811的孔隙率为35％，实施例18的811的孔隙率为28％，其他的与实施例18均相同。
对实施例20至21制得的锂离子电池的性能测试进行测试，测试结果如表6所示。
表6
Figure PCTCN2022095586-appb-000019
由表6数据可以看出，本申请的正极采用811，正极的孔隙率控制在20％至35％，可以更好的发挥电解液中化合物与极片之间的协同作用，使得锂电池具有更好的高温、室温循环性能、高温存储性能，以及更低的内阻，更优选地，正极的孔隙率控制在20％至28％。
实施例22、对比例4、实施例23至24的电解液组成如表7-1所示，采用上述制备方法制备锂离子电池，对其性能进行测试，测试结果如表7-2所示。
表7-1
Figure PCTCN2022095586-appb-000020
表7-2
Figure PCTCN2022095586-appb-000021
Figure PCTCN2022095586-appb-000022
由表7-2数据可以看出，正极采用811，负极采用碳硅，相对于对比例4不加式(I)所示的化合物，本申请实施例23、实施例24的电解液，通过添加式(I)所示的化合物，可与负极成膜添加剂共聚，达到改善负极成膜、改善内阻的效果，利用该电解液制成的电化学装置具有优良的高温、室温循环性能，同时具有较低的内阻。
相对于实施例18采用石墨做负极，实施例22至24的负极采用碳硅体系，加入式(I)所示的化合物后协同作用，可以提升电池的容量性能，进一步提升能量密度，更有利于满足电池的室温、高温循环要求。
实施例25
本实施例与实施例24的不同之处在于，硅碳中SiO x含量不同，其中，实施例25中碳硅中SiO x含量为1％，实施例24中碳硅中SiO x含量为10％，其他的与实施例24均相同。对其性能进行测试实施例26。
本实施例与实施例24的不同之处在于，碳硅中SiO x含量为5％，其他的与实施例24均相同。
实施例27
本实施例与实施例24的不同之处在于，碳硅中SiO x含量为15％，其他的与实施例24均相同。
实施例28
本实施例与实施例24的不同之处在于，碳硅中SiO x含量为20％，其他的与实施例24均相同。
对实施例24至28采用上述制备方法制备锂离子电池，对电池性能进行测试，测试结果如表8所示。
表8
Figure PCTCN2022095586-appb-000023
Figure PCTCN2022095586-appb-000024
由表8数据可以看出，负极采用碳硅时，其中SiO x含量1至20％之间，可以更好的发挥电解液中化合物与极片之间的协同作用，使得锂电池在能量密度大幅提高的同时保持了较好的高温、室温循环性能、高温存储性能，可以满足高能量密度、低循环需求的应用。
对比例5
对比例5与实施例3的区别仅在于HF的含量不同，对比例5中HF的含量为5000ppm，实施例3中HF的含量为100ppm。
将对比例5采用上述制备方法制备锂离子电池，对其性能进行测试，测试结果如表9所示。
表9
Figure PCTCN2022095586-appb-000025
由表9数据看出，在对比例5中，当电解液中HF含量过高时，室温循环80％圈数由实施例3的1826下降到431，高温循环80％圈数由实施例3的1607下降到266，初始DCR由实施例3的99mOhm变为122mOhm，60℃存储30天容量保持率由实施例3的96％降至53％，电池的综合性能大幅降低。
本申请通过上述实施例来说明本申请的详细工艺设备和工艺流程，但本申请并不局限于上述详细工艺设备和工艺流程，即不意味着本申请必须依赖上述详细工艺设备和工艺流程才能实施。所属技术领域的技术人员应该明了，对本申请的任何改进，对本申请产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本申请的保护范围和公开范围之内。
以上详细描述了本申请的优选实施方式，但是，本申请并不限于上述实施方式中的具体细节，在本申请的技术构思范围内，可以对本申请的技术方案进行多种简单变型，这些简单变型均属于本申请的保护范围。
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合，为了避免不必要的重复，本申请对各种可能的组合方式不再另行说明。
此外，本申请的各种不同的实施方式之间也可以进行任意组合，只要其不违背本申请的思想，其同样应当视为本申请所公开的内容。

Claims (13)

  1. 一种电解液，其包含式(I)所示的化合物：
    Figure PCTCN2022095586-appb-100001
    其中，R 1、R 3、R 4各自独立地选自氢、氰基、取代或未取代的C 1-12的烃基、取代或未取代的C 1-12的碳氧基、取代或未取代的C 6-26的芳基、取代或未取代的C 2-12的酰胺基、取代或未取代的C 0-12的磷酸酯基、取代或未取代的C 0-12的磺酰基、取代或未取代的C 0-12的硅氧基或取代或未取代的C 0-12的硼酸酯基，经取代时，取代基包括卤素原子；R 2选自C 1-12的取代或未取代的烃基、取代或未取代的C 1-12的碳氧基、取代或未取代的C 6-26的芳基、取代或未取代的C 2-12的酰胺基、取代或未取代的C 0-12的磷酸酯基、取代或未取代的C 0-12的磺酰基、取代或未取代的C 0-12的硅氧基或取代或未取代的C 0-12的硼酸酯基，经取代时，取代基包括卤素原子。
  2. 根据权利要求1所述的电解液，其中，基于所述电解液的质量，所述式(I)所示的化合物的质量含量为0.1％至5％。
  3. 根据权利要求2所述的电解液，其中，基于所述电解液的质量，所述式(I)所示的化合物的质量含量为0.3％至3％。
  4. 根据权利要求1至3的任一项所述的电解液，其中，R 1、R 3、R 4各自独立地选自氢、取代或未取代的C 1-12的烃基；R 2选自C 1-12的取代或未取代的烃基，经取代时，取代基为卤素原子。
  5. 根据权利要求1至3的任一项所述的电解液，其中，所述式(I)所示的化合物为富马酸二甲酯、甲基丙烯酸甲酯、顺丁烯二酸二甲酯、甲基丙烯酸1,1,1,3,3,3-六氟异丙酯、甲基丙烯酸乙烯酯中的任意一种或两种以上的混合物。
  6. 根据权利要求1至3的任一项所述的电解液，其中，所述电解液在温度为45℃，热压压强为0.1MPa的环境下进行化成后产生HF，基于所述化成后电解液的质量，产生的HF的质量含量为20至800ppm；
  7. 一种电化学装置，其包含负极、正极和权利要求1至6任一项所述的电解液。
  8. 根据权利要求7所述的电化学装置，其中，所述负极包括负极活性材料和集流体，所述负极活性材料包括石墨或硅碳负极活性材料；
    所述硅碳负极活性材料选自硅、硅氧化合物和硅基合金中的任意一种或两种以上的混合物。
  9. 根据权利要求8所述的电化学装置，其中，所述负极的孔隙率为20％至40％。
  10. 根据权利要求7-9的任一项所述的电化学装置，其中，所述正极包含正极活性材料；所述正极活性材料选自磷酸铁锂、锂镍过渡金属复合氧化物、具有尖晶石结构的锂镍锰复合氧化物的任意一种或两种以上的混合物。
  11. 根据权利要求10所述的电化学装置，其中，所述正极的孔隙率为20％至35％。
  12. 根据权利要求11所述的电化学装置，其中，所述磷酸铁锂为纳米磷酸铁锂或者磷酸铁锂二次球；
    所述纳米磷酸铁锂的Dv50粒径为0.8至2.5μm；
    所述磷酸铁锂二次球的Dv50粒径为7至11μm。
  13. 一种电子装置，其包括权利要求7至12的任一项所述的电化学装置。
PCT/CN2022/095586 2021-05-28 2022-05-27 一种电解液及其电化学装置和电子装置 Ceased WO2022247929A1 (zh)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US18/009,991 US20230231191A1 (en) 2021-05-28 2022-05-27 Electrolyte and electrochemical device thereof and electronic device
EP22810653.0A EP4350833A4 (en) 2021-05-28 2022-05-27 ELECTROLYTE, ASSOCIATED ELECTROCHEMICAL DEVICE AND ELECTRONIC DEVICE
CN202280004040.6A CN115606032A (zh) 2021-05-28 2022-05-27 一种电解液及其电化学装置和电子装置
JP2022580451A JP2024505315A (ja) 2021-05-28 2022-05-27 電解液およびその電気化学デバイスならびに電子デバイス

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202110592885.9A CN113328143A (zh) 2021-05-28 2021-05-28 一种锂电池用非水电解液及其制备方法和锂离子电池
CN202110592885.9 2021-05-28

Publications (1)

Publication Number Publication Date
WO2022247929A1 true WO2022247929A1 (zh) 2022-12-01

Family

ID=77422311

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2022/095586 Ceased WO2022247929A1 (zh) 2021-05-28 2022-05-27 一种电解液及其电化学装置和电子装置

Country Status (5)

Country Link
US (1) US20230231191A1 (zh)
EP (1) EP4350833A4 (zh)
JP (1) JP2024505315A (zh)
CN (7) CN113328143A (zh)
WO (1) WO2022247929A1 (zh)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113328143A (zh) * 2021-05-28 2021-08-31 远景动力技术(江苏)有限公司 一种锂电池用非水电解液及其制备方法和锂离子电池
CN115775908A (zh) * 2021-09-08 2023-03-10 东莞市杉杉电池材料有限公司 一种高镍三元锂离子电池电解液及含有该电解液的锂离子电池
EP4391136B1 (en) * 2021-10-26 2026-04-15 LG Energy Solution, Ltd. Lithium secondary battery comprising a non-aqueous electrolyte
CN114373991B (zh) * 2021-12-31 2024-10-25 远景动力技术(江苏)有限公司 一种锂电池用非水电解液及锂离子电池
US20230387466A1 (en) * 2022-05-27 2023-11-30 Aesc Japan Ltd. Electrolyte, electrochemical device thereof, and electronic device thereof
CN115360420A (zh) * 2022-08-11 2022-11-18 惠州锂威新能源科技有限公司 一种抗氧化耐高温电解液添加剂、电解液及二次电池
CN115360418A (zh) * 2022-08-11 2022-11-18 惠州锂威新能源科技有限公司 一种电解液添加剂、电解液及二次电池
WO2024120338A1 (zh) * 2022-12-09 2024-06-13 浙江蓝天环保高科技股份有限公司 含焦硫酸根三氟化硼复合锂盐的电解液及锂离子二次电池
CN116190794A (zh) * 2023-04-27 2023-05-30 广州天赐高新材料股份有限公司 非水电解液及含有该非水电解液的锂离子电池
CN116315106A (zh) * 2023-05-04 2023-06-23 珠海市赛纬电子材料股份有限公司 非水电解液及锂离子电池
CN116646606B (zh) * 2023-07-13 2024-05-03 常州千沐新能源有限公司 一种采用磺酸酯基深共晶溶剂的电解液、制备方法以及锂离子电池
CN117393858A (zh) * 2023-12-08 2024-01-12 宁德时代新能源科技股份有限公司 锂二次电池、其制备方法和用电装置
KR20250094335A (ko) * 2023-12-18 2025-06-25 삼성에스디아이 주식회사 리튬 이차 전지용 전해액 및 이를 포함하는 리튬 이차 전지
CN119994191A (zh) * 2025-02-26 2025-05-13 清陶(昆山)能源发展集团股份有限公司 高电压用电解液、锂离子电池

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007258102A (ja) * 2006-03-24 2007-10-04 Mitsubishi Chemicals Corp 非水系電解液及び非水系電解液電池
CN110061283A (zh) * 2005-10-20 2019-07-26 三菱化学株式会社 锂二次电池以及其中使用的非水电解液
WO2019181240A1 (ja) * 2018-03-23 2019-09-26 ダイキン工業株式会社 電解液、電気化学デバイス、リチウムイオン二次電池及びモジュール
CN112670576A (zh) * 2020-12-23 2021-04-16 远景动力技术(江苏)有限公司 一种兼具长循环与高温特性的非水电解液及锂离子电池
CN113328143A (zh) * 2021-05-28 2021-08-31 远景动力技术(江苏)有限公司 一种锂电池用非水电解液及其制备方法和锂离子电池
CN113871712A (zh) * 2021-09-24 2021-12-31 远景动力技术(江苏)有限公司 锂离子电池电解液及其制备方法和锂离子电池
CN114373991A (zh) * 2021-12-31 2022-04-19 远景动力技术(江苏)有限公司 一种锂电池用非水电解液及锂离子电池

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000223154A (ja) * 1999-01-29 2000-08-11 Sanyo Electric Co Ltd リチウム二次電池。
JP4411691B2 (ja) * 1999-06-30 2010-02-10 パナソニック株式会社 非水電解液二次電池および非水電解液二次電池の充電制御システムおよびこれを用いた機器
JP2004063432A (ja) * 2002-06-05 2004-02-26 Sony Corp 電池
JP4946437B2 (ja) * 2004-05-28 2012-06-06 宇部興産株式会社 非水電解液およびそれを用いたリチウム二次電池
JP5103765B2 (ja) * 2006-03-24 2012-12-19 三菱化学株式会社 非水系電解液及び非水系電解液電池
JP5222538B2 (ja) * 2007-05-22 2013-06-26 株式会社デンソー 非水電解液及び該電解液を用いた非水電解液二次電池
JP2009152133A (ja) * 2007-12-21 2009-07-09 Sony Corp 非水電解液二次電池
US8673508B2 (en) * 2008-04-02 2014-03-18 Ube Industries, Ltd. Nonaqueous electrolyte for lithium battery and lithium battery using same
CN101640290B (zh) * 2008-08-01 2014-05-07 三洋电机株式会社 非水电解质二次电池
JP2012119091A (ja) * 2010-11-29 2012-06-21 Tdk Corp 非水系電解液、電極、ならびに、当該非水系電解液及び電極を備える電気化学デバイス
US10644353B2 (en) * 2011-10-28 2020-05-05 Asahi Kasei Kabushiki Kaisha Non-aqueous secondary battery
JPWO2015046174A1 (ja) * 2013-09-24 2017-03-09 旭硝子株式会社 非水電解液二次電池
TWI575014B (zh) * 2014-04-08 2017-03-21 奇美實業股份有限公司 鋰電池負極用樹脂、樹脂組成物、漿料、負極以及鋰電池
JP2018085213A (ja) * 2016-11-22 2018-05-31 株式会社豊田中央研究所 リチウム二次電池
CN109119631B (zh) * 2017-06-26 2021-09-21 宁德时代新能源科技股份有限公司 一种二次电池
JP6527201B2 (ja) * 2017-09-08 2019-06-05 太平洋セメント株式会社 リチウムイオン二次電池用正極活物質複合体の製造方法
JP6924840B2 (ja) * 2017-10-12 2021-08-25 富士フイルム株式会社 全固体二次電池用バインダー組成物、固体電解質含有シート及び全固体二次電池、並びに、固体電解質含有シート及び全固体二次電池の製造方法
CN109119690A (zh) * 2018-08-03 2019-01-01 深圳市山木新能源科技股份有限公司 一种抗低温锂电池
EP3920302A4 (en) * 2019-02-27 2023-08-16 Daikin Industries, Ltd. ELECTROLYTE SOLUTION, ELECTROCHEMICAL DEVICE, SECONDARY LITHIUM-ION BATTERY, AND MODULE
CN109980225B (zh) * 2019-03-18 2020-09-08 宁德新能源科技有限公司 电化学装置及包含其的电子装置
CN112701349B (zh) * 2020-12-28 2022-07-12 宁德新能源科技有限公司 电解液及包含其的电化学装置和电子设备
CN112768773A (zh) * 2021-03-15 2021-05-07 蜂巢能源科技有限公司 电解液及锂离子电池

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110061283A (zh) * 2005-10-20 2019-07-26 三菱化学株式会社 锂二次电池以及其中使用的非水电解液
JP2007258102A (ja) * 2006-03-24 2007-10-04 Mitsubishi Chemicals Corp 非水系電解液及び非水系電解液電池
WO2019181240A1 (ja) * 2018-03-23 2019-09-26 ダイキン工業株式会社 電解液、電気化学デバイス、リチウムイオン二次電池及びモジュール
CN112670576A (zh) * 2020-12-23 2021-04-16 远景动力技术(江苏)有限公司 一种兼具长循环与高温特性的非水电解液及锂离子电池
CN113328143A (zh) * 2021-05-28 2021-08-31 远景动力技术(江苏)有限公司 一种锂电池用非水电解液及其制备方法和锂离子电池
CN113871712A (zh) * 2021-09-24 2021-12-31 远景动力技术(江苏)有限公司 锂离子电池电解液及其制备方法和锂离子电池
CN114373991A (zh) * 2021-12-31 2022-04-19 远景动力技术(江苏)有限公司 一种锂电池用非水电解液及锂离子电池

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4350833A4 *

Also Published As

Publication number Publication date
JP2024505315A (ja) 2024-02-06
CN114899491A (zh) 2022-08-12
CN114784379A (zh) 2022-07-22
CN114976242B (zh) 2024-01-26
CN114784380A (zh) 2022-07-22
EP4350833A1 (en) 2024-04-10
CN114976242A (zh) 2022-08-30
CN113328143A (zh) 2021-08-31
EP4350833A4 (en) 2025-08-27
CN115606032A (zh) 2023-01-13
US20230231191A1 (en) 2023-07-20
CN114976243A (zh) 2022-08-30
CN114976243B (zh) 2025-03-11

Similar Documents

Publication Publication Date Title
WO2022247929A1 (zh) 一种电解液及其电化学装置和电子装置
CN109873205B (zh) 一种适用于硅碳负极的电解液及包含该电解液的锂离子电池
WO2023040687A1 (zh) 一种电解液、包含该电解液的电化学装置和电子装置
CN111697266B (zh) 电解液和包括其的电化学装置及电子装置
CN112768770A (zh) 一种电解液及含有该电解液的锂离子电池
CN112400249A (zh) 一种电解液及电化学装置
CN111697267A (zh) 电解液和包含电解液的电化学装置及电子装置
CN118679615A (zh) 电化学装置和包含其的电子装置
CN109119599B (zh) 一种二次电池及其制备方法
CN114335685A (zh) 电化学装置及包含其的电子装置
CN112103561B (zh) 一种电解液及电化学装置
CN117199535A (zh) 一种电解液、电化学装置及电子装置
CN120149535A (zh) 电解液及包括其的电化学装置和电子装置
CN115832429A (zh) 一种电解液、电化学装置和电子装置
CN111600065B (zh) 电解液和使用其的电化学装置
CN115528300B (zh) 电解液、电化学装置和电子装置
WO2021128203A1 (zh) 一种电解液及电化学装置
CN113921914B (zh) 电解液以及使用其的电化学装置和电子装置
CN106941191B (zh) 锂离子电池及其非水电解液
CN116666759A (zh) 一种电解液、电化学装置以及电子设备
CN115621551A (zh) 电解液、电化学装置和电子装置
CN115000511A (zh) 一种电化学装置和电子装置
WO2023123427A1 (zh) 电化学装置和包含其的电子装置
CN112086682A (zh) 电解液、电化学装置和电子装置
JP7633987B2 (ja) 電解液、その電気化学デバイス、及びその電子デバイス

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 2022580451

Country of ref document: JP

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22810653

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2022810653

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 2022810653

Country of ref document: EP

Effective date: 20240102