WO2022204974A1 - 电化学装置及电子装置 - Google Patents

电化学装置及电子装置 Download PDF

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WO2022204974A1
WO2022204974A1 PCT/CN2021/084082 CN2021084082W WO2022204974A1 WO 2022204974 A1 WO2022204974 A1 WO 2022204974A1 CN 2021084082 W CN2021084082 W CN 2021084082W WO 2022204974 A1 WO2022204974 A1 WO 2022204974A1
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active material
lithium
material layer
negative electrode
electrochemical device
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PCT/CN2021/084082
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English (en)
French (fr)
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李鑫
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宁德新能源科技有限公司
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Priority to CN202180001361.6A priority Critical patent/CN113424336A/zh
Priority to PCT/CN2021/084082 priority patent/WO2022204974A1/zh
Priority to JP2021539131A priority patent/JP7499771B2/ja
Priority to EP21815094.4A priority patent/EP4095941A4/en
Priority to US17/708,375 priority patent/US20220320501A1/en
Publication of WO2022204974A1 publication Critical patent/WO2022204974A1/zh

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    • H—ELECTRICITY
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    • 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
    • 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
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    • 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
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    • 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
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    • 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
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    • 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
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
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    • 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
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • H—ELECTRICITY
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    • 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
    • H01M4/40—Alloys based on alkali metals
    • H01M4/405—Alloys based on lithium
    • H—ELECTRICITY
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    • 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
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    • 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
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    • 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
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    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
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    • 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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • 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, in particular, to electrochemical devices and electronic devices.
  • silicon-based anode materials have high gram capacity and are considered to be the most promising next-generation lithium-ion anode materials.
  • the silicon anode material in the charge-discharge process It will be pulverized and dropped from the current collector, causing the loss of electrical contact between the active material and the current collector, resulting in poor electrochemical performance, capacity decay, and cycle stability, which hinders its further application to a certain extent.
  • the method to improve the electrochemical performance of silicon materials is to composite silicon materials with carbon materials.
  • SiOC materials have attracted the attention of the market due to the smallest volume expansion, but SiOC materials realize lithium storage through the breaking of Si-O bonds, which will cause irreversible formation.
  • the high LiSiO 4 makes the coulombic efficiency of the SiOC material low in the first week and reduces the energy density of the electrochemical device.
  • the present application proposes an electrochemical device and an electronic device, which can improve the first-week coulombic efficiency of the electrochemical device and increase the energy density.
  • the present application provides an electrochemical device, comprising a positive pole piece and a negative pole piece, wherein the negative pole piece includes a negative electrode current collector and a negative electrode active material layer disposed on the surface of the negative electrode current collector; the negative electrode active material
  • the material layer includes an active material layer and a lithium-containing layer located on the surface of the active material layer; the active material layer includes SiOC material and graphite.
  • the lithium-containing layer comprises stabilized lithium metal powder.
  • the electrochemical device satisfies at least one of the following features (1) to (4):
  • the binding energy peak positions of Si2p include 101.4eV ⁇ 0.3eV, 102.2eV ⁇ 0.3eV, 103.1eV ⁇ 0.3eV, 104.40eV At least one of ⁇ 0.3eV;
  • the negative electrode active material layer is analyzed by X-ray diffraction method to obtain that the binding energy peak position of Li is between 55.6eV ⁇ 0.3eV;
  • the negative electrode active material layer is analyzed by X-ray diffraction, the negative electrode active material layer has Li 22 Si diffraction peaks, Li 22 Ge diffraction peaks, Li 22 Sn diffraction peaks, Li 2 O diffraction peaks, Li At least one of 2 SiO 3 diffraction peaks or Li 2 Si 2 O 5 diffraction peaks;
  • the chemical shift value of Si is obtained by analyzing the negative electrode active material layer by solid nuclear magnetic resonance technology, and the chemical shift value of Si includes -5ppm ⁇ 1ppm, -35ppm ⁇ 1ppm, -75ppm ⁇ 1ppm and -100ppm ⁇ 1ppm, And the half-peak width K of the chemical shift peak of Si at -5ppm ⁇ 1ppm satisfies the following relationship: 7ppm ⁇ K ⁇ 28ppm.
  • the electrochemical device satisfies at least one of the following features (5) to (9):
  • the median particle size of the mixed powder of the SiOC material and graphite is R 1 um, and the value range of R 1 is 0.01 to 50;
  • the median particle size of the stable lithium metal powder is R 2 um, and the value range of R 2 is 0.1 to 20;
  • the thickness of the active material layer is D 1 um, and the value range of D 1 is 40 to 150;
  • the thickness of the lithium-containing layer is D 2 um, and the value range of D 2 is 2 to 20;
  • the negative electrode active material layer has a diffraction peak of Li 15 Si 4 by an X-ray diffraction method.
  • the electrochemical device satisfies at least one of the following features (10) to (11):
  • the electrochemical device satisfies at least one of the following features (12) to (14):
  • the mass ratio of the SiOC material to the graphite is 5:95 to 45:55;
  • the mass ratio of the total mass of the SiOC material and the graphite to the stable lithium metal powder is 1.99 to 9;
  • the graphite includes at least one of natural graphite, artificial graphite, and mesocarbon microspheres.
  • the electrochemical device satisfies at least one of the following features (15) to (16):
  • the powder conductivity of the negative electrode active material layer is 2.0 S/cm to 30.0 S/cm;
  • the value range of the resistance of the negative electrode active material layer is 0.2 ⁇ to 1.0 ⁇ .
  • the negative electrode active material layer further includes a binder
  • the binder includes polyacrylate, polyimide, polyamide, polyamideimide, polyvinylidene fluoride, butyl At least one of styrene rubber, sodium alginate, polyvinyl alcohol, polytetrafluoroethylene, polyacrylonitrile, sodium carboxymethyl cellulose, potassium carboxymethyl cellulose, sodium carboxymethyl cellulose, potassium carboxymethyl cellulose A sort of.
  • the electrochemical device further includes an electrolyte, and the electrolyte includes an organic solvent and a lithium salt;
  • the organic solvent includes at least one of ethylene carbonate, propylene carbonate, diethyl carbonate, ethyl methyl carbonate, dimethyl carbonate, propylene carbonate, propyl propionate or ethyl propionate; and/ or,
  • the lithium salt includes at least lithium hexafluorophosphate, lithium tetrafluoroborate, lithium difluorophosphate, lithium bistrifluoromethanesulfonimide, lithium bis(fluorosulfonyl)imide, lithium bisoxalate borate or lithium difluorooxalate borate. A sort of.
  • the present application further provides an electronic device, the electronic device includes the electrochemical device described in the first aspect above.
  • the present application at least has the following beneficial effects:
  • the SiOC material in the active material layer and the stable lithium metal powder in the lithium-containing layer can be activated by contacting the electrolyte, providing more active lithium ions for the electrochemical device and supplementing the irreversible storage of the SiOC material.
  • the active lithium ions consumed after lithium improve the first efficiency of the negative electrode material and improve the energy density of the battery.
  • FIG. 1 is a schematic structural diagram of a negative pole piece provided by an embodiment of the present application.
  • Fig. 2 is the solid-state nuclear magnetic spectrum of the negative pole piece in the electrochemical device provided by the embodiment of the application;
  • FIG. 3 is a comparison diagram of the coulombic efficiency in the first week before and after adding a lithium-containing layer to the negative pole piece provided in the embodiment of the present application.
  • any lower limit can be combined with any upper limit to form an unspecified range; and any lower limit can be combined with any other lower limit to form an unspecified range, and likewise any upper limit can be combined with any other upper limit to form an unspecified range.
  • every point or single value between the endpoints of a range is included within the range, even if not expressly recited.
  • each point or single value may serve as its own lower or upper limit in combination with any other point or single value or with other lower or upper limits to form a range not expressly recited.
  • the present application provides an electrochemical device comprising a positive electrode and a negative electrode, the positive electrode comprising a positive current collector and a positive active material layer disposed on the surface of the positive current collector; the negative electrode
  • the sheet includes a negative electrode current collector and a negative electrode active material layer disposed on the surface of the negative electrode current collector;
  • the negative electrode active material layer includes an active material layer and a lithium-containing layer located on the surface of the active material layer; the active material includes SiOC material and graphite.
  • the SiOC material in the active material layer and the stable lithium metal powder in the lithium-containing layer can be activated by contacting the electrolyte, providing more active lithium ions for the electrochemical device, and supplementing the irreversible lithium storage of the SiOC material after consumption.
  • the active lithium ions can improve the first efficiency of the negative electrode material and improve the energy density of the battery.
  • the SiOC material is uniformly mixed with graphite to form an active material.
  • the SiOC material is mainly composed of Si-OC framework and free carbon, and the Si-OC framework and free carbon are connected by C-Si bonds.
  • the Si-OC framework can be regarded as the substitution of O by C in the SiO 4 tetrahedron. Therefore, the SiOC material can include four existing forms: SiO 2 C 2 , SiO 3 C, SiOC 3 , and SiO 4 . Among them, SiO 2 C 2.
  • SiO 3 C is a fully reversible lithium storage form, SiOC 3 is an irreversible lithium storage form, and SiOC 3 forms SiC 4 after lithium storage; SiO 4 is a partially reversible lithium storage form, and SiO 4 forms a reversible Li 2 SiO 5 after lithium storage and irreversible LiSiO 4 .
  • SiOC materials have excellent resistance to external force damage, and in the process of pyrolysis, SiOC materials can generate abundant nanopore structures, which can improve the toughness of the material.
  • SiOC materials include, but are not limited to: crystalline, amorphous carbon or their mixtures.
  • the morphology of the crystalline SiOC material can be amorphous, lamellar, platelet, spherical, square, nanoparticle or fibrous, and the like.
  • the mass ratio of the SiOC material to the graphite is 5:95 to 45:55; specifically, it can be 5:95, 10:90, 15:85, 45:55, etc., Of course, it can also be other values within the above range, which is not limited here.
  • the graphite may include at least one of natural graphite, artificial graphite, and mesocarbon microspheres, and it is only necessary to uniformly mix the graphite and the SiOC material.
  • the mass ratio of the active material to the stable lithium metal powder is 1.99 to 9; specifically, it can be 1.99, 2.5, 3.0, 4.5, 5.0, 5.8, 6.7, 8.0 or 9, etc. , and of course other values within the above range, which are not limited here.
  • the active material layer 11 is located on the surface of the negative electrode current collector 10
  • the lithium-containing layer 12 is located on the surface of the active material layer 11
  • the lithium-containing layer 12 contains stable lithium metal powder.
  • the negative electrode current collector includes, but is not limited to, copper foil, nickel foil, stainless steel foil, titanium foil, nickel foam, foamed copper or a polymer substrate coated with conductive metal.
  • the negative electrode current collector is copper foil.
  • the thickness of the active material layer 11 is D 1 um, and the value range of D 1 is 40 to 150; specifically, the thickness of the active material layer 11 can be 40um, 50um, 60um, 80um, 100um, 120um or 150um, etc. , and of course other values within the above range, which are not limited here.
  • the thickness of the lithium-containing layer 12 is D 2 um, and the value range of D 2 is 2 to 20; specifically, the thickness of the lithium-containing layer 12 may be 2um, 4um, 5um, 6um, 8um, 10um, 12um , 15um, 18um or 20um, etc., of course, other values within the above range can also be used, which are not limited here.
  • the ratio range of the thickness D 1 of the active material layer 11 to the thickness D 2 of the lithium-containing layer satisfies: 2 ⁇ D 1 /D 2 ⁇ 20.
  • the ratio of D 1 /D 2 may specifically be 2, 4, 5, 8, 10, 12, 15, 18, or 20, etc., and of course other values within the above range, which are not limited herein.
  • the stable lithium metal powder may be stable metal lithium powder and/or stable metal lithium compound, and specifically, the stable lithium metal powder includes Li element, Ge element, Sn element and the like.
  • the negative electrode active material layer is analyzed by X-ray diffraction, and the negative electrode active material layer has Li 22 Si diffraction peaks, Li 22 Ge diffraction peaks, Li 22 Sn diffraction peaks, Li At least one of 2 O diffraction peak, Li 2 SiO 3 diffraction peak or Li 2 Si 2 O 5 diffraction peak.
  • the median particle size of the active material is R 1 um, and the value range of R 1 is 0.01 to 50; specifically, the median particle size of the active material may be 0.01 um , 0.05um, 0.1um, 0.5um, 1um, 5um, 10um, 20um, 30um, 40um or 50um, etc. Of course, it can also be other values within the above range, which is not limited here.
  • the median particle size of the stable lithium metal powder is R 2 um, and the value range of R 2 is 0.1 to 20; specifically, the median particle size of the active material may be 0.1um, 0.5um, 1um, 3um, 5um, 8um, 10um, 15um, 18um, or 20um, etc. Of course, it can also be other values within the above range, which is not limited here.
  • the range of the ratio of the median particle size R 2 of the stable lithium metal powder to the median particle size R 1 of the active material satisfies: 0.01 ⁇ R 2 /R 1 ⁇ 1;
  • the ratio of 2 /R 1 may specifically be 0.01, 0.02, 0.03, 0.05, 0.1, 0.3, 0.5, 0.7, 0.8 or 1, etc., and of course other values within the above range, which are not limited herein.
  • the binding energy peak positions of Si2p include 101.4eV ⁇ 0.3eV, 102.2eV ⁇ 0.3eV, 103.1eV At least one of ⁇ 0.3eV, 104.40eV ⁇ 0.3eV. That is, each binding energy peak position corresponds to one Si existing form.
  • the negative electrode active material layer is analyzed by X-ray diffraction method, and it is obtained that the binding energy peak position of Li is between 55.6eV ⁇ 0.3eV.
  • the negative electrode active material layer is analyzed by solid-state nuclear magnetic resonance technology to obtain the chemical shift value of Si, and the chemical shift value of Si includes -5ppm ⁇ 1ppm, -35ppm ⁇ 1ppm, -75ppm ⁇ 1ppm and -100ppm ⁇ 1ppm, and the half-peak width K of the chemical shift peak of Si at -5ppm ⁇ 1ppm satisfies the following relationship: 7ppm ⁇ K ⁇ 28ppm.
  • the negative electrode active material layer when the electrochemical device is in a fully charged state, has a diffraction peak of Li 15 Si 4 through X-ray diffraction method.
  • Li 15 Si 4 grains, Li 2 SiO 3 grains and Li 2 Si 2 O 5 grains can also be seen through high-resolution images of Transmission Electron Microscope (TEM),
  • TEM Transmission Electron Microscope
  • the interplanar spacing of Li 15 Si 4 grains is about 0.2 nm; the interplanar spacing of Li 2 SiO 3 grains is about 0.27 nm; the interplanar spacing of Li 2 Si 2 O 5 crystal grains is about 0.196 nm.
  • the negative electrode active material layer includes a binder, and the binder can improve the bonding between the negative electrode active material particles and the bonding between the negative electrode active material and the negative electrode current collector.
  • the binder includes polyacrylate, polyimide, polyamide, polyamideimide, polyvinylidene fluoride, styrene-butadiene rubber, sodium alginate, polyvinyl alcohol, polytetrafluoroethylene, polyacrylonitrile, At least one of sodium carboxymethyl cellulose, potassium carboxymethyl cellulose, sodium carboxymethyl cellulose, potassium carboxymethyl cellulose, which is not limited here.
  • the negative electrode active material layer further includes conductive materials
  • the conductive materials include natural graphite, artificial graphite, carbon black, acetylene black, Ketjen black, carbon fiber, metal powder, metal fiber, copper, nickel, aluminum , silver or polyphenylene derivatives, etc., are not limited here.
  • the value range of the resistance of the negative electrode active material layer is 0.2 ⁇ to 1.0 ⁇ , specifically 0.2 ⁇ , 0.3 ⁇ , 0.5 ⁇ , 0.6 ⁇ , 0.8 ⁇ , 0.9 ⁇ or 1 ⁇ etc., of course other values within the above range are also possible.
  • the powder conductivity of the negative electrode active material layer is 2.0S/cm ⁇ 30.0S/cm; cm, 12S/cm, 15S/cm, 18S/cm, 20S/cm, 25S/cm, or 30S/cm, etc., of course, other values within the above range are also possible.
  • the electrochemical device further includes a positive electrode plate, and the positive electrode plate includes a positive electrode current collector and a positive electrode active material layer located on the positive electrode current collector.
  • the positive electrode active material includes at least one of lithium cobalt oxide (LiCoO 2 ), lithium nickel manganese cobalt ternary material, lithium iron phosphate, lithium manganese iron phosphate, and lithium manganate.
  • LiCoO 2 lithium cobalt oxide
  • nickel manganese cobalt ternary material lithium nickel manganese cobalt ternary material
  • lithium iron phosphate lithium manganese iron phosphate
  • lithium manganate lithium manganate
  • the positive electrode active material layer further includes a binder and 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 current collector.
  • the binder includes polyvinyl alcohol, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, ethylene oxide-containing polymers, polyvinylpyrrolidone , at least one of polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylic (esterified) styrene-butadiene rubber, epoxy resin or nylon.
  • the conductive material includes 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, or silver.
  • the conductive polymer is a polyphenylene derivative.
  • the positive electrode current collector includes, but is not limited to, aluminum foil.
  • the electrochemical device further includes an electrolyte, and the electrolyte includes an organic solvent, a lithium salt and an additive.
  • the organic solvent of the electrolytic solution according to the present application may be any organic solvent known in the prior art that can be used as a solvent of the electrolytic solution.
  • the electrolyte used in the electrolyte solution according to the present application is not limited, and it may be any electrolyte known in the prior art.
  • the additive for the electrolyte according to the present application may be any additive known in the art as an additive for the electrolyte.
  • the organic solvent includes, but is not limited to: ethylene carbonate (EC), propylene carbonate (PC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), at least one of propylene carbonate, propyl propionate, or ethyl propionate.
  • the lithium salt includes at least one of an organic lithium salt or an inorganic lithium salt.
  • the lithium salts include, but are not limited to: lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium difluorophosphate (LiPO 2 F 2 ), bistrifluoromethanesulfonimide Lithium LiN(CF 3 SO 2 ) 2 (LiTFSI), Lithium Bis(fluorosulfonyl)imide Li(N(SO 2 F) 2 )(LiFSI), Lithium Bisoxalate Borate LiB(C 2 O 4 ) 2 (LiBOB) ) or lithium difluorooxalate borate LiBF 2 (C 2 O 4 ) (LiDFOB).
  • LiPF 6 lithium hexafluorophosphate
  • LiBF 4 lithium tetrafluoroborate
  • LiPO 2 F 2 lithium difluorophosphate
  • LiPFSI bistrifluoromethanesulfonimide Lithium LiN(CF 3 SO
  • the concentration of the lithium salt in the electrolyte may be 0.5 mol/L to 3 mol/L.
  • the electrochemical device of the present application includes, but is not limited to: all kinds of primary batteries, secondary batteries, fuel cells, solar cells or capacitors.
  • the electrochemical device is a lithium secondary battery, wherein the lithium secondary battery includes, but is not limited to, a lithium metal secondary battery, a lithium ion battery, a lithium polymer secondary battery, or a lithium ion polymer secondary battery.
  • an embodiment of the present application further provides an electronic device, where the electronic device includes the electrochemical device described in the fourth aspect.
  • the electronic devices include, 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, etc. 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 equipment, toys, game consoles, clocks, power tools, flashlights, cameras, large household batteries or lithium-ion capacitors, etc.
  • lithium ion batteries The preparation of lithium ion batteries is described below by taking lithium ion batteries as an example and in conjunction with specific embodiments. Those skilled in the art will understand that the preparation methods described in this application are only examples, and any other suitable preparation methods are included in the scope of this application. within the range.
  • the stable metal lithium powder Dissolve the stable metal lithium powder in toluene and disperse it uniformly, wherein the stable metal lithium powder: the mass ratio of the active material (SiOC+graphite) is between 1.99 and 9.
  • the mass ratio of the active material SiOC+graphite
  • the powdered toluene solution is sprayed onto the surface of the initial pole piece, and left to stand for 4h-36h; and then the pole piece is cold-pressed.
  • the positive electrode active material, the conductive carbon black, and the binder polyvinylidene fluoride are mixed according to the weight ratio of 95:2.5:2.5, N-methylpyrrolidone (NMP) is added, and the positive electrode slurry is obtained by stirring uniformly under the action of a vacuum mixer. ; Coat the positive electrode slurry evenly on the positive electrode current collector aluminum foil; and then after drying, cold pressing, cutting, slitting and welding the tabs, the positive electrode pole piece is obtained.
  • NMP N-methylpyrrolidone
  • LiPF 6 LiPF 6 to a solvent mixed with propylene carbonate (PC) and ethylene carbonate (EC) (weight ratio of 1:1) and mix evenly to obtain an electrolyte, wherein The content of LiPF 6 was 1 mol/L.
  • PC propylene carbonate
  • EC ethylene carbonate
  • a polyethylene porous polymer film is used as the separator.
  • the positive pole piece, the separator and the negative pole piece in order, so that the separator is placed between the positive and negative pole pieces to play the role of isolation, and then roll up to obtain a bare cell; after welding the tabs, place the bare cell on the In the outer packaging foil aluminum-plastic film, the above-prepared electrolyte is injected into the dried bare cell, and the lithium-ion battery is obtained through the processes of vacuum packaging, standing, forming, shaping, and capacity testing.
  • the XPS test equipment is ESCLAB 250Xi from Thermo Fisher Scientific, with Al as the target as the excitation source, the power is 250w, and the vacuum degree is more than 10-9Pa.
  • the binding energy peak position of Si 2p and the binding energy peak position of Li were determined by XPS test.
  • Transmission electron microscopy characterization was performed on a JEOL JEM-2010 transmission electron microscope with an operating voltage of 200 kV.
  • the 29 Si SNMR spectra were performed on the instrument AVANCE III 400WB wide-cavity solid-state NMR instrument with a rotation rate of 8 kHz corresponding to 29 Si, respectively.
  • the resistance of the negative electrode active material layer is measured by the four-point probe method.
  • the instrument used for the four-point probe method is a precision DC voltage and current source (SB118 type).
  • SB118 type precision DC voltage and current source
  • Four copper plates with a length of 1.5cm*width of 1cm*2mm of thickness are fixed on a line at equal distances. Above, the distance between the two middle copper plates is L (1-2cm), and the base material for fixing the copper plates is an insulating material.
  • the copper plates at both ends are connected to the DC current I, and the voltage V is measured between the two copper plates in the middle, and the values of I and V are read three times.
  • the value of Va/Ia is the resistance of the negative active material layer at the test location. Take 12 test points for each negative pole piece and take the average value
  • the cycle capacity retention rate refers to the discharge capacity at 400 cycles divided by the first cycle discharge capacity.
  • Example 1 92.8 90.1 7.4
  • Example 2 92.7 87.9 7.8
  • Example 3 92.9 93.3 4.5
  • Example 4 92 82.3 6.8
  • Example 5 92.8 88.3 7.3
  • Example 6 92.1 88.7 8.5
  • Example 7 92.9 89.2 7.0
  • Example 8 92 88.3 7.4
  • Example 9 92.9 88.7 7.8
  • Example 10 92.8 88.9 8.0
  • Example 11 70 65.6 8.2
  • Example 12 85 66 8.5
  • Example 13 92.9 85 8.6
  • Example 14 89.9 86.7 8.2
  • Example 15 90.3 88.5 6.8
  • Example 16 89.6 87.1 6.4 Comparative Example 1 73 65.2 5.8 Comparative Example 2 72.6 65.2 9.8 Comparative Example 3 73.1 65.2 8.5
  • the first-week Coulombic efficiencies of the negative electrode plates of Examples 1 to 8 were significantly improved before and after covering the lithium-containing layer. Covering the lithium-containing layer on the surface of the active material layer can improve the first-week Coulombic efficiency of the battery.
  • the influence of the spraying times of the toluene solution of the stabilized metal lithium powder on the performance of the material and the cell during the preparation of the negative pole piece is illustrated.
  • the spraying times of the toluene solution of the stabilized lithium metal powder is controlled within the range of 1 to 7 times.
  • the content of the stable lithium metal powder on the surface of the active material layer also increases.
  • the thickness of the pole piece also increases; so that the stable lithium metal powder can generate more active lithium ions in the process of contacting the electrolyte, so the coulombic efficiency of the pole piece in the first week is also improved, and the first week of the battery Coulombic efficiency and cycle retention were both improved.
  • the ratio between the median particle size of the stable metal lithium powder and the median particle size of the active material has an effect on the performance of the material and the cell. influences. Under the condition that other influencing factors remain unchanged, the larger the ratio between the median particle size of the stabilized metal lithium powder and the median particle size of the active material, the smaller the median particle size of the active material, and its expansion during the cycle.

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Abstract

本申请提供了电化学装置及电子装置，其中，电化学装置包括正极极片及负极极片，所述负极极片包括负极集流体及设置于所述负极集流体表面的负极活性物质层；所述负极活性物质层包括活性材料层及位于所述活性材料层表面的含锂层；所述活性材料层包括SiOC材料及石墨。本申请提供的负极材料可以提高电化学装置的首周库伦效率，提高能量密度。

Description

电化学装置及电子装置 技术领域
本申请涉及储能技术领域，具体地讲，涉及电化学装置及电子装置。
背景技术
目前，硅基负极材料具有较高的克容量，被认为是最具有应用前景的下一代锂离子负极材料。但是硅的低电导性(>10 8Ω.cm)，以及其在充放电过程中具有约300％的体积膨胀并生成不稳定的固体电解质界面膜(SEI)，硅负极材料在充放电过程中会粉化从集流体上掉落，使得活性物质与集流体之间失掉电接触，导致电化学性能变差，容量衰减、循环稳定性下降，一定程度上阻碍了其进一步的应用。目前改善硅材料电化学性能的方法有将硅材料与碳材料复合，其中，SiOC材料由于体积膨胀最小而引起了市场的关注，但是SiOC材料通过Si-O键的断裂实现储锂，会形成不可逆的LiSiO 4，使得SiOC材料的首周库伦效率低，降低电化学装置的能量密度。
申请内容
鉴于此，本申请提出了电化学装置及电子装置，可以提高电化学装置的首周库伦效率，提高能量密度。
第一方面，本申请提供一种电化学装置，包括正极极片及负极极片，所述负极极片包括负极集流体及设置于所述负极集流体表面的负极活性物质层；所述负极活性物质层包括活性材料层及位于所述活性材料层表面的含锂层；所述活性材料层包括SiOC材料及石墨。
在一些可行的实施方式中，所述含锂层包含稳定锂金属粉末。
在一些可行的实施方式中，所述电化学装置满足以下特征(1)至(4)中的至少一者：
(1)通过X射线衍射法对所述负极活性物质层进行分析得到的Si2p谱中，Si2p的结合能峰位包括101.4eV±0.3eV、102.2eV±0.3eV、103.1eV±0.3eV、104.40eV±0.3eV中的至少一种；
(2)通过X射线衍射法对所述负极活性物质层进行分析得到Li的结合能峰位在55.6eV±0.3eV之间；
(3)通过X射线衍射法对所述负极活性物质层进行分析，所述负极活性物质层具有Li 22Si衍射峰、Li 22Ge衍射峰、Li 22Sn衍射峰、Li 2O衍射峰、Li 2SiO 3衍射峰或Li 2Si 2O 5衍射峰中的至少一种；
(4)通过固体核磁共振技术对所述负极活性物质层进行分析得到Si的化学位移值，Si的化学位移值包括-5ppm±1ppm、-35ppm±1ppm、-75ppm±1ppm与-100ppm±1ppm，且Si在-5ppm±1ppm处的化学位移峰的半峰宽K满足以下关系：7ppm<K<28ppm。
在一些可行的实施方式中，所述电化学装置满足以下特征(5)至(9)中的至少一者：
(5)所述SiOC材料与石墨的混合粉末的中值粒径为R 1um，R 1的取值范围为0.01至50；
(6)所述稳定锂金属粉末的中值粒径为R 2um，R 2的取值范围为0.1至20；
(7)所述活性材料层的厚度为D 1um，D 1的取值范围为40至150；
(8)所述含锂层的厚度为D 2um，D 2的取值范围为2至20；
(9)当所述电化学装置在满充状态下，通过X射线衍射法，所述负极活性物质层具有Li 15Si 4的衍射峰。
在一些可行的实施方式中，所述电化学装置满足以下特征(10)至(11)中的至少一者：
(10)所述稳定锂金属粉末的中值粒径R 2与所述混合粉末的中值粒径R 1的比值范围满足：0.01≤R 2/R 1≤1；
(11)所述活性材料层的厚度D 1与所述含锂层的厚度D 2的比值范围满足：2≤D 1/D 2≤20。
在一些可行的实施方式中，所述电化学装置满足以下特征(12)至(14)中的至少一者：
(12)所述SiOC材料与所述石墨的质量比为5:95至45:55；
(13)所述SiOC材料与所述石墨的总质量与所述稳定锂金属粉末的质量比为1.99至9；
(14)所述石墨包括天然石墨、人造石墨、中间相碳微球中的至少一种。
在一些可行的实施方式中，所述电化学装置满足以下特征(15)至(16)中的至少一者：
(15)所述负极活性物质层的粉末电导率为2.0S/cm至30.0S/cm；
(16)所述负极活性物质层的电阻的取值范围为0.2Ω至1.0Ω。
在一些可行的实施方式中，所述负极活性物质层还包括粘结剂，所述粘结剂包括聚丙烯酸酯、聚酰亚胺、聚酰胺、聚酰胺酰亚胺、聚偏氟乙烯、丁苯橡胶、海藻酸钠、聚乙烯醇、聚四氟乙烯、聚丙烯腈、羧甲基纤维素钠、羧甲基纤维素钾、羟甲基纤维素钠、羟甲基纤维素钾中的至少一种。
在一些可行的实施方式中，所述电化学装置还包括电解液，所述电解液包括有机溶剂及锂盐；
所述有机溶剂包括碳酸乙烯酯、碳酸丙烯酯、碳酸二乙酯、碳酸甲乙酯、碳酸二甲酯、碳酸亚丙酯、丙酸丙酯或丙酸乙酯中的至少一种；和/或，
所述锂盐包括六氟磷酸锂、四氟硼酸锂、二氟磷酸锂、双三氟甲烷磺酰亚胺锂、双(氟磺酰)亚胺锂、双草酸硼酸锂或二氟草酸硼酸锂中的至少一种。
第二方面，本申请还提供了一种电子装置，所述电子装置包括上述第一方面所述的电化学装置。
相对于现有技术，本申请至少具有以下有益效果：
本申请提供的电化学装置，活性材料层中SiOC材料与含锂层中的稳定锂金属粉 末能够通过和电解液接触被活化，为电化学装置提供更多的活性锂离子，补充SiOC材料不可逆储锂后消耗的活性锂离子，提升负极材料的首次效率，提升电池的能量密度。
附图说明
图1为本申请实施例提供的负极极片的结构示意图；
图2为本申请实施例提供的电化学装置中的负极极片的固体核磁图谱；
图3为本申请实施例提供的负极极片增加含锂层前后的首周库伦效率对比图。
具体实施方式
以下所述是本申请实施例的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本申请实施例原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也视为本申请实施例的保护范围。
为了简便，本文仅明确地公开了一些数值范围。然而，任意下限可以与任何上限组合形成未明确记载的范围；以及任意下限可以与其它下限组合形成未明确记载的范围，同样任意上限可以与任意其它上限组合形成未明确记载的范围。此外，尽管未明确记载，但是范围端点间的每个点或单个数值都包含在该范围内。因而，每个点或单个数值可以作为自身的下限或上限与任意其它点或单个数值组合或与其它下限或上限组合形成未明确记载的范围。
在本文的描述中，需要说明的是，除非另有说明，“以上”、“以下”为包含本数，“一种或多种”中“多种”的含义是两个以上。
本申请的上述申请内容并不意欲描述本申请中的每个公开的实施方式或每种实现方式。如下描述更具体地举例说明示例性实施方式。在整篇申请中的多处，通过一系列实施例提供了指导，这些实施例可以以各种组合形式使用。在各个实例中，列举仅作为代表性组，不应解释为穷举。
第一方面，本申请提供一种电化学装置，包括正极极片及负极极片，所述正极极片包括正极集流体及设置于所述正极集流体表面的正极活性物质层；所述负极极片包括负极集流体及设置于所述负极集流体表面的负极活性物质层；
所述负极活性物质层包括活性材料层及位于所述活性材料层表面的含锂层；所述活性材料包括SiOC材料及石墨。
在本申请中，活性材料层中SiOC材料与含锂层中的稳定锂金属粉末能够通过和电解液接触被活化，为电化学装置提供更多的活性锂离子，补充SiOC材料不可逆储锂后消耗的活性锂离子，提升负极材料的首次效率，提升电池的能量密度。
作为本申请可选的技术方案，SiOC材料与石墨均匀混合形成活性材料。
所述SiOC材料主要由Si-O-C骨架和自由碳组成，Si-O-C骨架和自由碳通过C-Si键相连。Si-O-C骨架可以看作是SiO 4四面体中的O被C取代，因此，SiOC材料可以包括SiO 2C 2、SiO 3C、SiOC 3、SiO 4这四种存在形态，其中，SiO 2C 2、SiO 3C为完全可逆储锂形态，SiOC 3为不可逆储锂形态，SiOC 3储锂后形成SiC 4；SiO 4为部分可逆储锂 形态，SiO 4储锂后形成可逆的Li 2SiO 5和不可逆的LiSiO 4。其中，不可逆的LiSiO 4会消耗电化学装置中的部分活性锂离子。但是，SiOC材料具有优良的抵抗外力破坏的能力，而且在热解过程中，SiOC材料能够产生丰富的纳米孔结构，可以提高材料的韧性。
作为本申请可选的技术方案，SiOC材料包括，但不限于：结晶、非晶碳或它们的混合物。结晶SiOC材料的形态可以是无定形、片层、小片形、球形、方块状、纳米颗粒状或纤维状等。
作为本申请可选的技术方案，所述SiOC材料与所述石墨的质量比为5:95至45:55；具体可以是5:95、10:90、15:85、45:55等等，当然也可以是上述范围内的其他值，在此不做限定。在本申请中，石墨可以包括天然石墨、人造石墨、中间相碳微球中的至少一种，只需将石墨与SiOC材料均匀混合即可。
作为本申请可选的技术方案，所述活性材料与所述稳定锂金属粉末的质量比值为1.99至9；具体可以是1.99、2.5、3.0、4.5、5.0、5.8、6.7、8.0或9等等，当然也可以是上述范围内的其他值，在此不做限定。
如图1所示，活性材料层11位于所述负极集流体10的表面，所述含锂层12位于所述活性材料层11表面，所述含锂层12包含稳定锂金属粉末。
作为本申请可选的技术方案，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。优选地，负极集流体为铜箔。
所述活性材料层11的厚度为D 1um，D 1的取值范围为40至150；具体地，活性材料层11的厚度可以是40um、50um、60um、80um、100um、120um或150um等等，当然也可以是上述范围内的其他值，在此不做限定。
所述含锂层12的厚度为D 2um，D 2的取值范围为2至20；具体地，所述含锂层12的厚度可以是2um、4um、5um、6um、8um、10um、12um、15um、18um或20um等等，当然也可以是上述范围内的其他值，在此不做限定。
所述活性材料层11的厚度D 1与所述含锂层的厚度D 2的比值范围满足：2≤D 1/D 2≤20。D 1/D 2的比值具体可以是2、4、5、8、10、12、15、18或20等等，当然也可以是上述范围内的其他值，在此不做限定。
作为本申请可选的技术方案，所述稳定锂金属粉末可以是稳定金属锂粉和/或稳定金属锂化物，具体地，稳定锂金属粉末包括Li元素、Ge元素、Sn元素等等。
作为本申请可选的技术方案，通过X射线衍射法对所述负极活性物质层进行分析，所述负极活性物质层具有Li 22Si衍射峰、Li 22Ge衍射峰、Li 22Sn衍射峰、Li 2O衍射峰、Li 2SiO 3衍射峰或Li 2Si 2O 5衍射峰中的至少一种。
作为本申请可选的技术方案，所述活性材料的中值粒径为R 1um，R 1的取值范围为0.01至50；具体地，所述活性材料的中值粒径可以是0.01um、0.05um、0.1um、0.5um、1um、5um、10um、20um、30um、40um或50um等等，当然也可以是上述范围内的其他值，在此不做限定。
作为本申请可选的技术方案，所述稳定锂金属粉末的中值粒径为R 2um，R 2的取值范围为0.1至20；具体地，所述活性材料的中值粒径可以是0.1um、0.5um、1um、3um、5um、8um、10um、15um、18um或20um等等，当然也可以是上述范围内的其 他值，在此不做限定。
作为本申请可选的技术方案，所述稳定锂金属粉末的中值粒径R 2与所述活性材料的中值粒径R 1的比值范围满足：0.01≤R 2/R 1≤1；R 2/R 1的比值具体可以是0.01、0.02、0.03、0.05、0.1、0.3、0.5、0.7、0.8或1等等，当然也可以是上述范围内的其他值，在此不做限定。
作为本申请可选的技术方案，通过X射线衍射法对所述负极活性物质层进行分析得到的Si2p谱中，Si2p的结合能峰位包括101.4eV±0.3eV、102.2eV±0.3eV、103.1eV±0.3eV、104.40eV±0.3eV中的至少一种。即每个结合能峰位分别对应一种Si存在形态。
作为本申请可选的技术方案，通过X射线衍射法对所述负极活性物质层进行分析得到Li的结合能峰位在55.6eV±0.3eV之间。
作为本申请可选的技术方案，如图2所示，通过固体核磁共振技术对所述负极活性物质层进行分析得到Si的化学位移值，Si的化学位移值包括-5ppm±1ppm、-35ppm±1ppm、-75ppm±1ppm与-100ppm±1ppm，且Si在-5ppm±1ppm处的化学位移峰的半峰宽K满足以下关系：7ppm<K<28ppm。
作为本申请可选的技术方案，当所述电化学装置在满充状态下，通过X射线衍射法，所述负极活性物质层具有Li 15Si 4的衍射峰。
作为本申请可选的技术方案，通过透射电子显微镜(Transmission Electron Microscope，TEM)高分辨图像还可以看到Li 15Si 4晶粒、Li 2SiO 3晶粒及Li 2Si 2O 5晶粒，Li 15Si 4晶粒的晶面间距约为0.2nm；Li 2SiO 3晶粒的晶面间距约为0.27nm；Li 2Si 2O 5晶粒的晶面间距约为0.196nm。
作为本申请可选的技术方案，负极活性物质层包括粘结剂，粘结剂可以提高负极活性材料颗粒彼此间的结合和负极活性材料与负极集流体的结合。所述粘结剂包括聚丙烯酸酯、聚酰亚胺、聚酰胺、聚酰胺酰亚胺、聚偏氟乙烯、丁苯橡胶、海藻酸钠、聚乙烯醇、聚四氟乙烯、聚丙烯腈、羧甲基纤维素钠、羧甲基纤维素钾、羟甲基纤维素钠、羟甲基纤维素钾中的至少一种，在此不做限定。
作为本申请可选的技术方案，负极活性物质层还包括导电材料，导电材料包括天然石墨、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等，在此不做限定。
作为本申请可选的技术方案，所述负极活性物质层的电阻的取值范围为0.2Ω至1.0Ω，具体可以是0.2Ω、0.3Ω、0.5Ω、0.6Ω、0.8Ω、0.9Ω或1Ω等，当然也可以是上述范围内的其他值。
作为本申请可选的技术方案，所述负极活性物质层的粉末电导率为2.0S/cm～30.0S/cm；具体可以是2.0S/cm、5.0S/cm、8.0S/cm、10S/cm、12S/cm、15S/cm、18S/cm、20S/cm、25S/cm或30S/cm等，当然也可以是上述范围内的其他值。
作为本申请可选的技术方案，电化学装置还包括正极极片，正极极片包括正极集流体和位于正极集流体上的正极活性物质层。
作为本申请可选的技术方案，正极活性材料包括钴酸锂(LiCoO 2)、锂镍锰钴三元材料、磷酸铁锂、磷酸锰铁锂、锰酸锂中的至少一种。
作为本申请可选的技术方案，正极活性物质层还包括粘合剂和导电材料。可以理解地，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集流体的结合。
具体地，粘合剂包括聚乙烯醇、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、环氧树脂或尼龙中的至少一种。
具体地，导电材料包括基于碳的材料、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、铝或银。在一些实施例中，导电聚合物为聚亚苯基衍生物。
作为本申请可选的技术方案，正极集流体包括，但不限于：铝箔。
作为本申请可选的技术方案，电化学装置还包括电解液，所述电解液包括有机溶剂、锂盐和添加剂。
根据本申请的电解液的有机溶剂可为现有技术中已知的任何可作为电解液的溶剂的有机溶剂。根据本申请的电解液中使用的电解质没有限制，其可为现有技术中已知的任何电解质。根据本申请的电解液的添加剂可为现有技术中已知的任何可作为电解液添加剂的添加剂。
在具体实施例中，所述有机溶剂包括，但不限于：碳酸乙烯酯(EC)、碳酸丙烯酯(PC)、碳酸二乙酯(DEC)、碳酸甲乙酯(EMC)、碳酸二甲酯(DMC)、碳酸亚丙酯、丙酸丙酯或丙酸乙酯中的至少一种。
在具体实施例中，所述锂盐包括有机锂盐或无机锂盐中的至少一种。
在具体实施例中，所述锂盐包括，但不限于：六氟磷酸锂(LiPF 6)、四氟硼酸锂(LiBF 4)、二氟磷酸锂(LiPO 2F 2)、双三氟甲烷磺酰亚胺锂LiN(CF 3SO 2) 2(LiTFSI)、双(氟磺酰)亚胺锂Li(N(SO 2F) 2)(LiFSI)、双草酸硼酸锂LiB(C 2O 4) 2(LiBOB)或二氟草酸硼酸锂LiBF 2(C 2O 4)(LiDFOB)。
在具体实施例中，所述电解液中锂盐的浓度可以为0.5mol/L至3mol/L。
作为本申请可选的技术方案，本申请的电化学装置包括，但不限于：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。
在具体实施例中，所述电化学装置是锂二次电池，其中，锂二次电池包括，但不限于：锂金属二次电池、锂离子电池、锂聚合物二次电池或锂离子聚合物二次电池。
第二方面，本申请实施例还提供一种电子装置，电子装置包括上述第四方面所述的电化学装置。
作为本申请可选的技术方案，所述电子装置包括，但不限于：笔记本电脑、笔输入型计算机、移动电脑、电子书播放器、便携式电话、便携式传真机、便携式复印机、便携式打印机、头戴式立体声耳机、录像机、液晶电视、手提式清洁器、便携CD机、迷你光盘、收发机、电子记事本、计算器、存储卡、便携式录音机、收音机、备用电源、电机、汽车、摩托车、助力自行车、自行车、照明器具、玩具、游戏机、钟表、电动工具、闪光灯、照相机、家庭用大型蓄电池或锂离子电容器等。
下面以锂离子电池为例并且结合具体的实施例说明锂离子电池的制备，本领域的技术人员将理解，本申请中描述的制备方法仅是实例，其他任何合适的制备方法均在本申请的范围内。
(1)负极极片的制备
将SiOC材料与石墨按比例(质量比为5：95至45：55之间)混合搅拌，将混合粉末、导电剂乙炔黑、聚丙烯酸锂按95：1.2：3.8的比例在去离子水溶剂体系中搅拌4h至36h，得到混合均匀的浆料；
将浆料涂敷于铜箔上，在真空条件下，置于130℃下烘干，得到初始极片；
将稳定金属锂粉溶于甲苯中分散均匀，其中，稳定金属锂粉：活性材料(SiOC+石墨)的质量比在1.99至9之间，在氩气保护下使用空气喷枪将混合均匀的稳定金属锂粉甲苯溶液喷涂到所述初始极片表面，静置4h-36h；然后对极片进行冷压处理。
重复喷涂稳定金属锂粉甲苯溶液及冷压处理1次至7次，得到了SiOC/稳定金属锂粉负极极片。
根据上述方法制备得到实施例1至16，以及对比例1至6，各参数见表1。
(2)正极极片的制备
将正极活性材料、导电炭黑、粘结剂聚偏二氟乙烯按照重量比95：2.5：2.5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均匀，获得正极浆料；将正极浆料均匀涂覆于正极集流体铝箔上；再经烘干、冷压、裁片、分切、焊接极耳后，得到正极极片。
(3)电解液
在干燥的氩气气氛手套箱中，将碳酸丙烯酯(PC)、碳酸乙烯酯(EC)(重量比为1：1)混合而成的溶剂中，加入LiPF 6混合均匀，得到电解液，其中LiPF 6的含量为1mol/L。
(4)隔离膜
以聚乙烯多孔聚合薄膜作为隔离膜。
(5)锂离子电池的制备
将正极极片、隔离膜、负极极片按顺序叠好，使隔离膜处于正、负极片之间起到隔离的作用，然后卷绕得到裸电芯；焊接极耳后将裸电芯置于外包装箔铝塑膜中，将上述制备好的电解液注入到干燥后的裸电芯中，经过真空封装、静置、化成、整形、容量测试等工序，获得锂离子电池。
二、锂离子电池的性能测试：
(1)XPS测试：
XPS测试设备为赛默飞公司的ESCLAB 250Xi，以Al为靶做激发源，功率250w，真空度＞10-9Pa。通过XPS测试确定Si 2p的结合能峰位、Li的结合能峰位。
(2)TEM测试：
透射电镜表征在日本电子JEOL JEM-2010透射电子显微镜上进行，操作电压为200kV。
(3)固体核磁测试：
29Si SNMR光谱在仪器AVANCE III 400WB宽腔固体核磁共振仪上进行，旋转速率8kHz分别对应 29Si。
(4)粒径测试：
50ml洁净烧杯中加入约0.02g粉末样品，加入约2 0ml去离子水，再滴加几滴1％的表面活性剂，使粉末完全分散于水中，120W超声清洗机中超声5min，利用MasterSizer 2000测试粒径分布。
(5)负极活性物质层的电阻测试：
采用四探针法测试负极活性物质层电阻，四探针法测试所用仪器为精密直流电压电流源(SB118型)，四只长1.5cm*宽1cm*厚2mm的铜板被等距固定在一条线上，中间两块铜板的间距为L(1-2cm)，固定铜板的基材为绝缘材料。测试时将四只铜板下端面压在所测负极上(压力为3000Kg)，维持时间60s，两端铜板接通直流电流I，在中间两只铜板测取电压V，读取三次I和V值，分别取I和V的平均值Ia和Va，Va/Ia的值即为测试处的负极活性物质层的电阻。每张负极极片取12个点测试，取平均值。
(6)粉末电导率测试：
采用电阻率测试仪(苏州晶格电子ST-2255A)，取5g粉末样品，用电子压力机恒压至5000kg±2kg，维持15-25s，将样品置于测试仪电极间，样品高度h(cm)，两端电压U，电流I，电阻R(KΩ)粉压片后的面积S＝3.14cm 2，根据公式δ＝h/(S*R)/1000计算得到粉末电子电导率，单位为S/m。
(7)首圈库伦效率和循环膨胀率测试：
利用千分尺测量锂离子电池的初始厚度为H0，将锂离子电池在25℃下以0.5C的倍率充电至充电截止电压，之后恒压充电至0.025C，再以0.5C的倍率放电至放电截止电压，从而得到首圈充电容量和首圈放电容量。首圈库伦效率＝首圈放电容量/首圈充电容量。
重复上述充放电循环400圈，利用千分尺测量锂离子电池此时的厚度为H1。循环400圈后膨胀率＝(H1-H0)/H0×100％。
循环容量保持率是指，循环至400圈时的放电容量除以首圈放电容量。
根据上述方法制得的实施例1至16的负极极片及对比例1至6的负极极片制备工 艺参数见表1，制得的负极极片性能参数见表2，其制得的锂电池的性能测试结果见3所示。
表1.负极极片制备工艺参数
Figure PCTCN2021084082-appb-000001
表2.负极极片性能参数
Figure PCTCN2021084082-appb-000002
Figure PCTCN2021084082-appb-000003
表3.锂电池性能参数
样本 全电池首次库伦效率(％) 25℃循环400圈时容量保持(％) 25℃循环400圈时电芯膨胀率(％)
实施例1 92.8 90.1 7.4
实施例2 92.7 87.9 7.8
实施例3 92.9 93.3 4.5
实施例4 92 82.3 6.8
实施例5 92.8 88.3 7.3
实施例6 92.1 88.7 8.5
实施例7 92.9 89.2 7.0
实施例8 92 88.3 7.4
实施例9 92.9 88.7 7.8
实施例10 92.8 88.9 8.0
实施例11 70 65.6 8.2
实施例12 85 66 8.5
实施例13 92.9 85 8.6
实施例14 89.9 86.7 8.2
实施例15 90.3 88.5 6.8
实施例16 89.6 87.1 6.4
对比例1 73 65.2 5.8
对比例2 72.6 65.2 9.8
对比例3 73.1 65.2 8.5
对比例4 72.9 65.2 8.6
对比例5 63 54.4 5.8
对比例6 52 48.8 9.8
如图3所示，实施例1至8的负极极片在覆盖含锂层前后的首周库伦效率均得到明显提升，可以在活性材料层表面覆盖含锂层能够提高电池的首周库伦效率。
根据实施例1至4的测试数据对比说明了不同SiOC材料与石墨的配比关系对材料和电芯性能的影响。在制备工艺、稳定锂金属粉末含量、极片厚度相同的情况下，随着活性材料中的SiOC材料的增加，负极极片的克容量增加，但是SiOC材料的增加会消耗更多的活性锂离子，从而使得负极极片的首周库伦效率下降。
根据实施例3、5至7的测试数据对比说明了在制备负极极片过程中，不同搅拌时间对材料和电芯性能的影响。在其他影响因素不变的情况下，将搅拌时间控制在4h至36h范围内，可以使得负极浆料中的材料混合均匀，因此，不同搅拌时间对负极极片与电芯的性能影响不大。
根据实施例3、8至10的测试数据对比说明了在制备负极极片过程中，不同静置时间对材料和电芯性能的影响。在其他影响因素不变的情况下，将静置时间控制在4h至36h范围内，使得稳定金属锂粉稳定覆盖在活性材料层上，因此，不同静置时间对负极极片与电芯的性能影响不大。
根据实施例3、11至13的测试数据对比说明了在制备负极极片过程中，稳定金属锂粉甲苯溶液的喷涂次数对材料和电芯性能的影响。在其他影响因素不变的情况下，将稳定金属锂粉甲苯溶液的喷涂次数控制在1次至7次范围内，随着喷涂次数的增加，活性材料层的表面的稳定锂金属粉末的含量也随之增加，极片厚度也随之增加；从而使得稳定锂金属粉末能够在与电解液接触过程中产生更多的活性锂离子，因此极片的首周库伦效率也有所提升，电池的首周库伦效率及循环保持率均有所提高。
根据实施例3、14至16的测试数据对比说明了在制备负极极片过程中，稳定金属锂粉的中值粒径与活性材料的中值粒径之间的比值对材料和电芯性能的影响。在其他影响因素不变的情况下，稳定金属锂粉的中值粒径与活性材料的中值粒径之间的比值越大，说明活性材料的中值粒径越小，其循环过程中膨胀率降低；稳定金属锂粉的中值粒径与活性材料的中值粒径之间的比值越小，说明活性材料的中值粒径越大，其循环过程中膨胀率上升，因此需要控制稳定金属锂粉的中值粒径与活性材料的中值粒径之间的比值，以提高电池循环稳定性。
本申请虽然以较佳实施例公开如上，但并不是用来限定权利要求，任何本领域技术人员在不脱离本申请构思的前提下，都可以做出若干可能的变动和修改，因此本申请的保护范围应当以本申请权利要求所界定的范围为准。

Claims (10)

  1. 一种电化学装置，包括正极极片及负极极片，所述负极极片包括负极集流体及设置于所述负极集流体表面的负极活性物质层；其特征在于，
    所述负极活性物质层包括活性材料层及位于所述活性材料层表面的含锂层；所述活性材料层包括SiOC材料及石墨。
  2. 根据权利要求1所述的电化学装置，其特征在于，所述含锂层包含稳定锂金属粉末。
  3. 根据权利要求1所述的电化学装置，其特征在于，其满足以下特征(1)至(4)中的至少一者：
    (1)通过X射线衍射法对所述负极活性物质层进行分析得到的Si2p谱中，Si2p的结合能峰位包括101.4eV±0.3eV、102.2eV±0.3eV、103.1eV±0.3eV、104.40eV±0.3eV中的至少一种；
    (2)通过X射线衍射法对所述负极活性物质层进行分析得到Li的结合能峰位在55.6eV±0.3eV之间；
    (3)通过X射线衍射法对所述负极活性物质层进行分析，所述负极活性物质层具有Li 22Si衍射峰、Li 22Ge衍射峰、Li 22Sn衍射峰、Li 2O衍射峰、Li 2SiO 3衍射峰或Li 2Si 2O 5衍射峰中的至少一种；
    (4)通过固体核磁共振技术对所述负极活性物质层进行分析得到Si的化学位移值，Si的化学位移值包括-5ppm±1ppm、-35ppm±1ppm、-75ppm±1ppm与-100ppm±1ppm，且Si在-5ppm±1ppm处的化学位移峰的半峰宽K满足以下关系：7ppm<K<28ppm。
  4. 根据权利要求2所述的电化学装置，其特征在于，其满足以下特征(5)至(9)中的至少一者：
    (5)所述SiOC材料与石墨的混合粉末的中值粒径为R 1um，R 1的取值范围为0.01至50；
    (6)所述稳定锂金属粉末的中值粒径为R 2um，R 2的取值范围为0.1至20；
    (7)所述活性材料层的厚度为D 1um，D 1的取值范围为40至150；
    (8)所述含锂层的厚度为D 2um，D 2的取值范围为2至20；
    (9)当所述电化学装置在满充状态下，通过X射线衍射法，所述负极活性物质层具有Li 15Si 4的衍射峰。
  5. 根据权利要求2所述的电化学装置，其特征在于，其满足以下特征(10)至(11)中的至少一者：
    (10)所述稳定锂金属粉末的中值粒径R 2与所述混合粉末的中值粒径R 1的比值范围满足：0.01≤R 2/R 1≤1；
    (11)所述活性材料层的厚度D 1与所述含锂层的厚度D 2的比值范围满足：2≤D 1/D 2≤20。
  6. 根据权利要求2所述的电化学装置，其特征在于，其满足以下特征(12)至(14)中的至少一者：
    (12)所述SiOC材料与所述石墨的质量比为5:95至45:55；
    (13)所述SiOC材料与所述石墨的总质量与所述稳定锂金属粉末的质量比为1.99至9；
    (14)所述石墨包括天然石墨、人造石墨、中间相碳微球中的至少一种。
  7. 根据权利要求1所述的电化学装置，其特征在于，其满足以下特征(15)至(16)中的至少一者：
    (15)所述负极活性物质层的粉末电导率为2.0S/cm至30.0S/cm；
    (16)所述负极活性物质层的电阻的取值范围为0.2Ω至1.0Ω。
  8. 根据权利要求1所述的电化学装置，其特征在于，所述负极活性物质层还包括粘结剂，所述粘结剂包括聚丙烯酸酯、聚酰亚胺、聚酰胺、聚酰胺酰亚胺、聚偏氟乙烯、丁苯橡胶、海藻酸钠、聚乙烯醇、聚四氟乙烯、聚丙烯腈、羧甲基纤维素钠、羧甲基纤维素钾、羟甲基纤维素钠、羟甲基纤维素钾中的至少一种。
  9. 根据权利要求1所述的电化学装置，其特征在于，所述电化学装置还包括电解液，所述电解液包括有机溶剂及锂盐；
    所述有机溶剂包括碳酸乙烯酯、碳酸丙烯酯、碳酸二乙酯、碳酸甲乙酯、碳酸二甲酯、碳酸亚丙酯、丙酸丙酯或丙酸乙酯中的至少一种；和/或，
    所述锂盐包括六氟磷酸锂、四氟硼酸锂、二氟磷酸锂、双三氟甲烷磺酰亚胺锂、双(氟磺酰)亚胺锂、双草酸硼酸锂或二氟草酸硼酸锂中的至少一种。
  10. 一种电子装置，其特征在于，所述电子装置包括权利要求1至9任一项所述的电化学装置。
PCT/CN2021/084082 2021-03-30 2021-03-30 电化学装置及电子装置 WO2022204974A1 (zh)

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