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WO2021174443A1 - 电化学装置和包含其的电子装置 - Google Patents

电化学装置和包含其的电子装置 Download PDF

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Publication number
WO2021174443A1
WO2021174443A1 PCT/CN2020/077769 CN2020077769W WO2021174443A1 WO 2021174443 A1 WO2021174443 A1 WO 2021174443A1 CN 2020077769 W CN2020077769 W CN 2020077769W WO 2021174443 A1 WO2021174443 A1 WO 2021174443A1
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Prior art keywords
negative electrode
lithium
layer
active material
electrochemical device
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PCT/CN2020/077769
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English (en)
French (fr)
Inventor
钟华炜
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宁德新能源科技有限公司
东莞新能源科技有限公司
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Application filed by 宁德新能源科技有限公司, 东莞新能源科技有限公司 filed Critical 宁德新能源科技有限公司
Priority to EP20922559.8A priority Critical patent/EP4102609A4/en
Priority to US17/909,075 priority patent/US20230058850A1/en
Priority to PCT/CN2020/077769 priority patent/WO2021174443A1/zh
Priority to JP2022544320A priority patent/JP7437516B2/ja
Priority to CN202080016450.3A priority patent/CN113614969A/zh
Publication of WO2021174443A1 publication Critical patent/WO2021174443A1/zh

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • H01M50/461—Separators, membranes or diaphragms characterised by their combination with electrodes with adhesive layers between electrodes and separators
    • 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
    • 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
    • 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
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • 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
    • 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

  • This application relates to the field of energy storage technology, in particular to electrochemical devices and electronic devices including the electrochemical devices.
  • electrochemical devices for example, lithium ion batteries
  • electrochemical devices that provide energy for electronic devices need to exhibit higher energy density, greater rate, higher safety, and smaller capacity decay after repeated charging and discharging processes.
  • the energy density and cycle performance of electrochemical devices are closely related to the positive electrode active material and the negative electrode active material.
  • people continue to make further research and improvement on negative electrode active materials in order to pursue negative electrode active materials with higher energy density.
  • negative active materials with higher energy density for example, silicon-based materials
  • problems that do not match the structure of existing electrode assemblies, such as too low electrical conductivity, too high thermal expansion rate, insufficient processing performance, etc. . Therefore, for electrochemical devices that use higher energy density materials as the negative electrode active materials, the improvement and optimization of the electrode assembly structure (for example, the negative electrode, the separator, and the positive electrode) are currently urgently needed research topics.
  • the present application provides an electrochemical device and an electronic device including the electrochemical device in an attempt to solve at least one problem existing in the related field at least to some extent.
  • the present application provides an electrochemical device, which includes: a positive electrode, a negative electrode, a separator, a binding layer, and a lithium compound layer, wherein the negative electrode includes a negative active material layer, and the separator is disposed on the positive electrode and the negative electrode.
  • the binding layer is disposed between the negative active material layer and the separation film
  • the lithium compound layer is disposed between the binding layer and the negative active material layer
  • the lithium compound layer includes at least one of lithium carbonate and lithium oxide.
  • the present application provides an electronic device including the above-mentioned electrochemical device.
  • the electrochemical device of the present application will further include a lithium compound layer formed on the surface of the negative electrode active material layer after the lithium supplementation process, and by providing a binding layer between the lithium compound layer and the separator, the gap between the negative electrode and the separator can be effectively improved. Adhesion. After the electrochemical device has undergone multiple charge and discharge cycles, the adhesion between the negative electrode and the separator is still maintained, thereby improving the cycle performance and safety performance of the electrochemical device.
  • FIG. 1 is a schematic diagram of the structure of an electrode assembly of an electrochemical device according to some embodiments of the application.
  • Figure 2 is an image of the negative electrode surface that has not undergone the lithium replenishment process at a 50-times scanning electron microscope.
  • Figure 3 is an electron microscope image of the negative electrode surface that has not undergone the lithium replenishment process at 400 times scanning.
  • Figure 4 is an image of the negative electrode surface after being processed by the lithium supplementation process under a 50x scanning electron microscope.
  • Figure 5 is an image of the negative electrode surface after being processed by the lithium supplementation process under a 400-time scanning electron microscope.
  • a list of items connected by the terms “at least one of”, “at least one of”, “at least one of” or other similar terms may mean the listed items Any combination of. For example, if items A and B are listed, then the phrase “at least one of A and B” means only A; only B; or A and B. In another example, if items A, B, and C are listed, then the phrase "at least one of A, B, and C” means only A; or only B; only C; A and B (excluding C); A and C (exclude B); B and C (exclude A); or all of A, B, and C.
  • Project A can contain a single element or multiple elements.
  • Project B can contain a single element or multiple elements.
  • Project C can contain a single element or multiple elements.
  • C x refers to containing x number of carbon atoms.
  • a C 1 to C 10 alkyl group is an alkyl group having 1 to 10 carbon atoms.
  • hydrocarbyl encompasses alkyl, alkenyl, alkynyl, cycloalkyl, and aryl groups.
  • the hydrocarbyl group is expected to be a straight chain hydrocarbon structure having 1 to 20 carbon atoms.
  • Hydrocarbyl is also expected to be a branched or cyclic hydrocarbon structure having 3 to 20 carbon atoms. When a hydrocarbyl group having a specific carbon number is designated, it is expected to encompass all geometric isomers having that carbon number.
  • the hydrocarbyl group herein may also be a C 1 to C 15 hydrocarbyl group, a C 1 to C 10 hydrocarbyl group, a C 1 to C 5 hydrocarbyl group, a C 5 to C 20 hydrocarbyl group, a C 5 to C 15 hydrocarbyl group, or a C 5 to C 10 hydrocarbyl group.
  • the hydrocarbyl group may be optionally substituted.
  • the hydrocarbyl group may be substituted with halogen, alkyl, aryl, or heteroaryl including fluorine, chlorine, bromine, and iodine.
  • hydroxyl refers to the -OH group.
  • amino refers to a base consisting of one nitrogen atom and two hydrogen atoms, that is, the -NH 2 group
  • carboxyl is a functional group of carboxylic acid, that is, refers to the -C(O)-OH group.
  • hydrocarbyloxy refers to the LO- group, where L is alkyl, alkenyl, alkynyl, cycloalkyl, aryl.
  • L is alkyl, alkenyl, alkynyl, cycloalkyl, aryl.
  • the “hydrocarbyloxy group” can be referred to as an "alkoxy group”; when the L group is a methyl group, the “hydrocarbyloxy group” can be referred to as a "methoxy group”.
  • the hydrocarbyloxy group herein may be a C 1 to C 20 hydrocarbyloxy group, a C 1 to C 15 hydrocarbyloxy group, a C 1 to C 10 hydrocarbyloxy group, a C 1 to C 5 hydrocarbyloxy group, a C 5 to C 20 hydrocarbyloxy group, C 5 to C 15 hydrocarbyloxy group, or C 5 to C 10 hydrocarbyloxy group.
  • ester group refers to the functional group of the ester in the carboxylic acid derivative, that is, refers to the -C(O)-OR group, where R encompasses alkyl, alkenyl, alkynyl, cycloalkyl, and aryl groups.
  • R encompasses alkyl, alkenyl, alkynyl, cycloalkyl, and aryl groups.
  • the ester group is expected to have a linear, branched, or cyclic structure with 1 to 200 carbon atoms.
  • “Ester groups” are also expected to have C 2 to C 10 ester groups. When an ester group with a specific carbon number is designated, it is expected to encompass all geometric isomers with that carbon number.
  • the hydrocarbyl group herein can also be a C 1 to C 15 ester group, a C 1 to C 10 ester group, a C 1 to C 5 ester group, a C 5 to C 20 ester group, a C 5 to C 15 ester group, or a C 5 to C 15 ester group.
  • C 10 ester group can also be a C 1 to C 15 ester group, a C 1 to C 10 ester group, a C 1 to C 5 ester group, a C 5 to C 20 ester group, a C 5 to C 15 ester group, or a C 5 to C 15 ester group.
  • alkyl is expected to have 1 to 20 linear saturated hydrocarbon structures. "Alkyl” is also expected to be a branched or cyclic hydrocarbon structure having 3 to 20 carbon atoms.
  • the alkyl group may be a C 1 to C 20 alkyl group, a C 1 to C 10 alkyl group, a C 1 to C 5 alkyl group, a C 5 to C 20 alkyl group, a C 5 to C 15 alkyl group, or a C 5 to C 10 alkyl.
  • butyl means to include n-butyl, sec-butyl, isobutyl, tert-butyl And cyclobutyl;
  • propyl includes n-propyl, isopropyl and cyclopropyl.
  • alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, Isopentyl, neopentyl, cyclopentyl, methylcyclopentyl, ethylcyclopentyl, n-hexyl, isohexyl, cyclohexyl, n-heptyl, octyl, cyclopropyl, cyclobutyl, norbornyl Base and so on.
  • the alkyl group may be optionally substituted.
  • alkenyl refers to a monovalent unsaturated hydrocarbon group that may be straight or branched and has at least one and usually 1, 2, or 3 carbon-carbon double bonds. Unless otherwise defined, the alkenyl group usually contains 2-20 carbon atoms, for example, it can be a C 2 to C 20 alkenyl group, a C 6 to C 20 alkenyl group, a C 2 to C 12 alkenyl group, or a C 2 to C 6 alkenyl group. base.
  • Representative alkenyl groups include, for example, vinyl, n-propenyl, isopropenyl, n-but-2-enyl, but-3-enyl, n-hex-3-enyl, and the like. In addition, alkenyl groups may be optionally substituted.
  • alkynyl refers to a monovalent unsaturated hydrocarbon group that can be straight or branched and has at least one and usually 1, 2, or 3 carbon-carbon triple bonds. Unless otherwise defined, an alkynyl group usually contains 2 to 20 carbon atoms, for example, a C 2 to C 20 alkynyl group, a C 6 to C 20 alkynyl group, a C 2 to C 10 alkynyl group, or a C 2 to C 6 alkynyl group. Alkynyl.
  • alkynyl groups include, for example, ethynyl, prop-2-ynyl (n-propynyl), n-but-2-ynyl, n-hex-3-ynyl, and the like. In addition, alkynyl groups may be optionally substituted.
  • acyl refers to the atomic group left after the hydroxyl (-OH group) is removed from the organic or inorganic oxyacid, that is, the RM(O)- group, where M is a carbon atom, R is an alkyl, alkenyl, Alkynyl, cycloalkyl, aryl or other common substituents. For example, when R is amino, “acyl” is "amide".
  • aryl encompasses both monocyclic and polycyclic ring systems.
  • a polycyclic ring may have two or more rings in which two carbons are shared by two adjacent rings (the rings are "fused"), where at least one of the rings is aromatic, for example, the other ring may be a ring Alkyl, cycloalkenyl, aryl, heterocyclic and/or heteroaryl.
  • the aryl group may be a C 6 to C 50 aryl group, a C 6 to C 40 aryl group, a C 6 to C 30 aryl group, a C 6 to C 20 aryl group, or a C 6 to C 10 aryl group.
  • aryl groups include, for example, phenyl, methylphenyl, propylphenyl, isopropylphenyl, benzyl and naphth-1-yl, naphth-2-yl, and the like. In addition, aryl groups may be optionally substituted.
  • heterocyclic group encompasses aromatic and non-aromatic cyclic groups. Heteroaromatic cyclic group also means aromatic hetero group.
  • the heteroaromatic cyclic group and the heteronon-aromatic cyclic group are C 1 to C 50 heterocyclic group, C 1 to C 40 heterocyclic group, C 1 to C 40 heterocyclic group including at least one heteroatom C 30 heterocyclic group, C 1 to C 20 heterocyclic group, C 1 to C 10 heterocyclic group, C 1 to C 6 heterocyclic group.
  • heterocyclic groups include, for example, morpholinyl, piperidinyl, pyrrolidinyl, etc., and cyclic ethers such as tetrahydrofuran, tetrahydropyran, and the like.
  • the heterocyclic group may be optionally substituted.
  • heteroaryl encompasses monocyclic heteroaromatic groups that can include one to three heteroatoms, such as pyrrole, furan, thiophene, imidazole, oxazole, thiazole, triazole, pyrazole, pyridine, Pyrazine and pyrimidine, etc.
  • heteroaryl also includes polycyclic heteroaromatic systems having two or more rings shared by two adjacent rings (rings are "fused") in which two atoms are Heteroaryl, other rings can be cycloalkyl, cycloalkenyl, aryl, heterocyclic and/or heteroaryl.
  • the heteroaryl group may be a C 6 to C 50 heteroaryl group, a C 6 to C 40 heteroaryl group, a C 6 to C 30 heteroaryl group, a C 6 to C 20 heteroaryl group, or a C 6 to C 10 heteroaryl group .
  • heteroaryl groups may be optionally substituted.
  • halogen can be F, Cl, Br, or I.
  • cyano encompasses organic functional groups containing -CN.
  • coverage rate refers to the degree of coverage of the coating layer on the surface of the coated object. For example, a coverage rate of 100% means that the coating layer completely covers the entire surface of the coated object.
  • coverage rate of 40% means that the coating layer only covers 40% of the surface of the coated object, and the other 60% of the surface of the coated object is exposed.
  • degree of substitution refers to the average number of substitutions by substituent groups in a single monomer on the main chain of the polymer. For example, a degree of substitution of 0.5 means that there are 0.5 functional groups with substituents on the monomers of the polymer on average.
  • particle size represents the Dv50 that characterizes the particle characteristics obtained by the sample through the laser particle size test, where Dv50 represents the particle size of the material in the volume-based particle size distribution, starting from the small particle size side and reaching 50% of the cumulative volume. .
  • the lithium supplement process is a method of supplementing lithium in the negative electrode active material to increase the energy density.
  • the more mature lithium supplement process is to compound and roll a certain amount of lithium metal on the surface of the negative electrode active material layer.
  • This kind of higher energy density negative electrode active material has a huge volume change effect (for example, greater than 300%) in the process of deintercalating lithium.
  • the severe expansion of the negative electrode will cause the interface between the negative electrode and the separator to deform or even separate, which will cause lithium ion batteries.
  • the cycle performance is reduced.
  • the lithium metal will react with moisture and oxygen in the air to form a lithium compound layer on the surface of the negative electrode active material layer.
  • the adhesion between the lithium compound layer and the conventional coating on the surface of the separator film is very weak (for example, less than 1 N/m), which may cause weak or no adhesion between the negative electrode and the separator film.
  • a binding layer is provided between the negative electrode and the separator, and the lithium compound layer produced by the lithium supplementation process is controlled to increase the binding force of the binding layer to the lithium compound layer, thereby effectively improving the separation film’s resistance to the negative electrode.
  • Adhesive force and improve the volume expansion rate of the negative electrode during the charge and discharge cycle, which is beneficial to reduce the deformation degree of the electrode assembly.
  • the binding layer of the present application can be used in an electrochemical device using a negative electrode active material with a higher energy density to improve the cycle stability and safety of the electrochemical device. At the same time, due to the suppression of expansion and deformation, the stability of the interface between the negative electrode and the separator is better, so that the cycle capacity retention rate is improved.
  • the embodiments of the present application provide a bonding layer disposed between the negative electrode and the separator.
  • the bonding layer can generate sufficient bonding force to the lithium compound layer in the lithium-supplemented negative electrode. Therefore, the electrochemical device can ensure its cycle performance and safety performance by adding a bonding layer disposed between the lithium compound layer and the isolation membrane.
  • FIG. 1 is a schematic diagram of the structure of an electrode assembly of an electrochemical device according to some embodiments of the application.
  • the present application provides an electrochemical device including: a positive electrode 40, a negative electrode 30, a separator 10 and a binding layer 20, wherein the negative electrode 30 includes a negative electrode active material layer 302.
  • the separation film 10 is provided between the positive electrode 40 and the negative electrode 30, and the binding layer 20 is provided between the negative electrode active material layer 302 and the separation film 10.
  • the negative electrode of the electrochemical device undergoes a lithium supplementation process, a lithium compound layer 303 is formed on the negative electrode active material layer 302, and the lithium compound layer 303 is disposed between the binding layer 20 and the negative electrode active material layer 302.
  • the lithium compound layer 303 includes at least one of lithium carbonate and lithium oxide
  • the lithium compound layer 303 is in contact with the negative active material layer 302, and the lithium compound layer 303 is in contact with the binding layer 20.
  • the term "layer” is used to describe the layered structure of each functional material in the electrochemical device, for example, a binding layer, a negative electrode active material layer, a positive electrode active material layer, a lithium compound layer, and the like.
  • the layered structure can be, but is not limited to, a continuous, discontinuous, through-hole, or a layered structure composed of multiple particles.
  • a continuous layered structure is a complete layer, and there are no gaps in the layer; a discontinuous layered structure contains multiple scattered or segmented layers, and each part of the layer exists between each other Section or gap.
  • 2 and 3 are 50 and 400 times scanning electron microscope images of the surface of the negative electrode that has not been processed by the lithium replenishment process.
  • 4 and 5 are 50 and 400 times scanning electron microscope images of the surface of the negative electrode after the lithium replenishment process.
  • the lithium compound layer presents a concave and convex vertical grain morphology, and is compared with the negative electrode without lithium supplement. Due to the coverage and distribution of the lithium compound layer on the negative electrode active material layer, the vertical deviation value of the surface formed by the exposed negative electrode active material layer and the part covering the lithium compound layer is increased, resulting in the roughness of the negative electrode surface facing the direction of the separator. Degree increases. In addition, because the lithium compound layer has a higher porosity, the porosity of the negative electrode after the lithium supplementation process is increased, thereby further improving the surface roughness of the negative electrode.
  • the distribution, shape and coverage of the lithium compound layer on the negative electrode active material layer can be controlled by the setting of lithium metal during the lithium supplementation process.
  • the lithium supplementation process is In this case, a lithium metal strip with a fixed length and width is used and arranged at a fixed interval, so that the formed lithium compound layer can be distributed in stripes on the negative electrode active material layer.
  • the lithium compound layer includes a flat shape, a striped shape, a spot shape, and an irregular shape. In some embodiments, the lithium compound layer is striped.
  • the coverage of the negative active material layer by the lithium compound layer is greater than or equal to 30%. In other embodiments, the coverage rate of the lithium compound layer to the negative active material layer is approximately, for example, 40%, 50%, 60%, 70%, 80%, 90%, or 100%.
  • the porosity of the negative active material layer and the lithium compound layer is 10% to 60%. In other embodiments, the porosity of the anode active material layer and the lithium compound layer is approximately, for example, 10%, 15%, 20%, 30%, 40%, 50%, 60% or any two of these values. The range of composition.
  • the surface roughness of the negative electrode is 0.5 ⁇ m to 4.0 ⁇ m. In other embodiments, the surface roughness of the negative electrode is approximately, for example, 0.5 ⁇ m, 1.0 ⁇ m, 1.5 ⁇ m, 2.0 ⁇ m, 2.5 ⁇ m, 3.0 ⁇ m, 3.5 ⁇ m, 4.0 ⁇ m, or a range of any two of these values. .
  • the contact area between the binding layer and the negative electrode can be further controlled, so that the high molecular polymer particles in the binding layer can be embedded on the surface of the negative electrode , So as to form a "riveted” state, enhance the mutual force.
  • the thickness of the lithium compound layer is 0.01 ⁇ m to 3 ⁇ m
  • the above-mentioned high molecular polymer is a modified polypropylene structural polymer, and the high molecular polymer includes a main chain and a substituent.
  • the main chain of the high molecular polymer is formed by at least one of the following monomers: methacryl, methacrylic acid, methyl methacrylate, imide, vinyl alcohol, and ethylene glycol. In some embodiments, the main chain of the high molecular polymer is formed by at least one of the following monomers: methacryl, imide, vinyl alcohol, and ethylene glycol.
  • the substituent of the high molecular polymer includes at least one of a carboxyl group, a hydroxyl group, an amino group, an amide group, a methoxy group, a cyano group, or an ester group. In some embodiments, the substituent of the high-molecular polymer includes at least one of a carboxyl group, a hydroxyl group, or an amino group.
  • the degree of substitution of the substituents in the polymer is 0.2 to 0.8.
  • the embodiments of this application select high-molecular polymers with highly electronegative substituents.
  • the greater the electronegativity the stronger the intermolecular force between the high-molecular polymer in the bonding layer and the bonded interface material. Thereby improving the bonding force of the bonding layer.
  • the dielectric constant of the high molecular polymer is 5F/m to 50F/m to achieve a strong intermolecular force on the bonding interface material.
  • the embodiments of the present application select a high molecular polymer composed of a specific main chain structure and specific substituents so that the bonding layer has a better ability to wet the electrolyte, thereby achieving a strong bond.
  • ethylene carbonate Due to its good electrochemical stability, ethylene carbonate has good solubility with common lithium battery additives such as fluoroethylene carbonate (FEC), and is the most common solvent system for electrolytes. Therefore, the contact angle of the high molecular polymer in the adhesive layer to ethylene carbonate can indicate the wettability of the adhesive layer to the electrolyte.
  • the contact angle of the high molecular polymer in the adhesive layer to ethylene carbonate is 0° to 90°. In some embodiments of the present application, the contact angle of the high molecular polymer to ethylene carbonate is 10° to 50° in order to achieve high wetting ability to the electrolyte.
  • the embodiments of this application can effectively improve the structural stability of the polymer in the lye by selecting high molecular polymers with specific substituents, so that the bonding layer remains after multiple charge and discharge cycles. Maintain the adhesion to the negative electrode and the separator, thereby increasing the cycle life of the electrochemical device.
  • the high molecular weight polymer in the bonding layer can indicate its structural stability through the weight loss rate tested by alkali resistance. The higher the weight loss rate, the more serious the peeling of the substituents of the high molecular polymer in the bonding layer. Represents the lower the bonding strength and structural stability of the bonding layer.
  • the weight loss rate of the high molecular polymer after immersing in a 1 mol/L sodium hydroxide solution for 0.5 hours is less than 20%. In other embodiments, the weight loss rate of the high molecular polymer after immersing in a 1 mol/L sodium hydroxide solution for 0.5 hours is less than or equal to 10%.
  • the binding force of the binding layer to the lithium compound layer or the separator film of the negative electrode may be greater than or equal to 10 N/m. In other embodiments, the binding force of the binding layer to the lithium compound layer or separator of the negative electrode is 15 N/m. In other embodiments, the binding force of the binding layer to the lithium compound layer or the separator film of the negative electrode is 20 N/m.
  • the high-molecular polymer is a particle, and the particle size of the high-molecular polymer is 0.01 ⁇ m to 20 ⁇ m. In other embodiments, the particle size of the polymer is approximately, for example, 0.01 ⁇ m, 0.05 ⁇ m, 0.1 ⁇ m, 0.5 ⁇ m, 1.0 ⁇ m, 5.0 ⁇ m, 10.0 ⁇ m, 20.0 ⁇ m, or any two of these values. Range.
  • the number average molecular weight of the high molecular weight polymer is 1 kDa to 1000 kDa. In other embodiments, the number average molecular weight of the high molecular polymer is approximately, for example, 1 kDa, 10 kDa, 100 kDa, 200 kDa, 400 kDa, 600 kDa, 800 kDa, 1000 kDa, or a range composed of any two of these values.
  • the bonding layer further includes inorganic particles, wherein the inorganic particles include SrTiO 3 , SnO 2 , CeO 2 , MgO, NiO, CaO, ZnO, ZrO 2 , Y 2 O 3 , Al 2 O 3 , TiO 2 , At least one of Al(OH) 3 , Mg(OH) 2 , SiC and boehmite.
  • the inorganic particles include SrTiO 3 , SnO 2 , CeO 2 , MgO, NiO, CaO, ZnO, ZrO 2 , Y 2 O 3 , Al 2 O 3 , TiO 2 , At least one of Al(OH) 3 , Mg(OH) 2 , SiC and boehmite.
  • the weight percentage of the inorganic particles is less than or equal to 50 wt%. In other embodiments, based on the total weight of the bonding layer, the weight percentage of the inorganic particles is less than or equal to 30 wt%.
  • the thickness of the bonding layer is 0.1 ⁇ m to 10 ⁇ m. In other embodiments, the thickness of the adhesive layer is approximately, for example, 0.1 ⁇ m, 0.5 ⁇ m, 1 ⁇ m, 1.5 ⁇ m, 2 ⁇ m, 3 ⁇ m, 4 ⁇ m, 5 ⁇ m, 10 ⁇ m, or a range composed of any two of these values.
  • the porosity of the bonding layer is 20% to 80%. In other embodiments, the porosity of the bonding layer is approximately, for example, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or a range composed of any two of these values.
  • the thickness and porosity range of the bonding layer in the examples of this application can ensure the contact area of the bonded interface to ensure a certain bonding force, and will not cause the bonding layer to block the isolation membrane or the ion channel of the negative electrode. In turn, a certain ionic conductivity is maintained.
  • the electrochemical device is a lithium ion battery.
  • the positive electrode 40 includes a positive current collector 401
  • the negative electrode 30 includes a negative current collector 301.
  • the positive electrode current collector 401 can be aluminum foil or nickel foil
  • the negative electrode current collector 301 can be copper foil or nickel foil.
  • other positive electrode current collectors and negative electrode current collectors commonly used in the art can be used without limitation.
  • the negative electrode 30 includes a negative active material layer 302.
  • the negative electrode active material layer 302 includes a negative electrode active material.
  • the negative electrode active material includes artificial graphite, natural graphite, mesophase carbon microspheres, hard carbon, soft carbon, lithium titanate, single crystal silicon, amorphous silicon, silicon-oxygen composite, and silicon. At least one of carbon composites.
  • the negative electrode active material layer further includes a negative electrode active material with high energy density, examples of which include, but are not limited to, simple substances of silicon, tin, germanium, antimony, bismuth, and aluminum, alloys or compounds thereof One or more.
  • the negative active material includes at least one of silicon, silicon-oxygen composite, or silicon-carbon composite.
  • the positive electrode 40 includes a positive electrode active material layer 402.
  • the positive electrode active material layer 402 includes a positive electrode active material capable of absorbing and releasing lithium (Li) (hereinafter, sometimes referred to as "a positive electrode active material capable of absorbing/releasing lithium Li").
  • positive electrode active materials capable of absorbing/releasing lithium (Li) may include lithium cobalt oxide, lithium nickel cobalt manganate, lithium nickel cobalt aluminate, lithium manganate, lithium iron manganese phosphate, lithium vanadium phosphate, lithium vanadyl phosphate, One or more of lithium iron phosphate, lithium titanate, and lithium-rich manganese-based materials.
  • the chemical formula of lithium cobaltate can be Li y Co a M1 b O 2-c , where the element M1 represents selected from nickel (Ni), manganese (Mn), magnesium (Mg), aluminum (Al ), boron (B), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe), copper (Cu), zinc (Zn), molybdenum (Mo), tin (Sn), calcium (Ca) ), at least one of strontium (Sr), tungsten (W), yttrium (Y), lanthanum (La), zirconium (Zr) and silicon (Si), the values of y, a, b and c are within the following ranges respectively :0.8 ⁇ y ⁇ 1.2, 0.8 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 0.2, -0.1 ⁇ c ⁇ 0.2;
  • the chemical formula of lithium nickel cobalt manganese oxide or lithium nickel cobalt aluminate can be Li z Ni d M2 e O 2-f , wherein the element M2 represents selected from cobalt (Co), manganese (Mn), Magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe), copper (Cu), zinc (Zn), molybdenum (Mo), At least one of tin (Sn), calcium (Ca), strontium (Sr), tungsten (W), yttrium (Y), lanthanum (La), zirconium (Zr) and silicon (Si), z, d, e
  • the and f values are in the following ranges respectively: 0.8 ⁇ z ⁇ 1.2, 0.3 ⁇ d ⁇ 0.98, 0.02 ⁇ e ⁇ 0.7, -0.1 ⁇ f ⁇ 0.2;
  • the chemical formula of lithium manganate is Li u Mn 2-g M 3g O 4-h , where the M3 element is selected from cobalt (Co), nickel (Ni), magnesium (Mg), aluminum (Al ), boron (B), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe), copper (Cu), zinc (Zn), molybdenum (Mo), tin (Sn), calcium (Ca) ), at least one of strontium (Sr), and tungsten (W), and the values of z, g, and h are in the following ranges: 0.8 ⁇ u ⁇ 1.2, 0 ⁇ g ⁇ 1.0, and -0.2 ⁇ h ⁇ 0.2.
  • the positive electrode active material layer and the negative electrode active material layer can each independently further include at least one of a binder and a conductive agent.
  • the binder includes polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, sodium carboxymethyl cellulose , At least one of polyvinylpyrrolidone, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene, polyhexafluoropropylene or styrene butadiene rubber.
  • the conductive agent includes at least one of carbon nanotubes, carbon fibers, conductive carbon black, acetylene black, graphene, or Ketjen black. It should be understood that those skilled in the art can select conventional adhesives and conductive agents in the art according to actual needs without limitation.
  • the lithium compound layer does not include a binder and a conductive agent.
  • the isolation film includes, but is not limited to, at least one selected from polyethylene, polypropylene, polyethylene terephthalate, polyimide, and aramid.
  • polyethylene includes at least one component selected from high-density polyethylene, low-density polyethylene, and ultra-high molecular weight polyethylene.
  • polyethylene and polypropylene they have a good effect on preventing short circuits, and can improve the stability of the battery through the shutdown effect.
  • the isolation film is polypropylene, and polypropylene has a good affinity with the high molecular polymer in the above-mentioned embodiments, which is beneficial to improve the adhesion between the adhesive layer and the isolation film.
  • the lithium ion battery of the present application also includes an electrolyte.
  • the electrolyte may be one or more of a gel electrolyte, a solid electrolyte, and an electrolyte.
  • the electrolyte includes a lithium salt and a non-aqueous solvent.
  • the lithium salt is selected from LiPF 6 , LiBF 4 , LiAsF 6 , LiClO 4 , LiB(C 6 H 5 ) 4 , LiCH 3 SO 3 , LiCF 3 SO 3 , LiN(SO 2 CF 3 ) 2 , One or more of LiC(SO 2 CF 3 ) 3 , LiSiF 6 , LiBOB and lithium difluoroborate.
  • LiPF 6 is selected as the lithium salt because it can give high ionic conductivity and improve cycle characteristics.
  • the non-aqueous solvent may be a carbonate compound, a carboxylate compound, an ether compound, other organic solvents, or a combination thereof.
  • the aforementioned carbonate compound may be a chain carbonate compound, a cyclic carbonate compound, a fluorocarbonate compound, or a combination thereof.
  • Examples of the above-mentioned other organic solvents are dimethyl sulfoxide, 1,2-dioxolane, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone, Formamide, dimethylformamide, acetonitrile, trimethyl phosphate, triethyl phosphate, trioctyl phosphate, and phosphate esters and combinations thereof.
  • the non-aqueous solvent is selected from ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, propylene carbonate, methyl acetate, ethyl propionate, fluorocarbon Group of ethylene carbonate and its combination.
  • the preparation method of the lithium ion battery of the present application includes the following steps:
  • Adhesive layer preparation using a multi-axis high-speed dispersion reactor, the high molecular polymer, antioxidant (412S, Tianjin Lianlong), emulsifier (N-dodecyldimethylamine) according to 99%, The weight ratio of 0.5% and 0.5% is added to the reaction kettle, the reaction temperature is controlled at 80°C to 160°C, the vacuum is drawn to -0.8 ⁇ -0.5MPa, the reaction is 4 hours, and the high molecular polymer slurry is prepared after filtration. The high molecular polymer slurry and the inorganic particles are mixed to form a bonding layer slurry, the bonding layer slurry is coated on the surface of the isolation film, and the isolation film with the bonding layer on the surface is obtained after drying.
  • Negative lithium replenishment process In a drying room, dry the negative electrode at 85°C for 24 hours, and control the moisture content to be less than 300 ppm.
  • the lithium metal foil is rolled to a thickness of micrometers, and then combined with the surface of the negative electrode active material layer and rolled to form a lithium-supplemented negative electrode.
  • Lithium-ion battery assembly then the above-mentioned positive electrode, separator (the side coated with the binding layer facing the negative electrode) and the lithium-supplemented negative electrode are arranged in order, and then wound, folded or stacked to form an electrode assembly, The electrode assembly is put into a packaging bag, and electrolyte is injected, and then vacuum packaging, standing, forming, shaping and other processes are performed to obtain a lithium ion battery.
  • the lithium ion battery is used as an example above, it should be understood by those skilled in the art after reading this application that, without departing from the spirit of this application, the specific examples of the electrochemical device of this application can include all kinds of primary batteries Or secondary battery.
  • 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.
  • Some embodiments of the present application further provide an electronic device, and the electronic device includes the electrochemical device in the embodiments of the present application.
  • electronic devices may include, but are not limited to, notebook computers, pen-input computers, mobile computers, e-book players, portable phones, portable fax machines, portable copiers, portable printers, headsets, Video recorders, LCD TVs, portable cleaners, portable CD players, mini discs, transceivers, electronic notebooks, calculators, memory cards, portable recorders, radios, backup power supplies, motors, automobiles, motorcycles, assisted bicycles, bicycles, Lighting equipment, toys, game consoles, clocks, power tools, flashlights, cameras, large household storage batteries and lithium-ion capacitors, etc.
  • a laser scanning confocal microscope (Olympus, LEXT 0LS3100) was used to obtain a three-dimensional topographic image of a part of the surface area of the lithium compound layer of a lithium ion battery, and the surface roughness and thickness of the area were obtained through image analysis. Repeated sampling of different areas of the same object to be tested to obtain the average surface roughness and thickness.
  • Lithium-ion battery volumetric energy density actual battery capacity/(lithium-ion battery length ⁇ width ⁇ thickness).
  • a high-speed rail tensile machine (AL-3000) with a peel angle of 180°, a tensile speed of 50mm/min, and a tensile displacement of 50mm to conduct the interface peel adhesion test.
  • a 600g flat thickness gauge (ELASTOCON, EV 01) was used to test the thickness of the lithium-ion battery. Place the lithium-ion battery in a thermostat at 25°C ⁇ 2°C for 2 hours, charge it to 4.45V at a constant current of 0.7C, then charge it to 0.05C at a constant voltage of 4.45V and let it stand for 15 minutes; then at 0.7C Discharge at a constant current to 3.0V. This is a cycle of charging and discharging. Record the thickness of the lithium-ion battery in the fully charged state during the first cycle; then repeat the charging and discharging cycle process for 800 times according to the above method, and record every time the lithium-ion battery is charged. The thickness in the fully charged state during the second cycle.
  • the cycle thickness expansion rate of the lithium ion battery (thickness of the lithium ion battery after 800 cycles/thickness of the lithium ion battery after formation-1) ⁇ 100%.
  • Lithium cobaltate, conductive carbon black, and polyvinylidene fluoride are dissolved in the N-methylpyrrolidone solution in a weight ratio of 97:1.4:1.6 to form a positive electrode slurry.
  • Aluminum foil is used as the positive electrode current collector, the positive electrode slurry is coated on the positive electrode current collector, and the positive electrode is obtained after drying, cold pressing, and cutting procedures.
  • the silicon-carbon composite, styrene-butadiene rubber and sodium carboxymethyl cellulose are dissolved in deionization in a weight ratio of 97.7:1.0:1.3 to form a negative electrode slurry, wherein the weight percentage of silicon is 10%.
  • Copper foil is used as the negative electrode current collector, the negative electrode slurry is coated on the negative electrode current collector, and the negative electrode is obtained after drying, cold pressing, and cutting procedures.
  • the polyvinylidene fluoride powder, dodecyl dimethyl amine (emulsifier) and water are mixed at room temperature for 1 hour at a weight ratio of 9.5:0.5:90, and left to stand for 3 hours to obtain polyvinylidene fluoride Water emulsion.
  • the polyvinylidene fluoride aqueous emulsion and dimethylacetamide are mixed in a weight ratio of 2:1 to form an adhesive layer coating.
  • Polyethylene is used as the isolation film, and the adhesive layer paint is coated on both sides of the isolation film. After drying, the adhesive layer and the isolation film are obtained.
  • the single-sided thickness of the adhesive layer is 2.0 ⁇ m and the thickness of the isolation film It is 5.0 ⁇ m.
  • the separator is placed between the positive electrode and the negative electrode for isolation, and the bonding layer is placed between the separator and the negative electrode for bonding.
  • the electrode assembly was then put into an aluminum plastic film packaging bag.
  • the above-mentioned electrolyte is injected into the dry electrode assembly, and the preparation of the lithium ion battery is completed through the steps of vacuum packaging, standing, forming, and shaping.
  • the preparation method is the same as that of Comparative Example 1, except that the bare polyethylene barrier film (without adhesive layer) used in Comparative Example 2 is used.
  • the preparation method is the same as that of Comparative Example 1, but the difference is that in Example 1, the negative electrode is further subjected to the lithium supplement process: a layer of lithium metal foil is placed on the surface of the negative electrode active material layer of the negative electrode to form a thickness of 0.04 ⁇ m The lithium compound layer, in which the coverage rate of the negative electrode active material layer by the lithium compound layer is 80%. Then, the above-mentioned positive electrode, separator, adhesive layer and negative electrode are arranged in order and assembled to obtain a lithium ion battery.
  • the preparation method is the same as that of Example 1, but the difference is that the polyvinylidene fluoride aqueous emulsion in Example 2-6 is replaced by the main chain monomer is propylene, the substituent is carboxyl, the degree of substitution is 0.65, and the molecular weight is 30,000.
  • the particle size is 1.1 ⁇ m, spherical particles of high molecular polymer (modified polypropylene polymer) formed by the high molecular polymer aqueous emulsion, and the thickness of the bonding layer has been changed, please refer to Table 1 for details.
  • the preparation method is the same as that of Example 4, except that the thickness of the lithium compound layer is changed in Examples 7-12. Please refer to Table 1 for details.
  • the preparation method is the same as that of Example 4, except that the surface roughness of the negative electrode is changed in Examples 13-18. Refer to Table 1 for details.
  • the preparation method is the same as that of Example 4, but the difference is that the coverage of the lithium compound layer is changed in Examples 19-21. Please refer to Table 1 for details.
  • the preparation method is the same as that of Example 4, but the difference is that the porosity of the negative electrode active material layer and the lithium compound layer is changed in Examples 22-26. Please refer to Table 1 for details.
  • the thickness, width, length and weight of the fresh lithium ion batteries of the above examples and comparative examples were measured. Subsequently, some fresh lithium-ion batteries were disassembled, and the surface roughness and thickness of the lithium compound layer were tested. The capacity test, adhesion test, cycle thickness expansion test and cycle performance test of the other part of the lithium-ion battery were performed, and Record the test results.
  • the lithium ion battery after the lithium replenishment process in the examples of the present application is provided with an adhesive layer with the polymer polymer of the present application, which can effectively improve the adhesive force of the adhesive layer to the lithium compound layer , And further reduce the cyclic thickness expansion rate of the lithium-ion battery while maintaining a certain volumetric energy density.
  • the polymer of the adhesive layer of Example 4 of the present application adopts The modified polypropylene polymer can effectively improve the binding force between the negative electrode and the separator after the lithium supplementation process, and the lithium ion battery after the lithium supplementation process has a higher volume energy density, so that the application can be implemented
  • the electrochemical device of Example 2-26 can be improved in cycle performance, electrochemical performance and safety performance.
  • Examples 2-6 it can be seen that the greater the thickness of the bonding layer of the lithium ion battery, the higher the bonding force to the lithium metal layer and the isolation film. However, the higher the thickness of the adhesive layer will further reduce the volumetric energy density of the lithium ion battery.
  • Examples 4 and 7-12 it can be seen that the higher the thickness of the lithium compound layer of the lithium ion battery, the higher the volumetric energy density. However, the greater the thickness of the lithium compound layer will further reduce the adhesion of the adhesive layer to the lithium compound layer.
  • the lithium ion battery within the scope of the embodiments of the present application can maintain a relatively low cycle thickness expansion rate while maintaining a relatively high volume energy density.
  • Example 4 By comparing Example 4 with 22-26, it can be seen that as shown in Table 3, the increase in the porosity of the negative electrode active material layer and the lithium compound layer can improve the cycle performance of the lithium ion battery. However, when the porosity of the negative electrode active material layer and the lithium compound layer exceeds 60%, the improvement of the cycle performance of the lithium ion battery is not obvious, and the excessively high porosity may lead to the structural stability of the lithium ion battery Decline.
  • the electrochemical device of the present application can effectively increase its energy density after being processed by the lithium supplementation process and form a lithium compound layer on the negative electrode.
  • the bonding layer is arranged between the negative electrode and the separator to increase the bonding force between the negative electrode and the separator, and reduce the cyclic thickness expansion rate and deformation of the electrochemical device under the condition of high energy density.
  • the present application can further ensure the binding force of the binding layer between the negative electrode and the separator by limiting the high molecular polymer of the binding layer, so that the safety performance and cycle performance of the electrochemical device can be significantly improved.
  • references to “some embodiments”, “partial embodiments”, “one embodiment”, “another example”, “examples”, “specific examples” or “partial examples” throughout the specification mean At least one embodiment or example in this application includes the specific feature, structure, material, or characteristic described in the embodiment or example. Therefore, descriptions appearing in various places throughout the specification, such as: “in some embodiments”, “in embodiments”, “in one embodiment”, “in another example”, “in an example “In”, “in a specific example” or “exemplified”, which are not necessarily quoting the same embodiment or example in this application.
  • the specific features, structures, materials or characteristics herein can be combined in one or more embodiments or examples in any suitable manner.

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Abstract

本申请涉及电化学装置及包含其的电子装置。电化学装置包括：正极、负极、隔离膜、粘结层及锂化合物层，其中负极包括负极活性材料层。隔离膜设置在正极与负极之间，粘结层设置在负极活性材料层与隔离膜之间，且锂化合物层设置在粘结层和负极活性材料层之间。锂化合物层包括碳酸锂及氧化锂中的至少一种。本申请通过在隔离膜与负极之间设置粘结层，以有效的增强补锂工艺处理后的负极对隔离膜的粘结能力，降低负极在充放电循环过程中由于体积膨胀所造成的变形并避免与隔离膜剥离。

Description

电化学装置和包含其的电子装置 技术领域
本申请涉及储能技术领域，尤其涉及电化学装置以及包括该电化学装置的电子装置。
背景技术
随着移动电子技术的高速发展，人们使用诸如手机、平板、笔记本电脑、无人机等的移动电子装置的频率和体验要求越来越高。因此，为电子装置提供能源的电化学装置(例如，锂离子电池)需要表现出更高的能量密度、更大的倍率、更高的安全性以及在反复充放电过程后更小的容量衰减。
电化学装置的能量密度和循环性能与正极活性材料和负极活性材料有密切的关联。有鉴于此，人们不断的对负极活性材料做进一步的研究及改进，以追求具有更高能量密度的负极活性材料。然而，具有更高能量密度的负极活性材料(例如，硅基材料)往往存在与现有电极组件结构不相匹配的问题，例如，电导性过低、受热膨胀率过高、加工性能不足等等。因此，针对采用更高能量密度的材料作为负极活性材料的电化学装置，对其电极组件结构(例如，负极、隔离膜及正极)的改进与优化是目前急需的研究课题。
发明内容
本申请提供一种电化学装置以及包括该电化学装置的电子装置以试图在至少某种程度上解决至少一个存在于相关领域中的问题。
根据本申请的一个方面，本申请提供了一种电化学装置，其包括：正极、负极、隔离膜、粘结层及锂化合物层，其中负极包括负极活性材料层，隔离膜设置在正极与负极之间，粘结层设置在负极活性材料层与隔离膜之间，且锂化合物层设置在粘结层和负极活性材料层之间，锂化合物层包括碳酸锂及氧化锂中的至少一种。
根据本申请的另一个方面，本申请提供了一种电子装置，电子装置包含上述的电化学装置。
本申请电化学装置经过补锂工艺后会进一步包含形成在负极活性材料层表面上的 锂化合物层，而通过在锂化合物层与隔离膜间设置粘结层，能够有效提高负极与隔离膜间的粘结力。在电化学装置经过多次充放电循环过程后，依然保持负极与隔离膜间的粘结力，从而提高电化学装置的循环性能及安全性能。
本申请实施例的额外层面及其他优点将部分地在后续说明中描述、显示、或是经由本申请实施例的实施而阐释。
附图说明
在下文中将简要地说明为了描述本申请实施例或现有技术所必要的附图以便于描述本申请的实施例。显而易见地，下文描述中的附图仅只是本申请中的部分实施例。对本领域技术人员而言，在不需要创造性劳动的前提下，依然可以根据这些附图中所例示的结构来获得其他实施例的附图。
图1为本申请部分实施例的电化学装置的电极组件的结构示意图。
图2为未经过补锂工艺处理的负极表面在50倍扫描是电子显微镜下的图像。
图3为未经过补锂工艺处理的负极表面在400倍扫描是电子显微镜下的图像。
图4为经过补锂工艺处理后的负极表面在50倍扫描是电子显微镜下的图像。
图5为经过补锂工艺处理后的负极表面在400倍扫描是电子显微镜下的图像。
具体实施方式
本申请的实施例将会被详细的描示在下文中。在本申请说明书全文中，将相同或相似的组件以及具有相同或相似的功能的组件通过类似附图标记来表示。在此所描述的有关附图的实施例为说明性质的、图解性质的且用于提供对本申请的基本理解。本申请的实施例不应该被解释为对本申请的限制。
在本说明书中，除非经特别指定或限定之外，相对性的用词例如：“中央的”、“纵向的”、“侧向的”、“前方的”、“后方的”、“右方的”、“左方的”、“内部的”、“外部的”、“较低的”、“较高的”、“水平的”、“垂直的”、“高于”、“低于”、“上方的”、“下方的”、“顶部的”、“底部的”以及其衍生性的用词(例如“水平地”、“向下地”、“向上地”等等)应该解释成引用在讨论中所描述或在附图中所描示的方向。这些相对性的用词仅用于描述上的方便，且并不要求将本申请以特定的方向建构或操作。
另外，有时在本文中以范围格式呈现量、比率和其它数值。应理解，此类范围格式是用于便利及简洁起见，且应灵活地理解，不仅包含明确地指定为范围限制的数值，而且包含涵盖于该范围内的所有个别数值或子范围，如同明确地指定每一数值及子范围一般。
在具体实施方式及权利要求书中，由术语“中的至少一者”、“中的至少一个”、“中的至少一种”或其他相似术语所连接的项目的列表可意味着所列项目的任何组合。例如，如果列出项目A及B，那么短语“A及B中的至少一者”意味着仅A；仅B；或A及B。在另一实例中，如果列出项目A、B及C，那么短语“A、B及C中的至少一者”意味着仅A；或仅B；仅C；A及B(排除C)；A及C(排除B)；B及C(排除A)；或A、B及C的全部。项目A可包含单个元件或多个元件。项目B可包含单个元件或多个元件。项目C可包含单个元件或多个元件。
除非另外明确指明，本文使用的下述术语具有下文指出的含义。
术语“C x”指含具有x个数量的碳原子。例如，C 1至C 10烷基是具有1至10个碳原子的烷基基团。
术语“烃基”涵盖烷基、烯基、炔基、环烷基、芳基。例如，烃基预期是具有1至20个碳原子的直链烃结构。“烃基”还预期是具有3至20个碳原子的支链或环状烃结构。当指定具有具体碳数的烃基时，预期涵盖具有该碳数的所有几何异构体。本文中烃基还可以为C 1至C 15烃基、C 1至C 10烃基、C 1至C 5烃基、C 5至C 20烃基、C 5至C 15烃基或C 5至C 10烃基。另外，烃基可以是任选地被取代的。例如，烃基可被包括氟、氯、溴和碘在内的卤素、烷基、芳基或杂芳基取代。
术语“羟基”是指-OH基团。
术语“氨基”是指由一个氮原子和两个氢原子组成的碱基，即指-NH 2基团
术语“羧基”是羧酸的官能团，即指-C(O)-OH基团。
术语“烃氧基”指L-O-基团，其中L为烷基、烯基、炔基、环烷基、芳基。例如，当L基团为烷基时，“烃氧基”可以称做“烷氧基”；当L基团为甲烷基时，“烃氧基”可以称做“甲氧基”。本文中烃氧基可为C 1至C 20烃氧基，还可以为C 1至C 15烃氧基、C 1至C 10烃氧基、C 1至C 5烃氧基、C 5至C 20烃氧基、C 5至C 15烃氧基或C 5至C 10烃氧基。
术语“酯基”是羧酸衍生物中酯的官能团，即指-C(O)-O-R基团，其中R涵盖烷基、烯基、炔基、环烷基、芳基。例如，酯基预期是具有1至200个碳原子直链、支链或环状结构。“酯基”还预期是具有C 2至C 10酯基。当指定具有具体碳数的酯基时，预期涵盖具有该碳数的所有几何异构体。本文中烃基还可以为C 1至C 15酯基、C 1至C 10酯基、C 1至C 5个酯基、C 5至C 20酯基、C 5至C 15酯基或C 5至C 10酯基。
术语“烷基”预期是具有1至20个直链饱和烃结构。“烷基”还预期是具有3至20个碳原子的支链或环状烃结构。例如，烷基可为C 1至C 20烷基、C 1至C 10烷基、C 1至C 5烷基、C 5至C 20烷基、C 5至C 15烷基或C 5至C 10烷基。当指定具有具体碳数的烷基时，预期涵盖具有该碳数的所有几何异构体；因此，例如，“丁基”意思是包括正丁基、仲丁基、异丁基、叔丁基和环丁基；“丙基”包括正丙基、异丙基和环丙基。烷基实例包括，但不限于甲基、乙基、正丙基、异丙基、环丙基、正丁基、异丁基、仲丁基、叔丁基、环丁基、正戊基、异戊基、新戊基、环戊基、甲基环戊基、乙基环戊基、正己基、异己基、环己基、正庚基、辛基、环丙基、环丁基、降冰片基等。另外，烷基可以是任选地被取代的。
术语“烯基”是指可为直链或具支链且具有至少一个且通常1个、2个或3个碳碳双键的单价不饱和烃基团。除非另有定义，否则烯基通常含有2-20个碳原子，例如可以为C 2至C 20烯基、C 6至C 20烯基、C 2至C 12烯基或C 2至C 6烯基。代表性烯基包括(例如)乙烯基、正丙烯基、异丙烯基、正-丁-2-烯基、丁-3-烯基、正-己-3-烯基等。另外，烯基可以是任选地被取代的。
术语“炔基”是指可为直链或具支链且具有至少一个且通常具有1个、2个或3个碳碳三键的单价不饱和烃基团。除非另有定义，否则炔基通常含有2个到20个碳原子，例如可以为C 2至C 20炔基、C 6至C 20炔基、C 2至C 10炔基或C 2至C 6炔基。代表性炔基包括(例如)乙炔基、丙-2-炔基(正-丙炔基)、正-丁-2-炔基、正-己-3-炔基等。另外，炔基可以是任选地被取代的。
术语“酰基”是指有机或无机含氧酸去掉羟基(-OH基团)后剩下的原子团，即指R-M(O)-基团，其中M为碳原子，R为烷基、烯基、炔基、环烷基、芳基或其他常见的取代基。例如，当R为氨基时，“酰基”为“酰胺基”。
术语“芳基”涵盖单环系统和多环系统。多环可以具有其中两个碳为两个邻接环(环是“稠合的”)共用的两个或更多个环，其中环中的至少一者是芳香族的，例如其它环可以是 环烷基、环烯基、芳基、杂环和/或杂芳基。例如，芳基可为C 6至C 50芳基、C 6至C 40芳基、C 6至C 30芳基、C 6至C 20芳基或C 6至C 10芳基。代表性芳基包括(例如)苯基、甲基苯基、丙基苯基、异丙基苯基、苯甲基和萘-1-基、萘-2-基等等。另外，芳基可以是任选地被取代的。
术语“杂环基”涵盖芳香族和非芳香族环状基团。杂芳香族环状基团还意指芳杂基。在一些实施例中，杂芳香族环状基团和杂非芳香族环状基团为包括至少一个杂原子的C 1至C 50杂环基、C 1至C 40杂环基、C 1至C 30杂环基、C 1至C 20杂环基、C 1至C 10杂环基、C 1至C 6杂环基。代表性杂环基包括(例如)吗啉基、哌啶基、吡咯烷基等，以及环醚，例如四氢呋喃、四氢吡喃等。另外，杂环基可以是任选地被取代的。
如本文所用，术语“杂芳基”涵盖可以包括一到三个杂原子的单环杂芳香族基团，例如吡咯、呋喃、噻吩、咪唑、噁唑、噻唑、三唑、吡唑、吡啶、吡嗪和嘧啶等。术语杂芳基还包括具有其中两个原子为两个邻接环(环是“稠合的”)共用的两个或更多个环的多环杂芳香族系统，其中环中的至少一者是杂芳基，其它环可以是环烷基、环烯基、芳基、杂环和/或杂芳基。例如杂芳基可为C 6至C 50杂芳基、C 6至C 40杂芳基、C 6至C 30杂芳基、C 6至C 20杂芳基或C 6至C 10杂芳基。另外，杂芳基可以是任选地被取代的。
如本文所用，术语“卤素”可为F、Cl、Br或I。
如本文所用，术语“氰基”涵盖含-CN的有机官能团。
在本文中，术语“覆盖率”表示涂覆层对被涂覆物表面的覆盖程度，例如，覆盖率为100％代表涂覆层完全覆盖被涂覆物表面全部的面积。覆盖率为40％代表涂覆层仅覆盖被涂覆物表面40％的面积，被涂覆物表面另外60％的面积呈暴露状态。
在本文中，术语“取代度”表示高分子聚合物的主链上单个单体中被取代基的基团取代的平均个数。例如，取代度为0.5代表高分子聚合物的单体上平均存在0.5个取代基的功能基团。
在本文中，术语“颗粒度”代表样品通过激光粒度测试所得到的表征颗粒特性的Dv50，其中Dv50表示材料在体积基准的粒度分布中，从小粒径侧起、达到体积累积50％的粒径。
在电化学装置的领域中，为了追求更高的能量密度，已尝试将传统负极活性材料中的石墨替换为具有更高能量密度的负极活性材料，但是在应用此类更高能量密度负极活性材料时，由于不同的材料特性还需要对其做进一步的工艺处理。举例来说，硅基材料 由于理论克容量高达4200m Ah/g，是未来更高体积能量密度的电化学装置(例如，锂离子电池)开发的主流负极活性材料。但是，硅基材料的首次库伦效率低，限制了锂离子电池的体积能量密度进一步提高。因此，需要通过补锂工艺提高硅基材料的首次库伦效率，才能够有效提高锂离子电池的体积能量密度。补锂工艺是对负极活性材料中补充锂以提高能量密度的方法，例如，较为成熟的补锂工艺是在负极活性材料层的表面复合、碾压一定量的锂金属。当锂离子电池在注入电解液后，这些金属锂能够迅速与负极活性材料反应，嵌入负极活性材料中，从而提高负极活性材料的首次库伦效率。
此类更高能量密度的负极活性材料在脱嵌锂过程中存在巨大的体积变化效应(例如，大于300％)，负极严重膨胀会造成负极与隔离膜的界面变形甚至分离，进而造成锂离子电池的循环性能降低。此外，经过补锂工艺处理后的负极由于制备工艺上的限制，锂金属会跟空气中的水分及氧气产生副反应以在负极活性材料层的表面上形成锂化合物层。锂化合物层与隔离膜表面的常规涂层的粘结力很弱(例如，小于1N/m)，会造成负极与隔离膜之间的弱粘结或无粘结。因此，若隔离膜涂层与硅负极表面表现出弱粘结或无粘结，在充放电循环过程中过大的体积膨胀不仅会造成电极组件变形降低循环性能，还容易导致锂离子电池的结构被破坏，严重影响锂离子电池的安全性能。
本申请从改善负极膨胀的角度出发，研究增加隔离膜对负极的界面粘结力来抑制负极在充电中的膨胀。本申请通过在负极与隔离膜之间设置粘结层，并通过控制补锂工艺所产生的锂化合物层，以增加粘结层对锂化合物层的粘结力，从而有效提升隔离膜对负极的粘结力，并改善充放电循环过程中负极的体积膨胀率而有利于减小电极组件的变形程度。本申请粘结层可用于采用具有更高能量密度的负极活性材料的电化学装置中，以改善电化学装置的循环稳定性及安全性。同时由于膨胀及变形被抑制，负极与隔离膜之间的界面稳定性更好，从而使得循环容量保持率提升。
根据本申请的一个方面，本申请的实施例提供一种设置在负极与隔离膜之间的粘结层，粘结层能够对补锂后的负极中的锂化合物层产生足够的粘结力。因此，电化学装置能够通过添加设置于锂化合物层与隔离膜之间的粘结层，以确保其循环性能跟安全性能。
图1为本申请部分实施例的电化学装置的电极组件的结构示意图。
如图1所示，本申请提供了一种电化学装置包括：正极40、负极30、隔离膜10及粘结层20，其中负极30包括负极活性材料层302。隔离膜10设置在正极40与负极30之间，粘结层20设置在负极活性材料层302与隔离膜10之间。电化学装置的负极经过 补锂工艺处理，负极活性材料层302上形成锂化合物层303，且锂化合物层303设置在粘结层20和负极活性材料层302之间。在一些实施例中，锂化合物层303包括碳酸锂及氧化锂中的至少一种
在一些实施例中，锂化合物层303与负极活性材料层302相接触，且锂化合物层303与粘结层20相接触。
在本文中，用语“层”被用于描述电化学装置中各个功能材料的层状结构，例如，粘结层、负极活性材料层、正极活性材料层、锂化合物层等。在具体实施例中，该层状结构能够为，但不限于，连续性的、非连续性的、具有通孔的或由多个颗粒组成的层状结构。举例而言，连续性的层状结构为完整的层，其层中不存在间隙；非连续性的层状结构中包含多个散布部分或分段部分的层，其层中各个部分彼此间存在断面或间隙。
图2及图3为未经过补锂工艺处理的负极表面的50及400倍扫描式电子显微镜图像。图4及图5为经过补锂工艺处理后的负极表面的50及400倍扫描式电子显微镜图像。
如图2至图5所示，锂化合物层呈现凹凸起伏的竖纹形貌，并且与未补锂的负极对比。由于锂化合物层在负极活性材料层上的覆盖分布，使得暴露的负极活性材料层部分及覆盖锂化合物层部分所构成的表面的垂直偏差值加大，从而导致负极面向隔离膜方向的表面的粗糙度增加。此外，由于锂化合物层具有较高的孔隙率，使得经补锂工艺处理后的负极的孔隙率增加，从而进一步提高负极的表面粗糙度。
应理解，锂化合物层在负极活性材料层上的分布、形状及覆盖率可通过补锂工艺处理时锂金属的设置来控制，举例来说，如图4及图5所示，补锂工艺处理时采用固定长宽的锂金属条并将其固定间隔距离设置，能够使所形成的锂化合物层在负极活性材料层上呈条纹状分布。在一些实施例中，锂化合物层包含呈平面状、呈条纹状、呈斑点状、呈不规则状。在一些实施例中，锂化合物层呈条纹状。
在一些实施例中，锂化合物层对负极活性材料层的覆盖率大于或等于30％。在另一些实施例中，锂化合物层对负极活性材料层的覆盖率大致为，例如，40％、50％、60％、70％、80％、90％或100％。
在一些实施例中，负极活性材料层及锂化合物层的孔隙率为10％至60％。在另一些实施例中，负极活性材料层及锂化合物层的孔隙率大致为，例如，10％、15％、20％、30％、40％、50％、60％或这些数值中任意两者组成的范围。
在一些实施例中，负极的表面粗糙度为0.5μm至4.0μm。在另一些实施例中，负极的表面粗糙度大致为，例如，0.5μm、1.0μm、1.5μm、2.0μm、2.5μm、3.0μm、3.5μm、4.0μm或这些数值中任意两者组成的范围。
通过调整负极活性材料层及锂化合物层的孔隙率及负极的表面粗糙度，能够进一步控制粘结层与负极的接触面积，使粘结层中的高分子聚合物的颗粒能够嵌入到负极的表面，从而形成“铆合”的状态，提升相互之间的作用力。
在一些实施例中，锂化合物层的厚度为0.01μm至3μm，
在一些实施例中，上述高分子聚合物为改性的聚丙烯类结构聚合物，高分子聚合物包括主链及取代基。
在一些实施例中，高分子聚合物的主链由以下至少一种单体形成：甲基丙烯、甲基丙烯酸、甲基丙烯酸甲酯、酰亚胺、乙烯醇及乙二醇。在一些实施例中，高分子聚合物的主链由以下至少一种单体形成：甲基丙烯、酰亚胺、乙烯醇及乙二醇。
在一些实施例中，高分子聚合物的取代基包含羧基、羟基、氨基、酰胺基、甲氧基、氰基或酯基中的至少一种。在一些实施例中，高分子聚合物的取代基包含羧基、羟基或氨基中的至少一种。
在一些实施例中，高分子聚合物中取代基的取代度为0.2至0.8。
本申请实施例一方面通过选择具有高电负性取代基的高分子聚合物，电负性越大，粘结层中的高分子聚合物与被粘结界面物质的分子间作用力越强，从而提升粘结层的粘结力。在本申请的一些实施例中，高分子聚合物的介电常数为5F/m至50F/m以实现对粘结界面物质的强分子间作用力。
本申请实施例另一方面通过选择特定主链结构及特定取代基所组成的高分子聚合物，使粘结层具有对电解液较好的浸润能力，从而实现强粘结。碳酸乙烯酯由于其电化学稳定性好，与常见锂电池添加剂如氟代碳酸乙烯酯(FEC)均具有很好的溶解性，是电解液最常见的溶剂体系。因此，粘结层中的高分子聚合物对碳酸乙烯酯的接触角能够表示粘结层对电解液的浸润性。在本申请的一些实施例中，粘结层中的高分子聚合物对碳酸乙烯酯的接触角为0°至90°。在本申请的一些实施例中，高分子聚合物对碳酸乙烯酯的接触角为为10°至50°以实现对电解液的高浸润能力。
本申请实施例另一方面通过选择具有特定的取代基的高分子聚合物，能够有效提升 高分子聚合物在碱液中的结构稳定性，使其粘结层在多次充放电循环过程后依然保持对负极及隔离膜的粘结力，从而提高其电化学装置的循环寿命。粘结层中的高分子聚合物能够通过经耐碱性测试的失重率来表示其结构稳定性，失重率越高代表粘结层中的高分子聚合物的取代基剥离的状况越严重，即代表粘结层的粘结力及结构稳定性越低。在一些实施例中，高分子聚合物在1mol/L的氢氧化钠溶液中浸泡0.5小时后的失重率小于20％。在另一些实施例中，高分子聚合物在1mol/L的氢氧化钠溶液中浸泡0.5小时后的失重率小于或等于10％。
在一些实施例中，粘结层对负极的锂化合物层或隔离膜的粘结力可以达到大于或等于10N/m。在另一些实施例中，粘结层对负极的锂化合物层或隔离膜的粘结力为15N/m。在另一些实施例中，粘结层对负极的锂化合物层或隔离膜的粘结力为20N/m。
在一些实施例中，高分子聚合物为颗粒，且高分子聚合物的颗粒度为0.01μm至20μm。在另一些实施例中，高分子聚合物的颗粒度大致为，例如，0.01μm、0.05μm、0.1μm、0.5μm、1.0μm、5.0μm、10.0μm、20.0μm或这些数值中任意两者组成的范围。
在一些实施例中，高分子聚合物的数均分子量为1kDa至1000kDa。在另一些实施例中，高分子聚合物的数均分子量大致为，例如，1kDa、10kDa、100kDa、200kDa、400kDa、600kDa、800kDa、1000kDa或这些数值中任意两者组成的范围。
在一些实施例中，粘结层进一步包含无机颗粒，其中无机颗粒包含SrTiO 3、SnO 2、CeO 2、MgO、NiO、CaO、ZnO、ZrO 2、Y 2O 3、Al 2O 3、TiO 2、Al(OH) 3、Mg(OH) 2、SiC及勃姆石中的至少一种。通过在粘结层中添加无机颗粒，可以提高粘结层的机械强度。当在充放电循环时遇到电极组件温度过高或失控的状况时，具有高机械强度的粘结层可以抑制隔离膜因为热收缩所导致的安全事故(例如，短路、破裂等等)。
在一些实施例中，以粘结层的总重量计，无机颗粒的重量百分含量小于或等于50wt％。在另一些实施例中，以粘结层的总重量计，无机颗粒的重量百分含量小于或等于30wt％。
在一些实施例中，粘结层的厚度为0.1μm至10μm。在另一些实施例中，粘结层的厚度大致为，例如0.1μm、0.5μm、1μm、1.5μm、2μm、3μm、4μm、5μm、10μm或这些数值中任意两者组成的范围。
在一些实施例中，粘结层的孔隙率为20％至80％。在另一些实施例中，粘结层的孔隙率大致为，例如20％、30％、40％、50％、60％、70％、80％或这些数值中任意两 者组成的范围。
本申请实施例中粘结层的厚度及孔隙率范围，可以确保被粘结界面的接触面积以确保一定的粘结力，且不会导致粘结层将隔离膜或负极的离子通道塞住，进而维持一定的离子导电率。
在一些实施例中，电化学装置为锂离子电池。
参考图1，在一些实施例中，正极40包含正极集流体401，且负极30包含负极集流体301。正极集流体401可以为铝箔或镍箔，负极集流体301可为铜箔或镍箔，然而，可以采用本领域常用的其他正极集流体及负极集流体，而不受其限制。
在一些实施例中，负极30包含负极活性材料层302。负极活性材料层302包括负极活性材料，负极活性材料包含人造石墨、天然石墨、中间相碳微球、硬碳、软碳、钛酸锂、单晶硅、无定形硅、硅氧复合物和硅碳复合物中的至少一种。
在另一些实施例中，负极活性材料层还包括具有高能量密度的负极活性材料，其实例包括，但不限于，硅、锡、锗、锑、铋、铝的单质、合金或其化合物中的一种或多种。在另一些实施例中，负极活性材料包含：硅、硅氧复合物或硅碳复合物中的至少一种。
在一些实施例中，正极40包含正极活性材料层402。正极活性材料层402包括能够吸收和释放锂(Li)的正极活性材料(下文中，有时称为“能够吸收/释放锂Li的正极活性材料”)。能够吸收/释放锂(Li)的正极活性材料的实例可以包括钴酸锂、镍钴锰酸锂、镍钴铝酸锂、锰酸锂、磷酸锰铁锂、磷酸钒锂、磷酸钒氧锂、磷酸铁锂、钛酸锂和富锂锰基材料中的一种或多种。
在上述正极活性材料中，钴酸锂的化学式可以为Li yCo aM1 bO 2-c，其中，M1元素表示选自镍(Ni)、锰(Mn)、镁(Mg)、铝(Al)、硼(B)、钛(Ti)、钒(V)、铬(Cr)、铁(Fe)、铜(Cu)、锌(Zn)、钼(Mo)、锡(Sn)、钙(Ca)、锶(Sr)、钨(W)、钇(Y)、镧(La)、锆(Zr)和硅(Si)中的至少一种，y、a、b和c值分别在以下范围内：0.8≤y≤1.2、0.8≤a≤1、0≤b≤0.2、-0.1≤c≤0.2；
在上述正极活性材料中，镍钴锰酸锂或镍钴铝酸锂的化学式可以为Li zNi dM2 eO 2-f，其中，M2元素表示选自钴(Co)、锰(Mn)、镁(Mg)、铝(Al)、硼(B)、钛(Ti)、钒(V)、铬(Cr)、铁(Fe)、铜(Cu)、锌(Zn)、钼(Mo)、锡(Sn)、钙(Ca)、锶(Sr)、钨(W)、钇(Y)、镧(La)、锆(Zr)和硅(Si)中的至少一种，z、d、e和f值分别在以下范围内：0.8≤z≤1.2、0.3＜d＜0.98、0.02＜e＜0.7、-0.1≤f≤0.2；
在上述正极活性材料中，锰酸锂的化学式为Li uMn 2-gM 3gO 4-h，其中M3元素表示选自钴(Co)、镍(Ni)、镁(Mg)、铝(Al)、硼(B)、钛(Ti)、钒(V)、铬(Cr)、铁(Fe)、铜(Cu)、锌(Zn)、钼(Mo)、锡(Sn)、钙(Ca)、锶(Sr)和钨(W)中的至少一种，z、g和h值分别在以下范围内：0.8≤u≤1.2、0≤g＜1.0和-0.2≤h≤0.2。
在一些实施例中，正极活性材料层与负极活性材料层能够各自独立地进一步包含粘结剂及导电剂中的至少一种。
在一些实施例中，粘结剂包含聚偏氟乙烯、偏氟乙烯-六氟丙烯的共聚物、聚酰胺、聚丙烯腈、聚丙烯酸酯、聚丙烯酸、聚丙烯酸盐、羧甲基纤维素钠、聚乙烯呲咯烷酮、聚乙烯醚、聚甲基丙烯酸甲酯、聚四氟乙烯、聚六氟丙烯或丁苯橡胶中的至少一种。在一些实施例中，导电剂包含碳纳米管、碳纤维、导电炭黑、乙炔黑、石墨烯或科琴黑中的至少一种。应理解，本领域技术人员可以根据实际需要选择本领域常规的粘结剂及导电剂，而不受其限制。
在一些实施例中，锂化合物层中不包括粘结剂及导电剂。
在一些实施例中，隔离膜包括，但不限于，选自聚乙烯、聚丙烯、聚对苯二甲酸乙二醇酯、聚酰亚胺和芳纶中的至少一种。举例来说，聚乙烯包括选自高密度聚乙烯、低密度聚乙烯和超高分子量聚乙烯中的至少一种组分。尤其是聚乙烯和聚丙烯，它们对防止短路具有良好的作用，并可以通过关断效应改善电池的稳定性。在一些实施例中，隔离膜为聚丙烯，聚丙烯与上述实施例中的高分子聚合物具有很好的亲和性，有利于提高粘结层与隔离膜的粘结力。
本申请的锂离子电池还包括电解质，电解质可以是凝胶电解质、固态电解质和电解液中的一种或多种，电解液包括锂盐和非水溶剂。
在一些实施例中，锂盐选自LiPF 6、LiBF 4、LiAsF 6、LiClO 4、LiB(C 6H 5) 4、LiCH 3SO 3、LiCF 3SO 3、LiN(SO 2CF 3) 2、LiC(SO 2CF 3) 3、LiSiF 6、LiBOB和二氟硼酸锂中的一种或多种。举例来说，锂盐选用LiPF 6，因为它可以给出高的离子导电率并改善循环特性。
非水溶剂可为碳酸酯化合物、羧酸酯化合物、醚化合物、其它有机溶剂或它们的组合。
上述碳酸酯化合物可为链状碳酸酯化合物、环状碳酸酯化合物、氟代碳酸酯化合物或其组合。
上述其它有机溶剂的实例为二甲亚砜、1，2-二氧戊环、环丁砜、甲基环丁砜、1，3-二甲基-2-咪唑烷酮、N-甲基-2-吡咯烷酮、甲酰胺、二甲基甲酰胺、乙腈、磷酸三甲酯、磷酸三乙酯、磷酸三辛酯、和磷酸酯及其组合。
在一些实施例中，非水溶剂选自由碳酸乙烯酯、碳酸丙烯酯、碳酸二乙酯、碳酸二甲酯、碳酸甲乙酯、碳酸亚丙酯、醋酸甲酯、丙酸乙酯、氟代碳酸乙烯酯及其组合所组成的群组。
应理解，本申请实施例中的正极、负极、隔离膜以及电解质的制备方法，在不违背本申请的精神下，可以根据具体需要选择本领域任何合适的常规方法，而不受其限制。
在一些实施例中，本申请锂离子电池的制备方法包括以下步骤：
(1)粘结层制备：采用多轴高速分散反应釜，将高分子聚合物、抗氧剂(412S，天津利安隆)、乳化剂(N-十二烷基二甲胺)按照99％、0.5％及0.5％的重量比加入反应釜中，控制反应温度为80℃至160℃，抽真空至-0.8～-0.5MPa，反应4小时，经过过滤，制得高分子聚合物浆料。将高分子聚合物浆料与无机颗粒混合以形成粘结层浆料，将粘结层浆料涂覆至隔离膜的表面，经过烘干处理得到表面带有粘结层的隔离膜。
(2)负极补锂工艺处理：在干燥房中，将负极在85℃烘干处理24小时，控制水份含量＜300ppm。锂金属箔经过碾压至微米级厚度，然后与上述负极活性材料层的表面进行复合、碾压处理以形成补锂后的负极。
(3)锂离子电池的组装；随后将上述正极、隔离膜(涂覆有粘结层的一面面对负极)及补锂后的负极按顺序排列后，卷绕、折叠或堆叠成电极组件，将电极组件装入包装袋中，并注入电解液，随后进行真空封装、静置、化成、整形等工序，以获得锂离子电池。
虽然上面以锂离子电池进行了举例说明，但是本领域技术人员在阅读本申请之后应可理解，在不违背本申请的精神下，本申请的电化学装置的具体实例能够包括所有种类的一次电池或二次电池。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。
本申请的一些实施例进一步提供了一种电子装置，电子装置包含本申请实施例中的电化学装置。
本申请实施例的电子装置没有特别限定，其可以是用于现有技术中已知的任何电子 装置。在一些实施例中，电子装置可以包括，但不限于，笔记本电脑、笔输入型计算机、移动电脑、电子书播放器、便携式电话、便携式传真机、便携式复印机、便携式打印机、头戴式立体声耳机、录像机、液晶电视、手提式清洁器、便携CD机、迷你光盘、收发机、电子记事本、计算器、存储卡、便携式录音机、收音机、备用电源、电机、汽车、摩托车、助力自行车、自行车、照明器具、玩具、游戏机、钟表、电动工具、闪光灯、照相机、家庭用大型蓄电池和锂离子电容器等。
具体实施例
下面列举了一些具体实施例及对比例并分别对其负极进行表面粗糙度及厚度测试，对其负极与隔离膜进行粘结力测试并对其电化学装置(锂离子电池)进行容量测试及循环厚度膨胀率测试以更好地对本申请的技术方案进行说明。
一、测试方法
1.1表面粗糙度及厚度测试：
采用激光扫描共聚焦显微镜(Olympus，LEXT 0LS3100)取得锂离子电池的锂化合物层的部分表面区域的三维形貌图像，并通过图像分析以取得该区域的表面粗糙度及厚度。重复对相同待测物的不同区域取样以获得表面粗糙度及厚度的平均值。
1.2容量测试：
将化成后的锂离子电池在25±3℃环境中静置30分钟，以0.5C倍率恒定电流充电至电压至4.45V，随后以4.45V恒定电压充电，直到电流至0.05C时停止充电，并将待测的锂离子电池放置30分钟。之后再以0.2C倍率将锂离子电池放电至3.0V，并将待测的锂离子电池放置30分钟。最后取放电容量作为锂离子电池的实际电池容量。锂离子电池体积能量密度＝实际电池容量/(锂离子电池的长度×宽度×厚度)。
1.3粘结力测试：
在干燥房环境将化成后的锂离子电池以及经过400次循环后的锂离子电池从正极与隔离膜界面处拆解，静置5分钟待电解液挥发干，裁剪150mm×20mm大小的负极、粘结层与隔离膜的层叠结构，用高铁拉力机(AL-3000)，并设置剥离角度180°，拉伸速度为50mm/min，拉伸位移为50mm以进行界面剥离粘结力测试。每组取4块锂离子电池，计算锂离子电池的负极与隔离膜之间的粘结力平均值。
1.4循环厚度膨胀率测试：
采用600g平板测厚仪(ELASTOCON，EV 01)测试锂离子电池的厚度。将锂离子电池置于25℃±2℃的恒温箱中静置2小时，以0.7C恒流充电至4.45V，然后以4.45V恒压充电至0.05C并静置15分钟；再以0.7C恒流放电至3.0V，此为一次充放电循环过程，记录锂离子电池在首次循环时满充状态下的厚度；而后按上述方法重复进行800次的充放电循环过程，并记录锂离子电池每次循环时在满充状态下的厚度。
每组取4块锂离子电池测试，计算锂离子电池的循环厚度膨胀率的平均值。锂离子电池的循环厚度膨胀率＝(800次循环后锂离子电池的厚度/化成后的锂离子电池的厚度-1)×100％。
1.5循环性能测试：
在25℃±2℃的恒温箱中，将锂离子电池以0.5C恒流充电至4.45V，然后以4.45V恒压充电至0.05C并静置15分钟：再以0.5C恒流放电至3.0V，静置5分钟，此为一次充放电循环过程。以首次放电的容量为100％，反复进行充放电循环过程，至放电容量衰减至80％时，停止测试，记录循环圈数，作为评价锂离子电池循环性能的指标。
二、制备方法
2.1正极的制备
将钴酸锂、导电炭黑、聚偏二氟乙烯按重量比97∶1.4∶1.6的比例溶于N-甲基吡咯烷酮溶液中，形成正极浆料。采用铝箔作为正极集流体，将正极浆料涂覆于正极集流体上，经过干燥、冷压、裁切程序后得到正极。
2.2负极的制备
将硅碳复合物、丁苯橡胶及羧甲基纤维素钠按重量比97.7∶1.0∶1.3的比例溶于去离子中，形成负极浆料，其中硅的重量百分比为10％。采用铜箔作为负极集流体，将负极浆料涂覆于负极集流体上，经过干燥、冷压、裁切程序后得到负极。
2.3电解液的制备
在含水量小于10ppm的环境下，将六氟磷酸锂与非水有机溶剂(碳酸乙烯酯(EC)∶碳酸二乙酯(DEC)∶碳酸亚丙酯(PC)∶丙酸丙酯(PP)∶碳酸亚乙烯酯(VC)＝20；30；20；28；2，重量比)按重量比8∶92配制以形成电解液。
对比例1
将聚偏二氟乙烯粉末、十二烷基二甲胺(乳化剂)与水按照重量比9.5∶0.5∶90的 比例在常温下混合1小时，并静置3小时以获得聚偏二氟乙烯水乳液。将聚偏二氟乙烯水乳液与二甲基乙酰胺按重量比2∶1的比例混合以形成粘结层涂料。采用聚乙烯作为隔离膜，将粘结层涂料涂覆在隔离膜的两侧表面，待烘干后得到粘结层与隔离膜，其中粘结层的单面厚度为2.0μm且隔离膜的厚度为5.0μm。
随后将上述正极、隔离膜、粘结层及上述负极按顺序排列后，使隔离膜处于正极与负极中间起到隔离的作用，并且使粘结层处于隔离膜与负极中间起到粘结的作用，卷绕成电极组件。随后将该电极组件装入铝塑膜包装袋中。随后将上述电解液注入干电极组件中，经过真空封装、静置、化成、整形等工序，即完成锂离子电池的制备。
对比例2
与对比例1制备方式相同，不同的是在对比例2中使用的聚乙烯的裸隔离膜(无粘结层)。
实施例1
与对比例1的制备方式相同，不同的地方是实施例1中进一步对负极进行补锂工艺处理：在负极的负极活性材料层的表面上设置一层锂金属箔，以形成厚度为0.04μm的锂化合物层，其中锂化合物层对负极活性材料层的覆盖率为80％。随后再将上述正极、隔离膜、粘结层及负极按顺序排列，并组装获得锂离子电池。
实施例2-6
与实施例1的制备方式相同，不同的地方是实施例2-6中聚偏二氟乙烯水乳液替换为由主链的单体为丙烯，取代基为羧基，取代度为0.65，分子量为30000，颗粒度为1.1μm，球状颗粒的高分子聚合物(改性聚丙烯聚合物)所形成的高分子聚合物水乳液，并对粘结层的厚度做了改变，具体请参考表1。
实施例7-12
与实施例4的制备方式相同，不同的地方是实施例7-12中对锂化合物层的厚度做了改变，具体请参考表1。
实施例13-18
与实施例4的制备方式相同，不同的地方是实施例13-18中对负极的表面粗糙度做了改变，具体参考表1。
实施例19-21
与实施例4的制备方式相同，不同的地方是实施例19-21中对锂化合物层的覆盖率做了改变，具体请参考表1。
实施例22-26
与实施例4的制备方式相同，不同的地方是实施例22-26中对负极活性材料层及锂化合物层的孔隙率做了改变，具体请参考表1。
对以上实施例及对比例的新鲜锂离子电池测量其厚度、宽度、长度及重量。随后拆解部分新鲜的锂离子电池，对其锂化合物层进行表面粗糙度及厚度测试，并对另一部分锂离子电池进行容量测试、粘结力测试、循环厚度膨胀率测试以及循环性能测试，并记录其测试结果。
实施例1-26及对比例1与2的负极及其功能层的统计数值如下表1所示。
表1
Figure PCTCN2020077769-appb-000001
Figure PCTCN2020077769-appb-000002
实施例1-21及对比例1与2的锂离子电池通过粘结力测试、容量测试以及循环厚度膨胀率测试的结果如下表2所示。
表2
Figure PCTCN2020077769-appb-000003
实施例22-26及对比例1与2的锂离子电池通过粘结力测试、容量测试、循环厚度膨胀率测试以及循环性能测试的结果如下表3所示。
表3
Figure PCTCN2020077769-appb-000004
Figure PCTCN2020077769-appb-000005
如表1-3所示，本申请实施例中经补锂工艺后的锂离子电池通过设置具有本申请高分子聚合物的粘结层，能够有效提高粘结层对锂化合物层的粘结力，进而在维持一定体积能量密度的状态下降低锂离子电池的循环厚度膨胀率。通过比较实施例1、4与对比例1与2可知，相较于无粘结层或使用常规的聚偏二氟乙烯作为粘结层，本申请实施例4粘结层的高分子聚合物采用改性聚丙烯聚合物能够有效的提高经补锂处理后的负极与隔离膜之间的粘结力，而且通过补锂工艺处理后的锂离子电池具有更高的体积能量密度，使本申请实施例2-26的电化学装置在循环性能、电化学性能及安全性能上都能够有所提升。
通过比较实施例2-6可知，锂离子电池的粘结层的厚度越大，其对锂金属层及隔离膜的粘结力就越高。然而，粘结层的厚度越高会进一步降低锂离子电池的体积能量密度。通过比较实施例4与7-12可知，锂离子电池的锂化合物层的厚度越高，其体积能量密度就越高。然而，锂化合物层的厚度越大会进一步降低粘结层对锂化合物层的粘结力。在本申请实施例范围内的锂离子电池，能够在维持较高的体积能量密度的状态下同时保持相对低的循环厚度膨胀率。
通过比较实施例4与13-18可知，锂离子电池的负极的表面粗糙度越高，其粘结层的粘结力也会提升，并能够降低其循环厚度膨胀率。然而，如表2所示，当负极的表面粗糙度超过3μm后，其锂离子电池的循环厚度膨胀率的下降并不明显。此外，过高的粗糙度能够进一步影响负极与隔离膜之间的结合，增加影响锂离子电池的安全性能的风险。
通过比较实施例4与19-21可知，锂化合物层对负极活性材料层的覆盖率越高，其锂离子电池的粘结层的粘结力就越高。
通过比较实施例4与22-26可知，如表3所示，负极活性材料层及锂化合物层的孔隙率的增加能够提升其锂离子电池的循环性能。然而，当负极活性材料层及锂化合物层的孔隙率超过60％后，其对锂离子电池的循循环性能的提升并不明显，且过高的孔隙率可能会导致锂离子电池的结构稳定性的下降。
通过上述实施例的比较，可以清楚的理解本申请的电化学装置，经过补锂工艺处理后能够有效提升其能量密度并会在负极上形成锂化合物层，而通过在锂化合物层与隔离 膜之间设置粘结层，可以使得负极与隔离膜之间的粘结力提升，在高能量密度的状况下降低电化学装置的循环厚度膨胀率及变形。同时，本申请通过限定粘结层的高分子聚合物，可以进一步确保负极与隔离膜之间的粘结层的粘结力，进而使得电化学装置的安全性能及循环性能能够有显著的提升。
整个说明书中对“一些实施例”、“部分实施例”、“一个实施例”、“另一举例”、“举例”、“具体举例”或“部分举例”的引用，其所代表的意思是在本申请中的至少一个实施例或举例包含了该实施例或举例中所描述的特定特征、结构、材料或特性。因此，在整个说明书中的各处所出现的描述，例如：“在一些实施例中”、“在实施例中”、“在一个实施例中”、“在另一个举例中”，“在一个举例中”、“在特定举例中”或“举例“，其不必然是引用本申请中的相同的实施例或示例。此外，本文中的特定特征、结构、材料或特性可以以任何合适的方式在一个或多个实施例或举例中结合。
尽管已经演示和描述了说明性实施例，本领域技术人员应该理解上述实施例不能被解释为对本申请的限制，并且可以在不脱离本申请的精神、原理及范围的情况下对实施例进行改变，替代和修改。

Claims (11)

  1. 一种电化学装置，其包括：
    正极；
    负极，其包括负极活性材料层；
    隔离膜，所述隔离膜设置在所述正极与所述负极之间；
    粘结层，所述粘结层设置在所述负极活性材料层与所述隔离膜之间；以及
    锂化合物层，所述锂化合物层设置在所述粘结层和所述负极活性材料层之间，所述锂化合物层包括碳酸锂及氧化锂中的至少一种。
  2. 根据权利要求1所述的电化学装置，其中，所述粘结层包括高分子聚合物，且所述高分子聚合物包括主链及取代基，所述主链由以下至少一种单体形成：甲基丙烯、甲基丙烯酸、甲基丙烯酸甲酯、酰亚胺、乙烯醇及乙二醇；所述取代基包含羧基、羟基、氨基、酰胺基、甲氧基、氰基或酯基中的至少一种。
  3. 根据权利要求2所述的电化学装置，其中，所述高分子聚合物为颗粒，且所述高分子聚合物的颗粒度为0.01μm至20μm。
  4. 根据权利要求1所述的电化学装置，其中，所述锂化合物层的厚度为0.01μm至3μm，所述粘结层的厚度为0.1μm至10μm，所述负极的表面粗糙度为0.5μm至4.0μm。
  5. 根据权利要求1所述的电化学装置，其中，所述锂化合物层与所述负极活性材料层相接触，且所述锂化合物层与所述粘结层相接触。
  6. 根据权利要求1所述的电化学装置，其中，所述锂化合物层对负极活性材料层的覆盖率大于30％。
  7. 根据权利要求1-6中任一项所述的电化学装置，其中，所述负极活性材料层及所述锂化合物层的孔隙率为10％至60％。
  8. 根据权利要求1所述的电化学装置，其中，所述负极活性材料层包括负极活性材料，所述负极活性材料包含以下群组中的至少一种：人造石墨、天然石墨、中间相碳微球、硬碳、软碳、钛酸锂、单晶硅、无定形硅、硅氧复合物和硅碳复合物。
  9. 根据权利要求8所述的电化学装置，其中，所述负极活性材料层进一步包括粘结剂及导电剂中的至少一种，其中所述粘结剂包含聚偏氟乙烯、偏氟乙烯-六氟丙烯的共聚物、聚酰胺、聚丙烯腈、聚丙烯酸酯、聚丙烯酸、聚丙烯酸盐、羧甲基纤维素钠、聚乙烯呲咯烷酮、聚乙烯醚、聚甲基丙烯酸甲酯、聚四氟乙烯、聚六氟丙烯或丁苯橡胶中的至少一种，且所述导电剂包含碳纳米管、碳纤维、导电炭黑、乙炔黑、石墨烯或科琴黑中的至少一种。
  10. 根据权利要求9所述的电化学装置，其中，所述锂化合物层不包含所述粘结剂及所述导电剂。
  11. 一种电子装置，其包含根据权利要求1至10中任一项所述的电化学装置。
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