CN115020915B - Electrochemical separator, preparation method and electrochemical device - Google Patents

Electrochemical separator, preparation method and electrochemical device Download PDF

Info

Publication number
CN115020915B
CN115020915B CN202210597292.6A CN202210597292A CN115020915B CN 115020915 B CN115020915 B CN 115020915B CN 202210597292 A CN202210597292 A CN 202210597292A CN 115020915 B CN115020915 B CN 115020915B
Authority
CN
China
Prior art keywords
coating layer
electrochemical
gamma
coating
spherical
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202210597292.6A
Other languages
Chinese (zh)
Other versions
CN115020915A (en
Inventor
房坦
陈红辉
陈立新
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinoma Lithium Film Changde Co ltd
Original Assignee
Sinoma Lithium Film Changde Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinoma Lithium Film Changde Co ltd filed Critical Sinoma Lithium Film Changde Co ltd
Priority to CN202210597292.6A priority Critical patent/CN115020915B/en
Publication of CN115020915A publication Critical patent/CN115020915A/en
Application granted granted Critical
Publication of CN115020915B publication Critical patent/CN115020915B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • 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
    • 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
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • 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
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • 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
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • 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

Abstract

The application provides an electrochemical diaphragm, a preparation method and an electrochemical device, wherein the electrochemical diaphragm comprises: a base film; a coating layer arranged on at least one side of the thickness direction of the basal membrane, the coating layer comprising a first coating layer and a second coating layer which are arranged in a laminated manner, the first coating layer comprising spherical alpha-Al 2 O 3 And spherical gamma-Al 2 O 3 The second coating layer comprises spherical alpha-Al 2 O 3 Linear gamma-Al 2 O 3 And gamma-AlOOH. The electrochemical membrane provided by the application adopts the composite coating, so that the wettability of the electrochemical membrane to electrolyte is improved, the liquid absorption rate is high, conductive ions can be conveniently penetrated, the electrochemical performance of the battery is improved, meanwhile, the thermal stability is good, the electrochemical window is stable, the secondary battery adopting the chemical membrane has high safety, the preparation process is simple, and the electrochemical membrane has larger application potential in the aspect of high-safety batteries such as lithium ion batteries.

Description

Electrochemical separator, preparation method and electrochemical device
Technical Field
The application relates to the technical field of electrochemistry, in particular to an electrochemical diaphragm, a preparation method and an electrochemical device.
Background
In recent years, electric devices powered by secondary batteries have been widely used and popularized in industries such as various electronic products and new energy automobiles. There are demands for higher cycle performance of the battery.
The separator is one of the key inner layer components of the secondary battery. The diaphragm is arranged between the positive pole piece and the negative pole piece, mainly plays a role in preventing the positive pole piece and the negative pole piece from being short-circuited, and can enable ions to pass through. Improving the performance of the separator is critical to improving the electrochemical performance of the battery.
Disclosure of Invention
The embodiment of the application provides an electrochemical diaphragm, a preparation method and an electrochemical device, which can improve the wettability of a separation film to electrolyte.
In a first aspect of embodiments of the present application, there is provided an electrochemical separator comprising: a base film; a coating layer disposed on at least one side of the base film in the thickness direction, the coating layer including a first coating layer and a second coating layer stacked, the first coating layer including spherical alpha-Al 2 O 3 And spherical gamma-Al 2 O 3 The second coating layer comprises spherical alpha-Al 2 O 3 Linear gamma-Al 2 O 3 And gamma-AlOOH.
Optionally, the number of layers of the first coating layer and the second coating layer in the coating layer is one, and the second coating layer is arranged on one side, far away from the base film, of the first coating layer; alternatively, the number of layers of the first coating layer and the second coating layer in the coating layer is multiple, and the layers are alternately distributed in the thickness direction.
Optionally, the spherical α -Al in the first coating layer 2 O 3 And spherical gamma-Al 2 O 3 The mass ratio is (3.0-5.0): (5.0 to 7.0); the spherical alpha-Al in the second coating layer 2 O 3 Linear gamma-Al 2 O 3 And gamma-AlOOH in a ratio of (3.0 to 5.0) by mass: (1.0-3.0): (1.0-4.0).
Optionally, the thickness of the first coating layer is 0.5 μm to 5.0 μm; and/or the thickness of the second coating layer is 0.1 μm to 5.0 μm.
Optionally, the spherical alpha-Al in the first coating layer 2 O 3 Particle size of 300nm to 800nm; and/or the spherical gamma-Al 2 O 3 The grain diameter is 100-500 nm; and/or the linear gamma-Al 2 O 3 The length of the polymer is 80-300 nm, and the diameter is 50-100nm; and/or the particle size of the gamma-AlOOH is 100-200 nm.
Optionally, the first coating layer and the second coating layer further comprise a dispersing agent, wherein the dispersing agent comprises at least one of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, styrene-butadiene latex, polyvinyl alcohol and polyurethane.
Optionally, the dispersing agent in the first coating layer and the second coating layer adopts polyvinylidene fluoride.
Optionally, the base film comprises at least one of a polypropylene film, a polyethylene film, and a propylene-ethylene copolymer film.
Optionally, the wettability of the electrochemical separator satisfies: 90% -120%; the specific capacity satisfies: 190 mAh/g-220 mAh/g; the shrinkage ratio satisfies: 0.6 to 1 percent; the hardness of the coating is as follows: 48-58 Hv.
Optionally, the wettability of the electrochemical separator satisfies: 100% -110%; the specific capacity satisfies: 200 mAh/g-210 mAh/g; the shrinkage ratio satisfies: 0.6 to 0.9 percent; the hardness of the coating is as follows: 50Hv to 58Hv.
In a second aspect of the embodiments of the present application, a method for preparing a release film is provided, including the following steps:
spherical alpha-Al 2 O 3 And spherical gamma-Al 2 O 3 Mixing to obtain a first composite substrate, and mixing the first composite substrate with a dispersing agent solution to obtain a first coating slurry; spherical alpha-Al 2 O 3 Linear gamma-Al 2 O 3 Mixing the slurry with gamma-AlOOH, grinding to obtain a second composite substrate, and mixing the second composite substrate with a dispersing agent solution to obtain second coating slurry; and laminating and coating the first coating layer slurry and the second coating layer slurry on at least one side of the base film, drying and pressing to obtain the electrochemical diaphragm, wherein the number of layers of the first coating layer and the second coating layer is single-layer or multi-layer.
In a third aspect of embodiments of the present application, there is provided an electrochemical device including the above separator.
Compared with the prior art, the application has the following beneficial effects:
the electrochemical diaphragm provided by the application adopts a composite coating, and spherical alpha-Al is arranged in a first coating layer 2 O 3 And spherical gamma-Al 2 O 3 Disposing spherical alpha-Al in the second coating layer 2 O 3 Linear gamma-Al 2 O 3 And gamma-AlOOH containing hydroxyl functional groups, using spherical alpha-Al 2 O 3 Stable and large lattice energy, can improve the strength of the electrochemical membrane and utilizes spherical gamma-Al 2 O 3 Has the characteristics of good dispersion performance and low hardness, improves the condition of large hardness of the traditional diaphragm, and in addition, the spherical particles have good fluidity, are easy to disperse, have good particle uniformity, and can increase the coating uniformity of the diaphragm coating layer. Linear gamma-Al 2 O 3 The specific surface area of the coating layer can be increased, the gamma-AlOOH contains hydroxyl functional groups with good hydrophilicity, the wettability of the electrochemical membrane to electrolyte is improved, the liquid absorption rate is high, conductive ions can be conveniently penetrated, the electrochemical performance of the battery is improved, meanwhile, the thermal stability is good, the electrochemical window is stable, the secondary battery adopting the chemical membrane has high safety, the preparation process is simple, and the application potential in the aspect of high-safety batteries such as lithium ion batteries is large.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments of the present application will be briefly described below, and it is obvious that the drawings described below are only some embodiments of the present application, and that other drawings may be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of a diaphragm structure in the present application.
FIG. 2 is a linear gamma-Al 2 O 3 Scanning electron microscope image of (2)
FIG. 3 is a scanning electron microscope image of a first composite substrate
FIG. 4 is a scanning electron microscope image of a second composite substrate
In the drawings, the drawings are not necessarily to scale. Wherein, each reference sign in the figure is:
1. a base film; 2. a first coating layer; 3. a second coating layer; 4. is linear gamma-Al 2 O 3 。
Detailed Description
In order to make the application purposes, technical solutions and beneficial technical effects of the present application clearer, the present application is further described in detail below with reference to examples. It should be understood that the embodiments described in this specification are for purposes of illustration only and are not intended to limit the present application.
For simplicity, only a few numerical ranges are explicitly disclosed in this application. However, any lower limit may be combined with any upper limit to form a range not explicitly recited; and any lower limit may be combined with any other lower limit to form a range not explicitly recited, and any upper limit may be combined with any other upper limit to form a range not explicitly recited. Furthermore, each point or individual value between the endpoints of the range is included within the range, although not explicitly recited. Thus, each point or individual value may be combined as a lower or upper limit on itself with any other point or individual value or with other lower or upper limit to form a range that is not explicitly recited.
In the description of the present application, unless otherwise indicated, "above" and "below" are intended to include the present number, and the meaning of "multiple" in "one or more" means two or more.
The above summary of the present application is not intended to describe each disclosed embodiment or every implementation of the present application. The following description more particularly exemplifies illustrative embodiments. Guidance is provided throughout this application by a series of embodiments, which may be used in various combinations. In the various examples, the list is merely a representative group and should not be construed as exhaustive.
The separator is one of the most critical inner layer components in the secondary battery structure, and the performance of the separator directly influences the capacity, multiplying power, service life, safety and other performances of the battery. The interfacial compatibility between the separator material and the electrode and the retention of the separator to the electrolyte have important effects on the charge and discharge performance, cycle performance and life of the secondary battery.
In the related art, in order to solve the temperature resistance and safety performance of the isolation film, a method of coating ceramic on a base film is generally adopted to form a composite coating on the surface of the base film, so as to improve the temperature resistance of the base film, for example, when the temperature in the working environment of the isolation film is too high, the isolation film is reducedAnd further reduces the short circuit condition of the battery in a high-temperature environment. However, conventional alpha-Al 2 O 3 The ceramic has the defects of poor wettability, poor dispersibility and the like, so that the penetration resistance of conductive ions in the internal reaction of the battery is increased, and the electrochemical performance of the battery is reduced. At the same time conventional Al 2 O 3 High hardness, is liable to cause great wear to the coating equipment and to pierce the membrane.
Based on the above, the inventors have made a great deal of research to provide an electrochemical separator with good wettability, high liquid absorption, good thermal stability and stable electrochemical window.
Electrochemical separator
Embodiments of the first aspect of the present application provide an electrochemical separator comprising: a base film; a coating layer arranged on at least one side of the thickness direction of the basal membrane, the coating layer comprising a first coating layer and a second coating layer which are arranged in a laminated manner, the first coating layer comprising spherical alpha-Al 2 O 3 And spherical gamma-Al 2 O 3 The second coating layer comprises spherical alpha-Al 2 O 3 Linear gamma-Al 2 O 3 And gamma-AlOOH.
Coating material Al 2 O 3 The crystal structure of (c) is divided into two types, face-centered cubic (FCC) and hexagonal close-packed (HCP). According to Al 3+ The difference of crystal lattice can also lead Al to 2 O 3 Divided into different crystal forms. Al (Al) 2 O 3 The crystal forms of the crystal form are more than ten, and the common crystal form is alpha-Al 2 O 3 、θ-Al 2 O 3 、κ-Al 2 O 3 、γ-Al 2 O 3 、δ-Al 2 O 3 And eta-Al 2 O 3 Etc.
The application provides spherical alpha-Al in a first coating layer 2 O 3 And spherical gamma-Al 2 O 3 Wherein, spherical alpha-Al 2 O 3 Is the most stable phase, has larger lattice energy, can improve the strength of the electrochemical membrane, and is spherical alpha-Al 2 O 3 The preparation cost is low, and the cost can be reduced; gamma-Al 2 O 3 Has the characteristics of good dispersion performance and low hardness, and in addition, the spherical particles have good propertiesIs easy to disperse, has better particle uniformity, and can increase the coating uniformity of the diaphragm coating layer. Providing spherical alpha-Al in the second coating layer 2 O 3 Linear gamma-Al 2 O 3 And gamma-AlOOH containing hydroxyl functional groups, wherein the components in the coating layer are mutually wrapped to form a three-dimensional interweaved coating layer structure, wherein the spherical alpha-Al 2 O 3 For reinforcing the strength of the coating layer, linear gamma-Al 2 O 3 The gamma-AlOOH is used for increasing the specific surface area of the coating layer, and the gamma-AlOOH contains hydroxyl functional groups with good hydrophilicity, so that the wettability and the liquid absorption rate of the electrochemical diaphragm to electrolyte can be enhanced.
In the embodiment of the application, the spherical alpha-Al in the first coating layer 2 O 3 And spherical gamma-Al 2 O 3 Referring to FIG. 3, the mixed SEM image shows spherical alpha-Al in the second coating layer 2 O 3 Linear gamma-Al 2 O 3 With reference to FIG. 4, FIG. 2 is a linear gamma-Al, a scanning electron microscope image of a mixture of the gamma-AlOOH compound containing hydroxyl functional groups 2 O 3 Is a scanning electron microscope image of (1).
The electrochemical diaphragm provided by the application adopts the composite coating to solve the problem of conventional alpha-Al 2 O 3 The problem of hardness is high, has improved the wettability of electrochemical diaphragm to electrolyte, and the imbibition rate is high, can be convenient for electrically conductive ion to pierce through, has improved the electrochemical performance of battery, and the heat stability is good simultaneously, and electrochemical window is stable, and the secondary cell of adopting the chemical diaphragm of this application safety is high to its preparation technology is simple, has great application potential in the aspect of high security battery such as lithium ion battery.
In some embodiments, the number of layers of the first coating layer and the second coating layer in the coating layer is one, and the second coating layer is arranged on one side, far away from the base film, of the first coating layer; alternatively, the number of layers of the first coating layer and the second coating layer in the coating layer is multiple, and the layers are alternately distributed in the thickness direction.
In this embodiment, the number of layers to the first coating layer and the second coating layer is not limited, and may be one, and the second coating layer is disposed on one side of the first coating layer away from the base film, as shown in fig. 1, and may also be multiple layers, where the multiple layers of the first coating layer and the second coating layer are alternately distributed in the thickness direction of the electrochemical membrane.
In some embodiments, spherical alpha-Al in the first coating layer 2 O 3 And spherical gamma-Al 2 O 3 The mass ratio is (3.0-5.0): (5.0 to 7.0); spherical alpha-Al in the second coating layer 2 O 3 Linear gamma-Al 2 O 3 And gamma-AlOOH in a ratio of (3.0 to 5.0) by mass: (1.0-3.0): (1.0-4.0).
In the embodiment of the application, the mass ratio of each component in the coating layer is controlled in a proper range, so that the wettability and the strength are improved, and the coating layer with high strength, good dispersibility and good wettability is formed.
In some embodiments, the thickness of the first coating layer is 0.5 μm to 5.0 μm; and/or the thickness of the second coating layer is 0.1 μm to 5.0 μm.
In the embodiment of the application, the thickness of each coating layer is controlled in a proper range, so that the wettability and strength are improved, the permeability of ions in the electrolyte in the coating layer is improved, and the secondary battery is ensured to have excellent cycle performance.
In some embodiments, spherical alpha-Al in the first coating layer 2 O 3 Particle size of 300nm to 800nm; and/or spherical gamma-Al 2 O 3 The grain diameter is 100-500 nm; and/or linear gamma-Al 2 O 3 The length of the polymer is 80-300 nm, and the diameter is 50-100nm; and/or the particle size of the gamma-AlOOH is 100-200 nm.
In the embodiment of the application, the volume average particle size of the non-conductive particles is in a proper range, so that the prepared coating layer slurry can obtain a stable dispersion state, and the coating layer slurry has higher shearing resistance in the coating process, and particles are uniformly stacked in the coating process, thereby being beneficial to improving the ion permeability in the electrolyte.
In some embodiments, the first coating layer and the second coating layer further include a dispersant, the dispersant including at least one of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, styrene-butadiene latex, polyvinyl alcohol, and polyurethane.
In the embodiment of the application, the dispersing agent can improve the dispersibility of each component in the coating layer on one hand, and can improve the bonding strength of the coating layer on the surface of the base film on the other hand, prevent the coating particles from falling off in the battery winding process, and inhibit the swelling and dissolution of the coating layer in the electrolyte, so that the influence of the falling-off of the coating layer on the battery circulation and high-temperature storage is prevented.
In some embodiments, the dispersing agent in the first coating layer and the second coating layer adopts polyvinylidene fluoride, and the polyvinylidene fluoride has the advantages of low density, good fluidity and the like.
In some embodiments, the base film comprises at least one of a polypropylene film, a polyethylene film, and a propylene-ethylene copolymer film.
In some embodiments, the wettability of the electrochemical separator satisfies: 90% -120%; the specific capacity satisfies: 190 mAh/g-220 mAh/g; the shrinkage ratio satisfies: 0.6 to 1 percent; the hardness of the coating is as follows: 48-58 Hv.
Optionally, the wettability of the electrochemical separator satisfies: 100% -110%; the specific capacity satisfies: 200 mAh/g-210 mAh/g; the shrinkage ratio satisfies: 0.6 to 0.9 percent; the hardness of the coating is as follows: 50Hv to 58Hv.
The wettability was characterized by the amount of liquid absorbed and the amount of liquid absorbed was measured using an electrolyte. The separator sample was cut into a square of 2 cm. Times.2 cm, and M1 was weighed, with lmol/L LiPF as the electrolyte 6 . The electrolyte system is Ethylene Carbonate (EC): dimethyl carbonate (DMC): diethyl carbonate (EMC) =1: 1:1 (V/V), immersing the sample film in an electrolyte for 30min, taking out, sucking the electrolyte on the surface of the sample film with filter paper, weighing M2, and calculating wettability according to the following formula.
The calculation formula is as follows: p= (M2-M1)/m1×100%
Wherein: ml—base film mass (g); m2-mass after soaking (g).
The wettability of the electrochemical diaphragm provided by the embodiment of the application meets the following conditions: 100% to 110%, for example, the wettability may be 100%, 101%, 102%, 103%, 104%, 105%, 106%, 107%, 108%, 109% or 110%, or any combination thereof.
The specific capacity measurement method in the application comprises the following steps: the positive electrode part of the battery is composed of active material LiCoO 2 Uniformly mixing a conductive agent (Super-P carbon) and a binder polyvinylidene fluoride according to a mass ratio of 8:1:1 to form slurry, uniformly coating the slurry on an aluminum foil by using a scraper, naturally airing the slurry, beating the slurry into a wafer, and vacuum drying the wafer at 105 ℃ to obtain an electrode plate, wherein the metal lithium plate is a negative electrode, and the electrolyte is 1mol/L LiPF 6 The volume ratio of Ethylene Carbonate (EC), diethyl carbonate (DEC) and dimethyl carbonate (DMC) is 1:1:1, and the isolating film obtained in the above example is adopted to assemble a CR2032 button battery in an argon environment, the electrochemical performance test is carried out by using a CT2001A battery test system, the constant-current charge and discharge method is adopted, the voltage is 2.0V to 4.2V at 25 ℃, and the specific capacity is measured.
The specific capacitance of the electrochemical diaphragm provided by the embodiment of the application meets the following conditions: the specific capacitance of 200mAh/g to 210mAh/g can be 200mAh/g, 201mAh/g, 202mAh/g, 303mAh/g, 204mAh/g, 205mAh/g, 206mAh/g, 207mAh/g, 208mAh/g, 209mAh/g or 210mAh/g, for example, or any combination range of the above values.
The shrinkage measurement method comprises the following steps:
(1) 5 isolation films with the width of 100mm multiplied by 100mm are cut (the width is less than 100mm, and the length direction is cut to 100 mm);
(2) The width of the test sample is measured by referring to national standards and is marked as L1;
(3) Placing the isolation film sample in an electrothermal constant temperature blast drying oven for characterization (DHG-9076A), drying, and standing at 105deg.C for 2 hr;
(4) Taking out the isolation film after high-temperature baking, and measuring the width of the isolation film, and marking as L2;
(5) Shrinkage (L1-L2)/L1 is 100% calculated.
The shrinkage rate of the electrochemical membrane provided by the embodiment of the application meets the following conditions: the shrinkage may be 0.6% to 0.9%, for example, 0.6%, 0.7%, 0.8% or 0.9%, or any combination thereof.
The application adopts the Vickers hardness meter to measure the hardness of the coating, and the hardness of the coating of the electrochemical diaphragm provided by the embodiment of the application meets the following conditions: the coating hardness may be 50Hv, 51Hv, 52Hv, 53Hv, 54Hv, 55Hv, 56Hv, 57Hv or 58Hv, for example, or any combination thereof.
Compared with the traditional separator, the electrochemical separator in the embodiment of the application has excellent wettability, smaller shrinkage and better specific capacity, and meanwhile, the hardness of the coating is reduced, so that the electrochemical performance of the battery is improved.
In some embodiments, the type of the base film is not particularly limited, and may be selected according to practical requirements, and any known porous structure film having good chemical stability and mechanical stability may be selected. For example, one or more selected from polyethylene, polypropylene, polyvinylidene fluoride-hexafluoropropylene, polyimide, polyethylene terephthalate, polysulfone and aromatic polyamide fibers may be used. From the viewpoint of film forming properties, it is preferable that the base film is selected from polyethylene and copolymers thereof.
Embodiments of the second aspect of the present application provide a method of preparing an electrochemical separator comprising mixing spherical α -Al 2 O 3 And spherical gamma-Al 2 O 3 Mixing to obtain a first composite substrate, and mixing the first composite substrate with a dispersing agent solution to obtain a first coating slurry; spherical alpha-Al 2 O 3 Linear gamma-Al 2 O 3 Mixing the slurry with gamma-AlOOH, grinding to obtain a second composite substrate, and mixing the second composite substrate with a dispersing agent solution to obtain second coating slurry; and laminating and coating the first coating layer slurry and the second coating layer slurry on at least one side of the base film, drying and pressing to obtain the electrochemical diaphragm, wherein the number of layers of the first coating layer and the second coating layer is single-layer or multi-layer.
The preparation method provided by the embodiment of the application has the characteristics of simple process, low cost and environment friendliness.
Embodiments of the third aspect of the present application provide an electrochemical device comprising an electrochemical separator as previously described.
Specifically, the electrochemical device may be a battery cell, and at least comprises a casing and a pole piece assembly disposed in the casing, wherein the pole piece assembly comprises a positive pole piece, a negative pole piece and a separation membrane disposed therebetween. The battery cell may be a secondary battery cell or a primary battery cell, or may be a lithium ion battery cell, a sodium ion battery cell, a magnesium ion battery cell, or the like, which is not limited in the embodiment of the present application. The battery cells may be cylindrical, flat, rectangular, or otherwise shaped.
Examples
The present disclosure is more particularly described in the following examples that are intended as illustrations only, since various modifications and changes within the scope of the present disclosure will be apparent to those skilled in the art. Unless otherwise indicated, all parts, percentages, and ratios reported in the examples below are by weight, and all reagents used in the examples are commercially available or were obtained synthetically according to conventional methods and can be used directly without further treatment, as well as the instruments used in the examples.
Example 1
Preparing an electrochemical separator:
preparing a first coating layer slurry: 0.4g of polyvinylidene fluoride (PVDF) was weighed into 9.6g of anhydrous N-methylpyrrolidone (NMP), and stirred at room temperature for 4 hours, to obtain a PVDF solution having a mass fraction of 5%. 3.0g of spherical alpha-Al with a particle size of 300nm 2 O 3 And 7.0g of spherical gamma-Al having a particle size of 200nm 2 O 3 And respectively adding the PVDF solutions to mix, stirring for 10 hours at room temperature and carrying out ultrasonic treatment for 1.5 hours to obtain the first coating layer slurry.
Preparing a second coating layer slurry: 0.1g of polyvinylidene fluoride (PVDF) was weighed into 5.6g of anhydrous N-methylpyrrolidone (NMP), and stirred at room temperature for 4 hours, to obtain a PVDF solution having a mass fraction of 3%. 3.0g of spherical alpha-Al with a particle size of 300nm 2 O 3 3.0g of linear gamma-Al with the length of 80nm and the diameter of 50nm 2 O 3 Adding 4.0g of gamma-AlOOH with the particle size of 100nm into the PVDF solution, mixing, taking the PVDF solution as a dispersing agent, grinding for 8 hours at room temperature by using a high-energy ball mill, and dissolving the complex and the PVDFMixing the solutions, stirring for 10 hours at room temperature, and carrying out ultrasonic treatment for 1.0 hour to obtain second coating layer slurry.
Coating: uniformly coating the slurry of the first coating layer on two sides of a 7-mu m-thick polyethylene diaphragm by using a scraper, controlling the thickness of the first coating layer to be 1 mu m, placing the first coating layer in a vacuum oven for vacuum drying for 10 hours at 70 ℃ after a large amount of solvent volatilizes, and pressing for 30 seconds under the pressure of 4MPa by using a hot press after drying. And uniformly coating one side, far away from the base film, of the first coating layer of the second coating layer by using a scraper, controlling the thickness of the second coating layer to be 0.6 mu m, placing the second coating layer in a vacuum oven for vacuum drying at 70 ℃ for 10 hours after a large amount of solvent volatilizes, pressing for 50 seconds under the pressure of 4MPa by using a hot press after drying, and placing the second coating layer in a glove box for storage to obtain the electrochemical diaphragm.
Example 2
Preparing an electrochemical separator:
preparing a first coating layer slurry: 0.4g of polyvinylidene fluoride (PVDF) was weighed into 9.6g of anhydrous N-methylpyrrolidone (NMP), and stirred at room temperature for 4 hours, to obtain a PVDF solution having a mass fraction of 5%. 4.0g of spherical alpha-Al with a particle size of 400nm 2 O 3 And 6.0g of spherical gamma-Al having a particle size of 400nm 2 O 3 And respectively adding the PVDF solutions to mix, stirring for 10 hours at room temperature and carrying out ultrasonic treatment for 1.5 hours to obtain the first coating layer slurry.
Preparing a second coating layer slurry: 0.1g of polyvinylidene fluoride (PVDF) was weighed into 5.6g of anhydrous N-methylpyrrolidone (NMP), and stirred at room temperature for 4 hours, to obtain a PVDF solution having a mass fraction of 3%. 4.0g of spherical alpha-Al with a particle size of 400nm 2 O 3 2.0g of linear gamma-Al with the length of 100nm and the diameter of 60nm 2 O 3 And adding 4.0g of gamma-AlOOH with the particle size of 150nm into the PVDF solution, mixing, taking the PVDF solution as a dispersing agent, grinding for 8 hours at room temperature by using a high-energy ball mill, mixing the composite with the PVDF solution, stirring for 10 hours at room temperature, and carrying out ultrasonic treatment for 1.0 hour to obtain the second coating slurry.
Coating: uniformly coating the slurry of the first coating layer on two sides of a polyethylene diaphragm with the thickness of 7 mu m by using a scraper, controlling the thickness of the first coating layer to be 2 mu m, placing the first coating layer in a vacuum oven for vacuum drying for 10 hours at the temperature of 70 ℃ after a large amount of solvent volatilizes, and pressing for 30 seconds under the pressure of 4MPa by using a hot press after drying. And uniformly coating one side, far away from the base film, of the first coating layer of the second coating layer by using a scraper, controlling the thickness of the second coating layer to be 1 mu m, placing the first coating layer in a vacuum oven for vacuum drying at 70 ℃ for 10 hours after a large amount of solvent volatilizes, pressing for 50 seconds under the pressure of 4MPa by using a hot press after drying, and placing the first coating layer in a glove box for storage to obtain the electrochemical diaphragm.
Example 3
Preparing an electrochemical separator:
preparing a first coating layer slurry: 0.4g of polyvinylidene fluoride (PVDF) was weighed into 9.6g of anhydrous N-methylpyrrolidone (NMP), and stirred at room temperature for 4 hours, to obtain a PVDF solution having a mass fraction of 5%. 5.0g of spherical alpha-Al with a particle size of 500nm 2 O 3 And 5.0g of spherical gamma-Al having a particle size of 500nm 2 O 3 And respectively adding the PVDF solutions to mix, stirring for 10 hours at room temperature and carrying out ultrasonic treatment for 1.5 hours to obtain the first coating layer slurry.
Preparing a second coating layer slurry: 0.1g of polyvinylidene fluoride (PVDF) was weighed into 5.6g of anhydrous N-methylpyrrolidone (NMP), and stirred at room temperature for 4 hours, to obtain a PVDF solution having a mass fraction of 3%. 5.0g of spherical alpha-Al with a particle size of 500nm 2 O 3 2.0g of linear gamma-Al with the length of 200nm and the diameter of 60nm 2 O 3 And adding 3.0g of gamma-AlOOH with the particle size of 200nm into the PVDF solution, mixing, taking the PVDF solution as a dispersing agent, grinding for 8 hours at room temperature by using a high-energy ball mill, mixing the composite with the PVDF solution, stirring for 10 hours at room temperature, and carrying out ultrasonic treatment for 1.0 hour to obtain the second coating slurry.
Coating: uniformly coating the slurry of the first coating layer on two sides of a 7-mu m-thick polyethylene diaphragm by using a scraper, controlling the thickness of the first coating layer to be 3 mu m, placing the first coating layer in a vacuum oven for vacuum drying for 10 hours at 70 ℃ after a large amount of solvent volatilizes, and pressing for 30 seconds under the pressure of 4MPa by using a hot press after drying. And uniformly coating one side, far away from the base film, of the first coating layer of the second coating layer by using a scraper, controlling the thickness of the second coating layer to be 2 mu m, placing the second coating layer in a vacuum oven for vacuum drying at 70 ℃ for 10 hours after a large amount of solvent volatilizes, pressing for 50 seconds under the pressure of 4MPa by using a hot press after drying, and placing the second coating layer in a glove box for storage to obtain the electrochemical diaphragm.
Example 4
Preparing an electrochemical separator:
preparing a first coating layer slurry: 0.4g of polyvinylidene fluoride (PVDF) was weighed into 9.6g of anhydrous N-methylpyrrolidone (NMP), and stirred at room temperature for 4 hours, to obtain a PVDF solution having a mass fraction of 5%. 3.0g of spherical alpha-Al with a particle size of 600nm 2 O 3 And 7.0g of spherical gamma-Al having a particle size of 500nm 2 O 3 And respectively adding the PVDF solutions to mix, stirring for 10 hours at room temperature and carrying out ultrasonic treatment for 1.5 hours to obtain the first coating layer slurry.
Preparing a second coating layer slurry: 0.1g of polyvinylidene fluoride (PVDF) was weighed into 5.6g of anhydrous N-methylpyrrolidone (NMP), and stirred at room temperature for 4 hours, to obtain a PVDF solution having a mass fraction of 3%. 5.0g of spherical alpha-Al with a particle size of 600nm 2 O 3 3.0g of linear gamma-Al with the length of 300nm and the diameter of 80nm 2 O 3 And adding 2.0g of gamma-AlOOH with the particle size of 200nm into the PVDF solution, mixing, taking the PVDF solution as a dispersing agent, grinding for 8 hours at room temperature by using a high-energy ball mill, mixing the composite with the PVDF solution, stirring for 10 hours at room temperature, and carrying out ultrasonic treatment for 1.0 hour to obtain the second coating slurry.
Coating: uniformly coating the slurry of the first coating layer on two sides of a 7-mu m-thick polyethylene diaphragm by using a scraper, controlling the thickness of the first coating layer to be 3 mu m, placing the first coating layer in a vacuum oven for vacuum drying for 10 hours at 70 ℃ after a large amount of solvent volatilizes, and pressing for 30 seconds under the pressure of 4MPa by using a hot press after drying. And uniformly coating one side, far away from the base film, of the first coating layer of the second coating layer by using a scraper, controlling the thickness of the second coating layer to be 2 mu m, placing the second coating layer in a vacuum oven for vacuum drying at 70 ℃ for 10 hours after a large amount of solvent volatilizes, pressing for 50 seconds under the pressure of 4MPa by using a hot press after drying, and placing the second coating layer in a glove box for storage to obtain the electrochemical diaphragm.
Example 5
Preparing an electrochemical separator:
preparing a first coating layer slurry: 0.4g of polyvinylidene fluoride (PVDF) was weighed into 9.6g of anhydrous N-methylpyrrolidone (NMP), and stirred at room temperature for 4 hours, to obtain a PVDF solution having a mass fraction of 5%. 3.0g of spherical alpha-Al with a particle size of 400nm 2 O 3 And 7.0g of spherical gamma-Al having a particle size of 400nm 2 O 3 And respectively adding the PVDF solutions to mix, stirring for 10 hours at room temperature and carrying out ultrasonic treatment for 1.5 hours to obtain the first coating layer slurry.
Preparing a second coating layer slurry: 0.1g of polyvinylidene fluoride (PVDF) was weighed into 5.6g of anhydrous N-methylpyrrolidone (NMP), and stirred at room temperature for 4 hours, to obtain a PVDF solution having a mass fraction of 3%. 5.0g of spherical alpha-Al 2 O 3 3.0g of linear gamma-Al 2O3 and 4.0g of gamma-AlOOH with the particle size of 400nm are added into the PVDF solution, mixed, and the PVDF solution is taken as a dispersing agent, ground for 5-10 hours at room temperature by a high-energy ball mill, then the composite is mixed with the PVDF solution, stirred for 10 hours at room temperature and then subjected to ultrasonic treatment for 1.0 hour, so that second coating slurry is obtained.
Coating: uniformly coating the slurry of the first coating layer on two sides of a polyethylene diaphragm with the thickness of 7 mu m by using a scraper, controlling the thickness of the first coating layer to be 4 mu m, placing the first coating layer in a vacuum oven for vacuum drying for 8-12 hours at the temperature of 50-80 ℃ after a large amount of solvent volatilizes, and pressing for 30 seconds under the pressure of 2-4 MPa by using a hot press after drying. And uniformly coating one side, far away from the base film, of the first coating layer of the second coating layer by using a scraper, controlling the thickness of the second coating layer to be 3 mu m, placing the second coating layer in a vacuum oven for vacuum drying at 50-80 ℃ for 8-12 hours after a large amount of solvent volatilizes, pressing for 50 seconds under the pressure of 2-4 MPa by using a hot press after drying, and placing the second coating layer in a glove box for storage to obtain the electrochemical diaphragm.
Example 6
This embodiment is substantially the same as embodiment 1 except that: the binding agent in the first coating layer and the second coating layer adopts polyvinylidene fluoride-hexafluoropropylene, the first coating layer and the second coating layer are two layers, and the first coating layer and the second coating layer are laminated in the thickness direction of the electrochemical diaphragm.
Example 7
This embodiment is substantially the same as embodiment 1 except that: the binding agent in the first coating layer and the second coating layer adopts polyvinylidene fluoride-hexafluoropropylene, and the base film adopts a polypropylene film.
Example 8
This embodiment is substantially the same as embodiment 1 except that: the adhesive in the first coating layer and the second coating layer adopts polyvinyl alcohol, and the base film is a propylene-ethylene copolymer film.
Comparative example 1
Preparing a separation film:
the alumina ceramic with the grain diameter of 500nm is dispersed by polyvinylidene fluoride to form uniform slurry, and double-sided coating is carried out on the surface of a polyethylene-based film with the thickness of 20 mu m according to the conventional coating process, so as to obtain the isolating film.
Test method
Wettability measurement:
the wettability was characterized by the amount of liquid absorbed and the amount of liquid absorbed was measured using an electrolyte. The separator sample was cut into a square of 2 cm. Times.2 cm, and M1 was weighed, with lmol/L LiPF as the electrolyte 6 . The electrolyte system is Ethylene Carbonate (EC): dimethyl carbonate (DMC): diethyl carbonate (EMC) =1: 1:1 (V/V), immersing the sample film in an electrolyte for 30min, taking out, sucking the electrolyte on the surface of the sample film with filter paper, weighing M2, and calculating wettability according to the following formula.
The calculation formula is as follows: p= (M2-M1)/m1×100%
Wherein: ml—base film mass (g); m2-mass after soaking (g).
Specific capacity measurement:
the positive electrode part of the battery is composed of active material LiCoO 2 Uniformly mixing a conductive agent (Super-P carbon) and a binder polyvinylidene fluoride according to a mass ratio of 8:1:1 to form slurry, uniformly coating the slurry on an aluminum foil by using a scraper, naturally airing the slurry, beating the slurry into a wafer, and vacuum drying the wafer at 105 ℃ to obtain an electrode plate, wherein the metal lithium plate is a negative electrode, and the electrolyte is 1mol/L LiPF 6 The volume ratio of Ethylene Carbonate (EC), diethyl carbonate (DEC) and dimethyl carbonate (DMC) was 1:1:1, and the separator obtained in the above example was used to assemble CR2032 button cell under argon atmosphere using CTThe 2001A battery test system performs electrochemical performance test, adopts a constant current charge and discharge method, tests at 25 ℃, and measures specific capacity with voltage of 2.0V to 4.2V.
Shrinkage measurement:
(1) 5 isolation films with the width of 100mm multiplied by 100mm are cut (the width is less than 100mm, and the length direction is cut to 100 mm);
(2) The width of the test sample is measured by referring to national standards and is marked as L1;
(3) Placing the isolation film sample in an electrothermal constant temperature blast drying oven for characterization (DHG-9076A), drying, and standing at 105deg.C for 2 hr;
(4) Taking out the isolation film after high-temperature baking, and measuring the width of the isolation film, and marking as L2;
(5) Shrinkage (L1-L2)/L1 is 100% calculated.
The specific test results are shown in Table 1.
Table 1: preparation parameters and test results of examples 1 to 10 and comparative example 1
As is clear from Table 1, the separators obtained in examples 1 to 8 of the present application had better shrinkage and specific capacity than comparative example 1, and the wettability fluids of the separators obtained in examples 1 to 8 of the present application were significantly better than comparative example 1.
Compared with the prior art, in the electrochemical diaphragm, the preparation method of the isolating film and the electrochemical device, the composite coating is adopted in the application, so that the conventional alpha-Al is solved 2 O 3 The problem of high hardness is solved, the wettability of the electrochemical diaphragm to electrolyte is improved, the liquid absorption rate is high, the penetration of conductive ions can be facilitated, the electrochemical performance of the battery is improved, meanwhile, the thermal stability is good, the electrochemical window is stable, the safety of the secondary battery adopting the chemical diaphragm is high, the preparation process is simple, and the electrochemical diaphragm is suitable for the electrochemical diaphragm of the applicationHigh safety batteries, such as lithium ion batteries, have great potential for use.
While the invention has been described with reference to certain preferred embodiments, it will be understood by those skilled in the art that various changes and substitutions of equivalents may be made and equivalents will be apparent to those skilled in the art without departing from the scope of the invention. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.

Claims (10)

1. An electrochemical separator, comprising:
a base film;
a coating layer disposed on at least one side of the base film in the thickness direction, the coating layer including a first coating layer and a second coating layer stacked, the first coating layer including spherical alpha-Al 2 O 3 And spherical gamma-Al 2 O 3 The second coating layer comprises spherical alpha-Al 2 O 3 Linear gamma-Al 2 O 3 And gamma-AlOOH; the spherical alpha-Al in the first coating layer 2 O 3 And spherical gamma-Al 2 O 3 The mass ratio is (3.0-5.0): (5.0 to 7.0); the spherical alpha-Al in the second coating layer 2 O 3 Linear gamma-Al 2 O 3 And gamma-AlOOH in a ratio of (3.0 to 5.0) by mass: (1.0-3.0): (1.0 to 4.0);
the spherical alpha-Al 2 O 3 Particle size of 300nm to 800nm; the spherical gamma-Al 2 O 3 The grain diameter is 100-500 nm; the linear gamma-Al 2 O 3 The length of the polymer is 80-300 nm, and the diameter is 50-100nm; the particle size of the gamma-AlOOH is 100-200 nm.
2. The electrochemical membrane of claim 1, wherein the number of layers of the first coating layer and the second coating layer in the coating layer is one, and the second coating layer is disposed on a side of the first coating layer away from the base film; or alternatively, the process may be performed,
the layers of the first coating layer and the second coating layer in the coating layer are multiple layers and are alternately distributed in the thickness direction.
3. The electrochemical membrane of any one of claims 1-2, wherein the first coating layer has a thickness of 0.5 μιη to 5.0 μιη; and/or
The thickness of the second coating layer is 0.1-5.0 mu m.
4. The electrochemical membrane of claim 1, wherein the first and second coating layers further comprise a dispersant, the dispersant comprising at least one of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, styrene-butadiene latex, polyvinyl alcohol, and polyurethane.
5. The electrochemical membrane of claim 4, wherein the dispersant in the first and second coating layers is polyvinylidene fluoride.
6. The electrochemical membrane of claim 1, wherein the base film comprises at least one of a polypropylene film, a polyethylene film, and a propylene-ethylene copolymer film.
7. The electrochemical separator according to any one of claims 1-2, wherein the wettability of the electrochemical separator satisfies: 90% -120%; the specific capacity satisfies: 190 mAh/g-220 mAh/g; the shrinkage ratio satisfies: 0.6-1%; the hardness of the coating is as follows: 48-58 Hv.
8. The electrochemical separator according to any one of claims 1-2, wherein the wettability of the electrochemical separator satisfies: 100% -110%; the specific capacity satisfies: 200 mAh/g-210 mAh/g; the shrinkage ratio satisfies: 0.6% -0.9%; the hardness of the coating is as follows: 50Hv to 58Hv.
9. A method for preparing an electrochemical separator according to any one of claims 1 to 8, comprising the steps of:
spherical alpha-Al 2 O 3 And spherical gamma-Al 2 O 3 Mixing to obtain a first composite substrate, and mixing the first composite substrate with a dispersing agent solution to obtain a first coating slurry;
spherical alpha-Al 2 O 3 Linear gamma-Al 2 O 3 Mixing the slurry with gamma-AlOOH, grinding to obtain a second composite substrate, and mixing the second composite substrate with a dispersing agent solution to obtain second coating slurry;
and laminating and coating the first coating layer slurry and the second coating layer slurry on at least one side of the base film, drying and pressing to obtain the electrochemical diaphragm, wherein the number of layers of the first coating layer and the second coating layer is single-layer or multi-layer.
10. An electrochemical device comprising the electrochemical separator of any one of claims 1-8.
CN202210597292.6A 2022-05-30 2022-05-30 Electrochemical separator, preparation method and electrochemical device Active CN115020915B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210597292.6A CN115020915B (en) 2022-05-30 2022-05-30 Electrochemical separator, preparation method and electrochemical device

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210597292.6A CN115020915B (en) 2022-05-30 2022-05-30 Electrochemical separator, preparation method and electrochemical device

Publications (2)

Publication Number Publication Date
CN115020915A CN115020915A (en) 2022-09-06
CN115020915B true CN115020915B (en) 2023-07-25

Family

ID=83070141

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210597292.6A Active CN115020915B (en) 2022-05-30 2022-05-30 Electrochemical separator, preparation method and electrochemical device

Country Status (1)

Country Link
CN (1) CN115020915B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116111281B (en) * 2023-04-10 2023-06-27 宁德新能源科技有限公司 Separator, electrochemical device and electronic device

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101755362A (en) * 2007-07-25 2010-06-23 株式会社Lg化学 Electrochemical device and its manufacturing method
EP2830125A1 (en) * 2013-07-22 2015-01-28 Sihl GmbH Separator for an electrochemical cell and method for producing the same
CN108695476A (en) * 2018-05-21 2018-10-23 湖南人文科技学院 Ceramic diaphragm and its preparation method and application
CN108711605A (en) * 2018-07-10 2018-10-26 深圳中兴新材技术股份有限公司 A kind of composite battery separator film, preparation method and battery
CN109075297A (en) * 2016-03-29 2018-12-21 赛尔格有限责任公司 It is improved for the deposition or layer of microporous barrier, improved film, improved lithium battery separator, improved battery, improved high pressure lithium battery with and related methods
CN109891633A (en) * 2016-11-18 2019-06-14 株式会社Lg化学 Partition and electrochemical appliance including the partition
CN110429224A (en) * 2019-06-26 2019-11-08 高芳 A kind of lithium battery diaphragm and preparation method thereof
CN110911620A (en) * 2019-10-19 2020-03-24 东莞东阳光科研发有限公司 Spotted coating diaphragm slurry, composite diaphragm and preparation method thereof
KR20220062856A (en) * 2020-11-09 2022-05-17 주식회사 엘지화학 Electrode assembly, method for preparing thereof, and electrochemical device comprising the electrode assembly

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150147621A1 (en) * 2013-11-26 2015-05-28 General Electric Company Methods for the formation of beta alumina electrolytes, and related structures and devices
KR102317502B1 (en) * 2019-03-06 2021-10-27 삼성에스디아이 주식회사 A separator, method of manufacturing the separator, and secondary battery comprising the separator
CN112467308B (en) * 2020-10-27 2023-09-05 惠州锂威新能源科技有限公司 Diaphragm, preparation method thereof and lithium ion battery

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101755362A (en) * 2007-07-25 2010-06-23 株式会社Lg化学 Electrochemical device and its manufacturing method
EP2830125A1 (en) * 2013-07-22 2015-01-28 Sihl GmbH Separator for an electrochemical cell and method for producing the same
CN109075297A (en) * 2016-03-29 2018-12-21 赛尔格有限责任公司 It is improved for the deposition or layer of microporous barrier, improved film, improved lithium battery separator, improved battery, improved high pressure lithium battery with and related methods
CN109891633A (en) * 2016-11-18 2019-06-14 株式会社Lg化学 Partition and electrochemical appliance including the partition
CN108695476A (en) * 2018-05-21 2018-10-23 湖南人文科技学院 Ceramic diaphragm and its preparation method and application
CN108711605A (en) * 2018-07-10 2018-10-26 深圳中兴新材技术股份有限公司 A kind of composite battery separator film, preparation method and battery
CN110429224A (en) * 2019-06-26 2019-11-08 高芳 A kind of lithium battery diaphragm and preparation method thereof
CN110911620A (en) * 2019-10-19 2020-03-24 东莞东阳光科研发有限公司 Spotted coating diaphragm slurry, composite diaphragm and preparation method thereof
KR20220062856A (en) * 2020-11-09 2022-05-17 주식회사 엘지화학 Electrode assembly, method for preparing thereof, and electrochemical device comprising the electrode assembly

Also Published As

Publication number Publication date
CN115020915A (en) 2022-09-06

Similar Documents

Publication Publication Date Title
CN110085904B (en) Flexible composite solid electrolyte, all-solid-state lithium ion battery and preparation method thereof
CN108598560B (en) Composite solid electrolyte and preparation method and application thereof
EP3373367B1 (en) Positive-electrode active material, positive electrode, battery, battery pack, electronic device, electric vehicle, electricity storage device, and electric power system
EP2634836B1 (en) Separator including coating layer of inorganic and organic mixture, and battery including the same
CN104600231B (en) A kind of barrier film of active nm-class boron nitride coating and preparation method thereof
CN109244546B (en) Solid composite electrolyte film, preparation method thereof and all-solid-state battery
CN103199301A (en) Composite gel polymer electrolyte based on solid polymer electrolyte, and preparation method and application thereof
CN105762317A (en) Water-soluble polymer assisted inorganic composite diaphragm preparation method
US11205822B2 (en) Non-porous separator and use thereof
EP2005502A1 (en) Electrode having porous active coating layer, manufacturing method thereof and electrochemical device containing the same
TW201505238A (en) Organic/inorganic composite separator having porous active coating layer and electrochemical device containing the same
US10862090B2 (en) Composite separator, preparation method of the same, and electrochemical device using the same
WO2011069331A1 (en) Lithium-ion battery
Li et al. Approaching high performance PVDF‐HFP based solid composite electrolytes with LLTO nanorods for solid‐state lithium‐ion batteries
JP7471477B2 (en) Separator for power storage device and power storage device
CN115020915B (en) Electrochemical separator, preparation method and electrochemical device
US10811660B2 (en) Separator, method for preparing separator and electrochemical device containing separator
EP3951935A1 (en) Negative electrode tab, secondary battery, and device comprising secondary battery
WO2018096909A1 (en) Negative electrode, battery, battery pack, electronic device, electric vehicle, electricity storage device, and power system
CN110858661A (en) Positive electrode assembly of lithium ion battery, preparation method of positive electrode assembly and all-solid-state lithium battery
JP4624722B2 (en) Negative electrode material for lithium secondary battery and manufacturing method thereof, negative electrode for lithium secondary battery using the same, and lithium secondary battery
CN116779767A (en) Electrode plate, preparation method thereof, secondary battery and device
CN114171849B (en) Composite diaphragm with core-shell structure and preparation method thereof
CN113097440B (en) Electrochemical device and electric equipment
CN112838265B (en) Thin layered composite solid electrolyte membrane and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant