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CN112531291A - Ceramic microsphere, diaphragm containing ceramic microsphere and lithium ion battery containing diaphragm - Google Patents

Ceramic microsphere, diaphragm containing ceramic microsphere and lithium ion battery containing diaphragm Download PDF

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Publication number
CN112531291A
CN112531291A CN201910883021.5A CN201910883021A CN112531291A CN 112531291 A CN112531291 A CN 112531291A CN 201910883021 A CN201910883021 A CN 201910883021A CN 112531291 A CN112531291 A CN 112531291A
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Prior art keywords
diaphragm
core
microsphere
parts
layer
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Chinese (zh)
Inventor
李素丽
张祖来
唐伟超
李俊义
徐延铭
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Zhuhai Cosmx Battery Co Ltd
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Zhuhai Cosmx Battery Co Ltd
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Priority to CN201910883021.5A priority Critical patent/CN112531291A/en
Priority to CN202311357801.9A priority patent/CN117423957A/en
Publication of CN112531291A publication Critical patent/CN112531291A/en
Pending legal-status Critical Current

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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
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M50/434—Ceramics
    • 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
    • H01M50/443—Particulate 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
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Composite Materials (AREA)
  • Cell Separators (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention provides a ceramic microsphere, a diaphragm containing the ceramic microsphere and a lithium ion battery containing the diaphragm. The microsphere has a core-shell structure, namely comprises a shell layer and a core, wherein the shell layer is made of a thermosensitive polymer, and the core is made of a ceramic material. The invention is different from the traditional lithium ion battery diaphragm, adopts the polymer orientation design coating method to screen the thermosensitive polymer coating ceramic material, and can effectively improve the high-temperature safety performance of the lithium ion battery by coating the microsphere containing the thermosensitive polymer coating ceramic material on the surface of the diaphragm on the premise of not influencing the performance of the lithium ion battery.

Description

Ceramic microsphere, diaphragm containing ceramic microsphere and lithium ion battery containing diaphragm
Technical Field
The invention belongs to the technical field of microspheres and lithium ion batteries, and particularly relates to a ceramic microsphere, a diaphragm containing the ceramic microsphere and a lithium ion battery containing the diaphragm, wherein the diaphragm has high safety performance.
Background
With the popularization of 3C products and the rise of the electric automobile market, the demand for lithium ion secondary batteries is increasing. The diaphragm is used as a key component of the lithium ion battery, the performance of the diaphragm determines the interface structure, internal resistance and the like of the battery, the characteristics of the battery such as capacity, cycle and safety performance are directly influenced, and the diaphragm with excellent performance plays an important role in improving the comprehensive performance of the battery. Therefore, the development of high-performance separators has become an important direction for improving the performance of lithium batteries, and particularly, the safety of separators has become a focus of our attention. The safety of lithium ion batteries is a major concern in the industry, and the safety of separators is an important factor. This requires separators with excellent mechanical properties, lower closed cell temperatures and the ability to retain shape at higher temperatures. At present, polyolefin materials such as polypropylene and polyethylene are mainly adopted for large-scale commercialized lithium battery diaphragms, and with the fact that the performance requirements of lithium batteries are higher and higher, the thermal safety and the electrolyte maintaining capacity of diaphragms made of the two materials are difficult to meet the requirements, and the research and preparation of high-performance composite diaphragms made of other materials and polyolefin become the most important direction for diaphragm modification at present.
The traditional method for improving the heat resistance of the diaphragm mainly comprises the step of coating one or more heat-resistant coatings on the surface of a polyolefin substrate. If the literature mentions that the heat resistance of the diaphragm is improved by coating a layer of inorganic ceramic particles on the surface of the polyolefin substrate diaphragm, the safety performance of the battery cannot be fundamentally solved; the literature also mentions that the surface of the polyolefin substrate diaphragm is coated with a layer of modified inorganic ceramic particles to improve the heat resistance of the diaphragm, but the safety performance of the battery cannot be fundamentally solved; in addition, the literature mentions that a layer of heat-sensitive coating is coated on the surface of the polyolefin substrate diaphragm to improve the overcharge resistance of the battery, and because a large amount of polymer thermal expansion microspheres are added into the coating, the cycle and rate performance of the battery are reduced.
Disclosure of Invention
The traditional method for solving the heat resistance of the diaphragm is to coat one or more layers of heat-resistant coatings on the surface of the polyolefin substrate diaphragm so as to improve the heat resistance of the diaphragm, but the method only improves the safety performance of the battery and cannot fundamentally solve the safety problem of the battery.
In order to overcome the defects of the prior art, the invention aims to provide a diaphragm containing a coating layer and a lithium ion battery containing the diaphragm, wherein the coating layer is coated by a mixed system containing microspheres with a core-shell structure, the microspheres have the core-shell structure, namely comprise a shell layer and a core, the material for forming the shell layer comprises a thermosensitive polymer, and the material for forming the core comprises a ceramic material. The diaphragm containing the coating layer cannot change in the conventional use process, but when the lithium ion battery is heated to reach a thermosensitive temperature range (such as 120-140 ℃) of the thermosensitive polymer, the thermosensitive polymer is melted and can be melted to form a protective layer, the protective layer can prevent lithium ions from passing through, and thermal runaway caused by a large amount of heat released by further reaction of the anode and the cathode of the battery is avoided, so that the safety performance of the battery is fundamentally solved.
Specifically, the invention provides the following technical scheme:
a ceramic microsphere having a core-shell structure, comprising a shell layer and a core, the shell layer being formed from a material comprising a thermosensitive polymer and the core being formed from a material comprising a ceramic material.
According to the invention, the ceramic microspheres can be used in the field of lithium ion batteries, and also can be used in the field of semiconductors, coatings, and primary batteries or secondary batteries of other ionic systems.
According to the invention, in the microsphere, the mass ratio of the shell layer to the core is (15-1200): 100-500).
According to the invention, in the microsphere, the shell layer has a thickness of 1nm-1000nm, preferably 50nm-100 nm. For example 1nm, 10nm, 50nm, 100nm, 200nm, 500nm or 1000 nm.
According to the invention, the microspheres have an average particle size of 0.01 μm to 10 μm. For example, 0.01. mu.m, 0.05. mu.m, 0.1. mu.m, 0.5. mu.m, 1. mu.m, 4. mu.m, 5. mu.m, 8. mu.m or 10 μm.
According to the invention, the heat-sensitive polymer is chosen from thermoplastic polymers which can form a relatively stable system with the electrolyte and which have phase-changing properties. The thermosensitive temperature range of the thermosensitive polymer is, for example, 100 ℃ to 140 ℃. Illustratively, the thermosensitive polymer is selected from at least one of polystyrene, polyethylene, polymethyl methacrylate, polyacrylic acid-butadiene-styrene, polylactic acid, polyvinyl chloride, polyvinyl butyral, and the like, or a monomer-modified copolymerized polymer thereof.
According to the invention, the particle size of the ceramic material is between 0.01 and 20 μm. For example, 0.01. mu.m, 0.05. mu.m, 0.1. mu.m, 0.5. mu.m, 1. mu.m, 4. mu.m, 5. mu.m, 8. mu.m, 10. mu.m, 12. mu.m, 15. mu.m, 18. mu.m or 20. mu.m.
According to the present invention, the ceramic material is at least one selected from the group consisting of silica, alumina, zirconia, magnesium hydroxide, boehmite, barium sulfate, fluorophlogopite, fluoroapatite, mullite, cordierite, aluminum titanate, titania, copper oxide, zinc oxide, boron nitride, aluminum nitride, magnesium nitride, attapulgite and the like.
According to the invention, when the temperature of the microsphere reaches a thermosensitive interval, the surface thermosensitive polymer is melted, and the melted thermosensitive polymer forms a protective layer, so that lithium ions can be prevented from passing through the protective layer, thermal runaway caused by a large amount of heat released by further reaction of the anode and the cathode of the battery is avoided, and the safety performance of the battery is fundamentally solved.
The invention also provides a preparation method of the ceramic microsphere, which comprises the following steps:
coating a shell forming material comprising a thermosensitive polymer on the surface of a core forming material comprising a ceramic material by adopting a liquid phase coating method or a solid phase coating method to prepare the microsphere; the microsphere has a core-shell structure, namely comprises a shell layer and a core, wherein the shell layer is made of a thermosensitive polymer, and the core is made of a ceramic material.
Illustratively, in the case of the liquid phase coating method, the liquid phase coating method includes the steps of:
dissolving the material for forming the shell layer in a solvent in a stirring manner to form a solution containing the material for forming the shell layer; adding a material for forming a core into the solution, and stirring and mixing uniformly; and removing the solvent in the mixed system by vacuum heating drying or spray drying and the like to obtain the microsphere, wherein the microsphere has a core-shell structure, namely comprises a shell layer and a core, the shell layer is formed by a material comprising a thermosensitive polymer, and the core is formed by a material comprising a ceramic material.
Wherein the solvent is at least one selected from cresol, benzene, acetone, N-methyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylformamide and tetrahydrofuran.
Illustratively, in the case of the solid phase coating method, the solid phase coating method includes the steps of:
and (3) performing solid phase coating on the material for forming the shell layer and the material for forming the core in a stirring, ball milling and mechanical fusion mode, and then heating to the temperature of the thermosensitive interval of the thermosensitive polymer to form a coating layer on the surface of the material for forming the core by the material for forming the shell layer.
The invention also provides a diaphragm which comprises a diaphragm base layer and a coating layer positioned on at least one side surface of the diaphragm base layer, wherein the coating layer is obtained by coating at least one side surface of the diaphragm base layer with a mixed system comprising the ceramic microspheres.
According to the invention, the thickness of the coating layer is 1-10 μm, for example 2-5 μm, such as 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, and the coating layer may be applied once or several times.
According to the present invention, if the separator includes a separator base layer and coating layers on both side surfaces of the separator base layer, the thicknesses of the coating layers on both side surfaces may be the same or different.
According to the invention, the mixed system also comprises at least one of a polymer binder and an auxiliary agent. For example, the mixing system includes a polymeric binder and an auxiliary agent.
According to the invention, the mixed system comprises the following components in parts by weight:
10-90 parts by mass of the ceramic microspheres, 0-20 parts by mass of a polymer binder and 0-10 parts by mass of an auxiliary agent.
For example, the mass parts of the components in the mixed system are as follows:
10-90 parts by mass of the ceramic microspheres, 1-20 parts by mass of a polymer binder and 1-10 parts by mass of an auxiliary agent.
For example, the ceramic microspheres are 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, or 90 parts by mass.
For example, the polymer binder is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 15, 18, or 20 parts by mass.
For example, the mass part of the above-mentioned auxiliary is 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 mass parts.
According to the present invention, the mixed system further comprises 100-5000 parts by mass of a solvent.
According to the invention, the polymer binder is selected from polytetrafluoroethylene, polyvinylidene fluoride-hexafluoropropylene, polyimide, polyacrylonitrile, poly (methyl) acrylate, aramid resin, poly (meth) acrylic acid, Styrene Butadiene Rubber (SBR), polyvinyl alcohol, polyvinyl acetate, carboxymethyl cellulose (CMC), sodium carboxymethyl cellulose (CMC-Na), carboxyethyl cellulose, polyacrylamide, phenolic resin, epoxy resin, aqueous polyurethane, ethylene-vinyl acetate copolymer, polyacrylic copolymer, polystyrene lithium sulfonate, aqueous silicone resin, butyronitrile-polyvinyl chloride blend, styrene-acrylic latex, pure benzene latex and the like, and one or more combinations of blends and copolymers derived from the modification of the aforementioned polymers.
According to the present invention, the auxiliary agent is selected from at least one of polybranched alcohol, triethyl phosphate, polyethylene glycol, fluorinated polyethylene oxide, stearic acid, sodium dodecylbenzenesulfonate, sodium hexadecylsulfonate, fatty acid glyceride, sorbitan fatty acid ester and polysorbate.
According to the present invention, the solvent is at least one selected from the group consisting of water, methanol, ethanol, acetone, N-methyl-2-pyrrolidone (NMP), chloroform, xylene, tetrahydrofuran, o-chlorobenzaldehyde, hexafluoroisopropanol, N-dimethylformamide, methyl ethyl ketone and acetonitrile.
The invention also provides a preparation method of the diaphragm, wherein the method comprises the following steps:
(a) adding the ceramic microspheres, optional polymer binder and optional auxiliary agent into a solvent, and mixing to obtain mixed slurry;
(b) and (b) coating the mixed slurry obtained in the step (a) on the surface of a diaphragm base layer, and drying to obtain the diaphragm.
According to the invention, in the step (a), in the mixed slurry, the mass parts of the ceramic microspheres, the optional polymer binder, the optional auxiliary agent and the solvent are as follows:
10-90 parts by mass of the ceramic microspheres, 0-20 parts by mass of a polymer binder (for example, 1-20 parts by mass), 0-10 parts by mass of an auxiliary agent (for example, 1-10 parts by mass), and 100 parts by mass of a solvent (for example, 5000 parts by mass).
According to the present invention, in the step (b), the coating is performed by, for example, spray coating, dip coating, gravure printing, extrusion coating, transfer coating, or the like.
According to the invention, in step (b), the porosity of the membrane substrate is 20-80%, the thickness is 5-50 μm, and the pore size is D <80 nm; the material system of the diaphragm base layer is at least one selected from polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, polystyrene, polynaphthalene, polyimide, polyamide, aramid fiber, poly (p-phenylene benzobisoxazole) and the like.
The invention also provides a lithium ion battery which comprises the diaphragm.
According to the invention, when the lithium ion battery is at thermal runaway or heat-sensitive temperature, a micro short circuit is formed inside the lithium ion battery, and the safety of the lithium ion battery is higher than that of the conventional lithium ion battery.
The invention has the beneficial effects that:
the invention provides a ceramic microsphere, a diaphragm containing the ceramic microsphere and a lithium ion battery containing the diaphragm. The invention is different from the traditional lithium ion battery diaphragm, adopts the polymer orientation design coating method to screen the thermosensitive polymer coating ceramic material, and can effectively improve the high-temperature safety performance of the lithium ion battery by coating the microsphere containing the thermosensitive polymer coating ceramic material on the surface of the diaphragm on the premise of not influencing the performance of the lithium ion battery.
The invention screens a thermosensitive polymer which is stable in electrolyte as a shell material of the microsphere, the thermosensitive polymer does not dissolve, swell and the like in the electrolyte, the polymer is taken as a coating layer, a solid-phase coating method or a liquid-phase coating method is adopted to prepare the microsphere with the thermosensitive polymer uniformly coating the ceramic material, the microsphere is uniformly mixed with an optional polymer binder, an optional auxiliary agent, a solvent and the like, and then the diaphragm with the thermosensitive barrier property is obtained on the surface of a diaphragm substrate by the technologies of direct spraying, dip coating, gravure printing, extrusion coating, transfer coating and the like, and the lithium ion battery assembled by the diaphragm, a positive electrode, a negative electrode, the electrolyte and the like has good safety.
Compared with the conventional safety lithium ion battery with high-temperature defects, the lithium ion battery has the following advantages:
1. the microsphere is relatively stable with most of solvents and electrolytes, can not be dissolved or swelled, effectively coats a ceramic material and has a heat-sensitive effect. The lithium ion battery is formed at a temperature of 60-90 ℃ in the production process, and the lithium ion battery is easy to generate heat and lose control in an environment of more than 160 ℃ so as to effectively improve the safety of the lithium ion battery, so that a thermosensitive polymer with a thermosensitive interval temperature of 100-140 ℃ is selected as a coating material of the microspheres;
2. the microsphere has good compatibility with the existing lithium ion battery manufacturing system, can be directly introduced into a production system, and reduces the processing cost;
3. the microsphere does not need to be additionally provided with an additional coating layer, can effectively reduce the influence on the performance of the lithium ion battery, and has good safety performance;
4. when the microspheres are heated to reach a thermosensitive interval, the coating layer containing the thermosensitive polymer begins to melt, and one or more isolating layers are formed on the surface and inside the coating layer, so that free shuttling of lithium ions in the lithium ion battery can be effectively prevented, and the thermal runaway degree of the lithium ion battery is reduced or thermal runaway is avoided.
Drawings
Fig. 1 is a diagram showing a construction of a separator in a normal state according to a preferred embodiment of the present invention.
FIG. 2 is a view showing a structure of a separator in a high temperature state according to a preferred embodiment of the present invention.
FIG. 3 is a schematic structural diagram of the microsphere according to a preferred embodiment of the present invention. Wherein, the 'organic layer' is the shell layer of the microsphere, and the material thereof comprises a thermosensitive polymer; the "inorganic layer" is the core of the microsphere, wherein the material comprises a ceramic material.
Figure 4 is a plot of cell ARC test "temperature-voltage-time" for example 1 and comparative example 1 separators.
Fig. 5 is a graph showing the results of rate tests of batteries assembled by the separators of example 1 and comparative example 1.
Fig. 6 is a graph showing the results of cycle tests of batteries assembled by the separators of example 1 and comparative example 1.
Detailed Description
The preparation method of the present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
The term "parts" in the following examples is to be construed as parts by mass unless otherwise specified.
Example 1
And (2) dissolving 20 parts of polylactic acid in cresol in a stirring manner to form a mixed solution, adding 200 parts of aluminum oxide, stirring and mixing uniformly, and removing the solvent in the mixture by a spray drying technology to obtain the microsphere of the thermosensitive polymer coated ceramic material.
In the prepared microsphere, the shell layer is polylactic acid, and the core is aluminum oxide; the mass ratio of the shell layer to the core is 20:200, the thickness of the shell layer is 10nm, and the average grain diameter of the microsphere is about 0.8 μm.
Adding 80 parts of the prepared microspheres, 20 parts of polyvinylidene fluoride-hexafluoropropylene and 2 parts of polyethylene glycol into 900 parts of acetone, uniformly mixing to obtain mixed slurry, coating the mixed slurry on the surface of a diaphragm base layer through a micro-gravure, and drying to obtain the diaphragm.
The diaphragm is a wet-process substrate diaphragm with the thickness of 12 mu m, the single surface of the diaphragm is coated, the coating thickness is 4 mu m, and the total areal density of the diaphragm is 14.4g/m2。
And preparing a lithium ion battery cell by laminating or winding the diaphragm, the anode and the cathode, and the like, and baking, injecting, forming and packaging to obtain the high-safety lithium ion battery.
Example 2
Dissolving 20 parts of polyacrylic acid-butadiene-styrene in cresol by stirring to form a mixed solution, adding 200 parts of aluminum oxide, stirring and mixing uniformly, and removing the solvent in the mixture by a spray drying technology to obtain the microsphere of the thermosensitive polymer coated ceramic material.
In the prepared microsphere, a shell layer is polyacrylic acid-butadiene-styrene, and a core is aluminum oxide; the mass ratio of the shell layer to the core is 20:200, the thickness of the shell layer is 10nm, and the average grain diameter of the microsphere is about 0.8 μm.
Adding 80 parts of the prepared microspheres, 20 parts of polyvinylidene fluoride-hexafluoropropylene and 2 parts of polyethylene glycol into 900 parts of acetone, uniformly mixing to obtain mixed slurry, coating the mixed slurry on the surface of a diaphragm base layer through a micro-gravure, and drying to obtain the diaphragm.
The diaphragm is a wet-process substrate diaphragm with the thickness of 12 mu m, the single surface of the diaphragm is coated, the coating thickness is 4 mu m, and the total areal density of the diaphragm is 14.4g/m2。
And preparing a lithium ion battery cell by laminating or winding the diaphragm, the anode and the cathode, and the like, and baking, injecting, forming and packaging to obtain the high-safety lithium ion battery.
Example 3
And dissolving 20 parts of polylactic acid in cresol by stirring to form a mixed solution, adding 200 parts of boehmite, stirring and mixing uniformly, and removing the solvent in the mixture by a spray drying technology to obtain the microspheres of the thermosensitive polymer coated ceramic material.
In the prepared microsphere, a shell layer is polylactic acid, and a core is boehmite; the mass ratio of the shell layer to the core is 20:200, the thickness of the shell layer is 10nm, and the average grain diameter of the microsphere is about 0.8 μm.
Adding 80 parts of the prepared microspheres, 20 parts of polyvinylidene fluoride-hexafluoropropylene and 2 parts of polyethylene glycol into 900 parts of acetone, uniformly mixing to obtain mixed slurry, coating the mixed slurry on the surface of a diaphragm base layer through a micro-gravure, and drying to obtain the diaphragm.
The diaphragm is a wet-process substrate diaphragm with the thickness of 12 mu m, the single surface of the diaphragm is coated, the coating thickness is 4 mu m, and the total areal density of the diaphragm is 14.4g/m2。
And preparing a lithium ion battery cell by laminating or winding the diaphragm, the anode and the cathode, and the like, and baking, injecting, forming and packaging to obtain the high-safety lithium ion battery.
Example 4
And (2) dissolving 20 parts of polylactic acid in cresol in a stirring manner to form a mixed solution, adding 200 parts of aluminum oxide, stirring and mixing uniformly, and removing the solvent in the mixture by a spray drying technology to obtain the microsphere of the thermosensitive polymer coated ceramic material.
In the prepared microsphere, the shell layer is polylactic acid, and the core is aluminum oxide; the mass ratio of the shell layer to the core is 20:200, the thickness of the shell layer is 10nm, and the average grain diameter of the microsphere is about 0.8 μm.
Adding 80 parts of the prepared microspheres, 20 parts of polymethyl (meth) acrylate and 2 parts of polyethylene glycol into 900 parts of acetone, uniformly mixing to obtain mixed slurry, coating the mixed slurry on the surface of a diaphragm base layer through a micro-gravure, and drying to obtain the diaphragm.
The diaphragm is a wet-process substrate diaphragm with the thickness of 12 mu m, the single surface of the diaphragm is coated, the coating thickness is 4 mu m, and the total areal density of the diaphragm is 14.4g/m2。
And preparing a lithium ion battery cell by laminating or winding the diaphragm, the anode and the cathode, and the like, and baking, injecting, forming and packaging to obtain the high-safety lithium ion battery.
Example 5
Dissolving 10 parts of polylactic acid and 10 parts of polyethylene in cresol in a stirring manner to form a mixed solution, adding 200 parts of aluminum oxide, stirring and mixing uniformly, and removing the solvent in the mixture by a spray drying technology to obtain the microsphere of the thermosensitive polymer coated ceramic material.
In the prepared microsphere, the shell layer is polylactic acid and polyethylene, and the core is aluminum oxide; the mass ratio of the shell layer to the core is 20:200, the thickness of the shell layer is 10nm, and the average grain diameter of the microsphere is about 0.8 μm.
Adding 80 parts of the prepared microspheres, 20 parts of polyvinylidene fluoride-hexafluoropropylene and 2 parts of polyethylene glycol into 900 parts of acetone, uniformly mixing to obtain mixed slurry, coating the mixed slurry on the surface of a diaphragm base layer through a micro-gravure, and drying to obtain the diaphragm.
The diaphragm is a wet-process substrate diaphragm with the thickness of 12 mu m, the single surface of the diaphragm is coated, the coating thickness is 4 mu m, and the total areal density of the diaphragm is 14.4g/m2。
And preparing a lithium ion battery cell by laminating or winding the diaphragm, the anode and the cathode, and the like, and baking, injecting, forming and packaging to obtain the high-safety lithium ion battery.
Example 6
And dissolving 500 parts of polylactic acid in cresol in a stirring manner to form a mixed solution, adding 400 parts of aluminum oxide, stirring and mixing uniformly, and removing the solvent in the mixture by a spray drying technology to obtain the microspheres of the thermosensitive polymer coated ceramic material.
In the prepared microsphere, the shell layer is polylactic acid, and the core is aluminum oxide; the mass ratio of the shell layer to the core is 500:400, the thickness of the shell layer is 200nm, and the average grain diameter of the microsphere is about 1.2 mu m.
Adding 80 parts of the prepared microspheres, 20 parts of polyvinylidene fluoride-hexafluoropropylene and 2 parts of polyethylene glycol into 900 parts of acetone, uniformly mixing to obtain mixed slurry, coating the mixed slurry on the surface of a diaphragm base layer through a micro-gravure, and drying to obtain the diaphragm.
The diaphragm is a wet-process substrate diaphragm with the thickness of 12 mu m, the single surface of the diaphragm is coated, the coating thickness is 4 mu m, and the total areal density of the diaphragm is 14.4g/m2。
And preparing a lithium ion battery cell by laminating or winding the diaphragm, the anode and the cathode, and the like, and baking, injecting, forming and packaging to obtain the high-safety lithium ion battery.
Example 7
Dissolving 1000 parts of polyacrylic acid-butadiene-styrene in cresol by stirring to form a mixed solution, adding 400 parts of aluminum oxide, stirring and mixing uniformly, and removing the solvent in the mixture by a spray drying technology to obtain the microsphere of the thermosensitive polymer coated ceramic material.
In the prepared microsphere, a shell layer is polyacrylic acid-butadiene-styrene, and a core is aluminum oxide; the mass ratio of the shell layer to the core is 1000:400, the thickness of the shell layer is 500nm, and the average grain diameter of the microsphere is about 1.5 mu m.
And adding 90 parts of the prepared microspheres, 10 parts of polyvinylidene fluoride-hexafluoropropylene and 2 parts of polyethylene glycol into 900 parts of acetone, uniformly mixing to obtain mixed slurry, coating the mixed slurry on the surface of a diaphragm base layer through a micro-gravure, and drying to obtain the diaphragm.
The diaphragm is a wet-process substrate diaphragm with the thickness of 12 mu m, single-side coating is carried out,the thickness of the coating layer is 4 mu m, and the total area density of the diaphragm is 14.4g/m2。
And preparing a lithium ion battery cell by laminating or winding the diaphragm, the anode and the cathode, and the like, and baking, injecting, forming and packaging to obtain the high-safety lithium ion battery.
Comparative example 1
Adding 80 parts of aluminum oxide, 20 parts of polyvinylidene fluoride-hexafluoropropylene and 2 parts of polyethylene glycol into 900 parts of acetone, uniformly mixing to obtain mixed slurry, coating the mixed slurry on the surface of a diaphragm base layer through a micro-gravure, and drying to obtain the diaphragm.
The diaphragm is a wet-process substrate diaphragm with the thickness of 12 mu m, the single surface of the diaphragm is coated, the coating thickness is 4 mu m, and the total areal density of the diaphragm is 14.4g/m2。
And preparing a lithium ion battery cell by laminating or winding the diaphragm, the anode and the cathode, and the like, and baking, injecting, forming and packaging to obtain the high-safety lithium ion battery.
Comparative example 2
Adding 20 parts of polylactic acid, 60 parts of aluminum oxide, 20 parts of polyvinylidene fluoride-hexafluoropropylene and 2 parts of polyethylene glycol into 900 parts of acetone, uniformly mixing to obtain mixed slurry, coating the mixed slurry on the surface of a diaphragm base layer through a micro-gravure, and drying to obtain the diaphragm.
The diaphragm is a wet-process substrate diaphragm with the thickness of 12 mu m, the single surface of the diaphragm is coated, the coating thickness is 4 mu m, and the total areal density of the diaphragm is 14.4g/m2。
And preparing a lithium ion battery cell by laminating or winding the diaphragm, the anode and the cathode, and the like, and baking, injecting, forming and packaging to obtain the high-safety lithium ion battery.
Test example 1
The lithium ion batteries prepared in examples 1 to 7 and comparative examples 1 to 2 were subjected to a voltage test and an internal resistance test, in which the lithium ion batteries prepared in examples 1 to 7 and comparative examples 1 to 2 were fully charged, then placed in an environment of 25 ℃ and 50% humidity, and the voltage and the internal resistance of the batteries in a full-charge state were measured using a voltage internal resistance meter (Anbo-Applent, model AT526B), and the results are shown in Table 1.
TABLE 1 results of Voltage test and internal resistance test of lithium ion batteries of examples 1 to 7 and comparative examples 1 to 2
Sample numbering Average voltage of lithium battery Lithium ion battery internal resistance
Example 1 4.2012V 11.68mΩ
Example 2 4.2013V 11.62mΩ
Example 3 4.2006V 11.39mΩ
Example 4 4.2011V 11.24mΩ
Example 5 4.2017V 11.69mΩ
Example 6 4.2011V 11.82mΩ
Example 7 4.2002V 11.19mΩ
Comparative example 1 4.2011V 12.06mΩ
Comparative example 2 4.2025V 16.46mΩ
Examples 1 to 7 use the microspheres of the thermal sensitive polymer coated ceramic material to be applied in the separator and assembled into the lithium ion battery, and it is known from the data in table 1 that after the lithium ion batteries prepared in examples 1 to 7 and comparative examples 1 to 2 are sorted, the voltage is normal, but the internal resistance of comparative example 2 is obviously increased because the permeability of lithium ions is affected by directly adding the thermal sensitive material into the slurry;
the lithium ion batteries prepared in example 1 and comparative example 1 were subjected to charge-discharge cycle and rate performance tests, and the charge-discharge cycle test was carried out by using a 1C charge/1C discharge system; the rate performance test was performed using a 0.2C charge/0.2C, 0.5C, 1C, 3C, 5C discharge regime, and the results are shown in fig. 5 and 6.
From the experimental results of comparative examples 1 to 7 and comparative examples 1 to 2, the following conclusions were drawn:
1. the thermosensitive polymer is directly added into the coating and applied to the lithium ion battery diaphragm, and the thermosensitive material can influence the permeability of lithium ions in the lithium ion battery, so that the internal resistance of the lithium ion battery is increased;
2. in the embodiments 1 to 7, the microspheres coated with the ceramic material by the thermosensitive polymer are applied to the lithium ion battery diaphragm, so that the internal resistance, the voltage and the charge-discharge cycle of the lithium ion battery are not influenced, and the application requirements are met.
Test example 2
The lithium ion batteries prepared in examples 1 to 7 and comparative examples 1 to 2 were subjected to internal resistance testing, in which the separators prepared in examples 1 to 7 and comparative examples 1 to 2 were treated at 90 ℃, 100 ℃ and 140 ℃ for 10 minutes, respectively, and then electrolyte was added dropwise to test the internal resistance of the separator, to obtain the results shown in table 2 below.
TABLE 2
Sample numbering Treatment at 90 deg.C Treatment at 100 deg.C Treatment at 140 deg.C
Example 1 11.54mΩ 187.12mΩ 4543.32Ω
Example 2 11.42mΩ 176.33mΩ 4757.43Ω
Example 3 11.43mΩ 173.30mΩ 4535.53Ω
Example 4 11.16mΩ 188.62mΩ 4432.64Ω
Example 5 11.37mΩ 187.34mΩ 4754.42Ω
Example 6 11.52mΩ 165.87mΩ 4165.54Ω
Example 7 11.46mΩ 154.62mΩ 4234.87Ω
Comparative example 1 12.14mΩ 12.23mΩ 12.03Ω
Comparative example 2 16.55mΩ 260.55mΩ 8260.11Ω
From the data in table 2 above, the experimental results of comparative examples 1 to 7, comparative examples 1 to 2, the following conclusions were drawn:
1. the temperature-sensitive interval of the temperature-sensitive polymer is 100-140 ℃;
2. the lithium ion battery using the microspheres containing the thermosensitive polymer coated ceramic material can well control or slow down the occurrence of thermal runaway.
Test example 3
The lithium ion batteries prepared in examples 1 to 7 and comparative examples 1 to 2 were subjected to puncture and extrusion tests, in which a full-charge cell obtained after charging and discharging of the lithium ion battery was treated at 140 ℃ for 10min, then cooled to normal temperature to perform puncture and extrusion experiments, and the battery conditions were observed, with the results shown in table 3.
TABLE 3
Sample numbering Puncture needle Extrusion
Example 1 By passing By passing
Example 2 By passing By passing
Example 3 By passing By passing
Example 4 By passing By passing
Example 5 By passing By passing
Example 6 By passing By passing
Example 7 By passing By passing
Comparative example 1 Thermal runaway fire Thermal runaway fire
Comparative example 2 By passing By passing
From the data in table 3 above, the following conclusions are drawn: when the microspheres coated with the ceramic material are applied to the diaphragm, the safety of the lithium ion battery can be effectively improved.
Test example 4
The lithium ion batteries prepared in example 1 and comparative example 1 were tested for temperature rise and voltage change due to exothermic reaction inside the cell using an adiabatic accelerated calorimeter test, as shown in fig. 4.
As can be seen from fig. 4, the experimental results comparing example 1 with comparative example 1 show that:
comparative example 1 a full-charge battery, in which the voltage of the battery is reduced as the temperature is increased, comparative example 1 shows thermal runaway of the battery at about 150 ℃, and ignition and explosion occur; example 1 a full-charge battery is characterized in that a thermosensitive polymer coats ceramic material microspheres at a temperature of 100 ℃ and starts to melt, so that the internal blocking of the battery is caused, and the voltage of the battery is reduced; therefore, in the embodiments 1 to 7, when the battery reaches the temperature-sensitive temperature range, the heat-sensitive polymer on the surface of the ceramic material microsphere coated by the heat-sensitive polymer is melted to form internal obstruction, so that the safety performance of the lithium ion battery is effectively improved.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A ceramic microsphere having a core-shell structure, comprising a shell layer and a core, the shell layer being formed from a material comprising a thermosensitive polymer and the core being formed from a material comprising a ceramic material.
2. The ceramic microsphere according to claim 1, wherein, in the microsphere, the mass ratio of the shell layer to the core layer is (15-1200): 100-500); and/or in the microsphere, the thickness of a shell layer is 1nm-1000 nm; and/or, in the microsphere, the average particle size of the microsphere is 0.01-10 μm.
3. The ceramic microspheres of claim 2, wherein the microspheres have a shell layer thickness of 50nm to 100 nm.
4. A method of preparing ceramic microspheres as claimed in any one of the claims 1-3, said method comprising the steps of:
coating a shell forming material comprising a thermosensitive polymer on the surface of a core forming material comprising a ceramic material by adopting a liquid phase coating method or a solid phase coating method to prepare the microsphere; the microsphere has a core-shell structure, namely comprises a shell layer and a core, wherein the shell layer is made of a thermosensitive polymer, and the core is made of a ceramic material.
5. The production method according to claim 4, wherein, in the case of using a liquid phase coating method, the liquid phase coating method comprises the steps of:
dissolving the material for forming the shell layer in a solvent in a stirring manner to form a solution containing the material for forming the shell layer; adding a material for forming a core into the solution, and stirring and mixing uniformly; removing the solvent in the mixed system through vacuum heating drying or spray drying and the like to obtain the microsphere, wherein the microsphere has a core-shell structure, namely comprises a shell layer and a core, the shell layer is formed by a material comprising a thermosensitive polymer, and the core is formed by a material comprising a ceramic material;
alternatively, in the case of a solid phase coating method, the solid phase coating method includes the steps of:
and (3) performing solid phase coating on the material for forming the shell layer and the material for forming the core in a stirring, ball milling and mechanical fusion mode, and then heating to the temperature of the thermosensitive interval of the thermosensitive polymer to form a coating layer on the surface of the material for forming the core by the material for forming the shell layer.
6. A separator comprising a separator base layer and a coating layer on at least one side surface of the separator base layer, the coating layer being coated on at least one side surface of the separator base layer from a hybrid system comprising the ceramic microspheres according to any one of claims 1 to 3.
7. A diaphragm according to claim 6, wherein the mixed system further comprises at least one of a polymeric binder and an auxiliary agent;
preferably, the mass parts of the components in the mixed system are as follows:
10-90 parts by mass of the ceramic microspheres, 0-20 parts by mass of a polymer binder and 0-10 parts by mass of an auxiliary agent;
still preferably, the mass parts of the components in the mixed system are as follows:
10-90 parts by mass of the ceramic microspheres, 1-20 parts by mass of a polymer binder and 1-10 parts by mass of an auxiliary agent.
8. The method for preparing the separator according to claim 6 or 7, wherein the method comprises the steps of:
(a) adding the ceramic microspheres, optional polymer binder and optional auxiliary agent into a solvent, and mixing to obtain mixed slurry;
(b) and (b) coating the mixed slurry obtained in the step (a) on the surface of a diaphragm base layer, and drying to obtain the diaphragm.
9. The method for preparing a separator according to claim 8, wherein, in the step (b), the porosity of the separator base layer is 20 to 80%, the thickness is 5 to 50 μm, and the pore size is D <80 nm;
preferably, the material system of the diaphragm base layer is selected from at least one of polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, polystyrene, polynaphthalene, polyimide, polyamide, aramid, and poly (p-phenylene benzobisoxazole).
10. A lithium ion battery comprising the separator of claim 6 or 7.
CN201910883021.5A 2019-09-18 2019-09-18 Ceramic microsphere, diaphragm containing ceramic microsphere and lithium ion battery containing diaphragm Pending CN112531291A (en)

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