CN112038572A - Composite binder, electrode plate and manufacturing method thereof - Google Patents
Composite binder, electrode plate and manufacturing method thereof Download PDFInfo
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- CN112038572A CN112038572A CN201910478957.XA CN201910478957A CN112038572A CN 112038572 A CN112038572 A CN 112038572A CN 201910478957 A CN201910478957 A CN 201910478957A CN 112038572 A CN112038572 A CN 112038572A
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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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
- 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
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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- 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 invention discloses a composite binder, an electrode plate and a manufacturing method thereof. The composite binder includes a shape memory polymer and a heat sensitive material. The electrode plate comprises a current collector and an active layer material layer distributed on the surface of the current collector, wherein the active layer material layer comprises an electrode material, a conductive agent and the composite binder. When thermal runaway occurs, when the environmental temperature rises to the shape transition temperature of the composite binder and the thermal polymerization sealing temperature, the electrode structure change caused by the recovery of the memory effect polymer to the initial state and the thermal polymer heated sealing ion transmission channel are caused, so that powder particles of positive and negative active materials (namely electrode materials and conductive agents) on the electrode plate are separated from a metal current collector foil, the internal resistance of the battery is obviously increased, the heat productivity of the battery is effectively reduced, the continuous heat production of the battery is inhibited before the thermal runaway of the battery reaches the combustion temperature of the battery, and the safety performance of the battery is improved.
Description
Technical Field
The invention particularly relates to a composite binder, an electrode plate and a manufacturing method thereof, belonging to the technical field of electrode materials and preparation.
Background
The lithium ion battery has the characteristics of high specific energy, high specific power, long service life and the like, and is the first choice of the current vehicle and energy storage battery. In recent years, with the rapid development of new energy automobiles, the industrial scale of lithium ion power batteries is expanding. However, as the demand for battery capacity, specific energy and fast charging capability in the field of application is continuously increased, the design limits of materials and batteries are continuously challenged. In addition, the safety accidents of battery fire or explosion are frequent due to the problems of the consistency of battery batches, the thermal stability of materials, the compatibility among the components of the battery, the high flammability of the electrolyte and the like. The safety problem of the lithium ion battery becomes an important technical challenge to be solved urgently in the field of electric automobiles and energy storage.
Unsafe behavior of lithium ion batteries stems from their thermal runaway. Although some conventional safety measures can improve the safety of the battery in use to some extent, the problem of safety of the battery due to thermal runaway cannot be fundamentally solved. From an electrochemical point of view, the electrode reaction must be designed for electron transport and ion transport. If a temperature sensing mechanism is built in the battery, when the temperature of the battery is too high, the mechanism can respond in time and cut off the transmission of electrons or ions, and then the battery reaction can be closed, so that the battery is prevented from being heated greatly, and the battery is prevented from entering a self-heating thermal runaway state.
Disclosure of Invention
Aiming at the defects of the prior art, the invention mainly aims to provide a composite adhesive based on a polymer with a shape memory effect and a thermosensitive material, an electrode plate and a manufacturing method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
embodiments of the present invention provide a composite adhesive comprising a shape memory polymer and a heat sensitive material.
Further, the composite binder comprises: 60-85 wt% of shape memory polymer and 15-40 wt% of heat-sensitive material.
Further, the shape memory polymer includes a thermoplastic shape memory polymer and/or a thermosetting shape memory polymer.
In some more specific embodiments, the shape memory polymer comprises any one or a combination of two or more of shape memory polyimide, shape memory epoxy, cyanate ester, polynorbornene, styrene/butadiene copolymer, trans 1, 4-polyisoprene, crosslinked polyethylene, or ethylene/vinyl acetate copolymer, but not limited thereto.
In some more specific embodiments, the thermosensitive material includes any one or a combination of two or more of paraffin, ethylene-vinyl acetate copolymer, polylactic acid-polybutylene succinate, N '- (4, 4' -methylenediphenyl) bismaleimide, 1, 3-Dioxolane (DN)/tributylamine, poly (N-isopropylacrylamide-co-acrylamide), and poly (N-isopropylacrylamide-co-acrylamide), but is not limited thereto.
Further, the viscosity of the composite binder is 1000-1000 cps.
The embodiment of the invention also provides a manufacturing method of the composite binder, which comprises the following steps: and dispersing the thermosensitive material in a precursor solution of the shape memory polymer to form the composite binder.
In some more specific embodiments, the manufacturing method specifically includes: dispersing a thermosensitive material in a precursor solution of the shape memory polymer under stirring; the stirring speed is 1000-1000 rpm/min, the temperature is 10-50 ℃, and the time is 60-1440 min.
The embodiment of the invention also provides an electrode plate which comprises a current collector and an active layer material layer distributed on the surface of the current collector, wherein the active layer material layer comprises an electrode material, a conductive agent and the composite binder.
In some specific embodiments, the active layer material layer comprises 60 to 95 wt% of an electrode material, 2.5 to 20 wt% of a conductive agent and 2.5 to 20 wt% of a composite binder.
Further, when the temperature of the electrode pole piece exceeds a preset temperature, the electrode material and the conductive agent in the active layer material layer are stripped off from the current collector and the transmission of lithium ions in the electrode pole piece is blocked, so that the electrochemical reaction in the electrode pole piece is stopped.
Furthermore, the predetermined temperature is 110-220 ℃.
Furthermore, the mass fraction of the composite binder in the electrode plate is 1-5%.
In some more specific embodiments, the electrode material powder includes any one or a combination of two or more of lithium cobaltate, lithium iron phosphate, lithium manganate, lithium titanate, a sulfur/carbon composite positive electrode, natural graphite, artificial graphite, and silicon carbon, but is not limited thereto.
In some specific embodiments, the conductive agent includes one or a combination of two or more of acetylene black, krypton gold black, carbon nanotubes, and graphene, but is not limited thereto.
In some more specific embodiments, the current collector includes any one of, but is not limited to, copper foil, aluminum foil, carbon-coated copper foil, carbon-coated aluminum foil, copper mesh, aluminum mesh, and nickel foam.
Furthermore, the thickness of the current collector is 6-12 microns.
The embodiment of the invention also provides a manufacturing method of the electrode plate, which comprises the following steps: mixing electrode material powder, a conductive agent, a composite binder and a solvent to form slurry, coating the slurry on the surface of a current collector, and drying to form the electrode plate.
Furthermore, the mass ratio of the electrode material powder, the conductive agent and the composite binder is 90: 5-96: 1.5: 2.5.
Further, the drying treatment temperature is 60-120 ℃, and the time is 2-24 h.
In some more specific embodiments, the solvent includes any one or a combination of two or more of distilled water, N-dimethylacetamide, dimethylsulfoxide, tetrahydrofuran, dichloromethane, ethyl acetate, toluene, diethyl ether, acetonitrile, dimethyl carbonate, dimethyl sulfate, ethyl methyl carbonate, carbon tetrachloride, chloroform, methanol, ethanol, N-hexane, and N-heptane, but is not limited thereto.
Compared with the prior art, when thermal runaway occurs and the environmental temperature rises to the shape transition temperature of the composite binder and the thermal polymerization sealing temperature, the electrode structure change caused by the recovery of the memory effect polymer to the initial state and the ion transmission channel is sealed by the thermal sensitive polymer when being heated, so that powder particles of positive and negative active materials (namely electrode materials and conductive agents) on the electrode plate are separated from a metal current collector foil, the internal resistance of the battery is obviously increased, the heat productivity of the battery is effectively reduced, the continuous heat production of the battery is inhibited before the thermal runaway of the battery reaches the combustion temperature of the battery, and the safety performance of the battery is improved.
Drawings
FIG. 1 is an electron micrograph of an electrode sheet of example 1 of the present invention after the temperature thereof exceeded the shape change temperature;
fig. 2a and 2b are respectively internal resistance pictures of the battery manufactured by using the electrode plate in the embodiment 1 of the invention before and after the temperature exceeds the shape change temperature;
FIG. 3 is a battery capacity map of a battery manufactured using the electrode sheet in example 1 of the present invention before and after exceeding the temperature of the shape change.
Detailed Description
In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to provide technical solutions of the present invention. The technical solution, its implementation and principles, etc. will be further explained as follows.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, and in case of conflict, the definitions in this specification shall control. All percentages, parts, ratios, etc., are by weight unless otherwise indicated.
When a value or range of values, preferred range or list of lower preferable values and upper preferable values is given, it is to be understood that this specifically discloses all ranges formed from any pair of values, either of any lower range limit or preferred value and any higher range limit or preferred value, regardless of whether ranges are disclosed; where numerical ranges are described herein, unless otherwise stated, the ranges are intended to include the endpoints of the ranges and all integers, fractions, and integers within the ranges.
When the term "about" is used to describe a numerical value or an end of range, the disclosure should be understood to include that specific value or end of range.
The use of "a" and "an" to describe elements and components of the invention is merely for convenience and to give a general sense of the invention, and the description should be read to include one or at least one unless explicitly stated otherwise.
In the practical use process of the battery, the thermal runaway of the battery can be caused due to internal short circuit, overcharge, overdischarge, mechanical extrusion and the like, the combustion and even explosion of the battery are caused, and the personal and property safety is threatened, when thermal runaway occurs, when the environmental temperature rises to the shape transition temperature of the composite binder and the thermal polymerization sealing temperature, the structural change of the electrode caused by the recovery of the memory effect polymer to the initial state and the sealing of the ion transmission channel caused by the heating of the thermosensitive polymer are triggered, thereby separating the powder particles of the positive and negative active materials (namely the electrode material and the conductive agent) on the pole piece from the metal current collector foil, obviously increasing the internal resistance of the battery, effectively reducing the heat productivity of the battery, therefore, the battery is restrained from continuously generating heat before the thermal runaway of the battery reaches the combustion temperature of the battery, and the safety performance of the battery is improved.
Specifically, when the heating temperature of the high-safety electrode pole piece rises and exceeds the conversion temperature, the composite binder of the polymer/thermosensitive material with the shape memory effect can be subjected to physical change and/or chemical change, the shape memory polymer deforms, so that the electrode material and the conductive agent are stripped from the current collector and fall off, and meanwhile, the thermosensitive material is subjected to heat melting and thermal polymerization reaction, so that lithium ions are prevented from being transmitted inside the battery pole piece, and the electrochemical reaction of the pole piece is stopped. In some specific embodiments, the conversion temperature is 110 to 200 ℃; the physical change comprises one or more of fragmentation, pulverization, curling and folding; the chemical change comprises that when the temperature-sensitive material with the thermal polymerization property exceeds the conversion temperature, the monomer is polymerized to solidify the electrolyte or the oligomer is polymerized into a compact film, and then the transmission of lithium ions is blocked.
The embodiment of the invention provides a preparation method and application of a high-safety lithium battery pole piece based on a composite binder of a shape memory polymer and a thermosensitive material. This pole piece includes: a composite binder of an active material, a shape memory polymer and a thermosensitive material, a conductive agent and a current collector.
The term shape memory polymer, i.e. polymer with shape memory effect, also called shape memory polymer, refers to a polymer material which can restore the initial shape of a product with the initial shape by the stimulation of external conditions (such as heat, electricity, light, chemical induction, etc.) after the initial condition is changed and fixed under certain conditions; the thermosensitive material is a material which is sensitive to temperature and generates physical and chemical changes such as deformation, polymerization and the like when the temperature exceeds a conversion temperature.
In one embodiment, the shape memory polymer is one of a thermoplastic shape memory polymer, a thermosetting shape memory polymer, or a composite of the two in any proportion. The thermoplastic shape memory polymer is characterized in that a high molecular chain forms a fixed phase and a reversible phase in a physical crosslinking mode; when the temperature is raised to be higher than the glass transition temperature (Tg), the microscopic Brownian motion of the reversible phase molecular chain is intensified, the stationary phase is still in a solidified state, at the moment, the shape memory polymer is deformed by a certain external force, the external force is kept for cooling the shape memory polymer, and the reversible phase is solidified to obtain a stable new shape, namely a deformed shape; when the temperature is raised to be higher than Tg, the reversible phase is softened, the fixed phase is kept solidified, the reversible phase molecular chain is reactivated in motion, and the thermodynamic equilibrium state is gradually reached under the action of the restoring stress of the fixed phase, namely the macroscopic appearance is the restored state.
The thermosetting shape memory polymer is prepared through heating the polymer to over the melting point (Tm), mixing with cross-linking agent, cross-linking reaction in mold, determining the shape, cooling and crystallizing to obtain the initial state with the chemical cross-linking structure as the fixed phase and the crystalline phase as the reversible phase. When the temperature is increased to be higher than Tm, the reversible phase is melted and softened, can be made into any shape under the action of external force, keeps external force, is cooled and fixed, and enables the molecular chain to be directionally frozen along the direction of the external force to obtain a deformed shape; when the temperature is increased to be higher than Tm, the reversible phase molecular chain is naturally curled under the action of entropy elasticity until reaching a thermodynamic equilibrium state, so that the reversible phase molecular chain is subjected to shape recovery and remembers the shape once.
Depending on the shape memory characteristic of the polymer substrate, the battery pole piece is folded and bent into a certain shape within the glass transition temperature range of the substrate, the deformation is fixed after the temperature is reduced, the light-emitting diode is driven to deform and return to the original shape through external stimulation, and the driving mode is one or more of heat, solution, pH value, electricity, magnetism, electromagnetism and light; the deformation recovery rate of the shape memory polyimide substrate is 90-99%, and the shape memory polyimide substrate can completely recover to the original shape within 20-60 s.
In a preferred embodiment, the shape memory polymer used in the present invention is a shape memory polyimide and the heat sensitive materials used are N, N '- (4, 4' -methylenediphenyl) Bismaleimide (BMI) and Azobisisobutyronitrile Initiator (AIBN).
In a preferred embodiment, the precursor solution of the shape memory polyimide is a polyamic acid solution prepared by the following process:
(1) adding 1, 3-bis (3-aminophenoxy) benzene and 4, 4' -bis (4-aminophenoxy) into N, N-dimethylacetamide, and stirring for 20-30 min under the conditions of nitrogen protection and room temperature to form a mixed system;
(2) and adding bisphenol A type diether dianhydride into the mixed system, and stirring for 18-24 hours under the conditions of nitrogen protection and room temperature to obtain a polyamic acid solution.
Preferably, the mass ratio of the 1, 3-bis (3-aminophenoxy) benzene to the 4, 4' -bis (4-aminophenoxy) benzene is 1 to (0.3-5.1); the mass ratio of the bisphenol A type diether dianhydride to the 1, 3-bis (3-aminophenoxy) benzene to the 4, 4' -bis (4-aminophenoxy) is 1: 0.4-0.7;
in some preferred embodiments, the heat-sensitive material precursor solution is prepared by stirring and mixing BMI in N, N-dimethylacetamide, and then adding AIBN to perform magnetic stirring and mixing, wherein the mass fraction of BMI in the heat-sensitive material precursor solution is 1-5%, the mass fraction of AIBN in the heat-sensitive material precursor solution is 0.005-0.05%, the mixing is performed by magnetic stirring (the preferred rotation speed is 1000-2000 rpm/min), and the mixing temperature is preferably room temperature.
In some preferred embodiments, the preparation method of the composite binder is to mix the polyamic acid solution and the heat-sensitive material precursor solution by magnetic stirring at room temperature, preferably, the rotation speed of the magnetic stirring is 1000-5000 rpm/min, and the temperature is room temperature.
In some preferred embodiments, the composite binder is pre-heated to improve its properties, in particular: heating the polyamic acid solution from room temperature to 80-100 ℃ at a heating rate of 1-2 ℃/min, keeping the temperature for 1 to 2 hours at the temperature of 80 to 100 ℃, then heating to 100 to 130 ℃ at the heating rate of 1 to 2 ℃/min, keeping the temperature for 1 to 2 hours at the temperature of between 100 and 130 ℃, then heating the temperature to between 160 and 190 ℃, keeping the temperature for 1 to 2 hours at the temperature of between 160 and 190 ℃, continuously heating to between 190 and 210 ℃ at the heating rate of between 1 and 2 ℃/min, keeping the temperature for 1 to 2 hours at the temperature of between 190 and 210 ℃, heating the mixture to between 230 and 250 ℃ at the heating rate of between 1 and 2 ℃/min, and preserving heat for 1-2 h at the temperature of 230-250 ℃, namely finishing the thermal amidation in a gradual heating and heat preservation mode.
In a preferred scheme, the composite binder, active material powder and a conductive agent are mixed to carry out the process steps of slurry mixing, coating, drying, rolling, slitting and the like so as to prepare the high-safety electrode plate.
Example 1:
step 1: preparing a precursor solution of shape memory polyimide: polyamic acid solution
Adding 1, 3-bis (3-aminophenoxy) benzene and 4, 4' -bis (4-aminophenoxy) into N, N-dimethylacetamide, stirring for 20min under the condition of nitrogen protection and room temperature, adding bisphenol A type diether dianhydride, continuously stirring for 24h to obtain a polyamic acid solution, and stopping introducing nitrogen; wherein the mass ratio of the 1, 3-bis (3-aminophenoxy) benzene to the 4, 4' -bis (4-aminophenoxy) benzene is 1: 0.9; the mass ratio of the bisphenol A type diether dianhydride to the 1, 3-bis (3-aminophenoxy) benzene to the 4, 4' -bis (4-aminophenoxy) biphenyl is 1: 0.62;
step 2: composite binder for preparing shape memory polymer/thermosensitive material
Slowly dripping heat-sensitive polymer precursor solution into the uniformly dispersed polyamic acid precursor solution under the condition of continuous stirring, wherein the mass fraction of BMI in the composite binder solution is 0.5-5%, the mass fraction of AIBN in the composite binder solution is 0.005-0.05%, the stirring speed is 1000-10000 rpm/min, the temperature is 10-50 ℃, and the time is 60-1440 min.
The method comprises the following steps of preheating the composite binder in a step-by-step temperature rising and preserving manner to improve the temperature sensitivity of the composite binder, wherein the specific process of carrying out thermal amidation in the step-by-step temperature rising and preserving manner comprises the following steps: heating the polyamic acid solution from room temperature to 80-100 ℃ at a heating rate of 1-2 ℃/min, keeping the temperature for 1 to 2 hours at the temperature of 80 to 100 ℃, then heating to 100 to 130 ℃ at the heating rate of 1 to 2 ℃/min, keeping the temperature for 1 to 2 hours at the temperature of between 100 and 130 ℃, then heating the temperature to between 160 and 190 ℃, keeping the temperature for 1 to 2 hours at the temperature of between 160 and 190 ℃, continuously heating to between 190 and 210 ℃ at the heating rate of between 1 and 2 ℃/min, keeping the temperature for 1 to 2 hours at the temperature of between 190 and 210 ℃, heating the mixture to between 230 and 250 ℃ at the heating rate of between 1 and 2 ℃/min, keeping the temperature for 1 to 2 hours at the temperature of 230 to 250 ℃, namely finishing the thermal amidation in a gradual heating and heat preservation mode;
and step 3: preparation of electrode sheet
The invention relates to a preparation method of a high-safety lithium ion battery pole piece, which comprises the following steps: and sequentially carrying out slitting and die cutting processes on the coated high-capacity electrode slice, and then carrying out a rolling process to obtain the high-compaction-density electrode slice.
The present embodiment shows a specific operation:
1) mixing a positive active material, a conductive agent SP, a conductive agent KS-6 and PVDF according to a conventional proportion to form slurry; in the embodiment, the positive active substance is a nickel-cobalt-manganese ternary positive material, the proportion of the positive material, the conductive agent SP and the composite binder is 91: 2: 3: 4, the mass fraction of BMI in the composite binder is 1%, the positive material, the conductive agent SP and the composite binder are added into a homogenizer for mixing, and then NMP is added for mixing until the viscosity of slurry is controlled to be 5500 +/-500 mpa · s, the solid content is 65-75%, and the fineness is controlled to be less than 30 mu m.
2) Uniformly coating the mixed slurry on a common aluminum foil current collector with the thickness of 12 mu m, wherein the tensile strength of the aluminum foil is 160 Mpa; the density of the coated surface of one surface is 16mg/cm2The density of the coated surface of the both surfaces is 32mg/cm2(ii) a Placing the coated pole roll in vacuum at 80 deg.CStanding the mixture in an oven for 12 h; the width B of the current collector 1 is 430mm, and the width a of the coating 2 is 400 mm.
3) Cutting the dried polar roll by a splitting machine, die-cutting by a die-cutting machine according to the VDA size, selecting a pair roller with the diameter of 300mm, and compacting the roll according to the design density of 3.65g/cm3Rolling; roll gap: 130 μm, pressure 30MPa, speed 2 m/min.
4) And (4) making the rolled pole piece, trimming and deburring to finish the preparation of the qualified electrode piece.
The current collector prepared by the method after rolling the pole piece has no wrinkles and smooth coating, and can obtain high load capacity and surface density of 32mg/cm under the continuous production condition2The high compaction density is 3.6mg/cm3Pole pieces (exerting material compaction limits).
Raising the temperature of the electrode plate, wherein when an electron microscope image of the electrode plate after the temperature exceeds the shape change temperature (which can also be understood as the transformation temperature) is shown in fig. 1, a battery is manufactured by using the electrode plate manufactured as described above, and the temperature of the manufactured battery is tested, and internal resistance diagrams of the battery before and after the temperature exceeds the shape change temperature are respectively shown in fig. 2a and fig. 2b, wherein fig. 2a is the internal resistance diagram of the battery before the temperature exceeds the shape change temperature, and fig. 2b is the internal resistance diagram of the battery after the battery; the change in battery capacity before and after the battery exceeds the shape change temperature is shown in fig. 3.
Example 2: the procedure and parameters of this example are substantially the same as those of example 1, except that the composite binder in this example comprises 60 wt% of the shape memory polymer and 40 wt% of the thermosensitive material, and the mass fraction of the BMI in the composite binder is 2%;
and the active layer material layer for manufacturing the formed electrode comprises 60 wt% of electrode material, 20 wt% of conductive agent and 20 wt% of composite binder.
Example 3: the procedure and parameters of this example are substantially the same as those of example 1, except that the composite binder in this example comprises 85 wt% of the shape memory polymer and 15 wt% of the thermosensitive material, and the mass fraction of the BMI in the composite binder is 5%;
and the active layer material layer of the formed electrode comprises 95 wt% of electrode material, 2.5 wt% of conductive agent and 2.5 wt% of composite binder.
Example 4: the procedure and parameters of this example are substantially the same as those of example 1, except that the composite binder in this example comprises 70 wt% of the shape memory polymer and 20 wt% of the thermosensitive material, and the mass fraction of the BMI in the composite binder is 3 wt%;
and the active layer material layer of the formed electrode comprises 60-95 wt% of electrode material, 2.5-20 wt% of conductive agent and 2.5-20 wt% of composite binder.
Example 5: the procedure and parameters of this example are substantially the same as those of example 1, except that the composite binder in this example comprises 80 wt% of the shape memory polymer and 20 wt% of the thermosensitive material, and the mass fraction of the BMI in the composite binder is 5 wt%;
and the active layer material layer for manufacturing the formed electrode comprises 80 wt% of electrode material, 10 wt% of conductive agent and 10 wt% of composite binder.
The transition temperature and the internal resistance of the composite binders of examples 1 to 5 were as shown in table 1:
TABLE 1 transition temperature and internal resistance changes of the composite binders of examples 1-5
The change in battery capacity before and after exceeding the shape change temperature of the batteries fabricated from the electrode sheets provided in examples 1 to 5 was substantially identical to the result in example 1.
It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, which are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and therefore, the protection scope of the present invention is not limited thereby. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. A composite binder is characterized by comprising a shape memory polymer and a heat-sensitive material.
2. The composite binder of claim 1, comprising: 60-85 wt% of shape memory polymer and 15-40 wt% of thermosensitive material; and/or, the shape memory polymer comprises a thermoplastic shape memory polymer and/or a thermoset shape memory polymer; and/or the shape memory polymer comprises any one or the combination of more than two of shape memory polyimide, shape memory epoxy resin, cyanate ester, polynorbornene, styrene/butadiene copolymer, trans-1, 4-polyisoprene, cross-linked polyethylene or ethylene/vinyl acetate copolymer; the thermosensitive material comprises any one or a combination of more than two of paraffin, ethylene-vinyl acetate copolymer, polylactic acid-polybutylene succinate, N '- (4, 4' -methylene diphenyl) bismaleimide, 1, 3-Dioxolane (DN)/tributylamine, poly (N-isopropylacrylamide-co-acrylamide) and poly (N-isopropylacrylamide-co-acrylamide), and/or the viscosity of the composite binder is 1000-1000 cps.
3. A method of making a composite binder as claimed in any one of claims 1 to 2, comprising: and dispersing the thermosensitive material in a precursor solution of the shape memory polymer to form the composite binder.
4. The manufacturing method according to claim 3, characterized by specifically comprising: dispersing a thermosensitive material in a precursor solution of the shape memory polymer under stirring; the stirring speed is 1000-1000 rpm/min, the temperature is 10-50 ℃, and the time is 60-1440 min.
5. The utility model provides an electrode plate, includes the mass flow body and distributes at the active layer material layer of current collector surface which characterized in that: the active layer material layer comprises an electrode material, a conductive agent and the composite binder of any one of claims 1-2.
6. The electrode sheet of claim 5, wherein: the active layer material layer comprises 60-95 wt% of electrode material, 2.5-20 wt% of conductive agent and 2.5-20 wt% of composite binder; and/or when the temperature of the electrode pole piece exceeds a preset temperature, the electrode material and the conductive agent in the active layer material layer are stripped from the current collector and fall off, the transmission of lithium ions in the electrode pole piece is blocked, and the electrochemical reaction in the electrode pole piece is stopped; and/or the preset temperature is 110-220 ℃; and/or the mass fraction of the composite binder in the electrode plate is 1-5%.
7. The electrode sheet of claim 5, wherein: the electrode material powder comprises any one or the combination of more than two of lithium cobaltate, lithium iron phosphate, lithium manganate, lithium titanate, a sulfur/carbon composite anode, natural graphite, artificial graphite and silicon carbon; and/or the conductive agent comprises one or the combination of more than two of acetylene black, krypton gold black, carbon nanotubes and graphene; and/or the current collector comprises any one of copper foil, aluminum foil, carbon-coated copper foil, carbon-coated aluminum foil, copper mesh, aluminum mesh and foamed nickel; and/or the thickness of the current collector is 6-12 mu m.
8. A method of making an electrode sheet as claimed in any one of claims 5 to 7, comprising: mixing electrode material powder, a conductive agent, a composite binder and a solvent to form slurry, coating the slurry on the surface of a current collector, and drying to form the electrode plate.
9. The method of manufacturing according to claim 8, wherein: the mass ratio of the electrode material powder to the conductive agent to the composite binder is 90: 5-96: 1.5: 2.5.
10. The method of manufacturing according to claim 8, wherein: the drying treatment temperature is 60-120 ℃, and the drying treatment time is 2-24 h; and/or the solvent comprises any one or the combination of more than two of distilled water, N, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dichloromethane, ethyl acetate, toluene, diethyl ether, acetonitrile, dimethyl carbonate, dimethyl sulfate, methyl ethyl carbonate, carbon tetrachloride, chloroform, methanol, ethanol, N-hexane and N-heptane.
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