CN116435713A - Diaphragm and battery comprising same - Google Patents
Diaphragm and battery comprising same Download PDFInfo
- Publication number
- CN116435713A CN116435713A CN202310461169.6A CN202310461169A CN116435713A CN 116435713 A CN116435713 A CN 116435713A CN 202310461169 A CN202310461169 A CN 202310461169A CN 116435713 A CN116435713 A CN 116435713A
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- Prior art keywords
- layer
- battery
- polymer
- separator
- negative electrode
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
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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
- H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
-
- 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
-
- 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
- H01M50/409—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
- H01M50/446—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
- H01M50/409—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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Ceramic Engineering (AREA)
- Secondary Cells (AREA)
- Cell Separators (AREA)
Abstract
The invention provides a separator and a battery including the same. Polymer microspheres with melting points between 90 ℃ and 130 ℃ are added into the ceramic layer, so that the diaphragm is closed before 130 ℃, lithium ions between the anode and the cathode in the battery are isolated from shuttling, and the aim of improving safety is fulfilled; meanwhile, a heat-resistant polymer layer is coated on the surface of the ceramic layer, so that the diaphragm is prevented from breaking holes at high temperature, the blocking effect of the diaphragm at high temperature is improved, the safety performance of the battery is improved, the graphite with amorphous carbon coated on the surface is further matched, the quick charge performance of the battery can be remarkably improved, and the prepared battery can be simultaneously provided with the quick charge performance and the safety performance.
Description
Technical Field
The invention belongs to the technical field of secondary batteries, and particularly relates to a diaphragm and a battery comprising the diaphragm.
Background
In recent years, lithium ion batteries have been widely used in the fields of smart phones, tablet personal computers, smart wear, electric tools, electric automobiles, and the like. With the wide application of lithium ion batteries, the service life and the application environment of the lithium ion batteries are continuously improved by consumers, so that the lithium ion batteries are required to have good safety performance while taking high quick charge performance into consideration.
Currently, the lithium ion battery has potential safety hazards in the use process, for example, when the temperature of the battery is increased to a certain degree, the internal temperature is out of control, serious safety accidents are easy to occur, and the lithium ion battery fires or even explodes. The main reason for the problem of thermal runaway of the battery is that on one hand, the heat resistance of the diaphragm is insufficient, so that the diaphragm is easy to shrink or even break holes at high temperature, and the positive and negative electrodes of the battery cannot be isolated; on the other hand, the diaphragm has too high a closing temperature, so that the diaphragm cannot be closed before thermal runaway, and even the ion channel in the battery cannot be blocked.
Under the current situation, there is an urgent need to develop a lithium ion battery with high safety, for example, by coating a heat-resistant layer on the surface of a separator, but coating a heat-resistant layer on the surface of a separator tends to improve only the heat shrinkage performance of the separator, and the safety problem of the battery cannot be thoroughly solved. Therefore, it is a primary task to develop a lithium ion battery with high safety while having excellent fast charge capability.
Disclosure of Invention
The invention aims to solve the problems that the existing lithium ion battery has potential safety hazard, the battery quick charge capability and the safety performance cannot be considered in the use process, and the like.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a separator comprising a separator substrate, a ceramic layer, a heat resistant polymer layer, and a glue layer; the ceramic layer is arranged on at least one side surface of the diaphragm substrate, the heat-resistant polymer layer is arranged on the surface of the ceramic layer, and the glue coating layer is arranged on the surface of the heat-resistant polymer layer;
the ceramic layer comprises ceramic powder, a binder and polymer microspheres; the heat resistant polymer layer comprises a heat resistant polymer; the adhesive layer includes an adhesive polymer.
According to an embodiment of the invention, the membrane has a closed cell temperature of 90 ℃ to 130 ℃, for example 90 ℃, 100 ℃, 110 ℃, 120 ℃ or 130 ℃. The closed pore temperature refers to the temperature at which the micropores in the separator close.
According to an embodiment of the present invention, the membrane rupture temperature of the membrane is 230 ℃ or higher, for example 230 ℃, 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃ or 350 ℃. The rupture temperature refers to the temperature at which the diaphragm blocked by the hole breaks the membrane (the diaphragm breaks), that is, the temperature at which the appearance of the diaphragm breaks after the diaphragm closes the hole.
According to an embodiment of the invention, the thickness of the ceramic layer is 1 μm to 10 μm, for example 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm or 10 μm.
According to an embodiment of the present invention, the ceramic powder is selected from at least one of alumina, boehmite, magnesium oxide, magnesium hydroxide, barium sulfate, barium titanate, zinc oxide, calcium oxide, silica, silicon carbide, nickel oxide.
According to an embodiment of the present invention, the binder is at least one selected from polytetrafluoroethylene, polyvinylidene fluoride-hexafluoropropylene, polyimide, polyacrylonitrile, poly (meth) acrylic acid methyl ester, aramid resin, poly (meth) acrylic acid, styrene Butadiene Rubber (SBR), polyvinyl alcohol, polyvinyl acetate, carboxymethyl cellulose (CMC), sodium carboxymethyl cellulose (CMC-Na), and carboxyethyl cellulose.
According to an embodiment of the present invention, the polymer microsphere is made of at least one material selected from polyethylene, polymethacrylic acid, polymethacrylate, polypropylene and polyvinylidene fluoride.
According to an embodiment of the present invention, the molecular weight of the polymer microsphere is 5 to 50 tens of thousands, the particle size distribution of the polymer microsphere is 0.1 to 10 μm (e.g., 0.1 μm, 0.2 μm, 0.5 μm, 0.8 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm or 10 μm), and the melting point of the polymer microsphere is 90 to 130 ℃ (e.g., 90 ℃, 100 ℃, 110 ℃, 120 ℃, or 130 ℃).
According to an embodiment of the present invention, in the ceramic layer, the ceramic powder is 50% -80% (e.g., 50%, 55%, 60%, 65%, 70%, 75%, 80%), the binder is 5% -40% (e.g., 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%), and the polymer microsphere is 10% -45% (e.g., 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%).
According to an embodiment of the invention, the thickness of the heat resistant polymer layer is 1 μm to 10 μm, for example 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm or 10 μm.
According to the embodiment of the invention, the heat-resistant polymer is at least one selected from aramid, polyimide, polyurethane, phosphonitrile chloride polymer, boron nitrogen polymer, polysulfone and polybenzimidazole.
According to an embodiment of the invention, the glue layer has a thickness of 1 μm to 10 μm, for example 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm or 10 μm.
According to the embodiment of the invention, the gumming polymer is at least one material selected from polytetrafluoroethylene, polyvinylidene fluoride-hexafluoropropylene modified and copolymers thereof, polyimide, polyacrylonitrile, polymethyl methacrylate and polyacrylic acid.
According to an embodiment of the present invention, the solvent used for preparing the ceramic layer, the heat-resistant polymer layer and the paste layer is at least one selected from the group consisting of acetone, tetrahydrofuran, methylene chloride, chloroform, dimethylformamide, N-methyl-2-pyrrolidone, cyclohexane, methanol, ethanol, isopropyl alcohol and water.
The invention also provides a battery, which comprises the separator.
According to an embodiment of the present invention, the battery includes a positive electrode sheet, a negative electrode sheet, a separator interposed between the positive electrode sheet and the negative electrode sheet, and a nonaqueous electrolyte.
According to the embodiment of the invention, the battery is a high-safety lithium ion battery with excellent quick charge capability.
According to an embodiment of the present invention, the positive electrode sheet includes a positive electrode current collector and a positive electrode active material layer coated on one or both side surfaces of the positive electrode current collector, the positive electrode active material layer including a positive electrode active material, a conductive agent, and a binder.
According to an embodiment of the present invention, the positive electrode active material is selected from lithium cobaltate or lithium cobaltate subjected to a doping coating treatment of two or more elements of Al, mg, mn, cr, ti, zr, and the chemical formula of the lithium cobaltate subjected to the doping coating treatment of two or more elements of Al, mg, mn, cr, ti, zr is Li x Co 1-y1-y2-y3-y4 A y1 B y2 C y3 D y4 O 2 The method comprises the steps of carrying out a first treatment on the surface of the X is more than or equal to 0.95 and less than or equal to 1.05,0.01, y1 is more than or equal to 0.1, y2 is more than or equal to 0.01 and less than or equal to 0.1, y3 is more than or equal to 0 and less than or equal to 0.1, y4 is more than or equal to 0 and less than or equal to 0.1, and A and B, C, D are selected from two or more elements of Al, mg, mn, cr, ti, zr.
According to an embodiment of the present invention, the negative electrode sheet includes a negative electrode current collector and a negative electrode active material layer coated on one or both side surfaces of the negative electrode current collector, the negative electrode active material layer including a negative electrode active material, a conductive agent, and a binder.
According to an embodiment of the present invention, the negative electrode active material is at least one selected from the group consisting of graphite coated with amorphous carbon on the surface, a composite material of graphite coated with amorphous carbon on the surface and silicon oxide, and a composite material of graphite coated with amorphous carbon on the surface and nano silicon.
Wherein, in the composite material of graphite with amorphous carbon coated on the surface and silicon oxide, the content of silicon oxide is 1-15 wt%. In the composite material of graphite with amorphous carbon coated on the surface and nano silicon, the content of nano silicon is 1-15 wt%.
The invention has the beneficial effects that:
the invention provides a separator and a battery including the same. The battery separator has the advantages that the safety performance of the battery can be effectively improved by reasonably designing the components of the ceramic layer, the heat-resistant polymer layer and the glue coating layer in the battery separator, and the battery separator can be further improved in quick charge performance by being matched with graphite with amorphous carbon coated on the surface as a negative electrode active substance. Specifically, polymer microspheres with melting points between 90 ℃ and 130 ℃ are added into the ceramic layer, so that the diaphragm is closed before 130 ℃, lithium ions between the anode and the cathode in the battery are isolated from shuttling, and the aim of improving safety is fulfilled; meanwhile, a heat-resistant polymer layer is coated on the surface of the ceramic layer, so that the diaphragm is prevented from breaking holes at high temperature, the blocking effect of the diaphragm at high temperature is improved, the safety performance of the battery is improved, graphite with amorphous carbon coated on the surface is further matched as a negative electrode active material, the quick charge performance of the battery can be remarkably improved, and the prepared battery can be simultaneously provided with the quick charge performance and the safety performance.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; the reagents, materials, etc. used in the examples described below are commercially available unless otherwise specified.
Comparative examples 1 to 4 and examples 1 to 9
The lithium ion batteries of comparative examples 1 to 4 and examples 1 to 9 were each prepared according to the following preparation method, except that the separator and the negative electrode were selected differently, and the specific differences are shown in table 1.
(1) Preparation of positive plate
LiCoO as positive electrode active material 2 Mixing polyvinylidene fluoride (PVDF) as binder and acetylene black as conductive agent at weight ratio of 97:1.0:2.0, adding N-methylpyrrolidone (NMP), and vacuum stirringStirring until the mixed system becomes anode slurry with uniform fluidity; uniformly coating the anode slurry on an aluminum foil with the thickness of 10 mu m; and baking the coated aluminum foil in 5 sections of ovens with different temperature gradients, drying the aluminum foil in an oven with the temperature of 120 ℃ for 8 hours, and rolling and slitting the aluminum foil to obtain the required positive plate.
(2) Preparation of negative plate
The preparation method comprises the steps of preparing a slurry from 96% by mass of artificial graphite anode material, 0.2% by mass of single-walled carbon nanotube (SWCNT) conductive agent, 1.0% by mass of conductive carbon black (SP) conductive agent, 1% by mass of sodium carboxymethylcellulose (CMC) binder and 1.8% by mass of styrene-butadiene rubber (SBR) binder by a wet process, coating the slurry on the surface of an anode current collector copper foil, and drying (temperature: 85 ℃ C., time: 5 h), rolling and die cutting to obtain the anode sheet. The artificial graphite anode material specifically selects artificial graphite 1 and artificial graphite 2, wherein the artificial graphite 1 is obtained after being purchased in a commercial way, the surface of the artificial graphite is not coated, the artificial graphite 2 is obtained after being purchased in a commercial way, and the surface of the artificial graphite is coated with a layer of amorphous carbon, and the details are shown in table 1.
(3) Preparation of nonaqueous electrolyte
In a glove box filled with argon (moisture)<10ppm, oxygen content<1 ppm), ethylene Carbonate (EC), propylene Carbonate (PC) and Propyl Propionate (PP) were uniformly mixed in a mass ratio of 2:1.5:2, and 14wt.% LiPF based on the total mass of the nonaqueous electrolytic solution was slowly added to the mixed solution 6 Stirring uniformly to obtain the non-aqueous electrolyte.
(4) Preparation of separator
Mixing polymer microspheres, alumina, polymethacrylic acid and water, and marking as a solution T; mixing a heat-resistant polymer and a DMAc solvent, and marking as a solution N; mixing the gumming polymer and DMAc solution, and marking as solution P;
coating the solution T on two sides of a membrane substrate PE with the thickness of 5 mu m by adopting a gravure roll coating mode, and drying to obtain a membrane with ceramic layers with the thickness of 2 mu m on two sides, wherein the membrane is named as a membrane TP; coating the solution N on two sides of a diaphragm TP in a gravure roll coating mode, and drying to obtain diaphragms with ceramic layers with the thickness of 2 mu m and heat-resistant polymer layers with the thickness of 2 mu m on the two sides, wherein the diaphragms are marked as diaphragms NP; the solution P is coated on the two sides of the diaphragm NP by adopting a gravure roll coating mode, and the diaphragm with the ceramic layer with the thickness of 2 mu m, the heat-resistant polymer layer with the thickness of 2 mu m and the rubberized layer with the thickness of 1 mu m on the two sides is obtained after drying.
Wherein, the types of polymer microspheres, the proportions of polymer microspheres, the melting point of the polymer, the types of heat-resistant polymers and the types of gumming polymers in the ceramic layer are shown in Table 1 in detail.
(5) Preparation of lithium ion batteries
Winding the prepared positive plate, diaphragm and negative plate to obtain a bare cell without liquid injection; and placing the bare cell in an outer packaging foil, injecting the prepared electrolyte into the dried bare cell, and performing the procedures of vacuum packaging, standing, formation, shaping, sorting and the like to obtain the required lithium ion battery.
Electrochemical performance tests were performed on the batteries obtained in the above comparative examples and examples, and the following description is given below:
1) 25 ℃ cycle experiment: the batteries obtained in the examples and the comparative examples were placed in an environment of (25.+ -. 2) ℃ and allowed to stand for 2-3 hours, when the battery body reached (25.+ -. 2), the cut-off current of the battery was 0.05C according to the 3C constant current charge, the battery was left for 5 minutes after full charge, then discharged to the cut-off voltage of 3.0V with the 3C constant current, the highest discharge capacity of the previous 3 cycles was recorded as the initial capacity Q, when the cycles reached 1000 times, the last discharge capacity Q of the battery was recorded, and the recording results are shown in Table 2.
The calculation formula used therein is as follows: capacity retention (%) =q 1 /Q×100％；
2) Thermal shock test at 150 ℃): the batteries obtained in the above examples and comparative examples were heated by convection or a circulating hot air box at an initial temperature of (25.+ -. 3) ℃ and a temperature change rate of (5.+ -. 2) °c/min, and then heated to (150.+ -. 2) °c, and after holding for 60 minutes, the test was ended, and the battery state results were recorded as shown in Table 2.
3) Closed cell test:
and baking the diaphragms obtained in the examples and the comparative examples at a certain temperature for 10min, testing the ventilation values of the diaphragms before and after baking, wherein when the ventilation values are increased by 10 times, the diaphragms begin to be closed, and when the ventilation values are increased by 100 times, the diaphragms are basically closed, and when the ventilation values are increased by 1000 times, the diaphragms are completely closed. And recording the corresponding baking temperature when the diaphragm is completely closed, namely the closed pore temperature of the diaphragm.
4) Membrane rupture test:
the diaphragms obtained in the examples and the comparative examples were subjected to TMA test, samples were cut into samples 4mm wide by 8mm long, the temperature was raised at a rate of 5 ℃/min and the applied force was 0.01N, and the temperature at which the diaphragms were broken was recorded as the rupture temperature of the diaphragms.
Table 1 composition of batteries of comparative examples 1 to 4 and examples 1 to 9
Table 2 results of the Performance test data for the separator of comparative examples 1 to 4 and examples 1 to 9
| Project | Closed cell temperature/°c | Rupture temperature/. Degree.C |
| Comparative example 1 | 143.2 | 153.2 |
| Comparative example 2 | 142.7 | 152.9 |
| Comparative example 3 | 143.6 | 267.4 |
| Comparative example 4 | 120.6 | 153.4 |
| Example 1 | 120.3 | 263.4 |
| Example 2 | 123.8 | 260.5 |
| Example 3 | 128.4 | 265.8 |
| Example 4 | 124.3 | 243.5 |
| Example 5 | 120.2 | 245.7 |
| Example 6 | 124.7 | 240.8 |
| Example 7 | 128.2 | 243.2 |
| Example 8 | 124.5 | 246.5 |
| Example 9 | 120.2 | 267.4 |
TABLE 3 Performance test results of the batteries of comparative examples 1 to 4 and examples 1 to 9
As can be seen from comparison of comparative examples 1 and 2, the battery obtained when assembled using the conventional separator and artificial graphite 1 can pass the furnace temperature test, but the quick charge capacity of the battery is greatly reduced, and after 1000 cycles, the battery has no capacity, which means that it cannot satisfy 1000 cycles; when the battery is assembled by adopting the conventional diaphragm and the artificial graphite 2, the quick charge capacity of the battery is remarkably improved, and when the battery is subjected to 1000 times of circulation, the capacity retention rate can reach 74.65 percent, but the safety performance of the battery is greatly reduced and the battery cannot pass the furnace temperature test. This may also indicate that the introduction of a fast-charge anode can deteriorate the safety performance of the battery. Comparison of comparative examples 2-4 and example 1 shows that the safety performance of the battery can be obviously improved, and meanwhile, the quick charge capability of the battery can be considered, so that the battery with the safety performance and the multiplying power performance can be obtained.
By comparing examples 1 to 8, it was found that a battery capable of achieving both safety performance and rate performance of the battery can be obtained by adjusting the compositions of the ceramic layer, the heat-resistant polymer layer, and the gel coat layer of the separator within a reasonable range. By comparing example 1 and example 9, it was found that the safety performance of the battery obtained when the separator of the present application and the artificial graphite 2 were assembled could be significantly improved while also maintaining the quick-charge capability of the battery. The diaphragm can avoid adverse effects of a fast-charge anode on battery safety performance.
In summary, according to the comparative example and the embodiment, the lithium ion battery assembled by the diaphragm can effectively improve the quick charge cycle life of the battery and simultaneously consider the safety performance of the battery.
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, improvement, etc. 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 separator, characterized in that the separator comprises a separator substrate, a ceramic layer, a heat resistant polymer layer and a glue layer; the ceramic layer is arranged on at least one side surface of the diaphragm substrate, the heat-resistant polymer layer is arranged on the surface of the ceramic layer, and the glue coating layer is arranged on the surface of the heat-resistant polymer layer;
the ceramic layer comprises ceramic powder, a binder and polymer microspheres; the heat resistant polymer layer comprises a heat resistant polymer; the adhesive layer includes an adhesive polymer.
2. The separator of claim 1, wherein the separator has a closed cell temperature of 90 ℃ to 130 ℃; and/or, the rupture temperature of the diaphragm is greater than or equal to 230 ℃.
3. The membrane of claim 1, wherein the ceramic layer has a thickness of 1 μm to 10 μm;
and/or, in the ceramic layer, the mass percent of the ceramic powder is 50% -80%, the mass percent of the binder is 5% -40%, and the mass percent of the polymer microsphere is 10% -45%.
4. The separator according to claim 1, wherein the ceramic powder is at least one selected from the group consisting of alumina, boehmite, magnesium oxide, magnesium hydroxide, barium sulfate, barium titanate, zinc oxide, calcium oxide, silica, silicon carbide, and nickel oxide;
and/or the material of the polymer microsphere is at least one selected from polyethylene, polymethacrylic acid, polymethacrylate, polypropylene and polyvinylidene fluoride.
5. The separator according to claim 1, wherein the molecular weight of the polymer microspheres is 5 to 50 ten thousand, the particle size distribution of the polymer microspheres is 0.1 to 10 μm, and the melting point of the polymer microspheres is 90 to 130 ℃.
6. The separator according to claim 1, wherein the thickness of the heat-resistant polymer layer is 1 μm to 10 μm;
and/or the heat-resistant polymer is at least one selected from aramid fiber, polyimide, polyurethane, phosphonitrile chloride polymer, boron nitrogen polymer, polysulfone and polybenzimidazole.
7. The membrane of claim 1, wherein the glue layer has a thickness of 1 μm to 10 μm;
and/or the material of the gumming polymer is at least one selected from polytetrafluoroethylene, polyvinylidene fluoride-hexafluoropropylene modified and copolymers thereof, polyimide, polyacrylonitrile, polymethyl methacrylate and polyacrylic acid.
8. A battery comprising the separator of any one of claims 1-7.
9. The battery of claim 8, wherein the battery comprises a positive electrode sheet, a negative electrode sheet, a separator interposed between the positive electrode sheet and the negative electrode sheet, and a nonaqueous electrolyte;
the negative electrode sheet includes a negative electrode current collector and a negative electrode active material layer coated on one or both side surfaces of the negative electrode current collector, the negative electrode active material layer including a negative electrode active material, a conductive agent, and a binder.
10. The battery according to claim 9, wherein the negative electrode active material is at least one selected from the group consisting of graphite coated with amorphous carbon on the surface, a composite material of graphite coated with amorphous carbon on the surface and silicon oxide, and a composite material of graphite coated with amorphous carbon on the surface and nano silicon.
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| CN202310461169.6A CN116435713A (en) | 2023-04-26 | 2023-04-26 | Diaphragm and battery comprising same |
| PCT/CN2024/087717 WO2024222501A1 (en) | 2023-04-26 | 2024-04-15 | Separator, and battery comprising same |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202310461169.6A CN116435713A (en) | 2023-04-26 | 2023-04-26 | Diaphragm and battery comprising same |
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| WO2024222501A1 (en) * | 2023-04-26 | 2024-10-31 | 珠海冠宇电池股份有限公司 | Separator, and battery comprising same |
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| KR102416526B1 (en) * | 2019-06-07 | 2022-07-01 | 삼성에스디아이 주식회사 | Separator for rechargeable lithium battery and rechargeable lithium battery including the same |
| CN110444718B (en) * | 2019-08-15 | 2022-04-19 | 宁德卓高新材料科技有限公司 | Preparation method of ceramic composite diaphragm with high-cohesiveness polymer coating film |
| CN113224465A (en) * | 2020-01-17 | 2021-08-06 | 厦门大学 | Ceramic diaphragm with multilayer composite structure and battery thereof |
| CN112652861A (en) * | 2020-12-21 | 2021-04-13 | 惠州锂威电子科技有限公司 | Lithium ion battery isolating membrane |
| CN116435713A (en) * | 2023-04-26 | 2023-07-14 | 珠海冠宇电池股份有限公司 | Diaphragm and battery comprising same |
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| WO2024222501A1 (en) * | 2023-04-26 | 2024-10-31 | 珠海冠宇电池股份有限公司 | Separator, and battery comprising same |
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