CN111564591B - Lithium metal battery diaphragm modified slurry and application thereof - Google Patents

Lithium metal battery diaphragm modified slurry and application thereof Download PDF

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Publication number
CN111564591B
CN111564591B CN202010365105.2A CN202010365105A CN111564591B CN 111564591 B CN111564591 B CN 111564591B CN 202010365105 A CN202010365105 A CN 202010365105A CN 111564591 B CN111564591 B CN 111564591B
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lithium metal
metal battery
graphite fluoride
modified
diaphragm
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CN111564591A (en
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宫勇吉
肖京
翟朋博
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Beijing zhongruitai New Material Co.,Ltd.
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Beihang University
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403Manufacturing processes of separators, membranes or diaphragms
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/42Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409Separators, membranes or diaphragms characterised by the material
    • H01M50/411Organic material
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409Separators, membranes or diaphragms characterised by the material
    • H01M50/431Inorganic material
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention discloses a lithium metal battery diaphragm modified slurry and application thereof, wherein the modified slurry is prepared from a graphite fluoride nanosheet dispersion liquid and a polymer base material, and the weight-volume ratio of the polymer base material to the graphite fluoride nanosheet dispersion liquid is 30-70 mg: 1ml, the concentration of the graphite fluoride nano-sheet dispersion liquid is 1-2 mg/ml; and uniformly coating the modified slurry on one surface of a commercial separator, and drying in vacuum to obtain the modified separator of the lithium metal battery. When the lithium metal battery modified diaphragm is applied to the assembly of a lithium metal battery, a layer of graphite fluoride/polyvinylidene fluoride protective layer can be formed on the surface of a lithium metal electrode in situ, the growth of lithium dendrites is favorably inhibited, the lithium metal negative electrode is effectively stabilized, the lithium affinity and the mechanical property are better, the interface resistance is lower, the cycle life of the lithium metal battery can be prolonged, the preparation is simple, and the lithium metal battery modified diaphragm is suitable for the large-scale production of the lithium metal battery diaphragm.

Description

Lithium metal battery diaphragm modified slurry and application thereof
Technical Field
The invention belongs to the technical field of lithium metal battery manufacturing, and particularly relates to a lithium metal battery diaphragm modified slurry and application thereof.
Background
With the continuous development of electronic devices, people also put higher and higher demands on the energy density, power density, cycle life and other indexes of rechargeable batteries. Meanwhile, the updating speed of the lithium ion battery technology based on the lithium ion topological intercalation principle is gradually behind the social development, and how to further improve the performance index of the rechargeable battery has important significance for the production and life of human beings. Among the negative electrode materials of many rechargeable batteries, lithium metal has received much attention from researchers due to its advantages of low electrochemical potential and low density.
However, the lithium metal electrode has problems of severe volume expansion and uncontrollable growth of lithium dendrite during battery cycling, which becomes a bottleneck that the lithium metal battery is difficult to commercialize. Among the methods for inhibiting the growth of lithium dendrites to stabilize the lithium metal negative electrode, the diaphragm modification technology has the outstanding advantages of simple and convenient operation, low cost and the like.
Therefore, the synthesis of the modified lithium metal battery separator with reasonable selection of the separator modified material and simple and cheap becomes a key for the commercialization of the lithium metal battery.
In view of this, the present invention is proposed.
Disclosure of Invention
The invention provides a lithium metal battery diaphragm modified slurry, which is prepared from a graphite fluoride nanosheet dispersion liquid and a polymer base material, wherein the weight volume ratio of the polymer base material to the graphite fluoride nanosheet dispersion liquid is 30-70 mg: 1ml, and the concentration of the graphite fluoride nano-sheet dispersion liquid is 1-2 mg/ml.
Specifically, the polymer base material has a relatively high dielectric constant, can be used as a modification material of artificial SEI on the surface of a lithium metal cathode, separates highly active lithium metal from organic electrolyte, effectively prevents the electrolyte from harmfully corroding the lithium metal cathode in the battery circulation process, and provides basic mechanical properties for inhibiting the growth of lithium dendrites by the molecular network of the polymer base material; on the other hand, the uniform introduction of the graphite fluoride nano-sheets can structurally improve the mechanical strength of the polymer and enhance the inhibition effect of the polymer substrate on the growth of lithium dendrites, meanwhile, the graphite fluoride and lithium metal react to further generate LiF and graphite nano-sheets in situ, so that a large number of lithium ion transmission channels and lithium metal nucleation sites are provided while the original SEI is improved in situ, and the surface bonding strength of the polymer substrate and the lithium metal cathode is improved.
In the above technical scheme, the weight-volume ratio of the polymer base material to the graphite fluoride nanosheet dispersion is 45-55 mg: 1 ml.
In particular, with the above volume ratio, a slurry with moderate viscosity and fluidity can be obtained, thus facilitating the mechanical coating and sizing thereof on the separator.
In the technical scheme, the concentration of the graphite fluoride nanosheet dispersion liquid is 1-2 mg/ml.
Specifically, the fluorinated graphite nanosheet dispersion liquid with the concentration can effectively enhance the mechanical strength of the polymer base material, has a good effect of improving the affinity between the polymer base material and lithium metal, does not need to be further concentrated, and is simple in process and cost-saving.
Further, in the above technical scheme, the polymer base material is one or more of sodium alginate, sodium carboxymethyl cellulose, styrene butadiene rubber and polyvinylidene fluoride.
Preferably, in the above technical solution, the polymer base material is a molecular weight (1.0-1.2) × 106The polyvinylidene fluoride polymer of (1).
Still further, in the above technical solution, the graphite fluoride nanosheet dispersion is an N-methylpyrrolidone dispersion of graphite fluoride nanosheets.
In detail, in the technical scheme, N-methyl pyrrolidone molecules can be inserted between graphite fluoride layers, so that the mechanical stripping efficiency of the graphite fluoride can be greatly improved; meanwhile, N-methylpyrrolidone (NMP) is used as a slurry mixed solvent commonly used by the lithium ion battery system, polyvinylidene fluoride can be fully dissolved, and uniform mixing of graphite fluoride and polyvinylidene fluoride is conveniently realized.
Preferably, in the above technical solution, the N-methylpyrrolidone dispersion liquid of graphite fluoride nanoplatelets is prepared by the following method: mixing graphite fluoride and N-methyl pyrrolidone, heating and stirring, ultrasonically stripping, centrifugally separating, naturally settling, and taking an upper layer solution.
Specifically, in the preparation process of the N-methylpyrrolidone dispersion liquid of the graphite fluoride nanosheets, the weight volume ratio of the graphite fluoride to the N-methylpyrrolidone is 1 g: mixing 60-90 ml.
Specifically, in the preparation process of the N-methylpyrrolidone dispersion liquid of the graphite fluoride nanosheets, the heating and stirring temperature and time are 70-90 ℃ and 3-7h, preferably 80 ℃ and 5-6h, respectively.
Specifically, in the preparation process of the N-methylpyrrolidone dispersion liquid of the graphite fluoride nanosheets, the temperature and time of ultrasonic stripping are 15-25 ℃ and 24-40h respectively.
Specifically, in the preparation process of the N-methylpyrrolidone dispersion liquid of the graphite fluoride nanosheets, the rotation speed and the time of centrifugal separation are 2500-3200rpm and 25-40min respectively.
Specifically, in the preparation process of the N-methylpyrrolidone dispersion liquid of the graphite fluoride nanosheet, the natural sedimentation is normal-temperature light-resistant sedimentation, and the sedimentation time is 7-20d, preferably 14-18 d.
The invention also provides a method for coating the lithium metal battery diaphragm by using the lithium metal battery diaphragm modified slurry, which comprises the following steps:
and uniformly coating the modified slurry of the lithium metal battery diaphragm on one surface of a commercial diaphragm, and drying in vacuum to obtain a finished product.
In the technical scheme, the temperature and the time of the vacuum drying are respectively 50-75 ℃ and 9-15 h.
In the above technical solution, the thickness, average pore diameter and void ranges of the commercial separator are 12-20 μm, 0.1-0.2 μm and 40-60%, respectively.
Preferably, in the above technical solution, the commercial diaphragm is a commercial polypropylene diaphragm.
The invention also provides a lithium metal battery modified diaphragm prepared by the method.
The invention also provides a lithium metal battery, which comprises a positive electrode material, a negative electrode material and the modified diaphragm of the lithium metal battery, wherein the modified diaphragm of the lithium metal battery is arranged between the positive electrode material and the negative electrode material.
The invention has the advantages that:
(1) according to the invention, the lithium metal battery diaphragm modified slurry prepared from the graphite fluoride nanosheet dispersion liquid and the polymer base material is coated on a commercial diaphragm to prepare the lithium metal battery modified diaphragm, and when the lithium metal battery modified diaphragm is applied to the assembly of a lithium metal battery, a graphite fluoride/polyvinylidene fluoride protective layer can be formed on the surface of a lithium metal electrode in situ, so that the growth of lithium dendrites can be inhibited, and the lithium metal cathode can be effectively stabilized;
(2) compared with the pure polyvinylidene fluoride modified diaphragm, the lithium metal battery modified diaphragm provided by the invention has better lithium affinity and mechanical property, lower interface resistance and longer cycle life of the lithium metal battery;
(3) the preparation method of the modified lithium metal battery diaphragm provided by the invention has the advantages of simple process, low equipment requirement, easily available and cheap raw materials, and suitability for large-scale production of the lithium metal battery diaphragm.
Drawings
FIG. 1 is an XRD spectrum of fluorinated graphite nanoplatelets (GFNs) prepared according to example 1 of the present invention;
FIG. 2 is a TEM photograph of fluorinated graphite nanoplatelets (GFNs) prepared according to example 1 of the present invention;
FIG. 3 is a mechanical property test curve of a graphite fluoride nanosheet/polyvinylidene fluoride modified diaphragm prepared in experimental example 2 of the present invention and a polyvinylidene fluoride modified diaphragm prepared in comparative example 1 under a universal testing machine;
FIG. 4 is a mechanical property test curve of a fluorinated graphite nanosheet/polyvinylidene fluoride modified diaphragm prepared in Experimental example 2 of the present invention and a polyvinylidene fluoride modified diaphragm prepared in comparative example 1 under a nanoindentor;
fig. 5 is a cycle test chart of a lithium metal button cell assembled by a graphite fluoride nanosheet/polyvinylidene fluoride modified membrane prepared in experimental example 2 of the present invention, a polyvinylidene fluoride modified membrane prepared in comparative example 1, and an unmodified original membrane;
fig. 6 is SEM photographs of a lithium metal negative electrode of a lithium metal button cell assembled by a fluorinated graphite nanosheet/polyvinylidene fluoride modified membrane prepared in experimental example 2 of the present invention at different cycle times (where 6a, 6b, and 6c are SEM photographs of the lithium metal negative electrode after 10 cycles, 20 cycles, and 30 cycles, respectively, and 6d is a cross-sectional SEM photograph of the lithium metal negative electrode after 30 cycles);
fig. 7 is SEM photographs of a lithium metal negative electrode of the polyvinylidene fluoride-modified separator-assembled lithium metal button cell prepared in comparative example 1 of the present invention at different cycle times (where, 7a, 7b, and 7c are SEM photographs of the lithium metal negative electrode after 10, 20, and 30 cycles of cycle, respectively, and 7d is a cross-sectional SEM photograph of the lithium metal negative electrode after 30 cycles of cycle);
fig. 8 is SEM photographs of lithium metal negative electrodes of unmodified raw separator assembled lithium metal coin cells of the present invention at different cycle numbers (where 8a, 8b, and 8c are SEM photographs of lithium metal negative electrodes after 10, 20, and 30 cycles of cycling, respectively, and 8d is a cross-sectional SEM photograph of lithium metal negative electrodes after 30 cycles of cycling).
Detailed Description
The following describes the embodiments of the present invention in further detail with reference to specific examples.
The following examples are intended to illustrate the present invention, but not to limit the scope of the invention, which is defined by the claims.
Unless otherwise specified, the test reagents and materials used in the examples of the present invention are commercially available.
Unless otherwise specified, the technical means used in the examples of the present invention are conventional means well known to those skilled in the art.
Example 1
The embodiment of the invention provides a graphite fluoride nanosheet dispersion liquid, and the preparation method comprises the following steps:
adding 1g of graphite fluoride into 80mL of N-methylpyrrolidone, heating to 80 ℃ in a water bath kettle, and stirring for 3-7h under the condition of heat preservation; then, taking out the mixed solution, cooling to room temperature, then placing the mixed solution in an ultrasonic machine for ultrasonic treatment at normal temperature for 30 hours to prepare a mother solution, and then centrifuging the mother solution in a centrifugal machine at the rotating speed of 3000rpm for 30 minutes; and finally, standing the centrifuged solution in a dark place for 14-18d, and taking the upper layer solution to obtain the compound.
Example 2
The embodiment of the invention provides a graphite fluoride nanosheet/polyvinylidene fluoride modified diaphragm, and the preparation method comprises the following steps:
s1, preparing a lithium metal battery diaphragm modified slurry, specifically comprising the steps of weighing 50mg of polyvinylidene fluoride powder, adding the polyvinylidene fluoride powder into 1mL of the graphite fluoride nanosheet dispersion prepared in the embodiment 1, and fully stirring until the slurry is transparent and does not contain the polyvinylidene fluoride powder;
s2, uniformly coating the modified slurry of the lithium metal battery diaphragm prepared in the step S1 on the surface of a polypropylene diaphragm, then placing the polypropylene diaphragm in a vacuum drying box, carrying out vacuum drying for 12 hours at the temperature of 60 ℃, cooling and taking out for later use.
Comparative example 1
The invention provides a polyvinylidene fluoride modified diaphragm, and the preparation method comprises the following steps:
s1, weighing 50mg of polyvinylidene fluoride powder, adding the polyvinylidene fluoride powder into 1mL of N-methyl pyrrolidone, and fully stirring until the slurry is transparent and does not contain polyvinylidene fluoride powder;
s2, uniformly coating the slurry prepared in the step S1 on the surface of a polypropylene diaphragm, then placing the polypropylene diaphragm into a vacuum drying box, carrying out vacuum drying for 12 hours at the temperature of 60 ℃, cooling and taking out for later use.
Results testing
Fig. 1 and 2 are an XRD spectrum and a transmission electron microscope photograph of graphite fluoride nano-Sheets (GFNs) prepared in example 1 of the present invention, respectively. As can be seen from fig. 1, the (001) characteristic peak appearing at 2 θ ═ 13 ° indicates that the exfoliated graphite fluoride nanoplatelets still retain a high fluorine content, while the (002) characteristic peak appearing at 2 θ ═ 26 ° indicates the layered stacking manner of the graphite fluoride nanoplatelets graphene; as can be seen from fig. 2, the prepared graphite fluoride nanoplatelets are uniform in thickness and disordered in atomic arrangement due to the high fluorine content.
In addition, the mechanical properties of the fluorinated graphite nanosheet/polyvinylidene fluoride modified diaphragm prepared in experimental example 2 and the polyvinylidene fluoride modified diaphragm prepared in comparative example 1 were detected by a universal testing machine and a nanoindenter, respectively, and the specific method was as follows:
the slurries of experimental example 2 and comparative example 1 were poured into teflon molds, respectively, placed in a vacuum drying oven, vacuum-dried at 60 c for 12 hours to prepare films, which were then tested using a universal tester and a nanoindenter, respectively, and the results are shown in fig. 3 to 4.
FIG. 3 shows the tensile length on the abscissa and the stress on the ordinate; fig. 4 shows displacement on the abscissa and load on the ordinate. The result shows that the mechanical property of the material is obviously improved by adding the graphite fluoride nano-sheet, and the tensile strength and the compressive strength are greatly improved.
In addition, the electrochemical test performance of the graphite fluoride nanosheet/polyvinylidene fluoride modified diaphragm prepared in experimental example 2, the polyvinylidene fluoride modified diaphragm prepared in comparative example 1 and an unmodified original diaphragm was tested.
The specific experimental method is as follows: the electrochemical performance test adopts a CR2032 type button battery, and takes the graphite fluoride nanosheet/polyvinylidene fluoride modified diaphragm prepared in experimental example 2, the polyvinylidene fluoride modified diaphragm prepared in comparative example 1 and an unmodified original diaphragm as diaphragms, lithium iron phosphate as a positive electrode, lithium metal as a negative electrode and ether-based battery electrolyte as the electrolyte. The battery cycling process is controlled by a battery tester (Land CT 3001A).
The experimental results are shown in figure 5; in the figure, GFNs/PVDF @ PP represents a fluorinated graphite nanosheet/polyvinylidene fluoride composite modified membrane, PVDF @ PP represents a polyvinylidene fluoride modified membrane, and PP represents an untreated membrane; in fig. 5, the abscissa represents the number of cycles, the left ordinate represents the specific discharge capacity, and the right ordinate represents the coulombic efficiency.
The result shows that compared with the polyvinylidene fluoride modified diaphragm and the original diaphragm, the diaphragm modified by the fluorinated graphite nanosheet/polyvinylidene fluoride composite material has the advantages that the cycle life of the lithium metal battery is greatly prolonged, and the coulombic efficiency is improved.
Fig. 6, 7 and 8 are SEM photographs of a lithium metal negative electrode of a lithium metal button cell assembled with a fluorinated graphite nanosheet/polyvinylidene fluoride modified membrane prepared in experimental example 2 of the present invention, a polyvinylidene fluoride modified membrane prepared in comparative example 1, and an unmodified original membrane, respectively, at different cycle times.
As can be seen from the comparative analysis of fig. 6-8, the diaphragm modified by the fluorinated graphite nanosheet/polyvinylidene fluoride composite can generate a protective layer on the surface of the lithium metal negative electrode in the battery cycle process, so that the growth of lithium dendrites on the surface of the negative electrode is mechanically inhibited and the lithium metal negative electrode is protected from being further corroded by the organic electrolyte; although a PVDF protective layer can be generated on the surface of the negative electrode by adopting the polyvinylidene fluoride modified diaphragm, the single PVDF protective layer is broken and loses efficacy within limited cycle number due to poor lithium affinity and low mechanical strength of the PVDF material; the original lithium metal negative electrode has no protective layer, so a large amount of lithium dendrites are generated on the surface, and the surface lithium metal deposition layer is easy to fall off from a current collector to form dead lithium.
Finally, the above is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. 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 (6)

1. The lithium metal battery diaphragm modified slurry is characterized by being prepared from a graphite fluoride nanosheet dispersion liquid and a polymer base material, wherein the polymer base material is a polymer with a molecular weight of (1.0-1.2) x 106The polyvinylidene fluoride polymer, the lithium metal battery diaphragm modified slurry is used for forming a layer of graphite fluoride/polyvinylidene fluoride protective layer on the surface of a lithium metal electrode in situ; the weight volume ratio of the polymer base material to the graphite fluoride nanosheet dispersion is 45-55 mg: 1ml, wherein the concentration of the graphite fluoride nano-sheet dispersion liquid is 1.4-1.85 mg/ml;
the graphite fluoride nanosheet dispersion liquid is an N-methyl pyrrolidone dispersion liquid of graphite fluoride nanosheets; the N-methylpyrrolidone dispersion liquid of the graphite fluoride nanosheet is prepared by the following method: mixing graphite fluoride and N-methyl pyrrolidone, heating and stirring, ultrasonically stripping, centrifugally separating, naturally settling, and taking an upper layer solution; the rotation speed and the time of the centrifugal separation are 2500-3200rpm and 25-40min respectively; the natural sedimentation is normal-temperature light-resistant sedimentation, and the sedimentation time is 14-18 d;
in the preparation process of the N-methylpyrrolidone dispersion liquid of the graphite fluoride nanosheet:
the weight volume ratio of the graphite fluoride to the N-methyl pyrrolidone is 1 g: mixing 60-90 ml; the heating and stirring temperature and time are respectively 80 ℃ and 5-6 h; the temperature and time of the ultrasonic stripping are respectively 15-25 ℃ and 24-40 h.
2. A method of coating a lithium metal battery separator with the lithium metal battery separator modified slurry of claim 1, comprising:
and uniformly coating the modified slurry of the lithium metal battery diaphragm on one surface of a commercial diaphragm, and drying in vacuum to obtain a finished product.
3. The method of claim 2,
the temperature and the time of the vacuum drying are respectively 50-75 ℃ and 9-15 h;
and/or the thickness, average pore size and void ranges of said commercial separator are 12-20 μm, 0.1-0.2 μm and 40-60% respectively.
4. The method of claim 3, wherein the commercial membrane is a commercial polypropylene membrane.
5. The modified lithium metal battery separator prepared according to the method of any one of claims 2-4.
6. A lithium metal battery comprising a positive electrode material and a negative electrode material, further comprising the lithium metal battery modified separator of claim 5 disposed between the positive electrode material and the negative electrode material.
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