CN113644380B - Adhesive for wet lamination and dry lamination of battery cells - Google Patents

Adhesive for wet lamination and dry lamination of battery cells Download PDF

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Publication number
CN113644380B
CN113644380B CN202110902682.5A CN202110902682A CN113644380B CN 113644380 B CN113644380 B CN 113644380B CN 202110902682 A CN202110902682 A CN 202110902682A CN 113644380 B CN113644380 B CN 113644380B
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pvdf
hfp
copolymer
separator
equal
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CN113644380A (en
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柳敏勇
R·M·曼克
吴宝利
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Apple Inc
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Apple Inc
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • H01M50/461—Separators, membranes or diaphragms characterised by their combination with electrodes with adhesive layers between electrodes and separators
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/443—Particulate material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—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
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Ceramic Engineering (AREA)
  • Cell Separators (AREA)
  • Fuel Cell (AREA)

Abstract

The present invention provides a battery stack that includes a binder for a wet lamination process and a dry lamination process. When laminated, the cell stack produces a cell (or portion thereof). The battery stack includes a cathode having a cathode active material disposed on a cathode current collector. The battery stack also includes an anode having an anode active material disposed on an anode current collector. The anode is oriented toward the cathode such that the anode active material faces the cathode active material. A separator is disposed between the cathode active material and the anode active material, and includes a binder including a PVdF-HFP copolymer. In some cases, an electrolyte fluid is in contact with the separator. Methods of laminating the battery stacks are also provided.

Description

Adhesive for wet lamination and dry lamination of battery cells
The present application is a divisional application of chinese invention patent application with international application date 2017, 03 month 03, national application number 201780014614.7, and the name of "adhesive for wet lamination and dry lamination of battery cells".
Cross Reference to Related Applications
The present application claims the benefit of U.S. patent application Ser. No. 62/303,276 entitled "Binders for Wet and Dry Lamination of Battery Cells" and U.S. patent application Ser. No. 15/375,905 entitled "Binders for Wet and Dry Lamination of Battery Cells" filed on date 2016, 3, and 35 U.S. C. ≡119 (e). The contents of both of these patent applications are incorporated herein by reference in their entirety.
Technical Field
The present disclosure relates generally to battery cells, and more particularly to adhesives for wet and dry laminated battery cells.
Background
The battery cells are typically manufactured using a lamination process that adheres the separator to one or more electrodes (such as the cathode or anode). These lamination processes may involve a "wet" process in which the separator is immersed in the electrolyte fluid, or a "dry" process in which the separator is free of the electrolyte fluid. During manufacture, the battery cells may undergo a combination of a "wet" lamination process and a "dry" lamination process. To facilitate adhesion of the separator to the electrode, the separator includes a binder, which may be deposited thereon as a coating. Adhesives suitable for both "wet" and "dry" lamination processes are desirable in battery manufacturing.
Disclosure of Invention
Embodiments provided herein relate to a battery stack including a binder for a wet lamination process and a dry lamination process. When laminated, the cell stack produces a cell (or portion thereof). The cell stack includes a cathode having a cathode active material disposed on a cathode current collector. The cell stack also includes an anode having an anode active material disposed on an anode current collector. The anode is oriented toward the cathode such that the anode active material faces the cathode active material. The separator is disposed between the cathode active material and the anode active material, and includes a binder including a PVdF-HFP copolymer. In some cases, the electrolyte fluid is in contact with the separator.
In some variations, the PVdF-HFP copolymer has a molecular weight greater than or equal to 1,000,000u and the weight percent of HFP is 5% to 15%. In other variations, the binder is a blended binder comprising a first PVdF-HFP copolymer and a second PVdF-HFP copolymer. The first PVdF-HFP copolymer has a first molecular weight greater than or equal to 1,000,000u, and the first weight percent HFP is less than or equal to 7%. The second PVdF-HFP copolymer has a second molecular weight of 500,000 to 1,000,000u, and the second weight percentage of HFP is 10% to 15%.
Embodiments provided herein also describe methods for laminating a battery stack of battery cells. The method may involve wet lamination and dry lamination. The method includes the step of contacting a separator with a first active material of a first electrode to form a first cell stack. The separator includes a binder including a PVdF-HFP copolymer. The method further includes the step of heating the first cell stack to laminate the separator to the first electrode. In some cases, the method additionally includes immersing the separator with an electrolyte fluid prior to heating the first cell stack.
In some variations of this method, the PVdF-HFP copolymer has a molecular weight greater than or equal to 1,000,000u and the weight percent of HFP is 5% to 15%. In other variations of the method, the binder is a blended binder comprising a first PVdF-HFP copolymer and a second PVdF-HFP copolymer. The first PVdF-HFP copolymer has a first molecular weight greater than or equal to 1,000,000u, and the first weight percent HFP is less than or equal to 7%. The second PVdF-HFP copolymer has a second molecular weight of 500,000 to 1,000,000u, and the second weight percentage of HFP is 10% to 15%.
Other cell stacks and lamination methods are provided.
Drawings
The present disclosure will be readily understood by the following detailed description in conjunction with the accompanying drawings, wherein like reference numerals designate like structural elements, and in which:
fig. 1 is a top view of a battery cell according to an exemplary embodiment;
FIG. 2 is a side view of a set of layers for a battery cell according to an exemplary embodiment;
fig. 3A is a side view of a battery stack with an adhesive suitable for both wet and dry lamination in accordance with an exemplary embodiment;
FIG. 3B is a side view of the cell stack of FIG. 3A, but wherein the separator includes a ceramic layer according to an exemplary embodiment; and is also provided with
Fig. 4 is a graph of peel strength data representing a cell stack formed using a blended binder, according to an illustrative embodiment.
Detailed Description
Reference will now be made in detail to the exemplary embodiments illustrated in the drawings. It should be understood that the following description is not intended to limit the embodiments to one preferred embodiment. On the contrary, it is intended to cover alternatives, modifications and equivalents as may be included within the spirit and scope of the embodiments as defined by the appended claims.
Fig. 1 shows a top view of a battery cell 100 according to an embodiment. The battery cell 100 may correspond to a lithium ion or lithium polymer battery cell for powering equipment used in consumer, medical, aviation, national defense, and/or transportation applications. The battery cell 100 includes a stack 102 that includes a plurality of layers including a cathode having a cathode active coating, a separator, and an anode having an anode active coating. More specifically, stack 102 may include a strip of cathode active material (e.g., aluminum foil coated with a lithium compound) and a strip of anode active material (e.g., copper foil coated with carbon). The stack 102 also includes a strip of separator material (e.g., a microporous polymer film or a nonwoven fabric mat) disposed between a strip of cathode active material and a strip of anode active material. The cathode, anode, and separator layers may lie flat in a planar configuration or may be wound into a wound configuration (e.g., a "jelly-roll").
During assembly of the battery cell 100, the stack 102 may be enclosed in a flexible pouch. The stack 102 may be in a planar configuration or a rolled configuration, although other configurations are possible. The flexible bag is formed by folding a flexible sheet of material along fold line 112. In some cases, the flexible sheet is composed of aluminum with a polymer film (such as polypropylene). After folding the flexible sheet, the flexible sheet may be sealed, for example, by applying heat along the side seals 110 and along the step seals 108. The thickness of the flexible pouch may be less than or equal to 120 micrometers to improve the packaging efficiency of the battery cell 100, the density of the battery cell 100, or both.
Stack 102 also includes a set of conductive tabs 106 coupled to the cathode and anode. Conductive tab 106 may extend through a seal in the pouch (e.g., a seal formed using sealing tape 104) to provide a terminal for battery cell 100. Conductive tab 106 may then be used to electrically couple the cell 100 with one or more other cells to form a battery. For example, the battery pack may be formed by coupling battery cells in a series, parallel, or series-parallel configuration. Such coupled units may be packaged in a rigid housing, or may be embedded within the casing of a portable electronic device, such as a laptop computer, tablet computer, mobile phone, personal Digital Assistant (PDA), digital camera, and/or portable media player, to complete a battery pack.
Fig. 2 presents a side view of a set of layers for a battery cell (e.g., battery cell 100 of fig. 1) in accordance with the disclosed embodiments. The set of layers may include a cathode current collector 202, a cathode active coating 204, a separator 206, an anode active coating 208, and an anode current collector 210. The cathode current collector 202 and the cathode active coating 204 may form a cathode for a battery cell, and the anode current collector 210 and the anode active coating 208 may form an anode for a battery cell. To form a battery cell, the set of layers may be stacked in a planar configuration, or stacked and then wound into a wound configuration. The set of layers may correspond to a battery stack prior to assembling the battery cells.
As described above, the cathode current collector 202 may be aluminum foil, the cathode active coating 204 may be a lithium compound, the anode current collector 210 may be copper foil, the anode active coating 208 may be carbon, and the separator 206 may include a microporous polymer film or a nonwoven fabric mat. Non-limiting examples of microporous polymer films or nonwoven fabric mats include microporous polymer films or nonwoven fabric mats of Polyethylene (PE), polypropylene (PP), polyamide (PA), polytetrafluoroethylene (PTFE), polyvinylchloride (PVC), polyester, and polyvinylidene fluoride (PVdF). However, other microporous polymer films or nonwoven mats are possible (e.g., gel polymer electrolytes).
In general, the separator represents a structure in the cell, such as an interposed layer, that prevents physical contact of the cathode and anode while allowing transport of ions therebetween. The separator is formed of a material having pores that provide channels for ion transport, which may include absorbing electrolyte fluids containing ions. The material of the separator may be selected according to chemical stability, porosity, pore size, permeability, wettability, mechanical strength, dimensional stability, softening temperature, and heat shrinkage. These parameters can affect battery performance and safety during operation.
The separator may incorporate a binder to improve adhesion to adjacent electrode layers (i.e., layers of the cathode and anode). These binders may also allow the ceramic material to adhere to the separator (e.g., filler and layer), thereby improving the mechanical strength and heat shrinkage resistance of the separator. The binder material may be selected according to a wet lamination process in which the battery cell stack is laminated with a separator immersed in an electrolyte fluid, and a dry lamination process in which the battery cell stack is laminated using a separator without an electrolyte fluid. The binder, which allows the battery cells to withstand both wet lamination and dry lamination, may be advantageous in reducing the materials and processing complexity of the battery cell fabrication.
Fig. 3A presents a side view of a battery stack 300 with an adhesive 302 suitable for wet lamination and dry lamination, according to an exemplary embodiment. When laminated, the battery stack 300 may produce a lithium ion battery cell. The cell stack 300 includes a cathode 304 having a cathode active material 306 disposed on a cathode current collector 308. The cell stack 300 also includes an anode 310 having an anode active material 312 disposed on an anode current collector 314. Anode 310 is oriented relative to cathode 304 such that anode active material 312 faces cathode active material 306.
The separator 316 is disposed in the femaleBetween the electrode active material 306 and the anode active material 312, and a binder 302 including a polyvinylidene fluoride hexafluoropropylene copolymer (i.e., PVdF-HFP copolymer) is included. In some embodiments, the cell stack 300 further includes an electrolyte fluid in contact with the separator 316. In these embodiments, the separator 316 may be immersed in the electrolyte fluid. The electrolyte fluid may be any type of electrolyte fluid suitable for use in a battery cell. Non-limiting examples of electrolyte fluids include propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, and ethylmethyl carbonate. The electrolyte fluid may also have a salt dissolved therein. The salt may be any type of salt suitable for use in a battery cell. For example, and without limitation, salts for lithium ion battery cells include: liPF (LiPF) 6 、LiBF 4 、LiClO 4 、LiSO 3 CF 3 、LiN(SO 2 CF 3 ) 2 、LiBC 4 O 8 、Li[PF 3 (C 2 CF 5 ) 3 ]LiC (SO) 2 CF 3 ) 3 . Other salts, including combinations of salts, are also possible.
Separator 316 may include a microporous polymer film or nonwoven fabric pad 318, as shown in fig. 3A. The microporous polymer film or nonwoven fabric pad 318 may be any type of microporous polymer film or nonwoven fabric pad suitable for use in a battery cell (e.g., polymer film, gel polymer, etc.). Non-limiting examples of microporous polymer film or nonwoven fabric mat 318 include microporous polymer film or nonwoven fabric mats of Polyethylene (PE), polypropylene (PP), polyamide (PA), polytetrafluoroethylene (PTFE), polyvinylchloride (PVC), polyester, and polyvinylidene fluoride (PVdF). In some cases, the separator 316 incorporates ceramic particles therein (i.e., as a filler), which may involve the binder 302, the woven or non-woven microporous membrane 318, or both. Non-limiting examples of ceramic materials for the ceramic particles include magnesia materials (e.g., mg (OH) 2 MgO, etc.) and alumina materials (e.g., al 2 O 3 ). However, other ceramic materials are also possible.
In fig. 3A, the adhesive 302 is shown as a layer disposed on a microporous polymer film or nonwoven fabric pad 318. However, this description is not intended to be limiting. For example, and without limitation, the binder 302 may also be present wholly or partially within the pores of the microporous polymer film or nonwoven fabric mat 318. Other configurations of the adhesive 302 are possible.
The PVdF-HFP copolymer of the binder 302 may have a molecular weight, HFP weight percent, acid number, or any combination thereof, which allows the cell 300 to be manufactured using a wet lamination process, a dry lamination process, or both. Without intending to be limited to a particular theory or mode of action, PVdF is a semi-crystalline polymeric material having a relatively high melting temperature (i.e., T m >170 c) and low swelling in the electrolyte fluid. HFP is gradually incorporated into semi-crystalline polymeric materials (i.e., PVdF) to give copolymers with increased amorphous content, reduced melting temperature, and increased swelling of the electrolyte fluid. By selecting the molecular weight and weight percent of HFP, these properties can be manipulated to better adapt the copolymer to wet lamination processes, dry lamination processes, or both. However, it should be appreciated that the applicability of dry lamination may be reversed from that of wet lamination (and vice versa).
For example, and without limitation, the weight percent of HFP may be increased to lower the softening point of the copolymer, making the copolymer more suitable for dry lamination. However, this increase in weight percent also increases the sensitivity of the copolymer to swelling during wet lamination. Swelling during wet lamination may weaken the contact between the separator 316 and the adjacent cathode 304 and anode 310, which may result in a loss of contact area.
In another non-limiting example, the molecular weight of the PVdF-HFP copolymer may be increased to improve the interaction of the copolymer with components contacted by the binder 302 (e.g., microporous polymer film or nonwoven fabric mat 318, cathode active material 306, anode active material 312, etc.). Such improved interactions may enhance adhesion during wet lamination or dry lamination. However, increasing the molecular weight can also increase the softening point of the copolymer, making the copolymer less suitable for dry lamination.
In another non-limiting example, the amorphous content of PVdF-HFP copolymer may be increased to improve the coating of the copolymer on the component contacted by the binder 302 (e.g., microporous polymer film or nonwoven fabric mat 318, cathode active material 306, anode active material 312, etc.). Higher amorphous content in the copolymer may increase its ductility and reduce the risk of micro-voids between the copolymer and the contacted part. However, increasing the amorphous content may also increase the swelling degree of the copolymer, making the copolymer less suitable for wet lamination.
Embodiments disclosed herein relate to binders comprising PVdF-HFP copolymers, the molecular weight and weight percentages of HFP of which are suitable for both wet processing and dry processing. Further, the PVdF-HFP copolymer has an acid number corresponding to the adhesive 302 with enhanced adhesion of components of the cell stack 300 (e.g., the microporous polymer film or nonwoven fabric mat 318, the cathode active material 306, the anode active material 312, etc.), which characterizes a certain amount of acidic functional groups disposed along the polymer chains of the PVdF-HFP copolymer. The presence of these functional groups may improve the adhesion of the PVdF-HFP copolymer to the component contacted by the adhesive 302. Non-limiting examples of acidic functional groups include carboxyl groups (e.g., formic acid, acetic acid, etc.) and hydroxyl groups. However, other acid functionalities are also possible.
In various aspects, the acid number is the amount of base required to neutralize the acidity of a given amount of chemical. As used herein, acid number refers to the amount of potassium hydroxide (milligrams) required to neutralize a given amount (grams) of PVdF-HFP copolymer. However, other equivalent units of measurement for acid number are possible. Techniques for determining acid number (and its corresponding measurement units) are known to those skilled in the art and will not be discussed further.
In one variation, the PVdF-HFP copolymer has a molecular weight greater than or equal to 1,000,000u and the weight percent of HFP is 5% to 15%. In further embodiments, the PVdF-HFP copolymer has an acid number of 3 to 15 milligrams potassium hydroxide per gram of copolymer. In further embodiments, the PVdF-HFP copolymer has an acid number of 1.5 to 15 milligrams of potassium hydroxide per gram of copolymer.
In some embodiments, the PVdF-HFP copolymer has a molecular weight greater than or equal to 1,000,000u and the weight percent of HFP is greater than or equal to 5%. In some embodiments, the PVdF-HFP copolymer has a molecular weight greater than or equal to 1,000,000u and the weight percent of HFP is greater than or equal to 10%. In some embodiments, the PVdF-HFP copolymer has a molecular weight greater than or equal to 1,000,000u and the weight percent of HFP is greater than or equal to 15%. In some embodiments, the PVdF-HFP copolymer has a molecular weight greater than or equal to 1,000,000u and the weight percent of HFP is greater than or equal to 20%.
In some embodiments, the PVdF-HFP copolymer has a molecular weight greater than or equal to 1,000,000u and the weight percent of HFP is less than or equal to 25%. In some embodiments, the PVdF-HFP copolymer has a molecular weight greater than or equal to 1,000,000u and the weight percent of HFP is less than or equal to 20%. In some embodiments, the PVdF-HFP copolymer has a molecular weight greater than or equal to 1,000,000u and the weight percent of HFP is less than or equal to 15%. In some embodiments, the PVdF-HFP copolymer has a molecular weight greater than or equal to 1,000,000u and the weight percent of HFP is less than or equal to 10%.
In some embodiments, the PVdF-HFP copolymer has an acid number greater than or equal to 1.5 milligrams potassium hydroxide per gram of copolymer. In some embodiments, the PVdF-HFP copolymer has an acid number greater than or equal to 1.8 milligrams potassium hydroxide per gram of copolymer. In some embodiments, the PVdF-HFP copolymer has an acid number greater than or equal to 3 milligrams potassium hydroxide per gram of copolymer. In some embodiments, the PVdF-HFP copolymer has an acid number greater than or equal to 8 milligrams potassium hydroxide per gram of copolymer. In some embodiments, the PVdF-HFP copolymer has an acid number greater than or equal to 13 milligrams potassium hydroxide per gram of copolymer. In some embodiments, the PVdF-HFP copolymer has an acid number greater than or equal to 12 milligrams of potassium hydroxide per gram of copolymer. In some embodiments, the PVdF-HFP copolymer has an acid number greater than or equal to 18 milligrams of potassium hydroxide per gram of copolymer.
In some embodiments, the PVdF-HFP copolymer has an acid number of less than 20 milligrams potassium hydroxide per gram of copolymer. In some embodiments, the PVdF-HFP copolymer has an acid number less than or equal to 15 milligrams potassium hydroxide per gram of copolymer. In some embodiments, the PVdF-HFP copolymer has an acid number less than or equal to 10 milligrams of potassium hydroxide per gram of copolymer. In some embodiments, the PVdF-HFP copolymer has an acid number less than or equal to 5 milligrams potassium hydroxide per gram of copolymer.
In another variation, the adhesive 302 of the separator 316 is a blended adhesive that includes a first PVdF-HFP copolymer and a second PVdF-HFP copolymer. The first PVdF-HFP copolymer has a first molecular weight greater than or equal to 1,000,000u, and the first weight percent HFP is less than or equal to 7%. The second PVdF-HFP copolymer has a second molecular weight of 500,000 to 1,000,000u, and the second weight percentage of HFP is 10% to 15%. In further embodiments, the first PVdF-HFP copolymer and the second PVdF-HFP copolymer each have an acid value of 1.5 to 15 milligrams of potassium hydroxide per gram of copolymer.
In some variations, the first PVdF-HFP copolymer and the second PVdF-HFP copolymer have an acid value of 1.5 to 15 milligrams potassium hydroxide per gram of copolymer. In some variations, the first PVdF-HFP copolymer has a first acid number of 1.8 to 2.4 milligrams potassium hydroxide per gram of copolymer. In some variations, the first PVdF-HFP copolymer has a first acid number of 2.1 milligrams potassium hydroxide per gram of copolymer. In some variations, the second PVdF-HFP copolymer has a second acid number of 12.3 to 12.9 milligrams potassium hydroxide per gram of copolymer. In some variations, the second PVdF-HFP copolymer has a second acid number of 12.6 mg potassium hydroxide per gram of copolymer. It should be understood that the first acid number and the second acid number described herein may be combined in any variation.
In some embodiments, the first PVdF-HFP copolymer has a first molecular weight greater than or equal to 1,000,000u and a first weight percent of HFP is less than or equal to 10%. In some embodiments, the first PVdF-HFP copolymer has a first molecular weight greater than or equal to 1,000,000u and a first weight percent of HFP is less than or equal to 8%. In some embodiments, the first PVdF-HFP copolymer has a first molecular weight greater than or equal to 1,000,000u and a first weight percent of HFP is less than or equal to 6%. In some embodiments, the first PVdF-HFP copolymer has a first molecular weight greater than or equal to 1,000,000u and a first weight percent of HFP is less than or equal to 4%. In some embodiments, the first PVdF-HFP copolymer has a first molecular weight greater than or equal to 1,000,000u and a first weight percent of HFP is less than or equal to 2%.
In some embodiments, the first PVdF-HFP copolymer has a first molecular weight greater than or equal to 1,000,000u, and the first weight percent of HFP is 1% to 3%. In some embodiments, the first PVdF-HFP copolymer has a first molecular weight greater than or equal to 1,000,000u, and the first weight percent of HFP is 3% to 5%. In some embodiments, the first PVdF-HFP copolymer has a first molecular weight greater than or equal to 1,000,000u, and the first weight percent of HFP is 5% to 7%. In some embodiments, the first PVdF-HFP copolymer has a first molecular weight greater than or equal to 1,000,000u, and the first weight percent of HFP is 7% to 9%.
In some embodiments, the first PVdF-HFP copolymer has a first molecular weight greater than or equal to 1,000,000u, and the first weight percent of HFP is 1% to 9%. In some embodiments, the first PVdF-HFP copolymer has a first molecular weight greater than or equal to 1,000,000u, and the first weight percent of HFP is 3% to 7%. In some embodiments, the first PVdF-HFP copolymer has a first molecular weight greater than or equal to 1,000,000u, and the first weight percent of HFP is 1% to 5%. In some embodiments, the first PVdF-HFP copolymer has a first molecular weight greater than or equal to 1,000,000u, and the first weight percent of HFP is 5% to 9%.
In some embodiments, the second PVdF-HFP copolymer has a second molecular weight greater than or equal to 750,000u, and the second weight percent of HFP is less than 14%. In some embodiments, the second PVdF-HFP copolymer has a second molecular weight greater than or equal to 750,000u, and the second weight percent of HFP is less than 13%. In some embodiments, the second PVdF-HFP copolymer has a second molecular weight greater than or equal to 750,000u, and the second weight percent of HFP is less than 12%. In some embodiments, the second PVdF-HFP copolymer has a second molecular weight greater than or equal to 750,000u, and the second weight percent of HFP is less than 11%.
In some embodiments, the second PVdF-HFP copolymer has a second molecular weight greater than or equal to 750,000u, and the second weight percent of HFP is greater than 11%. In some embodiments, the second PVdF-HFP copolymer has a second molecular weight greater than or equal to 750,000u, and the second weight percent of HFP is greater than 12%. In some embodiments, the second PVdF-HFP copolymer has a second molecular weight greater than or equal to 750,000u, and the second weight percent of HFP is greater than 13%. In some embodiments, the second PVdF-HFP copolymer has a second molecular weight greater than or equal to 750,000u, and the second weight percent of HFP is greater than 14%.
In some embodiments, the second PVdF-HFP copolymer has a second molecular weight less than or equal to 750,000u, and the second weight percent of HFP is less than 14%. In some embodiments, the second PVdF-HFP copolymer has a second molecular weight less than or equal to 750,000u, and the second weight percent of HFP is less than 13%. In some embodiments, the second PVdF-HFP copolymer has a second molecular weight less than or equal to 750,000u, and the second weight percent of HFP is less than 12%. In some embodiments, the second PVdF-HFP copolymer has a second molecular weight less than or equal to 750,000u, and the second weight percent of HFP is less than 11%.
In some embodiments, the second PVdF-HFP copolymer has a second molecular weight less than or equal to 750,000u, and the second weight percent of HFP is greater than 11%. In some embodiments, the second PVdF-HFP copolymer has a second molecular weight less than or equal to 750,000u, and the second weight percent of HFP is greater than 12%. In some embodiments, the second PVdF-HFP copolymer has a second molecular weight less than or equal to 750,000u, and the second weight percent of HFP is greater than 13%. In some embodiments, the second PVdF-HFP copolymer has a second molecular weight less than or equal to 750,000u, and the second weight percent of HFP is greater than 14%.
In certain variations of the cell stack 300, the separator 316 includes a polyolefin layer having a first side 320 and a second side 322 (i.e., the microporous polymer film or nonwoven fabric mat 318 is a polyolefin layer). Non-limiting examples of polyolefin layers include polyethylene layers, polypropylene layers, layers having a blend of polyethylene and polypropylene, and combinations thereof. The first side 320 forms a first interface 324 with the cathode active material 306. The second side 322 forms a second interface 326 with the anode active material 312. The adhesive 302 (or portions thereof) may be disposed as a layer along the first interface 324 and the second interface 326, as shown in fig. 3A.
In these variations of the cell stack 300, ceramic layers may be disposed along the first interface 324 and the second interface 326. Such ceramic layers may improve the chemical and dimensional stability of separator 316 during operation of battery cell 300 (i.e., after fabrication). Such a ceramic layer may also improve the mechanical strength of the separator 316. Non-limiting examples of ceramic materials for the ceramic layer include magnesia materials (e.g., mg (OH) 2 MgO, etc.) and alumina materials (e.g., al 2 O 3 ). Fig. 3B presents a side view of the cell stack 300 of fig. 3A, but wherein the separator 316 comprises a ceramic layer according to an exemplary embodiment.
In some cases, the first ceramic layer 328 is disposed along the first interface 324. The first ceramic layer 328 includes a plurality of first ceramic particles in contact with the binder 302. In some cases, the second ceramic layer 330 is disposed along the second interface 326. The second ceramic layer 330 includes a plurality of second ceramic particles in contact with the binder 302. In other cases, the first ceramic layer 328 is disposed along the first interface 324 and the second ceramic layer 330 is disposed along the second interface 326. In these cases, the first ceramic layer 328 includes a plurality of first ceramic particles in contact with the binder 302, and the second ceramic layer 330 includes a plurality of second ceramic particles in contact with the binder 302.
Contact with the binder 302 may involve blending the ceramic particles with the binder 302. In these cases, the plurality of first ceramic particles and the plurality of second ceramic particles may represent 60 wt% to 90 wt% of the first ceramic layer 328 and the second ceramic layer 330, respectively. In other cases, the plurality of first ceramic particles and the plurality of second ceramic particles represent less than or equal to 50 wt% of the first ceramic layer 328 and the second ceramic layer 330, respectively. In still other cases, the plurality of first ceramic particles and the plurality of second ceramic particles represent greater than or equal to 90 wt% of the first ceramic layer 328 and the second ceramic layer 330, respectively.
Contact with the binder 302 may also involve contact of the ceramic particles with a layer of the binder 302. Such layers of binder 302 may be interposed between first ceramic layer 328 and cathode active material 306, between second ceramic layer 330 and anode active material 312, or any combination thereof.
Fig. 4 presents a graph of peel strength data representing a cell stack formed using a blended binder, according to an illustrative embodiment. The ordinate indicates the peel strength of the cell stack. The abscissa indicates the peel strength corresponding to the dry lamination process and the wet lamination process. For each lamination process, a separator adhered to the cathode or a separator adhered to the anode is used to form a cell stack. Thus, the data plot shows four conditions for measuring peel strength.
In each case, three different binders were used, including a conventional (non-blended) binder, a first blended binder, and a second blended binder. Conventional binders have PVdF-HFP copolymer having a molecular weight of 1,200,000u, a weight percent HFP of 6%, and an acid number of 1 mg potassium hydroxide per gram of copolymer. The first blended binder has a first PVdF-HFP copolymer having a molecular weight of 1,100,000u, a weight percentage of HFP of 5%, and an acid value of 13 mg of potassium hydroxide per gram of copolymer, and a second PVdF-HFP copolymer having a molecular weight of 1,200,000u, a weight percentage of HFP of 0%, and an acid value of 10 mg of potassium hydroxide per gram of copolymer. The second blended binder had a first PVdF-HFP copolymer having a molecular weight of 1,100,000u, 5% HFP weight percentage, and an acid value of 13 mg potassium hydroxide/g copolymer, and a second PVdF-HFP copolymer having a molecular weight of 860,000u, 12% HFP weight percentage, and an acid value of 2 mg potassium hydroxide/g copolymer.
The separator in the cell stack includes a first ceramic layer and a second ceramic layer coated on the opposite side of the polyethylene-based film. The first ceramic layer and the second ceramic layer are composed of Mg (OH) corresponding to 70 wt.% 2 And 30 wt% of a blend binder. The first ceramic layer and the second ceramic layer are solution cast onto the separator of the cell stack. The activation temperature of the wet lamination process and the dry lamination process was 85 ℃. The cathode active material in the cathode includes a mixture of lithium cobalt oxide material, PVdF binder, and activated carbon. Anode active materials in the anode include graphite, SBR, and CMC. To laminate the cell stack, a pressure of about 1Mpa was applied.
In fig. 4, the peel strength of the first and second blended binders is significantly higher than that of the conventional (non-blended) binders. In addition, in all cases, the second blended binder exhibited a peel strength in excess of 1.5N/m. In contrast, in all cases, the peel strength of the conventional adhesive was less than 1.5N/m. In adhering the separator to the anode in a wet process, it is desirable for the first blended binder to reach or exceed 1.5N/m under all conditions. However, it should be understood that both the first and second blended binders are suitable for wet processing and dry processing.
It should be appreciated that one skilled in the art can use Differential Scanning Calorimetry (DSC) techniques to distinguish the melting temperatures of the blended binders using heat flow profiles. Such a heat flow profile may allow for the weight percent of PVdF-HFP copolymer to be determined within the blended binder. In addition, gel Permeation Chromatography (GPC) may also be utilized by those skilled in the art to determine the molecular weight of the PVdF-HFP copolymer within the blended binder.
According to an exemplary embodiment, a method for laminating at least one cell stack of a battery cell includes the step of contacting a separator with a first active material of a first electrode to form a first cell stack. The separator includes a binder including a PVdF-HFP copolymer. The PVdF-HFP copolymer has a molecular weight of 1,000,000u or more, and the HFP is 5 to 15% by weight. In some embodiments, the PVdF-HFP copolymer has an acid number of 3 to 15 milligrams potassium hydroxide per gram of copolymer. In some embodiments, the PVdF-HFP copolymer has an acid number of 1.5 to 15 milligrams potassium hydroxide per gram of copolymer.
The method further includes the step of heating the first cell stack to laminate the separator to the first electrode. The first active material of the first electrode may be a cathode active material of a cathode or an anode active material of an anode. In some embodiments, the method further comprises the step of immersing the separator with an electrolyte fluid prior to heating the first cell stack. In some embodiments, the method further comprises the step of, after heating the first cell stack, soaking the separator with an electrolyte fluid and reheating the first cell stack. It should be understood that the presence or absence of electrolyte fluid in the separator corresponds to a wet lamination process and a dry lamination process, respectively.
In some variations, the PVdF-HFP copolymer has a molecular weight greater than or equal to 1,000,000u and the weight percent of HFP is 5% to 15%. In a further variation, the PVdF-HFP copolymer has an acid number of 3 to 15 milligrams potassium hydroxide per gram of copolymer. In a further variation, the PVdF-HFP copolymer has an acid number of 1.5 to 15 milligrams potassium hydroxide per gram of copolymer.
In some variations, the PVdF-HFP copolymer has a molecular weight greater than or equal to 1,000,000u and the weight percent of HFP is greater than or equal to 5%. In some variations, the PVdF-HFP copolymer has a molecular weight greater than or equal to 1,000,000u and the weight percent of HFP is greater than or equal to 10%. In some variations, the PVdF-HFP copolymer has a molecular weight greater than or equal to 1,000,000u and the weight percent of HFP is greater than or equal to 15%. In some variations, the PVdF-HFP copolymer has a molecular weight greater than or equal to 1,000,000u and the weight percent of HFP is greater than or equal to 20%.
In some variations, the PVdF-HFP copolymer has a molecular weight greater than or equal to 1,000,000u and the weight percent of HFP is less than or equal to 25%. In some variations, the PVdF-HFP copolymer has a molecular weight greater than or equal to 1,000,000u and the weight percent of HFP is less than or equal to 20%. In some variations, the PVdF-HFP copolymer has a molecular weight greater than or equal to 1,000,000u and the weight percent of HFP is less than or equal to 15%. In some variations, the PVdF-HFP copolymer has a molecular weight greater than or equal to 1,000,000u and the weight percent of HFP is less than or equal to 10%.
In some variations, the PVdF-HFP copolymer has an acid number greater than or equal to 1.5 milligrams potassium hydroxide per gram of copolymer. In some variations, the PVdF-HFP copolymer has an acid number greater than or equal to 3 milligrams potassium hydroxide per gram of copolymer. In some variations, the PVdF-HFP copolymer has an acid number greater than or equal to 8 milligrams potassium hydroxide per gram of copolymer. In some variations, the PVdF-HFP copolymer has an acid number greater than or equal to 13 mg potassium hydroxide per gram of copolymer. In some variations, the PVdF-HFP copolymer has an acid number greater than or equal to 12 milligrams potassium hydroxide per gram of copolymer. In some variations, the PVdF-HFP copolymer has an acid number greater than or equal to 18 milligrams potassium hydroxide per gram of copolymer.
In some variations, the PVdF-HFP copolymer has an acid number of less than 20 milligrams potassium hydroxide per gram of copolymer. In some variations, the PVdF-HFP copolymer has an acid number less than or equal to 15 milligrams potassium hydroxide per gram of copolymer. In some variations, the PVdF-HFP copolymer has an acid value of less than or equal to 10 milligrams potassium hydroxide per gram of copolymer. In some variations, the PVdF-HFP copolymer has an acid value of less than or equal to 5 milligrams potassium hydroxide per gram of copolymer.
In some embodiments, the step of contacting the separator with the first active material of the first electrode comprises contacting the separator with the second active material of the second electrode. In these embodiments, a separator is disposed between the first electrode and the second electrode to form a first cell stack. The step of heating the first cell stack laminates the separator to both the first electrode and the second electrode. In some cases, the method includes the step of immersing the separator with an electrolyte fluid prior to heating the first cell stack. In other cases, the method includes the steps of, after heating the first cell stack, immersing the separator with an electrolyte fluid and reheating the first cell stack.
In other embodiments, the method further comprises the step of contacting the separator of the first cell stack with a second active material of a second electrode, thereby forming a second cell stack. The method further includes the step of heating the second cell stack to laminate the separator to the second electrode. In some cases, the method may involve the step of immersing the separator with an electrolyte fluid prior to heating the second cell stack. In other cases, the method may involve the step of, after heating the second cell stack, immersing the separator with an electrolyte fluid and then reheating the second cell stack.
In still other embodiments, the method includes the step of immersing the separator with an electrolyte fluid prior to heating the first cell stack. In such embodiments, the method further comprises the step of contacting the separator of the first cell stack with the second active material of the second electrode after heating the first cell stack, thereby forming a second cell stack. The second cell stack is heated to laminate the separator to the second electrode. In some cases, the method may involve the step of immersing the separator with an electrolyte fluid prior to heating the second cell stack. In other cases, the method may involve the step of, after heating the second cell stack, immersing the separator with an electrolyte fluid and then reheating the second cell stack.
According to another exemplary embodiment, a method for laminating at least one cell stack of a battery cell includes the step of contacting a separator with a first active material of a first electrode to form a first cell stack. The separator includes a blended binder including a first PVdF-HFP copolymer and a second PVdF-HFP copolymer. The first PVdF-HFP copolymer has a first molecular weight greater than or equal to 1,000,000u, and the first weight percent HFP is less than or equal to 7%. The second PVdF-HFP copolymer has a second molecular weight of 500,000 to 1,000,000u, and the second weight percentage of HFP is 10% to 15%. In some embodiments, the first PVdF-HFP copolymer and the second PVdF-HFP copolymer each have an acid value of 3 to 15 milligrams potassium hydroxide per gram of copolymer.
The method further includes the step of heating the first cell stack to laminate the separator to the first electrode. The first active material of the first electrode may be a cathode active material of a cathode or an anode active material of an anode. In some embodiments, the method further comprises the step of immersing the separator with an electrolyte fluid prior to heating the first cell stack. In some embodiments, the method further comprises the step of, after heating the first cell stack, soaking the separator with an electrolyte fluid and reheating the first cell stack. It should be understood that the presence or absence of electrolyte fluid in the separator corresponds to a wet lamination process and a dry lamination process, respectively.
In some variations, the first PVdF-HFP copolymer has a first molecular weight greater than or equal to 1,000,000u, and the first weight percent of HFP is less than or equal to 10%. In some variations, the first PVdF-HFP copolymer has a first molecular weight greater than or equal to 1,000,000u, and the first weight percent of HFP is less than or equal to 8%. In some variations, the first PVdF-HFP copolymer has a first molecular weight greater than or equal to 1,000,000u, and the first weight percent of HFP is less than or equal to 6%. In some variations, the first PVdF-HFP copolymer has a first molecular weight greater than or equal to 1,000,000u, and the first weight percent of HFP is less than or equal to 4%. In some variations, the first PVdF-HFP copolymer has a first molecular weight greater than or equal to 1,000,000u, and the first weight percent of HFP is less than or equal to 2%.
In some variations, the first PVdF-HFP copolymer has a first molecular weight greater than or equal to 1,000,000u, and the first weight percent of HFP is 1% to 3%. In some variations, the first PVdF-HFP copolymer has a first molecular weight greater than or equal to 1,000,000u, and the first weight percent of HFP is 3% to 5%. In some variations, the first PVdF-HFP copolymer has a first molecular weight greater than or equal to 1,000,000u, and the first weight percent of HFP is 5% to 7%. In some variations, the first PVdF-HFP copolymer has a first molecular weight greater than or equal to 1,000,000u, and the first weight percent of HFP is 7% to 9%.
In some variations, the first PVdF-HFP copolymer has a first molecular weight greater than or equal to 1,000,000u, and the first weight percent of HFP is 1% to 9%. In some variations, the first PVdF-HFP copolymer has a first molecular weight greater than or equal to 1,000,000u, and the first weight percent of HFP is 3% to 7%. In some variations, the first PVdF-HFP copolymer has a first molecular weight greater than or equal to 1,000,000u, and the first weight percent of HFP is 1% to 5%. In some variations, the first PVdF-HFP copolymer has a first molecular weight greater than or equal to 1,000,000u, and the first weight percent of HFP is 5% to 9%.
In some variations, the second PVdF-HFP copolymer has a second molecular weight greater than or equal to 750,000u, and the second weight percent of HFP is less than 14%. In some variations, the second PVdF-HFP copolymer has a second molecular weight greater than or equal to 750,000u, and the second weight percent of HFP is less than 13%. In some variations, the second PVdF-HFP copolymer has a second molecular weight greater than or equal to 750,000u, and the second weight percent of HFP is less than 12%. In some variations, the second PVdF-HFP copolymer has a second molecular weight greater than or equal to 750,000u, and the second weight percent of HFP is less than 11%.
In some variations, the second PVdF-HFP copolymer has a second molecular weight greater than or equal to 750,000u, and the second weight percent of HFP is greater than 11%. In some variations, the second PVdF-HFP copolymer has a second molecular weight greater than or equal to 750,000u, and the second weight percent of HFP is greater than 12%. In some variations, the second PVdF-HFP copolymer has a second molecular weight greater than or equal to 750,000u, and the second weight percent of HFP is greater than 13%. In some variations, the second PVdF-HFP copolymer has a second molecular weight greater than or equal to 750,000u, and the second weight percent of HFP is greater than 14%.
In some variations, the second PVdF-HFP copolymer has a second molecular weight less than or equal to 750,000u, and the second weight percent of HFP is less than 14%. In some variations, the second PVdF-HFP copolymer has a second molecular weight less than or equal to 750,000u, and the second weight percent of HFP is less than 13%. In some variations, the second PVdF-HFP copolymer has a second molecular weight less than or equal to 750,000u, and the second weight percent of HFP is less than 12%. In some variations, the second PVdF-HFP copolymer has a second molecular weight less than or equal to 750,000u, and the second weight percent of HFP is less than 11%.
In some variations, the second PVdF-HFP copolymer has a second molecular weight less than or equal to 750,000u, and the second weight percent of HFP is greater than 11%. In some variations, the second PVdF-HFP copolymer has a second molecular weight less than or equal to 750,000u, and the second weight percent of HFP is greater than 12%. In some variations, the second PVdF-HFP copolymer has a second molecular weight less than or equal to 750,000u, and the second weight percent of HFP is greater than 13%. In some variations, the second PVdF-HFP copolymer has a second molecular weight less than or equal to 750,000u, and the second weight percent of HFP is greater than 14%.
In some embodiments, the step of contacting the separator with the first active material of the first electrode comprises contacting the separator with the second active material of the second electrode. In these embodiments, a separator is disposed between the first electrode and the second electrode to form a first cell stack. The step of heating the first cell stack laminates the separator to both the first electrode and the second electrode. In some cases, the method includes the step of immersing the separator with an electrolyte fluid prior to heating the first cell stack. In other cases, the method includes the steps of, after heating the first cell stack, immersing the separator with an electrolyte fluid and reheating the first cell stack.
In other embodiments, the method further comprises the step of contacting the separator of the first cell stack with a second active material of a second electrode, thereby forming a second cell stack. The method further includes the step of heating the second cell stack to laminate the separator to the second electrode. In some cases, the method may involve the step of immersing the separator with an electrolyte fluid prior to heating the second cell stack. In other cases, the method may involve the step of, after heating the second cell stack, immersing the separator with an electrolyte fluid and then reheating the second cell stack.
In still other embodiments, the method includes the step of immersing the separator with an electrolyte fluid prior to heating the first cell stack. In such embodiments, the method further comprises the step of contacting the separator of the first cell stack with the second active material of the second electrode after heating the first cell stack, thereby forming a second cell stack. The second cell stack is heated to laminate the separator to the second electrode. In some cases, the method may involve the step of immersing the separator with an electrolyte fluid prior to heating the second cell stack. In other cases, the method may involve the step of, after heating the second cell stack, immersing the separator with an electrolyte fluid and then reheating the second cell stack.
The battery stacks described herein may be valuable in manufacturing electronic devices that include battery cells manufactured with wet lamination processes, dry lamination processes, or both. The electronic device herein may refer to any electronic device known in the art. For example, the electronic device may be a telephone such as a mobile telephone and a landline telephone, or any communication device such as a smart phone (including, for example ) An email transmission/reception apparatus. The electronic device may also be an entertainment device, including a portable DVD player, a conventional DVD player, a blu-ray disc player, a video game controller, a music player, such as a portable music player (e.g.; a->) Etc. The electronic device may be part of a display, such as a digital display, a television monitor, an electronic book reader, a portable web browser (e.g.,/->) A watch (e.g., appleWatch) or a computer monitor. Electronic equipmentMay also be part of a device providing control, such as controlling image, video and sound streams (e.g., apple +.>) Or it may be a remote control of the electronic device. Further, the electronic device may be part of a computer or an accessory thereof, such as a hard disk tower housing or case, a laptop housing, a laptop keyboard, a laptop touchpad, a desktop keyboard, a mouse, and speakers. Anode batteries, lithium metal batteries and battery packs are also applicable to devices such as watches or clocks.
In the above description, for purposes of explanation, specific nomenclature is used to provide a thorough understanding of the embodiments. It will be apparent, however, to one skilled in the art that these specific details are not required to practice the embodiments. Thus, the foregoing descriptions of specific embodiments described herein are presented for purposes of illustration and description. They are not intended to be exhaustive or to limit the embodiments to the precise forms disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art in light of the above teachings.

Claims (20)

1. A separator, comprising:
a polyolefin layer; and
a first ceramic layer disposed on a first side of the polyolefin layer,
wherein the first ceramic layer comprises a plurality of first ceramic particles blended with a binder;
the binder includes a first PVdF-HFP copolymer and a second PVdF-HFP copolymer;
wherein the first PVdF-HFP copolymer has a first molecular weight greater than or equal to 1,000,000 g/mole, and a first weight percent of HFP less than or equal to 7%;
wherein the second PVdF-HFP copolymer has a second molecular weight of 500,000 to 1,000,000 g/mole, and a second weight percentage of 10% to 15% HFP; and is also provided with
Wherein the first PVdF-HFP copolymer and the second PVdF-HFP copolymer have respective acid numbers of 1.5 to 15 mg potassium hydroxide per gram of copolymer.
2. The separator of claim 1 wherein
The first PVdF-HFP copolymer has a first acid value of 2.1 mg of potassium hydroxide per gram of copolymer, and
the second PVdF-HFP copolymer has a second acid number of 12.6 milligrams potassium hydroxide per gram of copolymer.
3. The separator of claim 1, wherein the first plurality of ceramic particles comprises magnesium hydroxide.
4. The separator of claim 1, wherein the plurality of first ceramic particles represents 60 wt% to 90 wt% of the first ceramic layer.
5. The separator of claim 4, wherein the first plurality of ceramic particles comprises magnesium hydroxide.
6. The separator of claim 1, comprising a second ceramic layer disposed on a second side of the polyolefin layer.
7. The separator of claim 6, wherein the second ceramic layer comprises magnesium hydroxide.
8. The separator of claim 6, wherein the second ceramic layer comprises a plurality of second ceramic particles blended with the binder.
9. The separator of claim 8, wherein the plurality of second ceramic particles represents 60 wt% to 90 wt% of the second ceramic layer.
10. The separator of claim 9, wherein the second ceramic layer comprises magnesium hydroxide.
11. A battery stack for a battery cell, comprising:
a cathode including a cathode active material disposed on a cathode current collector;
an anode comprising an anode active material disposed on an anode current collector, the anode oriented toward the cathode such that the anode active material faces the cathode active material;
The separator according to claim 1, which is disposed between the cathode active material and the anode active material.
12. The battery stack of claim 11, wherein
The first PVdF-HFP copolymer has a first acid value of 2.1 mg of potassium hydroxide per gram of copolymer, and
the second PVdF-HFP copolymer has a second acid number of 12.6 milligrams potassium hydroxide per gram of copolymer.
13. The battery stack of claim 11, wherein the first plurality of ceramic particles comprises magnesium hydroxide.
14. The battery stack of claim 11, wherein the plurality of first ceramic particles represents 60 wt% to 90 wt% of the first ceramic layer.
15. The battery stack of claim 14, wherein the first plurality of ceramic particles comprises magnesium hydroxide.
16. The battery stack of claim 11, comprising a second ceramic layer disposed on a second side of the polyolefin layer.
17. The battery stack of claim 16, wherein the second ceramic layer comprises magnesium hydroxide.
18. The battery stack of claim 16, wherein the second ceramic layer comprises a plurality of second ceramic particles blended with the binder.
19. The battery stack of claim 18, wherein the plurality of second ceramic particles represents 60 wt% to 90 wt% of the second ceramic layer.
20. The battery stack of claim 19, wherein the second ceramic layer comprises magnesium hydroxide.
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