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CN108780864B - Binder for wet-laminated and dry-laminated battery cells - Google Patents

Binder for wet-laminated and dry-laminated battery cells Download PDF

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Publication number
CN108780864B
CN108780864B CN201780014614.7A CN201780014614A CN108780864B CN 108780864 B CN108780864 B CN 108780864B CN 201780014614 A CN201780014614 A CN 201780014614A CN 108780864 B CN108780864 B CN 108780864B
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pvdf
hfp
copolymer
separator
active material
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CN108780864A (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
    • H01M50/46—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
    • H01M50/403—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
    • 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
    • H01M50/409—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
    • 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 invention provides a battery stack that includes a binder for use in wet and dry lamination processes. When laminated, the battery stack produces a battery 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. A separator is disposed between the cathode active material and the anode active material and includes a binder comprising PVdF-HFP copolymer. In some cases, an electrolyte fluid is in contact with the separator. Methods of laminating the cell stacks are also provided.

Description

Binder for wet-laminated and dry-laminated battery cells
Cross Reference to Related Applications
This application is entitled to U.S. provisional patent application Ser. No. 62/303,276 entitled "Binders for Wet and Dry catalysis of Battery Cells" and U.S. patent application Ser. No. 15/375,905 entitled "Binders for Wet and Dry catalysis of Battery Cells", filed 2016, 3/3.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 binders for wet-laminated and dry-laminated battery cells.
Background
Battery cells are typically manufactured using a lamination process that adheres a separator to one or more electrodes (such as a cathode or anode). These lamination processes may involve a "wet" process, in which the separator is immersed in an electrolyte fluid, or a "dry" process, in which the separator is free of electrolyte fluid. During manufacturing, the battery cell 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 that can be deposited thereon as a coating. Binders suitable for both "wet" and "dry" lamination processes are desirable in cell manufacture.
Disclosure of Invention
Embodiments provided herein relate to a battery stack including a binder for wet lamination processes and dry lamination processes. When laminated, the battery stack produces a battery cell (or portion thereof). The battery 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 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 percentage 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 percentage of 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 the separator with a first active material of a first electrode to form a first cell stack. The separator includes a binder comprising PVdF-HFP copolymer. The method also includes the step of heating the first cell stack to laminate the separator to the first electrode. In certain cases, the method additionally includes soaking 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 percentage 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 percentage of 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 battery 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 cell stack with a binder suitable for both wet and dry lamination according to an exemplary embodiment;
fig. 3B is a side view of the cell stack of fig. 3A, but where the separator includes a ceramic layer according to an exemplary embodiment; and is
Fig. 4 is a graph representing peel strength data for a cell stack formed using a blended binder, in accordance with an exemplary embodiment.
Detailed Description
Reference will now be made in detail to the exemplary embodiments illustrated in the accompanying 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 devices used in consumer, medical, aerospace, 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, the stack 102 can 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 be laid flat in a planar configuration or may be wound into a wound configuration (e.g., "jelly roll").
During assembly of the battery cell 100, the stack 102 may be enclosed in a flexible bag. The stack 102 may be in a planar configuration or a wound configuration, although other configurations are possible. The flexible bag is formed by folding a flexible sheet material along a 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 seal 108. The thickness of the flexible pouch may be less than or equal to 120 microns to improve the packaging efficiency of the battery cell 100, the density of the battery cell 100, or both.
The stack 102 also includes a set of conductive tabs 106 coupled to the cathode and anode. The conductive tab 106 may extend through a seal in the pouch (e.g., a seal formed using the sealing tape 104) to provide a terminal for the battery cell 100. Conductive tab 106 can then be used to electrically couple the battery cell 100 with one or more other battery cells to form a battery pack. For example, the battery pack may be formed by coupling the battery cells in a series, parallel, or series-parallel configuration. Such coupled units may be packaged in a rigid case or may be embedded within the housing 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 the battery cell, and the anode current collector 210 and the anode active coating 208 may form an anode for the battery cell. To form the 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 assembly of the battery cell.
As described above, the cathode current collector 202 may be an aluminum foil, the cathode active coating 204 may be a lithium compound, the anode current collector 210 may be a copper foil, the anode active coating 208 may be carbon, and the separator 206 may include a microporous polymer film or a non-woven 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), polyvinyl chloride (PVC), polyester, and polyvinylidene fluoride (PVdF). However, other microporous polymer membranes or nonwoven fabric mats are possible (e.g., gel polymer electrolytes).
Generally, the separator represents a structure in the battery, such as an interposed layer, which 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 a passage for ion transport, which may include absorption of an electrolyte fluid containing ions. The material of the separator can be selected based on chemical stability, porosity, pore size, permeability, wettability, mechanical strength, dimensional stability, softening temperature, and thermal 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 increasing the mechanical strength and resistance to thermal shrinkage of the separator. The binder material may be selected according to a wet lamination process in which the stack layers of the battery cells are laminated with the separator soaked in the electrolyte fluid, and a dry lamination process in which the stack layers of the battery cells are laminated using the electrolyte fluid-free separator. Binders that enable the cell to withstand both wet lamination and dry lamination can be beneficial in reducing the material and processing complexity of cell fabrication.
Fig. 3A presents a side view of a cell stack 300 with a binder 302 suitable for wet lamination and dry lamination according to an exemplary embodiment. When laminated, the battery stack 300 can 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.
A separator 316 is disposed between the cathode active material 306 and the anode active material 312, andand includes a binder 302 comprising polyvinylidene fluoride hexafluoropropylene copolymer (i.e., PVdF-HFP copolymer). In some embodiments, the cell stack 300 also includes an electrolyte fluid in contact with the separator 316. In these embodiments, separator 316 can be soaked 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 ethyl methyl 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: LiPF6、LiBF4、LiClO4、LiSO3CF3、LiN(SO2CF3)2、LiBC4O8、Li[PF3(C2CF5)3]And LiC (SO)2CF3)3. Other salts, including combinations of salts, are also possible.
The separator 316 can include a microporous polymer film or a nonwoven fabric mat 318, as shown in fig. 3A. The microporous polymer film or nonwoven fabric mat 318 can be any type of microporous polymer film or nonwoven fabric mat suitable for use in a battery cell (e.g., polymer film, gel polymer, etc.). Non-limiting examples of microporous polymer film or nonwoven fabric mats 318 include microporous polymer films or nonwoven fabric mats of Polyethylene (PE), polypropylene (PP), Polyamide (PA), Polytetrafluoroethylene (PTFE), polyvinyl chloride (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 nonwoven shaped microporous membrane 318, or both. Non-limiting examples of ceramic materials for the ceramic particles include magnesium oxide materials (e.g., Mg (OH)2MgO, etc.) and alumina materials (e.g., Al2O3). 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 mat 318. However, this description is not intended to be limiting. For example, and without limitation, the binder 302 may also be present in whole or in part 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 value, or any combination thereof that allows the cell 300 to be fabricated using a wet lamination process, a dry lamination process, or both. Without intending to be bound by 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 deg.c) and low swelling in the electrolyte fluid. Gradual incorporation of HFP into semi-crystalline polymeric materials (i.e., PVdF) results in copolymers with increased amorphous content, decreased melting temperature, and increased swelling of the electrolyte fluid. By selecting the molecular weight and weight percent of HFP, these characteristics can be manipulated to better adapt the copolymer to a wet lamination process, a dry lamination process, or both. However, it should be understood that the applicability of dry lamination may be opposite to the applicability of wet lamination (or vice versa).
For example, and without limitation, the weight percentage of HFP can be increased to lower the softening point of the copolymer, making the copolymer more suitable for dry lamination. However, this increase in weight percentage also increases the susceptibility of the copolymer to swelling during wet lamination. Swelling during wet lamination can weaken the contact between the separator 316 and the adjacent cathode 304 and anode 310, which can 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 the components (e.g., microporous polymer film or nonwoven fabric mat 318, cathode active material 306, anode active material 312, etc.) with which the binder 302 is in contact. Such improved interaction may enhance adhesion during wet lamination or dry lamination. However, increasing the molecular weight may 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 can be increased to improve the coating of the copolymer on the components (e.g., microporous polymer film or nonwoven fabric mat 318, cathode active material 306, anode active material 312, etc.) contacted by the binder 302. A 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 degree of swelling of the copolymer, making the copolymer less suitable for wet lamination.
Embodiments disclosed herein relate to binders comprising PVdF-HFP copolymers having a molecular weight and weight percent HFP suitable for both wet and dry processing. In addition, the PVdF-HFP copolymer has an acid number corresponding to the enhanced adhesion of the binder 302 to the 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.) that characterizes an 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 part with which the binder 302 is in contact. Non-limiting examples of acidic functional groups include carboxyl (e.g., formic acid, acetic acid, etc.) and hydroxyl. However, other acid functionalities are also possible.
In various aspects, the acid number is the amount of base needed to neutralize the acidity of a given amount of chemical. As used herein, acid number refers to the amount of potassium hydroxide (mg) required to neutralize a given amount (g) of PVdF-HFP copolymer. However, other equivalent units of measurement for acid number are possible. Techniques for determining acid number (and its corresponding units of measurement) 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 percentage of HFP is from 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 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 potassium hydroxide per gram of copolymer. In some embodiments, the PVdF-HFP copolymer has an acid number greater than or equal to 18 milligrams 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 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 binder 302 of the separator 316 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 percentage of 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 potassium hydroxide per gram of copolymer.
In some variations, the first PVdF-HFP copolymer and the second PVdF-HFP copolymer have an acid number 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 value 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 value of 12.6 milligrams potassium hydroxide per gram of copolymer. It is to be understood that the first acid value and the second acid value described herein can 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 the first weight percentage 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 the first weight percentage 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 the first weight percentage 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 the first weight percentage 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 the first weight percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage of HFP is greater than 14%.
In certain variations of the battery stack 300, the separator 316 comprises 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 provided 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, the ceramic layer 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 manufacture). Such ceramic layers may also improve the mechanical strength of the separator 316. Non-limiting examples of ceramic materials for the ceramic layer include magnesium oxide materials (e.g., Mg (OH)2MgO, etc.) and alumina materials (e.g., Al2O3). Fig. 3B presents a side view of the cell stack 300 of fig. 3A, but where separator 316 includes a ceramic layer according to an exemplary embodiment.
In some cases, first ceramic layer 328 is disposed along first interface 324. First ceramic layer 328 includes a plurality of first ceramic particles in contact with binder 302. In some cases, second ceramic layer 330 is disposed along second interface 326. Second ceramic layer 330 includes a plurality of second ceramic particles in contact with binder 302. In other cases, first ceramic layer 328 is disposed along first interface 324 and second ceramic layer 330 is disposed along second interface 326. In these cases, first ceramic layer 328 includes a plurality of first ceramic particles in contact with binder 302, and second ceramic layer 330 includes a plurality of second ceramic particles in contact with binder 302.
Contacting 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 first ceramic layer 328 and 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 first ceramic layer 328 and second ceramic layer 330, respectively. In still other instances, the plurality of first ceramic particles and the plurality of second ceramic particles represent greater than or equal to 90 wt% of first ceramic layer 328 and second ceramic layer 330, respectively.
Contacting with the binder 302 may also involve contacting the ceramic particles with a layer of the binder 302. Such a layer 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 representing peel strength data for a cell stack formed using a blended adhesive, in accordance with an exemplary 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 the cell stack. Thus, the data plots show 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 with a molecular weight of 1,200,000u, 6% weight percent HFP, and an acid number of 1 milligram of 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 percent of 5% HFP, and an acid value of 13 milligrams of potassium hydroxide per gram of copolymer, and a second PVdF-HFP copolymer having a molecular weight of 1,200,000u, a weight percent of 0% HFP, and an acid value of 10 milligrams of potassium hydroxide per gram of copolymer. The second blended binder has a first PVdF-HFP copolymer having a molecular weight of 1,100,000u, a weight percent of HFP of 5%, and an acid value of 13 milligrams of potassium hydroxide per gram of copolymer, and a second PVdF-HFP copolymer having a molecular weight of 860,000u, a weight percent of HFP of 12%, and an acid value of 2 milligrams of potassium hydroxide per gram of 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 and second ceramic layers are made of a material corresponding to 70% by weight of Mg (OH)2And 30 wt% of a blending binder. The first ceramic layer and the second ceramic layer are solution cast onto the separator of the cell stack. The activation temperature for 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. The anode active material in the anode includes 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) binder. Further, in all cases, the second blended binder exhibited peel strengths in excess of 1.5N/m. In contrast, the peel strength of conventional adhesives was below 1.5N/m in all cases. When adhering the separator to the anode in a wet process, it is desirable that the first co-binder reaches or exceeds 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 is understood that one skilled in the art can use Differential Scanning Calorimetry (DSC) techniques to distinguish the melting temperatures of the blended binders using a heat flow profile. Such a heat flow profile may allow for the determination of the weight percent of PVdF-HFP copolymer within the blended binder. In addition, Gel Permeation Chromatography (GPC) can also be used by those skilled in the art to determine the molecular weight of the PVdF-HFP copolymer in the blended binder.
According to an exemplary embodiment, a method for laminating at least one battery stack of battery cells includes the step of contacting a separator with a first active material of a first electrode to form a first battery stack. The separator includes a binder comprising PVdF-HFP copolymer. The PVdF-HFP copolymer has a molecular weight greater than or equal to 1,000,000u, and the weight percentage of HFP is 5% to 15%. 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 also 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 the cathode or an anode active material of the anode. In some embodiments, the method additionally includes the step of soaking the separator with an electrolyte fluid prior to heating the first cell stack. In some embodiments, the method additionally includes the step of soaking the separator with an electrolyte fluid and reheating the first cell stack after heating the first cell stack. It is to be understood that the presence or absence of the electrolyte fluid in the separator corresponds to the wet lamination process and the 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 milligrams 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 number less than or equal to 10 milligrams potassium hydroxide per gram of copolymer. In some variations, the PVdF-HFP copolymer has an acid number 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 soaking the separator with an electrolyte fluid prior to heating the first cell stack. In other cases, the method includes the step of soaking the separator with an electrolyte fluid and reheating the first cell stack after heating 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 also includes the step of heating the second cell stack to laminate the separator to the second electrode. In certain instances, the method can involve the step of soaking the separator with an electrolyte fluid prior to heating the second cell stack. In other cases, the method can involve the steps of soaking the separator with an electrolyte fluid after heating the second cell stack, and then heating the second cell stack again.
In still other embodiments, the method includes the step of soaking 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 certain instances, the method can involve the step of soaking the separator with an electrolyte fluid prior to heating the second cell stack. In other cases, the method can involve the steps of soaking the separator with an electrolyte fluid after heating the second cell stack, and then heating the second cell stack again.
According to another exemplary embodiment, a method for laminating at least one battery stack of battery cells includes the step of contacting a separator with a first active material of a first electrode to form a first battery 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 percentage of 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 number of 3 to 15 milligrams potassium hydroxide per gram of copolymer.
The method also 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 the cathode or an anode active material of the anode. In some embodiments, the method additionally includes the step of soaking the separator with an electrolyte fluid prior to heating the first cell stack. In some embodiments, the method additionally includes the step of soaking the separator with an electrolyte fluid and reheating the first cell stack after heating the first cell stack. It is to be understood that the presence or absence of the electrolyte fluid in the separator corresponds to the wet lamination process and the 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 percentage 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 soaking the separator with an electrolyte fluid prior to heating the first cell stack. In other cases, the method includes the step of soaking the separator with an electrolyte fluid and reheating the first cell stack after heating 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 also includes the step of heating the second cell stack to laminate the separator to the second electrode. In certain instances, the method can involve the step of soaking the separator with an electrolyte fluid prior to heating the second cell stack. In other cases, the method can involve the steps of soaking the separator with an electrolyte fluid after heating the second cell stack, and then heating the second cell stack again.
In still other embodiments, the method includes the step of soaking 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 certain instances, the method can involve the step of soaking the separator with an electrolyte fluid prior to heating the second cell stack. In other cases, the method can involve the steps of soaking the separator with an electrolyte fluid after heating the second cell stack, and then heating the second cell stack again.
The battery stacks described herein may have value in the manufacture of electronic devices that include battery cells manufactured with a wet lamination process, a dry lamination process, 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 smartphone (including, for example, a smart phone)
Figure BDA0001784871620000171
) And an electronic mail sending/receiving 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.,
Figure BDA0001784871620000172
) And the like. 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.,
Figure BDA0001784871620000173
) A watch (e.g., AppleWatch), or a computer monitor. The electronic device may also be part of a device providing control, such as controlling an imageStreaming, video streaming and audio streaming (e.g., Apple
Figure BDA0001784871620000174
) Or it may be a remote control of the electronic device. Further, the electronic device may be part of a computer or its accessories, such as a hard disk tower housing or protective case, a laptop housing, a laptop keyboard, a laptop touchpad, a desktop keyboard, a mouse, and a speaker. The anode battery, the lithium metal battery, and the battery pack may also be applied to devices such as a watch or a clock.
In the description above, 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 in order 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. It will be apparent to those skilled in the art that many modifications and variations are possible in light of the above teaching.

Claims (19)

1. A separator comprising a binder, the binder comprising PVdF-HFP copolymer;
wherein the PVdF-HFP copolymer has a molecular weight greater than or equal to 1,000,000 grams/mole and the weight percentage of HFP is from 5% to 15%; and is
Wherein the PVdF-HFP copolymer has an acid value of 1.5 to 15 milligrams potassium hydroxide per gram of copolymer.
2. 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; and
the separator of claim 1, disposed between the cathode active material and the anode active material.
3. The battery stack of claim 2 further comprising an electrolyte fluid in contact with the separator.
4. The battery stack of any of claims 2-3 wherein the separator further comprises a polyolefin layer comprising a first side and a second side, the first side forming a first interface with the cathode active material and the second side forming a second interface with the anode active material.
5. The battery stack of claim 4, wherein a first ceramic layer is disposed along the first interface, the first ceramic layer comprising a plurality of first ceramic particles in contact with the binder.
6. The battery stack of claim 5, wherein a second ceramic layer is disposed along the second interface, the second ceramic layer comprising a plurality of second ceramic particles in contact with the binder.
7. A separator comprising a blended binder comprising 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 percentage of HFP is less than or equal to 7%, and
wherein the second PVdF-HFP copolymer has a second molecular weight of 500,000 to 1,000,000 grams/mole and a second weight percentage of HFP is 10% to 15%, wherein each of the first PVdF-HFP copolymer and the second PVdF-HFP copolymer has an acid value of 1.5 to 15 milligrams of potassium hydroxide/gram of copolymer.
8. 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 of claim 7, disposed between the cathode active material and the anode active material.
9. The cell stack of claim 8, wherein the first PVdF-HFP copolymer has a first acid value of 2.1 milligrams potassium hydroxide per gram copolymer and the second PVdF-HFP copolymer has a second acid value of 12.6 milligrams potassium hydroxide per gram copolymer.
10. The battery stack of one of claims 8-9 wherein the separator further comprises a polyolefin layer comprising a first side and a second side, the first side forming a first interface with the cathode active material and the second side forming a second interface with the anode active material.
11. The battery stack of claim 10, wherein a first ceramic layer is disposed along the first interface, the first ceramic layer comprising a plurality of first ceramic particles in contact with the blended binder.
12. The battery stack of claim 10, wherein a second ceramic layer is disposed along the second interface, the second ceramic layer comprising a plurality of second ceramic particles in contact with the blended binder.
13. The battery stack according to claim 10,
wherein a first ceramic layer is disposed along the first interface, the first ceramic layer comprising a plurality of first ceramic particles in contact with the blended binder; and is
Wherein a second ceramic layer is disposed along the second interface, the second ceramic layer comprising a plurality of second ceramic particles in contact with the blended binder.
14. The battery stack of claim 8, wherein the blended binder has a peel strength to the anode of more than 1.5N/m in both wet and dry lamination processes.
15. A method for laminating at least one battery stack of battery cells, the method comprising:
contacting a separator with the first active material of the first electrode to form a first cell stack, the separator comprising a blended binder comprising a first PVdF-HFP copolymer and a second PVdF-HFP copolymer;
heating the first cell stack to laminate the separator to the first electrode; and is
Wherein the first PVdF-HFP copolymer has a first molecular weight greater than or equal to 1,000,000 g/mole and the first weight percentage of HFP is less than or equal to 7%, and
wherein the second PVdF-HFP copolymer has a second molecular weight of 500,000 to 1,000,000 grams/mole, and the second weight percentage of HFP is 10% to 15%,
wherein the first PVdF-HFP copolymer and the second PVdF-HFP copolymer each have an acid value of 1.5 to 15 milligrams potassium hydroxide per gram copolymer.
16. The method of claim 15, wherein the first PVdF-HFP copolymer has a first acid value of 2.1 milligrams potassium hydroxide per gram copolymer and the second PVdF-HFP copolymer has a second acid value of 12.6 milligrams potassium hydroxide per gram copolymer.
17. The method according to one of claims 15-16, further comprising:
after heating the first cell stack, soaking the separator with an electrolyte fluid and heating the first cell stack again.
18. Method according to one of the claims 15-16,
wherein contacting the separator with the first active material of the first electrode comprises contacting the separator with a second active material of a second electrode;
wherein the separator is disposed between the first electrode and the second electrode to form the first cell stack; and is
Wherein heating the first cell stack laminates the separator to both the first electrode and the second electrode.
19. The method according to one of claims 15-16, further comprising:
contacting the separator of the first cell stack with a second active material of a second electrode, thereby forming a second cell stack; and
heating the second cell stack to laminate the separator to the second electrode.
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