WO2019195605A1 - Glass fiber composite separator - Google Patents

Glass fiber composite separator Download PDF

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Publication number
WO2019195605A1
WO2019195605A1 PCT/US2019/025872 US2019025872W WO2019195605A1 WO 2019195605 A1 WO2019195605 A1 WO 2019195605A1 US 2019025872 W US2019025872 W US 2019025872W WO 2019195605 A1 WO2019195605 A1 WO 2019195605A1
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WIPO (PCT)
Prior art keywords
composite separator
glass fiber
layer
polymer layer
composite
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Application number
PCT/US2019/025872
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French (fr)
Inventor
Meng-Chang Lin
Chun-Jern Pan
Meijie TANG
Pengfei Qi
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Ab Systems, Inc. (Us)
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Publication of WO2019195605A1 publication Critical patent/WO2019195605A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • 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
    • 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
    • H01M50/454—Separators, membranes or diaphragms characterised by the material having a layered structure comprising a non-fibrous layer and a fibrous layer superimposed on one another
    • 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
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • 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

Definitions

  • the present disclosure concerns electrolyte separators for rechargeable (i.e., secondary) batteries as well as methods of making and using the same.
  • the present disclosure concerns electrolyte separators for rechargeable batteries such as, but not limited to, rechargeable batteries having an aluminum (Al) metal anode (i.e., negative electrode).
  • a battery energy density is related to the electrochemical potential difference for an atom (e.g ., Al) in the anode relative to its corresponding ion (e.g., Al 3+ or AICU ) in the cathode.
  • a rechargeable battery’s energy density is therefore maximized when the anode is a single metal.
  • the electrochemical potential for a metal atom in a metal made of identical metal atoms is 0 V.
  • the electrochemical potential for a metal atom in a intercalation host is greater than 0 V.
  • Metal anodes as compared to intercalation anodes therefore maximize the energy difference between the anode and any cathode. As such, to increase the energy density of current batteries, metal anode rechargeable batteries are desired but not yet commercially available.
  • Aluminum (Al) is an attractive metal for a metal anode rechargeable battery.
  • the three-electron redox properties of Al provide a theoretical gravimetric capacity as high as 2,980 mAh/g and a volumetric capacity as high as 804 Ah cm -3 , when paired with a carbon- containing cathode.
  • Al is also the third most abundant element in the Earth’s crust.
  • Al is generally less reactive than other metal anodes (e.g., lithium (Li) and sodium (Na)) and is easier to process. Al is therefore an economically viable choice for large scale battery applications.
  • Al-metal batteries which have been prepared suffer from a variety of disadvantages including instability during use, including instability over the total operation time of the battery.
  • Al-metal batteries were cycled, and, if they remained stable, for example, they only remained stable for up to 100 hours of operation time, e.g. , cycled at 70C rate for 7000 cycles.
  • What is needed, for example is batteries that can be cycled and remain stable at, for example, 1C rate for 7000 cycles, which would include 7000 hours of operation time.
  • the prior-published Al-metal batteries showed capacity and/or coulombic efficiency fade after a few electrochemical charge-discharge cycles.
  • One unresolved problem relates to the lack of chemically compatible materials which can be used with an Al-metal anode rechargeable battery.
  • such materials need to be chemically compatible with the acidic environment of the chloride-containing electrolytes suitable for use with Al-metal anode and also sufficiently strong to interact with the other battery components.
  • Such separators are those which only include porous, loosely bound glass fibers. If Al metal grows through the electrolyte separator and between the cathode and anode of a battery, a short- circuit results.
  • a composite separator including a glass fiber layer; a polymer layer, or a derivative thereof; and optionally a binder.
  • the composite separator is between a positive electrode and a negative electrode.
  • the composite separator is in contact with both the positive electrode and the negative electrode.
  • the glass fiber layer is between and in contact with the metal negative electrode and the polymer layer; and the polymer layer is between and in contact with the glass fiber layer and the positive electrode;
  • the glass fiber layer is between and in contact with the polymer layer and the positive electrode;
  • the glass fiber layer is between and in contact with the polymer layer and an additional polymer layer;
  • the polymer layer is between and in contact with the glass fiber layer and an additional glass fiber layer.
  • a process of making a composite separator including the following steps: (a) providing a binder solution; (b) providing a glass fiber layer; (c) contacting the binder solution to the glass fiber paper to form a binder glass fiber layer composite; (d) drying the binder glass fiber layer composite; and (e) contacting a solution of a polymer to the binder glass fiber layer composite to form a composite separator.
  • a process of making a composite separator including the following steps: (a) providing a binder solution; (b) providing a glass fiber layer; (c) providing a polymer layer; (d) contacting the binder solution to the glass fiber paper to form a binder glass fiber layer composite; (e) contacting the polymer layer to the binder glass fiber layer composite to form a composite separator; and (f) drying the composite separator.
  • electrochemical cells that include any composite separator set forth herein or any composite separator made by a process set forth herein.
  • rechargeable batteries that include any composite separator set forth herein or any composite separator made by a process set forth herein.
  • FIG. 1 shows an embodiment of a composite separator.
  • FIG. 2 shows an embodiment of a composite separator.
  • FIG. 3 shows an embodiment of a composite separator.
  • FIG. 4 shows an embodiment of a composite separator.
  • FIG. 5 shows cycle-life performance of a composite separator.
  • FIG. 6 shows cycle-life performance of a composite separator.
  • FIG. 7 shows cycle-life performance of a composite separator.
  • FIG. 8 shows cycle-life performance of a composite separator.
  • FIG. 9 shows cycle-life performance of a composite separator.
  • FIG. 10 shows cycle-life performance of a composite separator.
  • FIG. 11 shows cycle-life performance of a composite separator.
  • FIG. 12 shows cycle-life performance of a composite separator
  • FIG. 13 shows cycle-life performance of a composite separator.
  • FIG. 14 shows cycle-life performance of a composite separator.
  • FIG. 15 shows cycle-life performance of a composite separator.
  • FIG. 16 shows cycle-life performance of a composite separator.
  • FIG. 17 shows certain chemical reactions relevant to the instant disclosure.
  • FIG. 18 shows cycle-life performance of a composite separator.
  • FIG. 19 shows the 225 th cycle of a battery prepared in Example 4.
  • FIG. 20 shows cycle-life performance of a composite separator.
  • FIG. 21 shows the 315 th cycle of a battery prepared in Example 4.
  • separators include a glass fiber layer and a polymer layer.
  • the separators optionally include a binder.
  • the composite separator improves a battery’s cycle -life.
  • a non-limiting example includes an Al-ion battery with a nonaqueous electrolyte and a composite separator that includes a porous glass fiber layer; a hydrophilic PTFE layer; and a binder layer.
  • a non-limiting example includes an Al-ion battery with a nonaqueous electrolyte and a composite separator that includes a porous glass fiber layer; a hydrophilic polyimide (PI) layer; and a binder layer.
  • PI polyimide
  • a binder layer or a polymer layer is deposited onto a glass fiber layer using solutions of binders and/or polymers.
  • the composite separators set forth herein are in some embodiments thin, e.g ., 60-200 pm in thickness and are suitable for use with Al-ion batteries.
  • the cycle life of Al-ion batteries (AIB) having a composite separator set forth herein is at least 15-20 greater.
  • AIB having a composite separator set forth herein also show less capacity fade over time.
  • AIB having a composite separator set forth herein also show less Coulombic efficiency degradation over time.
  • the composite separators herein, are advantageous for many reasons, such as manufacturing reasons.
  • the term“about,” when qualifying a number, e.g, 100 °C, refers to the number qualified and optionally the numbers included in a range about that qualified number that includes ⁇ 10% of the number.
  • about 100 °C includes 100 °C as well as 90 °C, 91 °C, 92 °C, 93 °C, 94 °C, 95 °C, 96 °C, 97 °C, 98 °C, 99 °C, 100 °C, 101 °C, 102 °C, 103 °C, 104 °C, 105 °C, 106 °C, 107 °C, 108 °C, 109 °C, and 110 °C.
  • “selected from the group consisting of’ refers to a single member from the group, more than one member from the group, or a combination of members from the group.
  • a member selected from the group consisting of A, B, and C includes, for example, A only, B only, or C only, as well as A and B, A and C, B and C, as well as A, B, and C.
  • the phrases“electrochemical cell” or“battery cell” shall mean a single cell including an anode and a cathode, which have ionic communication between the two using an electrolyte.
  • the terms“cathode” and“anode” refer to the electrodes of a battery.
  • the anode of an Al-metal anode battery includes Al.
  • the cathode includes graphite.
  • AlClf ions de-intercalate from the graphite and conduct through the electrolyte to eventually plate out as Al at the anode (via AhCE ions).
  • Al 2 Cl 7 ions dissolve from the Al anode, convert into AlClf ions while conducting through the electrolyte and eventually intercalate into the graphite in the cathode.
  • the cathode refers to the positive electrode.
  • the anode refers to the negative electrode.
  • the term“separator,” refers to the physical barrier which electrically insulates the anode and the cathode from each other.
  • the separator is often porous so it can be filled or infiltrated with an electrolyte.
  • the separator is often mechanically robust so it can withstand the pressure applied to the electrochemical cell.
  • Example separators include, but are not limited to, Si0 2 glass fiber separators or Si0 2 glass fiber mixed with a polymer fiber or mixed with a binder.
  • C-rate refers to a measure of the rate at which a battery is discharged relative to its maximum capacity.
  • a 1C rate means that the discharge current will discharge the entire battery in 1 hour.
  • a 1C rate equates to a discharge current of 100 Amps.
  • the term“ionic liquid electrolyte” or“ILE,” refers to nonflammable electrolytes which include a mixture of a strong Lewis acid metal halide and Lewis base ligand. Examples include, but are not limited to, AlCb and l-ethyl-3- methylimidazolium chloride ([EMImJCl).
  • Lewis base ligands include, but are not limited to, urea, methylurea, acetamide, or 4-propylpyridine.
  • AlCL undergoes asymmetric cleavage to form a tetrachloroaluminate anion (AlCL ) and an aluminum chloride cation (AlCh + ) in which a ligand is datively bonded to (or associated through coordination via sharing of lone pair electrons) the AlCl 2 + cation, forming ([AlCL n(ligand)] + ).
  • Ionic liquids are useful as electrolytes for Al-metal anode batteries.
  • Examples include AlCb and 1 -ethyl-3 -methylimidazolium chloride (EMIC); AlCL and urea; AlCL and acetamide; AlCb and 4-propylpyridine; and AlCL and trimethylphenylammonium chloride.
  • EMIC AlCb and 1 -ethyl-3 -methylimidazolium chloride
  • AlCL and urea AlCL and acetamide
  • AlCb and 4-propylpyridine AlCL and trimethylphenylammonium chloride.
  • the term“deep eutectic solvent,”“deep eutectic solvent electrolyte,” or“DES,” refers to a mixture of a strong Lewis acid metal halide and a Lewis base ligand. See , for example, Hogg, JM, et al. , Green Chem 17(3): 1831-1841; Fang, Y, et al., Electrochim Act 160:82-88; Fang, Y, et al. , Chem. Commun. 51(68)13286-13289; and also Pulletikurthi, G., et al. , Nature , 520(7547):325-328 for a non-limiting set of example DES mixtures.
  • the content of each of these references is herein incorporated by reference in their entirety for all purposes. Examples include, but are not limited to, AlCb and urea.
  • metal halide salt refers to a salt which includes at least one metal atom and at least one halogen atom. Examples include, but are not limited to, AIF3, AlCb, AlBr3, AlL, and combinations thereof.
  • the phrases“hydrophilic polymer,” and“hydrophilic-treated polymer” refer to a polymer which wets an ILE or DES set forth herein.
  • the term“hydrophilic-treated polymer” refers to a polymer which is treated with, or reacted with, chemical groups that impart a hydrophilic property to the polymer.
  • a non-limiting set of example hydrophilic-treated polymer are found in Bi, et al, Journal of Power Sources 194 (2009) 838-842; S. Sugiyama et al., React. Polym.
  • a hydrophilic-treated polymer includes, but is not limited to, hydrophilic-treated pol ytetrafl uoroethyl ene (PTFE), hydrophilic-treated polyacrylonitrile (PAN), hydrophilic-treated fluorinated ethylene propylene (FEP), hydrophilic-treated polychlorotrifluoroethylene (PCTFE), hydrophilic- treated polyvinylidene fluoride (PVDF), hydrophilic-treated hexafluoropropylene (HFP), hydrophilic-treated PVDF-HFP, hydrophilic-treated polyfluoroalkoxy (PFA), and hydrophilic-treated polyimide (PI).
  • PTFE hydrophilic-treated pol ytetrafl uoroethyl ene
  • PAN hydrophilic-treated polyacrylonitrile
  • FEP hydrophilic-treated fluorinated ethylene propylene
  • PCTFE hydrophilic-treated polychlorotrifluoroethylene
  • a hydrophilic-treated polymer is a polymer which an ILE or DES wets. Wetting is determined by a contact angle measurement. In this contact angle measurement, an ILE or DES is deposited onto a polymer. The ILE or DES wets a polymer when the contact angle between the surface of the polymer and a line tangent to the surface of the ILE or DES, which is deposited on the polymer, is less than or equal to 90 °. The ILE or DES does not wets a polymer when the contact angle between the surface of the polymer and a line tangent to the surface of the ILE or DES is greater than 90 °.
  • Hydrophilic surfaces are observed to have low contact angles (less than or equal to 90 degrees) with respect to a solution on the hydrophilic surface. Hydrophobic surfaces are observed to have high contact angles (greater than 90 degrees) with respect to a solution on the hydrophobic surface.
  • a hydrophilic-treated polymer is made by bonding, through a chemical reaction, a polar chemical group to the polymer.
  • Example polar chemical groups include, but are not limited to amino (NH 2 ), carboxyl (COOH) and sulfonic acid (SO3H) groups.
  • a hydrophilic-treated polymer may be synthesized via hydrolytic polycondensation and free radical polymerization. Polymers may also be functionalized by physical entanglement with chemical species having polar chemical groups.
  • PTFE is functionalized with a sulfonic acid (SO3H) group.
  • SO3H sulfonic acid
  • Functionalized polymers are referred to herein as a derivative of the polymer which is functionalized.
  • functionalized PTFE is referred to herein as a derivative of PTFE.
  • hydrophobic polymer refers to a polymer which does not wets an ILE or DES set forth herein.
  • a hydrophobic polymer includes, but is not limited to, polytetrafluoroethylene (PTFE), polyacrylonitrile (PAN), fluorinated ethylene propylene (FEP), polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), hexafluoropropylene (HFP), PVDF-HFP, and polyfluoroalkoxy (PFA).
  • PTFE polytetrafluoroethylene
  • PAN polyacrylonitrile
  • FEP fluorinated ethylene propylene
  • PCTFE polychlorotrifluoroethylene
  • PVDF polyvinylidene fluoride
  • HFP hexafluoropropylene
  • PVDF-HFP polyfluoroalkoxy
  • particle size refers to the average dimension characteristic of the longest length, side, or diameter of the particle. For particles which are spherical or approximately spherical, particle size refers to the average diameter of the particles. As used herein, particle size is measured by scanning electron microscopy (SEM), unless specified otherwise to the contrary. In some specific examples, particle size may be selected by sieving through a well-defined mesh.
  • SEM scanning electron microscopy
  • graphitized refers to a material which includes graphite.
  • the term“crystalline,” refers to a material which diffracts x- rays.
  • Crystalline graphite is characterized by at least an XRD peak at 26.55 2Q (the (002) peak of graphite having a d-spacing of 3.35 A).
  • Graphite is mined as either vein, flake, or microcrystalline.
  • graphite can be vein, flake, microcrystalline, or a combination thereof.
  • the graphite is flake graphite.
  • the graphite is natural flake graphite.
  • the term“few defects,” refers to graphite that has less than 5% defects per mole.
  • Defects include, but are not limited to, misshaped particles, amorphous carbon, or particles having a particle size other than the average particle size.
  • Defects in graphite can be measured using Raman spectroscopy and comparing the defect D band intensity relative to the graphite G band.
  • the ratio D/G is about near zero for natural graphite with few defects. In some examples, the ratio D/G is about zero for natural graphite with few defects.
  • cycling refers to an electrochemical process whereby an electrochemical cell having an anode and a cathode is charged and discharged.
  • the composite separator is, in some examples, thin ( e.g ., 85 um), robust and protects the Al-ion battery from shorting during use.
  • FIGs. 1-4 show four alternatives in which glass fiber paper (GFP) and PTFE layers are assembled to form composite separators.
  • GFP glass fiber paper
  • PTFE PTFE layers
  • a binder or binders optionally included with any of these composite separators.
  • FIG. 1 shows an electrochemical cell, 100.
  • the electrochemical cell, 100 includes a positive electrode, 101, and a negative electrode, 104. Between the positive electrode, 101, and the negative electrode, 104, is a composite separator that is made of layers 102 and 103.
  • Layer 102 is a glass fiber layer.
  • Layer 103 is a polymer layer. In some examples, the polymer is a hydrophilic polymer. In some examples, the polymer is a hydrophobic polymer.
  • Layers 101, 102, 103, and 104 are in contact with each other such that ions can conduct from layer 101 to layer 104 and vice versa.
  • FIG. 2 shows an electrochemical cell, 200.
  • the electrochemical cell, 200 includes a positive electrode, 201, and a negative electrode, 204. Between the positive electrode, 201, and the negative electrode, 204, is a composite separator that is made of layers 202 and 203.
  • Layer 203 is a glass fiber layer.
  • Layer 202 is a polymer layer. In some examples, the polymer is a hydrophilic polymer. In some examples, the polymer is a hydrophobic polymer.
  • Layers 201, 202, 203, and 204 are in contact with each other such that ions can conduct from layer 201 to layer 204 and vice versa.
  • FIG. 3 shows an electrochemical cell, 300.
  • the electrochemical cell, 300 includes a positive electrode, 301, and a negative electrode, 305. Between the positive electrode, 301, and the negative electrode, 305, is a composite separator that is made of layers 302, 303 and 304.
  • Layer 303 is a glass fiber layer.
  • Layers 302 and 304 are polymer layers. In some examples, the polymer is a hydrophilic polymer. In some examples, the polymer is a hydrophobic polymer.
  • Layers 301, 302, 303, 304, and 305 are in contact with each other such that ions can conduct from layer 301 to layer 305 and vice versa.
  • FIG. 4 shows an electrochemical cell, 400.
  • the electrochemical cell, 400 includes a positive electrode, 401, and a negative electrode, 405. Between the positive electrode, 401, and the negative electrode, 405, is a composite separator that is made of layers 402, 403 and 404.
  • Layer 403 is a polymer layer.
  • Layers 402 and 404 are glass fiber layers.
  • the polymer is a hydrophilic polymer.
  • the polymer is a hydrophobic polymer.
  • Layers 401, 402, 403, 404, and 405 are in contact with each other such that ions can conduct from layer 401 to layer 404 and vice versa.
  • Glass fiber paper is used as an electrolyte separator in some aluminum- ion batteries (AIBs) which use ionic liquid electrolytes and have an Al anode and a graphite cathode.
  • AIBs aluminum- ion batteries
  • GFP is inexpensive and chemically-inert to an acidic electrolyte.
  • GFP is also resistant to corrosion during battery operation. Thick separators of GFP, with thickness ranging from
  • a composite separator includes a glass fiber layer and a polymer layer, or a derivative thereof.
  • the composite separator optionally includes a binder.
  • the composite separator When the composite separator is positioned between a positive electrode and a negative electrode, one of the following conditions (a), (b), (c), or (d) is satisfied: either (a) the glass fiber layer is between and in contact with the metal negative electrode and the polymer layer; and the polymer layer is between and in contact with the glass fiber layer and the positive electrode;
  • the glass fiber layer is between and in contact with the polymer layer and the positive electrode;
  • the glass fiber layer is between and in contact with the polymer layer and an additional polymer layer;
  • the polymer layer is between and in contact with the glass fiber layer and an additional glass fiber layer.
  • condition (c) when condition (c) is satisfied, then either: (cl) the polymer layer is in contact with the positive electrode and the additional polymer layer is in contact with the negative electrode; or (c2) the polymer layer is in contact with the negative electrode and the additional polymer layer is in contact with the positive electrode.
  • condition (d) when condition (d) is satisfied either: (dl) the glass fiber layer is in contact with the positive electrode and the additional glass fiber layer is in contact with the negative electrode; or (d2) the glass fiber layer is in contact with the negative electrode and the additional glass fiber layer is in contact with the positive electrode.
  • the polymer layer is a hydrophilic polymer layer.
  • the polymer layer is a hydrophilic-treated polymer layer.
  • the additional polymer layer is a hydrophilic polymer layer.
  • the additional polymer layer is the same type of polymer as the polymer layer.
  • the polymer layer is a hydrophilic polymer layer, and the hydrophilic polymer layer is between and in contact with the metal negative electrode and the glass fiber layer.
  • the polymer layer is a hydrophilic polymer layer, and the hydrophilic polymer layer is between and in contact with the positive electrode and the glass fiber layer.
  • the polymer layer is a hydrophilic polymer layer
  • the glass fiber layer is between and in contact with the metal negative electrode and the hydrophilic polymer layer.
  • the polymer layer is a hydrophilic polymer layer
  • the glass fiber layer is between and in contact with the positive electrode and the hydrophilic polymer layer.
  • the thickness of the glass fiber layer is 5 pm, 10 pm, 15 pm, 25 pm, 50 pm, 75 pm, or 100 pm.
  • the thickness of the additional glass fiber layer is 5 pm, 10 pm, 15 pm, 25 pm, 50 pm, 75 pm, or 100 pm.
  • the thickness of the polymer layer is 5 pm, 10 pm, 15 pm, 25 pm, 50 pm, 75 pm, or 100 pm.
  • the thickness of the additional polymer layer is 5 pm, 10 pm, 15 pm, 25 pm, 50 pm, 75 pm, or 100 pm.
  • the thickness of the glass fiber layer or additional glass fiber layer, or both is from 0 pm to 300 pm. In some examples, including any of the foregoing, the thickness of the glass fiber layer is from 0 pm to 300 pm. In some examples, including any of the foregoing, the thickness of the additional glass fiber layer, is from 0 pm to 300 pm. In some examples, including any of the foregoing, the thickness of both the glass fiber layer and the additional glass fiber layer is from 0 pm to 300 pm.
  • the thickness of the glass fiber layer or additional glass fiber layer, or both is from 20 pm to 300 pm. In some examples, including any of the foregoing, the thickness of the glass fiber layer is from 20 pm to 300 pm. In some examples, including any of the foregoing, the thickness of the additional glass fiber layer is from 20 pm to 300 pm. In some examples, including any of the foregoing, the thickness of both the glass fiber layer and additional glass fiber layer is from 20 pm to 300 pm.
  • the thickness of the glass fiber layer or additional glass fiber layer, or both is from about 50 pm to about 200 pm. In some examples, including any of the foregoing, the thickness of the glass fiber layer is from about 50 pm to about 200 pm. In some examples, including any of the foregoing, the thickness of the additional glass fiber layer is from about 50 pm to about 200 pm. In some examples, including any of the foregoing, the thickness of both the glass fiber layer and additional glass fiber layer is from about 50 pm to about 200 pm.
  • the glass fiber layer or additional glass fiber layer, or both includes glass fiber paper. In some examples, including any of the foregoing, the glass fiber layer includes glass fiber paper. In some examples, including any of the foregoing, the additional glass fiber layer includes glass fiber paper. In some examples, including any of the foregoing, both the glass fiber layer and additional glass fiber layer include glass fiber paper. [86] In some examples, including any of the foregoing, the glass fiber layer or additional glass fiber layer, or both, is porous. In some examples, including any of the foregoing, the glass fiber layer is porous. In some examples, including any of the foregoing, the additional glass fiber layer is porous. In some examples, including any of the foregoing, both the glass fiber layer and additional glass fiber layer are porous.
  • the porous glass fiber layer includes pores from about 0.1 pm to about 10 pm in diameter. In some examples, including any of the foregoing, the pores are about 0.6 pm in diameter. In some examples, including any of the foregoing, the pores are about 0.1 pm in diameter. In some examples, including any of the foregoing, the pores are about 0.2 pm in diameter. In some examples, including any of the foregoing, the pores are about 0.3 pm in diameter. In some examples, including any of the foregoing, the pores are about 0.4 pm in diameter. In some examples, including any of the foregoing, the pores are about 0.5 pm in diameter. In some examples, including any of the foregoing, the pores are about 0.6 pm in diameter.
  • the pores are about 0.7 pm in diameter. In some examples, including any of the foregoing, the pores are about 0.8 pm in diameter. In some examples, including any of the foregoing, the pores are about 0.9 pm in diameter. In some examples, including any of the foregoing, the pores are about 1.0 pm in diameter. In some examples, including any of the foregoing, the pores are about 1.5 pm in diameter. In some examples, including any of the foregoing, the pores are about 2.0 pm in diameter. In some examples, including any of the foregoing, the pores are about 3.0 pm in diameter. In some examples, including any of the foregoing, the pores are about 4.0 pm in diameter.
  • the pores are about 5.0 pm in diameter. In some examples, including any of the foregoing, the pores are about 6.0 pm in diameter. In some examples, including any of the foregoing, the pores are about 7.0 pm in diameter. In some examples, including any of the foregoing, the pores are about 8.0 pm in diameter. In some examples, including any of the foregoing, the pores are about 9.0 pm in diameter. In some examples, including any of the foregoing, the pores are about 10 pm in diameter.
  • the glass fiber layer or additional glass fiber layer, or both includes Si0 2. In some examples, including any of the foregoing, the glass fiber layer includes Si0 2. In some examples, including any of the foregoing, the additional glass fiber layer includes Si0 2. In some examples, including any of the foregoing, both the glass fiber layer and additional glass fiber layer include Si0 2. In some examples, including any of the foregoing, the glass fiber layer or additional glass fiber layer, or both, includes Si0 2 fibers. In some examples, including any of the foregoing, the glass fiber layer includes Si0 2 fibers. In some examples, including any of the foregoing, the additional glass fiber layer includes Si0 2 fibers. In some examples, including any of the foregoing, both the glass fiber layer and additional glass fiber layer include Si0 2 fibers.
  • the polymer layer or additional polymer layer, or both includes a multilayer.
  • the polymer layer includes a multilayer.
  • the additional polymer layer includes a multilayer.
  • both the polymer layer and additional polymer layer include a multilayer.
  • the multilayer is a multilayer of hydrophilic polymer layers.
  • the multilayer is a multilayer of hydrophobic polymer layers.
  • the multilayer includes 2, 3, 4, or 5 individual polymer layers.
  • the thickness of each individual polymer layer in the multilayer is from about 5 pm to about 50 pm.
  • the thickness of the hydrophilic polymer layer or additional hydrophilic polymer layer, or both is, individually in each instance, from about 5 pm to about 150 pm.
  • the thickness of the hydrophilic polymer layer or additional hydrophilic polymer layer, or both is, individually in each instance, from about 5 pm to about 50 pm.
  • the thickness of the hydrophilic polymer layer or additional hydrophilic polymer layer, or both is, individually in each instance, from about 15 pm to about 25 pm.
  • the hydrophilic polymer layer includes a porous substrate on which a hydrophilic polymer is coated.
  • the porous substrate is a hydrophobic or hydrophilic membrane.
  • the porous substrate is selected from the group consisting of a porous metal, a porous polymer, and a porous ceramic.
  • the porous substrate is selected from the group consisting of a porous glass fiber paper, a regenerated cellulose membrane, a polyester membrane, a polyethersulfone membrane, and a polyethylene membrane.
  • the polymer layer is a hydrophilic polymer layer comprising a hydrophilic polymer is selected from the group consisting of polytetrafluoroethylene (PTFE), polyacrylonitrile (PAN), fluorinated ethylene propylene (FEP), polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), hexafluoropropylene (HFP), PVDF-HFP, polyfluoroalkoxy (PFA), a derivative thereof, and combinations thereof.
  • PTFE polytetrafluoroethylene
  • PAN polyacrylonitrile
  • FEP fluorinated ethylene propylene
  • PCTFE polychlorotrifluoroethylene
  • PVDF polyvinylidene fluoride
  • HFP hexafluoropropylene
  • PVDF-HFP polyfluoroalkoxy
  • PFA polyfluoroalkoxy
  • the polymer layer is a hydrophilic polymer layer comprising a hydrophilic polymer is selected from the group consisting of polytetrafluoroethylene (PTFE), polyacrylonitrile (PAN), fluorinated ethylene propylene (FEP), polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), hexafluoropropylene (HFP), PVDF-HFP, polyfluoroalkoxy (PFA), polyimide (PI), a derivative thereof, and combinations thereof.
  • PTFE polytetrafluoroethylene
  • PAN polyacrylonitrile
  • FEP fluorinated ethylene propylene
  • PCTFE polychlorotrifluoroethylene
  • PVDF polyvinylidene fluoride
  • HFP hexafluoropropylene
  • PVDF-HFP polyfluoroalkoxy
  • PI polyimide
  • the polymer layer is a hydrophobic polymer layer comprising a hydrophobic polymer is selected from the group consisting of polytetrafluoroethylene (PTFE), polyacrylonitrile (PAN), fluorinated ethylene propylene (FEP), polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), hexafluoropropylene (HFP), PVDF-HFP, and polyfluoroalkoxy (PFA), and combinations thereof.
  • PTFE polytetrafluoroethylene
  • PAN polyacrylonitrile
  • FEP fluorinated ethylene propylene
  • PCTFE polychlorotrifluoroethylene
  • PVDF polyvinylidene fluoride
  • HFP hexafluoropropylene
  • PVDF-HFP polyfluoroalkoxy
  • the binder is selected from the group consisting of polyacrylate (PA), polyacrylic acid (PAA), polyvinyl alcohol (PVA), cross-linked PAA, cross-linked PVA, PAA-PVA, polyacrylic latex, cellulose, cellulose derivatives, alginate, polyethylene glycol, styrene-butadiene rubber, poly(styrene-co- butadiene), styrene-butadiene rubber, poly(3, 4-ethyl enedioxythiophene), acrylonitrile copolymer, acrylic latex, and combinations thereof.
  • PA polyacrylate
  • PAA polyacrylic acid
  • PVA polyvinyl alcohol
  • PAA-PVA polyvinyl alcohol
  • PAA-PVA polyacrylic latex
  • cellulose cellulose derivatives, alginate, polyethylene glycol, styrene-butadiene rubber, poly(styrene-co- butadiene), styrene-butad
  • the binder is selected from the group consisting of poly-acrylic acid (PAA), poly-vinyl alcohol (PVA), cross-linked PAA, cross-linked PVA, styrene-butadiene latex, acrylonitrile copolymer, and acrylic latex.
  • PAA poly-acrylic acid
  • PVA poly-vinyl alcohol
  • PAA poly-acrylic acid
  • PVA poly-vinyl alcohol
  • cross-linked PAA cross-linked PAA
  • styrene-butadiene latex styrene-butadiene latex
  • acrylonitrile copolymer acrylonitrile copolymer
  • acrylic latex acrylic latex
  • the binder is selected from the group consisting of PAA and PVA.
  • the binder is LA133TM
  • the LA133TM binder has a milky white appearance or a light yellow appearance when formulated as a water emulsion.
  • the viscosity of the binder in water emulsion is greater than or equal to 7300 mPAs at 40°C.
  • the binder has a D50 (pm) particle size of less than or equal to 1.0 pm.
  • the solid content (%) is l5.0 ⁇ 0.2.
  • the pH is about 7 ⁇ 9.
  • the total thickness of the composite separator is from about 20 pm to about 300 pm.
  • the total thickness of the composite separator is from about 20 pm to about 225 pm.
  • the total thickness of the composite separator is about 150 pm.
  • the total thickness of the composite separator is about 50 pm, 55 pm, 60 pm, 65 pm, 70 pm, 75 pm, 80 pm, 95 pm,
  • the composite separator further includes an aqueous liquid electrolyte in contact with the composite separator.
  • the composite separator further includes a nonaqueous liquid electrolyte in contact with the composite separator.
  • the composite separator further includes an ionic liquid or deep eutectic solvent electrolyte in contact with the composite separator.
  • the composite separator further includes a deep eutectic solvent electrolyte in contact with the composite separator.
  • the composite separator further includes an ionic liquid electrolyte in contact with the composite separator.
  • the glass fiber layer or additional glass fiber layer, or both is a glass fiber paper (GFP).
  • GFP glass fiber paper
  • the composite separator includes a layer of PTFE/GFP and an additional layer of PTFE.
  • the PTFE layer is in contact with the negative electrode.
  • the PTFE layer is in contact with the positive electrode.
  • the additional layer of PTFE layer is in contact with the negative electrode.
  • the additional layer of PTFE layer is in contact with the positive electrode.
  • the GFP is between and in contact with the layer of PTFE and the additional layer of PTFE.
  • the composite separator includes two layers of PTFE. In some examples, including any of the foregoing, the composite separator includes three layers of PTFE. In some examples, including any of the foregoing, the PTFE layer is 50 pm in thickness.
  • the composite separator includes a metal negative electrode that includes a metal selected from the group consisting of lithium (Li), sodium (Na), potassium (K), magnesium (Mg), calcium (Ca), aluminum (Al), germanium (Ge), tin (Sn), iron (Fe), zinc (Zn), combinations thereof, and alloys thereof.
  • the metal negative electrode is a foil, a mesh, or a foam.
  • the metal negative electrode is Al.
  • the metal negative electrode is a Al metal foil, Al mesh, Al foam, or porous Al film.
  • the composite separator includes a positive electrode that includes carbon selected from the group consisting of natural graphite, graphene, and synthetic graphite.
  • the graphene is provided as 1, 2, 3, 4, or 5 layers.
  • the positive electrode includes natural graphite flake of high purity and high degree of graphitization.
  • the graphite has a particle size of 1 pm to 500 pm. In some examples, including any of the foregoing, the graphite has a particle size between about 1 pm and 50 pm, between about 50 pm and 100 pm, between about 50 pm and 200 pm, or between about 50 pm and 300 pm.
  • the positive electrode includes carbon having a particle size between 20 pm - 300 pm. In some examples, including any of the foregoing, the positive electrode includes graphite and the graphite has a particle size of 40 pm to 200 pm.
  • the positive electrode includes carbon and the carbon having a particle size of at least 45 pm. In some examples, including any of the foregoing, the positive electrode includes carbon having a particle size of at least 20 pm. In some examples, including any of the foregoing, the positive electrode includes carbon having a particle size from about 45 pm to about 75 pm and carbon having a particle size from about 150 to about 250 pm. In some examples, including any of the foregoing, the carbon having a particle size from about 45 pm to about 75 pm to carbon having a particle size from about 150 to about 250 pm is 5:95 to 20:80 or 5:95 to 15:85. In some examples, including any of the foregoing, the graphite is pure natural graphite flake.
  • the graphite is crystalline and highly graphitized. In some examples, including any of the foregoing, the graphite is substantially free of defects. In some examples, including any of the foregoing, the graphite includes less than 10% defects. In some examples, including any of the foregoing, the positive electrode includes pyrolytic graphite.
  • the composite separator further includes a positive electrode current collector selected from the group consisting of a glassy carbon current collector, carbon fiber paper current collector, carbon fiber cloth current collector, graphite fiber paper current collector, and graphite fiber cloth current collector.
  • a positive electrode current collector selected from the group consisting of a glassy carbon current collector, carbon fiber paper current collector, carbon fiber cloth current collector, graphite fiber paper current collector, and graphite fiber cloth current collector.
  • the carbon fiber paper has a thickness between about 10 pm to 300 pm.
  • the composite separator further includes a positive electrode current collector selected from the group consisting of a metal substrate current collector.
  • the metal substrate is coated with a protective coating.
  • the metal substrate is a mesh, a foil, or a foam.
  • the metal substrate is a nickel (Ni) or tungsten (W) metal substrate.
  • the protective coating is selected from the group consisting of a Ni coating, a W coating, a carbon coating, a carbonaceous material, a conducting polymer, and a combination thereof.
  • the metal substrate is a Ni foil, a Ni mesh, a Ni foam, a W foil, a W mesh, or a W foam. In some examples, including any of the foregoing, the metal substrate is a metal foil coated with Ni coating. In some examples, including any of the foregoing, the metal substrate is a metal mesh or metal foam coated with Ni coating. In some examples, including any of the foregoing, the metal substrate is a metal foil coated with W coating. In some examples, including any of the foregoing, the metal substrate is a metal mesh or metal foam coated with W coating. In some examples, including any of the foregoing, the metal substrate is Ni and the protective coating is carbon.
  • Ionic liquid electrolytes can be formed by slowly mixing or otherwise combining an aluminum halide (e.g ., AlCh) and an organic compound.
  • the aluminum halide undergoes asymmetric cleavage to form a haloaluminate anion (e.g., AlCU ) and an aluminum halide cation that is datively bonded to the organic compound serving as a ligand (e.g., [AlCh n(ligand)] + ).
  • a mole ratio of the aluminum halide and the organic compound can be at least or greater than about 1.1 or at least or greater than about 1.2, and is up to about 1.5, up to about 1.8, up to about 2, or more.
  • the mole ratio the aluminum halide and the organic compound can be in a range of about 1.1 to about 1.7 or about 1.3 to about 1.5.
  • a ligand is provided as a salt or other compound including the ligand, and a mole ratio of the aluminum halide and the ligand-containing compound can be at least or greater than about 1.1 or at least or greater than about 1.2, and is up to about 1.5, up to about 1.8, up to about 2, or more.
  • An ionic liquid electrolyte can be doped, or have additives added, to increase its electrical conductivity and lower the viscosity, or can be otherwise altered to yield compositions that favor the reversible electrodeposition of metals.
  • 1, 2-dichlorobenzene can be added as a co-solvent to reduce electrolyte viscosity and increase the voltage efficiency, which can result in an even higher energy density.
  • alkali chloride additives can be added to increase the discharge voltage of a battery.
  • 1 -ethyl-3 -methylimidazolium tetrafluorob orate or 1- ethyl-3-methylimidazolium bis(trifluorom ethane sulfonimide) or l-ethyl-3- methylimidazolium hexafluorophosphate can be added as additives to increase the discharge voltage of a battery.
  • ionic liquid electrolytes are suitable for use with an Al-metal anode battery.
  • AlClvUrea can be used as an ionic liquid electrolyte.
  • Aluminum deposition proceeds through two pathways, one involving AI2CI7 anions and the other involving [AlCb (urea)n] + cations. The following simplified half-cell redox reactions describe this process:
  • ILE ionic liquid electrolyte
  • DES deep eutectic solvent
  • ILE ionic liquid electrolyte
  • DES deep eutectic solvent
  • ILE ionic electrolytes which include ionically bonded chemical species
  • DES ionic electrolytes which include ionically bonded chemical species as well as non- ionically bonded chemical species, e.g ., species which are bonded through hydrogen-bonds.
  • hydrogen bonding in a given DES can dominate (i.e., be stronger) ionic bonding.
  • the ILE or DES includes a member selected from the group consisting of alkylimidazolium aluminates, alkylpyridinium aluminates, alkylfluoropyrazolium aluminates, alkyltriazolium aluminates, aralkylammonium aluminates, alkyl alkoxyammonium aluminates, aralkylphosphonium aluminates,
  • the ILE or DES includes alkylimidazolium aluminates. In certain examples, the ILE or DES includes alkylpyridinium aluminates. In certain examples, the ILE or DES includes alkylfluoropyrazolium aluminates. In certain examples, the ILE or DES includes alkyltriazolium aluminates. In certain examples, the ILE or DES includes aralkylammonium aluminates. In certain examples, the ILE or DES includes alkyl alkoxyammonium aluminates.
  • the ILE or DES includes aralkylphosphonium aluminates. In certain examples, the ILE or DES includes aralkyl sulfonium aluminates. In certain examples, the ILE or DES includes alkylguanidinium aluminates. [123] In some examples, including any of the foregoing, the ILE or DES includes urea.
  • the metal halide is an aluminum halide.
  • the aluminum halide is AlCh.
  • the aluminum halide is AlCh
  • the organic compound includes: (a) cations selected from the group consisting of N-(n-butyl) pyridinium, benzyltrimethylammonium, l,2-dimethyl-3-propylimidazolium, trihexyltetradecylphosphonium, and 1 -butyl- l-methyl-pyrrolidinium, and (b) anions selected from the group consisting of tetrafluoroborate, tri-fluoromethanesulfonate, and
  • the aluminum halide is AlCh
  • the organic compound is selected from 4-propylpyridine, acetamide, N- methylacetamide, N,N-dimethylacetamide, trimethylphenylammonium chloride, l-ethyl-3- methylimidazolium bis(trifluorom ethyl sulfonyl)imide, and 1 -ethyl-3 -methylimidazolium chloride.
  • the aluminum halide is AlCh
  • the organic compound is l-ethyl-3-methylimidazolium chloride.
  • the ILE includes an aluminum halide cation that is datively bonded to the organic compound.
  • the aluminum halide is AlCh
  • the organic compound is an amide.
  • the amide is selected from urea, methylurea, ethylurea, and combinations thereof.
  • the amide is urea.
  • the amide is methylurea.
  • the amide is ethylurea.
  • the metal halide is AlCh; and the organic compound is selected from 1 -ethyl-3 -methyl imidazolium chloride, l-ethyl-3- methylimidazolium bis(trifluorom ethyl sulfonyl)imide, urea, methylurea, ethylurea, mixtures thereof, and combinations thereof.
  • the ILE includes AlCh and 1 -ethyl-3 -methyl imidazolium chloride
  • the mole ratio of AlChriL' is from 1.1 to 1.7. In some examples, the mole ratio is 1.1. In some examples, the mole ratio is 1.2. In some examples, the mole ratio is 1.3. In some examples, the mole ratio is 1.4. In some examples, the mole ratio is 1.5. In some examples, the mole ratio is 1.6. In some examples, the mole ratio is 1.7.
  • the ILE includes a mixture of 1.1 to 1.7 moles AlCh, 1.0 mole 1 -ethyl-3 -methyl imidazolium chloride and 0.1 to 0.5 mole 1 -ethyl -3 -methylimidazolium bis(trifluoromethylsulfonyl)imide.
  • the mixture includes 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, or 1.7 moles AlCh.
  • the mixture includes 0.1, 0.2, 0.3, 0.4, or 0.5 moles 1 -ethyl-3 -methylimidazolium
  • the mixture includes 0.1, 0.2, 0.3, 0.4, or 0.5 moles l-ethyl-3-methylimidazolium tetrafluorob orate. In some examples, the mixture includes 0.1, 0.2, 0.3, 0.4, or 0.5 moles 1 -ethyl -3 -methylimidazolium hexafluorophosphate,
  • the ILE includes AlCh and urea. In some examples, including any of the foregoing, the ILE includes AlCh and methylurea.
  • the mole ratio of AlCh to urea in the ILE is between 1.1 to 1.7.
  • the mole ratio of AlCh to methylurea is between 1.1 to 1.7.
  • the ILE is urea and the mole ratio of AlChmrea about 1.1 to about 1.7.
  • the ILE is methylurea and the mole ratio of AlCh:methylurea is about 1.1 to about 1.7.
  • the ILE is ethylurea and the mole ratio of AlCh: ethylurea is about 1.1 to about 1.7.
  • the ionic liquid electrolytes are made of chloroaluminate (A1C1 4 ) based ionic liquids. Ionic liquids can be represented by [AlCl 3 ]/[X], wherein X may include any organic salts or organic compounds which produces (A1C1 4 ) ions when mixed with AlCh powder to form ionic liquids. The [AlCh]/[X] ratios are ranging from 0.1 to 2.5 molar ratios.
  • X can be 1 -ethyl-3 -methylimidazolium chloride (EMIC), l-butyl-3- methylimidazolium chloride (BMIC), l-propyl-3-methylimidazolium chloride (PMIC), Urea, N-Methylurea, N-Ethylurea, dimethyl sulfone (DMS0 2 ), triethylamine hydrochloride, l-(2- methoxyethyl)-3-methylimidazolium chloride ([MoeMImJCl), n-butylpyridinium chloride (BPC), trimethylphenyl ammonium chloride (TMPAC), or combinations thereof.
  • EMIC 1 -ethyl-3 -methylimidazolium chloride
  • BMIC l-butyl-3- methylimidazolium chloride
  • PMIC l-propyl-3-methylimidazolium chloride
  • Urea N-Methyl
  • the amount of water or hydrochloric acid in the ionic liquid electrolyte is between 0 - 1000 ppm. In some examples, including any of the foregoing, the amount of water or hydrochloric acid in the ionic liquid electrolyte is less than 1000 ppm. In some examples, including any of the foregoing, the concentration of corrosion products content in the ionic liquid electrolyte is less than 1000 ppm.
  • Examples of ionic liquids include aluminates, such as ones including, or formed from, a mixture of an aluminum halide and an organic compound.
  • the organic compound can be subjected to heating and drying under reduced pressure, such as heating in vacuum (e.g., about 10 2 Torr, about 10 3 Torr, or less, and about 70°C-l l0°C) to remove water prior to mixing with an aluminum halide slowly under stirring with cooling to maintain a temperature near room temperature.
  • a suitable ionic liquid can include, or can be formed from, a mixture of an aluminum halide (e.g., AlCh) and urea; other aliphatic amides including from 1 to 10, 2 to 10, 1 to 5, or 2 to 5 carbon atoms per molecule, such as acetamide, as well as cyclic (e.g., aromatic, carbocyclic, or heterocyclic) amides, as well as combinations of two or more different amides are contemplated.
  • AlCh aluminum halide
  • urea other aliphatic amides including from 1 to 10, 2 to 10, 1 to 5, or 2 to 5 carbon atoms per molecule, such as acetamide, as well as cyclic (e.g., aromatic, carbocyclic, or heterocyclic) amides, as well as combinations of two or more different amides are contemplated.
  • a suitable ionic liquid can include, or can be formed from, a mixture of an aluminum halide (e.g., AlCh) and 4-propylpyridine; other pyridines, as well as other N-heterocyclic compounds (including EMIC or EMI) with 4 to 15, 5 to 15, 4 to 10, or 5 to 10 carbon atoms per molecule, as well as combinations of two or more different N-heterocyclic compounds are contemplated.
  • AlCh aluminum halide
  • 4-propylpyridine other pyridines, as well as other N-heterocyclic compounds (including EMIC or EMI) with 4 to 15, 5 to 15, 4 to 10, or 5 to 10 carbon atoms per molecule, as well as combinations of two or more different N-heterocyclic compounds are contemplated.
  • a suitable ionic liquid for high temperature operations can include, or can be formed from, a mixture of an aluminum halide and trimethylphenylammonium chloride; other cyclic (e.g., aromatic, carbocyclic, or heterocyclic) compounds including a cyclic moiety substituted with at least one amine or ammonium group, as well as aliphatic and cyclic amines or ammoniums, as well as combinations of two or more different amines or ammoniums are contemplated.
  • a suitable organic compounds include N-(n-butyl) pyridinium chloride, benzyltrimethylammonium chloride, 1, 2-dimethyl -3-propylimidazolium,
  • the aluminum halide is AlCh
  • the organic compound incudes cations selected from N-(n-butyl) pyridinium, benzyltrimethylammonium, l,2-dimethyl-3-propylimidazolium, trihexyltetradecylphosphonium, and 1 -butyl- l-methyl- pyrrolidinium, and anions selected from tetrafluorob orate, tri-fluoromethanesulfonate, and bis(trifluoromethanesulfonyl)imide.
  • the aluminum halide is AlCh
  • the organic compound is selected from 4-propylpyridine, acetamide, trimethylphenyl ammonium chloride, and l-ethyl-3-methylimidazolium chloride.
  • the processes for making a composite separator, or a battery having the composite separator can be used for a process for making a rechargeable battery.
  • a process for making a composite separator including the following steps: (a) providing a binder solution; (b) providing a glass fiber layer; (c) contacting the binder solution to the glass fiber paper to form a binder glass fiber layer composite; (d) drying the binder glass fiber layer composite; and (e) contacting a solution of a polymer to the binder glass fiber layer composite to form a composite separator.
  • set forth herein is a process for making a composite separator, including the following steps: (a) providing a binder solution; (b) providing a glass fiber layer; (c) providing a polymer layer; (d) contacting the binder solution to the glass fiber paper to form a binder glass fiber layer composite; (e) contacting the polymer layer to the binder glass fiber layer composite to form a composite separator; and (f) drying the composite separator.
  • set forth herein is a process for making a composite separator, including the following steps: (a) providing a binder solution; (b) providing a glass fiber layer; (c) contacting the binder solution to the glass fiber paper to form a binder glass fiber layer composite; (d) drying the binder glass fiber layer composite; and (e) contacting a solution of a polymer to the binder glass fiber layer composite to form a composite separator.
  • the polymer is a hydrophilic polymer.
  • the polymer is a hydrophobic polymer.
  • set forth herein is a process for making a composite separator, including the following steps: (a) providing a binder solution; (b) providing a glass fiber layer; (c) providing a polymer layer; (d) contacting the binder solution to the glass fiber paper to form a binder glass fiber layer composite; (e) contacting the polymer layer to the binder glass fiber layer composite to form a composite separator; and (f) drying the composite separator.
  • the solution of a polymer is a solution of a hydrophilic polymer.
  • the solution of a polymer is a solution of a hydrophobic polymer.
  • the polymer layer is a hydrophilic polymer layer.
  • the polymer layer is a hydrophobic polymer layer.
  • the binder solution is a hydrophilic binder solution.
  • the process further includes comprising drying the composite separator.
  • the glass fiber layer is a glass fiber paper.
  • the binder solution includes 5 to 50 % w/w binder in deionized water.
  • the glass fiber layer has a geometric surface area of 10 cm 2 .
  • the polymer is a hydrophilic polymer selected from the group consisting of polytetrafluoroethylene (PTFE), polyacrylonitrile (PAN), fluorinated ethylene propylene (FEP), polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), hexafluoropropylene (HFP), PVDF-HFP, polyfluoroalkoxy (PFA), a and combinations thereof.
  • PTFE polytetrafluoroethylene
  • PAN polyacrylonitrile
  • FEP fluorinated ethylene propylene
  • PCTFE polychlorotrifluoroethylene
  • PVDF polyvinylidene fluoride
  • HFP hexafluoropropylene
  • PVDF-HFP polyfluoroalkoxy
  • PFA polyfluoroalkoxy
  • the binder is selected from the group consisting of polyacrylate (PA), polyacrylic acid (PAA), polyvinyl alcohol (PVA), cross-linked PAA, cross-linked PVA, PAA-PVA, polyacrylic latex, cellulose, cellulose derivatives, alginate, polyethylene glycol, styrene-butadiene rubber, poly(styrene-co- butadiene), styrene-butadiene rubber, poly(3, 4-ethyl enedioxythiophene), acrylonitrile copolymer, acrylic latex, and combinations thereof.
  • PA polyacrylate
  • PAA polyacrylic acid
  • PVA polyvinyl alcohol
  • PAA-PVA polyvinyl alcohol
  • PAA-PVA polyacrylic latex
  • cellulose cellulose derivatives, alginate, polyethylene glycol, styrene-butadiene rubber, poly(styrene-co- butadiene), styrene-butad
  • the binder is selected from the group consisting of poly-acrylic acid (PAA), poly-vinyl alcohol (PVA), cross-linked PAA, cross-linked PVA, styrene-butadiene latex, acrylonitrile copolymer, and acrylic latex.
  • PAA poly-acrylic acid
  • PVA poly-vinyl alcohol
  • PAA poly-acrylic acid
  • PVA poly-vinyl alcohol
  • cross-linked PAA cross-linked PAA
  • styrene-butadiene latex styrene-butadiene latex
  • acrylonitrile copolymer acrylonitrile copolymer
  • acrylic latex acrylic latex
  • the binder is selected from the group consisting of PAA and PVA.
  • the binder is LA133TM [164]
  • the drying comprising drying under vacuum at about 200 °C.
  • the cathode uses graphite as an active materials and a metal substrate as a current collector.
  • Graphite can include, but is not limited to, natural graphite, synthetic graphite, graphite paper, pyrolytic graphite.
  • the metal substrate can include, but is not limited to, a Nickel (Ni) foil, Ni foam, Ni mesh, Tungsten (W) foil, W-mesh, or
  • the cathode includes a metal substrate.
  • the metal substrate is a nickel substrate and the substrate includes a protective coating of a carbonaceous material derived from pyrolysis of organic compounds deposited on the metal substrate from solution or gas phase, or a conducting polymer deposited on the metal substrate.
  • Natural graphite particles can be loaded onto such a Ni -based substrate with a binder. Ni and W are found to be more resistive to corrosion in Al-ion battery than most other metals on the cathode side.
  • Ni foil or Ni foam can be coated with a carbon or graphite layer by various methods to impart enhanced corrosion resistance.
  • One such method is to grow a carbon or graphitic layer on Ni by coating Ni with a carbon-rich material, such as pitch dissolved in a solvent, and then heating at about 400-800°C.
  • Another protective coating is a conducting polymer layer such as poly(3, 4-ethyl enedioxythiophene) polystyrene sulfonate
  • a graphite/polymer binder can also coat Ni densely and act as a protection layer as well as an active cathode layer.
  • cathodes having polymer binders with graphite particles.
  • a polyacrylic acid (PAA)/polyvinyl alcohol (PVA)-based polymer binder for graphite particles can be used.
  • natural graphite particles are dispersed in water containing about 10 wt% PAA and about 3 wt% PVA and stirred to make a slurry.
  • the slurry is applied to a current collector as described above, at a loading of about 2-20 mg/cm 2 , followed by drying at about 70-l50°C in vacuum for about 3 hours or longer to thoroughly remove water, leaving graphite particles packed on the current collector to form a cathode for an Al battery.
  • several weight percent of graphite fibers can be added to the slurry to improve electrical conductivity of the cathode.
  • CMC carboxymethyl cellulose
  • SBR styrene-butadiene rubber
  • graphite fiber-based polymer binder is used with graphite particles.
  • set forth herein are methods, which include using natural graphite particles dispersed in a water slurry, containing about 10 wt% CMC and about 1 wt% SBR.
  • the slurry is applied to a current collector as described above, at a loading of about 2-20 mg/cm 2 , followed by drying at about 70-200°C in vacuum for about 3 hours or longer to thoroughly remove water, leaving graphite particles packed on the current collector to form a cathode for an Al battery.
  • graphite fibers can be added to the slurry to improve electrical conductivity of the cathode.
  • a PEDOT/PSS/graphite fiber-based polymer binder for graphite particles is used.
  • set forth herein are methods which include using natural graphite particles dispersed in water slurry containing about 10 wt% PEDOT and about 1 wt% PSS conducting polymer.
  • the slurry is applied to a current collector as described above, at a loading of about 2-20 mg/cm 2 , followed by drying at about 70-200°C in vacuum for about 3 hours or longer to thoroughly remove water, leaving graphite particles packed on the current collector to form a cathode for an Al battery.
  • graphite fibers can be added to the slurry to improve electrical conductivity of the cathode.
  • an ionic liquid polymer binder for graphite particles is used.
  • set forth herein are methods, which include using natural graphite particles are dispersed in a water slurry, containing ionic liquid polymer or oligomer.
  • the slurry is applied to a current collector as described above, at a loading of about 2-20 mg/cm 2 , followed by drying at about 70-200°C in vacuum for about 3 hours or longer to thoroughly remove water, leaving graphite particles packed on the current collector to form a cathode for Al battery.
  • slurries useful with the compositions and methods described herein include the following slurries.
  • a slurry includes about 89 wt% graphite particles (grade 306l)/about 4 wt% CMC/about 2 wt% SBR/about 5 wt% graphite fibers, on ELAT® carbon fiber cloth, 70°C annealed for about 2 h).
  • a slurry also included is about 802 mg of 3 wt% Na-CMC gel in de-ionized (DI )water, about 241 mg of 5 wt% SBR dispersed in DI water, about 30 mg of chopped graphite fiber, about 534 mg of graphite (grade 3061), and about 1.2 mL of DI water.
  • a slurry includes about 87 wt% graphite parti cles/about 10 wt% PAA/about 3 wt% PVA, on M30 carbon fiber paper, l30°C annealed for about 2 h). In some examples, also included is about 225 mg of 25 wt% PAA aqueous solution, about 169 mg of 10 wt% PVA aqueous solution, about 489 mg of graphite particles, and about 0.4 mL of DI water.
  • the anode is an Aluminum
  • Al anode such as, but not limited to, an Al metal foil, Al mesh, Al foam and porous Al film.
  • the thickness may range, in some examples, from 10 pm to 500 pm.
  • set forth herein is an aluminum-graphite battery having an Al anode, a composite separator, an ionic liquid electrolyte and a graphite cathode.
  • the composite separator includes a glass fiber layer.
  • the composite separator includes a hydrophobic or hydrophilic polymer.
  • the composite separator includes a binder selected from poly-acrylic acid (PAA), poly-vinyl alcohol(PVA), cross-linked PAA, cross-linked PVA, styrene-butadiene latex, or an acrylic latex.
  • PAA poly-acrylic acid
  • PVA poly-vinyl alcohol
  • set forth herein is an electrochemical cell comprising any composite separator set forth herein.
  • set forth herein is a battery which includes a composite separator set forth herein. In some examples, set forth herein is a battery which includes an electrochemical cell set forth herein.
  • the battery includes an ionic liquid electrolyte (ILE) or deep eutectic solvent (DES).
  • ILE ionic liquid electrolyte
  • DES deep eutectic solvent
  • the battery includes a composite separator that is free of corrosion from an ILE or DES.
  • the polymer layer does not react with an ILE or DES.
  • the ILE includes l-ethyl-3- methylimidazolium chloride.
  • the DES includes urea.
  • the ILE includes a member selected from the group consisting of alkylimidazolium aluminates, alkylpyridinium aluminates, alkylfluoropyrazolium aluminates, alkyltriazolium aluminates, aralkylammonium aluminates, alkyl alkoxyammonium aluminates, aralkylphosphonium aluminates,
  • aralkyl sulfonium aluminates alkylguanidinium aluminates, and combinations thereof.
  • the DES includes a member selected from the group consisting of alkylimidazolium aluminates, alkylpyridinium aluminates, alkylfluoropyrazolium aluminates, alkyltriazolium aluminates, aralkylammonium aluminates, alkyl alkoxyammonium aluminates, aralkylphosphonium aluminates,
  • aralkyl sulfonium aluminates alkylguanidinium aluminates, and combinations thereof.
  • the ILE includes a mixture of a metal halide and an organic compound.
  • the metal halide is an aluminum halide.
  • the aluminum halide is AlCh
  • the organic compound includes:
  • anions selected from the group consisting of chloride, tetrafluorob orate, tri- fluoromethanesulfonate, hexafluorophosphate and bis(trifluoromethanesulfonyl)imide.
  • the aluminum halide is AlCh
  • the organic compound is selected from the group consisting of urea, methylurea, ethylurea, 4-propylpyridine, acetamide, N-m ethyl acetamide, N,N-dimethylacetamide, trimethylphenylammonium chloride, 1 -ethyl-3 -methylimidazolium
  • the aluminum halide is A1C13
  • the organic compound is 1 -ethyl-3 -methylimidazolium chloride.
  • the ILE includes an aluminum halide cation that is datively bonded to the organic compound.
  • the aluminum halide is AlCh
  • the organic compound is an amide
  • the amide is selected from the group consisting of urea, methylurea, ethylurea, and combinations thereof.
  • the metal halide is AlCh; and the organic compound is selected from the group consisting of 1 -ethyl-3 -methyl imidazolium chloride, 1 -ethyl-3 -methylimidazolium bis(trifluorom ethyl sulfonyl)imide, 1- ethyl-3 -methylimidazolium tetrafluorob orate, 1 -ethyl-3 -methylimidazolium
  • hexafluorophosphate urea, methylurea, ethylurea, mixtures thereof, and combinations thereof.
  • the ILE includes AlCh and 1 -ethyl-3 -methyl imidazolium chloride, wherein the mole ratio of AlCl 3 :IL' is from 1.1 to 1.7.
  • the ILE includes a mixture of 1.1 to 1.7 moles AlCh, 1.0 mole 1 -ethyl-3 -methyl imidazolium chloride and 0.1 to 0.5 mole 1 -ethyl -3 -methylimidazolium bis(trifluoromethylsulfonyl)imide or l-ethyl-3- methylimidazolium tetrafluorob orate or 1 -ethyl-3 -methylimidazolium hexafluorophosphate.
  • the ILE includes AlCh and urea.
  • the ILE includes AlCh and methylurea.
  • the mole ratio of AlCh to urea is between 1.1 to 1.7.
  • the mole ratio of AlCh to methylurea is between 1.1 to 1.7.
  • the ILE is urea.
  • the mole ratio of AlChmrea is about 1.1 to about 1.7.
  • the ILE is methylurea.
  • the mole ratio of AlCb:methylurea is about 1.1 to about 1.7.
  • the ILE is ethylurea.
  • the mole ratio of AlCh: ethylurea is about 1.1 to about 1.7.
  • the amount of water or hydrochloric acid in the ionic liquid electrolyte is between 0 - 1000 ppm.
  • the amount of water or hydrochloric acid in the ionic liquid electrolyte is less than 1000 ppm.
  • concentration of corrosion products content in the ionic liquid electrolyte is less than 1000 ppm.
  • the batteries described herein are useful for a variety of applications. In some of these applications, a high rate capacity battery is required. Some of these applications include grid-storage applications, uninterrupted power supply applications, home back-up applications, portable devices, and transportation.
  • Some of the methods herein include vacuum-pumping in combination with electrochemical cycling.
  • the battery when a battery is deployed for use in a particular application, the battery may be monitored by, for example, a battery management system (BMS). If the BMS determines that the battery might benefit from additional vacuum pumping, then a method of vacuum pumping in combination with electrochemical cycling may be employed while the battery is deployed in an application. Such a method can remove side reaction products, which may have accumulated during battery cycling.
  • BMS battery management system
  • the methods include monitoring at least one metric selected from current density, voltage, impedance, pressure, temperature and capacity in order to determining if the battery might benefit from additional vacuum-pumping.
  • the electrochemical cells may be stacked in series or in parallel.
  • the Examples herein show how to make and use composite separators for Al- ion batteries having an Al-metal anode.
  • the batteries in this example included an Al foil (Zhongzhoulvye Co., Ltd., 0.016-0.125 mm) metal anode.
  • a 3-mm-wide and 0.09- mm-thick nickel tab (MTI, EQ-PLiB-NTA3) was bonded to the battery cathode comprised of natural graphite flake (Ted Pella, 61-302 SP-l natural flake) mixed with a sodium alginate binder (Sigma) dried on a carbon fiber paper (CFP) (Mitsubishi, 30 g/m 2 ) as the cathode current collector.
  • CFP carbon fiber paper
  • Aluminum electrodes were washed with acetone and gently scrubbed with a Kimwipes before use. The separators used is described below.
  • battery cathodes were prepared by depositing a graphite slurry onto a substrate, such as carbon fiber paper (CFP) or a Ni or a W mesh or foil.
  • a substrate such as carbon fiber paper (CFP) or a Ni or a W mesh or foil.
  • Graphite was mixed with sodium alginate in a graphite: alginate mass ratio of 95:5.
  • 950 mg GP, 50 mg sodium alginate binder, and 2-3 mL distilled water was used as the slurry.
  • 5 mg of the slurry per cm 2 of the cathode substrate was loaded onto the cathode substrate (CFP), and the electrode was baked at 80 °C under vacuum overnight.
  • a Ni tab was used as a current collector, which was heat-sealed to attach it.
  • hydrochloric acid (HC1) and water were removed from electrolyte mixtures prepared herein.
  • the mixtures were heated (25-90 °C) and placed under vacuum pumping (about 10-3 Torr) until noticeable bubbling from the mixture ceased.
  • Galvanostatic charge/discharge measurements were performed outside of the glovebox (Vigor Tech). Cyclic voltammetry (CV) measurements were executed on a potentiostat/galvanostat model CHI 760D (CH Instruments) or on a potentiostat/galvanostat model VMP3 (Bio-Logic) in both three-electrode and two-electrode modes. Unless specified to the contrary, discharge/charge cycling was performed at cell voltages of 2.3 to 0.01 V at 100 mAh/g current density on a Battery testing instrument (Neware). The working electrode was an aluminum foil or a GF, the auxiliary electrode included a platinum foil, and an Al foil was used as the reference electrode.
  • CV Cyclic voltammetry
  • Al-ion batteries were assembled.
  • the batteries each included the following components.
  • An Al metal anode having dimensions of approximately 4 cm 2 ; a -2.25 cm 2 Ni foil coated with graphite (loading: ⁇ 5 mg/cm 2 ) for the cathode; and an 1.5-2.0 g ionic liquid electrolyte.
  • the Al metal anode was laminated to a separator to form a stack and the pure Ni (>99%) substrate coated with graphite was then laminated to the Al metal anode and the composite separator stack (composite separators detailed below).
  • the graphite loading in the cathode was 9-10 mg/cm 2 .
  • the Al-ion battery was hot-sealed in a conventional aluminum- laminated pouch (Showa Denko) having a polypropylene (PP) inner-layer pouch, aluminum foil as the middle layer and polyamide (PA) as the outer-layer.
  • PP polypropylene
  • PA polyamide
  • the six batteries were cycled to measure cycle-life performance with different combinations of composite separators and single glass fiber paper.
  • the batteries were cycled between 1.0-2.3V (voltage), at 100 mA/g current density and at room temperature ( ⁇ 25°C).
  • the ionic liquid electrolyte AlCh/EMIC having a molar ratio AlCh/EMIC of 1.4, was used for all batteries.
  • FIG. 5 shows the charge/discharge cycling results of this Al- ion battery.
  • the Coulombic efficiency (CE) in FIG. 5 was higher than 99% (2.3/100 stands for charge to 2.3V with 100 mA/g rate), but after around 35 cycles, the capacity dropped and a short circuit occurred. After this, the battery was not able to be charged.
  • the deposited Al metal penetrated the thin separator and caused an internal short circuit; the phenomena happened repeatedly when a thin GF was used as the separator.
  • FIG. 6 shows the charge/discharge cycling results of this Al-ion battery.
  • the GP paper was next to the Al anode. The battery was able to be charge/discharge over 270 cycles and remained stable with CE higher than 99% without short-circuiting (2.3/100 stands for charge to 2.3 V with 100 mA/g rate).
  • FIG. 7 shows the charge/discharge cycling results of this Al-ion battery.
  • the 25 pm PTFE layer was next to Al side and 100 um GFP was next to graphite side.
  • the battery was run -150 cycles.
  • FIG. 8 shows the charge/discharge cycling results of this Al-ion battery. The cycle-life was around 600 cycles with almost no capacity decay.
  • a composite separator was made and used. The composite separator had a 25 pm thick PTFE layer that was positioned between two layers of 60 pm thick GFP.
  • FIG. 9 shows the charge/discharge cycling results of this Al-ion battery. The battery was cycled to 110 cycles.
  • FIG. 10 shows the charge/discharge cycling results of this Al-ion battery. This configuration included 150 pm GFP without any PTFE film.
  • the thickness of the separator in the sixth battery was about the same as the thickness in the fifth battery, and was thicker than the separator used in the first, second and third batteries.
  • the cycle-life was observed to be only around 80 cycles. After the 80th cycle, the capacity and efficiency started to jump, likely due to micro-short circuiting between the Al foil anode and the graphite cathode.
  • PTFE in this example was hydrophilic-treated PTFE.
  • This Example shows the results for using a chemically-inert glass/PTFE film separator to improve the electrical insulation between an Al anode and a graphite cathode.
  • the hydrophilic PTFE film was chemical inert and stable to the acidic electrolyte.
  • This Example shows how to make a composite separator by combining a thin layer of PTFE with a glass fiber (GF) layer as a protection layer.
  • GF glass fiber
  • the total thickness of the composite separators (including GFP and PTFE) in this Example was less than or equivalent to 150 um.
  • the composite separators of GFP/PTFE improved the AIB’s cycle-life significantly and CE.
  • the composite separators of GFP/PTFE also stabilized the discharge capacity.
  • Two Al-ion batteries were assembled.
  • the batteries each included the following components.
  • An Al metal anode having dimensions of approximately 4 cm 2 ; a -2.25 cm 2 Ni foil coated with graphite (loading: ⁇ 5 mg/cm 2 ) for the cathode; and a 1.5-2.0 g ionic liquid electrolyte.
  • the Al metal anode was laminated to a separator to form a stack and the pure Ni (>99%) substrate coated with graphite was then laminated to the Al metal anode and separator stack.
  • the graphite loading in the cathode is 9-10 mg/cm 2 .
  • the Al-ion battery was hot-sealed in a conventional aluminum-laminated pouch (Showa Denko) having a polypropylene (PP) inner-layer pouch, aluminum foil as the middle layer and polyamide (PA) as the outer-layer.
  • PP polypropylene
  • PA polyamide
  • the two batteries were cycled to measure cycle-life performance for batteries using polymer binder reinforced glass fiber paper electrolyte separators as compared to pure GFP separators.
  • the batteries were cycled at 1.0-2.3V (voltage) at 100 mA/g current density and at room temperature ( ⁇ 25°C).
  • the ionic liquid electrolyte AlCh/EMIC having a ratio 1.4 was used for all batteries.
  • the glass fiber paper was made of individual glass fibers that are micrometers in diameter and 10-100 pm in length.
  • the glass fiber was wrapped mechanically together to form a paper film; the mechanical strength was relatively weak and the film was easy to peel off surfaces.
  • This Example shows how to bind the fiber together using a robust polymer binder, which was resistant to the electrolyte and was not being corroded in the acidic electrolyte environment.
  • the binder also did not degrade the battery performance in term of capacity, Coulombic efficiency and long-term stability.
  • LA133TM a polymer gel mainly comprised of co-polymers with acrylonitrile chain is a good candidate as a binder to reinforce the glass fiber paper.
  • the as-received commercially binder gel was diluted with deionized water to a binder content of 5-50% wt.
  • the diluted binder solution was sprayed onto glass fiber paper and the binder solution gradually infiltrated into the void/space between the glass fibers.
  • the wetted composite fiber paper were then dried in an oven at temperature 80-120 °C to remove water.
  • a 200 pm thick GFP separator and a drop 10 mL of 10 wt% binder solution (weight percent) were combined.
  • the GFP was 10*10 cm 2 GFP.
  • FIG. 11 shows the charge/discharge cycling results of this Al-ion battery.
  • FIG. 12 shows the charge/discharge cycling results of this Al-ion battery.
  • FIG. 11 shows the battery cycle-life performance for the binder-reinforced composite glass fiber paper separator.
  • FIG. 12 shows the performance of a battery using only a 200 pm glass fiber paper.
  • the cycle -life of the composite separator battery was improved (450 cycles) compared to pure GFP battery (300 cycles life).
  • the polymer binder binds the glass fiber together and fills the void space to improve mechanical property and density. This reinforces the separator to become a battery barrier for efficiently blocking Al metal dendrites, which may cause short-circuiting.
  • Al-ion batteries were assembled.
  • the batteries each included the following components.
  • An Al metal anode having dimensions of approximately 4 cm 2 ; a -2.25 cm 2 Ni foil coated with graphite (loading: ⁇ 5 mg/cm 2 ) for the cathode; and a 1.5-2.0 g ionic liquid electrolyte.
  • the Al metal anode was laminated to a separator to form a stack and the pure Ni (>99%) substrate coated with graphite was then laminated to the Al metal anode and separator stack.
  • the graphite loading in the cathode is 9-10 mg/cm 2 .
  • the Al-ion battery was hot-sealed in a conventional aluminum-laminated pouch (Showa Denko) having a polypropylene (PP) inner-layer pouch, aluminum foil as the middle layer and polyamide (PA) as the outer-layer.
  • PP polypropylene
  • PA polyamide
  • the six batteries were cycled to measure cycle-life performance.
  • the batteries were cycled at 1.0-2.3V (voltage) at 100 mA/g current density and at room temperature ( ⁇ 25°C).
  • the ionic liquid electrolyte AlCh/EMIC having a ratio 1.4 was used for all batteries.
  • This Example shows composite separators having PTFE films and binders.
  • the binder acted as glue to bond the GFP and PTFE film together to form a single separator film.
  • a composite separator was made having a binder, a 100 pm thick glass fiber layer and a 25 pm PTFE layer.
  • the PTFE layer was in contact with the positive electrode.
  • FIG. 13 shows the charge/discharge cycling results of this Al-ion battery.
  • the battery had a cycle-life of -700 cycles currently and it was much better than that the results shown in FIG. 5 (no binder in the battery used for FIG. 5).
  • FIG. 14 shows the charge/discharge cycling results of this Al-ion battery. Both of PTFE and binder synergistically improved cycle-life and did not degrade the CE or capacity.
  • the battery used for FIG. 14 used LA133TM as binder to bind these two films together. The battery was stable over 500 cycles. To date, no AIB with a 85 pm separator thickness has been cycled over 500 cycles without CE decay and capacity fade.
  • FIG. 15 shows the charge/discharge cycling results of this Al-ion battery.
  • the battery used for FIG. 15 included a stack of one layer of 60 pm GFP and 25 pm PTFE. The battery performed well for only a cycle-life of -100 cycles.
  • FIG. 16 shows the charge/discharge cycling results of this Al-ion battery.
  • the composite separator thickness was -215 pm ⁇ 10 pm thick. The thickness was measured using a Vernier Caliper. The cycle-life was over 1000 cycles and there was almost no decay in capacity or Coulombic efficiency.
  • the PTFE in this example was hydrophilic-treated PTFE.
  • Two Al-ion batteries were assembled.
  • the batteries each included the following components.
  • a 150 pm thick Al metal anode having dimensions of approximately 4 cm 2 ; a -2.25 cm 2 Ni foil coated with graphite (loading: -7.3 mg/cm 2 ) for the cathode; and a 1.5-2.0 g ionic liquid electrolyte.
  • the Ni foil coated with graphite was compressed from 151 pm thickness to 105 pm thickness, which resulted in a packing density of 1.7 g/cm.
  • the Al metal anode was laminated to a separator to form a stack and the pure Ni (>99%) substrate coated with graphite was then laminated to the Al metal anode and separator stack.
  • the graphite loading in the cathode is 7.3 mg/cm 2 .
  • the Al-ion battery was hot-sealed in a conventional aluminum-laminated pouch (Showa Denko) having a polypropylene (PP) inner- layer pouch, aluminum foil as the middle layer and polyamide (PA) as the outer-layer.
  • PP polypropylene
  • PA polyamide
  • the two batteries were cycled to measure cycle-life performance.
  • the batteries were cycled at 1.0-2.3V (voltage) at 100 mA/g current density and at room temperature ( ⁇ 25°C).
  • the ionic liquid electrolyte AlCh/EMIC having a ratio 1.4 was used for all batteries.
  • a composite separator was made having a binder, a 200 pm thick glass fiber layer and a 25 pm PTFE layer.
  • the PTFE layer was in contact with the positive electrode.
  • FIG. 18 shows the charge/discharge cycling results of this Al-ion battery. The 225 th cycle tested is shown in FIG. 19.
  • FIG. 20 shows the charge/discharge cycling results of this Al-ion battery. The 315 th cycle tested is shown in FIG. 21.

Abstract

Provided herein are new methods for making a highly stable metal anode (e.g., aluminum ion) battery. The battery includes, in some embodiments, a composite separator for an ionic liquid electrolyte.

Description

GLASS FIBER COMPOSITE SEPARATOR
CROSS-REFERENCE TO RELATED APPLICATIONS
[1] This application claims the benefit of priority to US Provisional Patent Application No. 62/652,850, filed April 4, 2018, the entire contents of which are herein incorporated by reference in its entirety for all purposes.
FIELD
[2] The present disclosure concerns electrolyte separators for rechargeable (i.e., secondary) batteries as well as methods of making and using the same. In some examples, the present disclosure concerns electrolyte separators for rechargeable batteries such as, but not limited to, rechargeable batteries having an aluminum (Al) metal anode (i.e., negative electrode).
BACKGROUND
[3] Some rechargeable batteries available today are insufficient to power a variety of applications due to their low energy density and specific capacity. A battery’s energy density is related to the electrochemical potential difference for an atom ( e.g ., Al) in the anode relative to its corresponding ion (e.g., Al3+ or AICU ) in the cathode. A rechargeable battery’s energy density is therefore maximized when the anode is a single metal. The electrochemical potential for a metal atom in a metal made of identical metal atoms is 0 V. The electrochemical potential for a metal atom in a intercalation host is greater than 0 V. Metal anodes as compared to intercalation anodes therefore maximize the energy difference between the anode and any cathode. As such, to increase the energy density of current batteries, metal anode rechargeable batteries are desired but not yet commercially available.
[4] Aluminum (Al) is an attractive metal for a metal anode rechargeable battery. The three-electron redox properties of Al provide a theoretical gravimetric capacity as high as 2,980 mAh/g and a volumetric capacity as high as 804 Ah cm-3, when paired with a carbon- containing cathode. Al is also the third most abundant element in the Earth’s crust. Al is generally less reactive than other metal anodes (e.g., lithium (Li) and sodium (Na)) and is easier to process. Al is therefore an economically viable choice for large scale battery applications.
[5] Key to commercializing Al-metal anode rechargeable batteries, is the development of electrolyte-including separators which are sufficiently ionically conductive and suitable for use with an Al-metal anode without degrading the rechargeable battery’s electrochemical performance, e.g ., degradation due to reactions between the separator and Al. Some researchers have developed Al-metal anode rechargeable batteries, which use ionic liquid electrolyte (ILE) mixtures of AlCh and 1 -ethyl-3 -methylimidazolium chloride
([EMImJCl) or AlCh and urea. See , for example, ETS Patent Application Publication No. 2015-0249261; International Patent Application Publication No. WO/2017/106337; Lin, M- C, et al., Nature, 2015, p. 1- doi: 1038/nature 143040; and Angell, et al, PNAS, Early Edition, 2016, p. 1-6, doi: 10. l073/pnas.1619795114, the entire contents of each of which are herein incorporated by reference in their entirety for all purposes.
[6] The Al-metal batteries which have been prepared suffer from a variety of disadvantages including instability during use, including instability over the total operation time of the battery. Previously, Al-metal batteries were cycled, and, if they remained stable, for example, they only remained stable for up to 100 hours of operation time, e.g. , cycled at 70C rate for 7000 cycles. What is needed, for example is batteries that can be cycled and remain stable at, for example, 1C rate for 7000 cycles, which would include 7000 hours of operation time. The prior-published Al-metal batteries showed capacity and/or coulombic efficiency fade after a few electrochemical charge-discharge cycles. One unresolved problem relates to the lack of chemically compatible materials which can be used with an Al-metal anode rechargeable battery. In certain Al-metal anode batteries, such materials need to be chemically compatible with the acidic environment of the chloride-containing electrolytes suitable for use with Al-metal anode and also sufficiently strong to interact with the other battery components.
[7] One way researchers have tried to improve Al-ion batteries is to incorporate thin electrolyte separators. A problem with thin electrolyte separators used with Al-ion batteries is that Al metal may grow through the thin electrolyte separators during
charging/discharging cycles and penetrate the thin electrolyte separators. Examples of such separators are those which only include porous, loosely bound glass fibers. If Al metal grows through the electrolyte separator and between the cathode and anode of a battery, a short- circuit results.
[8] In view of these as well as other unmet challenges, there exists a need for improved metal anode rechargeable batteries, including Al-metal anode rechargeable batteries and improved electrolyte separators.
SUMMARY
[9] In one embodiment, set forth herein is a composite separator, including a glass fiber layer; a polymer layer, or a derivative thereof; and optionally a binder. In these embodiments, the composite separator is between a positive electrode and a negative electrode. In certain embodiments, the composite separator is in contact with both the positive electrode and the negative electrode. In these embodiments, one of the following four features - (a), (b), (c), or (d) - is met:
(a) the glass fiber layer is between and in contact with the metal negative electrode and the polymer layer; and the polymer layer is between and in contact with the glass fiber layer and the positive electrode;
(b) the polymer layer is between and in contact with the metal negative
electrode and the glass fiber layer; and the glass fiber layer is between and in contact with the polymer layer and the positive electrode;
(c) the glass fiber layer is between and in contact with the polymer layer and an additional polymer layer; or
(d) the polymer layer is between and in contact with the glass fiber layer and an additional glass fiber layer.
[10] In a second embodiment, set forth herein is a process of making a composite separator, including the following steps: (a) providing a binder solution; (b) providing a glass fiber layer; (c) contacting the binder solution to the glass fiber paper to form a binder glass fiber layer composite; (d) drying the binder glass fiber layer composite; and (e) contacting a solution of a polymer to the binder glass fiber layer composite to form a composite separator.
[11] In a third embodiment, set forth herein is a process of making a composite separator, including the following steps: (a) providing a binder solution; (b) providing a glass fiber layer; (c) providing a polymer layer; (d) contacting the binder solution to the glass fiber paper to form a binder glass fiber layer composite; (e) contacting the polymer layer to the binder glass fiber layer composite to form a composite separator; and (f) drying the composite separator.
[12] Also set forth herein are electrochemical cells that include any composite separator set forth herein or any composite separator made by a process set forth herein.
[13] Also set forth herein are rechargeable batteries that include any composite separator set forth herein or any composite separator made by a process set forth herein.
[14] Also set forth herein are methods for using the composite separators, electrochemical cells, and rechargeable batteries set forth herein.
BRIEF DESCRIPTIONS OF THE DRAWINGS
[15] FIG. 1 shows an embodiment of a composite separator.
[16] FIG. 2 shows an embodiment of a composite separator.
[17] FIG. 3 shows an embodiment of a composite separator.
[18] FIG. 4 shows an embodiment of a composite separator.
[19] FIG. 5 shows cycle-life performance of a composite separator.
[20] FIG. 6 shows cycle-life performance of a composite separator. [21] FIG. 7 shows cycle-life performance of a composite separator. [22] FIG. 8 shows cycle-life performance of a composite separator.
[23] FIG. 9 shows cycle-life performance of a composite separator.
[24] FIG. 10 shows cycle-life performance of a composite separator.
[25] FIG. 11 shows cycle-life performance of a composite separator.
[26] FIG. 12 shows cycle-life performance of a composite separator
[27] FIG. 13 shows cycle-life performance of a composite separator.
[28] FIG. 14 shows cycle-life performance of a composite separator. [29] FIG. 15 shows cycle-life performance of a composite separator.
[30] FIG. 16 shows cycle-life performance of a composite separator.
[31] FIG. 17 shows certain chemical reactions relevant to the instant disclosure.
[32] FIG. 18 shows cycle-life performance of a composite separator.
[33] FIG. 19 shows the 225th cycle of a battery prepared in Example 4.
[34] FIG. 20 shows cycle-life performance of a composite separator.
[35] FIG. 21 shows the 315th cycle of a battery prepared in Example 4.
DETAILED DESCRIPTION
[36] The following description is presented to enable one of ordinary skill in the art to make and use the invention and to incorporate it in the context of particular applications. Various modifications, as well as a variety of uses in different applications will be readily apparent to those skilled in the art, and the general principles defined herein may be applied to a wide range of embodiments. Thus, the inventions herein are not intended to be limited to the embodiments presented, but are to be accorded their widest scope consistent with the principles and novel features disclosed herein.
[37] All the features disclosed in this specification, (including any accompanying claims, abstract, and drawings) may be replaced by alternative features serving the same, equivalent or similar purpose, unless expressly stated otherwise. Thus, unless expressly stated otherwise, each feature disclosed is one example only of a generic series of equivalent or similar features.
[38] Please note, if used, the labels left, right, front, back, top, bottom, forward, reverse, clockwise and counter clockwise have been used for convenience purposes only and are not intended to imply any particular fixed direction. Instead, they are used to reflect relative locations and/or directions between various portions of an object.
General [39] Set forth herein are materials and methods for making and using separators for rechargeable batteries. These separators include a glass fiber layer and a polymer layer. In some examples, the separators optionally include a binder. The composite separator improves a battery’s cycle -life. A non-limiting example includes an Al-ion battery with a nonaqueous electrolyte and a composite separator that includes a porous glass fiber layer; a hydrophilic PTFE layer; and a binder layer. A non-limiting example includes an Al-ion battery with a nonaqueous electrolyte and a composite separator that includes a porous glass fiber layer; a hydrophilic polyimide (PI) layer; and a binder layer.
[40] In some methods herein, a binder layer or a polymer layer is deposited onto a glass fiber layer using solutions of binders and/or polymers.
[41] The composite separators set forth herein are in some embodiments thin, e.g ., 60-200 pm in thickness and are suitable for use with Al-ion batteries. In certain embodiments, when compared to glass fiber separators, the cycle life of Al-ion batteries (AIB) having a composite separator set forth herein is at least 15-20 greater. AIB having a composite separator set forth herein also show less capacity fade over time. AIB having a composite separator set forth herein also show less Coulombic efficiency degradation over time.
[42] In certain embodiments, the composite separators herein, (e.g, binder reinforced glass fiber) are advantageous for many reasons, such as manufacturing reasons.
One manufacturing reason is the ability to automatically machine assemble batteries, which incorporate the composite separators set forth herein.
Definitions
[43] As used herein, the singular terms“a,”“an,” and“the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to an object can include multiple objects unless the context clearly dictates otherwise.
[44] As used herein, the term“about,” when qualifying a number, e.g, 100 °C, refers to the number qualified and optionally the numbers included in a range about that qualified number that includes ± 10% of the number. For example, about 100 °C includes 100 °C as well as 90 °C, 91 °C, 92 °C, 93 °C, 94 °C, 95 °C, 96 °C, 97 °C, 98 °C, 99 °C, 100 °C, 101 °C, 102 °C, 103 °C, 104 °C, 105 °C, 106 °C, 107 °C, 108 °C, 109 °C, and 110 °C. [45] As used herein,“selected from the group consisting of’ refers to a single member from the group, more than one member from the group, or a combination of members from the group. A member selected from the group consisting of A, B, and C includes, for example, A only, B only, or C only, as well as A and B, A and C, B and C, as well as A, B, and C.
[46] As used herein, the phrases“electrochemical cell” or“battery cell” shall mean a single cell including an anode and a cathode, which have ionic communication between the two using an electrolyte.
[47] As used herein, the terms“cathode” and“anode” refer to the electrodes of a battery. As shown in FIG. 17, the anode of an Al-metal anode battery includes Al. As shown in FIG. 17, the cathode includes graphite. During a charge cycle, AlClf ions de-intercalate from the graphite and conduct through the electrolyte to eventually plate out as Al at the anode (via AhCE ions). During a discharge cycle, Al2Cl7 ions dissolve from the Al anode, convert into AlClf ions while conducting through the electrolyte and eventually intercalate into the graphite in the cathode. During a charge cycle, electrons leave the cathode and move through an external circuit to the anode. During a discharge cycle, electrons leave the anode and move through an external circuit to the cathode. Unless otherwise specified, the cathode refers to the positive electrode. Unless otherwise specified, the anode refers to the negative electrode.
[48] As used herein, the term“separator,” refers to the physical barrier which electrically insulates the anode and the cathode from each other. The separator is often porous so it can be filled or infiltrated with an electrolyte. The separator is often mechanically robust so it can withstand the pressure applied to the electrochemical cell. Example separators include, but are not limited to, Si02 glass fiber separators or Si02 glass fiber mixed with a polymer fiber or mixed with a binder.
[49] As used herein, the term“C-rate” refers to a measure of the rate at which a battery is discharged relative to its maximum capacity. A 1C rate means that the discharge current will discharge the entire battery in 1 hour. For a battery with a capacity of 100 Amp- hrs, a 1C rate equates to a discharge current of 100 Amps.
[50] As used herein, the term“ionic liquid electrolyte” or“ILE,” refers to nonflammable electrolytes which include a mixture of a strong Lewis acid metal halide and Lewis base ligand. Examples include, but are not limited to, AlCb and l-ethyl-3- methylimidazolium chloride ([EMImJCl). Example Lewis base ligands include, but are not limited to, urea, methylurea, acetamide, or 4-propylpyridine. In a typical ILE having AlCL as a metal halide, AlCL undergoes asymmetric cleavage to form a tetrachloroaluminate anion (AlCL ) and an aluminum chloride cation (AlCh+) in which a ligand is datively bonded to (or associated through coordination via sharing of lone pair electrons) the AlCl2 + cation, forming ([AlCL n(ligand)]+). Ionic liquids are useful as electrolytes for Al-metal anode batteries. Examples include AlCb and 1 -ethyl-3 -methylimidazolium chloride (EMIC); AlCL and urea; AlCL and acetamide; AlCb and 4-propylpyridine; and AlCL and trimethylphenylammonium chloride.
[51] As used herein, the term“deep eutectic solvent,”“deep eutectic solvent electrolyte,” or“DES,” refers to a mixture of a strong Lewis acid metal halide and a Lewis base ligand. See , for example, Hogg, JM, et al. , Green Chem 17(3): 1831-1841; Fang, Y, et al., Electrochim Act 160:82-88; Fang, Y, et al. , Chem. Commun. 51(68)13286-13289; and also Pulletikurthi, G., et al. , Nature , 520(7547):325-328 for a non-limiting set of example DES mixtures. The content of each of these references is herein incorporated by reference in their entirety for all purposes. Examples include, but are not limited to, AlCb and urea.
[52] As used herein, the term“metal halide salt,” refers to a salt which includes at least one metal atom and at least one halogen atom. Examples include, but are not limited to, AIF3, AlCb, AlBr3, AlL, and combinations thereof.
[53] As used herein, the phrases“hydrophilic polymer,” and“hydrophilic-treated polymer” refer to a polymer which wets an ILE or DES set forth herein. As used herein, the term“hydrophilic-treated polymer” refers to a polymer which is treated with, or reacted with, chemical groups that impart a hydrophilic property to the polymer. A non-limiting set of example hydrophilic-treated polymer are found in Bi, et al, Journal of Power Sources 194 (2009) 838-842; S. Sugiyama et al., React. Polym. 21 (1993) 187-191; and Wang, et al, Journal of Water Process Engineering 8 (2015) 11-18, the content of each of which is herein incorporated by reference in its entirety for all purposes. For example, a hydrophilic-treated polymer includes, but is not limited to, hydrophilic-treated pol ytetrafl uoroethyl ene (PTFE), hydrophilic-treated polyacrylonitrile (PAN), hydrophilic-treated fluorinated ethylene propylene (FEP), hydrophilic-treated polychlorotrifluoroethylene (PCTFE), hydrophilic- treated polyvinylidene fluoride (PVDF), hydrophilic-treated hexafluoropropylene (HFP), hydrophilic-treated PVDF-HFP, hydrophilic-treated polyfluoroalkoxy (PFA), and hydrophilic-treated polyimide (PI). A hydrophilic-treated polymer, as used herein, is a polymer which an ILE or DES wets. Wetting is determined by a contact angle measurement. In this contact angle measurement, an ILE or DES is deposited onto a polymer. The ILE or DES wets a polymer when the contact angle between the surface of the polymer and a line tangent to the surface of the ILE or DES, which is deposited on the polymer, is less than or equal to 90 °. The ILE or DES does not wets a polymer when the contact angle between the surface of the polymer and a line tangent to the surface of the ILE or DES is greater than 90 °. Hydrophilic surfaces are observed to have low contact angles (less than or equal to 90 degrees) with respect to a solution on the hydrophilic surface. Hydrophobic surfaces are observed to have high contact angles (greater than 90 degrees) with respect to a solution on the hydrophobic surface. A hydrophilic-treated polymer is made by bonding, through a chemical reaction, a polar chemical group to the polymer. Example polar chemical groups include, but are not limited to amino (NH2), carboxyl (COOH) and sulfonic acid (SO3H) groups. A hydrophilic-treated polymer may be synthesized via hydrolytic polycondensation and free radical polymerization. Polymers may also be functionalized by physical entanglement with chemical species having polar chemical groups. In some examples, PTFE is functionalized with a sulfonic acid (SO3H) group. Functionalized polymers are referred to herein as a derivative of the polymer which is functionalized. For example, functionalized PTFE is referred to herein as a derivative of PTFE.
[54] As used herein, the term“hydrophobic polymer,” refers to a polymer which does not wets an ILE or DES set forth herein. A hydrophobic polymer includes, but is not limited to, polytetrafluoroethylene (PTFE), polyacrylonitrile (PAN), fluorinated ethylene propylene (FEP), polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), hexafluoropropylene (HFP), PVDF-HFP, and polyfluoroalkoxy (PFA). A hydrophobic polymer, as used herein, is a polymer which ILE or DES does not wet.
[55] As used herein, the term“particle size,” refers to the average dimension characteristic of the longest length, side, or diameter of the particle. For particles which are spherical or approximately spherical, particle size refers to the average diameter of the particles. As used herein, particle size is measured by scanning electron microscopy (SEM), unless specified otherwise to the contrary. In some specific examples, particle size may be selected by sieving through a well-defined mesh. [56] As used herein, the term“graphitized,” refers to a material which includes graphite.
[57] As used herein, the term“crystalline,” refers to a material which diffracts x- rays. Crystalline graphite is characterized by at least an XRD peak at 26.55 2Q (the (002) peak of graphite having a d-spacing of 3.35 A). Graphite is mined as either vein, flake, or microcrystalline. Herein, graphite can be vein, flake, microcrystalline, or a combination thereof. In some examples, the graphite is flake graphite. In some examples, the graphite is natural flake graphite.
[58] As used herein, the term“few defects,” refers to graphite that has less than 5% defects per mole. Defects include, but are not limited to, misshaped particles, amorphous carbon, or particles having a particle size other than the average particle size. Defects in graphite can be measured using Raman spectroscopy and comparing the defect D band intensity relative to the graphite G band. In some examples, the ratio D/G is about near zero for natural graphite with few defects. In some examples, the ratio D/G is about zero for natural graphite with few defects.
[59] As used herein, the term“cycling,” refers to an electrochemical process whereby an electrochemical cell having an anode and a cathode is charged and discharged.
Figures
[60] Set forth herein is a unique composite separator for use in, amongst many types of batteries, an Al-graphite/aluminum-ion batteries (AIB). The composite separator is, in some examples, thin ( e.g ., 85 um), robust and protects the Al-ion battery from shorting during use.
[61] FIGs. 1-4 show four alternatives in which glass fiber paper (GFP) and PTFE layers are assembled to form composite separators. Optionally included with any of these composite separators is a binder or binders.
[62] FIG. 1 shows an electrochemical cell, 100. The electrochemical cell, 100, includes a positive electrode, 101, and a negative electrode, 104. Between the positive electrode, 101, and the negative electrode, 104, is a composite separator that is made of layers 102 and 103. Layer 102 is a glass fiber layer. Layer 103 is a polymer layer. In some examples, the polymer is a hydrophilic polymer. In some examples, the polymer is a hydrophobic polymer. Layers 101, 102, 103, and 104 are in contact with each other such that ions can conduct from layer 101 to layer 104 and vice versa.
[63] FIG. 2 shows an electrochemical cell, 200. The electrochemical cell, 200, includes a positive electrode, 201, and a negative electrode, 204. Between the positive electrode, 201, and the negative electrode, 204, is a composite separator that is made of layers 202 and 203. Layer 203 is a glass fiber layer. Layer 202 is a polymer layer. In some examples, the polymer is a hydrophilic polymer. In some examples, the polymer is a hydrophobic polymer. Layers 201, 202, 203, and 204 are in contact with each other such that ions can conduct from layer 201 to layer 204 and vice versa.
[64] FIG. 3 shows an electrochemical cell, 300. The electrochemical cell, 300, includes a positive electrode, 301, and a negative electrode, 305. Between the positive electrode, 301, and the negative electrode, 305, is a composite separator that is made of layers 302, 303 and 304. Layer 303 is a glass fiber layer. Layers 302 and 304 are polymer layers. In some examples, the polymer is a hydrophilic polymer. In some examples, the polymer is a hydrophobic polymer. Layers 301, 302, 303, 304, and 305 are in contact with each other such that ions can conduct from layer 301 to layer 305 and vice versa.
[65] FIG. 4 shows an electrochemical cell, 400. The electrochemical cell, 400, includes a positive electrode, 401, and a negative electrode, 405. Between the positive electrode, 401, and the negative electrode, 405, is a composite separator that is made of layers 402, 403 and 404. Layer 403 is a polymer layer. Layers 402 and 404 are glass fiber layers. In some examples, the polymer is a hydrophilic polymer. In some examples, the polymer is a hydrophobic polymer. Layers 401, 402, 403, 404, and 405 are in contact with each other such that ions can conduct from layer 401 to layer 404 and vice versa.
Composite Separators
[66] Glass fiber paper (GFP) is used as an electrolyte separator in some aluminum- ion batteries (AIBs) which use ionic liquid electrolytes and have an Al anode and a graphite cathode. GFP is inexpensive and chemically-inert to an acidic electrolyte. GFP is also resistant to corrosion during battery operation. Thick separators of GFP, with thickness ranging from
500 pm to 1000 pm, have been used to separate the anode and cathode of AIBs. However, since the glass fiber paper is highly porous, thick separator are required and an excess amounts of electrolyte are also needed. Batteries with an excess amount of electrolyte have a correspondingly reduced energy density (Wh/kg). Therefore, such thick separators that only include GFP and an electrolyte are not commercially viable. The following sets forth improved thinner electrolyte separators for Al-graphite batteries.
[67] In some examples, set forth herein is a composite separator. The composite separator includes a glass fiber layer and a polymer layer, or a derivative thereof. In some examples, the composite separator optionally includes a binder. When the composite separator is positioned between a positive electrode and a negative electrode, one of the following conditions (a), (b), (c), or (d) is satisfied: either (a) the glass fiber layer is between and in contact with the metal negative electrode and the polymer layer; and the polymer layer is between and in contact with the glass fiber layer and the positive electrode;
(b) the polymer layer is between and in contact with the metal negative
electrode and the glass fiber layer; and the glass fiber layer is between and in contact with the polymer layer and the positive electrode;
(c) the glass fiber layer is between and in contact with the polymer layer and an additional polymer layer; or
(d) the polymer layer is between and in contact with the glass fiber layer and an additional glass fiber layer.
[68] In some examples, including any of the foregoing, when condition (c) is satisfied, then either: (cl) the polymer layer is in contact with the positive electrode and the additional polymer layer is in contact with the negative electrode; or (c2) the polymer layer is in contact with the negative electrode and the additional polymer layer is in contact with the positive electrode.
[69] In some examples, including any of the foregoing, when condition (d) is satisfied either: (dl) the glass fiber layer is in contact with the positive electrode and the additional glass fiber layer is in contact with the negative electrode; or (d2) the glass fiber layer is in contact with the negative electrode and the additional glass fiber layer is in contact with the positive electrode.
[70] In some examples, including any of the foregoing, the polymer layer is a hydrophilic polymer layer.
[71] In some examples, including any of the foregoing, the polymer layer is a hydrophilic-treated polymer layer.
[72] In some examples, including any of the foregoing, the additional polymer layer is a hydrophilic polymer layer.
[73] In some examples, including any of the foregoing, the additional polymer layer is the same type of polymer as the polymer layer.
[74] In some examples, including any of the foregoing, the polymer layer is a hydrophilic polymer layer, and the hydrophilic polymer layer is between and in contact with the metal negative electrode and the glass fiber layer.
[75] In some examples, including any of the foregoing, the polymer layer is a hydrophilic polymer layer, and the hydrophilic polymer layer is between and in contact with the positive electrode and the glass fiber layer.
[76] In some examples, including any of the foregoing, the polymer layer is a hydrophilic polymer layer, and the glass fiber layer is between and in contact with the metal negative electrode and the hydrophilic polymer layer.
[77] In some examples, including any of the foregoing, the polymer layer is a hydrophilic polymer layer, and the glass fiber layer is between and in contact with the positive electrode and the hydrophilic polymer layer.
[78] In some examples, including any of the foregoing, the thickness of the glass fiber layer is 5 pm, 10 pm, 15 pm, 25 pm, 50 pm, 75 pm, or 100 pm.
[79] In some examples, including any of the foregoing, the thickness of the additional glass fiber layer is 5 pm, 10 pm, 15 pm, 25 pm, 50 pm, 75 pm, or 100 pm. [80] In some examples, including any of the foregoing, the thickness of the polymer layer is 5 pm, 10 pm, 15 pm, 25 pm, 50 pm, 75 pm, or 100 pm.
[81] In some examples, including any of the foregoing, the thickness of the additional polymer layer is 5 pm, 10 pm, 15 pm, 25 pm, 50 pm, 75 pm, or 100 pm.
[82] In some examples, including any of the foregoing, the thickness of the glass fiber layer or additional glass fiber layer, or both, is from 0 pm to 300 pm. In some examples, including any of the foregoing, the thickness of the glass fiber layer is from 0 pm to 300 pm. In some examples, including any of the foregoing, the thickness of the additional glass fiber layer, is from 0 pm to 300 pm. In some examples, including any of the foregoing, the thickness of both the glass fiber layer and the additional glass fiber layer is from 0 pm to 300 pm.
[83] In some examples, including any of the foregoing, the thickness of the glass fiber layer or additional glass fiber layer, or both, is from 20 pm to 300 pm. In some examples, including any of the foregoing, the thickness of the glass fiber layer is from 20 pm to 300 pm. In some examples, including any of the foregoing, the thickness of the additional glass fiber layer is from 20 pm to 300 pm. In some examples, including any of the foregoing, the thickness of both the glass fiber layer and additional glass fiber layer is from 20 pm to 300 pm.
[84] In some examples, including any of the foregoing, the thickness of the glass fiber layer or additional glass fiber layer, or both, is from about 50 pm to about 200 pm. In some examples, including any of the foregoing, the thickness of the glass fiber layer is from about 50 pm to about 200 pm. In some examples, including any of the foregoing, the thickness of the additional glass fiber layer is from about 50 pm to about 200 pm. In some examples, including any of the foregoing, the thickness of both the glass fiber layer and additional glass fiber layer is from about 50 pm to about 200 pm.
[85] In some examples, including any of the foregoing, the glass fiber layer or additional glass fiber layer, or both, includes glass fiber paper. In some examples, including any of the foregoing, the glass fiber layer includes glass fiber paper. In some examples, including any of the foregoing, the additional glass fiber layer includes glass fiber paper. In some examples, including any of the foregoing, both the glass fiber layer and additional glass fiber layer include glass fiber paper. [86] In some examples, including any of the foregoing, the glass fiber layer or additional glass fiber layer, or both, is porous. In some examples, including any of the foregoing, the glass fiber layer is porous. In some examples, including any of the foregoing, the additional glass fiber layer is porous. In some examples, including any of the foregoing, both the glass fiber layer and additional glass fiber layer are porous.
[87] In some examples, including any of the foregoing, the porous glass fiber layer includes pores from about 0.1 pm to about 10 pm in diameter. In some examples, including any of the foregoing, the pores are about 0.6 pm in diameter. In some examples, including any of the foregoing, the pores are about 0.1 pm in diameter. In some examples, including any of the foregoing, the pores are about 0.2 pm in diameter. In some examples, including any of the foregoing, the pores are about 0.3 pm in diameter. In some examples, including any of the foregoing, the pores are about 0.4 pm in diameter. In some examples, including any of the foregoing, the pores are about 0.5 pm in diameter. In some examples, including any of the foregoing, the pores are about 0.6 pm in diameter. In some examples, including any of the foregoing, the pores are about 0.7 pm in diameter. In some examples, including any of the foregoing, the pores are about 0.8 pm in diameter. In some examples, including any of the foregoing, the pores are about 0.9 pm in diameter. In some examples, including any of the foregoing, the pores are about 1.0 pm in diameter. In some examples, including any of the foregoing, the pores are about 1.5 pm in diameter. In some examples, including any of the foregoing, the pores are about 2.0 pm in diameter. In some examples, including any of the foregoing, the pores are about 3.0 pm in diameter. In some examples, including any of the foregoing, the pores are about 4.0 pm in diameter. In some examples, including any of the foregoing, the pores are about 5.0 pm in diameter. In some examples, including any of the foregoing, the pores are about 6.0 pm in diameter. In some examples, including any of the foregoing, the pores are about 7.0 pm in diameter. In some examples, including any of the foregoing, the pores are about 8.0 pm in diameter. In some examples, including any of the foregoing, the pores are about 9.0 pm in diameter. In some examples, including any of the foregoing, the pores are about 10 pm in diameter.
[88] In some examples, including any of the foregoing, the glass fiber layer or additional glass fiber layer, or both, includes Si02. In some examples, including any of the foregoing, the glass fiber layer includes Si02. In some examples, including any of the foregoing, the additional glass fiber layer includes Si02. In some examples, including any of the foregoing, both the glass fiber layer and additional glass fiber layer include Si02. In some examples, including any of the foregoing, the glass fiber layer or additional glass fiber layer, or both, includes Si02 fibers. In some examples, including any of the foregoing, the glass fiber layer includes Si02 fibers. In some examples, including any of the foregoing, the additional glass fiber layer includes Si02 fibers. In some examples, including any of the foregoing, both the glass fiber layer and additional glass fiber layer include Si02 fibers.
[89] In some examples, including any of the foregoing, the polymer layer or additional polymer layer, or both, includes a multilayer. In some examples, including any of the foregoing, the polymer layer includes a multilayer. In some examples, including any of the foregoing, the additional polymer layer includes a multilayer. In some examples, including any of the foregoing, both the polymer layer and additional polymer layer include a multilayer. In some examples, including any of the foregoing, the multilayer is a multilayer of hydrophilic polymer layers. In some examples, including any of the foregoing, the multilayer is a multilayer of hydrophobic polymer layers. In some examples, including any of the foregoing, the multilayer includes 2, 3, 4, or 5 individual polymer layers. In some examples, including any of the foregoing, the thickness of each individual polymer layer in the multilayer is from about 5 pm to about 50 pm.
[90] In some examples, including any of the foregoing, the thickness of the hydrophilic polymer layer or additional hydrophilic polymer layer, or both, is, individually in each instance, from about 5 pm to about 150 pm.
[91] In some examples, including any of the foregoing, the thickness of the hydrophilic polymer layer or additional hydrophilic polymer layer, or both, is, individually in each instance, from about 5 pm to about 50 pm.
[92] In some examples, including any of the foregoing, the thickness of the hydrophilic polymer layer or additional hydrophilic polymer layer, or both, is, individually in each instance, from about 15 pm to about 25 pm.
[93] In some examples, including any of the foregoing, the hydrophilic polymer layer includes a porous substrate on which a hydrophilic polymer is coated.
[94] In some examples, including any of the foregoing, the porous substrate is a hydrophobic or hydrophilic membrane. [95] In some examples, including any of the foregoing, the porous substrate is selected from the group consisting of a porous metal, a porous polymer, and a porous ceramic.
[96] In some examples, including any of the foregoing, the porous substrate is selected from the group consisting of a porous glass fiber paper, a regenerated cellulose membrane, a polyester membrane, a polyethersulfone membrane, and a polyethylene membrane.
[97] In some examples, including any of the foregoing, the polymer layer is a hydrophilic polymer layer comprising a hydrophilic polymer is selected from the group consisting of polytetrafluoroethylene (PTFE), polyacrylonitrile (PAN), fluorinated ethylene propylene (FEP), polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), hexafluoropropylene (HFP), PVDF-HFP, polyfluoroalkoxy (PFA), a derivative thereof, and combinations thereof.
[98] In some examples, including any of the foregoing, the polymer layer is a hydrophilic polymer layer comprising a hydrophilic polymer is selected from the group consisting of polytetrafluoroethylene (PTFE), polyacrylonitrile (PAN), fluorinated ethylene propylene (FEP), polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), hexafluoropropylene (HFP), PVDF-HFP, polyfluoroalkoxy (PFA), polyimide (PI), a derivative thereof, and combinations thereof.
[99] In some examples, including any of the foregoing, the polymer layer is a hydrophobic polymer layer comprising a hydrophobic polymer is selected from the group consisting of polytetrafluoroethylene (PTFE), polyacrylonitrile (PAN), fluorinated ethylene propylene (FEP), polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), hexafluoropropylene (HFP), PVDF-HFP, and polyfluoroalkoxy (PFA), and combinations thereof.
[100] In some examples, including any of the foregoing, the binder is selected from the group consisting of polyacrylate (PA), polyacrylic acid (PAA), polyvinyl alcohol (PVA), cross-linked PAA, cross-linked PVA, PAA-PVA, polyacrylic latex, cellulose, cellulose derivatives, alginate, polyethylene glycol, styrene-butadiene rubber, poly(styrene-co- butadiene), styrene-butadiene rubber, poly(3, 4-ethyl enedioxythiophene), acrylonitrile copolymer, acrylic latex, and combinations thereof. [101] In some examples, including any of the foregoing, the binder is selected from the group consisting of poly-acrylic acid (PAA), poly-vinyl alcohol (PVA), cross-linked PAA, cross-linked PVA, styrene-butadiene latex, acrylonitrile copolymer, and acrylic latex.
[102] In some examples, including any of the foregoing, the binder is selected from the group consisting of PAA and PVA.
[103] In some examples, including any of the foregoing, the binder is LA133™ The LA133™ binder has a milky white appearance or a light yellow appearance when formulated as a water emulsion. The viscosity of the binder in water emulsion is greater than or equal to 7300 mPAs at 40°C. The binder has a D50 (pm) particle size of less than or equal to 1.0 pm. The solid content (%) is l5.0±0.2. The pH is about 7~9.
[104] In some examples, including any of the foregoing, the total thickness of the composite separator is from about 20 pm to about 300 pm.
[105] In some examples, including any of the foregoing, the total thickness of the composite separator is from about 20 pm to about 225 pm.
[106] In some examples, including any of the foregoing, the total thickness of the composite separator is about 150 pm.
[107] In some examples, including any of the foregoing, the total thickness of the composite separator is about 50 pm, 55 pm, 60 pm, 65 pm, 70 pm, 75 pm, 80 pm, 95 pm,
100 pm, 105 pm, or 110 pm.
[108] In some examples, including any of the foregoing, the composite separator further includes an aqueous liquid electrolyte in contact with the composite separator.
[109] In some examples, including any of the foregoing, the composite separator further includes a nonaqueous liquid electrolyte in contact with the composite separator.
[110] In some examples, including any of the foregoing, the composite separator further includes an ionic liquid or deep eutectic solvent electrolyte in contact with the composite separator.
[111] In some examples, including any of the foregoing, the composite separator further includes a deep eutectic solvent electrolyte in contact with the composite separator. [112] In some examples, including any of the foregoing, the composite separator further includes an ionic liquid electrolyte in contact with the composite separator.
[113] In some examples, including any of the foregoing, the glass fiber layer or additional glass fiber layer, or both, is a glass fiber paper (GFP).
[114] In some examples, including any of the foregoing, the composite separator includes a layer of PTFE/GFP and an additional layer of PTFE. In some examples, including any of the foregoing, the PTFE layer is in contact with the negative electrode. In some examples, including any of the foregoing, the PTFE layer is in contact with the positive electrode. In some examples, including any of the foregoing, the additional layer of PTFE layer is in contact with the negative electrode. In some examples, including any of the foregoing, the additional layer of PTFE layer is in contact with the positive electrode. In some examples, including any of the foregoing, the GFP is between and in contact with the layer of PTFE and the additional layer of PTFE. In some examples, including any of the foregoing, the composite separator includes two layers of PTFE. In some examples, including any of the foregoing, the composite separator includes three layers of PTFE. In some examples, including any of the foregoing, the PTFE layer is 50 pm in thickness.
[115] In some examples, including any of the foregoing, the composite separator includes a metal negative electrode that includes a metal selected from the group consisting of lithium (Li), sodium (Na), potassium (K), magnesium (Mg), calcium (Ca), aluminum (Al), germanium (Ge), tin (Sn), iron (Fe), zinc (Zn), combinations thereof, and alloys thereof. In some examples, including any of the foregoing, the metal negative electrode is a foil, a mesh, or a foam. In some examples, including any of the foregoing, the metal negative electrode is Al. In some examples, including any of the foregoing, the metal negative electrode is a Al metal foil, Al mesh, Al foam, or porous Al film.
[116] In some examples, including any of the foregoing, the composite separator includes a positive electrode that includes carbon selected from the group consisting of natural graphite, graphene, and synthetic graphite. In some examples, including any of the foregoing, the graphene is provided as 1, 2, 3, 4, or 5 layers. In some examples, including any of the foregoing, the positive electrode includes natural graphite flake of high purity and high degree of graphitization. In some examples, including any of the foregoing, the graphite has a particle size of 1 pm to 500 pm. In some examples, including any of the foregoing, the graphite has a particle size between about 1 pm and 50 pm, between about 50 pm and 100 pm, between about 50 pm and 200 pm, or between about 50 pm and 300 pm. In some examples, including any of the foregoing, the positive electrode includes carbon having a particle size between 20 pm - 300 pm. In some examples, including any of the foregoing, the positive electrode includes graphite and the graphite has a particle size of 40 pm to 200 pm.
In some examples, including any of the foregoing, the positive electrode includes carbon and the carbon having a particle size of at least 45 pm. In some examples, including any of the foregoing, the positive electrode includes carbon having a particle size of at least 20 pm. In some examples, including any of the foregoing, the positive electrode includes carbon having a particle size from about 45 pm to about 75 pm and carbon having a particle size from about 150 to about 250 pm. In some examples, including any of the foregoing, the carbon having a particle size from about 45 pm to about 75 pm to carbon having a particle size from about 150 to about 250 pm is 5:95 to 20:80 or 5:95 to 15:85. In some examples, including any of the foregoing, the graphite is pure natural graphite flake. In some examples, including any of the foregoing, the graphite is crystalline and highly graphitized. In some examples, including any of the foregoing, the graphite is substantially free of defects. In some examples, including any of the foregoing, the graphite includes less than 10% defects. In some examples, including any of the foregoing, the positive electrode includes pyrolytic graphite.
[117] In some examples, including any of the foregoing, the composite separator further includes a positive electrode current collector selected from the group consisting of a glassy carbon current collector, carbon fiber paper current collector, carbon fiber cloth current collector, graphite fiber paper current collector, and graphite fiber cloth current collector. In some examples, including any of the foregoing, the carbon fiber paper has a thickness between about 10 pm to 300 pm.
[118] In some examples, including any of the foregoing, the composite separator further includes a positive electrode current collector selected from the group consisting of a metal substrate current collector. In some examples, including any of the foregoing, the metal substrate is coated with a protective coating. In some examples, including any of the foregoing, the metal substrate is a mesh, a foil, or a foam. In some examples, including any of the foregoing, the metal substrate is a nickel (Ni) or tungsten (W) metal substrate. In some examples, including any of the foregoing, the protective coating is selected from the group consisting of a Ni coating, a W coating, a carbon coating, a carbonaceous material, a conducting polymer, and a combination thereof. In some examples, including any of the foregoing, the metal substrate is a Ni foil, a Ni mesh, a Ni foam, a W foil, a W mesh, or a W foam. In some examples, including any of the foregoing, the metal substrate is a metal foil coated with Ni coating. In some examples, including any of the foregoing, the metal substrate is a metal mesh or metal foam coated with Ni coating. In some examples, including any of the foregoing, the metal substrate is a metal foil coated with W coating. In some examples, including any of the foregoing, the metal substrate is a metal mesh or metal foam coated with W coating. In some examples, including any of the foregoing, the metal substrate is Ni and the protective coating is carbon.
Electrolytes
[119] Ionic liquid electrolytes can be formed by slowly mixing or otherwise combining an aluminum halide ( e.g ., AlCh) and an organic compound. In certain examples, the aluminum halide undergoes asymmetric cleavage to form a haloaluminate anion (e.g., AlCU ) and an aluminum halide cation that is datively bonded to the organic compound serving as a ligand (e.g., [AlCh n(ligand)]+). A mole ratio of the aluminum halide and the organic compound can be at least or greater than about 1.1 or at least or greater than about 1.2, and is up to about 1.5, up to about 1.8, up to about 2, or more. For example, the mole ratio the aluminum halide and the organic compound (e.g., urea) can be in a range of about 1.1 to about 1.7 or about 1.3 to about 1.5. In some embodiments, a ligand is provided as a salt or other compound including the ligand, and a mole ratio of the aluminum halide and the ligand-containing compound can be at least or greater than about 1.1 or at least or greater than about 1.2, and is up to about 1.5, up to about 1.8, up to about 2, or more. An ionic liquid electrolyte can be doped, or have additives added, to increase its electrical conductivity and lower the viscosity, or can be otherwise altered to yield compositions that favor the reversible electrodeposition of metals. For example, 1, 2-dichlorobenzene can be added as a co-solvent to reduce electrolyte viscosity and increase the voltage efficiency, which can result in an even higher energy density. Also, alkali chloride additives can be added to increase the discharge voltage of a battery. In some examples, 1 -ethyl-3 -methylimidazolium tetrafluorob orate or 1- ethyl-3-methylimidazolium bis(trifluorom ethane sulfonimide) or l-ethyl-3- methylimidazolium hexafluorophosphate can be added as additives to increase the discharge voltage of a battery. [120] Other ionic liquid electrolytes are suitable for use with an Al-metal anode battery. For example, AlClvUrea can be used as an ionic liquid electrolyte. In certain examples, Aluminum deposition proceeds through two pathways, one involving AI2CI7 anions and the other involving [AlCb (urea)n]+ cations. The following simplified half-cell redox reactions describe this process:
2 [AlCb n(urea)]+ + 3e -> Al + AlCU + 2n(urea)
3Cn(AlCl4) + 3e - 3Cn + 3 AlCU which gives an overall battery reaction (including counter ions):
2 ([AlCb n(urea)]+ AlCU ) + 3Cn - Al + 3CnAlCl4 + 2n(urea).
[121] In some examples, set forth herein is an ionic liquid electrolyte (ILE) or deep eutectic solvent (DES) including a mixture of a metal halide and an organic compound, wherein water content of the electrolyte is less than 1000 ppm. As used herein, ILE refers to ionic electrolytes which include ionically bonded chemical species. As used herein, DES refers to ionic electrolytes which include ionically bonded chemical species as well as non- ionically bonded chemical species, e.g ., species which are bonded through hydrogen-bonds.
In some examples, hydrogen bonding in a given DES can dominate (i.e., be stronger) ionic bonding.
[122] In some examples, including any of the foregoing, the ILE or DES includes a member selected from the group consisting of alkylimidazolium aluminates, alkylpyridinium aluminates, alkylfluoropyrazolium aluminates, alkyltriazolium aluminates, aralkylammonium aluminates, alkyl alkoxyammonium aluminates, aralkylphosphonium aluminates,
aralkyl sulfonium aluminates, alkylguanidinium aluminates, and combinations thereof. In certain examples, the ILE or DES includes alkylimidazolium aluminates. In certain examples, the ILE or DES includes alkylpyridinium aluminates. In certain examples, the ILE or DES includes alkylfluoropyrazolium aluminates. In certain examples, the ILE or DES includes alkyltriazolium aluminates. In certain examples, the ILE or DES includes aralkylammonium aluminates. In certain examples, the ILE or DES includes alkyl alkoxyammonium aluminates. In certain examples, the ILE or DES includes aralkylphosphonium aluminates. In certain examples, the ILE or DES includes aralkyl sulfonium aluminates. In certain examples, the ILE or DES includes alkylguanidinium aluminates. [123] In some examples, including any of the foregoing, the ILE or DES includes urea.
[124] In some examples, including any of the foregoing, the metal halide is an aluminum halide.
[125] In some examples, including any of the foregoing, the aluminum halide is AlCh.
[126] In some examples, including any of the foregoing, the aluminum halide is AlCh, and the organic compound includes: (a) cations selected from the group consisting of N-(n-butyl) pyridinium, benzyltrimethylammonium, l,2-dimethyl-3-propylimidazolium, trihexyltetradecylphosphonium, and 1 -butyl- l-methyl-pyrrolidinium, and (b) anions selected from the group consisting of tetrafluoroborate, tri-fluoromethanesulfonate, and
bis(trifluoromethanesulfonyl)imide.
[127] In some examples, including any of the foregoing, the aluminum halide is AlCh, and the organic compound is selected from 4-propylpyridine, acetamide, N- methylacetamide, N,N-dimethylacetamide, trimethylphenylammonium chloride, l-ethyl-3- methylimidazolium bis(trifluorom ethyl sulfonyl)imide, and 1 -ethyl-3 -methylimidazolium chloride.
[128] In some examples, including any of the foregoing, the aluminum halide is AlCh, and the organic compound is l-ethyl-3-methylimidazolium chloride.
[129] In some examples, including any of the foregoing, the ILE includes an aluminum halide cation that is datively bonded to the organic compound.
[130] In some examples, including any of the foregoing, the aluminum halide is AlCh, and the organic compound is an amide. In some of these examples, the amide is selected from urea, methylurea, ethylurea, and combinations thereof. In certain examples, the amide is urea. In certain examples, the amide is methylurea. In certain examples, the amide is ethylurea.
[131] In some examples, including any of the foregoing, the metal halide is AlCh; and the organic compound is selected from 1 -ethyl-3 -methyl imidazolium chloride, l-ethyl-3- methylimidazolium bis(trifluorom ethyl sulfonyl)imide, urea, methylurea, ethylurea, mixtures thereof, and combinations thereof.
[132] In some examples, including any of the foregoing, the ILE includes AlCh and 1 -ethyl-3 -methyl imidazolium chloride, the mole ratio of AlChriL' is from 1.1 to 1.7. In some examples, the mole ratio is 1.1. In some examples, the mole ratio is 1.2. In some examples, the mole ratio is 1.3. In some examples, the mole ratio is 1.4. In some examples, the mole ratio is 1.5. In some examples, the mole ratio is 1.6. In some examples, the mole ratio is 1.7.
[133] In some examples, including any of the foregoing, the ILE includes a mixture of 1.1 to 1.7 moles AlCh, 1.0 mole 1 -ethyl-3 -methyl imidazolium chloride and 0.1 to 0.5 mole 1 -ethyl -3 -methylimidazolium bis(trifluoromethylsulfonyl)imide. In some examples, the mixture includes 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, or 1.7 moles AlCh. In some examples, the mixture includes 0.1, 0.2, 0.3, 0.4, or 0.5 moles 1 -ethyl-3 -methylimidazolium
bis(trifluoromethylsulfonyl)imide. In some examples, the mixture includes 0.1, 0.2, 0.3, 0.4, or 0.5 moles l-ethyl-3-methylimidazolium tetrafluorob orate. In some examples, the mixture includes 0.1, 0.2, 0.3, 0.4, or 0.5 moles 1 -ethyl -3 -methylimidazolium hexafluorophosphate,
[134] In some examples, including any of the foregoing, the ILE includes AlCh and urea. In some examples, including any of the foregoing, the ILE includes AlCh and methylurea.
[135] In some examples, including any of the foregoing, the mole ratio of AlCh to urea in the ILE is between 1.1 to 1.7.
[136] In some examples, including any of the foregoing, the mole ratio of AlCh to methylurea is between 1.1 to 1.7.
[137] In some examples, including any of the foregoing, the ILE is urea and the mole ratio of AlChmrea about 1.1 to about 1.7.
[138] In some examples, including any of the foregoing, the ILE is methylurea and the mole ratio of AlCh:methylurea is about 1.1 to about 1.7.
[139] In some examples, including any of the foregoing, the ILE is ethylurea and the mole ratio of AlCh: ethylurea is about 1.1 to about 1.7. [140] In some examples, the ionic liquid electrolytes are made of chloroaluminate (A1C14 ) based ionic liquids. Ionic liquids can be represented by [AlCl3]/[X], wherein X may include any organic salts or organic compounds which produces (A1C14 ) ions when mixed with AlCh powder to form ionic liquids. The [AlCh]/[X] ratios are ranging from 0.1 to 2.5 molar ratios. X can be 1 -ethyl-3 -methylimidazolium chloride (EMIC), l-butyl-3- methylimidazolium chloride (BMIC), l-propyl-3-methylimidazolium chloride (PMIC), Urea, N-Methylurea, N-Ethylurea, dimethyl sulfone (DMS02), triethylamine hydrochloride, l-(2- methoxyethyl)-3-methylimidazolium chloride ([MoeMImJCl), n-butylpyridinium chloride (BPC), trimethylphenyl ammonium chloride (TMPAC), or combinations thereof.
[141] In some examples, including any of the foregoing, the amount of water or hydrochloric acid in the ionic liquid electrolyte is between 0 - 1000 ppm. In some examples, including any of the foregoing, the amount of water or hydrochloric acid in the ionic liquid electrolyte is less than 1000 ppm. In some examples, including any of the foregoing, the concentration of corrosion products content in the ionic liquid electrolyte is less than 1000 ppm.
[142] Examples of ionic liquids include aluminates, such as ones including, or formed from, a mixture of an aluminum halide and an organic compound. To reduce the water content in the ionic liquid, the organic compound can be subjected to heating and drying under reduced pressure, such as heating in vacuum (e.g., about 10 2 Torr, about 10 3 Torr, or less, and about 70°C-l l0°C) to remove water prior to mixing with an aluminum halide slowly under stirring with cooling to maintain a temperature near room temperature. For example, a suitable ionic liquid can include, or can be formed from, a mixture of an aluminum halide (e.g., AlCh) and urea; other aliphatic amides including from 1 to 10, 2 to 10, 1 to 5, or 2 to 5 carbon atoms per molecule, such as acetamide, as well as cyclic (e.g., aromatic, carbocyclic, or heterocyclic) amides, as well as combinations of two or more different amides are contemplated. In some examples, a suitable ionic liquid can include, or can be formed from, a mixture of an aluminum halide (e.g., AlCh) and 4-propylpyridine; other pyridines, as well as other N-heterocyclic compounds (including EMIC or EMI) with 4 to 15, 5 to 15, 4 to 10, or 5 to 10 carbon atoms per molecule, as well as combinations of two or more different N-heterocyclic compounds are contemplated. In some examples, a suitable ionic liquid for high temperature operations can include, or can be formed from, a mixture of an aluminum halide and trimethylphenylammonium chloride; other cyclic (e.g., aromatic, carbocyclic, or heterocyclic) compounds including a cyclic moiety substituted with at least one amine or ammonium group, as well as aliphatic and cyclic amines or ammoniums, as well as combinations of two or more different amines or ammoniums are contemplated. In some examples, a suitable organic compounds include N-(n-butyl) pyridinium chloride, benzyltrimethylammonium chloride, 1, 2-dimethyl -3-propylimidazolium,
trihexyltetradecylphosphonium chloride, and 1 -butyl- l-methyl-pyrrolidinium cations with anions such as tetrafluorob orate, tri-fluoromethanesulfonate and
bi s(trifluoromethanesulfonyl) imide .
[143] In some embodiments, the aluminum halide is AlCh, and the organic compound incudes cations selected from N-(n-butyl) pyridinium, benzyltrimethylammonium, l,2-dimethyl-3-propylimidazolium, trihexyltetradecylphosphonium, and 1 -butyl- l-methyl- pyrrolidinium, and anions selected from tetrafluorob orate, tri-fluoromethanesulfonate, and bis(trifluoromethanesulfonyl)imide.
[144] In some embodiments, the aluminum halide is AlCh, and the organic compound is selected from 4-propylpyridine, acetamide, trimethylphenyl ammonium chloride, and l-ethyl-3-methylimidazolium chloride.
Processes for Making a Rechargeable Battery
[145] The processes for making a composite separator, or a battery having the composite separator, can be used for a process for making a rechargeable battery. In some examples, set forth herein is a process for making a composite separator, including the following steps: (a) providing a binder solution; (b) providing a glass fiber layer; (c) contacting the binder solution to the glass fiber paper to form a binder glass fiber layer composite; (d) drying the binder glass fiber layer composite; and (e) contacting a solution of a polymer to the binder glass fiber layer composite to form a composite separator. In some examples, set forth herein is a process for making a composite separator, including the following steps: (a) providing a binder solution; (b) providing a glass fiber layer; (c) providing a polymer layer; (d) contacting the binder solution to the glass fiber paper to form a binder glass fiber layer composite; (e) contacting the polymer layer to the binder glass fiber layer composite to form a composite separator; and (f) drying the composite separator.
Incorporated by reference are the processes for making a rechargeable battery set forth in US 2015-0249261; WO 2015/131132; Lin, M-C, et al., Nature, 2015, p. 1- doi: 1038/nature 143040; and Angell, et al., PNAS, Early Edition, 2016, p. 1-6, doi: l0.l073/pnas.1619795114. Also incorporated by reference herein in its entirety is ETS Provisional Patent Application No. 62/483,830, filed April 10, 2017, and entitled BATTERY WITH LONG CYCLE LIFE.
Processes for Making a Composite Separator
[146] In some examples, set forth herein is a process for making a composite separator, including the following steps: (a) providing a binder solution; (b) providing a glass fiber layer; (c) contacting the binder solution to the glass fiber paper to form a binder glass fiber layer composite; (d) drying the binder glass fiber layer composite; and (e) contacting a solution of a polymer to the binder glass fiber layer composite to form a composite separator.
[147] In some examples, including any of the foregoing, the polymer is a hydrophilic polymer.
[148] In some examples, including any of the foregoing, the polymer is a hydrophobic polymer.
[149] In some examples, set forth herein is a process for making a composite separator, including the following steps: (a) providing a binder solution; (b) providing a glass fiber layer; (c) providing a polymer layer; (d) contacting the binder solution to the glass fiber paper to form a binder glass fiber layer composite; (e) contacting the polymer layer to the binder glass fiber layer composite to form a composite separator; and (f) drying the composite separator.
[150] In some examples, including any of the foregoing, the solution of a polymer is a solution of a hydrophilic polymer.
[151] In some examples, including any of the foregoing, the solution of a polymer is a solution of a hydrophobic polymer.
[152] In some examples, including any of the foregoing, the polymer layer is a hydrophilic polymer layer.
[153] In some examples, including any of the foregoing, the polymer layer is a hydrophobic polymer layer. [154] In some examples, including any of the foregoing, the binder solution is a hydrophilic binder solution.
[155] In some examples, including any of the foregoing, the process further includes comprising drying the composite separator.
[156] In some examples, including any of the foregoing, the glass fiber layer is a glass fiber paper.
[157] In some examples, including any of the foregoing, the binder solution includes 5 to 50 % w/w binder in deionized water.
[158] In some examples, including any of the foregoing, the glass fiber layer has a geometric surface area of 10 cm2.
[159] In some examples, including any of the foregoing, the polymer is a hydrophilic polymer selected from the group consisting of polytetrafluoroethylene (PTFE), polyacrylonitrile (PAN), fluorinated ethylene propylene (FEP), polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), hexafluoropropylene (HFP), PVDF-HFP, polyfluoroalkoxy (PFA), a and combinations thereof.
[160] In some examples, including any of the foregoing, the binder is selected from the group consisting of polyacrylate (PA), polyacrylic acid (PAA), polyvinyl alcohol (PVA), cross-linked PAA, cross-linked PVA, PAA-PVA, polyacrylic latex, cellulose, cellulose derivatives, alginate, polyethylene glycol, styrene-butadiene rubber, poly(styrene-co- butadiene), styrene-butadiene rubber, poly(3, 4-ethyl enedioxythiophene), acrylonitrile copolymer, acrylic latex, and combinations thereof.
[161] In some examples, including any of the foregoing, the binder is selected from the group consisting of poly-acrylic acid (PAA), poly-vinyl alcohol (PVA), cross-linked PAA, cross-linked PVA, styrene-butadiene latex, acrylonitrile copolymer, and acrylic latex.
[162] In some examples, including any of the foregoing, the binder is selected from the group consisting of PAA and PVA.
[163] In some examples, including any of the foregoing, the binder is LA133™ [164] In some examples, including any of the foregoing, the drying comprising drying under vacuum at about 200 °C.
[165] In some examples, set forth herein is a composite separator made by a process herein.
Processes for Making a Cathode to Use in a Rechargeable Battery
[166] In some examples, set forth herein are methods of making a cathode suitable for use in a rechargeable battery.
[167] In some examples, the cathode uses graphite as an active materials and a metal substrate as a current collector. Graphite can include, but is not limited to, natural graphite, synthetic graphite, graphite paper, pyrolytic graphite. The metal substrate can include, but is not limited to, a Nickel (Ni) foil, Ni foam, Ni mesh, Tungsten (W) foil, W-mesh, or
Molybdenum foil.
[168] In some embodiments, the cathode includes a metal substrate. In some examples, the metal substrate is a nickel substrate and the substrate includes a protective coating of a carbonaceous material derived from pyrolysis of organic compounds deposited on the metal substrate from solution or gas phase, or a conducting polymer deposited on the metal substrate.
[169] Bare Ni foil or Ni foam can be used as current collectors or the
aforementioned substrate. Natural graphite particles can be loaded onto such a Ni -based substrate with a binder. Ni and W are found to be more resistive to corrosion in Al-ion battery than most other metals on the cathode side.
[170] Ni foil or Ni foam can be coated with a carbon or graphite layer by various methods to impart enhanced corrosion resistance. One such method is to grow a carbon or graphitic layer on Ni by coating Ni with a carbon-rich material, such as pitch dissolved in a solvent, and then heating at about 400-800°C. Another protective coating is a conducting polymer layer such as poly(3, 4-ethyl enedioxythiophene) polystyrene sulfonate
(PEDOT:PSS). A graphite/polymer binder can also coat Ni densely and act as a protection layer as well as an active cathode layer. [171] In some examples, set forth herein are cathodes having polymer binders with graphite particles. For example, a polyacrylic acid (PAA)/polyvinyl alcohol (PVA)-based polymer binder for graphite particles can be used.
[172] In some examples, natural graphite particles are dispersed in water containing about 10 wt% PAA and about 3 wt% PVA and stirred to make a slurry. The slurry is applied to a current collector as described above, at a loading of about 2-20 mg/cm2, followed by drying at about 70-l50°C in vacuum for about 3 hours or longer to thoroughly remove water, leaving graphite particles packed on the current collector to form a cathode for an Al battery. Further, several weight percent of graphite fibers can be added to the slurry to improve electrical conductivity of the cathode.
[173] In some examples, a carboxymethyl cellulose (CMC)/styrene-butadiene rubber (SBR)/graphite fiber-based polymer binder is used with graphite particles.
[174] In some examples, set forth herein are methods, which include using natural graphite particles dispersed in a water slurry, containing about 10 wt% CMC and about 1 wt% SBR. In some examples, the slurry is applied to a current collector as described above, at a loading of about 2-20 mg/cm2, followed by drying at about 70-200°C in vacuum for about 3 hours or longer to thoroughly remove water, leaving graphite particles packed on the current collector to form a cathode for an Al battery. In some examples, graphite fibers can be added to the slurry to improve electrical conductivity of the cathode.
[175] In some examples, a PEDOT/PSS/graphite fiber-based polymer binder for graphite particles is used.
[176] In some examples, set forth herein are methods which include using natural graphite particles dispersed in water slurry containing about 10 wt% PEDOT and about 1 wt% PSS conducting polymer. In some examples, the slurry is applied to a current collector as described above, at a loading of about 2-20 mg/cm2, followed by drying at about 70-200°C in vacuum for about 3 hours or longer to thoroughly remove water, leaving graphite particles packed on the current collector to form a cathode for an Al battery. In some examples, graphite fibers can be added to the slurry to improve electrical conductivity of the cathode.
[177] In some examples, an ionic liquid polymer binder for graphite particles is used. [178] In some examples, set forth herein are methods, which include using natural graphite particles are dispersed in a water slurry, containing ionic liquid polymer or oligomer. In some examples, the slurry is applied to a current collector as described above, at a loading of about 2-20 mg/cm2, followed by drying at about 70-200°C in vacuum for about 3 hours or longer to thoroughly remove water, leaving graphite particles packed on the current collector to form a cathode for Al battery.
[179] In some examples, slurries useful with the compositions and methods described herein include the following slurries.
[180] In some examples, a slurry includes about 89 wt% graphite particles (grade 306l)/about 4 wt% CMC/about 2 wt% SBR/about 5 wt% graphite fibers, on ELAT® carbon fiber cloth, 70°C annealed for about 2 h). In some examples, also included is about 802 mg of 3 wt% Na-CMC gel in de-ionized (DI )water, about 241 mg of 5 wt% SBR dispersed in DI water, about 30 mg of chopped graphite fiber, about 534 mg of graphite (grade 3061), and about 1.2 mL of DI water.
[181] In some examples, a slurry includes about 87 wt% graphite parti cles/about 10 wt% PAA/about 3 wt% PVA, on M30 carbon fiber paper, l30°C annealed for about 2 h). In some examples, also included is about 225 mg of 25 wt% PAA aqueous solution, about 169 mg of 10 wt% PVA aqueous solution, about 489 mg of graphite particles, and about 0.4 mL of DI water.
[182] In some examples, including any of the foregoing, the anode is an Aluminum
(Al) anode, such as, but not limited to, an Al metal foil, Al mesh, Al foam and porous Al film. The thickness may range, in some examples, from 10 pm to 500 pm.
Electrochemical Cells and Batteries
[183] In some examples, set forth herein is an aluminum-graphite battery having an Al anode, a composite separator, an ionic liquid electrolyte and a graphite cathode. In some examples, the composite separator includes a glass fiber layer. In some examples, the composite separator includes a hydrophobic or hydrophilic polymer. In some examples, the composite separator includes a binder selected from poly-acrylic acid (PAA), poly-vinyl alcohol(PVA), cross-linked PAA, cross-linked PVA, styrene-butadiene latex, or an acrylic latex. [184] In some examples, set forth herein is a composite separator made by any process described herein or incorporated by reference.
[185] In some examples, set forth herein is an electrochemical cell comprising any composite separator set forth herein.
[186] In some examples, set forth herein is a battery which includes a composite separator set forth herein. In some examples, set forth herein is a battery which includes an electrochemical cell set forth herein.
[187] In some examples, including any of the foregoing, the battery includes an ionic liquid electrolyte (ILE) or deep eutectic solvent (DES).
[188] In some examples, including any of the foregoing, the battery includes a composite separator that is free of corrosion from an ILE or DES.
[189] In some examples, including any of the foregoing, the polymer layer does not react with an ILE or DES.
[190] In some examples, including any of the foregoing, the ILE includes l-ethyl-3- methylimidazolium chloride.
[191] In some examples, including any of the foregoing, the DES includes urea.
[192] In some examples, including any of the foregoing, the ILE includes a member selected from the group consisting of alkylimidazolium aluminates, alkylpyridinium aluminates, alkylfluoropyrazolium aluminates, alkyltriazolium aluminates, aralkylammonium aluminates, alkyl alkoxyammonium aluminates, aralkylphosphonium aluminates,
aralkyl sulfonium aluminates, alkylguanidinium aluminates, and combinations thereof.
[193] In some examples, including any of the foregoing, the DES includes a member selected from the group consisting of alkylimidazolium aluminates, alkylpyridinium aluminates, alkylfluoropyrazolium aluminates, alkyltriazolium aluminates, aralkylammonium aluminates, alkyl alkoxyammonium aluminates, aralkylphosphonium aluminates,
aralkyl sulfonium aluminates, alkylguanidinium aluminates, and combinations thereof.
[194] In some examples, including any of the foregoing, the ILE includes a mixture of a metal halide and an organic compound. [195] In some examples, including any of the foregoing, the metal halide is an aluminum halide.
[196] In some examples, including any of the foregoing, the aluminum halide is AlCh, and the organic compound includes:
(a) cations selected from the group consisting of 1 -ethyl-3 -methyl imidazolium, N-(n-butyl) pyridinium, benzyltrimethylammonium, 1,2- dimethyl-3-propylimidazolium, trihexyltetradecylphosphonium, and 1- butyl- 1 -methyl-pyrrolidinium, and
(b) anions selected from the group consisting of chloride, tetrafluorob orate, tri- fluoromethanesulfonate, hexafluorophosphate and bis(trifluoromethanesulfonyl)imide.
[197] In some examples, including any of the foregoing, the aluminum halide is AlCh, and the organic compound is selected from the group consisting of urea, methylurea, ethylurea, 4-propylpyridine, acetamide, N-m ethyl acetamide, N,N-dimethylacetamide, trimethylphenylammonium chloride, 1 -ethyl-3 -methylimidazolium
bis(trifluoromethylsulfonyl)imide, 1 -ethyl-3 -methylimidazolium tetrafluorob orate, l-ethyl-3- methylimidazolium hexafluorophosphate and 1 -ethyl-3 -methylimidazolium chloride.
[198] In some examples, including any of the foregoing, the aluminum halide is A1C13, and the organic compound is 1 -ethyl-3 -methylimidazolium chloride.
[199] In some examples, including any of the foregoing, the ILE includes an aluminum halide cation that is datively bonded to the organic compound.
[200] In some examples, including any of the foregoing, the aluminum halide is AlCh, and the organic compound is an amide.
[201] In some examples, including any of the foregoing, the amide is selected from the group consisting of urea, methylurea, ethylurea, and combinations thereof.
[202] In some examples, including any of the foregoing, the metal halide is AlCh; and the organic compound is selected from the group consisting of 1 -ethyl-3 -methyl imidazolium chloride, 1 -ethyl-3 -methylimidazolium bis(trifluorom ethyl sulfonyl)imide, 1- ethyl-3 -methylimidazolium tetrafluorob orate, 1 -ethyl-3 -methylimidazolium
hexafluorophosphate, urea, methylurea, ethylurea, mixtures thereof, and combinations thereof.
[203] In some examples, including any of the foregoing, the ILE includes AlCh and 1 -ethyl-3 -methyl imidazolium chloride, wherein the mole ratio of AlCl3:IL' is from 1.1 to 1.7.
[204] In some examples, including any of the foregoing, the ILE includes a mixture of 1.1 to 1.7 moles AlCh, 1.0 mole 1 -ethyl-3 -methyl imidazolium chloride and 0.1 to 0.5 mole 1 -ethyl -3 -methylimidazolium bis(trifluoromethylsulfonyl)imide or l-ethyl-3- methylimidazolium tetrafluorob orate or 1 -ethyl-3 -methylimidazolium hexafluorophosphate.
[205] In some examples, including any of the foregoing, the ILE includes AlCh and urea.
[206] In some examples, including any of the foregoing, the ILE includes AlCh and methylurea.
[207] In some examples, including any of the foregoing, the mole ratio of AlCh to urea is between 1.1 to 1.7.
[208] In some examples, including any of the foregoing, the mole ratio of AlCh to methylurea is between 1.1 to 1.7.
[209] In some examples, including any of the foregoing, the ILE is urea. In some of these examples, the mole ratio of AlChmrea is about 1.1 to about 1.7.
[210] In some examples, including any of the foregoing, the ILE is methylurea. In some of these examples, the mole ratio of AlCb:methylurea is about 1.1 to about 1.7.
[211] In some examples, including any of the foregoing, the ILE is ethylurea. In some of these examples, the mole ratio of AlCh: ethylurea is about 1.1 to about 1.7.
[212] In some examples, including any of the foregoing, the amount of water or hydrochloric acid in the ionic liquid electrolyte is between 0 - 1000 ppm.
[213] In some examples, including any of the foregoing, the amount of water or hydrochloric acid in the ionic liquid electrolyte is less than 1000 ppm. [214] In some examples, including any of the foregoing, the concentration of corrosion products content in the ionic liquid electrolyte is less than 1000 ppm.
Methods of Using
[215] The batteries described herein are useful for a variety of applications. In some of these applications, a high rate capacity battery is required. Some of these applications include grid-storage applications, uninterrupted power supply applications, home back-up applications, portable devices, and transportation.
[216] Some of the methods herein include vacuum-pumping in combination with electrochemical cycling. In some applications, when a battery is deployed for use in a particular application, the battery may be monitored by, for example, a battery management system (BMS). If the BMS determines that the battery might benefit from additional vacuum pumping, then a method of vacuum pumping in combination with electrochemical cycling may be employed while the battery is deployed in an application. Such a method can remove side reaction products, which may have accumulated during battery cycling.
[217] In some examples, including any of the foregoing, the methods include monitoring at least one metric selected from current density, voltage, impedance, pressure, temperature and capacity in order to determining if the battery might benefit from additional vacuum-pumping.
[218] In the methods described herein, the electrochemical cells may be stacked in series or in parallel.
[219] The following examples describe specific aspects of some embodiments of this disclosure to illustrate and provide a description for those of ordinary skill in the art. The examples should not be construed as limiting this disclosure, as the examples merely provide specific methodology useful in understanding and practicing some embodiments of this disclosure.
EXAMPLES
[220] The Examples herein show how to make and use composite separators for Al- ion batteries having an Al-metal anode. [221] Unless stated otherwise to the contrary, the batteries in this example included an Al foil (Zhongzhoulvye Co., Ltd., 0.016-0.125 mm) metal anode. A 3-mm-wide and 0.09- mm-thick nickel tab (MTI, EQ-PLiB-NTA3) was bonded to the battery cathode comprised of natural graphite flake (Ted Pella, 61-302 SP-l natural flake) mixed with a sodium alginate binder (Sigma) dried on a carbon fiber paper (CFP) (Mitsubishi, 30 g/m2) as the cathode current collector. Aluminum electrodes were washed with acetone and gently scrubbed with a Kimwipes before use. The separators used is described below.
[222] All electrolytes were made and batteries assembled in an Argon-filled glovebox with less than about 5 ppm water and oxygen in the glovebox. Aluminum Chloride (AlCh) (Alfa Aesar, anhydrous 99.9%) was used as received and opened inside the glovebox. 1 -ethyl-3 -methylimidazolium chloride, urea, and methyl urea were vacuum dried at 60-90 °C for 24 hours.
[223] Unless stated otherwise to the contrary, battery cathodes were prepared by depositing a graphite slurry onto a substrate, such as carbon fiber paper (CFP) or a Ni or a W mesh or foil. Graphite was mixed with sodium alginate in a graphite: alginate mass ratio of 95:5. Specifically, 950 mg GP, 50 mg sodium alginate binder, and 2-3 mL distilled water was used as the slurry. After stirring overnight, 5 mg of the slurry per cm2 of the cathode substrate (~7.5 mg total) was loaded onto the cathode substrate (CFP), and the electrode was baked at 80 °C under vacuum overnight. For construction of the pouch cell, a Ni tab was used as a current collector, which was heat-sealed to attach it.
[224] Unless specified to the contrary, all battery components were placed inside a pouch and were fixed in place using carbon tape, which was exposed to the electrolyte. The carbon tape was used to secure certain parts of the battery. However, the carbon tapes is not a necessary component and does not need to be present. A partially assembled cell was dried overnight at 80 °C under vacuum and transferred to the glovebox. In the glovebox, two layers of glass fiber filter paper separator (previously dried at 250 °C) and 1.5 g a 1.3: 1 mole ratio of an AlCb urea ionic liquid electrolyte.
Electrolyte Purification - Generally
[225] Prior to injection into an electrochemical cell or battery assembly,
hydrochloric acid (HC1) and water were removed from electrolyte mixtures prepared herein. The mixtures were heated (25-90 °C) and placed under vacuum pumping (about 10-3 Torr) until noticeable bubbling from the mixture ceased.
[226] To remove organic impurities, aluminum foil (Alfa Aesar, 99%) was added to an electrolyte after removing the Al foil’s surface oxide layer using sand paper. After stirring overnight, the electrolyte was placed under vacuum at 25-90 °C once more before injecting the electrolyte into the battery. The electrolyte mixture was a clear liquid following this procedure.
Electrochemical Analysis - Generally
[227] Galvanostatic charge/discharge measurements were performed outside of the glovebox (Vigor Tech). Cyclic voltammetry (CV) measurements were executed on a potentiostat/galvanostat model CHI 760D (CH Instruments) or on a potentiostat/galvanostat model VMP3 (Bio-Logic) in both three-electrode and two-electrode modes. Unless specified to the contrary, discharge/charge cycling was performed at cell voltages of 2.3 to 0.01 V at 100 mAh/g current density on a Battery testing instrument (Neware). The working electrode was an aluminum foil or a GF, the auxiliary electrode included a platinum foil, and an Al foil was used as the reference electrode. All three electrodes were sealed in an enclosure containing AlCl3:[EMIm]Cl having a mole ratio of about 1.5: 1 or 1.7: 1 unless specified otherwise. CV measurements were carried out in the laboratory at the ambient environment. The scanning range was set from -1 to 0.85 V (vs. Al) for the Al anode and 0 to 2.5 V (vs.
Al) for the graphite cathode, and the scan rate was 10 mV s_1.
[228] Instruments for electrochemical analysis were CHI 760D (CH Instruments), VMP3 (Bio-Logic) and Battery testing instrument (Neware).
[229] Set forth herein are at least four ways of making composite separators for AP3.
EXAMPLE 1 - COMPOSITE SEPARATOR FABRICATION AND COMPARISON:
Glass fiber paper/membrane combined with a hydrophilic PTFE film
[230] Six Al-ion batteries were assembled. The batteries each included the following components. An Al metal anode having dimensions of approximately 4 cm2; a -2.25 cm2 Ni foil coated with graphite (loading:~5 mg/cm2) for the cathode; and an 1.5-2.0 g ionic liquid electrolyte. The Al metal anode was laminated to a separator to form a stack and the pure Ni (>99%) substrate coated with graphite was then laminated to the Al metal anode and the composite separator stack (composite separators detailed below). The graphite loading in the cathode was 9-10 mg/cm2. The Al-ion battery was hot-sealed in a conventional aluminum- laminated pouch (Showa Denko) having a polypropylene (PP) inner-layer pouch, aluminum foil as the middle layer and polyamide (PA) as the outer-layer.
[231] The six batteries were cycled to measure cycle-life performance with different combinations of composite separators and single glass fiber paper. The batteries were cycled between 1.0-2.3V (voltage), at 100 mA/g current density and at room temperature (~25°C). The ionic liquid electrolyte AlCh/EMIC, having a molar ratio AlCh/EMIC of 1.4, was used for all batteries.
[232] In one battery, a 100 pm thick glass fiber (-6.25 cm2 S1O2 separator from Whatman) separator was used. FIG. 5 shows the charge/discharge cycling results of this Al- ion battery. The Coulombic efficiency (CE) in FIG. 5 was higher than 99% (2.3/100 stands for charge to 2.3V with 100 mA/g rate), but after around 35 cycles, the capacity dropped and a short circuit occurred. After this, the battery was not able to be charged. The deposited Al metal penetrated the thin separator and caused an internal short circuit; the phenomena happened repeatedly when a thin GF was used as the separator.
[233] In a second battery, a composite separator was made and used. The composite separator had a 100 pm thick glass fiber layer and a 25 pm PTFE layer. FIG. 6 shows the charge/discharge cycling results of this Al-ion battery. The GP paper was next to the Al anode. The battery was able to be charge/discharge over 270 cycles and remained stable with CE higher than 99% without short-circuiting (2.3/100 stands for charge to 2.3 V with 100 mA/g rate).
[234] In a third battery, a composite separator was made and used. The composite separator had a 100 pm thick glass fiber layer and a 25 pm PTFE layer. FIG. 7 shows the charge/discharge cycling results of this Al-ion battery. In this configuration, the 25 pm PTFE layer was next to Al side and 100 um GFP was next to graphite side. The battery was run -150 cycles. These results were improved compared to 100 pm GFP, only, separators.
[235] In a fourth battery, a composite separator was made and used. The composite separator had a 100 pm thick glass fiber layer that was positioned between two layers of 25 pm thick PTFE. FIG. 8 shows the charge/discharge cycling results of this Al-ion battery. The cycle-life was around 600 cycles with almost no capacity decay. [236] In a fifth battery, a composite separator was made and used. The composite separator had a 25 pm thick PTFE layer that was positioned between two layers of 60 pm thick GFP. FIG. 9 shows the charge/discharge cycling results of this Al-ion battery. The battery was cycled to 110 cycles.
[237] In a sixth battery, a 150 pm thick glass fiber separator was used. FIG. 10 shows the charge/discharge cycling results of this Al-ion battery. This configuration included 150 pm GFP without any PTFE film. The thickness of the separator in the sixth battery was about the same as the thickness in the fifth battery, and was thicker than the separator used in the first, second and third batteries. The cycle-life was observed to be only around 80 cycles. After the 80th cycle, the capacity and efficiency started to jump, likely due to micro-short circuiting between the Al foil anode and the graphite cathode.
[238] PTFE in this example was hydrophilic-treated PTFE.
[239] This Example shows the results for using a chemically-inert glass/PTFE film separator to improve the electrical insulation between an Al anode and a graphite cathode.
The hydrophilic PTFE film was chemical inert and stable to the acidic electrolyte.
[240] This Example shows how to make a composite separator by combining a thin layer of PTFE with a glass fiber (GF) layer as a protection layer. Several different configurations of stacking GFP and PTFE were used.
[241] The total thickness of the composite separators (including GFP and PTFE) in this Example was less than or equivalent to 150 um.
[242] The composite separators of GFP/PTFE improved the AIB’s cycle-life significantly and CE. The composite separators of GFP/PTFE also stabilized the discharge capacity.
EXAMPLE 2 - COMPOSITE SEPARATOR FABRICATION AND COMPARISON:
Polymer binder reinforced glass fiber paper
[243] Two Al-ion batteries were assembled. The batteries each included the following components. An Al metal anode having dimensions of approximately 4 cm2; a -2.25 cm2 Ni foil coated with graphite (loading:~5 mg/cm2) for the cathode; and a 1.5-2.0 g ionic liquid electrolyte. The Al metal anode was laminated to a separator to form a stack and the pure Ni (>99%) substrate coated with graphite was then laminated to the Al metal anode and separator stack. The graphite loading in the cathode is 9-10 mg/cm2. The Al-ion battery was hot-sealed in a conventional aluminum-laminated pouch (Showa Denko) having a polypropylene (PP) inner-layer pouch, aluminum foil as the middle layer and polyamide (PA) as the outer-layer.
[244] The two batteries were cycled to measure cycle-life performance for batteries using polymer binder reinforced glass fiber paper electrolyte separators as compared to pure GFP separators. The batteries were cycled at 1.0-2.3V (voltage) at 100 mA/g current density and at room temperature (~25°C). The ionic liquid electrolyte AlCh/EMIC having a ratio 1.4 was used for all batteries.
[245] The glass fiber paper was made of individual glass fibers that are micrometers in diameter and 10-100 pm in length. The glass fiber was wrapped mechanically together to form a paper film; the mechanical strength was relatively weak and the film was easy to peel off surfaces. This Example shows how to bind the fiber together using a robust polymer binder, which was resistant to the electrolyte and was not being corroded in the acidic electrolyte environment. The binder also did not degrade the battery performance in term of capacity, Coulombic efficiency and long-term stability. For example, LA133™, a polymer gel mainly comprised of co-polymers with acrylonitrile chain is a good candidate as a binder to reinforce the glass fiber paper.
[246] The as-received commercially binder gel was diluted with deionized water to a binder content of 5-50% wt. The diluted binder solution was sprayed onto glass fiber paper and the binder solution gradually infiltrated into the void/space between the glass fibers. The wetted composite fiber paper were then dried in an oven at temperature 80-120 °C to remove water. In one example, a 200 pm thick GFP separator and a drop 10 mL of 10 wt% binder solution (weight percent) were combined. The GFP was 10*10 cm2 GFP.
[247] In one battery, a polymer binder reinforced separator was used. FIG. 11 shows the charge/discharge cycling results of this Al-ion battery.
[248] In a second battery, a 200 pm thick glass fiber separator was used. FIG. 12 shows the charge/discharge cycling results of this Al-ion battery. [249] FIG. 11 shows the battery cycle-life performance for the binder-reinforced composite glass fiber paper separator. FIG. 12 shows the performance of a battery using only a 200 pm glass fiber paper. The cycle -life of the composite separator battery was improved (450 cycles) compared to pure GFP battery (300 cycles life). The polymer binder binds the glass fiber together and fills the void space to improve mechanical property and density. This reinforces the separator to become a battery barrier for efficiently blocking Al metal dendrites, which may cause short-circuiting.
EXAMPLE 3 - COMPOSITE SEPARATOR FABRICATION AND COMPARISON:
PTFE and glass fiber paper bound together as a single separator film
[250] Four Al-ion batteries were assembled. The batteries each included the following components. An Al metal anode having dimensions of approximately 4 cm2; a -2.25 cm2 Ni foil coated with graphite (loading:~5 mg/cm2) for the cathode; and a 1.5-2.0 g ionic liquid electrolyte. The Al metal anode was laminated to a separator to form a stack and the pure Ni (>99%) substrate coated with graphite was then laminated to the Al metal anode and separator stack. The graphite loading in the cathode is 9-10 mg/cm2. The Al-ion battery was hot-sealed in a conventional aluminum-laminated pouch (Showa Denko) having a polypropylene (PP) inner-layer pouch, aluminum foil as the middle layer and polyamide (PA) as the outer-layer.
[251] The six batteries were cycled to measure cycle-life performance. The batteries were cycled at 1.0-2.3V (voltage) at 100 mA/g current density and at room temperature (~25°C). The ionic liquid electrolyte AlCh/EMIC having a ratio 1.4 was used for all batteries.
[252] This Example shows composite separators having PTFE films and binders.
The binder acted as glue to bond the GFP and PTFE film together to form a single separator film.
[253] In one battery, a composite separator was made having a binder, a 100 pm thick glass fiber layer and a 25 pm PTFE layer. The PTFE layer was in contact with the positive electrode. FIG. 13 shows the charge/discharge cycling results of this Al-ion battery. The battery had a cycle-life of -700 cycles currently and it was much better than that the results shown in FIG. 5 (no binder in the battery used for FIG. 5).
[254] In a second battery, a composite separator was made and used. The composite separator had a binder, a 60 pm thick glass fiber layer and a 25 pm PTFE layer. The PTFE layer was in contact with the positive electrode. FIG. 14 shows the charge/discharge cycling results of this Al-ion battery. Both of PTFE and binder synergistically improved cycle-life and did not degrade the CE or capacity. The battery used for FIG. 14 used LA133™ as binder to bind these two films together. The battery was stable over 500 cycles. To date, no AIB with a 85 pm separator thickness has been cycled over 500 cycles without CE decay and capacity fade.
[255] In a third battery, a composite separator was made and used. The composite separator had a 60 pm thick glass fiber layer and a 25 pm PTFE layer. The PTFE layer was in contact with the positive electrode. FIG. 15 shows the charge/discharge cycling results of this Al-ion battery. The battery used for FIG. 15 included a stack of one layer of 60 pm GFP and 25 pm PTFE. The battery performed well for only a cycle-life of -100 cycles.
[256] In a fourth battery, a composite separator was made and used. The composite separator had a 200 pm thick GFP layer (S) and a 15 pm PTFE layer. The GFP layer was glued to PTFE by a binder layer. The PTFE side was in contact with positive electrode.“S” means GFP, FIG. 16 shows the charge/discharge cycling results of this Al-ion battery. The composite separator thickness was -215 pm ±10 pm thick. The thickness was measured using a Vernier Caliper. The cycle-life was over 1000 cycles and there was almost no decay in capacity or Coulombic efficiency. These results were superior to the results in FIG. 12, which employed a battery using a pure 200 pm GFP layer and which was observed to only cycle for 300 cycles.
[257] The PTFE in this example was hydrophilic-treated PTFE.
EXAMPLE 4 - COMPOSITE SEPARATOR FABRICATION AND COMPARISON:
PTFE and glass fiber paper bound together as a single separator film
[258] Two Al-ion batteries were assembled. The batteries each included the following components. A 150 pm thick Al metal anode having dimensions of approximately 4 cm2; a -2.25 cm2 Ni foil coated with graphite (loading: -7.3 mg/cm2) for the cathode; and a 1.5-2.0 g ionic liquid electrolyte. The Ni foil coated with graphite was compressed from 151 pm thickness to 105 pm thickness, which resulted in a packing density of 1.7 g/cm. The Al metal anode was laminated to a separator to form a stack and the pure Ni (>99%) substrate coated with graphite was then laminated to the Al metal anode and separator stack. The graphite loading in the cathode is 7.3 mg/cm2. The Al-ion battery was hot-sealed in a conventional aluminum-laminated pouch (Showa Denko) having a polypropylene (PP) inner- layer pouch, aluminum foil as the middle layer and polyamide (PA) as the outer-layer.
[259] The two batteries were cycled to measure cycle-life performance. The batteries were cycled at 1.0-2.3V (voltage) at 100 mA/g current density and at room temperature (~25°C). The ionic liquid electrolyte AlCh/EMIC having a ratio 1.4 was used for all batteries.
[260] In one battery, a composite separator was made having a binder, a 200 pm thick glass fiber layer and a 25 pm PTFE layer. The PTFE layer was in contact with the positive electrode. FIG. 18 shows the charge/discharge cycling results of this Al-ion battery. The 225th cycle tested is shown in FIG. 19.
[261] In a second battery, a composite separator was made having a binder, a 200 pm thick glass fiber layer and a 25 pm PTFE layer. The PTFE layer was in contact with the negative electrode. FIG. 20 shows the charge/discharge cycling results of this Al-ion battery. The 315th cycle tested is shown in FIG. 21.
[262] The battery in which the PTFE layer was in contact with the positive electrode performed better than the batter in which the PTFE layer was in contact with the negative electrode. This is evidenced by comparing FIGs. 18 and 20 with respect to cycling stability, specific capacity and coulombic efficiency.
[263] The embodiments and examples described above are intended to be merely illustrative and non-limiting. Those skilled in the art will recognize or will be able to ascertain using no more than routine experimentation, numerous equivalents of specific compounds, materials and procedures. All such equivalents are considered to be within the scope and are encompassed by the appended claims.

Claims

CLAIMS What is claimed is:
1. A composite separator, comprising:
a glass fiber layer; a polymer layer, or a derivative thereof; and optionally a binder;
wherein the composite separator is between a positive electrode and a negative electrode, and either (a), (b), (c), or (d):
(a) the glass fiber layer is between and in contact with the metal negative electrode and the polymer layer; and the polymer layer is between and in contact with the glass fiber layer and the positive electrode;
(b) the polymer layer is between and in contact with the metal negative
electrode and the glass fiber layer; and the glass fiber layer is between and in contact with the polymer layer and the positive electrode;
(c) the glass fiber layer is between and in contact with the polymer layer and an additional polymer layer; or
(d) the polymer layer is between and in contact with the glass fiber layer and an additional glass fiber layer.
2. The composite separator of claim 1, wherein in (c) either: (cl) the polymer layer is in contact with the positive electrode and the additional polymer layer is in contact with the negative electrode; or (c2) the polymer layer is in contact with the negative electrode and the additional polymer layer is in contact with the positive electrode.
3. The composite separator of claim 1, wherein in (d) either: (dl) the glass fiber layer is in contact with the positive electrode and the additional glass fiber layer is in contact with the negative electrode; or (d2) the glass fiber layer is in contact with the negative electrode and the additional glass fiber layer is in contact with the positive electrode.
4. The composite separator of any one of claims 1-3, wherein the polymer layer is a hydrophilic polymer layer.
5. The composite separator any one of claims 1-4, wherein the additional polymer layer is a hydrophilic polymer layer.
6. The composite separator of any one of claims 1-5, wherein the additional polymer layer is the same type of polymer as the polymer layer.
7. The composite separator of claim 1, wherein the polymer layer is a hydrophilic polymer layer, and the hydrophilic polymer layer is between and in contact with the metal negative electrode and the glass fiber layer.
8. The composite separator of claim 1, wherein the polymer layer is a hydrophilic polymer layer, and the hydrophilic polymer layer is between and in contact with the positive electrode and the glass fiber layer.
9. The composite separator of claim 1, wherein the polymer layer is a hydrophilic polymer layer, and the glass fiber layer is between and in contact with the metal negative electrode and the hydrophilic polymer layer.
10. The composite separator of claim 1, wherein the polymer layer is a hydrophilic polymer layer, and the glass fiber layer is between and in contact with the positive electrode and the hydrophilic polymer layer.
11. The composite of any one of claims 1-10, wherein the thickness of the glass fiber layer or additional glass fiber layer, or both, is, individually in each instance, from 0 pm to 300 pm.
12. The composite of any one of claims 1-11, wherein the thickness of the glass fiber layer or additional glass fiber layer, or both, is, individually in each instance, from 20 pm to 300 pm.
13. The composite separator any one of claims 1-12, wherein the thickness of the glass fiber layer or additional glass fiber layer, or both, is, individually in each instance, from about 50 pm to about 200 pm.
14. The composite separator of any one of claims 1-13, wherein the glass fiber layer or additional glass fiber layer, or both, comprises glass fiber paper.
15. The composite separator of any one of claims 1-14, wherein the glass fiber layer or additional glass fiber layer, or both, is porous.
16. The composite separator of claim 15, wherein each porous glass fiber layer comprises pores from about 0.1 pm to about 10 pm in diameter.
17. The composite separator of claim 16, wherein the pores are about 0.6 pm in diameter.
18. The composite separator of any one of claims 1-17, wherein the glass fiber layer or additional glass fiber layer, or both, comprises Si02.
19. The composite separator of any one of claims 1-18, wherein the glass fiber layer or additional glass fiber layer, or both, comprises Si02 fibers.
20. The composite separator of any one of claims 1-19, wherein the polymer layer or additional polymer layer, or both, comprises a multilayer.
21. The composite separator of claim 20, wherein the multilayer is a multilayer of hydrophilic polymer layers.
22. The composite separator of claim 20 or 21, wherein the multilayer comprises 2, 3, 4, or 5 individual polymer layers.
23. The composite separator of claim 22, wherein the thickness of each individual polymer layer in the multilayer is from about 5 pm to about 50 pm.
24. The composite separator of any one of claims 1-22, wherein the thickness of the hydrophilic polymer layer or additional hydrophilic polymer layer, or both, is, individually in each instance, from about 5 pm to about 150 pm.
25. The composite separator of any one of claims 24, wherein the thickness of the hydrophilic polymer layer or additional hydrophilic polymer layer, or both, is, individually in each instance, from about 5 pm to about 50 pm.
26. The composite separator of claim 24 or 25, wherein the thickness of the hydrophilic polymer layer or additional hydrophilic polymer layer, or both, is, individually in each instance, from about 15 pm to about 25 pm.
27. The composite separator of any one of claims 1-26, wherein the hydrophilic polymer layer comprises a porous substrate on which a hydrophilic polymer is coated.
28. The composite separator of claim 27, wherein the porous substrate is a hydrophobic or hydrophilic membrane.
29. The composite separator of claim 28, wherein the porous substrate is selected from the group consisting of a porous metal, a porous polymer, and a porous ceramic.
30. The composite separator of claim 28 or 29, wherein the porous substrate is selected from the group consisting of a porous glass fiber paper, a regenerated cellulose membrane, a polyester membrane, a polyethersulfone membrane, and a polyethylene membrane.
31. A composite separator, comprising:
a polymer layer, or a derivative thereof; and optionally a binder; wherein the composite separator is between a positive electrode and a negative electrode.
32. The composite separator of claim 31, comprising an additional polymer layer.
33. The composite separator any one of claims 31-32, wherein the polymer layer is a hydrophilic polymer layer.
34. The composite separator any one of claims 31-33, wherein the polymer layer is a hydrophilic-treated polymer layer.
35. The composite separator any one of claims 31-34, wherein the additional polymer layer is a hydrophilic polymer layer or a hydrophilic-treated polymer layer.
36. The composite separator of claims 31-35, wherein the additional polymer layer is the same type of polymer as the polymer layer.
37. The composite of any one of claims 31-36, wherein the thickness of the additional polymer layer is from 20 pm to 300 pm.
38. The composite separator of any one of claims 31-37, wherein the polymer layer or additional polymer layer, or both, comprises a multilayer.
39. The composite separator of claim 38, wherein the multilayer is a multilayer of hydrophilic polymer layers or hydrophilic-treated polymer layers.
40. The composite separator of claim 37 or 38, wherein the multilayer comprises 2, 3, 4, or 5 individual polymer layers.
41. The composite separator of claim 40, wherein the thickness of each individual polymer layer in the multilayer is from about 5 pm to about 50 pm.
42. The composite separator of any one of claims 1-41, wherein the hydrophilic polymer layer comprises a porous substrate on which a hydrophilic polymer is coated.
43. The composite separator of claim 42, wherein the porous substrate is a hydrophobic or hydrophilic membrane.
44. The composite separator of claim 42, wherein the porous substrate is selected from the group consisting of a porous metal, a porous polymer, and a porous ceramic.
45. The composite separator of any one of claims 4-44, wherein the hydrophilic polymer is selected from the group consisting of hydrophilic-treated polytetrafluoroethylene (PTFE), hydrophilic-treated polyacrylonitrile (PAN), hydrophilic-treated fluorinated ethylene propylene (FEP), hydrophilic-treated polychlorotrifluoroethylene (PCTFE), hydrophilic- treated polyvinylidene fluoride (PVDF), hydrophilic-treated hexafluoropropylene (HFP), hydrophilic-treated PVDF-HFP, hydrophilic-treated polyfluoroalkoxy(PFA), hydrophilic- treated polyimide (PI), and combinations thereof.
46. The composite separator of any one of claims 1-45, wherein the total thickness of the composite separator is from about 20 pm to about 300 pm.
47. The composite separator of any one of claims 1-46, wherein the total thickness of the composite separator is from about 20 pm to about 225 pm.
48. The composite separator of any one of claims 1-47, wherein the total thickness of the composite separator is about 50 pm.
49. The composite separator of any one of claims 31-48, wherein the hydrophilic polymer is selected from the group consisting of polytetrafluoroethylene (PTFE),
polyacrylonitrile (PAN), fluorinated ethylene propylene (FEP), polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), hexafluoropropylene (HFP), PVDF-HFP, polyfluoroalkoxy(PFA), hydrophilic-treated polyimide (PI), and combinations thereof.
50. The composite separator of any one of claims 1-49, wherein the binder is selected from the group consisting of polyacrylate (PA), polyacrylic acid (PAA), polyvinyl alcohol (PVA), cross-linked PAA, cross-linked PVA, PAA-PVA, polyacrylic latex, cellulose, cellulose derivatives, alginate, polyethylene glycol, styrene-butadiene rubber, poly(styrene- co-butadiene), styrene-butadiene rubber, poly(3,4-ethylenedioxythiophene), acrylonitrile copolymer, acrylic latex, and combinations thereof.
51. The composite separator of claim 52, wherein the binder is selected from the group consisting of poly-acrylic acid (PAA), poly-vinyl alcohol (PVA), cross-linked PAA, cross-linked PVA, styrene-butadiene latex, acrylonitrile copolymer, and acrylic latex.
52. The composite separator of claim 51, wherein the binder is selected from the group consisting of PAA and PVA.
53. The composite separator of any one of claims 1-52, wherein the binder is LA133™
54. The composite separator of any one of claims 1-54, wherein the total thickness of the composite separator is from about 20 pm to about 300 pm.
55. The composite separator of any one of claims 1-54, wherein the total thickness of the composite separator is from about 20 pm to about 225 pm.
56. The composite separator of any one of claims 1-55, wherein the total thickness of the composite separator is about 150 pm.
57. The composite separator of claim 56, wherein the total thickness of the composite separator is about 50 pm, 55 pm, 60 pm, 65 pm, 70 pm, 75 pm, 80 pm, 95 pm,
100 pm, 105 pm, or 110 pm.
58. The composite separator of any one of claims 1-57, further comprising an aqueous liquid electrolyte in contact with the composite separator.
59. The composite separator of any one of claims 1-57, further comprising a nonaqueous liquid electrolyte in contact with the composite separator.
60. The composite separator of any one of claims 1-57, further comprising an ionic liquid or deep eutectic solvent electrolyte in contact with the composite separator.
61. The composite separator of any one of claims 1-57, further comprising a deep eutectic solvent electrolyte in contact with the composite separator.
62. The composite separator of any one of claims 1-57, further comprising an ionic liquid electrolyte in contact with the composite separator.
63. The composite separator of any one of claims 1-62, wherein the glass fiber layer or additional glass fiber layer, or both, is a glass fiber paper (GFP).
64. The composite separator of any one of claims 1-63, comprising a layer of PTFE/GFP and an additional layer of PTFE.
65. The composite separator of claim 64, wherein the PTFE layer is in contact with the negative electrode.
66. The composite separator of claim 64, wherein the PTFE layer is in contact with the positive electrode.
67. The composite separator of claim 64, wherein the additional layer of PTFE layer is in contact with the negative electrode.
68. The composite separator of claim 64, wherein the additional layer of PTFE layer is in contact with the positive electrode.
69. The composite separator of any one of claims 64-68, wherein the GFP is between and in contact with the layer of PTFE and the additional layer of PTFE.
70. The composite separator of any one of claims 1-69, comprising two layers of
PTFE.
71. The composite separator of any one of claims 1-70, comprising three layers of
PTFE.
72. The composite separator of any one of claims 64-71, wherein the PTFE layer is 50 pm in thickness.
73. The composite separator of any one of claims 1-72, wherein the metal negative electrode comprises a metal selected from the group consisting of lithium (Li), sodium (Na), potassium (K), magnesium (Mg), calcium (Ca), aluminum (Al), germanium (Ge), tin (Sn), iron (Fe), zinc (Zn), combinations thereof, and alloys thereof.
74. The composite separator of claim 73, wherein the metal negative electrode is a foil, a mesh, or a foam.
75. The composite separator of claim 74, wherein the metal negative electrode is Al.
76. The composite separator of claim 74 or 75, wherein the metal negative electrode is an Al metal foil, Al mesh, Al foam, or porous Al film.
77. The composite separator of any one of claims 1-76, wherein the positive electrode comprises carbon selected from the group consisting of natural graphite, graphene, and synthetic graphite.
78. The composite separator of claim 77, wherein the graphene is provided as 1, 2, 3, 4, or 5 layers.
79. The composite separator of any one of claims 1-78, wherein the positive electrode comprises natural graphite flake of high purity and high degree of graphitization.
80. The composite separator of any one of claims 77-79, wherein the graphite has a particle size of 1 pm to 500 pm.
81. The composite separator of claim 80, wherein the graphite has a particle size between about 1 pm and 50 pm, between about 50 pm and 100 pm, between about 50 pm and 200 pm, or between about 50 pm and 300 pm.
82. The composite separator of any one of claims 77-81, wherein the positive electrode comprises carbon having a particle size between 20 pm - 300 pm.
83. The composite separator of any one of claims 77-82, wherein the positive electrode comprises graphite and the graphite has a particle size of 40 pm to 200 pm.
84. The composite separator of any one of claims 77-83, wherein the positive electrode comprises carbon and the carbon having a particle size of at least 45 pm.
85. The composite separator of claim 84, wherein the positive electrode comprises carbon having a particle size of at least 20 pm.
86. The composite separator of claim 84, wherein the positive electrode comprises carbon having a particle size from about 45 pm to about 75 pm and carbon having a particle size from about 150 to about 250 pm.
87. The composite separator of claim 86, wherein the gravimetric ratio of the carbon having a particle size from about 45 pm to about 75 pm to carbon having a particle size from about 150 to about 250 pm is 5:95 to 20:80 or 5:95 to 15:85.
88. The composite separator of any one of claims 77-87, wherein the graphite is pure natural graphite flake.
89. The composite separator of any one of claims 77-87, wherein the graphite is crystalline and highly graphitized.
90. The composite separator of any one of claims 77-87, wherein the graphite is substantially free of defects.
91. The composite separator of any one of claims 77-87, wherein the graphite comprises less than 10% defects.
92. The composite separator of any one of claims 1-91, wherein the positive electrode comprises pyrolytic graphite.
93. The composite separator of any one of claims 1-92, further comprises a positive electrode current collector selected from the group consisting of a glassy carbon current collector, carbon fiber paper current collector, carbon fiber cloth current collector, graphite fiber paper current collector, and graphite fiber cloth current collector.
94. The composite separator of claim 93, wherein the carbon fiber paper has a thickness between about 10 pm to 300 pm.
95. The composite separator of any one of claims 1-94, wherein the composite separator further comprises a positive electrode current collector selected from the group consisting of a metal substrate current collector.
96. The composite separator of claim 95, wherein the metal substrate is coated with a protective coating.
97. The composite separator of claim 95, wherein the metal substrate is a mesh, a foil, or a foam.
98. The composite separator of any one of claims 95-95, wherein the metal substrate is a nickel (Ni) or tungsten (W) metal substrate.
99. The composite separator of any one of claim 96-98, wherein the protective coating is selected from the group consisting of a Ni coating, a W coating, a carbon coating, a carbonaceous material, a conducting polymer, and a combination thereof.
100. The composite separator of claim 99, wherein the metal substrate is a Ni foil, a Ni mesh, a Ni foam, a W foil, a W mesh, or a W foam.
101. The composite separator of claim 99, wherein the metal substrate is a metal foil coated with Ni coating.
102. The composite separator of claim 99, wherein the metal substrate is a metal mesh or metal foam coated with Ni coating.
103. The composite separator of claim 99, wherein the metal substrate is a metal foil coated with W coating.
104. The composite separator of claim 99, wherein the metal substrate is a metal mesh or metal foam coated with W coating.
105. The composite separator of any one of claims 99-101, wherein the metal substrate is Ni and the protective coating is carbon.
106. A process of making a composite separator, comprising:
providing a binder solution;
providing a glass fiber layer;
contacting the binder solution to the glass fiber paper to form a binder glass fiber layer composite;
drying the binder glass fiber layer composite; and
contacting a solution of a polymer to the binder glass fiber layer composite to form a composite separator.
107. The process of claim 106, wherein the polymer is a hydrophilic polymer.
108. The process of claim 106, wherein the polymer is a hydrophobic polymer.
109. A process of making a composite separator, comprising:
providing a binder solution;
providing a glass fiber layer;
providing a polymer layer;
contacting the binder solution to the glass fiber paper to form a binder glass fiber layer composite;
contacting the polymer layer to the binder glass fiber layer composite to form a composite separator; and
drying the composite separator.
110. The process of claim 109, wherein the polymer layer is a hydrophilic polymer layer.
111. The process of claim 106, wherein the polymer layer is a hydrophobic polymer layer.
112. The process of any one of claims 106-111, wherein the binder solution is a hydrophilic binder solution.
113. The process of any one of claims 106-112, further comprising drying the composite separator.
114. The process of any one of claims 106-113, wherein the glass fiber layer is a glass fiber paper.
115. The process of any one of claims 106-113, wherein the binder solution comprises 5 to 50 % w/w binder in deionized water.
116. The process of any one of claims 106-113, wherein the glass fiber layer has a geometric surface area of 10 cm2.
117. The process of any one of claims 106-110, 112-116, wherein the polymer is a hydrophilic polymer selected from the group consisting of polytetrafluoroethylene (PTFE), polyacrylonitrile (PAN), fluorinated ethylene propylene (FEP), polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), hexafluoropropylene (HFP), PVDF-HFP, polyfluoroalkoxy(PFA), polyimide (PI), a derivative thereof, and combinations thereof.
118. The process of any one of claims 106-117, wherein the binder is selected from the group consisting of polyacrylate (PA), polyacrylic acid (PAA), polyvinyl alcohol (PVA), cross-linked PAA, cross-linked PVA, PAA-PVA, polyacrylic latex, cellulose, cellulose derivatives, alginate, polyethylene glycol, styrene-butadiene rubber, poly(styrene-co- butadiene), styrene-butadiene rubber, poly(3, 4-ethyl enedioxythiophene), acrylonitrile copolymer, acrylic latex, and combinations thereof.
119. The process of any one of claims 106-119, wherein the binder is selected from the group consisting of poly-acrylic acid (PAA), poly-vinyl alcohol (PVA), cross-linked PAA, cross-linked PVA, styrene-butadiene latex, acrylonitrile copolymer, and acrylic latex.
120. The process of any one of claims 106-119, wherein the binder is selected from the group consisting of PAA and PVA.
121. The process of any one of claims 106-120, wherein the binder is LA133™
122. The process of any one of claims 106-121, wherein the drying comprising drying under vacuum at about 200 °C.
123. A composite separator made by the process of any one of claims 106-122.
124. An electrochemical cell comprising the composite separator of any of claims 1 - 87 or 123.
125. A battery comprising the composite separator of any of claims 1 - 105, the composite separator of claim 123, or the electrochemical cell of claim 124.
126. The battery of claim 125, comprising an ionic liquid electrolyte (ILE) or deep eutectic solvent (DES).
127. The battery of claim 125 or 126, wherein the composite separator is free of corrosion from an ILE or DES.
128. The battery of any one of claims 125-126, wherein the polymer layer does not react with a ILE or DES.
129. The battery of any one of claims 126-128, wherein the ILE comprises l-ethyl- 3-methylimidazolium chloride.
130. The battery of any one of claims 126-128, wherein the DES comprises urea.
131. The battery of any one of claims 126-128, wherein the ILE comprises a member selected from the group consisting of alkylimidazolium aluminates, alkylpyridinium aluminates, alkylfluoropyrazolium aluminates, alkyltriazolium aluminates, aralkylammonium aluminates, alkyl alkoxyammonium aluminates, aralkylphosphonium aluminates, aralkyl sulfonium aluminates, alkylguanidinium aluminates, and combinations thereof.
132. The battery of any one of claims 126-128, wherein the DES comprises a member selected from the group consisting of alkylimidazolium aluminates, alkylpyridinium aluminates, alkylfluoropyrazolium aluminates, alkyltriazolium aluminates, aralkylammonium aluminates, alkyl alkoxyammonium aluminates, aralkylphosphonium aluminates,
aralkyl sulfonium aluminates, alkylguanidinium aluminates, and combinations thereof.
133. The battery of any one of claims 126-128, wherein the ILE comprises a mixture of a metal halide and an organic compound.
134. The battery of claim 133, wherein the metal halide is an aluminum halide.
135. The battery of claim 134, wherein the aluminum halide is AlCh, and the organic compound comprises:
(a) cations selected from the group consisting of 1 -ethyl-3 -methyl
imidazolium, N-(n-butyl) pyridinium, benzyltrimethylammonium,
1 ,2-dimethyl-3 -propylimidazolium, trihexyltetradecylphosphonium, and
1 -butyl- 1 -methyl -pyrrolidinium, and
(b) anions selected from the group consisting of chloride, tetrafluoroborate, tri-fluoromethanesulfonate, hexafluorophosphate and
bis(trifluoromethanesulfonyl)imide.
136. The battery of claim 135, wherein the aluminum halide is AlCh, and the organic compound is selected from the group consisting of urea, methylurea, ethylurea, 4- propylpyridine, acetamide, N-methylacetamide, N,N-dimethylacetamide, trimethylphenylammonium chloride, 1 -ethyl-3 -methylimidazolium bis(trifluoromethylsulfonyl)imide, 1 -ethyl-3 -methylimidazolium tetrafluoroborate, l-ethyl-3- methylimidazolium hexafluorophosphate and 1 -ethyl-3 -methylimidazolium chloride.
137. The battery of claim 135, wherein the aluminum halide is AlCh, and the organic compound is 1 -ethyl-3 -methylimidazolium chloride.
138. The battery of any one of claims 126-137, wherein the ILE comprises an aluminum halide cation that is datively bonded to the organic compound.
139. The battery of any one of claims 126-137, wherein the aluminum halide is AlCh, and the organic compound is an amide.
140. The battery of claim 139, wherein the amide is selected from the group consisting of urea, methylurea, ethylurea, and combinations thereof.
141. The battery of any one of claims 134-137, wherein the metal halide is AlCh; and the organic compound is selected from the group consisting of
1 -ethyl-3 -methyl imidazolium chloride,
1 -ethyl-3 -methylimidazolium bis(trifluoromethylsulfonyl)imide,
1 -ethyl-3 -methylimidazolium tetrafluorob orate,
1 -ethyl-3 -methylimidazolium hexafluorophosphate, urea, methylurea, ethylurea,
mixtures thereof, and combinations thereof.
142. The battery of any one of claims 126-137, wherein the ILE comprises AlCh and 1 -ethyl-3 -methyl imidazolium chloride, wherein the mole ratio of AlCh:IL is from 1.1 to 1.7.
143. The battery of any one of claims 125-137, wherein the ILE comprises a mixture of 1.1 to 1.7 moles AlCh, 1.0 mole 1 -ethyl-3 -methyl imidazolium chloride and 0.1 to 0.5 mole l-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide or l-ethyl-3- methylimidazolium tetrafluorob orate or 1 -ethyl-3 -methylimidazolium hexafluorophosphate.
144. The battery of any one of claims 126-138, wherein the ILE comprises AlCh and urea.
145. The battery of any one of claims 126-138, wherein the ILE comprises AlCh and methylurea.
146. The battery of claim 145, wherein the mole ratio of AlCh to urea is between 1.1 to 1.7.
147. The battery of claim 146, wherein the mole ratio of AlCh to methylurea is between 1.1 to 1.7.
148. The battery of claim 146, wherein the ILE is urea and the mole ratio of AlChmrea is about 1.1 to about 1.7.
149. The battery of claim 146, wherein the ILE is urea and the mole ratio of AlCh:methylurea is about 1.1 to about 1.7.
150. The battery of claim 146, wherein the ILE is urea and the mole ratio of AlCh:ethylurea is about 1.1 to about 1.7.
151. The battery of any one of claims 125-138, wherein the amount of water or hydrochloric acid in the ionic liquid electrolyte is between 0 - 1000 ppm.
152. The battery of any one of claims 125-151, wherein the amount of water or hydrochloric acid in the ionic liquid electrolyte is less than 1000 ppm.
153. The battery of any one of claims 125-151, wherein the concentration of corrosion products content in the ionic liquid electrolyte is less than 1000 ppm.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114039169A (en) * 2021-11-15 2022-02-11 中南大学 Composite diaphragm, preparation method thereof and application of composite diaphragm in water-based metal ion battery
EP4300694A1 (en) * 2022-06-30 2024-01-03 INL - International Iberian Nanotechnology Laboratory Separator for a battery, battery and method for producing a separator
CN117410649A (en) * 2023-09-27 2024-01-16 中能鑫储(北京)科技有限公司 Polymer-glass fiber composite diaphragm and aluminum ion battery

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030180622A1 (en) * 2000-05-29 2003-09-25 Takahiro Tsukuda Separator for electrochemical device and method for producing the same, and electrochemical device
WO2015131132A1 (en) 2014-02-28 2015-09-03 Board Of Trustees Of The Leland Stanford Junior University Ultra-fast rechargeable metal-ion battery
US20160190636A1 (en) * 2014-12-24 2016-06-30 Toyota Motor Engineering & Manufacturing North America, Inc. All-solid-state metal-metal battery comprising ion conducting ceramic as electrolyte
CN105762317A (en) * 2016-01-19 2016-07-13 合肥工业大学 Water-soluble polymer assisted inorganic composite diaphragm preparation method
CN105810870A (en) * 2016-05-24 2016-07-27 深圳市新技术研究院有限公司 Battery membrane and preparation method thereof, battery and application of 1-butenyl polymer in battery membrane
US20170062785A1 (en) * 2015-08-17 2017-03-02 Celgard, Llc Battery separators and related methods
WO2017106337A1 (en) 2015-12-15 2017-06-22 The Board Of Trustees Of The Leland Stanford Junior University Improved electrolytes, current collectors, and binders for rechargeable metal-ion batteries
CN107342434A (en) * 2017-07-17 2017-11-10 济南大学 A kind of rechargeable aluminium battery using ordered mesopore carbon as positive electrode and preparation method thereof
WO2017201124A2 (en) * 2016-05-17 2017-11-23 Eos Energy Storage, Llc Zinc-halide battery using a deep eutectic solvent-based electrolyte
CN109509860A (en) * 2018-11-27 2019-03-22 东华大学 Kynoar/glass fibre/porous silica battery diaphragm preparation method

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030180622A1 (en) * 2000-05-29 2003-09-25 Takahiro Tsukuda Separator for electrochemical device and method for producing the same, and electrochemical device
WO2015131132A1 (en) 2014-02-28 2015-09-03 Board Of Trustees Of The Leland Stanford Junior University Ultra-fast rechargeable metal-ion battery
US20150249261A1 (en) 2014-02-28 2015-09-03 Board Of Trustees Of The Leland Stanford Junior University Ultra-fast rechargeable metal-ion battery
US20160190636A1 (en) * 2014-12-24 2016-06-30 Toyota Motor Engineering & Manufacturing North America, Inc. All-solid-state metal-metal battery comprising ion conducting ceramic as electrolyte
US20170062785A1 (en) * 2015-08-17 2017-03-02 Celgard, Llc Battery separators and related methods
WO2017106337A1 (en) 2015-12-15 2017-06-22 The Board Of Trustees Of The Leland Stanford Junior University Improved electrolytes, current collectors, and binders for rechargeable metal-ion batteries
CN105762317A (en) * 2016-01-19 2016-07-13 合肥工业大学 Water-soluble polymer assisted inorganic composite diaphragm preparation method
WO2017201124A2 (en) * 2016-05-17 2017-11-23 Eos Energy Storage, Llc Zinc-halide battery using a deep eutectic solvent-based electrolyte
CN105810870A (en) * 2016-05-24 2016-07-27 深圳市新技术研究院有限公司 Battery membrane and preparation method thereof, battery and application of 1-butenyl polymer in battery membrane
CN107342434A (en) * 2017-07-17 2017-11-10 济南大学 A kind of rechargeable aluminium battery using ordered mesopore carbon as positive electrode and preparation method thereof
CN109509860A (en) * 2018-11-27 2019-03-22 东华大学 Kynoar/glass fibre/porous silica battery diaphragm preparation method

Non-Patent Citations (9)

* Cited by examiner, † Cited by third party
Title
ANGELL ET AL., PNAS, EARLY EDITION, 2016, pages 1 - 6
BI ET AL., JOURNAL OF POWER SOURCES, vol. 194, 2009, pages 838 - 842
FANG, Y ET AL., CHEM. COMMUN., vol. 51, no. 68, pages 13286 - 13289
FANG, Y ET AL., ELECTROCHIM ACT, vol. 160, pages 82 - 88
HOGG, JM ET AL., GREEN CHEM, vol. 17, no. 3, pages 1831 - 1841
LIN, M-C ET AL., NATURE, 2015, pages 1
PULLETIKURTHI, G. ET AL., NATURE, vol. 520, no. 7547, pages 325 - 328
S. SUGIYAMA ET AL., REACT. POLYM., vol. 21, 1993, pages 187 - 191
WANG ET AL., JOURNAL OF WATER PROCESS ENGINEERING, vol. 8, 2015, pages 11 - 18

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114039169A (en) * 2021-11-15 2022-02-11 中南大学 Composite diaphragm, preparation method thereof and application of composite diaphragm in water-based metal ion battery
EP4300694A1 (en) * 2022-06-30 2024-01-03 INL - International Iberian Nanotechnology Laboratory Separator for a battery, battery and method for producing a separator
WO2024003781A1 (en) 2022-06-30 2024-01-04 Inl - International Iberian Nanotechnology Laboratory Separator for a battery, battery and method for producing a separator
CN117410649A (en) * 2023-09-27 2024-01-16 中能鑫储(北京)科技有限公司 Polymer-glass fiber composite diaphragm and aluminum ion battery

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