US20150132642A1 - Lithium containing nanofibers - Google Patents

Lithium containing nanofibers Download PDF

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Publication number
US20150132642A1
US20150132642A1 US14/382,389 US201314382389A US2015132642A1 US 20150132642 A1 US20150132642 A1 US 20150132642A1 US 201314382389 A US201314382389 A US 201314382389A US 2015132642 A1 US2015132642 A1 US 2015132642A1
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Prior art keywords
lithium
nanofibers
nanofiber
precursor
metal
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Yong Lak Joo
Nathaniel S. Hansen
Daehwan Cho
Kyoung Woo Kim
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Cornell University
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Cornell University
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Priority to US14/382,389 priority Critical patent/US20150132642A1/en
Assigned to CORNELL UNIVERSITY reassignment CORNELL UNIVERSITY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CHO, DAEHWAN, HANSEN, NATHANIEL S., JOO, YONG LAK, KIM, KYOUNG WOO
Assigned to CORNELL UNIVERSITY reassignment CORNELL UNIVERSITY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CHO, DAEHWAN, HANSEN, NATHANIEL S., JOO, YONG LAK, KIM, KYOUNG WOO
Publication of US20150132642A1 publication Critical patent/US20150132642A1/en
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Definitions

  • Batteries comprise one or more electrochemical cell, such cells generally comprising a cathode, an anode and an electrolyte.
  • Lithium ion batteries are high energy density batteries that are fairly commonly used in consumer electronics and electric vehicles. In lithium ion batteries, lithium ions generally move from the negative electrode to the positive electrode during discharge and vice versa when charging. In the as-fabricated and discharged state, lithium ion batteries often comprise a lithium alloy/compound (such as a lithium metal oxide) at the cathode (positive electrode) and another material, such as carbon, at the anode (negative electrode).
  • nanofibers comprising a lithium material.
  • the nanofibers comprise a continuous matrix or backbone of the lithium material (e.g., does not comprise lithium-containing-nanoparticles or other lithium-containing-domains on or in another continuous matrix material).
  • the lithium-containing-continuous matrix or backbone comprises a core matrix material (e.g., the lithium material is not coated on another type of nanofiber).
  • the lithium-containing-nanofibers comprise non-aggregated lithium-containing-domains embedded within a continuous nanofiber matrix or backbone.
  • the continuous nanofiber matrix or backbone comprises or is carbon (e.g., amorphous or amorphous and crystalline carbon).
  • batteries e.g., lithium-ion batteries
  • an anode an electrolyte and a positive electrode (cathode) comprising a plurality of lithium-containing-nanofibers.
  • a nanofiber comprising a lithium material comprises a lithium-containing-material resented by the formula: Li a M b X c .
  • M is Fe, Ni, Co, Mn, V, Al, Li, or a combination thereof.
  • X is O, PO 4 , or SiO 4 .
  • a is 1-2; b is 0-2; and c is 1-4.
  • M is Ni, Co, Mn, or a combination thereof.
  • X is O.
  • a is 1 and b is 1.
  • a is 1, b is 1, and c is 2.
  • a is 1 and b is 2. In more specific embodiments, a is 1, b is 2, and c is 4.
  • the lithium-containing-material is LiCoO 2 , LiNiO 2 , LiNi 0.4 Co 0.4 Mn 0.2 O 2 , LiNi 1/3 Co 1/3 O 2 , LiMn 1.5 Ni 0.5 O 4 , or LiFePO 4 .
  • the lithium-containing material is Li 2 SO y′ , wherein y′ is 0-4. In more specific embodiments, the lithium-containing material is Li 2 S or Li 2 SO 4 .
  • the nanofiber comprises a Li 2 S/carbon nanocomposite (e.g., lithium sulfide domains in a continuous carbon matrix) or a Li 2 SO 4 /carbon nanocomposite (e.g., lithium sulfate in a continuous carbon matrix).
  • a Li 2 S/carbon nanocomposite e.g., lithium sulfide domains in a continuous carbon matrix
  • a Li 2 SO 4 /carbon nanocomposite e.g., lithium sulfate in a continuous carbon matrix
  • the lithium-containing-material comprises at least 50 wt. % (e.g., at least 80 wt. %) of the nanofiber. In further or alternative embodiments, the nanofiber comprises at least 2.5 wt. % lithium. In further or alternative embodiments, at least 10% (e.g., about 25%) of the atoms present in the nanofiber are lithium atoms.
  • the nanofibers provided herein have an initial capacity (e.g., specific, charge or discharge capacity) of at least 60 mAh/g as a positive electrode (cathode) in a lithium ion battery (e.g., at a charge/discharge rate of 0.1 C in a full or half-cell). In specific embodiments, the nanofibers provided herein have an initial capacity of at least 75 mAh/g as a positive electrode (cathode) in a lithium ion battery (e.g., at a charge/discharge rate of 0.1 C in a half-cell).
  • an initial capacity e.g., specific, charge or discharge capacity
  • the nanofibers provided herein have an initial capacity of at least 100 mAh/g as a positive electrode (cathode) in a lithium ion battery (e.g., at a charge/discharge rate of 0.1 C in a half-cell). In still more specific embodiments, the nanofibers provided herein have an initial capacity of at least 120 mAh/g as a positive electrode (cathode) in a lithium ion battery (e.g., at a charge/discharge rate of 0.1 C in a half-cell).
  • the nanofibers provided herein have an initial capacity of at least 150 mAh/g as a positive electrode (cathode) in a lithium ion battery (e.g., at a charge/discharge rate of 0.1 C in a half-cell). In more specific embodiments, the nanofibers provided herein have an initial capacity of at least 175 mAh/g as a positive electrode (cathode) in a lithium ion battery (e.g., at a charge/discharge rate of 0.1 C in a half-cell).
  • nanofibers provided herein have a capacity (e.g., specific, charge or discharge) retention as a positive electrode (cathode) in a lithium ion battery (e.g., at a charge/discharge rate of at least 0.1 C in a full or half-cell) of at least 50% after 50 cycles.
  • nanofibers provided herein have a capacity retention as a positive electrode (cathode) in a lithium ion battery (e.g., at a charge/discharge rate of at least 0.1 C in a full or half-cell) of at least 60% after 50 cycles.
  • nanofibers provided herein have a capacity retention as a positive electrode (cathode) in a lithium ion battery (e.g., at a charge/discharge rate of at least 0.1 C in a full or half-cell) of at least 70% after 50 cycles.
  • FIG. 4 and FIG. 13 illustrate capacity retention for various nanofibers provided herein.
  • the nanofiber comprises a continuous polymer matrix and a lithium component.
  • the polymer matrix comprising a polymer comprising a monomeric repeat unit of (CH 2 -CHOM 1 ), each M 1 being independently selected from H, a lithium ion, and a metal radical; at least 5% of M 1 is L + .
  • the metal radical is a metal halide, a metal carboxylate, a metal alkoxide, a metal diketone, a metal nitrate, or a combination thereof.
  • at least 10% of M 1 is Li + .
  • At least 10% (e.g., at least 20%, at least 25%, or at least 40%) of M 1 is cobalt radical or ion (e.g., —CoOCOCH 3 ). In further or alternative embodiments, at least 10% (e.g., at least 20%, at least 25%, or at least 40%) of M 1 is manganese radical or ion (e.g., —MnOCOCH 3 ). In further or alternative embodiments, at least 10% (e.g., at least 20%, at least 25%, or at least 40%) of M 1 is nickel acetate (e.g., —NiOCOCH 3 ).
  • a nanofiber provided herein has a diameter of less than 1 micron (e.g., less than 500 nm). In further or alternative embodiments, a nanofiber provided herein has an aspect ratio of at least 100 (e.g., at least 1,000, or at least 10,000). In further or alternative embodiments, a nanofiber provided herein has a specific surface are of at least 10 m 2 /g (e.g., at least 30 m 2 /g, at least 100 m 2 /g, at least 300 m 2 /g, at least 500 m 2 /g, or at least 1000 m 2 /g, e.g., as measured by BET). In further or alternative embodiments, a nanofiber provided herein has a length of at least 1 micron (e.g., at least 10 microns, at least 100 microns, at least 1,000 microns).
  • a nanofiber provided herein comprises a backbone of a first material, the backbone comprising non-aggregated nanoparticles embedded therein, the nanoparticles comprising a lithium-containing-material.
  • the backbone comprises carbon.
  • the lithium containing material is represented by the formula: Li a M b X c , e.g., wherein a, b, c, M and X are as discussed above.
  • a lithium-ion battery comprising an anode in a first chamber, a cathode in a second chamber, and a separator between the first chamber and the second chamber, the cathode comprising a plurality of nanofibers of any one of the preceding claims.
  • processes for producing a lithium-containing-nanofiber comprising electrospinning a fluid stock to produce a first (as-spun) nanofiber, the fluid stock comprising or prepared by combining a polymer and a lithium salt.
  • the first (as-spun) nanofiber is then thermally treated to produce the lithium containing nanofiber.
  • the electrospinning of the fluid stock is gas assisted (e.g., coaxially—along or around the same axis).
  • the polymer polyacrylonitrile (PAN) e.g., wherein the fluid further comprises DMF
  • polyvinyl alcohol (PVA) e.g., wherein the fluid further comprises water
  • the fluid stock is aqueous.
  • the fluid stock further comprises a non-lithium metal precursor.
  • the metal precursor is an iron precursor, a cobalt precursor, an aluminum precursor, a nickel precursor, a manganese precursor, or a combination thereof.
  • the process comprises thermally treating the first nanofiber at a temperature of at least 300° C.
  • the combined concentration of lithium salt and metal precursor is present in or provided into the fluid stock in a concentration of at least 200 mM (e.g., at least 250 mM, or at least 300 mM).
  • the polymer comprises a plurality of repeating monomeric residues, the combined lithium salt and metal precursor being present in or added in a lithium salt/metal precursor-to-monomeric residue ratio of at least 1:4 (e.g., at least 1:2, or at least 1:1).
  • the thermally treating step is performed under air—e.g., wherein the process produces a nanofiber comprising a continuous matrix of lithium metal oxide.
  • the fluid stock further comprises a calcination reagent, such as a non-metal precursor.
  • the non-metal precursor is elemental sulfur or a phosphite alkoxide.
  • the non-metal precursor is elemental sulfur—e.g., for producing lithium containing nanofiber comprising lithium sulfide.
  • the non-metal precursor is a phosphite alkoxide—e.g., for producing lithium containing nanofiber comprising lithium metal phosphate.
  • a process for producing a lithium-containing-nanofiber comprising:
  • methods for producing positive electrode comprising, for example:
  • Lithium-containing nanofibers described herein are optionally prepared by the first step alone or by the first and second steps.
  • disclosure of a single nanofiber having a given characteristic or characteristics includes disclosure of a plurality of nanofibers having an average of the given characteristic or characteristics.
  • disclosure of an average characteristic for a plurality of fibers includes disclosure of a specific characteristic for a single fiber.
  • FIG. 1 illustrates one embodiment of the method for producing lithium-containing nanofibers described herein (e.g., suitable for use in lithium ion batteries).
  • FIG. 2 shows a TEM image of LiCoO 2 nanofibers from electrospinning of aqueous solution of PVA/Li-Ac/Co—Ac followed by thermal treatment at 800° C. under air.
  • FIG. 3 shows an XRD spectra of LiCoO 2 nanofibers from electrospinning of aqueous solution of PVA/Li—Ac/Co—Ac followed by thermal treatment at 800° C. under air, confirming the formation of nanocrystals LiCoO 2 .
  • FIG. 4 illustrates the charge/discharge capacities for lithium cobalt oxide prepared using a one step thermal process (panel A) and a two step thermal process (panel B).
  • FIG. 5 illustrates (panel B) an SEM image of certain Li(Ni 1/3 Co 1/3 Mn 1/3 )O 2 nanofibers (i.e., nanofibers comprising a continuous core matrix, or backbone, of Li(Ni 1/3 Co 1/3 Mn 1/3 )O 2 ), as well as as-spun precursor nanofibers used to prepare the same (panel A).
  • Li(Ni 1/3 Co 1/3 Mn 1/3 )O 2 nanofibers i.e., nanofibers comprising a continuous core matrix, or backbone, of Li(Ni 1/3 Co 1/3 Mn 1/3 )O 2
  • as-spun precursor nanofibers used to prepare the same (panel A).
  • FIG. 6 illustrates an XRD pattern for certain Li(Ni 1/3 Co 1/3 Mn 1/3 )O 2 nanofibers.
  • FIG. 7 illustrates charge/discharge capacities for certain Li(Ni 1/3 Co 1/3 Mn 1/3 )O 2 nanofibers in a lithium ion battery half cell.
  • FIG. 8 illustrates (panel B) an SEM image of certain Li[Li 0.2 Mn 0.56 Ni 0.16 Co 0.08 ]O 2 nanofibers (i.e., nanofibers comprising a continuous core matrix, or backbone, of Li[Li 0.2 Mn 0.56 Ni 0.16 Co 0.08 ]O 2 ), as well as as-spun precursor nanofibers used to prepare the same (panel A).
  • FIG. 9 illustrates charge/discharge capacities for certain Li[Li 0.2 Mn 0.56 Ni 0.16 Co 0.08 ]O 2 nanofibers.
  • FIG. 10 illustrates (panel B) an SEM image of certain Li 0.8 Mn 0.4 Ni 0.4 Co 0.4 O 2 nanofibers (i.e., nanofibers comprising a continuous core matrix, or backbone, of Li 0.8 Mn 0.4 Ni 0.4 Co 0.4 O 2 ), as well as as-spun precursor monofibers used to prepare the same (panel A).
  • Li 0.8 Mn 0.4 Ni 0.4 Co 0.4 O 2 nanofibers i.e., nanofibers comprising a continuous core matrix, or backbone, of Li 0.8 Mn 0.4 Ni 0.4 Co 0.4 O 2
  • as-spun precursor monofibers used to prepare the same (panel A).
  • FIG. 11 illustrates (panel B) an SEM image of certain LiMn 2 O 4 nanofibers (i.e., nanofibers comprising a continuous core matrix, or backbone, of LiMn 2 O 4 ), as well as as-spun precursor nanofibers used to prepare the same (panel A).
  • Panel C illustrates a TEM image of certain LiMn 2 O 4 nanofibers.
  • FIG. 12 illustrates an XRD pattern for certain LiMn 2 O 4 nanofibers.
  • FIG. 13 illustrates charge/discharge capacity for certain LiMn 2 O 4 nanofibers in a lithium ion battery half cell.
  • FIG. 14 illustrates an XRD pattern for certain LiMn 2 O 4 nanofibers doped with nickel Li(Ni x Mn z )O 4 .
  • FIG. 15 illustrates (panel B) an SEM image of certain lithium iron phosphate nanofibers (i.e., nanofibers comprising a continuous core matrix, or backbone, of lithium iron phosphate), as well as as-spun precursor nanofibers used to prepare the same (panel A).
  • lithium iron phosphate nanofibers i.e., nanofibers comprising a continuous core matrix, or backbone, of lithium iron phosphate
  • as-spun precursor nanofibers used to prepare the same (panel A).
  • FIG. 16 illustrates an XRD pattern for certain lithium iron phosphate nanofibers.
  • FIG. 17 illustrates an SEM image of certain Li 2 S/C nanofibers, as well as as-spun precursor nanofibers used to prepare the same (panel A).
  • FIG. 18 illustrates an XRD pattern for certain Li 2 SO 4 /C nanofibers.
  • FIG. 19 illustrates a co-axial electrospinning needle apparatus that may be used for gas assisted electrospinning of a single fluid or for multilayered coaxial electrospinning (multi-layered gas assisted electrospinning is possible with an additional needle in the needle apparatus configured around the illustrated needles and aligned along the common axis).
  • a nanofiber e.g., of a plurality of nanofibers, of a nanofiber mat, or of a process described herein
  • a nanofiber comprise a lithium material (e.g., a continuous matrix of a lithium material).
  • a nanofiber provided herein comprises a first material and a second material, the first material comprising a lithium material.
  • the first material, the second material, or both form a continuous matrix within the nanofiber.
  • both the first and second materials form continuous matrix materials within the nanofiber.
  • the first material comprises a plurality of discrete domains within the nanofiber.
  • the second material is a continuous matrix material within the nanofiber.
  • batteries e.g., lithium-ion batteries
  • the electrode comprises a plurality of nanofibers, the nanofibers comprising domains of a high energy capacity material.
  • the electrode comprises porous nanofibers, the nanofibers comprising a high energy capacity material.
  • batteries e.g., lithium-ion batteries
  • methods for making a battery comprising a separator.
  • the battery comprises an anode in a first chamber, a cathode in a second chamber, and a separator between the first chamber and the second chamber.
  • the separator comprises polymer nanofibers.
  • the separator allows ion transfer between the first chamber and second chamber in a temperature dependent manner.
  • the lithium-ion battery comprises an electrolyte.
  • the lithium material is any material capable of intercalating and deintercalating lithium ions.
  • the lithium material is or comprises a lithium metal oxide, a lithium metal phosphate, a lithium metal silicate, a lithium metal sulfate, a lithium metal borate, or a combination thereof.
  • the lithium material is a lithium metal oxide.
  • the lithium material is a lithium metal phosphate.
  • the lithium material is a lithium metal silicate.
  • the lithium material is lithium sulfide.
  • a nanofiber comprising a lithium material (e.g., a continuous core matrix of a lithium material).
  • the nanofibers comprise a continuous matrix of a lithium material.
  • the nanofibers comprises a continuous matrix material (e.g., carbon, ceramic, or the like) and discrete domains of a lithium material (e.g., wherein the discrete domains are non-aggregated).
  • the continuous matrix material is a conductive material (e.g., carbon).
  • a cathode (or positive electrode) comprising a plurality of nanofibers comprising a lithium material.
  • less than 40% of the nanoparticles are aggregated (e.g., as measured in any suitable manner, such as by TEM). In specific embodiments, less than 30% of the nanoparticles are aggregated). In more specific embodiments, less than 25% of the nanoparticles are aggregated). In yet more specific embodiments, less than 20% of the nanoparticles are aggregated). In still more specific embodiments, less than 10% of the nanoparticles are aggregated). In more specific embodiments, less than 5% of the nanoparticles are aggregated).
  • the lithium material is or comprises LiCoO 2 , LiCo x1 Ni y1 Mn z1 O 2 , LiMn x1 Ni y1 Co z1 V a1 O 4 , Li 2 S, LiFe x1 Ni y1 Co z1 V a1 PO 4 , any oxidation state thereof, or any combination thereof.
  • x1, y1, z1, and a1 are independently selected from suitable numbers, such as a number from 0 to 5 or from greater than 0 to 5.
  • a plurality of nanofibers comprising lithium, such as a continuous matrix of a lithium containing material (e.g., a lithium salt or lithium alloy/insertion compound, such as a lithium metal oxide).
  • a lithium containing material e.g., a lithium salt or lithium alloy/insertion compound, such as a lithium metal oxide.
  • an electrode e.g., positive electrode or cathode
  • the nanofibers comprising (a) a continuous matrix material; and (b) discrete, isolated domains comprising lithium.
  • the continuous matrix or isolated domains comprise lithium in the form of a lithium containing metal alloy.
  • the lithium containing metal alloy is a lithium metal oxide.
  • the nanofiber(s) comprise a lithium containing material of the following formula (I):
  • M represents one or more metal element (e.g., M represents Fe, Ni, Co, Mn, V, Ti, Zr, Ru, Re, Pt, Bi, Pb, Cu, Al, Li, or a combination thereof) and X represents one or more non-metal (e.g., X represents C, N, O, P, S, SO 4 , PO 4 , Se, halide, F, CF, SO 2 , SO 2 Cl 2 , I, Br, SiO 4 , BO 3 , or a combination thereof) (e.g., a non-metal anion).
  • a is 0.5-5, or 1-5 (e.g., 1-2)
  • b is 0-2
  • c is 0-10 (e.g., 1-4, or 1-3).
  • X is selected from the group consisting of O, SO 4 , PO 4 , SiO 4 , BO 3 . In more specific embodiments, X is selected from the group consisting of O, PO 4 , and SiO 4 . In certain embodiments, M is Mn, Ni, Co, Fe, V, Al, or a combination thereof.
  • a lithium material of formula (I) is LiMn 2 O 4 , LiNi 1/3 Co 1/3 Mn 1/3 O 2 , LiCoO 2 , LiNiO 2 , LiFePO 4 , Li 2 FePO 4 F, or the like.
  • the lithium material of formula (I) is Li 2 SO y′ , wherein y′ is 0-4, such as Li 2 S or Li 2 SO 4 .
  • the lithium metal of formula (I) is represented by the lithium metal of formula (Ia):
  • a lithium metal of formula (Ia) has the structure LiMO 2 (e.g., LiNi 1/3 Co 1/3 Mn 1/3 O 2 ).
  • a and b are each 1 and the one or more metal of M have an average oxidation state of 3.
  • the lithium metal of formula (Ia) is represented by the lithium metal of formula (Ib):
  • M′ represents one or more metal element (e.g., M′ represents Fe, Ni, Co, Mn, V, Li, Cu, Zn, or a combination thereof).
  • g is 0-1 (e.g., 0 ⁇ g ⁇ 1).
  • M′ represents one or more metal having an average oxidation state of 3.
  • the lithium metal of formula (Ia) or (Ib) is represented by the lithium metal of formula (Ic):
  • M′′ represents one or more metal element (e.g., M′′ represents Fe, Ni, Co, Zn, V, or a combination thereof).
  • h is 0-0.5 (e.g., 0 ⁇ h ⁇ 0.5, such as 0.083 ⁇ h ⁇ 0.5).
  • the lithium metal of formula (Ic) is Li[Li (1-2h)/3 Ni h′ Co (h-h′) Mn (2-h)/3 )O 2 , wherein h′ is 0-0.5 (e.g., 0 ⁇ h′ ⁇ 0.5).
  • the lithium metal of formula (Ia) is represented by the lithium metal of formula (Id):
  • M′′′ represents one or more metal element (e.g., M′′′ represents Fe, Mn, Zn, V, or a combination thereof).
  • each of b′, b′′, and b′′′ is independently 0-2 (e.g., 0-1, such as 0 ⁇ b′, b′′, and b′′′ ⁇ 1).
  • the sum of b′, b′′, and b′′′ is 1.
  • the one or more metal of M′′′ when taken together with the Ni and Co have an average oxidation state of 3.
  • the lithium metal of formula (I) is represented by the lithium metal of formula (Ie):
  • a lithium metal of formula (Ie) has the structure Li 2 MO 3 (e.g., Li 2 MnO 3 ).
  • a is 2
  • b is 1 and the one or more metal of M have an average oxidation state of 4.
  • an electrode comprising a plurality of nanofibers, the nanofibers comprising a continuous matrix of a lithium containing metal (e.g., a lithium metal alloy, such as a lithium metal oxide).
  • a lithium containing metal e.g., a lithium metal alloy, such as a lithium metal oxide
  • an electrode e.g., positive electrode or cathode
  • the nanofibers comprising (a) a continuous matrix material; and (b) discrete, isolated domains of a lithium containing metal (e.g., a lithium metal alloy, such as a lithium metal oxide).
  • the plurality of nanofibers have a continuous matrix of a lithium containing material.
  • the continuous matrix of lithium containing material is porous (e.g., mesoporous).
  • the continuous matrix of lithium containing material is hollow (e.g., hollow lithium containing metal nanofibers).
  • the nanofibers comprise (e.g., on average) at least 50% lithium containing material (e.g., by elemental analysis). In specific embodiments, the nanofibers comprise (e.g., on average) at least 70% lithium containing material. In more specific embodiments, the nanofibers comprise (e.g., on average) at least 80% lithium containing material. In still more specific embodiments, the nanofibers comprise (e.g., on average) at least 90% lithium containing material. In yet more specific embodiments, the nanofibers comprise e.g., on average) at least 95% lithium containing material.
  • the nanofibers comprise (e.g., on average) at least 0.5 wt. % lithium (e.g., by elemental analysis). In specific embodiments, the nanofibers comprise (e.g., on average) at least 1 wt. % lithium (e.g., by elemental analysis). In more specific embodiments, the nanofibers comprise (e.g., on average) at least 1.5 wt. % lithium (e.g., by elemental analysis). In still more specific embodiments, the nanofibers comprise (e.g., on average) at least 5 wt. % lithium (e.g., by elemental analysis). In specific embodiments, the nanofibers comprise (e.g., on average) at least 7 wt. % lithium (e.g., by elemental analysis). In more embodiments, the nanofibers comprise (e.g., on average) at least 10 wt. % lithium (e.g., by elemental analysis).
  • lithium atoms constitute (e.g., on average) at least 10% of the atoms present in the nanofibers. In specific embodiments, lithium atoms constitute (e.g., on average) at least 20% of the atoms present in the nanofibers. In more specific embodiments, lithium atoms constitute (e.g., on average) at least 30% of the atoms present in the nanofibers. In still more specific embodiments, lithium atoms constitute (e.g., on average) at least 40% of the atoms present in the nanofibers. In yet more specific embodiments, lithium atoms constitute (e.g., on average) at least 50% of the atoms present in the nanofibers.
  • nanofibers comprising pure LiNi 1/3 Co 1/3 Mn 1/3 O 2 , which comprises about 7 wt. % lithium (6.94 mol wt. Li/96.46 mol wt. LiNi 1/3 Co 1/3 Mn 1/3 O 2 ) and about 25% lithium atoms (1 lithium atom/(1 lithium atom+1 ⁇ 3 nickel atom+1 ⁇ 3 manganese atom+1 ⁇ 3 cobalt atom+2 oxygen atoms)).
  • the electrode comprises a plurality of nanofibers comprising (a) a matrix; and (b) a plurality of isolated, discrete domains comprising a lithium containing metal (e.g., a lithium alloy/intercalculation compound, such as a lithium metal oxide).
  • the matrix is a continuous matrix of carbon (e.g., amorphous carbon).
  • the matrix and/or discrete lithium containing domains are porous (e.g., mesoporous).
  • the continuous matrix is hollow.
  • the nanofibers comprise (e.g., on average) at least 30% lithium material (e.g., by elemental analysis).
  • the nanofibers comprise (e.g., on average) at least 40% lithium material. In more specific embodiments, the nanofibers comprise (e.g., on average) at least 50% lithium material. In still more specific embodiments, the nanofibers comprise (e.g., on average) at least 70% lithium material. In yet more specific embodiments, the nanofibers comprise (e.g., on average) at least 80% lithium material. In some embodiments, the nanofibers comprise lithium containing domains that comprise (e.g., on average) at least 70% lithium material. In more specific embodiments, the domains comprise (e.g., on average) at least 80% lithium material. In still more specific embodiments, the domains comprise (e.g., on average) at least 90% lithium material.
  • the domains comprise (e.g., on average) at least 95% lithium material.
  • the nanofibers comprise (e.g., on average) at least 0.1 wt. % lithium (e.g., by elemental analysis).
  • the nanofibers comprise (e.g., on average) at least 0.5 wt. % lithium (e.g., by elemental analysis).
  • the nanofibers comprise (e.g., on average) at least 1 wt. % lithium (e.g., by elemental analysis).
  • the nanofibers comprise (e.g., on average) at least 2.5 wt. % lithium (e.g., by elemental analysis).
  • the nanofibers comprise (e.g., on average) at least 5 wt. % lithium (e.g., by elemental analysis). In more embodiments, the nanofibers comprise (e.g., on average) at least 10 wt. % lithium (e.g., by elemental analysis). In some embodiments, lithium atoms constitute (e.g., on average) at least 10% of the atoms present in the nanofibers. In specific embodiments, lithium atoms constitute (e.g., on average) at least 5% of the atoms present in the nanofibers or the domains. In more specific embodiments, lithium atoms constitute (e.g., on average) at least 10% of the atoms present in the nanofibers or domains.
  • lithium atoms constitute (e.g., on average) at least 20% of the atoms present in the nanofibers or domains. In yet more specific embodiments, lithium atoms constitute (e.g., on average) at least 30% of the atoms present in the nanofibers or domains. In further embodiments, lithium atoms constitute (e.g., on average) at least 40%, at least 50%, or the like of the atoms present in the domains.
  • lithium-containing-nanofibers comprising a lithium material described herein, wherein up to 50% of the lithium is absent.
  • the lithium is absent due to delithiation (de-intercalculation of lithium) during lithium ion battery operation.
  • the lithium is absent due to volatility and/or sublimation of the lithium component.
  • up to 40% of the lithium is absent.
  • up to 30% of the lithium is absent.
  • up to 20% of the lithium is absent.
  • up to 10% of the lithium is absent.
  • a battery comprising such an electrode (e.g., cathode).
  • the battery is a secondary cell.
  • nanofibers or nanofiber mats comprising one or more such nanofiber as described herein.
  • positive electrodes provided herein are prepared by depositing lithium-containing nanofibers onto a current collector (e.g., copper or aluminum), thereby creating a positive electrode comprising the nanofibers in contact with a current collector.
  • a current collector e.g., copper or aluminum
  • as-treated nanofibers are ground in a mortal and pestle to produce processed nanofibers, which are then deposited on a current collector.
  • the processed nanofibers are dispersed in a solvent to prepare a composition, the composition is deposited onto a current collector, and evaporation of the solvent results in formation of an electrode on the current collector.
  • the composition further comprises a binder.
  • the composition further comprises a conductive material (e.g., carbon black)—e.g., to improve electron mobility.
  • the nanofibers provide herein comprise a backbone material (a core matrix material).
  • the backbone material is a lithium material described herein.
  • the backbone material is a continuous matrix material with non-aggregated domains embedded therein, the non-aggregated domains comprising a lithium material described herein (e.g., a nanoparticle comprising a lithium material described herein).
  • nanofibers described herein comprise a hollow core.
  • the nanofibers described herein comprise a continuous matrix material surrounding the hollow core.
  • the continuous matrix material comprises a lithium material described herein.
  • the continuous matrix material comprises non-aggregated domains embedded therein, the non-aggregated domains comprising a lithium material described herein (e.g., a nanoparticle comprising a lithium material described herein).
  • a continuous matrix material is comprises a ceramic, a metal, or carbon.
  • the continuous matrix material is a conductive material.
  • the nanofibers have any suitable diameter.
  • a collection of nanofibers comprises nanofibers that have a distribution of fibers of various diameters.
  • a single nanofiber has a diameter that varies along its length.
  • fibers of a population of nanofibers or portions of a fiber accordingly exceed or fall short of the average diameter.
  • the nanofiber has on average a diameter of about 20 nm, about 30 nm, about 40 nm, about 50 nm, about 60 nm, about 70 nm, about 80 nm, about 90 nm, about 100 nm, about 130 nm, about 150 nm, about 200 nm, about 250 nm, about 300 nm, about 400 nm, about 500 nm, about 600 nm, about 700 nm, about 800 nm, about 900 nm, about 1,000 nm, about 1,500 nm, about 2,000 nm and the like.
  • the nanofiber has on average a diameter of at most 20 nm, at most 30 nm, at most 40 nm, at most 50 nm, at most 60 nm, at most 70 nm, at most 80 nm, at most 90 nm, at most 100 nm, at most 130 nm, at most 150 nm, at most 200 nm, at most 250 nm, at most 300 nm, at most 400 nm, at most 500 nm, at most 600 nm, at most 700 nm, at most 800 nm, at most 900 nm, at most 1,000 nm, at most 1,500 nm, at most 2,000 nm and the like.
  • the nanofiber has on average a diameter of at least 20 nm, at least 30 nm, at least 40 nm, at least 50 nm, at least 60 nm, at least 70 nm, at least 80 nm, at least 90 nm, at least 100 nm, at least 130 nm, at least 150 nm, at least 200 nm, at least 250 nm, at least 300 nm, at least 400 nm, at least 500 nm, at least 600 nm, at least 700 nm, at least 800 nm, at least 900 nm, at least 1,000 nm, at least 1,500 nm, at least 2,000 nm and the like.
  • the nanofiber has on average a diameter between about 50 nm and about 300 nm, between about 50 nm and about 150 nm, between about 100 nm and about 400 nm, between about 100 nm and about 200 nm, between about 500 nm and about 800 nm, between about 60 nm and about 900 nm, and the like.
  • “Aspect ratio” is the length of a nanofiber divided by its diameter. In some embodiments, aspect ratio refers to a single nanofiber. In some embodiments, aspect ratio is applied to a plurality of nanofibers and reported as a single average value, the aspect ratio being the average length of the nanofibers of a sample divided by their average diameter. Diameters and/or lengths are measured by microscopy in some instances.
  • the nanofibers have any suitable aspect ratio. In some embodiments the nanofiber has an aspect ratio of about 10, about 10 2 , about 10 3 , about 10 4 , about 10 5 , about 10 6 , about 10 7 , about 10 8 , about 10 9 , about 10 10 , about 10 11 , about 10 12 , and the like.
  • the nanofiber has an aspect ratio of at least 10, at least 10 2 , at least 10 3 , at least 10 4 , at least 10 5 , at least 10 6 , at least 10 7 , at least 10 8 , at least 10 9 , at least 10 10 , at least 10 11 , at least 10 12 , and the like.
  • the nanofiber is of substantially infinite length and has an aspect ratio of substantially infinity.
  • the lithium material (e.g., core matrix lithium material) provided herein is crystalline. In some embodiments, the lithium material comprises a layered crystalline structure. In certain embodiments, the lithium material comprises a spinel crystalline structure. In certain embodiments, the lithium material comprises an olivine crystalline structure.
  • domains of lithium material provided herein have any suitable size.
  • the domains have an average diameter of about 5 nm, about 10 nm, about 20 nm, about 30 nm, about 40 nm, about 50 nm, about 60 nm, about 70 nm, about 80 nm, about 90 nm, about 100 nm, about 130 nm, about 150 nm, about 200 nm, and the like.
  • the domains have an average diameter of at most 5 nm, at most 10 nm, at most 20 nm, at most 30 nm, at most 40 nm, at most 50 nm, at most 60 nm, at most 70 nm, at most 80 nm, at most 90 nm, at most 100 nm, at most 130 nm, at most 150 nm, at most 200 nm, and the like.
  • the domains of high energy material have a uniform size.
  • the standard deviation of the size of the domains is about 50%, about 60%, about 70%, about 80%, about 100%, about 120%, about 140%, about 200%, and the like of the average size of the domains (i.e., the size is uniform).
  • the standard deviation of the size of the domains is at most 50%, at most 60%, at most 70%, at most 80%, at most 100%, at most 120%, at most 140%, at most 200%, and the like of the average size of the domains (i.e., the size is uniform).
  • the domains of high energy material have any suitable distance between each other (separation distance). In some instances, the domains have an average separation distance of about 2 nm, about 5 nm, about 10 nm, about 20 nm, about 30 nm, about 40 nm, about 50 nm, about 60 nm, about 70 nm, about 80 nm, about 90 nm, about 100 nm, about 130 nm, about 150 nm, about 200 nm, and the like.
  • the domains have an average diameter of at most 2 nm, at most 5 nm, at most 10 nm, at most 20 nm, at most 30 nm, at most 40 nm, at most 50 nm, at most 60 nm, at most 70 nm, at most 80 nm, at most 90 nm, at most 100 nm, at most 130 nm, at most 150 nm, at most 200 nm, and the like.
  • the domains are uniformly distributed within the nanofiber matrix.
  • the standard deviation of the distances between a given domain and the nearest domain to the given domain is about 50%, about 60%, about 70%, about 80%, about 100%, about 120%, about 140%, about 200%, and the like of the average of the distances (i.e., uniform distribution).
  • the standard deviation of the distances between a given domain and the nearest domain to the given domain is at most 50%, at most 60%, at most 70%, at most 80%, at most 100%, at most 120%, at most 140%, at most 200%, and the like of the average of the distances (i.e., uniform distribution).
  • less than 40% of the domains are aggregated (e.g., as measured in any suitable manner, such as by TEM).
  • less than 30% of the domains are aggregated.
  • less than 25% of the domains are aggregated.
  • less than 20% of the domains are aggregated.
  • less than 10% of the domains are aggregated.
  • less than 5% of the domains are aggregated.
  • the domains of lithium material comprise any suitable mass of the nanofiber.
  • the domains comprise about 10%, about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, about 80%, about 90%, and the like of the mass of the nanofiber.
  • the domains comprise at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, and the like of the mass of the nanofiber.
  • the domains comprise at most 10%, at most 20%, at most 30%, at most 40%, at most 50%, at most 60%, at most 70%, at most 80%, at most 90%, and the like of the mass of the nanofiber.
  • the nanofibers have a high surface area and methods are described for making nanofibers having a high surface area. In some embodiments, ordering of the pores results in a high surface area and/or specific surface area (e.g., surface area per mass of nanofiber and/or surface area per volume of nanofiber) in some instances.
  • the nanofibers e.g., porous nanofibers
  • the nanofibers have a specific surface area of at least 10 m 2 /g, at least 50 m 2 /g, at least 100 m 2 /g, at least 200 m 2 /g, at least 500 m 2 /g, at least 1,000 m 2 /g, at least 2,000 m 2 /g, at least 5,000 m 2 /g, at least 10,000 m 2 /g, and the like.
  • the “specific surface area” is the surface area of at least one fiber divided by the mass of the at least one fiber. The specific surface area is calculated based on a single nanofiber, or based on a collection of nanofibers and reported as a single average value.
  • the surface area is measured by physical or chemical methods, for example by the Brunauer-Emmett, and Teller (BET) method where the difference between physisorption and desorption of inert gas is utilized to determine the surface area or by titrating certain chemical groups on the nanofiber to estimate the number of groups on the surface, which is related to the surface area by a previously determined titration curve.
  • BET Brunauer-Emmett, and Teller
  • the nanofiber has any suitable length.
  • a given collection of nanofibers comprises nanofibers that have a distribution of fibers of various lengths. Therefore, certain fibers of a population accordingly exceed or fall short of the average length.
  • the nanofiber has an (average) length of at least about 1 ⁇ m, at least about 10 ⁇ m, at least about 20 ⁇ m, at least about 50 ⁇ m, at least about 100 ⁇ m, at least about 500 ⁇ m, at least about 1,000 ⁇ m, at least about 5,000 ⁇ m, at least about 10,000 ⁇ m, at least about 50,000 ⁇ m, at least about 100,000 ⁇ m, at least about 500,000 ⁇ m, and the like.
  • Methods for measuring the length of a nanofiber include, but are not limited to microscopy, optionally transmission electron microscopy (“TEM”) or scanning electron microscopy (“SEM”).
  • the nanofiber has is substantially contiguous or has a continuous matrix material.
  • a nanofiber is substantially contiguous or a material constitutes a continuous matrix of the nanofiber if when following along the length of the nanofiber, the fiber material is in contact with at least some neighboring fiber material over substantially the entire nanofiber length. “Substantially” the entire length means that at least 80%, at least 90%, at least 95%, or at least 99% of the length of the nanofiber is contiguous.
  • the nanofiber is optionally substantially contiguous in combination with any of the porosities described herein (e.g., 35%).
  • the nanofiber is substantially flexible or non-brittle.
  • Flexible nanofibers are able to deform when a stress is applied and optionally return to their original shape when the applied stress is removed.
  • a substantially flexible nanofiber is able to deform by at least 5%, at least 10%, at least 20%, at least 50%, and the like in various embodiments.
  • a non-brittle nanofiber does not break when a stress is applied.
  • the nanofiber bends (e.g., is substantially flexible) rather than breaks.
  • a substantially non-brittle nanofiber is able to deform by at least 5%, at least 10%, at least 20%, at least 50%, and the like without breaking in various embodiments.
  • a process for producing lithium containing nanofibers.
  • the method comprises: (a) electrospinning a fluid stock to form nanofibers, the fluid stock comprising (i) a lithium precursor or lithium containing nanoparticles and (ii) a polymer; and (b) thermally treating the nanofibers.
  • electrospinning of the fluid stock is gas assisted (e.g., coaxially gas assisted).
  • a lithium ion battery electrode is optionally formed using such nanofibers (or smaller nanofibers, such as fragments produced by sonication of the thermally treated nanofibers).
  • a process for producing lithium containing nanofibers comprises (a) electrospinning a fluid stock to form as-spun nanofibers, the fluid stock comprising lithium precursor, a second metal precursor, and a polymer; and (b) thermally treating the as-spun nanofibers to produce the lithium containing nanofibers.
  • the process further comprises chemically treating (e.g., oxidizing, such as with air) the nanofibers.
  • the chemical treatment occurs simultaneously with step (b).
  • the chemical treatment step occurs after step (b).
  • the electrospinning is gas assisted.
  • the electrospinning is coaxially gas assisted.
  • the fluid stock is aqueous.
  • the polymer is a water soluble polymer, such as polyvinyl alcohol (PVA).
  • a process for producing lithium containing nanofibers comprises (a) electrospinning a fluid stock to form as-spun nanofibers, the fluid stock comprising a nanoparticle comprising a lithium material and a polymer; and (b) thermally treating the as-spun nanofibers to produce the lithium containing nanofibers.
  • the thermal treatment occurs under inert conditions (e.g., in an argon atmosphere).
  • the electrospinning is gas assisted.
  • the electrospinning is coaxially gas assisted.
  • the fluid stock is aqueous.
  • the polymer is a water soluble polymer, such as polyvinyl alcohol (PVA).
  • fluid is a solvent based solution.
  • the polymer is a solvent soluble polymer, such as polyacrylonitrile (PAN).
  • gas assisted electrospinning processes or apparatus described herein providing or providing a device configured to provide a flow of gas along the same axis as an electrospun fluid stock.
  • that gas (or gas needle) is provided along the same axis with the fluid stock (or fluid stock needle) (e.g., and adjacent thereto).
  • the gas (or gas needle) is provided coaxially with the fluid stock (or fluid stock needle).
  • FIG. 19 illustrates co-axial electrospinning apparatus 300 .
  • the coaxial needle apparatus comprises an inner needle 301 and an outer needle 302 , both of which needles are coaxially aligned around a similar axis 303 (e.g., aligned with 5 degrees, 3 degrees, 1 degree, or the like).
  • further coaxial needles may be optionally placed around, inside, or between the needles 301 and 302 , which are aligned around the axis 303 (e.g., as illustrated in FIG. 1 ).
  • the termination of the needles is optionally offset 304 .
  • gas assisted electrospinning is utilized (e.g., about a common axis with the jet electrospun from a fluid stock described herein). Exemplary methods of gas-assisted electrospinning are described in PCT Patent Application PCT/US2011/024894 (“Electrospinning apparatus and nanofibers produced therefrom”), which is incorporated herein for such disclosure.
  • the gas is optionally air or any other suitable gas (such as an inert gas, oxidizing gas, or reducing gas).
  • gas assistance increases the throughput of the process and/or reduces the diameter of the nanofibers.
  • gas assisted electrospinning accelerates and elongates the jet of fluid stock emanating from the electrospinner. In some instances, gas assisted electrospinning facilitates uniform dispersion of nanoparticles in the nanofibers.
  • gas assisted electrospinning e.g., coaxial electrospinning of a gas—along a substantially common axis—with a fluid stock comprising lithium containing nanoparticles
  • gas assisted electrospinning facilitates dispersion or non-aggregation of the nanoparticles in the electrospun jet and the resulting as-spun nanofiber (and subsequent nanofibers produced therefrom).
  • incorporating a gas stream inside a fluid stock produces hollow nanofibers.
  • the fluid stock comprises (i) a lithium-containing material (e.g., as a nanoparticle) or (ii) a lithium precursor (e.g., lithium salt).
  • the fluid stock comprises a lithium precursor and at least one additional metal precursor (e.g., a cobalt precursor, a manganese precursor, a nickel precursor, or a combination thereof).
  • each metal precursor is independently a metal acetate, metal nitrate, metal acetylacetonate, metal chloride, metal hydride, hydrates thereof, or any combination thereof.
  • the amount of lithium precursor and metal precursor utilized herein are used in a fluid stock or process described herein in a molar ratio that is the same as the lithium material being prepared.
  • the lithium precursor to additional metal precursor is present in an a:b ratio.
  • excess lithium precursor is optionally utilized (e.g., to make up for lithium that may be lost to sublimation during thermal processing).
  • at least a 50% molar excess of lithium is utilized.
  • at least a 100% molar excess is utilized.
  • the lithium precursor to additional metal precursor for preparing a material of formula (I) is present in a ratio of at least 1.5a:b (50% excess) or, more specifically, at least 2a:b (100% excess). Similar ratios for any of the lithium material formulas described herein are also contemplated.
  • metal precursor comprise alkali metal salts or complexes, alkaline earth metal salts or complexes, transition metal salts or complexes, or the like.
  • the fluid stock comprises a lithium precursor and at least one additional metal precursor, wherein the metal precursor comprises an iron precursor, a nickel precursor, a cobalt precursor, a manganese precursor, a vanadium precursor, a titanium precursor, a ruthenium precursor, a rhenium precursor, a platinum precursor, a bismuth precursor, a lead precursor, a copper precursor, an aluminum precursor, a combination thereof, or the like.
  • the additional metal precursor comprises an iron precursor, a nickel precursor, a cobalt precursor, a manganese precursor, a vanadium precursor, an aluminum precursor, or a combination thereof. In still more specific embodiments, the additional metal precursor comprises an iron precursor, a nickel precursor, a cobalt precursor, a manganese precursor, an aluminum precursor, or a combination thereof. In yet more specific embodiments, the additional metal precursor comprises a nickel precursor, a cobalt precursor, a manganese precursor, or a combination thereof. In still more specific embodiments, the additional metal precursor comprises at least two metal precursors from the group consisting of: a nickel precursor, a cobalt precursor, and a manganese precursor.
  • the additional metal precursor comprises a nickel precursor, a cobalt precursor, and a manganese precursor.
  • metal precursors include metal salts or complexes, wherein the metal is associated with any suitable ligand or radical, or anion or other Lewis Base, e.g., a carboxylate (e.g., —OCOCH 3 or another —OCOR group, wherein R is an alkyl, substituted alkyl, aryl, substituted aryl, or the like, such as acetate), an alkoxide (e.g., a methoxide, ethoxide, isopropyl oxide, t-butyl oxide, or the like), a halide (e.g., chloride, bromide, or the like), a diketone (e.g., acetylacetone, hexafluoroacetylacetone, or the like), a nitrates, amines (e.g.,
  • the weight ratio of the metal component(s) (including lithium precursor and additional metal precursors) to polymer is at least 1:5, at least 1:4, at least 1:3, at least 1:2, at least 1:1, at least 1.25:1, at least 1.5:1, at least 1.75:1, at least 2:1, at least 3:1, or at least 4:1.
  • the lithium material is prepared from a preformed lithium-containing-nanoparticle
  • the nanoparticle to polymer weight ratio is at least 1:5, at least 1:4, at least 1:3, at least 1:2, or the like.
  • the metal component of a process described herein comprises a lithium precursor and at least one additional metal precursor
  • the metal component (both lithium and additional metal precursors) to polymer ratio is at least 1:3, at least 1:2, at least 1:1, or the like.
  • the monomeric residue (i.e., repeat unit) concentration of the polymer in the fluid stock is at least 100 mM.
  • the monomeric residue (i.e., repeat unit) concentration of the polymer in the fluid stock is at least 200 mM.
  • the monomeric residue (i.e., repeat unit) concentration of the polymer in the fluid stock is at least 400 mM.
  • the monomeric residue (i.e., repeat unit) concentration of the polymer in the fluid stock is at least 500 mM.
  • the fluid stock comprises at least about 0.5 weight %, at least about 1 weight %, at least about 2 weight %, at least about 5 weight %, at least about 10 weight %, at least about 20 weight %, or at least about 30 weight % polymer.
  • a polymer in a process, fluid stock or nanofiber described herein is an organic polymer.
  • polymers used in the compositions and processes described herein are hydrophilic polymers, including water-soluble and water swellable polymers.
  • the polymer is soluble in water, meaning that it forms a solution in water.
  • the polymer is swellable in water, meaning that upon addition of water to the polymer the polymer increases its volume up to a limit.
  • Exemplary polymers suitable for the present methods include but are not limited to polyvinyl alcohol (“PVA”), polyvinyl acetate (“PVAc”), polyethylene oxide (“PEO”), polyvinyl ether, polyvinyl pyrrolidone, polyglycolic acid, hydroxyethylcellulose (“HEC”), ethylcellulose, cellulose ethers, polyacrylic acid, polyisocyanate, and the like.
  • PVA polyvinyl alcohol
  • PVAc polyvinyl acetate
  • PEO polyethylene oxide
  • polyvinyl ether polyvinyl pyrrolidone
  • polyglycolic acid polyglycolic acid
  • HEC hydroxyethylcellulose
  • cellulose ethers polyacrylic acid
  • polyisocyanate polyacrylic acid
  • the polyisocyanate and the like.
  • the polymer is isolated from biological material.
  • the polymer starch, chitosan, xanthan, agar, guar gum
  • silicon nanoparticles are utilized as the silicon component
  • other polymers such as polyacrylonitrile (“PAN”) are optionally utilized (e.g., with DMF as a solvent).
  • PAN polyacrylonitrile
  • a polyacrylate e.g., polyalkacrylate, polyacrylic acid, polyalkylalkacrylate, such as poly(methyl methacrylate) (PMMA), or the like
  • PMMA poly(methyl methacrylate)
  • the polymer is polyacrylonitrile (PAN), polyvinyl alcohol (PVA), a polyethylene oxide (PEO), polyvinylpyridine, polyisoprene (PI), polyimide, polylactic acid (PLA), a polyalkylene oxide, polypropylene oxide (PPO), polystyrene (PS), a polyarylvinyl, a polyheteroarylvinyl, a nylon, a polyacrylate (e.g., poly acrylic acid, polyalkylalkacrylate—such as polymethylmethacrylate (PMMA), polyalkylacrylate, polyalkacrylate), polyacrylamide, polyvinylpyrrolidone (PVP) block, polyacrylonitrile (PAN), polyglycolic acid, hydroxyethylcellulose (HEC), ethylcellulose, cellulose ethers, polyacrylic acid, polyisocyanate, or a combination thereof.
  • PAN polyacrylonitrile
  • PAN polyvinyl alcohol
  • a suitable polymer molecular weight is a molecular weight that is suitable for electrospinning the polymer as a melt or solution (e.g., aqueous solution or solvent solution—such as in dimethyl formamide (DMF) or alcohol).
  • the polymer utilized has an average atomic mass of 1 kDa to 1,000 kDa.
  • the polymer utilized has an average atomic mass of 10 kDa to 500 kDa.
  • the polymer utilized has an average atomic mass of 10 kDa to 250 kDa.
  • the polymer utilized has an average atomic mass of 50 kDa to 200 kDa.
  • the polymers described herein associate (e.g., through ionic, covalent, metal complex interactions) with metal precursors described herein when combined in a fluid stock.
  • a fluid stock that comprises (a) at least one polymer; (b) a lithium precursor; and (c) an additional metal precursor (e.g., a metal acetate or metal alkoxide), or is prepared by combining (i) at least one polymer; (ii) a lithium precursor; and (iii) at least one additional metal precursor.
  • a nanofiber comprising a polymer associated with the metal precursors is produced.
  • a fluid stock comprising PVA in association with a lithium precursor and at least one additional metal precursor.
  • this association is present in a fluid stock or in a nanofiber.
  • the association having the formula: —(CH 2 -CHOM 1 ) n1 -.
  • each M is independently selected from H, a metal ion, and a metal complex (e.g., a metal halide, a metal carboxylate, a metal alkoxide, a metal diketone, a metal nitrate, a metal amine, or the like).
  • a metal complex e.g., a metal halide, a metal carboxylate, a metal alkoxide, a metal diketone, a metal nitrate, a metal amine, or the like.
  • a polymer e.g., in a fluid stock or nanofiber having the following formula: (A d R 1 n -BR 1 m R 2 ) a .
  • each of A and B are independently selected from C, O, N, or S.
  • at least one of A or B is C.
  • each R 1 is independently selected from H, halo, CN, OH, NO 2 , NH 2 , NH(alkyl) or N(alkyl)(alkyl), SO 2 alkyl, CO 2 -alkyl, alkyl, heteroalkyl, alkoxy, S-alkyl, cycloalkyl, heterocycle, aryl, or heteroaryl.
  • the alkyl, alkoxy, S-alkyl, cycloalkyl, heterocycle, aryl, or heteroaryl is substituted or unsubstituted.
  • R 2 is M 1 , OM 1 , NHM 1 , or SM 1 , as described above.
  • any alkyl described herein is a lower alkyl, such as a C 1 -C 6 or C 1 -C 3 alkyl.
  • each R1 or R2 is the same or different.
  • d is 1-10, e.g., 1-2.
  • n is 0-3 (e.g., 1-2) and m is 0-2 (e.g., 0-1).
  • a is 100-1,000,000.
  • a substituted group is optionally substituted with one or more of H, halo, CN, OH, NO 2 , NH 2 , NH(alkyl) or N(alkyl)(alkyl), SO 2 alkyl, CO 2 -alkyl, alkyl, heteroalkyl, alkoxy, S-alkyl, cycloalkyl, heterocycle, aryl, or heteroaryl.
  • the block co-polymer is terminated with any suitable radical, e.g., H, OH, or the like.
  • At least 5% of M 1 are Li + . In more specific embodiments, at least 10% of M 1 are Li + . In more specific embodiments, at least 15% of M 1 are Li + . In still more specific embodiments, at least 20% of M 1 are Li + . In more specific embodiments, at least 40% of M 1 are Li + . In further embodiments, at least 10% of M 1 are a non-lithium metal complex (e.g., iron acetate, cobalt acetate, manganese acetate, nickel acetate, aluminum acetate, or a combination thereof). In more specific embodiments, at least 15% of M 1 are non-lithium metal complex. In still more specific embodiments, at least 20% of M 1 are non-lithium metal complex. In more specific embodiments, at least 40% of M 1 are non-lithium metal complex. In various embodiments, n1 is any suitable number, such as 1,000 to 1,000,000.
  • a method for producing an ordered mesoporous nanofiber comprising: (a) coaxially electrospinning a first fluid stock with a second fluid stock to produce a first nanofiber, the first fluid stock comprising at least one block co-polymer and a metal component (e.g., lithium precursor and at least one additional metal precursor), the second fluid stock comprising a coating agent, and the first nanofiber comprising a first layer (e.g., core) and a second layer (e.g., coat) that at least partially coats the first layer; (b) optionally annealing the first nanofiber; (c) optionally removing the second layer from the first nanofiber to produce a second nanofiber comprising the block co-polymer; and (d) thermally and/or chemically treating the first nanofiber or the second nanofiber (e.g.
  • the block copolymer orders itself upon annealing, with the metal component preferentially going into one phase (e.g., a hydrophilic phase of the copolymer)—and, upon thermal treatment (e.g., calcination of precursor), a mesoporous lithium material is produced.
  • Additional coaxial layers are optional—e.g., comprising a precursor and block copolymer for an additional mesoporous layer, or a precursor and a polymer as described herein for a non-mesoporous layer.
  • the block co-polymer comprises a polyisoprene (PI) block, a polylactic acid (PLA) block, a polyvinyl alcohol (PVA) block, a polyethylene oxide (PEO) block, a polyvinylpyrrolidone (PVP) block, polyacrylamide (PAA) block or any combination thereof (i.e., thermally or chemically degradable polymers).
  • the block co-polymer comprises a polystyrene (PS) block, a poly(methyl methacrylate) (PMMA) block, a polyacrylonitrile (PAN) block, or any combination thereof.
  • the coating layer and at least part of the block co-polymer is selectively removed in any suitable manner, such as, by heating, by ozonolysis, by treating with an acid, by treating with a base, by treating with water, by combined assembly by soft and hard (CASH) chemistries, or any combination thereof.
  • any suitable manner such as, by heating, by ozonolysis, by treating with an acid, by treating with a base, by treating with water, by combined assembly by soft and hard (CASH) chemistries, or any combination thereof.
  • the fluid stock further comprises a calcination reagent.
  • the calcination reagent is a phosphorus reagent (e.g., for preparing lithium metal phosphates or phosphides upon thermal treatment/calcination of a nanofiber spun from a fluid stock comprising lithium and at least one additional metal precursors), a silicon reagent (e.g., for preparing lithium metal silicates upon thermal treatment/calcination of a nanofiber spun from a fluid stock comprising lithium and at least one additional metal precursors), a sulfur reagent (e.g., for preparing lithium metal sulfides or sulfates upon thermal treatment/calcination of a nanofiber spun from a fluid stock comprising lithium and at least one additional metal precursors), or a boron reagent (e.g., for preparing lithium metal borates upon thermal treatment/calcination of a nanofiber spun from a fluid stock comprising lithium and at least one additional metal precursors).
  • the reagent is elemental material (e.g., phosphorus, sulfur) or any other suitable chemical compound.
  • the alkyl, alkoxy, S-alkyl, cycloalkyl, heterocycle, aryl, or heteroaryl is substituted or unsubstituted.
  • q is 0.
  • R1 is alkoxy (e.g., wherein the calcination reagent is triethylphosphite).
  • an oxygen reagent is air, which is provided in the atmosphere (e.g., which can react upon sufficient thermal conditions with the metal precursors or calcined metals).
  • a carbon reagent is the organic polymer material (e.g., which can react upon sufficient thermal conditions with the metal precursor(s)).
  • the process comprises electrospinning a fluid stock. Any suitable method for electrospinning is used.
  • elevated temperature electrospinning is utilized.
  • Exemplary methods for comprise methods for electrospinning at elevated temperatures as disclosed in U.S. Pat. No. 7,326,043 and U.S. Pat. No. 7,901,610, which are incorporated herein for such disclosure.
  • elevated temperature electrospinning improves the homogeneity of the fluid stock throughout the electrospinning process.
  • gas assisted electrospinning is utilized (e.g., about a common axis with the jet electrospun from a fluid stock described herein). Exemplary methods of gas-assisted electrospinning are described in PCT Patent Application PCT/US2011/024894 (“Electrospinning apparatus and nanofibers produced therefrom”), which is incorporated herein for such disclosure.
  • the gas is optionally air or any other suitable gas (such as an inert gas, oxidizing gas, or reducing gas).
  • gas assistance increases the throughput of the process and/or reduces the diameter of the nanofibers.
  • gas assisted electrospinning accelerates and elongates the jet of fluid stock emanating from the electrospinner.
  • gas assisted electrospinning disperses nanoparticles in nanocomposite nanofibers.
  • gas assisted electrospinning e.g., coaxial electrospinning of a gas along a substantially common axis—with a fluid stock comprising lithium containing nanoparticles
  • gas assisted electrospinning facilitates dispersion or non-aggregation of the Li containing nanoparticles in the electrospun jet and the resulting as-spun nanofiber (and subsequent nanofibers produced therefrom).
  • incorporating a gas stream inside a fluid stock produces hollow nanofibers.
  • the fluid stock is electrospun using any suitable technique.
  • the process comprises coaxial electrospinning (electrospinning two or more fluids about a common axis).
  • coaxial electrospinning a first fluid stock as described herein with a second fluid is used to add coatings, make hollow nanofibers, make nanofibers comprising more than one material, and the like.
  • the second fluid is either outside (i.e., at least partially surrounding) or inside (e.g., at least partially surrounded by) the first fluid stock.
  • the second fluid is a gas (gas-assisted electrospinning)
  • gas assistance increases the throughput of the process, reduces the diameter of the nanofibers, and/or is used to produce hollow nanofibers.
  • the method for producing nanofibers comprises coaxially electrospinning the first fluid stock and a gas.
  • the second fluid is a second fluid stock and comprises a polymer and an optional metal component (e.g., a silicon and/or non-silicon metal component).
  • the nanofibers comprise a core material.
  • the core material is highly conductive.
  • the highly conductive material is a metal.
  • described herein are methods for producing nanofibers, the nanofibers comprising a core material, optionally a highly conductive core material, optionally a metal core.
  • lithium nanoparticles are embedded within the core material/matrix.
  • the heating step performs any suitable function.
  • the heating step carbonizes the polymer.
  • the heating step removes the polymer.
  • the heating step selectively removes a polymer phase.
  • removing (e.g., selectively) the polymer and/or polymer phase results in porous nanofibers.
  • the heating step calcines and/or crystallizes the precursors.
  • the heating step calcines and/or crystallizes the precursors and/or nanoparticles.
  • the heating step determines the oxidation state of the high energy capacity material, precursors thereof and/or nanoparticles thereof, or any combination thereof.
  • the nanofibers are heated in oxidative (e.g., in air atmosphere), inert (e.g., under argon or nitrogen), or reductive conditions (e.g., under hydrogen or inert gas/hydrogen mixtures).
  • thermal treatment occurs in the presence of air, nitrogen, nitrogen/H 2 (e.g., 95%/5%), argon, argon/H 2 (e.g., 96%/4%), or any combination thereof.
  • oxidative conditions convert metal precursors to metal oxide or ceramic.
  • exposure to (e.g., concurrent with thermal treatment) oxidative conditions convert metal (e.g., metal prepared by calcination of metal precursor to metal under inert or inert/reductive conditions) to metal oxide or ceramic.
  • oxidative conditions are performed in an oxygen-rich environment, such as air. In one particular example where the nanofiber is a ceramic nanofiber, calcination is performed in air at about 600° C. for about 2 hours.
  • Thermal and/or chemical treatments are performed at any suitable temperature and for any suitable time. In some instances, higher temperature treatments produce nanofibers of a smaller diameter.
  • thermal treatment is performed at about 100° C., about 150° C., about 200° C., about 300° C., about 400° C., about 500° C., about 600° C., about 700° C., about 800° C., about 900° C., about 1,000° C., about 1,500° C., about 2,000° C., and the like.
  • thermal treatment is performed at a temperature of at least 100° C., at least 150° C., at least 200° C., at least 300° C., at least 400° C., at least 500° C., at least 600° C., at least 700° C., at least 800° C., at least 900° C., at least 1,000° C., at least 1,500° C., at least 2,000° C., and the like.
  • heating is performed at a temperature of at most 100° C., at most 150° C., at most 200° C., at most 300° C., at most 400° C., at most 500° C., at most 600° C., at most 700° C., at most 800° C., at most 900° C., at most 1,000° C., at most 1,500° C., at most 2,000° C., and the like.
  • heating is performed at a temperature of between about 300° C. and 800° C., between about 400° C. and 700° C., between about 500° C. and 900° C., between about 700° C. and 900° C., between about 800° C. and 1,200° C., and the like.
  • Heating is performed at a constant temperature, or the temperature is changed over time.
  • the rate of temperature increase is between about 0.1° C./min and 10° C./min, between about 0.5° C./min and 2° C./min, between about 2° C./min and 10° C./min, between about 0.1° C./min and 2° C./min, or the like.
  • Heating is performed for any suitable amount of time necessary to arrive at a nanofiber with the desired properties. In some embodiments, heating is performed for at least 5 minutes, at least 15 minutes, at least 30 minutes, at least 1 hour, at least 2 hours, at least 3 hours, at least 4 hours, at least 8 hours, at least 12 hours, at least 1 day, at least 2 days, and the like.
  • a lithium ion battery system comprising: (a) an electrolyte; (b) an anode in a first chamber; (c) a cathode in a second chamber, the cathode comprising a plurality of lithium containing nanofibers; and (d) a separator between the first chamber and the second chamber, and the separator allowing lithium ion transport between the first chamber and second chamber (e.g., in a temperature dependent manner).
  • a system for producing nanofibers for a lithium ion battery comprising: (a) a fluid stock comprising a polymer and inorganic precursors or nanoparticles; (b) an electrospinner suitable for electrospinning the fluid stock into nanofibers; (c) a heater suitable for heating the nanofibers; and (d) optionally a module suitable for contacting the nanofibers with an acid.
  • electrospinning allows for the high throughput generation of nanomaterials with the ability to control this crystal structure.
  • purely inorganic or organic/inorganic hybrid nanofibers are generated by inclusion of various metal/ceramic precursors (metal nitrate, acetate, acetylacetonate, etc.) or preformed nanoparticles (e.g., a lithium material described herein) within a polymer (PVA, PAN, PEO, etc.) solution, as shown in the schematic in FIG. 1 .
  • thermal treatment is used to carbonize polymers, remove polymers, selectively remove a single polymer phase, and/or crystallize and/or calcine included precursors or nanoparticles with controlled oxidation state.
  • porosity in the nanofibers is controlled by the removal of a polymer domain during thermal treatment, as demonstrated in FIG. 3 for porous LiCoO 2 nanofiber for cathode application. In some instances, this allows for greater surface area to volume ratio and/or greater electrolyte contact increasing ion transfer, while accommodating volume expansion during lithiation and de-lithiation processes.
  • FIG. 1 illustrates a process according to certain embodiments described herein.
  • a fluid stock 1003 is prepared by preparing by combining 1002 a fluid (e.g., water, alcohol, or dimethylformamide (DMF)), a polymer and a lithium component 1001 (e.g., lithium precursors and additional metal precursor(s) and/or lithium containing nanoparticles).
  • a homogenous fluid stock with a viscosity suitable for electrospinning is prepared 1004 by heating and/or mixing the combination.
  • the fluid stock is then electrospun from a needle apparatus 1006 (optionally via gas assisted, such as coaxially gas assisted, electrospinning), e.g., using a syringe 1005 .
  • the nanofibers 1008 are collected on a collector 1007 and optionally thermally treated 1009 to provide lithium-containing nanofibers 1010 described herein.
  • thermal treatment of the as-spun nanofibers carbonizes and/or removes (e.g., via carbonization and subsequent conversion to CO 2 ).
  • thermal treatment calcines metal precursor materials to provide a metal component (e.g., metals, metal oxides, metal phosphates, metal sulfides, metal silicates, metal borates, or the like (e.g., depending on what, if any, calcination reagents are utilized)).
  • a metal component e.g., metals, metal oxides, metal phosphates, metal sulfides, metal silicates, metal borates, or the like (e.g., depending on what, if any, calcination reagents are utilized).
  • calcination of the metal precursors provides a crystalline metal component (e.g., metal, metal oxide, etc.).
  • a first composition is prepared by combining 0.5 g PVA (79 kDa, 88% hydrolyzed) with 4.5 g water. The first composition is heated to 95 C for at least 8 hours.
  • a second composition is prepared by combining 1 g water, 0.5 g acetic acid, 3 drops x-100 surfactant, lithium acetate (hydrate) and one or more metal precursor (e.g., cobalt acetate (hydrate), manganese acetate (hydrate), nickel acetate (hydrate)). The second composition is mixed for at least 4 hours. The first and second compositions are combined and mixed for at least 2 hours to form a fluid stock.
  • the fluid stock is electrospun in a coaxial gas assisted manner, using a flow rate of 0.01 mL/min, a voltage of 20 kV and a tip to collector distance of 15 cm.
  • the fluid stock is also electrospun without coaxial gas assistance, using a flow rate of 0.005 mL/min, a voltage of 20 kV and a tip to collector distance of 18 cm. Electrospinning of the fluid stock prepares an as-spun precursor nanofiber, which is subsequently thermally treated.
  • a one step thermal treatment procedure involves treating the as-spun nanofibers in air at about 700 C (with a heat/cool rate of 2 C/min) for 5 hours.
  • a two step thermal treatment procedure involves a first thermal treatment under argon at about 700 C (with a heat/cool rate of 2 C/min) for 5 hours, and a second thermal treatment under air at about 500 C (with a heat/cool rate of 2 C/min).
  • X-Ray diffraction done using Scintag 2-theta diffractometer; scanning electron microscopy (SEM) with Leica 440 SEM; transmission electron microscopy (TEM) with FEI Spirit TEM.
  • lithium cobalt oxide nanofibers are prepared. Nanofibers are prepared using 1:1, 1:1.5, and 1:2 molar ratios of cobalt acetate-to-lithium acetate.
  • FIG. 2 illustrates an SEM image of such nanofibers (panel A).
  • FIG. 3 panel A) illustrates the XRD pattern for the lithium cobalt oxide nanofibers and illustrates the XRD pattern (panel B) for nanofibers prepared using 1:1, 1:1.5, and 1:2 molar ratios of cobalt acetate-to-lithium acetate (ratios in the figure are inverted).
  • FIG. 1 illustrates an SEM image of such nanofibers (panel A).
  • FIG. 2 panel B
  • FIG. 4 illustrates the charge/discharge capacities for lithium cobalt oxide prepared using a one step thermal process (panel A) and a two step thermal process (panel B).
  • the lithium cobalt oxide nanofibers produced is observed to have an initial capacity of about 120 mAh/g at 0.1 C.
  • Table 1 illustrates charge capacities determined using the various lithium-metal ratios and the one and two step thermal treatment processes.
  • Li a (Ni x Co y Mn z )O 2 nanofibers are prepared. Nanofibers are prepared using 1:1, 1:1.5, and 1:2 molar ratios of the combined nickel/cobalt/manganese acetate-to-lithium acetate. Various molar ratios of nickel acetate (x) to cobalt acetate (y) to manganese acetate (z) are utilized
  • FIG. 5 panel A illustrates an SEM image of as-spun nanofibers prepared using a 1:1:1 ratio of x:y:z.
  • Panel B illustrates an SEM image of thermally treated (Li(Ni 1/3 Co 1/3 Mn 1/3 )O 2 ) nanofibers (treated at 650 C in air).
  • Panel C illustrates a TEM image of the thermally treated nanofibers.
  • FIG. 6 illustrates the XRD pattern for the thermally treated nanofibers.
  • FIG. 7 illustrates the charge/discharge capacities for 1:1:1 (x:y:z) nanofibers prepared. The nanofibers produced is observed to have an initial capacity of about 180 mAh/g at 0.1 C.
  • FIG. 8 illustrates the as-spun and thermally treated (900 C for 5 hours under argon) nanofibers.
  • FIG. 9 illustrates the charge/discharge capacities for nanofibers prepared. The nanofibers produced is observed to have an initial capacity of about 90 mAh/g at 0.1 C.
  • FIG. 10 panel A illustrates as-spun nanofibers and (panel B) thermally treated (900 C for 5 hours under argon) nanofibers.
  • Nanofibers are prepared using 2:1, 3:2 (50% excess lithium acetate), and 1:1 (100% excess lithium acetate) molar ratios of the manganese acetate-to-lithium acetate.
  • FIG. 11 panel A illustrates an SEM image of as-spun nanofibers.
  • Panel B illustrates an SEM image of thermally treated nanofibers (treated at 650 C in air).
  • Panel C illustrates a TEM image of the thermally treated nanofibers.
  • FIG. 12 illustrates the XRD pattern for the thermally treated nanofibers.
  • FIG. 13 illustrates the charge/discharge capacity of the nanofibers for about 40 cycles. The lithium manganese oxide nanofibers produced is observed to have an initial capacity of about 95 mAh/g at 0.1 C.
  • Nanofibers are prepared using 2:1, 3:2, and 1:1 molar ratios of the combined nickel/manganese acetate-to-lithium acetate.
  • Various molar ratios of nickel acetate (x) to manganese acetate (z) are utilized (e.g., 1:3 for Li(Ni 0.5 Mn 1.5 )O 4 ).
  • FIG. 14 illustrates the XRD pattern for the thermally treated nanofibers.
  • a first composition is prepared by combining 0.5 g PVA (79 kDa, 88% hydrolyzed) with 4.5 g water. The first composition is heated to 95 C for at least 8 hours.
  • a second composition is prepared by combining 1 g water, 0.5 g acetic acid, 3 drops x-100 surfactant, lithium acetate (hydrate), one or more metal precursor (e.g., iron acetate (hydrate), cobalt acetate (hydrate), manganese acetate (hydrate), nickel acetate (hydrate)), and a phosphorus precursor (e.g., triethylphosphite). The second composition is mixed for at least 4 hours. The first and second compositions are combined and mixed for at least 2 hours to form a fluid stock.
  • the fluid stock is electrospun in a coaxial gas assisted manner, using a flow rate of 0.01 mL/min, a voltage of 20 kV and a tip to collector distance of 15 cm.
  • the fluid stock is also electrospun without coaxial gas assistance, using a flow rate of 0.005 mL/min, a voltage of 20 kV and a tip to collector distance of 18 cm. Electrospinning of the fluid stock prepares an as-spun precursor nanofiber, which is subsequently thermally treated.
  • a one step thermal treatment procedure involves treating the as-spun nanofibers in air at about 700 C (with a heat/cool rate of 2 C/min) for 5 hours.
  • a two step thermal treatment procedure involves a first thermal treatment under argon at about 700 C (with a heat/cool rate of 2 C/min) for 5 hours, and a second thermal treatment under air at about 500 C (with a heat/cool rate of 2 C/min).
  • Nanofibers are prepared using 1:1, 1:1.5, and 1:2 molar ratios of iron acetate-to-lithium acetate.
  • FIG. 15 illustrates an SEM image of the as-spun nanofibers (panel A) and thermally treated nanofibers (panel B).
  • FIG. 16 illustrates the XRD pattern for the lithium iron phosphate nanofibers.
  • a first composition is prepared by combining 0.5 g PVA (79 kDa, 88% hydrolyzed) with 4.5 g water. The first composition is heated to 95 C for at least 8 hours.
  • a second composition is prepared by combining 1 g water, 0.5 g acetic acid, 3 drops x-100 surfactant, lithium acetate (hydrate), and a sulfur precursor (e.g., elemental sulfur, such as sulfur nanoparticles). The second composition is mixed for at least 4 hours. The first and second compositions are combined and mixed for at least 2 hours to form a fluid stock.
  • the fluid stock is electrospun in a coaxial gas assisted manner, using a flow rate of 0.01 mL/min, a voltage of 20 kV and a tip to collector distance of 15 cm.
  • the fluid stock is also electrospun without coaxial gas assistance, using a flow rate of 0.005 mL/min, a voltage of 20 kV and a tip to collector distance of 18 cm. Electrospinning of the fluid stock prepares an as-spun precursor nanofiber, which is subsequently thermally treated.
  • FIG. 17 illustrates an SEM image of the as-spun nanofibers (panel A) and thermally treated nanofibers (panel B).
  • Panel C illustrates a TEM image of the thermally treated nanofibers.
  • FIG. 18 illustrates the XRD pattern for the oxidized nanofibers.
  • Li metal is used as a counter electrode and polyethylene (ca. 25 ⁇ m thickness) is inserted as a separator between working electrode and counter electrode.
  • the mass of working electrode is 3 ⁇ 4 mg/cm 2 .
  • the coin cell-typed Li-ion batteries are assembled in Ar-filled glove box with electrolyte.
  • the cut off voltage during the galvanostatic tests is 0.01 ⁇ 2.0 V for anode and 2.5 ⁇ 4.2 V by using battery charge/discharge cyclers from MTI.

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