Source: https://patents.google.com/patent/JP5882200B2/en
Timestamp: 2019-12-10 21:51:45
Document Index: 19952818

Matched Legal Cases: ['Application No. 60', 'Application No. 61', 'application No. 2008', 'Application No. 2008', 'art 2000', 'art 300', 'art 300', 'art 300', 'art 310', 'art 300', 'art 310', 'art 400', 'art 400', 'art 400', 'art 410', 'art 410', 'art 410', 'art 1900', 'art 1900', 'Application No. 61', 'Application No. 61', 'art 1700', 'Application No. 61']

JP5882200B2 - Nanostructured materials for battery applications - Google Patents
Nanostructured materials for battery applications Download PDF
JP5882200B2
JP5882200B2 JP2012511997A JP2012511997A JP5882200B2 JP 5882200 B2 JP5882200 B2 JP 5882200B2 JP 2012511997 A JP2012511997 A JP 2012511997A JP 2012511997 A JP2012511997 A JP 2012511997A JP 5882200 B2 JP5882200 B2 JP 5882200B2
JP2012511997A
JP2012527735A (en
イーミン・チュー
ジェイ・エル・ゴールドマン
ジェイソン・ハートラブ
ハンス・ユルゲン・ホフラー
バイシン・チエン
ヴィジェンドラ・サヒ
アイオネル・シー・ステファン
デーヴィッド・ピー・スタンボ
ワンディー マテリアル エルエルシー
2009-05-19 Priority to US61/179,663 priority
2009-06-29 Priority to US61/221,392 priority
2009-10-28 Priority to US61/255,732 priority
2010-05-19 Application filed by ワンディー マテリアル エルエルシー, ワンディー マテリアル エルエルシー filed Critical ワンディー マテリアル エルエルシー
2012-11-08 Publication of JP2012527735A publication Critical patent/JP2012527735A/en
2015-10-21 First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=43124765&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=JP5882200(B2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
2016-03-09 Publication of JP5882200B2 publication Critical patent/JP5882200B2/en
The present invention relates to nanostructured materials (including nanowires) for use in batteries. Exemplary materials include carbon-containing Si-based nanostructures, nanostructured materials disposed on carbon-based substrates , and nanostructures comprising a nanoscale skeleton. The present invention further provides battery electrodes and methods for preparing batteries using nanostructured materials.
Conventional batteries, including lithium (Li) ion batteries, include an anode, a separator material having an electrolyte medium, and a cathode. The anode electrode of most commercially available Li-ion batteries is a copper foil coated with a mixture of a polymer blend such as graphite powder and polyvinylidene difluoride (PVDF). The cathode generally comprises a mixture of lithium transition metal oxide, PVDF and carbon black coated on an aluminum foil. Graphite and LiCoO 2 are commonly used and there is a need for an improved anode material that has high coulomb efficiency but excellent storage capacity and thermal stability.
One material that has received much attention due to its high capacity is silicon (Si). However, repeated charge / discharge cycles have been found to cause Si volume changes that can ultimately cause material collapse and severely limit any potential battery life. For this reason, there is a need for improved electrode materials, particularly Si-based materials, for use in batteries.
In one embodiment, the present invention provides an additive for use in battery slurries. Suitably such additives comprise one or more carbon-containing Si-based nanostructures. Exemplary Si-based nanostructures include Si-based nanowires and Si-based nanoparticles. Suitably, the nanowire has a core-shell structure, and in an exemplary embodiment, the core comprises Si and the shell comprises C. Si-based nanowires suitably have a diameter of about 20 nm to about 200 nm and a length of about 0.1 μm to about 50 μm.
In embodiments, the additive comprises from about 1% to about 80% (more suitably about 10%) slurry by weight. In an exemplary embodiment, a conductive polymer such as polyvinylidene difluoride is disposed on the Si-based nanostructure. The present invention further provides a battery slurry comprising one or more carbon-containing Si-based nanostructures. Exemplary properties of Si-based nanostructures, including Si-based nanowires, are described herein. Suitably, the battery slurry comprises about 1 wt% to about 80 wt% (suitably about 10 wt%) of carbon-containing Si-based nanostructures. In an exemplary embodiment, the battery slurry further includes a carbon-based material such as carbon or graphite.
In another embodiment, the additive of the present invention comprises one or more nanostructures disposed on a carbon-based substrate . Exemplary nanostructures include nanowires or nanoparticles, such as nanowires having a core-shell structure. Suitably, the nanowire includes a crystalline core (eg, Si) and a non-oxide amorphous shell (eg, Si or C). In an exemplary embodiment, the nanowire or nanoparticle comprises Si. Suitably, the nanowire has a diameter of about 20 nm to about 200 nm and a length of about 0.1 μm to about 50 μm.
Exemplary carbon-based substrates include carbon-based powder, carbon black, graphite, graphene, graphene powder, and graphite foil. Suitably, the carbon-based powder comprises particles of about 5 microns to about 50 microns, such as about 20 microns. Suitably, the additive of the present invention comprises from about 1% to about 80% (eg, about 10%) slurry by weight. The additive can further include a conductive polymer such as polyvinylidene difluoride disposed on the nanostructure.
In a further embodiment, the additive of the present invention comprises one or more nanostructures comprising a nanoscale skeleton, a Si-based layer disposed on the nanoscale skeleton, and a carbon-based disposed on the Si-based layer. Including layers. Exemplary nanoscale scaffolds include nanowires, nanofibers, and nanotubes. Suitably, the nanowire has a diameter of about 20 nm to about 200 nm and a length of about 0.1 μm to about 50 μm.
The present invention further includes one of carbon-containing Si-based nanostructures, nanostructures disposed on a carbon-based substrate , and / or nanostructures comprising a nanoscale skeleton, as described herein. Battery slurries and / or battery electrodes (eg, anodes) are also provided, including one or more. Exemplary nanostructures including nanostructure composition and properties have been described throughout. In an exemplary embodiment, the nanostructure, such as a nanowire, includes Li inserted into the nanowire. In an exemplary embodiment, the electrode includes about 1 wt% to about 80 wt% (eg, about 10 wt%) nanostructures. Suitably the nanostructure is embedded in a Li foil.
The present invention further provides a battery having an anode comprising one or more of the nanostructures of the present invention. Suitably the battery is a Li-ion battery. The battery of the present invention suitably further includes a cathode and an electrolyte separator disposed between the anode and the cathode. Exemplary cathode materials include, but are not limited to, LiCoO 2 , LiFePO 4 , LiMnO 2 , LiMnO 4 , LiNiCoAlO / LiNiCoMnO + LiMn 2 O 4 , LiCoFePO 4 , and LiNiO 2 . Suitably, the battery further includes a housing containing an anode, an electrolyte separator, and a cathode.
The present invention further provides a method of preparing a battery electrode. Suitably, the method includes providing one or more of the nanostructures of the present invention. The nanostructure is mixed with a conductive polymer and a carbon-based material to form a slurry. The slurry is formed on the battery electrode.
The present invention further provides a method for preparing a battery. Suitably, the method includes providing one or more nanostructures. The nanostructure is mixed with a conductive polymer and a carbon-based material to form a slurry. The slurry is formed on the battery anode, and the separator is disposed between the anode and the cathode.
The present invention further provides a method for preparing carbon-coated nanostructures. Suitably, the method includes providing a nanoscale framework. The carbon-containing polymer is disposed on the nanoscale skeleton. The carbon-containing polymer is heated to form a carbon coating on the nanoscale backbone.
The present invention further provides a method of preparing an additive for use in battery slurries. Suitably, the method includes providing a carbon-based powder. The Si-based nanostructure is disposed on the carbon-based powder.
Further embodiments, features, and advantages of the present invention, as well as various structures and operations of the present invention, are described in detail below with reference to the accompanying drawings.
The present invention will be described with reference to the accompanying drawings. In the accompanying drawings, like reference numbers indicate identical or functionally similar elements. The drawing in which an element first appears in that drawing is indicated by the leftmost digit (s) in the corresponding reference number.
1 is a diagram illustrating a carbon-containing Si-based nanostructure according to one embodiment of the present invention. FIG. 3 shows a nanostructure disposed on a carbon-based substrate , according to one embodiment of the present invention. It is a figure which shows the battery electrode of one Embodiment of this invention. 1 illustrates a carbon-coated nanostructure of one embodiment of the present invention. FIG. FIG. 3 shows a nanostructure disposed on a carbon-based powder according to an embodiment of the present invention. It is a figure which shows the battery electrode of one Embodiment of this invention. FIG. 3 shows a battery according to an embodiment of the present invention. 2 is a flowchart of a method for preparing a battery electrode according to an embodiment of the present invention. 2 is a flowchart of a method for preparing a battery electrode according to an embodiment of the present invention. 3 is a flowchart of a method for preparing a battery according to an embodiment of the present invention. 3 is a flowchart of a method for preparing a battery according to an embodiment of the present invention. Scanning electron microscopy (SEM) micrographs of nanowires grown with a high degree of straightness and perpendicularity orientation (FIG. 5A) and with random intermingled, entangled and overlapping orientations (FIG. 5B) It is. It is a SEM micrograph of the silicon nanowire grown on carbon black. 7 is a low (FIG. 7A) and high (FIG. 7B) magnification SEM micrograph of silicon nanowires grown on a graphite foil. It is the SEM micrograph of the graphene microsheet powder (FIG. 8A) which is not solidified, and the silicon nanowire (FIG. 8B) which grew on the graphene powder. 2 is a transmission electron microscope (TEM) micrograph of a silicon nanowire having a crystalline core and an amorphous shell. It is a figure which shows the charge capacity (solid marker) and cycle efficiency (open marker) of the silicon nanowire with two different diameters grown on the steel substrate . FIG. 4 is a current versus potential curve for silicon nanowires with different diameters grown on a stainless steel substrate . 2 is a current versus potential curve for a silicon thin film and a silicon thin film plus silicon nanowires, both grown on a stainless steel substrate . FIG. 4 shows capacity as a function of charge / discharge cycle comparing the composition of the present invention with a control composition. It is a SEM micrograph of silicon nanowires after 60 charge cycles. FIG. 6 shows a comparison of fast charge cycling behavior of a cell comprising a Li silicon nanowire anode / LiCO 2 cathode compared to a Li anode / LiCO 2 cathode control cell. Scanning transmission electron microscope (STEM) reveals uniform and homogeneous distribution of carbon (FIG. 16B) and lead (Pb) as markers for NAFION® (FIG. 16C) on a silicon nanowire network (FIG. 16A) ) Energy dispersive X-ray (EDX) micrograph. FIG. 4 illustrates an exemplary process for generating a nanowire, according to one embodiment of the present invention. FIG. 2 illustrates an exemplary process / equipment design for introducing the additive of the present invention into an existing slurry preparation. 2 is a flowchart of a method for preparing a carbon-coated nanostructure, according to one embodiment of the present invention. 2 is a flowchart of a method for preparing an additive for use in a battery slurry, according to one embodiment of the present invention. 2 is a photomicrograph of a nanostructure with a carbon coating, according to one embodiment of the present invention. 2 is a photomicrograph of a nanostructure with a carbon coating, according to one embodiment of the present invention. 4 is a photomicrograph of a nanostructure with a carbon coating, according to another embodiment of the invention. 2 is a photomicrograph of a nanostructure of an embodiment of the present invention showing morphological changes after several charge / discharge cycles. 2 is a photomicrograph of a nanostructure of an embodiment of the present invention showing morphological changes after several charge / discharge cycles. 2 is a photomicrograph of a nanostructure of an embodiment of the present invention showing morphological changes after several charge / discharge cycles. 2 is a photomicrograph of a nanostructure of an embodiment of the present invention showing morphological changes after several charge / discharge cycles. 24 is a SEM micrograph of low (FIG. 24A) and high (FIG. 24B) magnification silicon nanowires. FIG. 2 is a TEM micrograph of a silicon nanowire having a crystalline core and a combination of amorphous Si and poly-Si shells. FIG. 2 is a TEM micrograph of a silicon nanowire having a crystalline core and a combination of amorphous Si and poly-Si shells. FIG. 4 is a diagram illustrating Fourier transform infrared spectroscopy (FTIR) measurement showing the difference between SiNW and Si powder. FIG. 6 is a graph of capacity as a function of cycle number for a first anode comprising 10% Si nanowires, 10% PVDF, and 80% graphitic carbon and a second anode comprising only graphite carbon and PVDF.
It is understood that the specific embodiments shown and described herein are examples of the present invention and that these embodiments are not intended to otherwise limit the scope of the invention in any way. Should be. In fact, for simplicity, conventional electronics, manufacturing, semiconductor devices, and other nanowire (NW), nanorod, nanotube and nanoribbon technologies, and other functional aspects of the system (and components of the individual operating components of the system) are , May not be described in detail herein. Further, for convenience, the present invention is often described herein as relating to nanowires, although other similar structures are encompassed herein.
Although nanowires are frequently cited, the techniques described herein apply to other nanostructures such as nanorods, nanoparticles, nanopowders, nanotubes, nanotetrapods, nanoribbons, nanosheets and / or combinations thereof. It should be understood that is also applicable.
As used herein, “aspect ratio” is the length of the first axis of the nanostructure divided by the average of the lengths of the second and third axes of the nanostructure, where The second and third axes are the two axes whose lengths are almost equal to each other. For example, the perfect rod aspect ratio is the length of the major axis divided by the diameter of the cross section perpendicular (perpendicular) to the major axis.
As used with reference to nanostructures, the term “heterostructure” refers to nanostructures characterized by at least two different and / or distinguishable material types. In general, a region of the nanostructure includes a first material type, while a second region of the nanostructure includes a second material type. In another embodiment, the nanostructure comprises a core of a first material and a shell of at least one of a second (or third etc.) material, wherein the different material types are, for example, nanowires It is distributed in the radial direction around the major axis, the major axis of the branched nanocrystal arm, or the center of the nanocrystal. In order to be considered as a shell, or for a nanostructure to be considered a heterostructure, the shell need not completely cover the adjacent material. For example, a nanocrystal characterized by a core of one material covered with a small island of a second material is a heterostructure. In other embodiments, different material types are distributed at different locations within the nanostructure. For example, the material type can be distributed along the major (long) axis of the nanowire or the major axis or arm of the branched nanocrystal. Different regions within the heterostructure can comprise completely different materials, or different regions can comprise a substrate.
As used herein, a “nanostructure” has at least one region or characteristic dimension that is less than about 500 nm, such as less than about 200 nm, less than about 100 nm, less than about 50 nm, or less than about 20 nm. It is a structure. In general, the area or characteristic dimension is along the smallest axis of the structure. Examples of such structures are nanowires, nanopowders, nanorods, nanofilms, nanotubes, branched nanocrystals, nanotetrapods, tripods, bipods, nanocrystals, nanodots, quantum dots, nanoparticles, branched tetrapods (eg inorganic dendrimers ) Etc. In material properties, the nanostructures can be substantially homogeneous, or in other embodiments can be heterogeneous (eg, heterostructures). The nanostructure can be, for example, substantially crystalline, substantially monocrystalline, polycrystalline, amorphous, or a combination thereof. In one aspect, one of the three dimensions of the nanostructure has a dimension of less than about 500 nm, such as less than about 200 nm, less than about 100 nm, less than about 50 nm, or less than about 20 nm.
As used herein, the term “nanowire” generally includes at least one cross-sectional dimension that is less than 500 nm, suitably less than 200 nm, or less than 100 nm, greater than 10, preferably greater than 50. And, more preferably, any elongated conductive or semiconductor material having an aspect ratio (length: width) of greater than 100, for example up to about 1000 or more (or others described herein) Material).
As used herein, a “nanoparticle” is at least one region of a dimension less than about 500 nm, suitably less than about 200 nm, less than about 100 nm, less than about 50 nm, less than about 20 nm, or less than about 10 nm or Refers to particles, crystals, spheres, or other shaped structures having characteristic dimensions. Suitably, all dimensions of the nanoparticles utilized in the present invention are less than about 50 nm, suitably from about 1 nm to about 30 nm, or from about 1 nm to about 20 nm, from about 1 nm to about 10 nm, from about 1 nm to About 9 nm, about 1 nm to about 8 nm, about 1 nm to about 7 nm, about 1 nm to about 6 nm, about 1 nm to about 5 nm, about 1 nm to about 4 nm, about 1 nm to about 3 nm, or about 1 nm to about 2 nm, such as about 1 nm , About 2 nm, about 3 nm, about 4 nm, about 5 nm, about 6 nm, about 7 nm, about 8 nm, about 9 nm, or about 10 nm.
The nanowires of the invention can be substantially homogeneous in material properties, or in other embodiments can be non-uniform (eg, nanowire heterostructures). Nanowires can be made essentially from any convenient material, for example, can be substantially crystalline, substantially monocrystalline, polycrystalline, amorphous, or a combination thereof. The nanowires can have a variable diameter, or a substantially uniform diameter, i.e. in the most variable region and in a linear dimension of at least 5 nm (e.g. at least 10 nm, at least 20 nm, or at least 50 nm). Can have a diameter that exhibits a difference of less than about 20% (eg, less than about 10%, less than about 5%, or less than about 1%). Typically, the diameter is evaluated away from the end of the nanowire (eg, at the center 20%, 40%, 50%, or 80% of the nanowire). A nanowire can be straight over its entire length or part of its long axis, or it can be bent or curved, for example. In other embodiments, the nanowires or portions thereof can exhibit two-dimensional or three-dimensional quantum confinement.
Examples of such nanowires are the semiconductor nanowires, carbon nanotubes, and the like described in published international patent application numbers WO02 / 017362, WO02 / 048701, and WO01 / 003208, which are incorporated herein by reference. Other elongated conductive or semiconductor structures of the dimensions of.
As used herein, the term “nanorod” is similar to a nanowire, but any elongated conductive or semiconductor material (or other) having an aspect ratio (length: width) that is less than the aspect ratio of the nanowire. Of the materials described herein). Note that two or more nanorods can be bonded together along their longitudinal axis. Alternatively, two or more nanorods can be substantially aligned along their longitudinal axis, but cannot be bonded together, and there is a small gap between the ends of the two or more nanorods. In this case, electrons can flow from one nanorod to another by hopping from one nanorod to another. Two or more nanorods can be substantially aligned to form a path through which electrons can travel.
For example, Si, Ge, Sn, Se, Te, B, C (including diamond), P, BC, BP (BP 6 ), BSi, SiC, SiGe, SiSn, GeSn, WC, SiO 2 , TiO 2 , BN, BAs, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe, HgTe, BeS, BeSe, BeTe, MgS, MgSe, GeS, GeSe, GeTe, SnS, SnSe, SnTe, PbO, PbS, PbSe, PbTe, CuF, CuCl, CuBr, CuI, AgF, AgCl, AgBr, AgI, BeSiN 2, CaCN 2, ZnGeP 2, CdSnAs 2, ZnSnSb 2, CuGeP 3, C Si 2 P 3, (Cu, Ag) (Al, Ga, In, Tl, Fe) (S, Se, Te) 2, Si 3 N 4, Ge 3 N 4, Al 2 O 3, (Al, Ga, In) 2 (S, Se, Te) 3 , Al 2 CO, and nanowires, nanocrystals, nanoparticles, nanopowders, nanorods, nanotubes comprising a semiconductor material selected from a suitable combination of two or more such semiconductors A wide variety of nanostructured materials can be used, including nanoribbons.
The nanowires of the present invention further comprise organic polymers, ceramics, inorganic semiconductors such as carbides and nitrides, and oxides (such as TiO 2 or ZnO), carbon nanotubes, biologically derived compounds such as fine fiber proteins. Etc. may be included. For example, in certain embodiments, inorganic nanowires such as semiconductor nanowires are used. The semiconductor nanowire can be composed of a number of Group IV, III-V or II-VI semiconductors or their oxides. In one embodiment, the nanowires, RuO 2, SiC, GaN, TiO 2, SnO 2, WC x, MoC x, ZrC, WN x, metal conductivity such as MoN x, semiconductors, carbides, nitrides, or oxide material May be included. As used throughout, the suffix “x” when used in a chemical formula refers to a positive integer (eg, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, etc.). Nanowires are suitable prepared with materials that resist degradation in weak acids. Nanowires according to the present invention can include carbon nanotubes or can explicitly exclude carbon nanotubes, and in certain embodiments are “whiskers” or “nanowhiskers”, particularly diameters greater than 100 nm or greater than about 200 nm. Exclude whiskers with
In other embodiments, the semiconductor comprises a p-type dopant from group III of the periodic table, an n-type dopant from group V of the periodic table, a p-type dopant selected from the group consisting of B, Al, and In; An n-type dopant selected from the group consisting of P, As and Sb, a p-type dopant from group II of the periodic table, a p-type dopant selected from the group consisting of Mg, Zn, Cd, and Hg; P-type dopant from group IV of the periodic table, p-type dopant selected from the group consisting of C and Si, or n selected from the group consisting of Si, Ge, Sn, S, Se, and Te A dopant from the group consisting of a type of dopant may be included. Other presently known or future developed dopant materials can be used.
In addition, the nanowires can include carbon nanotubes or nanotubes formed of conductive or semiconducting organic polymer materials (eg, pentacene, and transition metal oxides).
Spatial descriptions used herein (eg, “above”, “below”, “up”, “down”, “upper”, “lower”, etc.) are for illustrative purposes only. It should be understood that the device of the present invention can be spatially configured in any orientation or method.
Nanostructures are produced in a wide range of different ways. For example, solution-based, surfactant-mediated crystal growth has been described to produce spherical inorganic nanomaterials such as quantum dots, as well as elongated nanomaterials such as nanorods and nanotetrapods. Other methods, including gas phase methods, have also been used to generate nanostructures. For example, silicon nanocrystals have been reported to be produced by laser pyrolysis of silane gas.
Other methods include, for example, low-temperature wafer scale production of ZnO nanowire arrays, including low temperature synthesis methods for producing ZnO nanowires as described by Greene et al., “L. Greene, M., et al. Law, J. Goldberger, F. Kim, J. Johnson, Y. Zhang, R. Saykally, P. Yang, Angew. Chem . Int . Ed . 42 , 3031-3034, 2003), and for example, A higher temperature vapor-liquid-solid (VLS) method is utilized that utilizes catalytic gold particles deposited as colloids or thin films to form. For example, such a VLS method for producing nanowires is described in published International Patent Application No. WO02 / 017362, the complete disclosure of which is hereby incorporated by reference in its entirety for all purposes. Incorporated into.
Nanostructures can be made and their size can be controlled by any of a number of convenient methods that can accommodate different materials. For example, the synthesis of nanocrystals of various compositions is described, for example, in Peng et al. (2000) “Shape Control of CdSe Nanocrystals” Nature 404, 59-61, Puntes et al. (2001) “Colloidal nanocrystal shape and size control: The case of cobalt” Science 291, 2115-21117, U.S. Pat. No. 6,306,736 by Alivisatos et al. group III-VI semiconductor nanocrystals, and product formed using processes, USPN No. 6,225, 198 (May 1, 2001) by Alivitas et al., title “Process for forming group formed nd product formed using process ", USPN 5,505,928 (April 9, 1996) by Alivisatos et al., title" Preparation of III-V semiconductor nanocrystals 1, US 8 by Alivisatos 75, US8 " May 12, 1998), title "Semiconductor nanocrystallines bounded to solid organic surface using self-assembled monolayers", title 4th, 6th month, p. size doped semiconductor particles and method of manufacturing same ", and Weiss et al. USPN No. 5,990,479 (November 23, 1999), entitled" Organo luminescent semiconductor nanocrystal probes for biological applications and process for making and using such probes " It is described in. The disclosure of each of these documents is hereby incorporated by reference in its entirety.
Growth of nanowires with various aspect ratios, including nanowires with controlled diameter, is described in, for example, Gudiksen et al. (2000) “Diameter-selective synthesis of semiconductor nanowires”, J. Am . Am. Chem. Soc. 122, 8801-8802, Cui et al. (2001) “Diameter-controlled synthesis of single-crystal silicon nanos” Appl. Phys. Lett. 78, 2214-2216, Gudiksen et al. (2001) “Synthetic control of the diameter and length of single crystal nanowires” J. et al . Phys. Chem. B 105, 4062-4064, Morales et al. (1998) “A laser ablation method for the synthesis of crystalline nanowires” Science 279, 208-211, Duan et al. (2000) “General synthesis of compound semiconductors” Adv. Mater. 12, 298-302, Cui et al. (2000) “Doping and electrical transport in silicon nanowires” . Phys. Chem. B1 04,5213-5216, Peng et al. (2000) “Shape control of CdSe nanocrystals” Nature 404, 59-61, Puntes et al. (2001) “Colloidal nanocrystal shape and size control: The case of cobalt” Science 291, 1151-2117, USPN No. 6,306,736 by Alivisato et al. III-V semiconductor nanocrystals, and product formed using processes ", USPN No. 6,225, 198 (May 1, 2001) by Alivitas et al., Title" Process for forming radical capped II d product formed using process ", USPN 6,036,774 (March 14, 2000) by Lieber et al., title" Method of producing metal oxide nanorods ", USPN 5,899, 997 by Lieber et al. April 27), title “Metal oxide nanorods”, USPN 5,997,832 (December 7, 1999) by Lieber et al., “Preparation of carb nanods”, Urbau et al. (2002) “Synthesis of single-crystalline perovskite nanowires composed of barium titanate and strontium titanate” J. et al . Am. Chem. Soc. , 124, 1186, and Yun et al. (2002) “Ferroelectric Properties of Individual Barium Titanate Nanowires Invested by Scanned Probe Microscopy”, Nanoletters 2,447. The disclosure of each of these documents is hereby incorporated by reference in its entirety.
In certain embodiments, the nanowires of the present invention are generated by growing or synthesizing these elongated structures on the substrate interface. For example, published US patent application US-2003-0089899-A1, the disclosure of which is incorporated herein by reference, describes semiconductor nanowires from gold colloids that are adhered to a solid substrate using vapor phase epitaxy / VLS. A method of growing a uniform population of is disclosed. Greene et al. ("Low-temperature wafer scale production of ZnO nanoarrays", L. Greene, M. Law, J. Goldberger, F. Kime, J. Johnson, Y. Zhang., Y. Zhang. Chem. Int. Ed. 42, 3031-3034, 2003) discloses an alternative method of synthesizing nanowires using a solution-based low temperature wire growth process. Surfactant-based synthesis methods disclosed in US Pat. Nos. 5,505,928, 6,225,198, and 6,306,736, and carbon nanotubes to produce shorter nanomaterials Known methods (see for example US-2002 / 0179434 by Dai et al.), And methods for growing nanowires without using a growth substrate (see, for example, Morales and Lieber, Science, V., et al.). 279, p. 208 (January 9, 1998)), various other methods have been used to synthesize other elongated nanomaterials. As described herein, any or all of these different materials may be used to generate nanowires for use in the present invention. For some applications, a wide variety of Group III-V, Group II-VI, and Group IV semiconductors may be used based on the final application of the substrate or prepared article. In general, such semiconductor nanowires are described, for example, in US-2003-0089899-A1, which is incorporated herein above. The disclosures of each of these documents are hereby incorporated by reference in their entirety.
The growth of branched nanowires (eg, nanotetrapods, tripods, bipods, and branched tetrapods) is described, for example, in Jun et al. (2001) “Controlled synthesis of multi-armed CdS nanostructures using single-type surfactant system” J. et al . Am. Chem. Soc. 123, 5150-5151, and Manna et al. (2000) "Synthesis of Soluble and Processable Rod-, Arrow-, Teadrop-, and Tetrodod-Shaped CdSe Nanocrystals" J. et al . Am. Chem. Soc. 122, 12700-12706 ". The disclosure of each of these documents is incorporated herein by reference in its entirety.
Nanoparticle synthesis is described, for example, in Clark Jr. Et al., USPN 5,690,807 (November 25, 1997), titled “Method for producing semiconductor particles”, USPN 6,136,156 by El-Shall et al. (October 24, 2000), Title “Nanoparticulates of silicon oxide alloys”, USPN 6,413,489 (July 2, 2002) by Ying et al., Title “Synthesis of nanometer-sized reverse droplets. (2001) “Sol-Gel Synthesis of Free-Standing Ferroelectric Lead Zirconate Titanate Nanoparticulates” J. et al . Am. Chem. Soc. 123, 4344. The disclosure of each of these documents is hereby incorporated by reference in its entirety. In addition, nanoparticle synthesis is described in the above citation for the growth of nanocrystals, nanowires, and branched nanowires, where the generated nanostructures have an aspect ratio of less than about 1.5. .
The synthesis of core-shell nanostructure heterostructures, ie nanocrystals and nanowires (eg nanorods) core-shell heterostructures is described, for example, in Peng et al. (1997) “Epitaxial growth of high luminance CdSe / CdS core / shell nanocrystals with photoaccessibility and electronic accessibility” . Am. Chem. Soc. 119, 7019-7029, Dabbousi et al. (1997) “(CdSe) ZnS core-shell quantum dots: Synthesis and characterisation of a sizing series of high luminescent nucleocrystallines . Phys. Chem. B 101, 9463-9475, Manna et al. (2002) “Epitaxial growth and photochemical annealing of graded CdS / ZnS shells on colloidal CdSe nanoords” . Am. Chem. Soc. 124, 7136-7145, and Cao et al. (2000) "Growth and properties of semiconductor core / shell nanocrystals with InAs cores" J. Am. Chem. Soc. 122,9692-9702. Similar approaches can be applied to the growth of other core-shell nanostructures. The disclosure of each of these documents is hereby incorporated by reference in its entirety.
The growth of nanowire heterostructures in which different materials are distributed at different locations along the long axis of the nanowire has been described, for example, by Gudiksen et al. (2002) “Growth of nanostructure superstructure structures for nanoscale photonics and electronics” Nature 415, 617-620, Bjork et al. (2002) "One-dimensional steple for forrons rearranged" Nano Letters 2, 86-90, Wu et al. (2002) "Block-by-block growth of single-crystalline Si / SiGe superlattice nanowires" Nano Letters 2,83-86, and U.S. Patent Application No. 60 / 370,095 (2002) by Empedoles (2002). It is described in the title “Nanowire heterostructures for encoding information”. The disclosure of each of these documents is hereby incorporated by reference in its entirety. A similar approach can be applied to the growth of other heterostructures.
As described throughout this specification, and co-assigned published patent applications 2007/0212538 and 2008/0280169, the entire contents of each of which are hereby incorporated by reference, For example, a conductive inner core wire (for example to provide the necessary conductivity for electron transfer) (which may or may not be doped) and a suitable surface for polymer electrolyte bonding Nanowire structures with multiple shells, such as one or more outer shell layers, can also be made. Exemplary nanowires that can be used in the practice of the present invention further include carbon-containing nanowires such as those disclosed in published US Patent Application Nos. 2007/0212538 and 2008/0280169.
In one embodiment, the present invention provides an additive for use in battery slurries. As used herein, “additive” refers to a composition that is added to the battery slurry such that a portion (eg, wt%) of the original slurry replaces the additive composition. As used herein, “battery slurry” refers to a mixture of components used to form a battery electrode (anode or cathode).
In one embodiment, the additive includes one or more carbon-containing Si-based nanostructures. As used herein, “carbon containing” is used to indicate that the nanostructure includes at least some form of carbon. Suitably, the nanostructure comprises a carbon shell, or sheet, surrounding or at least partially surrounding the nanostructure. As used herein, “Si-based” is used to indicate that the nanostructure contains at least 50% silicon (Si). Suitably the nanostructure comprises at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, or at least 95% Si. FIG. 1A shows a carbon-containing Si-based nanostructure 100 (eg, nanowire) of the present invention that includes an exemplary Si core 102 and C shell 104. As shown in FIG. 1A, suitably the nanostructure is a Si-based nanowire, but in a further embodiment, the nanostructure can be a Si-based nanoparticle. It should be noted that carbon-containing Si-based nanostructures are generally referred to herein as “nanostructures” along with other nanostructures described herein.
In another embodiment, the additive comprises one or more nanostructures comprising a nanoscale framework, a Si-based layer disposed on the nanoscale framework, and a carbon-based layer disposed on the Si-based layer. including. As used herein, a “nanoscale scaffold” refers to a nanostructure on which one or more other materials, components, layers, coatings, shells, and / or films may be disposed. . Exemplary nanoscale frameworks include nanowires, nanopowders, nanorods, nanofilms, nanotubes, branched nanocrystals, nanotetrapods, tripods, bipods, nanocrystals, nanodots, quantum dots, nanoparticles, branched tetrapods (e.g. Inorganic dendrimer). FIG. 1D illustrates an exemplary nanoscale skeleton 152, an Si-based layer 154 disposed on the nanoscale skeleton 152, and a C shell 156 disposed on the Si-based layer 154. Structure 150 (eg, coated nanowire) is shown. Suitably, the nanoscale framework 152 includes nanowires (eg, Si nanowires), nanofibers, nanotubes (eg, C nanotubes), or some other nanoscale framework in which Si-based layers may be disposed.
The nanostructures of the present invention comprising a nanoscale framework, a Si-based layer disposed on the nanoscale framework, and a carbon-based layer disposed on the Si-based layer are further described herein as nanoscale. It is called a skeletal system composition, a nano skeletal system composition, or simply a skeletal system nanostructure.
In an exemplary embodiment, the Si-based nanostructure is a Si-based nanowire. Exemplary dimensions of the nanowires of the present invention are described throughout. Suitably, the nanowire has a diameter of about 10 nm to about 500 nm, or about 20 nm to about 400 nm, about 20 nm to about 300 nm, about 20 nm to about 200 nm, about 20 nm to about 100 nm, or about 40 nm to about 100 nm. Suitably, the nanowire has a length of about 100 nm to about 100 μm, or about 1 μm to about 75 μm, about 1 μm to about 50 μm, or about 1 μm to about 20 μm. Suitably, the aspect ratio of the nanowire is up to about 2000: 1, or suitably up to about 1000: 1, with a diameter of about 20 nm to about 200 nm and a length of about 0.1 μm to about 50 μm. Have.
A method for producing nanowires using a vapor-liquid-solid (VLS) process is disclosed, for example, in published U.S. Patent Application No. US-2003-0089899, the disclosure of which is incorporated herein by reference. The Additional methods for generating nanowires are described herein and are known in the art. In an exemplary embodiment, the United States Patent Provisional, filed June 29, 2009, the disclosure of which is incorporated herein by reference in its entirety, to produce large quantities of high density nanowires. The method disclosed in application 61 / 221,501, titled “Methods for Growth of High Density Nanowires”, Attorney Docket No. 212.06800000 is used. After nanowire growth, the nanowires are properly recovered (eg, by radio frequency decomposition or other mechanical means). The addition of a carbon-containing layer (eg, C shell) can be added to the nanowire immediately after growth or after collection. The nanowire can then be used as an additive as described herein. Additional processes such as ball milling, grinding, or other mechanical mechanisms to break the nanowires and additives into smaller pieces or shorter segments can also be used.
As described herein, suitably, the additive of the present invention can be added to an existing battery slurry, and a portion of the slurry, eg, a portion of the graphite component, can be added to the carbon-containing Si of the present invention. It replaces with the system nanostructure composition. Battery slurries utilized for commercial grade batteries generally include a mixture of graphite, carbon, and polymer electrolyte (eg, polyvinylidene difluoride (PVDF)). The amounts and proportions of these components generally vary from battery to battery, but slurries typically have about 50% to 80% graphite, about 40% to 10% carbon and about 10% PVDF (all percentages are weight percentages). including. In an exemplary embodiment, a portion of the graphite component of the slurry is suitably replaced with the additive of the present invention. For example, the additive replaces about 1 wt.% To about 80 wt.% Slurry (which replaces an equal amount of graphite). For example, the additive may be about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9% by weight. About 10%, about 11%, about 12%, about 13%, about 14%, about 15%, about 16%, about 17%, about 18%, about 19% About 20%, about 21%, about 22%, about 23%, about 24%, about 25%, about 26%, about 27%, about 28%, about 29% About 30%, about 31%, about 32%, about 33%, about 34%, about 35%, about 36%, about 37%, about 38%, about 39% About 40%, about 41%, about 42%, about 43%, about 44%, about 45%, about 46%, about 47%, about 48% %, About 49%, about 50%, about 51%, about 52%, about 53%, about 54%, about 55%, about 56%, about 57%, about 58% %, About 59%, about 60%, about 61%, about 62%, about 63%, about 64%, about 65%, about 66%, about 67%, about 68% %, About 69%, about 70%, about 71%, about 72%, about 73%, about 74%, about 75%, about 76%, about 77%, about 78% %, About 79% by weight, or about 80% by weight slurry.
In an exemplary embodiment, the additive of the present invention further comprises a conductive polymer (eg, a carbon-based polymer) disposed on the nanostructure. Exemplary conductive polymers are described herein and are otherwise known in the art, such as PVDF, polypyrrole, polythiophene, polyethylene oxide, polyacrylonitrile, poly (ethylene succinate). ), Polypropylene, poly (β-propiolactone), styrene butadiene rubber (SBR), carboxymethyl cellulose salt (CMC), and sulfonic acids such as NAFION® (commercially available from DuPont Chemicals of Wilmington) Including fluoropolymer, polyimide, poly (acrylic acid) and the like. The conductive polymer is suitably dispersed evenly on the nanostructure interface, eg, along the length of the nanowire. The nanostructure, suitably the interface between the nanowire and the conductive polymer, further allows for a fast charge / discharge cycle of electrodes produced using such materials. Furthermore, the conductive polymer coating on the nanowires helps to accommodate the nanowire volume changes associated with alkali metal intercalation.
In a further embodiment, the present invention provides a battery slurry comprising one or more of the carbon-containing Si-based nanostructures as described herein. Exemplary properties of nanostructures are described throughout. As described herein, the slurry suitably comprises about 1 wt% to about 80 wt% carbon-containing Si-based nanostructure (suitably replacing an equivalent amount of graphite in the slurry). .
As described herein, in an exemplary embodiment, the slurry further includes a carbon-based material in addition to the nanostructures described throughout. For example, the slurry suitably includes carbon or graphite in addition to the nanostructure (along with the polymer electrolyte).
In another embodiment, the additive of the present invention suitably comprises one or more nanostructures disposed on a carbon-based substrate (nanostructure-carbon-based substrate composition). As shown in FIG. 1B, additive 110 suitably includes nanostructures 114 disposed on a carbon-based substrate 112. In additional embodiments, as shown in FIG. 1E, additive 110 ′ suitably includes nanostructures 114 disposed on carbon-based powder 112 ′. Suitably, the carbon-based powder 112 'includes particles of about 5 microns to about 50 microns, about 10 microns to 30 microns, about 15 microns to about 25 microns, or about 20 microns. Note that the components shown in FIGS. 1A-1E are not to scale and are provided for illustration only. As described throughout, exemplary nanostructures that can be utilized in the practice of the present invention include nanowires, nanoparticles, or nanofilms.
As used herein, the term “disposed” includes following (or over) or adhering to another element and / or adjacent to another element. ) Refers to any method of placing a single element, including spraying, layering, deposition, painting, dipping, bonding, coating, growth, formation, deposition, and the like. Suitably the nanostructure is grown on a carbon-based substrate . For example, as described throughout, suitably the nanostructures 114 were grown directly on the carbon-based substrate 112, or grown separated from the carbon-based substrate 112, and then disposed on the carbon-based substrate 112 (Eg, attached or otherwise incorporated) nanowires.
For example, a catalytic metal including a metal foil or a colloid (eg, a gold colloid) is first disposed on a carbon-based substrate . The catalytic metal is then contacted with one or more precursor gases to grow the nanowire using a VLS process. A method for producing nanowires using such a VLS process is disclosed, for example, in published US patent application US-2003-0089899, the disclosure of which is incorporated herein by reference. Additional methods for producing nanowires are described herein and are known in the art. In an exemplary embodiment, in order to produce high density nanowires in large quantities, the disclosure of which is hereby incorporated by reference in its entirety, U.S. Provisional Application No. 61 / 221,501, the title “Methods for Growth of High Density Nanowires”, Attorney Docket No. 2132.06800000 is used. In such embodiments, after the nanowire growth, nanowires, alone can be recovered, then, can be disposed on the carbon-based substrate, or in other embodiments, the carbon-based substrate nanowires and the nanowires are disposed thereon Are collected together. Nanowires and nanowire-carbon-based substrates can then be utilized as additives as described herein. Additional processing such as ball milling, grinding or other mechanical mechanisms to break the nanowires and additives into smaller pieces or shorter segments can also be used.
In one embodiment, the Si-based nanostructure may be a carbon-based powder, such as graphite, without the micropores for making the Si-based nanostructure disposed on the graphite powder as shown in FIG. 1E. Grows on the powder. Suitably, the Si-based nanostructures may include Si-based nanowires, Si-based nanofibers, Si particles, Si-based thin layers, and / or Si-based films. In additional embodiments, other materials capable of Li intercalation can be used to grow nanostructures on carbon-containing powders (eg, graphite powder).
Embodiments of the present invention achieve improved conductivity by growing Si-based nanostructures on graphite powder. Furthermore, Si-based nanostructures disposed on graphite powder can be used in battery-electrode slurries and battery-electrode layers that take advantage of the high capacity of Si and the high conductivity of graphite powder.
Additional embodiments of the present invention provide a carbon coating on Si-based nanowires that may make it easier to integrate Si-based nanowires into carbon-based slurries for lithium ion batteries. In this way, improved conductivity is achieved. Lithium ion battery slurries typically include a binder comprising a carbon-containing polymer (eg, styrene butadiene rubber (SBR), carboxymethyl cellulose (CMC), polyvinylidene fluoride (PVDF), etc.). In embodiments, the binder is used as a carbon source for carbon-coated Si nanowires. Carbonization of Si nanowires using a battery slurry binder suitably improves the interaction between the carbonized Si nanowires and the battery slurry.
The composition of the present invention comprising nanostructures disposed on the carbon-based substrate is herein nanostructures - carbon-based substrate composition, the nanowire - carbon-based substrate composition, or simply also referred to as nanostructure composition or nanowire composition The
As used herein, “carbon-based substrate ” refers to a substrate comprising at least about 50% by weight carbon. Suitably, the carbon-based substrate comprises at least about 60 wt% carbon, 70 wt% carbon, 80 wt% carbon, 90 wt% carbon, 95 wt% carbon or about 100 wt% carbon, including 100% carbon. Exemplary carbon-based substrates that can be used in the practice of the present invention include, but are not limited to, carbon powders such as carbon black, fullerene soot, desulfurized carbon black, graphite, graphene, graphene powder or graphite foil. As used throughout, “carbon black” refers to a material produced by incomplete combustion of petroleum products. Carbon black is a form of amorphous carbon with a very high surface area to volume ratio. “Graphene” refers to a monoatomic layer of carbon formed as a sheet and can be prepared as graphene powder. See, for example, US Pat. Nos. 5,677,082, 6,303,266, and 6,479,030, the disclosures of each of which are incorporated herein by reference in their entirety. The “carbon base ” specifically excludes metal materials such as steel including stainless steel. The carbon-based substrate can be in the form of a sheet or individual particles, as well as a crosslinked polymer structure.
Suitably, the nanostructure-carbon-based substrate composition, the carbon-containing Si-based nanostructure, and / or the skeletal-based nanostructure can be easily manipulated as described herein, i.e., as additives An “ink” is formed which can be added to the battery slurry or used in preparing the battery electrode.
Si-containing nanostructures (ie, Si-based nanostructures), including Si nanowires and Si nanoparticles, are suitably due to their ability to absorb capacity changes associated with charging and discharging cycles of rechargeable batteries. Used in the practice of the present invention. Silicon has the highest known capacity of all materials, and lithiated silicon (Li 15 Si 4 , the highest lithiated phase achievable with silicon ambient temperature lithiation) is about 3579 mAh prior to lithiation. / G (milliampere hours per gram) corresponding capacity. In addition, silicon is abundant and inexpensive and safer to manufacture and use than graphite. However, from x-ray data, the calculated density of Li 15 Si 4 is 1.179 g / cm 3 . Thus, when silicon is fully lithiated to Li 14 Si 4 , a volume expansion of 280% occurs and has a maximum theoretical volume capacity of 2190 mAh / cm 3 after lithiation. Because of this volume expansion, bulk silicon has become impractical for use in batteries because the material decomposes during repeated charge and discharge cycles, thus greatly limiting battery life.
For example, the nanostructures of the present invention, such as skeletal nanostructures, nanowires comprising Si nanowires disposed on a carbon-based substrate , or carbon-containing Si-based nanowires can be used for lithiation during repeated charge / discharge cycles. Absorb the associated capacity changes. The use of carbon-based structures such as graphene, carbon black, and other carbon-based substrates helps absorb volume changes in the slurry because the structure is easily bent, bent and stretched. Furthermore, the overall structure of the nanowire allows for volume changes in the slurry without generating excessive force due to wire distortion during deformation. The carbon shell or sheet around the Si-based nanowire further helps to absorb the capacitance change.
As described herein, in embodiments, nanowires used in the practice of the present invention have a core-shell structure. Suitably, the nanowire includes a crystalline core and a non-oxide amorphous shell. That is, the nanowire shell does not contain oxides. In further embodiments, the shell can include an oxide, such as with silicon nanowires. In a further embodiment, the nanowire can be a core-shell-shell structure (or additional shell). Exemplary core shell (and core shell-shell) nanowire compositions are described throughout. Suitably, the nanowire shell is an alkali metal alloy forming material, such as a lithium alloy forming material. Suitably, it has a material that allows alkali metal (eg Li) intercalation, or high Li solubility (eg> 0.1%). Suitably, the core or first shell of the nanowire is a good thermal conductor (eg k> 0.2 Wm −1 K (watt per meter × Kelvin) thermal conductivity) at room temperature and good conductivity Body (eg R <5 ohm resistance).
In exemplary embodiments, the carbon-containing Si-based nanowires, nanowire carbon-based substrate compositions, or skeletal nanostructures of the present invention form a porous network in which the nanowires are intertwined, interlaced, or overlapped. This arrangement takes the form of a porous structure in which the pore sizes between the nanowires are suitably mesopores and macropores. As used herein, the term “mesopore” is larger than a micropore (a micropore is defined as less than about 2 nm in diameter), but is a macropore (a macropore is greater than about 50 nm in diameter) Smaller pores), suitably having a pore size in the range of greater than about 30 nm and less than about 200 nm in diameter. Suitably, the composition of the present invention is substantially free of micropores, ie, less than about 0.1% of the pores are micropores (ie, less than about 2 nm in diameter). Porous nature These nanowire structures allow for increased mass transport of electrolyte through the structure, resulting in rapid diffusion of alkali metal ions.
In a suitable embodiment, the nanowire comprises a shell comprising Si, suitably a Si core, and C. Nanowires comprising a SiC core or SiC shell can also be used, but suitably the nanowire does not contain a carbide shell (ie SP 3 carbon), but instead a carbon shell (ie SP 2 carbon) covalently bonded to the silicon core. Including only. In the case of SiC nanowires, the carburization process is appropriately controlled to produce partially carburized Si nanowires (see published US patent application No. 2008/0280169) with tightly bonded carbon nanoparticles. . The nanowires of the present invention can accommodate volume changes associated with alkali metal (eg, Li) intercalation. Other suitable materials for use in the nanowire core, are described herein, including TiO 2.
The use of a core-shell (or multiple-shell) nanowire structure in the composition of the present invention provides enhanced cycling (charge / discharge) performance, most likely due to the formation of a passivating film on the nanowire interface. provide. Initial capacity loss occurs due to electrolyte depletion on the nanowire surface, thereby forming a solid electrolyte interface (SEI) on the nanowire surface, or irreversible alkali metal (eg Li) insertion / intercalation into the nanostructure there is a possibility. Pre-formation (by chemical modification) of an artificial SEI layer on the nanostructure and / or pre-lithiation of the nanostructure can be used to improve performance. In an embodiment, the shell includes a metal such as Cu, tin oxide, Ni and / or a metal oxide. Si nanowire surface conductivity can be improved in this way, and the volume change of Cu / SiNWs or Ni / SiNWS can be reduced so that a thin, high density and stable SEI can be maintained on the surface. . Such metal and / or metal oxide shells can further reduce the consumption of Li in the battery. A shell containing a metal oxide such as tin oxide, for example, allows Li ions to diffuse through the shell and prevents penetration of the solvent in the electrolyte.
In embodiments, the nanowires used in the present invention can further include nanoparticles on their surface. For example, the nanoparticles can be graphite or graphene particles or layers. In embodiments where nanowires are used to prepare the anode, suitably the nanowires further comprise Si or TiO 2 nanoparticles on their interfaces, as described herein. Can do. In embodiments where nanowires are used to prepare the cathode, the nanowires can include nanoparticles such as LiNiSiO 4 , LiNiSiO, LiFeO 2 . The nanoparticles that decorate the surfaces of the nanowires of the present invention are utilized in an efficient manner (intercalating or alloying) due to the high curvature of the nanowire surfaces (eg, radii of less than about 100 nm) on which they are disposed. For this reason, a large number of nanoparticles are exposed to the external environment.
Li-Si alloy compositions can be passivated in a polar aprotic electrolyte solution and by a Li ion conductive surface film that behaves like a solid electrolyte interface. Ionic liquids can also be introduced to modify the Si nanowire surface chemistry. For this reason, surface chemical modification is realizable by adjusting the component in electrolyte solution.
Exemplary dimensions of the nanowires of the present invention are described throughout. Suitably, the nanowire has a diameter of about 10 nm to about 500 nm, or about 20 nm to about 400 nm, about 20 nm to about 300 nm, about 20 nm to about 200 nm, about 20 nm to about 100 nm, or about 40 nm to about 100 nm. Suitably, the nanowire has a length of about 100 nm to about 100 μm, or about 1 μm to about 75 μm, about 0.1 μm to about 50 μm, or about 1 μm to about 20 μm. Suitably, the aspect ratio of the nanowire is up to about 2000: 1, or suitably up to about 1000: 1. Such a high aspect ratio allows electrons generated on the nanowires to pass between the nanowires to the motorized electrode at high speed. In addition, nanowires having a diameter of less than about 50 nm and an aspect ratio greater than about 1000: 1 undergo volume changes associated with cycling during charge and discharge states, as described herein. Show greater flexibility.
In a further embodiment, the nanowire for use in the practice of the present invention can be a porous nanowire, such as a porous Si nanowire. Electrochemical cycling during lithiation and non-lithiation produces pores in the nanostructured walls. It is postulated that the presence of these pores may increase the ability of the nanostructure to accommodate volume changes and to expand the surface area available for contact with the conductive polymer and alkali metal. The preparation of porous nanostructures including porous nanowires can be performed by electrochemical cycling. In additional embodiments, the pore-forming material can be incorporated into the nanostructure and then removed to create a porous nanostructure. For example, Sn or other secondary components can be incorporated into the nanostructure (eg, Si nanowires) and then removed by chemical (eg, etching) or physical methods. These porous nanostructures, including porous Si nanowires, are then utilized in carbon-containing Si-based nanostructure compositions, nanostructured carbon-based substrate compositions, skeletal nanostructures, and additives of the present invention.
Preparation of the additive of the present invention, including carbon-containing Si-based nanowires, nanowire carbon-based substrate compositions, and skeletal nanostructures, is disclosed in published US Patent Application No. 2008/0224123 (disclosure thereof) for producing high density nanowire compositions. Appropriately utilize nanowire alignment methods such as those disclosed by reference), which are hereby incorporated by reference in their entirety. Exemplary alignment methods include deposition of the fluid using the flow and shear extrusion (shear extrusion), which as well as carbon-based substrate, e- field (e-field) alignment and various substrates for aligning nanowires . Spray can be utilized to introduce nanowires and / or conductive polymers into the nanowires. Nanowires can also be bent and compressed to form denser and interwoven compositions.
As described herein, the additive of the present invention can be added appropriately to current existing battery slurries, replacing a portion of the slurry, such as a portion of the graphite component. Battery slurries utilized in commercial grade batteries generally include a mixture of graphite, carbon and polymer electrolytes (eg, polyvinylidene difluoride (PVDF). The amounts and ratios of these components generally vary from battery to battery, The slurry typically includes about 50% to 80% graphite, about 40% to 10% carbon, and about 10% PVDF (all percentages are weight percentages) In an exemplary embodiment, the graphite component of the slurry Is suitably replaced by the additive of the present invention, for example, the additive replaces about 1% to about 80% by weight slurry (replaces an equal amount of graphite).
In an exemplary embodiment, the additive of the present invention further comprises a conductive polymer disposed on the nanostructure. Exemplary conductive polymers are described herein and are otherwise known in the art, such as PVDF, polypyrrole, polythiophene, polyethylene oxide, polyacrylonitrile, poly (ethylene succinate) Sulfonic acid fluoro, such as polypropylene, poly (β-propiolactone), styrene butadiene rubber (SBR), carboxymethylcellulose salt (CMC), and NAFION® (commercially available from DuPont Chemicals of Wilmington). Contains polymer. The conductive polymer is suitably uniformly distributed on the surface of the nanostructure, for example along the length of the nanowire. The interface between the nanostructures, suitably nanowires, and the conductive polymer further allows for fast charge / discharge cycles of electrodes prepared using such materials. In addition, conductive polymer coatings on the nanowires also help to accommodate the nanowire volume changes associated with alkali metal intercalation.
In further embodiments, the present invention includes one or more of carbon-containing Si-based nanostructures, nanostructure-carbon-based substrate compositions, and / or skeletal nanostructures, as described herein. A battery slurry is provided. Exemplary properties of nanostructures are described throughout. As described herein, suitably, the slurry has from about 1% to about 80% by weight of the nanostructured carbon-based substrate composition (suitably replaces an equal amount of graphite in the slurry). Including.
As described herein, in an exemplary embodiment, the slurry further includes a carbon-based material in addition to the nanostructures described throughout. For example, the slurry suitably includes carbon or graphite in addition to the nanostructure (as well as the polymer electrolyte).
The present invention further provides battery electrodes comprising one or more additives of the present invention (ie, carbon-containing Si-based nanostructures, nanostructure-carbon- substrate based compositions, and / or skeletal nanostructures). As shown in FIG. 1C and FIG. 1F, suitably such battery electrodes 120 and 120 ′ comprise the carbon-containing Si-based nanostructure 100 of FIG. 1A, the nanostructure-carbon- substrate composition 100 shown in FIG. 1B, Or prepared from 100 ′ shown in FIG. 1E and / or the skeletal nanostructure shown in FIG. 1D. As shown in FIG. 1F, suitably, the battery electrode 120 ′ may be further prepared from nanostructures 114 deposited on the carbon-based powder 112 ′. The additives of the present invention can be used to prepare battery anodes and / or cathodes. In exemplary embodiments, the electrode may be of some type of additive (eg, the carbon-only Si-based nanostructure 100 of FIG. 1A, the nanostructure-carbon- substrate system composition 110 shown in FIG. 1B, or the 100 shown in FIG. 1E. Or in other embodiments, the carbon-containing Si-based nanostructure 100 of FIG. 1A, the nanostructure-carbon- substrate system composition 110 shown in FIG. 1B, or 100 'of FIG. 1E and / or a mixture of skeletal nanostructures 150 shown in FIG. 1D.
As described throughout, suitably the nanostructure for use in the battery electrode is a nanowire, nanoparticle, or nanofilm. Exemplary compositions of nanostructures including core-shell and core-shell shell nanowires have been described throughout. In an exemplary embodiment, the nanostructure is a Si nanostructure comprising a Si nanowire and a core-shell nanowire whose core is Si, and a shell C covalently bonded to the core. Exemplary sizes of nanowires for use with battery electrodes are described throughout.
As described herein, suitably the nanostructure composition replaces about 1% to about 80% by weight of the battery slurry. Thus, when used to prepare battery electrodes, the nanostructure composition further comprises from about 1 wt% to about 80 wt% electrode, suitably from about 5 wt% to about 20 wt%, about 5 wt%. From about 5% to about 15%, about 5% to about 10%, or about 10% by weight of the battery electrode.
In suitable embodiments, the composition of the present invention suitably comprises a conductive polymer disposed on the nanostructure. Exemplary conductive polymers are described herein, for example, polyvinylidene difluoride, polypyrrole, polythiophene, polyethylene oxide, polyacrylonitrile, poly (ethylene succinate), polypropylene, poly (β-pro Piolactone), styrene butadiene rubber (SBR), carboxymethylcellulose salt (CMC), and NAFION® (commercially available from DuPont Chemicals, Inc., Wilmington). The conductive polymer further functions as a binder material when forming the electrode 120.
In a further embodiment, the carbon-containing Si-based nanostructure, the nanostructured carbon-based substrate , and the skeletal nanostructure of the battery electrode further comprises an alkali metal (eg, lithium (Li), sodium (Na), potassium (K), rubidium. (Rb), cesium (Cs), or francium (Fr)). For example, the nanostructure of the present invention can be embedded in an alkali metal foil such as a lithium (Li) foil. Composite materials of nanostructure compositions and alkali metals (eg, alkali metal films) have high electrical conductivity and, as described throughout, nanostructures (eg, Si) to accommodate large volume changes due to ion insertion. The ability of nanostructures.
The present invention further provides batteries comprising the various carbon-containing Si-based nanostructures, nanostructured carbon-based substrate compositions, and / or skeletal nanostructures of the present invention. The schematic shown in FIG. 2 of the battery 200 of the present invention is provided for illustration only. The schematic is not shown to scale, and the orientation and placement of the battery components is provided only to help explain the present invention. Additional components, orientation and arrangement of the battery are known in the art.
In an embodiment, the battery 200 suitably comprises an anode 202, as shown in FIG. Suitably, the anode 202 comprises one or more of the nanostructure compositions as described herein. In an exemplary embodiment, the anode includes a carbon-containing Si-based nanostructure. In other embodiments, the anode comprises a nanostructured carbon-based substrate composition. In a further embodiment, the anode comprises a skeletal nanostructure. In yet another embodiment, the anode can comprise any of these different nanostructure compositions, or a plurality of anodes, each comprising one or any of these nanostructure compositions. Exemplary nanostructures including nanowires and compositions of such nanostructures (and nanowires) are described herein. Suitable sizes for nanowires used in batteries are described throughout. In addition, exemplary carbon-based substrates are also described herein and include carbon-based powders, carbon black, graphite, graphene, graphene powder, and graphite foil.
Carbon-containing Si-based nanostructure compositions, nanostructured carbon-based substrate compositions, and skeletal nanostructures, and the additive of the present invention can be utilized in any battery type. In an exemplary embodiment, the battery of the present invention is a Li ion battery. That is, the battery is suitably a rechargeable battery in which lithium ions 206 move between the anode 202 and the cathode 204. Lithium ions move from the anode to the cathode during discharge, and conversely from the cathode to the anode during charging.
As described herein, the ability of Li to insert into an alkali metal, eg, a nanostructure of the present invention, provides increased capacitance. However, due to the ability of nanostructures to include nanowires (eg, Si nanowires) to absorb the volume changes associated with this insertion, the anode remains structurally sound. The ability of lithium to insert into nanowires, particularly Si nanowires, provides a dramatic improvement in the capacitance of anodes prepared from such materials.
Suitably, the anode 202 of the battery 200 of the present invention comprises from about 1 wt% to about 80 wt% (suitably from about 5 wt% to about 20 wt%, or about 10 wt%) of the nanostructure of the present invention. Including. Conductive polymers such as polyvinylidene difluoride, styrene butadiene rubber (SBR), or carboxymethylcellulose are also suitably disposed on the nanostructure. In the exemplary embodiment, anode 202 includes Si nanostructures embedded in a Li foil.
As shown in FIG. 2, suitably, the battery 200 not only separates the anode and cathode from each other, but also allows the passage of ions through the separator 208 between the anode 202 and the cathode 204. It further includes a cathode 204 and a separator 208 (eg, an electrolyte separator) disposed therebetween. In an exemplary embodiment, the cathode 204 is a lithium-based cathode such as, but not limited to, LiCoO 2 , LiFePO 4 , LiMnO 2 , LiMnO 4 , LiNiCoAlO / LiNiCoMnO + LiMn 2 O 4 , LiCoFePO 4 and LiNiO 2. Any suitable material known for use as a battery cathode can be included. Exemplary materials for separator 208 include porous polymeric materials that have good ionic conductivity and sufficiently low conductivity. Suitable materials include PVDF, polypyrrole, polythiophene, polyethylene oxide, polyacrylonitrile, poly (ethylene succinate), polypropylene, poly (β-propiolactone), and sulfonic acid fluoropolymers such as NAFION®, and , And others known in the art. Battery 200 further includes an electrolyte 218, suitably 1: 1 w: w, ethylene carbonate: diethyl carbonate, and an alkali metal salt (eg, Li salt) dissolved in an organic solvent, such as LiPF 6 . Alternatively, the electrolyte 218 can include an alkali metal salt (eg, a Li salt) mixed with an ion conductive material such as a polymer or inorganic material to form a suspension. Alternatively, the electrolyte 218 can include additives [including a list from an email. ]
As shown in FIG. 2, in the exemplary embodiment, battery 200 further includes a housing 210 that houses an anode, an electrolyte separator, and a cathode. Suitable shapes and materials for the housing 210 (e.g., metals, polymers, ceramics, composite materials, etc.) are known in the art and include laminate housings composed of a metal layer and a synthetic resin layer. For example, a nylon film, an aluminum foil and a polyolefin film layer constituted in this order. The polyolefin membrane is suitably melted or bonded with an adhesive to constitute the inside of the housing. The polyolefin film may be, for example, a polypropylene film, a polyethylene film, or a modified polyethylene film. Battery 200 further includes electrodes 214 and 216, suitably comprising a metal such as aluminum, copper, nickel or stainless steel, which can be coupled to load 212.
In an embodiment, the present invention provides a method for preparing an additive for use in a battery slurry. As shown in flowchart 2000 of FIG. 20, referring to FIG. 1E, such a method suitably includes, in step 2002, providing a carbon-based powder. The carbon-based powder may include, for example, graphite particles having a size of about 5 microns to about 50 microns, about 10 microns to about 30 microns, about 15 microns to about 25 microns, or about 20 microns. In step 2004, Si-based nanostructures are disposed on the carbon-based powder. Suitably, the Si-based nanostructure is a Si nanowire or Si nanofiber grown on a carbon-based powder. A method for growing Si nanowires is provided herein. Such a method includes disposing a carbon-containing polymer on the Si-based nanostructure and heating the carbon-containing polymer to form a carbon coating on the Si-based nanostructure, as shown in step 2006. Further, it may optionally be included. Exemplary heating temperatures and times are described herein.
In a further embodiment, the present invention provides a method of preparing a battery electrode. As shown in flowchart 300 of FIG. 3A, with reference to FIGS. 1A and 1C, suitably such method includes providing one or more carbon-containing Si-based nanostructures 100 at step 302. In step 304 of flowchart 300, the nanostructures are mixed with a conductive polymer and a carbon-based material to form a slurry. In step 306, slurry is formed on battery electrode 120.
Exemplary nanostructures including nanowires are disclosed herein as nanostructure compositions and properties. Suitably, the nanostructure is a Si nanowire comprising a core-shell (or core-shell shell) nanowire, wherein the core of the nanowire comprises Si.
As described throughout, suitably the carbon-containing Si-based nanostructure composition of the present invention is utilized as an additive to conventional battery slurries to produce electrodes (eg, anodes). As described throughout, suitably such additives are from about 1 wt% to about 80 wt% electrode, more suitably from about 5 wt% to about 20 wt%, or about 10 wt%. Provided at the electrode. As described herein, suitably the electrode prepared according to the method of the present invention is the anode of a lithium ion battery.
Step 304 of the flowchart 300 suitably mixes the carbon-containing Si-based nanostructure composition with a conductive polymer such as polyvinylidene difluoride, styrene butadiene rubber (SBR), and / or carboxymethyl cellulose salt (CMC). Including doing. Other suitable conductive polymers are described herein or otherwise known in the art. The carbon-containing Si-based nanostructure composition is further suitably mixed with additional carbon-based material. Examples of such additional carbon-based substrates are described throughout and include carbon, carbon black, graphite, graphene, graphene powder or graphite foil. This combination forms a battery slurry that is commonly used to form electrodes.
The present invention provides a further method of preparing battery electrodes. Referring to FIGS. 1B and 1C, as shown in flowchart 310 of FIG. 3B, suitably such method includes, in step 312, one or more nanostructures disposed on carbon-based substrate 112 or 112 ′. Providing 114 or 114 ′. In step 304 of flowchart 300, the nanostructures are mixed with a conductive polymer and a carbon-based material to form a slurry. In step 316, a slurry is formed on the battery electrode 120 or 120 ′.
Exemplary nanostructures including nanowires are disclosed herein, as well as the composition and properties of the nanostructures. Suitably, the nanostructure is a Si nanowire comprising a core-shell (or core-shell shell) nanowire in which the core of the nanowire comprises Si. Exemplary carbon-based substrates are further described herein and suitably include carbon black, graphite, graphene, carbon-based powder, graphene powder, or graphite foil.
As described throughout, the nanostructure-carbon-based substrate composition of the present invention is suitably utilized as an additive in conventional battery slurries to produce electrodes (eg, anodes). As stated throughout, such additives are suitable for about 1% to about 80% by weight electrode, more suitably about 5% to about 20% by weight, or about 10% by weight electrode. Provided to. As described herein, suitably the electrode prepared according to the method of the present invention is the anode of a lithium ion battery.
Step 314 of flowchart 310 suitably includes mixing the nanostructured carbon-based substrate composition with a conductive polymer such as polyvinylidene difluoride. Other suitable conductive polymers are described herein or otherwise known in the art. The nanostructured carbon-based substrate composition is suitably mixed with additional carbon-based material (in addition to the carbon-based substrate on which the nanostructure is disposed). Examples of such additional carbon-based substrates are described throughout and include carbon, carbon black, graphite, graphene, graphene powder or graphite foil. This combination forms a battery slurry that is typically used to form electrodes.
Referring to FIGS. 1A, 1C and 2, as shown in flowchart 400 of FIG. 4A, the present invention further provides a method of preparing battery 200. Suitably, in step 402 of flowchart 400, the method includes providing one or more carbon-containing Si-based nanostructures 100. In step 404, the nanostructures are mixed with a conductive polymer and a carbon-based material to form a slurry. In step 406 of flowchart 400, slurry is formed on anode 202. Separator material 208 is then disposed between anode 202 and cathode 204 at step 408.
Referring to FIGS. 1B, 1C, and 2, as shown in flowchart 410 of FIG. 4B, the present invention further provides an additional method of preparing battery 200. Suitably, in step 412 of flowchart 410, the method includes providing one or more nanostructures 114 disposed on the carbon-based substrate 112 or 112 ′. In step 414, the nanostructures are mixed with a conductive polymer and a carbon-based material to form a slurry. In step 416 of flowchart 410, slurry is formed on anode 202. Separator material 208 is then disposed between anode 202 and cathode 204 at step 418.
Methods for preparing lithium batteries and suitable components for cathodes, separator materials, and electrolytes are described, for example, in “Lithium batteries: Science and Technology”, G Nazri and G. Pistoia, eds. , Springer, New York (2004), the disclosure of which is hereby incorporated by reference in its entirety. These known methods are suitably combined with the methods and nanostructure compositions described herein for preparing batteries.
As described throughout, exemplary nanostructures include nanowires, nanoparticles, or nanofilms, suitably Si nanostructures such as Si nanowires, and core-shell (including core-shell shell) nanowires. Suitable properties and sizes of nanostructures such as nanowires have also been described throughout. Exemplary carbon-based substrates are also described herein.
Suitably, the carbon-containing Si-based nanostructures, nanostructured carbon-based substrate compositions, and skeletal nanostructures of the present invention comprise about 1 wt% to about 80 wt% anode, suitably about 10 wt%. In suitable embodiments, the nanostructures are mixed in step 404/414 with a polyvinylidene difluoride conductive polymer and graphite and / or carbon to prepare a slurry that will eventually become the battery anode. Additional conductive polymers and carbon-based materials are described herein.
In a suitable embodiment, a conductive polymer membrane (separator 208) is disposed between the anode and cathode at step 408/418. Exemplary conductive polymer films are disclosed herein or otherwise known in the art.
Methods for preparing anodes, separators and cathodes to form a battery include rolling, heating, drying and storage methods known in the art (including temperature and time). For example, “Lithium batteries: Science and Technology”, which is incorporated herein by reference in its entirety, and US Pat. Nos. 6,165,642, 7,541,114, 6,440. No. 5,606, No. 5,681,357, No. 5,688,293, and No. 5,834,135.
As described herein, the carbon-containing Si-based nanostructure composition, nanostructured carbon-based substrate composition, and skeletal nanostructure of the present invention are used as additives in conventional battery electrode (eg, anode) formation techniques. Used properly. For this reason, these additives simply add a portion of the battery electrode slurry to the currently disclosed additives (eg, from about 1 wt% to about 80 wt%, suitably from about 5 wt% to about 20 wt%). Or about 10% by weight) and can be easily substituted in the battery manufacturing process. The remainder of the conventional battery formation process is performed next. No additional modification is required when using the additive of the present invention, but the process can be further modified if desired.
The present invention provides a further method of preparing carbon-coated nanostructures. As shown in flowchart 1900 of FIG. 19, referring to FIG. 1D, suitably such a method includes providing a nanoscale scaffold 152 in step 1902. Exemplary nanoscale frameworks include nanowires, nanopowders, nanorods, nanofilms, nanotubes, branched nanocrystals, nanotetrapods, tripods, bipods, nanocrystals, nanodots, quantum dots, nanoparticles, branched tetrapods (e.g. Inorganic dendrimer).
In step 1904 of flowchart 1900, the carbon-containing polymer is disposed on the nanoscale backbone 152. The carbon-containing polymer may include, for example, styrene butadiene rubber (SBR), carboxymethyl cellulose (CMC), polyvinylidene fluoride (PVDF), and the like, and combinations thereof.
In step 1906, the carbon-containing polymer is heated to form a carbon coating 156 on the nanoscale framework 152. The carbon-containing polymer may be heated to about 160 ° C to about 1000 ° C. For example, the carbon-containing polymer may be heated to about 200 ° C to about 400 ° C, about 250 ° C to about 350 ° C, or about 300 ° C. As another example, it may be heated to about 600 ° C to about 800 ° C, about 650 ° C to about 750 ° C, or about 700 ° C. As a further example, this may be heated to about 800 ° C to about 1000 ° C, about 850 ° C to about 950 ° C, or about 900 ° C. The carbon-containing polymer may be heated for about 30 minutes to about 5 hours, about 1 hour to about 3 hours, or about 2 hours. Heating may be performed in the presence of an inert gas such as neon, argon, krypton, or xenon.
As illustrated in step 1908, such a method may further optionally include a Si-based layer 154 (eg, crystalline Si and / or non-crystalline) on the nanoscale framework 152 prior to the deposition of the carbon-containing polymer. Disposing crystalline Si), in which case the carbon-containing polymer is disposed on the Si-based layer 154.
As described herein, provisional patent application filed on May 19, 2009, in the examples set forth below, and the disclosure of which is hereby incorporated by reference in its entirety. In 61 / 179,663, the present invention overcomes the limitations of bulk silicon and takes advantage of the high charge capacity of silicon in the form of nanowires. The nanowires suitably have a diameter in the range of tens of nanometers and an aspect ratio of about 1000. Nanowires can absorb large volume changes caused by lithiation and non-lithiation on charge and discharge without losing their structural integrity.
The following example describes the performance of actual silicon nanowires (Si NW). For implementation in Li-ion batteries, Si NW is suitably used as a low weight (about 5-30% by weight) excipient in the anode. This approach allows easy integration into existing product lines while providing significant performance improvements. It has been found that the addition of 10% by weight of SiNW results in a battery anode volume increase of about 30% to 50%.
Those skilled in the relevant art may be able to make other suitable modifications and adaptations to the methods and applications described herein without departing from the scope of the invention or any embodiment thereof. It will be readily apparent. Although the present invention has been described in detail herein, it is included herein for purposes of illustration only and is not intended to limit the present specification. This will be more clearly understood.
Preparation and characterization of Si nanowires Growth and shape of Si nanowires
A vapor-liquid-solid (VLS) method is utilized to grow Si nanowires. The wire is monocrystalline with a diameter of about 20 nm to about 200 nm and a length of about 1 μm to about 50 μm. The growth process allows a high degree of freedom in designing the shape, size, composition, etc. For example, nanowires are substantially straight and can be prepared with yields greater than about 99% (see FIG. 5A). For battery applications, interwoven, alternating or overlapping structures are suitably used (see FIG. 5B). Nanowires can be easily doped and further grown as alloys or multiphase materials. Suitably, Si nanowires of approximately 20-60 nm in diameter are produced in a core / shell configuration where the shell consists of a thin layer of carbon mostly covalently bonded to silicon. This carbon layer provides a path for electrical conductivity.
Suitable growth substrates for silicon nanowires for battery applications: carbon black, graphite, graphene
The method of the present invention can be utilized to prepare silicon nanowires on a variety of different substrate materials and form factors. For use as an additive to battery slurries, nanowires are suitably grown on carbon black, graphite, or uncured graphene nanosheet powder interfaces. In all three cases, it is very simple to mix the substrate / Si nanowire composition / additive into the anode material. As described throughout, growing Si nanowires on graphene or carbon powder allows the structure to accommodate large volume changes during lithiation and non-lithiation of Si material. For this reason, the Si nanowire material can be directly used for graphite ink or slurry.
Carbon black is an efficient growth substrate for nanowires as well as matrix materials suitable for battery anodes and can be easily integrated into slurry formation. Nanowires can be grown on carbon black, as well as other substrates , at a density that can be tuned over a wide range and thus can meet the desired performance characteristics. FIG. 6 shows a SEM micrograph of silicon nanowires grown on carbon black. Nanowires form interwoven and overlapping networks that provide large surface areas and easy access for lithiation and ion and electron transfer.
The micrographs in FIGS. 7A and 7B show Si nanowires grown on high (A) and low (B) magnification graphite foils. FIGS. 24A and 24B show low magnification (A) and high magnification (B) Si nanowires. The average diameter of the nanowire is about 45 nm.
8A and 8B show SEM micrographs of unsolidified graphene microsheet powder (A) and silicon nanowires grown on graphene powder (B). The average diameter of the nanowire is 50 nm. Si nanowires grown on nano or micro graphene nanosheet powders provide the additive with high surface area and high mechanical flexibility. Both the graphite foil and the graphene powder both enable the volumetric variation of Si nanowires and provide high conductivity.
FIG. 9 shows a transmission electron microscope (TEM) micrograph of a silicon nanowire 900 having a crystalline core 902 and an amorphous shell 904. The Si nanowire suitably has a core-shell structure with a core that can be adjusted to the shell diameter ratio. The core is crystalline and shell amorphous. The final interfacial layer is a thin conductive layer of carbon that is largely covalently bonded to the shell. Nanowires have a radial dimension of approximately about 100 atomic radii, so that lattice distortion can be elastically absorbed during lithiation. If the strain becomes too large to be elastically compatible, a phase transformation from crystalline Si to amorphous Si occurs. Upon continuous incorporation of lithium atoms into the crystal, the nanowire eventually adapts to plastic deformation and increased strain due to protrusions or the generation of leaf-like structures 906 extending from the surface of the nanowire.
These protrusions of the thin film material reduce the conductivity of the Si material itself, thus reducing the capacity of the Si material during cycling. However, in the case of Si core nanowires coated with a C shell, these protrusions offer the advantage of creating a larger surface area and a shorter diffusion path for lithium ions compared to smooth nanowires. Furthermore, the loss of conductivity is avoided by the presence of carbon on the wire surface and on the carbon powder or graphite powder in the electrode. This additional surface area results in an increase rather than a reduction in the capacity of the battery anode containing the Si nanowires of the present invention with increasing number of charge cycles.
Nanowires provide an invisible continuous conductive path that is realized at the same level as spherical nanoparticles. Due to its inherent nature, a sphere has only a limited number of sphere-to-sphere point contacts that contribute to conductivity. Nanowires also provide additional degrees of freedom in adjusting porosity.
FIGS. 25A and 25B show a silicon nanowire with a crystalline core (about 15-20 nm thick), and a poly-Si shell covered with an amorphous (which may involve Si—O) and carbon shells (about TEM micrographs of combinations of 10-15 nm thickness). Referring to FIG. 25A, silicon nanowire 2500 has a crystalline core 2502 of approximately 14.76 nm with a carbon shell that includes a first side 2504 and a second side 2506. The first side 2504 of the carbon shell has a thickness of approximately 13.2 nm, and the second side 2506 of the carbon shell has a thickness of approximately 10.03 nm. Referring to FIG. 25B, silicon nanowire 2550 has a crystalline core 2552 of approximately 19.44 nm with a carbon shell that includes a first side 2554 and a second side 2556. The first side 2554 of the carbon shell has a thickness of approximately 13.93 nm and the second side 2556 of the carbon shell has a thickness of approximately 11.42 nm.
Capacity of Si nanowires on stainless steel electrode with lithium foil counter electrode
To measure the charge capacity and cycle efficiency of Si nanowires, nanowires were grown on a steel substrate as an anode, which was used with lithium foil as a counter electrode.
FIG. 10 shows the charge capacity and cycle efficiency of nanowires with two different diameters. A thinner (40 nm) diameter wire (black diamonds in the figure) has a bulk with a maximum capacity of 4200 mAh / g in the first cycle, with a first cycle efficiency of 85% (open squares in the figure). Realize the theoretical capacity of silicon. As the number of cycles increases, the charge capacity decreases, which is an experimental placement artifact caused by the loss of binders and additives. Thicker (80 nm) nanowires show less (2110 mAh / g) initial capacity (solid circles in the figure), which increases with increasing number of charge cycles. This behavior can be understood by the fact that the Li diffusion distance is longer and the strain relaxation due to surface protrusion is more difficult. The first cycle loss in this case is likewise 15% (open square in the figure).
These measurements clearly demonstrate that the theoretical charge capacity can be shown with a 40 nm thick wire. As described below, these Si nanowires have been used to develop electrodes that provide improved capacity that can be sustained for 80 cycles with little or no reduction.
Comparison of silicon nanowires with silicon thin films and powders
Si nanowires behave significantly differently than Si thin films, bulk Si, or Si powder. If silicon nanowires are generated on a stainless steel substrate, further, a thin layer of silicon is also generated between the nanowires based on stainless steel substrate. Thus, the measurements provided herein include contributions from both nanowires and Si thin films. FIG. 11 shows current versus potential curves obtained at 0.1 mV / s for Si NWs with different diameters. The acute apex at 0.48V is directly related to Si nanowires. A feature at 0.29 V is the signature of silicon in the form of a thin film. For very thin wires, the volume fraction of the thin film is large enough that its contribution can contribute to current versus potential scanning. The very large current at the silicon charge peak is part of the reason nanowires allow for rapid charging.
A distinctly different behavior is seen in FIG. 12, where a silicon thin film without nanowires is compared to a thin film with nanowires. In the scan on the sample with nanowires, an additional peak close to 0.5V is observed.
FIG. 26 shows a Fourier Transform Infrared Spectroscopy (FTIR) measurement showing the difference between SiNW and Si powder. FTIR suggests that Si—O extends at approximately 1070 cm −1 , indicating that SiO 2 may be present in the shell material.
Carbon coating on Si nanowires
The carbon coating suitably improves the conductivity of the Si nanowires and the ability to integrate the Si nanowires into the carbon-based slurry of the lithium ion battery. Carbon-based polymers (SBR, CMC, PVDF, etc.) are generally used as binders in battery slurries. In embodiments, the binder is used as a carbon source for carbon coating on Si nanowires. Carbonization of the carbon-based polymer to form a carbon coating on the Si nanowire may further improve the interaction between the carbon-based polymer and the carbon coating on the Si nanowire.
FIGS. 21A and 21B are photomicrographs showing Si nanowires 2104 having a carbon coating 2102. The carbon coating 2102 was realized by decomposing SBR (styrene butadiene rubber). In this example, Si nanowires 2104 were mixed with SBR and then heated at about 700 ° C. for 2 hours in the presence of argon to form a carbon coating 2102.
FIG. 22 is a photomicrograph showing Si nanowires 2204 having a carbon coating 2202. The carbon coating 2202 was realized by decomposing PVDF (poly (vinylidene fluoride)). In this example, Si nanowires 2204 were mixed with PVDF and then heated at about 900 ° C. for 2 hours in the presence of argon to form a carbon coating 2202.
Si nanowires with a carbon coating (eg carbon surface layer or carbon shell) exhibit better cycling performance when used in lithium ion batteries. The improved performance may be due to the formation of a passivation film on the surface of the electrode material, especially for Si and carbon coated Si.
23A and 23B are photomicrographs showing Si nanowires of embodiments of the present invention after several charge / discharge cycles. FIG. 23A shows that no significant morphological changes occurred after two charge / discharge cycles. FIG. 23B shows that the Si nanowires became more porous after 10 charge / discharge cycles.
Figures 23C and 23D are photomicrographs showing carbon-coated Si nanowires of embodiments of the present invention after several charge / discharge cycles. The Si nanowires in these figures were carbon coated using decomposed PVDF. After two charge / discharge cycles, as shown in FIG. 23C, there is no significant morphological change in the carbon-coated Si nanowires and the carbon coating remains unaffected. After 10 charge / discharge cycles, as shown in FIG. 23D, there is no significant morphological change in the carbon-coated Si nanowires, but the carbon coating splits along the length of the Si nanowires.
Preparation and characterization of anodes using nanowire carbon-based substrate additives Increased anode capacity and cycle life
A mixture of 80% graphite with 10% carbon and 10% PVDF (Li-GC-PVDF) was utilized as the battery slurry to approximate commercial battery specifications and for reference and control purposes. To determine the capacity of the nanowire material of the present invention, 10% graphite was replaced with 10% Si nanowire material (Li-SiNW-GC-PVDF). FIG. 13 shows the increase in capacity when using the resulting nanowires. The capacity increase is initially 30% and continues to increase to 50% after about 60 charge / discharge cycles. The increase in capacity with the number of cycles can be explained by examining the structure of Si NW after several cycles (FIG. 14) with SEM micrographs. The previously smooth nanowire surface has a fine structure and increased surface area, which increases the interfacial area between the silicon and the ion conductor and shortens the Li diffusion path in the Si nanowire.
FIG. 27 shows a graph of capacity as a function of cycle number for a first anode containing 10% Si nanowires, 10% PVDF, and 80% graphitic carbon, and a second anode containing only graphite carbon and PVDF. . Cycling performance was obtained for cells after 10 constant voltage (CV) and 3 constant current (CC) cycles. The cycling results shown in FIG. 27 were tested using a CC cycle of about 1.5 hours / half cycle. For the first anode (including Si nanowires, graphite, and PVDF), a capacity increase of more than 30% was realized in 250 cycles.
Li-ion battery: Fast response rate to current pulses for nanowire materials
FIG. 15 shows the charge cycling behavior of the Li SiNW anode / Li CoO 2 cathode cell compared to the same cell without nanowires as a control. A cell containing nanowires in the anode exhibits a very fast response rate to various current pulses (eg, 1 mA in a 3 second time slot). This fast velocity can contribute to the large surface area and short diffusion path for Li ions, along with a unique network structure that provides efficient conduction.
Uniform distribution of polymer binder
As described herein, suitably, the additive nanowires of the present invention are arranged in an interwoven, alternating or overlapping network. However, for efficient battery design, it is important that not only carbon but also a binder (eg, a conductive polymer or “polymer binder”) be uniformly dispersed. In order to show a uniform distribution of the polymer, NAFION® stained with lead (Pb) was used as a model material that could be traced using energy dispersive X-ray (EDX) analysis. FIGS. 16A-16C are scanning transmission electron microscope (STEM) EDX element maps of Si nanowires (16A), carbon (16B), and Pb (16C) showing the uniform distribution of C and binder on the Si nanowires. Show. The tissue surface area on the nanowire network can be adjusted to 30-100 m 2 / g for 20-60 nm nanowires, much larger than that of commercial battery graphite powder (˜1 m 2 / g).
A heat treated battery electrode may improve the binder distribution and thus may provide better cycling. In one example, a foil with PVDF-SiNW-graphite-conductive carbon black was heated at 300 ° C. under 4% hydrogen in argon for 8 hours. The melting point of PVDF is about 160 ° C. The starting temperature of PVDF is higher than 350 ° C, so 300 ° C is an effective temperature for the heat treatment of embodiments of the present invention.
A heat treated Si nanowire-graphite-PVDF electrode may improve adhesion with a current collector (eg, Cu) and, more importantly, may create a relatively dense / uniform coating layer. Improved adhesion of the coating layer on the current collector may result in better cycling performance. In addition, better interaction between the binder and the active material powder may further result in reduced changes in the solid electrolyte interface (SEI) that affect cycling performance.
Production of existing slurry preparations and integration into existing slurry preparations
As described herein, Si nanowires can be disposed on multiple substrates . Using the methods described throughout, nanowire diameter (eg 20-200 nm), length (eg about 50 um), taper (usually targeting zero), size distribution over a wide range and with high yield (> +/− 20% full width at half maximum) and doping (if desired) can be easily controlled. Nanowires with Si core and SiC shell with tunable core / shell ratio and graphic surface layer can be easily produced. The production output has been scaled up 100 times from the experimental scale and has been tested successfully on a production line prototype designed for mass production (50 tons of SiNW annually).
An exemplary manufacturing process is shown in FIG. This process is described in U.S. Provisional Application No. 61 / 221,2501, titled “Methods for Growth of High Density Nanowires” filed on June 29, 2009, Attorney Docket No. 2132.06800000, and 2009. As disclosed in U.S. Provisional Application No. 61 / 179,663, filed May 19, utilizes a high volume, high density method for growing nanowires. The growth of Si nanowires suitably utilizes nanowire nucleation from colloidal gold gold catalysts in a silicon rich chemical vapor deposition environment. As described in FIG. 17, the production method shown in flowchart 1700 suitably includes a step 1702 in which the aluminum foil is embossed. In step 1704, the foil is then cleaned using a conventional solvent, and in step 1706, the substrate surface is prepared (eg, a carbon-based substrate ). The gold colloid is disposed on the substrate at step 1708 and then dried at step 1710. Nanowire growth is then performed at step 1712 using a VLS-process (other processes described herein can also be used). The nanowire is then collected at step 1714 (eg, by sonication), filtered at step 1716 and dried at step 1718. The nanowires can be ball milled in step 1720 to be used as an additive as described herein. Suitably, U.S. Provisional Patent Application No. 61 / 221,501, entitled "Methods for Growth of High Density Nanowires" filed on June 29, 2009, Attorney Docket No. 2132.06800000, and U.S. Provisional Patent As described in application 61 / 179,663, cartridge assembly 1722 is used to facilitate the preparation of multiple nanowires.
FIG. 18 describes an exemplary process for introducing the additive of the present invention into an existing slurry preparation protocol / equipment design 1800. As shown in FIG. 18, an exemplary preparation protocol / device design 1800 suitably includes a pump 1802, powder transfer blowers 1804 and 1810, and a positive slurry mixer 1806 and a negative slurry mixer 1808. The positive and negative slurry mixers feed slurry pumps 1812 and 1814, respectively. Slurry pumps 1812 and 1814 supply to positive coater dryer 1818 and negative coater dryer 1820, respectively. A solvent recovery mechanism 1816 is also provided. Both the positive coater dryer 1818 and the negative coater dryer 1820 feed to a roll store 1822 that terminates the exemplary preparation protocol / device design 1800. As described throughout, the additive of the present invention is suitably added at 1824 to the powder transfer blower 1810, which is then mixed to prepare the anode. Other suitable preparation protocols / device designs will be readily envisioned by those skilled in the art. Also, the design shown in 1800 is intended to be exemplary only.
Exemplary embodiments of the present invention have been presented. The present invention is not limited to these examples. These examples are presented herein for purposes of illustration and not for purposes of limitation. Alternative embodiments will be apparent to those skilled in the art based on the teachings contained herein (including equivalents, extensions, modifications, inductions, etc. of the embodiments described herein). Such alternative embodiments are within the scope and spirit of the present invention.
All documents, patents, and patent applications mentioned in this specification are indicative of the level of skill of those skilled in the art to which the invention pertains, as if they were individual documents, patents or patent applications. Are hereby incorporated by reference to the same extent as specifically and individually indicated to be incorporated by reference.
An additive added to a slurry when manufacturing a battery electrode, comprising a plurality of Si-based nanowires grown on a carbon-based substrate, each Si-based nanowire having a carbon-containing shell covalently bonded to the Si-based nanowire.
The additive according to claim 1, wherein the Si-based nanowire has a diameter of 20 nm to 200 nm and a length of 0.1 μm to 50 μm.
The additive according to claim 1, wherein the carbon-based substrate is carbon black, graphite, graphene, graphene powder, or graphite foil.
A battery electrode including one or more active materials including one or more carbon-based substrates and Si-based nanowires individually grown on the one or more carbon-based substrates ,
The Si-based nanowire has a core-shell structure,
The battery electrode, wherein the core includes Si and the shell includes C.
The battery electrode according to claim 4, wherein the Si-based nanowire has a diameter of 20 nm to 200 nm and a length of 0.1 μm to 50 μm.
The battery electrode according to claim 4, wherein the carbon-based substrate is carbon black, graphite, graphene, graphene powder, or graphite foil.
The battery electrode according to claim 4, wherein the one or more active materials include 1 wt% to 80 wt% of the Si-based nanowire and the carbon-based substrate.
The battery electrode according to claim 7, wherein the electrode includes 10 wt% of the Si-based nanowire grown on the carbon-based substrate.
A method for preparing a battery electrode comprising:
(A) providing a plurality of Si-based nanowires grown on a carbon-based substrate;
(B) covalently bonding a shell containing carbon to the Si-based nanowire;
(C) mixing the Si-based nanowires with a polymer binder and a carbon-based material to form a slurry;
(D) forming the slurry on the battery electrode.
The method of claim 9, wherein the providing step comprises providing a Si-based nanowire having a diameter of 20 nm to 200 nm and a length of 0.1 μm to 50 μm.
10. The method of claim 9, wherein the providing step comprises providing Si-based nanowires grown on carbon black, graphite, graphene, graphene powder, or graphite foil.
The method of claim 9, wherein the providing step comprises providing 1 wt% to 80 wt% of the electrode as Si-based nanowires grown on the carbon-based substrate.
The method of claim 12, wherein the providing step comprises providing 10% by weight of the electrode as a Si-based nanowire.
The method of claim 9, wherein the mixing step comprises mixing with a polymeric binder comprising polyvinylidene difluoride (PVDF) or styrene butadiene rubber (SBR).
The method of claim 9, wherein the mixing comprises mixing with graphite.
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