WO2011068911A2 - High capacity electrode materials enhanced by amorphous silicon - Google Patents

High capacity electrode materials enhanced by amorphous silicon Download PDF

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Publication number
WO2011068911A2
WO2011068911A2 PCT/US2010/058616 US2010058616W WO2011068911A2 WO 2011068911 A2 WO2011068911 A2 WO 2011068911A2 US 2010058616 W US2010058616 W US 2010058616W WO 2011068911 A2 WO2011068911 A2 WO 2011068911A2
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particles
amorphous silicon
composition
cathode material
matter
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PCT/US2010/058616
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French (fr)
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WO2011068911A3 (en
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Lifeng Cui
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Cq Energy, Inc.
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/626—Metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • Lithium-ion batteries have long been used in portable electronics such as laptop computers and cell phones. In recent years, lithium-ion batteries have also become the choice batteries of the fast-growing electric vehicle industry.
  • the invention described here is directed to new electrode materials for lithium ion batteries, although such materials may also be used in other types of batteries. The new electrode materials exhibits significantly better performance than the prior art materials.
  • the present invention is directed in part at a composition of matter comprising anode material particles and amorphous silicon which is deposited onto the anode material particles.
  • One embodiment of the invention calls for anode materials selected from the group of crystalline silicon, carbon, lithium titanate, aluminum, and tin.
  • the anode material particles may be coated with carbon generated from carbonization of polymers.
  • the present invention is also directed at battery anode electrodes comprising the anode materials described above.
  • the present invention is further directed at a method of making battery anode material, comprising the steps of (a) creating a mixture comprising anode material particles, and (b) depositing amorphous silicon onto the mixture.
  • Another aspect of the present invention is directed at a composition of matter comprising cathode material particles and amorphous silicon deposited onto the cathode material particles.
  • the cathode material is selected from one or more of the following group: Lithium ferrous phosphate (LFP), LiMnP0 4 , LiCo0 2 , LiNi0 2 , LiMn0 2 , LiCo 0.333 Mn 0.333 Ni 0.333 O 2 , LiNio.8Coo.15Al o.o 5 0 2 , and LiMn 2 0 4 .
  • Another embodiment is a composition of matter comprising LFP, a conductive carbon, and a transition metal oxide such as titanium oxide.
  • the invention is also directed at battery cathodes comprising the cathode materials described above in this paragraph.
  • the invention is further directed at a method of producing a battery cathode material, comprising the steps of producing cathode material particles and depositing amorphous silicon onto the cathode material particles.
  • the step of producing cathode material particles comprises (a) making a mixture comprising lithium ferrous phosphate, a conductive carbon and a transition metal oxide; (b) forming particles using the mixture; and (c) converting the particles into composite crystalline particles.
  • the invention also includes the kind of battery cathodes containing the materials made using the above-described method.
  • Another aspect of the invention is directed at a method of making LFP composite crystalline particles as a battery cathode material, which comprises the following steps: (a) providing solid-state LFP; (b) creating a mixture comprising the solid-state LFP, a conductive carbon, and a transition metal oxide; and (c) grinding the mixture into fine particles; and (d) calcining the fine particles to form composite crystalline material.
  • the invention is further directed at a method of making battery cathode material using the LFP crystalline particles generated using the above described method.
  • FIG. 1A is an illustration of one anode material particle containing an anode material particle such as a crystalline silicon particle, a layer of carbon coating (C) and a layer of amorphous silicon coating (a-Si).
  • Fig. IB depicts a cathode material particle such as a lithium ferrous phosphate particle, coated with a layer of carbon coating (c) and a layer of amorphous silicon coating (a-Si).
  • FIG. 2 is an illustration of one anode using silicon particles (Si) which are carbonized (C) and also coated with amorphous silicon (a-Si) and mixed with carbon black (CB).
  • Si silicon particles
  • C carbonized
  • a-Si amorphous silicon
  • CB carbon black
  • FIG. 3 is an illustration of an anode electrode consisting of crystalline silicon particles, coated with a polymer binder Polyvinylidene Fluoride (PVDF).
  • PVDF Polyvinylidene Fluoride
  • FIG. 4 is an illustration of an anode material coated with a polymer after the carbonization process.
  • Fig. 5 shows scanning electron micrographs (SEM) of a silicon nano-particle (SiNP)- polymer film at about 4000x magnification (left) and 9000x magnification (right) after carbonization.
  • FIG. 6 is a scanning electron micrograph (SEM) of a SiNP-polymer film at about 2000x magnification after carbonization and fusion by silane chemical vapor deposition.
  • FIG. 7 is the cycling performance data of a silicon-carbon-amorphous-silicon anode electrode.
  • the cycling performance is a measurement of the specific capacity in milliampere hour per gram (mAh/g) versus number of cycles.
  • FIG. 8 is an illustration of a schematic view of one-dimensional conductive carbon for improving the conductivity of an LFP cathode.
  • FIG. 9 is an illustration of a composite cathode material containing LiFeP0 4 , carbon and oxide components.
  • FIG. 10 is an illustration of a layer of amorphous silicon deposited on the surface of an LFP/Carbon/Oxide particle.
  • a battery normally has an anode and a cathode.
  • the electrical current generated by the battery flows from the cathode to the anode through the electrical circuit that the battery powers. Inside the battery, however, the current flows from the anode to the cathode, thereby forming a complete electrical circuit.
  • the new kind of materials disclosed here can be used to enhance both the anode and cathode electrodes.
  • the material incorporates amorphous silicon into electrode materials to obtain a kind of high-capacity and high-conductance anode.
  • Amorphous silicon is the non-crystalline allotropic form of silicon. It can be deposited as a thin film onto a variety of substrates, and are widely used in liquid crystal displays and solar cells.
  • the new electrode materials disclosed here involve deposition of amorphous silicon onto the electrode materials to enhance the performance of the electrode.
  • FIG. 1A and IB are illustrations of two basic embodiments of the present invention.
  • Fig. 1A shows a particle of an anode material, such as crystalline silicon, coated with a layer of carbon (C) and further coated with a layer of amorphous silicon (a-Si).
  • the carbon shell has the beneficial effect of suppressing the expansion of the anode particle during lithium alloying.
  • the carbon coating is not required to implement the present invention.
  • the amorphous silicon layer which may be achieved by amorphous silicon deposition, significantly increases the conductivity of the anode material.
  • the amorphous silicon can be either intrinsic or doped.
  • Figure IB shows a similar arrangement with a cathode material particle, coated optionally with carbon, and further coated with amorphous silicon.
  • amorphous silicon is introduced onto the anode materials to enhance the performance of the material.
  • the enhanced performance may be resulted from many beneficial effects of amorphous silicon, for example, increased conductivity, increased Li + storage capacity, and the binding force which the amorphous silicon provides to hold the compositions together.
  • the amorphous silicon in the present invention may be either intrinsic or doped.
  • One embodiment of the invention is to deposit amorphous silicon onto an anode material containing silicon particles.
  • the anodes of secondary or rechargeable lithium batteries are made of graphite.
  • the lithium ion (Li + ) storage capacity of graphite is around 340 mAh/g, which is not very high.
  • crystalline silicon has theoretical Li + storage capacity of 4200 mAh/g, which is about 10 times higher than that of graphite.
  • previous efforts to use silicon as anode material largely failed, because of the poor electrical conductivity of silicon and other reasons.
  • the deposition of amorphous silicon significantly enhances the performance of the many anode materials including those containing silicon particles.
  • Fig. 2 shows an embodiment of the present invention.
  • amorphous silicon (a-Si) together with carbon (C) are coated on silicon particles (Si) and mixed with a conductive additive such as carbon black (CB).
  • CB carbon black
  • the mixture is then placed on metal current collector to form an anode electrode for lithium ion battery.
  • the conductive additive may not be needed, which would help reduce the size of the anode electrode.
  • the anode material disclosed here has excellent cycling life and has no or minimal loss of contact which may be a problem among the prior art techniques.
  • crystalline silicon particles other common anode material particles may be used to implement the present invention, for instance, carbon, lithium titanate, aluminum, and tin.
  • the anode material particles used here may be, but not required to be, nano-particles.
  • a polymer binder may be used to form the carbon coating on the silicon particle.
  • a polymer may be mixed with silicon particles and carbon black as conductive additive in a solvent to form a viscous slurry. Then the slurry may be bladed onto a metal current collector and dried to form an anode electrode.
  • Figure 3 shows silicon particles in an anode which are coated with a polymer binder, PVDF, and mixed with carbon black.
  • Figure 5 shows scanning electron micrographs (SEM) of a dried silicon particle-polymer film at about 4000x magnification (left) and at about 9000x magnification (right) after carbonization.
  • the sample in Figure 5 was generated using approximately 90% by weight of Si particles, mixed with about 10% by weight of a polymer binder in an organic or aqueous solvent to form a viscous slurry. The slurry is subsequently bladed onto stainless steel foil and dried. The carbonization of the polymer film takes place at a temperature range from about 500 °C to about 900 °C.
  • the silicon particles used in the process may include various silicon substances such as partially oxidized silicon powders, silicon carbon composite powders, silicon nitride powders, silicon nitride phosphate powders.
  • the polymer binder may be Polyacrylonitrile (PAN), Poly- methyl-methacrylate (PMMA), PVDF, and other carbon-based polymers.
  • the weight ratio of the silicon particles to the polymer binder may be 9: 1.
  • the present invention can also be used to improve cathode materials, especially lithium ferrous phosphate (LFP), or LiFeP0 4 , cathode material.
  • LFP lithium ferrous phosphate
  • LiFeP0 4 lithium ferrous phosphate
  • the present invention provides a cost- efficient way of improving LFP's conductivity as a cathode material for lithium secondary batteries.
  • This process involves composting LFP material with other conductive materials such as carbon black, carbon nanotube, and/or transition metal oxides. The composting step may occur either during or after the intrinsic crystallization of LFP powder.
  • a layer of amorphous silicon, intrinsic or doped, is then applied to the LFP powder to further improve the conductivity.
  • FIG. 8 is an illustration of a schematic view of a one-dimensional conductive carbon for improving the conductivity of an LFP cathode.
  • crystallized LFP particles may be coupled to one-dimensional conductive carbon, including, for examples, carbon nanofiber and carbon nanotube.
  • a cathode material which is a composite crystalline material having, among others, LFP, a transition metal oxide such as titanium oxide and carbon additive:
  • the carbon additive includes at least one of carbon black, carbon nanotube and carbon nanofiber, among others.
  • FIG. 9 is an illustration of a composite cathode material containing LiFeP0 4 , carbon and oxide components.
  • the LFP particle includes Ti0 2 (or other metal oxides) and carbon particles that may be embedded within, or on the surface of, the LFP particle.
  • FIG. 10 is an illustration of a layer of amorphous silicon, being deposited on the surface of an LFP/Carbon/Oxide particle using SiH 4 chemical-vapor-deposition (CVD) process to further increase the conductivity of the cathode material.
  • CVD chemical-vapor-deposition
  • the amorphous silicon coating technique can also be applied to other cathode material particles such as LiMnP0 4 , LiCo0 2 , LiNi0 2 , LiMn0 2 , LiCo 0.333 Mn o .333 Nio.3330 2 , LiNio .8 Coo.15Al o . os0 2 , and LiMn 2 0 4 .
  • cathode materials can be used either in their pure or doped forms.
  • Figure 6 shows an SEM of the anode material so produced.
  • Figure 7 is the cycling performance data of an anode electrode made with the process described above. As shown, the anode electrode was able to maintain at least about 90% capacity after 240 cycles.
  • Example 2
  • Amorphous silicon deposition is performed inside a rotary CVD tube furnace.
  • Anode or cathode electrode material powders are placed inside a rotary tube furnace which uses a 4-inch diameter quartz tube.
  • the purpose of the rotary motion of the quartz tube is to stir the powders inside and assure uniform coating of amorphous silicon on these powders.
  • the furnace is pumped to a vacuum, purged with pure argon and then heated to desired temperatures.
  • a compressed gas of 2% silane balanced in argon was flowed to produce amorphous silicon coating. Flow rates between 50 standard cubic centimeter per minute (seem) and 200 seem were used for the delivery of SiH4/Ar gas.
  • a simultaneous delivery of 5 to 20 seem of either 100 part per million (ppm) diborane balanced in argon (B2H6/Ar) or 100 ppm (PH3/Ar) makes the deposited amorphous p-type doped or n-type doped, respectively.
  • the furnace is kept at a constant pressure of 100 Torr and amorphous silicon coating is observed at temperatures between 460 0C and 550 0C. Generally, larger flows and higher temperatures promote faster deposition of amorphous silicon.

Abstract

The present invention discloses various high capacity electrode materials enhanced with amorphous silicon. One aspect of the invention is about using amorphous silicon to improve anode materials. Another aspect of the invention is about using amorphous silicon to improve cathode materials. The new electrode materials disclosed in this invention exhibit more optimal performance than the prior art materials.

Description

HIGH CAPACITY ELECTRODE MATERIALS ENHANCED BY AMORPHOUS SILICON
This Application claims priority to U.S. provisional application Serial No. 61/266,047, filed on December 2, 2009, which is hereby incorporated by reference in its entirety.
BACKGROUND
[0001] Lithium-ion batteries have long been used in portable electronics such as laptop computers and cell phones. In recent years, lithium-ion batteries have also become the choice batteries of the fast-growing electric vehicle industry. The invention described here is directed to new electrode materials for lithium ion batteries, although such materials may also be used in other types of batteries. The new electrode materials exhibits significantly better performance than the prior art materials.
SUMMARY
[0002] The present invention is directed in part at a composition of matter comprising anode material particles and amorphous silicon which is deposited onto the anode material particles. One embodiment of the invention calls for anode materials selected from the group of crystalline silicon, carbon, lithium titanate, aluminum, and tin. The anode material particles may be coated with carbon generated from carbonization of polymers. The present invention is also directed at battery anode electrodes comprising the anode materials described above.
[0003] The present invention is further directed at a method of making battery anode material, comprising the steps of (a) creating a mixture comprising anode material particles, and (b) depositing amorphous silicon onto the mixture.
[0004] Another aspect of the present invention is directed at a composition of matter comprising cathode material particles and amorphous silicon deposited onto the cathode material particles. In one embodiment, the cathode material is selected from one or more of the following group: Lithium ferrous phosphate (LFP), LiMnP04, LiCo02, LiNi02, LiMn02, LiCo0.333Mn0.333Ni0.333O2, LiNio.8Coo.15Al o.o502, and LiMn204. Another embodiment is a composition of matter comprising LFP, a conductive carbon, and a transition metal oxide such as titanium oxide. The invention is also directed at battery cathodes comprising the cathode materials described above in this paragraph.
[0005] The invention is further directed at a method of producing a battery cathode material, comprising the steps of producing cathode material particles and depositing amorphous silicon onto the cathode material particles. The step of producing cathode material particles comprises (a) making a mixture comprising lithium ferrous phosphate, a conductive carbon and a transition metal oxide; (b) forming particles using the mixture; and (c) converting the particles into composite crystalline particles. The invention also includes the kind of battery cathodes containing the materials made using the above-described method.
[0006] Another aspect of the invention is directed at a method of making LFP composite crystalline particles as a battery cathode material, which comprises the following steps: (a) providing solid-state LFP; (b) creating a mixture comprising the solid-state LFP, a conductive carbon, and a transition metal oxide; and (c) grinding the mixture into fine particles; and (d) calcining the fine particles to form composite crystalline material. The invention is further directed at a method of making battery cathode material using the LFP crystalline particles generated using the above described method.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] FIG. 1A is an illustration of one anode material particle containing an anode material particle such as a crystalline silicon particle, a layer of carbon coating (C) and a layer of amorphous silicon coating (a-Si). Fig. IB depicts a cathode material particle such as a lithium ferrous phosphate particle, coated with a layer of carbon coating (c) and a layer of amorphous silicon coating (a-Si).
[0008] FIG. 2 is an illustration of one anode using silicon particles (Si) which are carbonized (C) and also coated with amorphous silicon (a-Si) and mixed with carbon black (CB).
[0009] Fig. 3 is an illustration of an anode electrode consisting of crystalline silicon particles, coated with a polymer binder Polyvinylidene Fluoride (PVDF).
[0010] FIG. 4 is an illustration of an anode material coated with a polymer after the carbonization process.
[0011] Fig. 5 shows scanning electron micrographs (SEM) of a silicon nano-particle (SiNP)- polymer film at about 4000x magnification (left) and 9000x magnification (right) after carbonization.
[0012] FIG. 6 is a scanning electron micrograph (SEM) of a SiNP-polymer film at about 2000x magnification after carbonization and fusion by silane chemical vapor deposition.
[0013] FIG. 7 is the cycling performance data of a silicon-carbon-amorphous-silicon anode electrode. The cycling performance is a measurement of the specific capacity in milliampere hour per gram (mAh/g) versus number of cycles. [0014] FIG. 8 is an illustration of a schematic view of one-dimensional conductive carbon for improving the conductivity of an LFP cathode.
[0015] FIG. 9 is an illustration of a composite cathode material containing LiFeP04, carbon and oxide components.
[0016] FIG. 10 is an illustration of a layer of amorphous silicon deposited on the surface of an LFP/Carbon/Oxide particle.
DETAILED DESCRIPTION
[0017] It will be appreciated by those of ordinary skill in the art that the invention can be embodied in other specific forms without departing from the spirit or essential character thereof. The presently disclosed embodiments are therefore considered in all respects to be illustrative and not restrictive.
[0018] An important part of the present invention is related to a new material for battery electrodes. A battery normally has an anode and a cathode. The electrical current generated by the battery flows from the cathode to the anode through the electrical circuit that the battery powers. Inside the battery, however, the current flows from the anode to the cathode, thereby forming a complete electrical circuit. The new kind of materials disclosed here can be used to enhance both the anode and cathode electrodes. The material incorporates amorphous silicon into electrode materials to obtain a kind of high-capacity and high-conductance anode. Amorphous silicon is the non-crystalline allotropic form of silicon. It can be deposited as a thin film onto a variety of substrates, and are widely used in liquid crystal displays and solar cells. The new electrode materials disclosed here involve deposition of amorphous silicon onto the electrode materials to enhance the performance of the electrode.
[0019] FIG. 1A and IB are illustrations of two basic embodiments of the present invention. Fig. 1A shows a particle of an anode material, such as crystalline silicon, coated with a layer of carbon (C) and further coated with a layer of amorphous silicon (a-Si). The carbon shell has the beneficial effect of suppressing the expansion of the anode particle during lithium alloying. The carbon coating, however, is not required to implement the present invention. The amorphous silicon layer, which may be achieved by amorphous silicon deposition, significantly increases the conductivity of the anode material. The amorphous silicon can be either intrinsic or doped. Figure IB shows a similar arrangement with a cathode material particle, coated optionally with carbon, and further coated with amorphous silicon.
[0020] The Anode Materials [0021] In one category of embodiments of the present invention, amorphous silicon is introduced onto the anode materials to enhance the performance of the material. The enhanced performance may be resulted from many beneficial effects of amorphous silicon, for example, increased conductivity, increased Li+ storage capacity, and the binding force which the amorphous silicon provides to hold the compositions together. The amorphous silicon in the present invention may be either intrinsic or doped.
[0022] One embodiment of the invention is to deposit amorphous silicon onto an anode material containing silicon particles. Traditionally, the anodes of secondary or rechargeable lithium batteries are made of graphite. The lithium ion (Li+) storage capacity of graphite is around 340 mAh/g, which is not very high. In contrast, crystalline silicon has theoretical Li+ storage capacity of 4200 mAh/g, which is about 10 times higher than that of graphite. However, previous efforts to use silicon as anode material largely failed, because of the poor electrical conductivity of silicon and other reasons. The deposition of amorphous silicon significantly enhances the performance of the many anode materials including those containing silicon particles.
[0023] Fig. 2 shows an embodiment of the present invention. In this embodiment, amorphous silicon (a-Si), together with carbon (C) are coated on silicon particles (Si) and mixed with a conductive additive such as carbon black (CB). The mixture is then placed on metal current collector to form an anode electrode for lithium ion battery. The conductive additive may not be needed, which would help reduce the size of the anode electrode.
[0024] The anode material disclosed here has excellent cycling life and has no or minimal loss of contact which may be a problem among the prior art techniques. Besides crystalline silicon particles, other common anode material particles may be used to implement the present invention, for instance, carbon, lithium titanate, aluminum, and tin. The anode material particles used here may be, but not required to be, nano-particles.
[0025] In another embodiment, a polymer binder may be used to form the carbon coating on the silicon particle. For example, a polymer may be mixed with silicon particles and carbon black as conductive additive in a solvent to form a viscous slurry. Then the slurry may be bladed onto a metal current collector and dried to form an anode electrode. Figure 3 shows silicon particles in an anode which are coated with a polymer binder, PVDF, and mixed with carbon black.
[0026] After the anode is carbonized at a high temperature, the structure is illustrated in Figure
4.
[0027] Figure 5 shows scanning electron micrographs (SEM) of a dried silicon particle-polymer film at about 4000x magnification (left) and at about 9000x magnification (right) after carbonization. The sample in Figure 5 was generated using approximately 90% by weight of Si particles, mixed with about 10% by weight of a polymer binder in an organic or aqueous solvent to form a viscous slurry. The slurry is subsequently bladed onto stainless steel foil and dried. The carbonization of the polymer film takes place at a temperature range from about 500 °C to about 900 °C.
[0028] The silicon particles used in the process may include various silicon substances such as partially oxidized silicon powders, silicon carbon composite powders, silicon nitride powders, silicon nitride phosphate powders. The polymer binder may be Polyacrylonitrile (PAN), Poly- methyl-methacrylate (PMMA), PVDF, and other carbon-based polymers. The weight ratio of the silicon particles to the polymer binder may be 9: 1.
The Cathode Materials
[0029] The present invention can also be used to improve cathode materials, especially lithium ferrous phosphate (LFP), or LiFeP04, cathode material. LFP by itself normally do not have sufficient conductivity to act as a good cathode material. The present invention provides a cost- efficient way of improving LFP's conductivity as a cathode material for lithium secondary batteries. This process involves composting LFP material with other conductive materials such as carbon black, carbon nanotube, and/or transition metal oxides. The composting step may occur either during or after the intrinsic crystallization of LFP powder. A layer of amorphous silicon, intrinsic or doped, is then applied to the LFP powder to further improve the conductivity.
[0030] FIG. 8 is an illustration of a schematic view of a one-dimensional conductive carbon for improving the conductivity of an LFP cathode. As shown, crystallized LFP particles may be coupled to one-dimensional conductive carbon, including, for examples, carbon nanofiber and carbon nanotube.
[0031] The following is an embodiment of the process of producing a cathode material which is a composite crystalline material having, among others, LFP, a transition metal oxide such as titanium oxide and carbon additive:
[0032] (a) mixing a solution having at least one lithium compound, at least one ferrous compound, at least one phosphorous compound, and at least one additive, where the additive includes at least one of an acid and a surfactant;
[0033] (b) filtering the solution through a polypropylene filter to produce a solid-state mixture; [0034] (c) mixing a carbon additive (e.g., carbon black, carbon nanotube or carbon nanofiber) and a transition metal oxide to the solid-state mixture, whereby the transition metal oxide may have various forms of implementations, including titanium oxide powder, among others; and
[0035] (d) calcining the solid-state mixture to produce the cathode material.
[0036] In some embodiments, the carbon additive includes at least one of carbon black, carbon nanotube and carbon nanofiber, among others.
[0037] FIG. 9 is an illustration of a composite cathode material containing LiFeP04, carbon and oxide components. As shown, the LFP particle includes Ti02 (or other metal oxides) and carbon particles that may be embedded within, or on the surface of, the LFP particle.
[0038] The amorphous silicon deposition process discussed in connection with the anode materials may be applied to the composite cathode materials described above. FIG. 10 is an illustration of a layer of amorphous silicon, being deposited on the surface of an LFP/Carbon/Oxide particle using SiH4 chemical-vapor-deposition (CVD) process to further increase the conductivity of the cathode material.
[0039] Besides LFP particles, the amorphous silicon coating technique can also be applied to other cathode material particles such as LiMnP04, LiCo02, LiNi02, LiMn02, LiCo0.333Mn o.333Nio.33302, LiNio.8Coo.15Al o.os02, and LiMn204. These cathode materials can be used either in their pure or doped forms.
Example 1
[0040] The following is a specific example of producing anode material using the disclosed invention:
[0041] (a) Mixing 90% by weight of crystalline Si particles with 10% by weight of a polymer binder in an organic or aqueous solvent to form a viscous slurry.
[0042] (b) Blading the slurry onto a piece of stainless steel foil to dry.
[0043] (c) Carbonizing the polymer film at a high temperature ranging from 500 °C to 900 °C; and
[0044] (d) Depositing amorphous silicon using a SiH4 CVD process at a temperature range from about 400 °C to about 700 °C.
[0045] Figure 6 shows an SEM of the anode material so produced. Figure 7 is the cycling performance data of an anode electrode made with the process described above. As shown, the anode electrode was able to maintain at least about 90% capacity after 240 cycles. Example 2
[0046] One example of a process flow for producing composite cathode material having at least one of the following steps is described below.
[0047] (1) Dissolving 2 mole of diammonium hydrogen phosphate and 0.25 mole of citric acid in 300 mL of deionized water to form an acidic solution.
[0048] (2) Thoroughly mixing 10 mL of BS-12 (Cocoal kanoy lamido propyl betaine, an amphoteric surfactant) to the solution.
[0049] (3) Adding 2 mole of ferrous chloride to the solution and maintain the solution at from about 20 °C to about 30 °C.
[0050] (4) Adding 2 mole of lithium chloride to the solution and thoroughly mix the same.
[0051] (5) Titrating about 99% acetic acid until the pH value of the solution is maintained at about 5. With continuous and vigorous stirring (e.g., for at least about 48 hours), completely disperse the solution.
[0052] (6) Filtering the solution through a polypropylene filter to form a solid-state mixture of lithium ferrous phosphate.
[0053] (7) Washing the solid-state mixture with distilled water to remove possible contaminants.
[0054] (8) Mixing the solid-state mixture of lithium ferrous phosphate (LFP) with 600 mL of distilled water, 0.1 mole of conductive carbon (e.g., carbon black, carbon nanotube, carbon nanofiber) and 0.02 mole of titanium oxide powder; placing the same in a ball mill jar.
[0055] (9) Thoroughly milling and dispersing the solid-state mixture in the ball mill jar to form a nano-scale particle mixture.
[0056] (10) Spray-drying the solid-state mixture solution to form a precursor.
[0057] (11) Placing the precursor in an aluminum oxide crucible.
[0058] (12) Calcining the precursor in the aluminum oxide crucible in a furnace at about 800 °C at an incremental rate of about 20 °C per minute. Maintain the furnace at about 800 °C for about 24 hours under an inert gas environment (e.g., argon).
[0059] (13) Producing a composite material containing crystalline LFP, titanium oxide and carbon (LiFePCVTiCVC) after calcining and cooling of the precursor.
[0060] (14) Depositing amorphous silicon in the composite material using the SiH4 CVD process at a temperature range from about 400 to about 700 °C.
Example 3
[0061] Amorphous silicon deposition is performed inside a rotary CVD tube furnace. Anode or cathode electrode material powders are placed inside a rotary tube furnace which uses a 4-inch diameter quartz tube. The purpose of the rotary motion of the quartz tube is to stir the powders inside and assure uniform coating of amorphous silicon on these powders.
[0062] The furnace is pumped to a vacuum, purged with pure argon and then heated to desired temperatures. A compressed gas of 2% silane balanced in argon was flowed to produce amorphous silicon coating. Flow rates between 50 standard cubic centimeter per minute (seem) and 200 seem were used for the delivery of SiH4/Ar gas. A simultaneous delivery of 5 to 20 seem of either 100 part per million (ppm) diborane balanced in argon (B2H6/Ar) or 100 ppm (PH3/Ar) makes the deposited amorphous p-type doped or n-type doped, respectively. The furnace is kept at a constant pressure of 100 Torr and amorphous silicon coating is observed at temperatures between 460 0C and 550 0C. Generally, larger flows and higher temperatures promote faster deposition of amorphous silicon.

Claims

CLAIMS The claims of the invention are:
1. A composition of matter comprising anode material particles and amorphous silicon coated onto the anode material particles.
2. The composition of matter of claim 1 wherein the anode material is selected from one or more of the following: crystalline silicon, carbon, lithium titanate, aluminum, and tin.
3. The composition of matter of claim 2 wherein the anode material particles are further coated with carbon generated from carbonization of polymers.
4. A battery anode electrode comprising the composition of matter of claim 1, claim 2, or claim 3.
5. A method of making battery anode material, comprising generating a composition comprising anode material particles; and depositing amorphous silicon onto the composition.
6. The method of claim 5, wherein the anode material may be selected from one or more of the following: crystalline silicon, carbon, lithium titanate, aluminum, and tin.
7. A composition of matter comprising cathode material particles and amorphous silicon deposited onto the cathode material particles.
8. The composition of matter of claim 7, wherein the cathode material is selected from one or more of the following: LFP, LiMnP04, LiCo02, LiNi02, LiMn02, LiCo0.333Mn o.333Ni0.33302, LiNio.8Co0.i5Al o.os02, and LiMn204.
9. The composition of matter of claim 7, wherein the cathode material comprises LFP, a conductive carbon, and a transition metal oxide.
10. The composition of matter of claim 9, wherein the transition metal oxide is titanium oxide.
1
11. A battery cathode comprising one or more of the following: the composition of matter of claim 7, claim 8, claim 9, and claim 10.
12. A method of producing a battery cathode material, comprising:
producing cathode material particles; and
depositing amorphous silicon onto the cathode material particles.
13. The method of claim 12, wherein the step of producing cathode material particles comprises:
making a mixture comprising lithium ferrous phosphate, a conductive carbon and a transition metal oxide;
forming particles using the mixture; and
converting the particles into composite crystalline particles.
14. A method of making a battery cathode comprising the cathode material generated using the method of claim 12, claim 13, or claim 14.
15. A method of making LFP composite crystalline particles as a battery cathode material, comprising:
Providing solid-state LFP;
Creating a mixture comprising the solid-state LFP, a conductive carbon, and a transition metal oxide;
Grinding the mixture into fine particles; and
Calcining the fine particles to form a composite crystalline material.
16. A method of making battery cathode material using the method of claim 15, followed by a process comprising the step of depositing amorphous silicon onto the composite crystalline material.
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