WO2016091957A1 - Procédé permettant de produire une électrode contenant des particules de silicium recouvertes de carbone - Google Patents

Procédé permettant de produire une électrode contenant des particules de silicium recouvertes de carbone Download PDF

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Publication number
WO2016091957A1
WO2016091957A1 PCT/EP2015/079137 EP2015079137W WO2016091957A1 WO 2016091957 A1 WO2016091957 A1 WO 2016091957A1 EP 2015079137 W EP2015079137 W EP 2015079137W WO 2016091957 A1 WO2016091957 A1 WO 2016091957A1
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Prior art keywords
carbon
silicon particles
coating
particles coated
coated
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PCT/EP2015/079137
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English (en)
Inventor
Andreas Mueller
Matthias Georg SCHWAB
Mingjie ZHONG
Shyam Sundar Venkataraman
Klaus MÜLLEN
Hermann Sachdev
Axel Binder
Original Assignee
Basf Se
MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V.
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Publication of WO2016091957A1 publication Critical patent/WO2016091957A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of 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
    • H01M4/36—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
    • H01M4/625—Carbon or graphite
    • 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
    • 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
    • H01M4/366—Composites as layered products
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a process for producing an electrode containing silicon particles which are coated with carbon (SP2).
  • the respective process is carried out under plasma conditions in combination with a fluidized bed process since silicon particles (SP1 ) to be coated with carbon are fluidized into the reactive zone of an apparatus (A), employing a gaseous stream (G) containing at least one carbon- containing gas.
  • the coating of the silicon particles (SP1 ) in the reactive zone (RZ) of apparatus (A) is preferably carried out via a chemical vapor deposition (CVD) process.
  • the silicon particles coated with carbon (SP2) as obtained in step d) of the present invention are further processed in order to obtain an electrode containing such silicon particles coated with carbon (SP2).
  • the present invention further relates to such an electrode as well as to a battery containing such an electrode.
  • the present invention also relates to the use of such an electrode containing silicon particles coated with carbon (SP2) within such a battery which preferably is a lithium-ion-battery.
  • SP2 silicon particles coated with carbon
  • Li ion batteries have been considered as the core e-mobility technology.
  • Graphite with the theoretical specific capacity of 372 mAh/g is the most widely used commercial anode material for LIB because of its high Coulombic efficiency and good cycle performance. Desirable improvement levels of 20-35% of the electrode's total capacity are achieved when the negative electrode capacity reaches 1200mAh/g. To achieve this, the current graphite anode must be replaced with Li accommodation materials which can offer higher capacity.
  • Silicon with its high theoretical capacity of 4200 mAh/g has been considered as the most promising candidate.
  • the drawbacks of the high Li uptake are volume changes of the silicon of up to 300% during charging and discharging. The resulting fracturing of the silicon in the anode leads to contact and thus conductivity losses.
  • SEI solid electrolyte interface
  • WO 2013/078645 A1 discloses a silicon/carbon composite which comprises mesoporous silicon particles and carbon coating provided on the silicon particles, wherein the silicon particles have two pore size distribution of 2-4 nm and 20-40 nm. Further, a process of preparing the silicon/carbon composite is disclosed, which comprises the steps of preparing mesoporous silicon particles via a mechanochemical reaction between SiCI 4 and Li 13 Si 4 under ball milling and subsequent thermal treatment and washing process, and coating the mesoporous silicon particles with carbon. Further, an anode for lithium ion battery and a lithium ion battery is disclosed, which comprises the silicon/carbon composite.
  • US-A 5,620,743 discloses a process for coating solid particles such as granules or fibers composed of thermoplastic or thermoset polymers, pigments or granules composed of organic dyes or active substances in a fluidized bed by application of a gaseous coating agent from a plasma, wherein the plasma is generated outside the fluidized bed under 0.01 -500 mbar, and the plasma-activated gas is passed into the fluidized bed, which is operated under 0.1 -500 mbar, where a. the plasma is generated from the total amount of gaseous coating agent with or without another gas, or
  • the plasma is generated from a portion of the gaseous coating agent with or without another gas, and the remaining portion is introduced directly into the fluidized bed, or
  • the plasma is generated from another gas, and the total amount of gaseous coating agent is introduced directly into the fluidized bed.
  • CN-A 102332571 describes a silicon-carbon compound cathode material and a manufacturing method thereof.
  • the manufacturing method of the silicon-carbon compound cathode material comprises an etching step, a carbon-layer covering step, a scattering step, a spraying pelletizing step and a carbonizing treatment step.
  • the silicon-carbon compound cathode material prepared by using the method has a nano/micro structure, a first cycle efficiency over 85%, a first discharging capability over 1000mAh/g and a retention rate of 100 times cycle capacity over 90%.
  • US 2006/051670 A1 discloses a metallic silicon powder which is prepared by effecting chemical reduction on silica stone, metallurgical refinement, and metallurgical and/or chemical purification to reduce the content of impurities. The powder is best suited as a negative electrode material for non-aqueous electrolyte secondary cells, affording better cycle performance.
  • EP 1 363 341 A2 discloses a conductive silicon composite in which particles having a structure in which crystallites of silicon are dispersed in silicon dioxide are coated on their surfaces with carbon affords satisfactory cycle performance when used as the negative electrode material in a non-aqueous electrolyte secondary cell.
  • the object is achieved by a process for producing an electrode containing silicon particles coated with carbon (SP2), wherein the process comprises the following steps a) to e): a) provision of silicon particles (SP1 ) on a sample holder (SH) of an apparatus (A), which comprises a sample holder (SH) and a reactive zone (RZ) and the sample holder (SH) is located below the reactive zone (RZ), b) generation of plasma in the reactive zone (RZ) of apparatus (A),
  • Another major advantage in this process is the high flexibility according to treatment time, treatment energy, possible gases, mixing of gases or sequential use of gases and the number of possible process steps.
  • the electrodes obtained by the process of the present invention are advantageous since they combine the excellent mechanical, electrochemical and/or electrical properties of carbon with the superior lithium alloying ability of silicon. By consequence, they are to be suitable to overcome the limitations of pure silicon and offer significant improvements in the specific capacity and cycle stability.
  • the process according to the present invention provides the production of an electrode containing silicon particles coated with carbon (SP2) in an advantageous manner and the electrode in turn provides an improvement of cycle stability and capacity of silicon based materials for Li ion batteries.
  • SP2 silicon particles coated with carbon
  • any kind of carbon-containing gas e.g. alkanes or derivatives such as CH 4 or CH 2 CI 2 , alkenes such as C 2 H 4 , alkynes such as C 2 H 2 , aromatic compounds such as C 6 H 6 or C 7 H 8 , alcohols such as CH 3 OH or C 2 H 5 OH or any kind of carbon-containing compound that can be used in a controlled way for coating the particles (SP1 ) with carbon, or any mixture thereof, can be used.
  • alkanes or derivatives such as CH 4 or CH 2 CI 2
  • alkenes such as C 2 H 4
  • alkynes such as C 2 H 2
  • aromatic compounds such as C 6 H 6 or C 7 H 8
  • alcohols such as CH 3 OH or C 2 H 5 OH
  • Another advantage is that optionally further gases such as inert gases such as Ar and He, or reactive gases such as C0 2 , N 2 , H 2 , NH 3 , BCI 3 , BF 3 or any other reactive gas which can be used to incorporate nitrogen or boron heteroatoms into the carbon coating layer, or any mixture thereof, can be used together with the above mentioned carbon-containing gas or gas mixture.
  • further gases such as inert gases such as Ar and He, or reactive gases such as C0 2 , N 2 , H 2 , NH 3 , BCI 3 , BF 3 or any other reactive gas which can be used to incorporate nitrogen or boron heteroatoms into the carbon coating layer, or any mixture thereof, can be used together with the above mentioned carbon-containing gas or gas mixture.
  • Another advantage is the high flexibility according to the process excitation power and treatment/reaction times at variable pressure.
  • Another advantage is that stable plasma can be maintained using the mentioned different plasma gas mixtures at variable pressure, i.e. at low or at high pressure. Another advantage is that when a low pressure is used, stable plasma can be maintained using the mentioned different plasma gas mixtures. This is possible even at relatively low excitation energies.
  • step a) of the process according to the invention silicon particles (SP1 ) on a sample holder (SH) of an apparatus (A) are provided.
  • the apparatus (A) according to the present invention comprises a reactive zone (RZ) and a sample holder (SH) located below the reactive zone (RZ).
  • the reactive zone (RZ) is the area inside apparatus (A) in which reactions of particles (SP1 ) take place. This area can consume a large area inside apparatus (A).
  • apparatus (A) is freely adjustable to the conditions needed and can be a glass frit or anything which is suitable by any means which is known to a person skilled in the art. Further, apparatus (A) may comprise at least one inlet for gaseous stream (G), and an outlet (O) located at the top of apparatus (A).
  • Apparatus (A) may preferably be designed in such way in order to comply with a fluidized bed process under plasma conditions (as defined later in steps c) and d)).
  • Silicon particles (SP1 ) according to the present invention are different forms of silicon, like e.g. crystalline silicon, amorphous silicon, porous silicon or black silicon. Preferred forms of silicon according to the invention are selected from crystalline silicon and/or amorphous silicon. Further, the silicon particles (SP1 ) according to the invention may have different morphologies such as spheres, rods, fibers, (nano)wires or may be made of arbitrary geometry or may be a mixture of the aforementioned morphologies.
  • silicon particles (SP1 ) according to the invention may be solid or hollow, and/or they may have monomodal, bimodal or higher-order particle size distribution.
  • the silicon particles (SP1 ) may also be non-agglomerated particles or agglomerated.
  • the silicon particles (SP1 ) may be synthesized by e.g. laser ablation, laser synthesized from vapor phase, plasma synthesized, obtained by ball milling of silicon wafers or by any suitable method known in the state of the art. Silicon particles (SP1 ) with a particle size below 200 ⁇ , preferably below 100 ⁇ , more preferably below 50 ⁇ , even more preferably below 1 ⁇ , most preferably below 500 nm can be used in the process according to the invention.
  • the silicon particles (SP1 ) are usually not smaller than 1 nm, preferably the silicon particles (SP1 ) are not smaller than 5 nm.
  • these silicon particles (SP1 ) predominantly contain pure silicon.
  • the silicon particles (SP1 ) comprise at least 95 wt.-%, preferably at least 98 wt.-%, most preferably 99.9 wt.-% of pure silicon.
  • a native Si0 2 -layer may develop by oxidation.
  • the silicon particles (SP1 ) may contain impurities, e. g. oxygen, nitrogen, carbon or other elements due to the synthesis process of the silicon particles (SP1 ). These impurities may also be present in form of e. g. Si0 2 or SiC. These impurities may be present inside or on the surface of particles (SP1 ). Therefore, according to the present invention, the silicon particles (SP1 ) may comprise either pure silicon but also silicon with impurities, wherein pure silicon is preferred. Further, the mass percentage of the impurities is usually not higher than 15 wt.-%, preferably not higher than 10 wt.-%, more preferably not higher than 5 wt.-%.
  • a drying step may be carried out with the silicon particles (SP1 ).
  • This additional drying step may be carried out in order to remove volatiles and humidity from the silicon particles (SP1 ). Drying steps as such are known to persons skilled in the art.
  • the silicon particles (SP1 ) are dried for a period of usually more than 0.5 hours and/or at elevated temperatures of at least 50°C. More preferably the drying step is carried out for at least 12 hours at 120°C in vacuo at a pressure of below 100 mbar, preferably below 10 mbar.
  • the surface of the silicon particles (SP1 ) may also be treated to remove surface contaminations (e.g. carbon based compounds) or surface layers (e.g. Si0 2 ).
  • the treatment may be carried out, e.g. by an etching step using acids, in a plasma containing appropriate reactive gases, e.g. C x Fy compounds for removal of Si0 2 (see for example "Fluorocarbon-based plasma etching of Si0 2 : Comparison of C 4 F 6 /Ar and C 4 F 8 /Ar discharges, X. Li, X. Hua, L. Ling, G. S. Oehrlein, M. Barela, H. M. Anderson, J. Vac.
  • step b) of the process according to the invention the plasma in the reactive zone (RZ) of apparatus (A) is generated.
  • the expression "generation of plasma” in the context of the present invention is understood as the ignition of the plasma in step b) and the maintenance of the plasma in steps b), c) and/or d).
  • the generator is then switched on, and the plasma is ignited in the reactive zone (RZ) without any gas flow at low pressure (P ⁇ 0.1 mbar).
  • a generator may be used for the ignition of the plasma with electromagnetic excitation. This step may be conducted without any gas flow at low pressure (e.g. ⁇ 0.1 mbar).
  • the electromagnetic excitation frequency for the plasma generation in steps b), c) and/or d) is in the range selected from below 100 Hz, a low-frequency range between 100 Hz and 10 kHz, a radiofrequency range between 10 kHz and 300 MHz, a microwave frequency range between 300 MHz and 300 GHz, or above 300 GHz.
  • the power fed via the plasma into the reactive zone (RZ) in steps b), c) and/or d) may be between 0.05 kW and 50 kW, preferably between 0.1 kW and 5 kW, more preferably between 0.2 kW and 3 kW, and most preferably between 0.7 kW and 1 .6 kW.
  • step c) of the process according to the invention the silicon particles (SP1 ) are fluidized in apparatus (A) with a gaseous stream (G), containing at least one carbon- containing gas and optionally containing at least one further gas, into the reactive zone (RZ).
  • G gaseous stream
  • RZ reactive zone
  • Any kind of carbon-containing gas e.g. alkanes or derivatives such as CH 4 or CH 2 CI 2 , alkenes such as C 2 H 4 , alkynes such as C 2 H 2 , aromatic compounds such as C 6 H 6 or C 7 H 8 , alcohols such as CH 3 OH or C 2 H 5 OH or any kind of carbon-containing compound that can be used in a controlled way for coating the particles (SP1 ) with carbon, or any mixture thereof, can be used in the process according to the invention.
  • alkanes or derivatives such as CH 4 or CH 2 CI 2
  • alkenes such as C 2 H 4
  • alkynes such as C 2 H 2
  • aromatic compounds such as C 6 H 6 or C 7 H 8
  • alcohols such as CH 3 OH or C 2 H 5 OH
  • any kind of carbon-containing compound that can be used in a controlled way for coating the particles (SP1 ) with carbon, or any mixture thereof, can be used in the process according to the invention.
  • further gases such as inert gases such as Ar and He, or reactive gases such as C0 2 , N 2 , H 2 , NH 3 , BCI 3 , BF 3 or any other reactive gas which can be used to incorporate nitrogen or boron heteroatoms into the carbon coating layer, or any mixture thereof, can be used together with the above mentioned carbon-containing gas or gas mixture.
  • inert gases such as Ar and He
  • reactive gases such as C0 2 , N 2 , H 2 , NH 3 , BCI 3 , BF 3 or any other reactive gas which can be used to incorporate nitrogen or boron heteroatoms into the carbon coating layer, or any mixture thereof, can be used together with the above mentioned carbon-containing gas or gas mixture.
  • the at least one carbon-containing gas is preferably selected from CH 2 CI 2 , C 2 H 4 , C 6 H 6 , C 7 H 8 , CH 4 or C 2 H 2 , and/or the optional further gas is preferably selected from Ar or H 2 .
  • the at least one carbon-containing gas is most preferably selected from CH 4 or C 2 H 2 , and/or the optional further gas is most preferably Ar.
  • the gaseous stream (G) is fed into apparatus (A1 ) from below the sample holder (SH).
  • the gaseous stream (G) may be fed into apparatus (A1 ) at several positions below the sample holder (SH) at the same time.
  • the gaseous stream (G) is usually continuous. However, in one embodiment of the invention in steps c) and/or d), gaseous stream (G) may be blocked for a short period of time, wherein the period of time is not longer than 20 seconds, preferably not longer than 10 seconds, more preferably not longer than 5 seconds, even more preferably not longer than 1 second.
  • the blocking of gaseous stream (G) can be advantageous for the fluidization of the particles (SP1 ) in the reactive zone (RZ).
  • Another option to improve the fluidization of the particles (SP1 ) in the reactive zone (RZ) is to mix the particles (SP1 ) with e.g. micro-particles, which are between 200 and 1000 ⁇ . These particles can be filtered out after step d) of the process.
  • the system pressure in apparatus (A) in steps b), c) and/or d) may be kept between 50 mbar and 0.05 mbar, preferably between 25 mbar and 0.05 mbar, preferably between 10 mbar and 0.05 mbar, most preferably between 1 mbar and 0.05 mbar.
  • the gaseous stream (G) in the process according to the invention may have any suitable process flow rate known to a skilled person, for example it may have a process flow rate of about 100 seem.
  • the process flow rate is a measure for the amount of gas(es) used in the process per minute. However, the process flow rate can be higher e.g. up to 5000 seem, preferably up to 2000 seem, more preferably up to 500 seem. In principle, there is no upper limit for the gas flow.
  • step d) of the process according to the invention the silicon particles (SP1 ) are coated in the reactive zone (RZ) of apparatus (A) to obtain silicon particles coated with carbon (SP2).
  • the coating as such according to step d) means that the silicon particles (SP1 ), which are fluidized according to step c), react with the carbon-containing gas of gaseous stream (G) under plasma conditions in the reactive zone (RZ) of apparatus (A). By consequence, silicon particles coated with carbon (SP2) are obtained.
  • the coating can be performed both as a full and as a partial coating on the surface of the silicon particles (SP1 ) to obtain silicon particles coated with carbon (SP2).
  • Full coating of the silicon particles (SP1 ) is preferred.
  • "Partial coating” means that at least 30% of the surface of the silicon particles (SP1 ) is coated, preferably at least 50% of the surface of the silicon particles (SP1 ) is coated, more preferably at least 70% of the surface of the silicon particles (SP1 ) is coated, most preferably at least 90% of the surface of the silicon particles (SP1 ) is coated.
  • the thickness of the coating of the particles coated with carbon (SP2) can be adjusted as necessary.
  • the coating usually has a thickness of less than 1 ⁇ , preferably the coating has a thickness of less than 500 nm, more preferably the coating has a thickness of less than 150 nm, even more preferably the coating has a thickness of less than 50 nm and most preferably the coating has a thickness of less than 20 nm.
  • the coating of the particles coated with carbon may be porous. Further, the coating of the particles coated with carbon may be amorphous, graphitic or a mixture of both. Further, in the coating of the particles coated with carbon (SP2), heteroelements such as nitrogen, boron, sulfur, phosphorus or mixtures of different heteroelements may be included.
  • the silicon particles (SP1 ) are kept in the reactive zone (RZ) in steps c) and d) according to the invention for suitable times to fluidize and to coat them.
  • the time of the silicon particles (SP1 ) kept in the reactive zone (RZ) in steps c) and d) is usually between 0.1 seconds and 7 days, preferably between 1 second and 2 days, more preferably between 10 seconds and 12 hours, even more preferably between 30 seconds and 6 hours and most preferably between 1 minute and 3 hours.
  • the coating of the silicon particles (SP1 ) with carbon according to step d) is preferably carried out by chemical vapor deposition of at least one carbon-containing gas on the surface of the silicon particles (SP1 ) under plasma conditions.
  • CVD chemical vapor deposition
  • a plasma can be considered as an electrically neutral medium comprising electrons, ions and electronically excited species.
  • vapour reactants are ionised and dissociated by electron impact, and hence generating chemically active ions and radicals that undergo a chemical reaction at or near a substrate surface and deposit the solid material ("Chemical vapour deposition of coatings", K. L. Choy, Progress in Materials Science, 2003, 48, 57-170.).
  • the apparatus (A) according to the invention may be designed as a fluidized bed process under plasma conditions.
  • a fluidized bed process is known to the person skilled in the art.
  • particles are brought in contact with the plasma in the reactive zone (RZ) by lifting them (fluidizing) by the process gas flow.
  • the silicon particles coated with carbon (SP2) produced according to the invention have a particle size below 200 ⁇ , preferably below 100 ⁇ , more preferably below 50 ⁇ , even more preferably below 1 .2 ⁇ , most preferably below 700 nm.
  • the silicon particles (SP2) are usually not smaller than 2 nm, preferably the silicon particles (SP2) are not smaller than 10 nm.
  • silicon particles coated with carbon are preferably conducting particles.
  • the particles coated with carbon (SP2) may be treated to increase the porosity of the coating, e. g. by C0 2 etching, which is known by the person skilled in the art.
  • the particles coated with carbon (SP2) may be treated at high temperature in inert atmosphere to increase the graphitization degree of the coatings of the particles coated with carbon (SP2).
  • step e) of the process according to the invention the silicon particles coated with carbon (SP2) are further processed to obtain the electrode containing silicon particles coated with carbon (SP2).
  • step e) comprises the following partial steps e1 ) to e3).
  • the silicon particles coated with carbon (SP2) are mixed with graphite, a further conductive additive and a binder in a solution.
  • the solution used in partial step e1 ) of the process may comprise any organic solvent and/or water.
  • the solution used in partial step e1 ) is an aqueous solution.
  • the solution used in partial step e1 ) of the process may comprise at least partially an organic solvent.
  • the aqueous solution comprises a percentage of at least 5 wt.-%, preferably at least 10 wt.-%, more preferably of 20 wt.- % and most preferably of 50 wt.-% of an organic solvent.
  • Organic solvents are known to the person skilled in the art.
  • the concentration of the binder in the solution in partial step e1 ) is between 0.1 wt.-% and 20 wt.-%, preferably between 5 wt.-% and 15 wt.-%.
  • the binder is preferably polyacryllic acid.
  • the wt.-%-values of the concentration of the binder are related to the full amount of all components of the solution prepared in partial step e1 ).
  • the graphite content in partial step e1 ) is between 0.1 wt.-% and 80 wt.-%, preferably between 15 wt.-% and 60 wt.-%, and more preferably between 20 wt.-% and 40 wt.-%.
  • graphite can be used e.g. Timrex SFG6L (as commercially available by Timcal).
  • the wt.-%-values of the graphite content are related to the full amount of all components of the solution prepared in partial step e1 ).
  • the content of the further conductive additive in partial step e1 ) is between 0.1 wt.-% and 20 wt.-%, preferably between 5 wt.-% and 15 wt.-%.
  • the further conductive additive is preferably carbon black. Further, as carbon black can be used e.g. Super P (C65) (as commercially available by Timcal).
  • the wt.-%-values of the content of the further conductive additive are related to the full amount of all components of the solution prepared in partial step e1 ).
  • the mixing in partial step e1 ) may be carried out e.g. by adding the above mentioned components to a beaker and mechanically blending them by planetary mixing using a Thinky (Laguna Hills, California) ARE 200 mixer to obtain a homogeneous slurry. Mixing methods like the aforementioned or other suitable methods for mixing are known to the person skilled in the art.
  • partial step e2) which follows after partial step e1 ), an electrode support is coated with the mixture obtained in partial step e1 ).
  • the electrode support in partial step e2) is a metal foil, more preferably the electrode support in partial step e2) is a copper foil.
  • the coating (or casting) onto an electrode support may be carried out e.g. by the doctor blade method, which is known to the person skilled in the art, or any other suitable method known in the field.
  • partial step e3) which follows after partial step e2) the coated electrode support obtained in step partial e2) is dried and punched out to obtain an electrode containing silicon particles coated with carbon (SP2).
  • the drying of the coated electrode support in partial step e3) may be carried out at room temperature first, e.g. for 2h, followed by drying in a vacuum chamber. Drying in the vacuum chamber, which is generally know to the person skilled in the art, may be carried out for several hours e.g. 12 h at higher temperature, e.g. 100 °C and in vacuo, e.g. 1 mbar.
  • the punching out of the electrode containing silicon particles coated with carbon (SP2) is usually carried out with a cutter, e.g. an EL-Cut electrode cutter (as commercially available from EL-CELL (Hamburg, Germany)).
  • an electrode as e.g. produced by the process according to the invention can be an anode or a cathode. However, preferably here the electrode is an anode.
  • a preferred embodiment of the invention may comprise: i) gaseous stream (G) containing at least one carbon-containing gas, which is preferably selected from CH 2 CI 2 , C 2 H 4 , C 6 H 6 , C 7 H 8 , CH 4 or C 2 H 2 , and/or the optional further gas is preferably selected from Ar or H 2 , and/or
  • silicon particles (SP1 ) preferably having particle sizes below 50 ⁇ , and/or iii) a system pressure in apparatus (A) in steps b), c) and/or d), which is preferably kept between 25 mbar and 0.05 mbar, and/or
  • step c) blocking of gaseous stream (G) in step c) at least once for preferably not longer than 20 seconds, and/or
  • the time of the silicon particles (SP1 ) kept in the reactive zone (RZ) in steps c) and d) being preferably between 1 second and 2 days.
  • this embodiment contains all options i) to v) as defined above.
  • Another preferred embodiment of the invention contains at least the following options: i) gaseous stream (G) containing at least one carbon-containing gas, which is preferably selected from CH 4 or C 2 H 2 , and/or the optional further gas, which is preferably Ar, and/or
  • silicon particles (SP1 ) preferably having particle sizes below 1 ⁇
  • a system pressure in apparatus (A) in steps b), c) and/or d) which is preferably kept between 1 mbar and 0.05 mbar, and/or
  • step c) blocking of gaseous stream (G) in step c) at least once for preferably not longer than 10 seconds, and/or
  • the time of the silicon particles (SP1 ) kept in the reactive zone (RZ) in steps c) and d) being preferably between 1 minute and 3 hours.
  • this embodiment contains all options i) to v) as defined above.
  • Another preferred embodiment of the invention contains at least the following options: i) the concentration of the binder in the solution in step e1 ) is preferably between 5 wt.-% and 15 wt.-%, and/or
  • the graphite content in step e1 ) is preferably between 15 wt.-% and 60 wt.-%, and/or
  • the content of the further conductive additive in step e1 ) is preferably between 5 wt.-% and 15 wt.-%, and/or
  • the solution in step e1 ) is preferably an aqueous solution, and/or
  • the binder in step e1 ) is preferably polyacryllic acid, and/or
  • the further conductive additive in step e1 ) is preferably carbon black
  • the electrode support in step e2) is preferably a metal foil.
  • this embodiment contains all options i) to vii) as defined above.
  • Another preferred embodiment of the invention contains at least the following options: i) the concentration of the binder in the solution in step e1 ) is preferably between 5 wt.-% and 15 wt.-%,
  • the graphite content in step e1 ) is preferably between 20 wt.-% and 40 wt.-%, iii) the content of the further conductive additive in step e1 ) is preferably between 5 wt.-% and 15 wt.-%,
  • the solution in step e1 ) is preferably an aqueous solution
  • the binder in step e1 ) is preferably polyacryllic acid
  • the further conductive additive in step e1 ) is preferably carbon black, and/or vii) the electrode support in step e2) is preferably a copper foil.
  • this embodiment contains all options i) to vii) as defined above.
  • An electrode containing silicon particles coated with carbon (SP2) as such is an electrode containing silicon particles coated with carbon (SP2) as such.
  • An electrode can be an anode or a cathode, preferred is an anode.
  • Another subject of the present invention is a battery containing silicon particles coated with carbon (SP2) as such, preferably the battery is a lithium ion battery.
  • the electrode containing silicon particles coated with carbon (SP2) according to the present invention can be used in a battery, preferably the battery being a lithium ion battery and/or the electrode preferably being an anode.
  • Alfa Aesar silicon particles - 100 + 325 mesh size, which is corresponding to particles with a size between 44 ⁇ and 149 ⁇ (Alfa-Si-100-325)
  • the hereby disclosed process is designed as a fluidized bed plasma process with standard access to various gases to the reactor (apparatus (A)).
  • a Huettinger PFG 500 RF generator (13.56 MHz, 5 kW) is used as plasma reactor.
  • the RF power is applied through the matching circuit by an outer coil.
  • the reaction chamber consists of an inner quartz tube of 60 mm diameter and a concentrically arranged outer quartz tube.
  • a quartz frit below the induction coil serves as material support and gas distributor.
  • the space between inner and outer tube is used for the water cooling of the reactor.
  • the base pressure of the system is about 2e "3 mbar.
  • All silicon particles (SP1 ) are dried at 120°C in vacuo for at least 12 h prior to loading them in the reactor.
  • the reactor loading depends on the particles to be treated and is typically 30 g for Alfa-Si-100-325 and 1 g for 50 nm Alfa Si.
  • the reactor is evacuated.
  • the generator is then switched on, and the plasma is ignited in the reactive zone (RZ) without any gas flow at low pressure (P ⁇ 0.1 mbar).
  • the gas flow gaseous stream (G)) is increased to the process flow rate. This also starts the fluidization of the particles.
  • the operating pressure during plasma modifications is in the range of 0.1 - 5 mbar.
  • Typical process flow rates are about 100 seem. The process flow rates have to be adjusted to the used particles to provide satisfactorily fluidization. Blocking of gaseous stream (G) can be used to improve fluidization. The experiments are carried out for 2 - 120 minutes under stable plasma conditions. After synthesis, the product (silicon particles coated with carbon (SP2)) is collected. Table 1 provides an overview over the carried out examples.
  • Table 1 Overview of carried out examples with Alfa-Si-100-325.
  • Table 2 Elemental analysis of examples according to table 1 as well as of untreated particles (example 1v).
  • Example 1 b H 2 plasma (comparison example): No carbon coating is observed.
  • Example 1 d, CH 4 plasma A carbon coating is confirmed by imaging and EDXS (energy-dispersive X-ray spectroscopy). For some particles the amorphous C-Layer is continuous for other particles not. The thickness is up to about 10 nm.
  • EDXS energy-dispersive X-ray spectroscopy
  • Example 1 e, CH 4 plasma Carbon is detected by EDXS.
  • the thickness of the amorphous C-Layer is up to about 20 nm.
  • Example 1f, CH 4 plasma hP Carbon coating is observed only occasionally, most probably due to the insufficient particle mixing during the synthesis process.
  • Example 1 h, Ar/C 2 H 2 plasma The thickness of the amorphous C-Layer is up to about 80 nm.
  • Example 1 i Ar/C 2 H 2 plasma: The thickness of the amorphous C-Layer is up to about 80 nm.
  • Example 1 k, Ar/C 2 H 2 plasma The thickness of the amorphous C-Layer is up to about 50 nm.
  • Example 11 Ar/C 2 H 2 /C0 2 plasma: The thickness of the amorphous C-Layer is up to about 80 nm.
  • Example 1 m, Ar/C 2 H 2 /H 2 plasma: The thickness of the amorphous C-Layer is up to about 120 nm.
  • XPS is a surface sensitive analysis method.
  • the information depth is approximately 2- 10 nm ( ⁇ 1 -40 monolayers).
  • the size of the measurement spot is approximately 0.3 x 0.8 mm. Because of the surface sensitivity and the limited information depth the quantitative and in the extreme case even the qualitative results of the elemental composition as determined by XPS can differ from results obtained by bulk methods such as elemental analysis.
  • the surface elemental composition of three examples as determined by XPS analysis is shown in Table 3.
  • the relatively high C-content of the untreated material is due to surface contamination by adsorption of atmospheric carbon based impurities. This is a well known phenomenon.
  • the C-content of the examples 1 d and 1 h is significantly higher (more than double) compared to the untreated example 1 v, thus confirming the successful coating of the silicon particles (SP1 ) by the process according to the invention in examples 1 d and 1 h.
  • Table 3 Surface elemental composition of examples 1v, 1 d and 1 h.
  • Table 4 Overview of carried out example with 50 nm Alfa Si.
  • Table 5 Elemental analysis of the example according to table 4 as well as of untreated particles (example 2v).
  • SP2 silicon particles coated with carbon
  • CB graphite
  • CB Super P carbon black
  • PAA, Mw 450,000 grmol "1 Sigma-Aldrich
  • the as-prepared silicon particles (60 wt.-%), graphite (15 wt.-%), carbon black (15 wt.-%) and PAA binder in aqueous solution (10 wt.-%) are added to a beaker and mechanically blended by planetary mixing using a Thinky (Laguna Hills, California) ARE 200 mixer.
  • the homogeneous slurry is then cast onto a copper foil using the doctor blade method. After coating, the coated foil is dried at room temperature for 2 h and then transferred to a vacuum drying chamber at a temperature of 100 °C. The coated foil is dried overnight at 1 mbar. Thereafter, 14 mm diameter electrodes are punched out using an EL-Cut electrode cutter from EL-CELL (Hamburg, Germany) and introduced into an argon-filled glove box.
  • Example 4 Example 4:
  • Electrochemical testing/characterization Prior to assembling a test cell, the electrodes containing silicon particles coated with carbon (SP2), as prepared according to example 3 are evacuated at 70°C overnight.
  • the as-prepared electrode containing silicon particles coated with carbon (SP2) is tested as an anode material to investigate the effect of carbon coating on the electrochemical behavior (example 2a).
  • the bare silicon sample without carbon coating is also tested (example 2v).
  • the cells are cycled at the potential range 0.01 -1 V at various C-rate using galvonostat-potentiostat (Bio-Logic, France).
  • the C-rate is a measure of the rate at which a battery is charged/discharged relative to its maximum capacity.
  • a 1 C rate e.g. means that the charge/discharge current will charge/discharge the entire battery in 1 hour.
  • a C/10 rate e.g. means that the charge/discharge current will charge/discharge the entire battery in 10 hours.
  • the cells are put in a formation process consisting one C/20, 20 cycles of C/10, and 20 cycles of C/5.
  • the performance of the cell containing silicon particles coated with carbon (SP2) (example 2a) is superior compared to the reference anode.
  • the first discharge capacity is lower than that of reference cell, which is associated with lower silicon content (45 wt.-%) in the cell containing silicon particles coated with carbon (SP2).
  • the drop of capacity is much slower than that of reference cell and after 35 cycles approximate 66% of the initial capacity is recovered.
  • the noticeable improvement of stability under cycling might be attributed to the fact that the silicon particles (SP2) are protected by carbon, which buffers the large volume changes and enhances the conductivity during cycling.

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Abstract

La présente invention se rapporte à un procédé permettant de produire une électrode contenant des particules de silicium qui sont recouvertes de carbone (SP2). Le procédé en question est mis en œuvre dans des conditions de plasma en combinaison avec un procédé à lit fluidisé étant donné que des particules de silicium (SP1) qui doivent être recouvertes de carbone sont fluidisées dans la zone réactive d'un appareil (A), à l'aide d'un courant gazeux (G) contenant au moins un gaz contenant du carbone. Le revêtement des particules de silicium (SP1) dans la zone réactive (RZ) d'un appareil (A) est, de préférence, réalisé par l'intermédiaire d'un dépôt chimique en phase vapeur (CVD). Les particules de silicium recouvertes de carbone (SP2) obtenues au cours de l'étape de traitement d) de la présente invention sont en outre traitées afin d'obtenir une électrode contenant de telles particules de silicium recouvertes de carbone (SP2). La présente invention se rapporte en outre à une telle électrode ainsi qu'à une batterie contenant une telle électrode. La présente invention se rapporte également à l'utilisation d'une telle électrode contenant des particules de silicium recouvertes de carbone (SP2) à l'intérieur d'une telle batterie qui est, de préférence, une batterie au lithium-ion.
PCT/EP2015/079137 2014-12-10 2015-12-09 Procédé permettant de produire une électrode contenant des particules de silicium recouvertes de carbone WO2016091957A1 (fr)

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CN111900370A (zh) * 2020-07-24 2020-11-06 陕西煤业化工技术研究院有限责任公司 一种氧化亚硅/碳复合材料及制备方法和应用
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US11717886B2 (en) 2019-11-18 2023-08-08 6K Inc. Unique feedstocks for spherical powders and methods of manufacturing
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US11919071B2 (en) 2020-10-30 2024-03-05 6K Inc. Systems and methods for synthesis of spheroidized metal powders
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US11839919B2 (en) 2015-12-16 2023-12-12 6K Inc. Spheroidal dehydrogenated metals and metal alloy particles
US11110433B2 (en) 2016-03-18 2021-09-07 Basf Se Metal-doped tin oxide for electrocatalysis applications
CN108155353A (zh) * 2017-11-20 2018-06-12 中南大学 一种石墨化碳包覆电极材料及其制备方法和作为储能器件电极材料的应用
CN108155353B (zh) * 2017-11-20 2020-11-03 中南大学 一种石墨化碳包覆电极材料及其制备方法和作为储能器件电极材料的应用
US11633785B2 (en) 2019-04-30 2023-04-25 6K Inc. Mechanically alloyed powder feedstock
US11717886B2 (en) 2019-11-18 2023-08-08 6K Inc. Unique feedstocks for spherical powders and methods of manufacturing
US11590568B2 (en) 2019-12-19 2023-02-28 6K Inc. Process for producing spheroidized powder from feedstock materials
CN111900370A (zh) * 2020-07-24 2020-11-06 陕西煤业化工技术研究院有限责任公司 一种氧化亚硅/碳复合材料及制备方法和应用
CN112331817A (zh) * 2020-08-14 2021-02-05 安徽德亚电池有限公司 一种高导电性电极材料的制备方法
US11963287B2 (en) 2020-09-24 2024-04-16 6K Inc. Systems, devices, and methods for starting plasma
US11919071B2 (en) 2020-10-30 2024-03-05 6K Inc. Systems and methods for synthesis of spheroidized metal powders

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