US20140315086A1 - Positively Charged Silicon for Lithium-Ion Batteries - Google Patents

Positively Charged Silicon for Lithium-Ion Batteries Download PDF

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US20140315086A1
US20140315086A1 US14/364,326 US201214364326A US2014315086A1 US 20140315086 A1 US20140315086 A1 US 20140315086A1 US 201214364326 A US201214364326 A US 201214364326A US 2014315086 A1 US2014315086 A1 US 2014315086A1
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silicon
negative electrode
electrode material
oxide
particles
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Stijn Put
Jan Gilleir
Kris Driesen
Jean-Sebastien Bridel
Nicolas Marx
Delphine Longrie
Dan V. Goia
John I. Njagi
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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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
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    • 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
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • H—ELECTRICITY
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    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0416—Methods of deposition of the material involving impregnation with a solution, dispersion, paste or dry powder
    • H—ELECTRICITY
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    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0421—Methods of deposition of the material involving vapour deposition
    • H01M4/0428—Chemical vapour deposition
    • H—ELECTRICITY
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    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • H—ELECTRICITY
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    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/049—Manufacturing of an active layer by chemical means
    • H01M4/0492—Chemical attack of the support material
    • H—ELECTRICITY
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    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • 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

  • This invention relates to a negative electrode material for lithium-ion batteries comprising silicon and having a chemically treated or coated surface influencing the zeta potential of the surface.
  • an inherent drawback to electrodes based on alloys lies in their poor cycling life (e.g. rapid capacity fading) caused by the large volume swings upon subsequent charges/discharges, which results in an electrochemical grinding of the electrode, and hence its electric percolation loss, and in the mean time a huge electrolyte degradation on the particles surface.
  • the first optional solution was to use electrodes made of nanoparticles as the usual mechanisms of deformation and dislocation are not the same as the micro scale, with namely the small particles being capable of releasing strains without fracturing.
  • nanoscale silicon powders rapidly oxidize when exposed to air and the surface of commercially available Si or Si made in-situ in a plasma process, as disclosed in WO2012-000858, is covered by (protonated) silanol groups SiOH. These surface silanol groups cause a non-optimal behavior of the silicon particles in the anode electrode during the life of the battery.
  • the silicon based metal-based electrodes present generally a weak capacity retention with a cathode that contains a limited quantity of lithium. To avoid this issue, the silicon surface needs to be modified to limit the electrolyte degradation.
  • Si nanoparticles having a positive surface charge are coating with graphene.
  • the positive charge is caused by modification of the surface of the nanoparticles by functional groups, that are preferably selected from amino groups and ammonium groups, such as NR 2 and NR 3 + , where R is selected from H, C 1 -C 6 -alkyl or -hydroxyalkyl.
  • the invention aims at disclosing new Si based particles used in the negative electrode of a rechargeable battery that are capable of providing a better capacity retention during cycling.
  • the invention can provide a negative electrode material for use in a lithium rechargeable battery, the material comprising a core comprising silicon, wherein the material has a positive zeta potential in an interval between pH 3.5 and 9.5, and preferably between pH 4 and 9.5.
  • the zeta potential is at least +10 mV, preferably at least +20 mV, in the pH interval 3.5-9.5 and even in the interval 4-9.5.
  • the advantage of having a higher zeta potential is to improve the dispersion between carbon, active material and binder during the paste preparation in aqueous media.
  • zeta potential is naturally meant the potential measured in demineralized water.
  • the core material may be nanometric (thus having at least one dimension below 100 nm), of submicron size, or micron-sized, and may comprise a mixture of nano-sized Si particles and nano-sized Si wires, wherein the average particle size of the Si particles is at least 5 times the average width of the Si wires, and preferably at least 10 times the average width of the Si wires, such as described in WO2012-000854.
  • This negative electrode material for Li-ion secondary batteries offers considerable advantages in limiting the loss of capacity during cycling.
  • the material has a point of zero-charge at pH 4 or higher, preferably at pH 7 or higher.
  • the core has an average particle size between 20 nm and 200 nm (the average particle diameter was calculated assuming nonporous spherical particles and a theoretical density of the individual materials. Without going through the entire derivation, the equation for calculating the average particle diameter in nanometers is 6000/(BET surface area in m 2 /g) ⁇ (density in g/cm 3 )) and consists either of
  • the surface of the core carries O y SiH x groups, with 1 ⁇ x ⁇ 3, 1 ⁇ y ⁇ 3, and x>y.
  • the O y SiH x groups could also be considered to be a mixture of silanol (SiOH) and SiH x , with 1 ⁇ x ⁇ 3. The presence of silanol groups and SiH x can be detected by
  • the surface of the core is at least partly covered by a coating consisting of inorganic nanoparticles.
  • the surface being at least partly covered means that here too the surface of the core may further carry O y SiH x groups, with 1 ⁇ x ⁇ 3, 1 ⁇ y ⁇ 3, and x>y.
  • These inorganic nanoparticles may be either one of an aluminium compound (such as Al 2 O 3 ), a zinc compound (such as zinc oxide) and an antimony compound (such as antimony oxide).
  • the nanoparticles in the coating consist of a precursor material susceptible of being converted to either one of aluminium, zinc and antimony by reduction.
  • the nanoparticles may form a first coating layer on the core having a thickness of less than 10 nm.
  • a second coating layer located between the core and the first coating of nanoparticles, the second coating layer comprising either carbon or aluminium. Either one or both of the first and second coating layer may be electrochemically active.
  • the embodiment where the surface of the core is at least partly covered by a coating consisting of inorganic nanoparticles can be combined with the embodiment where the surface of the core carries O y SiH x groups, with 1 ⁇ x ⁇ 3, 1 ⁇ y ⁇ 3, and x>y.
  • the surface of the core is at least partly covered by adsorbed cationic polymers having either one or more of primary, secondary and tertiary amine functional groups.
  • the surface being at least partly covered means that here too the surface of the core may further carry O y SiH x groups, with 1 ⁇ x ⁇ 3, 1 ⁇ y ⁇ 3, and x>y.
  • the surface of the core is at least partly covered by adsorbed cationic multivalent metal ions. The surface being at least partly covered means that here too the surface of the core may further carry O y SiH x groups, with 1 ⁇ x ⁇ 3, 1 ⁇ y ⁇ 3, and x>y.
  • the metal ions may be either one or more of the group consisting of Al-, Sb-, Fe-, Ti- and Zn-ions.
  • This embodiment can be combined with the embodiment where the surface of the core carries O y SiH x groups, with 1 ⁇ x ⁇ 3, 1 ⁇ y ⁇ 3, and x>y.
  • the surface of the core is at least partly covered by adsorbed nanoparticles of cationic multivalent metal oxides. The surface being at least partly covered means that here too the surface of the core may further carry O y SiH x groups, with 1 ⁇ x ⁇ 3, 1 ⁇ y ⁇ 3, and x>y.
  • the metal oxides are either one or more of the group consisting of Al-oxide, Mg-oxide, Pb-oxide, Sb-oxide, Fe-oxide, Ti-oxide, Zn-oxide and In-hydroxide.
  • the surface of the core is at least partly covered by silanol groups (—Si—O ⁇ groups) covalently bound to amino-functional metal compounds, wherein the metal is either one or more of the group consisting of Si, Al and Ti.
  • the surface being at least partly covered means that here too the surface of the core may further carry O y SiH x groups, with 1 ⁇ x ⁇ 3, 1 ⁇ y ⁇ 3, and x>y.
  • the amino-functional metal compound used to chemically treat the core surface may be an alkoxide.
  • the invention can provide the use of the active material described before in a negative electrode further comprising either a water-soluble, or a N-methylpyrrolidone-soluble binder material.
  • the negative electrode may further comprising graphite.
  • the invention can provide a process for preparing a negative electrode material, comprising the steps of:
  • the invention can also provide a process for preparing a negative electrode material, comprising the steps of:
  • the invention can also provide a process embodiment for preparing a negative electrode material, comprising the steps of:
  • the invention can also provide a process for preparing a negative electrode material, comprising the steps of:
  • the invention can also provide a process for preparing a negative electrode material, comprising the steps of:
  • the final product may have an open porous volume lower than 0.01 cc/g.
  • the nanosized material in each of the processes above may consist of either particles or a mixture of particles and wires, wherein both the particles and the wires are nano-sized, and wherein the average particle size of the particles is at least 5 times the average width of the wires, and preferably at least 10 times the average width of the wires.
  • the silicon material may consist of either of
  • the invention can provide a process for preparing an electrode assembly for a rechargeable Li-ion battery comprising the negative electrode material described before, comprising the steps of:
  • FIG. 1 schematic representation of a silicon particle ( 21 ) with a positively charged layer ( 22 ) surrounded by a negatively charged polymer ( 23 )
  • FIG. 2 scheme of the silicon particles (or primary particles) ( 11 ) with A: coating with inorganic layer ( 12 ); B: physically adsorbed organic molecules ( 13 ); C: chemically attached organic molecules ( 14 ) and D: adsorbed nanoparticles (secondary particles) ( 15 ) at the surface of the primary particles
  • FIG. 3 scheme of the ALD reactor with P for pump, N-p for nanopowder and Ar for the Argon gas source.
  • FIG. 4 TEM picture of silicon particles ( 61 ) with alumina coating ( 62 )
  • FIG. 5 Zeta potential (mV) versus pH of coated silicon ( 1 ) and comparison with pristine silicon ( 2 ).
  • FIG. 7 Reversible delithiation capacity of a battery using coated silicon as anode material ( 1 ) and comparison with delithiation capacity of a battery using pristine silicon as anode material ( 2 ).
  • FIG. 8 Reversible delithiation capacity of a battery using alumina coated silicon (25 cycles of ALD) as anode material.
  • FIG. 9 TEM picture of silicon nanowires with alumina coating (a). EFTEM map of the samples with alumina contrast (b), silicon contrast (c) and oxygen contrast (d).
  • FIG. 10 Zeta potential (mV) according to pH of nanowires: coated nanowires ( 1 ) and comparison with pristine nanowires ( 2 ).
  • FIG. 11 Zeta potential (mV) according to pH of acid-base treated silicon
  • FIG. 12 Reversible delithiation capacity of a battery using treated silicon as anode material ( 1 ) and comparison with delithiation capacity of a battery using pristine silicon as anode material ( 2 ).
  • FIG. 14 Zeta potential (mV) versus pH of silicon carrying adsorbed alumina nanoparticles ( 1 ) and comparison with pristine silicon ( 2 ).
  • FIG. 15 Reversible delithiation capacity of a battery (mAh/g vs. cycle number) using alumina absorbed silicon as anode material ( 1 ) and reversible delithiation capacity of a battery using alumina treated silica absorbed silicon as anode material ( 2 ).
  • FIG. 16 Zeta potential (mV) versus pH of silicon carrying a physically adsorbed cationic polymer ( 1 ) and comparison with pristine silicon ( 2 ).
  • FIG. 17 Zeta potential (mV) versus pH of cation coated silicon ( 1 ) and comparison with pristine silicon ( 2 ).
  • FIG. 18 Reversible delithiation capacity of a battery (mAh/g vs. cycle number) using cation coated silicon as anode material
  • FIG. 19 Zeta potential (mV) versus pH of alumina coated silicon (different BET) ( 1 ) and comparison with pristine silicon (same initial BET) ( 2 ).
  • FIG. 20 Zeta potential (mV) versus pH of alumina coated silicon monoxide ( 1 ) and comparison with pristine silicon monoxide ( 2 ).
  • the goal of this invention is to propose a modified particle surface for a Si comprising particle, hereby maintaining the capacity throughout cycles by a good interaction with the binder, and decreasing the reactivity of the electrolyte with the surface.
  • the proposed approach in the invention is to modify the particle surface and to create a positively charged surface that is a surface having a positive zeta potential, in parts of the range of pH 3.5 to 9.5.
  • Positively charged particles are characterised by dispersing 20 g/l of powder in distilled water. Zeta potentials ‘Z’ of the dispersion in the aqueous medium are measured by using for example a Zetaprobe AnalyserTM from Colloidal Dynamics. Finally, a particle is defined as being a positively charged particle at a certain pH, if Z is higher than 0, and a negatively charged particle is defined as a particle having Z ⁇ 0. This is illustrated in FIG. 1 .
  • a silicon surface is natively negatively charged at neutral pH and can become positive between pH 2 and 3 (the isoelectric point or IEP of silica).
  • the chemical surface groups are mainly deprotonated silanol groups. This charge is not in favour of a good interaction with the negatively charged binder.
  • the preferred binder is a water soluble polymer, like carboxylmethylcellulose binder (CMC) or polyacrylates PM, which are negatively charged at neutral or even at lower pH.
  • FIG. 2 represents spherical particles, the particles may also consist of wires comprising silicon.
  • this coating may be insulating, since the lithium can diffuse through the thin layer (organic or inorganic layer). Also, when applying a thin metal oxide coating, there is the additional advantage that the oxide can be converted in a metal and lithium oxide during the first cycle in the lithium-ion battery. This irreversible conversion will create a metallic surface which can, as the silicon, create alloys with the lithium and generate extra capacity and allowing a volumic expansion; the proposed alumina/aluminium, zinc or antimony coating can grow with the volumic expansion of the silicon and protect continuously the electrolyte/silicon contact.
  • This positively charged silicon or material comprising silicon is tested as an anode material in a lithium-ion battery.
  • the powder is mixed with a binder and a carbon conductor to create a slurry that is coated on copper foil.
  • the invention allows to improve the electrochemical behaviour of the silicon comprising particles by improving the dispersion of the silicon, carbon and polymer in the coating on the copper foil, improving the capacity retention and lowering the irreversibility.
  • an alumina coating is applied by Atomic layer deposition (ALD), which is a deposition method to prepare nano-sized coatings.
  • ALD Atomic layer deposition
  • two (or more) alternating surface self-limiting chemical vapour deposition reactions are performed.
  • the technology is also used to coat nano-powders. Small quantities of powder can be coated using a stationary system, but for larger quantities a fluidized particle bed reactor or a rotating reactor can be used, as illustrated in US 2011/0200822.
  • a coating of Al 2 O 3 can be deposited by thermal ALD using Tri-Methyl Aluminium (TMA) and H 2 O as reactants.
  • TMA Tri-Methyl Aluminium
  • H 2 O reactants.
  • the reaction temperature is around 200° C.
  • the saturation of the reactive surface can be monitored using mass spectroscopy on the decomposition products of the precursors.
  • the reactor exit 3 is connected to a vacuum oil pump at 10 ⁇ 2 mbar.
  • the reactor gas inlet 1 is connected to a trimethyl aluminium (TMA) supply (97%, Sigma-Aldrich) using Swagelok® tubes and an automated valve.
  • TMA trimethyl aluminium
  • the reactor gas inlet 2 is connected to a glass bottle of H 2 O (de-ionized) using Swagelok® tubes and an automated valve.
  • HMA trimethyl aluminium
  • the valve connecting the reactor to TMA is opened until the surface is saturated with TMA (5 minutes) and closed. This is followed by opening the valve connecting the reactor to the H 2 O for 5 minutes. 6 cycles (TMA followed by water) are used for the preparation of the coating.
  • An equal quantity of pristine nano-silicon powder is used as reference example.
  • the microscopic pictures show conformal homogeneous and thin (3 nm) coatings of alumina on the surface of silicon particles (see FIG. 4 ).
  • the BET surface of this powder is determined at 20 m 2 /g (compared to 21 m 2 /g for the pristine silicon) and with a porous volume lower than 0.001 cc/g from the results of isotherm adsorption-desorption of N 2 at 77K after preheated for 1 h under a flow of argon at 150° C.
  • the aluminium quantity is measured by ICP and a value of 2 wt % is calculated.
  • the ALD process thus comprises the steps of:
  • the measure of the zeta potential of the resulting material is made according to the following procedure: 150 ml of both a reference 2 wt % nano-silicon powder and the alumina coated silicon suspension in demineralised water is prepared by ultrasonification (120 s at 225 W). The zeta potential of this suspension in the aqueous medium is measured with the Zetaprobe AnalyserTM from Colloidal Dynamics. The samples are automatically titrated from neutral pH to acid pH with 0.5 M HCl and to more basic pH with 0.5 M NaOH.
  • the high negative surface charge on nano-silicon powder can be clearly measured (see FIG. 5 , line 2 ).
  • the zeta potential is negative from pH 5 to 2.
  • the powder has a positive zeta potential from pH 9.5 to at least pH 2.5. ( FIG. 5 , line 1 )
  • a slurry is prepared using 50 wt % of this powder (based on the dry residue), 25 wt % of a Na-CMC binder (Molecular weight ⁇ 200 000) and 25 wt % of a conductive additive (Super C65, Timcal).
  • a conductive additive Super C65, Timcal
  • a 2.4% Na-CMC solution is prepared and dissolved overnight.
  • the conductive carbon is added to this solution and stirred for 20 minutes using a high-shear mixer. Once a good dispersion of the conductive carbon is obtained, the active material is added and the slurry is stirred again using a high-shear mixer during 30 minutes.
  • the electrodes are prepared by coating the resulting slurry on a copper foil (17 ⁇ m) using 125 ⁇ m wet thickness and then dried at 70° C. for 2 hours. Round electrodes are punched and dried at 150° C. during 3 hours in a small vacuum oven.
  • the electrodes are electrochemically tested versus metallic lithium using coin cells prepared in a glovebox (dry Argon atmosphere).
  • the electrolyte used is LiPF 6 1M in a mix of EC/DEC (50/50 wt %)+10% FEC+2% VC (Semichem).
  • the coin cells are tested in a CC mode between 10 mV and 1.5 Vat a C-rate of C/5 (meaning a full charge of discharge of 3570 mAh/g of active material in 5 hours). The result is shown in FIG. 7 .
  • Alumina coated silicon is prepared with the ALD process as in the Example 1. 25 cycles (TMA followed by water) are used for the preparation of this powder (compared to 6 cycles in the Example 1).
  • the alumina layer has a thickness of 12 nm.
  • the BET of the surface decreases to 16 m 2 /g and the quantity of alumina is measured at 8 wt % of the powder.
  • Slurries and batteries are prepared as in the Example 1, and the result is shown in the FIG. 8 .
  • the capacity is lower than 500 mAh/g from the first cycle, and this capacity drops in the following cycles. This result clearly shows the importance to have a thin layer at the surface of the silicon to allow the electrochemical reaction.
  • an alumina coating is applied by Atomic layer deposition (ALD) on Si particles and nanowires made according to WO2012-000854, and having an oxygen content ⁇ 4 wt %.
  • ALD Atomic layer deposition
  • the microscopic pictures show conformal homogeneous and thin coatings of alumina on the surface of the silicon particles.
  • the coated powder is dispersed in ethanol, after which it is placed on a carbon grid mounted on the Cu support.
  • the crushing step in the sample preparation was forgone, to avoid damaging the powder.
  • EFTEM maps showing silicon, alumina and oxygen contrast are acquired at 300 kV using the Philips CM30-FEG microscope (see FIG. 9 ).
  • the aluminium quantity is measured by ICP and a value of 2 wt % is calculated.
  • it is possible to prove that the silicon is fully covered with another material (here Al 2 O 3 ) by measuring the viscosity evolution of a CMC-powder solution according to time.
  • the measure of the zeta potential is made according to the following procedure: 150 ml of both a reference 2 wt % powder and the alumina coated silicon nanowires suspension in demineralised water is prepared by ultrasonification (120 s at 225 W). The zeta potential of this suspension in the aqueous medium is measured with the Zetaprobe AnalyserTM from Colloidal Dynamics. The samples are automatically titrated from neutral pH to acid pH with 0.5 M HCl and to more basic pH with 0.5 M NaOH.
  • the high negative surface charge on nanowires can be clearly measured (see FIG. 10 , line 2 ).
  • the zeta potential is negative from pH 8 to 2.
  • the powder has a huge positive zeta potential from pH 8 to at least pH 2. ( FIG. 10 , line 1 )
  • 150 ml of a 2 wt % nano-silicon suspension in demineralised water is prepared by ultrasonification (120 s at 225 W).
  • the nano-silicon is made according to WO2012-000858 and has a BET of 25 m 2 /g, an oxygen content ⁇ 4 wt %, a particle size defined as 80 nm ⁇ D80 ⁇ 200 nm, an aluminium contamination of at least 0.1 wt % (typical for a plasma generated silicon powder), the contamination being concentrated at the particles' surface, and has an initial negative zetapotential (defined at pH7 in water.
  • a known quantity of 0.5 M HCl is added to lower the pH to 2.
  • FIG. 11 describes the charge variation of the suspension during the acid-base treatment.
  • the measure has been done with the Zetaprobe AnalyserTM from Colloidal Dynamics and with solutions of 0.5 M HCl and 0.5 M NaOH.
  • a steep decrease in surface charge is observed (translated by a decrease of the absolute value of zetapotential), most probably due to the protonation of silanol groups on the oxidized Si-surface and due to a dissolution of the aluminium compound contaminant which liberates aluminium ions.
  • the zeta potential becomes positive between pH 3.4 and pH 4.9.
  • the first step is the preparation of 2.4% Na-CMC solution by dissolving overnight, and then adjusting its pH to the pH of the silicon suspension prepared previously.
  • the conductive carbon is added and the mixture is stirred for 20 minutes using a high-shear mixer.
  • the active material suspension treated silicon
  • the resulting slurry is stirred again using a high-shear mixer during 30 minutes.
  • the slurry is prepared with a final composition of 50 wt % of this powder, 25 wt % of a Na-CMC binder (Molecular weight ⁇ 200 000) and 25 wt % of a conductive additive (Super C65, Timcal).
  • Electrodes are prepared by coating the resulting slurry on a copper foil (17 ⁇ m) using 125 ⁇ m wet thickness and are then dried at 70° C. for 2 hours. Round electrodes are punched and dried at 150° C. during 3 hours in a small vacuum oven.
  • the electrodes are electrochemically tested versus metallic lithium using coin cells prepared in a glovebox (under dry Argon atmosphere).
  • the electrolyte used is LiPF 6 1M in a mix of EC/DEC (50/50 wt %)+10% FEC+2% VC (Semichem).
  • the coin cells are tested in a CC mode between 10 mV and 1.5 Vat a C-rate of C/5 (meaning a full charge of discharge of 3570 mAh/g of active material in 5 hours).
  • the result is shown in FIG. 12 , where the evolution of the capacity during cycling of the pristine nano-silicon powder ( 2 ) is compared to the evolution for alumina coated silicon ( 1 ).
  • the effectiveness of surface modification is evaluated by the zeta potential (ZP), which was determined from the electrophoretic mobility measurements over a broad range of pH values.
  • ZP zeta potential
  • the surface zeta potential of this powder is investigated using ZetaPALS from Brookhaven Instruments.
  • a dispersion containing 0.25 mg/cm 3 of modified silicon is prepared by dissolving the powder in 0.001 mol/L of KCl.
  • the pH is adjusted using 0.1 mol/L of KOH and 0.1 mol/L HCl solutions. Different weight ratios of APTS:Si were tested to concluded that a ratio of at least 1:2 is recommended to obtain a positive charge in the particles surface.
  • the success in surface modification is attested by the change in surface charge of the particles from negative to positive at pH values lower than 7, the amine treated particles having an iso-electric point at neutral pH.
  • the pristine Si particles are negatively charged over the pH range of 3-11. All the silicon particles traited with APTS have a similar zetapotential profile if the weight ratios of APTS:Si is higher than 1:2).
  • APTS is one of the examples of cationic silane which can be used to create a positive charge.
  • derivates of APTS such as aminomethyltriethoxysilane, 2-aminoethyltriethoxysilane, aminotriethoxysilane, 3-aminopropyltrimethoxysilane
  • derivates of APTS such as aminomethyltriethoxysilane, 2-aminoethyltriethoxysilane, aminotriethoxysilane, 3-aminopropyltrimethoxysilane
  • derivates of triethoxy(3-isocyanatopropyl)silane or derivates of N-[3-(Trimethoxysilyl)propyl]aniline.
  • the pH of the solution is equal to 6 and the zeta potential of this suspension in the aqueous medium is measured with the Zetaprobe AnalyserTM from Colloidal Dynamics.
  • the measured charge on these particles is positive as a zetapotential of +45 mV is measured. This value shows that the alumina colloids were absorbed on the surface of silicon particles.
  • the combined dispersion is then dried via a rotavap, heated to 80° C. under vacuum during 10 hours.
  • the measure of the zeta potential is made according to the following procedure: 100 ml of both a reference 1 wt % nano-silicon powder and the treated silicon powder suspension in demineralised water is prepared by ultrasonification (120 s at 225 W). The zeta potentials of these suspensions in the aqueous medium are measured with the Zetaprobe AnalyserTM from Colloidal Dynamics. The samples are automatically titrated from neutral pH to acid pH with 0.5 M HCl and to more basic pH with 0.5 M NaOH. The initial charge of the treaded silicon is positive as the zeta potential is measured at 53 mV. Thus, this value shows that the adsorption of nanoparticles of alumina is kept during the drying process.
  • the high negative surface charge on nano-silicon powder can be clearly measured (see FIG. 14 , line 2 ). While the zeta potential is negative from pH 2 to at least pH 5 in the case of the pristine silicon, the treated silicon powder has a positive zeta potential from pH 9.5 to at least pH 2.5. ( FIG. 14 , line 1 )
  • PEI Poly ethylene-imine
  • This polymer is a branched polymer containing primary, secondary and tertiary amine functional groups.
  • the nitrogen can be protonated to make the polymer highly positively charged. It also presents the advantages to be soluble in water.
  • a PEI/Si weight ratio of at least 0.35/1 is recommended or a mass of PEI of at least 14 mg per m 2 of silicon surface. This value shows that considerably less mass of PEI is necessary to obtain a positive charge than for nano-alumina in Example 5.
  • the combined dispersion is then dried via a rotavap, heated to 80° C. under vacuum during 10 hours.
  • the measure of the zeta potential is made according to the following procedure: 100 ml of both a reference 1 wt % nano-silicon powder and the treated silicon powder suspension in demineralised water is prepared by ultrasonification (120 s at 225 W). The zeta potentials of these suspensions in the aqueous medium are measured with the Zetaprobe AnalyserTM from Colloidal Dynamics. The samples are automatically titrated from neutral pH to acid pH with 0.5 M HCl and to more basic pH with 0.5 M NaOH. The initial charge of the treaded silicon is positive as the zeta potential is measured at +35 mV. Thus, this value shows that the adsorption of PEI is kept during the drying process.
  • the high negative surface charge on nano-silicon powder can be clearly measured (see FIG. 16 , line 2 ).
  • the treated silicon powder has a positive zeta potential from pH 6 to at least pH 2.5. ( FIG. 16 , line 1 ).
  • This effect can be also obtain by adsorption of others cationic surfactant and polymer based on pH-dependent primary, secondary, or tertiary amines as for example Octenidine dihydrochloride, Poly(4-vinylpyridine), Poly(2-vinylpyridine N-oxide), Poly(N-vinylpyrrolidone), . . . .
  • the measure of the zeta potential is made according to the following procedure: 100 ml of both a reference 1 wt % nano-silicon powder and the treated silicon powder suspension in demineralised water is prepared by ultrasonification (120 s at 225 W). The zeta potentials of these suspensions in the aqueous medium are measured with the Zetaprobe AnalyserTM from Colloidal Dynamics. The initial pH of this solution is 5.3 and the zetapotential is +40 mV. The sample is then automatically titrated from neutral pH to acid pH with 0.5 M HCl and to more basic pH with 0.5 M NaOH. The redispersed treated powder has a positive zetapotential from 2 to 7 ( FIG. 17 , line 1 ) with a stable value of +65 mV from 2 to 5. The zeta potential is negative from at least pH 5 to 2 in the case of the pristine silicon ( FIG. 17 , line 2 ).
  • Example 2 5 g of a nanosilicon powder, made according to WO2012-000858, and having a BET of 40 m 2 /g with a open porous volume lower than 0.001 cc/g (measurement done by ASAP equipment by isotherm adsorption-desorption of N 2 at 77K after preheated for 1 h under a flow of argon at 150° C.), an oxygen content ⁇ 4 wt %, and an initial negative zetapotential (defined at pH7 in water) are use and treated as in Example 1.
  • Microscopic pictures show conformal homogeneous and thin (3 nm) coatings of alumina on the surface of the silicon particles.
  • the BET surface of this powder is determined at 40 m 2 /g (no modification of the BET after the ALD treatment) and with a porous volume lower than 0.001 cc/g from the results of isotherm adsorption-desorption of N 2 at 77K after preheated for 1 h under a flow of argon at 150° C.
  • the aluminium quantity is measured by ICP and a value of 3.4 wt % is calculated.
  • the measure of the zeta potential of the resulting material is made according to the following procedure: 150 ml of both a reference 2 wt % nano-silicon powder and the alumina coated silicon suspension in demineralised water is prepared by ultrasonification (120 s at 225 W). The zeta potential of this suspension in the aqueous medium is measured with the Zetaprobe AnalyserTM from Colloidal Dynamics. The samples are automatically titrated from neutral pH to acid pH with 0.5 M HCl and to more basic pH with 0.5 M NaOH. The high negative surface charge on nano-silicon powder can be clearly measured (see FIG. 19 , line 2 ). The zeta potential is negative from pH 6 to 2. In the case of the alumina coated silicon, the powder has a positive zeta potential from at least pH 9 to at least pH 2.5. ( FIG. 19 , line 1 )
  • the electrodes are prepared and tested as described in the Example 1. The result shows that the behaviour of the electrode is improved with the coating of alumina: after 100 cycles, the delivered capacity remains around 2500 mAh/g, versus 1000 mAh/g for the pristine silicon (see FIG. 7 , line 2 ). It was found also that a coating that is thinner than 1 nm does not have the desired effect.
  • Example 1 5 g of a commercial micrometric powder (Aldrich), having a BET of 1 m 2 /g with a open porous volume lower than 0.001 cc/g (measurement done by ASAP equipment by isotherm adsorption-desorption of N 2 at 77K after preheated for 1 h under a flow of argon at 150° C.), an oxygen content ⁇ 4 wt %, and an initial negative zetapotential (defined at pH7 in water) are use and treated as in Example 1.
  • a commercial micrometric powder Aldrich
  • Example 8a Microscopic pictures show conformal homogeneous and thin (3 nm) coatings of alumina on the surface of the silicon particles.
  • the measure of the zeta potential of the resulting material is made as in Example 8a.
  • the negative surface charge on silicon powder can be clearly measured.
  • the zeta potential is negative from pH 6 to 2.
  • the powder has a positive zeta potential from at least pH 7 to at least pH 2.5.
  • Example 2 5 g of a micrometric silicon monoxide powder, which consists of a mixture at nanometric scale of Si and SiO 2 , and having a BET of 2 m 2 /g, an oxygen content around 32 wt %, and an initial negative zetapotential (defined at pH7 in water) are used and treated as in Example 1.
  • the high negative surface charge on micrometric silicon monoxide powder can be clearly measured (see FIG. 20 , line 2 ).
  • the zeta potential is negative from pH 7 to at least 4.
  • the powder has a positive zeta potential from at least pH 3 to pH 6.8. ( FIG. 20 , line 1 )
  • a carbon coated nanometric silicon powder which consists of a silicon core made according to WO2012-000858 with a carbon coating made by CVD (chemical vapour deposition of toluene) technic, and having a BET of 20 m 2 /g, an oxygen content around 4 wt %, and an initial zetapotential (defined at pH7 in water) near to zero are used and treated as in Example 1.
  • the particles characteristics alumina layer thickness and BET and oxygen content
  • the increase of positive charge can be measured by zetapotential measurement (performed as in the previous Examples).

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WO2013087780A1 (en) 2013-06-20
US20170244101A1 (en) 2017-08-24
TW201345027A (zh) 2013-11-01
KR20140110940A (ko) 2014-09-17
JP6104276B2 (ja) 2017-03-29
US10340516B2 (en) 2019-07-02

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