WO2015028542A1 - Prélithiation de particules de silicium - Google Patents

Prélithiation de particules de silicium Download PDF

Info

Publication number
WO2015028542A1
WO2015028542A1 PCT/EP2014/068240 EP2014068240W WO2015028542A1 WO 2015028542 A1 WO2015028542 A1 WO 2015028542A1 EP 2014068240 W EP2014068240 W EP 2014068240W WO 2015028542 A1 WO2015028542 A1 WO 2015028542A1
Authority
WO
WIPO (PCT)
Prior art keywords
lithium
silicon
nanoscale
silicon particles
anode
Prior art date
Application number
PCT/EP2014/068240
Other languages
German (de)
English (en)
Inventor
Mirko Herrmann
Janis DÖLLE
Original Assignee
Volkswagen Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Volkswagen Aktiengesellschaft filed Critical Volkswagen Aktiengesellschaft
Priority to KR1020167008477A priority Critical patent/KR101899223B1/ko
Publication of WO2015028542A1 publication Critical patent/WO2015028542A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • C01B33/021—Preparation
    • C01B33/023—Preparation by reduction of silica or free silica-containing material
    • C01B33/025—Preparation by reduction of silica or free silica-containing material with carbon or a solid carbonaceous material, i.e. carbo-thermal process
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • 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 method for producing at least one nanoscale silicon particle comprising silicon and a silicon dioxide reaction product, a silicon particle produced by this method and its use for producing an anode for a lithium-ion battery, and the method for producing a corresponding one Anode.
  • a lithium ion battery has a cathode, an anode and a separator.
  • the lithium ions are transported by means of electrolytes.
  • lithium iron phosphate, lithium nickel cobalt manganese dioxide and lithium cobalt dioxide are used as the cathode material.
  • the anode material used is graphite.
  • Total cell capacity result This is achieved for example by silicon-carbon composites. Silicon has a specific electrochemical capacity of 3580 mAh / g. in the
  • the lithium is incorporated, for example, in the form of lithium iron phosphate on the cathode side of the cell.
  • the corresponding lithium ions migrate to the anode side, where they can be intercalated between the graphene layers of the carbon and stored in the form of lithium-silicon alloys.
  • the intercalation of lithium ions into the carbon has a higher speed compared to the conversion reaction of lithium with silicon. Because of this, a composite of carbon or graphite with fine silicon powder is used for the anode side.
  • the carbon serves as an electrical conductor and as a fast buffer for lithium.
  • the silicon is mostly used for the storage of lithium. This process is slower compared to the intercalation of graphene layers.
  • the silicon can also store a larger amount of lithium than carbon or graphite.
  • Nanoscale silicon is also used in the technical field of high-energy anodes for lithium-ion batteries. Since pure silicon is pyrophoric, usually the nanoscale silicon modifications, such as powders, tubes, rods, films, or hedgehog particles, which are processed in air or with water-based binder, have a thin
  • Silicon dioxide layer also referred to as Si0 2 layer. Silicon could also be terminated, for example, with hydrogen or nitrogen, etc. Hedgehog particles have a massive core with many spines, mostly made by catalytic etching from massive silicon particles. As a rule, the silicon dioxide layer is between 1 and 20 nm in the case of a 50 nm silicon particle.
  • the thicker silicon dioxide layer reduces the specific capacity of the material containing the silicon particles and, secondly, the irreversible loss of lithium increases due to intercalation during the electrochemical process into the anode material During the electrochemical process, the silicon dioxide reacts with lithium and / or with constituents of the surface layer forming on the anode surface, also called the solid electrolyte interface (SEI), to form a lithium silicate. This leads to the irreversible loss of lithium in the lithium-ion battery. For example, a 5 nm silicon dioxide layer theoretically halves the theoretical specific capacity of the silicon particle.
  • SEI solid electrolyte interface
  • the purpose of this chemically modified silicon dioxide layer is to reduce the specific capacitance of an anode in a lithium-ion battery, in particular the loss of the specific
  • Capacity of a lithium-ion battery can be reduced, in particular by preventing the irreversible loss of lithium by incorporation into an anode material.
  • a method for producing at least one nanoscale silicon particle which comprises silicon and a silicon dioxide reaction product comprising the following steps: a) providing at least one nanoscale silicon particle, the silicon and silicon dioxide
  • step B) providing at least one silicon dioxide chemically altering, halogen-free silica change component, c) reacting the at least one nanoscale silicon particle provided in step a) with the at least one silicon dioxide modification component provided in step b) such that at least one nanoscale silicon particle having silicon and a silicon dioxide reaction product is obtained at a temperature of at least 400 ° C and d) obtaining the at least one silicon particle comprising silicon and a silicon dioxide reaction product.
  • the method according to the invention it is possible to chemically modify the silicon particles provided in step a) so that an incorporation of lithium and thus the irreversible loss of lithium during the charging and discharging of a lithium-ion battery are almost completely prevented at the same time no silicon is removed from the silicon particles.
  • the initial capacity or also as the initial capacity of a lithium-ion battery can be maintained and increased cycle stability of the lithium-ion battery can be provided.
  • nanoscale is understood as meaning a silicon particle having a mean diameter in the nanometer range, preferably 50%, preferably 80%, preferably 90%, preferably 99%, preferably 100% of that provided in step a)
  • nanoscale silicon particles has a diameter of less than 1000 nm, preferably less than 500 nm, preferably from 0.1 nm to 1000 nm, preferably from 1 nm to 1000 nm, preferably from 2 nm to 500 nm, preferably from 200 nm to 500 nm ,
  • the particle diameter can be determined by transmission-electrode microscopy (TEM) or scanning electron microscopy (SEM), preferably by transmission-electrode microscopy (TEM). Scanning electron microscopes can detect particle diameter> 20 nm, transmission electrode microscopes particle diameter up to 0.1 nm. (Literature: A. Aimable, P. Bowen: Processing and Application of Ceramics, 4, (3), 20120, 157-166).
  • the at least one nanoscale silicon particle provided in step a) preferably has a largely spherical, preferably a spherical, form.
  • step a) Preference is given in step a) more than 0.1 g, preferably more than 1 g nanoscale
  • Silicon particles provided. At least 0.01 mol, preferably 0.1 mol, preferably at least 1 mol of nanosize silicon particles in step a) are preferably provided.
  • at least one nanoscale silicon particle is preferably provided, which has a silicon core and a silicon dioxide coating.
  • the silicon particle with a silicon core and a silicon dioxide coating provided in step a) can preferably be produced by a CVD method ("Chemical Vapor Deposition" method).
  • CVD method Chemical Vapor Deposition
  • At least one vapor or gaseous dopant is present in the hot wall reactor.
  • the temperature of the process preferably the CVD process for producing the silicon particle with silicon and a silicon dioxide coating at a temperature of 1000 ° C or less, preferably from 600 ° C to 1000 ° C, preferably from 650 ° C to 950 ° C. ,
  • the silane is selected from SiH 4 , Si 2 H 6 , CISiH 3 , CI 2 SiH 2 , CI 3 SiH, SiCl 4 and
  • the silicon dioxide layer of the silicon particles provided in step a) is 0.1 to 100 nm, preferably 1 to 50 nm, preferably 1 to 20 nm thick.
  • the layer thickness can be determined by transmission electron microscopy (TEM) (literature: A. Aimable, P. Bowen: Processing and Application of Ceramics, 4 (3), 2010, 157-166).
  • TEM transmission electron microscopy
  • the ratio of the diameter of the at least one silicon particle provided in step a) to its silicon dioxide layer is preferably 1: 30 to 5: 1, preferably 1: 20 to 1: 1, preferably 1: 15 to 1: 5.
  • This ratio can be carried out by elemental analysis using energy-dispersive X-ray radiation (EDX) together with a transmission electron microscope (TEM) and preferably additionally by X-ray photoelectron spectroscopy (XPS). (Literature: A. Aimable, P. Bowen: Processing and Application of Ceramics, 4, (3), 2010, 157-166).
  • EDX energy-dispersive X-ray radiation
  • TEM transmission electron microscope
  • XPS X-ray photoelectron spectroscopy
  • At least one nanoscale silicon particle which has a silicon core and a silicon dioxide coating
  • at least one nanoscale silicon particle is provided in step a), wherein silicon and silicon dioxide are present randomly distributed in the silicon particle. They may be preferred as mixed particles of silicon and
  • the at least one silicon particle thus preferably has a skeleton structure of silicon and / or silicon dioxide, wherein the silicon and / or the silicon dioxide fills the cavities formed in the framework structure.
  • the at least one silicon particle provided in step a) is therefore preferably preparable by the disproportionation of silicon monoxide (SiO) at a temperature of at least 600 ° C., preferably at least 800 ° C., preferably at least 950 ° C., preferably from 600 ° to 1 100 ° C, preferably 900 to 1 100 ° C, preferably 950 ° C.
  • the silicon dioxide chemically changing, halogen-free silicon dioxide modification component provided in step b) is understood to mean a component which chemically converts silicon dioxide to another compound, preferably to a silicate and / or to silicon.
  • the silicon change component reduces the silica to silicon.
  • the silicon dioxide is converted to a silicate, preferably an alkali metal and / or alkaline earth metal silicate.
  • the silica-change component produces a chemical compound which contains the
  • the silicon dioxide change component does not form a chemical compound by reacting with silicon dioxide, which makes it possible to dissolve out silicon, as is the case for example with the reaction of silicon dioxide with HF and / or HCl.
  • the silica change component is free of hydrogen halide, preferably HF and HCl.
  • the reaction according to step c) preferably takes place at a temperature of at least 500.degree. C., preferably at least 600.degree. C., preferably from 500 to 800.degree. C., preferably from 600 to 700.degree.
  • the molar ratio of the silicon particles provided in step a) and the silica change component provided in step b) is 15: 1 to 1: 5, preferably 10: 1 to 5: 1.
  • Silicon dioxide present silica to the provided in step b) silica change component 5: 1 to 1: 5, preferably 2: 1 to 1: 2, preferably 1: 1.
  • silica change component Preferably, only a portion of the silica is reacted by a first silica change component.
  • the remaining silicon dioxide can be converted in a further process step by an inorganic and / or organic lithium compound to a lithium silicate, preferably Li 4 Si0 4 .
  • a lithium silicate preferably Li 4 Si0 4 .
  • step b) exactly two silica change components selected from the group consisting of an inorganic lithium compound, carbon, an organic compound with
  • Lithium compound and an organic compound containing carbon provided.
  • the at least one nanoscale silicon particle provided in step a) is reacted either simultaneously or sequentially with the exactly two silica change components provided in step b).
  • the at least one nanoscale silicon particle provided in step a) is preferably first reacted with the one silicon dioxide change component provided in step b) and then with the other silicon dioxide change component provided in step b).
  • a preferred embodiment of the invention provides a method, wherein the at least one silica change component is selected from an inorganic
  • Lithium compound, carbon, organic compound containing carbon, lithium organo compound and mixtures thereof It is advantageous that these silica change components form particularly stable silica reaction products.
  • a lithium silicate preferably Li 4 Si0 4 , is formed as the silicon dioxide reaction product.
  • silicon dioxide reaction product silicon dioxide reaction product. If carbon dioxide and / or an organic compound having a carbon content are used as the silicon dioxide modification component, silicon is formed as the silicon dioxide reaction product. If a lithium organo compound is used, the silicon dioxide reaction product is silicon on the one hand and lithium silicate on the other, preferably Li 4 Si0 4 .
  • a preferred embodiment of the invention provides a method wherein the inorganic lithium compound is selected from groups consisting of lithium oxide, lithium hydroxide, lithium peroxide, lithium carbonate and mixtures thereof.
  • Lithium compounds have the advantage that they particularly effectively form the lithium silicate as a silica reaction product.
  • a preferred embodiment of the invention provides a method wherein the organic compound with carbon content is selected from the group consisting of sugar, citric acid and polyacrylonitrile. These carbon-containing organic compounds have the advantage that they are particularly effective in reducing the silica to silicon.
  • the lithium organo compound is selected from the group consisting of lithium acetate, lithium lactate, monobasic lithium citrate, dibasic lithium citrate, tribasic lithium citrate, lithium lithium tartrate, lithium diisopropylamine,
  • Lithium bis (trimethylsilyl) amide lithium dimethylamide, lithium ethoxide, lithium ethoxide,
  • a preferred embodiment of the invention provides a method, wherein in a step d) downstream step e) of the at least one nanoscale silicon particle comprising silicon and a silicon dioxide reaction product is reacted with carbon, so that at least one nanoscale silicon and a silicon dioxide reaction product
  • the silicon particles thus produced advantageously have two functional shells, namely a shell of an electrically conductive carbon and a shell of a lithium ion conductive lithium silicate layer, preferably Li 4 Si0 4 layer.
  • the silicon particles thus produced have a silicon core, which represents the lithium storage when used in a lithium-ion battery.
  • the present invention provides a nanoscale silicon particle which can be produced by a method according to the invention.
  • the nanoscale silicon particles comprising silicon and a silicon oxide reaction product are doped, preferably with at least one element selected from the group consisting of phosphorus, arsenic, antimony, boron, aluminum, gallium, indium, and mixtures thereof.
  • Elements are present in the nanoscale silicon particles in an amount of 0 to 1 wt .-%, preferably 0.1 to 0.9 wt .-% (based on the total dry matter of the silicon particles).
  • the present invention provides a method for producing an electrode, preferably an anode for a lithium-ion battery, the method comprising the following steps: i) providing nanoscale silicon particles or silicon particles produced by a method according to the invention, ii) Providing graphite, carbon black and water-soluble or alcohol-soluble binder, iii) mixing the compounds provided in step i) and ii) to provide a paste, iv) preparing an electrode, preferably an anode from the paste provided in step iii) and v Receiving an electrode, preferably anode with the invention by a
  • the electrode contains, as conductive carbon black, a synthetic carbon black, preferably with an average particle size of 20 to 60 nm.
  • step ii) 5 to 25 wt .-%, preferably 5 to 10 wt .-% of a water-soluble binder (based on the total dry matter of the electrode) is provided.
  • the binder preferably contains at least one component selected from the group consisting of polyacrylic acid, sodium cellulose, sodium alginate and SBR ("styrene-butadiene-rubber" latex) .
  • the binder is preferably a polyacrylic acid-based binder.
  • the electrode is preferably a silicon anode or a silicon / carbon composite anode.
  • the electrode preferably has from 5 to 80% by weight, preferably from 10 to 70% by weight, preferably from 20 to 60% by weight (based on the total dry substance of the electrode) of nanoscale silicon particles which have silicon and a silicon dioxide reaction product.
  • the electrode preferably the silicon anode or the silicon / carbon composite anode, additionally comprises additives.
  • the invention likewise provides for the use of the nanoscale silicon particles produced by a method according to the invention and / or the nanoscale silicon particles according to the invention for producing an anode for a lithium-ion battery.
  • the invention likewise provides a lithium-ion battery comprising a) a housing, b) a battery core having at least one cathode, at least one anode, an electrically insulating element and c) an electrolyte composition, wherein the anode is nanoscale by a process according to the invention Silicon particles and / or
  • electrolyte composition is a solid electrolyte composition
  • electrolyte composition also functions as an electrically insulating element.
  • the silicon particles provided in step a) are first mixed with the at least one silicon dioxide modification component provided in step b) with an organic solvent and / or water and then ground, preferably with a ball mill, preferably for 1 to 2 hours, so that a Slurry arises. Subsequently, the slurry is pre-dried at a temperature of 70 ° C to 100 ° C, preferably 80 ° C and then thermally treated under a protective gas atmosphere at a temperature of 400 ° C for 1 to 5 hours, preferably for 3 hours, so that nanoscale silicon particles which have silicon and a silicon dioxide reaction product.
  • Figure 1 is a schematic sketch of a galvanic cell of a lithium-ion battery
  • Figure 2 is a schematic representation of the present method in a preferred embodiment
  • FIG. 1 shows a galvanic cell 1 of a lithium-ion battery with a cathode 2 and an anode 3, the cathode 2 and the anode 3 being separated by a separator element 4
  • Electrolyte composition is soaked.
  • the anode 3 has the nanoscale silicon particles produced according to the invention with silicon and a silicon dioxide reaction product.
  • FIG. 2 shows a preferred method according to the invention, wherein in step F1 silicon particles (E) having a silicon dioxide content with a silicon dioxide change component 1 (R1) are converted to a silicon particle (P1) with a reduced Si0 2 content and a Si0 2 reaction product. These obtained silicon particles (P1) are subsequently reacted in step F2 with another silica change component 2 (R2) to form silicon particles (P2) which have two different silicon dioxide reaction products.
  • the silicon particles (P2) are reacted with two different silicon dioxide reaction products with carbon (R3), so that silicon particles (P3) having two different silica reaction products and a carbon coating are obtained.
  • Example 1 inorganic treatment
  • an electrode preferably an anode
  • Example 2 inorganic lithium treatment including carbon content
  • Inert gas atmosphere thermally treated at 600 ° C for three hours. After the treatment, a paste is produced from the resulting silicon product, graphite, conductive carbon black and a water-soluble binder, from which, in a further step, an electrode, preferably an anode, is produced.
  • water-soluble binder made a paste from which, in a further step, an electrode, preferably anode, is manufactured.
  • an electrode preferably anode
  • a 50 ml grinding bowl In a 50 ml grinding bowl are 2.809 g of silicon powder (0.1 mol), that is silicon particles with Si0 2 coating, and 2.82 g of lithium citrate (tribasic) tetrahydrate (Li 3 C 6 H 5 0 7 * 4H 2 0; 0.01 mol) with 25 ml of distilled water and ground for one hour.
  • the slurry is predried at 80 ° C. and then thermally treated under a protective gas atmosphere for three hours at 600 ° C. After the treatment, a paste is produced from the resulting silicon product, graphite, conductive carbon black and a water-soluble binder a further step, an electrode, preferably anode, is made.
  • Example 5 Organic lithium treatment with additional carbon content
  • water-soluble binder made a paste from which, in a further step, an electrode, preferably anode, is manufactured.
  • Example 8 inorganic lithium treatment including carbon content
  • Inert gas atmosphere thermally treated at a temperature of 600 ° C for three hours. After the treatment, a paste is made from the silicon product, graphite, carbon black and water-soluble binder, from which, in the next step, an electrode is made.
  • Inert gas atmosphere thermally treated at a temperature of 600 ° C for three hours. After the treatment, a paste is made from the silicon product, graphite, carbon black and water-soluble binder, from which, in the next step, an electrode is made.
  • Example 10 Organic lithium treatment with additional carbon content
  • Example 1 1 - Pretreatment with carbon followed by inorganic
  • silica SiO 2, 0.1 mol
  • Citric acid (0.02 mol) and 25 ml of distilled water are added and ground for one hour.
  • the slurry is pre-dried at a temperature of 80 ° C and then thermally treated under inert gas atmosphere at a temperature of 950 ° C for three hours.
  • the treated silicon powder is treated with 1.478 g of lithium carbonate (0.02 mol) and 25 ml of hexane and ground for one hour using a ball mill.
  • the resulting slurry is again predried at 80 ° C. and then thermally treated under a protective gas atmosphere at 600 ° C. for three hours
  • water-soluble binder made a paste from which, in a further step, an electrode, preferably anode, is manufactured.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

La présente invention concerne un procédé de production d'au moins une nanoparticule de silicium contenant du silicium et un produit de réaction du dioxyde de silicium. Elle concerne également une particule de silicium produite par ce procédé et son utilisation pour fabriquer une anode destinée à une batterie lithium-ions, ainsi que le procédé de fabrication de l'anode.
PCT/EP2014/068240 2013-08-30 2014-08-28 Prélithiation de particules de silicium WO2015028542A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1020167008477A KR101899223B1 (ko) 2013-08-30 2014-08-28 규소 입자의 전-리튬화

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102013014627.5 2013-08-30
DE102013014627.5A DE102013014627A1 (de) 2013-08-30 2013-08-30 Pre-lithiierung von Siliziumpartikeln

Publications (1)

Publication Number Publication Date
WO2015028542A1 true WO2015028542A1 (fr) 2015-03-05

Family

ID=51492928

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2014/068240 WO2015028542A1 (fr) 2013-08-30 2014-08-28 Prélithiation de particules de silicium

Country Status (3)

Country Link
KR (1) KR101899223B1 (fr)
DE (1) DE102013014627A1 (fr)
WO (1) WO2015028542A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106495161A (zh) * 2016-10-24 2017-03-15 中南大学 一种基于金属介入金属热还原制备纳米硅的方法
US10193354B2 (en) 2016-04-06 2019-01-29 Rochester Institute Of Technology Near zero volt storage tolerant electrochemical cells through reversible ion management
CN111048764A (zh) * 2019-12-23 2020-04-21 北京理工大学重庆创新中心 一种硅碳复合材料及其制备方法和应用
CN111278769A (zh) * 2018-07-25 2020-06-12 瓦克化学股份公司 硅颗粒的热处理

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102423962B1 (ko) * 2017-05-24 2022-07-26 로베르트 보쉬 게엠베하 애노드 조성물 및 애노드를 사전 리튬화하기 위한 방법
CN113853695B (zh) 2019-05-21 2024-01-30 瓦克化学股份公司 锂离子电池
WO2022262981A1 (fr) 2021-06-17 2022-12-22 Wacker Chemie Ag Procédé de prélithiation d'anode contenant du silicium dans une batterie au lithium-ion
CN114044516B (zh) * 2021-10-19 2024-01-16 惠州锂威新能源科技有限公司 一种硅碳负极材料及其制备方法、负极片以及二次电池

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10353006A1 (de) 2003-11-13 2005-06-02 Aesculap Ag & Co. Kg Chirurgisches Rohrschaftinstrument
DE10353995A1 (de) 2003-11-19 2005-06-09 Degussa Ag Nanoskaliges, kristallines Siliciumpulver
DE102009029054A1 (de) * 2009-09-01 2011-03-03 Evonik Degussa Gmbh Herstellung von mit lochleitenden organischen Gruppen funktionalisierten nanoskaligen Siliziumpartikeln
FR2980191A1 (fr) * 2011-09-20 2013-03-22 Commissariat Energie Atomique Procede de fabrication d'un materiau composite silicium/carbone et utilisation d'un tel materiau
WO2014060535A1 (fr) * 2012-10-17 2014-04-24 Institutt For Energiteknikk Procédé, poudre, film & batterie lithium-ion
WO2014088187A1 (fr) * 2012-12-05 2014-06-12 삼성정밀화학 주식회사 Nanoparticules de silicium à surface modifiée pour matériau actif d'électrode négative et procédé de fabrication associé

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8231810B2 (en) * 2004-04-15 2012-07-31 Fmc Corporation Composite materials of nano-dispersed silicon and tin and methods of making the same
US7776473B2 (en) * 2006-03-27 2010-08-17 Shin-Etsu Chemical Co., Ltd. Silicon-silicon oxide-lithium composite, making method, and non-aqueous electrolyte secondary cell negative electrode material
US20100258759A1 (en) * 2006-06-06 2010-10-14 Cornell Research Foundation, Inc. Nanostructured Metal Oxides Comprising Internal Voids and Methods of Use Thereof
US20110129732A1 (en) * 2009-12-01 2011-06-02 Applied Materials, Inc. Compressed powder 3d battery electrode manufacturing
KR101846553B1 (ko) * 2011-12-20 2018-04-09 한국과학기술원 코어-쉘 구조의 실리콘-탄소 복합 음극 활물질, 그 제조방법 및 이를 포함하는 리튬이차전지

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10353006A1 (de) 2003-11-13 2005-06-02 Aesculap Ag & Co. Kg Chirurgisches Rohrschaftinstrument
DE10353995A1 (de) 2003-11-19 2005-06-09 Degussa Ag Nanoskaliges, kristallines Siliciumpulver
DE102009029054A1 (de) * 2009-09-01 2011-03-03 Evonik Degussa Gmbh Herstellung von mit lochleitenden organischen Gruppen funktionalisierten nanoskaligen Siliziumpartikeln
FR2980191A1 (fr) * 2011-09-20 2013-03-22 Commissariat Energie Atomique Procede de fabrication d'un materiau composite silicium/carbone et utilisation d'un tel materiau
WO2014060535A1 (fr) * 2012-10-17 2014-04-24 Institutt For Energiteknikk Procédé, poudre, film & batterie lithium-ion
WO2014088187A1 (fr) * 2012-12-05 2014-06-12 삼성정밀화학 주식회사 Nanoparticules de silicium à surface modifiée pour matériau actif d'électrode négative et procédé de fabrication associé

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
A. AIMABLE; P. BOWEN, PROCESSING AND APPLICATION OF CERAMICS, vol. 4, no. 3, 2010, pages 157 - 166
A. AIMABLE; P. BOWEN, PROCESSING AND APPLICATION OF CERAMICS, vol. 4, no. 3, pages 157 - 166

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10193354B2 (en) 2016-04-06 2019-01-29 Rochester Institute Of Technology Near zero volt storage tolerant electrochemical cells through reversible ion management
CN106495161A (zh) * 2016-10-24 2017-03-15 中南大学 一种基于金属介入金属热还原制备纳米硅的方法
CN111278769A (zh) * 2018-07-25 2020-06-12 瓦克化学股份公司 硅颗粒的热处理
CN111278769B (zh) * 2018-07-25 2023-08-11 瓦克化学股份公司 硅颗粒的热处理
CN111048764A (zh) * 2019-12-23 2020-04-21 北京理工大学重庆创新中心 一种硅碳复合材料及其制备方法和应用

Also Published As

Publication number Publication date
DE102013014627A1 (de) 2015-03-05
KR20160048969A (ko) 2016-05-04
KR101899223B1 (ko) 2018-09-14

Similar Documents

Publication Publication Date Title
WO2015028542A1 (fr) Prélithiation de particules de silicium
EP2303774B1 (fr) Insertion de silicium et/ou d'étain dans des substrats carbonés poreux
DE112013006722B4 (de) Negativelektrodenaktivmaterial, Herstellungsverfahren für selbiges und elektrischer Speicherapparat
DE112013005568T5 (de) Nanokristallines Siliciummaterial, Aktivmaterial für eine negative Elektrode, Herstellungsverfahren für das Material und elektrisches Speichergerät
EP3011621A1 (fr) Matériau d'électrode et son utilisation dans des batteries lithium-ion
EP2769427B1 (fr) Matière active pour batteries
DE112015002533B4 (de) Kupfer-enthaltendes Siliciummaterial, Verfahren für dessen Herstellung, Negativelektrodenaktivmaterial und Sekundärbatterie
EP3063811B1 (fr) Sulfure de lithium revêtu de carbon
DE112017006921T5 (de) Lithium-Ionen-Zelle und Verfahren zur Herstellung davon
DE102009033251A1 (de) Einlagerung von Silizium und/oder Zinn in poröse Kohlenstoffsubstrate
DE102013216814A1 (de) Positives, aktives Elektrodenmaterial, Herstellungsverfahren für dasselbige und wiederaufladbare Batterie aus nichtwässrigem Elektrolyt, welche dasselbige aufweist
DE102010021804A1 (de) Verbundmaterial enthaltend ein gemischtes Lithium-Metallphosphat
DE112015002524T5 (de) Nano-Silizium-Material, Verfahren zur Herstellung desselben und Negatvelektrode einer Sekundärbatterie
EP2529434A1 (fr) Électrode exempte d'additifs conducteurs pour une batterie au lithium-ion secondaire
DE102012200080A1 (de) Eisendotiertes Lithiumtitanat als Kathodenmaterial
DE102014210613A1 (de) Verfahren zur Herstellung von sphärischen Silizium-Kohlenstoff-Nanokompositen, sphärische Silizium-Kohlenstoff-Nanokomposite und deren Verwendung
DE102015103720B4 (de) Mittels eines neuen Reagens synthetisierte Metallnanopartikel und Anwendung auf elektrochemische Vorrichtungen
WO2016150639A1 (fr) Matériau d'anode constitué de particules composites à base de silicium et de nanoparticules de silicium
DE102013216816A1 (de) Positives, aktives Elektrodenmaterial, Herstellungsverfahren für dasselbige und wiederaufladbare Batterie aus nichtwässrigem Elektrolyt, welche dasselbige aufweist
DE112013005576T5 (de) Negativelektrodenaktivmaterial und Elektrizitätsspeichervorrichtung
EP3251160B1 (fr) Matériaux composites lithiés silicium/carbone et leur procédé de fabrication
DE102014207882A1 (de) Neue Beschichtung von Siliziumpartikeln für Lithium-Ionen-Batterien zur verbesserten Zyklenstabilität
DE102014106002A1 (de) Elektrodenmaterial für Natrium-basierte elektrochemische Energiespeicher
DE102014207881A1 (de) Herstellverfahren von nanoskaligen Siliziumpartikeln mit einer reduzierten Siliziumdioxid-Beschichtung
EP4162549A1 (fr) Procédé de fabrication d'un matériau d'électrode à base de silicium

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14761301

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20167008477

Country of ref document: KR

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 14761301

Country of ref document: EP

Kind code of ref document: A1