WO2017099523A1 - Procédé de préparation d'un matériau actif d'anode destiné à une batterie secondaire au lithium et batterie secondaire au lithium à laquelle le procédé est appliqué - Google Patents

Procédé de préparation d'un matériau actif d'anode destiné à une batterie secondaire au lithium et batterie secondaire au lithium à laquelle le procédé est appliqué Download PDF

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WO2017099523A1
WO2017099523A1 PCT/KR2016/014452 KR2016014452W WO2017099523A1 WO 2017099523 A1 WO2017099523 A1 WO 2017099523A1 KR 2016014452 W KR2016014452 W KR 2016014452W WO 2017099523 A1 WO2017099523 A1 WO 2017099523A1
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negative electrode
active material
electrode active
secondary battery
amorphous silicon
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PCT/KR2016/014452
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English (en)
Korean (ko)
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조래환
이용주
김은경
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주식회사 엘지화학
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Priority claimed from KR1020160166995A external-priority patent/KR101977931B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to EP16873388.9A priority Critical patent/EP3382779B1/fr
Priority to CN201680049763.2A priority patent/CN107925067B/zh
Priority to PL16873388T priority patent/PL3382779T3/pl
Priority to US15/751,916 priority patent/US10511048B2/en
Publication of WO2017099523A1 publication Critical patent/WO2017099523A1/fr

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/24—Deposition of silicon only
    • 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
    • H01M4/13—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
    • 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
    • H01M4/58—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
    • 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 a negative electrode active material for a lithium secondary battery, and a lithium secondary battery using the same.
  • Lithium secondary batteries are chargeable and dischargeable batteries that can best meet these requirements, and are currently used in portable electronic devices and communication devices such as small video cameras, mobile phones, and notebook computers.
  • a lithium secondary battery is composed of a positive electrode, a negative electrode, and an electrolyte, and lithium ions from the positive electrode active material are inserted into the negative electrode active material, that is, carbon particles, and desorbed again when discharged. Since it plays a role of transferring energy while reciprocating, charge and discharge are possible.
  • the silicon-based negative electrode active material is known as a high capacity negative electrode active material having a low price and high capacity, for example, a discharge capacity (about 4200 mAh / g) of about 10 times that of graphite, which is a commercial negative electrode active material.
  • the silicon-based negative electrode active material is a nonconductor, and due to the rapid volume change that occurs during the charging and discharging process, the accompanying side reactions, for example, pulverization of the negative electrode active material particles, or form an unstable solid electrolyte interface (SEI) layer.
  • SEI solid electrolyte interface
  • battery performance is deteriorated, such as a decrease in capacity due to electrical contact, and there is a significant limitation in commercialization.
  • the first technical problem of the present invention is to provide a method for producing a negative electrode active material for secondary batteries that can prevent oxidation during the production of nano-sized silicon particles.
  • a second object of the present invention is to provide a negative electrode active material for a secondary battery manufactured by the method for producing a negative electrode active material.
  • a third object of the present invention is to provide a negative electrode for a secondary battery including the negative electrode active material of the present invention.
  • a fourth technical object of the present invention is to provide a lithium secondary battery having improved discharge capacity, initial efficiency and output characteristics by providing the negative electrode of the present invention.
  • the heat treatment of the silicon-based composite precursor, to form a silicon-based composite comprising an amorphous carbon coating layer containing one or more amorphous silicon particles therein (S5); provides a method for producing a negative electrode active material for a lithium secondary battery comprising a. .
  • the amorphous silicon layer deposition step (S1) is 10 sccm / 60min silane gas at a temperature of 500 °C to 700 °C and 10 -8 Torr to 760 Torr (1 atmosphere), specifically 10 -2 Torr to 760 Torr It can be carried out while adding at a rate of from 50 sccm / 60 min.
  • the thickness of the deposited amorphous silicon layer is 20nm to 500nm.
  • the amorphous silicon layer crushing step (S2) is immersed in the acetone solution a glass substrate on which an amorphous silicon layer is deposited, and then pulverized for 10 minutes to 20 minutes at room temperature with an output between 50W and 200W using an ultrasonic grinder. It can be carried out.
  • the method of the present invention may further include preparing the amorphous silicon particles, and then collecting the pulverized amorphous silicon particles by volatilizing an acetone solvent.
  • the average particle diameter (D50) of the pulverized amorphous silicon particles is 5nm to 500nm.
  • the dispersion solution manufacturing step (S3) may be carried out by mixing carbonizable carbon-based materials in distilled water at a temperature of 1000 ° C. or less to prepare a carbon-based precursor solution, and then dispersing amorphous silicon particles.
  • the carbon-based precursor solution may be used from 25 parts by weight to 4,000 parts by weight based on 100 parts by weight of amorphous silicon particles.
  • At the time of dispersing the amorphous silicon particles at the time of dispersing the amorphous silicon particles, at least one conductive carbon-based material selected from the group consisting of crystalline and amorphous carbon may be dispersed together.
  • the conductive carbonaceous material may be used in an amount of 0.99 parts by weight to 1900 parts by weight based on 100 parts by weight of amorphous silicon particles.
  • the precursor solution may be supplied into a spray device to form a droplet by spraying, and then the drying of the droplet may be simultaneously performed.
  • the spray drying step may be carried out at a rate of 10 mL / min to 50 mL / min at about 50 °C to 300 °C.
  • step (S5) of the heat treatment of the silicon-based composite precursor may be performed at 400 °C to 1000 °C temperature, for about 10 minutes to 1 hour.
  • Amorphous carbon coating layer provides a negative electrode active material for a lithium secondary battery comprising a silicon composite consisting of one or more amorphous silicon particles contained in the amorphous carbon coating layer.
  • the amorphous silicon particles may include single amorphous particles or secondary amorphous silicon particles formed by aggregation of primary amorphous silicon particles formed of the single particles.
  • the amorphous silicon particles may be uniformly dispersed in the amorphous carbon coating layer.
  • the amorphous silicon particles may be included in an amount of 1 to 95% by weight, and specifically 5 to 90% by weight, based on the total weight of the negative electrode active material.
  • the weight ratio of the amorphous silicon particles to the amorphous carbon coating layer may be 1:99 to 95: 5, specifically 5:95 to 90:10.
  • the anode active material may further include at least one conductive carbon-based material selected from the group consisting of crystalline or amorphous carbon different from the amorphous carbon layer forming material in the amorphous carbon coating layer.
  • the negative electrode active material is an amorphous carbon coating layer; And it may include a silicon composite consisting of one or more amorphous silicon particles and amorphous carbon contained in the amorphous carbon coating layer.
  • the negative electrode active material is an amorphous carbon coating layer;
  • one or more amorphous silicon particles and crystalline carbon contained in the amorphous carbon coating layer, and the silicon composite may include the one or more amorphous silicon particles distributed on the surface of the crystalline carbon.
  • the conductive carbon-based material may be included in an amount of 0.1 wt% to 90 wt% based on the total weight of the negative electrode active material. Specifically, when the conductive carbon-based material is amorphous carbon, it may be included in an amount of 0.1% to 50% by weight based on the total weight of the negative electrode active material, and when the conductive carbon-based material is crystalline carbon, based on the total weight of the negative electrode active material 10 wt% to 90 wt% may be included.
  • a negative electrode comprising a current collector and a negative electrode active material produced by the method of the present invention formed on at least one surface of the current collector.
  • an embodiment of the present invention provides a lithium secondary battery having the negative electrode.
  • amorphous silicon particles for the negative electrode active material in which oxidation is prevented and crystallinity is controlled during the production of the nano silicon particles.
  • amorphous silicon particles it is possible to manufacture a negative electrode active material and a negative electrode including the same, the electrode thickness expansion phenomenon is reduced than when using the crystalline silicon particles.
  • a lithium secondary battery having improved initial efficiency, reversible capacity, and lifetime characteristics can be manufactured.
  • Example 1 is a schematic diagram of a negative electrode active material for a lithium secondary battery including the silicon composite prepared in Example 1 of the present invention.
  • Example 2 is a schematic view of a negative electrode active material for a lithium secondary battery including the silicon composite prepared in Example 2 of the present invention.
  • Example 3 is a schematic diagram of a negative electrode active material for a lithium secondary battery including the silicon composite prepared in Example 3 of the present invention.
  • a silicon-based negative electrode active material has been proposed as a negative electrode active material for a lithium secondary battery, but the silicon-based negative electrode active material is a nonconductor, and due to the rapid volume change that occurs during the charging and discharging process, crushing of the negative electrode active material particles occurs or an unstable SEI.
  • Solid Electrolyte Interface has a disadvantage in that the battery performance is reduced by forming a layer.
  • the brittle carbon has a problem of being broken by volume expansion of silicon generated during charge and discharge.
  • a method for preparing a nano-sized silicon-based powder has been developed, but as the silicon-based material is oxidized during the grinding process, another problem may occur that the initial efficiency is reduced.
  • amorphous silicon layer by depositing an amorphous silicon layer, and then performing an ultrasonic grinding, it is possible to provide a method for producing a negative electrode active material that can be used to prepare amorphous silicon particles that can easily control the crystallinity and prevent oxidation during the manufacturing process. Can be.
  • this as a negative electrode active material it is possible to manufacture a lithium secondary battery with improved initial efficiency, life characteristics and electrode thickness expansion characteristics.
  • the present invention in one embodiment
  • the heat treatment of the silicon-based composite precursor, to form a silicon composite comprising an amorphous carbon coating layer including one or more amorphous silicon particles therein (S5); provides a method for producing a negative electrode active material for a lithium secondary battery comprising a.
  • the amorphous silicon layer deposition step (S1) is 700 °C or less, specifically 500 °C to 700 °C temperature and 10 -8 Torr to 760 Torr (1 atm), specifically 10 -2 Torr
  • the silane gas may be carried out at a rate of 10 sccm / 60 min to 50 sccm / 60 min under a pressure condition of 760 Torr.
  • the bonding force between the silicon elements is weak, and thin enough to be easily broken in the ultrasonic grinding step described later.
  • a thick amorphous silicon layer can be deposited. If the silane gas is added at a temperature below 500 ° C., an amorphous silicon layer may not be deposited. On the other hand, when silane gas is added at a temperature above 700 ° C., crystal growth of silicon-based particles may be increased to form a crystalline silicon layer.
  • the method of the present invention by performing a chemical vapor deposition method in a low temperature range, crystal growth of silicon particles can be suppressed to form an amorphous silicon layer.
  • the nanoparticles have an advantage of excellent life characteristics and small volume expansion compared to the crystalline silicon layer.
  • the amorphous silicon layer may be deposited to a thickness of about 20nm to 500nm.
  • the deposition thickness of the amorphous silicon layer is less than 20 nm, when the subsequent ultrasonic grinding process is performed, the particle size of the collected silicon particles is very small, and the specific surface area is increased, thereby decreasing initial efficiency. On the other hand, when the deposition thickness of the amorphous silicon layer exceeds 500nm, it may be difficult to proceed with the subsequent ultrasonic grinding process stable.
  • the amorphous silicon layer grinding step (S2) is impregnated in the beaker containing acetone, the glass substrate on which the amorphous silicon layer is deposited, and then outputs 50 W to 200 W using an ultrasonic grinder.
  • Ultrasonic grinding may be performed at room temperature for 10 to 20 minutes. At this time, even if it is possible to grind
  • the amount of acetone used may be largely independent of the thickness ratio of the silicon layer, but may be used to the extent that the glass substrate on which the amorphous silicon layer is deposited is completely impregnated with acetone.
  • the drying process should proceed at the lowest possible temperature, for this purpose, it is preferable to use a solvent that is highly volatile even at low temperatures such as acetone during the ultrasonic grinding process.
  • a solvent that is highly volatile even at low temperatures such as acetone during the ultrasonic grinding process.
  • an organic solvent having high volatility may be used even at a low temperature such as ethanol or methanol.
  • the processing time is long, and the temperature may increase due to the friction between the particles during the grinding process.
  • the oxidation of the silicon particles may occur due to the reaction of surrounding oxygen or moisture with silicon particles.
  • the method of the present invention by depositing an amorphous silicon layer and then performing an ultrasonic grinding, not only can the amorphous silicon layer be ground in a short time at low temperature, but also the ultrasonically pulverized amorphous silicon particles Since the process of collecting is carried out, it is possible to prevent the problem that silicon grains grow or silicon particles are oxidized during the grinding process.
  • the method of the present invention may include the step of collecting the pulverized amorphous silicon particles by volatilizing acetone solvent after the completion of the ultrasonic grinding process.
  • the average particle diameter (D50) of the amorphous silicon particles obtained by the method of the present invention may be 5nm to 500nm, specifically 20nm to 200nm.
  • the average particle diameter of the amorphous silicon particles is less than 5 nm, the specific surface area may be too large, resulting in loss of reversible capacity. If the average particle diameter is larger than 500 nm, the particle size is large and the volume expansion becomes severe when reacting with lithium ions. The efficiency of buffering the volume expansion of the negative electrode active material is inferior.
  • the negative electrode active material reacts with the electrolyte during filling to form a protective film called an SEI film on the surface of the particle.
  • the SEI film does not decompose well once produced.
  • the SEI film may be broken by the volume change or crack of the negative electrode active material, or by heat or impact applied externally. In this case, when the electrode surface is exposed to the electrolyte, the SEI film may be regenerated. If the average particle diameter (D50) of the single silicon particles exceeds 500 nm, since cracks are repeatedly generated due to charge and discharge, the volume increases as the SEI film is repeatedly generated. As such, an increase in the volume of the silicon particles will soon lead to an increase in the volume of the final anode active material particles.
  • D50 average particle diameter
  • dispersion solution preparation step (S3) to prepare a carbon-based precursor solution by mixing a carbonaceous carbon material at a temperature of 1000 °C or less in distilled water, and then to disperse amorphous silicon particles Can be carried out in stages.
  • It can be prepared by mixing the distilled water: carbon-based material in a weight ratio of approximately 1: 2 to 10: 1.
  • the carbonaceous material which can be carbonized even at a low temperature of 1000 ° C. or lower may include a single substance or a mixture of two or more selected from the group consisting of sucrose, glucose, fructose, galactose, maltose, and lactose. Sucrose may be carbonized at a relatively low temperature.
  • the carbon-based precursor solution may be used from 25 parts by weight to 4,000 parts by weight based on 100 parts by weight of amorphous silicon particles. If the amount of the carbon-based precursor solution is less than 25 parts by weight, the viscosity of the amorphous silicon particles / carbon-based precursor solution is not easy to perform a spray process, when the amount of the carbon-based precursor solution exceeds 4,000 parts by weight, The content of amorphous silicon particles in the dispersion solution is so low that the role as a high capacity negative electrode material can be reduced.
  • the amorphous carbon is preferably a material different from the amorphous carbon layer forming material as described above.
  • the negative electrode active material of the present invention may further include a conductive carbon-based material to supplement the low conductivity of the silicon particles or to implement the role of the structural support when secondary particles are formed.
  • the conductive carbonaceous material may be dispersed in a range of 0.99 parts by weight to 1,900 parts by weight based on 100 parts by weight of amorphous silicon particles.
  • the amount of the conductive carbonaceous material is less than 0.99 parts by weight, the conductivity does not improve or serve as a structural support, and if the amount exceeds 1,900 parts by weight, the silicon-based active material content is reduced, the discharge capacity per weight (mAh / g Since) decreases, there is no advantage in terms of discharge capacity of the final active material.
  • the conductive carbon-based material is not particularly limited as long as it is a crystalline or amorphous carbon having conductivity without causing chemical change in the battery.
  • the crystalline carbon may include natural graphite, artificial graphite, graphene, or the like.
  • the amorphous carbon a single material or a mixture of two or more selected from the group consisting of hard carbon, soft carbon, carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, thermal black, and carbon nanofibers may be used. have.
  • the average particle diameter (D50) of the natural graphite or artificial graphite particles of the crystalline carbon may be 300nm to 30 ⁇ m.
  • the average particle diameter of the natural or artificial graphite particles is less than 300 nm, the role as a structural support may be reduced.
  • the average particle diameter of the natural or artificial graphite particles is greater than 30 ⁇ m, the average particle diameter of the final negative electrode active material is increased, making the coating process difficult in manufacturing a secondary battery. The disadvantage is that you can.
  • the negative electrode active material of the present invention may optionally add a single material selected from the group consisting of metal fibers, metal powders, zinc oxide, potassium titanate, titanium oxide, and polyphenylene derivatives, or two or more of these conductive materials. It can be included as.
  • the spray drying step (S4) for preparing a silicon-based composite precursor is supplied to the precursor solution into a spray device to form a droplet by spraying, and then the step of drying the droplet simultaneously Can be performed.
  • the spraying step may be carried out using a drying method including rotary spraying, nozzle spraying, ultrasonic spraying, or a combination thereof, from 10 mL / min to 50 mL / min at a temperature of about 50 ° C to 300 ° C, specifically 80 ° C to 250 ° C. Can be done at speed.
  • a drying method including rotary spraying, nozzle spraying, ultrasonic spraying, or a combination thereof, from 10 mL / min to 50 mL / min at a temperature of about 50 ° C to 300 ° C, specifically 80 ° C to 250 ° C. Can be done at speed.
  • the liquid crystal state and drying of the solvent is stably made when the spray drying within the temperature and speed range.
  • the average particle diameter (D50) of the amorphous silicon particles included in the present invention is 5 nm to 500 nm
  • the average particle diameter (D50) of the amorphous carbon particles is about 100 nm to 300 nm
  • the average particle diameter (D50) of the crystalline carbon particles is 300 nm.
  • the above is specifically several micrometers-30 micrometers. Therefore, in the spraying step, when the amorphous silicon particles and the amorphous carbon particles are sprayed together and complexed, the two particles do not have a large difference in average particle diameter, so that the amorphous silicon particles and the amorphous carbon particles are formed inside the final active material as shown in FIG. 2. It is produced in a form of even distribution.
  • the surface of the crystalline carbon particles may be prepared in a shape such that amorphous silicon particles are coated.
  • the step (S5) of heat treating the silicon-based composite precursor is at a temperature of 400 °C to 1000 °C, preferably 500 °C to 800 °C, about 10 minutes to 1 hour, preferably 20 It may be from minutes to 1 hour.
  • the heat treatment temperature is less than 400 ° C., the temperature is so low that the carbonization process does not occur sufficiently, making it difficult to form an amorphous carbon coating layer. If the temperature exceeds 1000 ° C., the crystallinity of the amorphous carbon coating layer included in the precursor is increased. There is a problem.
  • the heat treatment step is preferably performed in an inert atmosphere in which nitrogen gas, argon gas, helium gas, krypton gas, or xenon gas is present.
  • anode active material 10 for a lithium secondary battery including a silicon composite including one or more amorphous silicon particles 1 included in the amorphous carbon coating layer 5 (see FIG. 1).
  • the amorphous silicon particles included in the amorphous carbon coating layer may include secondary amorphous silicon particles formed by agglomeration of the single particles or primary amorphous silicon particles formed of the single particles.
  • the amorphous silicon particles may be uniformly dispersed in the amorphous carbon coating layer.
  • the average particle diameter of the amorphous silicon particles may be 5nm to 500nm, specifically 20nm to 200nm.
  • the amorphous silicon particles may be included in an amount of 1 to 95% by weight, and specifically 5 to 90% by weight, based on the total weight of the negative electrode active material.
  • the weight ratio of the at least one amorphous silicon particle: amorphous carbon coating layer may be in the range of 5:90 to 90:10, specifically 10:90 to 80:20.
  • the negative electrode active material may further include at least one conductive carbon-based material selected from the group consisting of crystalline or amorphous carbon different from forming the amorphous carbon coating layer inside the amorphous carbon coating layer.
  • the conductive carbon-based material may be included in an amount of 0.1 wt% to 90 wt% based on the total weight of the negative electrode active material.
  • An amorphous carbon coating layer 15 provides a negative electrode active material 50 for a lithium secondary battery comprising a silicon composite consisting of one or more amorphous silicon particles 11 and amorphous carbon 13 contained in the amorphous carbon coating layer (see FIG. 2).
  • the amorphous carbon may be included in 0.1 to 50% by weight based on the total weight of the negative electrode active material.
  • the content of the amorphous carbon is less than 0.1% by weight, it is difficult to describe the effect of improving the electrical conductivity by adding the conductive carbonaceous material, and when the content exceeds 50% by weight, the reversible capacity of the final negative electrode active material is lowered.
  • the crystalline carbon may include spherical / plate-shaped natural graphite or artificial graphite particles.
  • the average particle diameter (D50) of the crystalline carbon is 300 nm to 30 ⁇ m.
  • the average particle diameter of the crystalline carbon is less than 300 nm, the role as a structural support may be reduced, and if the average particle diameter exceeds 30 ⁇ m, the average particle size of the final negative electrode active material is increased to perform a uniform coating process in manufacturing a secondary battery. It can be difficult.
  • the crystalline carbon may be included in 10 to 90% by weight based on the total weight of the negative electrode active material.
  • the content of the crystalline carbon is less than 10% by weight, it is difficult to expect the effect of improving the electrical conductivity and the role of the structural support by adding crystalline carbon, when the content of the crystalline carbon exceeds 90% by weight of the reversible capacity of the final negative electrode active material There is a problem of being lowered.
  • the average particle diameter (D50) of the negative electrode active material of the present invention is 50nm to 35 ⁇ m.
  • the average particle diameter (D50) of the negative electrode active material is 50 nm to 30 ⁇ m
  • the average particle diameter (D50) of the negative electrode active material is 500 nm to 35 ⁇ m.
  • the average particle diameter of the negative electrode active material is within the above range, it is possible to reduce the stress of the silicon due to volume expansion generated during charging and discharging of the negative electrode active material, to increase the reversible capacity, and to inhibit the volume expansion during reaction with lithium, thereby improving cycle life. Characteristics are improved. If the average particle diameter of the negative electrode active material is less than 50 nm, the specific surface area is too large to cause a loss of reversible capacity. If the average particle diameter exceeds 35 ⁇ m, cracking and crushing of the negative electrode active material itself occurs very easily due to the stress caused by volume expansion. As the particle size is large, the volume expansion becomes severe upon reaction with lithium, thereby decreasing efficiency in buffering the volume expansion of the whole spherical particles.
  • the specific surface area (BET) of the negative electrode active material of the present invention may be 0.5 m 2 / g to 20 m 2 / g. In this case, when the specific surface area exceeds 20 m 2 / g, an irreversible reaction between the electrolyte and lithium ions occurs on the surface of the active material during charge and discharge, thereby causing consumption of lithium ions, which may cause initial efficiency reduction.
  • the negative electrode active material made of the composite including the amorphous silicon particle-amorphous carbon coating layer prepared by the method of the present invention can lower the overall process temperature to prevent the crystalline growth and oxidation of the silicon particles, the conventional crystalline Compared to the silicon-based nanoparticle-carbon composites, there is an advantage in that the life and volume expansion characteristics are excellent, and the initial efficiency is superior to the general crystalline silicon-based nanoparticle-carbon composites.
  • the initial efficiency is superior to the conventional crystalline silicon-based nanoparticles-carbon composites, the discharge capacity (mAh / g) compared to the conventional crystalline silicon-based nanoparticles-carbon composites
  • the discharge capacity (mAh / g) compared to the conventional crystalline silicon-based nanoparticles-carbon composites
  • the discharge capacity of the graphite itself is 360 mAh / g, which is not large compared to silicon, and when the amount of silicon compounded to increase the discharge capacity is increased, silicon particles are concentrated on the graphite surface. It may cause deterioration of lifespan characteristics.
  • the composite produced by the method of the present invention can evenly distribute the silicon particles in the carbon matrix to prevent degradation of life characteristics.
  • the negative electrode active material produced by the method of the present invention further includes a conductive material such as graphite particles or a conductive material therein, thereby further realizing a conductivity improving effect.
  • It provides a negative electrode comprising the negative electrode active material of the present invention formed on at least one surface of the current collector.
  • the negative electrode according to an embodiment of the present invention can be prepared by a conventional method known in the art.
  • a slurry is prepared by selectively mixing and stirring a solvent, a binder, and a conductive material in the negative electrode active material, if necessary, and then applying (coating) to a current collector of a metal material, compressing, and drying to prepare a negative electrode.
  • a slurry is prepared by selectively mixing and stirring a solvent, a binder, and a conductive material in the negative electrode active material, if necessary, and then applying (coating) to a current collector of a metal material, compressing, and drying to prepare a negative electrode.
  • the binder is used to bind the negative electrode active material particles to maintain the molded body, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), styrene butadiene rubber Binders) are used.
  • PTFE polytetrafluoroethylene
  • PVdF polyvinylidene fluoride
  • styrene butadiene rubber Binders styrene butadiene rubber Binders
  • the conductive material is natural graphite, artificial graphite, carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, thermal black, carbon nanotube, fullerene, carbon fiber, metal Fiber, carbon fluoride, aluminum, nickel powder, zinc oxide, potassium titanate, titanium oxide and polyphenylene derivatives may be any one selected from the group consisting of, or a mixture of two or more thereof, preferably carbon black.
  • the negative electrode current collector is not particularly limited as long as it has high conductivity without causing chemical changes in the battery.
  • copper, stainless steel, aluminum, nickel, titanium, calcined carbon, Surface treated with carbon, nickel, titanium, silver, or the like on the surface of copper or stainless steel, aluminum-cadmium alloy, etc. may be used.
  • the negative electrode current collector may have a thickness of about 3 to 500 ⁇ m, and like the positive electrode current collector, fine concavities and convexities may be formed on the surface of the current collector to enhance the bonding force of the negative electrode active material.
  • it can be used in various forms, such as a film, a sheet, a foil, a net, a porous body, a foam, a nonwoven body.
  • a lithium secondary battery including a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode and a non-aqueous electrolyte in which lithium salt is dissolved.
  • the positive electrode and the electrolyte used may be a material commonly used in the art, but is not limited thereto.
  • the positive electrode may be prepared by coating a positive electrode slurry including a positive electrode active material, a binder, a conductive material, a solvent, and the like on a positive electrode current collector, followed by drying and rolling.
  • the positive electrode active material is a compound capable of reversible intercalation and deintercalation of lithium, and may specifically include a lithium composite metal oxide containing lithium and one or more metals such as cobalt, manganese, nickel or aluminum. have. More specifically, the lithium composite metal oxide is a lithium-manganese oxide (eg, LiMnO 2 , LiMn 2 O 4, etc.), lithium-cobalt oxide (eg, LiCoO 2, etc.), lithium-nickel oxide (for example, LiNiO 2 and the like), lithium-nickel-manganese-based oxide (for example, LiNi 1-Y Mn Y O 2 (where, 0 ⁇ Y ⁇ 1), LiMn 2-z Ni z O 4 ( here, 0 ⁇ Z ⁇ 2) and the like), lithium-nickel-cobalt oxide (e.g., LiNi 1-Y1 Co Y1 O 2 (here, 0 ⁇ Y1 ⁇ 1) and the like), lithium-manganese-cobal
  • LiCoO 2 , LiMnO 2 , LiNiO 2 , and lithium nickel manganese cobalt oxides may be improved in capacity and stability of the battery.
  • lithium nickel cobalt aluminum oxide e.g., Li (Ni 0. 8 Co 0. 15 Al 0 .
  • the lithium composite metal oxide is Li (Ni 0.6 Mn 0.2 Co 0.2 ) O 2 , Li (Ni 0.5 Mn 0.3 Co 0.2 ) O 2 , Li (Ni 0.7 Mn 0.15 Co 0.15 ) O 2, or Li (Ni 0.8 Mn 0.1 Co 0.1 ) O 2 , and the like, and any one or a mixture of two or more thereof may be used. have.
  • the cathode active material may be included in an amount of 80 wt% to 99 wt% based on the total weight of the cathode slurry.
  • the conductive material is typically added at 1 to 30% by weight based on the total weight of the positive electrode slurry.
  • a conductive material is not particularly limited as long as it has conductivity without causing chemical change in the battery, and examples thereof include graphite; Carbon-based materials such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, and thermal black; Conductive fibers such as carbon fibers and metal fibers; Metal powders such as carbon fluoride powder, aluminum powder and nickel powder; Conductive whiskeys such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives and the like can be used.
  • conductive materials include Chevron Chemical Company, Denka Singapore Private Limited, Gulf Oil Company, Ketjenblack and EC, which are acetylene black series. Family (Armak Company), Vulcan XC-72 (manufactured by Cabot Company) and Super P (manufactured by Timcal).
  • the binder is a component that assists in bonding the active material and the conductive material and bonding to the current collector, and is generally added in an amount of 1 to 30 wt% based on the total weight of the positive electrode slurry.
  • binders include polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, Polyethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene-butadiene rubber, fluorine rubber, various copolymers, and the like.
  • the solvent may include an organic solvent such as N-methyl-2-pyrrolidone (NMP), and may be used in an amount that becomes a desirable viscosity when including the cathode active material, and optionally a binder and a conductive material.
  • NMP N-methyl-2-pyrrolidone
  • the concentration of the positive electrode active material and, optionally, the solid content including the binder and the conductive material may be included in an amount of 50 wt% to 95 wt%, preferably 70 wt% to 90 wt%.
  • the electrolyte is commonly used in manufacturing a lithium secondary battery, and includes a non-aqueous organic solvent and a lithium salt.
  • the non-aqueous organic solvent is not particularly limited as long as it can minimize decomposition by an oxidation reaction or the like in the process of charging and discharging a battery, and can exhibit desired properties with an additive.
  • examples thereof include a carbonate-based compound or propio. Nate type compounds etc. can be used individually, or can mix and use 2 or more types.
  • Examples of such carbonate compounds include dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC), methylethyl carbonate (MEC), Ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC) and vinylene carbonate (VC), any one selected from the group consisting of, or a mixture of two or more thereof.
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • DPC dipropyl carbonate
  • MPC methylpropyl carbonate
  • EPC ethylpropyl carbonate
  • MEC methylethyl carbonate
  • Ethylene carbonate EC
  • PC butylene carbonate
  • BC butylene carbonate
  • VC vinylene carbonate
  • propionate-based compound may be ethyl propionate (EP), propyl propionate (PP), n-propyl propionate, iso-propyl propionate, n-butyl propionate, iso One or a mixture of two or more selected from the group consisting of -butyl propionate and tert-butyl propionate.
  • non-aqueous organic solvent for example, N-methyl-2-pyrrolidone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, gamma-butyrolactone, 1,2 Dimethoxy ethane, 2-methyl tetrahydrofuran, dimethyl sulfoxide, 1,3-dioxolon, formamide, dimethylformamide, dioxolon, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphate triester , Trimethoxy methane, dioxorone derivative, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, propylene carbonate derivative, tetrahydrofuran derivative, ether, methyl propionate, ethyl propionate and the like Can be.
  • N-methyl-2-pyrrolidone propylene carbonate,
  • the anion wherein the lithium salt comprises a Li + cation are F -, Cl -, Br - , I -, NO 3 -, N (CN) 2 -, BF 4 -, ClO 4 -, AlO 4 -, AlCl 4 -, PF 6 -, SbF 6 -, AsF 6 -, BF 2 C 2 O 4 -, BC 4 O 8 -, (CF 3) 2 PF 4 -, (CF 3) 3 PF 3 -, (CF 3) 4 PF 2 - , (CF 3) 5 PF -, (CF 3) 6 P -, CF 3 SO 3 -, C 4 F 9 SO 3 -, CF 3 CF 2 SO 3 -, (CF 3 SO 2) 2 N -, ( F 2 SO 2) 2 N -, CF 3 CF 2 (CF 3) 2 CO -, (CF 3 SO 2) 2 CH -, CF 3 (CF 2) 7 SO 3 -, CF 3 CO 2
  • the said lithium salt can also be used 1 type or in mixture of 2 or more types as needed.
  • the lithium salt may be appropriately changed within a range generally available, but may be included in an electrolyte solution at a concentration of 0.8 M to 1.5 M in order to obtain an effect of forming an anti-corrosion coating on the surface of the electrode.
  • the lithium secondary battery according to the exemplary embodiment of the present invention may include all conventional lithium secondary batteries, such as a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery, or a lithium ion polymer secondary battery.
  • the external shape of the lithium secondary battery of the present invention is not particularly limited, but may be cylindrical, square, pouch type or coin type using a can.
  • the lithium secondary battery of the present invention can be used as a power source for various electronic products.
  • the present invention may be used in a portable telephone, a mobile phone, a game console, a portable television, a laptop computer, a calculator, and the like, but is not limited thereto.
  • Silane gas was added at a rate of 25 sccm / 60 min under a pressure condition of 500 ° C. and 760 Torr to deposit an amorphous silicon layer having a thickness of 100 nm on the surface of the glass substrate.
  • the glass substrate on which the amorphous silicon layer is deposited is impregnated in a beaker containing acetone, and then subjected to ultrasonic grinding for 10 minutes at room temperature at 100W output using an ultrasonic mill, thereby obtaining amorphous silicon particles having an average particle diameter (D50) of 100 nm.
  • D50 average particle diameter
  • sucrose 120 g was dissolved in 1 L of distilled water to prepare a carbon-based precursor solution, and then 50 g of the pulverized amorphous silicon particles were dispersed to prepare a dispersion solution.
  • the dispersion solution was spray dried at a rate of 20 mL / min at 220 ° C. to prepare a silicon-based composite precursor.
  • the silicon-based composite precursor was heat-treated at 600 ° C. for 15 minutes, and the average particle diameter (D5) including amorphous silicon particles 1 (50% by weight) inside the amorphous carbon coating layer 5 (50% by weight).
  • a 5 ⁇ m lithium secondary battery negative electrode active material 10 was prepared (see FIG. 1).
  • Example 2 When dispersing the pulverized amorphous silicon particles in the carbon-based precursor solution in Example 1, in the same manner as in Example 1, except that 2g of carbon black which is amorphous carbon is dispersed together to prepare a dispersion solution, amorphous Cathode active material for lithium secondary battery having an average particle diameter (D5) of 5 ⁇ m including amorphous silicon particles 11 (49 wt%) and conductive material 13 (2 wt%) in the carbon coating layer 15 (49 wt%). 50 was prepared (see FIG. 2).
  • Example 2 When dispersing the pulverized amorphous silicon particles in the carbon-based precursor solution in Example 1, in the same manner as in Example 1 except for dispersing the artificial graphite particles of crystalline carbon together to prepare a dispersion solution, A lithium secondary battery having an average particle diameter (D5) of 21 ⁇ m including amorphous silicon particles 111 (17 wt%) and graphite particle core 117 (66 wt%) inside an amorphous carbon coating layer 115 (17 wt%). A negative electrode active material 100 was prepared.
  • D5 average particle diameter of 21 ⁇ m including amorphous silicon particles 111 (17 wt%) and graphite particle core 117 (66 wt%) inside an amorphous carbon coating layer 115 (17 wt%).
  • a negative electrode active material 100 was prepared.
  • Nano-size crystalline silicon particles were prepared by pulverizing silicon powder (Sigma-aldrich) having an average particle diameter of 44 ⁇ m using a ball mill method. At this time, a zirconia ball having a diameter of 3mm was used as the milling media, and the ratio of the ball and the silicon powder was mixed in a 1: 1 mass ratio and pulverized for 2 hours. The average particle diameter of the crystalline silicon particles after grinding was 150 nm.
  • sucrose was dissolved in 1 L of distilled water to prepare a carbon-based precursor solution, and then 50 g of the pulverized crystalline silicon particles were dispersed to prepare a dispersion solution.
  • the dispersion solution was spray dried at a rate of 20 mL / min at 220 ° C. to prepare a silicon-based composite precursor.
  • the silicon-based composite precursor was heat-treated at 600 ° C. for 15 minutes to have an average particle diameter (D5) of 5 ⁇ m including amorphous silicon particles (50%) inside the amorphous carbon coating layer (50%) inside the amorphous carbon coating layer (50%).
  • D5 average particle diameter
  • a negative electrode active material for a lithium secondary battery was prepared.
  • the amorphous carbon coating layer ( 49%) to prepare a negative active material for a lithium secondary battery having an average particle diameter (D5) of 5 ⁇ m including amorphous silicon particles (49%) and carbon black (2%).
  • the negative electrode active material prepared in Example 1 as a negative electrode active material, acetylene black as a conductive material, styrene-butadiene rubber (SBR) as a binder, and carboxymethyl cellulose (CMC) as a thickener were mixed in a weight ratio of 96: 1: 2: 1. And, these were mixed with water (H 2 O) as a solvent to prepare a uniform negative electrode active material slurry.
  • the prepared negative electrode active material slurry was coated on one surface of a copper current collector to a thickness of 65 ⁇ m, dried and rolled, and then punched to a predetermined size to prepare a negative electrode.
  • Lithium metal foil was used as a counter electrode for the negative electrode.
  • a lithium secondary battery was manufactured in the same manner as in Example 4, except that the negative electrode active material prepared in Example 2 was used instead of the negative electrode active material prepared in Example 1 as the negative electrode active material.
  • a lithium secondary battery was manufactured in the same manner as in Example 4, except that the anode active material prepared in Example 3 was used instead of the anode active material prepared in Example 1 as the anode active material.
  • a lithium secondary battery was manufactured in the same manner as in Example 4, except that the negative electrode active material prepared in Comparative Example 1 was used as the negative electrode active material.
  • a lithium secondary battery was manufactured by the same method as Comparative Example 4, except that the negative electrode active material prepared in Comparative Example 2 was used as the negative electrode active material.
  • a lithium secondary battery was manufactured by the same method as Comparative Example 4, except that the negative electrode active material prepared in Comparative Example 3 was used as the negative electrode active material.
  • Oxygen analysis was performed on the negative electrode active materials prepared in Examples 1 to 3 and Comparative Examples 1 to 3 using the CS-800 equipment of ELTRA, and the specific surface area was measured using the BELSORP-max equipment of BEL JAPAN. It was.
  • the silicon grain size present in the negative electrode active materials of Examples 1 to 3 and the silicon grain size present in the negative electrode active materials of Comparative Examples 1 to 3 were measured through Bruker's D4 Endeavor XRD equipment. The results are shown in Table 1.
  • the silicon grain size contained in the negative electrode active material is small, it is known that the electrode volume expansion rate is low.
  • the negative electrode active material of Comparative Examples 1 to 3 including silicon particles obtained by grinding a commercially available bulk silicon powder by a ball mill process as shown in Table 1 after grinding according to the silicon grain size of the bulk silicon powder, Silicon grains of about 17 nm to 19 nm in size.
  • the negative electrode active material of Examples 1 to 3 including amorphous silicon particles prepared by ultrasonic grinding compared to the negative electrode active material of Comparative Examples 1 to 3, the silicon grains of 4.3 nm or less are included. Therefore, in the case of the electrode including the negative electrode active material of Examples 1 to 3 of the present invention, it can be predicted that the volume expansion ratio is reduced.
  • the secondary battery of Example 4 increased the initial efficiency by 10% and the discharge capacity by about 210 mAh / g, compared to the secondary battery of Comparative Example 4.
  • the secondary battery of Example 5 had an initial efficiency of 9% and a discharge capacity of about 210 mAh / g.
  • the secondary battery of Example 6 increased the initial efficiency by 9% and the discharge capacity by about 80 mAh / g.
  • the negative electrode active materials of Comparative Examples 4 to 6 including silicon particles prepared by pulverizing the bulk silicon powder are oxidized by frictional heat during grinding, and irreversible phase during initial charging as oxygen is bonded to the silicon particles. Since a phase formed by an irreversible reaction, which is produced during the discharge but is not decomposed again during discharge, is formed, the initial efficiency is lowered and the amount of silicon atoms that can participate in the reversible reaction is reduced. Therefore, as shown in Table 2, the charge and discharge reversible capacity of the secondary batteries of Comparative Examples 4 to 6 including the negative electrode active materials of Comparative Examples 1 to 3 is reduced.
  • the life characteristics are about 8% superior to the secondary battery life characteristics of Comparative Example 4.
  • the life characteristics of the secondary battery of Example 5 of the present invention are about 9% superior to those of the secondary battery of Comparative Example 5.
  • the life characteristics of the secondary battery of Example 6 of the present invention are about 6% superior to those of the secondary battery of Comparative Example 6.
  • the electrode thickness expansion ratio of the 51st cycle charged state of the secondary batteries of Examples 4 to 6 is significantly lower than that of each of the secondary batteries of Comparative Examples 4 to 6.

Abstract

La présente invention concerne : un procédé permettant de préparer un matériau actif d'anode destiné à une batterie secondaire, le matériau actif d'anode étant susceptible d'empêcher une oxydation pendant la préparation de particules de silicium nanométriques; un matériau actif d'anode destiné à une batterie secondaire et préparé par le procédé; une anode destinée à une batterie secondaire et comprenant le matériau actif d'anode destiné à une batterie secondaire; et une batterie secondaire au lithium.
PCT/KR2016/014452 2015-12-10 2016-12-09 Procédé de préparation d'un matériau actif d'anode destiné à une batterie secondaire au lithium et batterie secondaire au lithium à laquelle le procédé est appliqué WO2017099523A1 (fr)

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EP16873388.9A EP3382779B1 (fr) 2015-12-10 2016-12-09 Procédé de préparation d'un matériau actif d'anode destiné à une batterie secondaire au lithium et batterie secondaire au lithium à laquelle le procédé est appliqué
CN201680049763.2A CN107925067B (zh) 2015-12-10 2016-12-09 制备锂二次电池用负极活性材料的方法和使用所述负极活性材料的锂二次电池
PL16873388T PL3382779T3 (pl) 2015-12-10 2016-12-09 Sposób wytwarzania materiału czynnego anody dla akumulatora litowego i akumulator litowy, w którym stosuje się ten sposób
US15/751,916 US10511048B2 (en) 2015-12-10 2016-12-09 Method of preparing negative electrode active material for lithium secondary battery and lithium secondary battery using the same

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KR10-2015-0176259 2015-12-10
KR1020160166995A KR101977931B1 (ko) 2015-12-10 2016-12-08 리튬 이차전지용 음극활물질의 제조 방법 및 이를 적용한 리튬 이차전지
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