WO2018124448A1 - Composition d'anode destinée à une batterie secondaire au lithium et son procédé de préparation, et batterie secondaire au lithium comprenant ladite composition - Google Patents

Composition d'anode destinée à une batterie secondaire au lithium et son procédé de préparation, et batterie secondaire au lithium comprenant ladite composition Download PDF

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WO2018124448A1
WO2018124448A1 PCT/KR2017/012229 KR2017012229W WO2018124448A1 WO 2018124448 A1 WO2018124448 A1 WO 2018124448A1 KR 2017012229 W KR2017012229 W KR 2017012229W WO 2018124448 A1 WO2018124448 A1 WO 2018124448A1
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negative electrode
lithium secondary
material layer
active material
secondary battery
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PCT/KR2017/012229
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English (en)
Korean (ko)
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조재필
마지영
성재경
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울산과학기술원
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Publication of WO2018124448A1 publication Critical patent/WO2018124448A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • 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
    • H01M4/04—Processes of manufacture in general
    • 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
    • H01M4/04—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
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—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
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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

  • Embodiments of the present invention relate to a negative electrode composition for a lithium secondary battery, a method for manufacturing the same, and a lithium secondary battery including the same. More particularly, a negative electrode composition for a lithium secondary battery for realizing a high capacity negative electrode having an improved lifetime, and a method for manufacturing the same. It relates to a lithium secondary battery comprising the same.
  • Lithium secondary batteries which operate by repeatedly charging and discharging through insertion and desorption of lithium ions, are expected to be used not only as portable electronic devices such as mobile phones and laptops, but also as power supplies for medium and large devices such as electric vehicles and energy storage devices. do.
  • silicon-based anode materials with large lithium capacities.
  • the theoretical capacitance of silicon-based anode materials is 4200mAh / g, more than 10 times that of graphite, increasing the likelihood of becoming a next-generation cathode material in place of graphite.
  • silicon has poor cycle characteristics compared to the carbon-based negative electrode active material, which makes it an obstacle to practical use.
  • the reason is that about 400% of volume change occurs during the charging and discharging process, that is, the charging and dissociation of silicon with lithium ions, and the mechanical stress caused by this is applied to the inside and the surface of the silicon anode. This is because cracking occurs.
  • the silicon negative electrode active material is detached from the current collector, and electrical insulation may occur due to the cracks generated in the silicon negative electrode active material, thereby causing a problem in that the battery life is drastically reduced.
  • the present invention is to solve various problems including the above problems, and to provide a negative electrode composition for a lithium secondary battery, a method of manufacturing the same and a lithium secondary battery comprising the same for implementing a high capacity negative electrode with improved lifetime. do.
  • these problems are exemplary, and the scope of the present invention is not limited thereby.
  • Embodiments of the present invention to provide a negative electrode composition for a lithium secondary battery, a method of manufacturing the same and a lithium secondary battery comprising the same.
  • At least one active material layer disposed on the core and the surface of the core and reacting with lithium ions to generate a volume change, and at least one having a smaller volume change rate than the at least one active material layer Provided is a negative electrode composition for a lithium secondary battery having a shell in which an inactive material layer is alternately laminated.
  • the manufacturing cost can be reduced to contribute to mass production of a high capacity negative electrode active material.
  • FIG. 1 is a process diagram sequentially showing the manufacturing process of the negative electrode composition for a lithium secondary battery according to an embodiment of the present invention.
  • FIG. 2 is a cross-sectional view schematically showing a negative electrode composition for a rechargeable lithium battery according to another embodiment of the present invention.
  • FIG 3 is a cross-sectional view schematically showing a negative electrode composition for a rechargeable lithium battery according to another embodiment of the present invention.
  • FIG. 4 is a TEM photograph of a negative electrode composition for a rechargeable lithium battery according to one embodiment of the present invention.
  • FIG. 6 is a graph showing a change in discharge capacity according to the number of cycles of a lithium secondary battery according to an embodiment and a comparative example of the present invention.
  • FIG. 7 is a graph showing a change in coulombic efficiency according to the number of cycles of a lithium secondary battery according to an embodiment and a comparative example of the present invention.
  • FIG. 8 is an exploded perspective view of a rechargeable lithium battery according to one embodiment of the present invention.
  • At least one active material layer disposed on the core and the surface of the core and reacting with lithium ions to generate a volume change, and at least one having a smaller volume change rate than the at least one active material layer Provided is a negative electrode composition for a lithium secondary battery having a shell in which an inactive material layer is alternately laminated.
  • the shell may further include a conductive layer containing carbon.
  • the core may comprise Si.
  • the at least one active material layer may include Si.
  • the at least one inert material layer may include at least one of SiO 2 , Al 2 O 3 , TiO 2 , Fe 3 O 4 , soft carbon, hard carbon, and a polymer.
  • the lowermost layer of the shell may include at least one of SiO 2 , Al 2 O 3 , TiO 2 , Fe 3 O 4 , soft carbon, hard carbon, and a polymer.
  • the core has a spherical shape, and the shell may be arranged to surround at least a portion of the core.
  • the core may have a hollow spherical shape.
  • Each of the at least one active material layer and the at least one inert material layer may have a thickness of 1 to 200 nm.
  • the core may have a diameter of 1 to 500 nm.
  • the core may include Si
  • the at least one active material layer may include Si
  • the at least one inert material layer may include SiO 2
  • the lowermost layer of the shell may include SiO 2 .
  • step (e) after step (d), may further comprise the step of forming a conductive layer containing carbon.
  • the first negative electrode active material nanoparticles are Si, and the Si may be formed by decomposing silane gas.
  • the second negative electrode active material nanoparticles may be Si, the Si may be formed by decomposing silane gas, and the inactive material layer may include SiO 2 .
  • the third negative electrode active material nanoparticles are Si, and the Si may be formed by decomposing silane gas.
  • the core may be formed to have a spherical shape, and the active material layer and the inactive material layer may be formed to surround at least a portion of the core.
  • the core may be formed to have a hollow spherical shape.
  • Each of the active material layer and the inert material layer may have a thickness of 1 to 200 nm.
  • the core may have a diameter of 1 to 500 nm.
  • a lithium secondary battery having a cathode including an anode, an electrolyte, and a cathode composition for a lithium secondary battery according to any one of claims 1 to 10.
  • FIG. 1 is a process diagram sequentially showing the manufacturing process of the negative electrode composition for a lithium secondary battery according to an embodiment of the present invention.
  • a negative electrode composition 1 for a lithium secondary battery is subjected to the following processes.
  • the core 10 is formed.
  • the core 10 is formed to include the first negative electrode active material nanoparticles.
  • the first negative electrode active material nanoparticles may be formed of various materials, for example, may include at least one of Si, Ge, Mg, Al, P, Ga, As, Cd, Au, and Bi.
  • the first negative electrode active material nanoparticles may be Si.
  • the Si nanoparticles may be formed by decomposing silane gas. Specifically, Si nanoparticles may be obtained by introducing silane gas and a carrier gas into the reactor and decomposing the silane gas in the reactor. In this case, the size of the Si nanoparticles may be adjusted by changing the mixing ratio of the silane gas and the carrier gas.
  • the carrier gas H 2 , N 2 , Ar, HCl, Cl 2, etc. may be used, and a reaction temperature for decomposing the silane gas may be 500 to 1200 ° C., preferably 450 to 500 ° C., and the type of the silane gas It may be set to an appropriate temperature depending on the deposition conditions.
  • the core 10 may be formed using the Si nanoparticles generated as described above, but the core 10 may be formed to have a spherical shape as shown in FIG. 1, but is not limited thereto. no. That is, the shape of the wire and the tube, as well as may be formed in the form of a flat plate.
  • the core 10 will be described in detail with reference to a case having a spherical shape.
  • the core 10 may be formed to have a diameter of 1 to 500 nm, preferably 5 to 100 nm. As such, by forming the core 10 small to have a diameter of several hundred nm or less, crack generation due to volume expansion of Si may be partially reduced when the core 10 is used as a negative electrode active material of a lithium secondary battery.
  • the Si nanoparticles in the step (a) has been described as being formed by supplying the silane gas, in addition, it is also possible to form the commercialized Si particles by mechanical grinding through ball milling or the like.
  • step (b) a step of forming the inert material layer 21i on the surface of the core 10.
  • the step (b) may be subdivided into two steps.
  • the first step is to form a temporary active material layer on the surface of the core 10, and the second step is to heat-treat the temporary active material layer in an atmospheric atmosphere. Step.
  • the temporary active material layer formed on the surface of the core 10 is formed to include the second negative electrode active material nanoparticles.
  • the second negative electrode active material nanoparticles may be formed of various materials, for example, may include at least one of Si, Ge, Mg, Al, P, Ga, As, Cd, Au, and Bi.
  • the second negative electrode active material nanoparticles may be Si.
  • the Si nanoparticles may be formed by decomposing silane gas or by pulverizing commercially available Si particles by a method such as ball milling.
  • the temporary active material layer is heat-treated in an air atmosphere to supply oxygen gas to the temporary active material layer.
  • the oxygen gas must be supplied in a state in which silane gas is blocked, and the temperature for heat treatment may be 750 to 950 degrees.
  • the material included in the second negative electrode active material nanoparticles is changed into an oxide form to form the inactive material layer 21i.
  • the inactive material layer 21i is formed to include SiO 2 .
  • the inert material layer 21i is formed of SiO 2 , durability of the spherical core 10 enclosed by the inert material layer 21i may be improved.
  • SiO 2 has a small volume change and not only disperses the Si nanoparticles properly, but also traps the Si nanoparticles in a small space to prevent the Si nanoparticles from being micronized and released due to the volume change. Therefore, it is possible to prevent electrical shorts due to micronization of Si nanoparticles, thereby improving cycle characteristics of the battery.
  • the inert material layer 21i may include at least one of SiO 2 , Al 2 O 3 , TiO 2 , Fe 3 O 4 , soft carbon, hard carbon, and a polymer.
  • the inert material layer 21i formed as described above is not directly involved in the redox reaction of the lithium secondary battery, but serves to mitigate volume expansion or side reaction of the first negative electrode active material included in the core 10.
  • the material contained in the inactive material layer 21i may have a small volume change rate compared to the first negative electrode active material.
  • the active material layer 21 is formed on the inactive material layer 21i.
  • the active material layer 21 is formed to include the third negative electrode active material nanoparticles.
  • the third negative electrode active material nanoparticles may be formed of various materials, for example, may include at least one of Si, Ge, Mg, Al, P, Ga, As, Cd, Au, and Bi.
  • the third negative electrode active material nanoparticles may be Si. Therefore, the Si nanoparticles can be formed by decomposing silane gas or by pulverizing commercially available Si particles by a method such as ball milling.
  • the active material layer 21 including the negative active material is formed on the core 10 including the negative active material and the inactive material layer 21i surrounding the active material layer 21, thereby inactivating the inactive material layer not involved in the redox reaction of the battery.
  • the deterioration of the capacity characteristic due to (21i) can be compensated for.
  • the inactive material layer 21i and the active material layer 21 may be each formed to a thickness of 1 to 200 nm.
  • the step (b) and the step (c) is sequentially performed a plurality of times repeated. That is, the additional inactive material layer 22i is formed on the active material layer 21 formed in step (c), and the additional active material layer 22 is formed thereon again.
  • the additional inert material layer 22i may be formed to include at least one of SiO 2 , Al 2 O 3 , TiO 2 , Fe 3 O 4 , soft carbon, hard carbon, and a polymer.
  • the additional active material layer 22 may be formed to include at least one of Si, Ge, Mg, Al, P, Ga, As, Cd, Au, and Bi.
  • the silane gas is decomposed to form a temporary active material layer including Si nanoparticles, and then the temporary active material layer is heat-treated in an oxygen-containing atmosphere to further inert material containing SiO 2 .
  • Layer 22i may be formed. Thereafter, the silane gas may be again supplied on the additional inert material layer 22i to form the additional active material layer 22 including the Si nanoparticles. Therefore, since a plurality of active material layers and an inert material layer can be formed by alternately forming a silane gas atmosphere and an atmosphere atmosphere, a negative electrode composition for a lithium secondary battery is continuously formed without expensive equipment using a laser beam or plasma. can do.
  • the temporary active material layer and the additional active material layer 22 is formed, a method of grinding the commercialized Si particles by a method such as ball milling may be used.
  • the negative electrode composition 1 for a rechargeable lithium battery includes a core 20 and a shell 20 disposed to surround at least a portion of the core 10 on the surface of the core 10. It takes the form of a core-shell structure.
  • the shell 20 is formed such that at least one inert material layer 21i, 22i, ... 2ni and at least one active material layer 21, 22, ... are alternately stacked.
  • the core 10 may be formed of the same or similar material as the at least one active material layer 21, 22,..., So that the lowermost layer of the shell 20 in contact with the surface of the core 10 may be It is formed of an inert material layer 21i.
  • each of the at least one inert material layer 21i, 22i, ... 2ni may be formed of the same material, and the at least one active material layer 21, 22, ... Each may be formed of the same material.
  • the present invention is not limited thereto, and some of the at least one inert material layer 21i, 22i, ... 2ni may be formed of different materials, and at least one active material layer 21, 22, ... Some of them may also be formed of different materials.
  • FIG. 2 is a cross-sectional view schematically showing a negative electrode composition for a rechargeable lithium battery according to another embodiment of the present invention
  • FIG. 3 is a cross-sectional view schematically showing a negative electrode composition for a rechargeable lithium battery according to another embodiment of the present invention.
  • the negative electrode composition 2 for a rechargeable lithium battery surrounds the core 10 and at least a portion of the core 10 on the surface of the core 10.
  • the shell 20 arrange
  • the shell 20 is formed such that at least one inert material layer 21i, 22i, ... 2ni and at least one active material layer 21, 22, ... are alternately stacked.
  • the conductive layer 30 is formed on the outermost side of the core-shell structure that is the same as or similar to that shown in FIG. 1.
  • the embodiment shown in FIG. 3 is similar to the structure of the embodiment shown in FIG. 2, except that the core 10 has a hollow sphere shape. That is, the negative electrode composition 3 for a lithium secondary battery illustrated in FIG. 3 includes a core 10 having a hollow spherical shape and a shell disposed to surround at least a portion of the core 10 on the surface of the core 10. 20 and a conductive layer 30 disposed on the shell 20.
  • the shell 20 is formed such that at least one inert material layer 21i, 22i, ... 2ni and at least one active material layer 21, 22, ... are alternately stacked.
  • the conductive layer 30 may include carbon as a conductive material.
  • the conductive layer 30 may include crystalline carbon such as natural graphite, artificial graphite, amorphous carbon such as soft carbon, hard carbon, or the like. Can be formed.
  • FIG. 4 is a TEM photograph of a negative electrode composition for a rechargeable lithium battery according to an embodiment of the present invention
  • FIG. 5 is an enlarged TEM photograph of part A of FIG. 4.
  • the negative electrode composition for a rechargeable lithium battery according to an embodiment of the present invention has a spherical core and a core-shell structure formed to surround the core, which is more specifically illustrated in FIG. 5. It is.
  • the core is formed of Si
  • the shell is formed in a form in which SiO 2 and Si are alternately stacked.
  • Fig. 5 (i) is located a spherical core containing Si
  • Fig. 5 (ii) is located an inert material layer containing SiO 2
  • Fig. 5 (iii) an active material containing Si
  • the floor is located.
  • the inert material layer including SiO 2 is located, and the inactive material layer is formed to have the thinnest thickness among the shells.
  • the core located in (i) comprises crystalline Si
  • the inert material layer located in (ii) comprises amorphous SiO 2
  • the active material layer located in (iii) comprises amorphous Si
  • the inert material layer located at includes amorphous SiO 2 .
  • the anode composition in which a shell composed of three layers around the spherical core is disposed to surround the core may have a total diameter of 80 to 100 nm.
  • FIG. 6 is a graph showing a change in discharge capacity according to the number of cycles of a lithium secondary battery according to an embodiment and a comparative example of the present invention
  • Figure 7 is a cycle number of a lithium secondary battery according to an embodiment and a comparative example of the present invention This is a graph showing the change of coulombic efficiency.
  • the lithium secondary battery sample used in the experiment was provided with a negative electrode, a positive electrode, and an electrolyte, and had a coin cell shape.
  • the negative electrode is prepared by mixing Si nanoparticles, a conductive agent, a thickener and a binder in a ratio of 80: 10: 5: 5 and then adding water to make a slurry, and thinly applying the resulting slurry onto a copper foil.
  • the specific experimental method is as follows.
  • the lithium secondary battery sample starts charging at a charge rate of 0.1 C-rate, and the voltage is charged up to 0.005V, where it is charged to have a constant voltage at a constant current. After that, the discharge is performed at a discharge rate of 0.1 C-rate, but the voltage is discharged to 1.5V, and a constant current is applied even at this time. After one charge and discharge cycle as described above, the charge and discharge cycle is repeated continuously at a voltage section of 0.005 V to 1 V at a charge and discharge rate of 0.5 C-rate.
  • the discharge capacity is constant even if the number of cycles increases compared to the lithium secondary battery (indicated by a solid line) according to a comparative example. It can be confirmed that it is maintained.
  • the core (Si) -shell structured anode material as in one embodiment of the present invention shows much more stable life characteristics than a simple Si anode material.
  • the lithium secondary battery (indicated by a line connecting circular dots) according to an embodiment of the present invention is higher than the lithium secondary battery (indicated by a solid line) according to a comparative example. It can be seen that it has a coulombic efficiency (CE). This means that the core (Si) -shell structured anode material as one embodiment of the present invention has higher charge / discharge efficiency than a simple Si anode material.
  • FIG. 8 is an exploded perspective view of a rechargeable lithium battery according to one embodiment of the present invention.
  • the lithium secondary battery 100 includes a negative electrode 112, a positive electrode 114, a separator 113 disposed between the negative electrode 112 and the positive electrode 114, and a negative electrode. (112), an electrolyte (not shown) impregnated in the positive electrode 114 and the separator 113, the battery container 120, and the sealing member 140 for sealing the battery container 120 is composed as a main portion have.
  • the lithium secondary battery 100 is manufactured by stacking the negative electrode 112, the positive electrode 114, and the separator 113 in order, and then storing the lithium secondary battery 100 in the battery container 120 while being wound in a spiral shape.
  • the negative electrode 112 is formed of the negative electrode composition of the structure shown in Figure 1, 2 or 3, thereby minimizing the volume expansion of the high-capacity negative electrode active material to improve the life characteristics of the lithium secondary battery 100 including the same May be as described above.
  • the lithium secondary battery 100 is illustrated as having a cylindrical shape in FIG. 8, the lithium secondary battery 100 is not necessarily limited thereto and may be formed in various shapes such as a square shape, a coin shape, and a pouch type.
  • a negative electrode composition for a lithium secondary battery may be provided to implement a high capacity negative electrode having improved lifespan, and such a negative electrode composition for a secondary battery may be a mobile mobile electronic device such as a mobile phone, a laptop, an electric vehicle, or a hybrid. It can be used in automobiles, hybrid ships, electric bicycles and the like.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

La présente invention concerne une composition d'anode destinée à une batterie secondaire au lithium, comprenant : un noyau ; et une enveloppe disposée sur la surface du noyau et présentant au moins une couche de matériau actif et au moins une couche de matériau non actif stratifiées en alternance sur ladite enveloppe, ladite couche de matériau actif changeant en volume par réaction avec des ions lithium, et ladite couche de matériau non actif étant plus faible en taux de changement de volume que ladite couche de matériau actif.
PCT/KR2017/012229 2016-12-30 2017-11-01 Composition d'anode destinée à une batterie secondaire au lithium et son procédé de préparation, et batterie secondaire au lithium comprenant ladite composition WO2018124448A1 (fr)

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KR1020160184141A KR101908603B1 (ko) 2016-12-30 2016-12-30 리튬 이차 전지용 음극 조성물, 이의 제조 방법 및 이를 포함하는 리튬 이차 전지
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KR20220066655A (ko) * 2020-11-16 2022-05-24 부경대학교 산학협력단 리튬 이차전지용 복합 전극 활물질, 이의 제조방법 및 이를 포함하는 리튬 이차전지

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KR20160057813A (ko) * 2014-11-14 2016-05-24 삼성에스디아이 주식회사 음극 활물질 및 이를 포함하는 리튬 전지

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US20120264020A1 (en) * 2010-10-07 2012-10-18 Applied Sciences, Inc. Method of depositing silicon on carbon nanomaterials
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