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WO2018225971A1 - Matériau actif d'anode destiné à une batterie secondaire au lithium, anode destinée à une batterie secondaire au lithium, et batterie secondaire au lithium comprenant une telle anode - Google Patents

Matériau actif d'anode destiné à une batterie secondaire au lithium, anode destinée à une batterie secondaire au lithium, et batterie secondaire au lithium comprenant une telle anode Download PDF

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Publication number
WO2018225971A1
WO2018225971A1 PCT/KR2018/006043 KR2018006043W WO2018225971A1 WO 2018225971 A1 WO2018225971 A1 WO 2018225971A1 KR 2018006043 W KR2018006043 W KR 2018006043W WO 2018225971 A1 WO2018225971 A1 WO 2018225971A1
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Prior art keywords
negative electrode
silicon
active material
secondary battery
lithium secondary
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English (en)
Korean (ko)
Inventor
김향연
오민석
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Korea Institute of Industrial Technology KITECH
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Korea Institute of Industrial Technology KITECH
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Priority claimed from KR1020180050575A external-priority patent/KR102087134B1/ko
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Publication of WO2018225971A1 publication Critical patent/WO2018225971A1/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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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 negative electrode active material for a lithium secondary battery, a negative electrode for a lithium secondary battery and a lithium secondary battery comprising the same. More particularly, the present invention relates to a negative active material for a lithium secondary battery, an anode for a lithium secondary battery, and a lithium secondary battery including the same, including active silicon nanoparticles uniformly dispersed and precipitated in an inactive matrix including silicon, aluminum, iron, copper, and nickel. will be.
  • wireless charging technology that can charge the battery anytime and anywhere without a power connection by cable is being applied with IT. Accordingly, it is expected to be widely applied to wearable devices that can be worn or attached to a body as well as home appliances such as televisions and refrigerators or electric vehicles.
  • lithium secondary batteries are energy storage media applied to portable information devices such as smart phones, laptops, digital cameras, small home appliances and medical devices, electric vehicles, and large-capacity power storage systems.
  • portable information devices such as smart phones, laptops, digital cameras, small home appliances and medical devices, electric vehicles, and large-capacity power storage systems.
  • performance improvements such as high power, long life and high safety.
  • Lithium secondary batteries are manufactured by using a material capable of intercalation and deintercalation of lithium ions as a cathode and an anode, and injecting an electrolyte after installing porous separators between the electrodes.
  • electricity is generated or consumed by a redox reaction by insertion and desorption of lithium ions in the cathode and the anode.
  • the performance improvement of the lithium secondary battery can be attributed to the technology development of four core materials: positive electrode, negative electrode, electrolyte, and separator which have a decisive influence on various characteristics such as capacity and output. Since the capacity of the positive electrode active material and the negative electrode active material used in the lithium secondary battery has already approached the theoretical capacity, the need for a new negative electrode active material is increasing to realize a high capacity and high output battery suitable for wireless charging energy storage. .
  • graphite which is a negative electrode active material widely used in lithium secondary batteries, has a layered structure and thus has very useful characteristics for insertion and desorption of lithium ions.
  • Graphite theoretically has a capacity of 372 mAh / g, but as the demand for high-capacity lithium batteries increases recently, new electrodes are required to replace graphite. Accordingly, active research for commercialization of electrode active materials forming an electrochemical alloy with lithium ions such as silicon (Si), tin (Sn), antimony (Sb), and aluminum (Al) as a high capacity negative electrode active material is actively conducted. It is becoming.
  • Patent Document 1 Republic of Korea Patent No. 10-1385602
  • the technical problem to be achieved by the present invention is to improve the deterioration of the life characteristics due to the volume change when using a conventional silicon (Si) as a negative electrode active material, silicon (Si), aluminum (Al), iron (Fe), copper (Life time does not decrease even after repeated charging and discharging by using a negative electrode active material containing 1 nm to 30 nm of active silicon nanoparticles uniformly dispersed and deposited on an inert matrix including Cu) and nickel (Ni).
  • An object of the present invention is to provide a lithium secondary battery.
  • an embodiment of the present invention comprises the steps of preparing a melt by dissolving a mother alloy containing silicon; Preparing a silicon-based amorphous alloy by solidifying the melt by liquid quenching and solidification; And heat-treating the silicon-based amorphous alloy to produce a silicon-based composite metal, wherein the silicon-based composite metal comprises active silicon nanoparticles uniformly dispersed and precipitated in an inactive matrix. It provides a metal manufacturing method.
  • the silicon-based composite metal is silicon (Si) 30 at% to 60 at%, aluminum (Al) 15 at% to 50 at%, iron (Fe) 5 at% to 25 at%, copper ( Cu) 0.1 at% to 5 at% and nickel (Ni) 1 at% to 25 at%.
  • another embodiment of the present invention is silicon (Si) 30 at% to 60 at%, aluminum (Al) 15 at% to 50 at%, iron (Fe) 5 at% to 25 at%, Lithium secondary, characterized in that it comprises an inert matrix comprising 0.1 at% to 5 at% of copper (Cu) and 1 to 25 at% of nickel (Ni) and active silicon nanoparticles uniformly dispersed and precipitated in the inactive matrix It provides a battery negative electrode active material.
  • the inert matrix may be formed of at least 0.1 of zirconium (Zr), niobium (Nb), titanium (Ti), chromium (Cr), germanium (Ge), and calcium (Ca). It may be an anode active material for a lithium secondary battery, characterized in that it further comprises at% to 5 at%.
  • the inactive matrix may be a negative electrode active material for a lithium secondary battery, characterized in that it comprises any one or more of a crystalline matrix and an amorphous matrix.
  • the active silicon nanoparticles may be a negative electrode active material for a lithium secondary battery, characterized in that uniformly dispersed precipitation in the inactive matrix by copper clustering (Cu clustering) of the inactive matrix.
  • Cu clustering copper clustering
  • the active silicon nanoparticles may be a negative electrode active material for a lithium secondary battery, characterized in that the crystalline.
  • the particle size of the active silicon nanoparticles may be a negative electrode active material for a lithium secondary battery, characterized in that 1 nm to 30 nm.
  • another embodiment of the present invention includes a negative electrode active material layer and a negative electrode active material layer formed on at least one surface of the negative electrode current collector, the negative electrode active material layer 75 wt% to 92 wt %, 1 wt% to 10 wt% of a conductive material, and 7 wt% to 15 wt% of a binder, wherein the anode active material includes an inert matrix and active silicon nanoparticles uniformly dispersed and precipitated in the inactive matrix. It provides a negative electrode for a lithium secondary battery.
  • the inert matrix may be a negative electrode for a lithium secondary battery, characterized in that it comprises a five-component or more silicon alloy.
  • the five-component or more silicon alloy is silicon (Si) 30 at% to 60 at%, aluminum (Al) 15 at% to 50 at%, iron (Fe) 5 at% to 25 at%, It may be a negative electrode for a lithium secondary battery comprising 0.1 to 5 at% of copper (Cu) and 1 to 25 at% of nickel (Ni).
  • the five-component or more silicon alloy is made of one or more of zirconium (Zr), niobium (Nb), titanium (Ti), chromium (Cr), germanium (Ge) and calcium (Ca). It may be a negative electrode for a lithium secondary battery characterized in that it further comprises 0.1 to 5 at% of the material.
  • the active silicon nanoparticles may be a negative electrode for a lithium secondary battery, characterized in that uniformly dispersed precipitation in the inactive matrix by copper clustering (Cu clustering) of the inactive matrix.
  • Cu clustering copper clustering
  • the particle size of the active silicon nanoparticles may be a negative electrode for a lithium secondary battery, characterized in that 1 nm to 30 nm.
  • another embodiment of the present invention is a lithium secondary battery including a positive electrode, a negative electrode, an electrolyte and a separator, wherein the negative electrode is a negative electrode current collector and a negative electrode formed on at least one surface of the negative electrode current collector
  • An active material layer wherein the negative electrode active material layer comprises 75 wt% to 92 wt% of a negative electrode active material, 1 wt% to 10 wt% of a conductive material, and 7 wt% to 15 wt% of a binder; It provides a lithium secondary battery comprising the active silicon nanoparticles uniformly dispersed in the inert matrix.
  • the inactive matrix may be a lithium secondary battery comprising a silicon alloy of five or more components.
  • the five-component or more silicon alloy is silicon (Si) 30 at% to 60 at%, aluminum (Al) 15 at% to 50 at%, iron (Fe) 5 at% to 25 at%,
  • the lithium secondary battery may include 0.1 at% to 5 at% of copper (Cu) and 1 to 25 at% of nickel (Ni).
  • the five-component or more silicon alloy is made of one or more of zirconium (Zr), niobium (Nb), titanium (Ti), chromium (Cr), germanium (Ge) and calcium (Ca).
  • the lithium secondary battery may further include 0.1 at% to 5 at% of the material.
  • the active silicon nanoparticles may be a lithium secondary battery, characterized in that uniformly dispersed precipitation in the inactive matrix by copper clustering (Cu clustering) of the inactive matrix.
  • Cu clustering copper clustering
  • the particle size of the active silicon nanoparticles may be a lithium secondary battery, characterized in that 1 nm to 30 nm.
  • an anode comprising active silicon nanoparticles uniformly dispersed and precipitated in an inert matrix containing silicon (Si), aluminum (Al), iron (Fe), copper (Cu) and nickel (Ni) Since the active material tends to separate iron (Fe) and copper (Cu) in the inactive matrix, copper clustering may occur.
  • the Si-rich region having a low crystallization temperature is formed by the copper clustering phenomenon so that the active silicon particles are preferentially finely deposited during the heat treatment, and the inactive matrix has a crystalline structure or an amorphous structure. Can be formed.
  • the inactive matrix in the negative electrode active material may serve to suppress the volume expansion of the negative electrode active material while forming a structure that does not react with the lithium ions, the active silicon nanoparticles may be reversible reaction with lithium ions Therefore, the capacity of the negative electrode active material may be directly related to the capacity of the negative electrode active material.
  • the inactive matrix has a yield strength that can withstand the expansion stress of the silicon particles due to the intercalation of lithium ions during the charging and discharging of the negative electrode active material, thereby expanding the volume of the negative electrode active material during the charging and discharging process. And particle differentiation due to shrinkage can be suppressed.
  • the initial coulombic efficiency is excellent at 80% or more, and the capacity is maintained even after 30 cycles. It may have a lifetime characteristic.
  • FIG. 1 is a flow chart of a composite metal manufacturing method for a lithium secondary battery negative electrode active material according to an embodiment of the present invention.
  • FIG. 2 is a graph showing relative exothermic energy according to temperature with a differential scanning calorimetry (DSC) of a negative active material for a lithium secondary battery according to an exemplary embodiment of the present invention.
  • DSC differential scanning calorimetry
  • FIG. 3 is a diffraction pattern illustrating crystallinity of a negative electrode active material for a lithium secondary battery according to an exemplary embodiment of the present invention.
  • FIG. 4 is TEM-EDS images showing the distribution of components of the negative electrode active material for a lithium secondary battery according to an embodiment of the present invention.
  • FIG. 5 is a graph showing the charge and discharge cycle life of the lithium secondary battery according to an embodiment of the present invention.
  • silicon amorphous alloy design considering the microstructure of Cu clustering effect after heat treatment.
  • the 100 nm-class silicon phase is transformed into a matrix phase having a yield strength capable of withstanding the expansion stress of the silicon particles due to the intercalation of lithium ions during the charge and discharge cycle.
  • a uniformly dispersed precipitated microstructure it is intended to suppress the particle micronization due to volume expansion and contraction of silicon particles generated by the insertion and desorption reaction of lithium ions.
  • the present invention comprises the steps of preparing a melt by dissolving a mother alloy containing silicon (S100); Preparing a silicon-based amorphous alloy by solidifying the melt by liquid quenching and solidification (S200); And preparing a silicon-based composite metal by heat-treating the silicon-based amorphous alloy (S300), wherein the silicon-based composite metal includes active silicon nanoparticles uniformly dispersed and precipitated in an inactive matrix. It provides a method for producing a composite metal for an active material.
  • the silicon-based composite metal may include silicon at 30 to 60 at%, aluminum at 15 to 50 at%, iron at 5 to 25 at%, and copper at 0.1 to 5 at. % And 1 at% to 25 at% of nickel (Ni).
  • the anode active material for a lithium secondary battery of the present invention is silicon (Si) 30 at% to 60 at%, aluminum (Al) 15 at% to 50 at%, iron (Fe) 5 at% to 25 at%, copper (Cu) 0.1 at It may include an inert matrix including% to 5 at% and 1 at% to 25 at% of nickel (Ni) and active silicon nanoparticles uniformly dispersed and precipitated in the inactive matrix.
  • Silicon (Si) constituting the negative electrode active material is mixed with silicon (Si) and active silicon nanoparticles in an inactive matrix. Since the active silicon nanoparticles can be reversibly reacted with lithium ions, the active silicon nanoparticles are directly related to the capacity of the negative electrode active material, and the inactive matrix may serve to suppress the volume expansion of the negative electrode active material while forming a structure that does not react with the lithium ions. .
  • the active silicon nanoparticles may be uniformly dispersed and precipitated in an inactive matrix.
  • silicon (Si) may be involved in occlusion and release of lithium ions when the negative electrode active material is used as a negative electrode of a lithium secondary battery. Therefore, the amount of silicon (Si) included in the negative electrode active material for a lithium secondary battery is related to the capacity and life characteristics of the negative electrode active material. Specifically, the more silicon (Si) is included in the alloy, the capacity of the negative electrode active material may be improved, but the life characteristics may be somewhat lowered. Therefore, the content of silicon (Si) in the negative electrode active material is 30 to 60 at% level in order to improve the life characteristics rather than to improve the capacity of the negative electrode active material of the present invention.
  • the content of the silicon (Si) is less than 30 at%, it is not preferable to exhibit an excessively small capacity to implement the capacity as a negative electrode active material for a lithium secondary battery, the content of the silicon (Si) is greater than 60 at% In this case, since the content of components other than silicon (Si) constituting the inert matrix is small, the life improvement effect of the negative electrode active material for a lithium secondary battery may be difficult to appear, which is not preferable.
  • copper (Cu) and iron (Fe) are difficult to be dissolved in silicon (Si) when in a solid state at room temperature.However, using a manufacturing method such as liquid rapid solidification such as melt spinning, copper (Cu) may be converted into silicon (Si). Can be forcibly hired). Forced solid solution copper (Cu) tends to be separated from iron (Fe), which causes copper clustering (Cu clustering) phenomenon.
  • the active silicon nanoparticles may be uniformly dispersed and precipitated at a portion where the copper clustering phenomenon occurs, and the cathode active material of the present invention may include the active silicon nanoparticles uniformly dispersed and precipitated in an inactive matrix. have.
  • the content of copper (Cu) is preferably 0.1 at% to 5 at% when the content of the silicon (Si) is 30 at% to 60 at%. This is because when the content of copper (Cu) is less than 0.1 at%, the above-mentioned copper clustering phenomenon is insignificant and dispersion precipitation of active silicon nanoparticles may not occur, which is undesirable.
  • the copper (Cu) content is more than 5 at%, rather than copper (Cu) may act as an impurity, the content of the copper (Cu) is 0.1 at% to 5 at% is preferred level to be.
  • nickel (Ni) and iron (Fe) included in the inactive matrix can play a role of improving the capacity of the negative electrode active material, the capacity characteristics can be improved.
  • the inactive matrix may include a five-component silicon-based alloy including silicon (Si), aluminum (Al), iron (Fe), copper (Cu), and nickel (Ni).
  • Zirconium (Zr) may include a six-component silicon-based alloy further comprising 0.1 at% to 5 at%. At this time, zirconium (Zr) may serve to make the structure of the negative electrode active material fine, and improve the life characteristics.
  • a material consisting of at least one of niobium (Nb), titanium (Ti), chromium (Cr), germanium (Ge), and calcium (Ca) is further included. It is possible to use a silicon-based alloy containing a six-component or more as the inert matrix, it can be used as a component for improving the capacity characteristics or life characteristics.
  • the inert matrix may include any one or more of a crystalline matrix and an amorphous matrix, and the active silicon nanoparticles uniformly dispersed in the inactive matrix may be in a crystalline phase, and the particle size of the active silicon nanoparticles may be 1 nm. It may be from 30 nm, more preferably from 10 nm to 20 nm.
  • the negative electrode for a lithium secondary battery of the present invention includes a negative electrode current collector and a negative electrode active material layer formed on at least one surface of the negative electrode current collector, and the negative electrode active material layer is 75 wt% to 92 wt% of a negative electrode active material, and 1 wt% to conductive material. 10 wt% and 7 wt% to 15 wt% of the binder, wherein the negative electrode active material may include an inert matrix and active silicon nanoparticles uniformly dispersed in the inactive matrix.
  • the negative electrode current collector may include a conductive material, and specifically, may be a thin conductive foil or foam.
  • the negative electrode current collector may include, but is not limited to, copper, gold, nickel, stainless, or titanium.
  • the negative electrode active material layer may be prepared by mixing a negative electrode active material, a conductive material, and a binder in a solvent to prepare a composition for forming a negative electrode active material layer, and then coating the composition on a negative electrode current collector. Since such a negative electrode manufacturing method is well known in the art, detailed description thereof will be omitted.
  • the negative electrode active material may include an inert matrix and active silicon nanoparticles uniformly dispersed in the inactive matrix, and the inert matrix may include a five-component or more silicon alloy. More specifically, the five-component or more silicon alloy is silicon (Si) 30 at% to 60 at%, aluminum (Al) 15 at% to 50 at%, iron (Fe) 5 at% to 25 at%, copper (Cu) 0.1 at% to 5 at% and nickel (Ni) 1 at% to 25 at%.
  • Silicon (Si) constituting the negative electrode active material is mixed with silicon (Si) and active silicon nanoparticles in an inactive matrix. Since the active silicon nanoparticles can be reversibly reacted with lithium ions, the active silicon nanoparticles are directly related to the capacity of the negative electrode active material, and the inactive matrix may serve to suppress the volume expansion of the negative electrode active material while forming a structure that does not react with the lithium ions. .
  • the active silicon nanoparticles may be uniformly dispersed and precipitated in an inactive matrix.
  • silicon (Si) may be involved in occlusion and release of lithium ions when the negative electrode active material is used as a negative electrode of a lithium secondary battery. Therefore, the amount of silicon (Si) included in the negative electrode active material for a lithium secondary battery is related to the capacity and life characteristics of the negative electrode active material. Specifically, the more silicon (Si) is included in the alloy, the capacity of the negative electrode active material may be improved, but the life characteristics may be somewhat lowered. Therefore, the content of silicon (Si) in the negative electrode active material is 30 to 60 at% level in order to improve the life characteristics rather than to improve the capacity of the negative electrode active material of the present invention.
  • the content of the silicon (Si) is less than 30 at%, it is not preferable to exhibit an excessively small capacity to implement the capacity as a negative electrode active material for a lithium secondary battery, the content of the silicon (Si) is greater than 60 at% In this case, since the content of components other than silicon (Si) constituting the inert matrix is small, the life improvement effect of the negative electrode active material for a lithium secondary battery may be difficult to appear, which is not preferable.
  • copper (Cu) and iron (Fe) are difficult to be dissolved in silicon (Si) when in a solid state at room temperature.However, using a manufacturing method such as liquid rapid solidification such as melt spinning, copper (Cu) may be converted into silicon (Si). Can be forcibly hired). Forced solid solution copper (Cu) tends to be separated from iron (Fe), which causes copper clustering (Cu clustering) phenomenon. Active silicon nanoparticles may be uniformly dispersed and precipitated at a portion where copper clustering appears, and due to this phenomenon, the negative active material of the present invention may include active silicon nanoparticles uniformly dispersed and precipitated in an inactive matrix. .
  • the content of copper (Cu) is preferably 0.1 at% to 5 at% when the content of the silicon (Si) is 30 at% to 60 at%. This is because when the content of copper (Cu) is less than 0.1 at%, the above-mentioned copper clustering phenomenon is insignificant and dispersion precipitation of active silicon nanoparticles may not occur, which is undesirable.
  • the copper (Cu) content is more than 5 at%, rather than copper (Cu) may act as an impurity, the content of the copper (Cu) is 0.1 at% to 5 at% is preferred level to be.
  • nickel (Ni) and iron (Fe) included in the inactive matrix can play a role of improving the capacity of the negative electrode active material, the capacity characteristics can be improved.
  • the inactive matrix may include a five-component silicon-based alloy including silicon (Si), aluminum (Al), iron (Fe), copper (Cu), and nickel (Ni).
  • Zirconium (Zr) may include a six-component silicon-based alloy further comprising 0.1 at% to 5 at%. At this time, zirconium (Zr) may serve to make the structure of the negative electrode active material fine, and improve the life characteristics.
  • a material consisting of at least one of niobium (Nb), titanium (Ti), chromium (Cr), germanium (Ge), and calcium (Ca) is further included. It is possible to use a silicon-based alloy containing a six-component or more as the inert matrix, it can be used as a component for improving the capacity characteristics or life characteristics.
  • the inert matrix may include any one or more of a crystalline matrix and an amorphous matrix, and the active silicon nanoparticles uniformly dispersed in the inactive matrix may be in a crystalline phase, and the particle size of the active silicon nanoparticles may be 1 nm. It may be from 30 nm, more preferably from 10 nm to 20 nm.
  • the negative electrode active material layer may include 75 wt% to 92 wt% of the negative electrode active material, 1 wt% to 10 wt% of the conductive material, and 7 wt% to 15 wt% of the binder.
  • the conductive material is used to impart conductivity, and any lithium secondary battery configured may be used as long as it is an electron conductive material without causing chemical change.
  • any one or more of conductive polymer materials such as natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, carbon fiber, metal powder such as copper, nickel, aluminum, silver, metal fiber and polyphenylene derivatives Can be used, but is not limited thereto.
  • the content of the conductive material is less than 1 wt%, the effect of improving the conductivity and the lifespan characteristics according to the use of the conductive material is insignificant, and when the conductive material content is more than 5 wt%, the conductive material due to the increase in the specific surface area of the conductive material It is not preferable because the reaction between the electrolyte and the electrolyte may be increased to reduce the life characteristics. More specifically, the content of the conductive material may be 1 wt% to 3 wt%.
  • the binder adheres the particles of the negative electrode active material to each other well, and adheres the negative electrode active material to the negative electrode current collector, and specifically, polyimide, polyamideimide, polybenzimidazole, polyvinyl alcohol, carboxymethylcellulose, and hydroxide.
  • the binder content may be 7 wt% to 10 wt%.
  • the content of the conductive material is preferably 1 wt% to 10 wt%, and the content of the binder is preferably 7 wt% to 15 wt%, the content of the negative electrode active material in the negative electrode active material layer is 75 wt% to 92 wt%. Is the preferred level.
  • N-methylpyrrolidone or n-hexane may be used as a solvent for mixing the negative electrode active material, the conductive material and the binder, but is not limited thereto.
  • the lithium secondary battery of the present invention may include a positive electrode, a negative electrode, an electrolyte, and a separator, and the negative electrode may include a negative electrode current collector and a negative electrode active material layer formed on at least one surface of the negative electrode current collector.
  • the negative electrode current collector may include a conductive material, and specifically, may be a thin conductive foil or foam.
  • the negative electrode current collector may include, but is not limited to, copper, gold, nickel, stainless, or titanium.
  • the negative electrode active material layer may be prepared by mixing a negative electrode active material, a conductive material, and a binder in a solvent to prepare a composition for forming a negative electrode active material layer, and then coating the composition on a negative electrode current collector. Since such a negative electrode manufacturing method is well known in the art, detailed description thereof will be omitted.
  • the negative electrode active material may include an inert matrix and active silicon nanoparticles uniformly dispersed in the inactive matrix, and the inert matrix may include a five-component or more silicon alloy. More specifically, the five-component or more silicon alloy is silicon (Si) 30 at% to 60 at%, aluminum (Al) 15 at% to 50 at%, iron (Fe) 5 at% to 25 at%, copper (Cu) 0.1 at% to 5 at% and nickel (Ni) 1 at% to 25 at%.
  • Silicon (Si) constituting the negative electrode active material is mixed with silicon (Si) and active silicon nanoparticles in an inactive matrix. Since the active silicon nanoparticles can be reversibly reacted with lithium ions, the active silicon nanoparticles are directly related to the capacity of the negative electrode active material, and the inactive matrix may serve to suppress the volume expansion of the negative electrode active material while forming a structure that does not react with the lithium ions. .
  • the active silicon nanoparticles may be uniformly dispersed and precipitated in an inactive matrix.
  • silicon (Si) may be involved in occlusion and release of lithium ions when the negative electrode active material is used as a negative electrode of a lithium secondary battery. Therefore, the amount of silicon (Si) included in the negative electrode active material for a lithium secondary battery is related to the capacity and life characteristics of the negative electrode active material. Specifically, the more silicon (Si) is included in the alloy, the capacity of the negative electrode active material may be improved, but the life characteristics may be somewhat lowered. Therefore, the content of silicon (Si) in the negative electrode active material is 30 to 60 at% level in order to improve the life characteristics rather than to improve the capacity of the negative electrode active material of the present invention.
  • the content of the silicon (Si) is less than 30 at%, it is not preferable to exhibit an excessively small capacity to implement the capacity as a negative electrode active material for a lithium secondary battery, the content of the silicon (Si) is greater than 60 at% In this case, since the content of components other than silicon (Si) constituting the inert matrix is small, the life improvement effect of the negative electrode active material for a lithium secondary battery may be difficult to appear, which is not preferable.
  • copper (Cu) and iron (Fe) are difficult to be dissolved in silicon (Si) when in a solid state at room temperature.However, using a manufacturing method such as liquid rapid solidification such as melt spinning, copper (Cu) may be converted into silicon (Si). Can be forcibly hired). Forced solid solution copper (Cu) tends to be separated from iron (Fe), which causes copper clustering (Cu clustering) phenomenon. Active silicon nanoparticles may be uniformly dispersed and precipitated at a portion where copper clustering appears, and due to this phenomenon, the negative active material of the present invention may include active silicon nanoparticles uniformly dispersed and precipitated in an inactive matrix. .
  • the content of copper (Cu) is preferably 0.1 at% to 5 at% when the content of the silicon (Si) is 30 at% to 60 at%. This is because when the content of copper (Cu) is less than 0.1 at%, the above-mentioned copper clustering phenomenon is insignificant and dispersion precipitation of active silicon nanoparticles may not occur, which is undesirable.
  • the copper (Cu) content is more than 5 at%, rather than copper (Cu) may act as an impurity, the content of the copper (Cu) is 0.1 at% to 5 at% is preferred level to be.
  • nickel (Ni) and iron (Fe) included in the inactive matrix can play a role of improving the capacity of the negative electrode active material, the capacity characteristics can be improved.
  • the inactive matrix may include a five-component silicon-based alloy including silicon (Si), aluminum (Al), iron (Fe), copper (Cu), and nickel (Ni).
  • Zirconium (Zr) may include a six-component silicon-based alloy further comprising 0.1 at% to 5 at%. At this time, zirconium (Zr) may serve to make the structure of the negative electrode active material fine, and improve the life characteristics.
  • a material consisting of at least one of niobium (Nb), titanium (Ti), chromium (Cr), germanium (Ge), and calcium (Ca) is further included. It is possible to use a silicon-based alloy containing a six-component or more as the inert matrix, it can be used as a component for improving the capacity characteristics or life characteristics.
  • the inert matrix may include any one or more of a crystalline matrix and an amorphous matrix, and the active silicon nanoparticles uniformly dispersed in the inactive matrix may be in a crystalline phase, and the particle size of the active silicon nanoparticles may be 1 nm. It may be from 30 nm, more preferably from 10 nm to 20 nm.
  • the negative electrode active material layer may include 75 wt% to 92 wt% of the negative electrode active material, 1 wt% to 10 wt% of the conductive material, and 7 wt% to 15 wt% of the binder.
  • the conductive material is used to impart conductivity, and any lithium secondary battery configured may be used as long as it is an electron conductive material without causing chemical change.
  • any one or more of conductive polymer materials such as natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, carbon fiber, metal powder such as copper, nickel, aluminum, silver, metal fiber and polyphenylene derivatives Can be used, but is not limited thereto.
  • the content of the conductive material is less than 1 wt%, the effect of improving the conductivity and the lifespan characteristics according to the use of the conductive material is insignificant, and when the conductive material content is more than 5 wt%, the conductive material due to the increase in the specific surface area of the conductive material It is not preferable because the reaction between the electrolyte and the electrolyte may be increased to reduce the life characteristics. More specifically, the content of the conductive material may be 1 wt% to 3 wt%.
  • the binder adheres the particles of the negative electrode active material to each other well, and adheres the negative electrode active material to the negative electrode current collector, and specifically, polyimide, polyamideimide, polybenzimidazole, polyvinyl alcohol, carboxymethylcellulose, and hydroxide.
  • the binder content may be 7 wt% to 10 wt%.
  • the content of the conductive material is preferably 1 wt% to 10 wt%, and the content of the binder is preferably 7 wt% to 15 wt%, the content of the negative electrode active material in the negative electrode active material layer is 75 wt% to 92 wt%. Is the preferred level.
  • N-methylpyrrolidone or n-hexane may be used as a solvent for mixing the negative electrode active material, the conductive material and the binder, but is not limited thereto.
  • the positive electrode includes a positive electrode current collector and a positive electrode active material layer formed on the positive electrode current collector, and the positive electrode active material layer is mixed with a positive electrode active material, a binder and a conductive material in a solvent to form a positive electrode active material layer
  • the composition may be in a form coated on a positive electrode current collector. Since such a method for manufacturing a positive electrode is well known in the art, detailed description thereof will be omitted.
  • the cathode active material may include a material capable of reversibly inserting and detaching lithium ions.
  • the cathode active material may include a lithium-containing transition metal oxide, a lithium-containing transition metal sulfide, and the like.
  • the binder serves to adhere the positive electrode active material particles to each other and to adhere the positive electrode active material to the positive electrode current collector, and specifically, to polyimide, polyamideimide, polybenzimidazole, polyvinyl alcohol, carboxymethyl cellulose, and hydroxide.
  • the conductive material is used to impart conductivity, and any lithium secondary battery configured may be used as long as it is an electron conductive material without causing chemical change.
  • any one or more of conductive polymer materials such as natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, carbon fiber, metal powder such as copper, nickel, aluminum, silver, metal fiber and polyphenylene derivatives Can be used, but is not limited thereto.
  • N-methylpyrrolidone or n-hexane may be used as the solvent, but is not limited thereto.
  • the positive electrode current collector may include a conductive material, and specifically, may be a thin conductive foil or foam.
  • the positive electrode current collector may include, but is not limited to, aluminum, nickel or an alloy thereof.
  • the electrolyte may include a non-aqueous organic solvent and a lithium salt.
  • the non-aqueous organic solvent may be any one or more of a carbonate-based, ester-based, ether-based, ketone-based, alcohol-based and aprotic solvent.
  • the non-aqueous organic solvent is dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC), ethylene carbonate (EC), propylene carbonate (PC), n-methyl acetate, dibutyl ether , Cyclohexanone, isopropyl alcohol and sulfolane (sulfolane) may include one or more selected from the group consisting of solvents. These non-aqueous organic solvents may be used alone or in combination of two or more thereof.
  • the lithium salt may be LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiN (SO 2 C 2 F 5 ) 2 , Li (CF 3 SO 2 ) 2 N, LiN (SO 3 C 2 F 5 ) 2 , LiC 4 F 9 SO 3 , LiClO 4 , LiAlO 2 , LiAlCl 4 , LiN (C x F 2x + 1 SO 2 ) (C y F 2y + 1 SO 2 ) (x and y are natural numbers), LiCl, LiI and LiB (C 2 O 4 ) 2 It may include one or two or more selected from the group consisting of. These electrolyte salts may be used alone or in combination of two or more thereof.
  • the separator may be polyethylene, polypropylene, or polyvinylidene fluoride as a single layer, or two or more multilayer films thereof may be used.
  • Alloys containing silicon (Si), aluminum (Al), iron (Fe), copper (Cu) and nickel (Ni) are melted by an arc melting method to prepare a melt, and then the melt is rotated at a speed of 40 m / s.
  • the amorphous alloy having the composition of Si 56 Al 25 Fe 16 Cu 1 Ni 2 was prepared by applying to a single roll quench solidification method sprayed onto a copper roll.
  • Coin-shaped electrode plates were prepared by using the amorphous alloy as a negative electrode active material, and Ketjen Black as a negative electrode active material and a conductive material and PAI as a binder were mixed at a weight ratio of 87: 3: 10, and heat-treated at 400 ° C. for 1 hour in an Ar atmosphere. A negative electrode was prepared.
  • Alloys containing silicon (Si), aluminum (Al), iron (Fe), copper (Cu) and nickel (Ni) are melted by an arc melting method to prepare a melt, and then the melt is rotated at a speed of 40 m / s.
  • the amorphous alloy having the composition of Si 56 Al 25 Fe 16 Cu 1 Ni 2 was prepared by applying to a single roll quench solidification method sprayed onto a copper roll. The amorphous alloy was heat-treated at 450 ° C. to produce a silicon-based composite metal.
  • a coin-shaped electrode plate was manufactured by using the silicon-based composite metal as a negative electrode active material, and Ketjen Black as a negative electrode active material and a conductive material and PAI as a binder were mixed at a weight ratio of 87: 3: 10, and heat treated at 400 ° C. for 1 hour in an Ar atmosphere. To prepare a negative electrode.
  • An anode was prepared in the same manner as in Example 2 except that the amorphous alloy was heat-treated at 500 ° C. to produce a silicon-based composite metal.
  • a negative electrode was prepared in the same manner as in Example 2 except that the amorphous alloy was heat-treated at 550 ° C. to produce a silicon-based composite metal.
  • a negative electrode was prepared in the same manner as in Example 2 except that the amorphous alloy was heat-treated at 650 ° C. to produce a silicon-based composite metal.
  • FIG. 2 is a graph showing relatively exothermic energy according to temperature with a differential scanning calorimetry (DSC) of a negative active material for a lithium secondary battery of Example 1;
  • Figure 2 shows the crystallization behavior according to the temperature change of the amorphous negative electrode active material.
  • FIG. 3 is a diffraction pattern showing the crystallinity of the negative electrode active material for a lithium secondary battery of Example 1.
  • FIG. 4 is TEM-EDS images showing the component distribution of the negative electrode active material for a lithium secondary battery of Example 1.
  • Example 1 is an amorphous alloy having an amorphous phase.
  • Example 1 56 25 16 One 2 Amorphous Pristine 236.2 91.5 38.7
  • Example 2 56 25 16 One 2 Amorphous + crystalline 450 °C, 1hr 278.4 155.1 55.7
  • Example 3 56 25 16 One 2 Amorphous + crystalline 500 °C, 1hr 1100.9 943.5 85.7
  • Example 4 56 25 16 One 2 Crystalline 550 °C, 1hr 1192.3 1021.4 85.6
  • Example 5 56 25 16 One 2 Crystalline 650 °C, 1hr 1309.8 1144.9 87.4
  • 5 is a graph showing charge and discharge cycle lifetimes of Examples 1 to 5.
  • a lithium secondary battery using a negative electrode active material having a crystalline structure has a high initial Coulomb efficiency but a decrease in cycle life, and a lithium secondary battery using a negative electrode active material having an amorphous structure has a low initial Coulomb efficiency. It can be seen that the cycle life is maintained.
  • Embodiment of the present invention can produce amorphous alloy reproducibly in the range of 30 m / s to 60 m / s rotational linear velocity of the copper wheel in the melt spinning is a liquid quenching solidification method, more preferably 40 m / s It is possible to produce amorphous alloys reproducibly at speed.
  • the heat treatment is performed at a constant temperature to produce a cathode active material in which reproducible active silicon particles are uniformly dispersed and precipitated in a nano size in an inert matrix, and the capacity of the reproducible anode active material is maintained even after 30 cycles. It can be determined that it can have excellent life characteristics.

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Manufacturing & Machinery (AREA)
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Abstract

La présente invention porte : sur un matériau actif d'anode destiné à une batterie secondaire au lithium, le matériau actif d'anode comprenant une matrice inactive renfermant 30 % atomique à 60 % atomique de silicium (Si), 15 % atomique à 50 % atomique d'aluminium (A), 5 % atomique à 25 % atomique de fer (Fe), 0,1 % atomique à 5 % atomique de cuivre (Cu), et 1 % atomique à 25 % atomique de nickel (Ni), ainsi que des nanoparticules actives de silicium dispersées uniformément et déposées sur la matrice inactive ; sur un procédé de fabrication associé ; et sur une batterie secondaire au lithium comprenant un tel matériau actif d'anode. Par conséquent, la batterie secondaire au lithium de la présente invention dispose d'une limite d'élasticité conventionnelle suffisante pour supporter la contrainte d'expansion des particules de silicium causée par l'intercalation d'ions lithium pendant la charge et la décharge, ce qui permet de limiter le raffinage de particules dû à l'expansion et au rétrécissement volumique du matériau actif d'anode pendant la charge et la décharge, et dispose ainsi d'une propriété améliorée en ce qui concerne sa durée de vie.
PCT/KR2018/006043 2017-06-07 2018-05-28 Matériau actif d'anode destiné à une batterie secondaire au lithium, anode destinée à une batterie secondaire au lithium, et batterie secondaire au lithium comprenant une telle anode Ceased WO2018225971A1 (fr)

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KR10-2017-0070921 2017-06-07
KR1020180050575A KR102087134B1 (ko) 2017-06-07 2018-05-02 리튬이차전지용 음극활물질, 리튬이차전지용 음극 및 이를 포함하는 리튬이차전지
KR10-2018-0050575 2018-05-02

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CN111048770A (zh) * 2019-12-27 2020-04-21 中国科学院化学研究所 一种三元掺杂的硅基复合材料及其制备方法和应用
WO2025066342A1 (fr) * 2023-09-28 2025-04-03 贝特瑞新材料集团股份有限公司 Matériau d'électrode négative et procédé de préparation associé, et batterie

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WO2014092347A1 (fr) * 2012-12-12 2014-06-19 일진전기(주) Matériau actif d'électrode négative pour batterie secondaire au lithium et batterie secondaire utilisant celui-ci
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KR20130114007A (ko) * 2012-04-06 2013-10-16 삼성에스디아이 주식회사 음극 활물질, 이를 채용한 리튬 전지, 및 상기 음극 활물질의 제조방법
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111048770A (zh) * 2019-12-27 2020-04-21 中国科学院化学研究所 一种三元掺杂的硅基复合材料及其制备方法和应用
CN111048770B (zh) * 2019-12-27 2020-12-08 中国科学院化学研究所 一种三元掺杂的硅基复合材料及其制备方法和应用
WO2025066342A1 (fr) * 2023-09-28 2025-04-03 贝特瑞新材料集团股份有限公司 Matériau d'électrode négative et procédé de préparation associé, et batterie

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