WO2013151209A1 - Matériau actif de cathode pour condensateur à ion lithium et procédé de fabrication - Google Patents

Matériau actif de cathode pour condensateur à ion lithium et procédé de fabrication Download PDF

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WO2013151209A1
WO2013151209A1 PCT/KR2012/003860 KR2012003860W WO2013151209A1 WO 2013151209 A1 WO2013151209 A1 WO 2013151209A1 KR 2012003860 W KR2012003860 W KR 2012003860W WO 2013151209 A1 WO2013151209 A1 WO 2013151209A1
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lithium
metal oxide
composite metal
active material
ion capacitor
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PCT/KR2012/003860
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English (en)
Korean (ko)
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박민식
김점수
김영준
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전자부품연구원
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Publication of WO2013151209A1 publication Critical patent/WO2013151209A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/46—Metal oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • 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
    • 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
    • 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
    • Y02E60/13—Energy storage using capacitors

Definitions

  • the present invention relates to a lithium ion capacitor having excellent capacity characteristics and high energy density. More specifically, the present invention uses a specific lithium composite metal oxide as a positive electrode additive in a carbon-based material applied as a positive electrode active material, and a lithium ion capacitor positive electrode active material which is electrochemically doped with lithium and further improves energy density, and its preparation It is about a method.
  • a lithium ion capacitor is a new concept of a secondary battery system that combines the high power / long life characteristics of an existing electric double layer capacitor (EDLC) with the high energy density of a lithium ion battery.
  • EDLC electric double layer capacitor
  • Electrode double layer capacitors that use physical adsorption reactions of electrical charges in electrical double layers are limited to various applications due to their low energy density despite their excellent output and lifetime characteristics.
  • a hybrid capacitor having improved energy density using a material capable of inserting and detaching lithium ions as a positive electrode or a negative electrode active material has been proposed.
  • Lithium ion capacitors have been proposed that use a carbon-based material that can be used to insert and detach lithium ions as a negative electrode active material. For example, as shown in FIG.
  • an electric double layer capacitor exhibits excellent output characteristics by using charge bonding and desorption of charges using an activated carbon material having a large specific surface area symmetrically on the anode and the cathode, but has a low energy density (E a).
  • E a energy density
  • hybrid capacitors use a high capacity transition metal oxide as the anode material to increase capacity (),
  • the capacitor is characterized by improving the energy density (E d ) performance by using a carbon-based material capable of reversible insertion and removal of lithium ions as a cathode material.
  • the lithium ion capacitor may improve performance of energy density compared to other hybrid capacitors due to the property of using a material capable of inserting and detaching lithium ions at a low reaction potential as a negative electrode active material.
  • the lithium ion capacitor can be doped with a large amount of ion ion lithium ion in advance to significantly lower the potential of the negative electrode, the cell voltage is also possible to achieve a high voltage of 3.8 V or more improved significantly compared to the 2.5 V of the conventional electric double layer capacitor Energy density can be improved compared to other hybrid capacitors.
  • the electrons are transferred to the carbon-based material of the negative electrode during layer transfer, and the carbon-based material becomes negatively charged.
  • the negative electrode is inserted into the carbonaceous material of the negative electrode, and on the contrary, during discharge, lithium ions inserted into the carbonaceous material of the negative electrode are released, and the negative ions are again adsorbed to the positive electrode.
  • the lithium ion capacitor is a system that combines the energy storage capacity of the lithium ion battery with the output characteristics of the capacitor.
  • the lithium ion capacitor adopts a material capable of isochronizing two functions to show the characteristics of the capacitor at the time of high power use and to maintain the device. It is a future battery system that extends the usage time to the lithium ion battery level.
  • lithium ion capacitor requires a lithium doping process for insertion and desorption reaction of lithium as well as electrochemical adsorption and desorption reaction.
  • the conventional technique of doping lithium to the negative electrode in order to implement such a lithium silver capacitor is a metal laminated by the potential difference between the negative electrode and the metal lithium only by laminating the metal lithium on the electrode and then adding an electrolyte to short the negative electrode and the metal lithium. Lithium is melted into the cathode.
  • the present invention is to provide a cathode active material for a lithium ion capacitor can be doped with lithium in an electrochemical manner without using metal lithium, and can further improve the capacitor capacity and energy density.
  • the present invention also provides a method for producing a cathode active material for a lithium ion capacitor.
  • the present invention also provides a lithium ion capacitor including the cathode active material.
  • the present invention provides a cathode active material for a lithium ion capacitor comprising a first lithium composite metal oxide represented by Formula 1 below, a second lithium composite metal oxide represented by Formula 2 below, and a carbon-based material.
  • a, b, c, d, e, and f represent 0 ⁇ a ⁇ 6, 0 ⁇ b ⁇ 3, 0 ⁇ c ⁇ 4, 0 ⁇ d ⁇ 2, 0 ⁇ e ⁇ 3, and 0 ⁇ f ⁇ 4, respectively.
  • M 1 is one or more selected from the group consisting of Mo, Fe, and Co,
  • M 2 is at least one member selected from the group consisting of Mn, Ti, Ru, Ir, Pt, Sn, and Zr.
  • the present invention also provides a lithium composite metal oxide precursor represented by the following Chemical Formula 3 by a) mixing and heat treating a transition metal compound containing at least one selected from the group consisting of a) a lithium compound and Mo, Fe, and Co.
  • a, b, and c satisfy 0 ⁇ a ⁇ 6, 0 ⁇ b ⁇ 3, 0 ⁇ c ⁇ 4, respectively,
  • a ', b * , and c' satisfy 0 ⁇ a ' ⁇ 6, 0 ⁇ b' ⁇ 3, l ⁇ c ' ⁇ 5, respectively
  • M 1 and M 1 ' are each one or more selected from the group consisting of Mo, Fe, and Co;
  • M 2 is at least one member selected from the group consisting of Mn, Ti, Ru, Ir, Pt, Sn, and Zr.
  • the present invention also provides a lithium ion capacitor including the cathode active material.
  • a cathode active material for a lithium ion capacitor and a method of manufacturing the same, and a lithium ion capacitor including the same will be described in detail.
  • this is presented as an example of the invention, whereby the scope of the invention is not limited, it is apparent to those skilled in the art that various modifications to the embodiments are possible within the scope of the invention.
  • Constant refers to including any component (or component) without particular limitation and should not be construed to exclude the addition of other components (or components).
  • lithium ion capacitor is used to improve the capacitance characteristics by using different asymmetric electrodes for the positive electrode and the negative electrode, and the opposite pole using the high-capacity electrode material.
  • These lithium ion capacitors generally have a large capacity as a negative electrode material and a carbon-based material capable of inserting and desorbing lithium ions such as graphite, hard carbon, and soft carbon.
  • Lithium-ion capacitors are half of electric double layer capacitors and hybrid capacitors of about 3.0V Whereas with a potential having a high banung potential of 4.2V, is characterized in that expression of a high energy density as much excellent capacity characteristic ().
  • the lithium ion capacitor requires a lithium doping process for insertion and desorption reaction of lithium as well as an electrochemical adsorption and desorption reaction, and a doping method in which a conventional metal lithium is laminated on an electrode and electrically shorted. It is difficult to control the amount of silver lithium doped to the negative electrode, and it is difficult to maintain safety due to the lithium metal generated in the doping process.
  • the present invention by adding a specific positive electrode additive as a lithium source to the carbon-based material applied as the positive electrode active material, by electrochemically doping lithium to the negative electrode to significantly improve the doping efficiency and safety, It is possible to obtain a process improvement effect that ensures excellent safety enough for mass production.
  • a lithium ion capacitor is manufactured using a cathode active material including a lithium composite metal oxide having predetermined characteristics as a cathode additive, an excellent capacitor characteristic when used at high power, and excellent output with high energy density. It has been shown that it shows the characteristics and lifespan, and can replace the doping process using lithium metal, thereby ensuring excellent process safety.
  • a cathode active material for a lithium ion capacitor including a cathode additive having predetermined characteristics includes a specific cathode additive, that is, a first lithium composite metal oxide represented by the following Chemical Formula 1, and a second lithium composite metal oxide represented by the following Chemical Formula 2 in the carbon-based material.
  • a, b, c, d, e, and f represent 0 ⁇ a ⁇ 6, 0 ⁇ b ⁇ 3, 0 ⁇ c ⁇ 4, 0 ⁇ d ⁇ 2, 0 ⁇ e ⁇ 3, and 0 ⁇ £ ⁇ 4, respectively.
  • M 1 is one or more selected from the group consisting of Mo, Fe, and Co,
  • M 2 is at least one member selected from the group consisting of Mn, Ti, Ru, Ir, Pt, Sn, and Zr.
  • the positive electrode active material for a lithium ion capacitor of the present invention uses a specific positive electrode additive (the first lithium composite metal oxide) having a large initial irreversible capacity to a carbon-based material that is applied as the positive electrode active material. Doping improves fairness and safety by replacing lithium metal in the existing lithium ion doping method, and at the same time, the specific positive electrode additive (the second lithium composite metal oxide) having high reversibility in the operating potential region of the lithium ion capacitor To further increase the capacitor's capacity and energy density It is characterized by improving.
  • the specific positive electrode additive the second lithium composite metal oxide
  • the lithium metal used as a lithium source for doping lithium to the existing negative electrode, and the first lithium composite metal oxide as a positive electrode additive to be a lithium source in the present invention is represented by the formula (1).
  • the first lithium composite metal oxide of the present invention is characterized in that the initial capacity and the irreversible capacity are large, and can effectively and effectively do the lithium to the cathode of the lithium ion capacitor electrochemically.
  • the metal component Ml forming the oxide together with lithium in the first lithium composite metal oxide may be Mo, Fe, Co, or the like.
  • the Mo, Fe, Co and the like correspond to the transition metal
  • the positive electrode additive containing such a transition metalol is a transition metal oxide.
  • the Mo, Fe, Co and the like has an advantage that can more effectively induce the insertion and desorption of lithium electrochemical in crystal structure.
  • the first lithium composite metal oxide may have a crystal structure such as Rhombohedral, Monoclinic, Orthorhombic, or the like.
  • the first lithium composite metal oxide is 0V to 5V, preferably
  • the lithium composite metal oxide has a large initial irreversible capacity to supply lithium ions to the cathode in an electrochemical manner without using metal lithium.
  • the first lithium composite metal oxide may have an initial layer discharge efficiency () of 50% or less or 0% to 50%, preferably 40% or less or 0) to 40%, more preferably, according to Formula 1 below. Can be up to 30% or from 0% to 30%.
  • Q E represents the initial charge and discharge efficiency of the first lithium composite metal oxide
  • QD is the discharge capacity (mAh / g) at Li / Li + cut-off at a discharge voltage of 2.3 V
  • Qc shows the layer capacitance (mAh / g) at Li / Li + cut-off at the layer voltage 4.7 V.
  • the initial layer discharge efficiency Q E of the first lithium composite metal oxide is constant current or constant voltage in an electrochemical manner under a half cell condition in which lithium is opposed to a voltage of 2.3.
  • Discharge capacity per unit weight of the cathode active material at Li / Li + cut-off at V (Q D , mAh / g) and cathode active material at Li / Li + cut-of at 4.7 V The layer charge capacity (Qc, mAh / g) per unit weight of can be measured and calculated according to the above formula (1).
  • the discharge capacity per unit weight (QD) relative to the total weight of the lithium composite metal oxide at Li / Li + cut-off at a voltage of 2.3 V of the first lithium composite metal oxide is 135 mAh / g or less or 0 to 135 mAh / g, preferably 110 mAh / g or less or 0 to 110 mAh / g, more preferably 85 mAh / g or less or 0 to 85 mAh / g.
  • the charge capacity per unit weight (Qc) relative to the total weight of the first lithium composite metal oxide at a Li / Li + cut-off at a voltage of 4.7 V of the first lithium composite metal oxide is 200 mAh / g or more, preferably Preferably 230 mAh / g or more, more preferably 250 mAh / g or more or 250 to 700 mAh / g, and in some cases 700 mAh / g or less, 500 mAh / g or less, or 300 mAh / g or less Can be
  • Discharge capacity at Li / Li + cut-off at 2.3 V (Q D , mAh / g) and Layer capacity at Li / Li + cut-off at voltage 4.7 V (Qc, mAh / g ) Preferably maintains the range as described above in terms of capacity.
  • the cathode active material of the present invention includes a second lithium composite metal oxide represented by Chemical Formula 2 together with the first lithium composite metal oxide as a cathode additive serving as a lithium source.
  • the second lithium composite metal oxide corresponds to a high capacity transition metal oxide having a high reversibility in the operating potential region of the lithium ion capacitor, and can improve the energy density limit per volume and further improve the energy density of the conventional lithium ion capacitor. have.
  • M 2 is at least one member selected from the group consisting of Mn, Ti, Ru, Ir, Pt, Sn, and Zr.
  • the metal component M 2 forming the oxide together with lithium in the second lithium composite metal oxide may be Mn ⁇ Ti, Ru, Ir, Pt, Sn, Zr, or the like.
  • the Mn, Ti, Ru, Ir, Pt, Sn, Zr and the like correspond to a transition metal
  • the positive electrode additive containing such a transition metal is a transition metal oxide.
  • the Mn, Ti, Ru, Ir, Pt, Sn, and Zr has the advantage of more effectively inducing the insertion and desorption of the electrochemical lithium in the operating potential region of the lithium ion capacitor in the crystal structure.
  • the second lithium composite metal oxide may have a crystal structure such as Rhombohedral, Monocl inic, Orthorhombic, or the like.
  • the second lithium composite metal oxide has a characteristic of reversibly inserting or detaching lithium ions in a voltage range of IV to 5V, preferably 2.5V to 5V, more preferably 2V to 5V.
  • the second lithium composite metal oxide may improve the energy density limit per volume of the lithium ion capacitor according to the conventional lithium metal doping and further increase the energy density. It has a high reversibility characteristic in the operating potential region of a lithium ion capacitor.
  • the second lithium composite metal oxide has a layer discharge efficiency (,) of 503 ⁇ 4 or more or 50% to 100%, preferably 60% or more, more preferably, under a 2.3V to 4.7V potential according to the following Equation 2. May be greater than 70%.
  • 3 ⁇ 4 ⁇ is the charge and discharge efficiency under the 2.3V to 4.7V potential of the second lithium composite metal oxide
  • QD represents discharge capacity (mAh / g) at Li / Li + cut-off at a discharge voltage of 2.3 V
  • Qc ' represents the layer capacitance (mAh / g) at Li / Li + cut-off at the layer voltage 4.7V.
  • the layer discharge efficiency under the 2.3 V to 4.7 V potential of the second lithium composite metal oxide is determined by a constant current or a constant voltage method by an electrochemical method under a half cell condition with lithium as a counter electrode.
  • Discharge capacity per unit weight of positive electrode active material (, mAh / g) at Li / Li + cut-off at 2.3 V, and positive electrode active material at Li / Li + cut-off at 4.7 V The layer charge capacity (, mAh / g) per unit weight of can be measured and calculated according to the above formula (2).
  • the discharge capacity per unit weight (QD,) relative to the total weight of the lithium composite metal oxide at the Li / Li + cut-off at a voltage of 2.3 V of the lithium composite metal oxide is 100 mAh / g or more or 100 to 300 mAh / g, preferably 130 mAh / g or more, more preferably 150 mAh / g or more.
  • the layered capacity per unit weight (Qc is 150 mAh / g or more, preferably 170 mAh, for the total weight of the lithium composite metal oxide at Li / Li + cut-off at a voltage of 4/7 V of the lithium composite metal oxide).
  • lithium composite metal oxide is Li 2 Mn0 3, Li 2 Ti0 3, Li 2 Ru0 3 (
  • Li 2 Ir0 3L Li 2 Pt0 3) Li 2 Sn0 3) and Li 2 Zr can be used.
  • the positive electrode active material for a lithium ion capacitor of the present invention uses a specific first lithium composite metal oxide and a crab 2 lithium composite metal oxide as a positive electrode additive to a carbon-based material to be used as the positive electrode active material.
  • the energy density per volume can be improved and the safety of the doping process can be achieved simultaneously.
  • the conventional lithium ion capacitor laminates lithium metal on an electrode to form a lithium source for transferring lithium ions to the cathode through an electrical short circuit.
  • the lithium ion capacitor of the present invention as shown in Figure 3, by adding a specific positive electrode additive, such as Li 2 Mo0 3 and Li 2 Ru0 3 to the positive electrode active material to use as a lithium source, a separate lithium metal laminate layer It is characterized in that to effectively transfer the lithium ions toward the cathode and to improve the capacity and energy density of the capacitor without forming a.
  • the carbon-based material used as the positive electrode active material for lithium ion capacitor of the present invention refers to activated carbon having a large specific surface area, the specific surface area of 500 m7g or more, preferably 700 m 2 / g or more, more preferably 1,000 m 2 It may be more than / g or 1,000 to 3,000 m 2 / g, in some cases may be less than 2500 m 2 / g, 2,000 m 2 / g or less.
  • Such carbon-based materials may be used at least one of activated carbon, activated carbon and metal oxide composite, activated carbon and conductive polymer composite, and among these, activated carbon is preferable for the conductive aspect.
  • the positive electrode active material for a lithium ion capacitor according to the present invention is a positive electrode additive, that is, the lithium composite metal as a lithium source of a negative electrode material to a carbon-based material
  • the oxides have a composition mixed together.
  • the cathode active material for a lithium ion capacitor according to the present invention may include 0.5 to 49.5% by weight of the first lithium composite metal oxide, 0.5 to 49.5% by weight of the second lithium composite metal oxide, and 50 to 99% by weight of a carbon-based material. Can be.
  • the first lithium composite metal oxide, 1 to 34% by weight of the second lithium composite metal oxide, and 65 to 98% by weight of the carbon-based material are preferably, 1.5 to 18.5 weight% U lithium composite metal oxide, 1.5 to 18.5 weight% second lithium composite metal oxide, and 80 to 97 weight% carbonaceous materials.
  • the first lithium composite metal oxide, the second lithium composite metal oxide, and the carbon-based material are 0.5 weight 3 ⁇ 4 or more, 0.5 weight 3 ⁇ 4>, and 99 weight%, respectively, so as to effectively dope lithium to the negative electrode. It may be included in the following, in terms of ensuring excellent conductivity may be included in each of 49.5% by weight or less, 49.5% by weight or less, and 50% by weight or more.
  • the weight ratio of the two positive electrode additives that is, the weight ratio of the first lithium composite metal oxide to the second lithium composite metal oxide is 90:10 to 10:90, preferably 80:20 to 20:80, more preferably. May be from 70:30 to 30:70.
  • the first lithium composite metal oxide and the second lithium composite metal oxide may be used in a weight ratio of 90:10 or more in terms of improving negative electrode doping capacity, and may be used in a weight ratio of 10:90 or less in terms of improving energy density.
  • first lithium composite metal oxide and the second lithium composite metal oxide may be uniformly mixed throughout the carbon-based material or locally mixed only in part depending on the amount added to the carbon-based material.
  • the weight ratio of the total weight of the first lithium composite metal oxide and the second lithium composite metal oxide to the carbonaceous material is 10:90 to 90:10, preferably 15:85 to 85:15, and more preferably 20:80 to 80:20.
  • the weight ratio of the carbon-based material to the total weight of the first lithium composite metal oxide and the second lithium composite metal oxide may be 10:90 or more in terms of energy density improvement, and 90:10 or less in terms of power density improvement. .
  • the positive electrode additive according to the present invention that is, the first lithium composite metal oxide of Formula 1 and the second lithium composite metal of Formula 2
  • the oxide may be electrochemically doped with lithium on the carbon-based anode active material, and the doped lithium ions contribute to the capacitor characteristics, thereby lowering the Sal voltage, thereby significantly improving the capacity and energy density of the lithium ion capacitor.
  • a method of manufacturing the positive electrode active material for the lithium ion capacitor is provided.
  • the method of manufacturing a cathode active material for a lithium ion capacitor includes a) a first compound represented by the following Chemical Formula 3 by mixing and heat-treating a transition metal compound containing at least one selected from the group consisting of a lithium compound and Mo, Fe, and Co.
  • a lithium composite metal oxide precursor Generating a lithium composite metal oxide precursor; b) reducing the first lithium composite metal oxide precursor represented by Formula 3 to produce a first lithium composite metal oxide represented by Formula 1 below; c) a second lithium composite metal represented by the following Chemical Formula 2 by mixing and heat-treating a transition metal compound containing at least one selected from the group consisting of a lithium compound and Mn, Ti, Ru, Ir, Pt, Sn, and Zr Producing an oxide; And d) mixing the first lithium composite metal oxide and the low 12 lithium composite metal oxide with a carbonaceous material.
  • a, b, and c are each 0 ⁇ a ⁇ 6, 0 ⁇ b ⁇ 3, 0 ⁇ c ⁇ 5, and preferably 0 ⁇ a ⁇ 5
  • a ', b', c ' is 0 ⁇ a' ⁇ 6, 0 ⁇ b' ⁇ 3, l ⁇ c' ⁇ 5, preferably 0 ⁇ a' ⁇ 5, 0 ⁇ b ' ⁇ 2, 0 ⁇ c' ⁇ 4 More preferably, 0 ⁇ a ' ⁇ 5, 0 ⁇ b' ⁇ 1, 0 ⁇ c ' ⁇ 4.
  • M 1 and M 1 ′ are each one or more selected from the group consisting of Mo, Fe, and Co
  • M 2 is selected from the group consisting of Mn, Ti, Ru, Ir, Pt, Sn, and Zr 1 or more types.
  • a first lithium composite metal oxide and a precursor thereof, a second lithium composite metal oxide, and a carbon-based material as a cathode active material are described above with reference to the cathode active material for a lithium ion capacitor. As applicable.
  • the first lithium composite metal oxide precursor of Chemical Formula 3 is formed of a lithium compound such as Li 2 CO 3 , LiOH, Li, Mo0 3> ⁇ 0 2) ( ⁇ 4 ) 6 ⁇ 7 ⁇ 2 4 ⁇ 4H 2 0, MoS 2) Mo, FeO, Fe 2 0 3 , Fe 3 0 4) Transition metal compounds such as Fe, CoO, Co can be mixed to prepare a heat treatment process.
  • the lithium compound, Mo, Fe, Co itself and the transition metal compound containing the same, the exponential value a, b, c, a ', b', c ', etc.
  • the heat treatment process may be performed at 400 to 1,000 ° C., preferably 500 to 900 ° C., more preferably 500 to 800 ° C.
  • the lithium The heat treatment process for the compound and the composite metal compound may be performed for 0.5 to 20 hours, preferably 1 to 15 hours, more preferably 2 to 10 hours.
  • the heat treatment process for the lithium compound and the composite metal compound may be performed in an oxygen or air atmosphere.
  • Reducing the first lithium composite metal oxide precursor of Formula 3 in step b) may be carried out by heat treatment at 500 to 1,000 ° C, preferably 700 to 900 ° C, more preferably 700 to 800 ° C. have.
  • the heat treatment process may be performed for 2 to 50 hours, preferably 5 to 30 hours, more preferably 10 to 20 hours. Such heat treatment process By maintaining the temperature and time, it is possible to effectively convert the first lithium composite metal oxide precursor of Formula 3 to the first lithium composite metal oxide of Formula 1.
  • the reducing process of the first lithium composite metal oxide precursor may be performed under an inert atmosphere of argon (Ar) gas or nitrogen (N 2 ).
  • the inert gas quantum may further include hydrogen () and the like, and in terms of improving overall process efficiency, it is preferable to carry out under a condition containing 3 ⁇ 4 of 5% or less.
  • the first lithium composite metal oxide of Chemical Formula 1 having the characteristics as described above may be generated.
  • the second lithium composite metal oxide having Chemical Formula 2 may be selected from Li 2 CO 3> LiOH, Li, a round lithium compound, and MnO, Mn, Ti0 2 ⁇ Ti, Ru0 2) Ru, IrCl 3 , Ir0 2 , Transition metal compounds such as PtCl 4 , PtCl 2 , Pt0 2 , Pt (C 5 H 7 0 2 ) 2, Pt / C, Sn0 2 , Sn, Zr0 2l Zr may be mixed and prepared by a heat treatment process.
  • the lithium compound and Mn, Ti, Ru, Ir, Pt, Sn, and Zr itself and the transition metal compound containing the same, the molar ratio in consideration of the index values d, e, f, etc. in the second lithium composite metal oxide to be produced Can be mixed, for example, 2: 1 to 3: 1, preferably 2: 1 to 2.5: 1, more preferably 2: 1 to 2.3: 1.
  • the heat treatment process may be performed at 500 to 1,000 ° C, preferably 700 to 900 ° C, more preferably 700 to 800 ° C.
  • the heat treatment process may be performed for 2 to 50 hours, preferably 5 to 30 hours, more preferably 10 to 20 hours.
  • the heat treatment process for the lithium compound and the composite metal compound may be performed in an oxygen or air atmosphere.
  • the step d) of mixing the first lithium composite metal oxide and the second lithium composite metal oxide with a carbon-based material may be performed by various physical mixing methods.
  • the carbon-based material as the first lithium composite metal oxide, the second lithium composite metal oxide, and the positive electrode active material may be mixed at 0.5 to 49.5 weight 3 ⁇ 4>, 0.5 to 49.5 weight%, and 50 to 99 weight%, respectively.
  • a lithium ion capacitor including the cathode active material for the lithium ion capacitor is provided.
  • the lithium ion capacitor forms a separate lithium metal layer by using a specific first lithium composite metal oxide having a large initial irreversible capacity and a second lithium composite metal oxide having a high reversibility as an anode additive in an operating potential region of the lithium ion capacitor. It is characterized in that it can effectively transfer lithium ions to the negative electrode without having to.
  • the lithium ion capacitor according to the present invention can improve the process safety according to the generation of lithium metal by doping lithium ions to the cathode in an electrochemical manner, and at the same time, it is possible to secure the effect of further improving the capacity and energy density of the capacitor. have.
  • the lithium ion capacitor of the present invention includes a cathode including a cathode active material; An anode including an anode active material; And a separator between the anode and the cathode, wherein the cathode may be supplied with lithium ions only from the anode.
  • receiving lithium ions only from the positive electrode is included in a separate lithium ion supply layer for supplying lithium ions to the negative electrode, for example, the negative electrode or on the negative electrode
  • a separate lithium metal layer stacked (coated or laminated) is not included in the capacitor, and the negative electrode may mean that only lithium ions derived from the lithium composite metal oxide included in the positive electrode active material are supplied.
  • the lithium ion capacitor of the present invention is lithium in the voltage range of 0V to 5V It may include a carbon-based negative electrode active material for reversibly inserting or detaching ions.
  • a lithium ion capacitor including a positive electrode active material including the first lithium composite metal oxide and the second lithium composite metal oxide and a carbon-based negative electrode active material reversibly intercalating or deintercalating with lithium ionol may be formed. Characterized in that to effectively doping.
  • the first lithium composite metal oxide or the like according to the present invention is applied as a positive electrode additive to a hybrid capacitor using a conventional activated carbon negative electrode which is not a negative electrode active material of a lithium ion capacitor (positive electrode: activated carbon + Li 2 MoO ⁇ negative electrode: activated carbon) ), Due to the large initial irreversible nature of the positive electrode additive itself may cause a problem that the capacity and life performance of the capacitor is significantly reduced.
  • the second lithium composite metal oxide or the like according to the present invention is applied as a positive electrode additive to the hybrid capacitor or the like (anode: activated carbon + Li 2 Ru0 3 , negative electrode: activated carbon), the reversible lithium ions (Li + ), Due to the insertion and desorption properties, the effect of improving energy density may occur.
  • the lithium ion capacitor according to the present invention has a layer discharge capacity measured by an electrochemical method of 50 F / g or more, preferably 70 F / g or more, more preferably 100 F / g or more or 100 to 800 F /. It may exhibit excellent performance of g, and in some cases, 750 F / g or less, and 700 F / g or less.
  • the lithium ion capacitor according to the present invention uses a lithium composite metal oxide having a large initial irreversible capacity in a positive electrode active material to electrochemically dope lithium in a negative electrode, thereby providing a lithium metal electrode or a lithium metal as a separate lithium source. It can be prepared without using.
  • a specific example of a cathode active material for a lithium ion capacitor and a method of manufacturing a lithium ion capacitor using the same according to the present invention will be described in detail.
  • the second step of synthesizing a first step, and a ready-Li 2 Mo0 Li 2 Mo0 3 processes the reduction of 4 precursor to prepare a Li 2 Mo0 4 precursor, Li A third step of synthesizing 2 Ru0 3 , And a fourth step of mixing the Li 2 Mo 3 and the carbon-based material to form a cathode active material.
  • the first step of preparing the Li 2 Mo 0 4 precursor is more specifically, the first 1-step of mixing Li 2 C0 3 and Mo0 3 in a 1: 1 molar ratio, and the marks of Li 2 C0 3 and Mo0 3
  • the mixture is heat-treated at 400-1000 ° C. for 1-6 hours in air to form the first 1-2 steps to form a Li 2 Mo 4 precursor.
  • the first step 1-2 may be performed in the air.
  • the second step is the 2-1 step of uniformly mixing 10 wt% or less of Super-P in Li 2 Mo0 4 through mechanical milling, and the mixture of Li 2 Mo0 4 and Super-P 10%
  • the mixing step according to the mechanical milling in the 2-1 step may proceed for about 30 minutes.
  • the mechanical milling means for example, a mortar, a ball mill, a vibration mill, a satellite ball mill, a tube mill, a rod mill jet mill, a hammer mill, or the like can be used.
  • the reducing atmosphere according to step 2-2 may be performed under an Ar 2 atmosphere containing 3 ⁇ 4 gas of 5 ⁇ 10>.
  • the third step of synthesizing Li 2 Ru 0 3 is more specifically, the 3-1 step of mixing Li 2 C0 3 and Ru0 2 in a 1: 1 molar ratio, and a mixture of Li 2 C0 3 and Ru0 2 It comprises a 3-2 step of synthesizing Li 2 Ru3 ⁇ 4 by heat treatment at 500 to 1000 ° C for 10 to 30 hours in air. In this case, step 3-2 may be performed in the air.
  • step 3-2 may be performed in the air.
  • Li 2 Mo 0 3 and Li 2 Ru0 3 synthesized in the second and third steps are mixed with a carbon-based material to form a cathode active material for a lithium ion capacitor.
  • the cathode active material for a lithium ion capacitor may be formed by mixing Li 2 Mo0 3 3-50 weight%, Li 2 Ru 3-30 weight%, and carbonaceous material 60 to 94 weight%. Preferably 3 to 30% by weight of Li 2 Mo0 3 , 3 to 10% by weight of Li 2 Ru3 ⁇ 4, 60-94% by weight of the carbon-based material.
  • the electrochemical lithium doping may be performed in a voltage range of 5V or less.
  • a lithium ion capacitor was manufactured as follows. At this time, as described above, 92 wt% of the positive electrode active material prepared according to a specific example of the present invention and binder PVdF were 8 wt%, and a slurry was prepared using NMP as a solvent. The slurry was applied to an aluminum mesh (A1 mesh) having a thickness of 20 ⁇ , dried and compacted by a press, dried for 16 hours at 120 ⁇ : in a vacuum to prepare an electrode with a disc of 12 mm in diameter.
  • A1 mesh aluminum mesh having a thickness of 20 ⁇
  • the counter electrode lithium metal foil punched to a diameter of 12 mm was used, and a PP film was used as the separator.
  • a electrolyte solution a mixed solution in which EC / DMC of 1M LiPF 6 was mixed at 3: 7 was used. After the electrolyte solution was impregnated with the separator, the separator was sandwiched between the working electrode and the counter electrode, and a case of a stainless steel (SUS) product was prepared as a test cell for electrode evaluation, that is, a non-aqueous lithium ion capacitor half cell.
  • SUS stainless steel
  • the negative electrode active material is a crystalline or amorphous carbon such as artificial graphite, natural graphite, graphitized carbon fiber, graphitized mesocarbon microbead, petroleum coke, resinous body, carbon fiber, pyrolytic carbon, etc. At least one of the materials may be used.
  • the positive electrode additive reversibly inserts or detaches lithium ions in a voltage range of 5V or less, and is applicable to a lithium ion capacitor to which a non-aqueous electrolyte is driven in a voltage range of 5V or less.
  • the production of the positive electrode plate is one kind commonly used in the powder of the positive electrode active material containing the positive electrode additive according to the present invention, if necessary, a conductive agent, a binder, a thickener, a filler, a dispersant, an ion conductive agent, a pressure enhancer, etc. Or 2 or more types of addition components are added, and it slurry-pastes with suitable solvents, such as water and an organic solvent.
  • suitable solvents such as water and an organic solvent.
  • the binder may be, for example, a rubber binder such as styrene butadiene rubber (SBR), a fluorine resin such as polyethylene tetrafluoride or polyvinylidene fluoride (PVdF), polypropylene, polyethylene, or the like.
  • SBR styrene butadiene rubber
  • PVdF polyvinylidene fluoride
  • Thermoplastic resins, acrylic resins, etc. can be used.
  • the amount of the binder used is the electrical conductivity of the positive electrode active material, the electrode Although it may vary depending on the shape, it can be used in an amount of 2 to 40 parts by weight based on 100 parts by weight of the positive electrode active material.
  • examples of the conductive agent include alum, carbon black, acetylene black, Ketjen black, carbon fiber, and metal powder.
  • the amount of the conductive material used varies depending on the electrical conductivity, electrode shape, and the like of the positive electrode active material, but may be used in an amount of 2 to 40 parts by weight based on 100 parts by weight of the positive electrode active material.
  • CMC carboxymethyl cellulose
  • the electrode support substrate (also referred to as 'current collector') may be composed of copper, nickel, stainless steel, aluminum, foil, sheet, mesh or carbon fiber.
  • a lithium ion capacitor is manufactured using the anode prepared as described above.
  • the form of the lithium ion capacitor may be any one of a coin, a button, a sheet, a pouch, a cylinder, a square, and the like.
  • the negative electrode, electrolyte, and separator of the lithium ion capacitor may be selected and used in a range known to be applicable to a conventional lithium secondary battery.
  • the electrolyte solution is a non-aqueous electrolyte, an inorganic solid electrolyte, or an inorganic solid electrolyte in which lithium salt is dissolved in an organic solvent.
  • Composite materials, etc. can be used, It is not limited to this.
  • the solvent of the non-aqueous electrolyte solution is carbonate ester. Ethers or ketones may be used.
  • the carbonates 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 the like can be used.
  • Esters include butyrolactone (BL), decanolide, valerolactone, mevalonolactone, ⁇ "caprolactone n-decyl acetate, n-ethyl acetate, n -Propyl acetate, etc.
  • ether dibutyl ether can be used, etc.
  • ketone polymethylvinyl Ketones can be used.
  • the non-aqueous electrolyte according to the present invention is not limited to the type of non-aqueous organic solvent.
  • lithium salt of the non-aqueous electrolyte solution examples include LiPF 6> LiBF 4 , LiSbF 6 , LiAsF 6 , LiC10 4 , L1CF3SO3, LiN (CF 3 S0 2 ) 2) LiN (C 2 F 5 S0 2 ) 2 , LiA10 4 , LiAlCl 4 > LiN (C x F 2x + 1 S0 2 ) (CyF 2x + 1 S0 2 ) (where x and y are natural numbers) and LiS0 3 CF 3 is selected from the group consisting of one or more Include.
  • a porous film made from polyolefin such as polypropylene (PP) or polyethylene (PE), or a porous material such as nonwoven fabric can be used.
  • an electrochemical is added to a carbon-based material for a positive electrode active material of a lithium ion capacitor by adding a positive electrode additive having a large initial irreversible capacity as a source of lithium and a high reversible positive electrode additive to improve energy density in the operating potential region of the lithium ion capacitor.
  • a positive electrode additive having a large initial irreversible capacity as a source of lithium and a high reversible positive electrode additive to improve energy density in the operating potential region of the lithium ion capacitor.
  • the doping of lithium using the positive electrode additive according to the present invention has the effect of improving the energy density of the lithium ion capacitor by lowering the potential of the negative electrode.
  • a simple lithium doping process has the effect of improving the production efficiency of the lithium ion capacitor.
  • EDLC electric double layer capacitor
  • FIG. 2 is a schematic diagram showing a general structure of a conventional lithium ion capacitor (LIC).
  • LIC lithium ion capacitor
  • UC lithium ion capacitor
  • Figure 4 is a reference graph for the initial layer discharge efficiency of the positive electrode additive according to the present invention.
  • Example 5 is an XRD analysis graph of the positive electrode additives Li 2 Mo3 ⁇ 4 and Li 2 Ru0 3 synthesized according to Example 1 of the present invention.
  • Figure 6 is a FESEM and HRTEM picture of the positive electrode additive Li 2 Mo0 3 and Li 2 Ru0 3 synthesized according to Example 1 of the present invention [a) Li 2 Mo0 3 , b) Li 2 u0 3 , c) Li 2 Mo0 3l d) Li 2 Ru 0 3 , e) Li 2 Mo 0 3 , f) Li 2 Ru 0 3 ].
  • FIG. 7 is a graph illustrating a capacity evaluation result of lithium silver capacitors according to Examples 1 and 2 and Comparative Examples 1 and 2 of the present invention.
  • Example 1 is merely to illustrate the present invention is not limited to the scope of the following examples.
  • a high-performance cathode active material for a lithium ion capacitor including Li 2 Mo0 3 as a lithium source for lithium doping to a negative electrode of a lithium ion capacitor and Li 2 Ru0 3 as an additive for improving energy density was prepared.
  • Single phase Li 2 Mo 3 and Li 2 Ru3 ⁇ 4 were synthesized as follows. First, after mixing Li 2 C0 3 and Mo0 3 in a molar ratio of 1: 1, the mixture of Li 2 C0 3 and Mo0 3 is heat-treated at 600 ° C for 5 hours in air to form a lithium composite metal oxide precursor Li 2 Mo0 4 was synthesized. After uniformly mixing 7 parts by weight of Super-P with mechanical milling with respect to 100 parts by weight of Li 2 Mo0 4 thus synthesized, the mixture of Li 2 Mo0 4 and Super-P was mixed for 10 hours at 700 ° C. in an N 2 atmosphere. Heat treatment was performed to synthesize a first lithium composite metal oxide Li 2 M O 0 3 .
  • Li 2 CO 3 and Ru0 2 were mixed in a molar ratio of 1: 1, the mixture of Li 2 CO 3 and Ru0 2 was heat-treated at 900 ° C. for 12 hours in air to form a second lithium composite.
  • a metal oxide precursor Li 2 Ru 0 3 was synthesized.
  • 3 ⁇ 4 is the initial layer discharge efficiency of the lithium composite metal oxide
  • QD is the charge capacity per unit weight of the positive electrode active material (mAh / g) at the Li / Li + cut-off at a discharge voltage of 2.3 V
  • Q c is the Li / Li + cut-off at a layer voltage of 4.7 V. It shows the layer charge capacity (mAh / g) per unit weight of the positive electrode active material (cut-off).
  • the initial layer discharge efficiency () of the prepared first lithium composite metal oxide Li 2 Mo 0 3 was 43%, and it was confirmed that the initial irreversible capacity had a large characteristic.
  • I is the second layer will showing a discharge efficiency at 2.3V ⁇ 4.7V potential of the lithium-metal composite oxide
  • i is Li / Li + cut in the discharge voltage 2.3 V - off (cut off ⁇ ) when the discharge capacity (mAh / g)
  • Q c ⁇ represents the layer capacitance (mAh / g) at the Li / Li + cut-off at the layer voltage 4.7 V.
  • the layer discharge efficiency (3 ⁇ 4,) is more than 70% under the 2.3V to 4.7V potential of the prepared second lithium composite metal oxide Li 2 Ru0 3 , and has a high reversibility in the operating potential region of the lithium ion capacitor. Confirmed.
  • An active material was prepared.
  • a cathode active material for an ion capacitor was prepared.
  • the compositions of the positive electrode active materials according to Examples 1 and 2 and Comparative Examples 1 and 2 are as shown in Table 1 below.
  • slurries were prepared using N-methylpyrrolidone (NMP) as a solvent using 92% of the cathode active materials 92 3 ⁇ 4> and the binder PVdF according to Examples 1 and 2 and Comparative Examples 1 and 2 as 8%.
  • NMP N-methylpyrrolidone
  • the slurry was applied to an aluminum mesh (A1 mesh) having a thickness of 20, dried, compacted in a press, dried for 16 hours at 120 ° C. in a vacuum, and an electrode was prepared from a disk having a diameter of 12 mm 3.
  • the positive electrode plate was prepared by coating 92% of the active material (activated carbon + Li 2 Mo0 3 + Li 2 Ru0 3 ) with an NMP solution containing 8% PVDF binder and a slurry after coating on an aluminum mesh, hard carbon 80 % And a conductive material (super-P) 10 3 ⁇ 4) was prepared by coating the Cu mesh after preparing a slurry and NMP solution containing 10% PVDF binder.
  • a lithium metal foil punched to a diameter of 12 mm was used as an anode, and a polyethylene (PE) film was used as a separator.
  • PE polyethylene
  • a mixed solution in which ethylene glycol / dimethyl chloride (EC / DMC) of 1 M LiPF 6 was mixed at 3: 7 was used as the electrolyte solution.
  • Comparative Example 1 60% of the cathode capacity was doped in a CV (constant voltage) mode using lithium metal, and Comparative Examples 2 and 1 and 2 were electrochemically 4.7 V vs. Lithium was doped to the cathode through layer conversion with a constant current of 0,1 C up to Li / Li +. The amount of Li 2 Mo0 3 shown in Table 1 was fixed in an amount capable of doping the negative electrode in the negative electrode capacity 603 ⁇ 4> according to Comparative Example 1.
  • FIGS. 7 and 8 graphs of capacity evaluation and 1,000 cycle life of the lithium ion capacitor using the positive electrode active material according to Examples 1 to 2 and Comparative Examples 1-2 are shown in FIGS. 7 and 8, respectively.
  • FIG. 7 compares the layer discharge curves of the third cycle after lithium doping after the layer discharge curves, and it is confirmed that Examples 1 to 2 of Li-ion capacitors including Li 2 Ru0 3 additionally exhibit improved capacity.
  • Figure 8 Li 2 Ru 0 3
  • the lithium ion capacitors of Examples 1 to 2 additionally maintain high capacity without deterioration of life, and it was confirmed that the higher capacity was expressed as the amount of Li 2 Ru0 3 increased.
  • the first lithium composite metal oxide having a large initial irreversible capacity and the second lithium composite metal oxide having high reversibility in the operating potential region of the lithium ion capacitor are used together.
  • the lithium ion capacitor of 2 has a discharge capacity of 652 mF to 697 mF and a discharge capacity of 402 mF to 413 mF after 1,000 cycles.
  • the lithium ion capacitor of Comparative Example 1 has a discharge capacity of 386 mF, and after 1,000 cycles, it can be seen that the discharge capacity remarkably drops to 261 mF.
  • the lithium ion capacitor of Comparative Example 2 has a discharge capacity of 562 mF, and discharge capacity of 362 mF after 1,000 cycles is better than that of Comparative Example 1 but is significantly lower than Examples 1 to 2.
  • lithium could be electrochemically doped to the negative carbon material using the positive electrode additives of the Li 2 Mo0 3 and Li 2 Ru0 3 transition metal oxides according to the present invention. It can be seen that it is effective in securing the improved electrochemical properties of the ion capacitor and significantly increasing the energy density.

Abstract

L'invention concerne un condensateur à ion lithium possédant d'excellentes caractéristiques de capacitance et une grande densité énergétique, et plus particulièrement un matériau actif de cathode pour un condensateur à ion lithium dans lequel un oxyde métallique mélangé de lithium ayant une capacité irréversible initiale élevée en qualité de fournisseur de lithium pour un matériau au carbone appliqué comme matériau actif de cathode, et un oxyde métallique mélangé de lithium ayant une réversibilité élevée dans la zone de potentiel de fonctionnement du condensateur à ion lithium pour améliorer la densité énergétique, sont utilisés conjointement comme additif de cathode. L'invention concerne également un procédé de fabrication de celui-ci, et un condensateur à ion lithium le comprenant. Selon la présente invention, l'anode peut être dopée électrochimiquement avec du lithium sans utiliser du lithium métallique, et les caractéristiques de capacitance du condensateur à ion lithium et la sécurité du processus de dopage au lithium peuvent être sensiblement améliorées.
PCT/KR2012/003860 2012-04-04 2012-05-16 Matériau actif de cathode pour condensateur à ion lithium et procédé de fabrication WO2013151209A1 (fr)

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Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101892177B1 (ko) 2015-06-30 2018-08-28 전자부품연구원 고출력 에너지 저장 장치용 첨가제 및 이를 포함하는 고출력 에너지 저장 장치
KR101751213B1 (ko) * 2017-02-22 2017-06-28 전자부품연구원 고출력 에너지 저장 장치용 첨가제의 제조 방법, 이에 의하여 제조된 고출력 에너지 저장 장치용 첨가제, 및 이를 포함하는 고출력 에너지 저장장치
WO2018236166A1 (fr) * 2017-06-21 2018-12-27 주식회사 엘지화학 Batterie secondaire au lithium
KR102115602B1 (ko) 2017-06-21 2020-05-26 주식회사 엘지화학 리튬 이차전지
KR102093971B1 (ko) * 2017-06-21 2020-05-21 주식회사 엘지화학 리튬 이차전지
WO2018236168A1 (fr) * 2017-06-21 2018-12-27 주식회사 엘지화학 Batterie secondaire au lithium
US10403929B2 (en) 2017-11-30 2019-09-03 Lg Chem, Ltd. Additive for cathode, method for preparing the same, cathode including the same, and lithium secondary battery including the same
WO2020091428A1 (fr) * 2018-10-30 2020-05-07 주식회사 엘지화학 Accumulateur au lithium
EP3866224A4 (fr) * 2018-11-02 2021-12-08 Lg Energy Solution, Ltd. Batterie secondaire au lithium
US20210399276A1 (en) * 2018-11-02 2021-12-23 Lg Energy Solution, Ltd. Lithium secondary battery
KR102217302B1 (ko) * 2018-11-30 2021-02-18 주식회사 포스코 리튬 이차 전지용 양극 첨가제, 이의 제조방법, 이를 포함하는 리튬 이차 전지용 양극 및 이를 포함하는 리튬 이차 전지
KR102168789B1 (ko) * 2018-12-20 2020-10-22 한국전자기술연구원 리튬 이온 커패시터용 리튬코발트산화물-탄소 복합체, 이를 포함하는 양극 활물질, 이를 포함하는 리튬 이온 커패시터, 및 그 제조방법
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KR20220161653A (ko) * 2021-05-31 2022-12-07 주식회사 엘지에너지솔루션 양극활물질과 비가역 첨가제를 포함하는 마스터 배치 및 이를 함유하는 리튬 이차전지용 양극 슬러리
KR20230024858A (ko) * 2021-08-12 2023-02-21 주식회사 엘지에너지솔루션 리튬 이차 전지용 양극 첨가제를 포함하는 양극

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20050049746A (ko) * 2003-11-24 2005-05-27 전자부품연구원 리튬 2차전지용 양극 활물질, 그 제조 방법 및 그를포함하는 리튬 2차전지
KR20080081297A (ko) * 2005-12-28 2008-09-09 후지 주코교 카부시키카이샤 리튬이온 커패시터
KR20100002107A (ko) * 2008-06-25 2010-01-06 삼성에스디아이 주식회사 리튬 이차 전지
KR20120009701A (ko) * 2010-07-20 2012-02-02 삼성에스디아이 주식회사 양극 및 이를 포함한 리튬 전지

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20050049746A (ko) * 2003-11-24 2005-05-27 전자부품연구원 리튬 2차전지용 양극 활물질, 그 제조 방법 및 그를포함하는 리튬 2차전지
KR20080081297A (ko) * 2005-12-28 2008-09-09 후지 주코교 카부시키카이샤 리튬이온 커패시터
KR20100002107A (ko) * 2008-06-25 2010-01-06 삼성에스디아이 주식회사 리튬 이차 전지
KR20120009701A (ko) * 2010-07-20 2012-02-02 삼성에스디아이 주식회사 양극 및 이를 포함한 리튬 전지

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