Classifications

• • 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
  • H01M4/13—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
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
  • H01M10/38—Construction or manufacture
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/04—Processes of manufacture in general
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/04—Processes of manufacture in general
  • H01M4/0438—Processes of manufacture in general by electrochemical processing
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/134—Electrodes based on metals, Si or alloys
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/139—Processes of manufacture
  • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/362—Composites
  • H01M4/366—Composites as layered products
• • 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
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
  • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

• the present invention relates to an electrode active material, of which the stability is improved by adjusting an acid site of a surface of the electrode active material, an electrode containing the electrode active material, having a surface coated with a compound having an acid site, or mixed with the compound having the acid site and an electrode material, and an electrochemical device, such as a lithium secondary battery, having the electrode to enhance its performance.
• an electrode active material of which the stability is improved by adjusting an acid site of a surface of the electrode active material, an electrode containing the electrode active material, having a surface coated with a compound having an acid site, or mixed with the compound having the acid site and an electrode material, and an electrochemical device, such as a lithium secondary battery, having the electrode to enhance its performance.
• a lithium secondary battery Since a lithium secondary battery has been commercialized, the development of such a battery mainly aims to prepare a cathode active material with electrochemical properties such as high capacity, long lifespan, and the like. In addition to the electrochemical properties, the development of the cathode active material with improved stability is really needed to secure the stability and reliability of a battery system under abnormal conditions such as thermal exposure, burning, or overcharge.
• LiMO (M is a transition metal comprising Ni, Mn, Co, and so forth), which is widely used as the cathode active material of the lithium secondary battery, is reacted with an electrolyte in a charge state or an overcharge state to generate by-products or break down the structure of the electrode active material, thereby causing reduction of the battery performance. Consequently, many scientists have been conducting researches to enhance the performance of active material by treating the surface of the active material with stable oxide, but they are unable to enhance the stability and performance simultaneously in the electrode active material. Disclosure of Invention Technical Problem
• An object of the present invention is to provide an electrode active material comprising an acid site partially or wholly formed on its surface, an electrode comprising the electrode active material, and an electrochemical device, such as a lithium secondary battery, having the electrode.
• an electrode having a surface coated with a compound having an acid site or comprising the compound, and an electrochemical device, such as a lithium secondary battery, having the electrode.
• a method for manufacturing an electrode active material having a coating layer with adjusted acid strength which comprises the steps of: (i) reacting (a) a compound capable of donating or accepting proton, or a compound capable of donating or accepting electron-pair, with (b) a compound having an acid site; and (ii) coating the result of step (i) onto a surface of the electrode active material and drying the coating layer.
• the present invention is characterized in that an acid site is partially or wholly formed on a particle surface of an electrode active material capable of intercalating/ deintercalating lithium ions or inserting/deinserting the lithium ions, thereby modifying electrochemical physical properties of the electrode active material.
• the acid site is generally known as a reaction active site existed on a solid acid catalyst, such as zeolite, which induces a chemical reaction, for example, decomposition reaction.
• the acid site means an active region indicative of specific acid strength at a surface modified portion which is partially or wholly formed on the surface of the active material through the new surface modifying method.
• the acid strength is determined depending upon how to easily donate proton or how to easily accept electron-pair. Consequently, the characteristic of the acid site is generally associated not with the surface structure, but with the electronic property between atoms configuring the surface.
• the electrode active material with the acid site formed on the surface thereof reacts like a common acid material having positive charge partially, because of the possession of positive charge or an electronegativity difference. Therefore, since the reaction with Br ⁇ nsted acid serving as a proton donor or Lewis acid serving as an electron-pair acceptor is significantly reduced, it can enhance the performance of the battery, which can be presumed as follows.
• the electrode active material of the present invention carries the acid site on the surface thereof, it serves as an acid material. Consequently, the reaction with strong acid HX (X means a halogen element) is decreased, so that the above problem is substantially solved to secure the structure stability of the electrode active material and enhance the performance of the battery.
• a carbonate-based nonaqueous solvent is used as an electrolyte for a conventional battery.
• the carbonate-based nonaqueous solvent has carbon of a positive charge and oxygen of a negative charge in view of dipole moment, as disclosed in Equation 1 below.
• the Lewis base attacks the carbon having the positive charge, thereby further activating the electrophilic decomposition reaction of the electrolyte.
• the electrode active material of the present invention having the acid site is Lewis acid capable of not donating unshared electron pair but accepting the unshared electron pair.
• the above side reaction with the electrolyte is significantly reduced, thereby minimizing the deterioration of the performance of the battery.
• the acid site partially or wholly formed on the surface of the electrode active material according to the present invention means a common acid site widely known in the art.
• it may be Br ⁇ nsted acid capable of donating proton (i.e., proton donor) or Lewis acid capable of accepting unshared electro pair (i.e., electron-pair acceptor).
• the acid strength may be indicated by H (Hammett indicator), and is adjustable within a range generally known in the art, for example, the range of -20 to 20.
• H is in the range of -10 to 10, so as to prevent degradation of the electrode active material and suppress the side reaction with the electrolyte, through the adjustment of the acid site.
• a method of forming the acid site on the surface of the electrode active material is not limited, but two embodiment modes will be described by way of example.
• the surface of the electrode active material is treated with an inorganic substance.
• the inorganic substance treated on the surface of the electrode active material changes the electron distribution on the surface of the electrode active material due to the electronegativity difference of hetero-metal elements and/or the functional group of the proton donor partially or wholly existed on the surface of the inorganic substance, so that the acid site is formed on the surface of the electrode active material.
• the inorganic substance is widely known in the art, for example, ceramic, metal, or a compound thereof. If the electrochemical property of the surface of the electrode active material is changed when the inorganic substance is existed on the surface, it is not limited. Especially, a compound containing an element (e.g., B, Al, Ga, In, Ti or the like) of Group 13, Group 14, Group 15, or a mixture thereof, which can improve the structure stability of the electrode due to intercalation of Li is preferable, since it is easily doped on the surface of the electrode active material due to its atomic size.
• an element e.g., B, Al, Ga, In, Ti or the like
• Examples of the available inorganic substance may comprise an element of Group
• the inorganic substance may be M Si O (M is at least one element selected from the group l-x x 2 consisting of transition metal; 0 ⁇ x ⁇ l).
• the inorganic substance having the acid site may be formed through heat treatment after modifying the surface of the electrode active material.
• the heat treatment temperature is not specially limited, even if it is above a temperature to form the acid site. If a hydroxyl group is still existed on the surface, it is not possible to form strong Lewis acid site. Consequently, the temperature of 400 °C or more is preferable so as to eliminate the hydroxyl group.
• Embodiment Mode 2 In the embodiment mode, the surface of the electrode active material is treated with a hybrid of organic metalloid compound or organic metal compound, and an inorganic substance.
• the hybrid of the organic metalloid compound or the organic metal compound, and the inorganic substance treated on the surface of the electrode active material changes the electrochemical physical property of the surface due to the electronegativity difference between the organic metalloid (metal) compound and the inorganic substance which are bonded to each other and/or the organic substance bonded to the organic metalloid (metal) compound, so that the acid site can be formed on the surface of the electrode active material.
• the organic metalloid (metal) compound and the inorganic substance are bonded to each other through chemical bonding, and a shape and kind of the chemical bonding are not specially limited.
• it may be covalent bond or coordinate covalent bond.
• a hydrolysis speed of the inorganic component e.g., inorganic alkoxide compound
• it can not only create the more uniform surface, but also maintain the created surface continuously. Consequently, it can minimize the deterioration of the performance of the battery due to the lowered structural stability of the electrode active material and the collapsed structure thereof, with the progress of charge and discharge.
• it can effectively enhance the electric conductivity of the electrode active material by introducing the surface- modified layer using the inorganic compound contained in the organic-inorganic hybrid.
• the organic-inorganic hybrid induced in the surface of the electrode active material reacts with the moistures or carbon dioxide contained in the air to generate Li byproducts, thereby preventing aging characteristics which causes the side reaction.
• nickel-based cathode active material which is seriously changed by the moistures is more effective.
• one of the organic-inorganic hybrid capable of creating the acid site partially or wholly on the particle surface of the electrode active material may be a conventional organic metalloid compound or organic metal compound which is widely known in the art.
• an electron donating group for increasing the Br ⁇ nsted acid site.
• the electron donating group is not specially limited to structural formula, substituent, and a range of carbon number.
• hydrogen or hydrocarbon may be.
• Examples of the available organic metalloid compound or organic metal compound may comprise an element of Group 14, or a compound of an element of Group 14 and at least one selected from the group consisting of alkaline earth metal, alkaline metal, an element of Group 13, an element of Group 15, transition metal, lanthanide metal, and actinide metal, which does not limit the scope of the present invention.
• the organic metalloid compound or the organic metal compound is preferably a compound containing silicon (e.g., silane, silylizing agent, silane coupling agent, hydrogenated silicon, monosilane, silane polymer, or mixtures thereof).
• organic met alloid compound may be represented by any one of following
• Formulas 1 to 7. There is no limitation in the organic metalloid compound or the organic metal compound.
• Z is one element selected from the group consisting of halogen atoms
• M is at least one element selected from the group consisting of alkaline earth metal, alkaline metal, transition metal, lanthanide metal, and actinide metal;
• R is a substituent selected from the group consisting of Cl to C20 alkyl group, alkenyl group, alkynyl group, vinyl group, amino group, and mercapto group, the group is/are substituted or non-substituted by a halogen element.
• Another one of the organic-inorganic hybrid capable of creating the acid site partially or wholly on the particle surface of the electrode active material may be a common inorganic substance which can create the acid site due to a chemical bonding number difference between the above organic metalloid (metal) compound and the inorganic substance.
• Any compound containing inorganic instance may be used with no particular limitation.
• the above inorganic component may be used.
• the organic-inorganic hybrid consisting of the organic metalloid (metal) compound and the inorganic substance is not a simple mixture of an organic substance and an inorganic substance, but is a chemically bonded mixture thereof.
• it may comprise a metal-organic metalloid (metal) compound, a metal oxide-organic metalloid (metal) compound (Al O -SiOCH ), and a hydroxide-organic metalloid (metal) compound (AlOOH-Si-CH ).
• (metal) compound to the inorganic substance may be in the range of Owt% ⁇ 95wt% to 5wt% ⁇ 100wt%.
• the organic-inorganic compound of the present invention may comprise ad ditives which are generally known in the art, in addition to the above components.
• the electrode active material comprising an organic-inorganic hybrid coating layer.
• the surface of an electrode active material is partially or wholly coated with a compound comprising an acid site.
• the process may comprise the steps of (i) mixing a compound containing an inorganic substance or a compound containing an organic substance and an organic metalloid (metal) compound or dispersing them into a solvent, and (ii) adding an electrode active material into the mixture or dispersed solution and stirring and drying it.
• the compound containing the inorganic substance may be used a conventional water soluble or non- water soluble compound containing at least one element described above (e.g., alkoxide, nitrate, acetate, or the like, which contains the above inorganic substance).
• the solvent may comprise a conventional solvent widely known in the art (e.g., an organic solvent such as water, alcohol, or a mixture thereof).
• a conventional solvent widely known in the art (e.g., an organic solvent such as water, alcohol, or a mixture thereof).
• the electrode active material coated with the above prepared compound may be used a conventional cathode active material and a conventional anode active material, which are widely known in the art.
• the method of coating the surface of the electrode active material with the compound solution mixed with the inorganic substance with the organic metalloid (metal) compound may comprise a solvent evaporation, a coprecipitation method, a precipitation method, a sol-gel method, an absorption and filtering method, a sputtering method, a CVD method, and the other.
• a spray coating method is preferable.
• the mixed solution of the organic metalloid (metal) compound and the inorganic substance or the compound containing the inorganic substance is added in the electrode active material, preferably, 0.05 to 20 parts by weight of the mixed solution is added based on 100 parts by weight of the electrode active material, which does not limit the scope of the present invention. If the mixed solution is excessive, a lot of surface treated layers are existed on the surface of the electrode active material, so that lithium is not smoothly shifted to the electrode active material, thereby deteriorating the electrochemical characteristic thereof. Also, if the mixed solution is too insufficient, the acid site effect is slight. Then the coated electrode active material may be dried through a common method.
• the range of heat treating temperature is above 100 °C , but is not especially limited. Preferably, the range is 100 °C to 600 °C . Also, the heat treating may be conducted under conditions of atmosphere or inert gas.
• the conventional method does not obtain the wanted effect, since the organic substance is thermally unstable and/or is partially burnt, during a hot firing process. Consequently, the firing temperature is limited.
• the thermal instability of the organic substance is compensated by the inorganic component, thereby providing the electrode active material with the thermal stability. Also, since it can prepare the electrode active material through a conventional drying process or a low temperature firing process, it can improve the economical efficiency and achieve the mass, by simplifying the preparing method.
• the electrode active material prepared by the above method is provided with the inorganic or organic-inorganic hybrid layer on its surface, in which the inorganic or organic-inorganic hybrid creates the acid site.
• the present invention provides an electrode containing the electrode active material described above. In this instance, it is preferable that the electrode is a cathode which is seriously changed due to HF or moistures. [71] Also, the present invention provides an electrode having a surface coated with the compound having the acid site or containing the compound having the acid site.
• the method of preparing the electrode containing the compound having the acid site as a constituent component of the electrode is not specially limited, and the electrode may be prepared by a conventional method.
• the compound containing the inorganic substance or the compound containing the organic substance and the organic metalloid (metal) compound are mixed or dispersed into the solvent, and the electrode active material is added into the mixed or dispersed solution to form electrode slurry. Then, the slurry is applied on a collector to manufacture the electrode, and the electrode is dried.
• the slurry is applied on the collector.
• the method of manufacturing the electrode by using the organic-inorganic hybrid as a coating component of the electrode according to the present invention may be carried out by a conventional process.
• the compound containing the inorganic substance or the compound containing the organic substance and the organic metalloid (metal) compound are mixed, and the mixture is applied on the surface of the preliminarily formed electrode , and then the electrode is dried.
• the preliminary formed electrode may be manufactured by a conventional method known in the art.
• the present invention provides an electrochemical device comprising an anode, a cathode, a separator, and an electrolyte, wherein either or both of the anode and/or cathode contains the above electrode active material or above electrode.
• the electrochemical devices include all devices that perform electrochemical reactions, and specific examples thereof include all kinds of primary and secondary batteries, fuel cells, solar cells, and capacitors.
• the secondary batteries preferred are lithium secondary batteries, including lithium metal secondary batteries, lithium ion secondary batteries, lithium polymer secondary batteries and lithium ion polymer secondary batteries.
• the electrochemical device of the present invention can be fabricated according to any conventional method known in the art.
• the electrochemical device can be manufactured by interposing a porous separator between the cathode and the anode within a battery case and then injecting the electrolyte into the electrochemical device case.
• electrolyte and the separator which are used for the electrode are not specially limited, and those generally used in the electrochemical device may be used.
• the electrochemical device (e.g., lithium secondary battery) manufactured by the present invention may be formed in a cylinder, coin, prism or pouch shape, but it is not limited to the shape.
• the present invention provides a manufacturing method of an electrode active material, of which the acid strength of the surface is adjusted.
• the method comprises the steps of (i) reacting (a) a compound capable of donating or accepting proton, or a compound capable of donating or accepting electron-pair, with (b) a compound having an acid site; and (ii) coating the result of step (i) onto a surface of the electrode active material and drying the coating layer.
• the present invention is not limited thereto.
• Electrotron-pair is used as a factor to adjust the acid strength of the conventional compound in a specific range. In this instance, it can adjust the acid strength by controlling contents of the compound, the functional group existed in the compound, and a composition thereof.
• the adjusted acid strength of the surface of electrode active material is preferably adjusted within the range of -20 to 20 (i.e., -20 ⁇ H ⁇ 20), preferably -10 to 10 (i.e., -10 ⁇ H Q ⁇ 10). Description of Drawings
• FlG. 1 is a graph showing a charge/discharge capacity of a lithium secondary battery manufactured by using a cathode active material of Example 1 ;
• FIG. 2 is a graph showing a charge/discharge capacity of a lithium secondary battery manufactured by using a cathode active material of Example 2;
• FIG. 3 is a graph showing a charge/discharge capacity of a lithium secondary battery manufactured by using a cathode active material of Example 3;
• FIG. 4 is a graph showing a charge/discharge capacity of a lithium secondary battery manufactured by using a cathode active material of Comparative Example 1 ;
• FIG. 5 is a graph showing a charge/discharge capacity of a lithium secondary battery manufactured by using a cathode active material of Comparative Example 2;
• FIG. 6 is a graph showing a charge/discharge capacity of a lithium secondary battery manufactured by using a cathode active material of Comparative Example 3;
• FIG. 7 is an IR spectrometer graph showing surface characteristic variations according to temperature and measuring conditions of the cathode active material prepared in Example 1 ;
• FIG. 8 is an IR spectrometer graph showing surface characteristic variations according to temperature and measuring conditions of the cathode active material prepared in Comparative Example 1 ; and
• FIG. 9 is an IR spectrometer graph showing acid sites of the cathode active materials of Examples 1 to 3 and Comparative Examples 1 to 3, and acid strength thereof.
• a cathode active material was obtained by the same process as Example 1, except that the dried active material was additionally annealed at 300 °C . And then, a cathode active material, a cathode using the cathode active material, and a coil-shaped battery having the cathode were manufactured the same process as Example 1.
• a cathode active material was obtained by the same process as Example 1, except that the cathode active material prepared only using Al-isopropoxide was additionally annealed at 400 °C . And then, a cathode active material, a cathode using the cathode active material, and a coil-shaped battery having the cathode were manufactured the same process as Example 1.
• a cathode and a coil-shaped battery having the cathode were manufactured the same process as Example 1, except that conventional LiCoO was used as a cathode active material instead of the cathode active material with a treated surface.
• a cathode active material was obtained by the same process as Example 1, except that the cathode active material was prepared only using Al-isopropoxide. And then, a cathode active material, a cathode using the cathode active material, and a coil-shaped battery having the cathode were manufactured the same process as Example 1.
• a cathode active material was obtained by the same process as Example 1, except that the cathode active material was prepared only using CH Si(OCH ) . And then, a cathode active material, a cathode using the cathode active material, and a coil-shaped battery having the cathode were manufactured the same process as Example 1.
• a cathode active material with a surface modified by the organic-inorganic compound obtained by Example 1 was used as a sample, and a conventional cathode active material (i.e., LiCoO ) was used as a control.
• a conventional cathode active material i.e., LiCoO

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