US20110244326A1 - Electrode for secondary battery and manufacturing process for the same - Google Patents

Electrode for secondary battery and manufacturing process for the same Download PDF

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Publication number
US20110244326A1
US20110244326A1 US12/672,887 US67288708A US2011244326A1 US 20110244326 A1 US20110244326 A1 US 20110244326A1 US 67288708 A US67288708 A US 67288708A US 2011244326 A1 US2011244326 A1 US 2011244326A1
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United States
Prior art keywords
electrode
secondary battery
resin
alkoxy group
containing silane
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Abandoned
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US12/672,887
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English (en)
Inventor
Hitotoshi Murase
Toshio Otagiri
Kyoichi Kinoshita
Katsufumi Tanaka
Manabu Miyoshi
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Toyota Industries Corp
Arakawa Chemical Industries Ltd
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Toyota Industries Corp
Arakawa Chemical Industries Ltd
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Assigned to ARAKAWA CHEMICAL INDUSTRIES, LTD., KABUSHIKI KAISHA TOYOTA JIDOSHOKKI reassignment ARAKAWA CHEMICAL INDUSTRIES, LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KINOSHITA, KYOICHI, MIYOSHI, MANABU, MURASE, HITOTOSHI, OTAGIRI, TOSHIO, TANAKA, KATSUFUMI
Publication of US20110244326A1 publication Critical patent/US20110244326A1/en
Abandoned legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • 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
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49002—Electrical device making
    • Y10T29/49108—Electric battery cell making
    • Y10T29/49115—Electric battery cell making including coating or impregnating

Definitions

  • the present invention is one which relates to an electrode for secondary battery, and to a manufacturing process for the same.
  • lithium-ion secondary batteries are secondary batteries, which possess a higher energy density, among those that have been put in practical use. Even among those, the spreading of organic-electrolyte-system lithium-ion secondary batteries (hereinafter being recited simply as “lithium-ion secondary batteries”) has been progressing.
  • lithium-containing metallic composite oxides such as lithium-cobalt composite oxides
  • carbonaceous materials which have a multi-layered structure that enables the insertion of lithium ions between the layers (i.e., the formation of lithium intercalation complex) and the discharge of lithium ions out from between the layers, have been used mainly as an active material for the negative electrode.
  • the positive-electrode and negative-electrode polar plates are made in the following manner: these active materials, and a binder resin are dispersed in a solvent to make a slurry, respectively; then the resulting slurries are applied onto opposite faces of a metallic foil, namely, an electricity collector, respectively; and then the solvent is dry removed to form mixture-agent layers; and thereafter the resulting mixture-agent layers and electricity collector are compression molded with a roller pressing machine.
  • PVdf polyvinylidene fluoride
  • next-generation negative-electrode active materials which possess a charge/discharge capacity that exceeds the theoretical capacity of carbonaceous material
  • materials that include a metal, such as Si or Sn, which is capable of alloying with lithium are regarded prospective.
  • Si or Sn, and so forth for an active material, it is difficult to maintain the bonded state to electricity collector satisfactorily even when the aforementioned fluorinated resin is used for the binder, because the volumetric change of the aforementioned active material that is accompanied by the occlusion/release of Li at the time of charging/discharging is great.
  • Patent Literature No. 1 there is a recitation on a negative electrode for secondary battery that has excellent cyclic performance, and in which the battery reliability at high temperatures is improved by means of binding the following together with a binder, such as polyimide or polyamide-imide, which has been known as a heat-resistant polymer: an active material containing an element that is capable of alloying with lithium; a catalytic element for promoting the growth of carbon nano-fibers; and composite particles containing carbon nano-fibers that have been grown from the active material's surface.
  • a binder such as polyimide or polyamide-imide
  • a binder resinous composition for battery is disclosed, binder resinous composition in which a block copolymer is used, block copolymer in which nonpolar molecular species that do not have any ring on the principal-chain framework, and polar molecular species that have a ring on the principal-chain framework are bonded to each other.
  • Patent Literature No. 1 Japanese Unexamined Patent Publication (KOKAI) Gazette No. 2006-339,092; and
  • Patent Literature No. 2 Japanese Unexamined Patent Publication (KOKAI) Gazette No. 2004-221,014
  • the present invention is one which has been done in view of such circumstances, and it is an object to provide an electrode for secondary battery, electrode in which the active material is suppressed from coming off or falling down from the electricity collector, and which has excellent cyclic performance.
  • an electrode for secondary battery electrode in which the active material is suppressed from coming off or falling down from the electricity collector and which has good cyclic performance, by means of utilizing a specific resin that has not been utilized so far as a binder resin for secondary-battery electrode, that is, an alkoxysilyl group-containing resin that has a structure being specifiedby formula (I), as a binder resin for electrode.
  • an electrode for secondary battery according to the present invention is characterized in that, in an electrode for secondary battery, the electrode being manufactured via an application step of applying a binder resin and an active material onto a surface of electricity collector, said binder resin is an alkoxysilyl group-containing resin that has a structure being specified by formula (I).
  • R 1 is an alkyl group whose number of carbon atoms is from 1 to 8;
  • R 2 is an alkyl group or alkoxyl group whose number of carbon atoms is from 1 to 8.
  • the alkoxysilyl group-containing resin that has a structure being specified by formula (I) is a hybrid composite of resin and silica.
  • the thermal stability becomes higher than that of the resinous simple substance by means of turning into a hybrid composite of resin and silica.
  • said alkoxysilyl group-containing resin has a structure that is specified by formula (I).
  • the structure that is specified by formula (I) is a structure that is made of parts having undergone sol-gel reaction, and accordingly indicates that unreacted parts that undergo a sol-gel reaction remain. Consequently, the sol-gel reaction also occurs when the binder resin cures, and thereby not only the parts having undergone sol-gel reaction react with each other but also react with the resin's OH groups. Moreover, they are believed to react with the electricity collector's surface as well. Therefore, it is possible to retain the electricity collector and the active material firmly to each other.
  • alkoxysilyl group-containing resin it is possible the following can be used: an alkoxy group-containing silane-modified bisphenol type-A epoxy resin, an alkoxy group-containing silane-modified novolac-type epoxy resin, an alkoxy group-containing silane-modified acrylic resin, an alkoxy group-containing silane-modified phenolic resin, an alkoxy group-containing silane-modified polyamic acid resin, an alkoxy group-containing silane-modified soluble polyimide resin, an alkoxy group-containing silane-modified polyurethane resin, or an alkoxy group-containing silane-modified polyamide-imide resin.
  • said alkoxysilyl group-containing resin can be adapted into an alkoxy group-containing silane-modified polyamic acid resin or an alkoxy group-containing silane-modified polyamide-imide resin. Since the aforementioned alkoxysilyl group-containing resins not only exhibit good workabilitybut also can be handled simplyand easily, the workability improves furthermore.
  • an electrode for secondary battery according to the present invention is characterized in that, in an electrode for secondary battery, electrode in which an active material is bound on a surface of electricity collector by way of a binder, said binder is an alkoxysilyl group-containing resinous cured substance that has a structure being specified by formula (II):
  • R 1 designates an alkyl group or aryl group whose number of carbon atoms is 8 or less.
  • alkoxysilyl group-containing resinous cured substance it is possible to use the following: an alkoxy group-containing silane-modified bisphenol type-A epoxy resinous cured substance, an alkoxy group-containing silane-modified novolac-type epoxy resinous cured substance, an alkoxy group-containing silane-modified acrylic resinous cured substance, an alkoxy group-containing silane-modified phenolic resinous cured substance, an alkoxy group-containing silane-modified polyimide resinous cured substance, an alkoxy group-containing silane-modified soluble polyimide resinous cured substance, an alkoxy group-containing silane-modifiedpolyurethane resinous cured substance, or an alkoxy group-containing silane-modified polyamide-imide resinous cured substance.
  • the electrode for secondary battery can be an electrode for lithium-ion secondary battery.
  • the active material can also be one which includes carbon.
  • the electricity collector can comprise copper or aluminum, and that the active material can even be one which includes metal or metallic oxide that is capable of alloying with lithium.
  • the metal or metallic oxide that is capable of alloying with lithium includes Si and/or Sn
  • the aforementioned binder resin by means of using the aforementioned binder resin, it is possible to inhibit the active-material particles from pulverizing finely or detaching, namely, the drawback that results from the following fact: the active material exhibits a considerably great rate of volumetric change being accompanied by the insertion and elimination of lithium so that it expands and contracts repeatedly by means of charge/discharge cycle.
  • a manufacturing process for electrode for secondary battery is a manufacturing process for electrode for secondary battery, the manufacturing process comprising: an application step of applying a binder resin and an active material onto a surface of electricity collector; and a curing step of curing said binder resin and then binding said active material on said electricity-collector surface, and it is characterized in that said binder resin is an alkoxysilyl group-containing resin that has a structure being specified by formula (I).
  • the active material is suppressed from coming off or falling down from the electricity collector by means of utilizing an alkoxysilyl group-containing resin, which has a structure being specified by formula (I), as the binder resin for electrode, and thereby it is possible for the present electrode to exhibit excellent cyclic performance.
  • FIG. 1 illustrates a partial schematic explanatory diagram of an electrode for secondary battery
  • FIG. 2 illustrates a graph for comparing cyclic characteristics regarding batteries, in which negative electrodes according to Example Nos. 1 and 2 were used, with those regarding batteries, in which negative electrodes according to Comparative Example Nos. 1 and 2 were used;
  • FIG. 3 illustrates a graph for comparing a first-cycle charge/discharge curb regarding the battery, in which the negative electrode according Example No. 1 was used, in a cyclic test, with that regarding the battery, in which the negative electrode according to Comparative Example No. 2 was used, in that test.
  • An electrode for secondary battery according to the present invention is one which is manufactured via an application step of applying a binder resin and an active material onto a surface of electricity collector.
  • a secondary battery that has such a construction the following can be given: nickel-zinc secondary batteries; lithium-ion secondary batteries; silver oxide secondary batteries; and nickel-hydrogen secondary batteries.
  • the “applying” means that it is allowable that a binder resin, and an active material can be put onto an electricity collector.
  • an application method it is possible to use the following application methods that have been used generally when making electrodes for secondary battery: roll coating methods; dip coating methods; doctor blade methods; spray coating methods; and curtain coating methods.
  • the “electricity collector” refers to a chemically-inactive highly-electron-conductive body for keeping electric current flowing to electrodes during discharging or charging.
  • the electricity collector is formed as a configuration, such as a foil or plate that is formed of said highly-electron-conductive body.
  • the configuration is not limited to above especially as far as it is a configuration that fits for the objective.
  • the electricity collector it is possible to name copper foils, aluminum foils, and the like, for instance.
  • the “active material” refers to a substance that contributes directly to electrode reactions, such as charging reactions and discharging reactions.
  • the substance that makes the active material differs depending on the types of secondary battery, it is not limited especially as far as being one into which substances that fit the objective of that secondary battery are inserted and from which those substances are released reversibly by means of charging/discharging.
  • the active material that is used in the present invention has a powdery configuration, and is applied and then bound on the electricity collector's surface by way of the binder resin. Although the powder differs depending on batteries that are aimed for, it is preferable that the particle diameter can be 10 ⁇ m or less.
  • lithium-containing metallic composite oxides such as lithium-cobalt composite oxides, lithium-nickel composite oxides and lithium-manganese composite oxides
  • an active material for the positive electrode can be used as for an active material for the positive electrode.
  • an active material for the negative electrode the following can be used: carbonaceous materials that are capable of occluding and releasing lithium; and metals, which are capable of turning lithium into alloy, or oxides of these, and the like. It is possible to use these active materials independently, or it is possible to combine two or more species of them to use.
  • the metals that are capable of turning lithium into alloy the following can be given: Al, Si, Zn, Ge, Cd, Sn, Pb, and so forth.
  • Si and Sn are effective.
  • a theoretical capacity of carbon is 372 mAhg ⁇ 1
  • theoretical capacities of Si, Ge and Sn, which are the metals that are capable of alloying with lithium are 4,200 mAhg ⁇ 1 , 1,620 mAhg ⁇ 1 and 994 mAhg ⁇ 1 , respectively.
  • the alloyable metals, or oxides of these exhibit considerably great rates of volumetric change that is accompanied by the insertion and elimination of lithium, compared with those of the carbonaceous materials.
  • a composite powder of metals that are capable of turning lithium into alloy, or oxides thereof, and the like, can be produced by mean of mechanical alloying method.
  • mechanical alloying method it is feasible to form fine primary particles whose particle diameters are from 10 to 200 nm approximately with ease.
  • a composite powder namely, an active material that is aimed at, by means of setting the primary particle diameter to from 10 to 200 nm approximately by the following: mixing a raw-material substance comprising a plurality of components; and then carrying out a mechanical alloying treatment.
  • a centrifugal acceleration (or input energy) in the mechanical alloying treatment can be from 5 to 20 G approximately, and it is more preferable that it can be from 7 to 15 G approximately.
  • the conductive additive is one which is added in order to enhance electric conductivity when the active material is bound on the electricity collector by way of the binder resin.
  • the conductive additive it is allowable to add the following, namely, carbonaceous fine particles: carbon black, graphite, acetylene black, KETJENBLACK, carbon fibers, and the like, independently; or to combine two or more species of them to add.
  • the binder resin is used as a binding agent when applying these active material and conductive additive to the electricity collector. It is required for the binding resin to bind the active material and conductive additive together in an amount as less as possible, and it is desirable that that amount can be from 0.5% by weight to 50% by weight of a summed total of the active material, the conductive additive, and the binder resin.
  • the binder resin according to the present invention is an alkoxysilyl group-containing resin that has a structure being specified by formula (I).
  • the structure that is specified by formula (I) includes a structure that is made of parts having undergone sol-gel reaction, and the alkoxysilyl group-containing resin makes a hybrid composite of resin and silica.
  • the “structure that is made of parts having undergone sol-gel reaction” is a structure that contributes to reactions in carrying out sol-gel process.
  • the “sol-gel process” is process in which a solution of inorganic or organic metallic salt is adapted into a starting solution; and the resultant solution is turned into a colloid solution (Sol) bymeans of hydrolysis and condensation polymerization reactions; and then a solid (Gel) that has lost flowability is formed by facilitating the reactions furthermore.
  • metallic alkoxides i.e., compounds that are expressed by M(OR) X where “M” is a metal and “R” is an alkyl group) are adapted into a raw material in the sol-gel process.
  • the binder resin can react not only between parts having undergone sol-gel reaction but also with the resin's OH groups at the time of curing binder resin, because of having a structure, which is made of parts that have undergone sol-gel reaction, as indicated by formula (I). Moreover, the binder resin exhibits good adhesiveness to the electricity collector, active material and conductive additive, namely, inorganic components, because of being a hybrid composite of resin and silica, and consequently it is possible to retain the active material and conductive additive on the electricity collector firmly.
  • the resin that makes a hybrid composite with silica the following can be given: bisphenol type-A epoxy resins, novolac-type epoxy resins, acrylic resins, phenolic resins, polyamic acid resins, soluble polyimide resins, polyurethane resins, or polyamide-imide resins.
  • the binder resin has a structure that is specified by formula (I), and this indicates such a state that parts that have undergone sol-gel reaction still remain therein. Therefore, it is possible for the binder resin to react not only between the parts that have undergone sol-gel reaction but also with the resin's OH groups at the time of curing binder resin by adapting the binder resin into an alkoxysilyl group-containing resin that has a structure being specified by formula (I).
  • the binder resin can be formed by reacting precursors, namely, a polyamic acid comprising a carboxylic-acid-anhydride component and a diamine component, and an alkoxysilane partial condensate.
  • precursors namely, a polyamic acid comprising a carboxylic-acid-anhydride component and a diamine component
  • alkoxysilane partial condensate it is possible to use those which are obtained by condensing hydrolysable alkoxysilane monomers partially in the presence of acid or base catalyst and water.
  • the alkoxy group-containing silane-modified polyamic acid resin can be formed as follows: the alkoxysilane partial condensate is reacted with an epoxy compound in advance to turn it into an epoxy group-containing alkoxysilane partial condensate; and the resulting epoxy group-containing alkoxysilane partial condensate is then reacted with the polyamic acid.
  • binder resin it is possible to use commercial products suitably.
  • various commercial products are available as follows: “COMPOCERAN E (product name)” (produced by ARAKAWA CHEMICAL INDUSTRIES, LTD.), namely, an alkoxy group-containing silane-modified bisphenol type-A epoxy resin or alkoxy group-containing silane-modified novolac-type epoxy resin; “COMPOCERAN AC (product name)” (produced by ARAKAWA CHEMICAL INDUSTRIES, LTD.), namely, an alkoxy group-containing silane-modified acrylic resin; “COMPOCERAN P (product name)” (produced by ARAKAWA CHEMICAL INDUSTRIES, LTD.), namely, an alkoxy group-containing silane-modified phenolic resin; “COMPOCERAN H800 (product name)” (produced by ARAKAWA CHEMICAL INDUSTRIES, LTD.), namely, an alkoxy group-containing silane-modified polyamic acid resin
  • an electrode for secondary battery according to the present invention is an electrode for secondary battery, electrode in which an active material is bound on a surface of electricity collector. It is allowable that a conductive additive can also be bound on the surface of electricity collector together with the active material.
  • the electricity collector, active material and conductive additive are those which are the same as those being aforementioned.
  • the structure that is specified by formula (II) is a structure that is made of gelated fine silica parts (or a high-order network structure with siloxane bonds).
  • This structure is a structure of organic silicone polymer that comprises siloxane bonds, and is a structure that is obtainable by means of the polycondensation of silanol according to following equation (C).
  • alkoxysilyl group-containing resinous cured substance it is possible to use the following: alkoxy group-containing silane-modified bisphenol type-A epoxy resinous cured substances, alkoxy group-containing silane-modified novolac-type epoxy resinous cured substances, alkoxy group-containing silane-modified acrylic resinous cured substances, alkoxy group-containing silane-modified phenolic resinous cured substances, alkoxy group-containing silane-modified polyimide resinous cured substances, alkoxy group-containing silane-modified polyurethane resinous cured substances, or alkoxy group-containing silane-modified polyamide-imide resinous cured substances.
  • This binder corresponds to cured substances of the above-explained binder resins.
  • a manufacturing process according to the present invention for electrode for secondary battery comprises an application step, and a curing step.
  • the application step is a step of applying a binder resin and an active material onto a surface of electricity collector. Moreover, it is also permissible to apply a conductive additive together with them at the application step.
  • the curing step is a step of curing said binder resin and then binding said active material on said electricity-collector surface.
  • Said binder resin is characterized in that it is an alkoxysilyl group-containing resin that has a structure being specified by formula (I).
  • the curing step is a step of curing the binder resin, namely, an alkoxysilyl group-containing resin.
  • the active material is bound on the electricity-collector surface by means of curing the binder resin.
  • the conductive additive is also bound thereon similarly. It is permissible that the curing of the binder resin can be done in conformity to the curing condition of a binder resin to be made use of.
  • a sol-gel curing reaction also occurs, sol-gel reaction which results from the structure being specified by formula (I) that the binder resin has.
  • An alkoxysilyl group-containing resin in which the sol-gel curing reaction has occurred exhibits good adhesiveness to the active material, conductive additive and electricity collector, because it has a structure that is made of gelated fine silica parts (or a high-order network structure with siloxane bonds).
  • FIG. 1 A partial schematic explanatory diagram of an electrode for secondary battery according to the present invention is illustrated in FIG. 1 .
  • An example of the electrode for secondary battery according to the present invention is one in which active materials 2 , and conductive additives 3 are bound on a surface of electricity collector 1 by way of binder resins 4 .
  • the binder resins 4 are dispersed between the dispersed active materials 2 and the dispersed conductive additives 3 , and make such a state that they join the active materials 2 , conductive additives 3 and electricity collector 1 one another to put them together. Since FIG. 1 is a schematic drawing, the drawn configurations are not correct ones. Although the binder resins 4 are depicted as a powdery configuration in FIG.
  • the entire surface of the electricity collector 1 is not covered with the binder resins 4 , the active materials 2 and/or the conductive additives 3 completely, but minute pores exist between the respective substances and the surface of the electricity collector 1 here and there.
  • the electrode for secondary battery according to the present invention was made as follows, and then a discharging cyclic test was carried out using a model battery for evaluation. In the test, the negative electrode of lithium-ion secondary battery was adapted into an electrode to be evaluated, and a coin-shaped lithium-ion secondary battery was used.
  • Example No. 1 Example No. 2, Comparative Example No. 1, and Comparative Example No. 2
  • Si powder As an active material, an Si powder was used, Si powder whose discharge capacity was large, and whose particle diameters were about 4 ⁇ m or less. Although Si powder is good in terms of the discharge capacity compared with that of the other active materials, it is likely to come off from electricity collectors because of the expansion of its own particles; moreover, it has fallen down from them because the active materials are pulverized finely due to volumetric expansion that results from charging/discharging, and thereby the discharge capacity declines sharply at the time of cyclic test.
  • Si particles produced by KO-JUNDO KAGAKU
  • 4- ⁇ m-or-less particle diameters were made use of as they were.
  • Example No. 1 an alkoxy group-containing silane-modified polyamide-imide resin was used, alkoxy group-containing silane-modified polyamide-imide resin which was produced by ARAKAWA CHEMICAL INDUSTRIES, LTD.; whose product name was COMPOCERAN; whose product number was H901-2; whose solvent composition was NMP/xylene (or Xyl); which had cured residuals in an amount of 30%; which exhibited a viscosity of 8,000 mPa ⁇ s; and which had silica in an amount of 2% by weight in the cured residuals (note herein that the “cured residuals” means solid contents after removing the volatile components by curing the resinous components).
  • the alkoxy group-containing silane-modified polyamide-imide resin that was used in Example No. 1 was one of aforementioned COMPOCERAN (product name) H900-series products, and had a structure that is specified in above (Chemical Formula 7).
  • Example No. 2 an alkoxy group-containing silane-modified polyamic acid resin was used, alkoxy group-containing silane-modified polyamic acid resin which was produced by ARAKAWA CHEMICAL INDUSTRIES, LTD.; whose product name was COMPOCERAN; whose product number was H850D; whose solvent composition was N,N-dimethylacetamide (DMAc); which had cured residuals in an amount of 15%; which exhibited a viscosity of 5,000 mPa ⁇ s; and which had silica in an amount of 2% by weight in the cured residuals.
  • the alkoxy group-containing silane-modified polyamic acid resin that was used in Example No. 2 was one of aforementioned COMPOCERAN (product name) H800-series products, and had a structure that is specified in above (Chemical Formula 6).
  • Comparative Example No. 1 PVdF (produced by KUREHA) was used.
  • Comparative Example No. 2 a polyamide-imide resin (produced by ARAKAWA CHEMICAL INDUSTRIES, LTD.) was used.
  • the slurries are put on an electrolytic copper foil with 20- ⁇ m thickness, and were then formed as a film on the copper foil, respectively, using a doctor blade.
  • an electricity collector which comprised the electrolytic copper foil, and negative-electrode layers, which comprised the aforementioned complex powders, were joined together firmly by means of adhesion with a roller pressing machine. These were punched out with a 1-cm 2 circular punch, and were then adapted into an electrode with 100- ⁇ m-or-less thickness by vacuum drying them as follows, respectively: at 200° C. for 3 hours in Example No. 1 and Example No. 2; at 140° C. for 3 hours in Comparative Example No. 1; and at 200° C. for 3 hours in Comparative Example No. 2.
  • the coin-shaped model batteries were made by overlapping a spacer, an Li foil with 500- ⁇ m thickness making a counter electrode, a separator (“Celgard #2400” (trademark name) produced by CELGARD, LLC), and the evaluation electrodes in this order, and then subjecting them to a crimping process.
  • model batteries were discharged at a constant electric current of 0.2 mA until reaching 0 V, and were then charged at a constant electric current of 0.2 mA until reaching 2.0 V after having a 5-minute intermission. These were considered 1 cycle, and the charging/discharging was carried out repeatedly to examine their discharge capacities.
  • FIG. 2 illustrates a graph that shows the number of the cycles and the discharge capacities which are relevant to the model batteries according to the respective examples and comparative examples. It is apparent from FIG. 2 that the decrease magnitudes of the initial discharge capacity were small in the batteries in which the respective examples were adapted into the evaluation electrode, compared with those of the batteries in which the respective comparative examples were adapted into the evaluation electrode.
  • Comparative Example No. 1 As specified by Comparative Example No. 1, in the electrode that used PVdF, namely, a conventional binder resin, the discharge capacity dropped sharply to almost 10% approximately after being subjected to the cyclic test once, whereas the discharge capacities were maintained as much as from 70% to 80% approximately in Example No. 1 and Example No. 2. Besides, it is understood that the after-20-cycle discharge capacities of Comparative Example No. 1 and Comparative Example No. 2 were 0, whereas the afer-20-cycle discharge capacity was also maintained as much as 10% or more in Example No. 2.
  • the first-round discharge capacity exceeded 3,000 mAh/g. It is remarkable that the discharge capacity remained as much as 375 mAh/g approximately after 20 cycles in Example No. 2, because the first-round discharge capacity was 400 mAh/g or less usually in the case of using graphite as the active material.
  • Example No. 1 and Comparative Example No. 2 made one which comprised the polyamide-imide resin into which silica was incorporated, and another one which comprised the polyamide-imide resin into which no silica was incorporated, respectively. As illustrated in FIG. 2 , it is possible to see that the discharge characteristic of Example No. 1 was superior to the discharge characteristic of Comparative Example No. 2.
  • FIG. 3 illustrates a comparison between the charge/discharge curves at the first cycle in the cyclic test.
  • Example No. 1 comprised the binder resin into which silica was incorporated in an amount of 2%
  • Comparative Example No. 2 comprised the binder resin into which no silica was incorporated.
  • FIG. 3 when comparing the first-cycle discharge characteristic of Example No. 1 with that of Comparative Example No. 2, it is possible to see that the former was superior to the latter almost doubly.

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120177992A1 (en) * 2009-09-25 2012-07-12 Kabushiki Kaisha Toyota Jidoshokki Negative electrode for lithium-ion secondary battery and manufacturing process for the same
US20120244435A1 (en) * 2009-12-24 2012-09-27 Kabushiki Kaisha Toyota Jidoshokki Negative electrode for lithium-ion secondary battery
US20140099542A1 (en) * 2011-05-23 2014-04-10 Kabushiki Kaisha Toyota Jidoshokki Lithium ion secondary battery electrode, manufacturing process for the same, and lithium ion secondary battery using the electrode
US20140186704A1 (en) * 2011-05-23 2014-07-03 Kabushiki Kaisha Toyota Jidoshokki Lithium ion secondary battery electrode, manufacturing process for the same, and lithium ion secondary battery using the electrode
US20170117550A1 (en) * 2014-06-12 2017-04-27 Sumitomo Metal Mining Co., Ltd. Coated lithium-nickel composite oxide particles and method for producing coated lithium-nickel composite oxide particles
US9725590B2 (en) 2012-09-17 2017-08-08 Korea Institute Of Industrial Technology Epoxy compound having alkoxysilyl group, method for preparing the same, composition including the same, cured product made from the composition, and use of the composition
US10424791B2 (en) * 2007-08-10 2019-09-24 Arakawa Chemical Industries, Ltd Process for manufacturing electrode for secondary battery
US11424439B2 (en) 2016-11-25 2022-08-23 Dai-Ichi Kogyo Seiyaku Co., Ltd. Negative electrode of nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery
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Families Citing this family (16)

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Publication number Priority date Publication date Assignee Title
US20110031935A1 (en) * 2008-04-18 2011-02-10 Kabushiki Kaisha Toyota Jidoshokki Negative electrode for lithium-ion secondary battery and manufacturing process for the same
JP5316862B2 (ja) * 2009-02-04 2013-10-16 株式会社豊田自動織機 リチウムイオン二次電池用負極及びその製造方法
JP5431829B2 (ja) * 2009-08-17 2014-03-05 株式会社豊田自動織機 非水系二次電池用負極および非水系二次電池
JP5678419B2 (ja) * 2009-08-27 2015-03-04 日産自動車株式会社 電池用電極およびその製造方法
JP5360485B2 (ja) * 2009-09-16 2013-12-04 株式会社豊田自動織機 リチウムイオン二次電池用負極及びその製造方法
JP5130273B2 (ja) 2009-10-14 2013-01-30 株式会社豊田自動織機 非水系二次電池用負極およびその製造方法
JPWO2011074439A1 (ja) * 2009-12-16 2013-04-25 東洋紡株式会社 リチウムイオン二次電池用負極およびこれを用いたリチウムイオン二次電池
JP5626644B2 (ja) * 2010-11-18 2014-11-19 三洋電機株式会社 リチウム二次電池負極用バインダー、リチウム二次電池用負極、リチウム二次電池、リチウム二次電池負極用バインダー前駆体溶液及びリチウム二次電池用負極の製造方法
JP2012186119A (ja) * 2011-03-08 2012-09-27 Toyota Industries Corp 二次電池用負極合材、二次電池用負極、二次電池及びこれを用いた車両
WO2012153469A1 (ja) 2011-05-12 2012-11-15 株式会社豊田自動織機 リチウムイオン二次電池用電極、その製造方法及びその電極を用いたリチウムイオン二次電池
JP2013175313A (ja) * 2012-02-24 2013-09-05 Toyota Industries Corp リチウムイオン二次電池および車両
JP2013191327A (ja) * 2012-03-13 2013-09-26 Toyota Industries Corp 非水電解質二次電池および車両
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DE102012022607A1 (de) * 2012-11-19 2014-05-22 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Feststoff-/Gelelektrolyt-Akkumulator mit Binder aus anorganisch-organischem Hybridpolymer und Verfahren zu dessen Herstellung
JP6318859B2 (ja) * 2014-05-29 2018-05-09 株式会社豊田自動織機 銅含有シリコン材料及びその製造方法と負極活物質及び二次電池
CN110474052B (zh) * 2019-07-29 2022-09-02 湖南文理学院 一种锂离子电池电极材料及制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030104131A1 (en) * 2001-12-03 2003-06-05 Hidetaka Konno Preparation of C/Si/O composite material
US20040058240A1 (en) * 2002-09-20 2004-03-25 3M Innovative Properties Company Anode compositions having an elastomeric binder and an adhesion promoter
US20050214644A1 (en) * 2004-03-26 2005-09-29 Shin-Etsu Chemical Co., Ltd. Silicon composite particles, preparation thereof, and negative electrode material for non-aqueous electrolyte secondary cell

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5129007A (ja) * 1974-09-05 1976-03-11 Fujitsu Ltd Jidokeiyakusaabisuhoshiki
JPS5136180A (de) * 1974-09-21 1976-03-26 Kiichi Yamamoto
US5571638A (en) * 1993-09-30 1996-11-05 Sumitomo Chemical Company Limited Lithium secondary battery
JPH11130539A (ja) 1997-10-29 1999-05-18 Dow Corning Asia Kk 錫含有酸炭化ケイ素セラミック物質及びそれを用いたリチウム電池用電極物質並びにそれらの製造方法
JP2000223112A (ja) * 1999-02-02 2000-08-11 Mitsubishi Paper Mills Ltd 負極とリチウム２次電池及びその製造方法
JP2000223126A (ja) * 1999-02-02 2000-08-11 Mitsubishi Paper Mills Ltd 電極及びその製造方法
JP2001068115A (ja) * 1999-08-27 2001-03-16 Hitachi Chem Co Ltd 非水溶媒系バインダ組成物、電極の製造法、電極及び非水溶媒系二次電池
JP3669429B2 (ja) 2001-03-27 2005-07-06 信越化学工業株式会社 電極用組成物及び電極材
US7491467B2 (en) * 2002-12-17 2009-02-17 Mitsubishi Chemical Corporation Negative electrode for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery using the same
JP2004221014A (ja) 2003-01-17 2004-08-05 Hitachi Chem Co Ltd ブロック共重合体を用いた電池用バインダ樹脂組成物、電極及び電池
CN100591184C (zh) * 2004-03-15 2010-02-17 新日铁化学株式会社 有机电致发光元件
JP4623283B2 (ja) * 2004-03-26 2011-02-02 信越化学工業株式会社 珪素複合体粒子及びその製造方法並びに非水電解質二次電池用負極材
JP2006059558A (ja) * 2004-08-17 2006-03-02 Shin Etsu Chem Co Ltd 電気化学蓄電デバイス及びその製造方法
WO2006052313A1 (en) * 2004-11-08 2006-05-18 3M Innovative Properties Company Polyimide electrode binders
JP2006339092A (ja) 2005-06-06 2006-12-14 Matsushita Electric Ind Co Ltd 非水電解液二次電池およびその負極
JP5128873B2 (ja) * 2007-08-10 2013-01-23 株式会社豊田自動織機 二次電池用電極及びその製造方法
US20110031935A1 (en) * 2008-04-18 2011-02-10 Kabushiki Kaisha Toyota Jidoshokki Negative electrode for lithium-ion secondary battery and manufacturing process for the same
JP5129007B2 (ja) * 2008-04-18 2013-01-23 株式会社豊田自動織機 リチウムイオン二次電池用負極及びその製造方法
JP5136180B2 (ja) * 2008-04-18 2013-02-06 株式会社豊田自動織機 リチウムイオン二次電池の充電制御方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030104131A1 (en) * 2001-12-03 2003-06-05 Hidetaka Konno Preparation of C/Si/O composite material
US20040058240A1 (en) * 2002-09-20 2004-03-25 3M Innovative Properties Company Anode compositions having an elastomeric binder and an adhesion promoter
US20050214644A1 (en) * 2004-03-26 2005-09-29 Shin-Etsu Chemical Co., Ltd. Silicon composite particles, preparation thereof, and negative electrode material for non-aqueous electrolyte secondary cell

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Rossi, Nicholas A. A.; Zhang, Zhengcheng; Wang, Qingzheng; Amine, Khalil; West, Robert, Oligo(ethylene oxide)-functionalized siloxanes: decreasing viscosity and increasing conductivity, 2005, American Chemical Society, Division of Polymer Chemistry, 46(1), 723-724 *

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US20170117550A1 (en) * 2014-06-12 2017-04-27 Sumitomo Metal Mining Co., Ltd. Coated lithium-nickel composite oxide particles and method for producing coated lithium-nickel composite oxide particles
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