WO2016144144A1 - Batterie secondaire et son procédé de fabrication - Google Patents

Batterie secondaire et son procédé de fabrication Download PDF

Info

Publication number
WO2016144144A1
WO2016144144A1 PCT/KR2016/002486 KR2016002486W WO2016144144A1 WO 2016144144 A1 WO2016144144 A1 WO 2016144144A1 KR 2016002486 W KR2016002486 W KR 2016002486W WO 2016144144 A1 WO2016144144 A1 WO 2016144144A1
Authority
WO
WIPO (PCT)
Prior art keywords
electrode
secondary battery
supports
intermediate layer
salt structure
Prior art date
Application number
PCT/KR2016/002486
Other languages
English (en)
Korean (ko)
Inventor
윤영수
지승현
이강수
Original Assignee
가천대학교 산학협력단
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 가천대학교 산학협력단 filed Critical 가천대학교 산학협력단
Publication of WO2016144144A1 publication Critical patent/WO2016144144A1/fr

Links

Images

Classifications

    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0563—Liquid materials, e.g. for Li-SOCl2 cells
    • 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
    • H01M10/058—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
    • H01M2300/00—Electrolytes
    • 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 a secondary battery and a method for manufacturing the same, and more particularly, to a secondary battery using a liquid electrolyte and a method for manufacturing the same.
  • Power sources for portable electronic devices such as mobile phones, personal digital assistants (PDAs) and portable multimedia players (PMPs); Motor driving power supplies such as high-power hybrid vehicles and electric vehicles; And the use of secondary batteries as power sources for flexible displays, such as electronic ink (e-ink), electronic paper (e-paper), flexible liquid crystal display devices (LCDs), and flexible organic diodes (OLEDs).
  • e-ink electronic ink
  • e-paper electronic paper
  • LCDs flexible liquid crystal display devices
  • OLEDs flexible organic diodes
  • Korean Laid-Open Patent Publication No. 10-2010-0044087 (2010.04.29) or the like is a method of manufacturing an electrode, instead of the conventional slurry coating technique, the electrode for the secondary battery is thin, uniform and flat.
  • a cumbersome process for injecting a liquid electrolyte after forming and packaging the anode and the cathode, respectively, is not performed in one procedure. You have to go through.
  • Patent Document 1 Korean Patent Publication No. 10-2010-0044087
  • the present invention provides a secondary battery and a method of manufacturing the same, which can easily form a liquid electrolyte therein, can prevent electrical conduction between the positive electrode and the negative electrode with a simple structure, and are easy to package.
  • Secondary battery is a current collector to send and receive electrons; A first electrode containing a first active material and formed on the current collector; An electrolyte layer formed on the first electrode; And a second electrode formed on the electrolyte layer, wherein the electrolyte layer comprises: a plurality of supports spaced apart from each other; And it may include a liquid electrolyte provided in the spaced space between the plurality of supports.
  • the plurality of supports may be made of a solid electrolyte.
  • the liquid electrolyte may be formed by dissolving a solid salt structure having a continuous network structure provided in the separation space in a solvent.
  • the electrolyte layer may have a thickness of 1 to 200 ⁇ m.
  • a secondary battery manufacturing method comprises the steps of forming a current collector; Forming a first electrode on the current collector; Forming an intermediate layer on the first electrode, the intermediate layer including a plurality of supports spaced apart from each other and a salt structure provided in a spaced space between the plurality of supports; Forming a second electrode on the intermediate layer; And dissolving the salt structure in a solvent to form a liquid electrolyte.
  • the salt structure may be formed in a continuous network structure, and the plurality of supports may be formed in an isolated shape by the salt structure, respectively.
  • the current collector, the first electrode, the intermediate layer, and the second electrode may all be formed by a printing process.
  • any one selected from the plurality of supports and the salt structure may be formed first, and then the other one may be formed.
  • Forming the intermediate layer can be performed as a procedure.
  • the intermediate layer may be formed by 3D printing using a plurality of inks including the constituents of the plurality of supports and the constituents of the salt structure.
  • the plurality of supports may be formed of a solid electrolyte.
  • the intermediate layer may be formed to a height of 1 to 200 ⁇ m.
  • Secondary battery according to an embodiment of the present invention can easily form a liquid electrolyte therein by forming a salt structure using a salt (for example, lithium salt) and dissolving the salt structure with a solvent. Accordingly, since the salt structure can be formed by a printing technique, it is possible to form all of the current collector, the first electrode, the plurality of supports, the salt structure, and the second electrode at once by 3D printing. As a result, all manufacturing processes can be performed in an inline process, which can shorten the process time and improve productivity and process efficiency. In addition, packaging can be easily performed by packaging one stack formed at a time by 3D printing.
  • a salt for example, lithium salt
  • a plurality of supports are formed between the first electrode and the second electrode to physically block the positive electrode and the negative electrode during the 3D printing process, and to prevent the electrical conduction of the positive electrode and the negative electrode without a thick separator during charge and discharge of the secondary battery.
  • the thickness of the electrolyte layer can be increased by increasing the ratio of the positive electrode or the negative electrode per unit volume, thereby increasing the amount of the active material per unit volume, thereby improving the energy density of the separator.
  • the plurality of supports may be formed of a solid electrolyte to allow ions to move to the plurality of supports, thereby improving the overall ionic conductivity.
  • unit cells of the secondary battery may be stacked. Therefore, since a plurality of unit cells are formed to be stacked by 3D printing, the unit cells and the unit cells can be stacked during the continuous process, thereby increasing the process efficiency and reducing the process time, thereby obtaining a secondary battery having a high energy density.
  • FIG. 1 is a cross-sectional view showing a secondary battery according to an embodiment of the present invention.
  • Figure 2 is a perspective view showing a current collector formed by a secondary battery manufacturing method according to another embodiment of the present invention.
  • FIG 3 is a perspective view illustrating a first electrode formed on a current collector in a method of manufacturing a secondary battery according to another embodiment of the present invention.
  • Figure 4 is a perspective view showing an intermediate layer formed on the first electrode in a secondary battery manufacturing method according to another embodiment of the present invention.
  • FIG. 5 is a perspective view illustrating a second electrode formed on an intermediate layer in a method of manufacturing a secondary battery according to another embodiment of the present invention.
  • Figure 6 is a perspective view of a secondary battery packaged in a packaging material according to a secondary battery manufacturing method according to another embodiment of the present invention.
  • Figure 7 is a perspective view showing one embodiment of a method of forming a plurality of supports and salt structure according to another embodiment of the present invention.
  • FIG. 8 is a perspective view showing a modification of the method of forming a plurality of supports and salt structure according to another embodiment of the present invention.
  • FIG. 1 is a cross-sectional view of a rechargeable battery according to an exemplary embodiment of the present invention.
  • a secondary battery 100 includes a current collector 110 for sending and receiving electrons; A first electrode 120 containing a first active material and formed on the current collector 110; An electrolyte layer 130 formed on the first electrode 120; And a second electrode 140 including a second active material and formed on the electrolyte layer 130.
  • the current collector 110 serves to flow an electric current in a charging / discharging process by exchanging electrons, and may use a conductive substrate having no porous structure or a conductive substrate without holes.
  • the conductive substrate ie, current collector
  • the conductive substrate may be formed using one or more selected from copper, aluminum, stainless steel, molybdenum, tungsten, tantalum, titanium, and nickel.
  • the present invention is not limited thereto, and any electrode can be used as long as the electrode can be formed to have good adhesion on the surface.
  • the current collector 110 preferably has a thin thickness, and may be metal foil, and the thickness thereof may be 1 nm to 30 ⁇ m, preferably 10 ⁇ m to 30 ⁇ m.
  • the current collector 110 is most preferably aluminum foil, and the thickness thereof is preferably 10 ⁇ m to 30 ⁇ m.
  • the current collector 110 may be formed using a printing technique, electroless plating or electrolytic plating.
  • the current collector 110 may form a concave-convex structure or the like on the surface on which the electrode is formed to control the surface roughness, and may further be subjected to UV or plasma surface treatment.
  • the surface energy of the current collector 110 may be increased to increase the uniformity of the electrode when the electrode is formed of a low viscosity ink.
  • the first electrode 120 may contain a first active material and may be formed on the current collector 110.
  • the first electrode 120 may be any one of a positive electrode and a negative electrode, and the first active material may be an active material of any one of the same positive electrode and the negative electrode as the first electrode 120.
  • the first electrode 120 may include a first active material and a conductive agent, and may further include a binder for binding the first active material. When the first electrode 120 is a positive electrode, most of the ceramic-based positive electrode active material used as the positive electrode may be used.
  • lithium-containing cobalt oxide e.g., LiCoO 2
  • lithium-containing nickel cobalt oxide e.g., LiNi 0. 8 Co 0. 2 O 2
  • lithium manganese composite oxide for example, LiM 2 O 4 , LiMnO 2
  • the conductive agent may be acetylene black, carbon black, graphite, or the like as a material for improving conductivity of the active material.
  • the binder may be polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), ethylene propylene diene copolymer (EPDM), styrene butadiene rubber (SBR), or the like.
  • PTFE polytetrafluoroethylene
  • PVdF polyvinylidene fluoride
  • EPDM ethylene propylene diene copolymer
  • SBR styrene butadiene rubber
  • the electrolyte layer 130 may be formed on the first electrode 120, and may include a plurality of supports 131 and spaced apart from each other and a liquid electrolyte 132 provided in a space between the plurality of supports 131. It may include.
  • the plurality of supports 131 are formed to be spaced apart from each other, and provide a space for separating the liquid electrolyte 132 to have a continuous network structure.
  • a separator is required in the electrolyte layer in order to prevent an electrical conduction shape between the positive electrode and the negative electrode.
  • Conventional separators have a thickness of several tens of micrometers, which not only increases the thickness of the electrolyte layer but are also porous membranes. Therefore, when the second electrode is deposited on the separator in a continuous lamination process using a printing process or a thin-thick film process, Through the minute pores, the conductive material of the second electrode may be coated inside the pores of the separator, thereby causing an electrical short. For this reason, conventionally, there was a limitation in manufacturing the entire secondary battery by the printing process.
  • the second electrode 140 is formed on an intermediate layer made of a salt structure 132 provided in a space between the plurality of supports 131 and the plurality of supports 131 spaced apart from each other.
  • This intermediate layer does not contain micropores unlike conventional separators. Accordingly, when the second electrode is formed by the printing process, the conductive material may be coated inside the microcavity to solve a problem in which a short occurs. Details of the intermediate layer will be described later in the secondary battery manufacturing method according to another embodiment of the present invention.
  • ionic conductivity may be controlled through the plurality of supports 131.
  • the thickness of the electrolyte layer 130 may be reduced, and thus, the overall thickness of the secondary battery 100 may be reduced since the electrical conduction of the positive electrode and the negative electrode may be prevented without a thick separator in the electrolyte layer 130.
  • the ratio of the first electrode (or the anode) or the second electrode (or the cathode) per unit volume can be maximized, thereby increasing the amount of the active material per unit volume.
  • the present invention can improve the energy density in the present invention by solving the conventional problem of low energy density.
  • the distance between the positive electrode and the negative electrode can be kept constant by the plurality of supports 131.
  • the plurality of supports 131 may physically block the positive electrode and the negative electrode, printing of the current collector 110, the first electrode 120, the electrolyte layer (or the plurality of supports), and the second electrode 140 may be performed. It can be formed by technique. In particular, the secondary battery 100 can be manufactured easily and simply by 3D printing technique.
  • the plurality of supports 131 may be evenly distributed in the plane of the secondary battery 100 so as to make the distribution of the liquid electrolyte 132 uniform, and may be spaced apart from each other to distribute the force to the space.
  • the space between the plurality of supports 131 is arranged because the plurality of supports 131 are spaced apart from each other even when the plurality of supports 131 are made of a rigid material to support the laminated structure. Liquid electrolyte 132 may be provided. Accordingly, flexibility of the entire secondary battery 100 can be improved without sacrificing flexibility by the plurality of supports 131.
  • the plurality of supports 131 may be made of a solid electrolyte.
  • ions may also move to the plurality of supports 131, thereby improving ion conductivity of the secondary battery 100 than when forming the plurality of supports 131 with an insulating material. You can.
  • the said solid electrolyte is not restrict
  • it may be a single substance or a mixture of two or more selected from the group consisting of molybdenum oxide, titanium oxide, vanadium oxide, chromium oxide, tantalum oxide, zirconium oxide, hafnium oxide, niobium oxide and tungsten oxide.
  • the liquid electrolyte 132 may be formed to have a continuous network structure, and may be provided in a spaced space between the plurality of supports 131. Since the liquid electrolyte 132 has better overall ionic conductivity and transport rate than the solid electrolyte, the liquid electrolyte 132 may be used to improve the ionic conductivity of the secondary battery 100.
  • Examples of the material of the liquid electrolyte 132 include lithium perchlorate (LiClO 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium borofluoride (LiBF 4 ), lithium hexafluoride (LiAsF 6 ), and lithium trifluoromethsulfonate ( LiCF 3 SO 3 ), lithium titanate (Li 4 Ti 5 O 12 ; LTO), lithium iron phosphate (LiFePO 4 ; LFP), bistrifluoromethylsulfonylimide lithium [LiN (CF 3 SO 2 ) 2 ], etc.
  • One or two or more selected from the lithium salts thereof may be dissolved in a solvent and used.
  • lithium borofluoride (LiBF 4 ) can suppress the gas generation during supercharge.
  • the solvent may be a nonaqueous solvent, and a known nonaqueous solvent may be used as a solvent of a lithium secondary battery.
  • PC Propylene carbonate
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • DME 1,2-dimethoxyethane
  • ⁇ -BL ⁇ -butyrolactone
  • THF tetrahydrofran
  • 2-MeTHF 2-methyltetrahydrofran
  • 1,3-dioxolane 1,3-dimethoxypropane
  • vinylene carbonate (VC) etc.
  • a mixed solvent may be used, but is not particularly limited thereto.
  • the solid salt structure is formed to have a continuous network structure, and then a solvent for dissolving the salt is injected into one place.
  • the liquid electrolyte 132 may be formed by allowing a solvent to dissolve all of the salts through a continuous network structure. Accordingly, the liquid electrolyte 132 may be simply formed in the secondary battery 100, and since the solvent may be injected only to one place, the sealing area may be reduced, and thus the sealing process may be facilitated.
  • all the laminates that is, the current collector, the first electrode, the plurality of supports, the salt structure, and the second electrode
  • the liquid electrolyte 132 may be formed by dissolving a solid salt structure having a continuous network structure provided in a spaced space between the plurality of supports 131 in a solvent.
  • the electrolyte layer 130 may have a thickness of 1 to 200 ⁇ m.
  • the thickness of the electrolyte layer 130 is thinner than 1 ⁇ m, a short may be generated without preventing the electrical conduction between the positive electrode and the negative electrode.
  • the thickness of the electrolyte layer 130 is thicker than 200 ⁇ m, the output efficiency may be reduced because the moving distance of the ions is too long and the ion transfer time is long.
  • the ratio of the first electrode (or anode) or the second electrode (or cathode) per unit volume can be maximized, and thus the energy density can be improved because the amount of the active material per unit volume increases. have.
  • the second electrode 140 may contain a second active material and may be formed on the electrolyte layer 130.
  • the second electrode 140 may be the remaining electrode corresponding to the first electrode 120 among the positive electrode and the negative electrode, and the second active material may be determined according to the polarity of the second electrode 140.
  • the second electrode 140 may include a second active material and a conductive agent, and may further include a binder for binding the second active material.
  • the second active material is a conductive polymer such as polyacetal, polyacetylene, or polypyrrole capable of doping lithium ions, coke, carbon fiber, graphite, or mesophase capable of doping lithium ions.
  • Carbon materials such as pitch-based carbon, pyrolytic gaseous materials, and resinous plastics, and carbogen compounds such as titanium disulfide, molybdenum disulfide, and niobium selenide, silicon (Si), tin (Sn), vanadium (V), and titanium (Ti) ), Metal materials such as germanium (Ge), oxides thereof, or two or more compounds can be used.
  • the carbon material may be a graphite carbon material, a carbon material in which the graphite crystal part and the amorphous part are mixed, or a carbon material having a laminated structure in which the crystal layer is irregular.
  • the conductive agent may be acetylene black, carbon black, graphite, or the like as a material for improving conductivity of the active material.
  • the binder may be polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), ethylene propylene diene copolymer (EPDM), styrene butadiene rubber (SBR), or the like.
  • PTFE polytetrafluoroethylene
  • PVdF polyvinylidene fluoride
  • EPDM ethylene propylene diene copolymer
  • SBR styrene butadiene rubber
  • the first electrode 120 is a cathode and the second electrode 140 is an anode
  • the first electrode 120 and the second electrode 140 may be formed on the contrary, but the polarity of each electrode may vary.
  • the active material can be selected accordingly.
  • the current collector 110 may also be formed on the second electrode 140, and the components (that is, the current collector, the first electrode, the plurality of supports, the liquid electrolyte, and the second electrode) which are the base of the secondary battery 100 may be used. ) May be packaged into the exterior material 150.
  • unit cells of the secondary battery 100 may be stacked.
  • FIGS. 2 to 6 are perspective views sequentially showing a secondary battery manufacturing method according to another embodiment of the present invention
  • Figures 7 to 8 is a method of forming a plurality of supports and salt structure according to another embodiment of the present invention. It is a perspective view shown.
  • a secondary battery manufacturing method comprises the steps of forming a current collector; Forming a first electrode on the current collector; Forming an intermediate layer on the first electrode, the intermediate layer including a plurality of supports spaced apart from each other and a salt structure provided in a spaced space between the plurality of supports; Forming a second electrode on the intermediate layer; And dissolving the salt structure in a solvent to form a liquid electrolyte.
  • the current collector 110 serves to flow current by exchanging electrons in a charging / discharging process, and a conductive substrate having a porous structure or a conductive substrate having no hole may be used.
  • the conductive substrate ie, current collector
  • the conductive substrate may be formed using one or more selected from copper, aluminum, stainless steel, molybdenum, tungsten, tantalum, titanium, and nickel.
  • the present invention is not limited thereto, and any electrode can be used as long as the electrode can be formed to have good adhesion on the surface.
  • the current collector 110 may be formed using a printing technique (or 3D printing technique) as well as electroless plating or electrolytic plating. Meanwhile, in the forming of the current collector 110, the step of forming an uneven structure or the like on the surface of the current collector 110 on which the electrode is formed and the UV or plasma surface treatment of the current collector 110 may be further roughened. .
  • the first electrode 120 is formed on the current collector 110 (FIG. 3).
  • the first electrode 120 may include an active material and a conductive agent, and the first electrode 120 may be any one of an anode and a cathode.
  • the first electrode 120 is a positive electrode
  • most of the ceramic-based positive electrode active material used as the positive electrode may be used as the active material.
  • various oxides such as manganese dioxide, lithium manganese composite oxide, lithium-containing nickel oxide, lithium-containing cobalt compound, lithium-containing nickel cobalt oxide, lithium-containing iron oxide, and vanadium oxide containing lithium, titanium disulfide, and molybdenum disulfide And chalcogen compounds.
  • lithium-containing cobalt oxide e.g., LiCoO 2
  • lithium-containing nickel cobalt oxide e.g., LiNi 0. 8 Co 0. 2 O 2
  • lithium manganese composite oxide for example, LiM 2 O 4 , LiMnO 2
  • it may further comprise a binder for binding the active material, the conductive agent and the binder may be contained in a small amount compared to the active material.
  • the intermediate layer 130 is formed on the first electrode 120.
  • the plurality of supports 131 are formed to be spaced apart from each other, and the salt structure is provided in a spaced space between the plurality of supports 131.
  • 132 is formed (FIG. 4).
  • the salt structure 132 may be formed in a continuous network structure, a plurality of supports 131 may be formed in a shape isolated by the salt structure 132, respectively.
  • the solvent capable of dissolving the salt may move as a whole through the continuous network structure, the solvent is injected into one place to simplify the A liquid electrolyte can be formed inside.
  • the sealing area may be reduced, and thus the sealing process may be simplified, and the problem of using a liquid electrolyte in the conventional printing technique may be solved.
  • the salt since the salt may be stacked while maintaining the shape, all the laminates (ie, the current collector, the first electrode, the plurality of supports, the salt structure, and the second electrode) may be formed by a printing technique. Accordingly, it is possible to easily and simply form the laminate which is the basis of the secondary battery by 3D printing.
  • the salt structure 132 may provide a support structure on which the upper stack (eg, the second electrode) can be effectively stacked during the 3D printing process.
  • the salt may include lithium perchlorate (LiClO 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium borofluoride (LiBF 4 ), bisodium hexafluoride (LiAsF 6 ), and lithium trifluoromethsulfonate (LiCF). 3 SO 3 ), lithium titanate (Li 4 Ti 5 O 12 ; LTO), lithium iron phosphate (LiFePO 4 ; LFP), bistrifluoromethylsulfonylimide lithium [LiN (CF 3 SO 2 ) 2 ], and the like. It may be one kind or two or more kinds selected from lithium salts (electrolytes).
  • the solvent may be a non-aqueous solvent, propylene carbonate (PC), ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), 1,2-dimethoxyethane (DME), ⁇ -butyrolactone ( ⁇ -BL), tetrahydrofran (THF), 2-methyltetrahydrofran (2-MeTHF), 1,3-dioxolane, 1,3-dimethoxypropane, vinylene carbonate (VC) and the like
  • PC propylene carbonate
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • DME 1,2-dimethoxyethane
  • ⁇ -BL ⁇ -butyrolactone
  • THF tetrahydrofran
  • 2-MeTHF 2-methyltetrahydrofran
  • 1,3-dioxolane 1,3-dimethoxypropane
  • vinylene carbonate VC
  • the plurality of supports 131 are spaced apart or isolated from each other to provide a space for forming a liquid electrolyte.
  • a thick separator having a thickness of several tens of micrometers was required in order to prevent an electrical conduction shape between the positive electrode and the negative electrode.
  • the ionic conductivity can be adjusted through the plurality of supports 131, It is possible to prevent the electrical conduction between the positive electrode and the negative electrode without a separator.
  • the thickness of the intermediate layer 130 can be increased to increase the ratio of the first electrode (or anode) or the second electrode (or cathode) per unit volume, thereby increasing the amount of active material per unit volume, thereby improving energy density compared to using a separator.
  • the plurality of supports 131 together with the salt structure 132 provides a support structure on which the upper stack (eg, the second electrode) can be effectively stacked during the 3D printing process. It is possible to manufacture a secondary battery.
  • the plurality of supports 131 may be evenly distributed in the plane of the secondary battery 100 so as to make the distribution of the liquid electrolyte uniform, and may be spaced apart from each other to distribute the force to the space.
  • the plurality of supports 131 are made of a rigid material to support the stacked structure, the plurality of supports 131 are spaced apart from each other, so that the liquid electrolyte is disposed in the space between the plurality of supports 131. Since it is provided, flexibility of the entire secondary battery 100 can be improved without sacrificing flexibility by the plurality of supports 131.
  • the plurality of supports 131 may be formed of a solid electrolyte.
  • ions may also move to the plurality of supports 131, thereby improving ion conductivity of the secondary battery 100 than when forming the plurality of supports 131 with an insulating material. You can.
  • the said solid electrolyte is not restrict
  • it may be a single substance or a mixture of two or more selected from the group consisting of molybdenum oxide, titanium oxide, vanadium oxide, chromium oxide, tantalum oxide, zirconium oxide, hafnium oxide, niobium oxide and tungsten oxide.
  • any one of the plurality of supports 131 and the salt structure 132 may be formed, and the other one of the plurality of supports 131 and the salt structure 132 may be formed.
  • the salt structure 132 is first formed to provide a plurality of isolation spaces in which a plurality of supports 131 are formed, and then filled in the provided plurality of isolation spaces. Can be formed. Using this method, it is possible to form the plurality of supports 131 and the salt structure 132 using ink (or printing technique), and simply form the plurality of the supports 131 and the salt structure 132. Can be.
  • a method of providing a plurality of isolation spaces to the salt structure 132 includes a method of stacking only portions except for the plurality of isolation spaces and the method of etching all of the isolation spaces after stacking in a plane.
  • the method is not limited thereto, and the plurality of supports 131 may be formed first, and the salt structure 132 may be formed in the spaced space between the plurality of supports 131. It is sufficient if the intermediate layer 130 including the 131 and the salt structure 132 can be formed.
  • Forming the intermediate layer may be performed as one procedure.
  • the intermediate layer 130 may be formed in a single process, and when the printing technique is used, the intermediate layer 130 may be formed by moving the nozzle 10 in the shortest distance.
  • the intermediate layer 130 may be formed by a 3D printing technique using a plurality of inks including components of each of the plurality of supports 131 and the salt structure 132.
  • the intermediate layer 130 may be formed by 3D printing.
  • the plurality of supports 131 and the salt structure 132 may be formed by using a plurality of nozzles 10. It may be formed, and may have a thickness of the intermediate layer 130 at a time when the nozzle 10 passes.
  • the nozzle 10 may have a thickness of the intermediate layer 130 by stacking continuously varying the height in the z-axis, the formation method is not particularly limited.
  • the intermediate layer 130 When the intermediate layer 130 is formed by the 3D printing technique, the intermediate layer 130 may be easily and quickly formed by moving the shortest distance of the nozzle 10.
  • the intermediate layer 130 may be formed of the plurality of supports 131 and the salt structure 132 to form all the laminates that are the basis of the secondary battery by 3D printing. Accordingly, the secondary battery can be manufactured easily and quickly by 3D printing technique. Accordingly, all manufacturing processes of the secondary battery may be performed in an inline process, and thus, the process time may be shortened, and the productivity and process efficiency of the secondary battery may be improved.
  • the plurality of inks are made of powders of the constituents of the plurality of supports 131 and the constituents of the salt structure 132, and each includes a solvent in which powders of the respective constituents are dissolved or dispersed. It may further include an additive for improving the adhesion and ionic conductivity of.
  • the additive may include at least one or more of a binder, a conductive agent, a humectant, a dispersant, a thickener, and a buffer. In order to perform 3D printing, the ink must maintain an appropriate viscosity, and the additives can be added to prepare an ink having improved conductivity of the active material while maintaining the proper viscosity.
  • the solvent is a deionized water (Deionized water) as a main component, ethanol, methanol, butanol, propanol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, N-methyl-2-pyrrolidone, etc. to control the drying rate
  • deionized water a deionized water as a main component
  • ethanol, methanol, butanol, propanol isopropyl alcohol, isobutyl alcohol, ethylene glycol, N-methyl-2-pyrrolidone, etc.
  • the binder serves to impart a binding force to the ink, may be a binder, polyvinyl alcohol, ethylene-propylene-diene terpolymer, styrene-butadiene rubber, polyvinylidene fluoride (PVDF), polytetrafluoro One or more selected from ethylene, tetrafluoroethylene-hexafluoropropylene copolymer, carboxymethylcellulose (CMC) can be used.
  • the conductive agent may be acetylene black, carbon black, graphite, carbon fiber, carbon nanotube, or the like as a material for improving conductivity.
  • the moisturizing agent serves to prevent the clogging of the nozzle by inhibiting the drying of the ink, glycols, glycerol, pyrrolidone and the like can be used.
  • the dispersant serves to evenly disperse the active material and the conductive agent, and include fatty acid salts, alkyl dicarboxylic acid salts, alkyl sulfate ester salts, polyhydric acid ester alcohol salts, alkylnaphthalene sulfate salts, alkylbenzene sulfate salts, alkyl naphthalene sulfate salts, and alkyl salts.
  • the thickener serves to improve the viscosity
  • ethylene-vinyl alcohol copolymer, cellulose derivative (for example, carboxymethyl cellulose, methyl cellulose) and the like can be used.
  • the buffer is a material that maintains the stability of the ink and adjusts the appropriate pH, it may be used one or more amine compounds selected from trimethylamine, triethanolamine, diethanolamine, ethanolamine or sodium hydroxide, ammonium hydroxide.
  • the stack is formed by using each ink of the stack, and each of the ink is the powder of each component of the stack and the stack It may include a solvent for dissolving or dispersing each component powder.
  • the printer for 3D printing may be a printer that can be controlled by three axes of x, y, and z, and micronozzles and bulk nozzles may be used.
  • a pneumatic controller capable of controlling the ejection speed of the inks may be used.
  • the plurality of supports 131 and the salt structure 132 may be formed to a height of 1 to 200 ⁇ m.
  • the plurality of supports 131 and the salt structure 132 forms the intermediate layer 130 by dissolving the salt structure 132 in a solvent to form a liquid electrolyte.
  • the thickness of the intermediate layer 130 becomes too thin and becomes thinner than 1 ⁇ m, a short may not occur without preventing an electric conduction phenomenon between the positive electrode and the negative electrode.
  • the output distance may be reduced because the moving distance of the ions becomes too long and the ion transfer time is long.
  • the ratio of the first electrode (or anode) or the second electrode (or cathode) per unit volume can be maximized, and the energy density can be improved because the amount of the active material per unit volume increases.
  • the second electrode 140 is formed on the intermediate layer 130 (FIG. 5).
  • the second electrode 140 may include an active material and a conductive agent, and the second electrode 140 may be a remaining electrode corresponding to the first electrode 120 among the positive electrode and the negative electrode.
  • conductive polymers such as polyacetal, polyacetylene, polypyrrole and the like, which are capable of doping lithium ions with an active material, and coke, carbon fiber, graphite, and mesophase pitch system capable of doping lithium ions
  • Carbon materials such as carbon, pyrolytic gaseous carbon materials, resinous plastics, and carbogen compounds such as titanium disulfide, molybdenum disulfide, niobium selenide, silicon (Si), tin (Sn), vanadium (V), titanium (Ti), Metal materials such as germanium (Ge), oxides thereof, or two or more compounds may be used.
  • the carbon material may be a graphite carbon material, a carbon material in which the graphite crystal part and the amorphous part are mixed, or a carbon material having a laminated structure in which the crystal layer is irregular. And it may further comprise a binder (or binder) for binding the active material, the conductive agent and the binder may be contained in a small amount compared to the active material.
  • a binder or binder for binding the active material
  • the conductive agent and the binder may be contained in a small amount compared to the active material.
  • the first electrode 120 is a cathode and the second electrode 140 is an anode
  • the first electrode 120 and the second electrode 140 may be formed on the contrary, but the polarity of each electrode may vary.
  • the active material can be selected accordingly.
  • the current collector 110, the first electrode 120, the intermediate layer 130, and the second electrode 140 may all be formed by a printing process.
  • the intermediate layer 130 is composed of the plurality of supports 131 and the salt structure 132, and the current collector 110, the first electrode 120, the intermediate layer 130, which are the basis of the secondary battery in the printing process, and All of the second electrodes 140 may be formed. Accordingly, the secondary battery can be manufactured easily and quickly by 3D printing technique. Accordingly, all manufacturing processes of the secondary battery may be performed in an inline process, and thus, the process time may be shortened, and the productivity and process efficiency of the secondary battery may be improved.
  • the salt structure 132 is dissolved in a solvent to form a liquid electrolyte.
  • the laminate which is the basis of the secondary battery, may be packaged with the exterior material 150, and a solvent for dissolving the salt structure 132 may be injected into the salt structure 132 to form a liquid electrolyte. have.
  • the injection hole used for injection of the liquid electrolyte is sealed to prevent leakage of the liquid electrolyte after the injection of the solvent.
  • the method may further include forming a current collector 110 on the second electrode 140, and stacking unit cells of the secondary battery 100 to further improve energy density. It may further comprise a step.
  • the exterior member 150 may be formed by 3D printing, or a plurality of unit cells may be formed by 3D printing to be stacked. In this case, the unit cell and the unit cell can be stacked during the continuous process, thus increasing the process efficiency and reducing the process time, and when forming the exterior material 150 by 3D printing, the laminate which is the basis of the secondary battery is sealed.
  • a hole may be formed to form an injection hole for dissolving the salt structure 132.
  • the exterior member 150 may be formed so that the injection hole of the solvent for dissolving the salt structure 132 is formed, and the injection hole is also sealed.
  • the second electrode of one unit cell and the first electrode of another unit cell may be stacked so as to be in contact with each other.
  • the second electrode and the first electrode of another unit cell may be connected. At this time, there is no particular limitation in the method of connecting the second electrode of any one unit cell and the first electrode of the other unit cell.
  • the secondary battery according to an embodiment of the present invention can easily form a liquid electrolyte therein by forming a salt structure using a salt (for example, lithium salt) and dissolving the salt structure with a solvent.
  • Salt structures can be formed by printing techniques.
  • 3D printing can form all of the current collector, the first electrode, the plurality of supports, the salt structure, and the second electrode at once.
  • all manufacturing processes can be performed in an inline process, which can shorten the process time and improve productivity and process efficiency.
  • packaging can be easily performed by packaging one stack formed at a time by 3D printing.
  • a plurality of supports are formed between the first electrode and the second electrode to physically block the positive electrode and the negative electrode during the 3D printing process, and to prevent the electrical conduction of the positive electrode and the negative electrode without a thick separator during charge and discharge of the secondary battery.
  • the thickness of the electrolyte layer can be increased by increasing the ratio of the positive electrode or the negative electrode per unit volume, thereby increasing the amount of the active material per unit volume, thereby improving the energy density of the separator.
  • the plurality of supports may be formed of a solid electrolyte to allow ions to move to the plurality of supports, thereby improving the overall ionic conductivity. Meanwhile, in order to further improve energy density, unit cells of the secondary battery may be stacked.
  • the unit cells and the unit cells can be stacked during the continuous process, thereby increasing the process efficiency and reducing the process time, thereby obtaining a secondary battery having a high energy density.

Abstract

La présente invention porte sur une batterie secondaire comprenant : un collecteur destiné à donner ou accepter des électrons ; une première électrode contenant une première matière active et formée sur le collecteur ; et une couche d'électrolyte formée sur la première électrode ; et une seconde électrode contenant une seconde matière active et formée sur la couche d'électrolyte, la couche d'électrolyte comprenant : une pluralité de supports formés de telle sorte que les supports sont espacés les uns des autres ; et un électrolyte liquide disposé dans les intervalles espacés entre la pluralité de supports.
PCT/KR2016/002486 2015-03-12 2016-03-11 Batterie secondaire et son procédé de fabrication WO2016144144A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2015-0034409 2015-03-12
KR1020150034409A KR101642871B1 (ko) 2015-03-12 2015-03-12 이차전지 및 그 제조방법

Publications (1)

Publication Number Publication Date
WO2016144144A1 true WO2016144144A1 (fr) 2016-09-15

Family

ID=56681062

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2016/002486 WO2016144144A1 (fr) 2015-03-12 2016-03-11 Batterie secondaire et son procédé de fabrication

Country Status (2)

Country Link
KR (1) KR101642871B1 (fr)
WO (1) WO2016144144A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114530605A (zh) * 2022-04-11 2022-05-24 江苏东科新能源材料有限公司 一种用于集流体的高表面能涂液及其应用

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102205542B1 (ko) * 2019-09-05 2021-01-20 경희대학교 산학협력단 스마트 웨어러블 전자장치용 리튬이차전지의 제조방법

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1012212A (ja) * 1996-06-18 1998-01-16 Yuasa Corp 密閉形鉛蓄電池
JP2005339825A (ja) * 2004-05-24 2005-12-08 Nissan Motor Co Ltd 電池一体化回路装置
JP2007257863A (ja) * 2006-03-20 2007-10-04 Nissan Motor Co Ltd リチウムイオン二次電池用電解質層
JP2008103260A (ja) * 2006-10-20 2008-05-01 Idemitsu Kosan Co Ltd 固体電解質シート、電極シート及びそれを用いた全固体二次電池
KR20100017919A (ko) * 2007-05-25 2010-02-16 메사추세츠 인스티튜트 오브 테크놀로지 전지 및 그의 사용을 위한 전극

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20100044087A (ko) 2008-10-20 2010-04-29 삼성전자주식회사 잉크젯 프린트용 전극 조성물, 이를 사용하여 제조된 전극 및 이차 전지

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1012212A (ja) * 1996-06-18 1998-01-16 Yuasa Corp 密閉形鉛蓄電池
JP2005339825A (ja) * 2004-05-24 2005-12-08 Nissan Motor Co Ltd 電池一体化回路装置
JP2007257863A (ja) * 2006-03-20 2007-10-04 Nissan Motor Co Ltd リチウムイオン二次電池用電解質層
JP2008103260A (ja) * 2006-10-20 2008-05-01 Idemitsu Kosan Co Ltd 固体電解質シート、電極シート及びそれを用いた全固体二次電池
KR20100017919A (ko) * 2007-05-25 2010-02-16 메사추세츠 인스티튜트 오브 테크놀로지 전지 및 그의 사용을 위한 전극

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114530605A (zh) * 2022-04-11 2022-05-24 江苏东科新能源材料有限公司 一种用于集流体的高表面能涂液及其应用

Also Published As

Publication number Publication date
KR101642871B1 (ko) 2016-07-26

Similar Documents

Publication Publication Date Title
US9742000B2 (en) Electrode having a dual layer structure, method for manufacturing thereof, and lithium secondary battery comprising the same
WO2016048002A1 (fr) Élément de batterie prismatique comprenant deux éléments de boîtier ou plus
WO2015037867A1 (fr) Électrode au lithium et batterie secondaire au lithium comprenant celle-ci
WO2014185750A1 (fr) Solution électrolytique non aqueuse et batterie rechargeable au lithium comprenant ladite solution
KR101840494B1 (ko) 이차전지용 전극, 이의 제조방법, 이를 포함하는 이차전지
WO2013002497A2 (fr) Batterie secondaire à productivité et sécurité supérieures
CN111712949B (zh) 锂电极以及包含该锂电极的锂二次电池
WO2013157855A1 (fr) Électrolyte pour batterie rechargeable et batterie rechargeable au lithium le comprenant
WO2013157867A1 (fr) Batterie rechargeable au lithium présentant des caractéristiques de régime améliorées
US20240120498A1 (en) Electrode assembly and lithium battery comprising same
KR20160004737A (ko) 전해액 함침용 홀을 포함하고 있는 전지셀
WO2013157857A1 (fr) Électrolyte pour batterie rechargeable et batterie rechargeable le comprenant
KR20160040020A (ko) 전극 조립체 및 이를 포함하는 리튬 이차전지
CN112335073A (zh) 用于锂二次电池的负极、预锂化所述负极的方法和包括所述负极的锂二次电池
US20230282949A1 (en) Three-tab laminated composite battery
US20230335799A1 (en) Electrolyte, secondary battery including such electrolyte, and preparation method of such secondary battery
WO2020153790A1 (fr) Procédé de fabrication d'anode destinée à une batterie secondaire
CN111712950B (zh) 锂电极以及包含其的锂二次电池
WO2021045580A1 (fr) Procédé de pré-sodiation de l'électrode négative, électrode négative présodée et batterie secondaire au lithium la comprenant
EP3316380B1 (fr) Élément de batterie dans lequel le gélifiant d'électrolyte est inclu dans un pore de film de séparation constituant un ensemble électrode
US20210280859A1 (en) Method for manufacturing negative electrode for lithium secondary battery
WO2016144144A1 (fr) Batterie secondaire et son procédé de fabrication
WO2017039149A1 (fr) Liant pour batterie secondaire comprenant un matériau magnétique
WO2019221410A1 (fr) Électrode négative comprenant une couche de protection d'électrode et batterie secondaire au lithium l'utilisant
KR20210120686A (ko) 음극의 제조방법

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16762031

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16762031

Country of ref document: EP

Kind code of ref document: A1