KR101832252B1 - Anode structure for secondary battery and method of manufacturing the same - Google Patents

Abstract

Disclosed is a negative electrode for a secondary battery having a high capacity and a high efficiency of charge / discharge characteristics by preventing cracking and dropping of the negative electrode active material structure by alleviating the volume change, thereby improving the cycle characteristics of the secondary battery. A negative electrode for a secondary battery according to an embodiment of the present invention includes: a negative electrode collector; A plurality of negative electrode active material structures disposed on the negative electrode collector such that one end thereof is in contact with one end and the other end extends from the negative electrode collector in a predetermined direction; A fixed layer disposed between the lower regions of the plurality of negative electrode active material structures on the negative electrode collector to fix the plurality of negative electrode active material structures on the negative electrode collector, the fixed layer comprising a polymer material; And a porous packing layer disposed between the plurality of anode active material structures on the pinned layer to fill a space between the plurality of anode active material structures and having pores and including a polymer material.

Description

[0001] The present invention relates to a negative electrode for a secondary battery, and an anode structure for a secondary battery,

TECHNICAL FIELD The present invention relates to a secondary battery, and more particularly, to a negative electrode for a secondary battery capable of providing high capacity and high efficiency charging / discharging characteristics, and a method of manufacturing the same.

Recently, the lithium secondary battery has been used as a power source for portable electronic products including mobile phones and notebook computers, as well as being used as a medium and large power source for hybrid electric vehicles (HEV) and plug-in hybrid electric vehicles (plug-in HEV) Applications are rapidly expanding. The lithium secondary battery can provide a high voltage of about 3.7 V and has a higher energy density than other secondary batteries such as a nickel cadmium battery and thus can be miniaturized and can be recharged by repeated charging It is environmentally friendly because it does not contain environmentally regulated substances such as cadmium, lead, and mercury, and has a long lifetime because it can be charged and discharged more than 500 times.

The lithium secondary battery uses a material capable of intercalation and deintercalation of lithium ions as a cathode and an anode and generates electricity or consumes electricity by redox reaction by insertion and desorption of lithium ions at the cathode and anode do. Graphite, which is a negative electrode active material widely used in conventional lithium secondary batteries, has a layered structure and is very useful for insertion and desorption of lithium ions. Theoretically, graphite has a capacity of 372 mAh / g, but with the recent increase in demand for high capacity lithium batteries, a new electrode capable of replacing graphite is required.

Researches for the commercialization of an electrode active material that forms an electrochemical alloy with lithium ions such as silicon (Si), tin (Sn), antimony (Sb), and aluminum (Al) as a high capacity negative electrode active material have been actively conducted . However, silicon, tin, antimony, aluminum and the like have the characteristics of increasing / decreasing the volume during charging / discharging through the formation of an electrochemical alloy with lithium. The volume change due to such charging / Has the problem that the electrode cycle characteristics are deteriorated in the electrode in which the active material is introduced. Also, such a change in volume causes cracks on the surface of the electrode active material, and continuous crack formation causes undifferentiation of the surface of the electrode, thereby deteriorating cycle characteristics.

Accordingly, it is an object of the present invention to provide a negative electrode for a secondary battery and a method of manufacturing the negative electrode, which can prevent a drop of a material due to volume expansion of an electrode active material and provide a high capacity and high efficiency of charge / discharge characteristics.

According to another aspect of the present invention, there is provided a secondary battery having a negative electrode for a secondary battery.

However, these problems are illustrative, and the technical idea of the present invention is not limited thereto.

According to an aspect of the present invention, there is provided a negative electrode for a secondary battery comprising: a negative electrode collector; A plurality of negative electrode active material structures disposed on the negative electrode collector such that one end thereof is in contact with one end and the other end extends from the negative electrode collector in a predetermined direction; A fixed layer disposed between the lower regions of the plurality of negative electrode active material structures on the negative electrode collector to fix the plurality of negative electrode active material structures on the negative electrode collector, the fixed layer comprising a polymer material; And a porous packing layer disposed between the plurality of anode active material structures on the pinned layer to fill a space between the plurality of anode active material structures and having pores and including a polymer material.

In some embodiments of the present invention, the porous packing layer may comprise a plurality of spherical particles providing porosity.

In some embodiments of the present invention, the plurality of spherical particles may comprise spherical polyvinylidene fluoride material.

In some embodiments of the present invention, the porous packing layer may have a coarse structure as compared to the fixed layer.

In some embodiments of the present invention, at least one of the fixation layer and the porous filler layer may be formed using a spin coating.

According to an aspect of the present invention, there is provided a negative electrode for a secondary battery comprising: a negative electrode collector; A plurality of negative electrode active material structures disposed on the negative electrode collector such that one end thereof is in contact with one end and the other end extends from the negative electrode collector in a predetermined direction; A fixed layer disposed between the lower regions of the plurality of negative electrode active material structures on the negative electrode collector to fix the plurality of negative electrode active material structures on the negative electrode collector, the fixed layer comprising a polymer material; A porous packing layer disposed between the plurality of anode active material structures on the fixed layer to fill a space between the plurality of anode active material structures and having pores and including a polymer material; And a dense packing layer disposed between the plurality of negative electrode active material structures on the fixed layer to fill a space between the plurality of negative electrode active material structures, the dense packing layer including a polymer material and having a dense structure as compared with the porous filler layer; .

In some embodiments of the present invention, the porous packing layer and the dense packing layer may form a sandwich structure that is alternately located on the fixed layer.

In some embodiments of the present invention, the dense packing layer may be formed using spin coating.

According to an aspect of the present invention, there is provided a negative electrode for a secondary battery comprising: a negative electrode collector; A plurality of negative electrode active material structures disposed on the negative electrode collector such that one end thereof is in contact with one end and the other end extends from the negative electrode collector in a predetermined direction; And a plurality of anode active material structures disposed on the anode current collector between the lower regions of the plurality of anode active material structures and thus fixing the plurality of anode active material structures on the anode current collector, And a pinned space formed between the negative electrode active material structures on the fixed layer.

According to an aspect of the present invention, there is provided a method of manufacturing a negative electrode for a secondary battery, the method comprising: providing a negative electrode collector having negative electrode active material structures; A first spin coating of a first solution containing a first polymer material between the anode active material structures on the anode current collector; And drying the first solution to form a fixed layer including the first polymer material between the negative electrode active material structures.

In some embodiments of the present invention, after performing the step of forming the fixed layer, a second spin-coating of a second solution containing a second polymeric material between the negative electrode active material structures on the fixed layer may be performed. And drying the second solution to form a porous filler layer between the anode active material structures and the second active material structure to fill the spaces between the anode active material structures.

In some embodiments of the present invention, the step of primary spin coating comprises the step of coating the first solution with N-methyl-2-pyrrolidone (NMP) as a solvent, (PVDF) as a first polymer material at a concentration of 9 wt% to 11 wt%, and may be performed at a rate of 2500 rpm to 3500 rpm for 40 seconds to 60 seconds.

In some embodiments of the present invention, the step of primary spin coating comprises the step of coating the first solution with N-methyl-2-pyrrolidone (NMP) as a solvent, The first polymer material may include polyvinylidene fluoride (PVDF) at a concentration of 3 wt% to 5 wt%, and may be performed at a speed of 1500 rpm to 2500 rpm for 40 seconds to 60 seconds.

In some embodiments of the present invention, the second spin-coating step may include a step in which the second solution contains acetone as a solvent, and the second polymeric material includes polyvinylidene fluoride (PVDF) in an amount of 0.5 wt% 2 wt%, and may be performed one or more times at a speed of 500 rpm to 1500 rpm for 1 second to 120 seconds.

In some embodiments of the present invention, the second spin-coating step may include a step in which the second solution contains acetone as a solvent and the second polymeric material comprises polyvinylidene fluoride (PVDF) in an amount of 12 wt% 16 wt%, and may be performed one or more times at 1 to 120 seconds at a speed of 500 rpm to 1500 rpm.

In some embodiments of the present invention, the step of secondary spin coating is a step of coating a solution in which 1 wt% of polyvinylidene fluoride is dissolved or dispersed in acetone at a rate of 1000 rpm for 3 times Followed by coating a solution of polyvinylidene fluoride at a concentration of 14 wt% in acetone in a solution or dispersion at a rate of 1000 rpm twice at a time of 30 seconds.

In some embodiments of the present invention, a void space may be disposed between the upper regions of the anode active material structures on the fixed layer.

In some embodiments of the present invention, the second polymeric material comprises spherical particles, and the spherical particles may provide pores to the porous filler layer.

In some embodiments of the present invention, the step of secondary spin coating may be repeatedly performed.

According to an aspect of the present invention, there is provided a secondary battery including the negative electrode for a secondary battery.

The negative electrode for a secondary battery according to an embodiment of the present invention includes a void space or a porous filler layer between a plurality of negative electrode active material structures composed of nanomaterials so that the volume expansion of the negative electrode active material structure due to insertion / And volume shrinkage. By mitigating the volume change, it is possible to prevent the negative electrode active material structure from cracking and coming off, thereby improving the cycle characteristics of the secondary battery, thereby providing a secondary battery having a high capacity and high efficiency of charge / discharge characteristics.

The effects of the present invention described above are exemplarily described, and the scope of the present invention is not limited by these effects.

1 is a schematic view showing a secondary battery according to an embodiment of the present invention.
2 is a schematic cross-sectional view illustrating an anode for a secondary battery constituting the secondary battery of FIG. 1 according to an embodiment of the present invention
3 is a schematic cross-sectional view illustrating a negative electrode for a secondary battery constituting the secondary battery of FIG. 1 according to an embodiment of the present invention.
4 is a schematic cross-sectional view illustrating a negative electrode for a secondary battery constituting the secondary battery of FIG. 1 according to an embodiment of the present invention.
5 is a schematic cross-sectional view illustrating a negative electrode for a secondary battery constituting the secondary battery of FIG. 1 according to an embodiment of the present invention.
6 is a flowchart illustrating a method of manufacturing a negative electrode for a secondary battery constituting the secondary battery of FIG. 1 according to an embodiment of the present invention.
FIGS. 7 and 8 are SEM micrographs showing the microstructure of a cathode of a secondary battery according to an embodiment of the present invention.
9 is a graph illustrating a change in capacitance according to a charge cycle of a secondary battery according to an embodiment of the present invention.
FIGS. 10 to 12 are graphs showing the relationship between the charging capacity and the voltage at the time of charge / discharge of the secondary batteries, according to an embodiment of the present invention.
13 and 14 are SEM micrographs showing the microstructure of a cathode of a secondary battery after 100 charge / discharge cycle battery tests, according to an embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. It will be apparent to those skilled in the art that the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of the invention to those skilled in the art. The scope of technical thought is not limited to the following examples. Rather, these embodiments are provided so that this disclosure will be more thorough and complete, and will fully convey the scope of the invention to those skilled in the art. As used herein, the term "and / or" includes any and all combinations of one or more of the listed items. The same reference numerals denote the same elements at all times. Further, various elements and regions in the drawings are schematically drawn. Accordingly, the technical spirit of the present invention is not limited by the relative size or spacing depicted in the accompanying drawings.

1 is a schematic view showing a secondary battery 1 according to an embodiment of the present invention.

1, a secondary battery 1 includes a cathode 120, an anode 130, a separator 140 interposed between the cathode 120 and the anode 130, a battery container 150, and a sealing member 160 < / RTI > The secondary battery 1 may further include an electrolyte (not shown) impregnated into the cathode 120, the anode 130 and the separator 140. In addition, the cathode 120, the anode 130, and the separator 140 may be sequentially stacked and housed in the battery container 150 in a spirally wound manner. The battery container 150 can be sealed by the sealing member 160.

The secondary battery 1 may be a lithium secondary battery using lithium as a medium, and may be classified into a lithium ion battery, a lithium ion polymer battery and a lithium polymer battery depending on the type of the separator 140 and the electrolyte. The secondary battery 1 can be classified into a coin, a button, a sheet, a cylinder, a flat, a square, and the like depending on the form, and can be divided into a bulk type and a thin type according to the size. The secondary battery 1 shown in FIG. 1 is an example of a cylindrical secondary battery, and the technical idea of the present invention is not limited thereto.

The structures of the anode 130 and the cathode 120 will be described below with reference to FIGS. 2 and 3, respectively.

The separation membrane 140 may have porosity and may be composed of a single membrane or multiple membranes of two or more layers. The separation membrane 140 may include a polymer material and may include at least one of, for example, a polyethylene-based, polypropylene-based, polyvinylidene fluoride-based, and polyolefin-based polymer.

The electrolyte (not shown) impregnated in the cathode 120, the anode 130, and the separator 140 may include a non-aqueous solvent and an electrolyte salt. The nonaqueous solvent is not particularly limited as long as it is used as a nonaqueous solvent for a conventional nonaqueous electrolytic solution, and examples thereof include carbonate solvents, ester solvents, ether solvents, ketone solvents, alcohol solvents, Solvent. The non-aqueous solvent may be used singly or in a mixture of one or more thereof. When one or more of the non-aqueous solvents are used in combination, the mixing ratio may be appropriately adjusted according to the performance of the desired battery.

The electrolyte salt is not particularly limited as long as it is used as a conventional electrolyte salt for a non-aqueous electrolyte, and may be, for example, a salt having a structural formula of A ⁺ B ^- . Here, A ⁺ may be an ion including an alkali metal cation such as Li ⁺ , Na ⁺ , K ⁺ , or a combination thereof. Also. B ^- is _{^{PF 6 -, BF 4 -,}} Cl -, Br -, I -, ClO 4 -, ASF 6 -, CH 3 CO 2 -, CF 3 SO 3 -, N (CF 3 SO 2) 2 -, C (CF ₂ SO ₂ ) ₃ ^-, and the like, or a combination thereof. For example, the electrolyte salt may be lithium-based salts, such as _{LiPF 6, LiBF 4, LiSbF 6} , LiAsF 6, LiN (SO 2 C 2 F 5) 2, Li (CF 3 SO 2) 2 N, _{LiN (SO 3 C 2 F 5} ) 2, LiC 4 F 9 SO 3, LiClO 4, LiAlO 2, LiAlCl 4, LiN (C x F 2x + 1 SO 2) (C y F2 y + 1 SO 2) ( where , x and y are natural numbers), LiCl, LiI, and LiB (C ₂ O ₄ ) ₂ . These electrolyte salts may be used alone or in combination of two or more.

According to a modified example of this embodiment, the separation membrane 140 may be omitted and a solid electrolyte may be interposed between the cathode 120 and the anode 130. Examples of the solid electrolyte include Li ₂ SP ₂ S ₅ , Li ₂ S-SiS ₂ , Li ₂ S-Ga ₂ S ₃ -GeS ₂ , Li ₂ S-Sb ₂ S ₃ -GeS ₂ , Li ₂ S- _{GeS 2 -P 2 S 5, Li} 3.25 Ge 0.25 P 0.75 S 4, Li 4.2 Ge 0.8 Ga 0.2 S 4 sulfide-based glass or glass-like - and the _{ceramic, (La, Li) TiO 3} (LLTO), Li 5 La ₃ Ta ₂ O ₁₂ , Li ₆ La ₂ CaTa ₂ O ₁₂ , Li ₆ La ₂ ANb ₂ O ₁₂ (A = Ca, Sr), Li ₂ Nd ₃ TeSbO ₁₂ , Li ₃ BO _2.5 N _0.5 , Li ₉ SiAlO ₈ , Based glass or glass-ceramic and a glass-ceramic such as Li _{1 + x} Al _x Ge _2-x (PO ₄ ) ₃ , Li _{1 + x} Ti _{2 -x} Al _x (PO ₄ ) _3, Li _0.5 Ti _0.5 Zr _{1.5 4} ) _{3, a} phosphate-based glass such as LiPON, or glass-ceramics.

FIG. 2 is a schematic cross-sectional view showing a secondary battery anode 130 constituting the secondary battery 1 of FIG. 1 according to an embodiment of the present invention.

2, the anode 130 includes a cathode current collector 132 and a cathode active material layer 134 disposed on the cathode current collector 132.

The anode current collector 132 may be a thin conductive foil and may include, for example, a conductive material. The positive electrode collector 132 may include, for example, aluminum, nickel, or an alloy thereof. Alternatively, the cathode current collector 132 may be composed of a polymer containing a conductive metal. Alternatively, the positive electrode collector 132 may be formed by compressing the positive electrode active material.

The positive electrode active material layer 134 includes a positive electrode active material 135 and a positive electrode binder 136 for bonding the positive electrode active material 135 thereto. In addition, the positive electrode active material layer 134 may further include a positive electrode conductor 137 selectively. Further, although not shown, the positive electrode active material layer 134 may further include an additive such as a filler or a dispersant. The anode 130 is formed by mixing the cathode active material 135, the anode binder 136, and / or the cathode conductor 137 in a solvent to prepare a cathode active material composition. The cathode active material composition is applied onto the cathode current collector 132 As shown in FIG.

The cathode active material 135 may include, for example, a cathode active material for a lithium secondary battery, and may include a material capable of reversibly intercalating / deintercalating lithium ions. The positive electrode active material 135 may include a lithium-containing transition metal oxide, a lithium-containing transition metal sulfide, and the like, for example, LiCoO ₂ , LiNiO ₂ , LiMnO ₂ , LiMn ₂ O ₄ , Li (Ni _a Co _b Mn _c ) _{O 2 (0 <a <1} , 0 <b <1, 0 <c <1, a + b + c = 1), LiNi 1-y Co y O 2, LiCo 1-y Mn y O 2, LiNi 1 _-y Mn _y O ₂ (here, 0 = y <1), Li (Ni a Co b Mn c) O 4 (0 <a <2, 0 <b <2, 0 <c <2, a + b + c = 2), LiMn _2-z Ni _z O ₄ , LiMn _2-z Co _z O ₄ (where 0 <Z <2), LiCoPO ₄ , and LiFePO ₄ . The cathode active material 135 can determine the voltage and the capacity of the secondary battery.

The positive electrode binder 136 serves to adhere the particles of the positive electrode active material 135 to each other and to adhere the positive electrode active material 135 to the positive electrode collector 132. The positive electrode binder 136 may be, for example, a polymer and may include, for example, polyimide, polyamideimide, polybenzimidazole, polyvinyl alcohol, carboxymethylcellulose, hydroxypropylcellulose, polyvinylchloride, But are not limited to, polyvinyl chloride, polyvinyl fluoride, ethylene oxide, polyvinyl pyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene, acrylated styrene- Epoxy resin and the like.

Alternatively, the positive electrode active material 135 may use a bonding structure in which a coating layer is added to the surface of the active material layer, or a compound having an active material and a coating layer may be used. The coating layer may comprise at least one coating element compound selected from the group consisting of oxides, hydroxides of coating elements, oxyhydroxides of coating elements, oxycarbonates of coating elements, and hydroxycarbonates of coating elements. The compound constituting these coating layers may be amorphous or crystalline. In addition, the coating element contained in the coating layer is selected from the group consisting of Mg, Al, Co, K, Na, Ca, Si, Ti, V, Sn, Ge, Ga, B, As, Zr, Can be used.

The positive electrode conductor 137 may be a conductive material that can further provide conductivity to the anode 130 and does not cause chemical changes to the secondary battery 1 and may be made of a conductive material such as graphite, carbon black, acetylene black, Based conductive materials such as copper, nickel, aluminum, and silver, conductive polymer materials such as polyphenylene derivatives, or a mixture thereof.

However, the structure and material of the anode 130 are illustrative, and the technical idea of the present invention is not limited thereto.

3 is a schematic cross-sectional view showing a cathode 120 for a secondary battery constituting the secondary battery 1 of FIG. 1 according to an embodiment of the present invention.

3, the cathode 120 includes an anode current collector 121, an anode active material structure 122 positioned on the anode current collector 121, and a fixing layer 123. An empty space 129 may be disposed between the anode active material structures 122 on the fixed layer 123.

The anode current collector 121 may include a conductive material and may include, for example, a metal, for example, copper, nickel, titanium, gold, aluminum, or an alloy thereof. The anode current collector 121 can be formed by adhering, plating or vapor-depositing a foil.

The negative electrode active material structure 122 may include a plurality of negative electrode active material structures 122 and may be attached and positioned on the negative electrode collector 121. The negative electrode active material structure 122 may include, for example, a negative electrode active material for a lithium secondary battery, and may include a material capable of reversibly intercalating / deintercalating lithium ions provided from the positive electrode 130. For example, as shown in FIG. The anode active material structure 122 may have a shape of a nanowire whose one end is in contact with the anode current collector 121 and the other end is extended from the anode current collector 121 in a predetermined direction. However, this shape is exemplary and the shape of the anode active material structure 122 is not limited thereto.

The anode active material structure 122 may include a nanomaterial. The anode active material structure 122 may be formed of any material that can be used to form the anode active material structure 122. For example, the anode active material structure 122 may be formed of any material, including, for example, nanorods, nanowires, nanotubes, nanoparticles, nanowalls, a nano sheet, and a nanore ring. In addition, the anode active material structure 122 may form an array regularly arranged on the anode current collector 121. For example, the anode active material structure 122 may be attached to the anode current collector 121 to form a nanodrode array structure that grows in one axis direction and is regularly arranged. The material of the anode active material structure 122 may include any material capable of forming a nanomaterial and capable of intercalating / deintercalating lithium ions, and may include, for example, an inorganic material, for example, aluminum The same metal, a semi-metallic material such as silicon, or a metal oxide such as zinc oxide.

In order to increase the electrical conductivity of the negative electrode active material structure 122, the negative electrode active material structure 122 may further include at least one of group II, group III, group V, and group VI impurities. For this purpose, the negative electrode active material structure 122 may be doped with at least one of Group II, Group III, Group V, and Group VI impurities.

The pinning layer 123 is located between the lower regions of the anode active material structures 122 on the anode current collector 121 so as to fix the anode active material structures 122 on the anode current collector 121. The anode active material structures 122 may be fixed to the anode current collector 121 to prevent the anode active material structure 122 from being detached. Illustratively, the anode active material structures 122 may protrude from the pinned layer 123.

The pinned layer 123 may be formed using, for example, a spin coating method, which will be described below with reference to FIG.

The negative electrode active material structures 122 on the fixed layer 123 are disposed with an empty space 129 therebetween so that the volume of the negative electrode active material structure 122 due to insertion / Expansion and volume shrinkage can be alleviated. That is, in the case of the volume expansion of the anode active material structure 122, the empty space 129 is compressed to reduce the volume, and in the case of the volume contraction of the anode active material structure 122, the empty space 129 is expanded, And as a result, it copes with the change in volume of the negative electrode active material structure 122. By mitigating the volume change of the negative electrode active material structure 122, it is possible to prevent the negative electrode active material structure 122 from cracking and coming off, thereby improving the cycle characteristics of the secondary battery 1, The secondary battery 1 can be provided.

The fixed layer 123 may include various polymeric materials, and may include, for example, a conductive polymeric material. For example, the fixed layer 123 may be formed of a material selected from the group consisting of polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), polyethylene glycol ), Polypropylene glycol (PPG), toluene diisocyanate (TDI), polymethylmethacrylate, polyacrylonitrile, polyvinylpyrrolidone, polyvinyl But are not limited to, polyvinyl acetate, polyvinylacetate, polyethyleneco-vinyl acetate, polyethylene oxide, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate propionate, cyanoethyl pullulan, cyanoethyl polyvinyl alcohol (cyanoethyl hyl polyvinyl alcohol, cyanoethyl cellulose, cyanoethyl sucrose, pullulan, carboxyl methyl cellulose, acrylonitrile-styrene (styrene-butadiene) copolymer -butadiene copolymer, polyimide, polyethylene chlorotrifluoroethylene (ECTFE), polychlorotrifluoroethylene (PCTFE), and polyvinylidene fluoride-co-hexafluoropropylene (PVDF-co-HFP ), Poly methyl methacrylate (PMMA), polybutyl methacrylate (PBMA), polyacrylate (PAN), polyoxide (PEO), polyvinyl alcohol (PVA), polyvinyl pyrrolidone Carboxymethylcellulose (CMC), and styrene butadiene rubber (SBR) may be used alone or in combination of two or more thereof.

4 is a schematic sectional view showing a cathode 120a for a secondary battery constituting the secondary battery 1 of FIG. 1 according to an embodiment of the present invention.

4, the cathode 120a includes an anode current collector 121, an anode active material structure 122 disposed on the anode current collector 121, a fixing layer 123, and a porous filling layer 124 . The negative electrode current collector 121, the negative electrode active material structure 122, and the fixed layer 123, which are described above with reference to the embodiment shown in FIG. 3, will not be described.

The porous filling layer 124 is located on the fixed layer 123 and is located between the plurality of anode active material structures 122 and fills a space between the plurality of anode active material structures 122.

The porous filling layer 124 may be formed using, for example, a spin coating method, which will be described below with reference to FIG.

The porous filler layer 124 may include pores 128 and the pores 128 may facilitate the volume expansion and volume contraction of the anode active material structure 122 by insertion / have. That is, in the case of the volume expansion of the anode active material structure 122, the pore 128 of the porous filler layer 124 is compressed to reduce the volume, and in the case of the volume contraction of the anode active material structure 122, The pores 128 of the negative electrode active material structure 122 are expanded and the volume is increased, so that the negative electrode active material structure 122 is coped with to alleviate the volume change of the negative electrode active material structure 122. By mitigating the volume change of the negative electrode active material structure 122, it is possible to prevent the negative electrode active material structure 122 from cracking and coming off, thereby improving the cycle characteristics of the secondary battery 1, The secondary battery 1 can be provided.

The porous filler layer 124 may comprise a plurality of spherical particles and may provide porosity by the space between the spherical particles. For example, the porous fill layer 124 may comprise spherical particles comprised of a polyvinylidene fluoride (PVDF) material. However, the technical spirit of the present invention is not limited thereto, but may include porous filling layers 124 of various shapes and structures to provide porosity.

The porous filler layer 124 may comprise various polymeric materials and may include a conductive polymer. For example, the porous fill layer 124 may comprise a material such as polyvinylidene fluoride (PVDF) or the like, which constitutes the fixation layer 123 as described above. The fixation layer 123 and the porous filler layer 124 may comprise the same material or may comprise different materials. In addition, the fixed layer 123 and the porous filler layer 124 may have different densities. The pinned layer 123 may have a relatively dense structure, and may have, for example, a thin film structure. The porous packing layer 124 may have a relatively coarse structure and may have, for example, a porous structure. For example, even if both the pinned layer 123 and the porous filler layer 124 are formed of polyvinylidene fluoride (PVDF), the pinned layer 123 has a dense structure and the porous filler layer 124 has a coarse structure .

5 is a schematic cross-sectional view showing a cathode 120b for a secondary battery constituting the secondary battery 1 of FIG. 1 according to an embodiment of the present invention.

5, the cathode 120b includes an anode current collector 121, an anode active material structure 122 disposed on the anode current collector 121, a fixing layer 123, a porous filling layer 124, Layer &lt; / RTI &gt; The negative electrode current collector 121, the negative electrode active material structure 122, the fixed layer 123, and the porous filler layer 124 will not be described in detail with reference to the embodiment shown in FIG. 3 .

The dense packing layer 125 is located on the fixed layer 123 and is located between the plurality of negative electrode active material structures 122 and fills a space between the plurality of negative electrode active material structures 122. The dense packing layer 125 may have a dense structure compared to the porous packing layer 124. For example, dense filler layer 125 may have a dense structure that is the same as or similar to the fixation layer.

The dense packing layer 125 may have a dense structure to provide strength to the porous packing layer 124 having a coarse structure and to prevent the porous packing layer 124 from being detached from the negative electrode active material structure 122 .

The porous packing layer 124 and the dense packing layer 125 may form a sandwich structure that is alternately located on the fixed layer 123. 5, a porous filler layer 124, a dense filler layer 125, a porous filler layer 124, a dense filler layer 125, and a porous filler layer 124 are formed on the fixation layer 123. [ (124) may be alternately positioned. The sandwich structure shown in FIG. 5 is illustrative, and the technical idea of the present invention is not limited thereto. For example, the order and number of arrangements of the porous packing layer 124 and the dense packing layer 125 positioned on the fixed layer 123 can be varied variously.

The dense fill layer 125 may comprise various polymeric materials and may include a conductive polymer. For example, the dense fill layer 125 may comprise a material such as a material that constitutes the fixation layer 123 or the porous fill layer 124 as described above, such as polyvinylidene fluoride (PVDF) . The fixation layer 123, the porous fill layer 124, and the dense fill layer 125 may comprise the same material or may comprise different materials.

The dense filler layer 125 may be formed using, for example, a spin coating method, which will be described below with reference to FIG.

6 is a flowchart showing a manufacturing method (S100) of a negative electrode 120, 120a, 120b for a secondary battery constituting the secondary battery 1 of FIG. 1 according to an embodiment of the present invention.

Referring to FIG. 6, a method (S100) for manufacturing a negative electrode for a secondary battery includes the steps of: (S110) providing a negative electrode collector having negative electrode active material structures formed thereon; (S120) a first spin coating of a first solution containing a first polymer material between the anode active material structures on the anode current collector; And drying the first solution to form a fixed layer including the first polymeric material between the negative electrode active material structures (S130).

Next, a method (S100) for manufacturing a negative electrode for a secondary battery includes: (S140) a step of secondary spin coating a second solution containing a second polymer material between the negative electrode active material structures on the fixed layer; And drying the second solution to form a porous packing layer between the negative electrode active material structures and containing the second polymeric material and filling the spaces between the negative electrode active material structures (S150).

In the step of providing the anode current collector (S110), the anode current collector may be copper foil. The negative electrode active material structure may include a nanomaterial as described above, for example, nanowire, and may have a vertically grown shape from the negative electrode collector. The negative electrode active material structure may have a diameter of from several to several tens of nanometers and may have a length of, for example, from about 1 m to about 100 m, for example, from about 10 m to about 20 m. Further, although not shown, a buffer layer having a thickness of about 0.5 탆 to about 1 탆 may be further provided on the upper side or the lower side of the negative electrode active material structure.

In the first spin coating step (S120), the first polymer material may include a polymer material as described above. The first solution may include a solvent capable of dissolving or dispersing the first polymeric material. The solvent may be, for example, dimethylformamide, N-methyl-2-pyrrolidone (NMP), acetone, tetrahydrofuran, methylenechloride, chloroform, cyclohexane, water, or mixtures thereof. However, such a solvent is illustrative and the technical idea of the present invention is not limited thereto.

For example, the first polymer material may be polyvinylidene fluoride (PVDF), and the solvent may be NMP. The polymeric material may be dissolved or dispersed in the NMP at a concentration ranging, for example, from about 1 wt% to about 20 wt%, for example, from about 9 wt% to about 11 wt% May be dissolved or dispersed at a concentration of about 10 wt%. Alternatively, the polymeric material may be dissolved or dispersed in the NMP, for example, at a concentration of from about 3 wt% to about 5 wt%, for example, at a concentration of about 4 wt%. However, these concentrations are illustrative and the technical idea of the present invention is not limited thereto.

The primary spin coating may be a conventional spin coating method. The primary spin coating may be performed for a period of time ranging from about 500 rpm to about 4000 rpm, for example, from 1 second to 180 seconds. The primary spin coating may be performed, for example, at a rate of from about 2500 rpm to about 3500 rpm, for example, at a rate of about 3000 rpm, for a time of from about 40 seconds to about 60 seconds, . For example, from about 1500 rpm to about 2500 rpm, for example from about 2000 rpm to about 40 seconds to about 60 seconds, such as about 50 seconds. However, the speed and the execution time of the primary spin coating are illustrative, and the technical idea of the present invention is not limited thereto. The rate and duration of the primary spin coating may be varied according to the shape and length of the desired anode active material structures.

By the spin coating, the polymer material can be uniformly disposed between the anode active material structures on the anode current collector.

In the step of forming the fixing layer (S130), the drying may be carried out, for example, in a drying oven at a temperature ranging from about 30 캜 to about 90 캜, for example, from 1 hour to 24 hours. For example, the drying can be performed at about 50 &lt; 0 &gt; C for 12 hours. In addition, the drying temperature may range from about 50 캜 to about 70 캜. However, such drying temperature and drying time are illustrative, and the technical idea of the present invention is not limited thereto. For example, such drying temperature and drying time may be variously changed depending on the shape and length of the negative electrode active material structures.

In the second spin coating step (S140), the second polymer material may include a polymer material as described above. The second solution may include a solvent capable of dissolving or dispersing the second polymeric substance, as described above.

For example, the second polymeric material is polyvinylidene fluoride (PVDF) and may be composed of spherical particles. The spherical particles can provide pores in the porous packing layer.

In addition, the solvent may be acetone. The polymeric material may be dissolved or dispersed in the acetone, for example, at a concentration ranging from about 1 wt% to about 20 wt%, for example, at a concentration of from about 0.5 wt% to about 2.0 wt% May be dissolved or dispersed at a concentration of about 1 wt%, or may be dissolved or dispersed at a concentration of about 12 wt% to about 16 wt%, e.g., at a concentration of about 14 wt%. However, these concentrations are illustrative and the technical idea of the present invention is not limited thereto.

The secondary spin coating may be a conventional spin coating method. The secondary spin coating may be performed for a period of time ranging from about 500 rpm to about 4000 rpm for 1 second to 120 seconds, for example. For example, the primary spin coating may be performed at a rate of, for example, from about 500 rpm to about 1500 rpm, for example, at a rate of about 1000 rpm, for example from about 5 seconds to about 15 seconds, And can be performed for about 10 seconds. In addition, the spin coating can be performed a plurality of times, for example, three times at the same speed and time. Also, for example, the primary spin coating can be performed at a rate of, for example, from about 500 rpm to about 1500 rpm, for example, at a rate of about 1000 rpm, for example, from about 20 seconds to about 40 seconds, For about 30 seconds. In addition, the spin coating can be performed a plurality of times, for example, two times at the same speed and time. However, the speed and the execution time of the secondary spin coating are illustrative, and the technical idea of the present invention is not limited thereto. The rate and duration of the secondary spin coating may be varied according to the shape and length of the desired anode active material structures.

The secondary spin coating step (S140) may be repeatedly performed. At this time, the concentration of the second solution may be the same or different during repeated execution. For example, in the second spin coating step (S140), a solution in which about 1 wt% of polyvinylidene fluoride is dissolved or dispersed in acetone is coated three times at a speed of about 1000 rpm for about 10 seconds , Followed by coating a solution in which about 14 wt% of polyvinylidene fluoride is dissolved or dispersed in acetone at a rate of about 1000 rpm in a time of about 30 seconds twice.

In the step of forming the porous packing layer (S150), the drying can be carried out in a drying oven, for example a temperature range of from about 30 째 C to about 90 째 C, for example from 1 hour to 24 hours. For example, the drying can be performed at about 50 &lt; 0 &gt; C for 12 hours. In addition, the drying temperature may range from about 50 캜 to about 70 캜. However, such drying temperature and drying time are illustrative, and the technical idea of the present invention is not limited thereto. For example, such drying temperature and drying time may be variously changed depending on the shape and length of the negative electrode active material structures.

The negative electrode 120 for the secondary battery of FIG. 3 may be formed by performing the step of providing the negative electrode collector (S110) to the step of forming the fixed layer (S130). In the negative electrode for a secondary battery, the fixed layer fills a space between the lower regions of the negative electrode active material structures. An empty space may be disposed between the upper regions of the anode active material structures on the fixed layer.

The negative electrode 120a for the secondary battery of FIG. 4 may be formed by performing the step of providing the negative electrode collector (S110) to the step of forming the porous filling layer (S150). In the negative electrode for a secondary battery, the fixed layer fills a space between the lower regions of the negative electrode active material structures. A porous filler layer may be disposed between the upper regions of the anode active material structures on the fixed layer.

In addition, the cathode 120b for the secondary battery of FIG. 5 may be formed by performing the step of providing the anode current collector (S110) to the step of forming the porous packing layer (S150). In this case, before or after the step of forming the porous filler layer (S150), spin coating is performed by changing the concentration in the spin solution to form a dense filler layer 125 alternately disposed with the porous filler layer can do. For example, the dense packing layer 125 may be formed using a method of forming the fixed layer 123

Experimental Example

Hereinafter, results of an experimental example of a negative electrode for a secondary battery manufactured according to an embodiment of the present invention will be discussed.

(1) Production of negative electrode for secondary battery shown in Fig. 3

A copper foil formed with zinc oxide nanowires as negative electrode active material structures was used as an anode current collector. The nanowire has a length of about 10 [mu] m to about 20 [mu] m and includes a buffer layer having a thickness of about 0.5 [mu] m to about 1 [mu] m.

A solution in which 10 wt% of polyvinylidene fluoride was dissolved or dispersed in an NMP solvent was spin-coated on the negative electrode collector by spin coating at a speed of 3000 rpm for 50 seconds.

Subsequently, the fixed layer 123 of FIG. 3 was formed by drying at 50.degree. C. for 12 hours in a drying oven. Thus, the negative electrode 120 for a secondary battery shown in Fig. 3 was produced.

(2) Production of negative electrode for secondary battery of FIG. 4

A copper foil formed with zinc oxide nanowires as negative electrode active material structures was used as an anode current collector. The nanowire has a length of about 10 [mu] m to about 20 [mu] m and includes a buffer layer having a thickness of about 0.5 [mu] m to about 1 [mu] m.

A solution of 4 wt% polyvinylidene fluoride dissolved or dispersed in an NMP solvent was spin-coated on the negative electrode collector by spin coating at a speed of 2000 rpm for 50 seconds.

It was then dried in a drying oven at a temperature of 50 DEG C for 12 hours. Thus, the pinning layer 123 of FIG. 4 was formed

A solution in which 1 wt% of spherical polyvinylidene fluoride was dissolved or dispersed in an acetone solvent was spin-coated on the negative electrode current collector on which the fixed layer was formed, using spin coating at a rate of 1000 rpm for 10 seconds for 3 times . Subsequently, a solution in which 14 wt% of polyvinylidene fluoride in a spherical shape was dissolved or dispersed in an acetone solvent was spin-coated by spin coating twice at a speed of 1000 rpm for 30 seconds.

Subsequently, the porous filling layer 124 was formed by drying in a drying oven at a temperature of 50 DEG C for 12 hours. Thus, the negative electrode 120a for a secondary battery shown in Fig. 4 was produced.

(3) Secondary battery manufacturing

A secondary battery was manufactured by using the above-described two types of negative electrode for a secondary battery. The secondary battery was manufactured in a glove box under an argon atmosphere. In the secondary battery, 1.1 M LiPF ₆ (EC: DEC (1: 1)) was used as the electrolyte, a lithium metal foil was used as the anode, and a polyethylene separator having micropores was used as the separation membrane. The secondary battery was manufactured into a coin-type type such as CR2032.

(4) Secondary battery performance measurement

The performance of the secondary battery was measured under the condition of 0.5 C C-rate and 100 charge / discharge cycles in a voltage range of 0.05 V to 2.4 V.

Hereinafter, the secondary battery including the negative electrode for the secondary battery of FIG. 3 will be referred to as Experimental Example 1, and the secondary battery including the negative electrode for the secondary battery of FIG. 4 will be referred to as Experimental Example 2. It is noted that the result of the case having the spherical porous filling layer 124 is the experimental example 2.

FIGS. 7 and 8 are SEM micrographs showing the microstructure of a cathode of a secondary battery according to an embodiment of the present invention. FIG. 7 shows the case of Experimental Example 1, and FIG. 8 shows the case of Experimental Example 2.

Referring to FIG. 7, the nanowires corresponding to the anode active material structure were uniformly distributed, and the void spaces between the nanowires were observed.

Referring to FIG. 8, a spherical material was observed inside the negative electrode active material structure, which corresponds to the porous filler layer.

9 is a graph illustrating a change in capacitance according to a charge cycle of a secondary battery according to an embodiment of the present invention.

In Fig. 9, "ZnO" corresponds to a comparative example formed by a conventional method without applying the present invention, "ZnO / PVDF" corresponds to Experimental Example 1, "ZnO / spherical PVDF & .

Referring to FIG. 9, the initial charge capacity was reduced in the order of Experimental Example 2, Comparative Example, and Experimental Example 1. Specifically, Experimental Example 2 showed an initial charge capacity of about 760 mAh / g, Comparative Example 580 mAh / g, and Experimental Example 1 had an initial charge capacity of about 400 mAh / g. Especially in Experimental Example 2, the initial charge capacity was higher than that of Comparative Example.

As the charge / discharge cycles were increased, the charge capacity of the comparative example was drastically reduced. Especially after 40 cycles, the charge capacity stabilized at a very low value of about 10 mAh / g.

On the other hand, in Experimental Example 1 and Experimental Example 2, although the charging capacity was decreased as the charge-discharge cycle was increased, the charging capacity was higher than that of Comparative Example. Experimental Example 1 showed a charging capacity of about 150 mAh / g, and Experimental Example 2 showed a charging capacity of about 300 mAh / g even in a 100 charge / discharge cycle.

Particularly, in Experimental Example 2, the initial charge capacity and the charge capacity according to the charge-discharge cycle were higher than those of Comparative Examples and Experimental Example 1. [ This is because the porous packing layer included in the negative electrode for the secondary battery of Experimental Example 2 effectively responded to the volume change of the negative electrode active material structure.

FIGS. 10 to 12 are graphs showing the relationship between the charging capacity and the voltage at the time of charge / discharge of the secondary batteries, according to an embodiment of the present invention.

Fig. 10 shows a case of a comparative example, Fig. 11 shows a case of Experimental Example 1, and Fig. 12 shows a case of Experimental Example 2.

Referring to FIGS. 10 to 12, in the case of the comparative example, it is shown that the capacity significantly decreased during charging and discharging in 100 charge / discharge cycles. On the other hand, in Experimental Example 1 and Experimental Example 2, although the capacity was decreased during charging and discharging, it was found that it maintained a considerable level as compared with Comparative Example. Particularly, as shown in Fig. 12, Experimental Example 2 shows the best charge-discharge behavior. The results of FIGS. 10 to 12 coincide with the results of FIG. 9 described above.

Accordingly, the secondary battery produced according to the present invention exhibits excellent charging capacity characteristics in accordance with the charge / discharge cycle.

13 and 14 are SEM micrographs showing the microstructure of a cathode of a secondary battery after 100 charge / discharge cycle battery tests, according to an embodiment of the present invention.

13 and 14, no particular change in the microstructure of the secondary battery, such as cracking, dropout, or breakage, has been found after the test of 100 charge / discharge cycle batteries. Particularly, the spherical particles of Experimental Example 2 exhibited almost the same shape and arrangement structure after 100 charge / discharge cycles.

As a result, as shown in FIGS. 9 to 12, the secondary battery manufactured according to the present invention has durability against the charge / discharge cycle, thereby providing excellent charge capacity characteristics. Accordingly, the secondary battery manufactured according to the present invention can provide a secondary battery having a high capacity and high efficiency charge / discharge characteristics by improving the cycle characteristics of the secondary battery.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention as defined in the appended claims. Will be apparent to those of ordinary skill in the art.

1: secondary battery 120, 120a, 120b: cathode
121: negative electrode current collector 122: negative electrode active material structure,
123: fixed layer 124: porous packing layer
125: dense packing layer 128: porosity
129: Free space
130: positive electrode 132: positive electrode collector
134: positive electrode active material layer 135: positive electrode active material
136: positive electrode binder 137: positive electrode conductor
140: separator 150: battery container
160: sealing member

Claims (20)

Cathode collector;
A plurality of negative electrode active material structures disposed on the negative electrode collector such that one end thereof is in contact with one end and the other end extends from the negative electrode collector in a predetermined direction;
A fixed layer disposed between the lower regions of the plurality of negative electrode active material structures on the negative electrode collector to fix the plurality of negative electrode active material structures on the negative electrode collector, the fixed layer comprising a polymer material; And
A porous packing layer disposed between the plurality of anode active material structures on the pinned layer to fill a space between the plurality of anode active material structures and having pores and including a polymer material;
/ RTI &gt;
Wherein the porous packing layer comprises a plurality of spherical particles providing porosity, the porous packing layer having a coarse structure as compared to the fixed layer,
Cathode for secondary battery. delete The method according to claim 1,
Wherein the plurality of spherical particles comprise a spherical polyvinylidene fluoride material. delete The method according to claim 1,
Wherein at least one of the fixed layer and the porous filled layer is formed using spin coating. Cathode collector;
A plurality of negative electrode active material structures disposed on the negative electrode collector such that one end thereof is in contact with one end and the other end extends from the negative electrode collector in a predetermined direction;
A fixed layer disposed between the lower regions of the plurality of negative electrode active material structures on the negative electrode collector to fix the plurality of negative electrode active material structures on the negative electrode collector, the fixed layer comprising a polymer material;
A porous packing layer disposed between the plurality of anode active material structures on the fixed layer to fill a space between the plurality of anode active material structures and having pores and including a polymer material; And
A dense packing layer disposed between the plurality of negative electrode active material structures on the fixed layer to fill a space between the plurality of negative electrode active material structures and including a polymer material and having a dense structure as compared with the porous filler layer;
/ RTI &gt;
Wherein the porous packing layer comprises a plurality of spherical particles providing porosity, the porous packing layer having a coarse structure as compared with the fixed layer,
Wherein the porous packing layer and the dense packing layer form a sandwich structure that is alternately located on the fixed layer,
Cathode for secondary battery. delete The method according to claim 6,
Wherein the dense packing layer is formed using spin coating. delete Providing an anode current collector having anode active material structures formed thereon;
A first spin coating of a first solution containing a first polymer material between the anode active material structures on the anode current collector;
Drying the first solution to form a fixed layer including the first polymeric material between the negative electrode active material structures;
Second spin coating a second solution comprising a second polymeric material between the anode active material structures on the pinned layer; And
Drying the second solution to form a porous filler layer between the anode active material structures and the second polymeric material to fill the spaces between the anode active material structures;
Lt; / RTI &gt;
Wherein the porous packing layer comprises a plurality of spherical particles providing porosity, the porous packing layer having a coarse structure as compared to the fixed layer,
(Method for manufacturing negative electrode for secondary battery). delete delete delete delete delete delete delete delete delete A secondary battery comprising a negative electrode for a secondary battery according to any one of claims 1, 3, 5, 6, and 8.

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