KR101811495B1 - Negative electrode for rechargeable lithium battery and rechargeable lithium battery comprising same - Google Patents

Abstract

The present invention relates to a negative electrode for a lithium secondary battery and a lithium secondary battery comprising the negative electrode, wherein the negative electrode includes an active layer including lithium and a protective layer disposed on the active layer of the negative electrode, Or a polymer matrix containing a non-crosslinked linear polymer, and an electrolyte contained in the polymer matrix in an amount of 100 to 1000 parts by weight based on 100 parts by weight of the polymer matrix, , There is no fear of loss of the electrolytic solution and deterioration of the battery life characteristics due to the decrease of the electrolytic solution during the discharge, and further, the growth of dentritic lithium is suppressed and the cell safety can be improved.

Description

TECHNICAL FIELD The present invention relates to a negative electrode for a lithium secondary battery, and a lithium secondary battery including the same. BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a negative electrode for a lithium secondary battery,

Disclosed is a negative electrode for a lithium secondary battery which is free from the risk of deterioration of battery life characteristics and loss of an electrolytic solution during repetitive charging and discharging of the battery, Battery.

2. Description of the Related Art Lithium secondary batteries (for example, lithium ion batteries), nickel metal hydride batteries, and other secondary batteries are becoming increasingly important as power sources for vehicle-mounted power supplies and portable terminals such as notebook computers. In particular, a lithium secondary battery capable of obtaining a light energy with a high energy density can be preferably used as a high output power source for in-vehicle use, and it is expected that the demand for lithium secondary batteries will continue to increase in the future.

The lithium secondary battery is manufactured by using a material capable of inserting and desorbing lithium ions as an active material of a negative electrode and a negative electrode and by providing a porous separator between the positive electrode and the negative electrode and injecting a liquid electrolyte, Electricity is generated or consumed by the redox reaction resulting from the insertion and desorption of ions.

However, there is a problem in that the battery is not continuously driven due to the loss and depletion of the electrolyte due to the volume change of the electrode during repetitive charging and discharging of the battery.

Accordingly, it is required to develop an electrode material capable of preventing the loss of an electrolytic solution to improve lifetime characteristics of the battery, and also to suppress the growth of dendrite of lithium, thereby improving the safety of the lithium electrode.

Korean Registered Patent No. 10-0359605 (registered on October 22, 2002)

An object of the present invention is to provide a negative electrode which is free from the risk of deterioration of battery life characteristics and loss of electrolytic solution during repetitive charging and discharging of the battery and which is suppressed in growth of dentite of lithium.

Another object of the present invention is to provide a lithium secondary battery having improved battery performance and safety including the above-described negative electrode.

The negative electrode for a lithium secondary battery according to an embodiment of the present invention includes a negative electrode active layer including a lithium metal or an alloy of lithium metal and a protective layer disposed on the negative electrode active layer, Or a non-crosslinked linear polymer, and an electrolyte contained in the polymer matrix in an amount of 100 to 1000 parts by weight based on 100 parts by weight of the polymer matrix.

In the negative electrode for a lithium secondary battery, the protective layer may include a porous polymer matrix having a three-dimensional network structure of a polymer, and the electrolyte may be contained in pores of the porous polymer matrix.

The porous polymer matrix may have a porosity of 5 to 80% by volume.

The three-dimensional crosslinked network structure may be formed by chemical crosslinking by a polymeric branching chain, coupling between one or more monomers having a reactive multi-functional group, physical crosslinking of a cluster domain formed by phase- Bond and an ionic cross-linking of the ionomer.

The polymer matrix may comprise a crosslinked polymer of polydimethylsiloxane or a derivative thereof.

In addition, the polymer matrix may include polysilsesquioxane.

In addition, the polymer matrix may comprise a three-dimensional covalent organic framework by coupling between two or more monomers having reactive multi-functional groups.

The polymer matrix may include any one substituent selected from the group consisting of a sulfonic acid group (SO ₃ H), a phosphoric acid group (PO ₄ H ₂ ), a carbonic acid group (CO ₃ H), and combinations thereof. Or anion polymer electrolyte partially or wholly self-doped with lithium.

In the negative electrode for a lithium secondary battery, the protective layer may include a structure in which a non-crosslinked polymer having a weight average molecular weight of 1,000,000 g / mol or more is entangled with each other, and the electrolyte is supported on the structure.

The non-crosslinked linear polymer may be at least one selected from the group consisting of polyethylene oxide, polypropylene oxide, polyacrylonitrile, polyvinylidene fluoride-hexafluoropropylene, polyvinylidene fluoride-trichlorethylene, polymethyl methacrylate, Polystyrene-acrylonitrile copolymer, polyvinyl chloride, polyvinyl pyrrolidone, polyvinyl acetate, polyethylene vinyl acetate copolymer, and mixtures thereof.

In the negative electrode for a lithium secondary battery, the protective layer may have a thickness of 1 nm to 10 탆.

In the negative electrode for a lithium secondary battery, the electrolyte may be absorbed in the polymer forming the polymer matrix.

According to another embodiment of the present invention, there is provided a method of manufacturing a negative electrode for a lithium secondary battery, comprising the steps of: preparing an active layer including an anode; Forming a polymer matrix including a three-dimensional network structure of a polymer on the anode active layer, or forming a polymer matrix containing a non-crosslinked linear polymer; And impregnating, spraying or spraying an electrolyte with an amount of 100 to 1000 parts by weight based on 100 parts by weight of the polymer matrix to form an electrolyte in the polymer matrix to form a protective layer.

According to another embodiment of the present invention, a lithium secondary battery includes a positive electrode and a negative electrode arranged opposite to each other; A separator interposed between the anode and the cathode; And a nonaqueous electrolyte, wherein the negative electrode comprises an active layer comprising lithium, and a protective layer located above the active layer of the negative electrode, wherein the protective layer comprises a three-dimensional network structure of the polymer, And an electrolyte contained in the polymer matrix in an amount of 100 to 1000 parts by weight based on 100 parts by weight of the polymer matrix.

Other details of the embodiments of the present invention are included in the following detailed description.

The negative electrode for a lithium secondary battery of the present invention is free from the risk of loss of the electrolyte solution and deterioration of the battery life characteristic thereof during repetitive charging and discharging of the battery and also suppresses the growth of dentitre lithium and improves the safety of the battery .

1 is an exploded perspective view of a lithium secondary battery according to another embodiment of the present invention.
FIG. 2 is a schematic view of an electrode manufactured in the embodiment, and FIG. 3 is a schematic view of an electrode manufactured in a comparative example.
4 is a graph showing the cycle life of the lithium secondary battery produced in Examples and Comparative Examples.
FIG. 5 is a photograph of the electrode according to the embodiment after the completion of the cycle progress, and FIG. 6 is a photograph of the electrode according to the comparative example after the completion of the cycle progress.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In the present invention, terms such as "comprises" or "having" are used to designate the presence of stated features, integers, steps, operations, elements, components, or combinations thereof, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof.

The present invention relates to a method for manufacturing a negative electrode, which is capable of protecting the negative electrode on the negative electrode active layer including the negative active material and forming a protective layer capable of accumulating the electrolyte, There is no fear of deterioration of characteristics, and further, the growth of dentrite of lithium is suppressed to improve the safety of the battery.

That is, an anode for a lithium secondary battery according to an embodiment of the present invention includes an anode active layer including a lithium metal or an alloy of lithium metal and a protective layer positioned over the anode active layer, A polymer matrix comprising a network structure, or comprising a non-crosslinked linear polymer; And an electrolyte contained in the polymer matrix in an amount of 100 to 1000 parts by weight based on 100 parts by weight of the polymer matrix.

Specifically, in the negative electrode, the negative electrode active layer is an anode active material capable of reversible intercalation and deintercalation of lithium, and includes an alloy of lithium metal or lithium metal.

The lithium metal alloy may specifically be an alloy of lithium and a metal of Si, Al, Sn, Pb, Zn, Bi, In, Mg, Ga, or Cd.

The negative electrode active layer may further include a binder in addition to the negative electrode active material.

The binder acts as a paste for the anode active material, mutual adhesion between the active materials, adhesion between the active material and the current collector, buffering effect on expansion and contraction of the active material, and the like. Specifically, the binder is selected from the group consisting of polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, a polymer including ethylene oxide, polyvinyl pyrrolidone, polyurethane , Polytetrafluoroethylene, polyvinylidene fluoride (PVDF), polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, epoxy resin, nylon, and the like. The binder may be contained in an amount of 20% by weight or less, or 5 to 15% by weight based on the total weight of the negative electrode active layer.

Meanwhile, in the negative electrode for a lithium secondary battery, a protective layer including a polymer matrix and an electrolyte contained in the polymer matrix is disposed on the negative electrode active layer.

Specifically, the polymer matrix includes a three-dimensional network structure of the polymer, or includes a non-crosslinked polymer.

More specifically, when the polymer matrix has a three-dimensional crosslinked network structure of a polymer, the three-dimensional crosslinked network structure may be chemically crosslinked by a polymer intergranular chain, coupling between one or more monomers having a reactive multi-functional group, Physical crosslinking of the cluster domain formed by phase separation of the copolymer and ionic crosslinking of the ionomer.

Specific examples of chemical cross-linking by the intermolecular branching chain include those in which a main chain is cross-linked by a branch chain serving as a cross-linking agent such as polydimethylsiloxane (PDMS) or a derivative thereof to form a cross-linking structure.

Specific examples of the formation of a three-dimensional crosslinked network structure by coupling between one or more monomers having a reactive multi-functional group include a method of reacting polysilsesquioxane ( polysilsesquioxane).

[Chemical Formula 1]

(Wherein R ₁ is a straight chain, branched or cyclic divalent hydrocarbon group (e.g., an alkylene group, a benzene group, etc.), a moiety of lithium ion conductivity such as oligoethylene glycol, / RTI >

At this time, the monomers having the structure of the formula (1) reacting with each other may contain different R ₁ moieties. For example, R ₁ is a coupling with each other monomer having a moiety structure of the formula (1) that the monomers and R ₁ having the structure of Formula 1 moiety to better convey the lithium ions are excellently the mechanical strength So that a three-dimensional crosslinked network structure can be formed.

As a concrete example of the formation of a three-dimensional crosslinked network structure by coupling of two or more monomers, a three-dimensional covalent bonding organic skeleton structure by coupling of a monomer of the general formula (2) with a compound of the general formulas (3a) to And formation of a covalent organic framework.

[Reaction Scheme 1]

In the above formulas 2 and 3a to 3c, R and R 'are each independently a linear, branched or cyclic hydrocarbon group, and may further include a lithium ion conductive moiety such as oligoethylene glycol, and X And Y are functional groups capable of reacting with each other to form a bridge, X is an amino group or a hydroxy group, and Y may be an isocyanate group, a carboxylic acid group, or an aldehyde group. X and Y react with each other when electrons are exchanged. In this case, Y is an amino group or a hydroxy group and X is an isocyanate group, a carboxylic acid group, or an aldehyde group for smooth reaction according to the electronegativity of R or R ' have.

However, the present invention is not limited to these examples, and the above-mentioned formulas (2) and (3a) to (3c) may simultaneously contain X and Y in one molecule It is also possible.

As a concrete example of the physical crosslinking of the cluster domain formed by the phase separation of the block copolymer, physical crosslinking of the block copolymer as shown in the following Reaction Scheme 2 may be mentioned. The following Reaction Scheme 2 schematically shows the physical cross-linking of the block copolymer, which is an example for illustrating the present invention, but the present invention is not limited thereto.

[Reaction Scheme 2]

In addition, the block copolymer may include a block capable of conducting an ion in the molecule, thereby minimizing the resistance.

Specific examples of the ionic crosslinking of the ionomer include ionic crosslinking of ionomers in which the proton of the polysulfonic acid is substituted with lithium, as shown in the following structural formula (I).

(I)

(I)

The ionomer may be an anionic polymer electrolyte which is self-doped with lithium, specifically a sulfonic acid group (SO ₃ H), a phosphoric acid group (PO ₄ H ₂ ), a carbonic acid group (CO ₃ H ), And a combination thereof, and some or all of them may be self-doped with lithium. More specifically, it may be a polymer such as polystyrenesulfonic acid in which the terminal of the side chain of the polymer is substituted with a sulfonic acid group The polymer may be a polymer in which SO ₃ H is replaced with SO ₃ Li.

The ionic crosslinked polymer of the ionomer is composed of a single lithium ion conductive polymer, which inhibits the migration of anions and moves only lithium ions, thereby minimizing the ion concentration gradient, and as a result, the formation of dendrites can be suppressed .

The three-dimensional crosslinked network structure as described above is formed by cross-linking of polymer chains, so that pores in the structure can be formed. Accordingly, the polymer matrix may be a porous polymer matrix, wherein the electrolyte may be contained in the pores of the porous polymer matrix.

Specifically, the polymer matrix may preferably have a porosity of 5 to 80% by volume based on the total volume of the polymer matrix. When the porosity is less than 5% by volume, the content of the electrolyte solution impregnated in the pores is low, and the improvement effect due to the formation of the polymer matrix is insignificant. When the porosity exceeds 80% by volume, the mechanical properties of the polymer matrix itself may deteriorate have. However, in the case of a three-dimensional network structure, even if the porosity exceeds 80% by volume, it is possible to control the insertion of the organic moiety appropriately, and in the case of using two or more monomers, .

Also, the porous polymer matrix may be swollen by absorbing the electrolyte depending on the degree of crosslinking of the polymer forming the polymer matrix. Accordingly, the electrolyte may be contained in the polymer.

On the other hand, when the polymer matrix includes a non-crosslinked linear polymer, the electrolyte may be contained in the non-crosslinked linear polymer, or may be contained between the intercalated non-crosslinked linear polymers.

When the non-crosslinked linear polymer absorbs the electrolyte, the non-crosslinked linear polymer swells as the charged electrolyte is absorbed into the polymer, and may exhibit electrolyte ion conductivity due to the absorbed electrolyte. Accordingly, the greater the amount of the electrolyte absorbed into the non-crosslinked linear polymer, the more the ionic conductivity can be exhibited. However, if the amount of electrolyte absorption is excessively high, the mechanical properties of the polymer matrix may be deteriorated. Accordingly, it is preferable that the non-crosslinked polymer has a swelling rate of 300 to 700% by weight or 400 to 500% by weight based on the electrolyte obtained by the following formula (1).

[Equation 1]

Swelling rate (%) = P2 / Pl x lOO

In the above equation, P1 is the weight of the polymer compound adjusted to a thickness of 100 占 퐉 after drying the test piece, and P2 is the weight after impregnating the electrolytic solution to be used at 25 占 폚 for 10 hours.

The non-crosslinked linear polymer having a swelling ratio within the above range has a high degree of swelling of the electrolytic solution, allowing free permeation of ions constituting the electrolyte when the negative electrode and the electrolyte are in contact with each other, and increases the conductivity of such electrolyte ions The battery performance can be improved.

Specifically, the non-crosslinked linear polymer is selected from the group consisting of polyethylene oxide, polypropylene oxide, polyacrylonitrile, polyvinylidene fluoride-hexafluoropropylene, polyvinylidene fluoride-trichlorethylene, polymethyl methacrylate , A polystyrene-acrylonitrile copolymer, polyvinyl chloride, polyvinyl pyrrolidone, polyvinyl acetate, or a polyethylene vinyl acetate copolymer. These may be used singly or in combination of two or more. However, since the negative electrode according to the present invention contains a lithium-based compound such as lithium metal or lithium alloy as the negative active material, it is preferable to suitably select among the non-crosslinked linear polymers for forming the protective layer in consideration of interfacial bonding with lithium Do,

When the non-crosslinked linear polymer is a homopolymer having a weight average molecular weight of 1,000,000 g / mol or more, the non-crosslinked linear polymer is contained in the polymer matrix in an entangled state, and the electrolyte may be carried by the entangled structure.

Meanwhile, the electrolyte included in the polymer matrix may include an organic solvent and a lithium salt.

The organic solvent may be any organic solvent that can act as a medium through which ions involved in an electrochemical reaction of a battery can move. Specifically, examples of the organic solvent include an ester solvent, an ether solvent, a ketone solvent, an aromatic hydrocarbon solvent, an alkoxyalkane solvent, a carbonate solvent, etc. These solvents may be used singly or in combination of two or more.

Specific examples of the ester solvent include methyl acetate, ethyl acetate, n-propyl acetate, dimethyl acetate, methyl propionate, ethyl propionate, But are not limited to, ethyl propionate,? -Butyrolactone, decanolide,? -Valerolactone, mevalonolactone,? -Caprolactone (? -caprolactone, 隆 -valerolactone, 竜 -caprolactone, and the like.

Specific examples of the ether solvent include dibutyl ether, tetraglyme, 2-methyltetrahydrofuran, tetrahydrofuran, and the like.

Specific examples of the ketone-based solvents include cyclohexanone and the like. Specific examples of the aromatic hydrocarbon organic solvent include benzene, fluorobenzene, chlorobenzene, iodobenzene, toluene, fluorotoluene, xylene, (xylene), and the like. Examples of the alkoxyalkane solvent include dimethoxy ethane and diethoxy ethane.

Specific examples of the carbonate solvent include dimethylcarbonate (DMC), diethylcarbonate (DEC), dipropylcarbonate (DPC), methylpropylcarbonate (MPC), ethylpropylcarbonate (EPC) , Methyl ethylcarbonate (MEC), ethylmethylcarbonate (EMC), ethylene carbonate (EC), propylene carbonate (PC), butylenes carbonate (BC) And fluoroethylene carbonate (FEC).

The lithium salt can be used without particular limitation as long as it is a compound capable of providing lithium ions used in a lithium secondary battery. Specifically, the lithium salt may be LiPF ₆ , LiClO ₄ , LiAsF ₆ , LiBF ₄ , LiSbF ₆ , LiAlO ₄ , LiAlCl ₄ , LiCF ₃ SO ₃ , LiC ₄ F ₉ SO ₃ , LiN (C ₂ F ₅ SO ₃ ) _{2 , LiN (C 2 F 5 SO} 2) 2, LiN (CF 3 SO 2) 2. _{LiN (C a F 2a + 1} SO 2) (C b F 2b + 1 SO 2) ( However, a and b is a natural number, preferably 1≤a≤20, 1≤b≤20 and Im), LiCl, LiI, LiB (C ₂ O ₄ ) _2, and mixtures thereof. It is preferable to use lithium hexafluorophosphate (LiPF ₆ ).

When the lithium salt is dissolved in the electrolyte, the lithium salt functions as a source of lithium ions in the lithium secondary battery and can promote the movement of lithium ions between the anode and the cathode. Accordingly, the lithium salt is preferably contained in the electrolyte at a concentration of about 0.6 mol% to 2 mol%. If the concentration of the lithium salt is less than 0.6 mol%, the conductivity of the electrolyte may be lowered and the performance of the electrolyte may be deteriorated. If the concentration exceeds 2 mol%, the viscosity of the electrolyte may increase and the mobility of the lithium ion may be lowered. Considering the conductivity of the electrolyte and the mobility of lithium ions, it is more preferable that the lithium salt is controlled to be approximately 0.7 mol% to 1.6 mol% in the electrolyte.

The electrolyte further includes an additive (hereinafter, referred to as "other additive") which can be generally used for an electrolyte for the purpose of improving lifetime characteristics of the battery, suppressing the decrease of battery capacity, and improving the discharge capacity of the battery in addition to the electrolyte components can do.

Examples of the other additives include vinylene carbonate (vinylenecarbonate, VC), metal fluoride (metal fluoride, for example, LiF, RbF, TiF, AgF , AgF2, BaF 2, CaF 2, CdF 2, FeF 2, HgF ₂ , Hg ₂ F ₂ , MnF ₂ , NiF ₂ , PbF ₂ , SnF ₂ , SrF ₂ , XeF ₂ , ZnF ₂ , AlF ₃ , BF ₃ , BiF ₃ , CeF ₃ , CrF ₃ , DyF ₃ , EuF ₃ , GaF _{3, GdF 3, FeF 3,} HoF 3, InF 3, LaF 3, LuF 3, MnF 3, NdF 3, PrF 3, SbF 3, ScF 3, SmF 3, TbF 3, TiF 3, TmF 3, YF 3, _{YbF 3, TIF 3, CeF 4} , GeF 4, HfF 4, SiF 4, SnF 4, TiF 4, VF 4, ZrF4 4, NbF 5, SbF 5, TaF 5, BiF 5, MoF 6, ReF 6, SF 6 , WF ₆ , CoF ₂ , CoF ₃ , CrF ₂ , CsF, ErF ₃ , PF ₃ , PbF ₃ , PbF ₄ , ThF ₄ , TaF ₅ and SeF ₆ ), glutaronitrile Succinonitrile (SN), adiponitrile (AN), 3,3'-thiodipropionitrile (TPN), vinylethylene carbonate (VEC) Fluoroethylene carbo Fluoroethylene carbonate (FEC), difluoroethylenecarbonate, fluorodimethylcarbonate, fluoroethylmethylcarbonate, lithium bis (oxalato) borate, LiBOB ), Lithium difluoro (oxalate) borate, LiDFOB, lithium (malonato oxalato) borate, LiMOB) and the like. Of these, 1 Or a mixture of two or more species. The other additives may be included in an amount of 0.1 to 5% by weight based on the total weight of the electrolyte.

The electrolyte may be contained in an amount of 100 to 1000 parts by weight based on 100 parts by weight of the polymer matrix. A higher charging / discharging efficiency can be obtained when it is contained in the above-mentioned weight ratio. If the amount of the electrolyte is less than 100 parts by weight, the ion conductivity of the protective layer may be low, thereby deteriorating battery characteristics. If the amount of the electrolyte is more than 1000 parts by weight, an excessively large amount of electrolyte is concentrated on the negative electrode, There is a risk of degradation. Even when the content of the electrolyte is 100 parts by weight, it is possible to prevent problems caused by a decrease in ionic conductivity by allowing the organic block to be inserted to have an ionic conductivity when the organic solvent is reacted with an organic solvent or when two or more monomers are used have.

The protective layer may preferably have a thickness of 1 nm to 10 탆. If the thickness of the protective layer is less than 1 nm, the side reaction and the exothermic reaction of the electrode active material and the electrolyte, which are increased under the conditions such as overcharging or high-temperature storage, can not be effectively suppressed and safety can not be improved. Is required to be impregnated or swelled by the electrolyte solution for a long period of time, and the movement of lithium ions is lowered, thereby deteriorating overall battery performance. In consideration of the remarkable improvement effect due to the formation of the protective layer, it is more preferable that the protective layer is formed to a thickness of 10 nm to 1 탆.

The negative electrode may further include a current collector for supporting the negative electrode active layer.

Specifically, the current collector may be any metal selected from the group consisting of copper, aluminum, stainless steel, titanium, silver, palladium, nickel, alloys thereof, and combinations thereof. The stainless steel may be carbon, Titanium or silver. As the alloy, an aluminum-cadmium alloy may be preferably used. Alternatively, a non-conductive polymer surface-treated with a conductive material, a conductive polymer, or the like may be used.

The negative electrode having the above-described structure is obtained by preparing a negative electrode active layer containing lithium; Forming a polymer matrix including a three-dimensional crosslinked network structure on the anode active layer, or a non-crosslinked polymer; And impregnating, spraying or spraying an electrolyte with respect to the polymer matrix to form an electrolyte in the polymer matrix to form a protective layer.

Step 1 is a step of forming an anode active layer. The anode active material is prepared by mixing a negative electrode active material, and optionally a binder and a conductive agent to form an anode active layer composition, and drying the anode active material layer. Alternatively, the lithium metal thin film itself may be used as the negative electrode active layer without a separate process.

The composition for forming the negative electrode active layer may be prepared by dispersing a negative electrode active material, and optionally a binder and a conductive agent in a solvent. The types and contents of the negative electrode active material, the binder and the conductive agent are the same as those described above.

Preferable examples of the solvent include dimethyl sulfoxide (DMSO), alcohol, N-methylpyrrolidone (NMP), acetone or water.

The method for coating the current collector with the composition for forming the anode active material layer may be selected from known methods in consideration of the characteristics of the material and the like or may be carried out by a new suitable method. For example, it is preferable that the composition for forming the anode active material layer is dispersed on a current collector and then uniformly dispersed using a doctor blade or the like. In some cases, a method of performing the distribution and dispersion processes in a single process may be used. In addition, methods such as die casting, comma coating, and screen printing may be used. At this time, the current collector is the same as described above.

Thereafter, the negative electrode active layer formed on the current collector may be dried. The drying process may be performed by heat treatment at a temperature of 80 to 120 ° C or hot air drying.

Further, a process such as rolling may be optionally further performed so that the negative electrode mixture prepared after the drying has an appropriate mixture density. Since the rolling method can be carried out according to the rolling method in the production of an ordinary electrode, a detailed description thereof will be omitted.

Next, Step 2 is a step of forming a polymer matrix on the negative electrode active layer prepared above.

Specifically, the polymer matrix may be chemically crosslinked by intermolecular branching chains, coupling between at least one monomer having a reactive multi-functional group, physical crosslinking of a cluster domain formed by phase-separation of the block copolymer, or Ionic crosslinking of the ionomer, or may be formed by the non-crosslinked linear polymer.

Accordingly, as a polymer matrix forming compound, a polymer or a monomer which forms a three-dimensional network structure through physical or chemical crosslinking; Or by coating or spraying a composition for forming a polymer matrix prepared by dissolving or dispersing a non-crosslinked nonlinear polymer in a solvent on the active layer of the negative electrode, or by immersing the negative active layer in the composition for forming a polymer matrix and then drying.

The specific types and contents of the non-crosslinked linear polymer and the polymer forming the three-dimensional network structure through the physical and chemical crosslinking are the same as described above.

In addition, the solvent may vary depending on the kind of the polymer used. Specifically, the solubility index is similar to that of the above-mentioned polymers, so that uniform mixing is easy, and a boiling point is low May be preferred. Specific examples thereof include acetone, tetrahydrofuran, methylene chloride, chloroform, dimethylformamide, N-methyl-2-pyrrolidone, NMP), cyclohexane, water, and mixtures thereof, but are not limited thereto.

Specifically, when the polymer matrix contains polysilsesquioxane by an organic-base sol-gel reaction, crosslinking may be carried out by acid treatment or heat treatment. In addition, in the case of the acid treatment, the polymer matrix may be prepared on another substrate in advance in order to prevent contact with lithium in the anode active layer, and then the polymer matrix may be transferred onto the anode active layer containing lithium.

When the polymer matrix includes a three-dimensional covalent bond skeleton frame formed by coupling between two or more monomers having reactive multi-functional groups, the reactive multi-functional groups in the monomer may be crosslinked even under mild conditions It may be preferable to use a monomer having an easily functional group.

The composition for forming a polymer matrix may further include an inorganic filler to improve the mechanical strength of the polymer matrix. The inorganic filler may be specifically silica, alumina, or the like, and may be preferably contained in an amount of 0.1 to 10% by weight based on the total weight of the composition for forming a polymer matrix.

Meanwhile, the polymer matrix forming composition may be coated on the active layer of the anode by a conventional method known in the art. For example, a dip coating, a die coating, a roll coating, Various methods such as comma coating or mixing method thereof can be used.

The drying process may then be carried out at 150-250 < 0 > C under vacuum for 12-24 hours. Particularly, in the case of drying after coating on the lithium thin film, it is more preferable to conduct the coating at a melting point (about 180 캜) of lithium.

Normally, a negative electrode active material such as lithium metal exhibits a high charge / discharge capacity, but is poor in reversibility and stability. Also, during the charging / discharging of the lithium secondary battery, loss of electrolyte or exhaustion occurs due to the volume change of the electrode, which makes it difficult to continuously drive the battery.

On the other hand, the negative electrode prepared by the above-described manufacturing method includes the polymer matrix and the protective layer including the electrolyte on the active layer of the negative electrode, so that the negative reactivity of the electrode active material and the electrolyte generated under extreme conditions such as filling or high- As a result, the amount of heat generated by the side reaction between the electrode and the electrolyte decreases, and the formation of dendrite on the surface of the electrode is suppressed, so that the safety of the battery can be greatly improved. In addition, the protective layer may exhibit excellent mechanical properties such as stretching and bending properties by including a polymer matrix. Therefore, even if charging / discharging is continued, the battery can be stably present without being damaged inside the battery.

According to another embodiment of the present invention, there is provided a lithium secondary battery including a negative electrode manufactured according to the above-described manufacturing method.

Specifically, the lithium secondary battery includes a cathode including a cathode active material disposed opposite to each other, a cathode including a cathode active material, and an electrolyte interposed between the anode and the cathode, and the cathode is the same as described above.

The lithium secondary battery may be classified into a lithium ion battery, a lithium ion polymer battery, and a lithium polymer battery according to the type of the separator and electrolyte used. The lithium secondary battery may be classified into a cylindrical shape, a square shape, a coin shape, Depending on the size, it can be divided into bulk type and thin type.

1 is an exploded perspective view of a lithium secondary battery 1 according to another embodiment of the present invention. FIG. 1 is an illustration for illustrating the present invention, but the present invention is not limited thereto.

1, the lithium secondary battery 1 includes a separator 7 disposed between a cathode 3, an anode 5, the cathode 3, and an anode 5 to form an electrode assembly 9 The negative electrode 3, the positive electrode 5 and the separator 7 are impregnated with the electrolyte by placing an electrolyte (not shown) in the case 15 and injecting an electrolyte (not shown).

Conductive lead members 10 and 13 for collecting a current generated during a battery operation can be attached to the cathode 3 and the anode 5 respectively and the lead members 10 and 13 are respectively connected to the anode 5, And the current generated in the cathode (3) can be led to the positive electrode terminal and the negative electrode terminal.

The anode 5 is prepared by mixing a cathode active material, a conductive agent and a binder to prepare a composition for forming a cathode active material layer, applying the composition for forming a cathode active material layer to a cathode current collector such as aluminum foil, can do. It is also possible to produce the positive electrode plate by casting the positive electrode active material composition on a separate support, then peeling the film from the support, and laminating the film on the metal current collector.

As the cathode active material, a compound capable of reversibly intercalating and deintercalating lithium (a lithiated intercalation compound) can be used. Specifically, a lithium-containing transition metal oxide may be preferably used. For example, LiCoO ₂ , LiNiO ₂ , LiMnO ₂ , LiMn ₂ O ₄ , Li (Ni _a Co _b Mn _c ) O ₂ (0 < 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 (O≤ 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 (0 <z <2), LiCoPO ₄ and LiFePO ₄ , or a mixture of two or more thereof. In addition to these oxides, sulfide, selenide and halide may be used.

The conductive agent and the binder are the same as those described above for the cathode.

The separator 7 is not particularly limited as long as it is used as a separator in a lithium secondary battery. In particular, it is preferable that the separator 7 is low in resistance against ion movement of the electrolyte and excellent in electrolyte wettability. Specifically, a porous polymer film made of a polyolefin-based polymer such as an ethylene homopolymer, a propylene homopolymer, an ethylene / butene copolymer, an ethylene / hexene copolymer and an ethylene / methacrylate copolymer may be used alone Or they may be laminated. Alternatively, nonwoven fabrics made of conventional porous nonwoven fabrics such as glass fibers of high melting point, polyethylene terephthalate fibers and the like may be used, but the present invention is not limited thereto.

The electrolytic solution may be the same as that described above in the formation of the protective layer.

Although the cylindrical lithium secondary battery 1 has been described as an example in the present embodiment, the present invention is not limited to the cylindrical lithium secondary battery 1, and any shape can be used as long as it can operate as a battery.

As described above, since the lithium secondary battery including the negative electrode active material according to the present invention stably exhibits excellent discharge capacity, cycle life characteristics and rate characteristics, it is possible to provide a lithium secondary battery which can be used for a portable telephone, a notebook computer, a digital camera, (HEVs), plug-in HEVs (PHEVs) and the like, as well as medium to large-sized energy storage systems.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

[ Manufacturing example  1: manufacture of negative electrode]

( Example  One)

The Sylgard 184 monomers purchased from Dow Corning were mixed with the curing agent in a weight ratio of 10: 1 to 10: 5. To control the thickness to a level of 1 to 10 mu m, hexane was added to dilute by means of a concentration lowering. The prepared solution was coated on the lithium metal thin film and thermally cured at 50 to 100 ° C for 1 hour to 12 hours. At this time, the higher the temperature, the shorter the curing time.

( Example  2)

A single monomer having a structure represented by the following formula (1) was subjected to sol-gel reaction to form polysilsesquioxane.

[Chemical Formula 1]

(Wherein, in the formula (1), R ₁ is oligethylene glycol)

A polymer matrix-forming composition prepared by dissolving 10 weight% of polysilsesquioxane prepared above in THF was applied as a negative electrode active layer on a thin film of lithium metal and cured at 100 캜 to form a polymer matrix.

In this case, the curing time and the degree of curing can be shortened by changing the solvent to alcohol or adding an acid or a base to the solution. In this case, considering the reactivity of lithium, it is cured on the other substrate such as Teflon sheet or PET sheet, It may be transferred onto a thin film.

(Example 3)

A three-dimensional covalent organic framework was formed on the thin film of lithium metal as an anode active layer by coupling of the monomer of the general formula (2) and the compound of the general formula (3a) as in the reaction scheme 1 above.

In the above general formulas (2) and (3a), R and R 'are oligoethylene glycols, X and Y are each an amino group, and Y is an isocyanate group. (2) and (3a) were dissolved in anhydrous DMF (concentration 0.04 g / mL) in an equivalent ratio of 1: 1 at room temperature and under a nitrogen atmosphere. When stirred, it usually exists in the sol state before 3 to 4 days, and then it is gelated. After coating on the thin film in the sol state, the solvent is dried to prepare a three-dimensional porous film.

(Example 4)

A composition for forming a polymer matrix was prepared by dissolving 10 wt% of polystyrene sulfonic acid in which a sulfonic acid group (SO ₃ H) at the polymer side chain end was substituted with SO ₃ Li in THF as an anode active layer on a thin film of lithium metal, Lt; / RTI &gt; to form a polymer matrix.

(Comparative Example 1)

A lithium metal thin film was used as an anode active layer.

[Production Example 2: Production of lithium secondary battery]

A lithium complete symmetric cell was fabricated using the electrodes prepared in the above Examples and Comparative Examples. A lithium secondary battery was manufactured by preparing an electrode assembly between two lithium electrodes through a porous polyethylene separator, placing the electrode assembly in a case, and injecting an electrolyte into the case. At this time, the electrolyte is also impregnated into the polymer matrix formed on the electrode.

The electrolyte solution was prepared by dissolving 1 M lithium hexafluorophosphate (LiPF ₆ ) in an organic solvent composed of ethylene carbonate / dimethyl carbonate (EC / EMC mixing ratio = 1/1).

A schematic view of the electrode thus manufactured is shown in Figs. 2 and 3. Fig. FIG. 2 is a schematic view of an electrode according to an embodiment, and FIG. 3 is a schematic view of an electrode according to a comparative example. 2 and 3, the electrode according to the embodiment has the polymer matrix 113 formed on the lithium metal thin film 112 placed on the current collector 111, and the electrolyte solution accumulates in the polymer matrix 113 do.

[Experimental Example 1: Measurement of cycle life characteristics of lithium secondary battery]

The cycle life of the lithium secondary batteries prepared in the above Examples and Comparative Examples was measured, and the results are shown in FIG.

The time point at which the discharge capacity sharply decreases at the measured cycle life and the electrolyte uptake were measured. The results are shown in Table 1 below.

Meanwhile, the lithium secondary battery was decomposed after completion of the cycle progress, and electrodes of Examples and Comparative Examples were shown in FIGS. 5 and 6, respectively.

Electrolyte uptake (wt.%) ¹⁾ When the discharge capacity rapidly decreases Comparative Example 1 0 After 30 cycles Example 1 400 to 1100 After 45 cycles Example 2 500 to 900 After 40 cycles Example 3 40-100 After 42 cycles

1) Electrolyte uptake (wt.%): The mass of each polymer matrix having a diameter of 19 mm before and after electrolyte impregnation was measured and the increase was calculated as a percentage.

Referring to FIGS. 4 to 6 and Table 1, in the case of the comparative example in which the electrode containing no polymer matrix storing the electrolyte was used, it was confirmed that the electrolyte was completely consumed when the cell was disassembled after completion of the cycle progress However, in the case where the electrode including the polymer matrix storing the electrolyte is applied, it can be confirmed that the electrolytic solution remains when the cell is disassembled after the completion of the cycle progress.

As a result, it can be seen that the porosity, electrolyte uptake, and cycle life of the negative electrode prepared in each Example are improved compared to Comparative Example 1 according to the presence or absence of the polymer matrix.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, Of the right.

1: Lithium secondary battery
3: cathode
5: anode
7: Separator
9: Electrode assembly
10, 13: lead member
15: Case
111: The whole house
112: Lithium metal thin film
113: polymer matrix

Claims (14)

An anode active layer containing lithium metal or an alloy of lithium metal, and
And a protective layer disposed on the negative active layer,
The protective layer may be formed,
i) polysilsesquioxane prepared by sol-gel reaction of a monomer having a structure represented by the following formula (1);
ii) a three-dimensional covalent linkage organic framework frame by coupling a monomer of formula 2 with a compound of any one of formulas 3a to 3c; And
iii) any one substituent selected from the group consisting of a sulfonic acid group (SO ₃ H), a phosphoric acid group (PO ₄ H ₂ ), a carbonic acid group (CO ₃ H) and a combination thereof; An ionic crosslinked body of an ionomer self-doped with lithium;
Wherein the polymer matrix comprises a polymer matrix,
And an electrolyte contained in the polymer matrix in an amount of 100 to 1000 parts by weight based on 100 parts by weight of the polymer matrix.
[Chemical Formula 1]

Wherein R &lt; 1 _&gt; is oligoethylene glycol,

(2)

Wherein R is oligoethylene glycol, X is an amino group,

[Chemical Formula 3]

(3b)

[Chemical Formula 3c]

In the above formulas (3a) to (3c), R 'is oligoethylene glycol and Y is an isocyanate group. The method according to claim 1,
Wherein the protective layer comprises a porous polymer matrix having a three-dimensional network structure of a polymer, and the electrolyte is contained in pores of the porous polymer matrix. 3. The method of claim 2,
Wherein the porous polymer matrix has a porosity of 5 to 80% by volume. delete delete delete delete delete delete delete The method according to claim 1,
Wherein the protective layer has a thickness of 1 nm to 10 占 퐉. The method according to claim 1,
Wherein the electrolyte is absorbed and contained in the polymer forming the polymer matrix. A step of preparing an anode active layer containing lithium;
Forming a polymer matrix according to claim 1 on the anode active layer; And
And impregnating, spraying or spraying an electrolyte with the electrolyte in an amount of 100 to 1000 parts by weight based on 100 parts by weight of the polymer matrix, thereby forming an electrolyte in the polymer matrix. An anode and a cathode arranged opposite to each other;
A separator interposed between the anode and the cathode; And
A non-aqueous electrolyte,
Wherein the cathode comprises an anode active layer containing lithium and a protective layer located above the anode active layer,
Wherein the protective layer comprises the polymer matrix according to claim 1 and an electrolyte contained in the polymer matrix in an amount of 100 to 1000 parts by weight based on 100 parts by weight of the polymer matrix.

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