JP2001052683A - Electrode having void lattice layer and battery having the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the Coulomb efficiency by inhibiting the production of dendritic crystals on an interface of electrodes and to improve the electrochemical performance by forming at least one lattice layer with void connected to the surface of a collector, on an electrode. SOLUTION: An inert framework or a lattice layer 38 on a first electrode 32 or a second electrode, including a collector or a base made of copper or the like is preferably made of an insulating material, which improves the deposition dissolution of lithium or the like as an electromotive force material. A number of openings 42 and voids 44 of the lattice layer 38 are preferably formed by a photolithographic method or a laser grinding method, which improves the accuracy in size and provides the uniform surface with respect to the deposition of lithium. It is preferable for the battery capacity to increase an area ratio of voids 44 or the like for depositing/ dissolving lithium and charging and discharging, within a range not impairing the strength. The dendritic crystals are not substantially produced near the surface of a metallic collector connected with the lattice layer 38 on its surface, the charging and discharging can be repeatedly executed, and further the effect can be improved by controlling the height of the grating layer 38.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrode and a battery comprising the electrode, and more particularly, to a void grid layer associated with a current collector surface, which suppresses the formation of dendrites and improves Coulomb efficiency. A battery comprising electrodes having the same. The present invention further relates to a method for manufacturing and charging / discharging the battery. The present invention particularly relates to a lithium ion battery using lithium as an electromotive substance, a method of manufacturing the same, and a method of charging and discharging.

[0002]

2. Description of the Related Art Lithium secondary batteries are well known. In addition, experimental studies related to lithium-based secondary batteries having intercalation-type electrodes have been conducted. Despite the ongoing research related to batteries using intercalable electrodes, there are still problems with regard to energy density and battery voltage. For this reason, lithium is directly deposited on the current collector (platform) without substantially generating dendrite crystals at the electrode interface and the accompanying degradation.
e) A method of causing this is being studied. Such batteries are preferred because the thickness of the battery is significantly reduced due to the absence of conventional active materials in the electrodes, and as a result a battery with substantially improved energy density can be obtained.

[0003] During the operation of such batteries, the lithium intercalation / deintercalation and / or alloying / dealloying action in conventional battery cycles replaces the deposition of lithium on the current collector.
ng) and a stripping action occurs.
Furthermore, the voltage characteristics of a battery using an electrode exhibiting a deposition / dissolution action instead of an intercalation type electrode are as follows:
It is very preferable because it shows a large capacity in a very narrow voltage range. Therefore, it is desirable to maximize the electrochemical performance of such batteries.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an electrode and a method for maximizing the electrochemical performance of a battery without substantially causing dendrite formation and associated degradation at the electrode interface. It is to provide a battery using electrodes.

[0005]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that by providing a lattice layer having at least one void associated with the surface of the current collector, the dendritic crystal can be formed. It has been found that generation can be suppressed and Coulomb efficiency can be improved, and the present invention has been completed.

The present invention has been completed based on the above findings, and a first gist of the present invention is to provide a current collector having a surface,
A battery electrode comprising a grid layer having at least one void associated with the surface of the current collector.

A second subject of the present invention resides in the electrode according to claim 1, wherein the lattice layer is formed by a lithographic method.

A third aspect of the present invention resides in the electrode according to the first aspect, wherein the lattice layer is formed by a laser grinding method.

A fourth aspect of the present invention resides in the electrode according to the first or second aspect, wherein the lattice layer is made of an insulating material.

A fifth aspect of the present invention is a battery having an electrolyte, a first electrode and a second electrode, wherein at least one of the first electrode and the second electrode is one of the first to fourth aspects. The battery according to any one of claims 1 to 3, wherein

A sixth aspect of the present invention is a method of manufacturing a first electrode having a current collector having a surface; and a step of associating a grid layer having at least one void with the surface of the current collector; A method for manufacturing a battery, comprising: a step of manufacturing a second electrode having a surface; and a step of associating at least one electrolyte with the first and second electrodes.

According to a seventh aspect of the present invention, there is provided a first and second electrodes having a current collector having a surface, a grid layer having at least one void associated with the surface, and the first and second electrodes. An electrochemical process in an electrochemical cell having two electrodes and an associated electrolyte, wherein the charging of the electrochemical cell (CHARGE) comprises the steps of: charging a surface of a current collector and the gap of the grid layer; Depositing (PLATE) lithium with at least one of them.

According to an eighth aspect of the present invention, in a battery having an electrolyte, a first electrode, and a second electrode, at least one of the first electrode and the second electrode includes a current collector, and a current collector. And a lattice layer having voids in which an electromotive substance can be deposited.

A ninth aspect of the present invention resides in the battery according to the eighth aspect, wherein the electromotive substance is lithium.

A tenth aspect of the present invention resides in the battery according to the eighth or ninth aspect, wherein the lattice layer is made of an insulating material.

According to an eleventh aspect of the present invention, there is provided an electrolyte having an electrolyte, a first electrode, and a second electrode, wherein at least one of the first electrode and the second electrode is provided on a current collector and on the current collector. A method for charging and discharging a battery, which is a grid electrode having a grid layer having voids, wherein charging and discharging are performed by depositing and dissolving an electromotive substance in the voids of the grid electrode. Charge and discharge method.

A twelfth aspect of the present invention resides in the method according to the eleventh aspect, wherein the electromotive substance is lithium.

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to the drawings. The present invention is not limited to the embodiments and descriptions illustrated below, as the invention is capable of various embodiments.

FIG. 1 is a schematic view of a conventional battery before initial charging. The conventional battery 10 before the initial charge usually has the first electrode 12, the second electrode 14, and the electrolyte 16. The first electrode 12 is made of a transition metal such as copper, and the second electrode 14 is made of a transition metal oxide. The electrolyte 16 is made of propylene carbonate (PC) or ethylene carbonate (EC)
Organic solvent (not shown).

FIG. 2 is a schematic view of a conventional battery after the initial charge. A conventional battery 10 after a charge / discharge cycle includes a first electrode 12, a second electrode 14, an electrolyte 16, and a dendritic crystal product 18. As will be described in more detail below, dendritic crystal formation reduces the Coulomb efficiency of the battery and shortens the battery life. Further, although not shown, the solvent in the electrolyte of the battery chemically reacts with the electrode surface and then generates gas when decomposed, which not only makes the battery inoperable but also dangerous.

FIG. 3 is a schematic diagram of the battery according to the present invention before the initial charging. Battery 3 according to the present invention before initial charge application
0 is usually the first electrode 32, the second electrode 34, the electrolyte 36
And an inert framework or lattice layer 38. One of the electrodes 32 and 34 includes a metal current collector or a substrate. As the current collector, in addition to the above-mentioned copper, many other transition metals, alkali metals, alkaline metals, transition metal oxides or other metal species can be used. Preferred are metals or alloys such as aluminum, nickel, stainless steel, and copper, and particularly preferred is copper as described above.

As the electrolyte 36, commercially available or conventionally used solvents and salts or electrolyte systems (such as liquid, polymer, gel and plastic systems) can be used. Typically, propylene carbonate (PC) or ethylene An electrolyte in which a conventional salt such as LiAsF ₆ is dissolved in a conventional solvent such as carbonate (EC) is used.

The grid layer 38 is associated with the current collector surface 40 of the first electrode 32, but may also be associated with the second electrode 34 and each of both electrodes 32 and 34. The lattice layer 38 is not particularly limited as long as it is stably present with lithium as an electromotive substance, and preferably has compatibility with a lithographic process or a laser grinding process. A typical example is a polymer film.

The material of the lattice layer is preferably an insulating material, and as a result, lithium can be deposited and dissolved more favorably.

FIG. 4 is a partial cross-sectional view of the battery according to the present invention showing the voids in the lattice layer 38, and FIG. 5 is a top view of the lattice layer of the present invention. The lattice layer 38 has a large number of openings 42 and voids 44. As described in detail below, the openings 42 and the voids 44 are formed by photolithographic and / or laser grinding techniques, and therefore have extremely high dimensional accuracy. With such high dimensional accuracy of holes and voids,
A very uniform surface can be obtained for lithium deposition. The opening 42 and the related void 44 are illustrated as having a circular cross section, but the geometric shape is not particularly limited. In addition, other shapes such as a triangle, a square, a pentagon, a hexagon, and an arbitrary shape may be used. Geometries can be used as well.

FIG. 6 is a partial sectional view of the battery according to the present invention, showing the lattice layers before and after being occupied by lithium. After associating the lattice layer 38 with the surface 40 of the metal current collector 32, substantially no dendrites are formed near the current collector surface.
Battery 30 can be charged and discharged multiple times.
The reason why such stability is obtained is that, for example, during charging, the lithium 46 is uniformly deposited on both the surface 40 of the electrode 32 and the wall 48 of the gap 44, that is, in the gap. Substantially uniform deposition can reduce dendritic crystal formation near the electrode 32. Furthermore, the height of the lattice layer 38 is regulated so that the lithium 46 does not protrude above the lattice layer, and the generation of dendritic crystals is further suppressed.

Charging and discharging are performed by depositing and dissolving lithium in the voids of the lattice layer 38. Therefore, the area occupied by the void portion with respect to the entire surface of the current collector (the area of the current collector on which lithium can be deposited) is preferably larger because the battery capacity becomes larger, and is usually 30% or more, preferably 50% or more.
% Or more, more preferably 80% or more, and most preferably 90% or more. However, if the gap portion is too large, the strength of the lattice portion of the lattice layer becomes insufficient or the processing itself becomes difficult. Therefore, the content is usually 99.99% or less, preferably 99.9% or less.

On the other hand, as the thickness of the lattice layer 38 increases, the area in which lithium can be deposited increases as the thickness increases.
Since dissolution becomes difficult, it is usually at least 0.1 μm, preferably at least 0.5 μm, more preferably at least 1 μm, most preferably at least 5 μm, and usually at most 200 μm, preferably at most 100 μm, more preferably at most 50 μm.
μ or less, more preferably 30 μm or less, and most preferably 10 μm or less.

Further, the distance between adjacent voids of the lattice layer 38 depends on the precision of fine processing such as laser processing and lithography, but it is preferable that the distance be as short as possible to increase the battery capacity, usually 10 μm or less, preferably 5 μm. Hereinafter, the thickness is more preferably 1 μm or less, further preferably 0.5 μm or less, and most preferably 0.3 μm or less. If a recent fine processing technology is used, the processing itself can have an accuracy of 0.2 μm or less.

Next, a method for manufacturing the battery of the present invention (battery 30 in FIG. 3) will be described. The method of the present invention includes the following steps.

First, the electrodes 32 and 34 are manufactured. For example, the electrode 32 can be formed as an anode having a current collector, and the electrode 34 can be formed as a cathode. In another battery configuration, the anode and cathode are interchangeable, depending on whether the battery is in a charged or discharged state. Batteries 32 and 34 can be formed by conventional techniques.

Next, a photosensitive polymer film (forming a grid layer 38) is associated with the surface 40 of the electrode 32. Photosensitive polymer film, for example, spray method,
The electrode 32 is formed by a roll coating method, a dipping method or a coating method.
Surface 40. Also, the photosensitive polymer film may be associated with the second electrode 34.
Although not required for all types of films, a conventional adhesion promoter may be applied to the surface 40 of the electrode 32.

Examples of the photosensitive polymer film include a photosensitive resin composition containing a photosensitive agent, a binder resin and a solvent. The photosensitive resin composition has, for example, a property that the solubility in a developer varies depending on the presence or absence of light irradiation, and compositions used in various fine processing processes can be used.

Next, a template having a desired exposure pattern is associated with the photosensitive polymer film.

The film is then exposed with a conventional photoenergy source to develop the exposed areas of the film.

Next, the template layer is removed, and the unexposed portions of the film are removed with a developing solution or the like to obtain a lattice layer 38.

Next, an electrolyte 36 is associated with each of the electrodes 32 and 34. The electrolyte 36 can be formed from a salt such as LiAsF ₆ dissolved in at least one solvent such as PC or EC. The electrolyte is manufactured using conventional techniques. An electrolyte interface material can optionally be applied on top of the grid layer 38.

In another embodiment, the grating layer 38 can be manufactured by laser grinding.

An electrode provided with a lattice layer (lattice electrode)
A state corresponding to a charged and discharged state is obtained by the deposition and dissolution of an electromotive substance such as lithium in the void.

The above description is merely illustrative, and the present invention
Various modifications and changes can be made without departing from the gist of the invention. Hereinafter, as an example of the above change, a configuration of a lithium ion battery preferably used as a battery will be described.

A lithium ion battery usually includes first and second electrodes corresponding to a positive electrode and a negative electrode, and an electrolyte layer interposed therebetween. The first electrode and the second electrode can be formed by binding an active material over a current collector.

Current collector: The material of the current collector can be appropriately selected from the various materials described above depending on the active material used. Preferably, aluminum is used as the current collector substrate of the positive electrode, and copper is used as the current collector substrate of the negative electrode.

The thickness of the current collector is appropriately selected, but is preferably 1 to 30 μm, and more preferably 1 to 20 μm. If it is too thin, the mechanical strength tends to be weak, which is a problem in production. If it is too thick, the capacity of the battery as a whole decreases.

It is preferable that the surface of the current collector is previously subjected to a surface roughening treatment, since the adhesive strength of the electrode material is increased. Examples of the surface roughening method include a mechanical polishing method, an electrolytic polishing method, and a chemical polishing method. Examples of the mechanical polishing method include a method of polishing the surface of the current collector with a polishing cloth paper having abrasive particles fixed thereon, a grindstone, an emery buff, a wire brush provided with a steel wire, or the like. Further, an intermediate layer may be formed on the surface of the current collector to increase the adhesive strength and the conductivity.

Further, the shape of the current collector may be a plate shape other than the metal mesh.

Active material: The active material used for the first electrode or the second electrode may be appropriately selected according to the type and characteristics of the battery to be manufactured. In the present invention, as described above, at least one of the first electrode and the second electrode is provided with a grid layer on the current collector, and deposits and dissolves lithium in voids provided in the grid layer. The electrode provided with the lattice layer may be used as a positive electrode or a negative electrode, but is preferably used as a negative electrode.

When an electrode provided with a lattice layer is used as the first electrode, an inorganic compound or an organic compound can be used as an active material used for the second electrode as long as the material can function as a battery. Transition metal oxides as inorganic compounds,
Examples thereof include complex oxides of lithium and a transition metal such as the above-mentioned LiNiO ₂ , LiCoO ₂ , and LiMn ₂ O ₄ , and chalcogen compounds such as a transition metal sulfide. Here, Fe, Co, Ni, Mn, or the like is used as the transition metal. Specifically, transition metal oxides such as MnO, V ₂ O ₅ , V ₆ O ₁₃ and TiO ₂ , composite oxides of lithium and transition metal such as lithium nickelate, lithium cobaltate and lithium manganate, TiS ₂ , transition metal sulfides such as FeS and MoS ₂ . These compounds may be partially substituted with elements in order to improve their properties. Further, carbonaceous particles such as graphite and coke can also be used. Such a carbon-based material can also be used in the form of a mixture or coating with a metal, metal salt, oxide, or the like. Further, oxides and sulfates of silicon, tin, zinc, manganese, iron, nickel and the like, metallic lithium, Li-Al, L
lithium alloys such as i-Bi-Cd, Li-Sn-Cd,
Lithium transition metal nitride, silicon and the like can also be used. Examples of the organic compound include polyaniline, polypyrrole, polyacene, disulfide compounds, polysulfide compounds, and the like. Of course, a plurality of these can be used in combination. Preferably, it is a composite oxide of lithium and a transition metal, particularly a composite oxide of lithium and at least one transition metal selected from the group consisting of cobalt, nickel and manganese.

The particle size of the active material may be appropriately selected depending on the balance with other components of the battery.
The thickness is preferably from 30 to 30 μm, particularly from 1 to 10 μm, since battery characteristics such as initial efficiency and cycle characteristics are improved.

Other Structure of Electrode: It is preferable to use a binder to bind the active material on the current collector. As the binder, inorganic compounds such as silicate and glass, and various resins mainly composed of polymers can be used.

Examples of the resin include alkane polymers such as polyethylene, polypropylene and poly-1,1-dimethylethylene; unsaturated polymers such as polybutadiene and polyisoprene; polystyrene, polymethylstyrene, polyvinylpyridine and poly-N -Polymers having a ring such as vinylpyrrolidone; acrylic polymers such as polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polyethyl acrylate, polyacrylic acid, polymethacrylic acid and polyacrylamide Fluorinated resins such as polyvinyl fluoride, polyvinylidene fluoride (PVDF), and polytetrafluoroethylene; CN group-containing polymers such as polyacrylonitrile and polyvinylidene cyanide; polyvinyl acetate, polyvinyl Polyvinyl alcohol polymers, such as alcohol; polyvinyl chloride, halogen-containing polymers such as polyvinylidene chloride; and conductive polymers such as polyaniline can be used. Further, a mixture of the above-mentioned polymers and the like, a modified product, a derivative, a random copolymer, an alternating copolymer, a graft copolymer, a block copolymer and the like can also be used.

The blending amount of the binder with respect to 100 parts by weight of the active material is preferably 0.1 to 30 parts by weight, more preferably 1 to 15 parts by weight. If the amount of the resin is too small, the strength of the electrode may decrease. If the amount of the resin is too large, the capacity may decrease, or the late characteristics may decrease.

The electrodes may contain additives, such as conductive materials and reinforcing materials, which exhibit various functions, powders, fillers, and the like, if necessary. The conductive material is not particularly limited as long as it can impart conductivity by mixing an appropriate amount with the active material, but usually, acetylene black, carbon black, carbon powder such as graphite, and various metal fibers,
Foil and the like. As additives, trifluoropropylene carbonate, vinylene carbonate, 1,6-
Dioxaspiro [4,4] nonane-2,7
-Dione, 12-crown-4-ether and the like can be used to increase the stability and life of the battery. As the reinforcing material, various inorganic or organic spherical or fibrous fillers can be used.

As a method of forming an electrode on a current collector,
For example, a method in which a powdery active material is mixed with a solvent together with a binder, and if necessary, a ball mill, a sand mill, a twin-screw kneader or the like is used to form a dispersion paint, and then applied on a current collector and dried. Done. In this case, the type of the solvent used is not particularly limited as long as it is inert to the electrode material and can dissolve the binder. For example, any of commonly used inorganic and organic solvents such as N-methylpyrrolidone can be used. Can also be used.

Further, the electrode material layer can be formed by a method of pressing or spraying on the current collector in a state where the active material is mixed with a binder and heated to be softened. Furthermore, it can be formed by firing the active material alone on the current collector.

The thickness of the active material layer is usually at least 1 μm, preferably at least 10 μm. In addition, usually 200
μm or less, preferably 150 μm or less. If it is too thin, it becomes difficult to ensure uniformity of the active material layer, and the capacity tends to decrease. On the other hand, if the thickness is too large, the rate characteristics tend to decrease.

A primer layer can be provided between the current collecting substrate and the active material layer. As a result, the adhesiveness between the current collecting substrate and the active material layer can be further improved. The primer layer is a paint containing a conductive material, a binder and a solvent,
It can be formed by drying after coating on the current collecting substrate.

As the conductive material used for the primer layer, various materials such as carbonaceous particles such as carbon black and graphite, metal powders, and conductive polymers can be used. The same binder and solvent as those used for the active material layer can be used for the primer layer. The thickness of the primer layer is usually 0.05 μm or more, preferably 0.1 μm or more, and usually 20 μm or less, preferably 10 μm or less. If it is too thin, it tends to be difficult to ensure uniformity of the primer layer. If the thickness is too large, the capacity rate characteristics of the battery tend to decrease.

Electrolyte: The electrolyte interacts with the first and second electrodes and participates in ion transfer between the electrodes. The electrolyte usually exists as an electrolyte layer between the electrodes and also exists in the active material layer, and comes into contact with at least a part of the surface of the active material. The electrolyte can be related to the electrode or the electrode active material by being brought into contact with the first electrode or the second electrode by a method such as coating.

The electrolyte generally includes various electrolytes such as an electrolyte having fluidity, and a non-fluid electrolyte such as a gel electrolyte and a completely solid electrolyte. An electrolyte or a gel electrolyte is preferable in terms of battery characteristics, and a non-fluid electrolyte is preferable in terms of safety. In particular, when a non-fluid electrolyte is used, liquid leakage can be more effectively prevented for a battery using a conventional electrolyte.

The electrolytic solution used as the electrolyte is usually obtained by dissolving a supporting electrolyte in a non-aqueous solvent.

As the supporting electrolyte, any non-aqueous substance which is stable as an electrolyte with respect to the positive electrode and the negative electrode and which can transfer lithium ions to perform an electrochemical reaction with the positive electrode active material or the negative electrode active material can be used. Can also be used. Specifically, the LiAsF
₆ , LiBF ₄ , LiPF ₆ , LiSbF ₆ , LiCl
O ₄ , LiI, LiBr, LiCl, LiAlCl, L
Lithium salts such as iHF ₂ , LiSCN, and LiSO ₃ CF ₂ are mentioned. Of these, LiPF ₆ , Li
ClO ₄ is preferred.

When these supporting electrolytes are used in the state of being dissolved in a non-aqueous solvent, the concentration is usually 0.5 to 3 mol / mol.
L, preferably 0.5 to 2.5 mol / L.

As the solvent, a solvent having a relatively high dielectric constant is preferably used. Specifically, cyclic carbonates including ethylene carbonate and propylene carbonate, acyclic carbonates such as dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate, glymes such as tetrahydrofuran, 2-methyltetrahydrofuran and dimethoxyethane, and γ- Lactones such as butyrolactone, sulfur compounds such as sulfolane,
Examples thereof include nitriles such as acetonitrile. Also, one or a mixture of two or more of these can be used. Of these, especially ethylene carbonate,
One or more solvents selected from cyclic carbonates such as propylene carbonate, and non-cyclic carbonates such as dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate are preferred. In addition, those in which a part of hydrogen atoms in these molecules are substituted with halogen or the like can also be used. Other preferred solvents include cyclic carbonates, especially propylene carbonate.

The gel electrolyte that can be used as the electrolyte is
Usually, the above electrolyte is held by a polymer. In other words, the gel electrolyte is one in which the electrolyte is usually held in a polymer network and the fluidity as a whole is significantly reduced. Such a gel electrolyte exhibits properties such as ionic conductivity that are close to those of a normal electrolyte solution, but fluidity, volatility and the like are significantly suppressed, and safety is enhanced. The ratio of the polymer in the gel electrolyte is preferably 1 to
50% by weight. If the temperature is too low, the electrolyte cannot be held, and a liquid leak may occur. If it is too high, the ionic conductivity tends to decrease and battery characteristics tend to deteriorate.

Polymers used for the gel electrolyte include:
There is no particular limitation as long as it is a polymer that can form a gel together with the electrolytic solution, and polyester, polyamide, polycarbonate, those produced by polycondensation such as polyimide,
Polyurethane, polyurea, etc. produced by polyaddition, acrylic derivative polymers such as polymethyl methacrylate, and polyadditions produced by polyvinyl polymerization such as polyvinyl acetate, polyvinyl chloride, polyvinylidene fluoride, etc. and so on. Preferred polymers include polyacrylonitrile and polyvinylidene fluoride. Here, the polyvinylidene fluoride includes not only a homopolymer of vinylidene fluoride but also a copolymer with another monomer component such as hexafluoropropylene. Also, acrylic acid, methyl acrylate,
Ethyl acrylate, ethoxyethyl acrylate, methoxyethyl acrylate, ethoxyethoxyethyl acrylate, polyethylene glycol monoacrylate,
Ethoxyethyl methacrylate, methoxyethyl methacrylate, ethoxyethoxyethyl methacrylate, polyethylene glycol monomethacrylate, N, N-diethylaminoethyl acrylate, N, N-dimethylaminoethyl acrylate, glycidyl acrylate, allyl acrylate, acrylonitrile, N-vinylpyrrolidone, diethylene glycol di Acrylic derivative obtained by polymerizing monomers such as acrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and polyethylene glycol dimethacrylate. system Rimmer can also be preferably used.

The weight average molecular weight of the above polymer is usually 10
000 to 5,000,000. If the molecular weight is low, it is difficult to form a gel. If the molecular weight is high, the viscosity becomes too high and handling becomes difficult. The concentration of the polymer in the electrolytic solution may be appropriately selected according to the molecular weight, but is preferably from 0.1% by weight to 30% by weight. If the concentration is too low, it is difficult to form a gel, the retention of the electrolytic solution is reduced, and problems of flow and liquid leakage may occur. If the concentration is too high, the viscosity becomes too high, which causes difficulties in the process, and the proportion of the electrolytic solution is reduced, the ionic conductivity is reduced, and the battery characteristics such as rate characteristics may be reduced.

A completely solid electrolyte can be used as the electrolyte. As such a solid electrolyte, various solid electrolytes known so far can be used. For example, it can be formed by mixing the polymer used in the gel electrolyte and the supporting electrolyte salt at an appropriate ratio. In this case, in order to increase the conductivity, it is preferable to use a polymer having a high polarity and to have a skeleton having many side chains.

The above-mentioned additive can be added to the first or second electrode containing the carbonaceous material, but is usually added to the electrolyte to associate with the battery.

[0069]

The battery of the present invention is provided with a lattice layer having at least one void associated with the surface of the current collector, and deposits and dissolves an electromotive substance in the void to reduce the formation of dendritic crystals. It is a battery that can suppress and improve the Coulomb efficiency and maximizes the electrochemical performance of the battery, and the industrial value of the present invention is high.

[Brief description of the drawings]

FIG. 1 is a schematic diagram of a conventional battery before initial charging.

FIG. 2 is a schematic diagram of a conventional battery after initial charging.

FIG. 3 is a schematic diagram of a battery according to the present invention before initial charging.

FIG. 4 is a partial cross-sectional view of a battery according to the present invention, showing voids in a lattice layer.

FIG. 5 is a top view of the lattice layer of the present invention.

FIG. 6 is a partial cross-sectional view of the battery according to the present invention, showing the lattice layers before and after being occupied by lithium.

[Explanation of symbols]

 10: Conventional battery 12: First electrode 14: Second electrode 16: Electrolyte 18: Dendritic crystal product 30: Battery according to the present invention 32: First electrode 34: Second electrode 36: Electrolyte 38: Inactive frame Work or lattice layer 40: Current collector surface 42: Opening 44: Void 46: Lithium 48: Wall

Claims (12)

[Claims] 1. A battery electrode comprising: a current collector having a surface; and a grid layer having at least one void associated with the surface of the current collector. 2. The electrode according to claim 1, wherein said grid layer is formed by a lithographic method. 3. The electrode according to claim 1, wherein the grid layer is formed by a laser grinding method. 4. The electrode according to claim 1, wherein the lattice layer is made of an insulating material. 5. A battery having an electrolyte, a first electrode and a second electrode, wherein at least one of the first electrode and the second electrode is the electrode according to any one of claims 1 to 4. Battery. 6. A method of manufacturing a first electrode comprising a current collector having a surface; associating a grid layer having at least one void with the surface of the current collector; A method for manufacturing a battery, comprising: manufacturing; and associating at least one electrolyte with the first and second electrodes. 7. A first and second electrode having a current collector having a surface, a grid layer having at least one void associated with the surface, and an electrolyte associated with the first and second electrodes. An electrochemical process in an electrochemical cell having a charge, wherein the electrochemical cell is charged (CHARGE).
And depositing (PLATE) lithium on the surface of the current collector and at least one of the voids of the grid layer. 8. A battery having an electrolyte, a first electrode and a second electrode, wherein at least one of the first electrode and the second electrode is a current collector and an electromotive substance provided on the current collector. And a lattice layer having voids capable of precipitating water. 9. The battery according to claim 8, wherein the electromotive substance is lithium. 10. The lattice layer is made of an insulating material.
Or the battery according to 9. 11. A grid having an electrolyte, a first electrode, and a second electrode, wherein at least one of the first electrode and the second electrode has a current collector and a gap provided on the current collector and having a gap. And charging and discharging the battery by depositing and dissolving an electromotive substance in the gap of the grid electrode. 12. The method according to claim 1, wherein the electromotive substance is lithium.
2. The method according to 1.