CN106935793B - Negative electrode, method of preparing the same, and lithium secondary battery including the same - Google Patents

Negative electrode, method of preparing the same, and lithium secondary battery including the same Download PDF

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CN106935793B
CN106935793B CN201710133765.6A CN201710133765A CN106935793B CN 106935793 B CN106935793 B CN 106935793B CN 201710133765 A CN201710133765 A CN 201710133765A CN 106935793 B CN106935793 B CN 106935793B
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active material
negative electrode
anode
anode active
material layer
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CN106935793A (en
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安炳勋
裴峻晟
丘昌完
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LG Energy Solution Ltd
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LG Chem Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • H01M4/0435—Rolling or calendering
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a negative electrode, a method of preparing the negative electrode, and a lithium secondary battery including the negative electrode. The negative electrode includes: an electrode collector; and a multilayer active material layer formed on the electrode collector, wherein the multilayer active material layer includes: a primary anode active material layer containing a first anode active material; and a secondary anode active material layer including a second anode active material having a lower compacted density and a larger average particle size than the first anode active material, wherein the first anode active material and the second anode active material each include crystalline carbon. The negative electrode of the present invention can improve the porosity of the surface of the electrode even after the rolling step, and can improve the mobility of ions into the electrode, and thus can improve the charging characteristics and the life characteristics of the lithium secondary battery.

Description

Negative electrode, method of preparing the same, and lithium secondary battery including the same
The present invention is a divisional application of chinese patent application having application number 201480000767.2, entitled "negative electrode for lithium secondary battery and lithium secondary battery including the same" with application date of 2014, 1 month and 22 days.
Technical Field
The present invention relates to a negative electrode for a lithium secondary battery and a lithium secondary battery including the same, and more particularly, to a negative electrode including a plurality of active material layers having different compacted densities and average particle sizes of a negative electrode active material from each other and a lithium secondary battery including the same.
Background
With the rising energy prices and increasing concerns about environmental pollution caused by the depletion of fossil fuels, environmental protection as an alternative energy source is an indispensable factor for future life. Accordingly, many power generation technologies utilizing natural energy such as atomic energy, sunlight, wind power, and tidal power have been continuously studied, and power storage devices that more effectively utilize the energy generated in the above manner have also been attracting attention.
In particular, as technical research and development and demand for mobile devices increase, demand for secondary batteries as an environmentally-friendly alternative energy source is sharply increasing. Recently, the secondary battery is used as a power source for devices requiring large capacity power, such as Electric Vehicles (EV) and Hybrid Electric Vehicles (HEV), and is used in a wide range of applications, such as a Grid (Grid) powered electric power assist power source.
In order to be used as a power source for a device requiring such large-capacity electric power, it is necessary to have a high energy density of 10 years or more, excellent safety, and long-term life characteristics even under severe conditions in which charging and discharging are repeated at a high current for a short time, in addition to the property of exhibiting large power in a short time.
Although lithium metal has been conventionally used as a negative electrode of a secondary battery, carbon compounds capable of achieving reversible lithium ion insertion (intercalation) and desorption while maintaining structural and electrical properties have been replacing the lithium metal, with the understanding of the risk of battery short-circuiting due to dendrite (dendrite) formation and explosion due to dendrite formation.
The carbon-based compound has a very low discharge potential of about-3V with respect to a standard hydrogen electrode potential, and exhibits excellent electrode life characteristics due to a very reversible charge-discharge operation caused by a uniaxial orientation of a graphene layer. Further, when Li ions are charged, the electrode potential is 0VLi/Li +, and a potential almost similar to that of pure lithium metal can be exhibited, and therefore, there is an advantage that higher energy can be obtained when a battery is constituted with an oxide-based positive electrode.
The negative electrode for a secondary battery is prepared by mixing a carbon material as a negative electrode active material 13, and if necessary, a conductive material and a binder to prepare a negative electrode active material slurry, and then coating the slurry in a single layer on an electrode current collector 11 such as a copper foil and drying the same. At this time, a rolling step (see fig. 1) is performed to make the thickness of the electrode uniform by pressing the active material powder against the current collector when the slurry is applied.
However, in the conventional electrode rolling process, the pressing of the surface is increased as compared with the inside of the negative electrode active material, and the void (pore) ratio on the surface is decreased.
Such a phenomenon becomes more remarkable as the thickness of the electrode becomes thicker, and it becomes difficult to ensure a moving path of ions as the electrolyte is hardly impregnated into the electrode, and it becomes difficult to smoothly move the ions, thereby causing deterioration in battery performance and life characteristics.
Disclosure of Invention
Technical problem
The problem to be solved by the present invention is to provide an anode having improved ion mobility to the inside of an electrode by including a plurality of active material layers in the anode.
Also, the present invention provides a lithium secondary battery having improved charging characteristics and life characteristics by including the negative electrode.
Technical scheme
In order to solve the problem, a negative electrode according to an embodiment of the present invention includes:
an electrode collector; a multilayer active material layer formed on the electrode collector, wherein the multilayer active material layer comprises: a primary anode active material layer containing a first anode active material; and a secondary anode active material layer containing a second anode active material having a lower compacted density and a larger average particle size than the first anode active material.
Also, according to an embodiment of the present invention, there is provided a lithium secondary battery including the negative electrode.
Advantageous effects
The negative electrode according to an embodiment of the present invention includes a plurality of active material layers containing two types of negative electrode active materials having different compaction densities and average particle sizes of the negative electrode active materials on an electrode current collector, and thus can improve porosity (porosity) on the surface of the electrode even after a rolling process and improve mobility of ions into the inside of the electrode, and therefore, can be usefully applied to a lithium secondary battery, and can improve charging characteristics and life characteristics of the lithium secondary battery.
Drawings
Fig. 1 is a schematic view of a conventional negative electrode structure including a single active material layer.
Fig. 2 is a schematic view of a negative electrode structure composed of a plurality of active material layers according to an embodiment of the present invention.
Fig. 3 is a graph in which the charging characteristics of the lithium secondary batteries of example 1 and comparative examples 1 and 2 were measured according to experimental example 2.
Fig. 4 and 5 are graphs showing life characteristics of the lithium secondary batteries of example 1 and comparative example 1, which were measured based on the anode density, according to experimental example 3.
Description of reference numerals
11. 21: electrode collector
13: negative electrode active material
23: a first negative electrode active material
24: second negative electrode active material
A: primary negative electrode active material layer
B: secondary negative electrode active material layer
Detailed Description
The present invention will be described in detail below.
As shown in the schematic diagram of fig. 2, the negative electrode according to an embodiment of the present invention may include: an electrode collector 21; a primary anode active material layer a including a plurality of active material layers formed on the electrode collector, and the plurality of active material layers containing a first anode active material 23; and a secondary anode active material layer B containing a second anode active material 24 having a lower compacted density and a larger average particle size than the first anode active material.
In the negative electrode according to an embodiment of the present invention, the electrode current collector includes the multi-layer active material layer containing two types of negative electrode active materials having different compaction densities and average particle sizes of the negative electrode active materials, so that the porosity of the electrode surface can be increased even after the rolling step, and the mobility of ions into the electrode interior can be improved, thereby improving the charging characteristics and the life characteristics of the lithium secondary battery.
First, the electrode collector may be one or two selected from the group consisting of stainless steel, aluminum, nickel, titanium, calcined carbon, copper, stainless steel surface-treated with carbon, nickel, titanium or silver, aluminum-cadmium alloy, non-conductive polymer surface-treated with a conductive material, and conductive polymer.
In the negative electrode of the present invention, the first negative electrode active material and the second negative electrode active material may be crystalline carbon such as natural graphite and artificial graphite having a theoretical maximum capacity of 372mAh/g (844mAh/cc), amorphous carbon such as soft carbon and hard carbon, or a mixture thereof so that a high energy density can be secured.
Specifically, the first negative electrode active material and the second negative electrode active material may be crystalline carbons such as natural graphite and artificial graphite having a spherical shape or a sphere-like shape, or may be others.
Also, in the anode of one embodiment of the present invention, the ratio of the average particle size of the first anode active material to the average particle size of the second anode active material may be 1:9 to 5:5.1, more specifically, may be 1:1.3 to 1: 4. As a non-limiting example, the average particle size of the first negative electrode active material may be about 20 μm or less, and specifically, may be in a range of, for example, 10 μm to 18 μm.
For example, the average particle size of the negative electrode active material according to an embodiment of the present invention may be measured by a laser diffraction method. Generally, the laser diffraction method can measure a particle diameter of about a few mm from a submicron (submicron) range, and can obtain a result of high reproducibility and high resolution. Average particle size D of negative electrode active material50Can be defined as the particle size in 50% basis of the particle size distribution.
Also, in the anode of one embodiment of the present invention, a ratio of the compacted densities of the first anode active material and the second anode active material is 1.1:1 to 3:1, preferably 1.1:1 to 1.5:1 under a pressure condition of 12 to 16 MPa.
According to an embodiment of the present invention, the compacted densities of the first and second anode active materials are not particularly limited as long as the compacted density ratio of the first and second anode active materials that can satisfy the above-described range is satisfied. But preferably, for example, the first anode active material has a compacted density of 1.4 to 1.85g/cc at a pressure of 12 to 16MPa, and the second anode active material has a compacted density of 1.4 to 1.6g/cc at a pressure of 12 to 16 MPa.
The compaction density is a comparison of the degree of particle deformation of the negative electrode active material, and when calendering is performed at the same pressure, the lower the compaction density value, the better the compressive strength. The compacted density of the first and second negative electrode active materials can be measured using, for example, a powder resistance meter MCP-PD51 manufactured by Mitsubishi chemical corporation. In the case of using the powder resistance measuring instrument, a predetermined amount of negative electrode active material powder was put into a cylinder type load cell (load cell), and the pressure was continuously applied, and at this time, the density of the particles when pressed was measured. The stronger the particle, the less it will be pressed under the same pressure, and therefore, the lower the pressing density can be exhibited.
Also, in the anode of an embodiment of the present invention, a ratio of compressive strengths of the first anode active material and the second anode active material may be 2:8 to 5:5.1, specifically, may be in a range of 2:8 to 4:7 under a pressure condition of 12 to 16 MPa.
Also, the porosity of the entire volume of the primary anode active material layer, for example, the ratio of pores including a size of 0.1 to 10 μm is about 10 to 50 weight percent, and the porosity is about 10 to 50 weight percent in the entire volume of the secondary anode active material layer. At this time, the pore size and/or porosity in the secondary anode active material layer may be relatively large or high as compared to the pore size and/or porosity of the primary anode active material layer. For example, in the case where the porosity of the primary anode active material layer and the secondary anode active material layer is also 27%, the size of pores between the active material and the active material of the primary anode active material layer may be 0.4 to 3 μm, and the size of pores between the active material and the active material of the secondary anode active material layer may be 0.5 to 3.5 μm.
That is, the anode of the present invention can prevent damage to the surface of the anode active material layer at the time of the rolling process by increasing the porosity of the surface of the anode active material layer so as to form the secondary anode active material layer on the primary anode active material layer composed of the first anode active material having a higher compacted density and a relatively smaller average particle size than the second anode active material, and can improve the pore structure inside the electrode.
On the other hand, in the case of forming an electrode composed of a conventional single active material layer, since the pressure cannot be transmitted to the inside of the electrode due to the characteristics of the single negative electrode active material layer which is weak in stress due to softness (soft) at the time of rolling process, only the negative electrode active material on the surface of the electrode is pressed seriously. For example, in the case where an electrode is formed using only a single active material layer having a low compacted density and a large average particle size as in the second negative electrode active material, only the negative electrode active material on the surface of the electrode is severely compressed due to the characteristics of the single negative electrode active material layer having a weak stress at the time of the rolling process. As a result, the porosity between the negative electrode active materials near the surface of the electrode decreases, and thus the mobility of ions into the electrode decreases. This phenomenon may be more serious the thicker or higher the density of the electrode of the negative electrode.
However, as in the present invention, when two or more types of negative electrode active materials having high stress are used depending on the difference in the compacted density and the average particle size, and particularly when a negative electrode active material having a relatively lower compacted density in the secondary negative electrode active material layer than in the primary negative electrode active material layer is used, the more excellent the compressive strength of the negative electrode active material applied in the vicinity of the surface of the electrode, the more relaxed the pressing phenomenon of the electrode surface during rolling. Therefore, the porosity of the surface of the electrode, that is, the secondary anode active material layer is higher than that of the inside of the electrode, that is, the primary anode active material layer, and therefore, the movement of ions into the inside of the electrode is facilitated, and the ion mobility can be improved (see fig. 2).
The first negative electrode active material and the second negative electrode active material of the present invention may further contain a conductive material and a binder as needed.
In this case, examples of the conductive material include nickel powder, cobalt oxide, titanium oxide, carbon, and the like. Examples of the carbon include one selected from the group consisting of ketjen black, acetylene black, furnace black, graphite, carbon fiber, and fullerene, or a mixture of two or more of these.
The binder may be any binder resin conventionally used in lithium secondary batteries, and examples thereof include one selected from the group consisting of polyvinylidene fluoride, carboxymethyl cellulose, methyl cellulose, and sodium polyacrylate, or a mixture of two or more thereof.
Also, according to an embodiment of the present invention, there is provided a method of manufacturing a negative electrode, including: a step of applying a first negative electrode active material slurry containing a first negative electrode active material and a binder resin on an electrode collector; a step of forming a primary anode active material layer so as to dry the first anode active material slurry; a step of applying a second negative electrode active material slurry containing a second negative electrode active material and a binder resin on the primary negative electrode active material layer; a step of forming a secondary anode active material layer so as to dry the second anode active material slurry; and rolling the electrode current collector on which the primary and secondary negative electrode active material layers are formed.
Also, the above method may apply the second anode active material slurry before the first anode active material slurry is dried. That is, the steps of applying the first and second anode active material slurries may be continuously performed without a drying step, and the steps of drying and rolling the applied slurries may be implemented at one time.
The rolling process may be performed under the same process conditions as in a conventional electrode preparation method.
In the method of the present invention, before the rolling step, the pore size of the inside of the primary anode active material layer is about 1 to 20 μm, and the porosity in the entire volume of the primary anode active material layer is about 50%. However, after the rolling process is performed, the pore size of the inside of the primary anode active material layer is about 0.1 to 3 μm, and the porosity in the entire volume of the primary anode active material layer is about 10% to about 50%.
Before the rolling step, the pore size in the secondary anode active material layer is about 1 to 30 μm, and the porosity of the secondary anode active material layer in the entire volume is about 50%. However, after the rolling process is performed, the pore size of the inside of the secondary anode active material layer is about 0.1 to 5 μm, and the porosity in the entire volume of the secondary anode active material layer is about 10% to 50%.
In the primary anode active material layer and the secondary anode active material layer, the ratio of the porosity before rolling may be 5:5.1, and the ratio of the porosity after rolling may be 5:5.1 to 2: 8.
Also, the pore size and/or porosity in the secondary anode active material layer may be relatively larger or higher than that of the primary anode active material layer, and for example, in the case where the ratio of the porosities of the primary anode active material layer and the secondary anode active material layer is 4:6 (20%: 30%), the size of the pores of the primary anode active material layer may be 0.4 to 3 μm, and the size of the pores of the secondary anode active material layer may be 0.5 to 3.5 μm.
In general, in the negative electrode to which the negative electrode active material is applied, pores having a size of 0.1 to 10 μm play a role in increasing the impregnation rate of the electrolytic solution and the transfer rate of lithium ions. When a negative electrode composed of only a single active material layer is used as in the conventional art, the porosity, for example, the porosity of 5 μm or more, in the negative electrode is reduced to 50% or less after the rolling step, and the density is increased.
The porosity is not particularly limited and may be measured by, for example, the brownhol-Emmett-Teller (BET, Brunauer-Emmett-Teller) method or the mercury penetration method (Hg porometer) method according to an embodiment of the present invention.
In the present invention, a negative electrode is provided which is composed of a plurality of active material layers using two types of negative electrode active materials having different compacted densities and average particle sizes from each other, so that the porosity of the upper portion of the negative electrode is relatively higher than the porosity of the lower portion of the negative electrode after the rolling step, thereby reducing the density of the upper portion of the negative electrode. Therefore, the electrolyte can be easily impregnated into the electrode, and the ion mobility can be improved. Further, when the rolling step for the subsequent electrode production is performed, the form of the active material in which the surface of the electrode is not easily crushed or pressed can be maintained.
Also, the present invention provides a lithium secondary battery prepared in such a manner that the negative electrode, the positive electrode, the separator and the electrolyte are enclosed in a battery case by a conventional method.
The positive electrode is not particularly limited as long as it is a normal positive electrode used in the production of a lithium secondary battery, and for example, a slurry in which a positive electrode active material powder, a binder, and a conductive material are mixed may be applied to an electrode current collector, dried, and then rolled to form the positive electrode.
The positive electrode active material is preferably selected from the group consisting of LiMn2O4、LiCoO2、LiNiO2、LiFeO2And V2O5One of the group, or a mixture of two or more of them. Further, it is preferable to use a substance capable of adsorbing and desorbing lithium, such as TiS, MoS, an organic disulfide compound, or an organic polysulfide compound.
Examples of the binder include polyvinylidene fluoride, carboxymethyl cellulose, methyl cellulose, sodium polyacrylate, and the like, and examples of the conductive material include conductive auxiliary materials such as acetylene black, furnace black, graphite, carbon fiber, and fullerene.
The separator may be any material as long as it can be used in a lithium secondary battery, and examples thereof include polyethylene, polypropylene, multilayer films thereof, polyvinylidene fluoride, polyamide, glass fibers, and the like.
Examples of the electrolyte of the lithium secondary battery include an organic electrolyte solution or a polymer electrolyte solution in which a lithium salt is dissolved in a nonaqueous solvent.
Examples of the nonaqueous solvent constituting the organic electrolytic solution include nonaqueous solvents such as propylene carbonate, ethylene carbonate, butylene carbonate, benzonitrile, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, γ -butyrolactone, dioxolane, 4-methyldioxolane, N-dimethylformamide, dimethylacetamide, dimethylsulfoxide, dioxane, 1, 2-dimethoxyethane, sulfolane, dichloroethane, chlorobenzene, nitrobenzene, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate, ethyl butyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, diethylene glycol, and dimethyl ether, or mixed solvents of two or more of these solvents, or known solvents for lithium secondary batteries, particularly, preferably, one of dimethyl carbonate, ethyl methyl carbonate and diethyl carbonate is mixed with one of propylene carbonate, ethylene carbonate and butylene carbonate.
As the lithium salt, a lithium salt selected from LiCl, LiBr, LiI, LiClO can be used4、LiBF4、LiB10Cl10、LiPF6、LiCF3SO3、LiCF3CO2、LiAsF6、LiSbF6、LiAlCl4、CH3SO3Li、CF3SO3Li、(CF3SO2)2One or more lithium salts selected from the group consisting of NLi, chloroborane lithium, lithium lower aliphatic carboxylate and lithium 4-phenylboronate.
Examples of the polymer electrolyte include the organic electrolyte and a copolymer containing polyethylene oxide, polypropylene oxide, polyacetonitrile, polyvinylidene fluoride, polymethacrylate, polymethyl methacrylate and the like, which is excellent in wettability, in the organic electrolyte.
The secondary battery according to the present invention can be preferably used as a structural battery of a middle or large-sized battery module, in particular, since it exhibits high energy density, high power characteristics, and improved safety and stability. Accordingly, the present invention also provides a middle or large-sized battery module including the secondary battery as described above as a unit cell.
Such a large-and-medium-sized battery module can be preferably applied to a power source requiring high power and large capacity, such as an electric vehicle, a hybrid vehicle, and an electric storage device.
Examples and comparative examples of the present invention are described below. However, the following examples are descriptions of preferred embodiments of the present invention, and the present invention is not limited to the following examples.
Modes for carrying out the invention
(example 1)
97.3 parts by weight of a first negative electrode active material (artificial graphite) having a negative electrode density of 1.79g/cc when a pressure of 12.3MPa was applied, 0.7 part by weight of a conductive material (Super-P (conductive carbon black)), 1.0 part by weight of a thickener (carboxymethylcellulose), and 1.0 part by weight of a binder (styrene-butadiene rubber) were mixed, thereby preparing a first negative electrode active material slurry.
Next, 97.3 parts by weight of a second negative electrode active material (artificial graphite) having a negative electrode density of 1.51g/cc when a pressure of 12.3MPa was applied, 0.7 part by weight of a conductive material (Super-P), 1.0 part by weight of a thickener (carboxymethyl cellulose), and 1.0 part by weight of a binder (styrene-butadiene rubber) were mixed, thereby preparing a second negative electrode active material slurry.
The first negative electrode active material slurry and the second negative electrode active material slurry are sequentially applied to a copper current collector, and then dried, thereby forming a multilayer active material layer in which a primary negative electrode active material layer and a secondary negative electrode active material layer are stacked.
Then, the negative electrode on which the above-described multilayer active material layer was formed was rolled by a roll press. At this time, the anode density was 1.6 g/cc. Also, another anode having an anode density of 1.64g/cc was obtained by the same method.
Then, a positive electrode active material (LiCoO) was added2)97.2 parts by weight, 1.5 parts by weight of a binder (polyvinylidene fluoride) and 1.3 parts by weight of a conductive material (Super-P) were dispersed in N-methylpyrrolidone, to thereby prepare a positive electrode active material slurry. The slurry was applied to an aluminum current collector, followed by rolling with a roll press machine, to thereby prepare a positive electrode (positive electrode density: 3.4 g/cc).
After a polyethylene separator was interposed between the above negative electrode and positive electrode and was interposed in a battery case, an electrolyte was injected, thereby preparing a secondary battery. In this case, LiPF dissolved with 1.0M was used as the electrolyte6A mixed solution of ethylene carbonate/ethyl methyl carbonate and diethyl carbonate (1/2/1 volume ratio), thereby preparing a secondary battery.
Comparative example 1
97.3 parts by weight of a negative electrode active material (artificial graphite) having a compacted density of 1.51g/cc when a pressure of 12.3MPa was applied, 0.7 part by weight of a conductive material (Super-P), 1.0 part by weight of a thickener (carboxymethyl cellulose), and 1.0 part by weight of a binder (styrene-butadiene rubber) were mixed, thereby preparing a negative electrode active material slurry.
The negative electrode active material slurry was applied to a copper current collector and then dried, thereby forming a single-layer active material layer. Then, two kinds of negative electrodes and secondary batteries having negative electrode densities of 1.6g/cc and 1.64g/cc were prepared in the same manner as in example 1.
Comparative example 2
An anode having an anode density of 1.6g/cc and a secondary battery were prepared in the same manner as in comparative example 1, except that an anode active material having an anode density of 1.78g/cc when pressed with a force of 12.3MPa was used.
(Experimental example 1 measurement of average particle size of densitometer)
The compacted density of the negative electrode active material particles prepared in example 1 and comparative examples 1 and 2 was measured by using a powder resistance meter MCP-PD51 manufactured by mitsubishi chemical corporation.
In the case of the powder resistance measuring instrument, a predetermined amount of positive electrode active material powder is put into a cylinder-type load cell (load cell), and the pressure is continuously applied, and at this time, the density of the particles when pressed is measured. Therefore, the stronger the anode active material particle is, the less it is pressed under the same pressure, thereby exhibiting a lower density. At this time, the applied pressure appears to be about 12 to 16MPa or so.
The average particle size of the negative electrode active materials prepared in example 1, comparative example 1, and comparative example 2 was measured by a laser diffraction method.
The average particle size of the densitometer of the particles measured as described above is shown in table 1.
TABLE 1
Figure GDA0002065057530000131
Figure GDA0002065057530000141
(Experimental example 2 charging characteristics)
In order to evaluate the charging characteristics of the secondary batteries prepared in example 1, comparative example 1, and comparative example 2 described above, the secondary batteries prepared in example 1, comparative example 1, and comparative example 2 were charged to 4.2V, 0.05C under a constant current/constant voltage (CC/CV) condition at 0.1C under a condition of 23 ℃, then discharged to 3V under a Constant Current (CC) condition at 0.1C, and the capacities thereof were measured twice. Thereafter, the battery was charged to 4.2V and 0.05C at 0.5C under constant current/constant voltage (CC/CV), and then discharged to 3V at 0.2C under Constant Current (CC), and the charging characteristics at 0.5C-rate were measured. The results are shown in fig. 3.
That is, when a predetermined current of 0.5C-rate (rate) is charged, the constant current charging time of the battery of example 1 is longer than that of the batteries of comparative examples 1 and 2, as seen in fig. 3. Therefore, it was confirmed that the battery of example 1 having the negative electrode including the multi-layer active material layer was more excellent in the charging characteristics than the batteries of comparative examples 1 and 2 having the negative electrode including the single-layer active material layer.
(Experimental example 3: Life characteristics)
After the operation under the conditions of the above experimental example 2, the battery was charged to 4.2V and 0.05C under the condition of 0.2C under the condition of constant current/constant voltage (CC/CV), and then discharged to 3V under the condition of 0.2C under the condition of Constant Current (CC), and the cycle was repeatedly performed for 80 times. Fig. 4 and 5 show the life characteristic results.
At this time, FIG. 4 shows the life characteristics of the secondary batteries of example 1, comparative example 1 and comparative example 2 in which the negative electrode density was 1.6g/cc, and FIG. 5 shows the life characteristics of the secondary batteries of example 1 and comparative example 1 in which the negative electrode density was 1.64 g/cc.
First, it can be confirmed from an observation of fig. 4 that the batteries of comparative examples 1 and 2 having an anode including a single active material layer and the battery of example 1 having an anode including a multi-layer active material layer each exhibited a similar level of life characteristics when the anode density was reduced to 1.6 g/cc.
However, it was confirmed from observation of fig. 5 that, when the anode density was increased to 1.64g/cc, in the case of the electrode of example 1 having an electrode including a plurality of anode active material layers, the anode life characteristics were excellent even if the anode density was high, whereas in the case of the battery of comparative example 1 having an electrode including a single anode active material layer, the life characteristics were degraded if the anode density was high.
Therefore, it is understood that the electrode of example 1 having an electrode including a plurality of active material layers obtained in the present invention has improved ion mobility and thus improved speed and cycle characteristics, as compared with the electrode of comparative example 1.

Claims (13)

1. A negative electrode, comprising:
an electrode collector; and
a plurality of active material layers formed on the electrode current collector,
wherein the above-mentioned multilayer active material layer comprises:
a primary anode active material layer containing a first anode active material; and
a secondary anode active material layer containing a second anode active material having a lower compacted density and a larger average particle size than the first anode active material,
wherein the first negative electrode active material and the second negative electrode active material are crystalline carbon,
wherein the secondary anode active material layer is located on the surface of the anode, the primary anode active material layer is located inside the anode, and
wherein a ratio of compacted densities of the first negative electrode active material and the second negative electrode active material is 1.1:1 to 3:1 under a pressure condition of 12MPa to 16 MPa.
2. The anode according to claim 1, wherein the first anode active material and the second anode active material each comprise natural graphite, artificial graphite, or a mixture thereof in a spherical shape or a sphere-like shape.
3. The anode of claim 1, wherein a ratio of an average particle size of the first anode active material to the second anode active material is 1:9 to 5: 5.1.
4. The anode of claim 1, wherein a ratio of an average particle size of the first anode active material to the second anode active material is 1:1.3 to 1: 4.
5. The anode according to claim 1, wherein a ratio of compressive strengths of the first anode active material and the second anode active material is 2:8 to 5:5.1 under a pressure condition of 12MPa to 16 MPa.
6. The anode according to claim 1, wherein a porosity of the secondary anode active material layer is larger than a porosity of the primary anode active material layer.
7. The anode according to claim 1, wherein the primary anode active material layer and the secondary anode active material layer further contain a conductive material and a binder, respectively.
8. A method of making the anode of claim 1, the method comprising:
a step of applying a first negative electrode active material slurry containing the first negative electrode active material and a binder resin on an electrode collector;
a step of forming a primary anode active material layer by drying the first anode active material slurry;
a step of applying a second negative electrode active material slurry containing the second negative electrode active material and a binder resin on the primary negative electrode active material layer;
a step of forming a secondary anode active material layer by drying the second anode active material slurry; and
and rolling the electrode current collector on which the primary and secondary negative electrode active material layers are formed.
9. A method of making the anode of claim 1, the method comprising:
a step of applying a first negative electrode active material slurry containing the first negative electrode active material and a binder resin on an electrode collector;
a step of applying a second negative electrode active material slurry containing the second negative electrode active material and a binder resin on the first negative electrode active material slurry;
a step of forming a multilayer negative electrode active material layer by drying the first negative electrode active material slurry and the second negative electrode active material slurry; and
a step of rolling the electrode current collector on which the multilayer negative electrode active material layer is formed,
wherein the multilayer anode active material layer includes a primary anode active material layer and a secondary anode active material layer.
10. The method according to claim 8 or 9, wherein a porosity of the secondary anode active material layer is relatively larger than a porosity of the primary anode active material layer.
11. The method according to claim 10, wherein a ratio of porosities before rolling of the primary anode active material layer and the secondary anode active material layer is 5:5.1 to 4: 6.
12. The method according to claim 10, wherein a ratio of porosities after rolling of the primary anode active material layer and the secondary anode active material layer is 5:5.1 to 2: 8.
13. A lithium secondary battery comprising the anode of claim 1.
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