CN108539198B - Solvent for coating positive electrode active material for secondary battery, positive electrode active material slurry containing same, and secondary battery manufactured therefrom - Google Patents
Solvent for coating positive electrode active material for secondary battery, positive electrode active material slurry containing same, and secondary battery manufactured therefrom Download PDFInfo
- Publication number
- CN108539198B CN108539198B CN201810175705.5A CN201810175705A CN108539198B CN 108539198 B CN108539198 B CN 108539198B CN 201810175705 A CN201810175705 A CN 201810175705A CN 108539198 B CN108539198 B CN 108539198B
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- CN
- China
- Prior art keywords
- positive electrode
- active material
- electrode active
- secondary battery
- material slurry
- Prior art date
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Classifications
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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- 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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Abstract
The present invention relates to a solvent for coating a positive electrode active material for a secondary battery, a positive electrode active material slurry including the same, and a secondary battery manufactured therefrom. In detail, according to the present invention, a cathode active material can be very stably dispersed, and a cathode active material slurry loaded at a high content can be provided, by which not only a cathode active material layer in which load variation is significantly reduced can be formed, but also a secondary battery having significantly improved capacity characteristics and life characteristics can be provided.
Description
Technical Field
The present invention relates to a solvent for coating a positive electrode active material for a secondary battery, a positive electrode active material slurry including the same, and a secondary battery manufactured therefrom.
Background
With the rapid development of the electronic industry and the communication industry such as various information communications including mobile communications, the demand for the electronic devices to be light, thin and small is met, and portable electronic products and communication terminals such as notebook computers, netbooks, tablet computers, mobile phones, smart phones, PDAs, digital cameras, video cameras, etc. are becoming widely prevalent, and therefore, attention is paid to the development of batteries as driving power sources for these devices.
In addition, with the development of electric vehicles such as hydrogen fuel cell vehicles, hybrid vehicles, and fuel cell vehicles, great attention is focused on the development of batteries having high performance, large capacity, high density, high power, and high stability, and the development of batteries having rapid charge/discharge characteristics has been an unprecedented focus.
In light of such a trend, lithium secondary batteries having high energy density and voltage, long cycle life, and low self-discharge rate are now commercialized and widely used, and research into lithium secondary batteries is actively conducted in order to maximize the above effects.
A secondary battery basically includes a positive electrode (positive electrode), a negative electrode (negative electrode), a separator (separator), and an electrolyte (electrolyte). The positive electrode and the negative electrode have positive and negative potentials, respectively, as electrodes for converting and storing energy such as oxidation and reduction. The separation membrane is positioned between the positive electrode and the negative electrode, keeps electrical insulation and provides a moving channel of charges. In addition, the electrolyte functions as a medium for charge transfer.
In the case of a lithium secondary battery, which is one example of a secondary battery, battery performance (e.g., capacity, etc.) is most affected by a positive electrode active material used. In order to improve the performance of such a lithium secondary battery, the positive electrode active material should be supported at an appropriately high value while forming a uniform and stable thickness layer on the current collector. In order to solve such problems, the solid content, viscosity, and the like of the positive electrode active material slurry should be easily adjusted.
In this case, the positive electrode of the lithium secondary battery may be manufactured by coating a positive electrode active material slurry containing a positive electrode active material on a positive electrode current collector and drying, and the positive electrode active material slurry may be a mixture having fluidity, in which a binder and an organic solvent are added to and mixed with the positive electrode active material.
A typical positive electrode active material has a small particle size, a large specific surface area for carbon coating, and a low solid content concentration (at a level of 45% of solid content) in a positive electrode active material slurry containing the positive electrode active material, by adding a large amount of an organic solvent (e.g., N-methyl-2-pyrrolidone (NMP)) and appropriately adjusting the viscosity, thereby solving the above problems. However, when a large amount of organic solvent is used, an undried portion occurs even after drying, and a high-loading load cannot be achieved, and the process speed such as the drying speed increases, which causes a problem of lowering the productivity. In addition, the positive electrode active material slurry having a low solid content concentration has a problem that dispersion stability is lowered, and when a positive electrode active material layer is formed, variation in layer thickness and load may occur. In particular, the organic solvent is not environmentally friendly because of its harmful properties.
Under the circumstances as described above, the present inventors have intensively studied to improve the above problems, and have confirmed that the use of a coating solvent containing N-ethylformamide (N-ethylformamide) can dramatically improve the dispersibility of a slurry containing a positive electrode active material, and can stably form a positive electrode active material layer with a uniform thickness, thereby providing a positive electrode having improved capacity characteristics and life characteristics, and a secondary battery containing the same, and have completed the present invention.
Documents of the prior art
Patent document
Patent document 1: KR 10-0436708B1
Patent document 2: KR 10-1764470B1
Disclosure of Invention
The purpose of the present invention is to provide a solvent for coating a positive electrode active material for a secondary battery, which has a low viscosity even at a high solid content concentration and is excellent in dispersion stability of the positive electrode active material, and a positive electrode active material slurry containing the same.
Another object of the present invention is to provide a positive electrode including a positive electrode active material layer formed of the positive electrode active material slurry and a secondary battery including the same.
In order to solve the above problems, the present invention provides a solvent for coating a positive electrode active material of a secondary battery, comprising N-ethylformamide.
The present invention also provides a positive electrode active material slurry comprising a positive electrode active material, a binder, and N-ethylformamide.
The positive electrode active material slurry according to an embodiment of the present invention may be represented by the following chemical formula 1.
[ chemical formula 1]
Li 1+x [Ni a Co b Mn c ]O 2
[ in chemical formula 1 above, -0.5. Ltoreq. X.ltoreq. 0.6,0. Ltoreq. A, b, c. Ltoreq.1,x + a + b + c =1.]
In the positive electrode active material slurry according to an embodiment of the present invention, the binder may be selected from a fluorine-based binder and a rubber-based binder.
In the positive electrode active material slurry according to an embodiment of the present invention, the solid content of the positive electrode active material slurry may be 30 to 80% by weight, based on the total weight of the positive electrode active material slurry.
The positive electrode active material slurry according to an embodiment of the present invention may contain the positive electrode active material in an amount of 55 to 99 wt% based on the total solid content of the positive electrode active material slurry.
As for the positive electrode active material slurry according to an embodiment of the present invention, the positive electrode active material slurry may further include a conductive material.
In the positive electrode active material slurry according to an embodiment of the present invention, the conductive material may be selected from carbon-based materials.
The present invention also provides a positive electrode comprising a positive electrode active material layer formed from the positive electrode active material slurry.
The present invention may further include the positive electrode, the negative electrode, and a separator between the positive electrode and the negative electrode, and the positive electrode may have a positive electrode active material layer formed on one surface of a positive electrode current collector to have a thickness of 10 to 100 μm.
In the secondary battery according to an embodiment of the present invention, the initial discharge capacity of the secondary battery may be 200mAh/g or more, and the capacity retention rate in 50 cycles may be 90% or more.
In the secondary battery according to an embodiment of the present invention, the secondary battery may have a C-rate efficiency represented by formula 1 below of 90% or more.
[ formula 1]
C-rate (%) = [ (2C discharge capacity)/(0.1C discharge capacity) ] × 100
According to the present invention, the positive electrode active material has low viscosity even at a high solid content concentration, can easily exhibit a high loading content to the positive electrode active material, has excellent dispersibility when mixed with the positive electrode active material, and can maintain a very stable phase even in long-term use or storage.
In addition, according to the present invention, since an organic solvent (e.g., NMP or the like) which is highly environmentally harmful in the past is not used, a positive electrode active material and a positive electrode including the same can be provided in an environmentally friendly manner.
In addition, according to the present invention, a secondary battery having improved capacity characteristics and life characteristics can be provided. Particularly, according to the present invention, not only high initial discharge capacity but also high discharge capacity was exhibited even after 50 cycles, showing significantly improved capacity maintenance rate.
Detailed Description
The advantages and features of the present invention and the manner of attaining them will become apparent with reference to the following examples. However, the present invention is not limited to the embodiments disclosed below, and may be embodied in various forms different from each other, but the present embodiment is provided to fully inform the scope of the present invention to those skilled in the art by making the disclosure of the present invention more complete, and the present invention is defined only by the claims. The solvent for coating a positive electrode active material for a secondary battery of the present invention, a positive electrode active material slurry comprising the same, and a secondary battery manufactured therefrom will be described in detail below.
The present invention provides a solvent for coating a positive electrode active material for a secondary battery, which contains N-ethylformamide. The coating solvent of the present invention is characterized by exhibiting improved dispersibility when mixed with a positive electrode active material. Although the exact reason cannot be known, it is expected to be caused by the interaction of the N-ethylformamide of the present invention with the positive electrode active material. The above-mentioned interaction is considered to be a temporary or long-term influence due to physical entanglement characteristics of common and non-common interactions such as hydrogen bond, hydrophobic interaction, and the like.
This phenomenon is a surprising synergistic effect caused by the inclusion of N-ethylformamide, which is not recognized at all in formamide compounds (e.g., formamide, N-methylformamide, etc.) having structural characteristics similar to those of the above-mentioned N-ethylformamide, and is of great significance in this regard.
In addition, the solvent for coating a positive electrode active material for a secondary battery of the present invention does not use a harmful organic solvent such as N-methyl-2-pyrrolidone (NMP) which is generally used, so that a positive electrode active material layer and an electrode including the same can be provided in a more environmentally friendly method.
In addition, the present invention provides a positive electrode active material slurry including N-ethylformamide.
Specifically, the positive electrode active material slurry may include a positive electrode active material, a binder, N-ethylformamide, and the like.
The cathode active material slurry according to one embodiment of the present invention may include a cathode active material represented by the following chemical formula 1.
[ chemical formula 1]
Li 1+x [Ni a Co b Mn c ]O 2
[ in chemical formula 1 above, -0.5. Ltoreq. X.ltoreq. 0.6,0. Ltoreq. A, b, c. Ltoreq.1,x + a + b + c =1.]
The positive electrode active material slurry according to an embodiment of the present invention may contain a positive electrode active material selected from LiCoO in terms of not only effectively suppressing the capacity decrease of the positive electrode active material but also preventing the problem of battery swelling due to gas generation or the like caused by the increase in the content of residual lithium 2 、LiNiO 2 And LiMnO 2 And the like.
In addition, the positive electrode active material slurry according to an embodiment of the present invention may further include an additional positive electrode active material. As an example, the additional positive electrode active material may be selected from LiFePO 4 、LiFeMnPO 4 、LiFeMgPO 4 、LiFeNiPO 4 、LiFeAlPO 4 And LiFeCoNiMnPO 4 Etc., but is not limited toThis is done.
The positive electrode active material slurry according to one embodiment of the present invention is not limited as long as it is a component that contributes to the bonding of the metal oxide coating layer formed on the surface of the positive electrode active material or the bonding with an additional conductive material or the like, and the binder may be one or two or more selected from a fluorine-based binder, a rubber-based binder, and the like.
As an example, the fluorine-based binder may be polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HEP), chlorotrifluoroethylene (CFTF), polytetrafluoroethylene (PTFE), or the like.
As an example, the rubber-based adhesive may be Styrene Butadiene Rubber (SBR), butadiene Rubber (BR), nitrile Butadiene Rubber (NBR), isoprene Rubber (IR), or the like.
In the positive electrode active material slurry according to an embodiment of the present invention, the binder may further include an acrylic binder selected from polyacrylonitrile, polymethyl methacrylate, polyacrylic acid, and the like; polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene, polypropylene, olefin adhesives; and one or more cellulose binders such as carboxymethyl cellulose, hydroxypropyl methyl cellulose, and regenerated cellulose.
The cathode active material slurry according to one embodiment of the present invention may have a solid content of 30 to 80 wt% based on the total weight of the cathode active material slurry. In this case, the balance was N-ethylformamide.
As described above, the positive electrode active material slurry of the present invention uses N-ethylformamide as a dispersant, i.e., as a solvent for coating a positive electrode active material, and thus can exhibit not only low viscosity but also significantly improved dispersion stability even at a high solid content.
The positive electrode active material slurry according to an embodiment of the present invention may have a solid content of 30 to 70 wt%, or more specifically, 40 to 60 wt%, based on the total weight of the positive electrode active material slurry.
The positive electrode active material slurry according to one embodiment of the present invention may have a viscosity of 5000 to 30000g/cm · s (measured at 23 ℃ using a boehler-type viscometer at 20 rpm), specifically 8000 to 30000g/cm · s, more specifically 10000 to 25000g/cm · s. The above viscosity range corresponds to a low viscosity of about 30 to 60% when ordinary NMP or the like is used as a solvent.
As one example, the positive electrode active material slurry having a solid content of 45 wt% (positive electrode active material: binder =98 (wt: wt)) may have a viscosity of 11000 to 20000g/cm · s. In this case, the viscosity change rate (viscosity after 1 day high-temperature storage/initial viscosity × 100, 45 ℃ condition for high-temperature storage) of the positive electrode active material slurry is in the range of 1 to 5%.
As an example, positive electrode active material slurry having a solid content of 50 wt% positive electrode active material: binder =98 (wt: wt)) may have a viscosity of 15000 to 23000g/cm · s. In this case, the viscosity change rate (viscosity after 1-day high-temperature storage/initial viscosity × 100) of the positive electrode active material slurry is in the range of 1 to 5%.
The positive electrode active material slurry according to an embodiment of the present invention may contain the positive electrode active material in an amount of 55 to 99 wt%, specifically 60 to 99 wt%, and more specifically 65 to 99 wt%, based on the total solid content of the positive electrode active material slurry. At this time, the remaining amount may be an adhesive.
The positive electrode active material slurry according to one embodiment of the present invention forms a stable dispersed phase even at a high solid content as described above, and thus has no fear of changing physical properties (e.g., viscosity) even at a relatively low viscosity. As described above, the above-described positive electrode active material slurry forming a stable dispersed phase can maintain a very stable phase even in long-term use or storage, and thus can provide process advantages.
The positive active material paste according to an embodiment of the present invention may further include a conductive material. The conductive material is specifically a carbon-based material, and is not particularly limited as long as it exhibits surface roughness of the positive electrode active material layer and provides conductivity, and the battery does not induce chemical change and has conductivity. As an example, graphite such as natural graphite, artificial graphite, or the like; carbon black such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, and thermal black; and carbon fiber, etc.
The conductive material may further contain an additional conductive material in the carbon-based material. As an example, a metal-based material such as copper, nickel, aluminum, silver, zinc, titanium, or the like; a fiber-based material of the above metal; conductive polymers such as polyaniline (polyaniline), polyacetylene (polyacetylene), polypyrrole (polypyrole), and polythiophene ketone (polythiophenone), but the present invention is not limited thereto.
In this case, the conductive material may be used in an amount of 0.01 to 10 wt% based on the total solid content of the positive electrode active material slurry, although the amount is not limited thereto. In this case, the content of the inorganic filler may be, for example, 0.1 to 8% by weight, more specifically 0.5 to 5% by weight, in order to improve the capacity characteristics, but the present invention is not limited thereto.
The present invention provides a positive electrode including a positive electrode active material layer formed from the positive electrode active material slurry.
The positive electrode according to one embodiment of the present invention may include a positive electrode active material layer formed of the positive electrode active material slurry described above with a uniform composition. In addition, the positive electrode active material layer may be formed at a high density. That is, in the secondary battery using the positive electrode including the positive electrode active material layer of the present invention, since the improved ion conductivity is obtained, the mobility of lithium ions in the electrolytic solution can be remarkably improved. Therefore, even if the amount of the additional conductive material is reduced, improved battery characteristics can be exhibited.
The positive electrode according to one embodiment of the present invention may be manufactured in the following manner.
Specifically, the following steps may be included: a step of preparing a positive electrode active material slurry by adding a binder and a positive electrode active material to N-ethylformamide; and a step of coating the positive electrode active material slurry on a positive electrode current collector and drying the same.
The positive electrode current collector is not particularly limited as long as it has high conductivity without inducing chemical changes in the secondary battery, and examples thereof include copper, stainless steel, aluminum, nickel, titanium, calcined carbon, and a positive electrode current collector obtained by surface-treating the surface of aluminum or stainless steel with carbon, nickel, titanium, silver, or the like. In this case, the positive electrode current collector may have a thickness of 3 to 500 μm.
The above coating is not particularly limited and may be performed according to a method generally known in the art.
As an example, the coating may be performed by spraying or dispensing the positive electrode active material slurry onto at least one surface of the positive electrode current collector and then uniformly dispersing the slurry using a doctor blade (or the like).
As an example, the coating may be performed by die casting (die casting), comma coating (comma coating), screen printing (screen printing), or the like.
The drying may be a step of removing water remaining in the step after the formation of the positive electrode active material layer. In this case, the drying may be performed at a temperature range in which residual moisture is removed, specifically, at 50 to 200 ℃, and more specifically, at 80 to 200 ℃.
In this case, the drying time is applied differently depending on the temperature, and thus, although not uniformly determined, it may be performed for 1 hour or more, preferably, 5 to 24 hours, and more preferably, 5 to 12 hours.
The positive electrode active material layer produced by the above method may be formed on at least one surface of the positive electrode current collector to have a thickness of 10 to 100 μm. Specifically, the thickness of the film may be 10 to 80 μm, and more specifically, 10 to 50 μm.
According to one embodiment of the present invention, it is possible to provide not only a positive electrode including a positive electrode active material layer in which a load variation is significantly reduced and uniformity is ensured, but also a positive electrode active material layer of high density in a very simple process. Therefore, the secondary battery using the positive electrode of the present invention can exhibit excellent charge/discharge characteristics and life characteristics by remarkably improving lithium ion mobility in the electrolyte solution due to the improved ion conductivity.
In addition, the present invention provides a secondary battery including the positive electrode.
Specifically, the lithium secondary battery may include a positive electrode according to an embodiment of the present invention, a negative electrode, and a separator between the positive electrode and the negative electrode, wherein the positive electrode has a positive electrode active material layer formed on one surface of a positive electrode current collector to have a thickness of 10 to 100 μm.
The lithium secondary battery uses the positive electrode of the present invention, and therefore, the lithium secondary battery has improved lithium ion mobility in the electrolyte solution, and exhibits excellent charge/discharge characteristics and life characteristics.
The initial discharge capacity of the secondary battery according to an embodiment of the present invention may be 200mAh/g or more. Specifically, the initial discharge capacity may be 200 to 300mAh/g, more specifically, 200 to 250mAh/g.
Particularly, the secondary battery according to one embodiment of the present invention is used even after 50 cycles (50 times) th cycle), the variation in discharge capacity is still minimized. Specifically, the capacity retention rate of the secondary battery may be 90% or more in 50 cycles.
As an example, the initial discharge capacity of the secondary battery may be 200mAh/g or more, and the capacity retention rate in 50 cycles may be 90 to 99%.
As an example, the initial discharge capacity of the secondary battery may be 200mAh/g or more, and the capacity maintenance rate of the secondary battery may be 95 to 99% in 50 cycles.
In addition, the secondary battery according to one embodiment of the present invention may have a C-rate efficiency of 90% or more, which is represented by the following formula 1.
[ formula 1]
C-rate (%) = [ (2C discharge capacity)/(0.1C discharge capacity) ] × 100
As an example, the initial discharge capacity of the secondary battery may be 200mAh/g or more, the capacity maintenance rate may be 90 to 99% in 50 cycles, and the C-rate efficiency may be 90% to 99%.
As an example, the initial discharge capacity of the secondary battery may be 200mAh/g or more, the capacity maintenance rate of the secondary battery may be 95 to 99% in 50 cycles, and the C-rate efficiency may be 90% to 95%.
The lithium secondary battery according to one embodiment of the present invention is explained below.
The lithium secondary battery of the present invention may include a cathode, an anode, and a separation film.
The positive electrode may include a positive electrode active material layer formed of the positive electrode active material slurry on at least one surface of a positive electrode current collector. At this time, the lithium secondary battery of the present invention can exhibit excellent charge/discharge characteristics and life characteristics as described above because of including the positive electrode active material layer.
The negative electrode can be produced by coating a negative electrode active material slurry solution containing a negative electrode active material on a negative electrode current collector and drying the coating. In this case, the negative electrode active material slurry solution may contain the following components as necessary. The negative electrode active material is not limited as long as it is a material that is generally used, and examples thereof include carbon such as non-graphitizable carbon and graphite-based carbon; li x Fe 2 O 3 (0≤x≤1)、Li x WO 2 (0≤x≤1)、Sn x Me 1-x Me' y O z (Me: mn, fe, pb, ge; me': al, B, P, si, an element of groups 1,2, 3 of the periodic Table of the elements, halogen; 0<x is less than or equal to 1; y is more than or equal to 1 and less than or equal to 3; z is more than or equal to 1 and less than or equal to 8) and the like; lithium metal; a lithium alloy; a silicon-based alloy; a tin-based alloy; snO, snO 2 、PbO、PbO 2 、Pb 2 O 3 、Pb 3 O 4 、Sb 2 O 3 、Sb 2 O 4 、Sb 2 O 5 、GeO、GeO 2 、Bi 2 O 3 、Bi 2 O 4 And Bi 2 O 5 And the like metal oxides; conductive polymers such as polyacetylene; li-Co-Ni metal composites, and the like. The negative electrode current collector is not particularly limited as long as it has high conductivity without inducing chemical changes in the secondary battery,as an example, copper, stainless steel, aluminum, nickel, titanium, calcined carbon, or a negative electrode current collector whose surface is treated with carbon, nickel, titanium, silver, or the like on the surface of copper or stainless steel may be mentioned, and an aluminum-cadmium alloy or the like may be mentioned. The negative electrode current collector may be formed with fine irregularities on the surface to enhance the binding force of the negative electrode active material, or may be formed in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, a nonwoven fabric, and the like, as in the case of the positive electrode current collector. In this case, the negative electrode current collector may have a thickness of 3 to 500 μm.
The separator is interposed between the positive electrode and the negative electrode, and an insulating thin film having high ion permeability and mechanical strength is used. As an example, the separation membrane may have a pore diameter of 0.01 to 10 μm and a thickness of 5 to 300. Mu.m. Such a separation membrane is not limited as long as it is a generally used one, and examples thereof include olefin polymers such as chemically resistant and hydrophobic polypropylene; sheets or nonwoven fabrics made of colored glaze fibers, polyethylene, or the like. When a solid electrolyte such as a polymer is used as the electrolyte, the solid electrolyte may also serve as a separation membrane.
In addition, the lithium secondary battery may further include an electrolyte.
The electrolyte may be a lithium salt-containing nonaqueous electrolyte. As an example, the above lithium salt-containing nonaqueous electrolytic solution may contain a nonaqueous organic solvent and a lithium salt. Examples of the nonaqueous organic solvent include N-methyl-2-pyrrolidone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, γ -butyrolactone, 1,2-dimethoxyethane, and tetrahydrofuran (R)
(franc)), 2-methyltetrahydrofuran, dimethylsulfoxide, 1,3-dioxolane, formamide, dimethylformamide, dioxolane, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphotriester, trimethoxymethane, dioxolane derivatives, sulfolane, methylsulfolane, 1,3-dimethyl-2-imidazoleQuinolinone, propylene carbonate derivative, tetrahydrofuran derivative, diethyl ether, methyl propionate
Aprotic organic solvents such as ethyl propionate. In this case, the nonaqueous organic solvent may be one or a mixed solvent of two or more selected from the aprotic organic solvents.
The lithium salt is not limited as long as it is easily soluble in the nonaqueous organic solvent. As an example, liCl, liBr, liI, liClO can be mentioned 4 、LiBF 4 、LiB 10 Cl 10 、LiPF 6 、LiCF 3 SO 3 、LiCF 3 CO 2 、LiAsF 6 、LiSbF 6 、LiAlCl 4 、CH 3 SO 3 Li、CF 3 SO 3 Li、(CF 3 SO 2 ) 2 NLi, chloroborane lithium, lower aliphatic carboxylic acid lithium, 4-phenyl lithium borate, etc., most preferably LiPF 6 。
The electrolyte solution may be an organic solid electrolyte. As one example, it may be a polymer containing one or more ionic dissociation groups selected from polyethylene derivatives, polyethylene oxide derivatives, polypropylene oxide derivatives, phosphate ester polymers, poly alginate-lysine (gelation lysine), polyester sulfide, polyvinyl alcohol, polyvinylidene fluoride, and the like.
The electrolyte solution may be an inorganic solid electrolyte. As an example, li may be mentioned 3 N、LiI、Li 5 NI 2 、Li 3 N-LiI-LiOH、LiSiO 4 、LiSiO 4 -LiI-LiOH、Li 2 SiS 3 、Li 4 SiO 4 、Li 4 SiO 4 -LiI-LiOH、Li 3 PO 4 -Li 2 S-SiS 2 And the like, nitrides, halides, sulfates, and the like of Li.
In addition, the lithium secondary battery may further include additional additives.
As an example, for the purpose of improving charge/discharge characteristics, flame retardancy, and the likeFurther comprises a compound selected from the group consisting of pyridine, triethyl phosphite, triethanolamine, cyclic ethers, ethylenediamine, glyme (glyme), hexaphosphoric triamide, nitrobenzene derivatives, sulfur, quinoneimine dyes, N-substituted compounds
One or more of oxazolidinone, N-substituted imidazolidine, ethylene glycol dialkyl ether, ammonium salt, pyrrole, 2-methoxyethanol, aluminum trichloride and the like.
As an example, one or more halogen-containing solvents selected from carbon tetrachloride, ethylene trifluoride and the like may be further contained for the purpose of imparting flame retardancy.
As one example, carbon dioxide gas or the like may be further included for the purpose of imparting high-temperature storage characteristics.
The lithium secondary battery of the present invention can be used not only as a battery for use as a power source for small-sized devices
It may also be preferable to include multiple batteries
Is used as a unit cell in the middle or large-sized battery module.
The battery module of the present invention may provide a battery pack included as a power source for a middle or large-sized device, and the middle or large-sized device may provide an Electric Vehicle including an Electric Vehicle (EV), a Hybrid Electric Vehicle (HEV), a Plug-in Hybrid Electric Vehicle (PHEV), and the like, and a power storage device, but is not limited thereto.
The present invention will be described in more detail by way of examples. However, the following examples are intended to more specifically illustrate the present invention, and the scope of the present invention is not limited by the following examples. The following embodiments may be modified and changed as appropriate by those skilled in the art within the scope of the present invention.
In the present invention, unless otherwise specified, the temperature is in ° c, and the amount of each component used is in g unless otherwise defined.
(evaluation method)
1. Evaluation of Charge/discharge Capacity
The secondary battery cells (battery capacity 4.3 mAh) produced in the following examples and comparative examples were charged and discharged (charged at 0.5C and discharged at 1C) at 25 ℃ in a voltage range of 3 to 4.5V.
2.C-rate efficiency evaluation
The secondary battery cells (battery capacity 4.3 mAh) produced in the following examples and comparative examples were used to measure the C-rate efficiency in a high-temperature environment (45 ℃ C.). In this case, the C-rate efficiency is defined as a ratio of a capacity when a secondary battery charged at 0.5C is discharged at 0.1C to a capacity when discharged at 2C, as shown in the following formula 1.
[ formula 1]
C-rate (%) = [ (2C discharge capacity)/(0.1C discharge capacity) ] × 100
3. Evaluation of Life characteristic
Defined as 50 cycles (50) of charge and discharge measured in the above charge and discharge capacity evaluation th Discharge capacity) and initial discharge capacity (1) st Discharge capacity) (see the following formula 2).
[ formula 2]
Capacity retention rate (%) = [ (discharge capacity after 50 cycles)/(initial discharge capacity) ] × 100
(example 1)
Surface coated LiCoO 2 20g of a positive electrode active material, a conductive material (carbon black), and a binder (polyvinylidene fluoride, PVdF) were mixed at a weight ratio of 95. The positive electrode active material slurry was applied to an aluminum (Al) thin film having a thickness of about 20 μm as a positive electrode current collector, dried at 130 ℃ for 2 hours, and then rolled (rolled press) to produce a positive electrode. Lithium metal foil (foil) was used as the negative electrode. Ethylene Carbonate (EC) and Ethyl Methyl Carbonate (EMC) were used as the electrolyte in a volume of 1:2LiPF6 was added to the nonaqueous organic solvent thus prepared, to prepare a 1M LiPF6 nonaqueous electrolyte solution. The nonaqueous electrolyte solution was injected so as to include a polyethylene separation film (Tonen, F2OBHE, thickness =20 μm) between the positive electrode and the negative electrode, and a secondary battery cell for a polymer battery type test was fabricated.
The secondary battery cells manufactured in the above-described manner were evaluated for initial charge-discharge capacity, C-rate efficiency, and life characteristics (capacity retention rate), and are shown in table 1 below.
Comparative example 1
In the production of the positive electrode active material slurry, a positive electrode active material slurry (viscosity: 50000g/cm · s, viscosity change rate: 15%) was produced using N-methyl-2-pyrrolidone (NMP) as a solvent instead of N-ethylformamide. Then, a polymer battery type test secondary battery cell was produced in the same manner as in example 1.
The secondary battery cells produced by the above-described methods were evaluated for initial charge-discharge capacity, C-rate efficiency, and life characteristics (capacity retention rate), and are shown in table 1 below.
(Table 1)
The secondary battery of the present invention not only exhibits a remarkable charge capacity, but also has an initial discharge capacity of 200mAh/g or more, and is excellent in capacity retention rate.
Specifically, the secondary battery of the present invention exhibited a high initial discharge capacity (203.9 mAh/g), and it was confirmed that the C-rate efficiency was 91%. In particular, the secondary battery of the present invention was confirmed to have a capacity retention rate of 97%. The high capacity retention rate of the secondary battery of the present invention is equivalent to a significant effect of 114% or more as compared with the comparative example.
While the preferred embodiments of the present invention have been described above, it is to be understood that the present invention is not limited thereto, and various modifications may be made within the scope of the claims and the specification, and the scope of the present invention is also encompassed by the invention.
Claims (8)
1. A secondary battery, wherein the secondary battery comprises a positive electrode; a negative electrode in which a positive electrode active material layer formed from a positive electrode active material slurry containing a positive electrode active material, a binder, and N-ethylformamide serving as a solvent for coating the positive electrode active material is formed on a positive electrode current collector, and a separator between the positive electrode and the negative electrode, wherein the positive electrode active material slurry has a viscosity of 5000 to 30000g/cm s measured at 20rpm with a Bohler's spin viscometer at 23 ℃,
the solid content of the positive electrode active material slurry is 30 to 80% by weight based on the total weight of the positive electrode active material slurry,
the initial discharge capacity is more than 200mAh/g, and the capacity maintenance rate in 50 cycles is 95-99%.
2. The secondary battery according to claim 1, wherein the positive electrode active material is represented by the following chemical formula 1:
chemical formula 1
Li 1+x [Ni a Co b Mn c ]O 2
In chemical formula 1, -0.5 < x < 0.6,0 < a, b, c < 1,x + a + b + c =1.
3. The secondary battery according to claim 1, wherein the adhesive is selected from a fluorine-based adhesive and a rubber-based adhesive.
4. The secondary battery according to claim 1, wherein the positive electrode active material is 55 to 99 wt% based on the total solid content of the positive electrode active material slurry.
5. The secondary battery according to claim 1, wherein the positive electrode active material slurry further comprises a conductive material.
6. The secondary battery according to claim 5, wherein the conductive material is a carbon-based substance.
7. The secondary battery according to claim 1,
the thickness of the positive electrode active material layer is 10 to 100 [ mu ] m.
8. The secondary battery according to claim 1, wherein the C-rate efficiency represented by the following formula 1 is 90% or more,
formula 1
C-rate (%) = [ (2C discharge capacity)/(0.1C discharge capacity) ] × 100.
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| CN108539198A (en) | 2018-09-14 |
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