Patent Application
20210288328
This application is based on and claims the benefit of priority from Japanese Patent Application Mo. 2020-043339, filed on 13 Mar. 2020, the content of which is incorporated herein by reference.
The present invention relates to an electrode for a lithium ion secondary battery, and a lithium ion secondary battery using the electrode for a lithium ion secondary battery.
Conventionally, lithium ion secondary batteries have been widely available as secondary batteries having a high energy density.
A lithium ion secondary battery has a structure including a positive electrode, a negative electrode, and a separator provided between the positive electrode and the negative electrode, and a liquid electrolyte (an electrolytic solution) being filled.
Such a lithium ion secondary battery has various requirements depending on the application of use. For example, for automobiles etc., volumetric energy density is required to be further increased. Examples of method for this include a method for increasing a filling density of electrode active materials.
As the method for increasing a filling density of electrode active materials, use of a foamed metal as a current collector constituting a positive electrode layer and a negative electrode layer has been proposed (see Patent Documents 2 and 3).
The foamed metal has a network structure having uniform pore diameters, and having a large surface area.
By filling the inside of the network structure with an electrode mixture including an electrode active material, an amount of active materials per unit area of the electrode layer can be increased.
Patent Document 1: Japanese Unexamined Patent Application, Publication No. 2000-106154
However, an electrode using a foamed metal as a current collector can produce an electrode having a higher basis weight than a coated electrode using a metal foil as a current collector, but a film thickness becomes larger.
Therefore, due to expansion of a negative electrode active material during charging, an electrolytic solution is extruded from an electrode layer, so that a phenomenon that an electrolytic solution becomes short occurs. Consequently, repeating charge and discharge deteriorate the capacity.
In particular, when a fully charged state is repeated, the capacity remarkably deteriorated.
Furthermore, since the electrode layer has a large film thickness, the permeability of an electrolytic solution is deteriorated, infiltration of the electrolytic solution into the inside of the electrode becomes insufficient.
Therefore, the supply of anions and cations is insufficient so as to increase the internal resistance of the lithium ion secondary battery cell, also resulting in also a problem that the input/output characteristics (output density) of a battery is lowered.
The present invention has been made in view of the above, and has an object to provide an electrode for a lithium ion secondary battery being an electrode for obtaining a lithium ion secondary battery including a foamed metal as a current collector, having a high energy density, and further being capable of improving durability and input/output characteristics (output density), and a lithium ion secondary battery using the electrode for a lithium ion secondary battery.
The present inventors have extensively studied in order to solve the above-mentioned problem.
Then, the present inventors have found that when a porous coating layer is disposed on an electrode layer of the electrode for a lithium ion secondary battery using a current collector made of a foamed metal, an electrolytic solution extruded from the electrode layer due to expansion of a negative electrode active material can be absorbed and trapped in the coating layer, and as a result, it is possible to achieve a lithium ion secondary battery having improved durability and input/output characteristics (output density) with the energy density maintained high, and the present inventors have completed the present invention.
In other words, the present invention is an electrode for a lithium ion secondary battery, including a current collector being a porous foam made of metal, and an electrode layer including the current collector filled with an electrode mixture, in which the electrode layer includes a porous coating layer.
The coating layer may be disposed on the electrode layer, at least on a surface that is in contact with a separator when a lithium ion secondary battery is formed.
The coating layer may be disposed on all surfaces in the electrode layer.
The porous foam may be a copper foam.
The electrode for a lithium ion secondary battery may be a negative electrode.
The current collector may foe an aluminum foam.
The electrode for a lithium ion secondary battery may be a positive electrode.
Another aspect of the present invention is a lithium ion secondary battery including a positive electrode, a negative electrode and a separator located between the positive electrode and the negative electrode, wherein at least one of the positive electrode and the negative electrode is the electrode for a lithium ion secondary battery mentioned above.
Still another aspect of the present invention is a lithium ion secondary battery including a positive electrode, a negative electrode and a separator located between the positive electrode and the negative electrode, wherein the negative electrode includes a negative electrode collector being a porous foam made of metal, and a negative electrode layer including the negative electrode collector filled with a negative electrode mixture the negative electrode layer has a porous negative electrode coating layer, and the negative electrode coating layer is disposed on all surfaces in the negative electrode layer.
The positive electrode includes a positive current collector being a porous foam made of metal, and a positive electrode layer including the positive current collector filled with a positive electrode mixture. The positive electrode layer may have a porous positive electrode coating layer, rind the positive electrode coating layer may be disposed on a surface in contact with the separator in the positive electrode layer.
According to the electrode for a lithium ion secondary battery of the present invention, it is possible to obtain a lithium ion secondary battery having a high energy density, and having improved durability and input-output property.
Hereinafter, embodiments of the present invention will be described with reference to drawings.
The electrode for a lithium ion secondary battery of the present invention includes a current collector being a porous foam made of metal, and an electrode layer including the current collector filled with an electrode mixture.
The electrode layer has a porous coating layer.
Batteries to which the electrode for a lithium ion secondary battery of the present invention can be applied are not particularly limited as long as batteries use a liquid electrolytic solution.
Furthermore, the electrode for a lithium ion secondary battery of the present invention can be used for a positive electrode or a negative electrode or for both electrodes in lithium ion secondary battery without any problems.
In a case where a positive electrode and a negative electrode compared with each other, an active material used for a negative electrode is largely expanded, and too much electrolytic solution is extruded from the electrode layer, and therefore, the electrode for a lithium ion secondary battery of the present invention can have a higher effect when it is used for a negative electrode.
Furthermore, a structure of the electrode for a lithium ion secondary battery of the present invention is not particularly limited, and may be a laminated type or a wound type.
A current collector constituting the electrode for a lithium ion secondary battery of the present invention is a porous foam made of metal.
The porous foam made of metal is not particularly limited as long as it is a metal porous material having space by a foam.
The foamed metal body has a network structure and has a large surface area.
When the porous foam made of metal is used as the current collector, since the inside the network structure can be filled with an electrode mixture including an electrode active material, an amount of active materials per unit area of the electrode layer can be increased. As a result, the volumetric energy density of the lithium ion secondary battery can be improved.
Furthermore, since the electrode mixture can be fixed easily, a thickness of the electrode mixture layer can be increased without necessity of increasing the viscosity of the coating slurry serving as the electrode mixture.
Furthermore, a binding agent made of an organic polymer compound that has been needed for increasing the viscosity can be reduced.
Therefore, as compared with an electrode using a conventional metal foil as the current collector, a thickness of the electrode mixture layer can be increased. As a result, capacity per unit area of the electrode can be increased, and higher capacity of the lithium ion secondary battery can be achieved.
Examples of the porous foam made of metal include nickel, aluminum, stainless steel, titanium, copper, silver, and the like. Among them, as a current collector constituting a positive electrode, an aluminum foam is preferably used; as a current collector constituting a negative electrode, a copper foam or a stainless steel foam are preferably used.
An electrode layer in the electrode for a lithium ion secondary battery of the present invention includes a current collector being a porous foam made of metal, which is filled with an electrode mixture.
A thickness of the electrode layer is not particularly limited, but the electrode for a lithium ion secondary battery of the present invention uses a porous foam made of metal as the current collector, an electrode layer having a large thickness can be formed.
As a result, an active material amount per unit area of the electrode layer is increased, and a battery having a large energy density can be obtained.
A thickness of the electrode layer in the electrode for a lithium ion secondary battery of the present invention is, for example, 200 to 400 μm.
An electrode mixture constituting an electrode layer of the present invention includes at least an electrode active material.
The electrode mixture that can be applied to the present invention may include arbitrary other components as long as the electrode mixture includes an electrode active material as an essential component. Other components are not particularly limited, and may use components to be used for producing a lithium ion secondary battery can be used. Examples of the other components include a solid electrolyte, a conductive auxiliary agent, a binding agent, and the like.
A positive electrode mixture constituting a positive electrode layer contains at least a positive electrode active material, and may contain other components such as a solid electrolyte, a conductive auxiliary agent, and a binding agent.
The positive electrode active material is not particularly limited as long as it can absorb and release lithium ions. Examples thereof include LiCoQ2, Li(Ni5/10Co2/10Mn3/10)O2, Li(Ni6/10Co2/10Mn2/10)O2, Li(Ni8/10Co1/10Mn1/10)O2, Li(Ni0.8Co0.15Al0.05)O2, Li(Ni1/60Co4/6Mn1/6)O2, Li(Ni6/10Co2/10Mn2/10)O2, LiCoO4, LiMn2O4, LiNiO2, LiFePO4, lithium sulfide, sulfur, and the like,
A negative electrode mixture constituting an electrode layer of negative electrode contains at least a negative electrode active material, and may contain other components such as a solid electrolyte, a conductive auxiliary agent, and a binding agent.
The negative, electrode active material is not particularly limited as long as it can absorb and release lithium ions. Examples thereof include carbon materials such as metallic lithium, a lithium alloy, metal oxide, metal sulfide, metal nitride, Si, SiO, an artificial graphite, natural graphite, hard carbon, and soft carbon.
The electrode layer in the electrode for a lithium ion secondary battery of the present invention includes a porous coating layer. When the electrode layer includes a porous coating layer, an electrolytic solution extruded from the electrode layer due to expansion of a negative electrode active material during charging can be absorbed and trapped in the coating layer.
By absorbing and trapping the electrolytic solution in the coating layer, a phenomenon that the electrolytic solution runs out and drying up of liquid can be suppressed even if charge and discharge are repeated.
In particular, in a case of repeating fully charging and discharging, deterioration of the capacity can be remarkably suppressed.
As a result, it is possible to achieve a lithium ion secondary battery durability and input/output characteristics (output density) having improved with the energy density maintained high.
A material forming a coating layer is a porous material.
The porosity of the porous material is preferably 30 to 80%.
When the porosity is 30 to 80%, the electrolytic solution released from the negative electrode during charging can be sufficiently captured.
Examples of the porous material forming the coating layer include carbon black and activated carbon.
Carbon black is preferable because particles become a structure to form a microstructure, and therefore an electrolytic solution can be replenished.
Activated carbon is preferable because it has high specific surface area, and therefore the electrolytic solution can be replenished.
A thickness of the coating layer is not particularly limited, and, for example, a thickness of the coating layer of the negative electrode is preferably 1 to 20 μm, and a thickness of the coating layer of the positive electrode is preferably 1 to 10 urn.
When the thickness of the coating layer of the negative electrode is 1 to 20 μm, the durability can be improved without considerably increasing the cell resistance value.
When the thickness of the coating layer of the positive electrode is 1 to 10 μm, an electrolytic solution moving through the separator can be sufficiently captured.
The coating layer may be formed at the positive electrode or the negative electrode or both electrodes. However, the active material used for the negative electrode expands greatly during charging, and the electrolyte is extruded from the electrode layer. Therefore, when the coating layer is formed on the negative electrode, more effect can be obtained.
Furthermore, it is preferable that the coating layer is disposed on the surface in contact with the separator in the electrode layer, when at least a lithium ion secondary battery is formed.
The electrolytic solution can be trapped in a center portion of the cell.
Note here that in an embodiment in which a negative electrode layer includes a coating layer, the negative electrode coating layer is preferably disposed on all surfaces of the negative electrode layer.
In the negative electrode layer, since much electrolyte is extruded due to expansion of the negative electrode active material, by disposing the coating layer on all surfaces of the negative electrode layer, it is possible to trap the electrolytic solution efficiently from all the directions.
In the electrode 10 for a lithium ion secondary batter/shown in
Therefore, the electrode 10 for a lithium ion secondary battery shown in
Arrows shown in
Since a negative electrode active material is expanded during charging, an electrolytic solution is extruded from an electrode layer as shown in
Furthermore, as shown in
Furthermore, it is further preferable that the present invention has an embodiment in which the positive electrode layer also includes a porous coating layer in addition to the embodiment in which the negative electrode layer includes the coating layer.
When the coating layer is formed on the positive electrode layer, the coating layer is disposed on the surface in contact with the separator.
When the coating layer is disposed on the surface in contact with the separator, the electrolytic solution that cannot be absorbed only by the negative electrode side can be trapped also by the positive electrode side.
In the electrode 20 for a lithium ion secondary battery shown in
Therefore, the electrode 20 for a lithium ion secondary battery shown in
Arrows shown in
Since a negative electrode active material is expanded during charging, an electrolytic solution is extruded from the negative electrode side, reaches the positive electrode side through the separator as shown in
Furthermore, as shown in
The method for producing electrode for lithium ion secondary battery according to the present invention is not particularly limited, and can use usual methods in the field of this technology.
The electrode for a lithium ion secondary battery of the present invention has an electrode layer including a current collector including a porous foam made of metal and being filled with an electrode mixture. The electrode layer includes a plurality of electrode divided products.
A method for filling the current collector with an electrode mixture is not particularly limited, and examples of the method include a method for filling the inside of a network structure of the current collector with slurry including an electrode mixture using a plunger-type die coater, while pressure is applied.
The method for forming a porous coating layer on a desired surface of the formed electrode layer is not particularly limited, and examples of the method include dipping coating, plunger-type die coating, die coating, comma coating, and blade coating.
After the electrode mixture is filled to form a coating layer, an electrode for a lithium ion secondary battery can be obtained by applying usual methods in the field of this technology.
For example, the current collector filled with an electrode mixture is dried, and then is pressed to obtain an electrode for a lithium ion secondary battery.
Pressing can improve the density of the electrode mixture, and can adjust so as to have a desired density.
A lithium ion secondary battery of the present invention includes a positive electrode, a negative electrode, and a separator or a solid electrolyte layer located between the positive electrode and the negative electrode.
In the lithium ion secondary battery of the present invention, at least one of the positive electrode and the negative electrode is the above-mentioned electrode for a lithium ion secondary battery of the present invention.
In other words, in the lithium ion secondary battery of the present invention, the positive electrode may be the electrode for a lithium ion secondary battery of the present invention or the negative electrode may be the electrode for a lithium ion secondary battery of the present invention, or both electrodes may be the electrode for a lithium ion secondary battery of the present invention.
However, an active material used for a negative electrode is greatly expanded at the time of charging, and more electrolytic solution is extruded from the electrode layer, and therefore, when the electrode for a lithium ion secondary battery of the present invention is used for a negative electrode, a higher effect can be obtained.
Therefore, it is preferable that the lithium ion secondary battery of the present invention has an embodiment in which the negative electrode layer includes a porous negative electrode coating layer.
Furthermore, in the negative electrode layer, it is preferable that the negative electrode coating layer is disposed on all surfaces.
It is further preferable that the lithium ion secondary battery of the present invention has an embodiment in which the positive electrode layer also includes a porous positive electrode coating layer in addition to an embodiment in which the negative electrode layer includes a porous negative electrode coating layer.
In particular, in the positive electrode layer, when the positive electrode coating layer is disposed on the surface in contact with the separator, an electrolytic solution that cannot be absorbed only by a negative electrode side can be trapped by a positive electrode side.
In the lithium ion secondary battery of the present invention, a configuration of the positive electrode and the negative electrode in which the electrode for a lithium ion secondary battery of the present invention is not applied is not particularly limited, and arty configuration may be used as long as it functions as the positive electrode, and the negative electrode of the lithium ion secondary battery.
A positive electrode and a negative electrode constituting a lithium ion secondary battery can constitute any batteries by selecting two types of materials capable of constituting an electrode, comparing the charge and discharge potentials of two types of compounds with each other, and using one showing a noble potential as a positive electrode and one showing a base potential as a negative electrode.
When the lithium ion secondary battery of the present invention includes a separator, the separator is located between the positive electrode and the negative electrode.
The material, thickness, or the like, is not particularly limited, and known separators capable of being used for the lithium ion secondary battery can be applied.
Hereinafter, Examples etc. of the present invention will be described, but the present invention is not limited to these Examples etc.
As a current collector, a copper foam having a thickness of 1.0 mm, porosity of 95%, the number of cells of 46 to 50 cells/inch, a pore diameter of 0.5 mm, and a specific surface area of 5000 m2/m3 was prepared.
A mixture obtained by mixing 96.5% by mass of natural graphite 1% by mass of carbon black as a conductive auxiliary agent 1.5% by mass of styrene-butadiene rubber (SBR) as a binding agent, and 1% by mass of sodium carboxymethyl cellulose (CMC) as a thickener was dispersed in an appropriate amount of distilled water to produce a negative electrode mixture slurry,
The produced negative electrode mixture slurry was applied on a current collector using a die coater so that the coated amount was 45 mg/cm2.
The coated slurry was dried in a vacuum at 120° C. for 12 hours.
A surface of the produced electrode layer of negative electrode was coated by dipping in 20% by mass of carbon black solution.
The obtained product was dried in a vacuum at 120° C. for one hour. Next roll press was performed at a pressure of 10 ton to produce a negative electrode for a lithium ion secondary battery.
The produced negative electrode coating layer had a thickness of 15 μm.
The electrode layer in the obtained negative electrode for a lithium ion secondary battery had a basis weight of 45 mg/cm2, a density of 1.5 g/cm3, a thickness of 230 μm.
The produced negative electrode was punched into a size of 3 cm×4 art.
The negative electrode 30 for a lithium ion secondary battery produced in Example 1 includes a negative electrode coating layer 32 on all surfaces of the negative electrode layer 31.
As a current collector, an aluminum foam having a thickness of 1.0 mm, porosity of 95%, the number of ceils of 46 to 50 ceils/inch, a pore diameter of 0.5 mm, and a specific surface area of 5000 m2/m3 was prepared.
As the positive electrode active material, LiNi0.5Co0.2Mn0.3O2 was prepared.
A mixture obtained by mixing 94% by mass of positive electrode active material, 4% by mass of carbon black as a conductive auxiliary agent, and 2% by mass of polyvinylidene fluoride (PVDF) as a binding agent was dispersed in an appropriate amount of N-methyl-2-pyrrolidone (NMP) to produce a positive electrode mixture slurry.
The produced positive electrode mixture slurry was applied on a current collector using a plunger-type die coater so that the coated amount was 90 mg/an*.
Then, the obtained product was dried in a vacuum at 120° C. for 12 hours, and then roll-pressed at a pressure of 15 ton to produce a positive electrode for a lithium ion secondary battery.
The obtained electrode layer of the positive electrode for a lithium ion secondary battery had a basis weight of 90 mg/cm2 and a density of 3.2 g/cm*.
The produced positive electrode was punched into a size of 3 cm×4 cm, and the punched electrode was used as it is without forming a positive electrode coating layer.
As a separator, 25-μm microporous film as three-layered laminated product of polypropylene/polyethylene/polypropylene was prepared and punched in a size of 4 cm×5 cm.
The above-produced laminated product including the positive electrode, the negative electrode, and the separator disposed therebetween was inserted Into in a bag processed by heat-sealing an aluminum laminate for a secondary battery so as to produce a laminate cell.
As the electrolytic solution, a solution in which 1.2 mol of LiPF6 had teen dissolved in a solvent obtained by mixing ethylene carbonate, dimethyl carbonate, and ethyl methyl carbonate at a volume ratio of 3:4:3 was prepared, and the solution was injected into the above-mentioned laminate cell to produce a lithium ion secondary battery.
The electrode layer of the negative electrode was formed in the same manner as in Example 1, and used as a negative electrode for a lithium ion secondary battery without forming a negative electrode coating layer.
As a current collector, an aluminum foam having a thickness of 1.0 mm, porosity of 95%, the number of cells of 46 to 50 cells/inch, a pore diameter of 0.3 men, and specific surface area of 5000 m2/m3 was prepared.
Positive electrode mixture slurry was produced in the same manner as in Example 1.
To one side of the produced electrode layer of the positive electrode, the surface was coated with 20% by mass carbon black solution by blade coating.
The coated surface was dried in a vacuum at 120° C. for one hour.
Then, roll pressing was performed at a pressure of 15 ton to produce a positive electrode for a lithium ion secondary battery.
The produced positive electrode coating layer had a thickness of 10 μm.
A positive electrode mixture layer was produced and punched into a size of 3 cm×4 cm in the same manner as in Example 1.
The positive electrode 40 for a lithium ion secondary battery produced in Example 2 includes a positive electrode coating layer 42 on only one surface of a positive electrode layer 41.
Then, a lithium ion secondary battery was assembled such that the positive electrode coating layer 42 is brought into contact with a separator.
A lithium ion secondary battery was produced in the same manner as in Example 1 except that assembly was performed using the above-produced positive electrode and negative electrode so that the positive electrode coating layer was brought into contact with a separator.
A negative electrode for a lithium ion secondary battery including a negative electrode coating layer was produced in the same manner as in Example 1.
A positive electrode for a lithium ion secondary battery including a positive electrode coating layer was produced in the same manner as in Example 2.
A lithium ion secondary battery was produced in the same manner as in Example 1 except that assembly was performed using the above-produced positive electrode and negative electrode so that the positive electrode coating layer was brought into contact with a separator.
The negative electrode 30 for a lithium ion secondary battery produced in Example 3 includes the negative electrode coating layer 32 on all surfaces of the negative electrode layer 31.
Furthermore, the positive electrode 40 for a lithium ion secondary battery includes a positive electrode coating layer 42 only one surface of the positive electrode layer 41, and the positive electrode coating layer 42 is in contact with the separator 52.
Furthermore, the positive electrode, the separator, and the negative electrode are sealed by an outer body 33 and the outer body 43, including an aluminum foil, as a laminate film capable of heat sealing.
[Production of Negative Electrode for Lithium Ion Secondary Battery] A negative electrode for a lithium ion secondary battery, which does not have a negative electrode coating layer, was produced in the same manner as in Example 2.
A positive electrode for a lithium ion secondary battery, which does not have a positive electrode coating layer, was produced in the same manner as in Example 1.
A lithium ion secondary battery was produced in the same manner as in Example 1 except that the above-produced positive electrode and the negative electrode were used.
Lithium ion secondary batteries obtained in Examples 1 to 3, and Comparative Example 1 were subjected to the following evaluation,
The lithium ion secondary batteries were left stand at the measurement temperature (25° C.) for three hours, and constant current charge was performed at 0.33 C up to 4.2 V, then, constant voltage charge was performed at a voltage of 4.2 V for 5 hours, left stand for 30 minutes, then discharge was performed at a discharge rate of 0.33 C up to 2.5 V, and discharge capacity was measured.
The obtained discharge capacity was made to be initial discharge capacity.
A lithium ion secondary battery after measurement of the initial discharge capacity was adjusted to a charge level (SOC (State of Charge)) of 50%.
Next, discharge was performed for 10 seconds at a current value of 0.2 C, and a voltage after 10 seconds was measured.
Then, each voltage with respect to a current of 0.2 C, after 0.1 seconds, 1 second, and 10 seconds, were plotted with the abscissa as a current value and the ordinate as a voltage.
Next, after being left stand for 10 minutes, auxiliary charge was performed to return SOC to 50%, and then left stand for 10 minutes.
Next, for each C rate at 0.5 C, 1.0 C, 1.5 C, 2.0 C, and 2.5 C, the same operations as mentioned above were performed, and voltages with respect to the current at each C rate, after 0.1 seconds, 1 second, and 10 seconds, were plotted.
The gradient of the approximate straight line obtained from each plot was defined as the internal cell resistance of the lithium ion secondary battery.
As a charge and discharge cycle durability test, 200 cycles of operations were performed. Each cycle includes performing a constant current charge at 0.6 C up to 4.2 V in a constant temperature bath at 45° C., then performing constant voltage charge at a voltage of 4.2 V for 5 hours or until a current became 0.1 C, being left stand for 30 minutes, performing a constant current discharge at a discharge rate of 0.6 C up to 2.5 V, and being left stand for 30 minutes.
After completion of 200 cycles, the constant temperature bath was set at 25° C., and left stand in a state of discharge at 2.5 V for 24 hours, and then, similar to the measurement of the initial discharge capacity, the discharge capacity was measured.
The operation was repeated every 200 cycles, and measurement was performed up to 600 cycles.
[Cell Resistance after Endurance]
After completion of 600 cycles, a charge level (SOC (State of Charge)) was adjusted to 50% and the cell resistance after endurance was measured by the same measurement method for measurement of the initial cell resistance.
Discharge capacity for every 200 cycles with respect to the initial discharge capacity was obtained, the discharge capacity was made to be a capacity retention rate for each cycle.
Cell resistance with respect to the initial ceil resistance after 600 cycles endurance was obtained, and the obtained cell resistance was made to be a resistance change rate.
Table 1 shows various measurement results of lithium ion secondary battery produced in Examples and Comparative Examples.
As shown in
In other words, use of the battery using the electrode for a lithium ion secondary battery of the present invention including an electrode layer having a porous coating layer improved durability.
As shown in
In other words, in the batteries using the electrode for a lithium ion secondary battery of the present invention including an electrode layer having a porous coating layer, durability was improved.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2020-043839 | Mar 2020 | JP | national |
