Patent Description:
As technologies for mobile devices are developed and demand for the mobile devices increases, there has been a rapid increase in demand for secondary batteries as energy sources. Among such secondary batteries, lithium secondary batteries, which exhibit a high energy density and operational potential, a long cycle life, and a low self-discharge rate have been commercialized and widely used.

In recent years, there has been a growing interest in environmental issues, and as a result, recently, electric vehicles (EVs) and hybrid electric vehicles (HEVs), which can replace fossil-fueled vehicles such as gasoline vehicles and diesel vehicles, and the like are widely studied. Lithium secondary batteries having high energy density, high discharge voltage, and output stability are mainly studied and used as a power source for electric vehicles (EV) and hybrid electric vehicles (HEV).

In general, such a lithium secondary battery is manufactured by embedding an electrode assembly including a positive electrode, a negative electrode, and a separator in a battery case in a state impregnated with an electrolyte solution. The electrode such as the positive electrode or negative electrode has a structure in which an electrode mixture layer is formed on one or both surfaces of a current collector. In order to manufacture the electrode mixture layer, an electrode slurry including an active material, a conductive material, and a binder is prepared, and the slurry is then applied to an electrode current collector, which is then dried and rolled.

The performance of the lithium secondary battery is greatly affected by the manufactured electrode. For example, in the process of drying the electrode, a component in the mixture layer, particularly, a binder flows. The flow of the binder affects the interfacial bonding between the current collector and the mixture layer, and changes the conductivity in the electrode mixture layer. Therefore, there is a high need for a technology capable of effectively analyzing or evaluating the dispersibility of a binder in an electrode mixture layer.

Document <CIT> discloses a method for evaluating dispersibility of a conductive paste of a lithium ion battery, the method comprising: measuring the thickness of the conductive paste layer of the test sample, carrying out a four probe resistivity measurement at different surface locations of the layer and evaluating the dispersibility of the conductive paste based on the measured data.

The present invention was invented in consideration of the above problems, and the present invention relates to a method and apparatus for evaluating the dispersibility in the thickness direction of a binder in an electrode mixture layer by a non-destructive method.

The present invention relates to a method for evaluating the dispersibility of a binder in the thickness direction in an electrode mixture layer. The method according to the present invention is defined in claim <NUM>.

According to the claimed invention, the step of measuring the potential difference (V) includes:.

In a specific example, in the step of measuring the potential difference V, the processes of calculating each potential difference are performed simultaneously or sequentially.

According to the claimed invention, the step of measuring the potential difference (V) includes: a process of setting an arbitrary reference point (no) on the surface of the electrode mixture layer; a process of specifying n potential difference measurement points spaced apart from the set reference point (no) by a different distance; and a process of measuring the potential difference (V) between the reference point (no) and each voltage measurement point in a state where a current is applied to the electrode mixture layer.

In a specific example, in the step of measuring the potential difference (V), the process of specifying n potential difference measurement points includes designating a rectangular region which is formed within a constant voltage measurement region and where, on average, p voltage probes in a horizontal direction and q voltage probes in a vertical direction are arranged at regular intervals, in which p and q are each <NUM> or more, but a product of p and q is an integer equal to n.

In one example, in the method according to the present invention, at least two current application points are further included at an external side of n potential difference measurement points.

According to the claimed invention, in the step of calculating the voltage difference ΔV, the largest potential difference among the measured potential differences is set as the reference voltage.

The present invention provides an apparatus for evaluating the dispersibility of a binder in the thickness direction in the electrode mixture layer. The apparatus is an apparatus for performing the method described above.

According to the claimed invention, the apparatus includes a measuring unit in which a number of probes are formed on a measurement surface in contact with an electrode mixture layer to be measured.

In a specific example, on average, p voltage probes in a horizontal direction and q voltage probes in a vertical direction are arranged on a rectangular region at regular intervals. Herein, p and q are each <NUM> or more, but a product of p and q is an integer equal to n. For example, p and q are each an integer of <NUM> to <NUM>.

According to the claimed invention, the apparatus further includes a data processing unit configured to set one of potential differences measured from a measuring unit as a reference voltage, calculating a voltage difference (ΔV) from the reference voltage, and evaluate dispersibility in a thickness direction of a binder in an electrode mixture layer by comparing the calculated voltage difference (ΔV) with a preset reference value.

According to the method and apparatus for evaluating the binder dispersibility in the electrode mixture layer according to the present invention, the dispersibility in the thickness direction of the binder in the electrode mixture layer can be evaluated in a non-destructive manner.

The present invention provides a method for evaluating the dispersibility of a binder in the thickness direction in the electrode mixture layer. The method according to the present invention includes: a step of setting an arbitrary reference point (no) on a surface of an electrode mixture layer in a state where current is applied to the electrode mixture layer, and measuring a potential difference (V) with each reference point (no) at n points having different separation distances from the set reference point (no) where n is an integer greater than or equal to <NUM>; a step of setting any one potential difference among the measured potential differences as a reference voltage and calculating a voltage difference (ΔV) from the reference voltage; and a step of comparing the calculated voltage difference (ΔV) with a preset reference value, and calculating a dispersion in a thickness direction of a binder in the electrode mixture layer.

In the step of measuring the potential difference V with the reference point (no), the points for measuring the potential difference are two or more points, and specifically, may be <NUM> to <NUM> points or <NUM> to <NUM> points. If the number of points for measuring the potential difference increases, the reliability of the evaluation can be increased, but the manufacturing cost of the equipment performing the evaluation method increases. The points at which the potential difference is measured should have at least one point having a different separation distance from the reference point (no), and a case where two different points have the same separation distance from the reference point (no) may also be included.

In the evaluation method according to the present invention, a potential difference is measured at two or more points having different separation distances from the surface of the electrode mixture layer. Based on the measured results, by setting a reference voltage and calculating a voltage difference for each point, it is possible to check the dispersibility of the binder in the electrode mixture layer. Conventionally, in order to evaluate the dispersibility of the binder in the electrode mixture layer, the electrode mixture layer to be evaluated was cut and the degree of dispersion of the binder on the cut surface was measured using IR or Raman spectrum. However, the existing evaluation method is a destructive method in that the electrode mixture layer to be evaluated should be cut. On the other hand, the present invention can evaluate the dispersibility of the binder in the electrode mixture layer by a non-destructive method.

According to the claimed invention, the step of measuring the potential difference (V) includes: a process of calculating a potential difference (V<NUM>) between a reference point (no) on the surface of the electrode mixture layer and a first point (m) spaced apart from the reference point (no); and a process of calculating a potential difference (Vk) between the reference point (no) and a k-th point (nk) spaced from the reference point (no) by another interval where k is an integer in a range between <NUM> and n.

In a specific embodiment, in the step of measuring the potential difference V, the processes of calculating each potential difference are performed simultaneously or sequentially. For example, the step of measuring the potential difference V may be performed using an apparatus in which a plurality of voltage probes are formed on a measurement surface. In this case, it is possible to measure the potential difference at a plurality of points at the same time in a state that a current has been applied to the electrode mixture layer. Alternatively, it is also possible to measure the potential difference at a plurality of points sequentially in a state in which a current has been applied to the electrode mixture layer.

Still according to the claimed invention, the step of measuring the potential difference (V) includes: a process of setting an arbitrary reference point (no) on the surface of the electrode mixture layer; a process of specifying n potential difference measurement points spaced apart from the set reference point (no) by a different distance; and a process of measuring the potential difference (V) between the reference point (no) and each voltage measurement point in a state where a current is applied to the electrode mixture layer. For example, the step of measuring the potential difference V may be performed using an apparatus in which a ground probe and a plurality of voltage probes are formed on a measurement surface. In addition, the measurement surface may have a structure in which a current probe for applying a current is formed together.

In a specific example, in the step of measuring the potential difference (V), the process of specifying n potential difference measurement points includes designating a rectangular region which is formed within a constant voltage measurement region and where, on average, p voltage probes in a horizontal direction and q voltage probes in a vertical direction are arranged at regular intervals, in which p and q are each <NUM> or more, but a product of p and q is an integer equal to n. This means a structure in which points measuring the potential difference are arranged in a rectangular area. This is suggested as an example, and a structure in which points measuring the potential difference may be arranged in a radial, semicircular or circular shape, or may also be arranged in a form of a polygon such as a triangle or a hexagon.

According to the claimed invention, the evaluation method includes two or more current application points outside the n potential difference measurement points. This means measuring the potential difference at each point in a state where a current is applied to the electrode mixture layer. The current application points are formed outside the point where the potential difference is measured.

According to the claimed invention, in the step of calculating the voltage difference ΔV, the largest potential difference among the measured potential differences is set as the reference voltage. In the evaluation method according to the present invention, a potential difference is measured at a plurality of points in the electrode mixture layer. Among the measured potential differences, the point showing the largest potential difference can be interpreted as reflecting the resistance of both the upper and lower portions of the electrode mixture layer. However, points at which the measured potential difference is substantially close to "<NUM>" may be excluded from the evaluation.

In addition, the present invention provides an evaluation apparatus for performing the evaluation method described above. The evaluation apparatus is an evaluation apparatus for evaluating the dispersibility in the thickness direction of the binder in the electrode mixture layer. The apparatus according to the present invention includes a measuring unit in which a number of probes are formed on a measurement surface in contact with an electrode mixture layer to be measured. Herein, the measuring unit includes: a ground probe; n voltage probes arranged at different intervals from the ground probe where n is an integer of <NUM> or more; and current probes arranged at regular intervals at an external side of a region in which the voltage probes are formed. In addition, the potential difference between each voltage probe and the ground probe is measured in a state that the current is applied through the current probe.

Two or more voltage probes may be formed, and specifically, <NUM> to <NUM> or <NUM> to <NUM> voltage probes may be formed. If the number of voltage probes increases, the reliability of evaluation can be increased, but the unit cost of the apparatus increases. The position of the voltage probe should be at least one point having a different separation distance from the ground probe, but may include a case where two different voltage probes have the same separation distance as the ground probe.

In a specific example, on average, p voltage probes in a horizontal direction and q voltage probes in a vertical direction are arranged on a rectangular region at regular intervals. Herein, p and q are each <NUM> or more, but a product of p and q is an integer equal to n. For example, p and q are each an integer of <NUM> to <NUM>. The arrangement of the voltage probes refers to a structure in which a plurality of voltage probes are arranged in a rectangular area. This is suggested as an example, and includes cases in which the voltage probes are arranged in various forms described above.

In one example, the apparatus further includes a data processing unit configured to set one of potential differences measured from a measuring unit as a reference voltage, calculating a voltage difference (ΔV) from the reference voltage, and evaluate dispersibility in a thickness direction of a binder in an electrode mixture layer by comparing the calculated voltage difference (ΔV) with a preset reference value. The evaluation apparatus according to the present invention comprises a data processing unit that checks the degree of dispersion of the binder in the electrode mixture layer.

In addition, the electrode to be evaluated for the binder dispersibility in the present invention is a positive electrode or a negative electrode of the battery. The battery is a secondary battery, for example, a lithium secondary battery. The lithium secondary battery is a generic term for a case containing lithium in a secondary battery, and specifically includes a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode. Hereinafter, specific components of each electrode will be described, but the scope of the present invention is not limited thereto.

The positive electrode has a structure in which a positive electrode mixture layer is stacked on one or both sides of a positive electrode current collector. The positive electrode active materials may each independently be a lithium-containing oxide, and may be the same or different. A lithium-containing transition metal oxide may be used as the lithium-containing oxide. In one example, the positive electrode mixture layer includes a conductive material and a binder polymer in addition to the positive electrode active material, and if necessary, may further include a positive electrode additive commonly used in the art.

The positive electrode active material may be a lithium-containing oxide, and may be the same or different. A lithium-containing transition metal oxide may be used as the lithium-containing oxide.

For example, the lithium-containing transition metal oxide may be any one or a mixture of two or more selected from the group consisting of LixCoO<NUM>(<NUM><x<<NUM>), LixNiO<NUM>(<NUM><x<<NUM>), LixMnO<NUM>(<NUM><x<<NUM>), LixMn<NUM>O<NUM>(<NUM><x<<NUM>), Lix(NiaCobMnc)O<NUM>(<NUM><x<<NUM>, <NUM><a<<NUM>, <NUM><b<<NUM>, <NUM><c<<NUM>, a+b+c=<NUM>), LixNi<NUM>-yCoyO<NUM>(<NUM><x<<NUM>, <NUM><y<<NUM>), LixCo<NUM>-yMnyO<NUM>(<NUM><x<<NUM>, <NUM>≤y<<NUM>), LixNi<NUM>-yMnyO<NUM>(<NUM><x<<NUM>, O≤y<<NUM>), Lix(NiaCobMnc)O<NUM>(<NUM><x<<NUM>, <NUM><a<<NUM>, <NUM><b<<NUM>, <NUM><c<<NUM>, a+b+c=<NUM>), LixMn<NUM>-zNizO<NUM>(<NUM><x<<NUM>, <NUM><z<<NUM>), LixMn<NUM>-zCozO<NUM>(<NUM><x<<NUM>, <NUM><z<<NUM>), LixCoPO<NUM>(<NUM><x<<NUM>) and LixFePO<NUM>(<NUM><x<<NUM>), and the lithium-containing transition metal oxide may be coated with a metal or metal oxide such as aluminum (Al). Further, in addition to the lithium-containing transition metal oxide, one or more of sulfide, selenide, and halide may be used.

The positive electrode active material may be included in the range of <NUM> to <NUM> wt% in the positive electrode active material layer. When the content of the positive electrode active material satisfies the above range, it is advantageous in terms of manufacturing a high-capacity battery and providing sufficient conductivity of the positive electrode or adhesion between electrode materials.

The current collector used for the positive electrode is a metal having high conductivity, and any metal which the positive electrode active material slurry may be easily attached to and which is not reactive in the voltage range of the secondary battery can be used. Specifically, non-limiting examples of the current collector for the positive electrode include aluminum, nickel, or a foil manufactured by a combination thereof.

The positive electrode active material layer further includes a conductive material. The conductive material is usually added in an amount of <NUM> to <NUM>% by weight based on the total weight of the mixture including the positive electrode active material. Such a conductive material is not particularly limited as long as it has conductivity without causing a chemical change in the secondary battery. For example, one or more selected from the group consisting of graphite such as natural graphite or artificial graphite; carbon black such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, or thermal black; conductive fiber such as carbon fiber or metal fiber; metal powder such as carbon fluoride, aluminum, or nickel powder; conductive whiskey such as zinc oxide or potassium titanate; conductive metal oxide such as titanium oxide; and polyphenylene derivative may be used as the conductive material.

As the binder component, a binder polymer commonly used in the art may be used without limitation. For example, various kinds of binders such as polyvinylidene fluoride-co-hexafluoropropylene (PVDF-co-HFP), polyvinylidene fluoride (PVDF), polyacrylonitrile, polymethyl methacrylate, styrene-butadiene rubber (SBR), and carboxyl methyl cellulose (CMC) may be used.

Further, the negative electrode has a structure in which a negative electrode mixture layer is stacked on one or both sides of a negative electrode current collector. In one example, the negative electrode mixture layer includes a negative electrode active material, a conductive material, and a binder polymer, and if necessary, may further include a negative electrode additive commonly used in the art.

The negative electrode active material may include a carbon material, lithium metal, silicon or tin. When a carbon material is used as the negative electrode active material, both low crystalline carbon and high crystalline carbon may be used. Representative examples of low crystalline carbon include soft carbon and hard carbon are typical. Representative examples of high crystalline carbon include natural graphite, kish graphite, pyrolytic carbon, mesophase pitch based carbon fiber, mesocarbon microbeads, mesophase pitches, and high-temperature calcined carbons such as petroleum or coal tar pitch derived cokes.

Non-limiting examples of the current collector used for the negative electrode include copper, gold, nickel, or a foil manufactured by a copper alloy or a combination thereof. In addition, the current collector may be used by stacking substrates made of the above materials.

In addition, the negative electrode may include a conductive material and a binder commonly used in the art.

Hereinafter, the present invention will be described in more detail through drawings and the like.

<FIG> is a schematic diagram showing a process of performing an evaluation method according to an embodiment of the present invention. Referring to <FIG>, an apparatus for evaluating the dispersibility of a binder in an electrode mixture layer includes a measuring unit <NUM> in which a plurality of probes are formed. The measuring unit includes: a ground probe <NUM>; a plurality of voltage probes <NUM> arranged at different intervals from the ground probe; and current probes <NUM> arranged at regular intervals at an external side of a region in which the voltage probes are formed. In a state in which current is applied to the electrode mixture layer <NUM> through the current probe <NUM>, each voltage probe <NUM> measures a potential difference with the ground probe <NUM>.

The electrode <NUM> to be evaluated has a structure in which a mixture layer <NUM> is formed on both surfaces of the current collector <NUM>. For example, the current collector <NUM> is formed of aluminum foil, and the mixture layer <NUM> is a positive electrode mixture layer containing lithium.

Each probe measures a potential, and a potential difference measurement result <NUM> is calculated. The potential measured by the ground probe <NUM> becomes the reference potential (<NUM>), and a potential difference for each point is derived from the difference between the reference potential (<NUM>) and the potentials (<NUM> to <NUM>) measured by each voltage probe.

<FIG> is a schematic diagram showing a measurement surface of an evaluation apparatus according to another embodiment of the present invention. Referring to <FIG>, the measuring unit includes: a ground probe <NUM>; a plurality of voltage probes <NUM> arranged at different intervals from the ground probe; and current probes <NUM> arranged at regular intervals at an external side of a region in which the voltage probes are formed. In a state in which current is applied to the electrode mixture layer <NUM> through the current probe <NUM>, the potential difference between each voltage probe <NUM> and the ground probe <NUM> is measured. A total of <NUM> voltage probes <NUM> are formed, and <NUM> voltage probes in a horizontal direction and <NUM> voltage probe in a vertical direction are arranged in a rectangular region.

A ground probe <NUM> is positioned on one side of the measuring unit <NUM>, and a current probe <NUM> is positioned outside the rectangular region in which the voltage probes <NUM> are arranged. The current probes <NUM> have a structure in which a total of <NUM> current probes are formed, <NUM> each on one side.

Hereinafter, the present invention will be described in more detail through examples. However, the embodiments described in the specification and the configurations described in the drawings are only the most preferred embodiments of the present invention, and do not represent all of the technical ideas of the present invention, which is defined in the appended, independent claims.

Graphite as a negative electrode active material, cyanoethyl polyvinyl alcohol as a dispersant, and PVdF (polyvinylidene fluoride) as a binder were weighed in a weight ratio of <NUM> : <NUM> : <NUM> : <NUM>, respectively, which was put in NMP and was mixed for <NUM> hour at <NUM>,<NUM> rpm in a Homo mixer, to thereby prepare a slurry for a negative electrode.

The prepared slurry for negative electrode was applied to a copper foil having a thickness of <NUM> at a thickness of <NUM>. Then, the copper foil was dried at <NUM> and was then rolled to thereby prepare a negative electrode.

A slurry for negative electrode was prepared in the same manner as in Preparation Example <NUM>. The prepared slurry for negative electrode was applied to a copper foil having a thickness of <NUM> at a thickness of <NUM>. Then, the copper foil was dried at <NUM> and was then rolled to thereby prepare a negative electrode.

LiNi<NUM>Mn<NUM>Co<NUM> as positive electrode active material, Super C as conductive material, cyanoethyl polyvinyl alcohol as dispersion material, and PVdF as binder were weighed in a weight ratio of <NUM> : <NUM> : <NUM> : <NUM>, respectively, which was then put in NMP and was mixed for <NUM> hour at <NUM>,<NUM> rpm in a Homo mixer, to thereby prepare a slurry for a positive electrode.

The prepared slurry for positive electrode was applied to an aluminum foil having a thickness of <NUM> at a thickness of <NUM>. Then, the aluminum foil was dried at <NUM> and was then rolled to thereby prepare a positive electrode.

A slurry for positive electrode was prepared in the same manner as in Preparation Example <NUM>. The prepared slurry for positive electrode was applied to an aluminum foil having a thickness of <NUM> at a thickness of <NUM>. Then, the aluminum foil was dried at <NUM> and was then rolled to thereby prepare a positive electrode.

Using the evaluation apparatus according to the present invention, the binder dispersibility was evaluated for the electrode specimens prepared in Preparation Examples <NUM> to <NUM>.

Specifically, the evaluation apparatus illustrated in <FIG> was used, and the measuring unit of the apparatus includes: a ground probe; <NUM> voltage probes arranged at different intervals from the ground probe; and current probes arranged at regular intervals at an external side of a region in which the voltage probes are formed.

In a state in which a current was applied to the electrode mixture layer through a current probe, a potential difference was measured in each voltage probe. The measured results are shown in <FIG>. Referring to <FIG>, it was measured that the potential difference was the largest at point <NUM>. This indicates the resistance from the upper portion to the lower portion of the mixture layer as point <NUM> is the farthest from the ground probe. The potential difference at points <NUM>, <NUM> and <NUM> reflects the resistance of the upper portion of the mixture layer. And, at point <NUM>, the potential difference was measured to be close to <NUM>, and this is excluded from the evaluation.

Then, the measured value at the point <NUM> having the largest potential difference was set as the reference voltage, the voltage difference (ΔV) from the reference voltage was calculated for each point, and the result is shown in <FIG>. Referring to <FIG>, it can be seen that the voltage difference ΔV at points <NUM>, <NUM>, and <NUM> increases as the drying temperature of the specimen increases. The fact that the difference (ΔV) between the potential difference at points <NUM>, <NUM> and <NUM> reflecting the resistance of only the upper portion and the potential difference at point <NUM> reflecting the resistance of the upper portion and the lower portion is large means that relatively more binders are distributed in the upper portion.

This means that the binder moves toward the upper portion during the drying process of the electrode, and a larger amount of the binder is placed on the upper portion as the drying temperature increases.

Binder dispersibility was verified for the electrode specimens prepared in Preparation Examples <NUM> to <NUM>. Each electrode specimen was obliquely cut at an angle of <NUM>°, and then IR and Raman spectra were measured for the inclined surface to confirm actual binder dispersibility. <FIG> is a graph showing the dispersibility of the binder according to the depth of the mixture layer.

Referring to <FIG>, it can be seen that the binder moves to the upper portion of the mixture layer according to the drying temperature of the electrode specimen. This corresponds to the result of Example <NUM> that the binder moves toward the upper portion of the mixture layer as the drying temperature of the electrode increases.

Using the evaluation apparatus according to the present invention, the binder dispersibility was evaluated for the electrode specimens prepared in Preparation Examples <NUM> and <NUM>.

Binder dispersibility was verified for the electrode specimens prepared in Preparation Examples <NUM> and <NUM>. Each electrode specimen was obliquely cut at an angle of <NUM>°, and then IR and Raman spectra were measured for the inclined surface to confirm actual binder dispersibility. To check the dispersibility, the experiment was repeated three times for each specimen. <FIG> is a graph showing the experimental results for the electrode specimen according to Preparation Example <NUM>, and <FIG> is a graph showing experimental results for an electrode specimen according to Preparation Example <NUM>.

Referring to <FIG>, it can be seen that in the electrode specimen of Preparation Example <NUM> dried at <NUM>, the binder was evenly dispersed in the thickness direction of the mixture layer. On the other hand, referring to <FIG>, it can be seen that in the electrode specimen of Preparation Example <NUM> dried at <NUM>, the binder was somewhat concentrated toward the upper portion of the mixture layer and dispersed.

Claim 1:
A method for evaluating dispersibility of a binder in thickness direction in an electrode mixture layer (<NUM>), comprising:
setting an arbitrary reference point (no) on a surface of the electrode mixture layer in a state where current is applied to the electrode mixture layer, and measuring potential differences (V) with respect to the set reference point (no) at n points each having different separation distances from the set reference point (no) where n is an integer greater than <NUM>;
setting a potential difference at a point having the largest potential difference with respect to the reference point among the measured potential differences as a reference voltage and calculating a voltage difference (ΔV) between the reference voltage and each of the other measured potential differences (V) at other points with respect to the set reference point (no); and
evaluating a dispersion of a binder in a thickness direction in the electrode mixture layer at each point based on calculated voltage difference (ΔV),
wherein in the evaluating the dispersion, it is evaluated that the larger the calculated voltage difference (ΔV) is, the more the binder is distributed in the upper layer of the electrode at the corresponding point.