WO2023068880A1 - 음극 선분산액, 이를 포함하는 음극 조성물, 음극 조성물을 포함하는 리튬 이차 전지용 음극, 음극을 포함하는 리튬 이차 전지 및 음극 조성물의 제조 방법 - Google Patents
음극 선분산액, 이를 포함하는 음극 조성물, 음극 조성물을 포함하는 리튬 이차 전지용 음극, 음극을 포함하는 리튬 이차 전지 및 음극 조성물의 제조 방법 Download PDFInfo
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- WO2023068880A1 WO2023068880A1 PCT/KR2022/016187 KR2022016187W WO2023068880A1 WO 2023068880 A1 WO2023068880 A1 WO 2023068880A1 KR 2022016187 W KR2022016187 W KR 2022016187W WO 2023068880 A1 WO2023068880 A1 WO 2023068880A1
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- negative electrode
- weight
- parts
- dispersion
- anode
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Definitions
- the present application relates to a negative electrode pre-dispersion liquid, a negative electrode composition including the same, a negative electrode composition for a lithium secondary battery including the negative electrode composition, a lithium secondary battery including the negative electrode, and a method for preparing the negative electrode composition.
- a secondary battery is a representative example of an electrochemical device using such electrochemical energy, and its use area is gradually expanding.
- lithium secondary batteries having high energy density and voltage, long cycle life, and low self-discharge rate have been commercialized and widely used.
- an electrode for such a high-capacity lithium secondary battery research is being actively conducted on a method for manufacturing a high-density electrode having a higher energy density per unit volume.
- a secondary battery is composed of an anode, a cathode, an electrolyte, and a separator.
- the negative electrode includes a negative electrode active material for intercalating and deintercalating lithium ions from the positive electrode, and silicon-based particles having a high discharge capacity may be used as the negative electrode active material.
- volume expansion itself is suppressed, such as a method of adjusting the driving potential, a method of additionally coating a thin film on the active material layer, and a method of controlling the particle diameter of the silicon-based compound.
- Various methods for preventing or preventing the conductive path from being disconnected are being discussed, but in the case of the above methods, the performance of the battery may be deteriorated, so there is a limit to the application, and a negative electrode battery with a high silicon-based compound content is still Commercialization of manufacturing has limitations.
- Patent Document 1 Japanese Unexamined Patent Publication No. 2009-080971
- the degree of dispersion of carbon nanotubes and the subsequent bonding relationship between SWCNTs and silicon-based active materials are important.
- a specific functional group is included as a functional group of the dispersant included in the carbon nanotube pre-dispersion, the degree of dispersion is excellent, and a hydrogen bond is formed with the -OH group on the surface of the silicon-based active material later to strengthen the binding force between the carbon nanotube and silicon.
- the present application relates to a negative electrode pre-dispersion solution, a negative electrode composition including the same, a negative electrode for a lithium secondary battery including the negative electrode composition, a lithium secondary battery including the negative electrode, and a method for preparing the negative electrode composition.
- An exemplary embodiment of the present specification is a pre-dispersion material including carbon nanotubes and a dispersant; and a dispersion medium, wherein the dispersant includes a carboxyl group as a functional group, the solids content of the linear dispersion material is 5% or less based on the cathode linear dispersion, and based on 100 parts by weight of the linear dispersion material. 20 parts by weight or more and 60 parts by weight or less of the carbon nanotubes; and 40 parts by weight or more and 80 parts by weight or less of the dispersant.
- a silicon-based active material in another exemplary embodiment, a silicon-based active material; a cathode predispersion solution according to the present application; and a negative electrode binder, wherein the silicon-based active material is present in an amount of 60 parts by weight or more based on 100 parts by weight of the negative electrode composition.
- a pre-dispersion material by mixing carbon nanotubes and a dispersant containing a carboxyl group as a functional group; including a dispersion medium in the linear dispersion material such that the solid content of the linear dispersion material is 5% or less; dispersing the linear dispersion material containing the dispersion medium; mixing an anode binder with water to form a mixture, and first mixing by adding the pre-dispersion material to the mixture; and adding a silicon-based active material to the mixed mixture and performing second mixing. and 40 parts by weight or more and 80 parts by weight or less of the dispersant.
- a negative electrode current collector layer In another exemplary embodiment, a negative electrode current collector layer; and a negative electrode active material layer including the negative electrode composition according to the present application formed on one side or both sides of the negative electrode current collector layer.
- the anode A negative electrode for a lithium secondary battery according to the present application; a separator provided between the anode and the cathode; And an electrolyte; it provides a lithium secondary battery comprising a.
- the dispersant includes a carboxyl group as a functional group
- the solid content of the pre-dispersion material is 5% or less based on the cathode pre-dispersion solution
- the pre-dispersion material 100 Based on parts by weight, 20 parts by weight or more and 60 parts by weight or less of the carbon nanotubes; and 40 parts by weight or more and 80 parts by weight or less of the dispersant.
- the cathode pre-dispersion solution according to the present application is a solution in which carbon nanotubes are first dispersed before being included in the cathode composition, and the solid content of the pre-dispersion material, the content of carbon nanotubes, and the content of the dispersant in the pre-dispersion solution satisfy a certain range, so that the carbon nanotubes are satisfied.
- the dispersibility of the tube is excellent.
- a carboxyl group is included as a functional group of the dispersant included in the carbon nanotube predispersion, and hydrogen bonds are formed with -OH groups on the surface of the silicon-based active material later to form carbon nanotubes. It has a feature capable of strengthening the binding force between the tube and the silicone.
- the path between the conductive materials is maintained even during repeated charging and discharging, and the use of silicon active materials can be uniformed.
- volume expansion during charging and discharging By using the negative electrode composition according to the present invention, it has characteristics that can be minimized.
- FIG. 1 is a diagram showing a laminated structure of a negative electrode for a lithium secondary battery according to an exemplary embodiment of the present application.
- FIG. 2 is a diagram showing a laminated structure of a lithium secondary battery according to an exemplary embodiment of the present application.
- FIG. 3 is a diagram showing the results of half-cell initial capacity evaluation of negative electrodes of Examples 1 and 2 according to the present application.
- FIG. 4 is a diagram showing the results of half-cell evaluation of negative electrodes of Examples 1 and 2 according to the present application.
- FIG. 5 is a diagram showing CHC cycle evaluation results of negative electrodes manufactured in Examples 1, 2, and Comparative Example 1 according to the present application.
- 'p to q' means a range of 'p or more and q or less'.
- specific surface area is measured by the BET method, and is specifically calculated from the nitrogen gas adsorption amount under liquid nitrogen temperature (77K) using BELSORP-mino II of BEL Japan. That is, in the present application, the BET specific surface area may mean the specific surface area measured by the above measuring method.
- Dn means the average particle diameter, and means the particle diameter at the n% point of the cumulative distribution of the number of particles according to the particle diameter. That is, D50 is the particle size at the 50% point of the cumulative distribution of the number of particles according to the particle size, D90 is the particle size at the 90% point of the cumulative distribution of the number of particles according to the particle size, and D10 is the 10% of the cumulative distribution of the number of particles according to the particle size. is the particle diameter at the point.
- the average particle diameter can be measured using a laser diffraction method. Specifically, after dispersing the powder to be measured in a dispersion medium, it is introduced into a commercially available laser diffraction particle size measuring device (e.g. Microtrac S3500) to measure the difference in diffraction pattern according to the particle size when the particles pass through the laser beam to distribute the particle size. yields
- a laser diffraction particle size measuring device e.g. Microtrac S3500
- a polymer includes a certain monomer as a monomer unit means that the monomer participates in a polymerization reaction and is included as a repeating unit in the polymer.
- this is interpreted as the same as that the polymer includes a monomer as a monomer unit.
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) are measured using a commercially available monodisperse polystyrene polymer (standard sample) of various degrees of polymerization for molecular weight measurement as a standard material, and gel permeation chromatography (Gel Permeation It is the molecular weight in terms of polystyrene measured by chromatography; GPC).
- molecular weight means a weight average molecular weight unless otherwise specified.
- An exemplary embodiment of the present specification is a pre-dispersion material including carbon nanotubes and a dispersant; and a dispersion medium, wherein the dispersant includes a carboxyl group as a functional group, the solids content of the linear dispersion material is 5% or less based on the cathode linear dispersion, and based on 100 parts by weight of the linear dispersion material. 20 parts by weight or more and 60 parts by weight or less of the carbon nanotubes; and 40 parts by weight or more and 80 parts by weight or less of the dispersant.
- the pre-dispersion means a dispersion before a material is included in the negative electrode composition, and the pre-dispersion and negative electrode composition are used in different meanings.
- the dispersant is xanthan gum (Xanthan gum); Alginate; And a compound represented by Formula 1; it may be one selected from the group consisting of.
- n is an integer from 1 to 10;
- n is an integer from 1 to 1000;
- m is an integer of 1 to 10, preferably an integer of 1 to 5, and more preferably an integer of 1 to 3.
- the dispersant is a group consisting of PPBP (Poly[3-(Potassium-4-butanoate)thiophne-2,5-diyl]; Xanthan gum; and alginate; Provides a cathode pre-dispersion solution containing one selected from
- the dispersant may include CMC.
- the dispersant may be a conjugated polymer including a carboxyl group as a functional group and having single bonds and double bonds alternately present in a molecule.
- the dispersant contains a carboxy group as a functional group, and when the dispersant is used, the dispersibility of the carbon nanotubes is excellent, and in particular, when included in a negative electrode composition later, the surface of the silicon-based active material used together It has a characteristic that the bond between the carbon nanotube and the silicon-based active material can be strengthened through hydrogen bonding with the Si-OH group of .
- the dispersant according to the present application includes a carboxyl group as a functional group, and can form a hydrogen bond with the Si-OH group on the surface of the silicon-based active material. Hydrogen bonding can also be achieved with an amine group, but in the case of having a carboxy group as in this application, the enthalpy between functional groups related to the hydrogen bond strength is 21 kJ / mol or 5.0 kcal / mol in the case of having a carboxy group, and 8 kJ / mol in the case of having an amine group mol or 1.9 kcal/mol.
- the binding force with the Si active material is lower than that of the dispersant having a carboxy group intended in the present invention, so that the effect of improving electrical connectivity may be rapidly reduced.
- the effect of improving the binding force with Si can be expected along with the dispersing performance.
- the PPBT dispersant is a conjugated polymer having a carboxyl group and having single bonds and double bonds in the main chain alternately.
- the PPBT dispersant wraps the SWCNT well by ⁇ - ⁇ interaction between the ⁇ electrons present in the main chain and the surface where the ⁇ electrons of the SWCNT exist, and at the same time, the PPBT side chain Due to the effect of the carboxy group present in the present, the SWCNTs present in a bundle form are effectively debundled to have a characteristic that can particularly improve the dispersibility.
- the solid content of the linear dispersion material based on the negative electrode linear dispersion may be 5% or less.
- the solids content of the linear dispersion material based on the cathode linear dispersion may be 5% or less, preferably 3% or less, more preferably 2% or less, 0.1% or more, and preferably 1% may be ideal
- the solid content of the pre-dispersion material satisfies the above range, and as the range is satisfied, the carbon nanotubes included in the pre-dispersion material are efficiently dispersed and the viscosity range can satisfy a certain range, Accordingly, it is characterized in that the agglomeration of the pre-dispersed liquid does not occur.
- carbon nanotubes with a large specific surface area are used in the linear dispersion according to the present application, and at this time, the solid content must satisfy the above range to indicate a viscosity range in which dispersion is possible, and smooth linear dispersion is possible.
- the linear dispersion material based on 100 parts by weight of the linear dispersion material, 20 parts by weight or more and 60 parts by weight or less of the carbon nanotubes; and 40 parts by weight or more and 80 parts by weight or less of the dispersant.
- the carbon nanotubes are 20 parts by weight or more and 60 parts by weight or less, preferably 25 parts by weight or more and 55 parts by weight or less, more preferably 30 parts by weight or more and 50 parts by weight. The following can be satisfied.
- the dispersant is 40 parts by weight or more and 80 parts by weight or less, preferably 45 parts by weight or more and 75 parts by weight or less, more preferably 50 parts by weight or more and 70 parts by weight or less. can be satisfied.
- the contents of the carbon nanotubes and the dispersant in the pre-dispersion material satisfy the above ranges, it is possible to form a mixture viscosity range sufficient for subsequent dispersion, and when the content of the carbon nanotubes is lower than the above ranges, the conductivity is improved. The effect of is reduced, and if it is higher than the above range, agglomeration between carbon nanotubes increases, resulting in smooth dispersion.
- the dispersion medium is a nonionic compound having no ionic functional group, which can act as an anode binder after film formation and does not affect electrical characteristics, or is heat treated during manufacture of an electrode. It is preferably a compound having a low decomposition temperature that can be removed by using a compound having ionicity in a polar solvent, or having a hydroxyl group as a functional group in order to improve solubility in a solvent.
- the dispersion medium may be water.
- the cathode pre-dispersion solution having a viscosity of 100 cP or more and 10,000 cP or less is provided.
- the viscosity of the cathode predispersion liquid may be 100 cP or more and 10,000 cP or less, preferably 300 cP or more and 7,000 cP or less.
- the viscosity of the cathode pre-dispersion solution may vary depending on the solid content of the pre-dispersion material and the pre-dispersion material, but as described above, when the solid content of the pre-dispersion material and the pre-dispersion material are used, the above range may be satisfied.
- the content of the pre-dispersion material for the cathode pre-dispersion solution is included, and the viscosity is adjusted by a dispersing process to be described later, and as the viscosity range is satisfied, mixing may be excellent when included in the anode composition later. Accordingly, the output of the secondary battery is improved.
- the cathode pre-dispersion solution according to an exemplary embodiment of the present application is carbon nanotubes having high hydrophobic properties, and relates to a pre-dispersion solution in which the carbon nanotubes are first dispersed. As a result, the performance of the electrode has excellent characteristics.
- the cathode pre-dispersion is prepared by first mixing the carbon nanotubes and the dispersing agent, then adding a dispersion medium, adjusting the solid content, and using a homogenizer capable of applying high stress or pressure or at a high speed. It can be dispersed using a homomixer capable of mixing or a mill equipment using beads.
- the PSD particle size analysis is performed to confirm that a constant particle size is obtained, and then the dispersion is checked for a shear viscosity curve using a rheometer to confirm that a constant slope is obtained.
- a negative electrode pre-dispersion liquid having a weight average molecular weight of 10,000 g/mol or more and 100,000 g/mol or less is provided.
- the weight average molecular weight of the dispersant is 10,000 g / mol or more and 100,000 g / mol or less, preferably the weight average molecular weight of the dispersant is 10,000 g / mol or more and 50,000 g / mol or less.
- the viscosity of the predispersion itself can be adjusted within a certain range, thereby preventing aggregation of the carbon nanotubes.
- a silicon-based active material in one embodiment, a silicon-based active material; a cathode predispersion solution according to the present application; and a negative electrode binder, wherein the silicon-based active material is present in an amount of 60 parts by weight or more based on 100 parts by weight of the negative electrode composition.
- a carboxyl group is included as a functional group of the dispersant included in the carbon nanotube pre-dispersion, and later -OH and hydrogen on the surface of the silicon-based active material By forming a bond, it has a feature that can strengthen the binding force between the carbon nanotube and silicon.
- the negative electrode composition includes the silicon-based active material of the above content, and as the above range is satisfied, the dispersion having a carboxyl group included in the pre-dispersion liquid and the OH group on the surface of the silicon-based active material are hydrogen bonded to form a bond between the carbon nanotube and the active material characteristics that can be strengthened.
- the silicon-based active material may use pure silicon (Si) as the silicon-based active material.
- a cathode predispersion is prepared to improve the dispersibility of carbon nanotubes and The existing problems were solved by strengthening the bonding.
- the average particle diameter (D50) of the silicon-based active material of the present invention may be 5 ⁇ m to 10 ⁇ m, specifically 5.5 ⁇ m to 8 ⁇ m, and more specifically 6 ⁇ m to 7 ⁇ m.
- the average particle diameter is within the above range, the viscosity of the negative electrode slurry is formed within an appropriate range, including the specific surface area of the particles within a suitable range. Accordingly, the dispersion of the particles constituting the negative electrode slurry becomes smooth.
- the size of the silicon-based active material has a value greater than or equal to the lower limit
- the contact area between the silicon particles and the conductive material is excellent due to the composite composed of the conductive material and the negative electrode binder in the negative electrode slurry, so that the possibility of continuing the conductive network increases.
- the capacity retention rate is increased.
- the average particle diameter satisfies the above range, excessively large silicon particles are excluded to form a smooth surface of the negative electrode, thereby preventing current density non-uniformity during charging and discharging.
- the silicon-based active material generally has a characteristic BET surface area.
- the BET surface area of the silicon-based active material is preferably 0.01 to 150.0 m 2 /g, more preferably 0.1 to 100.0 m 2 /g, particularly preferably 0.2 to 80.0 m 2 /g, and most preferably 0.2 to 18.0 m 2 /g.
- the BET surface area is measured according to DIN 66131 (using nitrogen).
- the silicon-based active material may exist, for example, in a crystalline or amorphous form, and is preferably not porous.
- the silicon particles are preferably spherical or fragment-shaped particles. Alternatively but less preferably, the silicon particles may also have a fibrous structure or be present in the form of a silicon-comprising film or coating.
- the silicon-based active material provides a negative electrode composition that is 60 parts by weight or more based on 100 parts by weight of the negative electrode composition.
- the silicon-based active material may include 60 parts by weight or more, preferably 65 parts by weight or more, more preferably 70 parts by weight or more, based on 100 parts by weight of the negative electrode composition, and 95 parts by weight or less , preferably 90 parts by weight or less, more preferably 80 parts by weight or less.
- the negative electrode composition according to the present application uses a specific conductive material and a negative electrode binder that can control the volume expansion rate in the charging and discharging process even when a silicon-based active material having a significantly high capacity is used in the above range, and even within the above range, the negative electrode composition It does not degrade performance and has excellent output characteristics in charging and discharging.
- the silicon-based active material may have a non-spherical shape and its sphericity is, for example, 0.9 or less, for example, 0.7 to 0.9, for example 0.8 to 0.9, for example 0.85 to 0.9 am.
- the circularity (circularity) is determined by the following formula 1, A is the area, P is the boundary line.
- the negative electrode composition further includes a negative electrode conductive material, and the negative electrode conductive material includes a dotted conductive material; And planar conductive material; provides a negative electrode composition comprising at least one selected from the group consisting of.
- the dotted conductive material may be used to improve conductivity of the negative electrode, and preferably has conductivity without causing chemical change.
- the conductive material is natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, channel black, farnes black, lamp black, thermal black, conductive fiber, fluorocarbon, aluminum powder, nickel powder, zinc oxide, titanic acid It may be at least one selected from the group consisting of potassium, titanium oxide, and polyphenylene derivatives, and preferably may include carbon black in terms of implementing high conductivity and excellent dispersibility.
- the point-shaped conductive material may have a BET specific surface area of 40 m 2 /g or more and 70 m 2 /g or less, preferably 45 m 2 /g or more and 65 m 2 /g or less, more preferably 50 m 2 /g or less . /g or more and 60 m 2 /g or less.
- the particle diameter of the dotted conductive material may be 10 nm to 100 nm, preferably 20 nm to 90 nm, and more preferably 40 nm to 60 nm.
- the conductive material may include a planar conductive material.
- the planar conductive material may serve to improve conductivity by increasing surface contact between silicon particles in the negative electrode, and at the same time suppress disconnection of the conductive path due to volume expansion.
- the planar conductive material may include at least one selected from the group consisting of plate-like graphite, graphene, graphene oxide, and graphite flakes, and preferably may be plate-like graphite.
- the average particle diameter (D50) of the planar conductive material may be 2 ⁇ m to 7 ⁇ m, specifically 3 ⁇ m to 6 ⁇ m, and more specifically 4 ⁇ m to 5 ⁇ m. .
- D50 average particle diameter
- the planar conductive material provides a negative electrode composition in which D10 is 0.5 ⁇ m or more and 1.5 ⁇ m or less, D50 is 2.5 ⁇ m or more and 3.5 ⁇ m or less, and D90 is 7.0 ⁇ m or more and 15.0 ⁇ m or less.
- the planar conductive material may have a BET specific surface area of 100 m 2 /g or more.
- the planar conductive material may have a BET specific surface area of 100 m 2 /g or more and 500 m 2 /g or less, preferably 150 m 2 /g or more and 300 m 2 /g or less, more preferably 200 m 2 /g or more. g or more and 300 m 2 /g or less.
- conductive materials may include linear conductive materials such as carbon nanotubes included in the cathode predispersion solution.
- Carbon nanotubes may be bundled carbon nanotubes.
- the bundled carbon nanotubes may include a plurality of carbon nanotube units.
- the term 'bundle type' herein means, unless otherwise specified, a bundle in which a plurality of carbon nanotube units are arranged side by side or entangled in substantially the same orientation with axes in the longitudinal direction of the carbon nanotube units. It refers to a secondary shape in the form of a bundle or rope.
- the carbon nanotube unit has a graphite sheet having a cylindrical shape with a nano-sized diameter and an sp2 bonding structure.
- the characteristics of a conductor or a semiconductor may be exhibited according to the angle and structure of the graphite surface being rolled.
- the bundled carbon nanotubes can be uniformly dispersed during manufacturing of the negative electrode, and the conductivity of the negative electrode can be improved by smoothly forming a conductive network in the negative electrode.
- the carbon nanotubes may be SWCNTs.
- the average length of the SWCNTs may satisfy a range of 500 nm or more and 20 ⁇ m or less.
- the cathode pre-dispersion may mean pre-dispersed carbon nanotubes, and the cathode pre-dispersion includes pre-dispersed carbon nanotubes and a dispersing agent.
- the dispersion medium when the negative electrode pre-dispersion is included in the negative electrode, the dispersion medium is removed and may include the pre-dispersed carbon nanotubes and the dispersant.
- the negative electrode conductive material is provided in an amount of 5 parts by weight or more and 40 parts by weight or less based on 100 parts by weight of the negative electrode composition.
- the negative electrode conductive material is 5 parts by weight or more and 40 parts by weight or less, preferably 5 parts by weight or more and 30 parts by weight or less, more preferably 7 parts by weight or more and 25 parts by weight based on 100 parts by weight of the negative electrode composition. May include the following.
- the negative electrode predispersion liquid is provided in an amount of 0.01 parts by weight or more and 20 parts by weight or less based on 100 parts by weight of the negative electrode composition.
- the negative electrode predispersion is 0.01 parts by weight or more and 20 parts by weight or less based on 100 parts by weight of the negative electrode composition; Preferably, it may contain 0.02 parts by weight or more and 18 parts by weight or less, more preferably 0.03 parts by weight or more and 15 parts by weight or less.
- the cathode pre-dispersion solution may be used as a conductive material.
- the cathode pre-dispersion may have a solid content of 5% or less.
- the negative electrode pre-dispersion liquid satisfies the above composition and ratio, it does not significantly affect the lifespan characteristics of an existing lithium secondary battery, and the number of points available for charging and discharging increases, resulting in a high C-rate. has excellent output characteristics.
- the negative electrode conductive material according to the present application has a completely different configuration from the conductive material applied to the positive electrode. That is, in the case of the anode conductive material according to the present application, it serves to hold the contact between silicon-based active materials whose volume expansion of the electrode is very large due to charging and discharging. As a role of imparting, its composition and role are completely different from those of the negative electrode conductive material of the present invention.
- the negative electrode conductive material according to the present application is applied to a silicon-based active material, and has a completely different configuration from that of a conductive material applied to a graphite-based active material. That is, since the conductive material used in the electrode having the graphite-based active material simply has smaller particles than the active material, it has characteristics of improving output characteristics and imparting some conductivity, unlike the negative electrode conductive material applied together with the silicon-based active material as in the present invention. Their composition and role are completely different.
- the plate-shaped conductive material used as the negative electrode conductive material described above has a different structure and role from the carbon-based active material generally used as the negative electrode active material.
- the carbon-based active material used as the negative electrode active material may be artificial graphite or natural graphite, and refers to a material processed into a spherical or dotted shape to facilitate storage and release of lithium ions.
- the plate-shaped conductive material used as the negative electrode conductive material is a material having a plane or plate shape, and may be expressed as plate-shaped graphite. That is, as a material included to maintain a conductive path in the negative active material layer, it means a material used to secure a conductive path in a planar shape inside the negative active material layer, rather than playing a role in storing and releasing lithium.
- plate-like graphite is used as a conductive material means that it is processed into a planar or plate-like shape and used as a material that secures a conductive path rather than a role of storing or releasing lithium.
- the negative active material included together has high capacity characteristics for storing and releasing lithium, and serves to store and release all lithium ions transferred from the positive electrode.
- a carbon-based active material as an active material means that it is processed into a point shape or sphere and used as a material that stores or releases lithium.
- the negative electrode binder is polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinylidenefluoride, polyacrylonitrile, Polymethylmethacrylate, polyvinyl alcohol, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, polyacrylic acid, ethylene -Selected from the group consisting of propylene-diene monomer (EPDM), sulfonated EPDM, styrene butadiene rubber (SBR), fluororubber, polyacrylic acid, and materials in which hydrogen is substituted with Li, Na or Ca, etc. It may include at least one that is, and may also include various copolymers thereof.
- PVDF-co-HFP polyvinylidene fluoride-hexafluoropropylene copolymer
- the negative electrode binder serves to hold the active material and the conductive material in order to prevent distortion and structural deformation of the negative electrode structure in volume expansion and relaxation of the silicon-based active material.
- All of the binders can be applied, specifically, a water-based binder can be used, and more specifically, a PAM-based binder can be used.
- the negative electrode binder may include 30 parts by weight or less, preferably 25 parts by weight or less, more preferably 20 parts by weight or less, and 5 parts by weight or more based on 100 parts by weight of the negative electrode composition. , 10 parts by weight or more.
- a water-based binder is applied in the above weight part to use a point-type conductive material having a low functional group content. It has a characteristic that the bonding strength is excellent.
- a negative electrode composition in which a hydroxyl group (-OH) on the surface of the silicon-based active material and a carboxyl functional group of the negative electrode pre-dispersion liquid form a hydrogen bond with each other.
- the cathode pre-dispersion liquid according to the present application is used as a material capable of strengthening the bond between carbon nanotubes and silicon-based active materials while serving as a dispersant, and the dispersibility of carbon nanotubes using the dispersant according to the present application and has a feature capable of maintaining the conductive path of the conductive material.
- a pre-dispersion material by mixing carbon nanotubes and a dispersant containing a carboxyl group as a functional group; including a dispersion medium in the linear dispersion material such that the solid content of the linear dispersion material is 5% or less; dispersing the linear dispersion material containing the dispersion medium; mixing a binder with water to form a mixture, and first mixing by adding the pre-dispersion material to the mixture; and adding a silicon-based active material to the mixed mixture and performing second mixing. and 40 parts by weight or more and 80 parts by weight or less of the dispersant.
- the method for preparing the negative electrode composition includes a negative electrode active material; cathode conductive material; and forming a negative electrode slurry by including a solvent for forming the slurry in the negative electrode composition including the negative electrode binder. Specifically, mixing a binder with water to form a mixture, and first mixing by adding the pre-dispersion material to the mixture; and a second mixing step by adding a silicon-based active material to the mixed mixture to form a negative electrode slurry.
- the solids content of the negative electrode slurry may be 10% to 40%, and the negative electrode slurry may be coated on a negative electrode current collector to form a negative electrode.
- the negative electrode composition may further include a conductive material, and specifically, a point-shaped conductive material in the first mixing (mixing) step; And planar conductive material; provides a method for producing a negative electrode composition that further comprises at least one selected from the group consisting of.
- each composition and content are the same as described above.
- the first mixing and the second mixing step is mixing at 2,000 rpm to 3,000 rpm for 10 minutes to 60 minutes.
- the step of dispersing the line dispersion material provides a method for preparing a negative electrode composition in which the dispersion is performed using a dispersion device capable of dispersing at high stress, high pressure, or high speed.
- the step of dispersing the pre-dispersion material may include, in detail, dispersing the pre-dispersion material including carbon nanotubes and a dispersing agent containing a carboxyl group in water using an ultrasonicator. there is.
- the negative current collector layer In one embodiment of the present application, the negative current collector layer; and a negative electrode active material layer including the negative electrode composition according to the present application formed on one side or both sides of the negative electrode current collector layer.
- FIG. 1 is a diagram showing a laminated structure of a negative electrode for a lithium secondary battery according to an exemplary embodiment of the present application. Specifically, the negative electrode 100 for a lithium secondary battery including the negative electrode active material layer 20 on one surface of the negative electrode current collector layer 10 can be confirmed, and FIG. 1 shows that the negative electrode active material layer is formed on one surface, but the negative electrode collector It can be included on both sides of the entire layer.
- the negative current collector layer generally has a thickness of 1 ⁇ m to 100 ⁇ m.
- Such an anode current collector layer is not particularly limited as long as it does not cause chemical change in the battery and has high conductivity.
- a surface treated with carbon, nickel, titanium, silver, or the like, an aluminum-cadmium alloy, or the like may be used.
- fine irregularities may be formed on the surface to enhance the bonding strength of the negative active material, and may be used in various forms such as films, sheets, foils, nets, porous materials, foams, and nonwoven fabrics.
- the negative electrode current collector layer has a thickness of 1 ⁇ m or more and 100 ⁇ m or less, and the negative electrode active material layer has a thickness of 20 ⁇ m or more and 500 ⁇ m or less.
- the thickness may be variously modified depending on the type and purpose of the negative electrode used, but is not limited thereto.
- FIG. 2 is a diagram showing a laminated structure of a lithium secondary battery according to an exemplary embodiment of the present application.
- the negative electrode 100 for a lithium secondary battery including the negative electrode active material layer 20 on one surface of the negative electrode current collector layer 10 can be confirmed, and the positive electrode active material layer 40 on one surface of the positive electrode current collector layer 50
- the positive electrode 200 for a lithium secondary battery including a and the negative electrode 100 for a lithium secondary battery and the positive electrode 200 for a lithium secondary battery are formed in a laminated structure with a separator 30 interposed therebetween.
- a secondary battery may include the anode for a lithium secondary battery described above.
- the secondary battery may include a negative electrode, a positive electrode, a separator interposed between the positive electrode and the negative electrode, and an electrolyte, and the negative electrode is the same as the negative electrode described above. Since the cathode has been described above, a detailed description thereof will be omitted.
- the positive electrode may include a positive electrode current collector and a positive electrode active material layer formed on the positive electrode current collector and including the positive electrode active material.
- the positive electrode current collector is not particularly limited as long as it has conductivity without causing chemical change in the battery.
- stainless steel, aluminum, nickel, titanium, fired carbon, or carbon on the surface of aluminum or stainless steel. , those surface-treated with nickel, titanium, silver, etc. may be used.
- the cathode current collector may have a thickness of typically 3 to 500 ⁇ m, and adhesion of the cathode active material may be increased by forming fine irregularities on the surface of the current collector.
- it may be used in various forms such as films, sheets, foils, nets, porous materials, foams, and non-woven fabrics.
- the cathode active material may be a commonly used cathode active material.
- the cathode active material may include layered compounds such as lithium cobalt oxide (LiCoO 2 ) and lithium nickel oxide (LiNiO 2 ), or compounds substituted with one or more transition metals; lithium iron oxides such as LiFe 3 O 4 ; lithium manganese oxides such as Li 1+c1 Mn 2-c1 O 4 (0 ⁇ c1 ⁇ 0.33), LiMnO 3 , LiMn 2 O 3 , LiMnO 2 ; lithium copper oxide (Li 2 CuO 2 ); vanadium oxides such as LiV 3 O 8 , V 2 O 5 , Cu 2 V 2 O 7 ; Represented by the formula LiNi 1-c2 M c2 O 2 (where M is at least one selected from the group consisting of Co, Mn, Al, Cu, Fe, Mg, B, and Ga, and satisfies 0.01 ⁇ c2 ⁇ 0.6) Ni site-type lithium nickel oxide; Formula Li
- the positive electrode active material includes a lithium composite transition metal compound including nickel (Ni), cobalt (Co), and manganese (Mn), and the lithium composite transition metal compound is a single particle or a secondary particle.
- the average particle diameter (D50) of the single particles may be 1 ⁇ m or more.
- the average particle diameter (D50) of the single particles is 1 ⁇ m or more and 12 ⁇ m or less, 1 ⁇ m or more and 8 ⁇ m or less, 1 ⁇ m or more and 6 ⁇ m or less, 1 ⁇ m or more and 12 ⁇ m or less, 1 ⁇ m or more and 8 ⁇ m or less, or 1 ⁇ m. It may be more than 6 ⁇ m or less.
- the particle strength may be excellent.
- the single particle may have a particle strength of 100 to 300 MPa when rolling with a force of 650 kgf/cm 2 . Accordingly, even if the single particle is rolled with a strong force of 650 kgf/cm 2 , the phenomenon of increasing fine particles in the electrode due to particle breakage is alleviated, thereby improving the lifespan characteristics of the battery.
- the single particle may be prepared by mixing and calcining a transition metal precursor and a lithium source material.
- the secondary particles may be prepared in a different way from the single particles, and their composition may be the same as or different from that of the single particles.
- the method of forming the single particles is not particularly limited, but generally can be formed by underfiring by raising the firing temperature, using additives such as grain growth promoters that help underfiring, or by changing the starting material. can be manufactured
- the firing is performed at a temperature capable of forming single particles.
- firing should be performed at a temperature higher than that of the secondary particles, for example, if the composition of the precursor is the same, firing should be performed at a temperature about 30° C. to 100° C. higher than that of the secondary particles.
- the firing temperature for forming the single particle may vary depending on the metal composition in the precursor. For example, a high-Ni NCM-based lithium composite transition metal oxide having a nickel (Ni) content of 80 mol% or more is used. In the case of forming single particles, the firing temperature may be about 700°C to 1000°C, preferably about 800°C to 950°C.
- a cathode active material including single particles having excellent electrochemical properties may be prepared. If the firing temperature is less than 790 ° C, a cathode active material containing a lithium complex transition metal compound in the form of secondary particles can be prepared, and if it exceeds 950 ° C, excessive firing occurs and the layered crystal structure is not properly formed, resulting in electrochemical characteristics may deteriorate.
- the single particle is a term used to distinguish from conventional secondary particles formed by aggregation of tens to hundreds of primary particles, and includes a single particle composed of one primary particle and 30 or less primary particles. It is a concept that includes pseudo-single-particle forms that are aggregates.
- the single particle may be in the form of a single particle composed of one primary particle or a quasi-single particle, which is an aggregate of 30 or less primary particles, and the secondary particle may be in the form of an aggregate of hundreds of primary particles. .
- the lithium composite transition metal compound which is the cathode active material, further includes secondary particles, and the average particle diameter (D50) of the single particles is smaller than the average particle diameter (D50) of the secondary particles.
- the single particle may be in the form of a single particle composed of one primary particle or a quasi-single particle, which is an aggregate of 30 or less primary particles, and the secondary particle may be in the form of an aggregate of hundreds of primary particles.
- the above-described lithium composite transition metal compound may further include secondary particles.
- a secondary particle means a form formed by aggregation of primary particles, and can be distinguished from the concept of a single particle including one primary particle, one single particle, or a quasi-single particle form, which is an aggregate of 30 or less primary particles. .
- the secondary particle may have a particle diameter (D50) of 1 ⁇ m to 20 ⁇ m, 2 ⁇ m to 17 ⁇ m, and preferably 3 ⁇ m to 15 ⁇ m.
- the specific surface area (BET) of the secondary particles may be 0.05 m 2 /g to 10 m 2 /g, preferably 0.1 m 2 /g to 1 m 2 /g, and more preferably 0.3 m 2 /g to 0.8 m 2 /g.
- the secondary particles are aggregates of primary particles, and the average particle diameter (D50) of the primary particles is 0.5 ⁇ m to 3 ⁇ m.
- the secondary particles may be in the form of an aggregate of hundreds of primary particles, and the average particle diameter (D50) of the primary particles may be 0.6 ⁇ m to 2.8 ⁇ m, 0.8 ⁇ m to 2.5 ⁇ m, or 0.8 ⁇ m to 1.5 ⁇ m. .
- the average particle diameter (D50) of the primary particles satisfies the above range, a single-particle cathode active material having excellent electrochemical properties may be formed. If the average particle diameter (D50) of the primary particles is too small, the number of agglomerations of the primary particles forming lithium nickel-based oxide particles increases, reducing the effect of suppressing particle breakage during rolling, and the average particle diameter (D50) of the primary particles is too small. If it is large, the lithium diffusion path inside the primary particle becomes long, and resistance may increase and output characteristics may deteriorate.
- the average particle diameter (D50) of the single particles is smaller than the average particle diameter (D50) of the secondary particles.
- the average particle diameter (D50) of the single particles is smaller than the average particle diameter (D50) of the secondary particles by 1 ⁇ m to 18 ⁇ m.
- the average particle diameter (D50) of the single particles may be 1 ⁇ m to 16 ⁇ m smaller, 1.5 ⁇ m to 15 ⁇ m smaller, or 2 ⁇ m to 14 ⁇ m smaller than the average particle diameter (D50) of the secondary particles.
- the single particles When the average particle diameter (D50) of the single particles is smaller than the average particle diameter (D50) of the secondary particles, for example, when the above range is satisfied, the single particles may have excellent particle strength even if they are formed with a small particle diameter, and thereby The phenomenon of increasing fine particles in the electrode due to cracking is alleviated, and there is an effect of improving the lifespan characteristics and energy density of the battery.
- the single particle is included in 15 parts by weight to 100 parts by weight based on 100 parts by weight of the positive electrode active material.
- the single particle may be included in an amount of 20 parts by weight to 100 parts by weight, or 30 parts by weight to 100 parts by weight based on 100 parts by weight of the cathode active material.
- the single particle may be included in an amount of 15 parts by weight or more, 20 parts by weight or more, 25 parts by weight or more, 30 parts by weight or more, 35 parts by weight or more, 40 parts by weight or more, or 45 parts by weight or more based on 100 parts by weight of the positive electrode active material.
- the single particle may be included in an amount of 100 parts by weight or less based on 100 parts by weight of the positive electrode active material.
- the single particle within the above range When the single particle within the above range is included, excellent battery characteristics may be exhibited in combination with the anode material described above.
- the single particle when the single particle is 15 parts by weight or more, the increase in fine particles in the electrode due to particle breakage during the rolling process after fabrication of the electrode can be alleviated, and thus the lifespan characteristics of the battery can be improved.
- the lithium composite transition metal compound may further include secondary particles, and the secondary particles may be 85 parts by weight or less based on 100 parts by weight of the positive electrode active material.
- the amount of the secondary particles may be 80 parts by weight or less, 75 parts by weight or less, or 70 parts by weight or less based on 100 parts by weight of the cathode active material.
- the secondary particles may be 0 parts by weight or more based on 100 parts by weight of the positive electrode active material.
- the component may be the same as those exemplified in the single-particle cathode active material described above, or may be other components, and may mean a form in which a single particle form is aggregated.
- the positive electrode active material in 100 parts by weight of the positive electrode active material layer is 80 parts by weight or more and 99.9 parts by weight or less, preferably 90 parts by weight or more and 99.9 parts by weight or less, more preferably 95 parts by weight or more and 99.9 parts by weight or less. parts or less, more preferably 98 parts by weight or more and 99.9 parts by weight or less.
- the positive electrode active material layer may include a positive electrode conductive material and a positive electrode binder together with the positive electrode active material described above.
- the positive electrode conductive material is used to impart conductivity to the electrode, and in the configured battery, any material that does not cause chemical change and has electronic conductivity can be used without particular limitation.
- any material that does not cause chemical change and has electronic conductivity can be used without particular limitation.
- Specific examples include graphite such as natural graphite or artificial graphite; carbon-based materials such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, summer black, and carbon fiber; metal powders or metal fibers such as copper, nickel, aluminum, and silver; conductive whiskeys such as zinc oxide and potassium titanate; conductive metal oxides such as titanium oxide; or conductive polymers such as polyphenylene derivatives, and the like, and one of them alone or a mixture of two or more may be used.
- the positive electrode binder serves to improve adhesion between particles of the positive electrode active material and adhesion between the positive electrode active material and the positive electrode current collector.
- specific examples include polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinyl alcohol, polyacrylonitrile, carboxymethylcellulose (CMC) ), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene polymer (EPDM), sulfonated-EPDM, styrene butadiene rubber (SBR), fluororubber, or various copolymers thereof, and the like may be used alone or in a mixture of two or more of them.
- PVDF polyvinylidene fluoride
- PVDF-co-HFP vinylidene fluoride-
- the separator separates the negative electrode and the positive electrode and provides a passage for lithium ion movement. If it is normally used as a separator in a secondary battery, it can be used without particular limitation. It is desirable Specifically, a porous polymer film, for example, a porous polymer film made of polyolefin-based polymers such as ethylene homopolymer, propylene homopolymer, ethylene/butene copolymer, ethylene/hexene copolymer, and ethylene/methacrylate copolymer, or these A laminated structure of two or more layers of may be used.
- a porous polymer film for example, a porous polymer film made of polyolefin-based polymers such as ethylene homopolymer, propylene homopolymer, ethylene/butene copolymer, ethylene/hexene copolymer, and ethylene/methacrylate copolymer, or these A laminated structure of two or more layers of may be used.
- porous non-woven fabrics for example, non-woven fabrics made of high-melting glass fibers, polyethylene terephthalate fibers, and the like may be used.
- a coated separator containing a ceramic component or a polymer material may be used to secure heat resistance or mechanical strength, and may be selectively used in a single-layer or multi-layer structure.
- electrolyte examples include, but are not limited to, organic liquid electrolytes, inorganic liquid electrolytes, solid polymer electrolytes, gel polymer electrolytes, solid inorganic electrolytes, and molten inorganic electrolytes that can be used in manufacturing a lithium secondary battery.
- the electrolyte may include a non-aqueous organic solvent and a metal salt.
- non-aqueous organic solvent for example, N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, gamma-butyllolactone, 1,2-dimethine Toxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethylsulfoxide, 1,3-dioxorane, formamide, dimethylformamide, dioxorane, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphoric acid Triester, trimethoxy methane, dioxolane derivative, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, propylene carbonate derivative, tetrahydrofuran derivative, ether, methyl propionate, propionic acid
- An aprotic organic solvent such as ethyl may be used.
- ethylene carbonate and propylene carbonate which are cyclic carbonates
- an electrolyte having high electrical conductivity can be made and can be used more preferably.
- the metal salt may be a lithium salt, and the lithium salt is a material that is easily soluble in the non-aqueous electrolyte.
- the anion of the lithium salt is F - , Cl - , I - , NO 3 - , N (CN ) 2 - , BF 4 - , ClO 4 - , PF 6 -, (CF 3 ) 2 PF 4 - , (CF 3 ) 3 PF 3 - , (CF 3 ) 4 PF 2 - , (CF 3 ) 5 PF - , (CF 3 ) 6 P - , CF 3 SO 3 - , CF 3 CF 2 SO 3 - , (CF 3 SO 2 ) 2 N - , (FSO 2 ) 2 N - , CF 3 CF 2 (CF 3 ) 2 CO - , (CF 3 SO 2 ) 2 CH - , (SF 5 ) 3 C - , (CF 3 SO 2 ) 3 C
- the electrolyte may include, for example, haloalkylene carbonate-based compounds such as difluoroethylene carbonate, pyridine, and triglycerides for the purpose of improving battery life characteristics, suppressing battery capacity decrease, and improving battery discharge capacity.
- haloalkylene carbonate-based compounds such as difluoroethylene carbonate, pyridine, and triglycerides
- Ethyl phosphite triethanolamine, cyclic ether, ethylene diamine, n-glyme, hexaphosphoric acid triamide, nitrobenzene derivative, sulfur, quinone imine dye, N-substituted oxazolidinone, N,N-substituted imida
- One or more additives such as zolidine, ethylene glycol dialkyl ether, ammonium salt, pyrrole, 2-methoxy ethanol or aluminum trichloride may be further included.
- One embodiment of the present invention provides a battery module including the secondary battery as a unit cell and a battery pack including the same. Since the battery module and the battery pack include the secondary battery having high capacity, high rate and cycle characteristics, a medium or large-sized device selected from the group consisting of an electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, and a power storage system can be used as a power source for
- binder A weight average molecular weight 650,000 to 700,000 g/mol
- silicon-based active material Si, D50: 3 ⁇ m ⁇ 8 ⁇ m
- both sides of a copper current collector were coated with the negative electrode slurry at a loading amount of 85 mg/25 cm 2 , rolled, and dried in a vacuum oven at 130° C. for 10 hours to obtain a negative electrode
- An active material layer (thickness: 33 ⁇ m) was formed and used as a negative electrode (thickness of negative electrode: 41 ⁇ m, porosity of negative electrode 40.0%).
- both sides of a copper current collector were coated with the negative electrode slurry at a loading amount of 85 mg/25 cm 2 , rolled, and dried in a vacuum oven at 130° C. for 10 hours to obtain a negative electrode
- An active material layer (thickness: 33 ⁇ m) was formed and used as a negative electrode (thickness of negative electrode: 41 ⁇ m, porosity of negative electrode 40.0%).
- the preparation of the SWCNT pre-dispersion used for the cathode was prepared by adding 0.4wt% of SWCNT and 0.6wt% of a dispersant (tannic acid/PVP) to solvent water (H 2 O), and then dispersing using an ultrasonicator (Ultrasonicator) to pre-disperse ( 1% solid content) was produced. (amplitude 40%, 10min)
- both sides of a copper current collector were coated with the negative electrode slurry at a loading amount of 85 mg/25 cm 2 , rolled, and dried in a vacuum oven at 130° C. for 10 hours to obtain a negative electrode
- An active material layer (thickness: 33 ⁇ m) was formed and used as a negative electrode (thickness of negative electrode: 41 ⁇ m, porosity of negative electrode 40.0%).
- Example 1 the preparation of the SWCNT pre-dispersion used for the negative electrode was prepared by adding 0.7 wt% of SWCNT and 0.3 wt% of a dispersant (PPBT) to solvent water (H 2 O), and then using an ultrasonicator (Ultrasonicator).
- An anode was prepared in the same manner as in Example 1, except that a pre-dispersion solution (solid content: 1%) was prepared by dispersing. (amplitude 40%, 10min)
- Example 1 the preparation of the SWCNT pre-dispersion used for the negative electrode was prepared by adding 0.1 wt% of SWCNT and 0.9 wt% of a dispersant (PPBT) to solvent water (H 2 O), and then using an ultrasonicator (Ultrasonicator).
- An anode was prepared in the same manner as in Example 1, except that a pre-dispersion solution (solid content: 1%) was prepared by dispersing. (amplitude 40%, 10min)
- Example 1 the solid content of the cathode pre-dispersion was prepared to be 7%. However, in the case of Comparative Example 4, the solid content exceeded 5%, and the content of SWCNT was too high, so the dispersion was not properly performed and the viscosity was very high, so the pre-dispersion itself was not prepared. Accordingly, the evaluation could not proceed because the negative electrode slurry for forming the negative electrode active material layer was not prepared.
- Example 1 (Average) 3831.25 3400.36 88.76 1-#1 3787.74 3412.59 90.10 1-#2 3838.08 3373.94 87.91 1-#3 3867.92 3414.56 88.28
- Example 2 (Average) 3821.16 3397.55 88.91 2-#1 3823.03 3420.80 89.48 2-#2 3819.29 3374.30 88.35 Comparative Example 1 3816.11 3326.4 87.17 Comparative Example 2 3811.64 3385.7 88.63 Comparative Example 3 3775.2 3023.3 80.08 Comparative Example 4 Pre-dispersion cannot be manufactured
- FIG. 3 is a diagram showing the results of half-cell initial capacity evaluation of negative electrodes of Examples 1 and 2 according to the present application.
- Table 2 shows the results of half-cell evaluation (0.005V-1.0V, 0.1C, 50cycle) of the anodes prepared in the above Examples and Comparative Examples.
- the electrode performance of Examples 1 and 2 is improved.
- PPBT is used as a dispersant to wrap the SWCNT well by ⁇ - ⁇ interaction between the ⁇ electrons present in the main chain and the surface where the ⁇ electrons of the SWCNT exist.
- the effect of the carboxy group present in the PPBT side chain effectively debundles the SWCNTs present in a bundle form, thereby improving the dispersibility in particular, confirming that the electrode performance is further improved. .
- FIG. 4 is a diagram showing the results of half-cell evaluation of negative electrodes of Examples 1 and 2 according to the present application.
- the cathode pre-dispersion solution according to the present application satisfies a certain range in the solid content of the pre-dispersion material, the content of carbon nanotubes, and the content of the dispersant in the pre-dispersion solution, so that the content of the carbon nanotubes It was confirmed that the acidity had excellent characteristics. Accordingly, if the binding force between the carbon nanotubes and silicon is strengthened, the path between the conductive materials is maintained even during repeated charging and discharging, and the use of silicon active materials can be uniformed. It was confirmed that swelling also has a feature that can be minimized by using the negative electrode composition according to the present invention.
- Example 1 unlike other dispersants, it has a carboxyl group as a functional group and at the same time has an intramolecular conjugation structure, contributing to the improvement of electrode life performance, and it was confirmed that the performance was particularly excellent.
- the pre-dispersion liquid had a feature capable of strengthening the binding force between the carbon nanotubes and silicon by including a carboxyl group as a functional group of the dispersant and forming a hydrogen bond with the -OH group on the surface of the silicon-based active material.
- the binding force between carbon nanotubes and silicon is strengthened, the path between the conductive materials is maintained even during repeated charging and discharging, and the use of silicon active materials can be uniformed.
- volume expansion during charging and discharging is maintained.
- the negative electrode composition according to the present invention has characteristics that can be minimized.
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Abstract
Description
1st lithiation | 1st delithiation | Efficiency(%) | |
실시예 1 (Average) | 3831.25 | 3400.36 | 88.76 |
1-#1 | 3787.74 | 3412.59 | 90.10 |
1-#2 | 3838.08 | 3373.94 | 87.91 |
1-#3 | 3867.92 | 3414.56 | 88.28 |
실시예 2(Average) | 3821.16 | 3397.55 | 88.91 |
2-#1 | 3823.03 | 3420.80 | 89.48 |
2-#2 | 3819.29 | 3374.30 | 88.35 |
비교예 1 | 3816.11 | 3326.4 | 87.17 |
비교예 2 | 3811.64 | 3385.7 | 88.63 |
비교예 3 | 3775.2 | 3023.3 | 80.08 |
비교예 4 | 선분산액 제조 불가 |
Cycle retention(%) | |
실시예 1 (Average) | 45.3 |
1-#1 | 46.9 |
1-#2 | 43.7 |
실시예 2(Average) | 32.2 |
2-#1 | 32.5 |
2-#2 | 31.9 |
비교예 1 | 28.9 |
비교예 2 | 13.6 |
비교예 3 | 2.37 |
비교예 4 | 선분산액 제조 불가 |
Claims (17)
- 탄소 나노 튜브 및 분산제를 포함하는 선분산재; 및분산매;를 포함하는 음극 선분산액으로,상기 분산제는 작용기로 카복시기(Carboxyl group)를 포함하며,상기 음극 선분산액 기준 상기 선분산재의 고형분 함량이 5% 이하이고,상기 선분산재 100 중량부 기준 상기 탄소 나노 튜브 20 중량부 이상 60 중량부 이하; 및 상기 분산제 40 중량부 이상 80 중량부 이하;를 포함하는 것인 음극 선분산액.
- 청구항 1에 있어서, 상기 분산제의 중량 평균 분자량이 10,000g/mol 이상 100,000g/mol 이하인 것인 음극 선분산액.
- 청구항 1에 있어서, 상기 음극 선분산액의 점도가 100cP 이상 10,000cP이하인 것인 음극 선분산액.
- 실리콘계 활물질; 청구항 1 내지 4 중 어느 한 항에 따른 음극 선분산액; 및 음극 바인더;를 포함하는 음극 조성물로,상기 실리콘계 활물질은 상기 음극 조성물 100 중량부 기준 60 중량부 이상인 것인 음극 조성물.
- 청구항 5에 있어서,상기 음극 조성물은 음극 도전재를 더 포함하며,상기 음극 도전재는 점형 도전재; 및 면형 도전재;로 이루어진 군에서 선택되는 1 이상을 포함하는 것인 음극 조성물.
- 청구항 6에 있어서,상기 음극 도전재는 상기 음극 조성물 100 중량부 기준 5 중량부 이상 40 중량부 이하인 것인 음극 조성물.
- 청구항 5에 있어서,상기 음극 선분산액은 상기 음극 조성물 100 중량부 기준 0.01 중량부 이상 20 중량부 이하로 포함하는 것인 음극 조성물.
- 청구항 5에 있어서,상기 실리콘계 활물질은 SiOx (x=0), SiOx (0<x<2), SiC, 및 Si 합금으로 이루어진 군에서 선택되는 1 이상을 포함하는 것인 음극 조성물.
- 청구항 5에 있어서, 상기 실리콘계 활물질은 SiOx (x=0), SiOx (0<x<2) 및 금속 불순물로 이루어진 군에서 선택되는 1 이상을 포함하며, 상기 실리콘계 활물질 100 중량부 기준 상기 SiOx (x=0)를 70 중량부 이상 포함하는 것인 음극 조성물.
- 청구항 5에 있어서, 상기 실리콘계 활물질 표면의 히드록시기(-OH)와 상기 음극 선분산액의 카르복시기 작용기가 서로 수소 결합을 형성하는 것인 음극 조성물.
- 탄소 나노 튜브 및 작용기로 카복시기(Carboxyl group)를 포함하는 분산제를 혼합하여 선분산재를 형성하는 단계;상기 선분산재의 고형분 함량이 5% 이하가 되도록 분산매를 상기 선분산재에 포함시키는 단계;상기 분산매가 포함된 선분산재를 분산하는 단계;물에 음극 바인더를 혼합하여 혼합물을 형성하고, 상기 혼합물에 상기 선분산재를 추가하여 제1 믹싱(mixing)하는 단계; 및상기 믹싱된 혼합물에 실리콘계 활물질을 첨가하여 제2 믹싱(mixing)하는 단계;를 포함하는 음극 조성물의 제조 방법으로,상기 선분산재 100 중량부 기준 상기 탄소 나노 튜브 20 중량부 이상 60 중량부 이하; 및 상기 분산제 40 중량부 이상 80 중량부 이하;를 포함하는 것인 음극 조성물의 제조 방법.
- 청구항 12에 있어서,상기 제1 믹싱(mixing)하는 단계에서 점형 도전재; 및 면형 도전재;로 이루어진 군에서 선택되는 1 이상을 더 포함하는 것인 음극 조성물의 제조 방법.
- 청구항 12에 있어서, 상기 제1 믹싱 및 제2 믹싱하는 단계는 2,000rpm 내지 3,000rpm으로 10분 내지 60 분간 믹싱하는 단계인 것인 음극 조성물의 제조 방법.
- 청구항 12에 있어서, 상기 선분산재를 분산하는 단계는 고응력, 고압력 또는 고속도로 분산할 수 있는 분산 장치를 이용하여 분산하는 것인 음극 조성물의 제조 방법.
- 음극 집전체층; 및상기 음극 집전체층의 일면 또는 양면에 형성된 청구항 5에 따른 음극 조성물을 포함하는 음극 활물질층;을 포함하는 리튬 이차 전지용 음극.
- 양극;청구항 16에 따른 리튬 이차 전지용 음극;상기 양극과 상기 음극 사이에 구비된 분리막; 및전해질;을 포함하는 리튬 이차 전지.
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US18/563,561 US20240266544A1 (en) | 2021-10-22 | 2022-10-21 | Anode pre-dispersion solution, anode composition comprising same, anode for lithium secondary battery comprising anode composition, lithium secondary battery comprising anode, and method for preparing anode composition |
EP22884102.9A EP4336598A1 (en) | 2021-10-22 | 2022-10-21 | Anode pre-dispersion solution, anode composition comprising same, anode for lithium secondary battery comprising anode composition, lithium secondary battery comprising anode, and method for preparing anode composition |
CN202280038070.9A CN117397068A (zh) | 2021-10-22 | 2022-10-21 | 负极预分散液、包含负极预分散液的负极组合物、包含负极组合物的锂二次电池用负极、包含负极的锂二次电池及负极组合物的制备方法 |
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- 2022-10-21 JP JP2023572201A patent/JP2024521139A/ja active Pending
- 2022-10-21 WO PCT/KR2022/016187 patent/WO2023068880A1/ko active Application Filing
- 2022-10-21 US US18/563,561 patent/US20240266544A1/en active Pending
- 2022-10-21 KR KR1020220136761A patent/KR20230057988A/ko unknown
- 2022-10-21 CN CN202280038070.9A patent/CN117397068A/zh active Pending
- 2022-10-21 EP EP22884102.9A patent/EP4336598A1/en active Pending
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KR20230057988A (ko) | 2023-05-02 |
US20240266544A1 (en) | 2024-08-08 |
JP2024521139A (ja) | 2024-05-28 |
CN117397068A (zh) | 2024-01-12 |
EP4336598A1 (en) | 2024-03-13 |
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