JP5761725B2 - Electrode active material with improved safety, electrochemical device using the same, electrode and method for producing electrode active material - Google Patents

Description

  The present invention relates to an electrode active material whose safety is improved by adjusting the acid point strength of the surface of the electrode active material, the electrode active material, a compound having an acid point being coated on the electrode surface or mixed with the electrode material. The present invention relates to an electrode, and an electrochemical device, preferably a lithium secondary battery, which is provided with the electrode to improve performance.

  Since the commercialization of lithium secondary batteries, the primary goal in battery development is the development of positive electrode active materials with high dose and long life and excellent electrochemical properties. In addition to electrochemical characteristics, we are eager to develop positive active cathode materials with excellent safety that can ensure the safety and reliability of battery systems even under abnormal conditions such as heat exposure, combustion or overcharge. It is requested.

LiMO ₂ (transition metals such as M = Ni, Mn, Co, etc.) widely used as the positive electrode active material of lithium secondary batteries reacts with the electrolyte in the charged state or overcharged state to generate by-products. In addition, the battery performance is reduced due to the structural collapse of the electrode active material. Therefore, most researchers have been working to improve the performance of the active material by surface treatment with a stable oxide, but it is difficult to improve the safety and performance of the desired electrode active material at the same time. There is.

  On the other hand, when using the conventional surface modification method in which the surface of the electrode active material particles is coated with a compound having low reactivity, the safety of the electrode active material is ensured, but the performance of the battery is always ensured. Recognized that the decline. Therefore, instead of the conventional surface modification method described above, the surface of the electrode active material is coated with a compound with adjusted acid point strength, thereby improving the structural safety of the electrode active material and preventing material changes. Therefore, it is intended to adopt and use a novel surface modification method that can significantly reduce the reactivity with the electrolyte and improve various performances of the battery.

  An object of the present invention is to provide an electrode active material containing acid sites on part or all of the surface, an electrode including the electrode active material, and an electrochemical device including the electrode, preferably a lithium secondary battery. It is to provide.

  Another object of the present invention is to provide an electrode characterized in that a compound having an acid site is coated on the surface of an already produced electrode or mixed with an electrode material, and an electrochemical device comprising the electrode, preferably lithium. It is to provide a secondary battery.

Furthermore, the object of the present invention is to react (i) (a) a compound that provides a proton (or electron pair) or accepts a proton (or electron pair) and (b) a compound having an acid point; And (ii) coating the surface of the electrode active material with the resultant product of step (i) and drying the coating layer, and an electrode having a coating layer with adjusted acid point strength The object is to provide a method for producing an active material.
[Aspect of the Invention]
[1] An electrode active material characterized in that part or all of the surface contains acid sites.
[2] The electrode active material according to [1], wherein the acid point is a Bronsted acid point or a Lewis acid point.
[3] The electrode active material according to [1], wherein the acid point intensity is such that H ₀ (Hammett indicator) is in the range of −10 to 10.
[4] The electrode active material according to [1], wherein the acid point is formed by a composite of an inorganic material or an organic (semi) metal compound and an inorganic material surface-treated on the electrode active material. .
[5] The inorganic substance is characterized in that an acid point is formed by a proton donor functional group present on a part or all of the surface, a difference in electronegativity of different metal atoms, or all of them. 4].
[6] The electrode active material according to [4], wherein the electrode active material surface-treated with the inorganic material is heat-treated at a temperature of 400 ° C. or higher after the surface treatment with the inorganic material.
[7] The inorganic substance is
(a) a group 13 element-containing compound, or
(b) one or more elements selected from the group consisting of (i) group 13 elements and (ii) alkaline earth metals, alkali metals, group 14 elements, group 15 elements, transition metals, lanthanoid metals and actinide metals The electrode active material according to [4], which is a compound to be contained.
[8] A composite of the organic (semi) metal compound and the inorganic material is a difference in electronegativity between the organic (semi) metal compound and the inorganic material bonded to each other, an organic material bonded to the organic (semi) metal compound The electrode active material according to [4], wherein an acid point is formed by all of these.
[9] The organic (semi) metal compound is
(a) a group 14 element-containing compound, or
(b) A compound containing a group 14 element and one or more elements selected from the group consisting of alkaline earth metals, alkali metals, group 13 elements, group 15 elements, transition metals, lanthanoid metals, and actinide metals. The electrode active material according to [4], wherein
[10] The electrode active material according to [4], wherein the organic (semi) metal compound contains one or more electron donating groups.
[11] The electrode active material according to [4], wherein the organic (semi) metal compound is a silicon (Si) -containing compound.
[12] The silicon-containing organic (semi) metal compound is at least one selected from the group consisting of silane, silylating agent, silane coupling agent, silicon hydride, monosilane, and silane polymer, [11] The electrode active material according to [11].
[13] The electrode active material according to [4], wherein the organic (semi) metal compound is represented by any one of the following chemical formulas 1 to 7.
[Chemical 1]
SiH ₄
[Chemical 2]
Si (OR) _4-x R _x (0.1 ≦ x ≦ 3)
[Chemical formula 3]
Si (OR) _{4-(x + y)} R _x Z _y (0.1 ≦ x + y ≦ 3.9) [Chemical Formula 4]
Si (OR) _4-x R _x Si (0.1 ≦ x ≦ 3)
[Chemical formula 5]
Si (OR) _{4− (x + y)} R _x Z _y Si (0.1 ≦ x + y ≦ 3.9) [Chemical formula 6]
R _x M (OR) _4-x (1 ≦ x ≦ 3)
[Chemical 7]
R _x MZ _y (OR) _{4- (x + y)} (0.1 ≦ x + y ≦ 3.9)
[In the above formula,
Z is a halogen element,
M is one or more elements selected from the group consisting of alkaline earth metals, alkali metals, transition metals, lanthanoid metals and actinide metals,
R is a substituent selected from the group consisting of a C1-C20 alkyl group, an alkenyl group, an alkynyl group, a vinyl group, an amino group, and a mercapto group, which is substituted or unsubstituted with a halogen element. ]
[14] The electrode active material according to [4], wherein the component ratio of the organic (semi) metal compound to the inorganic material is in the range of 0 wt% to 95 wt%: 5 wt% to 100 wt%.
[15] The content of the composite of the inorganic material or the organic (semi) metal compound and the inorganic material is 0.05 to 20 parts by weight per 100 parts by weight of the electrode active material. Electrode active material.
[16] An electrode comprising the electrode active material according to any one of [1] to [15].
[17] The electrode according to [16], wherein the electrode is a positive electrode.
[18] Reactivity of the electrode active material with HX (X = F, Cl, Br, I) present in the battery due to acid sites formed on part or all of the surface of the electrode active material. The electrode according to [16], characterized in that is reduced.
[19] An electrode characterized in that a compound having an acid point is coated on an electrode surface and mixed with an electrode material.
[20] An electrochemical device comprising a positive electrode, a negative electrode, a separation membrane, and an electrolyte solution, wherein the positive electrode, the negative electrode, or both electrodes are any one of [1] to [15] An electrochemical element comprising an electrode comprising an active material or the electrode according to [19].
[21] The electrochemical device according to [20], wherein the electrochemical device is a lithium secondary battery.
[22] (i) (a) reacting a compound that donates a proton (or electron pair) or accepts a proton (or electron pair) and (b) a compound having an acid point; and
(ii) An electrode active material having a coating layer with adjusted acid point strength, comprising the step of coating the surface of the electrode active material with the resultant product of step (i) and drying the coating layer Manufacturing method.
[23] The production method according to [22], wherein the acid point strength is such that H ₀ is in the range of −10 to 10.

  Hereinafter, the present invention will be described in detail.

  In the present invention, acid sites are formed on a part or all of the surface of the electrode active material particles for intercalation / deintercalation of lithium, or insertion and release, and the surface of the electrode active material is electrically charged. It is characterized by modifying chemical properties.

  In general, an acid site is known as a reaction active site that exists in a solid acidic catalyst such as zeolite and causes a chemical reaction such as a decomposition reaction. On the other hand, in this invention, the active point which shows the specific acid point intensity | strength in the surface modification part formed in a part or all of the surface of an active material with a novel surface modification method is called.

  The acid point intensity is determined by how easily a proton can be donated or how easily an electron pair can be accepted. Therefore, it can be said that such acid point characteristics are generally related to the electronic properties between atoms constituting the surface rather than the surface structure.

  Thus, the electrode active material having acid spots formed on the surface has a positive charge, or acts in a similar manner to a normal acidic substance having a positive charge partially due to a difference in electronegativity. Therefore, the reactivity itself between the acidic substance (Bronsted acid) that donates protons and the electrophilic substance (Lewis acid) that accepts an electron pair existing in the battery is significantly reduced, and various kinds of battery Performance can be improved. This can be estimated as follows.

  1) The surface of the conventional electrode active material is weakly basic due to lithium by-product or hydrophilic surface treatment. Therefore, there was practically no recognition of acid sites.

A battery using such a conventional electrode active material, preferably a positive electrode active material, forms HF, which is a strong acid, by reacting with water and lithium salt (eg, LiPF ₆ ) present in the electrode or the electrolyte solution. The generated HF reacts spontaneously with the electrode active material exhibiting weak basicity to elute the electrode active material component and degenerate. In addition, LiF is formed on the surface of the positive electrode to reduce the battery life by increasing the electrical resistance in the electrode and generating gas. In particular, since the elution rate of the electrode by HF increases at a high temperature, HF has a significant problem in battery cycle life and storage stability at a high temperature.

  On the other hand, the electrode active material of the present invention has an acid point on the surface, and thus acts substantially as an acidic substance. Therefore, since the reactivity with HX (X = halogen element) which is a kind of strong acid is lowered, the above-mentioned problems can be fundamentally solved, the structural safety of the electrode active material is ensured, and the battery performance is improved. Can be achieved.

  2) A carbonate-based nonaqueous solvent is used as a conventional battery electrolyte. Such a carbonate-based electrolyte solvent includes carbon having a relatively positive charge (+) and oxygen having a negative charge (-) on the dipole moment as represented by the following reaction formula 1. To come. At this time, when there is a Lewis base capable of donating an unshared electron pair on the surface of the electrode active material, the Lewis base attacks the positively-charged carbon, and the electrophilic decomposition reaction of the electrolyte is more activated. The

In contrast, the electrode active material of the present invention having an acid point is a Lewis acid that accepts an unshared electron pair rather than donating an unshared electron pair. Thereby, the side reaction with the electrolytic solution described above is significantly reduced, and the deterioration of the battery performance can be minimized.

  The acid point formed on part or all of the surface of the electrode active material according to the present invention means a known ordinary acid point. As an example, it can be a Bronsted acid point that can donate a proton or a Lewis acid point that can accept an unshared electron pair.

The acid point intensity is represented by H ₀ (Hammett indicator) and can be adjusted within a known normal range, for example, −20 to 20. It is preferable that H ₀ is −10 to 10 in order to prevent degeneration of the electrode active material and suppression of side reaction with the electrolytic solution by adjusting the acid point strength.

  The method for forming acid sites on the surface of the electrode active material is not particularly limited, and there are the following two embodiments as an example.

  1) In the first embodiment, the electrode active material is surface-treated with an inorganic substance.

  As described above, the inorganic material surface-treated on the surface of the electrode active material has an electrode due to a difference in electronegativity of proton donor functional groups and / or different metal atoms present on a part or all of the surface of the inorganic material. By changing the distribution of surface electrons of the active material, the electrochemical properties of the surface are changed, whereby acid spots are formed on the surface of the electrode active material.

  The inorganic substance is a known normal inorganic substance such as ceramic, metal, or a mixture thereof, and specially provided that it can change the electrochemical properties of the surface when it is present on the surface of the electrode active material. There is no limit. In particular, a group 13 element, a group 14 element, a group 15 element, for example, having a small atomic size and being easily doped on the surface of the electrode active material, can achieve structural safety of the electrode according to Li intercalation. A compound containing B, Al, Ga, In, Ti or a combination thereof is preferred.

Non-limiting examples of usable inorganic materials include: (a) Group 13 element-containing compounds; (b) (i) Group 13 elements; and (ii) Alkaline earth metals, alkali metals, Group 14 elements, Group 15 elements And compounds containing one or more elements selected from the group consisting of transition metals, lanthanoid metals and actinide metals. As an example, the inorganic substance may be M _1-X Si _X O ₂ (one or more elements selected from the group consisting of M = 13 groups and transition metals; 0 ≦ x <1).

  The inorganic substance having an acid point can be formed by heat treatment after the surface modification of the electrode active material. At this time, the heat treatment temperature is not particularly limited as long as it is higher than the temperature at which acid sites are formed. When a hydroxyl group is present on the surface as it is, a strong Lewis acid point cannot be formed.

  The particle size and content of the inorganic substance described above are not particularly limited, and can be appropriately adjusted within a known normal range.

  2) In the second embodiment, the surface of the electrode active material is surface-treated with a composite of an organic (semi) metal compound and an inorganic substance.

  The organic (semi) metal compound and inorganic composite formed on the surface of the electrode active material may have a difference in electronegativity between the organic (semi) metal compound and the inorganic combined with each other and / or The organic substance bonded to the organometallic compound can change the electrochemical properties of the surface to form acid spots.

  At this time, in the composite, the organic (semi) metal compound and the inorganic substance are connected to each other through a chemical bond, and the form and type of such a chemical bond are not particularly limited. For example, it may be a covalent bond or a coordinate bond.

  As described above, when an organic (semi) metal compound and an inorganic composite are commonly used as an electrode active material or an electrode surface modifier, an inorganic component such as an inorganic alkoxide compound is added depending on the organic component contained in the organic-inorganic composite. The hydrolysis rate of can be reduced. Therefore, since a more uniform surface can be generated and the generated surface can be maintained continuously, the structural safety and structural collapse of the electrode active material due to the progress of charging and discharging are minimized, and the deterioration of the battery performance due to this is minimized. Can be In addition, the decrease in the electrical conductivity of the electrode active material according to the introduction of the surface modification layer can be efficiently improved by the inorganic component contained in the organic-inorganic composite.

  In addition, the organic-inorganic composite introduced on the surface of the electrode active material reacts with moisture or carbon dioxide in the air to generate a Li-byproduct, thereby preventing a change over time causing a side reaction. Therefore, it is possible to prevent the material change of the electrode active material by an external person. In particular, a nickel-based positive electrode active material that changes drastically due to moisture is more effective.

  Furthermore, the safety of the battery can be improved by reducing the side-reactive contact surface between the positive electrode and the electrolyte in a battery made of an electrode active material that has not been surface-modified.

  As described above, one of the organic-inorganic composite components capable of forming acid sites on part or all of the surface of the electrode active material particles is specially known as long as it is a known ordinary organic (semi) metal compound. There is no limit. In order to enhance the effect of adjusting the acid point strength and the effect of preventing change over time, it is preferable to include an electron donating group capable of increasing the Bronsted acid point. The electron-donating group is not particularly limited in the structural formula, substituent, or carbon number range, and includes, for example, hydrogen or hydrocarbon.

  The organic (semi) metal compound includes (a) a group 14 element-containing compound; or (b) (i) a group 14 element; and (ii) an alkaline earth metal, an alkali metal, a group 13 element, a group 15 element, a transition metal, Although there is a compound containing one or more elements selected from the group consisting of lanthanoid metals and actinide metals, it is not limited thereto. As the organic (semi) metal compound, a silicon-containing compound is preferable, and specific examples thereof include silane, silylating agent, silane coupling agent, silicon hydride, monosilane, silane polymer, or a mixture thereof.

The organic (semi) metal compound is represented by the following chemical formulas 1 to 7, but is not limited thereto.
[Chemical 1]
SiH ₄
[Chemical 2]
Si (OR) _4-x R _x (0.1 ≦ x ≦ 3)
[Chemical formula 3]
Si (OR) _{4− (x + y)} R _x Z _y (0.1 ≦ x + y ≦ 3.9)
[Chemical formula 4]
Si (OR) _4-x R _x Si (0.1 ≦ x ≦ 3)
[Chemical formula 5]
Si (OR) _{4− (x + y)} R _x Z _y Si (0.1 ≦ x + y ≦ 3.9)
[Chemical 6]
R _x M (OR) _4-x (1 ≦ x ≦ 3)
[Chemical 7]
R _x MZ _y (OR) _{4- (x + y)} (0.1 ≦ x + y ≦ 3.9)
In the above formula,
Z is a halogen element,
M is one or more elements selected from the group consisting of alkaline earth metals, alkali metals, transition metals, lanthanoid metals and actinide metals,
R is a substituent selected from the group consisting of a C1-C20 alkyl group, an alkenyl group, an alkynyl group, a vinyl group, an amino group, and a mercapto group, which are substituted or unsubstituted by a halogen element.

  Another of the organic-inorganic composite components that can form acid sites on part or all of the surface of the electrode active material particles of the present invention is the difference in the number of chemical bonds with the organic (semi) metal compound described above. If it is a normal inorganic substance which can form an acid point, there will be no restriction | limiting in particular. As an example, the inorganic component described above is used. At this time, in order to prevent a decrease in conductivity of the electrode active material due to the introduction of the organic-inorganic composite, if possible, a conductive metal, a metal-containing oxide, a metal-containing hydroxide, or a mixture thereof It is preferable to use a form or the like.

The organic-inorganic composite composed of an organic (semi) metal compound and an inorganic material described above is not a simple mixed form of an organic substance and an inorganic substance but a form in which they are chemically bonded to each other. As an example, (a) a form in which a metal-organic (semi) metal compound is bonded, a form in which a metal oxide-organic (semi) metal compound is bonded (Al ₂ O ₃ —Si—CH ₃ ), or metal water oxide - an organic form (semi) metal compound is bonded _{(AlOOH-Si-CH 3)} .

  Among the compounds that form acid sites, the ratio of the organic (semi) metal compound: inorganic component is not particularly limited, but is preferably in the range of 0 wt% to 95 wt%: 5 wt% to 100 wt% if possible.

  Moreover, the organic-inorganic composite of the present invention can further contain known ordinary components such as additive components in addition to the components described above.

  The electrode active material according to the present invention can be produced by surface-treating part or all of the surface of the electrode active material with a compound having an acid site.

  According to the preferred embodiment, (a) a step of mixing an inorganic substance-containing compound or an inorganic substance-containing compound and an organic (semi) metal compound, or dispersing in a solvent; and (b) electrode activity in the mixture or dispersion. A step of drying after adding and stirring the substance may be included.

  As said inorganic substance containing compound, the normal water-soluble or water-insoluble compound containing 1 or more types of the element mentioned above is used. For example, there are alkoxides, nitric acid, acetate, etc. containing the inorganic substances described above.

  As the solvent, a known ordinary solvent is used, and non-limiting examples include water, organic solvents such as alcohol, and mixtures thereof.

  As the electrode active material to be added, mixed and stirred to the mixture or dispersion medium described above, known normal positive electrode active materials and negative electrode active materials can be used without limitation.

  At this time, a method of coating the surface of the electrode active material with a mixed solution of an inorganic substance and an organic (semi) metal compound is a known ordinary method, for example, a solvent evaporation method, a coprecipitation method, a precipitation method, a sol-gel (sol -gel) method, post-adsorption filter method, sputtering method, CVD, etc. are used. Of these, the spray coating method is preferred.

  When an inorganic substance-containing compound or a mixed solution (or dispersion) of an inorganic substance and an organic (semi) metal compound is added to the electrode active material, it is added in the range of 0.05 to 20 parts by weight per 100 parts by weight of the electrode active material. Is preferred. However, the present invention is not limited to this. When the amount of the mixed solution is too large, a large amount of a surface treatment layer is present on the surface of the active material, so that lithium transfer and transmission to the electrode active material is not smooth, and electrochemical characteristics may be reduced. Moreover, when there is too little said mixed solution, it is difficult to exhibit a desired acid point effect. Thereafter, the coated electrode active material can be dried by a known ordinary method.

  If necessary, a step of heat treating the dried electrode active material can be added. At this time, if heat processing temperature is 100 degreeC or more, there will be no restriction | limiting in particular, Preferably it is the range of 100-600 degreeC. The heat treatment may be performed in air or under inactive conditions.

  Conventionally, during high-temperature firing, the organic matter is thermally unstable, and a portion of the organic matter is consumed, so that it is difficult to exert a desired effect. This places restrictions on the firing temperature. On the other hand, in the present invention, the thermal instability of the organic substance can be compensated for by the inorganic component, thereby showing thermal safety. Moreover, since it can manufacture by a normal drying step or low temperature baking, the improvement of economical efficiency and mass productivity which follow simplification of a manufacturing method can be aimed at.

  In the electrode active material thus manufactured, an inorganic or organic-inorganic composite layer is formed on the surface, but the formed inorganic or organic-inorganic composite forms acid spots as described above. become.

  In the present invention, it was confirmed through the experimental example of the present application that the surface properties of the electrode active material surface-modified with an inorganic substance or an organic-inorganic composite have acid sites (see FIG. 9). In particular, the organic-inorganic composite not only shows a form in which the organic substance and the inorganic substance are bonded to each other (see FIG. 7), but also has a Bronsted acid point of the inorganic substance due to the functional group that donates electrons present in the organic substance in the composite. It was confirmed that the acid point strength was further increased by the relative increase (see FIG. 9).

  The present invention provides an electrode including the electrode active material as described above. In this case, it is preferable that the electrode is a positive electrode that is greatly changed by HF or moisture.

  At the same time, the present invention provides an electrode in which a compound having an acid site is coated on the surface of the electrode or mixed with an electrode material.

  The method for producing an electrode containing a compound having an acid point as a constituent component of the electrode according to the present invention is not particularly limited, and can be produced by a usual method. According to the preferred embodiment, an inorganic substance-containing compound or a mixture or dispersion prepared by mixing an inorganic substance-containing compound and an organic (semi) metal compound or dispersing it in a solvent is mixed with an electrode active material to form an electrode slurry. Can be completed by applying the produced slurry to a current collector to produce an electrode and then drying.

  At this time, in the step (b), as an example of a mixing process, an electrode slurry is manufactured by mixing the mixture or dispersion and an electrode active material, and then the manufactured slurry is applied to a current collector. It is.

  In addition, a method for producing an electrode using an organic-inorganic composite as an electrode coating component according to the present invention can also be produced by a known ordinary method. According to one embodiment, the inorganic substance-containing compound or the inorganic substance-containing compound and the organic (semi) metal compound may be mixed or dispersed in a solvent, and then coated and dried on the surface of the electrode already produced. At this time, the already manufactured electrode can be manufactured by a known ordinary method.

  Further, the present invention provides an electrochemical element comprising a positive electrode, a negative electrode, a separation membrane, and an electrolyte solution, wherein the positive electrode, the negative electrode, or both electrodes include the electrode active material described above or are electrodes. provide.

  The electrochemical element includes all elements that perform an electrochemical reaction, and specific examples include all types of primary and secondary batteries, fuel cells, solar cells, and capacitors. In particular, among secondary batteries, lithium secondary batteries including lithium metal secondary batteries, lithium ion secondary batteries, lithium polymer secondary batteries, or lithium ion polymer secondary batteries are preferable.

  The electrochemical device of the present invention can be produced by inserting a porous separation membrane between a positive electrode and a negative electrode and introducing the electrolytic solution by a known ordinary method.

  The electrolyte solution and the separation membrane applied together with the electrode are not particularly limited, and usual ones used for conventional electrochemical devices can be used.

  The outer shape of the electrochemical device, preferably a lithium secondary battery, manufactured by the method presented in the present invention is not particularly limited, but can be cylindrical, coin-shaped, rectangular, or pouch-shaped.

  Furthermore, this invention provides the manufacturing method of the electrode active material by which the acid point intensity | strength of the surface was adjusted. According to one embodiment of such a production method, (a) a compound having an acid point; and (b) a compound that provides a proton (or electron pair) or accepts a proton (or electron pair) is reacted. Thereafter, a part or all of the surface of the electrode active material is subjected to a surface treatment, but is not limited thereto.

  A compound that provides a proton (or electron pair) or accepts a proton (or electron pair) is used as an influencing factor that can adjust the acid point intensity of a conventional compound to a specific range. At this time, the acid point strength can be adjusted to a desired range by adjusting the content of the compound, the functional group present in the compound, and the component ratio.

At this time, the compound that provides proton (or electron pair) or accepts proton (or electron pair) is not particularly limited as long as the above-described action is performed. The acid point strength on the surface of the adjusted active material is preferably H ₀ in the range of −10 to 10 but is not limited thereto. In addition, it is also within the scope of the present invention to adjust H ₀ to the -20 to 20 range by the same action.

  According to the present invention, by adjusting the acid point strength of the surface of the electrode active material, the performance of the battery can be improved by reducing the side reactivity with the electrolytic solution and ensuring the structural safety of the electrode active material.

  Hereinafter, in order to facilitate understanding of the present invention, preferred examples will be presented. However, the following examples are merely illustrative of the present invention and do not limit the present invention.

Example 1
1-1 Production of Positive Electrode Active Material Aluminum isopropoxide (Al-isopropoxide) and CH ₃ Si (OCH ₃ ) ₃ were each placed in 200 ml of anhydrous alcohol so as to be 0.8 mol% with respect to the active material. Stir for hours. Thereafter, 100 g of LiCo ₂ was added and the mixture was re-stirred for 1 hour and 20 minutes, and then filtered using a vacuum filter. The obtained active material was dried in a vacuum oven at 130 ° C. to obtain a surface-treated active material.

1-2 Production of Positive Electrode A positive electrode produced after a slurry was produced in an NMP solvent so that the ratio of the produced positive electrode active material: conductive agent: binder was 95: 2.5: 2.5. The slurry was applied on a 20 μm aluminum foil and then dried in an oven at 130 ° C. to obtain a positive electrode.

1-3 Production of Lithium Secondary Half Battery After rolling the obtained electrode to have a porosity of 25%, a coin-like battery was produced by punching into a coin shape. At this time, Li-metal was used as the counter electrode, and an electrolytic solution in which 1M LiPF ₆ was dissolved in a 1: 2 mixture of EC: EMC was used as the electrolytic solution.

Example 2
A coin-shaped battery including a positive electrode active material, a positive electrode using the positive electrode active material, and the positive electrode was manufactured in the same manner as in Example 1 except that the dried active material was further heat-treated at 300 ° C.

Example 3
A positive electrode active material, a positive electrode using the positive electrode active material, and the positive electrode were obtained in the same manner as in Example 1 except that the positive electrode active material obtained by using aluminum isopropoxide alone was heat-treated at 400 ° C. A coin-shaped battery comprising

Comparative Example 1
A coin-shaped battery including a positive electrode and the positive electrode was manufactured in the same manner as in Example 1 except that normal LiCoO ₂ that was not surface-treated was used as the positive electrode active material.

Comparative Example 2
A positive electrode active material, a positive electrode using the positive electrode active material, and the positive electrode were prepared in the same manner as in Example 1 except that aluminum isopropoxide was used alone without using CH ₃ Si (OCH ₃ ) _3. A coin-shaped battery including a positive electrode was manufactured.

Comparative Example 3
Except for using CH ₃ Si (OCH ₃ ) ₃ alone without using aluminum isopropoxide, the positive electrode active material, the positive electrode using the positive electrode active material, and A coin-shaped battery including the positive electrode was manufactured.

Experimental Example 1 Analysis of Surface Properties of Electrode Active Material In order to evaluate the physical properties of the electrode active material whose surface was modified according to the present invention, the following experiment was conducted.

As the sample, the positive electrode active material surface-modified with the organic-inorganic composite in Example 1 was used, and as the control group, a normal positive electrode active material (LiCoO ₂ ) was used.

Using the positive electrode active material described above, analysis was performed with an IR spectrum device in normal temperature air, normal temperature vacuum, 50 ° C. vacuum, 100 ° C. vacuum, 200 ° C. vacuum, and 300 ° C. vacuum. As a result, the alkyl group (—CH ₂ CH ₃ ) that appears in the vicinity of 2800 to 3000 cm ⁻¹ does not appear in the positive electrode active materials of Comparative Example 1 and Comparative Example 2 (see FIG. 8), whereas the positive electrode active of the present invention. The substance was confirmed to have an alkyl group contained in the organic substance (see FIG. 7). Therefore, it was confirmed that the surface modifying material present on the electrode active material of the present invention was present by forming a complex between the organic material and the inorganic material.

Experimental Example 2 Analysis of Acid Site of Electrode Active Material In order to evaluate the physical properties of the surface of the electrode active material according to the present invention, the following experiment was conducted.

As a sample, a positive electrode active material surface-modified with an organic-inorganic composite in Example 1 and a positive electrode active material surface-modified with an inorganic substance having an acid point in Example 3 were used. As the control group, the normal positive electrode active material (LiCoO ₂ ) of Comparative Example 1 and the positive electrode active materials of Comparative Example 2 and Comparative Example 3 that were respectively surface-treated with an inorganic material and an organic material were used.

The CH ₃ CN compound was adsorbed on the positive electrode active material described above, and the acid point intensity was measured by analysis with an IR spectrum apparatus. For reference, a CH ₃ CN compound is a basic compound having an unshared electron pair, and therefore, by generating surface adsorption by a neutralization reaction with a compound having an acid point, it may show a peak change on the IR spectrum. it can. Therefore, the acid point strength of a compound having an acid point can be measured.

As a result of the experiment, the positive electrode active material of Comparative Example 1 using a normal positive electrode active material, the positive electrode active material of Comparative Example 2 treated with an inorganic material alone, and the positive electrode active material of Comparative Example 3 treated with an organic material alone. With substance, no special change appeared on IR data. In contrast, the positive electrode active material of Example 3 that was surface-treated alone with an inorganic substance having an acid point and the positive electrode active material of Example 1 that was surface-treated with a composite of an organic material and an inorganic material were 2200 to 2400 cm ^−1. A peak for the nitrile group (—CN) appeared in the vicinity, confirming the presence of acid sites on the surface (see FIG. 9).

  In particular, as a result of comparing the positive electrode active material of Example 3 that was surface-treated alone with the same inorganic material and the positive electrode active material of Comparative Example 2, the positive electrode active material of Comparative Example 2 was electrolyzed by the inorganic surface treatment. Even if the side reactivity with the liquid was stopped, acid sites were not formed, so the performance of the battery was significantly reduced (see FIG. 5), whereas the positive electrode active material of Example 3 in which acid sites were formed was used. The battery was found to have improved performance (see FIG. 3). Therefore, it was confirmed that acid spot formation is a factor relating to various performances of the battery.

Experimental Example 3 Evaluation of Performance of Lithium Secondary Battery Performance evaluation of a lithium secondary battery manufactured using an electrode active material having acid sites on the surface according to the present invention was performed as follows.

  Comparative examples in which the coin-shaped batteries of Examples 1 to 3 manufactured using a positive electrode active material having acid sites were not surface-modified as a control group, or were individually surface-treated with an inorganic material and an organic material, respectively. The coin-shaped battery of 1 to Comparative Example 3 was used.

  Each battery was subjected to CC / CV charge / discharge at 50 ° C. to 3 to 4.5 V to 0.5 C, and the obtained results are shown in FIG. 1 to FIG.

  As a result of the experiment, the batteries of Examples 1 to 3 manufactured using an electrode active material having an acid point on the surface maintained cycle characteristics by maintaining excellent charge / discharge efficiency as the cycle progressed. It was confirmed that it was remarkably improved (see FIGS. 1 to 3). On the other hand, the batteries of Comparative Examples 1 to 3 manufactured using the positive electrode active material having no acid sites on the surface could confirm that the charge / discharge characteristics were degraded (FIGS. 3 to 5). reference).

The charging / discharging graph of the lithium secondary battery manufactured using the positive electrode active material of Example 1 is shown. The charging / discharging graph of the lithium secondary battery manufactured using the positive electrode active material of Example 2 is shown. The charging / discharging graph of the lithium secondary battery manufactured using the positive electrode active material of Example 3 is shown. The charging / discharging graph of the lithium secondary battery manufactured using the positive electrode active material of the comparative example 1 is shown. The charging / discharging graph of the lithium secondary battery manufactured using the positive electrode active material of the comparative example 2 is shown. The charging / discharging graph of the lithium secondary battery manufactured using the positive electrode active material of the comparative example 3 is shown. The graph of IR spectrum which shows the change of the surface characteristic according to the temperature of the positive electrode active material manufactured in Example 1, and the change of measurement conditions is shown. The graph of IR spectrum which shows the change of the surface characteristic according to the temperature of the positive electrode active material manufactured by the comparative example 1 and the change of measurement conditions is shown. The IR spectrum apparatus which shows the surface acid point and acid point intensity | strength of the positive electrode active material of Example 1 and Example 3, and the positive electrode active material of Comparative Example 1- Comparative Example 3 is shown.

Claims (19)

Comprising acid sites on part or all of the surface;
The acid point is formed by a composite of an organic (semi) metal compound and an inorganic material surface-treated on an electrode active material, and the composite has a form in which a metal-organic (semi) metal compound is bonded. , A form in which a metal oxide-organic (semi) metal compound is bonded, or a form in which a metal hydroxide-organic (semi) metal compound is bonded,
An electrode active material in which the organic (semi) metal compound is represented by any one of the following chemical formulas 1 to 7.
[Chemical Formula 1] SiH ₄
[Chemical Formula 2] Si (OR) _4−x R _x (0.1 ≦ x ≦ 3)
[Chemical Formula 3] Si (OR) _{4− (x + y)} R _x Z _y (0.1 ≦ x + y ≦ 3.9)
[Chemical Formula 4] Si (OR) _4-x R _x Si (0.1 ≦ x ≦ 3)
[Chemical Formula 5] Si (OR) _{4− (x + y)} R _x Z _y Si (0.1 ≦ x + y ≦ 3.9)
[Chemical Formula 6] R _x M (OR) _4-x (1 ≦ x ≦ 3)
[Chemical Formula 7] R _x MZ _y (OR) _{4- (x + y)} (0.1 ≦ x + y ≦ 3.9)
[In the above formula,
Z is a halogen element,
M is one or more elements selected from the group consisting of alkaline earth metals, alkali metals, transition metals, lanthanoid metals and actinide metals,
R is a substituent selected from the group consisting of a C1-C20 alkyl group, an alkenyl group, an alkynyl group, a vinyl group, an amino group, and a mercapto group, which is substituted or unsubstituted with a halogen element. ]   The electrode active material according to claim 1, wherein the acid point is a Bronsted acid point or a Lewis acid point. The electrode active material according to claim 1 or 2, wherein the acid point has an intensity of H ₀ (Hammett indicator) in a range of -10 to 10.   4. The inorganic substance according to any one of claims 1 to 3, wherein an acid site is formed by a proton donor functional group present on a part or all of the surface, a difference in electronegativity of different metal atoms, or all of them. The electrode active material according to one item. The inorganic substance is
(a) a group 13 element-containing compound, or
(b) one or more elements selected from the group consisting of (i) group 13 elements and (ii) alkaline earth metals, alkali metals, group 14 elements, group 15 elements, transition metals, lanthanoid metals and actinide metals The electrode active material according to any one of claims 1 to 4, which is a compound to be contained.   The complex of the organic (semi) metal compound and the inorganic substance is a difference in electronegativity between the organic (semi) metal compound and the inorganic substance bonded to each other, an organic substance bonded to the organic (semi) metal compound, or these The electrode active material according to any one of claims 1 to 5, wherein an acid point is formed by all of the above. The organic (semi) metal compound is
(a) a group 14 element-containing compound, or
(b) A compound containing a group 14 element and one or more elements selected from the group consisting of alkaline earth metals, alkali metals, group 13 elements, group 15 elements, transition metals, lanthanoid metals, and actinide metals. The electrode active material according to any one of claims 1 to 6.   The electrode active material according to claim 1, wherein the organic (semi) metal compound comprises one or more electron donating groups.   The electrode active material according to any one of claims 1 to 7, wherein the organic (semi) metal compound is a silicon (Si) -containing compound.   The silicon-containing organic (semi) metal compound is one or more selected from the group consisting of silane, silylating agent, silane coupling agent, silicon hydride, monosilane, and silane polymer. The electrode active material according to any one of the above.   The electrode active material according to any one of claims 1 to 10, wherein a component ratio between the organic (semi) metal compound and the inorganic substance is in a range of 0 wt% to 95 wt%: 5 wt% to 100 wt%.   The content of the composite of the inorganic material or organic (semi) metal compound and the inorganic material is 0.05 to 20 parts by weight per 100 parts by weight of the electrode active material, according to any one of claims 1 to 11. Electrode active material.   The electrode provided with the electrode active material as described in any one of Claims 1-12.   The electrode according to claim 13, wherein the electrode is a positive electrode.   The reactivity of HX (X = F, Cl, Br, I) present in the battery with the electrode active material is reduced due to acid sites formed on part or all of the surface of the electrode active material. The electrode according to claim 13, wherein   The electrode according to claim 13, wherein a compound having an acid point is coated on the electrode surface and mixed with an electrode material. An electrochemical element,
A positive electrode, a negative electrode, a separation membrane, and an electrolyte;
The positive electrode, the negative electrode, or both electrodes are electrodes comprising the electrode active material according to any one of claims 1 to 12, or the electrodes according to any one of claims 13 to 16. Electrochemical element. (i) (a) reacting a compound that provides a proton (or electron pair) or accepts a proton (or electron pair) and (b) a compound having an acid point; and
(ii) A coating layer having a controlled acid point strength, comprising coating the resultant product of step (i) onto the surface of an electrode active material and drying the coating layer. The manufacturing method of the electrode active material as described in any one of these. The acid sites strength, _{H 0} is in the range of -10 to 10, the manufacturing method according to claim 18.

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