KR20220071079A - Solid-type oxidative-stress suppressant for secondary batteries and Secondary batteries included the same and Lithium-air battery - Google Patents

Abstract

The present invention relates to a solid-state oxidative stress inhibitor for a secondary battery using an organic metal polymer and a secondary battery including the same, and specifically, to a solid-state oxidative stress inhibitor for a secondary battery using an organic metal polymer, a secondary battery including the same, and a lithium-air battery, wherein the solid-state oxidative stress inhibitor for a secondary battery suppresses side reactions that can occur inside various secondary batteries including organic or aqueous electrolytes and solid electrolytes, prevents oxidation of the electrolytes, and prevents corrosion of a secondary battery using metal negative electrodes.

Description

Solid-type oxidative-stress suppressant for secondary batteries and Secondary batteries included the same and Lithium-air battery using organometallic polymer

The present invention relates to a solid-type oxidative stress inhibitor for a secondary battery, a secondary battery comprising the same, and a lithium-air battery, and more particularly, inhibits side reactions that may occur inside various secondary batteries including organic, aqueous, or solid electrolytes. It relates to a solid-type oxidative stress inhibitor for secondary batteries using an organometallic polymer capable of preventing oxidation of electrolytes and corrosion of secondary batteries using metal electrodes, and secondary batteries and lithium-air batteries including the same.

In general, in order to suppress side reactions that reduce the performance of the secondary battery's charge/discharge cycle and energy efficiency, a solid electrolyte containing an additive is prepared or an organic catalyst (redox mediator) is dissolved in a liquid electrolyte. have.

However, since the conventional electrolyte additive for suppressing side reactions is applied in a dissolved state in the organic electrolyte and can move to the positive and negative electrodes of the battery, the oxidative stress material that reduces energy efficiency cross-reacts, followed by lowering the charge/discharge cycle characteristics. There is a problem that side reactions inevitably occur.

In particular, a next-generation secondary battery using a metal anode has a problem of being very vulnerable to cross-reaction that corrodes the metal anode.

On the other hand, there are several types of secondary batteries such as lithium-air batteries, lithium-sulfur batteries, zinc-air batteries, zinc-ion batteries, and all-solid-state secondary batteries. Among them, lithium-air batteries use a chemical reaction between lithium and oxygen. It is a method of increasing energy efficiency and has recently attracted intensive attention because of its high theoretical energy density.

This lithium-air battery stores energy through the reversible growth and decomposition of Li ₂ O ₂ , and most studies have applied a catalyst suitable for promoting the reversible growth and decomposition of Li ₂ O ₂ , and The focus is on improving reversibility.

However, the catalytic activity increases the efficiency of the discharging and charging process, but has a disadvantage of causing various side reactions due to the severe decomposition of the electrolyte due to poor selectivity of the catalyst.

_In addition, when lithium _- air batteries are discharged and charged, an oxygen reduction reaction (ORR) and an oxygen evolution reaction (OER; It causes growth and decomposition of O ₂ .

It contributes to the surface adsorption pathway and solution-mediated growth pathway by determining the production and consumption rates of superoxide species through electrochemical oxidation or disproportionation reaction, and in the case of low donor number (DN) solvents, the adsorbed LiO than the disproportionation pathway Due to the low kinetic barrier and free energy for ₂ , a surface adsorption pathway occurs. In contrast, solvated LiO ₂ formation via a solvation-mediated growth pathway occurs via disproportionation. This solvated LiO ₂ formation can maintain a higher specific discharge capacity and a lower discharge overvoltage than adsorbed LiO ₂ .

However, the imbalance of solvated LiO ₂ can promote parasitic reactions leading to high charge overvoltage and low discharge charge reversibility, and the solvated superoxide species (active oxygen species) formed during the oxygen reduction reaction (ORR) ⁺ Problems arise when they attack organic solvents or lithium salts instead of reacting with cations.

These superoxide species can also oxidatively decompose the Li negative electrode and the O ₂ positive electrode. As a result, achieving oxidative stability of the electrolyte solvent and salt is an important task for lithium-air batteries with limited electrochemical stability, and energy efficiency Redox mediators (RMs) such as LiI, TEMPO, DBBQ and AQ are dissolved in organic electrolyte solvents and rapidly oxidized during charging to prevent decomposition of the electrolyte solution, and catalysts for effective decomposition of Li ₂ O ₂ produced is being used as Such redox mediators (RMs) can also control the toxic activity of solvated superoxide species in the electrolyte.

However, soluble redox mediators (RMs) can have undesirable effects such as promoting redox migration reactions and detrimental cross-reactions with lithium (Li) negative electrodes. This may be because the negative and positive sides share the same electrolyte solution without separation in the lithium-air battery.

Accordingly, the applicant of the present application intends to solve the above-mentioned problems occurring in secondary batteries as described above, and in the prior art, most of them only utilize liquid catalyst technology, and they are fixed to a separator or electrode to capture and purify oxidative stress materials such as active oxygen species. I can't find any description of an insoluble solid oxidative stress inhibitor that does this.

Republic of Korea Patent Publication No. 10-2018-0126588 Republic of Korea Patent Publication No. 10-2020-0125263 Republic of Korea Patent Publication No. 10-2017-0133544

The present invention has been devised in consideration of and solving the problems of the prior art, and suppresses side reactions that may occur inside the secondary battery in various secondary batteries including organic, aqueous, or solid electrolytes, and prevents oxidation of the electrolyte. An object of the present invention is to provide a solid-type oxidative stress inhibitor for a secondary battery using an organometallic polymer capable of preventing corrosion of a secondary battery using a metal electrode, a secondary battery including the same, and a lithium-air battery.

The present invention produces a stable material by generating harmful superoxide species (active oxygen species) that are the cause of parasitic reactions in various secondary batteries including lithium-air batteries, An object of the present invention is to provide a solid-type oxidative stress inhibitor for a secondary battery using an organometallic polymer capable of inducing a strong surface adsorption reaction while suppressing the peroxide, and a secondary battery and a lithium-air battery including the same.

The present invention uses an organometallic polymer to relieve toxic oxidative stress on the secondary battery side, thereby stabilizing the organic electrolyte and promoting excellent growth, as well as extending the lifespan of the electrolyte and enabling impressive recharging on the secondary battery side. An object of the present invention is to provide a solid-type oxidative stress inhibitor for a secondary battery using the same, and a secondary battery and a lithium-air battery including the same.

A solid-type oxidative stress inhibitor for a secondary battery using an organometallic polymer according to the present invention for achieving the above object comprises the steps of: (A) dissolving an organometallic polymer in a mixed solvent; (B) immersing the fiber-based material in a solution in which the organometallic polymer is dissolved; (C) freezing the result of step (B); (D) growing an organometallic polymer by freeze-drying the frozen product of the step (C) to obtain an organometallic polymer powder; characterized in that it is synthesized.

Here, the organometallic polymer is at least one of organic germanium (Propa germanium), zinc acetate, sodium selenite, silicon tetraacetate, and sodium metasilicate. or more may be used.

Here, the solid-type oxidative stress inhibitor for the secondary battery may be used in any one group of a lithium-air battery, a lithium-sulfur battery, a zinc-air battery, a zinc-ion battery, and an all-solid secondary battery.

In addition, the secondary battery according to the present invention for achieving the above object is provided with a solid-type oxidative stress inhibitor for secondary batteries using an organometallic polymer, which is fixedly arranged and used as one component in the secondary battery. do.

Here, the solid-type oxidative stress inhibitor for a secondary battery using the organometallic polymer may be formed of a membrane film.

In addition, the lithium-air battery according to the present invention for achieving the above object is a lithium-air battery comprising a lithium negative electrode, an O ₂ positive electrode, and a separator disposed between the lithium negative electrode and the O ₂ positive electrode, A solid-type oxidative stress inhibitor for a secondary battery using an organometallic polymer is fixedly disposed on the outside of the O ₂ positive electrode.

Here, the solid-type oxidative stress inhibitor for a secondary battery using the organometallic polymer may be formed of a membrane film.

In addition, the lithium-air battery according to the present invention for achieving the above object is a lithium-air battery comprising a lithium negative electrode, an O ₂ positive electrode, and a separator disposed between the lithium negative electrode and the O ₂ positive electrode, It is characterized in that a solid-type oxidative stress inhibitor for secondary batteries using an organometallic polymer is fixedly disposed on the separator, or the separator itself is composed of a solid-type oxidative stress inhibitor for secondary batteries using an organometallic polymer.

Here, the solid-type oxidative stress inhibitor for a secondary battery using the organometallic polymer may be formed of a membrane film.

Meanwhile, various features of the solid-type oxidative stress inhibitor for secondary batteries using the organometallic polymer according to the present invention and secondary batteries and lithium-air batteries including the same will be described below.

According to the present invention, it is possible to provide a solid-type oxidative stress inhibitor capable of increasing the performance and efficiency of a secondary battery by utilizing an organometallic polymer including organo-germanium, and it can be applied to various types of secondary batteries, especially secondary batteries. By effectively reducing active oxygen species (superoxide species), which are oxidative stress-inducing substances in the battery, it is possible to achieve usefulness of suppressing side reactions that may occur in electrolytes and electrodes.

According to the present invention, by using a solid-type oxidative stress inhibitor, it is possible to inhibit the oxidation of the electrolyte and the corrosion of the electrode in the secondary battery to prevent swelling of the secondary battery, and cross-reaction, which is a disadvantage of the existing soluble electrolyte additives It can block oxidative stress by Therefore, it is possible to achieve usefulness that enables high efficiency and long life performance by preventing corrosion of secondary batteries using metal electrodes.

According to the present invention, by utilizing a solid-type oxidative stress inhibitor, harmful superoxide species (active oxygen species) that are the cause of parasitic reactions in various secondary batteries including lithium-air batteries are generated to produce stable substances, and organic Due to the high peroxide disproportionation activity in the electrolyte, it suppresses solvated peroxide and induces a strong surface adsorption reaction. It is possible to achieve the usefulness of enabling impressive recharging on the secondary battery side while enabling life extension.

1 is a synthesis process diagram showing a solid-type oxidative stress inhibitor for a secondary battery using an organometallic polymer according to the present invention.
FIG. 2 is a photograph showing an example in which a nanowire-type solid-type oxidative stress inhibitor synthesized by the synthesis process of FIG. 1 and a carbon fiber fabric were fixed and grown.
3 is data obtained by analyzing the XRD diffraction pattern of a solid-type oxidative stress inhibitor synthesized using organo-germanium as an organometallic polymer.
4 is an example by titration of CoCl ₂ -DME solution for activity evaluation of a solid-type oxidative stress inhibitor synthesized using organo-germanium as an organometallic polymer (a: CoCl ₂ -DME, b: CoCl ₂ -DME + KO ₂ + H ₂ O c: b solution + commercial Ge-132, d: b solution + synthesized organic germanium).
5 is a data showing the performance evaluation of the lithium-air battery containing the solid-state oxidative stress inhibitor according to the present invention.
6 is data showing the performance evaluation of a lithium-sulfur battery containing a solid-state oxidative stress inhibitor according to the present invention.
7 is a data showing the performance evaluation of the zinc-air battery containing the solid-type oxidative stress inhibitor according to the present invention.
8 is data showing the performance evaluation of the zinc-ion battery containing the solid-state oxidative stress inhibitor according to the present invention.
9 is data showing the performance evaluation of an all-solid lithium-air battery containing a solid-type oxidative stress inhibitor according to the present invention.
10 is data presented to evaluate the performance of a lithium-air battery including a soluble redox mediator and a synergistic effect with a solid-type oxidative stress inhibitor.
11 is a schematic illustration of applying a solid-type oxidative stress inhibitor for a secondary battery using an organometallic polymer according to the present invention as a component of a secondary battery as a fixed body.
12 is an exemplary view showing a configuration in which the solid-type oxidative stress inhibitor according to the present invention is applied to a secondary battery as a fixed body.
13 is an exemplary view in which the solid-type oxidative stress inhibitor according to the present invention is fabricated with an OG NW membrane, (a) is a schematic diagram of a lithium-air battery using an ASD membrane (OG NW membrane), (b) and ( c) is a FESEM image of the OG NW membrane, (d) is a low-magnification TEM image of the OG NW membrane, (e) is a high-resolution TEM image, and (f) is an XRD pattern of the OG NW membrane.
Figure 14 is data showing OG NW performance through Au negative electrode including lithium-air battery test, CV for lithium-known battery with and without OG NW membrane using (a) TEGDME and (b) DMAc solvent ( = 100 mV/S scan rate) comparative data, and data showing capacity versus voltage curves (corresponding to CV) for lithium-air cells with and without OG NW membrane using (c) TEGDME and (d) DMAc solvents .
15 is data showing the change in the performance and Li ₂ O ₂ growth path of a lithium-air battery to which an OG NW membrane according to the present invention is applied, (a) is discharge comparison data, (b) is a Li ₂ O ₂ cell are the normalized capacity curves for , (c) and (d) are the Raman spectra of Au anode without OG NW membrane and Au anode with OG NW membrane, (e) and (f) are Li ₂ O in TEGDME solvent. ₂ Data showing the change in shape of the product, (g) and (h) are data showing the change in shape of the Li ₂ O ₂ product in DMAc solvent, (i) and (j) are data showing the change in the shape of the product with and without OG NW membrane Data showing AFM images for Li ₂ O ₂ products.
16 is data showing the ASD performance of the OG NW membrane, (a) is data showing the color change with time of a CoCl ₂ saturated DME solution after addition of KO ₂ and KO ₂ , (b) is a CoCl ₂ -DME solution Data showing the UV-vis spectrum of, (c) is data showing the UV-vis spectrum of CoCl ₂ -DME.
17 is a schematic diagram showing the Li ₂ O ₂ growth pathway and the tunable Li ₂ O ₂ growth pathway through ASD activity of OG NW membranes in various DN solvents.
18 is data showing a performance test of a lithium-air battery to which an OG NW membrane is applied. (a) is a discharge-charge curve of a lithium-air battery using DMAc electrolyte in the 30th cycle, and (b) is an overvoltage during cycling. Comparative data, (c) is performance data of lithium-air cells with OG NW membrane using DME electrolyte at various current rates, and (d) is lithium-air battery with OG NW membrane at current rate of 1000 mA g-1. It is a discharge-charge curve of an air battery, and (e) is data showing the discharge-charge retention performance of a lithium-air battery with or without OG NW membrane.

Preferred embodiments of the present invention will be described with reference to the accompanying drawings as follows, and through such detailed description, it will be possible to better understand the purpose and configuration of the present invention and its features.

The solid-type oxidative stress inhibitor for a secondary battery using an organometallic polymer according to an embodiment of the present invention is, as shown in FIG. 1, an organometallic polymer dissolution step (S10), a fiber-based material dipping step (S20), and a freezing step (S30) , and is synthesized through a process including a freeze-drying step (S40).

Organometallic polymer dissolution step (S10)

The organometallic polymer dissolving step (S10) is a step of dissolving the organometallic polymer in a mixed solvent.

To this end, the mixed solvent is preferably distilled water (H ₂ O): isopropyl alcohol = 9 to 12: mixed in a volume or weight ratio of 0.8 to 1.2, and an organometallic polymer 0.1 in such a mixed solvent Add ~10g to dissolve.

The organometallic polymer is at least one or more of organic germanium, zinc acetate, sodium selenite, silicon tetraacetate, and sodium metasilicate. can be used

The organic germanium may be represented by O[Ge(=O)CH ₂ CH ₂ CO ₂ H] ₂ }.

The organic germanium may be represented by 3-[(2-Carboxyethyl-oxogermyl)oxy-oxogermyl]propanoic acid.

The germanium may be represented by Chemical Formula 1 below.

[Formula 1]

The zinc acetate may be represented by Chemical Formula 2 below.

[Formula 2]

The sodium selenite may be represented by Chemical Formula 3 as follows.

[Formula 3]

The silicon tetraacetate (Silicon tetraacetate) may be represented by the following formula (4).

[Formula 4]

The sodium metasilicate may be represented by the following Chemical Formula 5.

[Formula 5]

Fiber-based material dipping step (S20)

The dipping step (S20) of the fiber-based material is a step of dipping and immersing the fiber-based material in a solution prepared by dissolving the organometallic polymer in a mixed solvent through the step S10.

As the fiber-based material, a fabric made of carbon fiber may be used for synthesis efficiency with respect to the organometallic polymer.

Freezing step (S30)

The freezing step (S30) is a step of freezing the results completed up to the step S20.

In the freezing step (S30), the resultant finished up to step S20 is put in a low-temperature freezer, and it is preferable to freeze it at -5 to 10° C. for 10 to 20 hours.

Freeze drying step (S40)

The freeze-drying step (S40) is a step of obtaining an organometallic polymer-based powder by growing an organometallic polymer by freeze-drying the freeze-treated product finished up to the step S30.

To this end, in the freeze-drying step (S40), freeze-drying is preferably performed at -30 to 50° C. for 18 to 24 hours.

At this time, the organometallic polymer-based powder is grown and synthesized into nanowire-type particles by growing vertically on the fiber-based material.

Here, the organometallic polymer-based powder may have an average diameter of 80 to 100 nm.

The solid-type oxidative stress inhibitor for secondary batteries synthesized by the above-described process can be used by grafting in the form of isolation or fixing to the electrodes constituting the secondary battery, and sometimes by coating or grafting itself to the components of the secondary battery. can be provided in the form.

The solid-type oxidative stress inhibitor for a secondary battery can be applied to a secondary battery using an organic electrolyte including a lithium-air battery or a lithium-sulfur battery, and a secondary using an aqueous electrolyte including a zinc-air battery or a zinc-ion battery It can be applied to a battery, and can be applied to an all-solid secondary battery including a solid electrolyte.

The solid-type oxidative stress inhibitor for the secondary battery may be used by adjusting the arrangement position in the secondary battery.

For example, it can be fixedly arranged on the side of both electrodes, can be fixedly arranged between solid electrolytes or liquid electrolytes, and can be coated on a separator (separator) or electrode, or it can be used by itself.

For the solid-type oxidative stress inhibitor for secondary batteries using the organometallic polymer according to the present invention, KO ₂ and H ₂ O are added to the CoCl ₂ -Dimethylether solution to cause non-uniformity and to observe the color change generated by the titration method. It is possible to test and evaluate the oxidative stress suppression performance.

Figure 2 shows an example in which the synthesized solid-type oxidative stress inhibitor and the carbon fiber fabric were fixed and grown and synthesized, and in Figure 3, an XRD diffraction pattern analysis of the synthesized solid-type oxidative stress inhibitor using organic germanium. The data is shown, and in FIG. 3, an example of a CoCl ₂ -DME solution titration method for evaluating the oxidative stress inhibitory activity of synthesized organic germanium (a: CoCl ₂ -DME, b: CoCl ₂ -DME + KO ₂ + H ₂ O c: b solution + commercial Ge-132, d: b solution + synthesized organic germanium).

4 shows an example of performance evaluation of a lithium-air battery containing a solid-type oxidative stress inhibitor, and FIG. 5 shows an example of performance evaluation of a lithium-sulfur battery containing a solid-type oxidative stress inhibitor, 6 shows an example of performance evaluation of a zinc-air battery containing a solid-type oxidative stress inhibitor, and FIG. 7 shows an example of performance evaluation of a zinc-ion battery containing a solid-type oxidative stress inhibitor, 8 shows an example of performance evaluation of an all-solid-state lithium-air battery containing a solid-type oxidative stress inhibitor, and FIG. An example of synergistic effect evaluation is shown.

That is, as can be confirmed through the above-described performance evaluation, the solid-type oxidative stress inhibitor for secondary batteries using the organometallic polymer according to the present invention is injected into the secondary battery in a solid state, and is caused by oxidative stress in the secondary battery. It can prevent deterioration of secondary battery characteristics, prevents corrosion of metal electrodes and gas generation caused by electrolyte oxidation, can prevent swelling of secondary batteries, and prevents oxidation of soluble additives in secondary batteries and It has been shown to inhibit cross-reactivity and improve forward reactivity.

Meanwhile, a secondary battery including a solid-type oxidative stress inhibitor for secondary batteries using an organometallic polymer according to an embodiment of the present invention will be described in detail below.

Here, the secondary battery may be a secondary battery using an organic electrolyte including a lithium-air battery or a lithium-sulfur battery, and may be a secondary battery using an aqueous electrolyte including a zinc-air battery or a zinc-ion battery, It may be an all-solid-state secondary battery including a solid electrolyte.

The solid-type oxidative stress inhibitor for secondary batteries using the organometallic polymer according to the present invention can be applied to these various types of secondary batteries.

Hereinafter, for convenience of explanation, the present invention will be described by way of an example grafting a lithium-air battery to a solid-type oxidative stress inhibitor for a secondary battery using an organometallic polymer according to the present invention, and the present invention is specifically limited to these examples It will be self-evident that it is not.

As shown in FIG. 11 , a secondary battery 100 including a solid-type oxidative stress inhibitor for secondary batteries using an organometallic polymer according to an embodiment of the present invention includes a negative electrode 110 , a positive electrode 120 , and the negative electrode. A separator 130, which is a separator positioned between 110 and the positive electrode 120, and the electrolyte 140 filled on the negative electrode 110 and the positive electrode 120, constituting a secondary battery It includes a solid-type oxidative stress inhibitor 150 for a secondary battery using an organometallic polymer that is disposed and fixed as one component.

The solid-type oxidative stress inhibitor 150 for a secondary battery using an organometallic polymer, which is a component of the secondary battery 100, is synthesized by selectively using an organometallic polymer including organogermanium, as described above, as described above. shall apply mutatis mutandis.

In this case, the solid-type oxidative stress inhibitor 150 for a secondary battery using the organometallic polymer is preferably manufactured as a membrane film using the organometallic polymer-based nanowire powder synthesized through the above-described process when applied to a secondary battery.

Here, the solid-type oxidative stress inhibitor 150 for a secondary battery using the organometallic polymer is shown as only one type of being positioned and fixed on the outside of the positive electrode 120, but the position in the secondary battery can be adjusted.

As described above, it can be fixedly arranged on the side of the positive or negative electrode, can be fixedly arranged between solid electrolytes or liquid electrolytes, and can be coated on a separator or electrode, or modified or modified in various ways, such as using it by itself can do it will do

Meanwhile, FIGS. 12 to 18 are data obtained by applying the solid-type oxidative stress inhibitor for a secondary battery using an organometallic polymer according to an embodiment of the present invention to a lithium-air battery and performance evaluation.

Here, a specific example in which a solid-type oxidative stress inhibitor for a secondary battery using an organometallic polymer is applied to a lithium-air battery will be described below.

That is, the lithium-air battery includes a solid-type oxidative stress inhibitor for a secondary battery using an organometallic polymer according to an embodiment of the present invention, and the solid-type oxidative stress inhibitor is a membrane membrane (hereinafter referred to as 'membrane'). Manufactured and installed.

Herein, the membrane is manufactured by synthesizing organic germanium, and is hereinafter defined as 'OG NW (Organogermanium Nanowires) membrane'.

12 and 13 , the lithium-air battery has a structure using lithium (Li) as a negative electrode and oxygen (O ₂ ) as a positive electrode, and may include a current collector.

With respect to the OG NW (Organogermanium Nanowires) membrane, at the same position as a typical gas diffusion layer, an O ₂ anode (also referred to as an 'air electrode') and a current collector plate may be inserted and disposed.

The OG NW membrane was grown on carbon fabric by freeze-drying for use as an anti-superoxide disproportionation (ASD) membrane, and the fabricated ASD membrane was denoted as an OG NW membrane.

Here, the OG NW is made of a solid-type oxidative stress inhibitor for a secondary battery using the organometallic polymer as described above, and the ASD membrane is made of an organic germanium nanowire (OG NW).

Here, the morphology and crystal structure of OG NWs were observed by field emission scanning electron microscopy (FESEM), scanning transmission electron microscopy (TEM), and small-angle X-ray diffraction (XRD).

The morphology of OG NWs exhibits a one-dimensional needle shape, as shown in FIGS. 13 (b) and (c), showing that OG NWs are individually separable without significant aggregation.

As can be seen from the TEM images shown in Figs. 13 (d) and (e), OG NWs are formed of nanowires.

In FIG. 13(d), the average diameter of OG NWs is estimated to be about 100 nm, and high-resolution TEM images of individual OG NWs show an amorphous shape consistent with the general polymer microstructure.

The scanning transmission electron microscopy-energy dispersive X-ray spectroscopy (STEM-EDS) mapping profile shows that the OG NWs are composed of a homogeneous mixture of carbon, oxygen and germanium components, suggesting that the OG NWs undergo dehydration-mediated polymerization indicates that it was successfully synthesized.

13(f) shows that the OG NW membrane is identified in the XRD pattern of a small angle corresponding to the propa germanium phase.

In addition, in the present invention, high DN or low DN solvents [eg, dimethylacetamide (DMAc), DN = 27.8; Tetraethylene glycol dimethyl ether (TEGDME), DN = 16.6)] was introduced into the OG NW membrane to examine oxygen reduction behavior and changes in Li ₂ O ₂ growth.

In the lithium-air battery, it was assembled in a form having Au coated on nickel foam as an O ₂ positive electrode (air electrode), and all Au positive electrodes were coated on Ni foam (diameter = 1 cm).

In the test for the lithium-air battery, in order to clearly determine the Li ₂ O ₂ growth behavior, no binder and conductive carbon were included in order to minimize contamination that may occur due to side effects.

First, the electrocatalyst of the OG NW membrane was identified.

Testing of a lithium-air battery including an OG NW membrane on the outer surface of an O ₂ positive electrode was performed at a current rate of 500 mAg ⁻¹ .

As shown in FIG. 14 , the lithium-air battery with the OG NW membrane is not discharged and overcharged in the subsequent charging process. The OG NW membrane appears to be inert to the electrocatalyst, and it has been demonstrated that the OG NW membrane plays a role in stabilizing the ORR/OER by anti-superoxide disproportionation (ASD) activity.

14 shows a cyclic voltammetry (CV) for O ₂ reduction during discharge in each of two solvents using 0.5M LiClO ₄ in a wide voltage range (3-2V).

As shown in (a) and (b) of Fig. 14, the low DN TEGDME shows a relatively sharp ORR peak at a voltage of 2.29V (Fig. 12a), and the high DN DMAc shows a relatively broad ORR peak at a voltage of 2.40V. have.

The ORR peak of TEGDME appears at a lower voltage than DMAc, which shows a similar phenomenon to the above DN dependence by application of the OG NW membrane.

In the case of TEGDME, when the OG NW membrane was present, the ORR peak showed a slight negative shift of 0.06V, whereas in the case of DMAc, the ORR peak showed a negative shift of 0.27V, which is 4.5 times larger.

As shown in the discharge curves of Fig. 14 (c) and (d), it shows that the OG NW membrane is supported with and without.

In both the TEGDME solvent and DMAc solvent, the onset voltage of the lithium-air battery containing the OG NW membrane was low, and the discharge capacity of the lithium-air battery containing the OG NW membrane was lower than that of the lithium-air battery without the OG NW membrane. It shows that the capacity is higher than the capacity.

This behavior is more pronounced at high DN DMAc, demonstrating that lithium-air cells with OG NW membrane provide a wider operating voltage range and larger peak area.

In addition, as can be seen from the CV graph, ORR activity is considered to operate due to the overlap of the surface adsorption pathway and the solvation-mediated growth pathway by the broad operating ORR peak, and thus the formation of Li ₂ O ₂ by the surface adsorption pathway. This can be said to have been strengthened.

Here, in the case of DN DMAc, lithium-air cells with OG NW membranes can not only operate in the high voltage range (> 2.4 V), but also Li ₂ O ₂ formation by the surface adsorption pathway can be actively operated due to capacity accumulation. It suggests that there is, and appears in the low voltage range (<2.4V).

Fig. 15 (a) shows a lithium-air battery including an OG NW membrane and a lithium-air battery without an OG NW membrane in each of the two solvents with 0.5 M LiClO ₄ A current of 0.25 mA cm-1 It shows the rectified discharge curve at speed.

In the case of TEGDME solvent, the discharge capacity (0.65 mA h cm ^-2 ) with the OG NW membrane increased by about 15% compared to the battery without the OG NW membrane (0.57 mA h cm ^-2 ), and more importantly In the case of DMAc solvent, the lithium-air battery with the OG NW membrane (1.41 mA h cm ^-2 ) has a 70% greater discharge capacity than the lithium-air battery without (0.83 mA h cm ^-2 ). have.

As shown in (b) of Figure 15, the normalized capacity curve for the DMAc solvent shows that the lithium-air battery including the OG NW membrane exhibits a lower discharge voltage stabilization of 22 mV than that of the lithium-air battery without the OG NW membrane. . In contrast, the normalized capacity curves for the TEGDME solvent show similar discharge voltage plateaus for all Li-air batteries.

The electrochemical results for such CV and rectified discharge curves show great activity in high DN solvents. Previously, in situ electrochemical surface-enhanced Raman spectroscopy showed that the imbalance supported by the solvation-mediated growth pathway in high DN solvents was dominant at high voltages (low overpotentials), and high for lithium-air cells using the same solvent. It was found that overpotential promotes a surface adsorption pathway that accelerates Li ₂ O ₂ formation through a second 1e-reduction at the expense of imbalance. That is, it was confirmed that the overpotential could increase because the resistance of the lithium-air battery could be increased by applying the OG NW membrane.

Here, electrochemical impedance spectroscopy (EIS) was used to compare the resistance of lithium-air cells containing high DN DMAc solvents at open circuit voltages before and after the discharging process, and OG NW membranes (16.7Ω ) shows that the total resistance (Rb) of the lithium-air battery is similar to the total resistance (Rb) of the lithium-air battery (15.1Ω) without it.

The charge transfer resistance (Rct) of the lithium-air battery with the OG NW membrane (207.8Ω) was slightly lower than the charge transfer resistance (Rct) of the lithium-air battery without the OG NW membrane (207.8Ω). It is confirmed that it does not affect the conductivity of the initial stage of the air cell. Rather, it was shown to suppress the spontaneous solid electrolyte interface (SEI) layer formation due to the high DN DMAc solvent at the electrode/electrolyte interface.

After the discharge process, the Rb of the lithium-air battery with the OG NW membrane (12.0Ω) was slightly higher than that of the lithium-air battery without it (8.2Ω). However, the Rct of the lithium-air battery with the OG NW membrane (353.2Ω) is much lower than the Rb of the lithium-air battery without it (502.3Ω).

This behavior appears to depend on the formation of inert by-products (e.g., Li ₂ CO ₃ ) or thick Li ₂ O ₂ , whereby the OG NW membrane inhibits the formation of parasitic products through solvation-mediated growth pathways and reduces the surface adsorption pathways. Through this, it can be said that it exhibits anti-superoxide disproportionation (ASD) ability to promote the formation of desirable Li ₂ O ₂ .

Here, the Li ₂ O ₂ growth mechanism is generally considered to be two different growth pathways, including a solvation-mediated growth pathway model and a surface adsorption pathway model, the different mechanisms affecting the performance of lithium-air batteries. have.

Here, for low DN solvents, the predominance of thin-film Li ₂ O ₂ growth is likely to lead to premature cell death due to high discharge overvoltage and small specific capacity. This Li ₂ O ₂ formation mechanism has the following surface adsorption pathway model.

O ₂ is adsorbed on the active surface of the O ₂ positive electrode in a lithium-air battery to generate adsorbed oxygen (O ₂ *) in a low DN solvent.

O ₂ * + e ^- + Li ⁺ → LiO ₂ * (1)

Here, * denotes surface adsorbed species.

LiO ₂ * + e ^- + Li ⁺ → Li ₂ O ₂ * (electrochemical reduction route) (2)

LiO ₂ * + LiO ₂ *Li ₂ → O ₂ + O ₂ * (disequilibrium) (3)

Here, the electrochemical reduction pathway is more likely to occur due to the lower kinetic barrier and free energy for LiO ₂ than the disproportionation pathway. Conversely, in the case of a high DN solvent, the adsorbed LiO ₂ * can be dispersed.

LiO ₂ (sol) + LiO ₂ (sol) → Li ₂ O ₂ + O ₂ (4)

Toroidal Li ₂ O ₂ grows as a solvation-mediated growth pathway model through disproportionation of soluble LiO ₂ (sol), which is called a solution mechanism. The predominance of toroidal Li ₂ O ₂ growth can maintain a higher specific discharge capacity and lower over-discharge voltage than low DN solvents. Unfortunately, high DN solvents that favor solvation-mediated pathways can promote parasitic reactions leading to high charge overpotentials and low discharge charge reversibility. A major factor in parasitic reactions is the solvation of superoxide intermediates by electrolyte interactions with Li ⁺ or O ₂ ⁻ through solvents and salts. Recent studies have shown that parasitic reactions are caused by single oxygen ( ¹ O ₂ ) during discharging and charging. Overall, the cause of the generation of single oxygen ( ¹ O ₂ ) during discharge seems to be the disproportionation of the peroxide in the presence of Li ⁺ or H ⁺ . Accordingly, it can be said that the parasitic reaction is inhibited by preventing the imbalance of superoxide species.

15 (c) and (d) show the Raman spectrum for the Au anode with or without the OG NW membrane, and in the case of the Au anode without the OG NW membrane, the Raman spectrum is O ₂ ^- 1107 cm ^- assigned to A distinct characteristic peak around ¹ is shown.

As demonstrated by the disappearance of the peak for O ₂ ⁻ in the case of Au anode with OG NW membrane, this result can be said to be in exact agreement with preventing the imbalance of peroxide by ASD activity. Accordingly, as shown in (e) and (h) of FIG. 15 , the role of the OG NW membrane is demonstrated by the morphological characteristics of Li ₂ O ₂ after discharge.

In the case of TEGDME, the FESEM image of the Au anode without the OG NW membrane at a full discharge voltage of 2.0 V shows that the Li ₂ O ₂ discharge product has a large flower-like shape (1–2 μm in diameter) (Fig. 15e). . It has been shown that the low DN solvent provides an electrochemical reduction pathway (ie, a model of the surface adsorption pathway) due to the lower kinetic barrier and free energy for LiO ₂ than the disproportionation pathway.

As a result, it can be said that the fast growth mode _of Li ₂ O ₂ contributes to the formation of thin structures such as films and flower-like morphologies _. An Au anode without the absence of the Au anode is produced. That is, some LiO ₂ * readily diffuses into the electrolyte, indicating the formation of LiO ₂ (sol) and rapidly forming micrometer-sized flower-like Li ₂ O ₂ .

On the contrary, in Fig. 15(f), in the case of the Au anode with the OG NW membrane, the Li ₂ O ₂ discharge product is assembled with a much smaller diameter (<500 nm) than the Au anode without the OG NW membrane. This behavior follows a strong surface adsorption pathway and appears to block LiO ₂ * diffusion into the electrolyte by ASD activity, in contrast to Fig. The ₂ O ₂ product shows a toroidal shape with a diameter of about 500 nm.

In addition, in FIG. 15(f), when the OG NW membrane is present, the shape of the Li ₂ O ₂ product of the Au anode appears to be quite different, and the toroidal shape disappears.

Here, the difference in Li ₂ O ₂ morphology was further measured via atomic force microscopy (AFM) 3D imaging (height and amplitude profiles), AFM on the surface of Au anode without OG NW membrane and Au anode with OG NW membrane. Images are shown in FIGS. 15 (i) and 15 (j). The AFM image of Au anode clearly shows the conformational change of Li ₂ O ₂ after full discharge due to the ADS activity of the OG NW membrane.

Here, the AFM image of the Au anode without the OG NW membrane shows that the maximum height is about 150 nm for large particles, whereas the AFM image of the Au anode with the OG NW membrane shows the maximum height of about 40 nm with the large particles. shows that it has

As such, it can be said that the shape is formed on the surface _of the Au anode by the anti _- superoxide disproportionation (ASD) effect and demonstrates a strong surface reaction. It shows that it is flatter than the shape of the non-Au anode. In particular, in the presence of the OG NW membrane, the Li ₂ O ₂ product inhibits vertical grain growth toward the electrolyte and promotes growth on the surface of the Au anode, indicating that the surface adsorption pathway is dominant.

Next, paying attention to the relationship of parasitic reactions after investigating the morphological differences of Li ₂ O ₂ products, X-ray photoelectron spectroscopy (XPS) analysis of the composition of the Li ₂ O ₂ product formed on the Au anode with or without OG NW membrane , and the Li 1s spectrum of the two Au anodes shows the formation of Li ₂ O ₂ at a binding energy of 54.5 eV and the formation of residual lithium salt (LiClO ₄ ) containing the compound at a binding energy of 56.4 eV, respectively. The C 1s spectrum shows that the two Au anodes are covered with carbonaceous contamination with an SEI layer at a binding energy of 284.7 eV.

The O 1s spectra of the two Au anodes show the formation of Li ₂ O ₂ at a binding energy of 531.5 eV. Importantly, the Li 1s, C 1s and O 1s spectra for the Au anode without the OG NW membrane indicate the presence of significant amounts of by-products such as Li ₂ CO ₃ at binding energies of 55.5, 289.4 and 532.1 eV, respectively. This XPS spectrum is consistent with the electrolyte decomposition during discharge in the Li-O ₂ battery, indicating that most of Li ₂ CO ₃ comes from the peroxide imbalance.

That is, in the present invention, by applying the OG NW membrane, deterioration due to peroxide imbalance was successfully removed, thereby achieving a stable electrolyte and improved capacity performance.

In addition, inhibition of parasitic reactions by the OG NW membrane suggests that singlet oxygen, superoxide radicals and hydroxyl radicals are important controlled intermediates in Li-O ₂ cell chemistry, and reactivity with superoxides, as shown in Fig. 16 . was evaluated by the titration method, and it was possible to confirm the anti-superoxide disproportionation (ASD) activity of the OG NW membrane in DME where the well-known KO ₂ and water disproportionation reaction occurred.

2KO ₂ + H ₂ O → 2K ⁺ + 2O ₂ ^- + H ₂ O (5)

When KO ₂ was added to a CoCl ₂ -DME solution saturated with 2000 ppm of water, spontaneous oxygen gas evolution and precipitation of cobalt (III) oxyhydroxide (CoOOH) were induced, and the solution gradually became colorless after 43 hours. Over time, the reaction between Co ²⁺ ions and O ₂ ⁻ was changed from initial blue to colorless stepwise. The concentration of Co ^II species (CoCl ₂ ) in all solutions decreased in proportion to the increase of Co ^III species (CoOOH) according to the UV-vis absorption analysis results (see FIGS. 16b and 16c ).

Here, the UV-vis spectrum of the solution showed a broad signal of 500 to 750 nm (see FIG. 16b ) corresponding to blue, which may be due to the presence of Co ²⁺ ions in octahedral and tetrahedral coordination. After 43 hours, when KO ₂ and water were added, UV-vis absorption signals of two saturated CoCl ₂ -DME solutions containing OG NW or commercial Ge-132 were still observed, unlike the case of pure CoCl ₂ -DME solution (control). became The results show that OG NW can effectively prevent oxidative stress as a reducing agent acting as an electron acceptor and metal chelator.

In addition, in the UV-vis absorption spectrum of each OG NW or CoCl ₂ -DME solution containing organic germanium in (c), the reaction of OG NW and O ₂ ^- was delayed compared to the reaction of organic germanium. are giving The chromaticity diagram of the CoCl ₂ -DME solution containing OG NW is closer to blue than the CoCl ₂ -DME solution containing organogermanium. In other words, it can be said that the application of OG NW membrane in chemical and electrochemical tests proves that peroxide attack is prevented.

In addition, in the present invention, anti _- superoxide disproportionation (ASD) mechanism of OG NW membrane due to KO ₂ imbalance was investigated. ) was added to the solution. Since the OG NW membrane has a unique chemical structure, it can induce high-efficiency ASD s1 activity through multiple pathways (see Fig. 17).

Here, the first pathway occurs through the Ge–O link, and the ASD activity of the OG NW membrane is triggered by the hydrolysis of the Ge–O link, which promotes the conversion of reactive superoxide species, and the conversion to stable chemical species. The OG NW membrane catalyzing the reaction reduces the oxidized Ge-O links by reacting with reactive O ₂ ⁻ and then oxidizes the reduced Ge-O links. Fourier transform infrared spectroscopy (FTIR) results show that the hydrolysis evidence is strongly assigned to binding of the OG NW membrane at ~3000 cm ⁻¹ (CH stretch), 1692 cm (CO stretch). 1432 cm ^-1 (CH stretch) and 1413-1253 cm ^-1 (OH stretch) than the activated OG NW membrane. In addition, the peak of the OG NW membrane by O 1s XPS spectrum shows a negative shift from the binding energy of 532 eV(OH ^- ) to the binding energy of 530.8 eV (O ₂ ^- ) after ASD activity.

Overall, it appears that the hydroxyl and organic fragment peaks are attenuated after ASD activity according to the hydrolysis assignment, and as a result, it can be confirmed that the ASD activity is related to hydrolysis.

Here, the second pathway occurs through Ge–C bonding leading to electron scavenging. The OG NW membrane has a unique chemical structure with Ge-C bonds, which tends to cause electron transfer between Ge and reactive O ₂ ⁻ . According to the NMR spectra, the chemical shifts of the 13C and 1H NMR spectra are not significantly altered in the OG NWs before and after ASD activity. In the FTIR results, the peak of the Ge-O-Ge bond was observed to be weakened after ASD activity, indicating cleavage of the Ge-O-Ge bond.

Thus, the Ge-C bond was demonstrated to have a stable carbon frame in situ.

In other words, the OG NW membrane reacts with reactive O ₂ ⁻ to reduce the oxidized Ge–O linkages and catalyze them to convert to stable chemical species, while the Ge–C bond acts as an electron transfer between Ge and reactive O ₂ ⁻ . tends to That is, the Ge-C bond receives electrons from the reduced Ge-O link and induces electron scavenging which oxidizes the reduced Ge-O link. Organogermanium polymers appear to modulate both immune responses and leukocyte functions in vivo due to their high reactive oxide scavenging activity, and this mechanism can be beneficially utilized for superoxide capture and conversion, thereby reducing oxidative damage caused by oxidative stressors during cycling. can be reduced

After investigating the differences in Li ₂ O ₂ growth pathways on ASD activity, rechargeable battery performance with ASD membranes was tested, and rectifying discharge-charge cycling in OG NW membranes to explore the role of ASD effects on lithium-air cells. The test was performed, and is shown in FIG. 17 .

To evaluate the practical application of the OG NW membrane, the lithium-air battery was assembled with a nickel foam coated with RuO2@ graphene composite as an O ₂ positive electrode, and the RuO ₂ @G positive electrode with a loading mass of ~0.6 mg cm ^-2 . prepared.

In (a) of FIG. 18, the lithium-air battery with the OG NW membrane and the lithium-air battery without the OG NW membrane were galvanostatically cycled using the LiNO ₃ -DMAc electrolyte at a current rate of 200 mA g ^-1 .

Here, the charge overvoltage was much smaller up to 0.37 V for the lithium-air cell with OG NW membrane than without the OG NW membrane. In most cycles, the charge curves show similar behavioral stagnation. As shown in Fig. 18(b), the discharge and charge stable voltages and overpotentials were collected for each RuO ₂ @G anode, and both RuO ₂ @G anodes shows similar discharge stagnation voltage values during 90 cycles, but there is a significant difference in charge stagnation voltage values.

Specifically, the RuO ₂ @G anode using the OG NW membrane shows an overvoltage value that is about 0.4V lower than the RuO ₂ @G anode without the OG NW membrane, which appears to be controlled by stable battery performance. The RuO ₂ @G anode with OG NW membrane shows that the parasitic reaction on the anode surface is suppressed. After the charging process, RuO ₂ @G anodes without OG NW membranes were observed by FESEM with many irreversible particles due to various parasitic reactions in contrast to RuO ₂ @G anodes using OG NW membranes.

XPS analysis was used to characterize the formed irreversible particles, and the Li 1s spectrum shows the irreversible formation of Li ₂ CO ₃ on the surface of the charged anode.

Here, the lithium-air battery has a major problem with respect to stability, which will be described as follows.

(i) RuO ₂ shows the instability of the inorganic electrolyte, which can lead to severe cycle collapse of the lithium-air battery accompanied by CO ₂ gas evolution. (ii) Excessive amount of LiNO ₃ salt can react with the carbon material of the anode to passivate the carbon surface. (iii) Parasitic products such as Li ₂ CO ₃ and CO ₂ gas are also produced when the voltage rises above 4V with LiNO ₃ salt due to oxidative decomposition of electrolyte or carbon electrode.

As a result, the charge potential can gradually increase due to by-products, and it can be seen that the OG NW membrane clearly reduces the formation of Li ₂ CO ₃ to greatly reduce the charge potential, effectively inhibits oxidative damage, and Reduction and oxidation reactions can be maintained stably. The DME solvent has a medium DN (20.0) and makes a significant contribution in both the solution and surface pathways, which occurs simultaneously at high voltage (low overvoltage). During the charging process, the redox couple acts as a suitable medium for Li ₂ O ₂ decomposition and corresponds to the redox-related stabilizer in the electrochemical reaction of I ^- / I ₃ ^- (3.05 V vs. Li/Li ⁺ ). Unfortunately, water additives can promote an imbalance of superoxide species in the presence of solvated Li ⁺ or O ₂ ⁻ , which triggers a solvation-adsorption pathway leading to toroidal Li ₂ O ₂ growth. Consequently, disproportionation of superoxide species in the presence of H ₂ O or other proton source appears to be the ¹ O ₂ source upon discharge.

In the present invention, it was demonstrated that the OG NW membrane can effectively inhibit the above parasitic reaction. Fig. 18 (c) shows the electrochemical performance of a lithium-air battery using the OG NW membrane, 200 mAg ^-1 When cycling at the current rate, the overvoltage is only ~0.06V, which is the lowest overvoltage reported to date, showing that at higher current rates the overvoltage becomes wider and increases to 0.58V at 5000mAg ^-1 . At current rates of 200 and 1000 mAg ^-1 , the lithium-air cell with OG NW membrane exhibits a very low overpotential value of less than 0.2 V and a terminal charging voltage of ~3.1 V, which is also in good agreement with the thermodynamic equilibrium potential. have. The low redox potential of LiI-RM is important in terms of long-term durability of the electrolyte, which can prevent certain harmful side reactions, but at current rates of 200 and 1000 mAg ^-1 , lithium-air cells without OG NW membrane lose their capacity after 100 hours. shows a significant decrease.

In (d) and (e) of Figure 18, when the current speed is increased to 1000mA ^g-1 , stable cycling is maintained with an overvoltage of less than 0.2V for 250 or more times, and the ASD activity of the OG NW membrane is the cause of the parasitic reaction. It has been shown to effectively prevent O ₂ formation.

Hereinafter, specific examples for carrying out such a test will be described.

1. Material preparation

DME (Acros Organics, 99+%), TEGDME (Sigama-Aldrich, 99+%) and DMAc (Acros Organics, 99.5%) were stored on molecular sieves (Alfa Aesar, 3 Å) under argon, and the molecular sieves were mixed with ethanol and acetone. and dried in an oven at 150° C. under vacuum for 24 hours, LiClO ₄ (Sigma-Aldrich, 99.99%), LiNO ₃ (Sigma-Aldrich, ReagentPlus), LiTFSI (Sigma-Aldrich, 99.95%) and LiI (Sigma). -Aldrich, 99.999%) was dried in a freeze dryer for 12 hours. Before using for electrolyte preparation, CoCl ₂ (Sigma-Aldrich, 97%) was dried in a freeze dryer and then stored in a glove box filled with Ar and used to prepare a titration solution. Graphene and RuCl ₃ ·xH ₂ O (99%) were respectively provided. Cetyl trimethyl ammonium bromide (CTAB; Sigma-Aldrich, 95%), KO ₂ (Sigma-Aldrich) and Ge-132 (Sigma-Aldrich, 99%) were prepared.

All materials were stored in an Ar-filled glove box before being used for testing, and an electrolyte or DME-based solution containing a water additive was prepared by adding distilled water (18.2 MΩcm) to a dry solvent outside the glove box.

2. Preparation of OG NW Membrane

OG NW powder (0.15 g) was dissolved in 10 mL of distilled water with 1 mL of isopropyl alcohol. Carbon cloth (W0S1002, CeTech) was immersed in the prepared solution and then frozen overnight at -5°C in a refrigerator and then dried in a freeze dryer for 24 hours.

3. Preparation of RuO ₂ @graphene

Graphene (0.02 g), RuCl ₃ ·xH ₂ O (0.015 g) and CTAB (1 g) were dispersed in 25 mL of distilled water and ethanol (4: 1, v/v). The solution was sealed in a 30 mL Teflon lined stainless steel autoclave and heated to 150° C. for 10 hours. The autoclave was cooled to room temperature, and the obtained particles were washed several times with a nylon membrane (Durapore, 0.22 mm, Millipore) using distilled water, filtered, and dried at 70° C. overnight. The obtained particles were heat-treated at 500° C. for 2 hours and then heat-treated at 800° C. for 5 hours under a N2 flow of 100 sccm.

4. Material Characterization

The morphology and topological evolution of the samples were investigated using TEM (Talos F200X, FEI), FESEM (S-4300, Hitachi) and XRD (Smartlab, Rigaku). The wavelength of copper K-alpha X-ray used for XRD analysis (λ is 1.5404 Å, data were collected in the 2θ range of 5.3° to 17.7°. STEM-EDS (Talos F200X, FEI) was used to investigate the chemical composition of the sample. to obtain element mapping data, and 1 H NMR and 13 C NMR spectra were recorded on a 500 MHz NMR instrument (Unity Inova, Varian Technology). OG NW was dissolved in DO at 298 K at a concentration of 5 mg/mL. The chemical interactions of the samples were Measured by FTIR and Raman (LabRam ARAMIS IR2, Horiba Jobin Yvon) and XPS (K-Alpha+, Thermo Fisher Scientific Messtechnik). To detect solvated superoxide species on the anode surface, the sample preparation consists of a discharged discharge containing electrolyte. Consists of rapidly transferring the anode to liquid nitrogen and freezing for 1 hour.After discharge, surface observation was performed with AFM (XE-7, Park Systems, Korea) in NCHR non-contact mode. Here, the scan size of the AFM image is 1 × It was set as 1 micrometer ² .

5. Assembly and Characterization of Lithium-Air Cells Containing Au Anodes

Lithium-air cells with and without OG NW membrane were evaluated using Swagelok type cells. To prepare an Au anode, Ni foam (diameter = 1 cm) was coated with Au using an ion coater (ionization current 3 mA, SPT-20, COXEM). To prepare a TEGDME or DMAc-based electrolyte, 0.5M LiClO ₄ was dissolved in TEGDME or DMAc solvent. Lithium-air batteries were assembled in Ar-filled glove boxes. The lithium-air battery was composed of a Li-foil negative electrode, a glass fiber separator (Whatman), an Au positive electrode, and an OG NW membrane in two prepared electrolytes. All measurements were performed in 1.5 atm of dry O ₂ to avoid negative effects of humidity and CO ₂ . The assembled lithium-air cells were tested at room temperature with an automatic battery cycler (WBCS 3000, WonAtech).

6. Assembly and Characterization of Lithium-Air Cells Containing RuO ₂ @G Anodes

RuO ₂ @G ink was prepared by mixing RuO ₂ @G (80wt%) and carboxymethylcellulose (20wt%, Aldrich average Mw 700000 or less). RuO ₂ @G anode (mass load of ~ 0.6 mg cm ^-2 ) was prepared by uniformly coating RuO ₂ @G ink on nickel foam. To prepare a DMAc-based electrolyte, 1M LiNO ₃ was dissolved in DMAc. For the DME-based electrolyte, 0.2 M LiTFSI and 0.2 M LiI were dissolved in DME with 1000 ppm distilled water. The prepared electrolyte was stored in a glove box filled with Ar for 1 day before being used for testing. Lithium-air batteries were assembled in Ar-filled glove boxes. The lithium-air battery was composed of a Li-foil negative electrode, a glass fiber separator, a RuO ₂ @G positive electrode, and an OG NW membrane in two prepared electrolytes. All measurements were performed in 1.5 atm of dry O ₂ to avoid negative effects of humidity and CO ₂ . The assembled lithium-air cells were tested with an automatic battery cycler (WBCS 3000, WonAtech) in a voltage window of 2.5-4.5 V at room temperature.

7. CoCl ₂ and CoI ₂ -DME solution preparation and ASD activity test

CoCl ₂ (0.3 g) was dissolved in 100 mL of DME. ADS capacity was investigated using completely dissolved species, and the disproportionation reaction was initiated by adding 0.03 g of KO ₂ and 0.2 mL of deionized water to the prepared solution. The content of OG NW and organic germanium was 0.3 g, respectively.

Accordingly, through the present invention, it is possible to suppress side reactions that may occur inside various secondary batteries including organic, aqueous, or solid electrolytes, prevent oxidation of electrolytes, and prevent corrosion of secondary batteries using metal electrodes. It is possible to provide a solid-type oxidative stress inhibitor for a secondary battery using an organometallic polymer, a secondary battery including the same, and a lithium-air battery.

The embodiments described above are merely illustrative of preferred embodiments of the present invention and are not limited to these embodiments, and various modifications and variations or modifications by those skilled in the art within the spirit and claims of the present invention It will be said that the substitution of steps may be made, and this will be said to be within the scope of the technical rights of the present invention.

100: secondary battery
110: cathode electrode
120: positive electrode
130: separator
140: electrolyte
150: solid oxidative stress inhibitor

Claims (21)

(A) dissolving the organometallic polymer in a mixed solvent;
(B) immersing the fiber-based material in a solution in which the organometallic polymer is dissolved;
(C) freezing the result of step (B);
(D) growing an organometallic polymer by freeze-drying the frozen product of the step (C) to obtain an organometallic polymer-based powder; A solid-type oxidative stress inhibitor for secondary batteries using an organometallic polymer, characterized in that it is synthesized as The method of claim 1,
The organometallic polymer is
Organic germanium (Propa germanium), zinc acetate (Zinc acetate), sodium selenite (Sodium selenite), silicon tetra acetate (Silicon tetraacetate), characterized in that at least one or more of sodium metasilicate (Sodium metasilicate) is used A solid-type oxidative stress inhibitor for secondary batteries using an organometallic polymer. 3. The method of claim 2,
The organic germanium is
O[Ge(=O)CH ₂ CH ₂ CO ₂ H] ₂ } A solid-type oxidative stress inhibitor for secondary batteries using an organometallic polymer, characterized in that it is. The method of claim 1,
The mixed solvent is
Distilled water (H ₂ O): isopropyl alcohol = 9-12: Solid-type oxidative stress inhibitor for secondary batteries using an organometallic polymer, characterized in that it is mixed in a volume or weight ratio of 0.8-1.2. 5. The method of claim 4,
A solid-type oxidative stress inhibitor for a secondary battery using an organometallic polymer, characterized in that 0.1 to 10g of the organometallic polymer was dissolved in the mixed solvent. The method of claim 1,
The fiber-based material,
A solid-type oxidative stress inhibitor for secondary batteries using an organometallic polymer, characterized in that it is a fabric made of carbon fiber. The method of claim 1,
The step (C) is,
A solid-type oxidative stress inhibitor for a secondary battery using an organometallic polymer, characterized in that it is frozen at -5 to 10° C. for 10 to 20 hours. The method of claim 1,
The step (D) is,
A solid-type oxidative stress inhibitor for secondary batteries using an organometallic polymer, characterized in that it was freeze-dried at -30 to 50° C. for 18 to 24 hours. The method of claim 1,
The organometallic polymer powder obtained in step (D) is a solid-type oxidative stress inhibitor for a secondary battery using an organometallic polymer, characterized in that it is a nanowire type particle. 10. The method of claim 9,
The organometallic polymer powder obtained in step (D) has an average diameter of 80 to 100 nm. A solid-type oxidative stress inhibitor for secondary batteries using an organometallic polymer. 11. The method according to any one of claims 1 to 10,
The solid-type oxidative stress inhibitor for secondary batteries,
Lithium-air battery, lithium-sulfur battery, zinc-air battery, zinc-ion battery, solid-state oxidative stress inhibitor for secondary batteries using an organometallic polymer, characterized in that it is grafted to any one group of all-solid secondary batteries. A secondary battery comprising a solid-type oxidative stress inhibitor for a secondary battery using an organometallic polymer, wherein the secondary battery is fixedly arranged and used as a component in the secondary battery. 13. The method of claim 12,
The solid-type oxidative stress inhibitor for a secondary battery using the organometallic polymer is a secondary battery, characterized in that it consists of any one of claims 1 to 10. 13. The method of claim 12,
The solid-type oxidative stress inhibitor for a secondary battery using the organometallic polymer is a secondary battery, characterized in that it consists of a membrane membrane. 15. The method of claim 14,
A secondary battery, characterized in that the solid-type oxidative stress inhibitor for secondary batteries using the organometallic polymer can be used by changing the arrangement position in the secondary battery. In a lithium-air battery comprising a lithium negative electrode, an O ₂ positive electrode, and a separator disposed between the lithium negative electrode and the O ₂ positive electrode,
A lithium-air battery, characterized in that a solid-type oxidative stress inhibitor for a secondary battery using an organometallic polymer is fixed to the outside of the O ₂ positive electrode. 17. The method of claim 16,
The solid-state oxidative stress inhibitor for a secondary battery using the organometallic polymer is a lithium-air battery, characterized in that it comprises any one selected from among 1 to 10. 17. The method of claim 16,
The solid-state oxidative stress inhibitor for secondary batteries using the organometallic polymer is a lithium-air battery, characterized in that it consists of a membrane membrane. In a lithium-air battery comprising a lithium positive electrode, an O ₂ negative electrode, and a separator disposed between the lithium positive electrode and the O ₂ negative electrode,
A lithium-air battery, characterized in that a solid-type oxidative stress inhibitor for a secondary battery using an organometallic polymer is fixedly disposed on the separator, or the separator itself is configured with a solid-type oxidative stress inhibitor for a secondary battery using an organometallic polymer. 20. The method of claim 19,
The solid-state oxidative stress inhibitor for a secondary battery using the organometallic polymer is a lithium-air battery, characterized in that it comprises any one selected from among 1 to 10. 20. The method of claim 19,
The solid-state oxidative stress inhibitor for secondary batteries using the organometallic polymer is a lithium-air battery, characterized in that it consists of a membrane membrane.

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