KR20160055710A - Method of preparing a glass ceramic ionic conductor - Google Patents

Abstract

The present invention relates to a method of manufacturing a glass ceramic ionic conductor. The method includes the following steps: providing a recycling material from spent batteries containing a glass ceramic ionic conductor; melting the recycling material; adding a raw glass material; homogenizing the melted material; forming a glass; and ceramizing the glass. By using the recycling material from spent batteries, an ionic conductor which is similar to the conventional glass ceramic ionic conductor (e.g. an LiSiCon structure), in particular, suitable as a solid-state electrolyte can be produced.

Description

TECHNICAL FIELD [0001] The present invention relates to a glass ceramic ion conductor,

The present invention relates to a method for producing glass-ceramic ion conductors.

Regarding the regenerative battery or the accumulator, the prior art has focused on regeneration of the metal from the used battery. At this time, the battery must be fully discharged in a verbose manner and disassembled into its parts. Thereafter, chemical regeneration of the individual metals is typically carried out. This process is tedious and costly. Regeneration of liquid electrolytes conventionally used today is technologically complex and usually not cost effective. Throughout this application the term "battery" should be understood to also include a rechargeable battery (battery).

Partial solid electrolytes are used in future battery designs. Compared to a liquid electrolyte or a polymer electrolyte, the solid electrolyte has an advantage that it is not flammable. Moreover, they typically do not produce harmful reaction products upon contact with air or water. However, solid electrolytes usually contain rare and expensive starting materials such as rare earths, noble metals or germanium. The starting materials make it difficult to use solid electrolytes on a large scale due to their price and partly poor availability.

Various methods for regeneration of the metal from the battery are known. For historical reasons, many of these methods have been associated with the regeneration of lead from lead-acid batteries (see for example US 3,395,010). Also for regeneration of cadmium and nickel (DE 1 583 874 A1), methods for the recovery of zinc and manganese from waste products of zinc-carbon-manganese oxide batteries are known (EP 0 158 627 A2).

A regeneration method for a more recent lithium battery is also known. According to KR 100796369 B, a complicated method for enabling the regeneration of contained plastics from a separator is also known. However, the regeneration is usually for the contained metals, especially lithium (JP 2010-040458 A, US 2014/0069234 A1, US 2014/174256 A1, US 2014/060250 A1, US 2014/0102256 A1). In all of the above methods, the discharged battery is separated and melted as non-mixed as possible.

It is also known to use liquid chemical methods, or a combination of chemical production and heating (see US 2014/0227153 A1 and US 2013/0313485 A1).

Regeneration of solid electrolytes is described only indirectly. Thus, in US 2005/0100793 Al, regeneration of lithium from various battery components, particularly also from solid electrolytes, is known. However, only the regeneration of lithium is covered.

In this respect, it is an object of the present invention to disclose a process for the production of cost effective and environmentally pollutible, solid electrolytes.

This object is achieved by a method for producing a glass ceramic ion conductor,

- Providing a recycling material from a used battery comprising a glass ceramic ion conductor;

- Adding a glass raw material;

- Melting the recycling material;

- Homogenizing the melt;

- Forming a glass and transforming it into a glass ceramic

≪ / RTI >

The problem of the present invention is completely solved in this way.

According to the present invention, during the production of the glass ceramic ion conductor, the recycling material from the used battery is mixed and the melting process is performed, thereby making it possible to use the recycling material in a cost-effective manner in a simple manner. This method is particularly simple, cost effective and environmentally pollution-free since no special chemical processes are required for selective regeneration of individual components.

In some cases the conversion to glass ceramics occurs naturally during cooling of the glass, but in most cases a specific tempering process (ceramification) is performed to achieve the transformation into a glass ceramic.

According to a further development of the present invention, the pre-melting regeneration material is heated at a temperature of from 500 ° C to a maximum of 650 ° C, preferably in the range of from 550 ° C to 620 ° C, in particular, in order to discharge undesired residues, especially organic residues Lt; RTI ID = 0.0 > 600 C. < / RTI >

In this way, unwanted organic residues can be released safely. Therefore, pre-separation of the organic regeneration material from the residue is not necessary. However, depending on the nature of the residue, and also depending on the composition of the reclaimed material, the separate calcination may be omitted, since the residues will also dissolve during normal melting. However, when a separate calcination is used, it can be ensured that by a special process sequence, especially at a temperature lower than the melting temperature, the residue can be discharged safely without dissolving the residue in the melt.

Preferably, the regenerant material is initially melted separately, cooled and milled, then mixed with the glass raw material and melted.

In addition, preferred solid electrolytes and / or electrode portions from the used batteries, particularly the lithium-ion batteries used, are used as recycling materials. The regenerant material may contain only an electrolyte, especially a solid electrolyte, contain an adhesive material or a contained substance with the electrolyte, or may contain an organic component and part of the electrolyte, in particular an anode and possibly a separator, together with the electrolyte.

The melting of the recycled material and the glass raw material is preferably carried out under oxidizing conditions, preferably at a temperature of more than 700 占 폚.

In this way, undesired reduction of the contained ions (for example, reduction of Ti ⁴⁺ to Ti ³⁺ in the LiSiCon compound), which may interfere with the production of the ion conductor, is prevented because it causes unwanted electrical conductivity.

This can be accomplished by melting under air, or by making further measurements to stabilize the oxidation conditions, e.g., by oxygen bubbling.

Preferably, the method according to the invention can also be used for the production of lithium ion conductors. However, other glass ceramic ion conductors, such as sodium ion conductors, potassium ion conductors, magnesium ion conductors, etc., may also be used or manufactured, respectively.

The process according to the invention can be carried out in the presence of a lithium germanium phosphate phase, a lithium titanium phosphate phase, a lithium zirconium phosphate phase, a lithium lanthanide zirconate phase, a lithium lanthanum titanate phase, a spinel phase, a garnet phase or a similar phase, lt; / RTI > phase as a glass ceramic.

However, also a glassy or partially crystalline electrolyte system can be used when the melting temperature exceeds 700 DEG C, and when the melting can be performed under oxidizing conditions.

A preferred application is a glass ceramic ion conductor comprising a NaSiCON crystalline phase or a lithium compound which is analogous thereto, and in particular its isostructure, for example a solid electrolyte originally known from the prior art which is fully incorporated by reference (DE 10 2011 013 018 B3 ).

Wherein the glass ceramic is used as a glass ceramic ion conductor comprising Li _{1 + xy} M ⁵⁺ _y M ³⁺ _x M ⁴⁺ _2-xy (PO ₄ ) ₃ wherein 0? _X , y? 1 + xy) > 1, and M is a cation having a valence of +3, +4 or +5.

Preferably wherein M ⁵⁺ is configured as a Ta ⁵⁺ and / or Nb ⁵⁺ / or configured,

M ³⁺ is composed and / or composed of Al ³⁺ , Cr ³⁺ , Ga ³⁺ and / or Fe ³ ,

M ⁴⁺ is composed of Ti ⁴⁺ , Zr ⁴⁺ , Si ⁴⁺ and / or Ge ⁴⁺ .

When glass ceramics are prepared as glass-ceramic ion conductors containing garnet-type crystal phases, this can be carried out according to US 2014/0057162 Al, which is hereby incorporated by reference in its entirety.

Thus, glass ceramics include garnet-type crystalline phases of the total formula:

Li _{7 + vw} M _v ²⁺ M _{3 -v} ³⁺ M _{2 -w} ⁴⁺ M _w ⁵⁺ O ₁₂

In the formula, M ²⁺ is the cation of valency 2, M ⁺³ is a trivalent cation, and M is a ⁴⁺ valence 4 cations, M ⁵⁺ is a pentavalent cation, preferably 0≤v <3, more preferably 0? V? 2, 0? W <2, and particularly preferably 0? W <

Garnet-type solid ion conductors tend to have natural crystallization. The production of amorphous glass is not possible (at normal cooling rates), but is not necessary, because the desired crystalline phase naturally crystallizes.

Preferably at least 5% by weight, preferably at least 10% by weight, of regenerable material is added to produce a glass ceramic ion conductor. Even if the recycled material is not completely pure and rather varied in composition, up to about 70% by weight of the recycled material may be added. By adding recycled materials, melting behavior is generally improved, as is theoretically known in the art of making glass when glass cullet is added.

If the composition of the recycled material is fully and exactly known, the share of recycled material can be further increased to about 90% by weight or 95% by weight. If the composition of the regenerating material is sufficiently pure, basically melting of the regenerating material is also possible without addition of additional glass raw material.

Preferably, the mixture of raw materials is adjusted to a known or nearly known composition of the reclaimed material so that the desired composition is kept as precisely as possible.

Preferably, in order to obtain a recycling material, the battery used, especially the lithium-ion battery, is first fully discharged and then disassembled. After the liquid electrolyte that may be present is removed, the selected portions, especially the anode (e.g. lithium foil), the separator, and the solid electrolyte that may be present, may be used as long as they do not impair the properties of the glass- do. If the cathode is made of, for example, graphite or silicon oxide, as long as it does not contain the components in question, they can also be used.

When the recycled material is homogenized and refined as a glass melt together with the glass raw material, the molding may be carried out by any known molding method such as casting, drawing, rolling, foil casting, for example by draw-down- fusion process. Furthermore, further processing by subsequent powder production, coating method, screen printing or the like is also possible by adding a polymer component in general.

Basically, the glass-ceramic ion conductors produced in accordance with the present invention are particularly suitable for use with any suitable battery system, especially a lithium-ion battery, an all-solid-state battery, a lithium-air battery, As a solid electrolyte or as an electrolyte additive.

In the present application, all known methods of integration, such as direct use as a solid electrolyte, use as a thin layer or a thin film, or use as part of an electrolyte together with other materials can be considered. Also, the use as an electrode or other part, for example as a coating on a receiving part, is possible, preferably by adding a polymer additive as a binder.

In the present application, a glass ceramic is a material starting from a green glass produced by melting and deformed (ceramicized) into a glass ceramic (including a glass phase and a crystal phase) by a temperature treatment under controlled conditions do.

The composition in the present application should always be understood as being in the form contained therein, or as an open composition in which any additional components may be contained as long as they are provided in a form containing the specified ingredients .

However, in another aspect of the present invention, the proposed composition should be understood to include only those specific ingredients present therein (closed composition), but due to the nature of the glass manufacturing, there may also be unavoidable impurities. Depending on the purity of the raw materials used, these unavoidable impurities may be limited to a maximum of 1 wt.%, Preferably 0.5 wt.%, More preferably 0.1 wt.%, Or even 0.05 wt.%.

As long as these compositions are presented in the form of a specific component, the compositions in the present application should always be understood to contain those components only (the closed composition), but inevitable impurities may be contained due to the nature of the production of the glass. Depending on the purity of the raw material used, these unavoidable impurities are limited to a maximum of 1 wt.%, Preferably 0.5 wt.%, More preferably 0.1 wt.%, Or even 0.05 wt.%.

In the present application, as long as the compositions in the examples are shown by listing specific components, the data should be understood as a closed composition, but inevitable impurities may be contained in manufacturing characteristics. Depending on the purity of the raw materials used, these unavoidable impurities may be limited to a maximum of 1 wt.%, Preferably 0.5 wt.%, More preferably 0.1 wt.%, Or even 0.05 wt.%.

It is to be understood that the features of the invention mentioned above and described below can be used in different combinations or independently without departing from the scope of the invention, as well as the combinations provided.

Additional features and advantages of the present invention will become apparent from the following description of the preferred embodiments.

Example 1

5.5 wt% Al ₂ O _3, 4.5 weight% Li ₂ O, 47 wt% P ₂ O _5, 21 wt% Ta ₂ O _5, 16 wt% TiO _2, 6 wt.% SiO ₂ glass consisting LiSiCon glass ceramic of the following composition The ceramic polymer membrane and polyethylene oxide (PEO) were first calcined at 600 ° C for 4 hours, then cooled and pulverized.

The powder 30 g obtained in this manner was mixed with a mixture of 70 g of the following composition: 5.4 wt.% Al ₂ O _2, 5.2 wt.% Li _{2 O,} 45.9 wt% P ₂ O _5, 23.1 wt.% Ta ₂ O _5, 16.4 wt% TiO _2, 4 wt% SiO _2.

The mixture was then melted in a quartz glass pot at 1500 ° C to 1650 ° C, homogenized and then poured onto a copper plate and then slowly cooled from 750 ° C to room temperature in a cooling furnace. Obtaining an amorphous glass with a slight crystallization in the outer region.

Thereafter, the glass was ceramized at 850 캜 for 12 hours. Through XRD inspection, major crystalline phases of LiSiCon-structure similar to LiTi ₂ (PO ₄ ) ₃ were identified.

From the glass ceramics obtained in this way, a disk having a diameter of 12 mm and a thickness of 1 mm was prepared and sputtered with gold to measure the conductivity. Conductivity was measured in the range of 10 ^-2 to 10 ⁷ Hz and at 25 ° C to 350 ° C using frequency- and temperature-dependent impedance measurements.

10^-5 S/cm였다. 임피던스 측정으로 구한 입자 코어(grain core) 전도도는 약 1

10^-4 S/cm였다.The conductivity of the ceramic sample was 1

10 ^-5 S / cm. The grain core conductivity measured by the impedance measurement was about 1

10 ^-4 S / cm.

Comparative Example 1

A prior art glass ceramic of LiSiCon-structure was prepared in the following manner:

5.4 wt% Al ₂ O ₃ , 5.2 wt% Li ₂ O, 45.9 wt% P ₂ O ₅ , 23.1 wt% Ta ₂ O ₅ , 16.4 wt% TiO ₂ , and 4 wt% Wt% SiO ₂ .

The glass was obtained by subsequent melting, and the casting and subsequent ceramization was performed according to Example 1.

Samples were also prepared therefrom for conductivity measurements and measured in the same manner.

The conductivity and the particle-core conductivity within the measurement error range were the same as the results obtained in Example 1 above. The XRD test also confirmed major crystalline phases of the LiSiCon-structure similar to LiTi ₂ (PO ₄ ) ₃ .

Therefore, the prior art glass ceramics of the LiSiCon-structure are almost the same as the glass ceramics obtained according to the present invention by adding recycled materials, particularly in terms of electrical conductivity, in their properties.

Claims (20)

CLAIMS 1. A method for producing a glass ceramic ion conductor,
Providing a recycling material from a used battery comprising a glass ceramic ion conductor;
- adding a glass raw material;
Melting the recycled material;
Homogenizing the melt;
- forming a glass and transforming it into a glass ceramic
&Lt; / RTI &gt; The method of claim 1, wherein the glass is ceramized by a tempering treatment. The process according to any one of claims 1 to 4, wherein the pre-melting regeneration material is heated at a temperature of not less than 500 ° C to not more than 650 ° C, preferably not more than 550 ° C to not more than 620 ° C in order to discharge undesired residues, Particularly preferably at about &lt; RTI ID = 0.0 &gt; 600 C. &lt; / RTI &gt; The method according to any one of claims 1 to 3, wherein the regeneration material is first melted, cooled and crushed separately, and then mixed with the glass raw material and melted. 5. A method according to any one of claims 1 to 4, wherein the used battery, especially the solid electrolyte and / or electrode portion from the used lithium-ion battery, is used as recycling material. 6. The method of claim 5, wherein the recycling material comprises an organic component. 7. A process according to any one of claims 1 to 6, wherein the melting of the recycling material and the glass raw material is carried out under oxidizing conditions, preferably at a temperature of more than 700 占 폚. 8. A process according to claim 7, wherein the melting is carried out under air, and in particular by means of oxygen bubbling, further measures are taken to stabilize the oxidation conditions. 9. A method according to any one of claims 1 to 8, wherein the glass ceramic is constituted as a lithium-ion conducting glass ceramic or the sodium-ion, potassium-ion or magnesium-ion conducting glass ceramic is produced as a glass ceramic ion conductor / RTI &gt; 10. The method according to any one of claims 1 to 9, wherein the recycling material is obtained from a lithium-ion conducting glass ceramic or from a sodium-ion, potassium-ion or magnesium-ion conducting glass ceramic. 11. The method according to any one of claims 1 to 10, wherein the lithium germanium phosphate phase, the lithium titanium phosphate phase, the lithium zirconium phosphate phase, the lithium lanthanide zirconate phase, the lithium lanthanide titanate phase, the spinel phase, the garnet phase, Phase, in particular a glass ceramic comprising an isostructural phase is produced. 12. The method according to any one of claims 1 to 11, wherein the glass ceramic is produced as a Na2SiCON crystal phase or a similar lithium composition, especially as a glass ceramic ion conductor comprising an isostructure composition. The glass ceramic according to claim 12, wherein the glass ceramic is produced as a glass-ceramic ion conductor comprising Li _{1 + x y} M ⁵⁺ _y M ³⁺ _x M ⁴⁺ _2-xy (PO ₄ ) ₃ , 1 and (1 + xy) > 1, and M is a cation having a valence of +3, +4 or +5. 14. The method of claim 13, M ⁵⁺ is configured as a Ta ⁵⁺ and / or Nb ⁵⁺ / or,
M ³⁺ is constituted as Al ³⁺ , Cr ³⁺ , Ga ³⁺ and / or Fe ³⁺ and /
M ⁴⁺ is configured as Ti ⁴⁺ , Zr ⁴⁺ , Si ⁴⁺ and / or Ge ⁴⁺ . 15. The method according to any one of claims 1 to 14, wherein the glass-ceramic ion conductor is produced as a glass-ceramic with a garnet-type crystal phase, in particular a garnet-type crystal phase with the following overall formula:
Li _{7 + vw} M _v ²⁺ M _{3 -v} ³⁺ M _{2 -w} ⁴⁺ M _w ⁵⁺ O ₁₂
M ²⁺ is a cation with a valence of 2, M ³⁺ is a cation with a valence of 3, M ⁴⁺ is a cation with a valence of 4, M ⁵⁺ is a cation with a valence of 5, preferably 0 ≦ v <3, more preferably 0? V? 2, 0? W <2, and particularly preferably 0? W < 16. Process according to any one of the claims 1 to 15, wherein at least 5% by weight, preferably at least 10% by weight, of regenerable material is added to produce a glass ceramic ion conductor. 17. A process according to any one of claims 1 to 16, wherein a recycled material is added in an amount of not more than 70% by weight, or not more than 95% by weight, when the composition of the recycled material is known. 18. The process according to any one of claims 1 to 17, wherein the mixture of raw materials is adjusted to a known or substantially known composition of the reclaimed material to obtain the desired composition. 19. The method according to any one of claims 1 to 18, wherein the used battery, in particular the lithium-ion battery, is completely discharged and decomposed, the liquid electrolyte which may be present is removed and the selected portion, Wherein the separator and the solid electrolyte that may be present are used so long as the composition does not impair the properties of the glass-ceramic ion conductor to be produced. A glass ceramic ion conductor for a lithium-ion battery, an all-solid-state battery, a lithium-air battery or a lithium-sulfur battery, produced according to the method of any one of claims 1 to 19, Especially solid electrolytes or electrolyte additives.