Macroporous silver-carbon composite material

Abstract

The invention relates to a porous silver-carbon composite material which contains a carbon powder. The carbon powder contains porous carbon particles, and the carbon particles have pores with an open and continuous pore structure. The porous silver-carbon composite material further contains silver particles, which are at least partly bonded to the surface of the porous carbon particles. The silver-carbon composite material can be used in an electrode of a solid-state battery.

Description

[0001] Macroporous silver-carbon composite material

[0002] The present invention relates to a porous silver-carbon composite material, a process for producing the porous silver-carbon composite material and the use of the material in a solid-state battery.

[0003] Battery-powered applications have become indispensable in most areas of life. Lithium-ion batteries are frequently used as batteries. Today's standard lithium-ion batteries use a liquid electrolyte. The advantages of a liquid electrolyte are high ionic conductivity, which enables rapid charging and discharging. Furthermore, these electrolytes exhibit high chemical stability, which ensures high safety and no undesirable side reactions. The low viscosity leads to good ion transport within the cell. The disadvantages of a liquid electrolyte are its high flammability and limited operating temperature of the battery.

[0004] One way to increase energy density and safety compared to existing lithium-ion batteries is to use solid-state batteries. These no longer contain a liquid electrolyte that can leak. Sulfide solid electrolytes (SSE) are particularly suitable as solid electrolytes due to their high lithium-ion conductivity (1-25 mS cm). -1 ) at room temperature, comparable to that of conventional liquid electrolytes, best suited for use in electric vehicle (EV) batteries.

[0005] The article High-energy long-cycling all-solid-state lithium metal batteries enabled by silvercarbon composite anodes (Nature Energy, volume 5, pages 299-308 (2020) https: / / doi.org / 10.1038 / s41560-020-0575-z, hereinafter referred to as "Nature Energy") describes a simplified solid-state battery based on a sulfide solid electrolyte with a very high energy density of over 900 Wh / I. The following layer structure is used: A layer of an NMC active material is used as the cathode. A layer of a solid sulfide electrolyte of the Agyrodite type is arranged on top of this. A layer of an Ag-C nanocomposite is then applied to the solid electrolyte, which in turn is contacted by a stainless steel charge collector (current collector). The silver-carbon (Ag-C) nanocomposite is a mixture of silver nanoparticles (NPs) and carbon black in a weight ratio of 1:3, as well as a polyvinylidene fluoride binder.In this design, no dedicated anode material is placed on the anode side. Instead, during the charging process, lithium migrates to the charge collector and is deposited between the silver-carbon layer and the charge collector. This allows for particularly thin lithium layers, which are very difficult to incorporate into the design in foil form. A disadvantage of the described Ag-C composite is that the silver nanoparticles are loosely mixed with the carbon and can migrate over the course of several charge and discharge cycles. It is described there that the silver nanoparticles gradually migrate to the charge collector.

[0006] Nature Energy further describes that the battery materials must be compressed at relatively high pressure. This reduces the porosity of the structure, especially of the Ag-C nanocomposite, which in turn can lead to reduced charge carrier mobility. Another typical problem with loose mixtures of silver particles and other particles is Ostwald ripening. In this process, large silver particles grow at the expense of small silver particles. This changes the silver particle size during electrochemical operation, and the material becomes less electrochemically active.

[0007] It was an object of the invention to overcome at least one disadvantage of the prior art.

[0008] In particular, it was an object of the invention to provide a silver-carbon composite material for a battery electrode in which silver migration is reduced so that this material can retain its original structure for longer as part of an anode.

[0009] Another preferred object was to provide a silver-carbon composite material with improved permeability to lithium and lithium ions.

[0010] A further task was to provide a simple manufacturing process for the improved silver-carbon composite material.

[0011] Another preferred object was to provide a silver-carbon composite material that can be processed at lower pressure.

[0012] At least one object is achieved by the subject matter of the independent claims. The dependent claims describe preferred embodiments.

[0013] A first aspect of the invention relates to a porous silver-carbon composite material comprising, a) carbon powder comprising porous carbon particles, wherein the carbon particles

[0014] pores with an open and continuous pore structure and b)silver particles which are at least partially present on the surface, in particular the accessible

[0015] Surface to which porous carbon particles are attached.

[0016] In the porous silver-carbon composite material of the present invention, the Ostwald ripening of the silver particles can be significantly reduced or suppressed. This can significantly slow down the aging of the material as part of a battery electrode.

[0017] A composite material refers to a material in which two or more components are present as distinct substances—in this case, carbon and silver—that are bonded or mixed together. Preferably, the components are bonded at least partially via chemical bonds, particularly ionic or covalent bonds.

[0018] Preferably, the carbon in the porous silver-carbon composite material is amorphous, graphitic, non-graphitic, or a combination of these modifications. Further preferably, the porous silver-carbon composite material is a powder.

[0019] The porous silver-carbon composite material contains carbon powder. This carbon powder contains porous carbon particles to whose surface silver particles are bonded, particularly by chemical deposition.

[0020] The porous carbon particles of the silver-carbon composite material exhibit a particle size distribution. The average particle size d50 of the porous carbon particles of the silver-carbon composite material is preferably in the range of 1 pm to 5 pm. These porous carbon particles can exhibit a monomodal, bimodal, or multimodal distribution. In a preferred embodiment, the porous carbon particles are not carbon black.

[0021] The porous silver-carbon composite material exhibits a pore size distribution. A distinction is made between micropores with a pore diameter of <2 nm, mesopores with a pore diameter of 2 nm to 50 nm, and macropores with a pore diameter of >50 nm. The average pore size of the porous silver-carbon composite material is preferably in the range of >50 nm to 280 nm, in particular in the range of 60 nm to 250 nm. The average pore size is particularly preferably in the range of 75 nm to 150 nm.

[0022] Preferably, the pore volume of the micropores in the porous silver-carbon composite material is 0.01 - 0.5 cm 3 G -1 , especially 0.02 - 0.25 cm 3 G -1 . The pore volume of the macropores, for example, is in the range of 0.3 - 0.5 cm 3 G -1. Furthermore, the proportion of the macropore volume to the total pore volume of the silver-carbon composite material is preferably at least 30% or at least 40%, in particular at least 50%. The total pore volume of the porous silver-carbon composite material, in particular of the pores in the range of 10 nm - 1000 nm, measured by mercury porosimetry, is preferably in the range of 0.2 cm 3 / g to 1.0 cm 3 / G.

[0023] The carbon powder of the present invention can be purchased, for example, under the name Porocarb from Heraeus Battery Technology GmbH, Germany. Alternatively, the porous carbon material can be produced according to WO2019081732A1, Example 2 in conjunction with Table 2, using Alnovol PN 320 Paste and Genapol PF20 in a ratio of 10:6.

[0024] The porous carbon particles of the porous silver-carbon composite material have an open and continuous pore structure. This means that preferably at least 50% of the pore volume, in particular at least 75% of the pore volume, or very particularly preferably at least 90% of the pore volume is accessible from the outside. The open and continuous pore structure can be determined, for example, using a 3D representation of the primary particle created using FIB / SEM tomography. In a preferred embodiment, the tortuosity of the porous carbon particles can be in the range of 1.5 - 3. One advantage of the open and continuous pore structure is that the permeability of lithium atoms and ions through the porous carbon particles is improved.

[0025] The porous carbon composite material contains silver particles. The silver particles are at least partially bonded to the surface of the porous carbon particles. The bonding can preferably be via chemical bonds. The chemical bond can be, for example, a covalent, ionic, or coordinate bond. The bonding can preferably be achieved by directly depositing the silver particles as elemental silver by reducing a silver precursor compound.

[0026] In particular, bonding does not mean a physical adhesion of silver particles that are mixed into the porous carbon material.

[0027] The proportion of silver particles is preferably in the range of 2-45 wt.%, in particular in the range of 5-10 wt.%, based on the total weight of the porous carbon composite material. The average particle size d50 of the silver particles is preferably in the range of 5 nm to 150 nm, in particular in the range of 10 nm-120 nm, particularly preferably in the range of 20 nm-110 nm. It has proven advantageous if the average particle size d50 of the silver particles is at least 5 nm, in particular at least 10 nm, particularly preferably at least 20 nm. The particle size can be determined by XRD using the Bragg equation and the Deby-Scherer method on the 111 reflection.

[0028] In one possible embodiment, the silver particles are at least partially arranged in the pores of the porous carbon particles of the silver-carbon composite material, in particular in the macropores.

[0029] In a particularly preferred embodiment, the silver particles are homogeneously distributed throughout the porous silver-carbon composite material. The distribution can be determined using spatially resolved EDX in a scanning electron microscope.

[0030] In a preferred embodiment, the porous carbon composite material contains no other metals besides silver, especially no intentionally added metals. This excludes unavoidable impurities. The weight-based amount of unavoidable metallic impurities can, for example, be a maximum of 1000 ppm or a maximum of 500 ppm.

[0031] The specific surface area of ​​the porous silver-carbon composite material determined by the BET method is preferably in the range of 50 m 2 / g up to 800 m 2 / G.

[0032] In a second aspect, the invention relates to a method for producing the porous carbon composite material, comprising the steps of: a) providing a carbon powder containing porous carbon particles with an open and interconnected pore structure and a silver precursor compound, b) combining the carbon powder with the silver precursor compound in a

[0033] solvent, c) converting the silver precursor compound into elemental silver, to obtain a

[0034] Suspension of the porous carbon composite material, and d) Isolating the porous silver-carbon composite material.

[0035] Preferably, the carbon in the carbon powder is amorphous, graphitic, non-graphitic, or a combination of these modifications.

[0036] The carbon powder contains porous carbon particles. The porous carbon particles of the carbon powder have a particle size distribution. The average particle size d50 of the porous carbon particles of the carbon powder is preferably in the range of 1 pm to 5 pm. These porous carbon particles can have a monomodal, bimodal, or multimodal distribution. In a preferred embodiment, the porous carbon particles are not carbon black.

[0037] The carbon powder has pores with a pore size distribution. A distinction is made between micropores with a pore diameter of <2 nm, mesopores with a pore diameter of 2 nm to 50 nm, and macropores with a pore diameter of >50 nm. The average pore size of the carbon powder is preferably in the range of >50 nm to 280 nm, in particular in the range of 60 nm to 250 nm. The average pore size of the carbon powder is particularly preferably in the range of 75 nm to 150 nm.

[0038] Preferably, the micropore volume in the carbon powder is 0.01 - 0.5 cm 3 G -1 , especially 0.02 - 0.25 cm 3 G -1 . The pore volume of the macropores, for example, is in the range of 0.3 - 0.5 cm 3 G -1. Furthermore, the proportion of macropore volume to the total pore volume of the carbon powder is preferably at least 30%, in particular at least 50%. The total pore volume of the carbon powder, in particular the volume of the pores in the range of 10 - 1000 nm, measured by mercury porosimetry, is preferably in the range of 0.2 cm 3 / g to 1 .0 cm 3 / G.

[0039] The carbon powder of the present invention can be purchased, for example, under the name Porocarb from Heraeus Battery Technology GmbH, Germany. Alternatively, the porous carbon material can be produced according to WO2019081732A1, Example 2 in conjunction with Table 2, using Alnovol PN 320 Paste and Genapol PF20 in a ratio of 10:6.

[0040] Furthermore, at least one silver precursor compound is provided. Silver precursor compounds can be selected from the group consisting of silver salts and silver complexes. The silver precursor compounds are preferably silver compounds. Examples of silver(I) compounds are silver acetate, silver nitrate, silver halides, and silver sulfate.

[0041] Preferably, the silver precursor compound is present in a solution. Suitable solvents can, for example, be selected from the group consisting of aqueous solvents and polar organic solvents. In particular, the solvent is water.

[0042] The silver precursor compound can optionally be partially or completely dissolved in the solvent; more preferably, it is completely dissolved. Completely dissolved can be understood, for example, as a solution containing at most 0.5 wt.% solids of the silver precursor compound. In an optional embodiment, no other metals or metal compounds are provided besides the silver precursor compound.

[0043] The carbon powder is combined with the silver precursor compound in a common solvent. In the context of the invention, the carbon powder can also be referred to as a solvent, even though the carbon powder does not dissolve in the solvent but forms a suspension of porous carbon particles. Optionally, a suspension of the porous carbon particles can first be prepared, to which the silver precursor compound is added. Alternatively, the porous carbon particles can be added to an existing solution of the silver precursor compound. In a further alternative, a suspension of the porous carbon particles and a solution of the silver precursor compound are combined. The suspending agent for the carbon particles and the solvent for the silver precursor compound can be the same or different. The respective solvents orSuspension agents are miscible with each other. Solvents and suspension agents within the scope of the invention can be organic or aqueous. Preferred organic solvents and suspension agents are polar.

[0044] In step c), the silver precursor compound is converted to elemental silver in the oxidation state. The conversion is preferably carried out by adding a reducing agent, by temperature, or by exposure to light. The conversion is preferably carried out by adding a reducing agent. The pH of the suspension is particularly preferably adjusted to a value greater than 8, in particular to a value greater than 8.5, before the conversion. The choice of reducing agent is preferably not further restricted, and suitable reducing agents can be selected by a person skilled in the art for particle synthesis for the respective silver precursor compound. The reducing agent is particularly preferably a nitrogen-containing reducing agent, such as hydrazine. The reducing agent used can preferably be removed from the reaction without leaving any residue.

[0045] After conversion to elemental silver, the porous carbon composite material is isolated. Common methods such as filtration, centrifugation, or similar processes can be used for isolation.

[0046] In a third aspect, the invention relates to a battery electrode comprising the porous silver-carbon composite material. The battery electrode is preferably an anode, in particular the anode of a solid-state battery. Optionally, the battery electrode can contain a binder, such as polyvinylidene fluoride.

[0047] The battery electrode can preferably additionally comprise lithium, in particular in the form of a lithium layer. The lithium layer can preferably be an in-situ deposited lithium layer. The deposited lithium preferably originates from the cathode material of a solid-state battery and migrates during the charging process through the electrochemical cell to the charge collector on the side on which the anode is to be formed. The porous carbon composite material can act as a separating layer between the solid-state electrolyte and the charge collector, e.g., a steel foil. The in-situ deposition of lithium between a layer of carbon and silver (Ag-C) and a charge collector (e.g., a stainless steel foil) is described, for example, in Nature Energy.

[0048] The use of the porous silver-carbon composite material can lead to an improved lithium redox reaction and thus enable faster charging and discharging of a solid-state battery.

[0049] In a fourth aspect, the invention relates to an all-solid-state battery comprising the porous carbon composite material of the present invention. Preferably, the powder mixture of carbon black and silver nanoparticles in the battery according to Nature Energy can be replaced with the porous carbon composite material of the present invention.

[0050] The solid-state battery preferably has the following structure. A lithium layer is arranged on a charge collector, which can be made of steel, for example. The porous silver-carbon composite material of the present invention is arranged on the lithium layer. A solid electrolyte is arranged on the silver-carbon composite material, and a cathode material, e.g., an NMC material as known in the art, is arranged on the solid electrolyte.

[0051] Preferred aspects of the invention are explained below with reference to exemplary figures. Figure 1 shows a schematic representation of a particle of the silver-carbon composite material.

[0052] Figure 2 shows a schematic representation of a cross section through a solid-state battery according to the present invention.

[0053] The silver-carbon composite particle shown in Figure 1 contains a porous carbon particle (60). The porous carbon particle has pores, which can be either open pores (66) and accessible from the outside, or closed pores (65) that are not accessible from the outside. Silver particles (50) are arranged on the accessible surface of the porous carbon particle (60). These silver particles (50), preferably nanoparticles with an average diameter d50 of, for example, 70 nm, can be arranged on the outer surface of the porous carbon particle (60) or in the open pores (66).

[0054] Figure 2 shows a schematic layer structure of a solid-state battery. Figure 2A shows a layer of a cathode material (10), which can be, for example, an NMC material (NMC layer (nickel manganese cobalt oxide)). A layer of a solid electrolyte (20) is arranged on top of this. The layer of the solid electrolyte (20) is contacted by a layer of the silver-carbon composite material (30) according to the invention. For charge extraction, a charge collector (40), which can be, for example, a steel foil, is arranged on the silver-carbon composite material (30). The layer structure shown preferably corresponds to the state of the solid-state battery before the first charge.

[0055] Figure 2B shows the same solid-state battery as in Figure 2A, with the difference that a lithium layer (35) is arranged between the silver-carbon composite material (30) and the charge collector (40). This lithium layer (35) can preferably be formed by lithium ions migrating from the cathode material (e.g., NMC 622 or NMC 811) to the charge collector and being deposited there during charging of the solid-state battery. Alternatively, the lithium layer can also be introduced directly during the manufacture of the solid-state battery.

[0056] Measurement methods

[0057] Mercury porosimetry

[0058] The total pore volume, the specific pore volume, and the pore sizes can be determined using mercury porosimetry according to DIN ISO 15901-1:2016. The measurements were carried out using the device: Porotec Pascal 140 + 440. The measurement details can be summarized as follows: Sample mass 30 mg; surface tension of mercury 0.48 N / m; contact angle of mercury 141.3°; measurement method: scanning; initial filling pressure 0.0128 MPa; dilatometer: powder, small volume. For sample preparation, the samples were degassed for 8 h at 110°C under vacuum. Before the measurement, porous glass beads with a modal pore diameter of 140.2 nm and a pore volume of 924.4 mm 3 / g (ERM-FD122 reference material from BAM). The Washburn method was used for the evaluation, and the Hg density was corrected for the current temperature. Particle size distribution laser diffraction (D , Dso, D90): A laser diffraction method according to ISO standard 13320:2020 was used to determine the particle size. A Malvern Mastersizer 3000, equipped with a He-Ne laser (wavelength of 632.8 nm with a maximum power of 4 mW) and a blue LED (wavelength of 470 nm with a maximum power of 10 mW) and a wet dispersion unit (Hydro MV), was used for the measurements at an ambient temperature of 23 °C. A mixture of isopropanol and deionized water (50% / 50%) was used as the measuring medium. The mixture was degassed in the dispersing unit using the built-in stirrer at 3500 rpm and sonicated with ultrasound at maximum power for 10 seconds.The sample material was placed in a 5% igepal solution. The sample was predispersed for 30 seconds using an ultrasonic oscillator. The sample was added dropwise to the dispersing unit using a pipette until the transmission of the laser beam was reduced by 3-7%. The values ​​of D, Dso, and D90 (volume-based) were determined using Malvern Mastersizer 3000 Software 3.30. The Fraunhofer theory is used for samples with particles > 10 pm, and the Mie theory is applied to materials with particles < 10 pm.

[0059] Specific surface area (SSA)

[0060] Nitrogen physisorption measurements to determine the specific surface area of ​​particles are carried out according to DIN ISO 9277:2010. A NOVA 3000 (from Quantachrome) is used for the measurement, which operates according to the SMART method (Sorption Method with Adaptive Dosing Rate). Quantachrome aluminum oxide SARM catalog no. 2001 (13.92 m 2 / g according to the multi-point BET method) and SARM Catalogue No. 2004 (214.15 m 2 / g according to the multi-point BET method) from Quantachrome is used. Filling rods are added to the reference and sample measuring cells to reduce the dead volume. The measuring cells are placed in the BET apparatus. The saturation vapor pressure of nitrogen gas (N2 4.0) is determined. A sample is weighed into a glass measuring cell in such a quantity that the measuring cell is completely filled with the filling rods and a minimum of dead volume is created. The sample is kept under vacuum at 200°C for 10 hours to dry it. After cooling, the weight of the sample is determined. The glass measuring cell containing the sample is placed on the measuring apparatus. To degas the sample, it is evacuated to a final pressure of 10 mbar at a pumping speed selected so that no material is sucked into the pump. NovaWin 11.04 software is used for data evaluation.A multi-point analysis with 15 measuring points is carried out and the resulting total specific surface area (BET. to tai) in m 2 / g. The glass measuring cells are cooled to 77 K in a liquid nitrogen bath. For adsorption, N2 4.0 with a molecular cross-sectional area of ​​0.162 nm 2 at 77 K was used for the calculation.

[0061] The empirical T-plot method is used according to ISO 15901-3:2007 to distinguish between contributions from micropores and the remaining porosity at relative pressures greater than 0.1 (i.e., contributions from mesoporosity, macroporosity, and external surface area) and to calculate the micropore surface area (BETmicro) and the micropore volume. The data points of the low-pressure isotherm up to a cut-off p / po, typically up to 0.1 p / po, are selected to determine the linear intercept of the t-plot. The selection of data points is validated by obtaining a positive C constant. The micropore volume is determined from the ordinate intercept. The specific surface area of ​​the micropores (BETmicro) can be calculated from the slope of the t-plot. The external specific surface area BETextemai is defined by subtracting the specific surface area of ​​the micropore from the total specific surface area: BETextemai = BET to tai - BETmicro.

[0062] Fl B / REM tomography

[0063] Tomography using a combination of focused ion beam (FIB) and scanning electron microscopy (SEM) was used to obtain information about the 3D microstructure of the porous carbon particles.

[0064] The method includes the following steps:

[0065] - Sample preparation

[0066] - Repeated milling using FIB and 2D image acquisition using SEM

[0067] - 3D reconstruction of the structure of the porous carbon material from the set of 2D

[0068] Image capture by stacking,

[0069] - Model creation by segmenting the 3D image reconstruction and

[0070] - Analysis of the porosity on the created model.

[0071] Sample preparation: The porous carbon material is mixed with 5 wt% binder and rolled out into a layer. A piece of this sample was prepared for FIB / SEM treatment.

[0072] A ZEISS 1540XB CrossBeam® (Carl Zeiss AG, Oberkochen, Germany) can be used for image acquisition. A thin layer of the sample is precisely milled using a beam of accelerated Ga ions (FIB), and then an image is acquired using an electron beam (SEM). This process is repeated several hundred times to obtain a set of consecutive images. These images form the basis for the 3D reconstruction. The images were acquired with a spacing of 15 nm between consecutive images, and the pixel size in each image was 15 nm. The dataset was first corrected for brightness gradients in the imaging direction, and the images were further processed with an anisotropic diffusion filter to clearly differentiate between pores and carbon. The images were then stacked and aligned in three dimensions using the ImageJ and Matlab software tools.A digital 3D representation of the porous carbon material was obtained.

[0073] In the next step, the 3D representation obtained by image stacking was segmented. Segmentation in this context means calculating a 3D model based on the reconstructed image, with each volume element (voxel) being assigned either to the carbon material or to a pore.

[0074] The image data was segmented using a region-growing segmentation algorithm. The algorithm is described in detail in "Quantification of double-layer Ni / YSZ fuel cell anodes from focused ion beam tomography data," J. Joos et al., J. of power sources 246, 819–830 (2014). The model obtained by image segmentation can be analyzed with respect to porosity, i.e., whether a pore is connected to the pore network, which is connected to the environment, or whether a pore is isolated and has no connection to the environment. A pore accessible from the surface of a primary particle can be considered an open pore.

[0075] Tortuosity

[0076] For the determination of tortuosity, a sample volume of 7.5 x 7.5 x 4.5 pm 3, which corresponds to 500x500x300 voxels of the model obtained by segmentation. This model was used to obtain porosity information using a coarse-grained 3D finite element method (FEM) model with equal-sized cubes. A homogenization approach was used for modeling to determine the effective conductivity a eff, from which the tortuosity can be derived. To do this, the approach is followed that the volume of the pores is filled with a material with a given volume conductivity Oo. The porous structure leads to a reduction in the effective conductivity compared to the initial conductivity. The reduction in conductivity is directly related to the tortuosity via Formula 1 given below. For this purpose, a mesh is created by converting each voxel of the investigated phase (the segmented model) into a cubic 8-node element. Only voxels connected via faces (and not just edges or corners) were added to the mesh to avoid singularities at the model boundaries. Equipotential values ​​are imposed on two opposite outer surfaces (1 V on the upper surface, 0 V on the lower surface).A zero-flow boundary condition was applied to the remaining four outer surfaces, as well as to the interfaces between the two phases, material and pore. The transport equation: is solved using the FEM (finite element method) as described in J. Joos et al., Journal of Power Sources 196 (2011) and M. Ender et al., Electrochemistry Communications 13 (2011) 166, where the intrinsic conductivity of the material Oo is specified. The tortuosity T can then be calculated using the following formula:

[0077] Formula 1 where the porosity

[0078] £=Ni / N ges is with

[0079] Nj= number of voxels of pore phase i and

[0080] Ng e s,: Total number of voxels of the segmented model.

[0081] If the dataset for a coarse-grained 3D FEM model is too large for the available computational resources, the created model can be extended, e.g., to a high-resolution 3D FEM model based on C++ code. Details of the tortuosity calculation are presented in J. Joos et al., Electrochimica Acta 82 (2012) 268-276 (Chapter 7, Calculation of Microstructure Parameters).

[0082] Example

[0083] Example 1

[0084] An aqueous solution prepared from 9.45 g of silver nitrate (silver content 63.69 wt%;

[0085] 55.63 mmol Ag) and 100 mL water, was rapidly added to a suspension of 14.15 g of porous carbon (commercially available as Porocarb L11--, Heraeus Battery Technology GmbH, Germany) in 1000 mL of deionized water. This suspension was stirred at 75°C for 12 hours. The pH of the suspension was then adjusted to 9 using 10 wt% aqueous sodium hydroxide solution. Subsequently, a solution consisting of 2 g of hydrazine solution (hydrazine content 35 wt%), 9.65 g of sodium hydroxide, and 40 ml of water was added over a period of 0.5 hour (1.3 ml / min), and stirring was continued for a further 1 hour. The suspension was then cooled overnight with stirring (12 h), and the material was filtered and washed with a total of 15 L of warm water. Finally, the material was dried in a drying oven at 110°C under vacuum and nitrogen.

[0086] By means of thermogravimetric measurement, a silver content of 32.18 wt.% of the product (based on 0 wt.% residual moisture) was determined.

[0087] Example 2

[0088] An aqueous solution prepared from 9.45 g of silver nitrate (silver content 63.69 wt%;

[0089] 55.63 mmol Ag) and 100 mL water was rapidly added to a suspension of 14.15 g of porous carbon (commercially available as Porocarb L11—, Heraeus Battery Technology GmbH, Germany) in 1000 mL of deionized water. This suspension was stirred for 1 hour at room temperature. The pH of the suspension was then adjusted to 9 using 10 wt% aqueous sodium hydroxide solution. Subsequently, a solution consisting of 2.8 g of hydrazine solution (hydrazine content 35 wt%), 9.65 g of sodium hydroxide, and 50 ml of water was added over a period of 0.5 hour (1.3 ml / min). The mixture was then heated to 60°C and stirred for a further 3 hours. After acidification to pH 4.2 with dilute nitric acid, the suspension was cooled overnight with stirring (12 h). The material was then filtered and washed with a total of 10 L of warm water until a conductivity of 3.2 was reached.Finally, the material was dried in a drying cabinet at 110°C under vacuum and nitrogen inert gas.

[0090] By means of thermogravimetric measurement, a silver content of 31.53 wt.% of the product (based on 0 wt.% residual moisture) was determined.

Claims

Claims 1) Porous silver-carbon composite material, comprising, a) carbon powder containing porous carbon particles, wherein the carbon particles pores with an open and continuous pore structure, and b)silver particles that are at least partially bound to the surface of the porous carbon particles. 2) Porous silver-carbon composite material according to claim 1, wherein the porous silver-carbon composite material has macropores, wherein the proportion of the macropore volume to the total pore volume is at least 30%, measured by mercury porosimetry. 3) Porous silver-carbon composite material according to claim 1 or 2, wherein the silver particles are at least partially chemically bonded to the surface of the porous carbon particles. 4) Porous silver-carbon composite material according to one of claims 1-3, wherein the proportion of the silver particles is in the range of 2-45 wt.%, based on the total weight of the porous silver-carbon composite material. 5) Porous silver-carbon composite material according to one of claims 1-4, wherein the total pore volume of the porous silver-carbon composite material is in the range of 0.2 cm 3 / g to 1 cm 3 / g, measured by mercury porosimetry. 6) Porous silver-carbon composite material according to one of claims 1-5, wherein the average pore size of the porous silver-carbon composite material is in the range of 50 nm to 280 nm, measured by mercury porosimetry. 7) Porous silver-carbon composite material according to any one of claims 1-6, wherein the average particle size dso of the silver particles is in the range of 5 nm to 150 nm, measured by XRD. 8) Porous silver-carbon composite material according to one of claims 1-7, wherein the average particle size dso of the porous carbon particles of the silver-carbon composite material is in the range of 1 pm to 5 pm, measured by laser diffraction. 9) Porous silver-carbon composite material according to any one of claims 1-8, wherein the BET-measured specific surface area of ​​the porous silver-carbon composite material is in the range of 50 m 2 / g up to 800 m 2 / g. 10) A method for producing the porous silver-carbon composite material according to any one of claims 1-9, comprising the steps of: a) providing a carbon powder containing porous carbon particles, wherein the porous carbon particles have an open and interconnected pore structure, and a silver precursor compound, b) combining the porous carbon powder with the silver precursor compound in a solvent, c) converting the silver precursor compound into elemental silver to obtain a suspension of the porous carbon composite material, and d) isolating the porous silver-carbon composite material. 11) The method according to claim 10, wherein the silver precursor compound is selected from the group consisting of silver salts and silver complexes. 12) A method according to claim 11, wherein the silver precursor compound is present in a solution. 13) Process according to claim 12, wherein the initiation of the conversion reaction is carried out by adding a reducing agent, in particular a nitrogen-containing reducing agent. 14) A battery electrode comprising the porous silver-carbon composite material according to any one of claims 1-9. 15) The battery electrode according to claim 14, wherein the battery electrode is the anode of a solid-state battery. 16) The solid-state battery comprising the porous silver-carbon composite material according to any one of claims 1-9.

Images