DE102018218414A1 - Process for the production of composite electrodes and electrolytes for lithium-ion batteries - Google Patents

Abstract

The invention relates to a method for producing a composite electrode, a solid electrolyte, a polymer electrolyte and / or a layer arrangement comprising these, wherein layers of the composite electrode, the solid electrolyte and / or the polymer electrolyte by means of solidification of a Mixture comprising a binder and an ion-conducting solid electrolyte material and / or a lithium salt, and optionally active material and conductive additive, are formed, the binder being a one-component polymerization adhesive. The invention further relates to a correspondingly manufactured lithium-ion battery, composite electrode, solid electrolyte or polymer electrolyte.

Description

The invention relates to a method for producing a composite electrode, a solid electrolyte, a polymer electrolyte and / or a layer arrangement comprising these.

Battery components, primarily electrodes, are now manufactured using the slip process. The slips for the anode and cathode are each coated on a metal foil. Aluminum foil is usually used for the cathode and copper foil for the anode. In order to achieve a high energy density of the battery cell, a lithium foil can be pressed onto the copper foil for the anode. The anode is then joined together with the remaining components to form a solid-state battery. The processing of lithium metal requires a drying room and further safety precautions.

Polymers that act as binders and hold the electrode layers together are added to the slips for the electrode layers. After coating, a long drying section in the processing is necessary, during which the solvent of the slip is evaporated. In the production of a solid-state battery, in addition to the electrode mixture, a solid-state electrolyte, usually on a ceramic basis, which in this case also serves as a separator, is implemented between the anode and cathode. Various methods are used for this. The slip process is also frequently used for the production of the solid electrolyte, which is also used to produce free-standing membranes or coatings on the cathode. In these cases too, intensive drying is necessary to remove the solvent.

The drying and removal of the solvent creates a porosity in the layers, which is disadvantageous for the solid-state battery, since these interrupt the contact paths for the charge transport. Furthermore, by applying a slip for the ceramic solid electrolyte layer to the cathode layer, solvents from the slip can penetrate into the already dried cathode layer and redissolve it. A production in which the use of solvents can be dispensed with would be desirable. In addition, commonly used binder systems for cathodes are sometimes unsuitable for solid electrolytes, since chemical reactions can occur.

It is the object of the invention to provide a method by means of which the use of solvents can be dispensed with.

According to the invention, the object is achieved by the features of claim 1. The object is also achieved by the features of claims 8 to 10. Advantageous refinements and developments of the invention are specified in the subclaims.

The object is achieved in particular by a method for producing a composite electrode, a solid electrolyte, a polymer electrolyte and / or a layer arrangement comprising these, wherein layers of the composite electrode, the solid electrolyte and / or the polymer electrolyte by solidifying a mixture comprising a binder and an ion-conducting solid electrolyte material and / or a lithium salt, and optionally active material and conductive additive, wherein the binder is a one-component polymerization adhesive.

The use of one-component polymerization adhesives as binders allows composite electrodes, polymer and solid-state electrolytes or separators, as well as layer arrangements comprising these, to be produced without solvents.

The term one-component polymerization adhesive denotes a chemically curing adhesive, the curing of which is initiated by changing the ambient conditions. The curing takes place by chemical reaction (polymerization). The initiators of the polymerization can be made available from the environment by radiation, additives or water. Metal ions from the environment can also act as initiators of the hardening, for example if a chemically hardening adhesive is used in the absence of air.

The one-component polymerization adhesives can be mixed with the materials for the production of composite electrodes or polymer and solid-state electrolytes, with no solvent being required for the production of a slip. As a result, the drying step usually required can be omitted or at least significantly reduced. This eliminates the need for complex drying sections during manufacture or can be significantly shortened. This results in a reduction in material costs as well as process costs. In addition, the weight of a correspondingly manufactured component does not increase, or at most only to a small extent. The fact that no more solvent has to be driven off means that the porosity of the layers produced is still significantly lower. Post-compaction can optionally be achieved by calendering.

In embodiments, the one-component polymerization adhesive is selected from the Group comprising acrylate adhesives and / or anaerobic curing adhesives.

Acrylate adhesives are one-component adhesives based on cyanoacrylic acid esters with alkyl chains of different lengths. Suitable cyanoacrylate adhesives are, for example, from the US 6977278 B1 and the US 20080241249 A1 known. A cyanoacrylate-based adhesive can comprise monomers selected from methyl 2-cyanoacrylate, ethyl 2-cyanoacrylate, n-butyl cyanoacrylate, isobutyl cyanoacrylate, octyl cyanoacrylate, 2-octyl cyanoacrylate and mixtures thereof. The polymerization reaction leading to curing can be started with only small amounts of water. Water, which is contained in the materials used for the production of cathodes and electrolyte layers, such as active material or solid-state ion conductors, can in particular serve as a starter for the polymerization. The reactone can also dry the produced electrode with water as the initiator. Additives such as plasticizers, radical inhibitors or anionic polymerization inhibitors can be added.

Anaerobically curing adhesives harden in the absence of air through radical polymerization, which is prevented as long as the adhesive is in contact with oxygen. Suitable anaerobically curing adhesives, monomers, radical initiators and activators are for example from the WO 2001/051577 A2 and the US 3682875 A known. In embodiments, the anaerobic curing adhesive comprises an anaerobic cross-linking di (meth) acrylate monomer, preferably an alkylene glycol diacrylate. Mono-, di-, tri-, tetra- and polyethylene glycol dimethacrylate and corresponding diacrylates are selected, for example, from the group comprising di (pentamethylene glycol) dimethacrylate, tetraethylene glycol di (chloroacrylate), diglycerol diacrylate, diglycerol tetramethacrylate, butylene glycol dimethacrylate, neopentyl methacrylate, neopentyl methacrylate, neopentyl methacrylate, neopentyl methacrylate Tetraethylene glycol diacrylate, diglycerol diacrylate, tetramethylene dimethacrylate, ethylene dimethacrylate and mixtures thereof.

In addition to the polymerizable di (meth) acrylate monomers, anaerobically curing adhesives can include a curing system comprising at least one material which forms free radicals and starts crosslinking (free radical initiator), a reducing additive for free radical stabilization, and one or more accelerators or co-accelerators and / or activators included. Amines or amides can be used as a reducing additive. Hydroperoxides can be used as radical initiators, for example in amounts of 0.1 to 10% by weight based on the total weight of the hardener system. Activators can be contained in amounts of 0.1 to 5% by weight, based on the total weight of the hardener system. Accelerators, co-accelerators and activators that can be used can be selected from sulfonamide, amines or amides, in particular saccharin and / or dimethyl-p-toluidine. These can be used with particular advantage if dense oxide layers have formed on the metal surfaces.

Alkylene glycol diacrylates which have -CH ₂ -CH ₂ -O- or -CH ₂ -CH ₂ -O-like structural sections can be mixed with a lithium salt, which acts as a conductive salt. These alkylene glycol diacrylates can then not only act as a binder, but also act as a polymer electrolyte in the presence of a conductive salt. The polymer electrolyte can then support the conduction path of the ceramic solid electrolyte.

Metal ions from the environment can in particular serve as starters for the polymerization of an anaerobically curing adhesive, in particular if the adhesive is used with the exclusion of air. The metal ions can originate from metal foils that are used as current collectors for electrodes, for example copper foils and / or aluminum foils.

The anaerobically curing adhesive or its monomers can be mixed with a solid electrolyte material and the mixture can be applied to a metal foil, for example a copper foil, which serves as an anodic current collector. This layer can serve as a separator in an vacuumator. Since the crosslinking takes place only in the absence of air, a further layer for a composite electrode can be applied to this layer, which can still be moist. The mixture that forms this layer also contains an anaerobic curing adhesive. A further metal foil, for example an aluminum foil, which serves as a cathodic current collector, can be applied to this. The layer arrangement is sealed off from the surroundings by the second metal foil, and crosslinking by means of the metal ions from the metal foils can take place.

• - Bereitstellen einer ersten Metallfolie;
• - Aufbringen einer ersten Schicht eines ersten Gemischs umfassend einen anaerob härtenden Klebstoff sowie ein ionenleitendes Festkörperelektrolytmaterial und/oder ein Lithiumsalz auf die erste Metallfolie;
• - Aufbringen einer zweiten Schicht eines zweiten Gemischs umfassend einen anaerob härtenden Klebstoff, ein ionenleitendes Festkörperelektrolytmaterial, ein Kathoden-Aktivmaterial und einen Leitzusatz auf die erste Schicht;
• - Aufbringen einer zweiten Metallfolie auf die zweite Schicht; und
• - Vernetzen der Schichten unter Luftabschluss.

Accordingly, in embodiments, the method may include the following steps:

• - Providing a first metal foil;
• Applying a first layer of a first mixture comprising an anaerobic curing adhesive and an ion-conducting solid electrolyte material and / or a lithium salt to the first metal foil;
• - Applying a second layer of a second mixture comprising an anaerobic curing adhesive, an ion-conducting Solid electrolyte material, a cathode active material and a conductive additive on the first layer;
• Applying a second metal foil to the second layer; and
• - Crosslinking the layers with exclusion of air.

In this embodiment, the first metal foil serves in particular as an anodic current collector and the second metal foil serves as a cathodic current collector. Metal foils can be formed, for example, from copper, brass, bronze, low-alloy steels or aluminum. In particular, an aluminum foil can be used as the cathodic current collector and a copper foil as the anodic current collector.

The sequence of the steps is not fixed here, in particular the structure for a layer arrangement for a solid-state accumulator can also be reversed.

• - Bereitstellen einer ersten Metallfolie;
• - Aufbringen einer ersten Schicht eines ersten Gemischs umfassend einen anaerob härtenden Klebstoff, ein ionenleitendes Festkörperelektrolytmaterial, ein Kathoden-Aktivmaterial und einen Leitzusatz auf die erste Metallfolie;
• - Aufbringen einer zweiten Schicht eines zweiten Gemischs umfassend einen anaerob härtenden Klebstoff sowie ein ionenleitendes Festkörperelektrolytmaterial und/oder ein Lithiumsalz auf die erste Schicht;
• - Aufbringen einer zweiten Metallfolie auf die zweite Schicht; und
• - Vernetzen der Schichten unter Luftabschluss.

In other embodiments, the method may accordingly include the following steps:

• - Providing a first metal foil;
• Applying a first layer of a first mixture comprising an anaerobically curing adhesive, an ion-conducting solid electrolyte material, a cathode active material and a conductive additive to the first metal foil;
• Applying a second layer of a second mixture comprising an anaerobic curing adhesive and an ion-conducting solid electrolyte material and / or a lithium salt to the first layer;
• Applying a second metal foil to the second layer; and
• - Crosslinking the layers with exclusion of air.

In this embodiment, the first metal foil serves in particular as a cathodic current collector and the second metal foil serves as an anodic current collector, an aluminum foil as cathodic current collector and a copper foil as anodic current collector preferably being used in turn.

In both embodiments, a layer arrangement for a solid-state accumulator is obtained. After the polymerization, the layer structure can be cut for the layering of the solid-state cells. In particular, the handling of the thin copper foils, which are used as anodic current collectors, is made easier. The anode, lithium metal, is formed in-situ during the first charge. Advantageously, it is therefore not necessary to process lithium metal, which, inter alia, requires a drying room.

When using an acrylate adhesive, the crosslinking is started by water from the environment or the raw materials used for a layer structure. As a result, networking begins within a short time. Since this causes the layer to self-dry, only a short or drying section is necessary. If necessary, a drying section can also be dispensed with. In a next step, another layer can be applied to the layer.

1. a) Bereitstellen eines kathodischen Stromsammlers;
2. b) Aufbringen einer ersten Schicht eines ersten Gemischs umfassend einen Acrylat-Klebstoff, ein ionenleitendes Festkörperelektrolytmaterial, ein Kathoden-Aktivmaterial und einen Leitzusatz auf den kathodischen Stromsammler;
3. c) Aufbringen einer zweiten Schicht eines zweiten Gemischs umfassend einen Acrylat-Klebstoff sowie ein ionenleitendes Festkörperelektrolytmaterial und/oder ein Lithiumsalz auf die erste Schicht.

A corresponding method is suitable for producing a solid-state accumulator. Accordingly, in embodiments, the method may include the following steps:

1. a) providing a cathodic current collector;
2. b) applying a first layer of a first mixture comprising an acrylate adhesive, an ion-conducting solid electrolyte material, a cathode active material and a conductive additive to the cathodic current collector;
3. c) applying a second layer of a second mixture comprising an acrylate adhesive and an ion-conducting solid electrolyte material and / or a lithium salt to the first layer.

Here, the drying of the first cathode layer by water from the environment and / or the mixture can begin immediately, the second separator layer taking place on a layer that has already dried or dried. In a subsequent step, the anode, for example a lithium metal foil, can be applied, in particular pressed, onto the sandwich arrangement obtained from the cathode and separator layer.

The one-component polymerization adhesive can be the same or different in a first and a second mixture. In embodiments, the one-component polymerization adhesive is the same in both mixtures. This can lead to a higher homogeneity of the layers and / or improved connection of the layers to one another. Likewise, the ion-conducting solid electrolyte material can be the same or different in a first and a second mixture. In embodiments, the ion-conducting solid electrolyte material is the same in both mixtures. This can lead to an improved ion conduction in the layer arrangement.

Mixtures for forming electrolyte layers each contain at least the one-component polymerization adhesive and furthermore an ion-conductive solid electrolyte material, or a lithium salt, or an ion-conductive solid electrolyte material and a lithium salt. When using a solid electrolyte material and the one-component polymerization adhesive, a layer of an ion-conducting solid electrolyte can be produced. When using a solid electrolyte material and a lithium salt and one-component polymerization adhesive, a polymer electrolyte can be produced. Polymer electrolytes can also be produced by using a lithium salt and the one-component polymerization adhesive.

Mixtures to form a composite electrode contain the one-component polymerization adhesive, an ion-conducting solid electrolyte material, an active material for the electrode and a conductive additive. The term “active material” refers to a material that can reversibly absorb and release lithium ions under the working conditions of a lithium-ion battery. To produce a composite electrode, the electrode material is applied in the form of a mixture to a metal foil, preferably aluminum for the cathode, which serves as a current collector. Such an electrode is generally referred to as a composite or composite electrode.

The solid electrolyte material can be a ceramic, glass ceramic and / or glassy lithium ion conductor. A glass ceramic can in particular be a lithium germanium phosphate phase, a lithium titanium phosphate phase, a lithium zirconium phosphate phase, a lithium lanthanum zirconate phase, a lithium lanthanum titanate phase, a spinel phase, a garnet phase, or a similar one, especially isostructural phases.

In embodiments, the ion-conducting solid electrolyte material is selected from the group comprising LiPON, lithium-containing ceramic and glass-ceramic ion conductors which have a LiSICon or LiSICon-like, NaSICon or NaSICon-like, garnet-like, perovskite or anti-Perovkit, or argyrodite crystal phase, lithium containing nitrides, hydrides or halides, lithium-containing glassy ion conductors and combinations thereof. The crystal structure represents an essential factor for a high ionic conductivity over crystal defects. In glass ceramics it is important for the ion conduction that the solid electrolyte material additionally have amorphous, for example glassy, structures which allow or support the charge transport.

Preferred are lithium phosphorus oxynitride (LiPON) and a class of glass-ceramic materials commonly referred to as LiSICon (an acronym for Lithium Super-Ionic Conductor) structure type materials and NaSICon (an acronym for Sodium Super-Ionic Conductor) structural materials. LiPON is a commonly used solid electrolyte. The abbreviation LiPON stands for "Lithium Phosphor Oxynitrid" and is used as a synonym for materials with the composition Li _x PO _y N _z .

Preferred lithium-containing ceramics or glass ceramics with a crystalline NaSICon or NaSICon-like structure are selected from Li _1.3 Al _0.3 Ti _1.7 (PO ₄ ) ₃ , LiTi ₂ (PO ₄ ) ₃ , LiGe ₂ (PO ₄ ) ₃ and LiZr (PO ₄ ) ₃ . Preferred lithium-containing ceramics or glass ceramics with a crystalline LiSICon or LiSICon-like structure are selected from Li ₁₀ GeP ₂ S ₁₂ , Li ₃ PS ₄ , Li ₃ Si _0.4 P _0.6 S ₄ and Sn-doped Li ₃ PS ₄ . Preferred lithium-containing ceramics or glass ceramics with a garnet crystal phase are selected from Li _6.75 La ₃ Zr ₂ Ta _0.25 O ₁₂ and Li ₇ La ₃ Zr ₂ O ₁₂ (LLZO). Preferred lithium-containing ceramics or glass-ceramics with perovskite crystal phase selected from Li _{0, 34} La _0.51 TiO _2.94, LisR ₂ Ti ₂ NbO ₉ and Li _0.06 La _0.66 Ti _0.93 Al _0.03 O ₃ . Preferred lithium-containing ceramics or glass ceramics with an anti-perovkite crystal phase are selected from Li ₃ OCl and Li ₃ OCl _0.5 Br _0.5 . Preferred lithium argyrodite are selected from Li ₆ PS ₅ Br, Li ₆ PS ₅ Cl, Li ₇ PS ₆ and Li ₆ PO ₅ Cl. Preferred lithium-containing nitrides are selected from LiPON, Li ₃ N, Li ₇ PN ₄ and LiSi ₂ N ₃ ). Preferred lithium-containing hydrides are selected from Li ₂ NH, LiBH ₄ , LiAlH ₄ and Li ₃ (NH ₂ ) ₂ I. Preferred lithium-containing halides are selected from Li ₂ CdCl ₄ , Li ₂ MgCl ₄ and Li ₂ ZnI ₄ .

Glassy solid electrolytes which have an amorphous structure can also be used. It is also possible to use lithium-containing glassy electrolytes such as lithium silicates, lithium borates, lithium aluminates, lithium phosphates, lithium phosphorus oxynitrides, lithium silicon sulfides, lithium germanium sulfides, lithium lanthanum oxides, lithium titanium oxides, lithium borosulfides, lithium aluminum sulfides and lithium To use phosphorus sulfides and combinations thereof.

Lithium transition metal oxides which contain at least one element selected from the group comprising cobalt, nickel, manganese, vanadium, iron, antimony, tin and tellurium and optionally niobium, tungsten, zirconium, aluminum and chromium can be used in particular as active material for a composite cathode , Magnesium or titanium are doped. A lithium transition metal oxide which can be used in a lithium-ion solid-state battery preferably has the general formula Li _x M _y O _z , where M is at least one metal selected from Co, Mn, Ni, V, Fe, Nb, W, Sb and / or Te, preferably a transition metal selected from Co, Ni and / or Mn. The lithium transition metal oxide is preferably selected from the group comprising LiCoO ₂ , LiMnO ₂ , LiNiO ₂ , LiVO ₂ , LiV ₂ O ₅ , LiNi _1/3 Co _1/3 Mn _1/3 O ₂ , LiMn ₂ O, Li (Ni _0.5 Mn _1.5 ) O ₄ , Li _{1, 3} Nb _0.3 Mn _0.4 O ₂ , Li _x Nb ₂ O ₅ and Li ₄ Ti _4.95 Nb _0.05 O ₁₂ . Polyanionic materials with olivine structure such as LiFePO ₄ , LiMnPO ₄ , LiNiPO ₄ or LiCoPO ₄ can also be used. Li ₂ FeSiO ₄ , Li ₂ MnSiO ₄ , Li ₃ V ₂ (PO ₄ ) ₃ or LiFe _x Mn _1-x PO ₄ , fluorophosphates such as LiVPO ₄ F, or fluorosulfates such as LiFeSO ₄ F, LiCoSO ₄ F, LiNiSO can also be used ₄ F. Furthermore, lithium-rich cathode materials are suitable, which are described by the empirical formula Li _{1 + x} Me _1-x O ₂ , "Me" being at least one metal selected from Co, Mn and / or Ni. The active material of the composite cathode preferably has a potential against lithium of at least 2.8 V.

The lead additive can be selected from graphite; Carbon blacks such as carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black and thermal black; conductive fibers such as carbon fibers and metallic fibers; Metal powders such as aluminum powder and nickel powder; conductive whiskers such as zinc oxide and potassium titanate; conductive metal oxides such as titanium oxide; and polyphenylene derivatives. The additive is preferably selected from the group of carbon black, graphite, carbon nanotubes or carbon nanowires.

Acrylate adhesives can also be used in particular for the production of individual electrode layers, or solid-state electrolyte, polymer electrolyte or separator layers. A method for producing a composite electrode, solid electrolyte or polymer electrolyte can accordingly comprise a mixture comprising acrylate adhesive and an ion-conducting solid electrolyte material and / or a lithium salt, or a mixture comprising acrylate adhesive, an ion-conducting solid electrolyte material Active material and a conductive additive are applied to a substrate, the substrate being optionally removed after the acrylate adhesive has been crosslinked. Such a substrate can be, for example, a polyethylene terephthalate (PET) film or a polyethylene terephthalate polyester film.

• - Graphit, Hartkohlenstoff (hard carbons), Weichkohlenstoff (soft carbons), Graphit-Silicium-Komposite, Elemente und Zusammensetzungen der Gruppe IV wie Silizium, Si-M, Si-MC wobei M jeweils für wenigstens eines ausgwählt aus Mg, Ca, Ni, Fe, Co, Ag und Cu steht, Si-C, SiO und dessen Verbundwerkstoffe, Sn, Sn-basierte Oxidmaterialien und deren Verbundwerkstoffe wie SnO, SnO₂, Sn-M, Sn-MC wobei M jeweils für wenigstens eines ausgwählt aus Mo, B, Si, AI, Co, Cu, Mn, Fe, Ce, Mg und Sb steht, Sn-MO wobei M für wenigstens eines ausgwählt aus Mo, B, Si, AI, Co, Cu, Mn, Fe, Ce, Mg und Sb steht, Sn_1,0B_0,5P_0,5Al_0,4M_0,1O_3,7 wobei M ein Alkalimetalle wie K ist, Ge, Pb, Elemente der Gruppe V wie P, As, Sb und Bi;
• - Phosphor-basierte Intermetallverbindungen und ihre Komposite MP_y (M = Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Sn und y = 1,2,3,4);
• - Intermetallische Verbindungen auf Sb-Basis und ihre Verbundwerkstoffe MSby mit y = 1,2,3 wobei M für wenigstens eines ausgwählt aus Ti, V, Mn, Fe, Co, Ni, Cu und Zn steht;
• - Bi und seine Komposite und As und seine Komposite;
• - Elemente wie Mg, AI, Galn, Ag, AuZn, Cd;
• - Übergangsmetalloxide MO_x wobei M für wenigstens eines ausgwählt aus Mo, Fe, Co, Ni und Cu steht;
• - Lithiumtitanat Li_xTi_yO₁₂ wobei das Li / Ti-Verhältnis im Bereich von 0,78 bis 0,82 liegt, x im Bereich von 3 bis 5 liegt und y im Bereich von 4 bis 6 liegt;

sowie Mischungen der vorgenannen Materialien.The following materials in particular can be used as active material for a composite anode:

• - Graphite, hard carbon (hard carbons), soft carbon (soft carbons), graphite-silicon composites, elements and compositions of group IV such as silicon, Si-M, Si-MC where M is selected for at least one of Mg, Ca, Ni , Fe, Co, Ag and Cu, Si-C, SiO and its composite materials, Sn, Sn-based oxide materials and their composite materials such as SnO, SnO ₂ , Sn-M, Sn-MC where M is selected for at least one of Mo , B, Si, Al, Co, Cu, Mn, Fe, Ce, Mg and Sb, Sn-MO where M is at least one selected from Mo, B, Si, Al, Co, Cu, Mn, Fe, Ce, Mg and Sb, Sn _1.0 B _0.5 P _0.5 Al _0.4 M _0.1 O _3.7 where M is an alkali metal such as K, Ge, Pb, elements of group V such as P, As, Sb and Bi;
• - Phosphorus-based intermetallic compounds and their composites MP _y (M = Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Sn and y = 1,2,3,4);
• - Sb-based intermetallic compounds and their composite materials MSby with y = 1,2,3 where M stands for at least one selected from Ti, V, Mn, Fe, Co, Ni, Cu and Zn;
• - Bi and its composites and As and its composites;
• - Elements such as Mg, Al, Galn, Ag, AuZn, Cd;
• - Transition metal oxides MO _x where M stands for at least one selected from Mo, Fe, Co, Ni and Cu;
• Lithium titanate Li _x Ti _y O ₁₂ where the Li / Ti ratio is in the range from 0.78 to 0.82, x is in the range from 3 to 5 and y is in the range from 4 to 6;

as well as mixtures of the aforementioned materials.

The lithium salt can be selected from the group comprising lithium chlorate (LiClO ₄ ), lithium tetrafluoroborate (LiBF ₄ ), lithium hexafluorophosphate (LiPF ₆ ), lithium hexafluoroarsenate (LiAsF ₆ ), lithium trifluoromethanesulfonate (LiSO ₃ CF ₃ ), lithium bis (trifluoromethylsulphonyl) ₂ CF ₃ ) ₂ ) (LiTFSI), lithium bis (pentafluoroethylsulphonyl) imide (LiN (SO ₂ C ₂ F ₅ ) ₂ ), lithium bis (oxalato) borate (LiBOB, LiB (C ₂ O ₄ ) ₂ ), lithium difluoro (oxalato) borate (LiBF ₂ (C ₂ O ₄ )), lithium tris (pentafluoroethyl) trifluorophosphate (LiPF ₃ (C ₂ F ₅ ) ₃ ) and combinations thereof.

Individual solid electrolyte, polymer electrolyte and / or electrode layers can be produced and used separately, in particular using an acrylate adhesive, or can be combined subsequently, as a result of which lithium-ion batteries with a variable structure are available. Alternatively, the layers can be produced jointly in the form of a layer arrangement, in particular using an anaerobically curing adhesive.

A mixture for forming a composite electrode layer can contain active material in the range of 50-95% by weight, and / or solid-state ion conductor in the range of 5-35% by weight, and / or conductive additive in the range of 1-10% by weight. and / or binders in the range of 0.01-10% by weight, and / or additives in the range of 0-5% by weight, in each case based on a total weight of the mixture of 100% by weight.

A mixture for forming a solid electrolyte or polymer electrolyte layer can contain solid ion conductors in the range of 60-99% by weight, and / or binders in the range of 1-20% by weight, and / or additives in the range of 0-5% by weight based on a total weight of the mixture of 100% by weight. The mixture for forming a polymer electrolyte may contain a lithium salt with a concentration in the range of 0.2 to 3 mol / L.

The layer thickness of a cross-linked composite electrode layer, in particular composite cathode, can be in the range of 50-300 μm. The layer thickness of a crosslinked solid electrolyte layer or polymer electrolyte layer can be in the range of 5-50 μm.

Another aspect of the invention relates to the use of a one-component polymerization adhesive, in particular an acrylate adhesive or an anaerobically curing adhesive, for the production of a composite electrode, a solid electrolyte, a polymer electrolyte and / or a layer arrangement comprising this, in particular one Solid-state accumulator. For the description of the one-component polymerization adhesives, the electrodes and the electrolytes and the process, reference is made to the above description.

Another aspect of the invention relates to a lithium-ion battery, in particular a lithium-ion solid-state battery, produced by the method according to the invention. One aspect of the invention also relates to a lithium-ion battery containing a composite electrode, a solid electrolyte and / or a polymer electrolyte, produced by the method according to the invention, in particular using an acylate adhesive. Another aspect of the invention relates to a composite electrode, a solid electrolyte or a polymer electrolyte, produced by the method according to the invention, in particular using an acylate adhesive.

With regard to further advantages and technical features of the lithium-ion accumulator, the composite electrode, the solid electrolyte and the polymer electrolyte, reference is hereby explicitly made to the explanations in connection with the method according to the invention and to the examples.

The invention is explained below by way of example using preferred exemplary embodiments.

example 1

Production of a layer system from composite cathode and solid electrolyte separator with cyanoacrylate adhesive

To produce a mixture for the composite cathode, the active material lithium-nickel-cobalt-manganese oxide was premixed dry with the solid-state ion conductor LATP and conductive carbon black. The components were present in a ratio of 65% by weight of active material, 20% by weight of fixed conductor and 5% by weight of conductive carbon black, based on a total weight of 100% by weight. 10% by weight of octyl cyanoacrylate was then added to this mixture as binder material. After another short mixing, the mixture was coated on a current collector. The mixture cured within a few minutes. A mixture of solid ion conductor LATP and octyl cyanoacrylate was then coated in a weight ratio of 4 to 1 onto this hardened layer for a composite cathode. This also hardened after a short time.

Example 2

Production of a layer system from a composite cathode and a solid electrolyte separator with anaerobic cross-linking adhesive

To produce a mixture for the composite cathode, the active material lithium-nickel-cobalt-manganese oxide was premixed dry with the solid-state ion conductor LLZO and conductive carbon black. The components were present in a ratio of 60% by weight of active material, 20% by weight, fixed conductor and 5% by weight of conductive carbon black, based on a total weight of 100% by weight. 12.5% by weight of triethylene glycol dimethacrylate was then added to this mixture as a binder. After another short mixing, the mixture was coated on an aluminum current collector. Another mixture for a separator layer comprising LLZO and triethylene glycol dimethacrylate in a ratio of 17 to 3 was applied to the not yet hardened layer of the composite cathode. As a radial starter and as an accelerator, 0.5% by weight of cumene hydroperoxide and 1% by weight of saccharin and dimethyl-p-toluidine were added to the mixtures before application. A copper foil was applied to this layer system as an anodic current collector and the crosslinking of the layers starts through the metal ions from the current collectors. After about 15 minutes the system was set and could be processed further. After a further waiting period of at least 120 minutes, the layer system was completely hardened.

QUOTES INCLUDE IN THE DESCRIPTION

This list of documents listed by the applicant has been generated automatically and is only included for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Patent literature cited

• US 6977278 B1 [0012]
• US 20080241249 A1 [0012]
• WO 2001/051577 A2 [0013]
• US 3682875 A [0013]

Claims (10)

A method for producing a composite electrode, a solid electrolyte, a polymer electrolyte and / or a layer arrangement comprising the same, wherein layers of the composite electrode, the solid electrolyte and / or the polymer electrolyte by solidifying a mixture comprising a binder and an ion-conducting solid electrolyte material and / or a lithium salt, and optionally active material and conductive additive, are formed, characterized in that the binder is a one-component polymerization adhesive. Procedure according to Claim 1 , characterized in that the one-component polymerization adhesive is selected from the group comprising acrylate adhesives and / or anaerobic curing adhesives. Procedure according to Claim 2 , characterized in that the anaerobically curing adhesive comprises an anaerobically crosslinking di (meth) acrylate monomer, preferably an alkylene glycol diacrylate. Procedure according to one of the Claims 1 to 3rd , characterized in that the method comprises the steps: - providing a first metal foil; Applying a first layer of a first mixture comprising an anaerobic curing adhesive and an ion-conducting solid electrolyte material and / or a lithium salt to the first metal foil; Applying a second layer of a second mixture comprising an anaerobically curing adhesive, an ion-conducting solid electrolyte material, a cathode active material and a conductive additive to the first layer; Applying a second metal foil to the second layer; and - crosslinking the layers with exclusion of air. Procedure according to one of the Claims 1 to 3rd , characterized in that the method comprises the steps: - providing a first metal foil; Applying a first layer of a first mixture comprising an anaerobically curing adhesive, an ion-conducting solid electrolyte material, a cathode active material and a conductive additive to the first metal foil; Applying a second layer of a second mixture comprising an anaerobic curing adhesive and an ion-conducting solid electrolyte material and / or a lithium salt to the first layer; Applying a second metal foil to the second layer; and - crosslinking the layers with exclusion of air. Procedure according to one of the Claims 1 or 2nd , characterized in that the method comprises the following steps: a) providing a cathodic current collector; b) applying a first layer of a first mixture comprising an acrylate adhesive, an ion-conducting solid electrolyte material, a cathode active material and a conductive additive to the cathodic current collector; c) applying a second layer of a second mixture comprising an acrylate adhesive and an ion-conducting solid electrolyte material and / or a lithium salt to the first layer. Procedure according to one of the Claims 1 or 2nd , characterized in that a mixture comprising an acrylate adhesive and an ion-conducting solid electrolyte material and / or a lithium salt, or a mixture comprising acrylate adhesive, an ion-conducting solid electrolyte material, an active material and a conductive additive are applied to a substrate, optionally using the substrate removed after crosslinking the acrylic adhesive. Use of a one-component polymerization adhesive, in particular an acrylate adhesive or an anaerobically curing adhesive, for producing a composite electrode, a solid electrolyte, a polymer electrolyte and / or a layer arrangement comprising these, in particular a solid-state accumulator. Lithium-ion battery, in particular lithium-ion solid-state battery, produced by the method according to one of the Claims 1 to 6 , or containing a composite electrode, a solid electrolyte and / or a polymer electrolyte, produced by the method according to one of the Claims 1 to 7 . Composite electrode, solid electrolyte or polymer electrolyte, produced by the method according to one of the Claims 1 to 7 .