EP3308418A1

EP3308418A1 - Na-doped and nb-, w- and/or mo-doped he-ncm

Info

Publication number: EP3308418A1
Application number: EP16724429.2A
Authority: EP
Inventors: Malte ROLFF; Anika Marusczyk; Thomas Eckl
Original assignee: Robert Bosch GmbH
Current assignee: Robert Bosch GmbH
Priority date: 2015-06-15
Filing date: 2016-05-24
Publication date: 2018-04-18
Also published as: KR20180017043A; US20180138497A1; JP2018524769A; CN107710461A; JP6576476B2; DE102015210895A1; WO2016202536A1

Abstract

An active material for an electrochemical energy storage means, especially for a lithium cell. In order to increase the lifetime of the electrochemical energy storage means, the active material is based on the general chemical formula: x (LiMO₂) : 1-x (Li_2-yNa_yMn_1-zM'_zO₃), where M is nickel and/or cobalt and/or manganese and M' is niobium and/or tungsten and/or molybdenum and where 0 < x < 1, 0 < y < 0,5 and 0 < z < 1. The invention further relates to an electrode material and to an electrode comprising this active material, to a process for production thereof and to an electrochemical energy storage means equipped therewith.

Description

Description title

Na-doped and Mb, W and / or Mo-doped HE-NCM

The present invention relates to an active material, an electrode material and an electrode for an electrochemical energy store, in particular a lithium cell, a manufacturing method thereof and an electrochemical energy store equipped therewith.

PRIOR ART At the moment, the electrification of the automobile is advancing strongly, with the lithium-ion battery in particular being the focus of research. For applications in electric cars batteries should ensure a long life, for example, of> 10 years. In this case, the cell voltage and the energy released during a discharge should still be, for example, even after 10 years, approximately> 90% of the initial values.

So-called high-energy materials, such as high-energy nickel-cobalt-manganese oxide (HE-NCM) of general chemical formula: x LiM0 ₂ : 1-x Li ₂ Mn0 ₃ , where M is nickel (Ni), cobalt (Co) and Manganese (Mn), which is also referred to as Overlithiated Layered Oxide (OLO), are very interesting battery materials because of high starting energy densities and starting voltages, but so far have limited rate capability and exhibit lifetime performance a significant loss of voltage (English: Voltage Fade), which with a Capacity decline (English: Capacity Fade) goes along, why they are not yet used commercially.

W. He et al. describe in the Journal of Materials Chemistry A, 2013, 1, pages 11397-11403, a sodium-stabilized, layered Lii. ₂ [Coo.i3 io.i3Mn ₀ .54] 0 ₂ Cathode material.

The document US 2009/0155691 Al relates to a process for producing a lithium alkali transition metal oxide as a positive electrode material for a lithium secondary battery.

Document US 2008/0090150 A1 relates to active material particles of a lithium-ion secondary battery, which comprises at least one first lithium-nickel composite oxide.

Document EP 2 720 305 A1 relates to a cathode active material and a nickel composite hydroxide as a precursor of the cathode active material.

US 2009/0297947 A1 relates to nanostructured, dense and spherically layered positive active materials.

Disclosure of the invention

The present invention is a, for example, overlithiated, for example, sodium-doped, in particular lithiierbares,

transition metal oxide based, active material, in particular a

A cathode active material or an active material for a positive electrode, for an electrochemical energy store, in particular for a lithium cell, for example for a lithium-ion cell, based on the general chemical formula:

x (LiM0 ₂ ): 1-x (Li ₂ -yNa _y Mni. _z M ' _z 0 ₃ )

where M is nickel (Ni) and / or cobalt (Co) and / or manganese (Mn), where M 'is niobium (Nb) and / or tungsten (W) and / or molybdenum (Mo), for example niobium ( Nb) and / or tungsten (W), and, where 0 <x <1, 0 <y <0.5 and 0 <z <1.

An active material may, in particular, be understood as meaning a material which participates in particular in a charging process or discharging process and thus may constitute the actually active material.

In the context of the present invention, an electrochemical energy store may in particular be understood as any battery. In particular, an energy store may comprise a primary battery or, in particular, a secondary battery, that is to say a rechargeable accumulator. A battery can be a galvanic element or a plurality of

include or be interconnected galvanic elements.

For example, an energy store may comprise a lithium-based energy store, such as a lithium-ion battery. In this case, a lithium-based energy store, such as a lithium-ion battery, can be understood to mean in particular an energy store whose electrochemical processes are at least partially based on lithium ions during a charging or discharging process. Such an energy store can be used, for example, as a battery for laptop, PDA, mobile phone and other consumer applications, power tools, garden tools and vehicles, for example hybrid, plug-in hybrid vehicles and

Electric vehicles.

A lithium cell may, in particular, be understood to mean an electrochemical cell whose anode (negative electrode) comprises lithium.

By way of example, this may be a lithium-ion cell, a cell whose anode (negative electrode) comprises an intercalation material, for example graphite and / or silicon, in which lithium can be reversibly stored and displaced, or a lithium metal Cell, a cell with an anode (negative electrode) of lithium metal or a lithium alloy act.

A lithiatable material may, in particular, be understood to be a material which reversibly absorbs and releases lithium ions. For example, a lithiatable material may be intercalatable with lithium ions and / or can be alloyed with lithium ions and / or lithium ions

Record phase change and release again.

A transition metal may, in particular, be understood as meaning an element which has an atomic number of 21 to 30, 39 to 48, 57 to 80 and 89 to 112 in the periodic table.

Such active materials, for example high energy (HE) -NCM materials, advantageously a significantly improved rate capability and a stabilized active material structure and associated stabilization of the voltage and capacitance or a prevention or at least significant reduction in voltage drop and an improved output power, in particular an increased output voltage and output capacity and thus discharge capacity.

By stabilizing the voltage level and capacity, in turn, advantageously, the life of a battery equipped with it can be increased and a high-energy battery, for example a high-energy lithium-ion battery, can be utilized for commercial applications.

Overall, thus advantageously the life of a

electrochemical energy storage, such as a lithium cell, for example, a lithium-ion cell, increased and, for example, a

electrochemical energy storage for commercial applications,

especially high-energy applications, such as automotive applications.

Nickel, cobalt and manganese can advantageously form lithium layer oxides whose electrochemical potentials, for example those for automotive applications, in particular with regard to the highest possible

Voltage and high capacity, are interesting.

By doping with sodium, which can in particular replace lithium in part, due to the larger ionic radius of sodium the

Lithium layer can be widened, resulting in a reduction of intrinsic Material resistance and thus a significant improvement in

Can lead to installment.

In one of the general formula: x (LiM0 _2): 1-x _(y Na _y Li2- Mni- _z M _'z 0 ₃₎ based active material may, in _{particular, for} on Li2- _y Na _y Mni- M' _z 0 ₃ based Structures structurally integrated into LiM0 ₂ based areas. In this may, in particular, the doped Li2- _y Na _y Mni- _z M _'z 0 ₃ -like regions, the stabilization of the active material structure and the associated

Stabilizing the voltage level and capacitance and improving the output voltage and output capacitance and thus discharge capacity.

Niobium, in particular niobium (IV), tungsten, in particular tungsten (IV), and molybdenum, in particular molybdenum (IV), can advantageously have a very similar ionic radius as the redoxin-active tin (IV) known as a structure stabilizer. In contrast to the redoxin-active tin (IV), niobium,

in particular niobium (IV), tungsten, in particular tungsten (IV), and molybdenum, in particular molybdenum (IV), but redox-active - in particular with a small change in the ionic radius - and advantageously - in contrast to redoxin-active doping elements, such as tin and magnesium, additional

Provide capacity. This can advantageously - compared with redoxinaktiven doping elements such as tin and magnesium - an improved output energy density, in particular an increased output voltage and output capacitance and thus discharge capacity can be achieved.

During the formation, the electrochemically at the beginning with respect to the manganese still inactive Li2- _y Na _y Mni- _z M _'z 0 ₃ - component under irreversible elimination of oxygen can be activated with a proportionate Mn (IV) by electrochemically active niobium, in particular niobium (IV), tungsten, in particular tungsten (IV), and / or molybdenum, in particular molybdenum (IV), can be replaced. Thus, the necessary activation of the material and thus a formation of oxygen vacancies, which is the migration of

Transition metals, in particular of manganese and / or nickel, and thereby a voltage drop, for example, by local structural transformations in the active material, would favor reduced. In particular, so can be achieved that less oxygen is irreversibly cleaved than in an undoped or with a redoxin-active element, such as tin (IV), doped material. This can advantageously lead to a stabilization of the structure and thus the voltage situation, since fewer defects in the active material or electrode material arise over which transition metals, especially manganese and / or nickel, migrate and thus change or destabilize the structure.

M 'may in particular stand for niobium (IV) and / or tungsten (IV) and / or molybdenum (IV). Niobium (IV), tungsten (IV) and molybdenum (IV) may advantageously have an ionic radius, for example in a range of> 70 pm to <85 pm, which is almost identical to the ionic radius of the ion

structure-stabilizing, but redoxin-active tin (IV) may be. A

Widening of the crystal lattice, which may be characterized, for example, by an increase in the lattice parameters a, b and / or c, may favor the migration of transition metals, in particular manganese and / or nickel, during the cyclization. By doping with niobium (IV) and / or tungsten (IV) and / or molybdenum (IV) and the thus reduced

Oxygen release during activation, however, can advantageously both a widening of the crystal lattice in the active material or electrode material and thus a migration of transition metals, in particular of manganese and / or nickel, reduced, as well as a protection against a dissolution of transition metal, in particular manganese and / or nickel , will be realized. So can advantageously the capacity and

Voltage drop further reduced and the life of the electrochemical energy storage, such as a lithium cell and / or lithium battery can be increased.

In addition, niobium (IV), tungsten (IV) and molybdenum (IV) can advantageously be used in at least two successive oxidation stages, in particular in the

Go through the redox reaction, have a small change in the ionic radius. For example, these can be at least two

successive oxidation stages have an ionic radius, which may each be, for example, in a range of> 70 pm to <85 pm. Because a strong change in the ionic radius during cyclization, the migration would favor the transition metals further, a small change in the ionic radius can provide better protection against dissolution of the ion

Provided transition metals and the active material or electrode material are further stabilized.

M may in particular stand for nickel (II) and / or cobalt (II) and / or manganese (II). For example, 0.2 <x <0.7, for example, 0.3 <x <0.55. For example, M may be manganese (Mn) and nickel (Ni) and / or cobalt.

In one embodiment, M is nickel (Ni), cobalt (Co) and manganese (Mn).

In a specific embodiment of this embodiment, the at least one active material is based on the general chemical formula:

x (LiNi _a CobMni _a .b0. _2): 1-x (Li ₂ -yNa Mni _y _z M _'z 0. _3),

where 0 <a <1, for example 0.2 <a <0.8, for example 0.3 <a <0.45, and where 0 <b <1, for example 0 <b <0.5, for example 0 , 2 <b <0.35. For example, a and b may be 1/3, for example, where LiNi _a Co _b Mni _a - _b 0 ₂ LiMni / ₃ Nii / ₃ Coi / ₃ 02.

In another embodiment, 0.01 <z <0.3. In particular, 0.01 <z <0.2.

In a further embodiment, M 'is niobium, in particular niobium (IV), and / or tungsten, in particular tungsten (IV).

With regard to further technical features and advantages of the active material according to the invention is hereby explicitly to the explanations in connection with the electrode material according to the invention, the inventive

Manufacturing method, the electrode according to the invention, the

Referenced the electrochemical energy storage device according to the invention and to the figures and the description of the figures. Another object of the invention is an electrode material, in particular a cathode material or an electrode material for a positive electrode, for an electrochemical energy storage, in particular for a lithium cell, for example for a lithium-ion cell comprising particles having at least one, for example, over-lithiated, in particular with sodium (Na) doped, lithiierbares, transition metal oxide-based, active material, wherein the particles or a particles having body is at least partially provided with a functional layer is, which lithium ions is conductive and niobium (Nb) and / or tungsten (W) and or molybdenum (Mo).

Under a particle may in particular a primary particle and / or a

Secondary particles, such as a starting powder, to be understood.

A basic body may in particular be understood to mean, for example, a completely processed body of electrode material which contains or consists of particles which comprise the at least one active material.

A functional layer may, in particular, be understood as meaning a protective layer which prevents interaction of the active material with an electrolyte, for example when used in a lithium cell.

By providing the functional layer which comprises lithium ions and comprises niobium, tungsten and / or molybdenum, it is advantageously possible to very effectively protect the active material or electrode material from loss or dissolution of the transition metals, in particular manganese and / or nickel, in an electrolyte which would otherwise result in deposition of lithium-containing transition metal compounds on the anode, and thus loss of available transition metal and / or lithium, and thus capacity degradation. The functional layer can advantageously act as a kind of barrier, wherein the

structure-stabilizing and redox-active niobium, tungsten and / or molybdenum an interaction of the active material of the particles with an electrolyte, for example, when used in a lithium cell, prevent and thus prevent dissolution or washing out of the transition metal. Thus, advantageously, a reduction of the capacity drop and thus an increase in the life of the lithium cell and / or lithium battery can be achieved.

When coating the particles or the body having the particles advantageously in one process step, the doping with niobium, tungsten and / or molybdenum in the at least one

Active material, in particular in the Li ₂ - _y Na _y Mni- _z M _'z 0 ₃ - component are introduced. Thus, two central problems of HE-NCM materials, namely the capacity drop through the functional layer and the voltage drop due to doping with niobium, tungsten and / or molybdenum originating from the functional layer, can advantageously be counteracted in a very efficient and cost-effective manner by only one method step become.

For example, the at least one active material, in particular the particle, comprise or be at least one, for example, over-lithiated, for example sodium-doped, in particular lithiatable, transition-metal oxide-based, active material, for example manganese oxide, in particular nickel-cobalt-manganese oxide.

In one embodiment, the at least one active material, in particular the particle, is based on the general chemical formula:

x (LiMO ₂ ): 1-x (Li ₂ -yNa _y MnO ₃ ), where M is nickel (Ni) and / or cobalt (Co) and / or manganese (Mn) and where 0 <x <1 and 0 <y <0.5.

For example, M may be manganese (Mn) and nickel (Ni) and / or cobalt.

In one embodiment of this embodiment, M is nickel (Ni), cobalt (Co) and manganese (Mn).

In particular, the at least one active material, in particular

Particles, on the general chemical formula: x (LiNi _a CobMni- _a -b0 ₂₎ 1-x (Li ₂ - _y Na _y Mn0 ₃₎ are based, where 0 <a <1,

For example, 0.2 <a <0.8, for example, 0.3 <a <0.45, and wherein 0 <b <1, for example, 0 <b <0.5, for example, 0.2 <b <0 , 35, is.

The functional layer may in particular comprise niobium (IV) and / or tungsten (IV) and / or molybdenum (IV).

In one embodiment, the functional layer comprises niobium, in particular niobium (IV), and / or tungsten, in particular tungsten (IV).

As already explained, the at least one active material, in particular of the particles, can be doped by niobium, tungsten and / or molybdenum from the functional layer. In particular, therefore, the at least one active material, in particular the particles, a, for example, überithiated, manganese oxide, in particular nickel-cobalt-manganese oxide, which with sodium and niobium and / or tungsten and / or molybdenum, for example with sodium and niobium and / or tungsten, is doped, include or be.

Within the scope of a further embodiment, the at least one active material, in particular the particle, comprises or is an active material according to the invention explained above.

In addition to the particles, the base body may for example comprise at least one conductive additive, for example elemental carbon, for example carbon black, graphite and / or carbon nanotubes, and / or at least one binder, for example selected from the group of natural or synthetic polymers, for example polyvinylidene fluoride (PVDF). , Alginates, styrene-butadiene rubber (SBR), polyethylene glycol and / or polyethyleneimine.

The base body may, for example, have a gradient of niobium, tungsten and / or molybdenum pointing in its thickness direction. In this case, the gradient, in particular starting from the functional layer, can decrease, for example to a metal support, in particular serving as a current conductor. This may advantageously be sufficient because the interaction of the Active material with the electrolyte takes place predominantly in the surface region and thus the costs can be reduced by the redox-active doping elements.

Furthermore, if appropriate, a coating of the particles and / or of the basic body, for example, which aluminum oxide (Al ₂ 0 ₃ ), aluminum fluoride (AIF ₃ ), lithium aluminum oxide (LiAIO _x ), zirconium dioxide (Zr0 ₂ ), titanium dioxide (Ti0 ₂ ), aluminum phosphate (AIPO4 ) and / or lithium phosphorous oxynitride (LiPON;

Lithium phosphorous oxynitride) and / or another compound, for example, which can dissolve transition metal dissolution and / or other material-electrolyte interactions C, single particle coating ") may be present.

With regard to further technical features and advantages of the electrode material according to the invention, reference is explicitly made to the explanations in

Connection with the active material according to the invention, the

Inventive manufacturing method, the electrode according to the invention, the electrochemical energy storage device according to the invention and to the figures and the description of the figures referenced.

Another object of the invention is a method for producing an active material, in particular a cathode active material, and / or an electrode material, in particular a cathode material, and / or an electrode, in particular a cathode or positive electrode, for an electrochemical energy storage. In particular, the method for producing an active material according to the invention and / or a

be designed according to the invention electrode material and / or an electrode according to the invention.

The method may in particular include the method steps:

Providing particles having at least one lithiatisable,

transition metal oxide-based active material or a body having the particles, wherein the at least one active material by means of a polymer pyrolysis method is prepared and / or doped with sodium or is; and

Coating the particles and / or the base body with a

Functional layer which is conductive to lithium ions and comprises niobium (Nb) and / or tungsten (W) and / or molybdenum (Mo),

For example, the at least one active material, in particular the particle, may comprise at least one, for example, over-lithiated, for example, sodium-doped, in particular lithiatable, transition-metal oxide-based, active material, for example

Example, manganese oxide, in particular nickel-cobalt-manganese oxide include or be.

By the method, on the one hand, a protective functional layer for the active material can be provided in a very simple manner in order to obtain a

Dissolution or leaching of transition metals, in particular nickel and / or manganese, and the concomitant drop in capacity

prevent. On the other hand, the method can additionally offer the considerable advantage that a portion of the niobium and / or tungsten and / or molybdenum of the functional layer in the coating of the particles or the

Basic body can be introduced as a doping element in the active material. As a result, doping of the active material with niobium and / or tungsten and / or molybdenum can advantageously be effected, which in turn can result in a structural stabilization. The latter can be attributed, as explained above, to the fact that in the first formation cycle in which the electrochemically inactive Li ₂ MnO ₃ component is activated, less oxygen is irreversibly removed and thus fewer oxygen vacancies are formed than in the undoped HE NCM. Material. Thus, with only one process step, two central problems of HE-NCM material, namely the capacity drop by the coating of the particles or the

Basic body with the functional layer and the voltage drop due to the simultaneous doping of the active material with the redox-active niobium and / or tungsten and / or molybdenum originating from the functional layer,

Be taken into account. For example, when providing or producing the particles, for example by the polymer pyrolysis process, to a

Admixing of at least one compound which contains niobium and / or tungsten and / or molybdenum, and for example also to a coating based on redoxin-active elements, for example Al ₂ O ₃ , LiAlO _x , ZrO ₂ , TiO ₂ , AIPO 4, LiPON , a magnesium compound and / or a

Tin compound, can be omitted in order to introduce both a material doping for controlling the voltage loss layer and a protective layer for controlling the capacity drop in a single process step.

In one embodiment, the polymer pyrolysis process comprises the process steps:

Dissolving and / or dispersing at least one lithium salt and one

Transition metal salt in a solution containing at least one

polymerizable monomer comprises;

- polymerizing the at least one polymerizable monomer to at least one polymer;

- Pyrolyzing the at least one polymer; and

Calcining the residue remaining after pyrolysis.

For example, the at least one polymerizable monomer may include or be acrylic acid. The at least one polymer may in particular comprise or be a polyacrylate.

The fact that the salts are first dissolved in the monomer-containing solution and then the monomers are polymerized to form a polymer, may advantageously a polymer metal salt precursor, for example a

Polyacrylate, are formed, in particular in which the metals are finely dispersed.

The solution may be, for example, an aqueous solution.

In the context of one embodiment of this embodiment, at least one lithium salt, a sodium salt and a transition metal salt, in particular manganese salt, are dissolved and / or dispersed in the solution. Additionally, in the Solution, for example, dissolved and / or dispersed at least one nickel salt and / or cobalt salt. For example, at least one lithium salt, a sodium salt, a manganese salt, a nickel salt, and a cobalt salt may be dissolved and / or dispersed in the solution.

The lithium salt may, for example, include or be lithium hydroxide, for example LiOH-H ₂ O. The sodium salt may, for example, include or be sodium hydroxide, for example NaOH. The manganese salt may, for example, comprise or be a manganese (II) salt and / or manganese nitrate, in particular manganese (II) nitrate, for example Mn (NO ₃ ) ₂ . The nickel salt may, for example, comprise or be a nickel (II) salt and / or nickel nitrate, in particular nickel (II) nitrate, for example Ni (NO ₃ ) ₂ -6 H ₂ O. The cobalt salt may, for example, comprise or be a cobalt (II) salt and / or cobalt nitrate, in particular cobalt (II) nitrate, for example Co (NO ₃ ) ₂ -6 H ₂ O.

The metal salts can be used, for example, in stoichiometric amounts. Of the lithium salt, however, in particular one, for example 5 greasy, excess can be used. So can advantageously a

Lithium loss can be compensated for later calcination.

For polymerizing the at least one polymerizable monomer, for example acrylic acid, to the at least one polymer, for example polyacrylate, in particular at least one polymerization initiator may be added to the solution and / or dispersion. For example, as a polymerization initiator at least one peroxodisulfate, for example

Ammonium peroxodisulfate, for example (NH ₄ ) ₂ S ₂ 0 ₈ , can be used.

Optionally, the at least one polymer, in particular before the pyrolysis, for example at a temperature of> 100 ° C, for example about 120 ° C, dried.

The pyrolyzing of the at least one polymer can be carried out in particular under an air atmosphere. For example, the pyrolyzing of the at least one polymer at a temperature of> 450 ° C, for example at about 480 ° C, to be performed. For example, the pyrolysis may be carried out for a period of> 4 hours, for example about 5 hours.

The calcining of the residue remaining after the pyrolysis can in particular also be carried out under an air atmosphere.

For example, calcination of the residue remaining after pyrolysis may be carried out at a temperature of> 850 ° C, for example at about 900 ° C. For example, calcination may be performed for a period of> 4 hours, for example about 5 hours.

For example, at least one active material, in particular of the particles to the general chemical formula: x (LiM0 ₂₎ 1-x (Li ₂ - _y Na _y Mn0 ₃₎ are based, where M is nickel (Ni) and / or cobalt (Co) and / or manganese (Mn) and wherein 0 <x <1 and 0 <y <0.5. For example, M can stand for manganese (Mn) and nickel (Ni) and / or cobalt (Co). In particular, M can for

Nickel (Ni), cobalt (Co) and manganese (Mn). For example, at least one active material, in particular of the particles to the general chemical formula: x (LiNi _a Co _b Mni- _a - _b 0 ₂₎ 1-x (Li ₂ - _y Na _y Mn0 ₃₎ are based, where 0 <a <1, for example 0.2 <a <0.8, for example 0.3 <a <0.45, and wherein 0 <b <1, for example 0 <b <0.5, for example 0, 2 <b <0.35, is.

The functional layer may in particular comprise niobium (IV) and / or tungsten (IV) and / or molybdenum (IV). Within the scope of a further embodiment, the functional layer comprises niobium, in particular niobium (IV), and / or tungsten, in particular tungsten (IV).

The coating of the particles, for example of primary and / or

Secondary particles, with the functional layer can in particular be such that the particles, for example a powder obtained by the polymer pyrolysis process, for example in water and / or another

Dispersing medium together with at least one compound containing niobium (Nb) and / or tungsten (W) and / or molybdenum (Mo) are mixed. Then the solids of the dispersion can be separated off, for example filtered off. The solids or the residue can then optionally, for example at a temperature of> 100 ° C, for example at about 105 ° C, for example for several hours, for example about 10 h, dried. The solids may be (then) annealed at a temperature of> 450 ° C, for example for several hours, for example for about 5 hours. For coating the particles with the functional layer, however, it is also possible to carry out other coating methods known to the person skilled in the art, such as sputtering, with at least one compound containing niobium and / or tungsten and / or molybdenum. The coating of the base body or of the finished, for example laminated, electrode with the functional layer can be carried out by methods known to those skilled in the art, for example atomic layer deposition and / or sputtering, with at least one compound, which niobium and / or tungsten and / or

Molybdenum contains, be carried out.

For example, as the niobium compound Li ₇ La ₃ Nb ₂ 0i ₃ , Li ₇ Nb0 ₆ , Li ₃ Nb0 ₄ , LiTiNb ₂ 0 ₉ and / or Li ₈ - _x Zri- _x Nb _x 0 ₆ are used. As tungsten compound, for example, Li ₆ W0 ₆ , Li ₄ W0 ₅ and / or Li ₆ W20 ₉ , are used.

In the context of one embodiment, in particular in the context of which the particles are coated ("single particle coating"), the method may comprise the following method steps:

Providing particles having at least one lithiatisable,

transition metal oxide-based active material or a body having the particles, wherein the at least one active material is prepared by means of a polymer pyrolysis process and / or doped with sodium or is;

in particular wherein the polymer pyrolysis process comprises the process steps: dissolving and / or dispersing at least one lithium salt and a

Transition metal salt in a solution containing at least one

polymerizable monomer comprises;

- polymerizing the at least one polymerizable monomer to at least one polymer;

- optionally drying the at least one polymer; - Pyrolyzing the at least one polymer; and

- calcining the residue remaining after pyrolysis;

includes;

- Coating the particles with a functional layer, which

Is lithium ion conductive and comprises niobium and / or tungsten and / or molybdenum, for example niobium and / or tungsten,

- adding a conductive additive and a binder;

Dry pressing of the components from the group consisting of

Particles with the functional layer, the conductive additive and the binder, or dispersing the component from the group consisting of the particles with the functional layer, the conductive additive and the binder in a solvent, for example in N-methyl-2-pyrrolidone;

Applying the thus obtained press-bonding or applying, in particular knife-coating, the dispersion thus obtained to a metal support, for example to an aluminum foil; and

- optionally drying the dispersion.

As part of an embodiment - especially in the context of which the

GJarninate coating ") - the process may comprise the following process steps:

Providing particles having at least one lithiatisable,

in particular wherein the polymer pyrolysis process comprises the process steps:

Dissolving and / or dispersing at least one lithium salt and one transition metal salt in a solution containing at least one

polymerizable monomer comprises;

- polymerizing the at least one polymerizable monomer to at least one polymer;

- optionally drying the at least one polymer;

- Pyrolyzing the at least one polymer; and

- calcining the residue remaining after pyrolysis;

includes; - adding a conductive additive and a binder;

Dry pressing of the components from the group consisting of

Particles, the conductive additive and the binder, or dispersing the component selected from the group consisting of the particles, the conductive additive and the binder in a solvent, for example in N-methyl-2-pyrrolidone;

Applying the thus-obtained press-bonding or applying, in particular knife-coating, the dispersion thus obtained to a metal support, for example to an aluminum foil, to form a body having the particles;

- optionally drying the dispersion;

- Coating the body with a functional layer, which

Lithium ion conducting and niobium and / or tungsten and / or molybdenum, for example niobium and / or tungsten, comprises.

Objects of the present invention are further characterized by a

Active material produced according to the method according to the invention and / or an electrode material produced by a method according to the invention.

With regard to further technical features and advantages of the manufacturing method according to the invention and of the active material or electrode material produced thereby, explicit reference is made to the explanations in connection with the active material according to the invention, the

Inventive electrode material, the electrode according to the invention, the electrochemical energy storage device according to the invention and to the figures and the description of the figures referenced.

A further subject of the present invention is an electrode, in particular a cathode, which comprises at least one active material according to the invention and / or produced by an inventive method and / or an electrode material according to the invention and / or produced by a method according to the invention and / or produced by a method according to the invention is. With regard to further technical features and advantages of the electrode according to the invention, explicit reference is made here to the explanations in connection with the active material according to the invention, the electrode material according to the invention, the production method according to the invention, the electrochemical energy store according to the invention and to the figures and FIGS

Figure description referenced.

Furthermore, the invention relates to an electrochemical energy storage, in particular a lithium cell and / or lithium battery, for example a

Lithium-ion cell and / or lithium-ion battery, comprising

Inventive and / or according to the invention produced active material and / or an inventive and / or produced according to the invention electrode material and / or an electrode according to the invention and / or according to the invention.

With regard to further technical features and advantages of the electrochemical energy storage device according to the invention is hereby explicitly to the explanations in connection with the active material according to the invention, the

Inventive electrode material, the inventive

Production method, the electrode according to the invention and to the figures and the description of the figures referenced.

drawings

Further advantages and advantageous embodiments of the subject invention are illustrated by the drawings and explained in the following description. It should be noted that the drawings have only descriptive character and are not intended to limit the invention in any way. Show it

1 shows a schematic cross section through an embodiment of an electrode. FIG. 2 shows a schematic cross section through an embodiment of a particle coated with a functional layer; FIG.

3 shows a schematic cross section through a further embodiment of an electrode;

4 is a flowchart of an embodiment of a method according to the invention for producing an electrode shown in FIG. 1; and

5 is a flowchart of another embodiment of a

A method according to the invention for producing an electrode shown in FIG.

FIG. 1 shows an electrode 10 which has a metal carrier 12. The metal carrier 12 can serve as Abieiter, in particular cathodes in a lithium cell or lithium battery. The electrode 10 further includes a plurality of particles 14 disposed on the metal support 12. The particles 14 have at least one, with sodium-doped, lithiierbares, transition metal oxide-based active material.

As can be seen from Figures 1 and 2, the particles 14 are with a

Function layer 16 provided or coated. The

Functional layer 16 according to the invention is lithium-ion conductive and comprises niobium and / or tungsten and / or molybdenum. Due to the redox-active niobium and / or tungsten and / or molybdenum, the functional layer 16 is designed such that it interacts with the active material

Prevent electrolyte, for example, during use or in an operation of a lithium cell, and thus can protect the electrode from loss of transition metal. The particles 14 may be completely or only partially enclosed by the functional layer 16. For the sake of illustration, it has been omitted in FIG. 1 to individually draw in the functional layers 16 of all the particles 14. It is quite conceivable that a number of particles 14 are arranged on the surface of the electrode 10 and protrude from this, without being covered by the functional layer 16.

As further shown in FIGS. 1 and 2, a majority of the particles 14 further comprise redox-active niobium and / or tungsten and / or molybdenum 18 as

Doping on. In particular, the particles 14 have at least one Active material which is doped with niobium and / or tungsten and / or molybdenum 18. The redox-active niobium and / or tungsten and / or molybdenum can originate in particular from the functional layer 16. In addition to the at least one active material, the electrode 10 may, for example, further comprise at least one conductive additive and at least one binder (not shown).

In this case, for example, the at least one active material, the at least one conductive additive and the at least one binder form the electrode material of the electrode 10. FIG. 3 shows an electrode 10 ^' , which is 10 ^' analogous to the electrode

10 in Figure 1 has a metal carrier 12. On the metal support 12, a base body 20 is arranged, which comprises the particles 14 or consists of the particles 14. The individual particles 14 are uncoated here and also have the at least one, with sodium-doped, lithiatable transition metal oxide-based active material. The electrode 10 ^'

or the base body 20 may in addition to the active material additionally have a suitable conductive additive and a suitable binder (not shown). FIG. 3 further shows that the main body 20 is provided with the functional layer 16. The functional layer 16 is analogous to the functional layer explained in connection with FIGS. 1 and 2.

Lithium ions conductive and includes niobium and / or tungsten and / or molybdenum. The functional layer 16 may, in particular due to their composition, be designed in such a way that they prevent an interaction of the active material with an electrolyte, for example during use or in operation of a lithium cell, and thus prevent the electrode 10 'from being exposed

Can protect loss of transition metal. The electrode 10 ^' can

be laminated, for example, before the coating of the base body 20 takes place with the functional layer 16. As also shown in FIGS. 1 and 2, the electrode 10 ^' or the main body 20 furthermore has redox-active niobium and / or tungsten and / or molybdenum 18 as doping element. In particular, the

Base body 20 or the particles 14 of the main body 20 at least one active material, which is doped with niobium and / or tungsten and / or molybdenum 18. The redox-active niobium and / or tungsten and / or Molybdenum may originate in particular from the functional layer 16. Furthermore, the main body 20 can have a gradient of the redox-active niobium and / or tungsten and / or molybdenum 18 pointing in its thickness direction. The gradient of the redox-active niobium and / or tungsten and / or molybdenum 18 can decrease in particular from the functional layer 16 to the metal carrier 12.

4 shows a flowchart of a method for producing an electrode 10, in particular a cathode for a lithium cell, according to FIG. 1C, single particle coating. "The method comprises a step of providing

100 of particles 14 comprising at least one lithiierbares,

transition metal oxide-based active material, wherein the at least one active material by means of a polymer pyrolysis process

100a, 100b, 100c, 100d, 100e is prepared and / or doped with sodium or is. The polymer pyrolysis process comprises a

Step of dissolving and / or dispersing 100a at least one lithium salt and one transition metal salt in a solution comprising at least one polymerizable monomer; a step of polymerizing 100b the at least one polymerizable monomer to at least one polymer; optionally a step of drying 100c of the at least one

Polymer, a step of pyrolysing lOOd of the at least one polymer and a step of calcining lOOe of the residue remaining after the pyrolysis. Furthermore, the method comprises the step 102 of coating 102 of the particles 14 with a functional layer 16, which is conductive to lithium ions and comprises niobium and / or tungsten and / or molybdenum, the step 104 of FIG

Adding 104 a conductive additive and a binder, a step of dry-pressing 106 the components from the group consisting of the particles 14 with the functional layer 16, the conductive additive and the binder, or a step of dispersing 106 the component from the group consisting of the particles 14 with the functional layer 16, the Leitzusatz and the

Binder in a solvent, a step of applying 108 of the thus obtained Pressverbundes or applying 108,

in particular, doctoring the dispersion thus obtained onto a metal support 12, and optionally a step of drying the dispersion (not shown). 5 shows a flowchart of a method for producing an electrode 10 ^' , in particular a cathode for a lithium cell, according to FIG. 3Caminate Coating. "The method has a step of providing 100 ^' of particles 14 comprising at least one lithiatable,

100a ', 100b', 100c ', 100d', 100e 'and / or is doped with sodium. Here, the polymer pyrolysis process comprises a step of dissolving and / or dispersing 100a 'at least one lithium salt and a transition metal salt in a solution comprising at least one polymerizable monomer; a step of polymerizing 100b 'of the at least one polymerizable monomer to at least one polymer; optionally a step of drying 100c 'of the at least one polymer, a step of pyrolyzing 100d' of the at least one polymer and a step of calcining 100e 'of the residue remaining after pyrolysis. Furthermore, the method comprises the step of adding 102 ^' a conductive additive and a binder, a step of dry-pressing 104 ^' the components from the group consisting of the particles 14, the conductive additive and the binder, or a step of

Dispersing 104 ^', the component from the group consisting of the particles 14, the conductive additive and the binder in a solvent, a step of applying 106' of the thus obtained press assembly or the application 106 ', in particular knife coating, the dispersion thus obtained on a metal support 12th to form a base 20 having the particles 14, optionally a step of drying the dispersion (not shown) and a step of coating 108 ^'of the base 20 with a functional layer 16 which is lithium ion conductive and niobium and / or tungsten and / or molybdenum.

Claims

claims

1. active material, in particular cathode active material, for a

electrochemical energy storage, in particular for a lithium cell, based on the general chemical formula:

x (LiM0 ₂ ): 1-x (Li ₂ -yNa _y Mni. _z M ' _z 0 ₃ )

where M stands for nickel and / or cobalt and / or manganese,

where M 'stands for niobium and / or tungsten and / or molybdenum,

where 0 <x <1, 0 <y <0.5 and 0 <z <1. 2. Active material according to claim 1, wherein M stands for nickel, cobalt and manganese, in particular wherein the at least one active material has the general chemical formula:

x (LiNi _a Co _b Mni- _a - _b 0 ₂₎ 1-x (Li ₂ -yNa Mni- _y _z M _'z 0 ₃₎

wherein 0 <a <1, in particular 0.2 <a <0.8, and wherein

0 <b <1, in particular 0 <b <0.5, is.

3. Active material according to claim 1 or 2, wherein M 'stands for niobium and / or tungsten and / or wherein 0.01 <z <0.3, in particular 0.01 <z <0.2, is. 4. electrode material, in particular cathode material, for a

electrochemical energy store, in particular for a lithium cell, comprising particles (14) having at least one sodium-doped, lithiierbares, transition metal oxide-based active material, wherein the particles (14) or the particles (14) having basic body (20) at least partially with a Function layer (16) are provided or is which lithium ions is conductive and comprises niobium and / or tungsten and / or molybdenum. The electrode material according to claim 4, wherein the functional layer (16) comprises niobium, in particular niobium (IV), and / or tungsten, in particular tungsten (IV).

An electrode material according to claim 4 or 5, wherein the at least one active material has the general chemical formula:

x (LiMO ₂ ): 1-x (Li ₂ -yNa _y MnO ₃ ),

where M is nickel and / or cobalt and / or manganese and where 0 <x <1 and 0 <y <0.5,

in particular where M is nickel, cobalt and manganese,

in particular wherein the at least one active material is based on the general chemical formula:

x (LiNi _a Co _b Mni _a - _b 0 ₂ ): 1-x (Li ₂ -yNa _y MnO ₃ )

wherein 0 <a <1, in particular 0.2 <a <0.8, and wherein

0 <b <1, in particular 0 <b <0.5, is.

An electrode material according to any one of claims 4 to 6, wherein the at least one active material is an active material according to any one of claims

1 to 3 includes or is.

Process for the preparation of an active material, in particular

Cathode active material, and / or an electrode material, in particular a cathode material, and / or an electrode (10,10 '), in particular a cathode, for an electrochemical energy store, in particular for producing an active material according to one of claims 1 to 3 and / or an electrode material according to one of claims 4 to 7 and / or an electrode (10, 10 ') according to claim 14, comprising the method steps:

- Providing (100, 100 ') of particles (14) comprising at least one lithiierbares, transition metal oxide-based active material or a particle (14) having the base body (20), wherein the at least one active material by means of a polymer pyrolysis process

(100a, 100b, 100d, 100e _, 100a ', 100b', 100d ', 100e') and / or is doped with sodium; and - Coating (102,108 ') of the particles and / or the base body (20) with a functional layer (16) which is conductive lithium ions and niobium and / or tungsten and / or molybdenum.

The method of claim 8, wherein the polymer pyrolysis method (100a, 100b, 100d, 100e _, 100a ', 100b', 100d ', 100e') comprises the steps of:

Dissolving and / or dispersing (100a, 100a ') at least one

Lithium salt and a transition metal salt in a solution comprising at least one polymerizable monomer, especially acrylic acid;

Polymerizing (100b; 100b ') the at least one polymerisable monomer to at least one polymer, in particular polyacrylate;

- Pyrolysing (100d, 100d ') of the at least one polymer; and

Calcination (100e, 100e ') of the one remaining after pyrolysis

Residue.

The method of claim 9, wherein at least one lithium salt, a

Sodium salt and a transition metal salt, in particular manganese salt, dissolved and / or dispersed in the solution (100a, 100a '), in particular wherein at least one lithium salt, a sodium salt, a manganese salt, a nickel salt and a cobalt salt are dissolved and / or dispersed in the solution ( 100a, 100a ').

Method according to one of claims 8 to 10, wherein the functional layer (16) comprises niobium and / or tungsten.

A method according to any one of claims 8 to 11, wherein the at least one active material is based on the general chemical formula:

x (LiMO ₂ ): 1-x (Li ₂ -yNa _y MnO ₃ ),

x (LiNi _a Co _b Mni _a - _b 0 ₂ ): 1-x (Li ₂ -yNa _y MnO ₃ ) wherein 0 <a <1, in particular 0.2 <a <0.8, and wherein

0 <b <1, in particular 0 <b <0.5, is.

13. Active material and / or electrode material, produced by a method according to one of claims 8 to 12.

14 electrode (10,10 '), in particular cathode, comprising at least one active material according to any one of claims 1 to 3 or 13 and / or an electrode material according to any one of claims 4 to 7 or 13 and / or produced by a method according to one of Claims 8 to 12.

15. Electrochemical energy store, in particular lithium cell and / or lithium battery, comprising at least one active material according to one of claims 1 to 3 or 13 and / or an electrode material according to one of claims 4 to 7 or 13 and / or an electrode according to claim 14th