EP3384541A1

EP3384541A1 - Sic separator and sic cell

Info

Publication number: EP3384541A1
Application number: EP16805039.1A
Authority: EP
Inventors: Ulrich Sauter; Frank Baumann; Joerg Thielen
Original assignee: Robert Bosch GmbH
Current assignee: Robert Bosch GmbH
Priority date: 2015-12-04
Filing date: 2016-11-24
Publication date: 2018-10-10
Also published as: WO2017093107A1; US20200274124A1; DE102015224345A1; CN108292727A

Abstract

The invention relates to a separator and/or to a protective layer (4) for a lithium cell (1). In order to permit fast charging of the cell (1) and to prolong the service life of the cell (1), the separator and/or the protective layer (4) comprise a copolymer and/or a polymer mixture, wherein the copolymer comprises at least one repetition unit for forming a polymer having a lithium iron transference number > 0.7 and at least one mechanically stabilizing repetition unit, and/or wherein the polymer mixture comprises at least one polymer having a lithium ion transference number > 0.7 and at least one mechanically stabilizing polymer. The invention further relates to cells and to copolymers, polymer mixtures, and polymer electrolytes based on polymers having a lithium iron transference number > 0.7.

Description

description

title

SIC separator and SIC cell

The present invention relates to a separator and / or protective layer for a lithium cell and such cells as well as copolymers, polymer blends and polymer electrolytes therefor.

State of the art

Lithium battery cells include a cathode, an anode, and a separator. The cathode and the anode are electrically conductively connected to one another, in particular via current collectors for the supply and removal of electric current via an external circuit. In the cell, in particular between the cathode and the anode, the circuit is at least one

Electrolyte closed.

Mostly, liquid electrolytes are used from a liquid solvent in which a conducting salt is dissolved.

Some battery cells have one instead of one liquid electrolyte

Polymer electrolytes based on a polymer having a conductive salt dissolved therein. In order to increase the conductivity, a liquid solvent may be mixed with polymer electrolytes, whereby a polymer gel electrolyte may be formed. Anodes of metallic lithium tend, especially when using liquid electrolytes or polymer gel electrolytes and / or mechanically not sufficiently stable polymer electrolytes, to form dendrites.

The document EP 1098382 relates to a polyelectrolyte gel for a

electrochemical device.

The document US 2006/0177732 relates to battery electrodes and method for the production of alkali metal electrodes with a reinforced glassy

Protective layer.

Disclosure of the invention

The present invention is a separator and / or a

Protective layer for a lithium cell, for example for a lithium-ion cell or a lithium-sulfur cell, in particular in the form of a solid cell, which comprises a copolymer and / or a polymer mixture (blend).

In particular, the copolymer comprises at least one

Repeating unit for forming a polymer with a lithium ion transfer number> 0.7 and at least one mechanically stabilizing repeating unit and / or in this case comprises the polymer mixture at least one polymer having a lithium ion transfer number> 0.7 and at least one mechanically stabilizing polymer.

In this case, the separator and / or the protective layer, for example, a

(simple) separator or separator with protective layer function for an anode or cathode, in particular against dendrite growth, for example for a lithium-metal anode, or a protective layer for an anode or cathode, in particular against dendrite growth, for example for a lithium-metal anode Anode, his.

Under a mechanically stabilizing repeating unit can

in particular a repeating unit are understood which rigid Groups, in particular aromatic groups includes. For example, the mechanically stabilizing repeat unit may comprise an aromatic group. For example, the mechanically stabilizing

Repeat unit be a styrene and / or phenylene-based unit. The at least one mechanically stabilizing repeating unit can be designed, in particular, to form a mechanically stabilizing polymer.

A mechanically stabilizing polymer may, in particular, be understood as meaning a polymer which has rigid groups, in particular aromatic groups

Groups, includes. For example, the mechanically stabilizing polymer may be an aromatic group-having polymer. For example, the mechanically stabilizing polymer may be a styrenic and / or phenylene based polymer, for example, a polystyrene and / or polyphenylene.

By the at least one repeating unit to form a polymer having a lithium ion transfer number> 0.7 or at least one polymer having a lithium ion transfer number> 0.7 can

Advantageously, extreme concentration gradient, which in an application of high current densities over long periods of classical

Liquid electrolytes, for example a solution of the conductive salt

Lithium bis- (trifluoromethane-sulfonyl) imide (LiTFSI) in a mixture of

Ethylene carbonate (EC), dimethyl carbonate (DMC) and / or diethyl carbonate (DEC), which typically have only transfer numbers <0.5, and in classical polymer electrolytes, for example a mixture of

Polyethylene oxide (PEO) and the conductive salt lithium bis (trifluoromethane "sulfonyl) imide (LiTFSI), which typically have only about 0.25 transfer coefficients occur and can lead to high overvoltages, which can limit the achievable current densities, at least minimized or be avoided. By minimizing or avoiding extreme concentration gradients, it is possible, in particular, to prevent areas of conductive salt from becoming depleted, resulting in a high degree of concentration

Reduction of the electrochemical kinetics and thus to an increase of the kinetic overvoltages and to a preference of unwanted electrochemical side reactions and possibly even to Cell damage can result. On the other hand, it is thus possible in particular to avoid conductive salts precipitating in areas of very high salt concentration, which may lead to blockage of pores and optionally even to a reduction of the local conductivity by several orders of magnitude.

Thus, advantageously high current densities over long periods or large Δ-SOC regions, in particular for a constant high current load, for example of 3C or higher, in charging and

Entladerichtung, maintained and in particular a fast charging of the cell can be realized.

In addition, a high lithium dendritic resistance, in particular of the separator and / or the protective layer, can be achieved by the at least one mechanically stabilizing repeating unit or the at least one mechanically stabilizing polymer, which is advantageous for the

Life of a cell equipped with it, for example, with a lithium metal anode, can affect.

In addition to an increase in mechanical stability, mechanically stabilizing units or polymers, in particular styrene-based units or polymers, in particular in the copolymer, may optionally advantageously improve the solubility of the block copolymer in comparison to a pure single-ion conducting polymer homopolymer. Thus, the production and application of thin film can be simplified to a cathode and / or anode.

Overall, therefore, by using the copolymer and / or the polymer mixture or the separator based thereon and / or the protective layer based thereon, lithium cells, in particular based on solid electrolyte, can be provided in a simple manner, which can be charged and discharged quickly and have a long service life and can be used in particular in electric vehicles.

In one embodiment, the at least one mechanically stabilizing repeating unit comprises or is at least one styrene based repeating unit and / or comprises or is the at least one mechanically stabilizing polymer at least one styrene-based polymer.

Styrene-based repeating unit may, for example, styrene and / or styrene derivatives, for example by simple or multiple

Substitution and / or functionalization of styrene are derivable to be.

A styrene-based polymer may in particular be understood as meaning a polymer obtainable by polymerization of styrene and / or styrene derivatives, for example derivable by simple or multiple substitution of styrene.

For example, the at least one styrene-based repeat unit and / or the at least one styrene-based polymer may be prepared by polymerization of styrene and / or o-methylstyrene and / or p-methylstyrene and / or mt-butoxystyrene and / or 2,4-dimethylstyrene and / or m-chlorostyrene and / or p-chlorostyrene and / or 4-carboxystyrene and / or vinylanisole and / or vinylbenzoic acid and / or vinylaniline and / or vinylnaphthalene.

The at least one repeating unit for forming a polymer having a lithium ion transfer number> 0.7 and / or the at least one polymer having a lithium ion transfer number> 0.7 may in particular have a lithium ion transfer number> 0.8.

For example, the at least one repeating unit may be formed to form a polymer having a lithium ion transduction number> 0.7, in particular

> 0.8, a borate-based unit and / or a sulfonic acid-based unit and / or an imide-based, in particular sulfonylimide-based, unit and / or a unit based on lithiated acrylic acid and / or methacrylic acid and / or a Include or be perfluoroether-based moiety. From such units formed polymers can advantageously transfer numbers

> 0.8.

Alternatively or additionally, the at least one polymer having a lithium ion transfer number> 0.7, in particular> 0.8, a borate-based Polyelectrolytes and / or a sulfonic acid-based polyelectrolyte and / or an imide-based, in particular sulfonylimide-based, polyelectrolyte and / or a polyelectrolyte based on lithiated acrylic acid and / or methacrylic acid and / or a perfluoropolyether-based polymer include or be. Such polymers may advantageously have transfer numbers> 0.8.

In particular, the at least one repeat unit for forming a polymer having a lithium ion transfer number> 0.7 and / or the at least one polymer having a lithium ion transfer number> 0.7 may have a lithium ion transfer number> 0.9.

Single-ion-conducting polyelectrolytes may advantageously have lithium-ion transfer numbers> 0.9, which in particular may even be close to 1.

In the context of a further embodiment, therefore, the at least one repeating unit for forming a polymer having a lithium ion transfer number> 0.7, in particular> 0.9, to form a

designed and / or comprises or is the at least one polymer having a lithium ion transfer number> 0.7, in particular> 0.9, a single-ion conducting polyelectrolyte.

Under a single ion conducting polyelectrolyte (SIC, English: Single Ion Conductor) can in particular an electrolyte, in particular polymer

or polymer electrolyte, understood in the anions firmly, in particular covalently, attached to a polymer back and / or, in particular directly, in a polymer back or in a

Polymer scaffold are integrated and thus only the corresponding cations, especially lithium ions, mobile / are mobile. Thus, only the type of ion, namely the lithium ions, which also participates in the electrochemical electrode reaction, is mobile.

Single-ion-conducting polyelectrolytes are characterized by transfer numbers for lithium ions (Li ⁺ ) close to 1. Therefore, by single ion-conducting Polyelectrolytes extreme concentration gradient avoided and particularly high current densities are achieved.

In particular, the copolymer may comprise at least one repeating unit for forming a single-ion conducting polyelectrolyte and at least one styrene-based repeating unit and / or the polymer mixture at least one single-ion conducting polyelectrolyte and at least one styrene-based polymer.

A repeating unit for forming a single ion conducting

Polyelectrolytes may comprise, for example, a solid, in particular covalent, bound to the polymer back, for example tethered or integrated therein, negatively charged group Q ^" or an anion and a mobile positively charged counterion, in particular lithium ion.

A single ion conducting polyelectrolyte may in particular have a solid,

in particular covalently, bound to a polymer backbone unit, for example bound or integrated therein, negatively charged group Q ^" or an anion and a mobile positively charged counterion, in particular lithium ion.

In a further embodiment, the at least one repeating unit comprises or is for forming a polymer with a

Lithium ion transfer number> 0.7, in particular> 0.9, or the at least one repeating unit to form a

single-ion conducting polyelectrolytes a borate-based unit and / or a sulfonic acid-based unit and / or an imide-based, in particular

Sulfonylimide-based, unit and / or a unit based on lithiated acrylic acid and / or methacrylic acid, and / or comprises or is the at least one polymer having a lithium ion transfer number> 0.7, in particular> 0.9, or the at least one single-ion conducting polyelectrolyte a borate-based polyelectrolyte and / or a sulfonic acid-based

Polyelectrolyte and / or an imide-based, in particular sulfonyl imide-based, polyelectrolyte and / or a polyelectrolyte based on lithiated acrylic acid and / or methacrylic acid. In the following some examples of such units or polymers are explained, which can have transfer numbers> 0.8.

Borate-based single-ion-conducting polyelectrolytes can be formed, for example, in the form of an anionic borate network (borate anion network). The anionic borate network may be formed by borate anions, which are bound by at least one linker, for example tartaric acid. An example of such a borate-based

Polyelectrolytes with the general chemical formula:

is described in Solid State Ionics 262, 2014, pp. 747-753.

However, borate-based polyelectrolytes may also be formed, for example, in the form of polymers having, in particular covalently, borate groups attached to the polymer back of the polymer. An example of such a borate-based polyelectrolyte, which consists of monomers of the general chemical formula:

rc is trained in Polym. Chem., 2015, 6, p. 1052. However, these polyelectrolytes usually reach sufficient conductivity only in the form of a gel with a liquid component.

In the context of a specific embodiment, the at least one repeating unit for forming a polymer having a lithium ion transfer number> 0.7, in particular> 0.9, comprises or is a borate-based unit of the general chemical formula:

where at least one X, in particular at least two X, for example or four X, for

where 2 <n <10, in particular 3 <n <10, where the remaining X are in each case independent of each other

or R ', where 2 <m <10, in particular 3 <m <10, and wherein R' is hydrogen or fluorine. By at least two double bonds so advantageously a network can be formed and in this way the mechanical stability and thus lithium dendrite resistance can be improved. By extending the linker and / or introducing further ethylene oxide groups, the lithium ion conductivity can thus advantageously be improved even without the addition of liquid components. Examples of sulfonic acid-based polyelectrolytes are Li-Nafion, for example the general chemical formula:

and / or comparable sulfonic acid-based polymers such as those described in Zhibin Zhou et al in Electrochimica Acta, 93, 2013, pp. 254-263

Sulfonic acid-based polyelectrolytes of the general chemical formula:

Imide-based, especially sulfonylimide-based, polyelectrolytes may be based on, for example, poly (perfluoroalkylsulfonyl) imide. Imide-based, in particular sulfonylimide-based, polyelectrolytes of the general chemical formula:

are in J. Mater. Chem. A, 2014, 2, 15952. For example, imide-based, especially sulfonylimide-based, polyelectrolytes may also be based on (4-styrenesulfonyl) (trifluoromethanesulfonyimide) monomers. Examples of these are homopolymers or copolymers of the general chemical formula: o = s = o

® Li® Nö Li® i [o o

o = s = o 0 = S = 0

by

and or

Examples of polyelectrolytes based on lithiated acrylic acid and / or methacrylic acid are, for example, poly-MMALi or related polyelectrolytes.

Examples of perfluoropolyether-based polymers of the general chemical formulas:

(-Diol) and

(PFPE-DMC)

are described in Proceedings of the National Academy of Sciences, 111, 2014, p. 3327. Such perfluoropolyether-based polymers are - in contrast to the other polyelectrolytes described above - usually no single-ion conducting polyelectrolytes, but lithium ion conductive polymers which have neither tightly bound anions nor mobile cations and only with the addition of a Lithiumleitsalzes, such as Lithiumbis-- (trifluor- methane - sulfonyl) imide (LiTFSI), lithium ion conducting. Nevertheless, they can have high transfer rates. This could be due to the fact that the fluorination reduces the electron density on the perfluoropolyether oxygen and thus weakens the coordination between oxygen and lithium ion and thus increases the lithium cation dynamics, at the same time the fluorinated salt anion interacts very strongly with the perfluoropolyether and its Mobility is reduced and thus the amount of the transfer number is positively influenced. Insofar as the electrolyte of the cathode (catholyte) and / or the anode (anolyte) is based solely on single-ion conducting polyelectrolytes and / or inorganic single-ion conductors which do not require the addition of lithium conducting salt, the copolymer and / or the polymer mixture

preferably free of such perfluoropolyether-based units / polymers in order to avoid depletion of the perfluoropolyether-based units / polymers and thus of the separator by dissolution and diffusion of the salts into the cathode or anode.

For example, at least one repeating unit for forming a polymer having a lithium ion transference number> 0.7, in particular> 0.9, or the at least one repeating unit for forming a single-ion conducting polyelectrolyte

a borate-based unit of general chemical formulas:

, where at least one X, in particular Rei X or four

stand,

where 2 <n <10, in particular 3 <n <10,

where the remaining X are each independently

or R 'stand,

wherein 2 <m <10, in particular 3 <m <10, and wherein R 'is hydrogen or fluorine; and or

an imide-based, in particular sulfonylimide-based, unit of the

general chemical formula:

; and or

a sulphonic acid based unit of general chemical formula:

include or be.

The at least one repeat unit for forming a polymer having a lithium ion transfer number> 0.7 and / or the at least one polymer having a lithium ion transfer number> 0.7 can be obtained in particular by polymerizing at least one double bond. For example, the borate-based unit and / or the sulfonic acid-based unit and / or the imide-based, in particular sulfonylimide-based, unit and / or the unit based on lithiated acrylic acid and / or methacrylic acid and / or the perfluoroether based unit and / or the borate-based polyelectrolyte and / or the sulfonic acid-based polyelectrolyte and / or the imide-based, in particular sulfonylimide-based, polyelectrolyte and / or the polyelectrolyte based on lithiated acrylic acid and / or methacrylic acid and / or the Perfluoropolyether-based polymer can be obtained by polymerization of at least one double bond. Such units or polymers can advantageously be copolymerized by classical copolymerization with styrene, in particular so as to obtain in a simple manner a mechanically stabilized copolymer for use as a separator and / or protective layer.

For example, the copolymer may be prepared by copolymerizing styrene and / or a styrene derivative, for example o-methylstyrene and / or p-methylstyrene and / or mt-butoxystyrene and / or 2,4-dimethylstyrene and / or m-chlorostyrene and / or p-chlorostyrene and / or 4-carboxystyrene and / or vinylanisole and / or vinylbenzoic acid and / or vinylaniline and / or vinylnaphthalene, with a monomer of the general chemical formula:

where at least one X, in particular at least two X, for example three X or four X, for

or or R ', where 2 <m <10, in particular 3 <m <10, and wherein R' is hydrogen or fluorine, and / or with a monomer of the general chemical formula:

, in particular by means of a hydrolysis to sulfonic acid with subsequent lithiation, and / or

m monomer of general chemical formula;

O ™ ~ S ™ * ~ 0

i

® Li®

0 = 5 = 0

i

3

getting produced.

In another embodiment, the copolymer is a block copolymer. In this case, the block copolymer may in particular at least one, in particular single-ion conducting, block (b-A) of at least one

Repeating unit for forming a polymer having a lithium ion transfer number> 0.7 (A) and at least one, in particular mechanically stabilizing, block (b-B) comprising at least one mechanically stabilizing repeat unit (B).

In particular, the block copolymer (b-SIC-b-PS) at least one, in particular single-ion conducting, block (b-SIC) of at least one

Repeating unit for forming a single-ion conducting polyelectrolyte (SIC) and at least one, in particular mechanically stabilizing, block b-PS) comprising at least one styrene-based repeating unit (PS).

The, in particular single-ion conducting, block (b-A) can both a

Homopolymer of a repeating unit for forming a polymer having a lithium ion transmittance> 0.7 (A), in particular, a single-ion conductive polyelectrolyte, as well as a random copolymer of a plurality of different repeating unit to form a Polymer with a lithium ion transfer number> 0.7 (A), in particular a single-ion conducting polyelectrolyte.

The, in particular mechanically stabilizing, block (bB) can be both a homopolymer of a mechanically stabilizing, in particular styrene-based, repeating unit (B) and a random copolymer of several different mechanically stabilizing, in particular styrene-based, repeating unit (B) ,

In addition to a di-block copolymer (b-A-b-B), for example, tri-block copolymers (b-A-b-B-b-A or b-B-b-A-b-B, such as b-PS-b-SIC-b-PS) and multi-block copolymers are possible.

Within the scope of a further embodiment, the copolymer furthermore comprises at least one lithium ion-conductive repeat unit and / or the polymer mixture furthermore comprises at least one lithium ion-conductive polymer.

Thus, advantageously, the mobility of the lithium ions in the system and thus the conductivity at a consistently high transfer ratio can be increased close to 1. This may be advantageous in particular in the case of borate-based units / polyelectrolytes and / or imide-based units / polyelectrolytes.

Under a lithium ion conductive material, such as a

Lithium ion conductive repeating unit or a

Lithium ion conductive polymer, in particular a material, for example a repeating unit or a polymer can be understood, which itself may be free of the conductive ions, for example lithium ions, but is designed to the conductive ions themselves, for example lithium ions coordinate and / or solvate and / or coordinate counter ions of the ions to be conducted, for example lithium lead salt anions, and for example with the addition of the conductive ions, for example lithium ions, in particular in the form of a single-ion conducting polyelectrolyte and / or optionally in the form a conducting salt, becomes lithium ion conductive. In a further embodiment, the at least one lithium ion-conducting repeat unit comprises or is an alkylene oxide unit, for example an ethylene oxide unit (EO) and / or a propylene oxide unit (PO), in particular an ethylene oxide unit (EO), and / or one

Oligoethylenglycolmethacrylat unit (OEGMA) and / or a

Oligoethylenglycolacrylat unit, in particular a

Oligoethylenglycolmethacrylat unit (OEGMA), and / or comprises or is the at least one lithium ion conductive polymer is a polyalkylene oxide,

For example, polyethylene oxide and / or polypropylene oxide, in particular polyethylene oxide, and / or poly (oligoethylenglycol) methacrylate (P- (OEGMA) and / or poly (oligoethylenglycol) acrylate, in particular poly (oligoethylenglycol) methacrylate (P- (OEGMA).

The at least one lithium ion conductive repeating unit can, for example, via a block copolymerization or as statistical

Copolymerization in the copolymer, in particular block copolymer can be integrated.

For example, the block copolymer may further comprise at least one, especially lithium ion-conductive, block (b-C, for example b-OEGMA /

/ EO / PO) from at least one lithium ion-conducting repeat unit (C, for example OEGMA / EO / PO).

The integration of the at least one, in particular lithium ion-conductive, block can, for example, from a terminal hydroxide group (OH-

Group) of the at least one, in particular lithium ion conductive, block, which is reacted with, for example, with acryloyl chloride or a-bromoisobutyryl bromide, followed by a radical polymerization can follow, by which the at least one, in particular mechanically

stabilizing, block of at least one mechanically stabilizing, in particular styrene-based, repeating unit and / or the at least one, in particular single-ion conducting, block of at least one

Repeating unit for forming a polymer having a lithium ion transfer number> 0.7, in particular a single-ion conducting

Polyelectrolyte, is linked. For example, the integration of the at least one, in particular lithium ion-conductive, blocks of a terminal hydroxide group (OH group) of the at least one,

in particular lithium ion-conductive blocks emanating, which is reacted with a-bromoisobutyryl bromide, which can be followed by an atom transfer radical polymerization (ATRP), by which the at least one, in particular mechanically stabilizing, block of at least one mechanically stabilizing, in particular styrene-based .

Repeat unit and / or the at least one, in particular

single-ion conducting, block of at least one repeating unit to form a polymer having a lithium ion transfer number> 0.7, in particular a single-ion conducting polyelectrolyte, is attached. By such a reaction with acid chlorides, in particular, an integration of perfluoropolyether-based polymers can be achieved. In a further embodiment, the block copolymer is a di-

Block copolymer (bAbB, for example b-SIC-b-PS) or a tri-block copolymer (bAbBbA or bBbAbB or bAbBbC, for example b-SIC-b-PS-b-SIC or b-PS-b-SIC) b-PS or bAbBb-OEGMA / EO / PO) or a multi-block copolymer (bAbCbBbCbA or bBbCbAbCbB, for example b-SIC-b-OEGMA / EO / PO-b-PS-b-OEGMA / EO / PO-b -SIC or b-

PS-B-EGMA / EGA / EO / PO-b-SIC-b-OEGMA / EO / PO-b-B).

In the case of block copolymers, if appropriate-for example when casting a polymer layer from a solution-a lamellar self-assembly can take place, which leads to improved properties of the separator and / or the

Protective layer can lead.

To optimize the mechanical stability and / or the

Transport properties, the above-mentioned (co) polymers and block copolymers, for example, also be mixed together

(Blends). In this case, for example, polymer mixtures of at least one polymer having a lithium ion transfer number> 0.7, in particular at least one single-ion conducting polyelectrolyte, and at least one mechanically stabilizing, in particular styrene-based, polymer and optionally at least one lithium ion conductive polymer - for example, even without block copolymerization - provide a Separatorschicht, which may have sufficient lithium ion transport properties and sufficient mechanical stability. However, a tendency can be better by copolymers, in particular by block copolymers

Assembly of the conductive and stabilizing units can be achieved and so better lithium ion transport properties can be achieved.

In order to further increase the mechanical stability or lithium dendrite resistance, for example, a mixture of a copolymer, in particular a block copolymer, with at least one further mechanically stabilizing polymer can be used.

In order to further increase the lithium ion transport properties, can

Example, a mixture of a copolymer, in particular block copolymer, be used with at least one further polymer having a lithium ion transfer number> 0.7 and / or with at least one further lithium ion conductive polymer.

For example, to improve bonding properties, a blend of a copolymer, especially a block copolymer, and at least one polyvinylidene fluoride (PVDF) based binder may be used.

Also mixtures of different block copolymers with other block copolymers, for example, b-A-b-B with b-A-b-B ', b-A-b-B-b-A with b-A-b-B-b-A', B-B-b-A-b-B with b-B-b-A-b-B 'or b-A-b-B-b-C and b-A-b-B-b-c, b-A-b-B-b-C and b-A-b-B-b-A, b-A-b-B-b-C and b-B-b-A-b-B.

For additional optimization of the mechanical stability and / or the

Transport properties of the separator and / or the protective layer, the separator and / or the protective layer further at least one, in particular ceramic and / or glassy, inorganic ion conductor, in particular single-ion conductors, and / or at least one further additive, for example at least one filler, for example silica ( S1O2), titanium dioxide (T1O2) or alumina (Al2O3). Within the scope of a further embodiment, the separator and / or the protective layer therefore furthermore comprises at least one, in particular ceramic and / or glass-like, inorganic ion conductor, in particular single ion conductor. For example, the at least one, in particular ceramic and / or glassy, inorganic ion conductor, in particular single-ion conductor, a lithium ion transfer number> 0.7, for example> 0.8, for example> 0.9, have.

Under an inorganic single ion conductor can in particular a

inorganic electrolyte, understood to be solid in the anions,

in particular ionically, to a structure, for example a crystal lattice, connected and / or, in particular directly, into a structure, for example a crystal lattice, are integrated and thereby only the corresponding cations, in particular lithium ions, are mobile / movable. Thus, only the type of ion, namely the lithium ions, which also participates in the electrochemical electrode reaction, is mobile.

Inorganic single ion conductors are also known

Transfer numbers for lithium ions (Li ⁺ ) close to 1 out. Therefore, it is also possible to avoid extreme concentration gradients and high current densities by means of inorganic single-ion conductors.

For example, the at least one, in particular ceramic and / or glassy, inorganic ion conductor, in particular single ion conductor, comprise or be at least one sulfidic ion conductor, in particular single ion conductors. The at least one inorganic, in particular sulfidic, ion conductor can be glassy, for example. For example, the at least one inorganic, especially sulfidic, ionic conductor may be based on the general chemical formula: (Li 2 S) _x : (P 2 S s) _y : D _z , where D _{z is} one or more additives, for example LiCl and / or LiBr and / or Lil and / or LiF and / or Li2Se and / or L12O and / or P2Ses and / or P2O5 and / or L13PO4 and / or one or more sulphides of germanium, boron, aluminum,

Molybdenum, tungsten, silicon, arsenic and / or niobium, in particular germanium, stand, x, y and z may stand in particular for component ratios. Such ion conductors can be made, for example, from the individual components L12S and P2S5 and optionally D are synthesized. The synthesis may optionally be carried out under protective gas.

In particular, the at least one, in particular ceramic and / or glassy, inorganic ion conductor, in particular single ion conductor, may comprise or be a lithium argyrodite and / or a sulfidic glass.

These single ion conductors have proven to be particularly advantageous because they can have high ionic conductivity and low contact junction resistances at the grain boundaries within the material as well as to other components, for example the cathode active material. In addition, these ion conductors can be ductile, which is why they can be used particularly advantageously in the case of porous active materials, which may, for example, also have a rough surface. Overall, so can advantageously the long-term stability and performance of the cathode material

equipped cell further improved.

Lithium argyrodites may in particular be understood as meaning compounds derived from the mineral argyrodite of the general chemical formula: AgeGeS6, where silver (Ag) is replaced by lithium (Li) and in particular germanium (Ge) and / or sulfur (S ) by other elements, for example I II., IV., V., VI. and / or VI I. main group, may be replaced.

Examples of lithium argyrodites are:

Compounds of the general chemical formula:

Li ₇ PCh ₆

where Ch is sulfur (S) and / or oxygen (O) and / or selenium (Se), for example sulfur (S) and / or selenium (Se), in particular sulfur (S)

Compounds of the general chemical formula:

Li ₆ PCh ₅ X

where Ch is sulfur (S) and / or oxygen (O) and / or selenium (Se), for example sulfur (S) and / or oxygen (O), in particular sulfur (S), and X is chlorine (Cl) and / or bromine (Br) and / or iodine (I) and / or fluorine (F), for example X represents chlorine (Cl) and / or bromine (Br) and / or iodine (I), Compounds of the general chemical formula:

Ι_ΐ7-δΒΟΪΐ6-δΧδ

where Ch is sulfur (S) and / or oxygen (O) and / or selenium (Se), for example sulfur (S) and / or selenium (Se), in particular sulfur (S), B is phosphorus (P) and / or Arsenic (As), X is chlorine (Cl) and / or bromine (Br) and / or iodine (I) and / or fluorine (F), for example X is chlorine (Cl) and / or bromine (Br) and / or iodine (I), and 0 <δ <1.

For example, the at least one inorganic ion conductor at least one lithium Argyroditen the chemical formula: Li ₇ PS6, Li ₇ PSe6, LiePSsCI, Li ₆ PS ₅ Br, Li ₆ P ₅ L, Li _{_7-5} P ₆ -5CI _5, Li ₇ - ₅ HP ₆ -5Br ₅ , Li ₇ -öPS «Lö, Li ₇ - ₅ PSe ₆ - ₅ CI ₅ , Li ₇ - ₅ PSe ₆ - ₅ Br ₅ , Li ₇ - ₅ PSe6-5lö, Li _7-5 AsS6-5Br ₅ , Li ₇ - ₅ AsS6-5l5, Li ₆ AsS ₅ l, Li ₆ AsSe ₅ l, Li ₆ P0 ₅ Cl, LiePOsBr and / or L16PO5I. Lithium argyrodites are described, for example, in the publications: Angew. Chem. Int. Ed., 2008, 47, 755-758; Z. Anorg. Gen. Chem., 2010, 636, 1920-1924; Chem. Eur. J., 2010, 16, 2198-2206; Chem. Eur. J., 2010, 16, 5138-5147; Chem. Eur. J., 2010, 16, 8347-8354; Solid State Ionics, 2012, 221, 1-5; Z. Anorg. Gen. Chem., 201 1, 637, 1287-1294; and Solid State Ionics, 2013, 243, 45-48.

In particular, the lithium argyrodite may be a sulphidic lithium argyrodite, for example where Ch is sulfur (S).

Lithium argyrodites can be prepared in particular by a mechanical-chemical reaction process, for example, wherein starting materials such as lithium halides, for example LiCl, LiBr and / or Lil, and / or

Lithium chalcogenides, for example L12S and / or Li2Se and / or L12O, and / or chalcogenides of main group V, for example P2S5, P2Ses, L13PO4, in particular in stoichiometric amounts, are milled together. This can, for example, in a ball mill, in particular a

High energy ball mill, for example, with a number of revolutions of 600 rpm done. In particular, the grinding can be carried out under a protective gas atmosphere.

For example, the at least one inorganic ionic conductor may comprise at least one sulfidic glass of the chemical formula LiioGeP2Si2, Li2S- (GeS2) -P2Ss

and / or L12S-P2S5. For example, the at least one inorganic ionic conductors comprise a germanium-containing sulphidic glass, for example LiioGeP2Si2 and / or Li2S- (GeS2) -P2Ss, in particular LiioGeP2Si2. Sulfide lithium ionic conductors can advantageously have a high

Have lithium ion conductivity and chemical stability.

In a specific embodiment, the at least one inorganic ion conductor comprises or is a lithium argyrodite. Lithium argyrodites are advantageously characterized by particularly low

Contact contact resistances at the grain boundaries within the material and to other components, such as the active material particles, from. Thus, advantageously, a particularly good ion conduction can be achieved at and within the grain boundary surfaces. Advantageously, lithium argyrodites can also have a low contact resistance between grains even without a sintering process. Thus, advantageously, the production of the electrode or the cell can be simplified.

With regard to further technical features and advantages of the separator according to the invention and the protective layer according to the invention, reference is hereby explicitly made to the explanations in connection with the cells according to the invention, the copolymer according to the invention, the polymer mixture according to the invention and the polymer electrolyte according to the invention and to the figures and the description of the figures.

Another object of the invention is a lithium cell, such as a lithium-ion cell or lithium-sulfur cell, and / or solid cell, which is a separator according to the invention and / or a novel

Protective layer comprises. In this case, the cell may comprise a cathode and an anode, wherein the separator and / or the protective layer between the cathode and the anode is arranged. The anode may be, for example, a lithium-metal anode, in particular of metallic lithium.

The separator according to the invention and / or the protective layer according to the invention can advantageously additionally have the function of a barrier for liquid

Components, for example liquid electrolytes and / or ionic liquids, in the electrolyte of the cathode (catholyte) and / or in the electrolyte of the anode (anolyte) take over, since the separator and / or the protective layer is soluble only to a very limited extent of these and thus hardly swellable by them.

The cathode, in particular the catholyte, and / or the anode, in particular the anolyte, can therefore in combination with a separator according to the invention at least one liquid electrolyte, for example from at least one solvent, for example at least one organic carbonate, and at least one lithium conducting salt, for example

Lithium bis (trifluoromethane-sulfonyl) imide (LiTFSI), and / or at least one ionic liquid (English: lonic liquid) have. Through this

Liquid components can advantageously be increased significantly with continued high lithium ion transfer number (t +), the conductivity and lithium diffusion of the catholyte or anolyte.

Calculations have shown that when using a separator according to the invention and / or a protective layer according to the invention it may be sufficient to use in the cathode and / or anode optionally also an electrolyte, for example catholyte or anolyte, which only has a transfer coefficient of <0.7, preferably of> 0.5. Therefore, in combination with a separator according to the invention, the cathode and / or the anode optionally also at least one

Liquid electrolytes and / or polymer gel electrolytes with at least one dissolved therein lithium conductive salt, for example

Lithium bis (trifluoromethane-sulfonyl) imide (LiTFSI), with a transfer number <0.7, preferably of> 0.5, can be used.

In one embodiment, however, the cathode, in particular the catholyte, comprises at least one polymer with a lithium ion

Conversion number> 0.7, in particular> 0.8, for example> 0.9, and / or at least one, in particular ceramic and / or glassy, inorganic ion conductor, in particular single-ion conductors, for example with a lithium ion transfer coefficient> 0.7, in particular> 0.8, for example> 0.9, and / or comprises the anode, in particular the anolyte, at least one Polymer having a lithium ion transfer coefficient> 0.7, in particular> 0.8, for example> 0.9, and / or at least one, in particular ceramic and / or glassy, inorganic ion conductor, in particular single-ion conductor, for example with a lithium ion transfer coefficient> 0 , 7, in particular> 0.8, for example> 0.9.

With regard to further technical features and advantages of such a cell according to the invention, reference is explicitly made to the explanations in

Related to the cell according to the invention described below.

A further subject of the invention is namely a lithium cell, for example a lithium-sulfur cell or lithium-ion cell, and / or solid cell, comprising a cathode and an anode, wherein a separator and / or between the cathode and the anode a protective layer is arranged. In this case, the separator and / or the protective layer comprises at least one polymer having a lithium ion transfer number> 0.7, in particular> 0.8, for example> 0.9, and / or at least one, in particular ceramic and / or glassy, inorganic ion conductor, in particular having a lithium ion transference number> 0.7, in particular> 0.8, for example> 0.9, for example a single-ion conductor, the cathode, in particular the catholyte, (likewise) at least one polymer having a lithium-ion transference number> 0, 7, in particular> 0.8, for example> 0.9, and / or at least one, in particular ceramic and / or glassy,

Inorganic ion conductor, for example, with a lithium ion transfer number> 0.7, in particular> 0.8, for example> 0.9, for example, a single ion conductor, and / or wherein the anode, in particular the anolyte, (also) at least one polymer with a lithium ion transfer coefficient> 0.7, in particular> 0.8, for example> 0.9, and / or at least one, in particular ceramic and / or glassy,

inorganic ion conductor, for example with a lithium ion transfer coefficient> 0.7, in particular> 0.8, for example> 0.9, for example a single-ion conductor. Within the scope of a further embodiment, the at least one polymer having a lithium ion transference number> 0.7, in particular> 0.9, of the separator and / or the protective layer comprises or is a single-ion conducting polyelectrolyte.

In the context of a further, alternative or additional embodiment, the at least one polymer having a lithium ion transfer number> 0.7, in particular> 0.9, comprises or is the cathode a single-ion conducting polyelectrolyte.

In the context of a further, alternative or additional embodiment, the at least one polymer having a lithium ion transfer number> 0.7, in particular> 0.9, comprises or is the anode a single-ion conducting polyelectrolyte.

Characterized in that at least one polymer having a lithium ion transfer number> 0.7, in particular a single-ion conducting polyelectrolyte, and / or at least one inorganic ion conductor, in particular single ion conductor, in particular instead of a polymer electrolyte based on a lithium ion conductive polymer having at least one dissolved therein lithium conductive salt , is used both in the separator and / or the protective layer as well as in the cathode and / or anode, advantageously extreme concentration gradient and concomitant overvoltages, which can limit the achievable current density, at least minimized or avoided. By minimizing or avoiding extreme concentration gradients, it is possible, in particular, to prevent areas of conducting salt from becoming depleted, which leads to a considerable reduction in the electrochemical kinetics and thus to an increase in the kinetic overvoltages and to a preference for undesirable electrochemical side reactions

possibly even lead to cell damage. On the other hand, in particular, it can be avoided that in areas of very high

Salt concentration Conducting salt precipitates, which can lead to a blockage of pores and possibly even to a reduction of the local conductivity by several orders of magnitude. Thus, advantageously high current densities over long periods or large Δ-SOC regions, in particular for a constant high current load, for example of 3C or higher, in charging and

In addition to the function of the electronic insulation of the anode and cathode, the separator can also assume the function of a protective layer for one or both electrodes, for example the anode and / or the cathode, for example a lithium-metal anode, resulting in an improved lithium ion.

Dendrite resistance can be achieved, which is beneficial to the

Life of a cell equipped with it, for example, with a lithium metal anode, can affect. Overall, therefore, through the use of at least one polymer having a lithium ion transfer number> 0.7, in particular of

single ion conducting polyelectrolyte, and / or the at least one inorganic ion conductor, in particular single ion conductor, for example with a lithium ion transfer ratio> 0.7, both in the separator and / or the protective layer as well as in the cathode and / or anode rapid charging and discharging and an extended life of the cell allows and the cell are used in particular in electric vehicles.

Single-ion conducting polyelectrolytes can be compared with the commonly used polymer electrolytes, for example based on

Polyethylene oxide / salt mixtures, which have an electrochemical stability significantly below 4 V compared to lithium metal, advantageously have a higher electrochemical stability. This may be particularly relevant for their use as electrolyte in the cathode (catholyte), especially if their entire capacity is to be used, since many known

Intercalation compounds, such as nickel-cobalt-aluminum oxide (NCA), nickel-cobalt-manganese oxide (NCM), high-energy nickel-cobalt-manganese oxide (HE-NCM), lithium manganese oxide (LMO) and / or Hochvoltspinelle (HV-LMO), which are used as cathode material and are predestined for their properties for cells with high energy densities due to their properties the one compared to LiS-based cells for the

Battery management system have more advantageous comparatively higher mean charge / discharge voltage in the delithiated state potentials> 4 V have.

In the context of a further embodiment, the at least one, in particular ceramic and / or vitreous, inorganic comprises or is

Single ion conductor of the separator and / or the protective layer of a lithium argyrodite and / or a sulfidic glass.

In the context of a further, alternative or additional embodiment, the at least one, in particular ceramic and / or glassy, inorganic individual ion conductor of the cathode comprises or is a lithium argyrodite and / or a sulfidic glass.

In the context of a further, alternative or additional embodiment, the at least one, in particular ceramic and / or glassy, inorganic individual ion conductor of the anode comprises or is a lithium argyrodite and / or a sulfidic glass.

In particular, the separator and / or the protective layer and the cathode may comprise at least one polymer having a lithium ion transference number> 0.7, in particular> 0.8, for example> 0.9, for example a

single ion conducting polyelectrolytes.

For example, the at least one polymer having a lithium ion transfer coefficient> 0.7, in particular> 0.9, or the at least one single-ion conducting polyelectrolyte of the separator and / or the protective layer and / or the cathode and / or the anode, a borate-based polyelectrolyte and / or a sulfonic acid-based polyelectrolyte and / or an imide-based, in particular sulfonylimide-based, polyelectrolyte and / or a polyelectrolyte based on lithiated acrylic acid and / or methacrylic acid and / or a perfluoropolyether-based polymer Within the scope of a further embodiment, the at least one polymer having a lithium ion transfer number> 0.7, in particular> 0.9, or the at least one single-ion conducting polyelectrolyte of the separator and / or the protective layer comprises or is a borate-based polyelectrolyte and / or one Sulfonic acid-based polyelectrolyte and / or an imide-based, in particular sulfonylimide-based, polyelectrolyte and / or a polyelectrolyte based on lithiated acrylic acid and / or methacrylic acid.

In the context of a further, alternative or additional embodiment, the at least one polymer having a lithium ion transference number of> 0.7, in particular> 0.9, or the at least one single-ion conductive polyelectrolyte of the cathode comprises or is a borate-based polyelectrolyte and / or a sulfonic acid -based polyelectrolyte and / or an imide-based, in particular sulfonylimide-based, polyelectrolyte and / or a polyelectrolyte based on lithiated acrylic acid and / or methacrylic acid.

In the context of a further, alternative or additional embodiment, the at least one polymer having a lithium ion transference number of> 0.7, in particular> 0.9, or the at least one single-ion conducting polyelectrolyte of the anode comprises or is a borate-based

Polyelectrolyte and / or a sulfonic acid-based polyelectrolyte and / or an imide-based, in particular sulfonylimide-based, polyelectrolyte and / or a polyelectrolyte based on lithiated acrylic acid and / or methacrylic acid.

In another embodiment, the separator and / or the

Protective layer is a mixture of at least one polymer with one

Lithium ion transfer number> 0.7, in particular> 0.8, for example> 0.9, in particular single-ion conducting polyelectrolyte, and at least one, in particular ceramic and / or glassy, inorganic ion conductor, for example with a lithium ion transfer number> 0.7, in particular > 0.8, for example> 0.9, in particular single-ion conductors, for example a lithium argyrodite and / or a sulfidic glass. In the context of a further, alternative or additional embodiment, the cathode comprises a mixture of at least one polymer having a lithium ion transfer number> 0.7, in particular> 0.8, for example> 0.9, in particular single-ion conducting polyelectrolytes, and at least one, in particular ceramic and / or glassy, inorganic ionic conductor, for example, with a lithium ion transfer number> 0.7, in particular

> 0.8, for example> 0.9, in particular single-ion conductors, for example a lithium argyrodite and / or a sulfidic glass. In the context of a further, alternative or additional embodiment, the anode comprises a mixture of at least one polymer having a lithium ion transfer number> 0.7, in particular> 0.8, for example> 0.9, in particular single-ion conductive polyelectrolytes, and at least one, in particular ceramic and / or glassy, inorganic ionic conductor, for example, with a lithium ion transfer number> 0.7, in particular

> 0.8, for example> 0.9, in particular single-ion conductors, for example a lithium argyrodite and / or a sulfidic glass.

The advantage of such mixtures is that the mixture with comparatively soft polymer, in particular einzelionenleitendem

Polyelectrolyte, the production of a dense cathode with low porosity can be simpler and / or the contact resistance may be even lower than in the case of pure inorganic ion conductor, such as lithium argyrodite and / or sulfidic glass, as the catholyte or anolyte. In the case of a separator can be further improved by such a mixture also advantageously the mechanical stability.

The at least one polymer having a lithium ion transfer coefficient> 0.7 and / or the at least one, in particular ceramic and / or glassy, inorganic ion conductor of the separator and / or the protective layer and the

The cathode and / or the anode do not necessarily have to be identical.

The cathode may, for example, at least one, in particular ceramic and / or glassy, inorganic ion conductor, in particular single ion conductor, or a mixture of at least one, in particular ceramic and / or glassy, inorganic ionic conductors, in particular single-ion conductors, for example a lithium argyrodite and / or a sulfidic glass, and at least one polymer having a lithium ion transfer number> 0.7, for example a single-ion conducting polyelectrolyte.

The separator and / or the protective layer can in particular be at least one polymer having a lithium ion transference number> 0.7, for example a single-ion conducting polyelectrolyte, or a mixture of at least one polymer having a lithium ion transference number> 0.7, for example a single-ion conducting polyelectrolyte, and at least one, in particular ceramic and / or glassy, inorganic ion conductor, in particular single-ion conductors, for example a lithium argyrodite and / or a sulfidic glass and at least one polymer having a lithium ion transfer number> 0.7, for example a single-ion conducting

Polyelectrolytes include. Thus, the separator and / or the protective layer can advantageously be produced in a simple manner as a thin film of <50 μm, for example by a slurry and / or casting process, and can be applied directly to the cathode or anode, for example. In addition, polymers with a lithium ion transmittance> 0.7, for example, single-ion conducting polyelectrolytes, tend to be softer than inorganic ionic conductors, such as sulfidic ones

Glasses and / or lithium Argyrodite, and therefore can tend to realize lower contact resistance.

In one embodiment, the separator and / or the protective layer is a separator according to the invention and / or an inventive

Protective layer. In this case, the lithium cell may be, for example, a lithium cell according to the invention first explained.

In particular, the cathode may comprise a particulate cathode active material. The cathode active material may include, for example

Lithium conversion material, ie a material which can undergo a conversion reaction with lithium, for example based on sulfur, or a lithium intercalation material, ie a material which can intercalate lithium, for example based on metal oxide, for example nickel-cobalt-aluminum Oxide (NCA) and / or nickel-cobalt-manganese oxide (NCM), high-energy nickel-cobalt Manganese oxide (HE-NCM), lithium manganese oxide (LMO) and / or high-voltage spinel (HV-LMO) may comprise or be formed from.

In a specific embodiment, the cathode active material comprises a sulfur-carbon composite, in particular sulfur-polymer and / or carbon-modification composite, or is formed therefrom. For example, the cathode active material may comprise or be formed from a sulfur-polymer composite, for example a composite of one, in particular electrically conductive, polymer with covalently and / or ionically, in particular covalently bonded, sulfur. For example, the cathode active material may include or be formed from a sulfur-polyacrylonitrile composite. For example, the cathode active material may include or be formed from SPAN.

Under SPAN can be understood in particular a based on polyacrylonitrile (PAN), in particular cyclized polyacrylonitrile (cPAN), composite or polymer with, in particular covalently bound sulfur, in particular which by a thermal reaction and / or chemical reaction of polyacrylonitrile in the presence of sulfur is available.

In particular, nitrile groups can react to form a polymer, in particular with a conjugated ττ system, in which the nitrile groups form nitrogen-containing rings, in particular six-membered rings, which are attached to one another.

in particular with covalently bonded sulfur. For example, SPAN can be prepared by heating polyacrylonitrile (PAN) with a

Excess of elemental sulfur, in particular to a temperature of> 300 ° C, for example, about> 300 ° C to <600 ° C, are produced. In this case, the sulfur in particular on the one hand, the polyacrylonitrile (PAN) to form hydrogen sulfide (H2S) and on the other hand - for example, forming a covalent SC bond - finely distributed in the cyclized matrix, for example, where a cyclized polyacrylonitrile structure with covalent sulfur chains, is formed. SPAN is described in Chem. Mater., 201 1, 23, 5024 and J. Mater. Chem., 2012, 22, 23240, J. Electrochem. Soc, 2013, 160 (8) A1 170, and in the publication

WO 2013/182360 A1. When sulfur, for example SPAN, is used as the active material, the separator and / or the protective layer may additionally have the function of a

Take over diffusion barrier. The anode may in particular be a lithium-metal anode. Thus, advantageously, a particularly high specific energy density can be achieved. In this case, the separator and / or the protective layer and the cathode, in particular in each case, at least one polymer having a lithium ion transfer number> 0.7, in particular> 0.8, for example> 0.9, for example, a single-ion conducting polyelectrolyte include

However, it is also possible an anode based on a particulate

To use anode active material. Thus, advantageously, a particularly high rate capability can be achieved. For example, the particulate

Anode active material may include or be formed from a lithium intercalation material, for example graphite and / or amorphous carbon and / or lithium titanate, and / or a lithium alloy material, for example silicon and / or tin. In this case, the anode active material can be in particular in the form of, for example, spherical and / or elongated and / or flake-like and / or fibrous, particles formed and surrounded by the electrolyte.

In particular insofar as the anode comprises a particulate anode active material, for example a lithium intercalation material or lithium alloy material, the separator and / or the protective layer and the cathode and the anode, in particular respectively or all, at least one polymer having a lithium ion transfer coefficient> 0, 7, in particular> 0.8,

for example,> 0.9, for example, a single ion conducting polyelectrolyte.

The at least one polymer having a lithium ion transmittance> 0.7, in particular> 0.8, for example> 0.9, for example the single-ion conductive polyelectrolyte, the separator and / or the protective layer and the cathode and optionally the anode do not necessarily have to be identical but can be tailored to the particular needs, for example with regard to solution behavior, voltage stability, volume work, et cetera, in the respective area of application of the cell, adapted and / or optimized.

The cathode and / or the anode may further comprise at least one conductive additive. The at least one conductive additive of the cathode and / or the anode may, for example, comprise or be at least one carbon modification, for example carbon black and / or graphite. Thus, a percolating electrically conductive network can be formed or improved and in this way the electrical conductivity can be increased. In particular, the cathode and / or the anode can at least one cathode active material or

Anode active material, at least one polymer having a lithium ion transfer number> 0.7 and / or at least one, in particular ceramic and / or glassy, inorganic ion conductor, in particular single-ion conductor, and at least one Leitzusatz include.

Furthermore, the separator and / or the protective layer and / or the cathode and / or the anode may, for example, comprise at least one lithium ion-conductive polymer, in particular a polyalkylene oxide, for example polyethylene oxide and / or polypropylene oxide, for example polyethylene oxide, and / or poly (oligoethylene glycol) methacrylate ( P- (OEGMA) and / or poly

(oligoethylene glycol) acrylate, especially poly (oligoethylene glycol) methacrylate (P- (OEGMA).

Furthermore, the cathode may optionally, in particular in addition to the at least one single-ion conducting polyelectrolyte, at least one

Liquid electrolytes, for example from at least one solvent, for example at least one organic carbonate, such as ethylene carbonate (EC) and / or dimethyl carbonate (DMC) and / or diethyl carbonate (DEC), and at least one lithium conducting salt, for example

Lithium bis (trifluoromethane-sulfonyl) imide (LiTFSI), for example, EC: DMC: DEC +

LiTFSI, and / or at least one ionic liquid (English: lonic liquid). By adding a liquid electrolyte and / or an ionic liquid can advantageously - while still sufficiently high

Lithium ion transference numbers (t +) near 1 - increases lithium ion conductivity and lithium ion diffusion and optimizes lithium ion transport in the cell become. In this case, the separator, in particular according to the invention, can additionally assume the function of a barrier for the liquid components of the catholyte and / or of the anolyte. It can, in particular

Separator according to the invention advantageously its mechanical

Properties, in particular the property of suppressing dendrites, maintained and, for example, hardly ever dissolved or swollen.

For example, the cells according to the invention can be used in a battery for a vehicle, for example for an electric and / or hybrid vehicle, and / or for a consumer application, for example for a mobile device, such as a mobile computer and / or a tablet and / or or a smartphone.

With regard to further technical features and advantages of the cells according to the invention, reference is hereby explicitly made to the explanations in connection with the separator according to the invention, the protective layer according to the invention, the copolymer according to the invention, the polymer mixture according to the invention and the polymer electrolyte according to the invention and to the figures and the description of the figures.

Furthermore, the invention relates to a copolymer and / or polymer mixture (blend) and / or a polymer electrolyte, in particular for a lithium cell, for example for a lithium-sulfur cell or a lithium-ion cell, and / or for a solid cell.

In particular, the copolymer comprises at least one

Repeating unit for forming a polymer having a lithium ion transfer number> 0.7, in particular> 0.8, for example> 0.9, in particular for forming a single-ion-conducting polyelectrolyte, and at least one mechanically stabilizing repeat unit.

The polymer mixture may in particular be at least one polymer having a lithium ion conversion number> 0.7, in particular> 0.8, for example > 0.9, in particular at least one single-ion conducting polyelectrolyte, and at least one mechanically stabilizing polymer.

The polymer electrolyte can thereby at least at least one

Repeating unit for forming a polymer with a lithium ion

Conversion number> 0.7, in particular> 0.8, for example> 0.9, in particular for forming a single-ion conducting polyelectrolyte, and / or at least one polymer having a lithium ion transfer coefficient> 0.7, in particular> 0.8, for example> 0 9, in particular at least one single-ion conducting polyelectrolyte. Optionally, the polymer electrolyte may further comprise at least one mechanically stabilizing repeating unit and / or at least one mechanically stabilizing polymer. For example, polymer electrolyte can be based on one, for example, such a copolymer and / or one, for example, such, a polymer blend (blend).

In this case, the at least one mechanically stabilizing

Repeating unit, in particular at least one styrene-based

Repeat unit and / or the at least one mechanically stabilizing polymer include or be a styrene-based polymer.

Lithium ion transfer number> 0.7, in particular for the formation of a single-ion conducting polyelectrolyte, of the copolymer and / or

Polymer electrolytes a borate-based unit and / or a sulfonic acid-based unit and / or an imide-based, in particular sulfonylimide-based, unit and / or a unit based on lithiated acrylic acid and / or

Methacrylic acid and / or a perfluoroether-based unit and / or the at least one polymer having a lithium ion transfer number> 0.7, in particular the at least one single-ion conducting polyelectrolyte, the

Polymer mixture and / or the polymer electrolyte, a borate-based polyelectrolyte and / or a sulfonic acid-based polyelectrolyte and / or an imide-based, in particular sulfonylimide-based, polyelectrolyte and / or a polyelectrolyte based on lithiated acrylic acid and / or methacrylic acid and / or a perfluoropolyether-based polymer. The at least one styrene-based repeat unit and / or the at least one polymer can be synthesized, for example, by polymerization of styrene and / or o-methylstyrene and / or p-methylstyrene and / or mt-butoxystyrene and / or 2,4-dimethylstyrene and / or m -Chlorostyrene and / or p-chlorostyrene and / or 4-carboxystyrene and / or vinylanisole and / or vinylbenzoic acid and / or vinylaniline and / or vinylnaphthalene and / or analogs.

The at least one repeating unit for forming a polymer with a lithium ion transfer ratio> 0.7 can be designed in particular for forming a single-ion-conducting polyelectrolyte. The at least one polymer having a lithium ion transference number> 0.7 may in particular be a single-ion conducting polyelectrolyte. The at least one repeating unit for forming a polymer having a lithium-ion transduction number> 0.7, in particular> 0.9,

or the at least one repeating unit for forming a single-ion-conducting polyelectrolyte may, for example, a borate-based unit and / or a sulfonic acid-based unit and / or an imide-based, in particular sulfonylimide-based, unit and / or a unit

Include or be based on lithiated acrylic acid and / or methacrylic acid.

The at least one polymer having a lithium ion transfer number> 0.7, in particular> 0.9, or the at least one single-ion conducting polyelectrolyte may, for example, be a borate-based polyelectrolyte and / or a sulfonic acid-based polyelectrolyte and / or an imide-based, in particular Sulfonylimide-based, polyelectrolytes and / or a polyelectrolyte based on lithiated acrylic acid and / or methacrylic acid include or be.

In another embodiment, the copolymer is a block copolymer. In this case, the block copolymer may comprise at least one, in particular single-ion conducting, block (bA, for example b-SIC) of at least one repeating unit to form a polymer with a lithium ion transfer number> 0.7 (A, for example SIC) and at least one, in particular mechanically stabilizing block (bB, for example b-PS) comprising at least one mechanically stabilizing, in particular styrene-based, repeating unit. In a further embodiment, the copolymer further comprises at least one lithium ion-conductive repeating unit. In this case, the at least one lithium ion-conductive repeating unit can be an alkylene oxide unit, in particular an ethylene oxide unit (EO) and / or a propylene oxide unit (PO), in particular an ethylene oxide unit (EO), and / or a

Oligoethylenglycolmethacrylat unit (OEGMA) and / or a

Oligoethylenglycolacrylat unit, in particular a

Oligoethylenglycolmethacrylat unit (OEGMA), include or be.

In the context of a further, alternative or additional embodiment, the polymer mixture further comprises at least one lithium ion conductive

Polymer. In this case, the at least one lithium ion-conductive polymer is a polyalkylene oxide, in particular polyethylene oxide and / or polypropylene oxide, in particular polyethylene oxide, and / or poly (oligoethylenglycol) methacrylate (P- (OEGMA) and / or poly (oligoethylenglycol) acrylate, in particular poly (oligoethylenglycol ) methacrylate (P- (OEGMA), include or be.

For example, the block copolymer may further comprise at least one, in particular lithium ion-conductive, block of at least one

lithium ion conductive repeating unit.

For example, the block copolymer may be a di-block copolymer (bAbB, for example b-SIC-b-PS) or a tri-block copolymer (bAbBbA or bB-bAbB, for example b-SIC-b-PS-b- SIC or b-PS-b-SIC-b-PS) or multi-block copolymer (bAbCbBbCbA, for example b-SIC-b-OEGMA / / EO / PO-b-PS-b-OEGMA / EO / PO-b -SIC).

With regard to further technical features and advantages of the copolymer according to the invention, the polymer mixture according to the invention and the

Polymer polymer according to the invention is hereby explicitly referred to the

Explanations in connection with the separator according to the invention, the Reference is made to the protective layer of the invention and the cells according to the invention and to the figures and the description of the figures.

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 a lithium cell according to the invention; and

Fig. 2 is a graph illustrating the relationship between a minimum necessary transfer number (t ⁺ _m in) for a cathodic

Polymer electrolyte with an assumed ionic conductivity or diffusion coefficient of the cathodic

Polymer electrolytes in a cell to achieve 1C, 2C and 3C rate capability of the cell.

1 shows a lithium cell 1, in particular in the form of a solid cell, which comprises a cathode 2 and an anode 3, wherein between the cathode 2 and the anode 3, a separator 4 is arranged. The anode 3 is a lithium-metal anode of metallic lithium. The separator 4 also fulfills the function of a protective layer against dendrite formation from the anode 3.

The separator 4 comprises in particular at least one polymer with a lithium ion transfer number> 0.7. In particular, the separator 4 for this purpose may comprise at least one single-ion conducting polyelectrolyte. For example, the separator 4 may comprise a borate-based polyelectrolyte and / or a sulfonic acid-based polyelectrolyte and / or an imide-based, in particular sulfonylimide-based, polyelectrolyte and / or a

Polyelectrolytes based on lithiated acrylic acid and / or methacrylic acid include. Furthermore, the separator 4 may comprise at least one, in particular ceramic and / or glassy, inorganic ion conductor, in particular single-ion conductor, with a lithium ion transfer number> 0.7, for example a lithium argyrodite and / or a sulfidic glass (not shown).

The cathode 2 comprises a, in particular particulate,

Cathode-active material 5, for example based on metal oxide, such as nickel-cobalt-aluminum-oxide (NCA), nickel-cobalt-manganese-oxide (NCM), high-energy nickel-cobalt-manganese-oxide (HE-NCM), lithium Manganese Oxide (LMO) and / or

High-voltage spinel (HV-LMO), or based on sulfur, and, in particular as catholyte 6, at least one polymer with a lithium ion transfer number> 0.7 and / or at least one, in particular ceramic and / or glassy, inorganic ion conductor, in particular single ion conductor , with a lithium ion transfer coefficient> 0.7. In particular, the cathode 2 for this purpose may comprise at least one single-ion conductive polyelectrolyte and / or at least one lithium argyrodite and / or sulfidic glass. For example, the cathode 2 may comprise a borate-based polyelectrolyte and / or a sulfonic acid-based polyelectrolyte and / or an imide-based, in particular sulfonylimide-based, polyelectrolyte and / or a

Polyelectrolytes based on lithiated acrylic acid and / or methacrylic acid. Furthermore, the cathode 2 comprises a conductive additive 7, for example carbon black and / or graphite, for improving the electrical conductivity of the cathode 2.

The at least one polymer having a lithium ion transfer coefficient> 0.7, in particular the at least one single-ion conducting polyelectrolyte, of the separator 4 and the at least one polymer having a lithium ion transfer number> 0.7, in particular the at least one single-ion conductive polyelectrolyte, the cathode 2 can different or possibly at least similar.

FIG. 1 further shows that the cathode 2 is equipped with a current collector 8. In the context of a special embodiment, the separator 4 comprises a

Copolymer and / or a polymer mixture (blend), wherein the copolymer comprises at least one repeating unit for forming a polymer having a lithium ion transfer number> 0.7, in particular for forming a single-ion conductive polyelectrolyte, and at least one mechanically stabilizing repeating unit and / or wherein the

Polymer mixture comprises at least one polymer having a lithium ion transfer number> 0.7, in particular at least one single-ion conducting polyelectrolyte, and at least one mechanically stabilizing polymer. In this case, the at least one mechanically stabilizing

Repeat unit at least one styrene-based repeating unit and / or the at least one mechanically stabilizing polymer comprise or be at least one styrene-based polymer. In particular, the at least one polymer having a lithium ion transfer number> 0.7 of the separator 4 and the at least one polymer having a lithium ion

Transfer number> 0.7 of the cathode 2 thereby at least

differ from each other that the at least one polymer having a lithium ion transfer ratio> 0.7 of the cathode 2 is free of a mechanically stabilizing, for example styrene-based, repeating unit and / or a mechanically stabilizing, especially styrene-based, polymer. The at least one repeating unit for forming a polymer having a lithium ion transfer number> 0.7 and / or the at least one polymer having a lithium ion transfer number> 0.7 of the separator 4 and the at least one polymer having a lithium ion transfer number> 0.7 Otherwise, the cathode 2 may also be different or, in particular, at least similar to each other or may even be the same.

Figure 2 illustrates the results of calculations in which minimum required lithium ion transfer numbers t ⁺ _m in a cathodic

Polymer electrolytes with an assumed conductivity, respectively

Diffusion coefficients were calculated for a cell, which are needed to realize a constant C rate charging from SOC = 0% to SOC = 75%. As a base served a cell with a 10 μηη thick

Separator, as a classical polymer electrolyte, for example PEO / LiTFSI, with a conductivity of 4 e ^"4 S / cm, a salt diffusion coefficient of 1 e ^{" 12} m ² / s and a lithium ion transference number t ⁺ of 0.25 and its transport properties are not varied, and with a cathode having a loading of 4 mAh / cm ² and which also contains a polymer electrolyte, for example PEO / LiTFSI, whose However, transport properties were varied. In particular, the conductivity I and the diffusion coefficient D of a conducting salt in the polymer electrolyte of the cathode were varied from the transport properties of the polymer electrolyte of the cathode.

FIG. 2 shows the results for simulated charging processes with constant C rate, namely for IC in curve 10, for 2C in curve 11 and for 3C in curve 12. Curve 12 can be interpreted in Figure 2 at about 1 e ^"2 S / cm to the effect that a transfer coefficient t ⁺ > 0.5 is required for a constant current charge of 3 C. However, in the calculation of the graph shown in FIG. polymer electrolyte with a lithium ion transfer coefficient t ⁺ of 0.25 as a separator, which leads to an additional concentration polarization and thus increases the requirement for the transfer coefficient of the polymer electrolyte of the cathode (catholyte) When using a polymer having a lithium ion transfer coefficient> 0 , 7 and in particular when using a single-ion conducting polyelectrolyte, for example with a lithium ion transfer number> 0.8 or> 0.9, as a separator and / or protective layer, advantageously reduce the

Requirements with respect to the minimum required lithium ion transfer numbers min of the catholyte over that shown in Figure 2. Thus seems advantageously, for example, a 3C charging process even at a catholyte conductivity of 1 e ^{"t 3} S / cm, and a lithium ion transference number ⁺ <0.7, for example, already for a lithium ion transport number t ⁺ = 0.5, in the

To reach catholyte reach (not shown in the figures).

Claims

claims

A separator and / or protective layer (4) for a lithium cell (1) comprising a copolymer and / or a polymer mixture,

wherein the copolymer is at least one repeating unit for

Forming a polymer having a lithium ion transfer number> 0.7 and at least one mechanically stabilizing repeating unit comprises, and / or

wherein the polymer mixture comprises at least one polymer having a

Lithium ion transference number> 0.7 and at least one mechanically stabilizing polymer.

2. Separator and / or protective layer (4) according to claim 1,

wherein the at least one mechanically stabilizing

Repeating unit at least one styrene-based

Repeating unit includes or is, and / or

wherein the at least one mechanically stabilizing polymer comprises or is at least one styrene-based polymer.

3. Separator and / or protective layer (4) according to 1 or 2,

wherein the at least one repeating unit is designed to form a polymer with a lithium ion transfer number> 0.7 to form a single-ion conductive polyelectrolyte, and / or wherein the at least one polymer having a lithium ion transfer number> 0.7 is a single-ion conductive polyelectrolyte.

4. Separator and / or protective layer (4) according to claim 1 or 3,

wherein the at least one repeating unit for forming a polymer having a lithium ion transfer number> 0.7 or the at least one repeating unit for forming a single-ion conducting polyelectrolyte, a borate-based unit and / or a sulfonic acid based unit and / or an imide based,

in particular sulfonylimide-based, unit and / or a unit based on lithiated acrylic acid and / or methacrylic acid comprises or is, and / or

wherein the at least one polymer having a lithium ion transfer number> 0.7 or at least one

single-ion-conducting polyelectrolyte comprises or is a borate-based polyelectrolyte and / or a sulfonic acid-based polyelectrolyte and / or an imide-based, in particular sulfonylimide-based, polyelectrolyte and / or a polyelectrolyte based on lithiated acrylic acid and / or methacrylic acid.

Separator and / or protective layer (4) according to any one of claims 1 to 4, wherein the copolymer is a block copolymer, wherein the block copolymer at least one block of at least one repeating unit to form a polymer having a lithium ion transfer number> 0.7 , in particular a single-ion conducting polyelectrolyte, and at least one block of at least one mechanically stabilizing,

especially styrene-based, repeating unit comprises.

Separator and / or protective layer (4) according to one of claims 1 to 5, wherein the copolymer further comprises at least one lithium ion conductive repeating unit, and / or

wherein the polymer mixture further comprises at least one

lithium ion conductive polymer.

Separator and / or protective layer (4) according to claim 6,

wherein the at least one lithium ion conductive repeating unit a

Alkylene oxide unit, in particular an ethylene oxide unit, and / or a

Oligoethylene glycol methacrylate unit and / or oligoethylene glycol acrylate

Unit, in particular an oligoethylene glycol methacrylate unit, is and / or

wherein the at least one lithium ion conductive polymer

Polyalkylene oxide, in particular polyethylene oxide, and / or poly (Oligoethylenglycol) methacrylate and / or poly (oligoethylenglycol) acrylate, in particular poly (oligoethylenglycol) methacrylate, is.

A separator and / or protective layer (4) according to any one of claims 5 to 7, wherein the block copolymer is a di-block copolymer or a tri-block copolymer or multi-block copolymer.

Separator and / or protective layer (4) according to one of claims 1 to 8, wherein the separator and / or the protective layer (4) further comprises at least one inorganic single-ion conductor, in particular wherein the at least one inorganic single-ion conductor is a lithium argyrodite and / or a sulfidic Glass is.

Lithium cell (1), comprising a separator and / or a protective layer (4) according to one of claims 1 to 9.

A lithium cell (1) comprising a cathode (2) and an anode (3), wherein a separator and / or a protective layer (4) is arranged between the cathode (2) and the anode (3),

wherein the separator and / or the protective layer (4) comprises at least one polymer having a lithium ion transfer coefficient> 0.7 and / or at least one, in particular ceramic and / or glassy, inorganic ion conductor, in particular single ion conductor, with a lithium ion transfer coefficient> 0, 7 includes, and

wherein the cathode (2) comprises at least one polymer having a lithium ion transfer coefficient> 0.7 and / or at least one, in particular ceramic and / or glassy, inorganic ion conductor, in particular single ion conductor, and / or

wherein the anode (3) comprises at least one polymer having a lithium ion transfer coefficient> 0.7 and / or at least one, in particular ceramic and / or glassy, inorganic ion conductor, in particular single ion conductor.

12. Lithium cell (1) according to claim 11, wherein the at least one inorganic single ion conductor of the separator and / or the protective layer (4) is a lithium argyrodite and / or a sulfidic glass, and / or

wherein the at least one inorganic single-ion conductor of the cathode (2) is a lithium argyrodite and / or a sulfidic glass, and / or wherein the at least one inorganic single-ion conductor of the anode (3) is a lithium argyrodite and / or a sulfidic glass.

Lithium cell (1) according to claim 11 or 12,.

wherein the at least one polymer having a lithium ion transference number> 0.7 of the separator and / or the protective layer (4) comprises or is a single-ion conductive polyelectrolyte, and wherein the at least one polymer having a lithium ion transfer number> 0.7 of the cathode (2 ) comprises or is a single ion conducting polyelectrolyte, and / or

wherein the at least one polymer having a lithium ion transference number> 0.7 of the anode (3) comprises or is a single-ion conductive polyelectrolyte.

Lithium cell (1) according to one of claims 11 to 13,

wherein the at least one polymer having a lithium ion transfer number> 0.7 or the at least one single-ion conducting polyelectrolyte of the separator and / or the protective layer (4) is a borate-based polyelectrolyte and / or a sulfonic acid-based polyelectrolyte and / or an imide-based , in particular sulfonylimide-based, polyelectrolytes and / or a polyelectrolyte based on lithiated acrylic acid and / or methacrylic acid comprises or is, and

wherein the at least one polymer having a lithium ion transfer number> 0.7 or the at least one single-ion conducting polyelectrolyte of the cathode (2) is a borate-based polyelectrolyte and / or a sulfonic acid-based polyelectrolyte and / or an imide-based, in particular sulfonylimide-based , Polyelectrolytes and / or a polyelectrolyte based on lithiated acrylic acid and / or methacrylic acid comprises or is, and / or wherein the at least one polymer having a lithium ion transfer number> 0.7 or the at least one single-ion conducting polyelectrolyte of the anode (3) is a borate-based polyelectrolyte and / or a sulfonic acid-based polyelectrolyte and / or an imide-based, in particular sulfonylimide-based , Polyelectrolytes and / or a polyelectrolyte based on lithiated acrylic acid and / or methacrylic acid comprises or is.

15. Lithium cell (1) according to one of claims 11 to 14,

wherein the separator (4) and / or the protective layer comprises a mixture of at least one polymer having a lithium ion transfer number> 0.7, in particular single-ion conductive polyelectrolytes, and at least one inorganic ion conductor, in particular a lithium argyrodite and / or a sulfidic glass , and

wherein the cathode (2) is a mixture of at least one polymer having a lithium ion transfer number> 0.7, in particular single-ion conductive polyelectrolytes, and at least one inorganic ion conductor, in particular a lithium argyrodite and / or a sulfidic glass, and / or

wherein the anode (3) comprises a mixture of at least one polymer having a lithium ion transference number> 0.7, in particular single-ion conductive polyelectrolytes, and at least one inorganic ion conductor, in particular a lithium argyrodite and / or a sulfidic glass.

16. Lithium cell (1) according to one of claims 11 to 15,

wherein the anode (3) is a lithium-metal anode and wherein the separator and / or the protective layer (4) and the cathode (2) comprise at least one single-ion conducting polyelectrolyte, or

wherein the anode (3) comprises a particulate anode active material, wherein the separator and / or the protective layer (4) and the cathode (2) and the

Anode (3) comprise at least one single-ion conducting polyelectrolyte. The lithium cell (1) according to any one of claims 11 to 16, wherein the separator and / or the protective layer (4) is a separator and / or a protective layer (4) according to any one of claims 1 to 9.

Copolymer and / or polymer mixture and / or polymer electrolyte based on a copolymer and / or a polymer mixture,

wherein the copolymer is at least one repeating unit for

Formation of a polymer having a lithium ion transfer number> 0.7, in particular a borate-based unit and / or a sulfonic acid-based unit and / or an imide-based, in particular sulfonylimide-based unit and / or a unit based on lithiated Acrylic acid and / or methacrylic acid and / or a perfluoroether-based unit, and at least one styrene-based repeating unit, and / or wherein the polymer mixture comprises at least one polymer having a

Lithium ion transfer number> 0.7, in particular a borate-based polyelectrolyte and / or a sulfonic acid-based polyelectrolyte and / or an imide-based, in particular sulfonylimide-based, polyelectrolyte and / or a polyelectrolyte based on lithiated acrylic acid and / or methacrylic acid and / or a perfluoropolyether-based polymer, and at least one styrene-based polymer.

The copolymer and / or polymer mixture and / or polymer electrolyte of claim 18, wherein the copolymer is a block copolymer, wherein the block copolymer comprises at least one block of at least one

Repeating unit for forming a polymer with a

Lithium ion transfer number> 0.7 and at least one block of at least one styrene-based repeat unit comprises.

Copolymer and / or polymer mixture and / or polymer electrolyte according to claim 18 or 19,

wherein the copolymer further comprises at least one lithium ion conductive repeating unit, in particular wherein the at least one lithium ion conductive repeating unit is an alkylene oxide unit, in particular an ethylene oxide unit, and / or a Oligoethylenglycolmethacrylat unit and / or a

Oligoethylenglycolacrylat unit includes or is, and / or

wherein the polymer mixture further comprises at least one

Lithium ion conductive polymer, in particular wherein the at least one lithium ion conductive polymer is a polyalkylene oxide, in particular polyethylene oxide, and / or poly

(oligoethylene glycol) methacrylate and / or poly (oligoethylene glycol) acrylate comprises or is,

in particular wherein the block copolymer further comprises at least one block of at least one lithium ion-conducting repeat unit.