EP1364424A2

EP1364424A2 - Electrochemically activable layer or film

Info

Publication number: EP1364424A2
Application number: EP01978345A
Authority: EP
Inventors: Ulf Zum Felde; Gerold Neumann; Peter Gulde
Original assignee: Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Current assignee: Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Priority date: 2000-09-14
Filing date: 2001-09-06
Publication date: 2003-11-26
Also published as: WO2002023662A2; US20030180610A1; WO2002023662A3; CA2422212A1; CN1516907A; JP2004537139A

Abstract

The invention relates to an electrochemically activable layer or film for use in electrochemical components. Said layer or film comprises a textile fabric and a substance which is located at least in the intermediate spaces in said textile fabric, consisting of at least one matrix containing or consisting of an organic polymer, precursors thereof or prepolymers thereof and an electrochemically activable inorganic material which is insoluble in the matrix, in the form of a solid substance. The invention also relates to layered composites and to rechargeable electrochemical cells which are constructed with layers or films of this type, and to a number of methods for producing said layers or films.

Description

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Φ ß- rt SD Φ cn ß φ PJ CD Φ co t Φ PJ tt i tr tr to tt H Ω cn cn tt tt ß CQ • tr P "o 1

^ P- Φ er PJ rt iß ω o DJ: ^ ß: P- tt φ PJ cn tr rt P- P Φ SD: 3 ß α J ri ^¬ Ω ß P- g P ^J rt rt CL> ß et et er Φ or P "φ P- 3 s rt Cd Φ Ω ri ^¬ ß rt Φ P" d ß tt ß ^* P "ß 3 P- • p- Φ ß φ ιp tt p- Φ ß co M et ß P- Φ p- ß tr tt-. Cn N et rt φ ^ T rt

Location 23 φ Hl Φ Ω Hι tt *. tt rt O <tt for P- Φ ^ Φ tt Φ ß φ et co G P "tr φ tt et φ

Ω <Φ -> iß ß r ö P- φ fr Ω Φ tr N o Ω ß σ co ß fr tri φ Ω P ¹ P- • ^• ß cn φ ß t Φ P- J co P- NO ß DJ ^* cn P- d TJ T • ß »^ DJ φ to ri ^¬ P- rt tr <! Ω cn rt tt tt rt <ie φ t Φ P- Φ d tt Φ ß P- Φ. 3 O cn ß tt tt rt Φ ß tr φ s ■ 3 co o er Φ o Φ rt O: φ ß ¹ ß Hi Φ 3 S ß tn <H P <P- Φ o tr s: cn rt ß d P- Ω

3 ß: tt tt N tr <tt J ß r & p- SD d P- ¹ Ω 2 Φ φ P- Φ tri P- P- o P- Φ <1 tt et Qr tr

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Cd Φ tt eats iP • ß cn er d P- tr tt cn tt Cfl ιp DJ Hi Φ d rt cn cn Φ M Φ ß • P- Hi

SD ß PJ co Φ 3 0- Φ tt Φ φ P- rt d P- Φ Ω tt Φ ß Ω ß ß <J tt S! φ rt et ß tt s: <! ß> Φ P- Φ P- Ω tt ß PJ ^• Φ ß ß ß ^• ß ^* Φ tt Cd -Ω. tr H φ Φ φ rt σ tr

Er er er Φ O H ß ß to to r rt P "ιp α P- rt P- cn P- N ß ß P- N ß P- tt cπ

I- ¹ Φ Φ P- tt 3 P- TJ TJ • M to TJ m P P- ß DJ Ω cn α Ω rt tn d Ω

Φ tt P- to P ^J Φ Φ tt Q. TJ P- Φ Qr Φ Φ H Φ Hi ιP Qr ß tr N ß Φ tr Φ 3 tr Ό

3 Φ rt φ P- Ω tt o Φ O Φ P- σ Φ ß ß tt cn J Ω Φ ß Φ co et s: CP s: 3 TJ TJ o φ P- d φ tr Qr ISl tt P ¹ ß P- 3 tt fl O cn tr cn ß tt SD: ß P- M ß <! ß Φ α VD ß rt ß co υa PJ P- Φ l-rf φ Φ Φ α Ω ß rt ß et iP et P- tt Qr φ P- Ω ß et tt 3 rt IS1 «P φ φ ß ß ß Jö ß P- tr α P- G Φ P- N ß P- ι tr tt Φ Ω Cfl D

Φ ß cn er ß P- ιp rt Φ Φ ^' P- rt <! rt Qr Φ φ Φ Hi P ¹ Φ ß Φ ^■ Φ - Φ φ P- ß tr Φ ~ J

CQ Φ Cfl cn cn J ιp tt ß Φ o Φ ß P- tt P- o ß tt ß φ n 1 ß tt ß rt H rt o

O rt P- rt Φ Ω ß Φ Φ P- tt to CO Cd ß ß N iß ß Hi Qr P ¹ ß P) Cd co ß o N

Qr Φ ι rt ß ß ^J H rt P "ß P. P" rt - _^ P- d P- P- G P- p- φ to od Ω φ rt α tt d Qr

Φ P ¹ φ tt J Φ φ S, Φ P- ß ß SD Φ φ tt Φ Cfl fr rt ß rt tr ß Φ CΛ ß ß Φ tt P ^J ß J Pd co cn P- Qr Cd ß Φ P- Qr P - P- «Q ß tt s: Qr r + ri ^¬ P- φ ^ ß r rt iP ß

Φ co ιp tt rt cn Φ p- P- P ¹ P- φ φ Φ Ω Φ s. Φ φ TJ tt Cfl ß tt Hi tr α Cπ

P- ß Ω Φ Hi PJ Φ Φ ß ß o to Φ Φ tt ß tr tt φ P- tt ß ιP o Ω P "G rt ß P- d Φ Cd

Φ tr ß p- er ß rt Qr er φ H tt rt cn φ Ω tr φ p ^J Φ ^• - • Φ O ß P- p- tt SD P- ß P- cn P ^J Φ Φ P- i ß s. s- er ß- P- Φ P- rt 3 tr P- ß ß et co J-- P- ß ß ιP P- Hi Φ Qr P ¹ cn P- P- tt ß Jö φ G Φ φ P- Φ P - Φ tt Ω Φ φ Φ Φ rt Ω φ Φ P »Φ Cfl

P ^J P- rd Φ P- ß Ω co φ tt ß tt P- Φ P- ß ß <! tr ß P- 3 tt Hi r ß ß tt ß CQ ß φ Φ Φ CΛ ß Ω Qr tr iP IQ rt N Φ - _* ß P- tr ß: O d üü ß et

P- ß Ω iß ^ tr ß Φ ß ^ r P- ip CE P "ß 3 tt cn cn tn O: tr ß Hi P- J iti ω Hi N

Ω SD ß ^" o P- ß: ß ß pr o Φ Φ φ tt PJ: ιp Φ DJ P- s 8J Ω tr P- CQ lo <\ Ω Φ tr" Hl P- er P ¹ 3 ß er Qr J et tt ß- ß: ß Φ P- tt ß p- 3 tr et iP Cf φ rt * tr CQ Φ

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Φ P ¹ P- ß tr tr O o tt ß Qr Φ ιp Φ Φ tt ß P- er Φ cn P ß • fr tt φ ß- Φ TJ tt d Φ er φ. φ tt Φ 'Φ -> ß DJ P- ß p- ß N tt ß O IP

≤; 3, - tt Ω oo α J tt PJ Qr Φ P- tri tt ip> p- φ Hi 3 ß • ß <! φ Φ & P ¹ Φ

Φ d JE Qr to tr tt "Φ φ PJ tt PJ φ et PJ α N Φ Φ d ß ß: Cd o P- Φ>; H ß P ¹ Φ ^ PJ er Φ P- s. Co rt Cd er i ^ cn et iP P- d iP tn Φ tt <tt ri ^¬ er to Φ Hl

SD tt o tt φ ß Φ P- φ ß Φ et tt H, Φ Φ 3 ^ d Φ iP Φ 3 Φ N tt rt rt G:

Φ ri- Cfl H P- P ^J ß Ω ß φ P- p- O ß: tt o er PJ tt φ P- tt Φ ß O Cd r tt rt 0 rt P- ß H tr rt tt rt <! Ω ß- ß ß m Φ ß tr ß Φ iP P ^J P- ι P * Φ Φ

" _^ << 3 tt Φ Φ φ ß et Φ iP ß Φ tr tt ß P- Φ P- ß ιp Φ rt ß H ¹ P ß CO ß. • <: P- Cfl H P-

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T ß tt ¹ . _T 3 • Ω J φ iß 3 ß tr P ¹ cn TJ P "ß H P- tt P- Φ Φ Φ tt ß Φ tt ß Φ tr tt er Qr S P- et N Φ tt P- P- Ω P- P- P- ß ß O ß

Qr ß 3 Ω O Φ P- S D to Φ d P- 0 0 DJ ß tr P- J ω tr X

Φ ιP P- tr NH Ω Φ rt Ω tt ß ß Qr ⁴ er Cfl ß 0 Φ H P- ß r PJ Φ φ ß "tt Φ tr d ß Φ Φ ß N iP P ¹ P- φ

<i ß ß ιp rt tt tt 3 tt rt dn P- ß ß ß 1 O p- et φ Φ Φ P- et N 3 tt ß co ß ß ß P- φ sα Ω P ¹ ß to Cfl Φ tr co E rt tt

can and do not have the disadvantages that arise from the high levels of organic polymer material or plasticizer.

In particular, the layers and foils according to the invention or the layer produced therefrom should provide products with electrochemical properties, such as rechargeable batteries (accumulators), electrochromic components or the like, which have high flexibility and very good electron and ion conduction properties.

The object is achieved in that pastes with relatively low binder / plasticizer contents are introduced into a preferably flexible textile fabric. The fabric takes on the task of mechanical stability

Ensure foils. The flexibility of the fibers that make up the structure does not adversely affect the mechanical flexibility of the layers.

The invention accordingly provides an electrochemically activatable layer or film for use in electrochemical components which contains a textile fabric and, at least in the interstices of the textile fabric, a mass composed of at least one organic polymer, its precursors or its prepolymers, or of these components existing matrix and an electrochemically activated, non-soluble in the matrix inorganic material in the form of a solid substance.

The expression "usable in electrochemical components" implies that the electrochemically activatable inorganic material in the form of a solid substance must be an ion-conducting or electron-conducting material, or both at the same time, which can be used as electrode material or solid electrolyte or the like. suitable in a corresponding electrochemical component. According to the invention, the term “flat textile structure” is understood to mean any structure that can be produced using textile fiber materials (textile fibers) and that is a flat structure. Textile fibers include natural fibers (vegetable and animal fibers), so-called chemical fibers from essentially organic polymers, as well as all other industrially producible fibers such as glass, ceramic, metal, mineral or carbon fibers. For the rest, reference is made to the definition in Römmp's Chemielexikon, 8th edition, Frauck'sche Verlagshandlung Stuttgart (1988), where the keyword "textiles" also contains examples of sheet-like structures such as felts, fabrics and nonwovens.

FIG. 1 shows the sequence of a layer composite according to the invention, in which both the electrodes and the electrolyte are embedded in a tissue.

Figure 2 shows an electrode film with embedded metallized tissue.

FIG. 3 shows a charge-discharge curve of a lithium battery according to example 4.

FIG. 4 shows the decrease in the initial capacity of this cell with an increasing number of charge-discharge steps (number of cycles).

Textile fabrics in the form of woven fabrics are well suited for the present invention, the mechanical behavior and mobility of their fabric being well adapted to their environment in the electrochemical component. In the case of lithium accumulators with intercalation electrodes in particular, which experience permanent expansion and contraction in electrical operation, this leads to increased long-term stability, that is to say improved cycle stability. Instead of as a fabric, the fibers of the textile fabric can of course also be in a different form, for example laid as a fleece or the like, knitted or otherwise combined to form a flat textile structure. ω o σ

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P- d P- ß φ Φ d = P- φ s: 3 φ tt φ s; Φ ß Cfl tt φ Ω o P- rt φ φ Φ EP 3 ß 3 ß Φ rt 3 CQ er fr ^• Φ et ß φ 3 Φ tt Φ φ P- Φ tn s; tr tt Cfl Cd ß tt φ er Φ

Φ P- TJ P- ri ^¬ et P- N -> Φ er Φ ß P- he iP Cfl Φ Φ • ^ iß JP "P ⁴ ri ^¬ ^ ß tu P- er Φ tt ß P- tt tt et Hl tt Φ ß ß rt ß Φ Φ ß Φ ß ß Q ß P- φ P "tt d 1 φ Φ P- d ß" P- φ o O Φ d ß ≤, ß Ω dd fr Φ rt sα co P ¹ ß φ ^ er O ß Hi P- P- ß ω

P- d cn Ω ß tt ß 3 ß: d tr ß to ß ri ^¬ r ISI Cfl d φ ß P- P ¹ et Φ P- p O Cfl CQ P φ s: ß 3 Φ P- tr P- ^' tr <1 ß w ιp d tt Φ P- ß tt cn co tt cn Φ e Φ TJ P- Qr tt ß Φ. tn Φ et P- ß Φ P- ri m CQ O tn ß Ω i ß Ω φ o Ω ß P- P- P- P- Φ ■ φ tr

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TJ S Ω ß P ¹ σ ß O P> 3 • O ß ß to tt - <l φ tr 3 P- ^• ^ α Qr iß iP P ¹ Φ

IP Hi iP Φ tr P "α φ 0: Φ iP sα TJ ß p- er o ß et Φ Φ O: P- H N CQ

Cfl φ Φ rt Φ tri Φ Φ ^ ß P- Φ ß • _ 3 tn Φ d r w TJ tt φ ß CQ ß CO φ P- • ß tt. Φ ß ß φ ß cn er ß rt Φ ß to Φ Ω o P- ß d Φ Φ o N <! et rt ß Φ φ tr

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P- Φ CQ iP tt φ P- φ n Φ tr er tt co Ω co p- φ s: dt ^ d Φ O CO Φ OP ¹ o tt ß. Ω rt P- Φ? et ß P- CQ rt ß P- Cd N tr rt Φ tt Φ iP P "Ω 3 O Pl tt P- ß P-

P- fr Φ φ er • P- O: P- CQ φ P- Φ Φ co P "ß P- Cd P- o ß ß P- co: tr ß P- ß ß P- Ω ß

Φ Φ tt ß ß ß P- Ω ß ß tt s. O α d Φ Φ Ω Hl Φ Cfl s: Ω Φ er Ω φ tr ^ d P ⁴

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M ß d N tt -S tt ¹ s: ß α Φ P- Φ P- Hi P ¹ sα tr 3 Φ ß ß Φ ISJ ß: P- Cd φ Φ er Hi Ω

Φ ß P- φ P ¹ SD: Φ Φ tt tt tn Hi Φ rt CΛ • dn Φ tr I- ¹ er n Φ ß tr φ ß ß Φ Ω P- φ tr er sα P- P- Ω Φ ß er Hi S Φ o ß ß? R P- tt Qr φ P- P- tt Φ

^ φ P ⁴ tr P ¹ ß Φ 3 φ ß ß tr Φ ß: φ tt P ¹ d sα 2 O ß Φ Φ H Φ H ß ri ^¬ s: ß P ¹ rt P- s et ß φ ß CQ φ P - tt t Ω cn Φ - \ P- 3 ß rt ß CQ ß tt P- ιp φ Φ rt • er P. TJ CO ß ^ d tr Φ o Ω 3 sα iP tt Φ P- φ

O φ cn φ - Φ rt ß Φ N Cd P- O J α o Φ o P- tr Φ P tn Φ fr er

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P- rt P- ß O tt Φ CQ φ d ß rt rt α • <P- cn P- tt P- P- ß ß α SD:

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P- P- 0 = f d rt <j tt rt P- P- ß 0 er tt fr φ tt LQ P- er ß o tt P- EP

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P- Φ Φ tr Cd 0- rt> sα Cd Hl TI O p. ß Φ tt he Ϊ> Φ φ Φ tt TJ ß ß Φ

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«Tt, -,:>? R Φ ß Ω CQ φ Ω rt er φ d for P- r pr ß tt H φ tr N Φ O ß ß

P- 6 o Φ Φ ß tr P- Φ tr CQ φ rt tt &. rt rt Φ ri ^¬ et P- ß ß φ ß s tt r P. m tt f P- tt ß S er et er ß ß d φ φ Φ P- tt tt Φ for φ tt- - ¹ ß ß tr Φ φ rt ß φ Φ P- ß Φ ß 3 Φ ISl ra Φ er d IQ P- tt <! S P- 0 P- ß ß ß rt rt ß £ P ß tt tt

• CQ H- tt Φ f CQ Φ <! d $ P- ra ß ri ß t ¹ P- ß ra Ω ß ß φ Φ d ß ß 3 tt rt ß ri ^¬ tfl Hi tt o ra Φ ß rt P- Φ φ Φ φ CQ Ω tr N ß er tt d Hi ß Qr ß ß

Φ Hi Φ φ tt φ PJ = P- tt φ tt iQ ß ß Φ P "P- tt CQ tr Φ Φ <l ß tr Φ P ¹ rt ß ß = P- £ - ■ P- tt" t N rt rt φ ß ß = ri φ rt er Φ Φ 3 P 'iP Φ Q o P- y ß cn Φ

N tr ß P-. 0 CQ sα P- d N m N d W $, pr Hi tt - ß P P- φ ß ß Φ Φ tt

Φ P- ß Ω Ω Φ Φ ra CQ Φ φ I) d ß ri ^¬ DJ »tt Φ ra Φ Hl rs: ≤ rt ß ß sα P- ß UQ tr tΛ tr er tt ß Ω rt ß 3 rt _^ ~, φ CQ tt tr Φ P- Ω ß • rt P- Φ Φ Φ ß fr 0 Φ tr P- N Cd tt φ sα 0 P- tt ß 0 er Ω Φ ß P- 3 TJ tt P ¹

ISl Φ 3 Φ ß tt Cd CQ 3 ß et * - _" P ¹ P ¹ φ Ω IQ Φ ß« iP rt er s: μ. P ¹ P- P ¹ co

P- 0 P- P "tt 0 P- er sα Φ P- J 3 er for Tl rt ß 0 = ß tt rt Φ IP Φ ß ß S

P- rt tQ ß rt «Hi IQ ß Φ Φ ß Φ Ω ß Φ Φ Φ ß ß fr tt ß o 10 Φ P- cn ß P-

CQ - Φ Φ 0 P- ß ß P- <! ra P- er Ω IQ 3 P- mdp rr ß N rt J tt <! 3 rt ri ^¬ ß

Ω ß N tt ß ß tt rt o rt S ß Φ f φ P- rt rt ra et P- φ N tt co O p- P- tt tr, -. Φ Z ß rt s Φ tt Φ ß φ d Hl m Φ ra tt <tt <! sα o tt ß Φ Hi f- α

Φ π tt Φ ß ß d er tt Φ N ß rt Ω ß d = Ω ß d φ CQ - ß φ Φ N Φ tt P- Φ ß - P- rt? R ß P- rt dm Φ d Φ tQ er er P- Φ φ tt 3 φ ip 0- rt N ß rt P- rt iQ CQ LQ tt 0 m P "≤ ra Ω ä. Tt sα N ß ß d (l P-

Φ tQ Φ <! 3 ß rt cn P- rr Φ rt ß Φ rt er ß = er φ P- rt ß N s: Φ tfl CΛ

P- Φ tt ti Φ ISl CQ o ß P "ß ß Φ fr tt ß Φ tr tt Ω ß • ISl - <Φ tt O Ω ß 3 0 s: P- d ri ι ra Φ P ¹ rt ß rt sα ß ß tt tt he Φ O tt Φ s: he

LQ P- H P- P- ß ß = o P- <P- rt ra P- φ N P-. P ¹ Φ P- rt <l ö er tt P ¹ Qr tt P- d Φ CD 0 Φ CQ ß lO ß ß 0 Φ ra JE! ß Φ φ ß ß φ o P- Φ rt ri Φ cn φ Ω ß m Ω ß tt Ω tt cπ P- <! α tt ¹ ß J P. tt ß P- φ P- rt φ co 3 ß tr sα Φ t φ er er Φ 0 d P- Φ P- d φ P- ß s CQ ^ Qr os: Φ ^{• 1} sα et rt rt ß tsi Φ Φ ß P ¹ Φ 3 Φ φ tt Ω 3 tt ß rt Φ rt Φ P- s: Φ 3 ß φ ß ß Φ Φ

, -. ISl Φ 1 d ß P- 0 d ra φ rt P ¹ er er ß er ß Φ ra φ Φ 3 Φ α tt 1 sα ß cn ß ω et tt CQ rt P ^{1 for} 3 ß €, φ Φ et P- ß pj. tQ rt rt tt Ω Φ o \ ° ß

- α ß d ß = P- Φ φ 3 1 ß ß P ¹ . ß tt P ¹ Φ CQ S Qr G tr tt Φ _^ to er O

^■ F ß rt Φ ß 1 ß ß P- TJ m Φ Φ Φ rt P- d ß Φ 3 ß to ß sα P- P- ß P- φ sα N ß o \ ° ß 1 ß tt p ü φ ß tt , ß ra er riß Hi ß <! er d cn φ tt P- ^ TJ 0 ra p riß P- N ß rt m tt • ß er O Φ tt er tt

Cfl Qr rt o P-? *! **. 3 tt N Ω ß tt ß Tl P- - rt P- ß Cfl Φ Cd tt P- Ω Φ

Φ P. Ω o = Φ ß o Φ er ß 0 ß Φ Φ φ d ß X ιp Ω <! Φ N EP tr tt ^ d sα tt φ er tt ra ß N φ ß s: ß Ω ß tt ra P ¹ ra P- ß ro co d rt od = Q> «• tt ß rt Φ rt rt ß er rt rt rt tt ra N _^ -, Φ φ tt o iß sα 3 tt ¹ ß φ ß Φ ra er ß $ ß sα Φ ß = ra φ rt> tt N ß ω L_l. P- φ ß tt d tt d P- rt ß ß f Φ 3 tt d P- _^ - _^ tr d 0- s: Φ φ tt- φ

Φ Φ Ω ß er ω • ß Φ tt P- P ¹ er Ω φ Cd ß iP φ Φ s: cn ß er CQ CTi ß m P- ra φ er ra -— - tt "rt tt Φ et ß sα rt N α 01 Ω Ω rt ß Φ rt tfl tn P- ß Φ ß d P- er er ß ß ß φ φ Φ P ¹ P-

Ω tt ß Φ td ß sα P- ß ω ß tr N ra N Φ ß •

The mass, which is at least in the spaces between the textile fabric, can be produced as follows:

A variety of materials can be used for the matrix (A). You can work with solvent-free or solvent-based systems. Suitable solvent-free systems are, for example, crosslinkable, liquid or pasty resin systems. Examples of these are resins made from crosslinkable addition polymers or condensation resins. For example, pre-condensates of phenoplasts (novolaks) or aminoplasts can be used which, after the pasty mass has been shaped, are finally crosslinked to form an electrochemical layer composite. Further examples are unsaturated polyesters which can be crosslinked by graft copolymerization with styrene, by bifunctional ones

Reactants curable epoxy resins (example: bisphenol A epoxy resin, cold-cured with polyamide), crosslinkable polycarbonates such as polyisocyanurate crosslinkable by a polyol, or binary polymethyl methacrylate, which can also be polymerized with styrene. A paste-like mass is obtained, each of which consists of the more or less viscous precondensate or uncrosslinked polymer as the matrix (A) or using essential constituents thereof, together with the. Component (B) is formed.

Another possibility is the use of polymers or polymer precursors together with a solvent or swelling agent for the organic polymer. In principle, there is no restriction with regard to the synthetic or natural polymers that can be used. Not just polymers with carbon

Main chain are possible, but also polymers with heteroions in the main chain such as polyamides, polyesters, proteins or polysaccharides. The polymers can be homo- or copolymers; the copolymers can be random copolymers, graft copolymers, block copolymers or polyblends; there is no restriction here. Natural or synthetic rubbers, for example, can be used as polymers with a pure carbon main chain. Fluorinated ones are particularly preferred Hydrocarbon polymers such as Teflon, polyvinylidene fluoride (on PVDF) or polyvinyl chloride, since this enables particularly good water-repellent properties to be achieved with the films or layers formed from the pasty mass. This gives the electrochemical components produced in this way particularly good long-term stability. Other examples are polystyrene or polyurethane. Examples of copolymers are copolymers of Teflon and amorphous fluoropolymer and polyvinylidene fluoride / hexafluoropropylene (commercially available as Kynarflex). Examples of polymers with heteroatoms in the main chain are polyamides of the diamine-dicarboxylic acid type or of the amino acid type, polycarbonates, polyacetals, polyethers and acrylic resins. Other materials include natural and synthetic polysaccharides (homo- and heteroglycans), proteoglycans, for example starch, cellulose,

Methyl cellulose. Substances such as chondroitin sulfate, hyaluronic acid, chitin, natural or synthetic waxes and many other substances can also be used. In addition, the abovementioned resins (precondensates) can also be used in solvents or diluents.

Solvents or swelling agents for the abovementioned polymers are known to the person skilled in the art.

Regardless of whether the matrix (A) is a solution or

Contains swelling agent or not, there may be a plasticizer (also plasticizer) for the polymer or polymers used. “Plasticizers” or “plasticizers” are to be understood here as substances whose molecules are bound to the plastic molecules by secondary valences (Van der Waals forces). By doing so, you reduce the

Interaction forces between the macromolecules and thus reduce the softening temperature and the brittleness and hardness of the plastics. This distinguishes them from swelling and solvents. Because of their lower volatility, they cannot usually be removed from the plastic by evaporation at room temperature, but may have to be dissolved out using an appropriate solvent. The Incorporation of a plasticizer results in a high mechanical flexibility of the layer that can be produced from the pasty mass.

The person skilled in the art knows suitable plasticizers for the respective plastic groups. They must be compatible with the plastic in which they are to be incorporated. Common plasticizers are high-boiling esters of phthalic acid or phosphoric acid, for example dibutyl phthalate or dioctyphthalate. Also suitable are, for example, ethylene carbonate, propylene carbonate, dimethoxyethane, dimethyl carbonate, diethyl carbonate, butyrolactone, ethyl methyl sulfone, polyethylene glycol, tetraglyme, 1,3-dioxolane or S, S-dialkyldithiocarbonate.

If a combination of plastic and plasticizer is used as the matrix, the plasticizer can then be detached from the pasty mass with a suitable solvent or by evaporation (for example under vacuum and / or elevated temperatures). Any cavities that may arise may be caused by the following. Pressing and lamination processes for joining the different layers are closed. This improves the electrochemical stability of the charged accumulator. When using a solid electrolyte in the plastic matrix described, it is desirable to have an ionic conductivity of at least 10 ^"4 S cm"" ¹ .

Instead of later compressing the cavities, these can also be filled with a second solid or liquid electrolyte or electrode material after the plasticizer has been removed.

As already mentioned, the present layers according to the invention are suitable for a large number of electrochemical components such as accumulators, electrochromic components and in particular rechargeable electrochemical cells based on solids. For this purpose, the person skilled in the art can select the same solid substances (B) that he uses for classic electrochemical components, ie those without the addition of plastics, would use.

Possible solid substances (B) for an accumulator in lithium technology are mentioned below as examples:

- lower lead electrode AI, Cu, Pt, Au, C

- positive electrode LiF, Li _x NiVθ4, Li _x [Mn] 2θ4, LiCoθ2,

LiNi0 ₂ , LiNi _0/5 Co _{0 /} 5θ2, LiNi _0/8 Co _0/2 θ2, V ₂ 0 ₅ , Li _x V ₆ 0 ₁₃

- Electrolyte (here solid) _ ± 3AI0 3Tiχ 7 (PO4) 3,

LiTa0 ₃ ^• SrTiθ3, iTi2 (PO4) 3 -Liθ2, LiH ₂ (Pθ4) 3 -Li 0, Li ₄ Si0 ₄ -Li3P0 ₄ , LiX + ROH with X = C1, Br, I (1, 2 or 4 ROH per LiX). - negative electrode Li, Li _{+ x} Ti5θ] _2, Li _x Moθ2, Li _x θ2,

Li _x Cτ_2 / ^L i ^c 6 'lithium alloys

- Upper lead electrode AI, Cu, Mo, W, Ti, V, Cr, Ni

The present invention is of course not limited to batteries in lithium technology, but, as already mentioned above, includes all those systems that are also "conventional" technology, i. H. can be produced without incorporating an organic polymer matrix.

Some special configurations of the masses which are suitable for special components or component components are to be described below. Insofar as the electrochemically activatable constituents used therein are not yet state of the art, it should be clear that these substances also in "bulk form", i.e. H. without polymer matrix, can be used in corresponding electrochemical components.

By a suitable choice of the electrochemically active substances, electrochemical components, for example accumulators, can be produced, which are located in the charging / discharging curves

Have characteristics by means of which a targeted control of the charge and discharge status of the battery is possible. So as an electrochemically activatable solid substance (B) for the positive or the negative electrode mixtures of two of the above-mentioned electrode materials or corresponding other electrode materials are used, which have different oxidation / reduction levels. Alternatively, one of the two substances can be replaced by carbon. This leads to characteristic curves of the loading and unloading curves, which enable an advantageous detection of the loading or unloading. Allow discharge state of a battery manufactured using such masses. The curves have two different plateaus. If the plateau closer to the discharge state is reached, this state can be displayed to the user, so that he knows that he will have to recharge soon, and vice versa.

If carbon and a lithium alloy element are incorporated into a layer provided for a negative electrode, this gives the electrode that can be produced from it (with properties of an alloy and an intercalation electrode) a particularly high one. Capacity with improved electrochemical stability. In addition, the volume expansion is less than with a pure intercalation electrode.

Graphite or amorphous carbon (soot) or a mixture of both can also be incorporated into the pasty mass with electrode material for a positive or negative electrode. In particular, parts by weight of 20 to 80% by weight of amorphous carbon, based on the electrochemically activatable component, are advantageous. If the mass is provided for a positive electrode, the lubricating effect of the carbon is to be mentioned as an advantageous property, which improves the mechanical flexibility of a layer produced from the pasty mass. If the mass is provided for a negative electrode, the electrochemical stability and the electronic conductivity are additionally improved, as already described above.

The layer according to the invention can also be used for electrodes other than Intercalation electrodes are used. An example of this is the use of metal powder in combination with an alkali or alkaline earth salt as an electrochemically activatable solid substance (B). A pasty mass produced in this way can be used for the production of decomposition electrodes. This eliminates the volume expansion typical of intercalation electrodes, which leads to improved aging resistance. An example of this is the combination of copper plus lithium sulfate.

A very special electrode variant is available if the electrode material (B) is a metal that does not react with lithium and also contains a lithium salt. As already described above, the matrix (A) in this variant is produced from a combination of plastic with a plasticizer, which is then removed from the pasty mass again. In this variant, however, the cavities formed should not be used when the electrochemically activatable layers are subsequently laminated under pressure or the like. getting closed; rather, it is important to ensure that they remain open. In combination with a lithium salt in the adjacent electrolyte layer such composite electrode has the ^'property of reversibly switched lithium in the resulting cavities, and can expand. It has the advantages of an intercalation electrode, but avoids its disadvantages (e.g. volume expansion) and has excellent electrical properties due to the large inner surface. Nickel is an example of a metal that does not react with lithium.

Surprisingly, it has also been shown that the incorporation of a phase mixture of Li4SiÜ4 -Li ₃ pθ ₄ into the mass to be introduced into the fabric, regardless of its intended electrochemical use, leads to an improvement in the plasticity of the electrodes or solid electrolytes produced therefrom. The prerequisite for this is that the phase mixture is extremely finely ground. The extremely small grain sizes are likely to be the cause of an improved internal sliding effect. Regardless of whether the solid substance (B) is an electrode material or an electrolyte material, it can consist of a lithium ion conductor and one or more further ion conductors (eg for Li, Cu, .Ag, Mg, F, Cl, H). Electrodes and electrolyte layers produced in this way have particularly favorable electrochemical properties such as capacity, energy density, mechanical and electrochemical stability.

As mentioned, in one embodiment of the invention, the mass to be introduced into the fabric can additionally contain a second solid ion, electron and / or ¹ a mixed conductor (C). This can be worked into the matrix in different ways. If it is an ion conductor which is soluble in a solvent - for example that in which the matrix material (A) is also soluble - the mass can be produced by the solvent for the matrix material containing this second ion conductor. The vapor pressure of the solvent must be so high that it can be expelled at a later stage (e.g. after intimately mixing the constituents of the mass, even if it has a pasty consistency without the presence of the solvent, or after generating the Layer or foil). If a plasticizer is also to be present in such an embodiment of the invention, it is advisable to choose a plasticizer which is also soluble in the solvent and which can then optionally be removed again using the solvent mentioned. This embodiment of the invention can also be accomplished with such conductors (C) which have a relatively poor conductivity (in particular ion conductivity if this property is to be present).

In a further embodiment of the invention, an ion, electron or mixed conductor (C) can be selected, which is soluble in the selected plasticizer for the system. In this case, the plasticizer should have a relatively low vapor pressure. Here, when intimately mixing in ω o O σ

P- P- sα W <J si N tr s! CQ φ P- Pl Φ tα er j ^ 3 TJ $ TJ er CΛ t ¹ tr ¹ f α φ Φ Pi TI JN Cd J φ 0 Φ o 0 ß d ^> 0 ß J P- ß ß m ß Φ 0 0 = H P- P ¹ 0 ß = Cϊ Φ P- P- I- ¹ P ¹ Φ φ 3 Φ P ¹ ra ß CQ tt (- ^■ m tQ ß CQ ß = ß ß ra tr CQ ß tt ß er CΛ) ß P- - et 3 φ Φ d ra ß ra ß

P- ß dm tr tt Φ ra rt I 3 P- ß P. rt tt ¹ ! - ^■ ra P- ra Φ ri er rt cn tr P- pr fr rt rt ra ra rt ra td m I- ¹ IQ 3 φ P- o ß Φ φ φ ß P- d Φ Φ Φ P- rt rt 3 P- Hi P- P- Pt ri ^¬ ri ^¬ ra rt Ω ß er o φ tt φ tt tt ¹ ra tt ¹ tt tt ß ra φ o P ^J er Ω P- P- to ß = O d tt tt P- d P- tr ß P- φ tr P- Φ ß ra P- pr Φ φ tt ra ra er rt rt he Hi ö Hi α P - P- he. 3 P ¹ 0 0 Ω er N Φ sα Hi pr Φ rt ß ß Φ 0 P- ß ra er Φ φ ß P- ß P- Ω ri P- • P- ß Ω Ω er Q P- ß rt P- riΦ N d ß ß TJ ri d Φ tt tt 3 Φ ra tsa m ISI 3 er ß = CQ tr ¹ 0 ra er er rt rt φ IS1 tt tr ¹ ß Φ m P ¹ P- Φ Hi t ^H P- Hl 0 = m ra P- P- TJ rt pr P- ß ra Φ Φ 3 ß ß = sα P- P-

0 Φ P- ß sα m ra tt CQ ß rt tt CQ Φ Φ φ tr <φ Hi ^■ ra Φ σi φ φ 3 3 Φ ß rt Φ P ¹ Φ

P ¹ P- Φ pr Φ PT Ω m Φ tQ Φ φ d ra tt ß tt 0 = tt P- φ Hl P- ß ß P- P- ß. N ß φ tt rt ß 0 tr «ß er •• ß Φ rt P- CQ H- P- ra ß φ CQ φ tt P- Φ rt P ¹ P ¹ ram P- ß ß Φ et Hi ß ß tt ß T 0 dd. φ CQ Ω Ω rt tt d tt d rt ß O Φ ra Ω Ω CQ -, d tt φ ß = rt d P- ß P- 3 ß tt φ ß ^J tr 0 P- ß Ω Φ ra P. P- P - he er Φ ö Hl Φ Pi ß tr 0 ß ß ra H P- 3 -S ra Hi P- CQ P? tt ri Φ er Ω tt - $, P- Φ CQ

P- ß IQ ri _* 0 Φ Φ P- ß = 0 rt er Hi φ td ra P- φ tt ß Φ er tt ß Φ ri tt Φ pr tQ CQ et ß d ß p ß er P- ß er Φ 1 P - 3 φ _^ - _^ m tt P ¹ tt Φ pr er P- P- Φ P ¹ ß pr m tt Φ φ tt Φ P- P- TJ S ß p- N rt Q ω P- P- ¹ et o ß ra ß J o ß Φ ß ra rt Ω ß P- φ φ tt ri φ 0 ß φ rt α • Φ <! tt 3 ß Φ P- er tt rt Pi ß m es P- ö Ω ß 3 er ß α μ. ß d tt P- rirt P- P- Φ 0 = ^ P- <l <i Φ Hi Φ ra er rt er rt ß Φ φ ß ß P- 3 ß Hl Φ 1 tt ra Φ er LXJ Q tt IΛ 0 φ P- ß P- ß rt Φ ra P- ß et m P- s Φ ß CQ d = 3 P- 0 P "d Φ Φ Φ - ß Φ tr ¹ P-

Hi Hl m P- rt CQ d tt P- m tt Φ XP ¹ rt tt ^• - • - σ 0 = 3

P- P P- ß M P

TJ t- <φ rt tt Φ ß P- cd ra

Ω Φ φ Hi P- φ Φ Φ Φ tt Φ ra P- f tt Ω ≤. td ß ß 0 0 P- ra Φ er P- Φ φ φ td tr ra rt ß tt tt 3 Ω Hl ra φ Φ φ φ Φ TJ er p- tt ¹ rr P- tt ß φ ß ß rt i ra ß φ ds td P- er Φ tt tt P- P- Φ tt TJ er CQ sα Φ CΛ tt tt Hl P- φ er m tr td 3 d Φ P- P- P- ra d ß ß rt Φ. O Pt er Φ £. Φ ß ß P- Cd Φ SD: φ ß S rt

P- CQ ß ß ß ß ß ra Φ Ω Φ tt K Φ ß rt rt tt Φ ß d rt O Φ er CQ φ ß ß ß ra φ Φ P- tt ¹ φ ß er tt 3 tt er tt rt 0 d tr ß • ß Φ> ß m> τl P- Φ PiPi ra ß

Pier φ ß sα r rt- ß φ Hl ^> : tr P- m tr ß 0 ß CQ tt rt Φ CQ tt er rt ra sα

ISl er Φ Pi s P- tQ Φ TJ ra P- tt tt P- tQ _^ - _^ ß = φ CQ p- s α, -. tf P- ß ra pr tt Φ φ ct d tt ß d P- ß Φ tt P ¹ rt CQ er ß tt o P ¹ tt Φ φ ß Φ N P- P> Cd P- ß ß et Φ 0 P- Φ

0 sα tt Φ φ tt ß Φ pr Φ TI sα 0 - rr ra tt rt tt d φ o - ') ß Pi ra P- d Ω P ¹ φ P- φ - ¹ Φ Ω d Ir ¹ m er Φ P- 0 dm J rt - ra 1 J rt et d rt ra er φ P- P ¹

P- tr Φ Hl ß ß rt rt P- rt tt ß pr d 0 <ι ß ß ö PJ: J cn Φ O Φ Φ tr CQ Φ ß ß ß et w p- φ CQ tQ P- rt d 3 tQ 0 3 sα tj P ¹ P ¹ P-> - ri P ¹ P- tt-. P- ra ß Φ 3 φ. -, φ Φ ^ Qr ß ra Φ N Φ ra ß J Φ T! et CQ ß 3 N ß o ß ß tt ¹ rt d 0! P- φ o

3 ß sα P- φ rt P- P- P- er CQ P- 3 P- Φ tt d φ I- ¹ ra ~ ^ ra d ß Hi rt ra tt 3 - 'tt Φ ß Φ Φ P- rt ß ra ß P- ra P- 0 ß 3 sα rt tt- rr Ω φ tr Ω P- ß ^ ß Ω N o Q <CQ ra ß = Φ <! tt Ω ß P- P- CQ 0 P- tr Ω P- 3 rt P- er φ tsi φ P ¹ er Φ Pi 3

Ra Φ rt ra <! ^ rt rt rt o sα P. er Φ 3 φ s φ 0 ß ^* NN. tt P- rt d P- P-

3 tt tr Ω φ 0 φ ^ P- tt P- Φ ß tt P- P- X P- 3 Φ cn N ra d ß CQ ttl rt

P- er d = er tt tt P- ß 0 CQ IQ φ P- ra • co 3 ^• <; Φ ri P- ß P- S öd Φ ß fr rt P- ra Φ s; he ß ß pr dtt Φ ß Φ P) Φ ß rt P- ß Φ P- ß = r • _^ O tt- * - ß CQ rt "« IS1 P- m ra ß = Φ CQ P. tt Hi ß ß ß- J tt CΛ o ra ß N m rr ß ri! l-. cd ra P- P- Φ φ m Φ Ω CQ tt P- p- 3 tQ CQ ß ß ß φ. er P- ra er φ Φ s • <Ω ß s <! I φ ß ß φ tr ra Φ Hi ra Φ tt mm H φ ß φ Φ φ φ ß P. P- P- tr ¹ er P- Φ P- P- tt tt ß Φ Φ ß Hi rt P- Φ 3 rt 0 l ß rt tt P- tt ß CD Φ ß Φ P- Λ d P- ra tt Φ Φ rt 3

Q rt d tt tt N d ß m ß CQ, -, 0 = ß P ¹ φ ra 3 φ d tt Φ ISJ d ß Φ tt Φ Φ tt Ω Φ rt Φ ß tt ¹ et N Φ 0 ra φ Φ φ P - TJ P- P- Hl er 3 Φ cn ß CQ Φ td er φ P- ß -, tr Φ sα P- "• Φ er φ ß P- P- Ω er P- ri ß d = ra« P- O tt P- tt ß P- * Ά rt sα sα ß φ P- P- d φ ß rt er ß φ rt CQ tt r O er ß. rt P. Φ ß Hi tt ß 0 Φ

Φ ß sα P- Φ ß s! Qr ß tt 3 Φ 1SI Φ Φ P ^J Φ φ ß tt 0 φ PJ: ß ß Φ P- Φ φ tt tt ra P- & ß tt φ φ P- CQ ß P- d tt ß 0 m ß ß ß 0 tt tt ß ß Φ

P- φ P- φ Φ ß φ ~ * C-. ra tm • _^ CQ ^■ € tt N CQ Φ P- sα φ m Φ i CQ CQ ß ß «ß ß t-! ß ra d ra Φ Φ P- Φ h tr tt 3 0 rt H- C α> tt ß P- sα Φ tt Φ tt rt m ß ß P- d = φ 3 Φ ß tt φ ß ß Φ

CQ rt d Φ sα sα ra P- Ω N o tt P- CQ tt P- P- ß P- ^• - • N CQ P- ß.

Φ P- ß ß tt φ tt er, - φ ß Φ φ rt rt N ra P ¹ P- ra N

P- 0 iQ ß tt P- π ß P- d tt sα Φ Φ Ω rt CQ Φ ra Φ ß ß rr - - m ra rt φ rt ß er • Φ P- Φ

Φ Φ rt Φ ß Φ ß ß tt φ

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P- Φ H Φ P- P- 0 d P- P ¹ Φ Φ Φ P- P- P- 0 0 Φ φ Φ ß Φ P- Φ 0 ß> ß Φ Φ P- ß 0

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a few μm). However, this application is likely to be limited, since corresponding components may not meet the current capacity requirements in a large number of cases. However, the application for backup chips, for example, is conceivable.

The present invention therefore encompasses self-supporting or electrochemically active or activatable layers, preferably in the indicated thicknesses, which can be produced from the pasty materials and textile fabrics described above. The layers are preferably flexible.

To produce both the self-supporting layers (films, tapes) on the layers lying on a substrate, use can be made of the customary methods known in the prior art which can be used for the corresponding polymer materials of the matrix. Depending on the material, the pasty masses are solidified, for example, by hardening (of resins or other precondensates), by crosslinking prepolymers or linear polymers, by evaporation of solvents or in a similar manner.

In a preferred embodiment of the invention, crosslinkable resin compositions (precondensates), as described above for the pasty compositions, are used and, after the layer has been formed, cured by UV or electron radiation. Curing can of course also be effected thermally or chemically (for example by immersing the layer produced in a corresponding bath). If appropriate, suitable initiators or accelerators or the like are added to the compositions. added for the respective networking.

The present invention further relates to laminates with electrochemical properties, such as _. in particular accumulators and other batteries or electrochromic components, very particularly preferably rechargeable electrochemical cells,

Layer is connected to a carrier layer by pressure rollers, calender coating with two or three nips, in which in addition to the pasty mass, the carrier web comes in, or doubling (bonding under pressure and back pressure of preferably heated rollers). The specialist will do the appropriate

Easily find techniques that result or offer through the choice of matrices for the respective pasty masses.

A pressing process during the bonding (lamination) of the individual layers can often be desired, not only for better bonding (and thus achieving better conductivity) of the individual layers, but also, for example, in order to eliminate any cavities that may be present in the individual layers for example, as described above, by washing plasticizers or the like. Common techniques can be used for this. Cold pressing (at temperatures below 60 ° C.) can advantageously be carried out, provided the materials used allow this. This ensures particularly good contact between the individual layers.

In an advantageous embodiment of the invention, the layers produced as described can be impregnated with an electrolyte solution (e.g. a lithium salt dissolved in an organic solvent such as propyl carbonate and / or ethyl carbonate or the like) before or after lamination. Such electrolyte solutions are known to the person skilled in the art and some are also commercially available.

The electrochemical components that can be produced with the paste-like materials according to the invention are not restricted. The configurations described below are therefore only to be understood as examples or particularly preferred configurations.

In this way, rechargeable electrochemical cells can be produced using thick-film technology, ie with individual, do H ¹ cπ O oo cπ

Sealing it is also possible to introduce sealing compound into the tissue in the area where the contact tongue is passed through the sealing seam before the sealing, for example using a dispenser. Due to the fabric structure, this adheres particularly well in contrast to application to metal strips.

2 shows an electrode film 1 with an embedded metallized tissue. In the area of the contact tongue 2, the tissue has been pressed to the required reduced thickness for implementation through the sealed seam. In this embodiment, too, it is of course not imperative, as shown in the figure, that a continuous film of the mass of polymer matrix and electrochemically activatable solid substance is located above and / or below the textile fabric.

The following examples are intended to explain the invention in more detail.

Example 1 To produce a positive electrode, 2 g of PVDF-HFP are combined with 1 g of ethylene carbonate and 100 g of acetone. Then 14 g of LiCo0 ₂ and 3 g of conductive carbon black are added in the form of fine powders. These constituents are then intimately mixed with one another by vigorous stirring. A commercially available aluminum-coated fabric is then dipped into this paste. The fabric thickness was 150 μm. After the tissue has been pulled out of the paste in a controlled manner, it is filled with paste. The filled tissue is then dried and dipped again. The desired layer thickness can be set by alternately drying and dipping. A stable and highly flexible film was obtained which was used as a positive electrode in a lithium accumulator.

Example 2 A negative electrode was produced by alternately dipping and drying a copper-coated fabric 150 μm thick. The paste was prepared as follows. 2 g of PVDF-HFP were stirred with 1 g of ethylene carbonate and 100 g of acetone O

charged, then a decreasing charging current is impressed at constant voltage. The cell was then discharged down to 3 V at constant current. Figure 3 shows the diagram of such a charge and discharge cycle. FIG. 4 shows the decrease in the initial capacity as a function of the number of cycles.

Claims

Expectations :

1. Electrochemically activatable layer or film for use in electrochemical components which (a) is a textile fabric and

(b) a mass of at least in the spaces between the textile fabric made of at least

(A) a matrix containing or consisting of an organic polymer, its precursors or its prepolymers and

(B) an electrochemically activatable, non-soluble in the matrix inorganic material in the form of a solid substance.

2. Electrochemically activatable layer or film according to claim 1, characterized in that it can be used as a cathode or anode and the textile fabric consists of a metallized plastic material or metal.

3. Electrochemically activatable layer or film according to claim 1, characterized in that it can be used as an electrolyte layer and the textile fabric consists of an organic or inorganic-organic polymer material, glass or ceramic.

4. Electrochemically activatable layer or film according to claim 2 or 3, characterized in that the textile fabric is a flexible fabric.

5. Electrochemically activatable layer or film according to one of the preceding claims, characterized in that the organic polymer of the matrix (A) is a swellable and / or chlorinated or fluorinated polymer, preferably polyvinylidene chloride, polyvinylidene fluoride, polyethylene oxide or a polyvinylidene fluoride-hexafluoropropylene copolymer or a polymer mixture containing at least one of these polymers.

6. Electrochemically activatable layer or film according to claim 5, characterized in that it- optionally one

Contains plasticizer, the proportion of which in the layer or film is not more than 15% by volume, preferably 0-3% by volume.

7. Electrochemically activatable layer or film according to one of the preceding claims, characterized in that the proportion of polymer material of the matrix (A) in the layer or film is not more than -15% by volume, preferably not more than 6% by volume ,

8. Layer composite with electrochemical properties, comprising an electrochemically activatable layer or film according to one of the preceding claims, which is suitable as a cathode and / or an electrochemically activatable layer or film according to one of the preceding claims, which is suitable as an electrolyte layer, and / or a Electrochemically activatable layer or film according to one of the preceding claims, which is suitable as an anode.

9. Rechargeable electrochemical cell, comprising a layer composite according to claim 8.

10. Rechargeable electrochemical cell according to claim 9, characterized in that the electrochemically active

Layers or foils are enclosed by a housing and the cathode layer and anode layer each contain metallized flat structures, which protrude as contact tongues over the cathode or anode surface and are guided through the housing wall to the outside.

11. Rechargeable electrochemical cells according to claim 10, characterized in that the housing consists of a metallized plastic film which is closed by sealing seams, and the contact tongues are guided through the sealing seam to the outside.

12. A method for producing an electrochemically activatable layer or film according to one of claims 1 to 7, comprising the following steps: - producing a pasty mass from at least

(B) an electrochemically activatable, in the matrix insoluble, inorganic material in

Form of a solid substance,

- Fill at least the spaces between the textile fabric with the pasty mass, and

- Solidify the pasty mass into a layer or flexible film.

13. The method according to claim 12, characterized in that the textile fabric is immersed in the pasty mass one or more times and is pulled out again in a controlled manner, such that at least the interstices of the textile fabric are filled with the pasty mass.

14. The method according to claim 12, characterized in that the textile fabric is coated by printing with the aid of rotating rollers with the pasty mass such that the mass penetrates into the spaces between the textile fabric.

15. The method according to claim 12, characterized in that the pasty mass is pressed by pouring under pressure into the spaces between the textile fabric.

6. A method for producing an electrochemically activatable layer or film according to one of claims 1 to 7, comprising the following steps:

- Making a pasty mass from at least (A) an organic polymer, the

Precursors or their prepolymers containing or consisting of them and

(B) an electrochemically activatable, inorganic material which is not soluble in the matrix in the form of a solid substance,

Solidifying the pasty mass to form a layer or flexible film,

- Laminating the textile fabric into the solidified layer or film using pressure and / or heat.