DE10251241A1 - A process for preparation of Li-polymer batteries involving a composite system comprising a conductor, anode, cathode and separator giving improved cyclic and storage stability with suppression of disturbing side reactions - Google Patents

Abstract

A process for preparation of Li-polymer batteries including a composite system involving a conductor, anode and cathode electrode compositions, and a separator, where the conductor film is impacted with electrode composition paste and is combined with a separator so that the electrode substrate side impacted with the paste makes contact with the separator material is new.

Description

The invention relates to a method for the production of lithium polymer batteries using an arrester, Compound system comprising electrode masses and separator. In detail The invention relates to a method in which the arrester foils pasty extruded electrode masses and then with Separator material are joined so that the with the Electrode mass applied to the electrode substrate side with the separator material is contacted.

Details of the production of lithium polymer batteries are known from the literature and can be found in the "Handbook of Battery Materials", published by IO Besenhard, Verlag VCH, Weinheim, 1999 (1). Special manufacturing processes, such as B. the so-called Bellcore process are in "Lithium Ion Batteries", publisher: M. Wakihara et 0. Yamamoto, Verlag VCH, Weinheim 1998 p. 235 u. 10.9 (2).

• 1. der Beschichtungsprozess, bei dem (die) der für die Kathoden bzw. Anodenmasse erforderliche Polymerbinder gelöst wird. Beispielsweise wird eine 5-10%ige Lösung aus Fluorelastomeren, die als Homo- oder Copolymere vorliegen, mit z.B. N-Methylpyrrolidon (NMP) als Lösungsmittel hergestellt und diese Polymerlösung mit den kathoden- bzw. anodenspezifischen Zusätzen wie Li-interkalierbare Metalloxide bzw. Liinterkalierbare Kohlenstoffe (Ruß, Graphit o.ä.) versetzt und dispergiert. Diese Dispersion wird dann mit einem in der Technik bekannten Beschichtungsverfahren auf Stromkollektoren) aufgetragen.

The following fundamentally different methods are used in the prior art for producing the lithium polymer batteries:

• 1. the coating process in which the polymer binder required for the cathode or anode mass is dissolved. For example, a 5-10% solution of fluoroelastomers, which are present as homopolymers or copolymers, is prepared with, for example, N-methylpyrrolidone (NMP) as a solvent, and this polymer solution with the cathode- or anode-specific additives such as Li-intercalatable metal oxides or Liintercalable ones Carbon (carbon black, graphite, etc.) added and dispersed. This dispersion is then applied to current collectors using a coating method known in the art.

A variant (1a) of that described above Coating technology consists in the use of aqueous Polymer dispersions instead of polymer solutions with organic solvents.

The coatings obtained according to 1 or 1a are processed into rectangular or winding cells after drying (wrapped), with a so-called separator with porous structures, e.g. from Cellgard or similar, is used. A system manufactured in this way is encapsulated and before closing with saline solution (Electrolyte, i.e. conductive salt dissolved in aprotic solvents), e.g. by applying a vacuum.

The Bellcore process (1b) is one Another variant of the coating technology, here the anode or cathode mass with a component (e.g. dibutyl phthalate DBP) incorporated before the merging of anode / cathode / separator is extracted in the so-called Bellcore process (cf.Lit 2) to ensure sufficient porosity i.e. Absorption capacity for the conductive salt solution (electrolyte) to accomplish.

The U.S. patent US-A-5,296,318 describes a rechargeable lithium intercalation battery with hybrid polymer electrolyte. An essential element of this patent are polymeric electrolytes, which are formed as self-supporting films and consist of a copolymer of vinylidene fluoride and hexafluoropropylene in a weight ratio, in that hexafluoropropylene copolymer does not crystallize or gel, so that good film strength and ionic conductivity are achieved. This patent also describes only solvent-based processes for forming the laminate structure.

The US-A-5,456,000 describes the manufacture of a rechargeable lithium ion battery cell. The electrode and separator layers are built up from self-supporting film layers. Its essential element is its polymer binder content from a polyvinylidene fluoride copolymer matrix and a compatible organic plasticizer, which is later removed. This gives a homogeneous composition in the form of a flexible, self-supporting film. Such polymer materials in the film layers provide homogeneous compositions without the formation of salt and polymer crystallites at or below room temperature. Furthermore, the membrane shows no leakage of the solvent. The assembled battery cell is in the "inactive" state, ie without electrolyte salt in the binder matrix. For activation, the laminate structure is impregnated in an electrolyte salt solution, preferably after the plasticizer has been largely extracted. The crucial copolymer for the polymer binder comprises vinylidene fluoride and hexafluoropropylene as co-monomers in defined weight ratios. Although the extrusion is briefly mentioned as a process variant for the lamination of electrode and electrolyte elements, the entire remaining description only carries out a coating of liquid mixtures on carrier substrates.

The US-A-5,631,103 builds on the US patent 5,456,000 discussed above and particularly takes into account the combined improvement in mechanical integrity as well as the improvement in ionic conductivity. The most important element of this patent is the film-like electrolyte material system 26. It comprises an active electrolyte species (conductive salt) and a multi-phase polymer carrier structure consisting of a gel polymer and filler material.

A fundamentally different process (2) is extrusion. For example, U.S. Patent No. 4,818,643 (corresponds to EP 0 145 498 B1 and DE 34 85 832 T. ) a process for producing a polymer gel electrolyte and a cathode without the use of a carrier solvent, both components being extruded through a die in film form.

The patent DE 100 20 031 discloses a process for the production of lithium polymer batteries, in which anode composition, separator (polymer gel electrolyte) and cathode composition, which are each free of carrier solvent, are extruded in extruders connected in parallel and then combined as a unit which is laminated with collector foils.

According to this procedure, a carrier solvent-free Manufacture of lithium polymer batteries can be achieved that the two electrode masses and polymer gel electrolyte by mixing the respective Components are made separately, with the polymer gel electrolyte contains a polymer mixture, that of polyvinylidene fluoride-co-hexafluoropropylene (PVdF-HFP) and consists of polymethyl methacrylate, the three mass flows for the anode, the polymer gel electrolyte and cathode then largely merged and the anode, the polymer gel electrolyte and the cathode are simultaneously laminated to the collector foils. The three product streams leave the discharge nozzle of the extruder not as discrete, separate and independent product flows, but as a mixture of anode mass with polymer gel and cathode mass. The means such a mixture of components is a battery system not working, Moreover the masses are unable to measure the amounts of saline solution tie. There is also a risk that unbound solvent, that sweats during processing and when operated on batteries Collector foil lamination infiltrates to increased internal resistance the battery leads the detachment of the electrodes leads to a steady, irreversible failure mechanism leads. Furthermore, temperatures between 95 and 165 ° C on, to ensure thermoplastic processing of the masses. At such temperatures, however, the masses are melted and form layers with considerable surface roughness after lamination. The disadvantages of such surface roughness are in H.G. Elias, macromolecules, Volume II, pages 388-399 [1992], Hüthig and Wepf Verlag, Basel, New York.

The methods described so far all have disadvantages, albeit different:
In the coating processes (1-1a) the organic solvent or water (introduced by the polymer solution or dispersion) must be removed in all cases.

Remaining solvent leads to "fading", i.e. less Battery efficiency and poor cycle stability. The organic solvent must for cost reasons and be removed for environmental protection, resulting in high drying temperatures or in the continuous process longer drying times with lower ones Drying temperatures and vacuum means. The same applies to the separation of water. Furthermore does this to quality deficits in the manufactured product, such as inhomogeneities, cracking in the narrow Winding, reduced liability on the current collectors, damage to the Current collectors, infiltration of the film by the electrolyte. When filling there is insufficient wetting of the anode with the electrolyte or cathode mass.

In process 1b, the porosity is to be absorbed of the electrolyte, but all others mentioned in 1 - 1a apply Disadvantages for 1b.

The following disadvantages arise in (2) the extruder process: The process disclosed in US Pat. No. 4,818,643 uses polyethylene oxide (PEO), which, however, has no long-term stability when operated on batteries, ie cycle stability <100. The other extruder process ( DE 10020031 ) works, cf. Examples, with electrolytes based on EC / γ-BL (ie ethylene carbonate, γ-butyrolactone) with LiClO ₄ as the conductive salt, whereby this system also shows low cycle stability (<100) because the γ-BL reacts under the operating conditions of the battery and supplies disruptive by-products. In addition, the claimed polymer PMM (polymethyl (meth) acrylate) is also not stable and leads to troublesome side reactions. The recipes for anode, cathode and separator (polymer gel electrolyte) mentioned in the examples and that in example (1) of DE 10020031 The cited methods do not lead to a functional battery with the disclosed data.

The object of the invention is thus therein, an improved process for the manufacture of lithium polymer batteries to provide, which avoids the disadvantages described above, Ensure in particular lithium polymer batteries with improved cycle stability can.

This task is due to the characteristics of the independent Claim 1 solved. Preferred embodiments are in the dependent claims 2 to 22 defined.

1 shows schematically the preferred embodiment of the method according to the invention, in which the coated arresters are brought together synchronously with the separator material. Alternatively, the arrester can also be charged with the pasty electrode masses using pasting machines and then combined with the separator as a separating layer.

2 shows a schematic view of the composite system according to the invention consisting of conductor anode A and conductor cathode K, electrode masses (anode mass AM and cathode mass KM) and separator.

The present invention circumvents the disadvantages of the prior art methods by a complete new manufacturing principle.

Discharge foils are made with pasty electrode masses acted upon and then assembled with separator material so that the electrode mass loaded electrode side with the separator material is contacted. Anode, cathode and separator are brought together, see above that a composite arises with the separator as an intermediate layer for anode / cathode serves.

The composite obtained can then preferably processed into multiple layers and into rectangular or winding cells are manufactured. After encapsulation and poling, there is a lithium polymer battery before, after shaping with a tension of, for example approx. 4 volts and cycle times> 300 is ready for operation.

The following are the individual Components of the manufactured according to the invention Lithium polymer batteries described using preferred embodiments.

Specifically, arrester A, for example Cu foil (mesh) for the anode or arrester K, for example Al foil (preferably for the cathode), is charged with the anode mass AM or the cathode mass KM (separately) or in parallel and synchronously then laminated with the separator S as an intermediate layer (L). This is in 1 shown. The result is a composite system consisting of the arresters with the electrode masses and the separator as an intermediate layer.

As an arrester are, for example Foils, nets or fabrics or nonwovens made of metals, but also foils made of electrically conductive Polymers such as polypyrrole, polythiophene, polyphenylene, polyaniline, but also nonwoven made of carbon fibers or carbon foils. Cu is preferred for the anode and Al for the cathode.

The arresters can be in thicknesses from 0.1 to 30 µm, preferably from 0.5 to 25 µm, more preferably 2 - 20 µm; in particular 3 - 9 μm used become.

To avoid corrosion and better Contact to the anode or To reach cathode masses, the metallic arresters are preferred the cathode conductor is primed before applying the electrode mass (i.e. provided with an electrically conductive adhesive layer).

• a) Li-interkalationsfähige Materialien, vorzugsweise Kohlenstoff (synth. oder natürlich), Graphit, MCMB^®, Ruß in Form von Pulver oder Fasern, oder deren Mischung. Die Menge beträgt vorzugsweise 50 – 75 Gew.-% der gesamten Anodenmasse.
• b) Elektrolyt aus Lithiumsalz und aprotischem lösungsmittel. Das Lithiumsalz kann z.B. aus LiClO₄, LiPF₆, Lithiumorganoboraten bzw. Triflaten, Lithiumfluorsulfo-Derivaten, sowie solchen die im vorstehenden Dokument (1) beschrieben sind oder deren Mischung ausgewählt sein. Die Leitsalze liegen vorzugsweise gelöst vor, weiter bevorzugt 1 – 1,5 Molar. Das aprotische Lösungsmittel kann aus z.B. Propylencarbonat, Ethylencarbonat, Diethylcarbonat, Dimethylcarbonat, Perfluoralkylether, vorzugsweise alkylierten Ethylen- bzw. Propylenglykolen oder solchen, die im vorstehenden Dokument (1), Kapitel 7.2 beschrieben sind, ausgewählt sein. Ein bevorzugtes aprotisches Lösungsmittel ist ein Gemisch aus verschiedenen Alkylcarbonaten, insbesondere bevorzugt Ethylen-, Diethyl-, Dimethylcarbonat in Mischungsverhältnissen von 1:1:1 bis 4:2:1. Die Menge Lithiumsalz + Lösungsmittel beträgt vorzugsweise 25 – 40 Gew.-% bezogen auf die Gesamtanodenmasse.
• c) Zusätze, wie z.B. Verdicker auf anorganischer Basis, vorzugsweise MgO, Al₂O₃,TiO₂, Borat, weiter bevorzugt MgO, Al₂O₃, oder auf organischer Basis wie Polybutadienöle, Polyvinylpyrrolidon oder Polyalkylenoxide – Copolymere von Ethylenoxid, mit Propen oder Isobutenoxid mit verkappten Endgruppen können in Mengen von 0 bis 10 Gew.-%, vorzugsweise 0,1 bis 8 Gew.-%, insbesondere bevorzugt bei 7,5 Gew.-% vorliegen.

The electrode masses according to the invention can be composed as follows: The electrode mass for the anode A can comprise:

• a) Li-intercalation materials, preferably carbon (synthetic or natural), graphite, MCMB ^® , carbon black in the form of powder or fibers, or a mixture thereof. The amount is preferably 50-75% by weight of the total anode mass.
• b) Electrolyte from lithium salt and aprotic solvent. The lithium salt can be selected, for example, from LiClO ₄ , LiPF ₆ , lithium organoborates or triflates, lithium fluorosulfo derivatives, and those described in document (1) above or a mixture thereof. The conductive salts are preferably in solution, more preferably 1 to 1.5 molar. The aprotic solvent can be selected from, for example, propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, perfluoroalkyl ether, preferably alkylated ethylene or propylene glycols or those described in the above document (1), chapter 7.2. A preferred aprotic solvent is a mixture of various alkyl carbonates, particularly preferably ethylene, diethyl, dimethyl carbonate in mixing ratios of 1: 1: 1 to 4: 2: 1. The amount of lithium salt + solvent is preferably 25-40% by weight based on the total anode mass.
• c) additives, such as, for example, thickeners on an inorganic basis, preferably MgO, Al ₂ O ₃ , TiO ₂ , borate, more preferably MgO, Al ₂ O ₃ , or on an organic basis such as polybutadiene oils, polyvinylpyrrolidone or polyalkylene oxide copolymers of ethylene oxide with propene or isobutene oxide with capped end groups can be present in amounts of 0 to 10% by weight, preferably 0.1 to 8% by weight, particularly preferably 7.5% by weight.

A particularly preferred composition for the Anode mass is as follows:

MCMB 6/28 ^® 65% by weight Li-oxalatoborate LiOB 8% by weight Dimethoxyethane DME 1% by weight Ethylene carbonate EC 7Gew .-% Diethyl carbonate DEC 7Gew .-% Dimethyl carbonate DMC 2% by weight Polyethylene oxide Polyox WSR 301 ^® 10% by weight (Molecular weight 4,000,000)

Another particularly preferred mixture for the anode mass comprises the following: MCMB 6/28 ^® 65%, electrolyte, consisting of a 1 molar LiPF ₆ solution in ethylene, diethyl, dimethyl carbonate 1: 1: 1 30%, and polybutadiene oil (molecular weight 15 - 20,000, 1,2-vinyl content approx. 22%) 5%. The percentages are percentages by weight based on the total anode mass.

The components can e.g. at temperatures from 20 - 80 ° C, preferably up to 50 ° C to a spreadable Paste to be mixed. The mixing components are preferred in the specified order in a mixer, e.g. B. a Voith mixer and Z. B. mixed 20 minutes after each addition at 40 rpm, preferably in the absence of atmospheric moisture, further preferably under protective gas, e.g. B. argon (purest).

The electrode mass for the cathode K can include:

• a) Li intercalation-capable heavy metal oxides, preferably Oxides of Co, Ni, Mn, Cr, W, Ta, Mo, V; the Li intercalation-capable metal oxides are preferably used in amounts of 50-85% by weight (based on the cathode mass) used.
• b) Furthermore, the electrolyte, type and amount correspond largely to the under A b) (above) (Amount preferably 15-40 Wt .-%).
• c) In addition can the additives described under c) are also used become.

For the cathode is particularly preferred the following cathode mass:

LiCo oxide 75% by weight Li-oxalatoboratLiOB 5% by weight Dimethoxyethane DME 1 wt .-% Ethylene carbonate EC 6Gew .-% Diethyl carbonate DEC 4% by weight Dimethyl carbonate DMC 1% by weight Polyethylene 205 ^® 8% by weight (molar mass 600,000)

Another particularly preferred Electrode mass includes the following: LiCo oxide in an amount of 75% by weight, electrolyte 20% by weight (see anode mass), 5% by weight polybutadiene oil (see.

Anode mass).

The cathode mass is preferred analogous to the anode mass at temperatures of e.g. 20 to 80 ° C, preferably up to 60 ° C prepared.

As separators for the method according to the invention are polymer gel electrolytes with and without conductive salt, tissue or

Nonwovens with porous structure, e.g. Celgard, suitable. The term "gel" is used in H.G. Elias, Macromolecules Volume II, page 735 [1992], Hüthig and Wepf Verlag, Basel, New York.

Suitable separators are described, for example, in document (1), part II, chapter 9 and part III, chapter 8. Polymer-gel electrolytes are preferably used as separators for the process according to the invention. They consist of a polymer or polymer mixtures which contain the aprotic solvent (s), preferably alkyl carbonates, optionally also a conducting salt and / or conducting salt mixtures, as well as mineral additives such as Al ₂ O ₃ , MgO, TiO ₂ , borate.

The polymers can e.g. from polyolefins, Polyisobutene, butyl rubber, polybutadiene, anionically produced Block copolymers based on styrene (α-methylstyrene) with butadiene and / or isoprene, and fluoroelastomers, preferably terpolymers based on TFE / PVDF / HFP, as well as polyvinylpyrrolidone, polyvinylpyridine, or their mixture selected his.

The proportion (Sp) of the polymer (or of the mixture) is preferably 30-70% by weight (based on the total mass of the separator). The proportion of the electrolyte (S _E ) is preferably 30-70% by weight. The proportion of the additives is preferably 0-20% by weight, based in each case on the total mass of the separator.

The manufacture of the separator can by mixing the individual components, preferably at temperatures of 25 ° C up to 160 ° C, e.g. in a Voith mixer.

The thickness of the separator is preferably 5 - 100 μm, further preferably 10-50 μm.

The electrode mass can be in one defined thickness of preferably 5-100 μm, more preferably 10-100 μm, in particular 20 - 60 μm on the Arrester can be applied.

The anode mass AM, which is present as a paste, is preferably at temperatures of 20-65 ° C, z.8. applied to the trap A from a slot die and preferably drawn, for example using a doctor blade device, to a defined thickness of 55-60 μm. In the next step, the arrester A coated with AM is brought together with the separator; either synchronously with the coated arrester K (corresponding to 1 ) or in separate, non-synchronous work steps. The cathode mass KM can be applied analogously to the arrester.

It is important that each with of the electrode mass coated conductor side with the separator is occupied.

As in 1 shown, the current collectors are preferably coated continuously with anode mass or cathode mass, for example with pasting devices and then combined in a laminator together with the separator to form a firm bond, optionally at elevated temperatures up to 100 ° C. Alternatively, the masses can also be discharged by means of extrusion, provided that a suitable, moderate temperature control below the melting temperature of the masses processed is ensured.

In a variant of the method furthermore, the current collectors are applied synchronously.

The network according to 2 of anode (A), anode mass (AM), separator (S), cathode mass (KM), cathode (K) and arrester (current collector) can be rectangular or round cells after lamination, with subsequent encapsulation and contacting (ie combining the anode or . Cathode to positive or negative pole of the batteries) are continuously processed.

The overall process can be continuous take place, with the anode mass or cathode mass applied Arresters are preferably merged synchronously with the separator. The belt speeds are preferably 0.1-10 m / min, if necessary, also with higher Speeds are worked.

Processing is preferably done at room temperature.

A major advantage of the network system corresponding

2 consists in the fact that it is in the form of a film that can be shaped in a variety of ways. Therefore, battery shapes can be created that do not correspond to the classic battery cell shapes, but are adapted to the intended use and / or are integrated in the working device.

• – Herstellen der Elektrodenmassen bei Raumtemperatur
• – glatte Strukturen ohne Oberflächenrauhigkeiten
• – Wegfall von Trocknungszeiten und konventionellen Beschichtungseinrichtungen
• – Keine Unkosten durch Lösungsmittel
• – Kein Recyclen erforderlich
• – Kontinuierliche Herstellung betriebsbereiter Batterien
• – kostengünstige einfache Fertigung

und in seiner umweltschonenden Konzeption.The overall advantages of this method according to the invention are its economy:

• - Manufacture of the electrode masses at room temperature
• - smooth structures without surface roughness
• - Eliminate drying times and conventional coating equipment
• - No expense from solvents
• - No recycling required
• - Continuous production of operational batteries
• - Cost-effective, simple manufacture

and in its environmentally friendly conception.

In the examples below further details of the method according to the invention explained. (parts are parts by weight)

Examples

Application and preparation of the anode mass: The anode mass is prepared in a mixer (e.g. Voith) at room temperature under argon (pure) as a protective gas. MCMB 6/28 ^® 65%, electrolyte, consisting of a 1 molar LiPF ₆ solution in ethylene, diethyl, dimethyl carbonate 1: 1: 1 30%, and polybutadiene oil (molecular weight 15 - 20,000, 1.2 Vinyl content approx. 22%) 5%. The% figures are percentages by weight based on the total anode mass.

The components are mixed into a spreadable paste, which is then added accordingly 1 is applied to the continuously passing separator film with a thickness of 20 μm by means of a slot die at room temperature.

Application and preparation of the cathode mass: Corresponding to the preparation mentioned above, LiCo oxide is pasted in an amount of 75% by weight, with electrolyte 20% by weight (see above) (1 molar LiPF ₆ solution in ethylene carbonate, diethyl carbonate, dimethyl carbonate) , with 5 wt .-% polybutadiene oil (cf.

above) and then corresponds to 1 applied to the opposite side of the separator film (coated on one side with anode material), thickness 25 μm.

Apply the electrode masses the arrester anode mass AM on the arrester A (Cu foil) The anode mass according to the invention consists:

MCMB 6/28 ^® 65% by weight Li-oxalatoborate LiOB 8% by weight Dimethoxyethane DME 1% by weight Ethylene carbonate EC 7% by weight Diethyl carbonate DEC 7% by weight Dimethyl carbonate DMC 2% by weight Polyethylene oxide Polyox WSR 301 10% by weight (molecular weight 4,000,000)

It is compounded at temperatures of 20 - 50 ° C into a spreadable paste, in which the specified sequence, the mixing components are added to the Voith mixer and 20 minutes after each addition at 40 rpm. be mixed.

The anode mass AM, which is in the form of a paste, is applied at a temperature of 20-65 ° C. by means of a pasting machine from a slot die onto the conductor A and drawn to a thickness of 55-60 μm using a doctor device. In the next step, the arrester A coated with AM is brought together with the separator; either synchronously with the coated arrester K (corresponding to 1 ) or in separate, non-synchronous work steps.

KM cathode mass on the arrester K (primed Al foil).

The cathode mass according to the invention consists of:

LiCo oxide 75% by weight Lioxalatoborate LiOB 5% by weight Dimethoxyethane DME 1 wt .-% Ethylene carbonate EC 6% by weight Diethyl carbonate DEC 4% by weight Dimethyl carbonate DMC 1% by weight Polyethylene 205 ^® polyethylene oxide 8% by weight (molar mass 600,000)

It becomes one at temperatures of 20 - 60 ° C spreadable Compound (see anode mass, above) and then compounded using a slot die (with a squeegee) applied in a defined thickness of 50 - 55 μm and then likewise combined with the separator film.

Manufacture separator:
15% by weight of Kynar 2801 ^® , 15% by weight of Dyneon THV 120 ^® , 5% by weight of Styroflex ^® and 10% by weight of MgO are mixed in a mixer, e.g.

Voith, mixed at temperatures from 25 ° C to 160 ° C, the mixture is stirred intensively and up to 150 ° C heated up and then discharged and granulated.

The mixture described above is then fed to a Collin extruder and then 55% by weight of a 1 molar LiPF ₆ solution in ethylene carbonate / diethyl carbonate (1: 1) are added via a metering pump (continuously) and at an extruder temperature of 105 ° C. mixed and discharged at an outlet temperature of 90 ° C at the slot die with a width of 150 mm and a thickness of 30 microns. In the processes carried out in batches (with insulating paper as an intermediate layer), the separator film obtained is wound up in the continuous processes according to the invention directly for further processing, ie coating with anode or cathode materials.

Preparation of the separator: S without conductive salt If the procedure described above is followed, but without the addition of conductive salt (LiPF ₆ ), only the aprotic solvents (ethylene carbonate / diethyl carbonate 1: 1) are incorporated into the polymer mixture + MgO via the metering pump in the extruder. The amount of aprotic solvents is 55% by weight (based on the total separator mass).

In this case too, a separator film obtained with a width of 150 mm and a thickness of 25 microns.

Fabric or fleece with a porous structure as a separator z. B. Celgard.

Example 1:

Production of an anode mass (pure tarpaulin as protective gas) 54 parts of MCMB 6/28 are intimately mixed with 8 parts of ethylene carbonate, 8 parts of diethyl carbonate and 10 parts of polybutadiene oil (molar mass 10-15000; 1,2-vinyl content 22%) in a Voith mixer at room temperature (45 min) and then 8 parts of dimethyl carbonate and 6 parts of Li-oxalatoborate and 1 part of MgO and mixed again at room temperature for 45 min. Then 5 parts of Ensaco ^® carbon black are added and stirred for about 5 to 10 minutes and the mixture is opened using a slot die a copper foil applied.

Example 2:

Preparation of an anode mass (corresponding to Ex. 1) Instead of 10 parts of polybutadiene oil, 10 parts of a copolymer of ethylene oxide / propylene oxide (1: 1 molar), with CH ₃ -capped OH end groups and a molar mass of 25-30,000 are added.

Example 3:

Preparation of an anode mass (corresponding to Ex. 1) 56 parts of MCMB 6/28 ^{® are} mixed with 10 parts of ethylene, 10 parts of diethyl and 10 parts of propylene carbonate and 4 parts of LiOB and at room temperature for 45 min. stirred, then 10 parts of polybutadiene oil (as above Ex. 1) are added again 45 min. and then stirred for a further 3 parts Ensaco ^® was added, stirred for 10 minutes and coated the pasty mass by means of a slot die onto a Cu foil.

Example 4:

Preparation of a cathode mass (pure argon protective gas) 30 parts of Li-Co-Oxide SS5 ^® are mixed with 9 parts of ethylene, 9 parts of diethyl, 9 parts of dimethyl carbonate and 3 parts of LiOB and stirred at room temperature for 60 minutes, then 25 parts of Li Co-oxide and 10 parts of polybutadiene oil (corresponding to Ex. 1) were added, mixed again (30 minutes) and then 5 parts of Ensaco ^{® were} metered in and mixed in for 10 minutes. The resulting mass is used to coat a primed aluminum foil.

Example 5:

Production of the cathode mass Ex. 4 As described above, but instead of polybutadiene oil Polyalkylene oxide (copolymer ethylene / propylene oxide) described in Example 2 is used. The resulting pasty Mass is used to coat a primed aluminum foil.

Example 6:

Production of a separator film 20 parts of fluoroelastomer Kynar 28 ^® , 10 parts of fluoropolymer THV Dyneon ^® , 2 parts of Li metaborate, 2 parts of Styroflex ^® styrene / butadiene block copolymer, 6 parts of MgO, 5 parts of Ensaco ^® turn 60 at 120 - 130 ° C Minutes in a Voith mixer (under pure argon) to a homogeneous mass, then granulated and metered in a Collin extruder, which is operated at temperatures of 90-95 ° C.

In parallel to the above mass, an electrolyte: LP40 ^® consisting of ethylene, diethyl carbonate 1: 1, LiOB dissolved 1 M (45 parts) is metered into the extruder. After a dwell time of 6-9 minutes, a 150 mm wide and 10 μm thick separator film is discharged through an extruder nozzle with an exit temperature of 90 ° C., which is stacked with release paper for discontinuous use, or is fed directly continuously to the process according to the invention.

Example 7:

Manufacture of a composite system Anode mass with arrester and separator foil The anode mass accordingly Example 1, is by means of a nozzle in a thickness of 20 μm applied to the Cu foil (150 mm wide) and in a synchronous Work step covered with a separator film

Example 8:

Coating with cathode mass + Arresters on the network according to Ex. 7

On the composite system consisting of Cu foil - anode mass and separator foil - the cathode mass according to Ex. 4 is applied to the uncoated side of the separator foil, namely in a thickness of 25 μm and a width of 150 mm, the cathode mass is coated with a Discharge conductor 15.7 mm wide, primed with a layer of Dyneon THV ^® / carbon black mixture 2: 1, thickness 0.1 - 1 μm. This composite system is laminated at a temperature of 90 ° C, with a contact pressure of 3 MPa.

Then this composite is made up consisting of anode with arrester and cathode with arrester and the separator as a layer between the electrodes, enclosed and anodes or Pole arrester polarized to the positive or negative pole of the battery.

Example 9:

The one prepared according to Example 8 The composite system is rolled up into a roll on the end faces (protruding 0.6 or 0.7 mm) electrically contacted and housed.

The winding diameter is 7.5 cm, the galvanostatic charging takes place in stages with a Digatron charger 1 to 3.0 volts, then to 3.6 volts and then to 4.1 volts, each with currents of 0.15 mA / cm ² ,

The discharge is also carried out with currents of 0.15 mA / cm ² . The winding cell has an unloading capa 40 Ah with an active area of 1.45 m ² .

The cycle stability is at> 200, the "fading" (loss) is at not more than 2%.

Claims (27)

Process for the production of Li-polymer batteries by means of a conductor, electrode masses for cathode and anode, as well as a composite system comprising separator, characterized in that conductor foils are acted upon by pasty electrode masses and then joined together with separator material in such a way that the electrode substrate side which is acted upon by the electrode mass is included the separator material is contacted. A method according to claim 1, characterized in that the arresters are made of metal foils, nets or fabrics or foils or nonwovens made of electrically conductive polymers or carbon fibers, preferably made of Cu foils the anode or Al foils for the cathode are. Method according to one of the preceding claims, characterized characterized in that the arrester thicknesses of 0.1 to 30 microns, preferably from 0.5 to 25 μm, more preferably 2 - 20 μm, in particular 3 - 9 μm. Method according to one of the preceding claims, characterized characterized in that the arrester is preferably the cathode arrester before applying the electrode mass with an electrically conductive adhesive layer be provided. Method according to one of the preceding claims, characterized characterized that the pasty electrode masses for the Anode mixtures of natural or synthetically produced intercalable carbons, aprotic liquids and conductive salts. A method according to claim 5, characterized in that the amounts of intercalable carbons in the electrode mass for the Anode 50-75 % By weight of the electrode mass is. Method according to one of claims 1 to 4, characterized in that that the pasty Electrode masses for the cathode intercalable metal oxides, preferably oxides of Co, Ni, Mn, Cr, Mo, W, Ti, aprotic liquids and conductive salts. A method according to claim 7, characterized in that the amount of intercalable metal oxides in the electrode mass for the Cathode 50-85 % By weight of the electrode mass is. Method according to one of claims 5 to 8, characterized in that that the aprotic liquids selected are made of alkyl carbonates, preferably ethylene, propylene, diethyl, or dimethyl carbonate, perfluoroalkyl ether, alkylated ethylene or Propylene glycols or mixtures thereof. A method according to claim 9, characterized in that the amount of aprotic liquids is 10 to 30% of Electrode mass is. Method according to one of claims 5 to 10, characterized in that the conductive salt is selected from LiPF ₆ , LiClO ₉ , Li organoborates, Li trifluoromethylsulfonylimides. A method according to claim 11, characterized in that the amount of lead salts 10-15 % By weight of the electrode mass is. A method according to claim 12, characterized in that the lead salts as a solution or dispersion in the aprotic liquids. Method according to one of the preceding claims, characterized in that the electrode mass further comprises organic-based thickeners, preferably low molecular weight polyvinyl ether and / or polyalkylene oxides, polybutadiene oils, polyvinylpyrrolidone, or inorganic-based thickeners, preferably MgO, C, Al ₂ O ₃ , or mixtures thereof includes. A method according to claim 14, characterized in that the amount of the thickener on an organic or inorganic basis 0 to 10 wt .-%, preferably 0.1 to 8 wt .-%, in particular 7.5 wt .-% of Electrode mass is. Method according to one of the preceding claims, characterized characterized in that the separator material is a prefabricated porous membrane or by coating or Extrusion process is made. A method according to claim 16, characterized in that the separator material is polymers, preferably polyolefins, fluoroelastomers, preferably terpolymers based on TFE / PDV / HFP, anionically produced Block polymers, preferably made of styrene and diene, are further preferred from α-methylstyrene, Butadiene and / or isoprene, or a mixture thereof. A method according to claim 17, characterized in that the amount of polymers 30 to 70 wt .-% of the separator material is. Method according to one of claims 16 to 18, characterized in that that the separator material further comprises thickeners as defined in claim 14, aprotic liquids and / or conductive salts. A method according to claim 19, characterized in that the amount of thickeners is 0.5-20% by weight and / or the amount of aprotic liquids 10 - 50 % By weight, based in each case on the separator material. Method according to one of the preceding claims, characterized characterized that after coating the arrester with the electrode masses the separator is inserted as an intermediate layer and a lamination the bond takes place at temperatures up to 100 ° C and pressures from 0.1 to 20 MPa. Method according to one of the preceding claims, characterized characterized in that the process is carried out continuously. Method according to one of the preceding claims, characterized characterized in that the cathode and anode are produced synchronously. Method according to one of the preceding claims, characterized characterized that the process is carried out at room temperature. Method according to one of the preceding claims, characterized characterized in that the electrode masses in mixing units Temperatures of 20-80 ° C, preferably at room temperature under protective gas, preferably pure argon, mixed become. Method according to one of the preceding claims, characterized characterized in that the application of the pasty electrode masses from wide slot nozzles with Widths according to the drainage film to be coated. Method according to one of the preceding claims, characterized characterized in that the electrode mass in a defined thickness from 5 to 100 μm, preferably 10 to 100 μm, in particular 20 to 60 μm is applied to the arrester.