DE102004053479A1 - Lithium-polymer-system based high duty batteries comprises lithium-intercalable titanate as negative electrode and lithium-intercalable iron phosphate as positive electrode - Google Patents

Abstract

Lithium-polymer-system based high duty batteries (I) comprises lithium-intercalable titanate (A) as negative electrode and lithium-intercalable iron phosphate (A1) as positive electrode. Independent claims are also included for: (1) high speed lithium-polymer-energy storage (having an active cathode mass, an active anode mass and an arrester, where the active electrode masses are mixed and/or mixed intensively with lead salt and/or solvent, and then extruded and separately laminated on the arrester material to electrodes) comprising forming the active electrode masses following the intensive mixing and before extruding with polymer binder to active substance-concentrated; (2) a method for preparing lithium-polymer batteries by means of a arrester, electrode mass for cathode and anode and separator comprising compound system comprising subjecting the arrester foil to extrusion with electrode mass and subsequently joining with separator material, which is in contact with the electrode mass at the electrode substrate side; and (3) lithium polymer high speed energy storage obtained by the method.

Description

The invention relates to a method for producing high-performance lithium polymer batteries with titanates as negative and iron phosphates as positive electrode material. In particular, the invention relates to a method in which conductor sheets are subjected to extruded electrode masses and then combined with separator material to form a trilaminate. Details on the production of lithium polymer batteries are known from the literature and can be taken from the "Handbook of Battery Materials", published by: IO Besenhard, Verlag VCH, Weinheim 1999. (1) Special production methods, such as, for example, the so-called Bellcore method. Process are in "Lithium Ion Batteries", published by: M. Wakihara and O. Yamamoto, Verlag VCH, Weinheim 1998, p 235 u. 10.9 (2).

The use of iron phosphates z. B. LiFePO ₄ as an interesting cathode material is described inter alia in the abstracts of the Battery and Fuel Cell Symposium, Graz Apr. 18-22, 2004, page 127 and in US Pat 2004/0185343 (3). Further information LiFePO ₄ are in the Journal of Power Sources 119-121 (2003), 239-246; 247-251, 252-257, 258-261 and 278-284 (4). The use as a cathode material also as a carbon-coated material is described inter alia in US 2003/0064287 and US 200/20182497 and US 005910382 described. It is interesting that in all cases the LiFePO _{4 is used} as a positive electrode material with Li or Li on mesocarbon microbeads (MCMB) as a negative electrode.

However, this invention relates to Li battery systems in which titanates are used as the negative electrode material as a counter electrode to the iron phosphates as a positive electrode material. The use of titanates z. B. Li ₄ Ti ₅ O ₁₂ as a negative electrode is already described in US Pat. 2002/20102205 and US Pat. 5514490, but corresponds to US Pat. 5460904 with Mn or Co or Nioxiden as a positive counter electrode.

An essential feature of this invention is the simultaneous ie parallel use of titanates as a negative electrode material and iron phosphates as a positive electrode material. Both materials are used as lithium intercalates (intercalation compounds). Important and quality determining here are the shape and size of the components. In the case of the titanates, distorted octahedra are corresponding to the brookite structure with three, corresponding to the rutile structure with two and corresponding to the anatase structure with four common TiO ₆ octahedral edges, but preferably also perovskite structures with O ₆ octahedral gaps , in which Ti ⁺⁴ ions are embedded, are suitable; also spinel types (Electrochem., Soc., 142, 1431 [1995].

From elementary importance is the presence of ordered nano-structures, i.e. amorphous materials are largely unsuitable. At least 60% by weight of the titanates used according to the invention should be nanostructured available. To improve the electrical conductivity the titanates become sooty, natural Graphite and / or synthetic graphite or tin powder coated (co-coated) or mixed. The amount of blending or additive component is 1-10% by weight based on the amount of Li-intercalatable titanates.

The Li-intercalatable iron phosphate is preferably used nanostructured and in amounts of 60-85 wt .-% based on the material of the positive electrode. As with the anode, additions of electrically conductive material based on carbon (carbon black, graphite) or electrically conductive polymers such as polyaniline, polypyrrole, polythiophene are used to reduce contact resistance. The amount of these additives which are used as a coating or as a blend, is 1-10 wt .-%, based on the FePo ₄ mass of the positive electrode.

The Particle size is on average at about 400 nm, where 90 <700 nm. The BET surface area is 10-20 m2 / g (Battery and Fuel Symposium, Graz Ap. 18-22, 2004, p. 127/128).

One The essential aim of this invention is not only the novelty of the system, but also by high order states of the used crystallites, both for the anode and for the cathode and a defined nano-particle structure, 1. to improve the cycle skill but also the battery power to increase significantly.

• 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-Methyl-pyrrolidon (NMP) als Lösungsmittel hergestellt und diese Polymerlösung mit den kathoden- bzw. anodenspezifischen Zusätzen wie Li-interkalierbare Metalloxide bzw. Li-interkalierbare 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) required for the cathode or anode material polymer binder is dissolved. For example, a 5-10% solution of fluoroelastomers, which are present as homopolymers or copolymers, with z. B. N-methyl-pyrrolidone (NMP) prepared as a solvent and this polymer solution with the cathode or anode-specific additives such as Li-intercalatable metal oxides or Li-intercalatable carbons (carbon black, graphite o. Ä.) And dispersed. This dispersion is then applied to current collectors using a coating process known in the art.

A Variant (1a) of the coating technique described above in the use of aqueous Polymer dispersions instead of the polymer solutions with inorganic solvents.

The Coatings obtained according to 1 or 1a are after drying processed into rectangular or wound cells (wound), wherein as a separator, a so-called. Separator with porous structures, eg. From Cellgard o. Ä., is used. A system made in this way is encapsulated and before closing with conductive salt solution (Electrolyte, that is dissolved electrolyte salt in aprotic solvents), z. B. by applying vacuum is filled.

Of the Bellcore process (1b) is another variant of the coating technique, Here was already in the anode or cathode material a component (For example, dibutyl phthalate DBP) incorporated before the merger of Anode / cathode / separator is dissolved in the so-called Bellcore process (see reference 2), sufficient porosity d. H. receptivity for the conducting salt To create (electrolyte).

The U.S. Patent US-A-5,296,318 describes a rechargeable lithium intercalation battery with hybrid polymer electrolyte. Essential element of this patent are polymeric electrolytes, which are formed as self-supporting films and from a copolymer of vinylidene fluoride and hexafluoropropylene in a weight ratio consist of hexafluoropropylene copolymer does not crystallize or gelled, giving good film strength as well as ionic conductivity is achieved. This patent also describes only solvent-bound Process for forming the laminate structure.

The US-A-5,456,000 describes the preparation of a rechargeable Lithium ion battery cell. The electrode and separator layers become off built up self-supporting film layers. Your essential element is their content of polymer binder from a polyvinylidene fluoride copolymer matrix and a compatible organic plasticizer, which will be removed later becomes. So a homogeneous composition in the form of a flexible, self-supporting film received. Such polymer materials in The film layers provide homogeneous compositions without 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 "inactive" state, d. H. without electrolyte salt in the binder matrix. To activate the laminate structure is impregnated in an electrolyte salt solution, preferably after the plasticizer has been extracted to a large extent. The ultimate copolymer for the polymer binder includes vinylidene fluoride and hexafluoropropylene as co-monomers in defined weight ratios. Although the extrusion as a process variant for the lamination of electrode and electrolyte elements is mentioned briefly, leads the entire remaining description only a coating of liquid mixtures on carrier substrates out.

The US-A-5,631,103 is based on US Patent 5,456,000 discussed above up and taken into account in particular the combined improvement of mechanical integrity as well the improvement of ionic conductivity. Most important element This patent is the film-like electrolyte material system 26. It comprises an active electrolyte species (conducting salt) and a multi-phase polymer carrier structure consisting of a gel polymer and filler.

A fundamentally different process (2) is extrusion. For example, US Pat. No. 4,818,643 (corresponding to US Pat. EP 0 145 498 B1 and DE 34 85 832 T ) a process for producing a polymer gel electrolyte and a cathode without using a carrier solvent, wherein both components are extruded through a nozzle in film form.

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

According to this method, a carrier solvent-free production of lithium polymer batteries should be achieved by separately preparing the two electrode masses and polymer gel electrolyte by mixing the respective components, the polymer gel electrolyte corresponding to a polymer mixture consisting of polyvinylidene fluoride-co-hexafluoropropylene (PVdF-HFP) and 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 simultaneously on the collector foil be laminated. The three product streams do not leave the extruder discharge nozzle as discrete, separate and independent product streams, but rather as a mixture of anode mass with polymer gel and cathode mass. This means that such a mixture of components is not functional as a battery system, moreover, the masses are unable to bind the amounts of electrolyte solution. Furthermore, there is a risk that unbound solvent that swells during processing and undercuts collector foil lamination during battery operation results in increased internal resistance of the battery, causes detachment of the electrodes, and results in a steady, irreversible failure mechanism. Furthermore, temperatures between 95 and 165 ° C occur in the extruder 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 roughnesses are described in HG Elias, Makromolekule, Volume II, page 388-399 [1992], Hüthig and Wepf Verlag, Basel, New York.

The methods described so far all have, albeit different disadvantages:
In the coating processes (1-1a), the organic solvent or the water (introduced by the polymer solution or dispersion) must be removed in all cases. Remaining solvent leads to "fading", ie decreasing battery efficiency and lack of cycle stability.The organic solvent must be removed for reasons of cost and environmental protection, which means high drying temperatures or longer drying times at low drying temperatures and vacuum during the continuous process In addition, this leads to quality deficiencies in the manufactured product, such as inhomogeneities, cracking during tight winding, reduced adhesion to the current collectors, damage to the current collectors, infiltration of the film by the electrolyte the anode or cathode ground.

At the Process 1b is the porosity to receive the electrolyte, however, all other apply at 1-1a mentioned Disadvantages also for 1b.

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

Consequently the object of the invention is an improved extrusion process to provide high performance lithium polymer batteries, which avoids the disadvantages described above, in particular Lithium-polymer batteries can provide improved cycle stability.

These The object is solved by the features of independent claim 1. preferred embodiments are in the dependent claims 2 to 22 defined.

The preferred embodiment of the extrusion process according to the invention consists of the arrester coated with the electrode material synchronously with the separator material.

The Conductive foils are exposed to the extruded electrode masses and subsequently assembled with separator material such that with the electrode mass applied electrode substrate side with the separator material will be contacted. Anode, cathode and separator are merged, so that a composite arises in which the separator as an intermediate layer for anode / cathode serves.

Of the The composite obtained can then preferably be processed into multiple layers and are made into rectangular or winding cells. After this Encapsulate and Poland is a lithium polymer battery before shaping with a voltage of, for example, about 4 volts and cycle times> 300 ready for operation is.

in the The following are the individual components of the invention Lithium polymer batteries described by means of preferred embodiments.

in the individual become arrester A, z. B. Cu foil (mesh) for the anode or arrester K, z. B. Al foil (preferably for the cathode) with the anode mass AM or the cathode material KM for acted on (separately) or in parallel synchronously and then with the separator S as an intermediate layer laminated (L). As a result, results a composite system consisting of the arresters with the electrode masses and the separator as an intermediate layer.

When Arresters are, for example, films, nets or fabrics or nonwovens made of metals, but also films of electrically conductive polymers, such as polypyrrole, polythiophene, polyphenylene, polyaniline, but Also fleece made of carbon fibers or carbon films, suitable. Prefers be cu for the anode and Al for the cathode.

The Arresters can in thicknesses of 0.1 to 30 μm, preferably from 0.5 to 25 μm, more preferably 2-20 μm; especially 3-9 mm be used.

Around To avoid corrosion and better contact with the anode or cathode masses To achieve the metallic arrester are preferably the Cathode conductor primed before applying the electrode composition (i.e., provided with an electrically conductive adhesion layer).

The electrode masses according to the invention can be composed as follows:
The electrode composition for the anode A comprises:
Li-titanates, which may be:

• a. Carbon (synth. Or natural), graphite MCMB ^® or Ä. Are coated or blended. The amount of titanates is 65-85% by weight of the anode mass. The amount of coating or blending material is from 0.5 to 10% by weight, based on Li titanate.
• b. Electrolyte of lithium salt and aprotic solvent. The lithium salt may, for. Example, from LiClO ₄ , LiPF ₆ , Lithiumorganoboraten or triflates, lithium fluorosulfonic derivatives, and those described in the above document (1) or be selected their mixture. The conductive salts are preferably dissolved, more preferably 1-1.5 molar. The aprotic solvent can be prepared from z. Example, propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, perfluoroalkyl ethers, preferably alkylated ethylene or propylene glycols or those described in the above document (1), Chapter 7.2 be selected. A preferred aprotic solvent is a mixture of different alkylcarbonates, in particular preferred 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 wt .-% based on the total anode mass.
• c. Additives, such as inorganic-based thickeners, preferably MgO, Al ₂ O ₃ , TiO ₂ , borate, more preferably MgO, Al ₂ O ₃ , or on an organic basis such as polybutadiene, polyvinylpyrrolidone or polyalkylene oxides - copolymers of ethylene oxide, with propene or isobutene with capped end groups can be present in amounts of 0 to 10 wt .-%, preferably 0.1 to 8 wt .-%, particularly preferably 7.5 wt .-%.

A particularly preferred composition for the anode mass is as follows: Li-titanate 70% 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 Dyneon THV 220 ^® 5% by weight

Terpolymer based on of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride

Another particularly preferred mixture for the anode composition comprises the following: Li titanate 65%, electrolyte consisting of a 1 molar LiPF ₆ solution in ethylene, diethyl, dimethyl carbonate 1: 1: 1 30%, and Dyneon THV X 310 ^® (corresponds to the THV 220 ^® only with a melting range of 140 ° C instead of 120 ° C) 5%. The% data are percentages by weight based on the total anode mass.

• a) Li-interkalationsfähiges Eisenphosphat, gegebenenfalls Zusätze 1 bis 10 Gew.-% von Ruß, synth. oder natürl. Graphit oder Sn, vorzugsweise als Pulver in Mengen von 60–80 Gew.-% (bezogen auf die Kathodenmasse) eingesetzt.
• b) Ferner Elektrolyt, Art und Menge entsprechen weitgehend den unter A b) (oben) aufgeführten (Mengen vorzugsweise 15–40 Gew.-%)
• c) Außerdem können noch die bei der Anodenmasse unter c) beschriebenen Zusätze eingesetzt werden.

The components are z. B. at temperatures of 20-60 ° C, preferably mixed to 50 ° C. The mixing components are preferably in the order specified in a mixer, z. B. a Voith mixer, and z. B. 20 min. After each addition mixed at 40 rpm, preferably with the exclusion of atmospheric moisture, more preferably under inert gas, for. B. argon (reinst), is working. The extrusion then takes place in a Collin extruder, the mass being applied directly to the trap. The electrode composition for the cathode K comprises:

• a) Li-intercalating iron phosphate, optionally additives 1 to 10 wt .-% of carbon black, synth. or nat. Graphite or Sn, preferably used as a powder in amounts of 60-80 wt .-% (based on the cathode mass).
• b) Further electrolyte, type and amount largely correspond to those listed under A b) (above) (amounts preferably 15-40% by weight)
• c) In addition, the additives described under c) can also be used.

For the cathode, the following cathode composition is particularly preferred: Li-iron phosphate 75% by weight Li-oxalatoborate LiOB 5% by weight Dimethoxyethane DME 1% by weight Ethylene carbonate EC 6% by weight Diethyl carbonate DEC 4% by weight Dimethyl carbonate DMC 1% by weight Dyneon THV ^220® 8% by weight

A further particularly preferred electrode composition comprises the following: Li iron phosphate in an amount of 75% by weight, electrolyte 20% by weight (See Anode mass), 5 wt .-% Kynar 2801 (copolymer: vinylidene fluoride / hexafluoropropylene 75:25).

The Cathode material is preferably analogous to the anode composition at temperatures from Z. B. 20 to 60 ° C, preferably up to 50 ° C prepared.

When Separators for the inventive method are polymer gel electrolytes with and without conductive salts, tissue or Nonwovens with porous Structure, e.g. As Celgard suitable. The term "gel" is used in H.G. Elias, Macromolecules, Vol II, page 735 [1992], Hüthig and Wepf Verlag, Basel, New York.

suitable Separators are z. In document (1), part II, chapter 9 and part III, chapter 8. For the process according to the invention are preferred polymer gel electrolytes used as separators. They consist of a polymer or polymer mixtures, the aprotic solvent (s), preferably alkyl carbonates, optionally also a conductive salt and / or Conducting salt mixtures, as well as mineral additives, such as Al2O3, MgO, TiO2, borate.

The Polymers can e.g. from polyolefins, polyisobutene, butyl rubber, polybutadiene, anionic block copolymers based on styrene (Α-methylstyrene) with butadiene and / or isoprene, as well as fluoroelastomers, preferably Terpolymers based on TFE / PVDF / HFP, as well as polyvinylpyrrolidone, Polyvinylpyridine, or their mixture may be selected.

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

The Preparation of the separator can be achieved by mixing the individual components, preferably at temperatures of 25 ° C to 160 ° C, z. B, in a Voith mixer, respectively.

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

The Electrode mass can be in a defined thickness of preferably 5-100 mm, more preferably 10-100 microns, in particular 20-60 mm are applied to the arrester.

The Anode mass AM is at temperatures of preferably 50-100 ° C, z. B. from a slot die applied to the arrester A and preferably, for. B. over a Doctor blade, drawn to a defined thickness of 55-60 microns. In the next Step, the AM coated arrester A is merged with the separator; either synchronous with the coated arrester K or in separate, not synchronous work steps. The application of the cathode material KM the arrester can be analogue.

Important is that in each case coated with the electrode ground arrester side is occupied with the separator.

The Current collectors are preferably continuous with anode material or cathode material coated, z. B. with pasting and then in a laminator together with the separator to a solid Composite, optionally at elevated Temperatures up to 100 ° C together. Alternatively, the discharge of the masses can also take place by means of extrusion, provided a suitable, moderate temperature control below the melting temperature of the processed masses is respected.

In A variant of the method may further include the application of the current collectors done synchronously.

Of the Composite according to anode (A), anode mass (AM), separator (S), cathode mass (KM), cathode (K) and arrester (current collector) may become rectangular after lamination or round cells, followed by Encapsulating and contacting (i.e., summarizing the anode or Cathode to positive or negative pole of the batteries) continuously processed become.

Of the Overall process can be continuous, with the anode mass or cathode material acted upon arrester preferably synchronously merged with the separator become. The tape speed can also work at higher speeds become.

The Processing preferably takes place at room temperature.

One An essential advantage of the composite system is that this is present as a film, which are shaped in many ways can. Therefore, you can Battery shapes are created that do not correspond to the classic battery cell shapes, but adapted to the purpose and / or integrated into the implement are.

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

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

• - Preparation of the electrode masses at room temperature
• - Smooth structures without surface roughness
• - Elimination of drying times and conventional coating equipment
• - No expenses due to solvents
• - No recycle required
• - Continuous production of ready-to-use batteries
• - Cost-effective simple production

and in its environmentally friendly conception.

In The following examples give further details of the process according to the invention explained. (parts are parts by weight)

Application and preparation the anode mass:

The anode mass is prepared in a mixer (eg Voith) at room temperature under argon (purest) as inert gas. Li-titanate 65%, electrolyte consisting of a 1 molar LiPF ₆ solution in ethylene, propylene carbonate 1: 2: 1 25%, and Dyneon THV 220 5% are used. The% data are percentages by weight based on the total anode mass.

The Components are mixed in the extruder and then continuously on passed Separator foil applied with a thickness of 20 microns by means of a slot die.

Application and preparation the cathode mass:

According to the above preparation, LiFePO ₄ is compounded 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% by weight of polybutadiene oil (see above) and then applied to the opposite side of the (with anode mass coated on one side) Separatorfolie, thickness 25 microns. The LiFePO ₄ used is coated with 2 wt .-% MCMB.

Applying the electrode masses on the arrester anode mass AM on the arrester A (Cu foil)

The anode composition according to the invention consists of: Li-titanate coated with 2 wt .-% MCMB 68% by weight Li-oxalatoborate LiOB 8% by weight Ethylene carbonate EC 7% by weight Propylene carbonate PC 7% by weight Dyneon THV ^220® 10% by weight

she is compounded at temperatures of 20-50 ° C, wherein in the order given the mixing components in the Given Voith mixer are mixed and each 20 min after each addition at 40 U / min become.

The anode material AM is applied at temperatures of 85-90 ° C by means of a Collin extruder from a slot die on the arrester A and applied with a thickness of 55-60 microns. In the next step, the AM coated arrester A is merged with the separator; either synchronously with the coated arrester K (acc. 1 ) or in separate, non-synchronous work steps.

Cathode mass KM on the Arrester K (primed Al foil).

The cathode composition according to the invention consists of: Li-iron phosphate 75% by weight Lioxalatoborate LiOB 5% by weight Dimethoxyethane DME 1% by weight Ethylene carbonate EC 6% by weight Propylene carbonate PC 5% by weight Dyneon THV ^220® 8% by weight (molecular weight 600,000)

she is at temperatures of 20-60 ° C in the extruder compounded and then by means of a slot die at 80 ° C in a defined thickness of 50-55 microns applied and then also combined with the separator film.

Production separator:

15 wt .-% Kynar ^® 2801, 15 wt .-% Dyneon THV ^® 120, 5 wt .-% Styroflex ^® and 10 wt .-% MgO in a mixing device, such. B. Voith, mixed at temperatures of 25 ° C to 160 ° C, the mixture is stirred vigorously and heated to 150 ° C and then discharged and granulated.

The mixture described above is then fed to a Collin extruder and then added via a metering pump (continuously) with 55 wt .-% of a 1 molar LiPF ₆ solution in ethylene carbonate / diethyl carbonate (1: 1) 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. The resulting separator film is wound in the batch processes (wound with insulating paper as an intermediate layer) in the continuous processes according to the invention directly to the further processing ie coating with anode or cathode materials supplied.

Preparation of the separator: S without conductive salt

If the procedure is as described above, but without Leitsalzzusatz (LiPF ₆ ), then only the aprotic solvent (ethylene carbonate / diethyl carbonate 1: 1) are incorporated via the metering pump in the extruder in the polymer mixture + MgO. The amount of aprotic solvent is 55 wt .-% (based on the total separator mass). Also in this case, a separator film having a width of 150 mm and a thickness of 25 μm is obtained.

Also Tissues or fleeces with porous Structure are suitable as separators. (eg Celgard)

example 1

Preparation of an anode material (pure argon as protective gas) 64 parts of Li-titanate are intimately mixed with 8 parts of ethylene carbonate, 8 parts of propylene carbonate and 10 parts of Dyneon THV ^220® in a Voith mixer at room temperature (45 min.) And then 6 parts of Li-oxalatoborate and 1 part MgO and again mixed at room temperature for 45 min, then 3 parts of carbon black Ensaco ^® added about 5-10 stirred and the mass by means of a Collin extruder through a slot die at 85 ° C on a Cu foil (Gould Film 10 microns) applied (thickness of the coating about 30-35 microns).

Example 2:

Production of an anode material (corresponding to example 1)

Instead of 10 parts of Dyneon THV ^220® , 10 parts of a copolymer HFP / PVDF (1: 1) Kynar 2801 are added.

Example 3:

Production of an anode material (corresponding to example 1)

There are added 72 parts of Li-titanate with 10 parts of ethylene, and 7 parts of propylene carbonate and 3 parts of LiOB and at room temperature for 45 min. stirred, then 15 parts of Dyneon THV X 330 ^® (as in Example 1 above) added again 45 min. stirred and then added 3 parts of Ensaco ^® , stirred for 10 minutes and the mass by means of an extruder at 110-115 ° C by a slot die on a Cu film. The thickness of the coating is 35-40μm.

Example 4:

Preparation of a cathode material (argon reinst-protective gas) 70 parts of Li-iron phosphate are mixed with 10 parts of ethylene, 5 parts of propylene carbonate and 3 parts of LiOB and stirred at room temperature for 60 minutes, then 10 parts of Dyneon THV 220 ^® (according to Ex ) was added, again mixed (30 min.), and then 5 parts Ensaco ^® metered and 10 min. mixed. The resulting mass is applied by extruder coating on a primed Al foil. The thickness of the coating is 30-40 μm.

Example 5:

Preparation of the cathode composition according to example 4

As described above, but the terpolymer described in Example 3 is Dyneon THV X 330 used. The resulting mass is used for extruder coating a primed Al foil.

Example 6:

Preparing a separator, 20 parts fluoroelastomer Kynar 2801 ^®, 10 parts Dyneon THV fluoroterpolymer 220 ^®, 2 parts of lithium metaborate, 2 parts Styroflex ^® styrene / butadiene block copolymer, 6 parts of MgO, 5 parts Ensaco ^® are at 120-130 ° C Processed in a Voithmischer (under pure argon) for 60 minutes to a homogeneous mass, then granulated and dosed in a Collin extruder, which is operated at temperatures of 90-95 ° C.

Parallel to the above composition is an Electrolyte: LP40 ^® consisting of ethylene, - diethyl 1: 1, LiOB dissolved 1 M (45 parts) metered into the extruder. After a residence time of 6-9 min., A 150 mm wide and 10 microns thick Separatorfolie is discharged through an extruder die with an outlet temperature of 75-80 ° C, which is stacked with release paper for discontinuous use, or fed directly to the process according to the invention becomes.

Example 7:

Produce a composite system of anode mass with arrester and separator foil. The anode mass according to Ex. 1, By means of a nozzle in a Thickness of 20 microns applied to the Cu foil (150 mm width) and in a synchronous Working step covered with a separator film.

Example 8:

Coating with cathode material + Arrester on the composite according to example 7

On the composite system consisting of Cu foil - anode mass and Separatorfolie - is applied to the uncoated side of the separator, the cathode composition according to Ex. Ex 4 and in a thickness of 25 microns and a width also of 150 mm, the cathode material is mixed with a arrester 15, 7 mm wide aluminum foil primed with a layer Dyneon THV ^® 220 / Rußgemisch 2: 1, thickness of 0.1-1 microns. This composite system is laminated at a temperature of 90 ° C, with a contact pressure of 3 Mpa.

Subsequently, will this composite consisting of anode with arrester and cathode with Arrester and the separator as a layer between the electrodes, housed and anode or cathode arrester to the plus or minus pole the battery is polarized.

Example 9:

The Composite system produced according to Example 8 becomes a coil rolled up at the winding end faces (Protruding 0.6 or 0.7 mm) electrically contacted and housed.

The winding diameter is 7.5 cm, the galvanostatic charge is carried out stepwise 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 also takes place with currents of 0.15 mA / cm ² . The winding cell has a discharge capacity of 40 Ah with an active area of 1.45 m ² .

The cycle stability is> 300, which is "fading" at not more than 1.5%.

Claims (57)

High-performance battery based on Li-polymer systems, characterized in that Li-intercalatable titanates are used as negative electrode and Li-intercalated iron phosphates as positive electrode. High performance lithium polymer energy storage, the has an active cathode material, an anode active composition and an arrester wherein the active electrode masses with conductive salt and / or solvent ground and / or mixed thoroughly, and then extruded and separately laminated to the drainage material to electrodes, characterized in that the active electrode masses in the connection on intensive mixing and before extrusion with polymer binder to drug-concentrated polymers are formed. High-performance batteries according to Claim 1, characterized that the active electrode mass further in the mixing step, a conductive salt additive is added. Heavy duty batteries after one of the previous ones Claims, characterized in that the electrodes further after extrusion and lamination with separator as intermediate layer in sandwich layer together become. High-performance battery according to one of the preceding claims, characterized in that the active electrode masses are degassed at temperatures between -20 and 200 ° C, preferably at 20 to 150 ° C, in particular room temperature to 100 ° C, preferably at pressures between 10 ^-1 and 10 ^-9 Torr. Heavy duty batteries after one of the previous ones Claims, characterized in that the work under protective gas preferably Argon performed become. High-performance batteries according to Claim 1, characterized that the active electrode materials are nanostructured or amorphous available. High-performance batteries according to claim 1 and 7, characterized characterized in that the particle size of the electrode materials used between 2 and 700 nm, preferably between 50 and 500 nm. High-performance batteries according to claim 1, 7 and 8, characterized in that the particle size of the electrode materials used shows a close monomodal distribution of the Gauss type. High-power batteries according to claim 1, 7, 8 and 9, characterized in that the BET surface area of the electrode materials used is between 10 and 20 m ² / g. High-power batteries according to claim 1, 7, 8, 9 and 10, characterized in that Li-intercalatable titanates and / or the Li-intercalatable iron phosphates with nat. or synthet. Graphite or carbon black coated or mixed in amounts of from 0.5 to 10% by weight, based on the masses of the respective electrode materials. Method according to claim 11, characterized in that that the coating or blending material for the electrode masses the group consisting of synthetic and / or natural Graphites, preferably those with globular and nanodimensioned Structures, graphenes, polyphenylenes, polyacetylenes, carbon fibers, preferably with porous Structure or as hollow fibers are selected. High-performance batteries according to claim 1, 7-11, characterized in that the Li-intercalatable titanates are preferably distorted octahedron structures and have the spinel or perovskite lattice derived. High-performance batteries according to claim 1, 7-11, characterized in that the Li-intercalatable iron phosphates are preferably O phosphate is isostructured to olivine. High-performance batteries according to claim 9 or 10, characterized in that the electrode masses: Li titanates for the anode, Li-iron phosphates for the cathode, are used. Heavy duty batteries after one of the previous ones Claims, characterized in that the polymer binder consists of the group from polyolefins, polyethylene, polypyrrolidone, polybutenes as well their homologues and copolymers, polyvinyl ethers, polystyrene and its copolymers with butadiene or isoprene, anionic produced Block polymers, SBR rubber, cis-polybutadienes, fluoroelastomers, co-polymers or terpolymers based on vinylidene fluoride, hexafluoropropene, Tetrafluoroethene, perfluoroalkoxy derivatives, polyalkylene oxides with capped end groups, e.g. With methoxy groups, cyclic ethers, including Crown ethers and ethers of strength and selected from sugars and in amounts of 5-10% by weight, is used based on the total electrode mass. Heavy duty batteries after one of the previous ones Claims, characterized in that the respective electrode mass a Conducting salt from the group consisting of lithium compounds such as Li organoborates or ä. in amounts of 0.1 to 3 wt .-% based on the respective electrode mass is used. High-performance batteries according to claim 1-17, characterized characterized in that as aprotic solvent alkylcarbonates such as ethylene, propylene carbonate, or propyl carbonate, vinylene carbonate but also glycol ethers in amounts of 1-20 wt .-% based on the respective electrode mass are used. High-performance batteries according to one of the preceding claims, characterized in that additives such as Al ₂ O ₃ , SiO ₂ , MgO are used in amounts of 0.5 to 5 wt .-% based on the respective electrode masses. Process for the production of Li-polymer batteries by means of a 4 arrester, electrode masses for cathode and anode, as well Separator comprehensive composite system, characterized in that Ableitfolien be subjected to extrusion by electrode masses and subsequently be assembled with separator material such that with the Electrode mass acted upon electrode substrate side with the separator material will be contacted. Method according to claim 1, characterized in that the arresters are made of metal foils, nets or fabrics or films or fleeces of electrically conductive polymers or carbon fibers, preferably made of Cu foils for the anode or Al foils for the cathode, selected are. Method according to one of the preceding claims, characterized in that the arresters have thicknesses of 0.1 to 30 μm, preferably from 0.5 to 25 μm, more preferably 2-20 microns, in particular 3-9 microns have. Method according to one of the preceding claims, characterized in that the arrester is preferably the cathode arrester before applying the electrode composition with an electrically conductive adhesive layer (Primer layer) are provided. Method according to one of the preceding claims, characterized characterized in that the electrode masses for the anode mixtures Li titanates, polymer binders, aprotic liquids and conductive salts include. Method according to one of the preceding claims, characterized in that the electrode masses for the cathode are Li iron phosphates, Polymer binders, aprotic liquids and conducting salts. Method according to one of the preceding claims and Claim 17, characterized in that the Li-organoborate conductive salts as a dispersion or solids are used. A method according to claim 25, characterized in that conductive salts such as LiPF ₆ , Li-Trifluormethylsufonylimiden or Ä. As a solution after completion of the Batterietrilaminates from anode-separator cathode and its housing are filled into a battery cell. Method according to claim 26, characterized in that that as a solvent those listed in claim 18 aprotic systems come into question. Method according to one of the preceding claims, characterized characterized in that the application of the electrode masses of slot dies with Widths corresponding to the conductor foil to be coated. Method according to one of the preceding claims, characterized characterized in that the electrode mass in a defined thickness of 5-100 μm, preferably 10 to 100 μm, in particular 20 to 60 microns is applied to the arrester. Method according to one of the preceding claims, characterized characterized in that after coating the arrester with the electrode masses the separator is inserted as an intermediate layer and a lamination of the composite at temperatures up to 100 ° C and pressures of 0.1 to 20 MPa. Method according to one of the preceding claims, characterized characterized in that the method is carried out continuously. Method according to one of the preceding claims, characterized in that the separator material is a prefabricated porous membrane is, or produced by coating or extrusion process becomes. Method according to one of the preceding claims, characterized in that the separator material comprises polymers, preferably Polyolefins, fluoroelastomers, preferably terpolymers based of TFE / PDV / HFP, anionically prepared block polymers, preferably of styrene and diene, more preferably of α-methylstyrene, butadiene and / or Isoprene, or their mixture. Method according to one of the preceding claims, characterized in that the amount of Polymers 30 to 70 wt .-% of the separator material. Method according to one of the preceding claims, characterized in that the separator material is further defined in claim 19 defined additives, as well as aprotic liquids and / or conductive salts. Method according to one of the preceding claims, characterized characterized in that the amount of thickener 0.5-20 wt .-% and / or the amount the aprotic liquids 10-50 % By weight, based in each case on the separator material. Method according to one of the preceding claims, characterized characterized in that as a separator foils, nets, fabrics, and / or Nonwovens are used. Method according to one of the preceding claims, characterized characterized in that the separator in the joining of Anode and cathode with the separator with conductive salt, conductive salt additive and solvents is offset. Method according to one of the preceding claims, characterized characterized in that the separator is separate from the active electrode masses is extruded and at this time already conductive salt, Leitsalzadditiv and / or solvents contains and in a subsequent process step between the cathode and Anode is used. Method according to one of the preceding claims, characterized characterized in that the separator is extruded onto substrate film becomes. Method according to one of the preceding claims, characterized characterized in that the substrate film before insertion of the separator detached between the cathode and anode becomes. Method according to one of the preceding claims, characterized characterized in that the preparation of the electrode masses gradually takes place by dividing the respective active components with proportional ones Amounts of conductive salt and / or conductive salt additive and / or solvent, be intimately mixed. Method according to claim 41, characterized that the mixing takes place in a fluidized bed or ultrasonic bath A method according to claim 41 or 42, characterized that in a subsequent process step, the remaining electrode components are incorporated, preferably on calender or extruder. Method according to one of the preceding claims, characterized characterized in that the polymer binder as a conductive compound or drug-concentrated Polymer with additives of conductive Carbon black, carbon fibers, Conducting salts, and / or conductive salt additives is used. Method according to claim 44, characterized in that that the polymer binder is swollen with the solvent is used. Method according to one of the preceding claims, characterized characterized in that the primer layers have a thickness between 0.1-10 microns. Method according to one of the preceding claims, characterized characterized in that the surface of the Discharge before application of the primer fat-free and / or coating-free is done. Method according to one of the preceding claims, characterized characterized in that metal foil, carbon fiber fabric, Nets, nonwovens and / or films of electrically conductive polymers be used. Method according to one of the preceding claims, characterized characterized in that used as Kathodenableiter primed Al foil becomes. Method according to one of the preceding claims, characterized characterized in that the electrode masses with or without arrester laminated with the separator to form a composite. Method according to one of the preceding claims, characterized characterized in that the lamination takes place at temperatures up to 100 ° C. Method according to one of the preceding claims, characterized characterized in that the manufacturing of the high-performance lithium energy storage takes place continuously or discontinuously. Use of the method according to one of claims 1 to 52 for producing a high performance lithium polymer battery by lamination and / or winding the obtained lithium polymer energy storage followed by Einhausen and Poland. Use of the method according to one of claims 1 to 52 for the production of electrophoretic systems, diodes, sensors or energy storage. Lithium polymer high performance energy storage, available after the method according to a the claims 1 to 52.