Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
  • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
  • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
  • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
  • H01M50/406—Moulding; Embossing; Cutting
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/411—Organic material
  • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/431—Inorganic material
  • H01M50/434—Ceramics
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/443—Particulate material
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/463—Separators, membranes or diaphragms characterised by their shape
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
  • H01M50/491—Porosity
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
  • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

• Separating layer for separating anode and cathode in lithium-ion batteries or batteries
• the invention relates to a separating layer (separator) for the separation of anode and cathode in lithium-ion batteries or batteries and a method for their preparation.
• Switch-off function in the event of an overload to maintain the basic function and increase the general reliability, especially for large-volume applications, for example in the automotive sector.
• the basic principle of this known solution is to apply on a polymer film such as polyester, polyacrylonitrile or polyolefins, as a mechanical skeleton, a ceramic slurry, for example of Al 2 O 3 or SiO 2 , whose adhesive strength must be increased by the addition of adhesion promoters such as silanes.
• the ceramic particles then act in the accumulator or battery assembly as a kind of spacer between the anode and cathode and provide as a heat conductor for the removal of thermal energy.
• the object of the invention is to provide a separating layer (separator) which eliminates the existing disadvantages of the current state of the art.
• a separating layer separatator
• the invention consists of a novel separation layer (separator) based on an organic slurry solution for the separation of anode and cathode in Li-ion batteries or batteries.
• binders are dissolved in organic solvents and a so-called pre-slip is produced by suitable mixing processes, for example in dissolvers, jet mixers or mills.
• polymers or polymer-like substances are used with which the separating layer produced therefrom has a high Li-ion conductivity.
• These are, for example, polymers from the class of so-called inorganic-organic hybrid polymers, which are also known under the name Ormocere.
• These polymers or polymer-like substances are used in a proportion of 0.5% by weight to 30% by weight (proportion by weight), preferably in a proportion of 1% by weight to 15% by weight.
• the inorganic portion of these polymers or polymer-type substances essentially provides a skeleton of siloxanes contains, for a high thermal, mechanical and electrochemical stability of the release layer made therefrom.
• this prior art plasticizer with a proportion of up to 5% by weight, preferably with a proportion of less than 3% by weight, and also dispersants with a proportion of up to 5% by weight, preferably to be mixed with a proportion of less than 3 wt .-%.
• the plasticizers provide some flexibility of the later release layer and the dispersants help to evenly distribute the components of the release layer.
• so-called shutdown particles with a proportion of up to 30% by weight, preferably with a proportion of up to 10% by weight, are added to this slurry, which ensure that in the separating layer during subsequent operation in an accumulator or a battery a thermal overload or other disturbance, such as a mechanical defect, the function of the separation layer is locally overridden without jeopardizing the function of the accumulator or the battery in general.
• the size of these particles is on the order of that of the salts or of the ceramic particles, between 0.5 ⁇ m and 5 ⁇ m, preferably between 1 ⁇ m and 3 ⁇ m.
• the shutdown particles can be waxes or low-melting polymers that melt under thermal overload and locally flow around the particles of the film and prevent the conduction of the Li ions or prevent an electronic short circuit.
• ceramic powders for example of Al 2 O 3 , SiO 2 , TiO 2 , ZrO 2 , AlN or mixtures thereof, are then added to this pre-slip with a proportion of up to 90% by weight, preferably with a proportion of less than 80% by weight .-%, added.
• the particle size of these powders is between 0.01 mm and 10 .mu.m, preferably between 0.5 .mu.m and 5 .mu.m, and is characterized by a narrow particle size distribution.
• the ceramic particles in the separating layer take over the formation of the framework, thus ensuring a defined distance between the anode and the cathode and, due to their electrically insulating properties, preventing the electronic short circuit.
• the ceramic particles Due to their thermal properties, in particular a relatively high thermal conductivity, the ceramic particles continue to ensure the uniform distribution of the resulting during operation of a battery or a battery thermal energy and ensure the removal of heat to the outside.
• electrolytic salts in a proportion of 10% by volume (proportion in volume percent) to 50% by volume, preferably in a proportion of 20 Vol .-% to 30 Vol .-%, necessary, which are largely responsible for the high Li-ion conductivity.
• Suitable electrolytic salts are a multiplicity of Li compounds, for example LiPF 6 , LiBF 4 , Li-imide Li [N (SO 2 CFa) 2 ], Li-methide Li [C (SO 2 CF 3 ) 3 ], LiBOB (Lithium bis-oxalatoborate), LiTFSi.
• the particle sizes and the particle size distribution of the salt particles are of a similar order of magnitude as those of the ceramic particles.
• the proportion of salts and any necessary additives should be above the percolation threshold which, depending on the particle shape and the proportion of ion-conductive polymers or polymer-type substances, is typically from 20% by volume to 30% by volume, ie. to form an efficient Li-ion line, the salts in the release layer should be uniformly and contiguously distributed so that a conductive network is formed.
• the slurry After the addition of the ceramic particles and the salt particles to the pre-solution, the slurry must be homogenized, i. All components should be distributed as evenly as possible and this distribution should be maintained in the further process step of film casting or film drawing.
• the homogenization of the slurry can be carried out by standard mixing methods, for example in drum mills with mixing times of a few hours to a few days.
• the proportion of pores should therefore be less than 5% by volume, preferably less than 1% by volume, more preferably less than 0.1% by volume.
• the pores should be closed-pored and not larger than 10 microns and do not form the separating layer by passing pore chains.
• the release layer should have no mechanical defects.
• debinding can also be carried out, this step and the temperature after the composition of the
• Substitution of a substance may occur in a direction that the
• the thermal treatment in the debinding takes place at temperatures between 200 0 C and 500 0 C. A debindering is easily carried out, if no
• the debindering is usually carried out in the stacked composite with the anode and cathode materials, which may also not be destroyed.
• the separating layer should contain as few components as possible.
• the polymers used to form the stacked composite anode-separator cathode are removed-similar to the construction of a piezoceramic multilayer actuator.
• the polymers contained in the anode and cathode are also removed.
• the composite is then supported by the remaining components, including the ceramic components and the inorganic portion of the polymers or polymer-like substances.
• porous polymer support film as starting material can be completely eliminated, since the essential components for the operation, if necessary, until debindering, are held together by the organic binder system.
• the complex process of wetting the carrier film with the electrolytic salt solutions can be omitted since the electrolytic substances are also integrated into the green film according to the invention.
• the porosity of the film is not a decisive factor, since the degree of filling with electrolyte is ensured by the mixture of the starting materials, and not by a subsequent wetting.
• the separation layer according to the invention is designed by its geometry and its composition so that it has a high Li-ion conductivity and thus a low internal resistance, at the same time it is electrically insulating and prevents the short circuit between the cathode and anode.
• FIG. 1 shows a separating layer according to the invention as a ceramic green sheet with a ceramic binder system
• FIG. 2 shows an example of a Li-ion accumulator constructed with the separating layer according to the invention
• FIG. 3 shows an example of a Li-ion accumulator constructed with the separating layer according to the invention, wherein the separating layer has been freed from its organic binder system
• FIG. 4 shows an example of a typical stack construction consisting of anode, cathode, the separating layer according to the invention and a heat-conducting intermediate layer for heat dissipation and FIG
• FIG. 5 shows an example of the structure of a rechargeable battery with an alternating sequence of cathodes and anodes.
• Figure 1 shows a release layer according to the invention in section as a composite of electrolytic salts, ceramic particles and Abschaltpumblen embedded in an organic matrix of Li-ion conducting polymers as a binder.
• the film has a thickness of 30 microns.
• the ceramic particles form a Scaffolding, so that the dense packing ensures good heat distribution and heat dissipation.
• LiBOB electrolytic salt with high ionic conductivity in an amount of about 35% by weight, which is above the percolation threshold, and a particle size of between 1 mm and 3 ⁇ m.
• the polymer matrix consists of Ormoceren with a share of about 37 wt .-% and the shutdown particles, consisting of a low-melting polymer.
• the proportion of shutdown particles is about 20 wt .-% of the total organic content.
• FIG. 2 shows an exemplary embodiment of a basic illustration of a rechargeable battery 1 with the separating layer 2 according to the invention.
• the separation layer 2 is located between a layer 3, which consists essentially of lithium metal oxide and together with the Aluminiumabieiter 4, the cathode K of the accumulator 1, and a layer 5 made of graphite, which together with the Kupferabieiter 6 represents the anode A.
• the Li ions migrate through the separating layer 2 according to the invention from the cathode K to the anode A, during the discharging process in the opposite direction, as the double arrow 7 indicates.
• the layer 3 is composed of a lithium metal oxide, for example, LiNio, 85Co 0 , iAlo, o5 ⁇ 2 , LiNio, 33Co 0 , 33Mno, 33O 2 or LiMn 2 O 4 .
• 12 denotes the lithium ion, 13 the metal ion and 14 the oxygen ion.
• the embodiment of the accumulator 19 in FIG. 3 corresponds to that in FIG. 2 except for the composition of the separating layer 20 according to the invention. Therefore, matching features are designated by the same reference numerals.
• the difference in the composition of the release layer 20 to the release layer 2 of Figure 2 is that it contains no shutdown particles and the organic polymers and the organic binder system have been removed in the course of further Akkumulatorher too. This can be done by suitable thermal processes in the context of a debindering. Since the organic constituents are removed during debindering, it is also possible to use binder systems which have a less optimal Li-ion conductivity, but ensure a good mechanical stability of the separating layer, for a separating layer treated in this way. This has the advantage that the release layer can be handled very well in the course of further shaping in the construction of a rechargeable battery or a battery.
• Figure 4 is a typical stack construction of a rechargeable battery or a battery 1; 19 shown.
• the individual packets 21 consisting of the cathode K, the separating layer 2 or 20 according to the invention and the anode A are separated by separating layers 22 having good thermal conductivity. These may have the same composition and structure as the other separation layers.
• the heat-dissipating separating layers 22 may be connected, for example, to a ceramic housing or to an otherwise good heat-conducting material or network, via which the heat can be dissipated to the environment. However, it must not cause a short circuit
• FIG. 5 shows, for example, the construction of an accumulator 23 with an alternating sequence of cathodes K and anodes A, each separated by a separating layer 20 and in which the separating layer 20 in the present exemplary embodiment has a composition as shown in FIG , By thermal treatment of the release layer, the organic polymers and binders have been removed. With the embodiment of Figure 3 matching features are designated by the same reference numerals. Of course, a composition of the release layer with polymers is possible, as shown and described in Figure 2.
• cathode K consists of the aluminum drain 4, which is coated on both sides with a layer of lithium -Metalloxid 3 is occupied.
• Anode A consists of the Kupferabieiter 6, which is covered on both sides with a layer of graphite.
• the Li ions migrate from the cathode K from the side facing the anode through the separating layer 20 according to the invention to the anode A lying between the cathodes K, during the discharging process from the anode A to both sides in the opposite direction to the respectively adjacent cathode K.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Electrochemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Manufacturing & Machinery (AREA)
• Inorganic Chemistry (AREA)
• Materials Engineering (AREA)
• Composite Materials (AREA)
• Dispersion Chemistry (AREA)
• General Physics & Mathematics (AREA)
• Condensed Matter Physics & Semiconductors (AREA)
• Physics & Mathematics (AREA)
• Ceramic Engineering (AREA)
• Cell Separators (AREA)
• Secondary Cells (AREA)
• Battery Electrode And Active Subsutance (AREA)

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• 2009
  • 2009-10-29 EP EP09749057A patent/EP2342773A1/de not_active Withdrawn
  • 2009-10-29 KR KR1020117012198A patent/KR20120002519A/ko not_active Application Discontinuation
  • 2009-10-29 WO PCT/EP2009/064266 patent/WO2010049478A1/de active Application Filing
  • 2009-10-29 US US13/126,187 patent/US20110217595A1/en not_active Abandoned
  • 2009-10-29 CN CN2009801529819A patent/CN102265426A/zh active Pending
  • 2009-10-29 DE DE102009046134A patent/DE102009046134A1/de not_active Withdrawn

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