Classifications

• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C3/00—Glass compositions
  • C03C3/04—Glass compositions containing silica
  • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C12/00—Powdered glass; Bead compositions
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C3/00—Glass compositions
  • C03C3/04—Glass compositions containing silica
  • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
  • C03C3/07—Glass compositions containing silica with less than 40% silica by weight containing lead
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C3/00—Glass compositions
  • C03C3/04—Glass compositions containing silica
  • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C3/00—Glass compositions
  • C03C3/04—Glass compositions containing silica
  • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
  • C03C3/078—Glass compositions containing silica with 40% to 90% silica, by weight containing an oxide of a divalent metal, e.g. an oxide of zinc
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C3/00—Glass compositions
  • C03C3/04—Glass compositions containing silica
  • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
  • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
  • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
  • C09K15/02—Anti-oxidant compositions; Compositions inhibiting chemical change containing inorganic compounds
• • 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
• • 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
• • 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
  • H01M10/0566—Liquid materials
  • H01M10/0567—Liquid materials characterised by the additives
• • 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
  • H01M50/409—Separators, membranes or diaphragms characterised by the 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
  • H01M50/431—Inorganic material
  • H01M50/434—Ceramics
  • H01M50/437—Glass
• • 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
  • H01M2220/00—Batteries for particular applications
  • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M2300/00—Electrolytes
  • H01M2300/0017—Non-aqueous electrolytes
  • H01M2300/0025—Organic electrolyte
• • 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

• the present invention includes an additive for electrochemical energy storage and an electrochemical energy storage.
• Energy stores or additives which in particular contain glass powder, are known, for example, from the following documents: DE 10 2009 056 756 A1, WO 201 1/124347 A1, WO 2012/045514 A2, WO 2012/045662 A2, DE 10 201 1 1 14876.4, JP 2005-1 1614 A.
• US 2006/0292446 A1 and US Pat. No. 7,655,358 B2 describe a rechargeable lithium battery with a positive electrode which contains, as positive-active material, a lithium-containing transition metal compound and an additive.
• the additive comprises at least elemental Si, B, Ge, Ga, Mg, Ca, Sr, Ba or at least one oxide of these elemental substances.
• the elements or oxides of these elements react with RF unwanted in the battery.
• S1O 2 reacts with HF to form H 2 SiF 6
• the alkaline earth metal oxides (RO) react with HF to form alkaline earth metal fluorides (RF 2 ).
• Future energy storage such as lithium-ion batteries for mobile or stationary applications, require an improvement of energy storage in terms of their safety, cost and weight, the latter with a view to increasing the specific energy or power density.
• the lifetime, in particular of energy storage devices containing lithium ions both during operation (charging or discharging operations) and during the general service life (calendar life) also plays an important role.
• the life-impairing effects are, for example, the increasing formation of a surface layer on the anode (Solid Electrolyte Interphase (SEI)) with the consequence of increasing lithium deficiency and increasing the internal resistance.
• SEI Solid Electrolyte Interphase
• HF Hydrogen fluoride
• the formation of HF depends in particular on the water content in the energy store, wherein the water reacts with fluorine-containing conductive salts. Moisture (water) can get into this during the manufacture of the energy storage in particular. But even during the operating time, due to the smallest leaks, e.g. In the area of the polymer-carrying contact feed-through, moisture creepingly enters the energy store.
• additives e.g. to the liquid electrolyte of an energy storage, e.g. a lithium-ion cell minimized (cryogenic additives, SEI formation enhancers or controllers, flame retardants, wetting agents, anion receptors,
• an energy storage e.g. a lithium-ion cell minimized (cryogenic additives, SEI formation enhancers or controllers, flame retardants, wetting agents, anion receptors,
• Overcharge protection additives water or acid scavengers, additives for smooth lithium deposition, etc.
• Behind the additives are almost exclusively organic, aromatic or metal-organic compounds, which often contain halogens or sulfur. These are therefore often toxic, also expensive and often easily flammable due to lack of temperature resistance.
• Another disadvantage is the lack of flexibility of integration of the previously known additives in existing energy storage. In the form of a liquid It is not possible, if necessary, to develop the effect locally, in the form of a non-coatable solid which is immediately and completely soluble in the electrolyte.
• Cathode material such as LiMn 2 O 4 (LMO) before HF and water.
• LMO LiMn 2 O 4
• NiO or ZnO is added. This can be optionally integrated by coating the electrode particles or the entire electrode or by admixture with the cathode material in the composite.
• LIB cell rechargeable lithium ion battery cell
• Additive does not damage the cell chemistry of a LIB cell by delivering
• an additive for electrochemical energy storage wherein the additive contains at least one silicon and Erddalkalimetallumble compound V1, in contact with a fluorine-containing compound V2 in the energy storage at least one
• Compound V3 forms, wherein the compound V3 is selected from the group of silicon and fluorine-containing, lithium-free compounds V3a, the
• alkali metal and fluorine-containing, lithium-free compounds V3b the silicon-, erdalkalimetall- and fluorine-containing, lithium-free compounds V3c or
• the compound V3 is in particular a non-volatile, non-gaseous compound which binds the fluorine very well (under normal conditions of use of the energy store).
• the compound V1 is preferably a powder, in particular a glass powder, which comprises at least the following composition constituents (in% by weight):
• SiO 2 > 0 to ⁇ 100, preferably> 40 to ⁇ 70,
• M is selected from the group of alkaline earth metal elements.
• the compound V1 is preferably a glass powder, in particular a glass powder, which at least one glass composition constituents
• the compound V1 is preferably a glass powder, the following
• the compound V1 is preferably a glass powder, the following
• the compound V1 is preferably a glass powder, the following
• the compound V3a or the compound V3c preferably contains [SiF 6 ] 2 " groups.
• the compound V3b or the compound V3c preferably contains MSiF 6 , wherein M is at least one alkaline earth metal element, in particular barium.
• the compound V3b or the compound V3c preferably contains MF 2 , where M is at least one alkaline earth metal element, in particular barium.
• the compound V3 is preferably formed on the surface of the compound V1.
• the additive is preferably part of an electrode, an electrolyte or a separator of an energy store.
• the additive preferably contains at least one silicon and
• an electrochemical energy store which contains an additive according to at least one of claims 1 to 13;
• the additive contains at least one silicon and Erddalkalimetallumble compound V1, in contact with a fluorine-containing compound V2 in the energy storage at least one
• Compound V3 forms, wherein the compound V3 is selected from the group of silicon and fluorine-containing, lithium-free compounds V3a, the
• alkali metal and fluorine-containing, lithium-free compounds V3b the silicon-, erdalkalimetall- and fluorine-containing, lithium-free compounds V3c or
• the additive in contact with an electrolyte of the energy store preferably has at least one of the following three properties:
• the electrochemical energy store preferably contains a glass powder which has all three properties.
• the better binding of HF, the better binding of H 2 O or the lower release of H 2 O is preferably qualitatively evident by cyclic voltammetry.
• the HF property or preferably additional H 2 O properties of a glass powder are compared with the corresponding properties of an Al 2 O 3 powder, both powders having a comparable average grain size and the three properties being determined under comparable conditions.
• the better binding of HF and the better binding of H 2 O are probably due to a better chemical bonding of these substances by the appropriate glass powder than by the comparable Al 2 O 3 powder.
• the lower release of H 2 O is presumably due to a better adsorption of H 2 O in the liquid electrolyte by the glass powder than by the comparable Al 2 O 3 powder.
• At least one of the three properties of the additive preferably improves with time, in particular within a period of up to 2 to 5 days after contact of the additive, in particular of the glass powder, with the electrolyte. That, for example, the better binding of HF gradually improves over time from the completion of the energy storage, so it is initially bound little HF and then more over time.
• the electrolyte is preferably a nonaqueous electrolyte, an electrolyte based on carbonic solvents and / or the electrolyte preferably contains at least LiPF 6 as a conducting salt.
• the energy store is preferably a lithium-ion cell.
• the energy store preferably contains an anode, a cathode and a separator. Surprisingly, it has been shown that much better electrochemical energy stores are obtained by these simple measures.
• electrochemical energy storage comprises primary and secondary batteries, rechargeable batteries, lithium-ion cells, Lithium metal cells and capacitors. Rechargeable lithium-ion cells are preferred.
• glass powder in the sense of the invention comprises glass powder and / or glass ceramic powder.
• fluorine-containing compound V2 includes HF.
• HF in the sense of the invention includes HF, fluorine and fluoride ions.
• lithium-free compound in the sense of the invention means that the compound is free of lithium except for unavoidable traces, preferably the lithium-free compound contains no lithium. Ultimately, it's about as impossible to demobilize any lithium of the energy storage in the compound V3.
• the glass powder in contact with the electrolyte forms a sparingly soluble Si-F compound in the electrolyte and thus bonds HF more effectively.
• the formation of the sparingly soluble fluoride is not necessarily but preferably carried out on the surface of the glass powder particles.
• the formation of finest colloids of the poorly soluble fluoride phase in the electrolyte is conceivable.
• the better binding of HF in the electrochemical energy storage can be explained as a conceivable possibility as follows:
• the glass powder is deliberately adjusted in the production process so that the alkaline earth metal ions, preferably barium ions, which are particularly important for the getter effect, are enriched on the surface of the glass particles and, in contact with the electrolyte, change from the surface of the glass particles into the electrolyte and here to a sparingly soluble fluorine-containing compound can react. In these reactions, water is consumed and is thus not available to the system for the formation of additional HF, which also positively affects the life of the energy storage.
• the alkaline earth metal ions preferably barium ions, which are particularly important for the getter effect
• the electrochemical energy store is preferably a rechargeable lithium-ion cell.
• the glass powder is part of a separator of the energy store, in particular a filler and / or a coating of a separator and / or part of an electrode of the energy store, in particular and / or anode, and preferably the glass powder is integrated or integrated in the electrode applied their surface.
• the glass powder is contained in the electrolyte of the energy store, in particular in one
• Solid electrolyte and / or a liquid electrolyte Solid electrolyte and / or a liquid electrolyte.
• a functional, glassy or glass-conducting or ceramic powdery Add additive of a lithium-ion cell describe.
• the ingredient chemically binds harmful fluoride.
• water is chemically bound and it is further prevented the formation of HF. The bonding of HF and water takes place under standstill as well
• the electrochemical energy store particularly preferably contains a glass powder which has the following composition ranges (in% by weight).
• Composition area 1 is a composition of Composition area 1:
• Composition area 2 is a composition of Composition area 2:
• Composition area 5
• refining agents in conventional amounts of up to 2 wt .-% can be added in all composition ranges.
• refining agents can SnO2, AS2O3, Sb2O3, sulfur, CeO2, etc.
• refining agents may possibly be completely dispensed with, provided that the glass is close to the application, i. is produced as a fine powder and the claim to freedom from bubbles is not high.
• Glass powder may be included: Fe, Ni, Cu, Bi.
• Electyls form SiF 6 compounds.
• silicon is basically necessary in the glass, but should be well balanced with other glass components.
• a MO / SiO 2 ratio particularly preferably a BaO / SiO 2 ratio of 0.65 to ⁇ 1.0 to ensure.
• This is preferably combined with not too high SiO 2 contents of ⁇ 75% by weight, particularly preferably ⁇ 50% by weight, most preferably even contents of ⁇ 40% by weight.
• SiF 6 compounds mentioned above which are formed according to the invention, are sparingly soluble alkaline earth hexafluorosilicates. Any formation of corresponding lithium salts, as described, for example, in JP 2005-011614 A, is undesirable in the sense of the application, since in this way lithium is withdrawn from the system, which accordingly can no longer be used for energy storage. In JP 2005-01 1614 A, lithium is deliberately demobilized in case of abnormal cell behavior.
• the present invention also provides a non-toxic, temperature stable inorganic additive (solid state additive) for flexible use in all areas of an energy storage, e.g. a reloadable one
• Lithium ion cell ready to make their use more durable.
• the invention provides functionality for binding
• the added glass powder gives off much less surface water compared to the other materials used in the energy storage.
• the invention also includes:
• Rechargeable lithium-ion cell characterized by a powdery solid glassy or glass ceramic or ceramic additive component which chemically binds fluoride.
• Rechargeable lithium-ion cell characterized by a powdery, solid glassy or glass-ceramic or ceramic additive component which binds water (chemically).
• Rechargeable lithium-ion cell characterized by a powdery, solid glassy or glass-ceramic or ceramic additive component which surface water does not give off to the electrolyte.
• LIB cell wherein the glass powder leads to barium oxide.
• LIB cell wherein the glass powder free fluorine or HF intercepts under Potentiallast and life.
• LIB cell wherein the glass powder-free H 2 O under Potentiallast and
• LIB cell wherein the glass powder traps free fluorine or HF to form electrolyte insoluble barium species.
• LIB cell wherein the glass powder integrated in the region of the separator or is part of a separator. 8. LIB cell wherein the glass powder as a filler or as a
• LIB cell wherein the glass powder is part of a cathode composite (LCO, NMC, LFP, etc.).
• LIB cell wherein the glass powder is part of an anode composite (C, Si, Sn or similar).
• LIB cell wherein the glass powder is part of a liquid electrolyte.
• the glass powder was placed in a battery electrolyte and allowed to stand at 60 ° C for seven days. After separating the electrolyte and drying the material, the BaSiF 6 (eg on the surface of the glass powder) can be detected by XRD (X-ray powder diffractometry), alternatively EDX and SEM in the case of the formation of non-crystalline phase.
• Compositions in which BaSiF 6 was detected Table 1): VB 1 Comparative Example 100% Al 2 O 3
• the electrolyte used is essentially a mixture of one or more nonaqueous, preferably carbonate solvents and at least one fluoride conducting salt.
• LiPF 6 was used as the conductive salt.
• Suitable solvents are, for example:
• PC Propylene carbonate
• EC ethylene carbonate
• BC butylene carbonates
• DMC dimethyl carbonate
• DEC diethyl carbonate
• VVC vinylene carbonate
• EMC methyl ethyl carbonate
• DME 1, 2-dimethoxyethane
• DEE 1, 2-diethoxyethane
• ⁇ -BL ⁇ -butyrolactone
• sulfolane acetonitrile
• NMP N-methyl-2-pyrrolidone
• DMSO Dimethyl sulfoxide
• EA ethyl acetate
• DOL 1,3-dioxolane
• THF tetrahydrofuran
• TEGDME tetra (ethylene glycol) dimethyl ether
• PC PC, EC, ⁇ -BL, DMC, DEC, EMC or DME.
• the solvents can be used alone or as suitable mixtures.
• Exemplary blends are EC / DMC in the ratio 50/50 (wt%) or electrolyte blends with ratio EC to (DMC + EMC) ⁇ 1 LiPF 6 can be used alone or in combination with other conductive salts.
• the latter comprise for example L1BF4, LiAsFe, LiCIO4, LiB (cehs Li CH3 SO3, Li CF3 SO3, Li N (SO 2 CF 3) 2, Li C (SO2 CF3) 3, LiAICU, LiSiF 6, Li [(OCO) 2 ] 2 B, LiDFOB, LiCl, and LiBr.
• non-aqueous solvents is not limited, but should preferably remain in the following range: 0.1 M (mol / dm 3 ) to 5.0 M, preferably 0.5 M to 3.0 M.
• the electrolyte consisting of solvent and conductive salt has the following
• the glass powder AB 17 has the following composition in mol%:
• the inorganic material brings an equal amount of surface water (2000 - 3000 ppm) into the system when integrated into the LIB cell. This is emitted by material b in the smallest amount in the cell, in particular the electrolyte compared to the electrode materials. This can be visualized by cyclic voltammetry (CV):
• the respective material is after drying in the test cell consisting of two Pt electrodes as a counter electrode and working electrode, which is uncoated, introduced.
• Materials a and b are added with a mixture of electrolyte and water to enhance the formation of harmful HF and by means of
• the cathode material LiMn 2 O 4 (LMO) was added to the respective above-mentioned CV measurements in the next step. LMO is destroyed by the reaction with HF, Mn is dissolved out of the crystal compound.
• the evaluation of the CV data (plotting of the peak heights) also shows here that the inorganic filler materials getter in addition to an electrode material HF.
• the supernatant solution was assayed for Mn 2+ by ICP-OES. This shows that in the sample with material b significantly less Mn is leached from the cathode material in comparison to material a and the system without inorganic additive.
• the getter effect of the material b sets in after a certain time (in CV further significant decrease of the RF peak after 5 cycles). This is necessary because during the formation of a LIB cell, small amounts of HF are needed to form the SEI, as well as to passivate the Al current collector of the cathode.
• materials a and b were stored for 7 days in a moistened electrolyte and then the fluoride content was determined by means of ion chromatography. Material b significantly binds HF during service life.
• a separator coated with the additive (glass powder) was coated in
• Cathode Half Cells Li / LP30 / Glass-Polyethylene Separator / LP30 / Cathode Material; 1) Lithium Manganese Oxide (LMO) 2) Lithium Nickel Cobalt Manganese Oxide (NCM)) installed for battery test.
• LMO Lithium Manganese Oxide
• NCM Lithium Nickel Cobalt Manganese Oxide
• Swaglok cells were used for the experiment with a lithium reference. It was cycled according to a CC-CV protocol. At the beginning, 5 forming cycles are carried out at a current for C / 10 (corresponding to a charging or discharging step of 10 h),
• the electrolyte LP30 [EC: DMC (1: 1) +1 mol / L LiPF6] was dry (H 2 O ⁇ 20 ppm).
• the glass powder used had the following composition in mol%:

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