TW201304240A - Composite ionic conducting electrolytes - Google Patents

Abstract

Ionically conducting, redox active additive composite electrolytes are disclosed. The electrolytes include an ionically conductive component and a redox active additive. The ionically conductive component may be an ionically conductive material such as an ionically conductive polymer, ionically conducting glass-ceramic, ionically conductive ceramic, and mixture thereof.Electrical energy storage devices that employ the ionically conducting, redox active additive composite electrolytes also are disclosed.

Description

Composite ion conductive electrolyte

no.

Modern electrochemical energy storage devices, such as lithium ion batteries and electrochemical double layer capacitors (EDLC), comprise an anode and a cathode, the anode and cathode being separated by an electrolyte. The function of the electrolyte is to pass the ionophore between the anode and the cathode, and it is electrochemically stable over the operating voltage range. The electrolyte can also act as an electrical insulator to avoid short circuits between the anode and the cathode. These needs are met in this art by using a porous polymer film immersed in a solution of an ion conductive electrolyte.
In lithium ion batteries, Li ⁺ ₆ and PF ₆ conductive electrolyte solutions of LiPF ₆ in an ethylene carbonate (EC) solvent and/or a dimethyl carbonate (DMC) solvent have been used. This type of Li ⁺ conductive electrolyte provides greater voltage stability to lithium compared to aqueous systems. However, the conductivity of this type of Li ⁺ conductive electrolyte is generally several orders of magnitude lower than that of aqueous systems.
The ion conductive electrolyte can also be formed from a single phase material such as an ion conductive polymer. The limiting factor in the selection of ionically conductive electrolytes for use in energy storage/production devices is electrolyte conductivity. Low electrolyte conductivity increases the internal electrical impedance of the device and reduces spike power output.
In energy storage devices using Li ⁺ electrolytes (e.g., capacitors), the maximum operating voltage at which the device can be charged is limited by decomposition of the electrolyte and/or reaction between the electrolyte and the carbon electrode. Currently, the achievable volumetric energy density of a capacitive energy storage device is about 100 times lower than that of a battery.
There is still a need for improved energy density of energy storage devices, such as capacitive devices.

The disclosed invention relates to an ion conductive redox active additive composite electrolyte, and a device using the same, such as an energy storage device. The electrodes used in these types of devices can function to exchange ion carriers in the electrolyte, and the other electrode used in these types of devices can function as ion blocking or redox activity. The ion conductive redox active additive composite electrolyte can use an ion conductive component and a redox active additive, wherein the ion conductive component is any one or more kinds of ion conductive polymers, ion conductive glass ceramics, and ionic conductivity. Ceramics and their mixtures.
In one concept, the present invention relates to an ion conductive polymer redox active additive composite electrolyte. In the second concept, the present invention relates to an ion conductive glass ceramic redox active additive composite electrolyte. In a third concept, the present invention relates to an ion conductive ceramic redox active additive composite electrolyte. In a fourth concept, the present invention relates to an electrical energy storage/generation device using an ion conductive redox active additive composite electrolyte.
Any one or more of an ion conductive polymer and a redox active additive, an ion conductive glass, a redox active additive, an ion conductive glass ceramic, a redox active additive, an ion conductive ceramic, and a redox active addition The ion conductive composite electrolyte of the substance, the ion conductive colloid and the redox active additive can achieve high voltage operation stability, and can use a large amount of electrolyte to store energy.
The ionically conductive composite electrolyte can be used in a variety of different energy storage/generation devices (eg, capacitor and battery energy storage), electrochemical devices (eg, fuel cells), electrochromic devices, and gas sensors. The ion conductive composite electrolyte can also be used for catalysis, and as a gas separation film.

The following nouns used herein shall be understood to have the following meanings:
CTFE: chlorotrifluoroethylene
HFP: hexafluoropropylene
DMC: dimethyl carbonate
EC: ethyl carbonate
HFP: hexafluoropropylene
LAGP: lithium aluminum bismuth phosphate
LiTf: lithium trifluoromethane
LIBETI: LiNC ₂ F ₅ (SO ₂ ) ₂
LiBOB: Lithium bis(dicarboxylate)
LiTFSI: lithium trifluoromethanesulfonate
MBL: α-methylene-γ-butyrolactone
MEEP: Polymerization (bis(methoxyethoxy)ethoxy)phosphazene
MEK: methyl ethyl ketone
Nafion: tetrafluoroethylene-perfluoro-3,6-diepoxy-4-methyl-7-decenesulfonic acid copolymer
PAEOA: poly(ethenyl-oligo(oxyethylene) acrylate)
PBI: polybenzimidazole
PDE: poly(ethylene glycol) dimethacrylate
PEEK: polydiether ketone
PEDA: polyester diacrylate
PEDOT: poly(3,4-ethylenedioxythiophene)
PEG: poly(ethylene glycol)
PEGMA: poly(ethylene glycol) methyl ether methacrylate
PEO: poly(oxyethylene)
PEOMA: Poly(oxyethylene) methyl ether methacrylate
PES: polyether oxime
PME: poly(ethylene glycol) methacrylate
PPI: poly(propyleneimine)
PPO: poly(propylene oxide)
PS: Poly (碸)
PVA: poly(vinyl alcohol)
PVDF: Polyvinylidene fluoride
SMA: octadecyl methacrylate
TEGDA: tris(ethylene glycol) diacrylate
TFE: tetrafluoroethylene
TrFE: Trifluoroethylene The present invention discloses an ion conductive polymer composite electrolyte, and one or more ion conductive polymers having one or more redox active inclusions, a redox active phase, and Its mixture.
In general, the ion conductive polymer redox active additive composite electrolyte can be obtained by mixing an ion conductive polymer solution with a redox active additive. Alternatively, the non-conductive polymer containing the redox additive may also be treated with a desired metal ion conductive solution to provide polymer ion conductivity to produce an ion conductive polymer redox active additive composite electrolyte. .
Polymers useful in solutions of ionically conductive polymers include, but are not limited to, fluoropolymers and copolymers such as, but not limited to, PVDF, PVDF-HFP, PVDF-TFE, PVDF-CTFE, PVDF-TrFE, and mixtures thereof . Other polymers that can be used include, but are not limited to, oxyethylene, such as PEO, PEOMA, PAEOA, PEG, PEDAO-PEG copolymer, PDE, PME, PEGMA, TEGDA, poly(dimethyloxane), poly(formaldehyde). [oxyethylene]), MEEP, copolymer (eg PEOMA-MBL, PAEOA, PEDA-PEG, PME-SMA, PDE-PME-PEG, PS-PEGMA, PPI, PS-PDVP, polystyrene copolymer, none Synthetic copolymer), polyphosphazene, and mixtures thereof, such as poly(dioxane), polyoxyalkylene, polyphosphazenes such as, but not limited to, poly(dichlorophosphazene), PVA, PPO .
Solvents useful in the ionically conductive polymer solution include, but are not limited to, aprotic solvents such as DMAc, NMP, DMF, and mixtures thereof. When DMF is used, the amount of polymer soluble in DMF may range from about 1% by weight to about 50% by weight, preferably from about 5% by weight to about 40% by weight, more preferably from about 10% by weight to about 30% by weight. % by weight, all amounts are based on the weight of the polymer.
Many ion conductive polymer solutions are available for the manufacture of ion conductive polymer redox active additive composite electrolytes. The ion conductive polymer solution can be obtained by treating a solvent solution of the polymer with an ionic salt. The ion conductive polymer solution which can be used for the ion conductive polymer redox active additive composite electrolyte includes, but is not limited to, a silver ion (Ag ⁺ ) conductive polymer solution, a hydrogen ion (H ⁺ ) conductive polymer solution, Hydroxide (OH ^- ) conductive polymer solution, lithium ion (Li ⁺ ) conductive polymer solution, magnesium ion (Mg ⁺ ) conductive polymer solution, sodium ion (Na ⁺ ) conductive polymer solution, oxygen Ionic (O ^- ) conductive polymer solution and mixtures thereof.
Ag ⁺ may be used a conductive polymer solution comprising a polymer (such as but not limited to PEO, PVDF, PVDF-HFP, PBI , and mixtures thereof) of the conductive polymer solution of Ag ^+. The Ag ⁺ conductive polymer solution can be obtained by polymerizing a solution of an Ag ⁺ salt such as, but not limited to, silver iodide, silver chloride, silver nitrate, and a mixture thereof with an Ag ⁺ conductive polymer and an aprotic solvent (for example, It is not limited to EC and DMC).
H H ⁺ can be used a conductive polymer solution comprising a polymer (such as but not limited to PEO, PBI, Nafion, PEEK, PES , and mixtures thereof) ⁺ the conductive polymer solution. The H ⁺ conductive polymer solution can be obtained by polymerizing a solution of an aprotic acid (such as, but not limited to, phosphoric acid, sulfuric acid, and mixtures thereof) with an H ⁺ conductive polymer and an aprotic solvent (such as, but not limited to, EC, DMC) is formed by mixing.
Usable OH ^- conducting polymer solution comprises a polymer (such as but not limited to PEO, PBI, Nafion, PEEK, PES , and mixtures thereof) of OH ^- conductive polymer solution. The OH ^- conductive polymer solution can be obtained by using a polymerization solution of an OH ^- salt (such as, but not limited to, sodium hydroxide, potassium hydroxide, and a mixture thereof) with an OH ^- conductive polymer and an aprotic solvent (for example, It is not limited to EC and DMC).
The Li ⁺ conductive polymer solution that can be used comprises a Li ⁺ conductive polymeric material such as, but not limited to, PEO, PVDF-HFP, PVDF-TFE, LiTf, LiTfSI, LIBETI, LiClO ₄ , LiBOB, LiPF ₆ , LiBF ₄ and Its mixture. Li ⁺ by the conductive polymer solution may be Li ⁺ salts (e.g., but not limited _{LiTf, LiTfSI, LIBETI, LiClO 4} , LiBOB, LiPF 6, LiBF 4 , and mixtures thereof) Li ⁺ polymerization of the conductive polymer The solution is formed by mixing a mixture of aprotic solvents such as, but not limited to, EC, DMC. Preferably, a LiPF ₆ solution in a 1:1 EC:DMC (w/w) mixture can be used. In this aspect, the concentration of LiPF ₆ in the 1:1 EC:DMC mixture can vary from about 0.5 M to about 1.2 M, preferably from about 0.8 M to about 1 M.
Mg ⁺ conductive polymer solution may be used include a polymer (e.g., but not limited to PEO, PVDF-HFP, PBI, PEEK, PES , and mixtures thereof) of Mg ⁺ conductive polymer solution. The Mg ⁺ conductive polymer solution can be obtained by polymerizing a Mg ⁺ salt such as, but not limited to, magnesium chloride, magnesium perchlorate and a mixture thereof with a Mg ⁺ conductive polymer and an aprotic solvent (for example, It is formed by mixing without being limited to EC and DMC.
Na ⁺ can be used in the conductive polymer solution containing a polymer (such as but not limited to PEO, PVDF-HFP, PBI, PEEK, PES , and mixtures thereof) of the conductive polymer solution of Na ^+. The Na ⁺ conductive polymer solution can be obtained by polymerizing a Na ⁺ salt (for example, but not limited to, sodium iodide, sodium chloride, sodium nitrate, and a mixture thereof) with a Na ⁺ conductive polymer and an aprotic solvent. Formed by, for example, but not limited to, EC, DMC. When a Na ⁺ conductive polymer solution is used for the composite electrolyte, the electrode active material may be a sodium metal or a non-stoichiometric sodium oxide compound that allows sodium ions to be exchanged into the electrolyte.
The redox active additive may be incorporated into the ionically conductive polymer in various forms, for example, in the form of a precursor of a redox active additive, a solution of a redox active additive, and a particle of a redox active additive. The redox active additive which can be used in the solution of the ion conductive polymer can be changed depending on the ion conductive polymer to be used. When the redox active additive is used in the form of granules, the granules may have a size of from about 5 nanometers to about 100 micrometers, preferably from about 10 nanometers to about 100 nanometers.
When an Ag ⁺ conductive polymerization solution is used to produce an Ag ⁺ conductive polymer redox active composite electrolyte, the redox active additive may include, but is not limited to, a metal such as copper, lead, antimony, tin, which may be relative to When SCE (saturated calomel electrode) has a potential of less than about -0.8 V, it is alloyed with silver. When an H ⁺ conductive polymer is used, the redox active additive includes, but is not limited to, a metal oxide having a potential of about 1 V with respect to SCE (saturated calomel electrode).
When a Mg ⁺ conductive polymer is used, the redox active additive may include, but is not limited to, TiS ₂ , V ₆ O _{13 ,} and chromium oxide. When a Na ⁺ conductive polymer is used, the redox active additive includes, but is not limited to, TiS ₂ , V ₆ O _{13 ,} and chromium oxide.
When a Li ⁺ conductive polymerization solution is used to produce a Li ⁺ conductive polymer redox active composite electrolyte, the redox active additive may include, but is not limited to, an anode type metal oxide having a ratio with respect to a redox potential of lithium a potential of 2 V or less, a metal oxide particle of a cathode type (having a potential of about 2 V or more with respect to a redox potential of lithium), a metal particle (having about 2 V or more with respect to lithium/lithium) Alloy potential), a mixture of a cathode metal oxide and a metal particle, a mixture of an anode metal oxide and a metal particle, and a mixture of a cathode oxide and an anode oxide. The redox active oxide having a low oxidation-reduction potential of about 2 V or less (relative to lithium/lithium) in the Li ⁺ conductive polymer may be used, but not limited to MoO ₃ , SnO ₂ , WO ₃ , PbO ZnO, Fe ₂ O ₃ , Cr ₂ O ₃ , V ₂ O ₅ , MnO ₂ , Li ₄ Ti ₅ O ₁₂ , Li _4+x Ti ₅ O ₁₂ and mixtures thereof. Redox active oxides having a high oxidation-reduction potential of about 2 V or more (relative to lithium/lithium), including but not limited to LiMn ₂ O ₄ , LiCoO ₂ , LiNiO ₂ , LiFeO ₂ , Li _x (Co _y Al _1-y ) _(1-x) O ₂ (where 0 < x < 1, 0 < y < 1) and mixtures thereof.
The high redox oxide, the low redox oxide, and mixtures thereof may be added to the Li ⁺ conductive polymer in an amount of from about 0.5% by weight to about 30% by weight, preferably from about 1% by weight to about 10% by weight. (Based on the weight of the Li ⁺ conductive polymer solution). When molybdenum trioxide is used as the redox active additive, the molybdenum trioxide may be present in the Li ⁺ conductive polymerization in an amount of from about 1% by weight to about 30% by weight, preferably from about 1% by weight to about 10% by weight. In the solution of the solution, all amounts are based on the weight of the polymer solution.
The redox active metal that can be used as a redox additive in the Li ⁺ conductive polymer solution includes, but is not limited to, platinum, gold, tin, lead, zinc, antimony, mixtures thereof, and alloys thereof. When gold particles are used, the size of the particles can vary from about 1 nanometer to about 200 nanometers. The redox active metal may be present in the solution of the Li ⁺ conductive polymer in an amount of from about 0.1% by weight to about 10% by weight, preferably from about 1% by weight to about 5% by weight, based on the weight of the polymer solution Benchmark.
Production of a product comprising an ion conductive polymer redox active additive composite electrolyte:
Ionically Conductive Polymer Redox Active Additive The composite electrolyte can be cast by, for example, spin coating, thin film sputtering, gas gel spray, gas gel particle deposition, electrophoretic deposition, ribbon forming, screen printing, and doctor blade forming. Various products (such as film). When formed using a doctor blade, the composite electrolyte can be blade formed on a moving substrate (e.g., a glass substrate or a polymer substrate) to form a cast sheet of a composite electrolyte (e.g., a film sheet).
The thickness of the cast film sheet of the composite electrolyte can be varied by controlling the solvent content of the slurry, the speed of moving the substrate, and the width of the blade forming opening. The thickness of the film sheet can thus vary widely. Typically, the cast film sheet has a thickness of from about 1 micron to about 450 microns, preferably from about 10 microns to about 100 microns.
The cast film sheet is dried on a substrate and then reversed by contact with a lower alkanol such as, but not limited to, ethanol, methanol, isopropanol, and mixtures thereof, preferably ethanol. After the reverse rotation, the cast film sheet is removed from the glass substrate and again with a lower alkanol (such as, but not limited to, ethanol, methanol, isopropanol, and mixtures thereof, preferably ethanol) at about 20 degrees Celsius The treatment is carried out at about 50 degrees Celsius for about 1 hour to about 16 hours. The film to be treated is dried, for example, at about 20 degrees Celsius to about 60 degrees Celsius, preferably about 20 degrees Celsius to about 40 degrees Celsius, by vacuum drying. Typically, drying is carried out at temperatures and times sufficient to achieve <1% moisture content. The dried film sheet is then immersed in an ionically conductive solution to expand the polymer. The expansion can be enhanced by heating the film in an ionically conductive solution to about 55 degrees Celsius for about 2 hours to about 4 hours.
Preparation of a separator formed by an ion-conductive polymer redox active metal oxide composite electrolyte:
Example P1: Li ⁺ Conductive PVDF-HFP Polymer Molybdenum Trioxide Composite Electrolyte Isolation Membrane 2 g of PVDF-HFP reagent grade particles (from Aldrich, molecular weight 400,000 g/mol) were dissolved at 19 ml of reagent at 19 ° C. DMF to produce a polymer solution. Ten grams of the polymer solution was mixed with 0.05 grams of molybdenum trioxide redox active particles having an average size of 100 nanometers to form a mixture.
Molybdenum trioxide particles were prepared by dissolving 0.8467 g of H ₂ MoO ₄ in a 2 M aqueous ammonia solution to produce a 5 mM H ₂ MoO ₄ solution. The pH of the solution was adjusted to pH 2-3 by dropwise addition of 4 M hydrochloric acid.
Additional 4 M hydrochloric acid was added with continuous stirring to form a white precipitate. The precipitate was collected by centrifugation and rinsed with absolute ethanol to form a rinsed precipitate. Next, 0.8 g of the rinsed precipitate was dispersed in 15 ml of absolute ethanol and heated at 150 ° C for 8 hours to obtain a treated precipitate.
The treated precipitate was further washed with absolute ethanol and dried at 80 ° C for 16 hours to obtain a dried precipitate. The dried precipitate was heated to a temperature of 5 degrees Celsius per minute to 350 degrees Celsius, maintained at 350 degrees Celsius for 5 hours, and then cooled to obtain α-molybdenum trioxide. The mixture of redox active molybdenum trioxide particles and the polymer solution was subjected to ultrasonic vibration for 20 minutes to produce a treated mixture. The treated mixture doctor blade was formed on a glass substrate to produce a cast film sheet having a thickness of 25 μm.
The cast film sheet was dried for 1 hour (atmospheric conditions). The dried sheet was then reversed by contacting the sheet with absolute ethanol for 5 minutes. The resulting treated film sheet was removed from the substrate, immersed in absolute ethanol for 16 hours, and vacuum dried at 20 degrees Celsius to form a dried film of PVDF-HFP having molybdenum trioxide particles therein.
The dried film was immersed in a Li ⁺ conductive polymer solution which was formed by dissolving 0.46 g of LiPF ₆ in a 1:1 weight ratio mixture of EC:DMC. The film was immersed in a Li ⁺ conductive solution for 2 days to obtain a Li ⁺ conductive PVDF-HFP polymer molybdenum trioxide composite electrolyte separator.
Example P2: Li ⁺ Conductive PVDF-HFP Polymer Tin Dioxide Composite Electrolyte Isolation Film The procedure of Example P1 was followed (except for the replacement of molybdenum trioxide with 0.05 g of tin dioxide) to obtain a film having a thickness of 240 μm. Tin dioxide is available from Aldrich.
Example P3: Li ⁺ Conductive PVDF-HFP Polymer Tungsten Oxide Composite Electrolyte Separation Film 2 grams of PVDF-HFP reagent grade particles (from Aldrich, molecular weight 400,000 g/mol) were dissolved at 19 ° C in 19 ml reagent grade DMF to enable the formation of a polymer solution. Ten grams of the polymer solution was mixed with 0.05 grams of tungsten oxide redox active particles having an average size of 100 nanometers to form a mixture.
The mixture of redox active tungsten trioxide particles and the polymer solution was subjected to ultrasonic vibration for 20 minutes to enable the formed mixture to be formed. The treated mixture doctor blade is formed on a glass substrate to form a cast film sheet. The cast film sheet was dried for 1 hour (atmospheric conditions), contacted with absolute ethanol for 5 minutes, removed from the substrate, soaked in absolute ethanol for 16 hours, vacuum dried at 20 degrees Celsius, and in a Li ⁺ conductive polymer solution. Soak for 2 days (formed by dissolving 0.46 grams of LiPF ₆ in a 1:1 weight ratio mixture of EC:DMC).
Example P4: Li ⁺ Conductive PVDF-HFP Polymer Lead Oxide Composite Electrolyte Isolation Film Following the procedure of Example P3 (except for replacing tungsten trioxide with 0.05 grams of lead oxide). Lead oxide is available from Aldrich.
Example P5: Li ⁺ Conductive PVDF-HFP Polymer Zinc Oxide Composite Electrolyte Isolation Film Following the procedure of Example P3 (except for replacing tungsten trioxide with 0.05 g of zinc oxide). Zinc oxide is available from Aldrich.
Example P6: Li ⁺ conductive PVDF-HFP polymer Li _1-x Mn ₂ O ₄ composite electrolyte isolating film according to the procedure of Example P3 (except for replacing tungsten trioxide with 0.05 g of Li _1-x Mn ₂ O ₄ ) . Li _1-x Mn ₂ O ₄ is available from Aldrich.
Example P6A: Li ⁺ Conductive PVDF-HFP Polymer LiMn ₂ O ₄ Composite Electrolyte Isolation Film Following the procedure of Example P3 (except for replacing tungsten trioxide with 0.05 g of LiMn ₂ O ₄ ). LiMn ₂ O ₄ is available from Aldrich.
Example P7: Li ⁺ conductive PVDF-HFP polymer Li _x CoO ₂ composite electrolyte isolating film Following the procedure of Example P3 (except for replacing tungsten trioxide with 0.05 g of Li _x CoO ₂ ). Li _x CoO ₂ is available from Aldrich.
Example P7A: Li ⁺ Conductive PVDF-HFP Polymer LiCoO ₂ Composite Electrolyte Isolation Film Following the procedure of Example P3 (except for replacing tungsten trioxide with 0.05 gram of LiCoO ₂ ). LiCoO ₂ is available from Aldrich.
Example P8: Li ⁺ conductive PVDF-HFP polymer molybdenum trioxide composite electrolyte 2 g of Li ⁺ conductive PVDF polymer together with 0.46 g of LiPF _{6 was} dissolved in 19 ml of DMF solvent to form Li ⁺ conductive polymer Solution. 0.05 g of molybdenum trioxide having an average size of 100 nm was added to this solution. The resulting mixture was cast into a film by the procedure of Example P1 and dried to constant weight at 20 ° C to form a Li ⁺ conductive polymer molybdenum trioxide composite electrolyte.
Preparation of a separator film formed by an ion conductive polymer redox active metal additive composite electrolyte:
Dissolving a metal precursor (eg, acetamidine metal, metal hydroxide, medium chain/long chain carboxylic acid metal salt), chlorometal acid (eg, HPtCl ₄ , HAuCl _{4 ,} and mixtures thereof) in an alkyl diol (eg, Ethylene glycol, 1,2-butanediol, C4-C8 alkanol, and mixtures thereof) to give a mixture. The mixture is refluxed at about 110 degrees Celsius to about 190 degrees Celsius for about 2 hours to about 16 hours to obtain a gel of redox active metal. The ethyl acetonide metal which can be used includes, but is not limited to, acetamidineacetate, acetamidineacetone, acetoacetate tin dichloride, acetamidine lead, acetophenone zinc hydrate, mixtures thereof and alloys thereof.
The redox active metal gel is mixed with the ion conductive polymer solution to form an ion conductive polymer redox active metal composite electrolyte mixture. The mixture can then be cast into a product, such as a film, using techniques such as knife forming as described above.
Preparation of a separator thin film Li ⁺ PVDF-HFP polymer redox active platinum composite electrolyte:
A PVDF-HFP film having redox active platinum in the form of nanoparticles can be prepared by dissolving a platinum precursor such as platinum acetoacetate in a lower alkyl diol such as ethylene glycol to form a platinum precursor. Solution. The platinum precursor may be present in the platinum precursor solution in an amount from about 1% to about 10% by weight, preferably from about 1% to about 5% by weight, and the alkyl diol may be from about 90% to about 99% The amount by weight is present in the platinum precursor solution, all percentages being based on the total weight of the precursor solution.
The precursor solution is refluxed to obtain a platinum gel having an average particle size of from about 2 nm to about 10 nm, preferably about 10 nm. Approximately 1% by weight of platinum gel to about 15% by weight of platinum gel, preferably about 1% by weight of platinum gel to about 5% by weight of platinum gel, mixed with a solution of the polymer to form a polymerization Platinum redox additive mixture. The treated mixture can then be formed into a glass substrate by doctor blade to produce a cast film sheet.
The cast film sheet can be dried, for example, for about 1 hour (atmospheric conditions). The dried sheet was then reversed by contacting the sheet with absolute ethanol for 5 minutes. The resulting treated film sheets were removed from the substrate, soaked in absolute ethanol for 16 hours, and dried under vacuum at 20 degrees Celsius.
The dried film was immersed in a Li ⁺ conductive polymer solution which was formed by dissolving 0.46 g of LiPF ₆ in a 1:1 weight ratio mixture of EC:DMC. The film was then immersed in a Li ⁺ conductive solution for 2 days.
Example P9: Li ⁺ PVDF-Platinum Redox Additive Composite Electrolyte Film 0.63 g of reagent grade acetoacetate platinum was dissolved in 10 ml of ethylene glycol at 20 ° C to form a metal precursor solution.
The precursor solution was refluxed at 190 ° C for 5 hours to obtain a platinum gel of 10 nm platinum particles. One gram of PVDF-HFP particles from Sigma-Aldrich was dissolved in 9.5 ml of reagent grade DMF at 20 degrees Celsius to produce a PVDF/DMF solution.
A 1.9 gram platinum gel was mixed with 10 grams of a 10% by weight PVDF/DMF solution to form a mixture. The mixture of platinum particles in PVDF/DMF solution was subjected to ultrasonic vibration for 20 minutes to produce a treated mixture. The treated mixture doctor blade was formed on a glass substrate to produce a cast film sheet having a thickness of 250 μm. The cast film sheet was dried for 4 hours (atmospheric conditions). The dried sheet was then reversed by contacting the film sheet with absolute ethanol for 5 minutes to form a treated film sheet. The treated film sheets were removed from the substrate, soaked in absolute ethanol for 16 hours, and then dried under vacuum at 20 degrees Celsius. The resulting dried film was then immersed in a solution of 0.46 g of LiPF ₆ in a 1:1 weight ratio mixture of EC:DMC for 2 days to produce a Li ⁺ conductive platinum additive composite electrolyte having a film thickness of 240 μm.
Example P10: Li ⁺ PVDF - Gold Redox Additive Composite Electrolyte 0.63 g of reagent grade ethyl acetonide gold was dissolved in 10 ml of ethylene glycol at 20 ° C to form a metal precursor solution.
The precursor solution was refluxed at 190 ° C for 5 hours to obtain a gold gel of 10 nm gold particles. One gram of PVDF-HFP particles from Sigma-Aldrich was dissolved in 9.5 ml of reagent grade DMF at 20 degrees Celsius to produce a PVDF/DMF solution.
A 1.9 gram gold gel was mixed with 10 grams of a 10% by weight PVDF/DMF solution to form a mixture. The mixture of gold particles in PVDF/DMF solution was subjected to ultrasonic vibration for 20 minutes to produce a treated mixture.
The treated mixture doctor blade was formed on a glass substrate to produce a cast film sheet having a thickness of 250 μm.
The cast film sheet was dried for 4 hours (atmospheric conditions), reversed by contact with absolute ethanol for 5 minutes, soaked in absolute ethanol for 16 hours, vacuum dried at 20 degrees Celsius, and then at 0.46 g of LiPF ₆ in the EC. : DMC was soaked in a 1:1 weight ratio mixture for 2 days.
Example P11: Li ⁺ PVDF-tin redox additive composite electrolyte 0.63 g of reagent grade acetamidine acetone was dissolved in 10 ml of ethylene glycol at 20 ° C to form a metal precursor solution. The precursor solution was refluxed at 190 ° C for 5 hours to obtain a tin gel of 10 nano tin particles. One gram of PVDF-HFP particles from Sigma-Aldrich was dissolved in 9.5 ml (reagent grade) of DMF at 20 degrees Celsius to produce a PVDF/DMF solution.
A 1.9 gram tin gel was mixed with 10 grams of a 10% by weight PVDF/DMF solution to form a mixture. The mixture of tin particles in PVDF/DMF solution was subjected to ultrasonic vibration for 20 minutes to produce a treated mixture. The treated mixture doctor blade was formed on a glass substrate to produce a cast film sheet having a thickness of 250 μm.
The cast film sheet was dried for 4 hours (atmospheric conditions). The dried sheet was then reversed by contacting the film sheet with absolute ethanol for 5 minutes to form a treated film sheet. The treated film sheets were removed from the substrate, immersed in absolute ethanol for 16 hours, then vacuum dried at 20 degrees Celsius, followed by soaking in a solution of 0.46 grams of LiPF ₆ in a 1:1:1 weight ratio mixture of EC:DMC. day.
Example P12: Li ⁺ PVDF - Lead Redox Additive Composite Electrolyte Following the procedure of Example P10 (except for the replacement of acetamidine acetone with lead acetonide).
Example P13: Li ⁺ PVDF-zinc redox additive The composite electrolyte was subjected to the procedure of Example P10 (except for the replacement of ethyl acetonide with zinc acetoacetate).
Example P14: Li ⁺ PVDF-矽 redox additive The composite electrolyte was subjected to the procedure of Example P10 (except for the replacement of ethyl acetonide gold with 0.05 g of 100 nm ruthenium particles available from Reade).
Example P5:
Two grams of Li ⁺ conductive polymer (for example, PVDF) was dissolved in 19 ml of DMF solvent together with 0.46 g of LiPF ₆ to form a Li ⁺ conductive polymer solution. 0.05 g of platinum having an average size of 100 nm was added to this solution. The obtained polymer solution was cast into a film by the procedure of Example P1, and dried to constant weight at 20 ° C to form a Li ⁺ conductive polymer platinum composite electrolyte.
Application of ion conductive polymer composite film in coin battery:
Example C1:
The film produced in Example P1 was used as an isolating electrolyte in a 2032 coin cell. In the battery, activated carbon having a surface area of 1700 m ² /g and derived from polyfuranol was used as a cathode, and lithium metal was used as an anode.
The cathode was prepared by mixing activated carbon, a polytetrafluoroethylene (Teflon) emulsion obtained from Electrochem Co., and acetylene black to form a slurry. In the slurry, activated carbon is present in an amount of 85% by weight, polytetrachloroethylene emulsion is present in an amount of 10% by weight, and acetylene black is present in an amount of 5% by weight, all of which are Based on the total weight of the slurry. The slurry was applied to carbon paper to a thickness of 250 microns and then dried at 20 degrees Celsius to form a current collector.
Example C2:
The procedure of Example C1 was followed (except for the film produced using Example P9).
Example C3:
The procedure of Example C1 was followed (except for the film produced using Example P2).
The performance of coin cells was tested using electrochemical impedance spectroscopy and fixed current charging/discharging. Electrochemical impedance measurements were made before and after charge/discharge measurements in an open loop voltage state. The charge/discharge measurement of the battery was carried out using a fixed load current of 100 mA/g based on the mass of activated carbon. The mass of activated carbon used as a cathode was 1 mg. The battery is cycled between 5.2 volts and 2 volts for at least 25 cycles. The charge/discharge measurement is repeated at 200 mA/g.
The performance of the coin cells fabricated in Examples C1-C3 is shown in Table 1. In Table 1, the performance of the coin cell was compared to the performance of the control coin cell. The control coin cell was the same coin cell as in Example 1, except that the film used in the control cell was prepared according to the procedure of Example P1 and the film did not contain molybdenum trioxide. The energy density calculation is based on the total volume of the sample cells containing activated carbon, lithium, and polymer films.

Ionic Conductive Glass Redox Additive Composite Electrolyte:
The ion conductive glass redox additive composite electrolyte contains an ion conductive glass and a redox additive. The ion conductive glass may include, but is not limited to, an ion conductive sulfur-based compound glass, an ion conductive fluorine glass, an ion conductive oxide glass, an ion conductive phosphate glass, an ion conductive oxynitride glass, and an ion conductivity. Oxyfluoride glass, ionically conductive oxychloride glass, and mixtures thereof. Any of these glasses can be Ag ⁺ Conductivity, F ^- Conductivity, H ⁺ Conductivity, K ⁺ Conductivity, Li ⁺ Conductivity, Mg ²⁺ Conductivity, Na ⁺ Conductivity, Mg ²⁺ Conductivity, O ^2- Conductivity or a combination thereof.
The material to be used as the ion conductive glass includes, but is not limited to, an ion conductive glass itself, a mixture of a raw material suitable for producing an ion conductive glass, and an ion conductive glass and a mixture of such raw materials.
Li ⁺ Conductive sulfur-based compound glass may include, but is not limited to, Li ₂ S-SiS ₂ -Li ₄ SiO ₄ Li ₂ S-SiS ₂ -Li ₃ PO ₄ Li ₂ SP ₂ S ₅ -LiI, Li ₂ S-SiS ₂ -LiI, Li ₂ S-SiS ₂ Li ₂ SB ₂ S ₃ Li ₂ SP ₂ S ₅ Li ₂ S-GeS ₂ Li ₂ S-Ga ₂ S ₃ - GeS ₂ Li doped with an iodide dopant such as LiI ₂ S-Ga ₂ S ₃ -GeS ₂ Li doped with an iodide dopant such as LiI ₂ S-Ga ₂ S ₃ -GeS ₂ Li ₂ S-Sb ₂ S ₃ -GeS ₂ Li ₂ S-GeS ₂ -P ₂ S ₅ Li ₃ PO ₄ -Li ₂ S-SiS ₂ Li ₂ S-GeS ₂ -P ₂ S ₅ And mixtures thereof.
Li ⁺ Conductive fluorine-based glass may include, but is not limited to, ZrF ₄ -BaF ₂ -LaF ₃ -LiF and mixtures thereof. Li ⁺ Conductive oxide, oxychloride, and oxyfluoride glass glasses may include, but are not limited to, Li-FBO compositions such as, but not limited to, Li ₂ O-LiF-B ₂ O ₃ And mixtures thereof; Li-BO compositions such as, but not limited to, Li ₄ SiO ₄ -Li ₃ BO ₄ Li ₂ O-LiCl-B ₂ O ₃ And mixtures thereof; Li-BSO compositions such as, but not limited to, Li ₂ SO ₄ -Li ₂ OB ₂ O ₃ And mixtures thereof. Li ⁺ Conductive oxynitride glasses can include, but are not limited to, lithium phosphorus oxynitrides and mixtures thereof.
The redox active additive used in the ion conductive glass may be in the form of a redox active metal, a redox active oxide, a redox active oxynitride, and a mixture thereof. Redox active metals that may be used include, but are not limited to, gold, platinum, palladium, tin, aluminum, iron, ruthenium, tin alloys, niobium alloys, niobium, niobium alloys thereof, and mixtures thereof. When gold particles are used, the size of the particles can vary from about 3 nanometers to about 190 nanometers, preferably from about 3 nanometers to about 10 nanometers, more preferably about 10 nanometers.
Redox active oxides which may be used include, but are not limited to, cerium oxide, cerium oxide, chromium oxide, cobalt oxide, copper oxide, cerium oxide, indium oxide, iron oxide, lead oxide, lithium cobalt oxide, lithium oxide, and titanic acid. Lithium, lithium vanadium, lithium vanadium oxide, lithium phosphorus oxide, phosphorus oxide, lithium iron oxide, iron phosphorus oxide, manganese oxide, molybdenum oxide, cerium oxide, silver oxide, cerium oxide, cerium oxide, tin oxide, Titanium oxide, tungsten oxide, vanadium oxide, zinc oxide, and mixtures thereof. Redox reactive oxynitrides that may be used include, but are not limited to, Li _7.9 MnN _3.2 O _1.6 And mixtures thereof.
The redox active additive for producing the ion conductive glass redox active composite electrolyte may be in the form of a precursor solution of a redox active additive, a solution of a redox additive, and a particle of a redox active additive. When particles of the redox active additive are used, the particle size of the redox active additive can vary from about 1 nanometer to about 500 nanometers.
The ion conductive glass redox active additive composite electrolyte can be obtained by melting a mixture of a redox active additive and an ion conductive glass. The amount of the ion conductive glass and the redox additive in the ion conductive glass redox additive composite electrolyte can be widely changed. The amount of the redox additive used in the ion conductive glass redox additive composite electrolyte is sufficient to have an increased ion current and compared to the ion conductive glass used in the ion conductive glass redox additive composite electrolyte / or higher voltage ionic conductive glass redox additive composite electrolyte. Typically, the redox additive is present in an amount from about 0.1% to about 50% by weight, preferably from about 5% to about 20% by weight, based on the weight of the ionically conductive glass.
The amount of redox additive used in the ion-conductive glass ceramic redox additive composite electrolyte is sufficient to have an increase compared to the ion-conductive glass ceramic used in the ion-conductive glass ceramic redox additive composite electrolyte Ionically conductive glass ceramic redox additive composite electrolyte with ion current and/or higher voltage. Generally, the redox additive is present in an amount from about 0.5% to about 20% by weight, preferably from about 5% to about 10% by weight, of the ionically conductive glass ceramic.
The amount of the redox additive used in the ion conductive ceramic redox additive composite electrolyte is sufficient to have an increased ion current compared to the ion conductive ceramic used in the ion conductive ceramic redox additive composite electrolyte. Ionic conductive ceramic redox additive composite electrolyte. Generally, the redox additive is present in an amount from about 0.5% to about 20% by weight, preferably from about 5% to about 10% by weight of the ionically conductive ceramic.
When the ion conductive glass is Ag ⁺ When conductive glass (for example, any Ag ⁺ Conductive sulfur-based compound glass, Ag ⁺ Conductive fluoride glass, Ag ⁺ Conductive oxide glass and mixtures thereof) compared to those used in Ag ⁺ Ag in conductive glass redox additive composite electrolyte ⁺ Conductive glass, the amount of redox active additive used is sufficient to achieve Ag with increased ion current ⁺ Conductive glass redox additive composite electrolyte. Typically, the amount of redox active additive is from about 0.1% to about 50% by weight Ag ⁺ Conductive glass.
When the ion conductive glass is Cs ⁺ When conductive glass (for example, any Cs ⁺ Conductive sulfur-based compound glass, Cs ⁺ Conductive fluoride glass, Cs ⁺ Conductive oxide glass and mixtures thereof) compared to use in Cs ⁺ Cs in conductive glass redox additive composite electrolyte ⁺ Conductive glass, the amount of redox active additive used is sufficient to achieve Cs with increased ion current ⁺ Conductive glass redox additive composite electrolyte. Typically, the amount of redox active additive is from about 0.1% to about 50% by weight of Cs ⁺ Conductive glass.
When the ion conductive glass is F ^- When conductive glass (for example, any F ^- Conductive sulfur-based compound glass, F ^- Conductive fluoride glass, F ^- Conductive oxide glass and mixtures thereof) compared to used in F ^- Conductive glass redox additive F in composite electrolyte ^- Conductive glass, the amount of redox active additive used is sufficient to achieve an increased ion flux F ^- Conductive glass redox additive composite electrolyte. Typically, the amount of redox active additive is from about 0.1% to about 50% by weight of F. ^- Conductive glass.
When the ion conductive glass is H ⁺ When conductive glass (for example, any H ⁺ Conductive sulfur-based compound glass, H ⁺ Conductive fluoride glass, H ⁺ Conductive oxide glass and mixtures thereof) compared to used in H ⁺ Conductive glass redox additive H in composite electrolyte ⁺ Conductive glass, the amount of redox active additive used is sufficient to achieve an increased ion current H ⁺ Conductive glass redox additive composite electrolyte.
When the ion conductive glass is K ⁺ When conductive glass (for example, any K ⁺ Conductive sulfur-based compound glass, K ⁺ Conductive fluoride glass, K ⁺ Conductive oxide glass and mixtures thereof) compared to used in K ⁺ K in conductive glass redox additive composite electrolyte ⁺ Conductive glass, the amount of redox active additive used is sufficient to achieve K with increased ion current ⁺ Conductive glass redox additive composite electrolyte. Typically, the amount of redox active additive is from about 0.1% to about 50% by weight K ⁺ Conductive glass.
When the ion conductive glass is Li ⁺ When conductive glass (for example, any Li ⁺ Conductive sulfur-based compound glass, Li ⁺ Conductive fluoride glass, Li ⁺ Conductive oxide glass and mixtures thereof) compared to used in Li ⁺ Li in conductive glass redox additive composite electrolyte ⁺ Conductive glass, the amount of redox active additive used is sufficient to achieve Li with increased ion current ⁺ Conductive glass redox additive composite electrolyte. Typically, the amount of redox active additive is from about 0.1% to about 50% by weight of Li. ⁺ Conductive glass.
When the ion conductive glass is Na ⁺ When conductive glass (for example, any Na ⁺ Conductive sulfur-based compound glass, Na ⁺ Conductive fluoride glass, Na ⁺ Conductive oxide glass and mixtures thereof) compared to used in Na ⁺ Conductive glass redox additive Na in a composite electrolyte ⁺ Conductive glass, the amount of redox active additive used is sufficient to achieve Na with increased ion current ⁺ Conductive glass redox additive composite electrolyte. Typically, the amount of redox active additive is from about 0.1% to about 50% by weight Na ⁺ Conductive glass.
When the ion conductive glass is O ^2- When conductive glass (for example, any O ^2- Conductive sulfur-based compound glass, O ^2- Conductive fluoride glass, O ^2- Conductive oxide glass and mixtures thereof) compared to used in F ^- O in conductive glass redox additive composite electrolyte ^2- Conductive glass, the amount of redox active additive used is sufficient to achieve an increased ion current ^2- Conductive glass redox additive composite electrolyte. Typically, the amount of redox active additive is from about 0.1% to about 50% by weight of O. ^2- Conductive glass.
Ionic conductive glass ceramic redox additive composite electrolyte:
The ion conductive glass ceramic redox additive composite electrolyte contains an ion conductive glass ceramic and a redox additive. The ion conductive glass ceramic may include, but is not limited to, a sulfur-based compound glass ceramic, a fluoride glass ceramic, an oxide glass ceramic, a phosphate glass ceramic, a sulfide glass ceramic, and a mixture thereof. Any of these glass ceramics can be Ag ⁺ Conductivity, F ^- Conductivity, H ⁺ Conductivity, K ⁺ Conductivity, Li ⁺ Conductivity, Mg ²⁺ Conductivity, Na ⁺ Conductivity, O ^2- Conductivity or a combination thereof.
The ion conductive sulfur-based compound glass ceramic may include, but is not limited to, Li ₂ SP ₂ S ₅ Glass and mixtures thereof. The ion conductive oxide glass ceramics may include, but are not limited to, lithium aluminum silicate phosphoric acid glass ceramics and mixtures thereof.
The redox active additive for use in the ion conductive glass ceramic may be in the form of a redox active metal, a redox active oxide, a redox active oxynitride, and mixtures thereof. Redox active metals that may be used include, but are not limited to, gold, platinum, palladium, tin, aluminum, iron, ruthenium, copper-tin alloys, copper-bismuth alloys, ruthenium, alloys thereof, and mixtures thereof. When gold particles are used, the size of the particles can vary from about 1 nanometer to about 200 nanometers. Redox active oxides include, but are not limited to, cerium oxide, cerium oxide, cerium oxide, boron oxide, calcium oxide, chromium oxide, cobalt oxide, copper oxide, cerium oxide, indium oxide, iron oxide, lead oxide, lithium cobalt oxide. , lithium oxide, lithium titanate, lithium iron phosphorus oxide, iron phosphorus oxide, phosphorus oxide, lithium vanadium oxide, manganese oxide, molybdenum oxide, cerium oxide, silver oxide, tin oxide, titanium oxide, tungsten oxide, oxidation Vanadium, zinc oxide and mixtures thereof. Redox reactive oxynitrides that may be used include, but are not limited to, Li _7.9 MnN _3.2 O _1.6 And mixtures thereof.
The redox active additive for producing the ion conductive glass ceramic redox active composite electrolyte may be in the form of a precursor solution of a redox active additive, a solution of a redox additive, and a particle of a redox active additive. When particles of the redox active additive are used, the particle size of the redox active additive can vary from about 1 nanometer to about 500 nanometers.
The ion conductive glass ceramic redox active additive composite electrolyte can be obtained by forming a melt of a mixture of an ion conductive glass and a redox active additive. The material to be used as the ion conductive glass ceramic may include, but is not limited to, an ion conductive glass ceramic itself, a mixture of raw materials suitable for producing an ion conductive glass ceramic, and an ion conductive glass ceramic and a mixture of such materials.
The amount of the ion conductive glass ceramic and the redox additive in the ion conductive glass ceramic redox additive composite electrolyte can be widely changed. The amount of the redox additive used in the ion conductive glass ceramic redox additive composite electrolyte is sufficient to form a glass ceramic redox additive composite electrolyte, which is more conductive than the ion electrolyte used in the composite electrolyte Glass ceramics have a larger ion current. Typically, the redox additive is present in an amount of from about 0.1% to about 50% by weight, preferably from about 0.1% to about 40% by weight, preferably from about 1% to about 25% by weight, More preferably, it is present in an amount of from about 1% by weight to about 20% by weight based on the weight of the ion-conductive glass ceramic.
When the ion conductive glass ceramic is Ag ⁺ Conductive glass ceramics (for example, any Ag ⁺ Conductive sulfur-based compound glass ceramic, Ag ⁺ Conductive Fluoride Glass Ceramics, Ag ⁺ Conductive oxide glass ceramics and mixtures thereof), the amount of redox active additive used is sufficient to reach Ag ⁺ Conductive glass ceramic redox additive composite electrolyte, the Ag ⁺ Conductive glass ceramic redox additive composite electrolyte is used for Ag in composite electrolyte ⁺ Conductive glass ceramics have a larger ion current. Typically, the amount of redox active additive is from about 0.1% to about 30% by weight Ag ⁺ The weight of the conductive glass ceramic.
When the ion conductive glass ceramic is F ^- When conducting glass ceramics (for example, any F ^- Conductive sulfur-based compound glass ceramic, F ^- Conductive Fluoride Glass Ceramic, F ^- Conductive oxide glass ceramics and mixtures thereof), the amount of redox active additive used is sufficient to achieve F ^- Conductive glass ceramic redox additive composite electrolyte, the F ^- Conductive glass ceramic redox additive composite electrolyte ratio F used in composite electrolyte ^- Conductive glass ceramics have a larger ion current. Typically, the amount of redox active additive is from about 0.1% to about 30% by weight of F. ^- Conductive glass ceramic.
When the ion conductive glass ceramic is Li ⁺ Conductive glass ceramics (for example, any Li ⁺ Conductive sulfur-based compound glass ceramic, Li ⁺ Conductive Fluoride Glass Ceramic, Li ⁺ Conductive oxide glass ceramics and mixtures thereof), the amount of redox active additive used is sufficient to achieve Li ⁺ Conductive glass ceramic redox additive composite electrolyte, the Li ⁺ Conductive glass ceramic redox additive composite electrolyte ratio for Li in composite electrolyte ⁺ Conductive glass ceramics have a larger ion current. Typically, the amount of redox active additive is from about 0.1% to about 40% by weight of Li. ⁺ Conductive glass ceramic.
When the ion conductive glass ceramic is Na ⁺ When conducting glass ceramics (for example, any Na ⁺ Conductive sulfur-based compound glass ceramic, Na ⁺ Conductive Fluoride Glass Ceramic, Na ⁺ Conductive oxide glass ceramics and mixtures thereof), the amount of redox active additive used is sufficient to reach Na ⁺ Conductive glass ceramic redox additive composite electrolyte, the Na ⁺ Conductive glass ceramic redox additive composite electrolyte is used for Na in composite electrolyte ⁺ Conductive glass ceramics have a larger ion current. Typically, the amount of redox active additive is from about 0.1% to about 50% by weight Na ⁺ Conductive glass ceramic.
When the ion conductive glass ceramic is O ^2- Conductive glass ceramics (for example, any O ^2- Conductive sulfur-based compound glass ceramic, O ^2- Conductive fluoride glass ceramic, O ^2- Conductive oxide glass ceramics and mixtures thereof), the amount of redox active additive used is sufficient to achieve O ^2- Conductive glass ceramic redox additive composite electrolyte, the O ^2- Conductive glass ceramic redox additive composite electrolyte is used in composite electrolyte ^2- Conductive glass ceramics have a larger ion current. Typically, the amount of redox active additive is from about 0.1% to about 50% by weight of O. ^2- Conductive glass ceramic.
Redox active species formed in situ in ionically conductive glass and glass ceramics:
The in-situ redox active species ion conductive glass and the in situ formed redox active species ion conductive glass ceramic each comprise an in situ formed ionically conductive glass or glass ceramic and a redox additive species. The ion conductive glass and the glass ceramic may include, but are not limited to, a sulfur-based compound glass and a glass ceramic, a fluoride glass and a glass ceramic, an oxide glass and a glass ceramic, a phosphate glass, and a glass ceramic, and a mixture thereof. Any of these ceramics can be Ag ⁺ Conductivity, F ^- Conductivity, H ⁺ Conductivity, K ⁺ Conductivity, Li ⁺ Conductivity, Mg ²⁺ Conductivity, Na ⁺ Conductivity, O ^2- Conductivity or a combination thereof. Ion-conductive sulfur-based compound glass ceramics that can be used include, but are not limited to, Li ₂ SP ₂ S ₅ Glass and mixtures thereof.
The redox active additive for use in ion conductive glass or glass ceramic may be in the form of a redox active metal, a redox active oxide, a redox active oxynitride, and mixtures thereof. Redox active metals that may be used include, but are not limited to, gold, platinum, palladium, tin, aluminum, iron, ruthenium, copper-tin alloys, copper-bismuth alloys, niobium, niobium alloys thereof, and mixtures thereof. When gold particles are used, the size of the particles can vary from about 3.0 nanometers to about 500 nanometers.
The redox active oxide may include, but is not limited to, cerium oxide, chromium oxide, cobalt oxide, copper oxide, cerium oxide, indium oxide, iron oxide, lead oxide, lithium cobalt oxide, lithium oxide, lithium titanate, lithium vanadium oxide. , manganese oxide, molybdenum oxide, cerium oxide, silver oxide, tin oxide, titanium oxide, tungsten oxide, vanadium oxide, zinc oxide, and mixtures thereof. Redox reactive oxynitrides that may be used include, but are not limited to, Li _7.9 MnN _3.2 O _1.6 And mixtures thereof.
The redox active additive for producing ion-conductive glass and glass ceramic-in-situ formed redox active species composite electrolyte may be a precursor solution of a redox active additive, a solution of a redox additive, and a redox activity addition. The form of the particles of the object. When particles of the redox active additive are used, the particle size of the redox active additive can vary from about 1 nanometer to a major particle size of about 100 nanometers.
The ion conductive glass and the glass ceramic - the redox active species composite electrolyte formed in situ can be obtained by melting a mixture of ion conductive glass and glass ceramics and a redox active additive. Alternatively, the ionically conductive glass and the glass ceramic, redox active additive composite electrolyte can be prepared by chemical properties that are separated within the microstructure.
The material to be used as the ion conductive glass and the glass ceramic may include, but is not limited to, an ion conductive glass and a glass ceramic itself, a mixture of raw materials suitable for producing an ion conductive glass and a glass ceramic, and an ion conductive glass and a glass ceramic. And a mixture of such materials. The amount of the ion conductive glass and the glass ceramic and the redox additive in the redox active species ion conductive glass and the glass ceramic electrolyte formed in situ can be widely changed. The amount of the redox additive present in the ion conductive glass or the glass ceramic electrolyte is sufficient to achieve an ion conductive glass or a glass ceramic redox additive composite electrolyte, and the ion conductive glass or glass ceramic redox additive composite electrolyte is used. Ionic glass or glass ceramics in the electrolyte have a larger ion current. Typically, the redox additive is present in an amount from about 0.01% to about 60% by weight of the ionically conductive ceramic, preferably from about 0.1% to about 25% by weight, more preferably about 10% by weight. The amount of % to about 20% by weight, more preferably about 5% by weight to about 20% by weight.
When ionic conductive glass or glass ceramic is Ag ⁺ When ceramics (for example, any Ag ⁺ Conductive sulfur-based compound glass and glass ceramic, Ag ⁺ Conductive Fluoride Glass and Glass Ceramic, Ag ⁺ Conductive oxide glass and glass ceramics and mixtures thereof), the amount of redox active additive used is sufficient to reach Ag ⁺ Conductive glass or glass ceramic - in situ formed redox additive composite electrolyte, the Ag ⁺ Conductive glass or glass ceramic - in situ formed redox additive composite electrolyte than Ag used in electrolytes ⁺ Conductive glass or glass ceramics have a larger ion current. Typically, the amount of redox active additive is from about 0.5% to about 40% by weight Ag ⁺ Conductive glass or glass ceramic.
When the ion conductive ceramic is F ^- Glass or glass ceramic (for example, any F ^- Conductive sulfur-based compound glass and glass ceramic, F ^- Conductive Fluoride Glass and Glass Ceramic, F ^- Conductive oxyfluoride glass and glass ceramics and mixtures thereof), the amount of redox active additive used is sufficient to achieve F ^- Conductive glass or glass ceramic - in situ formed redox additive composite electrolyte, the F ^- Conductive glass or glass ceramic - in situ formed redox additive composite electrolyte than used in electrolytes ^- Conductive glass or glass ceramics have greater ionic conductivity. Typically, the amount of redox active additive is from about 0.1% to about 50% by weight of F. ^- Conductive glass or glass ceramic.
When the ion conductive ceramic is H ⁺ Glass or glass ceramic (for example, any H ⁺ Conductive sulfur-based compound glass and glass ceramic, H ⁺ Conductive Fluoride Glass and Glass Ceramic, H ⁺ Conductive oxyfluoride glass and glass ceramics and mixtures thereof), the amount of redox active additive used is sufficient to reach H ⁺ Conductive glass or glass ceramic - in situ formed redox additive composite electrolyte, the H ⁺ Conductive glass or glass ceramic - in situ formed redox additive composite electrolyte than H used in electrolytes ⁺ Conductive glass or glass ceramics have greater ionic conductivity. Typically, the amount of redox active additive is from about 0.1% to about 50% by weight of H. ⁺ Conductive glass or glass ceramic.
When the ion conductive ceramic is Li ⁺ Glass or glass ceramic (for example, any Li ⁺ Conductive sulfur-based compound glass and glass ceramic, Li ⁺ Conductive Fluoride Glass and Glass Ceramic, Li ⁺ Conductive oxyfluoride glass and glass ceramics and mixtures thereof), the amount of redox active additive used is sufficient to achieve Li ⁺ Conductive glass or glass ceramic - in situ formed redox additive composite electrolyte, Li ⁺ Conductive glass or glass ceramic - in situ formed redox additive composite electrolyte than Li used in electrolytes ⁺ Conductive glass or glass ceramics have greater ionic conductivity. Typically, the amount of redox active additive is from about 0.1% to about 50% by weight of Li. ⁺ Conductive glass or glass ceramic.
When the ion conductive ceramic is Na ⁺ Glass or glass ceramic (for example, any Na ⁺ Conductive sulfur-based compound glass and glass ceramic, Na ⁺ Conductive Fluoride Glass and Glass Ceramic, Na ⁺ Conductive oxyfluoride glass and glass ceramics and mixtures thereof), the amount of redox active additive used is sufficient to reach Na ⁺ Conductive glass or glass ceramic - in situ formed redox additive composite electrolyte, the Na ⁺ Conductive glass or glass ceramic - in situ formed redox additive composite electrolyte than Na used in electrolytes ⁺ Conductive glass or glass ceramics have greater ionic conductivity. Typically, the amount of redox active additive is from about 0.1% to about 50% by weight Na ⁺ Conductive glass or glass ceramic.
When the ion conductive ceramic is O ^2- Glass or glass ceramic (for example, any O ^2- Conductive sulfur-based compound glass and glass ceramic, O ^2- Conductive fluoride glass and glass ceramic, O ^2- Conductive oxyfluoride glass and glass ceramics and mixtures thereof), the amount of redox active additive used is sufficient to achieve O ^2- Conductive glass or glass ceramic - in situ formed redox additive composite electrolyte, the O ^2- Conductive glass or glass ceramic - in situ formed redox additive composite electrolyte than used in electrolytes ^2- Conductive glass or glass ceramics have greater ionic conductivity. Typically, the amount of redox active additive is from about 0.1% to about 50% by weight of O ^2- Conductive glass or glass ceramic.
ION conductive glass redox active additive composite electrolyte manufacturing:
In general, the ionically conductive glass redox additive composite electrolyte may comprise from a redox active additive, one or more glass former oxides, optionally a glass modifier oxide, and at least one act as a conductive ion ( For example but not limited to one or more Ag ⁺ , F ^- , H ⁺ , K ⁺ Li ⁺ , Mg ²⁺ Na ⁺ And O ^2- ) is prepared from a mixture of oxides of the source. The mixture is then melted and cooled to form an ion conductive glass redox additive composite electrolyte. Alternatively, the ion conductive glass redox additive composite electrolyte can be added to a glass containing a redox active additive by adding an oxide as a source of conductive ions (for example, an oxide glass, a sulfur-based compound glass, Made from a melt of phosphate glass and its mixture). Alternatively, the ion-conducting glass redox additive composite electrolyte can also be prepared by adding a redox active additive to the ground ion-conducting glass.
Li ⁺ Manufacture of conductive yttrium phosphate glass ceramic redox active composite electrolyte:
Will Li ⁺ Precursor material (such as Li ₂ CO ₃ ), phosphate precursor (NH ₄ H ₂ PO ₄ ), as needed glass modifier (Al ₂ O ₃ And glass former (Ge ₂ O ₃ The composition formed by the mixture is ground to produce a ground powder. The ground powder can be calcined at about 750 degrees Celsius to about 850 degrees Celsius for about 30 minutes to about 60 minutes to produce a calcined material. The calcined material can be ground again to produce a ground material. The ground material can be melted from about 1200 degrees Celsius to about 1400 degrees Celsius for about 2 hours to about 4 hours to produce a melt. The melt may be quenched by casting onto an electric roller at about 1400 degrees Celsius to about 1100 degrees Celsius to form a glass sheet. The glass sheet is then optionally annealed at about 450 degrees Celsius to about 550 degrees Celsius for about 1 hour to about 3 hours, and then cooled to room temperature at a rate of about 1 degree Celsius per minute to about 2 degrees Celsius per minute to produce Cooled Li ⁺ Conductive yttrium phosphate glass sheet.
Li can be ⁺ The conductive barium phosphate glass is crushed, ground, and mixed with from about 0.1% to about 40% by weight of the redox active additive, and ball milled in a lower alkanol such as ethanol to produce a ground slurry. The ground slurry can be passed through a 300-mesh screen to produce a screened slurry that is dried at about 80 degrees Celsius to about 120 degrees Celsius to form a ground powder. The ground powder is mixed with from about 5% by weight to about 20% by weight of the binder and up to about 5% by weight of the plasticizer (all amounts are based on the weight of the ground powder) to form a bond A powder-powder mixture is mixed with a solvent mixture (e.g., 50/50 methyl ethyl ketone/ethanol) to form a slurry that can be cast onto the belt. Adhesives that can be used include, but are not limited to, polyvinyl butyral, poly(propylene carbonate), polyvinyl alcohol, and mixtures thereof. Plasticizers that can be used include, but are not limited to, dioctyl phthalate, butyl benzyl phthalate, propylene carbonate, and mixtures thereof. The cast strip can be formed, for example, by screen printing a thick film conductive ink (e.g., platinum, gold or palladium, silver) onto the strip. The resulting print ribbon can then be aligned, for example, in an isostatic pressure of from about 50 degrees Celsius to about 80 degrees Celsius, from about 3000 pounds per square inch to about 4000 pounds per square inch, and laminated for about 10 minutes to about 30 seconds. Minutes to produce a green laminate. The green laminate is burned at about 800 degrees Celsius to about 1000 degrees Celsius for about 1 hour to about 12 hours to form a ceramic redox additive composite electrolyte.
Example LGC1: Lithium phosphate bismuth glass tin dioxide composite electrolyte:
Will 3.74 g Li ₂ CO ₃ , 27.92 grams of NH ₄ H ₂ PO ₄ , 1.04 grams of Al ₂ O ₃ , 14.81 g Ge ₂ O ₃ And 5.42 grams of SnO ₂ The composition formed by the mixture is ground to produce a ground powder. The ground powder was calcined at 750 degrees Celsius for 30 minutes to produce a calcined material. The calcined material was again ground for 24 hours to produce a ground material. The ground material was heated at 1350 degrees Celsius for 2 hours to produce a melt. The melt was quenched by casting on a motorized roller at 1300 ° C to form a glass sheet. The glass sheet was heated at 450 degrees Celsius for 1 hour and cooled to room temperature at a rate of 1 degree Celsius per minute to produce a cooled glass sheet. The cooled glass sheet was heat treated at 850 ° C for 2 hours to form Li ⁺ A conductive lithium aluminum phosphide glass ceramic in which a redox active tin dioxide phase is formed.
Example LGC2:
Will be 1.53g Li ₂ CO ₃ , 11.44 grams of NH ₄ H ₂ PO ₄ , 0.42 g of Al ₂ O ₃ , 6.07 g Ge ₂ O ₃ And 5.00 grams of HAuCl ₄ ‧3H ₂ The composition formed by the mixture of O is ground to produce a ground powder. The ground powder was calcined at 750 degrees Celsius for 30 minutes to produce a calcined material. The calcined material was again ground for 24 hours to produce a ground material. The ground material was heated at 1350 degrees Celsius for 2 hours to produce a melt. The melt was quenched by casting on a motorized roller at 1300 ° C to form a glass sheet. The glass sheet was heated at 450 degrees Celsius for 1 hour and cooled to room temperature at a rate of 1 degree Celsius per minute to produce a cooled glass sheet. The cooled glass sheet was heat treated at 950 ° C for 2 hours to form Li ⁺ Conductive lithium aluminum strontium phosphate glass ceramic in which the redox active nanoparticle is dispersed.
Manufacture of ion conductive ceramic redox additive composite electrolyte:
The ionically conductive ceramic redox additive composite electrolyte can be prepared by forming a mixture of one or more ionically conductive ceramic materials and one or more redox active ceramic additives. The mixture is ground, dried and burned to form an ion conductive ceramic redox additive composite electrolyte. The mixtures used may be random, identical, non-identical or hierarchical by their thickness. The redox active additive used with the ion conductive ceramic material is selected based on its ability to undergo redox reactions with ionic conductive species in the ceramic material. For the sake of explanation, when the ion conductive ceramic is Li ⁺ In the case of conductive ceramics (for example, (LiLa)TiO ₃ The redox active ceramic additive is selected based on its ability to undergo a redox reaction with Li. Li ⁺ Conductive ceramics (which can be used to make Li ⁺ Conductive ceramic redox additive composite electrolyte) including but not limited to Li ⁺ Conductive pomegranate ceramics (such as but not limited to Li ₇ La ₃ Zr ₂ O ₁₂ Li ₅ La ₃ M ₂ O ₁₂ (where M = Ta, Nb)); Lithium superionic conductor (LISICON) type ceramics (such as but not limited to Li ₁₄ ZnGe ₄ O ₁₆ Li _3.4 Si _0.4 P _0.6 S ₄ ); Li ₃ PO ₄ Based ceramics (such as but not limited to Li ₂ Ge ₂ (PO ₄ ) ₃ And Li _1+x Ti _2-x M _x (PO ₄ ) ₃ (where M = Al, Ga, In, Sc)); binary nitride (such as but not limited to Li ₃ N) and lithium salts (such as but not limited to Li ₄ SiO ₄ ) and mixtures thereof.
Can be combined with ion conductive ceramics (such as Li ⁺ Redox active additives used together with conductive ceramics include, but are not limited to, LiMn ₂ O ₄ LiCoO ₂ LiNiO ₂ LiFeO ₂ Li _x (Co _y Al _1-y ) _(1-x) O ₂ (where 0 < x < 1, 0 < y < 1) and mixtures thereof.
A mixture of ionically conductive ceramic material and redox active ceramic additive can be ball milled in a suitable liquid such as ethanol, water, acetone or a mixture thereof to produce a ground powder. Mixing the ground powder with up to about 5% by weight of a binder such as polyvinyl butyral, polyvinyl alcohol, polymethyl methacrylate, polyoxyethylene, and mixtures thereof to form a binder - a powder mixture. The binder-powder mixture can be compressed under uniaxial pressure and then compressed in isostatic pressing to produce a subsequent combustible crucible. Further, according to one option, the ground powder is added with from about 5% by weight to about 50% by weight of the binder and, if desired, up to about 5% by weight of the plasticizer (all amounts are based on the weight of the ground powder) The base is mixed to form a binder-powder mixture which is mixed with a solvent mixture (e.g., a solvent mixture of 50/50 methyl ethyl ketone/ethanol) to form a slurry that can be cast into the belt. Adhesives that can be used include, but are not limited to, polyvinyl butyral, poly(propylene carbonate), poly(oxyethylene), and mixtures thereof. Plasticizers that can be used include, but are not limited to, dioctyl phthalate, butyl benzyl phthalate, and mixtures thereof. The cast strip can then be formed by screen printing a thick film conductive ink (e.g., platinum, palladium or silver) onto the strip. The resulting print ribbon can then be aligned and laminated for 10 minutes to about 30 minutes, for example, at an isostatic pressure of from about 50 degrees Celsius to about 80 degrees Celsius, from about 3000 pounds per square inch to about 4000 pounds per square inch. To produce a green laminate. The green laminate is burned at about 1150 degrees Celsius to about 700 degrees Celsius for about 1 hour to about 4 hours to form a ceramic redox additive composite electrolyte. Alternatively, the green ribbon can be used in an unburned state as a ceramic polymer redox additive composite electrolyte.
The composite electrolyte of each of the specific examples can be formed by sputtering, evaporation or screen printing. Examples of metals that can be used as electrodes include aluminum, silver, platinum, alloys thereof, and mixtures thereof. The electrode can be redox active.
Example LC1: (Li _0.33 La _0.55 TiO _3-δ Ceramic-LiCoO ₂ Redox composite electrolyte
Will be 96.644g La ₂ O ₃ 59.900 g TiO ₂ And 9.145 grams of LiCO ₃ The mixture was ball milled in ethanol for 24 hours to produce a slurry. The slurry was dried at 80 ° C for 8 hours to form a dry powder. The dried powder was calcined at 900 ° C for 6 hours to produce a calcined powder. The calcined powder was ball milled in ethanol for 16 hours, dried at 80 degrees Celsius for 24 hours, and calcined at 1100 degrees Celsius for 6 hours to produce (Li _0.33 La _0.55 TiO _3-δ Electrolyte powder.
Will (Li _0.33 La _0.55 TiO _3-δ Electrolyte powder with 10% by weight of LiCoO ₂ (based on the weight of the electrolyte powder) by ball milling in ethanol for 24 hours to produce (Li _0.33 La _0.55 TiO _3-δ Ceramic-LiCoO ₂ A mixed ground powder of a redox composite electrolyte. The mixed ground powder was dried at 80 ° C for 8 hours, and compressed into pellets under a uniaxial pressure of 200 MPa, and then pressed in a cold isostatic pressing at 250 MPa.
Example LC2: (Li _0.33 La _0.55 TiO _3-δ Ceramic-MoO ₃ Redox composite electrolyte
Will be 96.644g La ₂ O ₃ 59.900 g TiO ₂ And 9.145 grams of LiCO ₃ The mixture was ball milled in ethanol for 24 hours to produce a slurry. The slurry was dried at 80 ° C for 8 hours to form a dry powder. The dried powder was calcined at 900 ° C for 6 hours to produce a calcined powder. The calcined powder was ball milled in ethanol for 16 hours, dried at 80 degrees Celsius for 24 hours, and calcined at 1100 degrees Celsius for 6 hours to produce (Li _0.33 La _0.55 TiO _3-δ Electrolyte powder.
Will (Li _0.33 La _0.55 TiO _3-δ The electrolyte powder was ball-milled with 10% by weight of 100 nm-sized molybdenum trioxide (based on the weight of the electrolyte powder) in ethanol for 24 hours, dried at 80 ° C for 8 hours, and compressed into pellets under a uniaxial pressure of 200 MPa. And then cold isostatic compression at 250 MPa.
Example LC3: Li ₇ La ₃ Zr ₂ O ₁₂ Ceramic-LiCoO ₂ Redox composite electrolyte
Will 29.32g La ₂ O ₃ , 17.069 grams of Li ₂ CO ₃ And 14.786 grams of ZrO ₂ By with ZrO ₂ The balls were ball milled in 2-propanol for 24 hours to mix to produce a slurry. The slurry was dried, and the resulting dry powder was calcined at 900 ° C for 6 hours. The calcined powder was ground, dried, and calcined at 1100 ° C for 6 hours to obtain Li ₇ La ₃ Zr ₂ O ₁₂ Ceramic electrolyte.
Will Li ₇ La ₃ Zr ₂ O ₁₂ Ceramic electrolyte with 10% by weight of LiCoO ₂ (Based on the weight of the electrolyte powder), ball milling in ethanol for 24 hours to produce Li ₇ La ₃ Zr ₂ O ₁₂ Ceramic-LiCoO ₂ A mixed ground powder of a redox composite electrolyte. The mixed ground powder was dried at 80 ° C for 8 hours, and compressed into pellets under a uniaxial pressure of 200 MPa, and then pressed in a cold isostatic pressing at 250 MPa.
The redox active additive composite electrolyte using a redox active additive (such as in the form of particulate inclusions disclosed herein) can be used in various devices with different electrochemical compositions, such as, but not limited to, energy storage devices. , lithium ion mixed composite film, gas barrier film, film for hydrogen isolation, film for water desalination, potentiometric chemical sensor and electrochromic device.
Examples of energy storage devices that may use redox active additives include, but are not limited to, batteries, capacitors, hybrid battery-capacitors, and fuel cells. Examples of batteries that can use redox active additive composite electrolytes include, but are not limited to, metal-air batteries (such as, but not limited to, lithium-air batteries and magnesium-air metal-air batteries); primary batteries (eg, but Not limited to lithium ion type primary batteries and magnesium ion type primary batteries; secondary batteries (such as, but not limited to, lithium ion type secondary batteries, proton ion type secondary batteries, and magnesium ion type secondary batteries); high temperature batteries (for example) But not limited to Na-S type high temperature battery and LiZr ₂ (PO ₄ ) ₃ (LiZP) type high temperature battery). Examples of capacitors that can use redox active additive composite electrolytes include, but are not limited to, electrochemical capacitors, proton capacitors (such as, but not limited to, potassium hydroxide proton capacitors and phosphoric acid proton type capacitors); lithium ion capacitors ( For example, but not limited to, a polyvinylidene fluoride lithium ion type capacitor (wherein the lithium salt is LiPF) ₆ LiClO ₄ , LiTFSi salt)); poly(oxyethylene) lithium ion type capacitor (wherein the lithium salt is, for example, LiCl, LiBr, LiClO ₄ Salt); high temperature capacitors (such as, but not limited to, LAGP glass-ceramic high-temperature capacitors and sulfur-based high-temperature capacitors). Examples of hybrid battery-capacitors that can use redox active additive composite electrolytes include, but are not limited to, lithium ion hybrid battery-capacitors. Examples of fuel cells that can use redox active additive composite electrolytes, including but not limited to ZrO ₂ Based on solid oxide fuel cells.
Examples of the lithium ion mixed composite film which can use the redox active additive composite electrolyte include, but are not limited to, a lithium metal/PVDF/carbon mixed composite film and a lithium iron phosphate mixed type composite film.
Examples of gas barrier films that can use redox active additive composite electrolytes include, but are not limited to, vanadium (LSV, La _0.7 Sr _0.3 VO ₃ ) / yttria-stabilized zirconium dioxide (YSZ) composite electrolyte type gas barrier film and ruthenium vanadium / antimony doped ruthenium dioxide (GDC) type gas barrier film.
Examples of potentiometric chemical sensors that can use redox active additive composite electrolytes include, but are not limited to, manganese dioxide doped lithium borosilicate glass type potentiometric chemical sensors.
Examples of electrochromic devices that can use redox active additive composite electrolytes include, but are not limited to, devices that employ PVDF-HFP electrolytes having one or more oxide fillers such as molybdenum trioxide and vanadium pentoxide.
Lithium-air battery using redox active composite electrolyte:
A lithium-air battery using a redox active additive composite electrolyte is disclosed in a first embodiment. A lithium-air battery as shown in Fig. 22 uses a lithium anode which is electrochemically coupled to an oxidizing environment, for example, by an air cathode. At the time of discharge, a lithium ion current from the lithium anode through the redox active additive composite electrolyte is combined with oxygen at the cathode to form Li ₂ O or Li ₂ O ₂ . The lithium ion stream is coupled to the flow of electrons from the anode to the cathode through an external load loop. A lithium-air battery using a redox active additive composite electrolyte can exhibit improved ion current and coulombic efficiency compared to a lithium-air battery that does not use a redox active additive composite electrolyte.
Many lithium-air battery structures can be formed with the use of redox active additive composite electrolytes. The lithium-air battery structure uses a redox active additive composite electrolyte comprising one or more redox active additives and any glass electrolyte, ceramic electrolyte, glass ceramic electrolyte, and mixtures thereof. Examples of redox active additives that may be used include, but are not limited to, ferric oxide, molybdenum trioxide, tin oxide zinc oxide, gold, platinum, and mixtures thereof.
Examples of ceramic electrolytes that can be used in the redox active additive composite electrolyte include, but are not limited to, (Li, La) TiO ₃ (LLTO) type ceramic electrolyte (for example, Li _3x La _{(2/3)-x□(1/3)-2x} TiO ₃ , where □ represents the vacancy position, and where 0<x<0.16)), ((Li, La)(Ti, Zr, Hf))O ₃ And mixtures thereof to impart improved ion exchange numbers. ((Li, La)(Ti,Zr,Hf))O ₃ Type materials are made from standard solid state procedures.
The ionically conductive ceramic redox additive composite electrolyte can be prepared by forming a mixture of one or more ionically conductive ceramic materials and one or more redox active ceramic additives. The mixture is ground, dried and burned to form an ion conductive ceramic redox additive composite electrolyte. As noted above, the mixture may be random, identical, non-identical or graded by its thickness.
Examples of glass electrolytes that can be used in the redox active additive composite electrolyte include, but are not limited to, lithium phosphate glass such as, but not limited to, Li(AlGeTi) (PO) ₄ ) ₃ Li _1+x Al _x Ge _2-x (PO ₄ ) ₃ (where 0<x<1.0), Li(AlGeTi,Hf)(PO ₄ ) ₃ And mixtures thereof. Lithium aluminum bismuth phosphate (LAGP) glass can be derived from lithium ion precursor materials (eg Li ₂ CO ₃ ), phosphate precursors (such as NH ₄ H ₂ (PO ₄ )), Al ₂ O ₃ As a glass modifier and glass former (such as Ge ₂ O ₃ Formed by a mixture of ). The mixture is ground to form a ground powder. The ground powder can be calcined at about 750 degrees Celsius to about 850 degrees Celsius for about 30 minutes to about 60 minutes to produce a calcined material. The calcined material can be ground again to produce a ground material. The ground material can be melted from about 1100 degrees Celsius to about 1200 degrees Celsius for about 2 hours to about 4 hours to produce a melt. The melt may be quenched by casting onto an electric roller at about 1400 degrees Celsius to about 1100 degrees Celsius to form a glass sheet. The glass sheet is then optionally annealed at about 450 degrees Celsius to about 550 degrees Celsius for about 1 hour to about 3 hours, and then cooled to room temperature at a rate of about 1 degree Celsius per minute to about 2 degrees Celsius per minute to produce Cooled Li ⁺ Conductive yttrium phosphate glass sheet. Li can be ⁺ The conductive barium phosphate glass is crushed, ground, and mixed with from about 0.1% to about 40% by weight of the redox active additive, and ball milled in a lower alkanol such as ethanol to produce a ground slurry. The ground slurry can be passed through a 300-mesh screen to produce a screened slurry that is dried at about 80 degrees Celsius to about 120 degrees Celsius to form a ground powder.
The ground powder is mixed with from about 5% by weight to about 20% by weight of the binder and up to about 5% by weight of the plasticizer (all amounts are based on the weight of the ground powder) to form a bond A powder-powder mixture is mixed with a solvent mixture (e.g., 50/50 methyl ethyl ketone/ethanol) to form a slurry that can be cast onto the belt. Adhesives that can be used include, but are not limited to, polyvinyl butyral, poly(propylene carbonate), polyvinyl alcohol, and mixtures thereof. Plasticizers that can be used include, but are not limited to, dioctyl phthalate, butyl benzyl phthalate, propylene carbonate, and mixtures thereof.
The cast strip can be formed, for example, by screen printing a thick film conductive ink (e.g., platinum, gold or palladium, silver) onto the strip. The resulting electrode strip can then be aligned, for example, in an isostatic pressure of from about 50 degrees Celsius to about 80 degrees Celsius, from about 3000 pounds per square inch to about 4000 pounds per square inch, and laminated for about 10 minutes to about 30 minutes. Minutes to produce a green laminate. The green laminate is burned at about 800 degrees Celsius to about 1000 degrees Celsius for about 1 hour to about 12 hours to form a ceramic redox additive composite electrolyte.
Examples of sulfur-based compound glass electrolytes that can be used include, but are not limited to, Li-sulfides, such as Li ₂ SP ₂ S ₅ . Examples of glass ceramic electrolytes that can be used include, but are not limited to, 70Li ₂ S-30P ₂ S ₅ . 70Li ₂ S-30P ₂ S ₅ Glass ceramic electrolyte can be obtained by reagent grade Li ₂ S and P ₂ S ₅ With 70Li ₂ S/30P ₂ S ₅ A mixture of molar ratios is obtained by ball milling and forms an amorphous material. The amorphous material is heated to 200-300 degrees Celsius for 2 hours to form a glass ceramic.
A lithium-air battery using a redox active composite electrode is further illustrated by the following non-limiting examples:
Example LA1:
The composite electrolyte of the example LGC2 was used in a lithium-air battery configuration. A lithium foil (200 micrometers thick) was used as the anode, and a platinum coated carbon foil was used as the cathode. An example LGC2 having an electrolyte thickness of 200 microns and a diameter of 10 mm was embedded between the anode and the cathode to form a lithium-air battery in the form of a coin cell having a mesh-like hole on the cathode side to allow air to flow. The anode is isolated from the interaction of air using high temperature wax.
Manufacture of lithium-air batteries using redox active composite electrolytes:
A lithium-air battery using a redox active additive composite electrolyte can be placed in a lithium foil as an anode and a carbon layer as a cathode by a redox active additive composite glass ceramic electrolyte film (for example, a LAGP glass ceramic electrolyte film) Formed between.
A redox active additive for a lithium-air battery The glass ceramic electrolyte composite film can be produced by a number of methods such as casting and extrusion. For example, a frit of a redox active additive composite ceramic electrolyte, a redox active additive-doped ceramic glass electrolyte or a mixture thereof may be mixed with a liquid carrier (for example, water, a lower alkanol or a mixture thereof) to form a band. The body is formed into a slurry. The cast formed strip is then dried and formed into a strip. The multilayer film can be produced by forming a laminated board of two or more cast strips containing a redox active additive composite electrolyte, and heat treating the laminated board. For purposes of illustration, two or more layers may comprise one or more redox active additives and glass frits (eg, lithium-ceramics, such as (LiLa) TiO. ₃ The composition is screen printed on a ceramic strip or crystal stone and stacked to form a multilayer structure which can then be heat treated, for example by hot pressing and sintering procedures to densify the laminated sheet.
A lithium ion type primary battery and a secondary battery using a redox active additive composite electrolyte:
In another specific embodiment, a lithium ion primary battery and a lithium ion secondary battery using a redox active additive lithium ion conductive composite electrolyte are disclosed. A lithium ion battery comprising a redox active additive composite electrolyte can be used to support devices that require severe, high current requirements (such as digital cameras) and can replace alkaline batteries. These types of batteries can be used in portable consumer electronic devices such as, but not limited to, implantable electronic medical devices such as artificial rhythms, clocks, camcorders, digital cameras, thermometers, computers, laptops. Basic input/output system, communication equipment and remote control car lock.
A lithium ion battery using a redox active additive composite electrolyte can be used in various configurations, for example, a 3 volt "coin" type lithium manganese battery, which is usually about 20 mm in diameter and has a thickness of about 1.6 mm to about 4 mm. .
A lithium ion primary battery and a secondary battery using a redox active composite electrode are further described with reference to the following non-limiting examples:
Example LP1:
The film of Example P1 was used in a Lithium-ion Primary Battery. The battery comprises a lithium metal anode and a manganese dioxide cathode. The battery is assembled into a coin battery architecture. The manganese dioxide powder is mixed with acetylene black and Teflon binder at a mass ratio of 85:5:10. This mixture was formed into a paste and rolled to a thickness of 100 μm. A circle having a diameter of 0.635 inch was punched out from the rolling paste and dried under vacuum for 24 hours to form a cathode electrode. The cathode electrode is transferred to a glove box where it is placed into the coin cell housing. Add a few drops of electrolyte to the cathode electrode (EC: DMC (50:50 weight), 1M LiPF ₆ ). The film of Example P1 was immersed in this electrolyte and placed over the cathode. Finally, a lithium anode was placed over the film by pressing the lithium metal onto a copper current collector to form an anode having a thickness of 40 microns. The coin cell is then folded to form a lithium ion galvanic cell.
Example LS1 (Lithium Ion Secondary Battery):
Follow the procedure of example LP1 (except with LiCoO ₂ To replace manganese dioxide as a cathode material).
Example LS2 (Lithium Ion Secondary Battery):
The procedure of Example LP1 was followed (in addition to replacing manganese dioxide as a cathode material with lithium manganese oxide).
Example LS3 (Lithium Ion Secondary Battery):
Follow the procedure of example LP1 (except with LiFePO ₄ To replace manganese dioxide as a cathode material).
A lithium ion primary battery using a redox active additive lithium ion conductive composite electrolyte:
A lithium primary battery using a redox active additive lithium ion conductive composite electrolyte uses an anode including one or more of lithium metal and a lithium compound, and includes a film of a redox active additive lithium conductive composite electrolyte, and includes a cathode of manganese dioxide, molybdenum trioxide, and a mixture thereof; wherein the lithium compound is such as a lithium halide (such as lithium sulfoxide, lithium bromide, lithium iodide, and mixtures thereof), lithium/sulfur dioxide (Li-SO) ₂ ) and mixtures thereof.
A lithium ion primary battery using a film containing a redox active additive lithium ion conductive composite electrolyte can exhibit a larger power density than a lithium ion primary battery not using a lithium ion conductive composite electrolyte. For example, an anode of a lithium metal, a cathode of manganese dioxide, and a film containing a redox active additive and a composite electrolyte using molybdenum trioxide as a redox active additive and using PVDF HFP as an electrolyte are used. Lithium/manganese dioxide primary cells exhibit enhanced power density and specific permittivity.
An electrolyte for use with a redox active additive for a redox active additive composite electrolyte in a lithium primary battery includes, but is not limited to, lithium perchlorate in propylene carbonate; tetrachloroethylene in sulfite dichloride Lithium aluminate; lithium bromide in a mixture of sulfur dioxide and propionitrile; lithium tetrafluoroborate in propylene carbonate; lithium tetrafluoroborate in dimethoxyethane; tetrafluoro in γ-butyrolactone Lithium borate; organic charge transfer complex, for example, poly-2-vinyl pyridine (P ₂ VP); lithium hexafluorophosphate in a mixture of propylene carbonate and dimethoxyethane; lithium hexafluoroarsenate in a mixture of propylene carbonate and dimethoxyethane; and mixtures thereof.
The redox active additive for the redox active additive composite electrolyte used in the lithium primary battery includes, but is not limited to, molybdenum trioxide (MoO) ₃ ), gold (Au), platinum (Pt), SiO _1-x (where 0.1<x<1.5), manganese dioxide (MnO) ₂ ), ferrous oxide (FeO), and mixtures thereof. The redox active additives used are in the form of granules, fine rods, mesh and rods, and combinations thereof. The redox active additives may be in contact with each other in the electrolyte or may be isolated from each other. The amount of the redox active additive in the redox active additive composite electrolyte used in the lithium primary battery is sufficient to achieve high energy density and high power density. The amount of redox active additive can range from about 0.05% to about 50% by weight of the electrolyte.
A lithium ion galvanic cell using a redox active additive composite electrolyte can be made by the method described in US 2009/0123844, the teachings of which are hereby incorporated by reference in its entirety.
A lithium ion secondary battery using a redox active additive lithium ion conductive composite electrolyte:
In another embodiment, a lithium ion secondary battery comprising an anode, a cathode, and a redox active additive composite electrolyte is disclosed. A lithium ion secondary battery system using a redox active additive composite electrolyte can be used in various consumer electronic products and electric vehicles. Compared with a lithium ion secondary battery that does not use a redox active additive composite electrolyte, a lithium ion secondary battery system using a redox active additive composite electrolyte exhibits a much higher energy density, enhanced coulomb effect and improvement Its anti-attenuation effect and self-discharge that is reduced when not in use.
The polymerizable electrolyte used in the redox active additive composite electrolyte used for the lithium ion secondary battery includes, but is not limited to, PVDF, PEO, and a mixture thereof. The redox active additive used in the redox active additive composite electrolyte used in the lithium ion secondary battery includes, but is not limited to, MnO ₃ , FeO, Fe ₂ O ₃ V ₂ O ₅ , SnO ₂ , Au, Pt and mixtures thereof. The amount of redox active additive may be present in an amount from about 0.05% to about 50% by weight, preferably from about 1% to about 10% by weight, based on the weight of the electrolyte.
Materials which can be used as anodes in lithium ion secondary batteries include, but are not limited to, lithium, lithiated carbon, lithium titanate (Li-titanate), and mixtures thereof. The material used for the cathode used in the lithium ion secondary battery using the redox active additive composite electrolyte includes, but is not limited to, carbon, LiCoO _3-x (where 0<x<1), LiFePO _4-y (where 0 < y < 1) and mixtures thereof. A lithium ion secondary battery system using a redox active additive composite electrolyte can be obtained by a method as disclosed in U.S. Patent Publication No. 2010/0129719, the entire disclosure of which is incorporated herein by reference.
High temperature batteries and high temperature capacitors using a redox active additive composite electrolyte:
In another embodiment, a high temperature battery and a high temperature capacitor (e.g., a high temperature supercapacitor that operates generally at about 20 degrees Celsius to about 250 degrees Celsius and uses a redox active additive composite electrolyte) is disclosed. High temperature batteries and capacitors using redox active additive glass-ceramic composite electrolytes can withstand higher voltages and/or currents to achieve energy density compared to high temperature batteries and capacitors that do not use redox active additive composite electrolytes With increased power density.
The redox active additive composite electrolyte which can be used for a high temperature battery and a capacitor includes, but is not limited to, a redox active additive glass ceramic composite electrolyte. The thickness of the redox active additive glass ceramic composite electrolyte for a high temperature battery or a high temperature capacitor may vary from about 1 cm to about 1.0 μm.
The glass ceramic electrolyte that can be used with the redox active additive for use in high temperature batteries and high temperature capacitors includes, but is not limited to, a LAGP-based glass ceramic (for example, LiAlGe-phosphate glass ceramic), a tantalum-based glass ceramic (for example, Li). ₂ SP ₂ O ₅ -TeO ₂ ), a glass-ceramic of a selenium base (for example, a chalcogenide glass ceramic such as Li) ₂ SP ₂ S ₅ And mixtures thereof).
Redox active additives that can be used with glass ceramic electrolytes for use in high temperature batteries include, but are not limited to, platinum, gold, molybdenum trioxide, tungsten oxide, tin dioxide, lithium titanium oxide, and mixtures thereof.
Manufacturing of high temperature batteries and capacitors:
The cathode and anode electrodes used in the high temperature battery and capacitor using the redox active additive composite electrolyte are screen printed onto the redox active additive ceramic glass composite. The electrodes can be screen printed, for example in the form of an organic ink, in the form of a thick film frit, or a combination thereof. The electrodes can also be deposited as a thin film, for example by chemical vapor deposition.
The redox active additive composite electrolyte film used in a high temperature battery and a capacitor is formed by laminating a stack of cast tapes formed by a redox active additive composite electrolyte slurry. The surface area of the electrolyte is increased by the addition of a fugitive material to the top and bottom layers of the stack. Short-acting promoter materials include, but are not limited to, carbon, starch, and mixtures thereof. The fugitive catalyz material can be added to the slurry used to form the top and bottom layers of the stack. During the heat treatment, the fugitive chemist material is vaporized to produce increased porosity to enhance the bonding of the electrode to the redox active additive composite electrolyte film.
The anode material can be formed on the porous surface of the redox active additive composite electrolyte membrane by placing the anode material in contact with the porous surface of the composite electrolyte membrane and then heating the anode material to above the melting point thereof, wherein the anode material is formed on the porous surface of the redox active additive composite electrolyte membrane. For example, lithium metal, lithium glass (such as LAGP), glass frit of lithium glass (such as LiBO borate), and mixtures thereof. The molten anode material will then flow into and bond with the porous surface of the composite electrolyte membrane. Similarly, lithium-containing cathodes (such as LiCoO) ₃ LiFePO ₄ And a mixture thereof may be formed on a porous surface of an electrolyte such as a ceramic glass electrolyte.
High temperature supercapacitors:
In another embodiment, a high temperature supercapacitor that can operate at about 50 degrees Celsius to about 400 degrees Celsius is disclosed. The high temperature supercapacitor uses a redox active additive composite electrolyte, a cathode mixture and an anode, wherein the cathode mixture comprises an electrode blocking metal powder and a lithium glass frit, and the anode is made of carbon, lithium metal, LiTiO, and The mixture is formed. The glass ceramic electrolyte that can be used with the redox active additive in the redox active additive composite electrolyte includes, but is not limited to, a LAGP-based glass ceramic, a selenium sulfide based glass ceramic, a bismuth glass ceramic, and mixtures thereof. Useful LAGP-based glass ceramics include, but are not limited to, LiAlGe-phosphate glass, LiAlGeTi-phosphate glass, and mixtures thereof. Selenium sulfide glass ceramics that can be used include, but are not limited to, Li ₂ SP ₂ S ₅ .
Redox active additives useful for redox active additive glass ceramic composite electrolytes include, but are not limited to, molybdenum trioxide, manganese dioxide, titanium sulfide, lithium sulfide, and mixtures thereof. In general, the amount of redox active additive is between about 0.05% and about 50% by weight based on the weight of the glass ceramic electrolyte.
The barrier metal powder used in the cathode mixture includes, but is not limited to, nickel, copper, tungsten, rhenium, ruthenium, iron-chromium-nickel, and alloys and mixtures thereof. The glass frit of lithium glass used in the cathode mixture includes, but is not limited to, lithium-borate. The amount of the barrier metal present in the cathode mixture is between 40% and about 95% by weight based on the weight of the glass frit of the lithium glass. Carbon additions such as stone milling and carbon black can also be added to the cathode mixture to reduce oxidation during heat treatment. When a carbon additive is used in the cathode mixture, the amount of the additive is between about 1% by weight and about 10% by weight based on the combined weight of the metal and the glass frit. Blocking the mixture of metal and frit (adding carbon additives as needed) in a controlled environment for heating, such as N ₂ -H ₂ Or argon to minimize oxidation.
A high temperature supercapacitor system using a redox active additive composite electrolyte can be made according to the procedures set forth in US 2009/0214957 and US 2010/001095, the teachings of which are hereby incorporated by reference in its entirety. A high temperature supercapacitor using a redox active additive composite electrolyte is further illustrated by the following non-limiting examples.
Example LG1: Li ⁺ Conductive LAGP-Au redox additive composite electrolyte
Mixing the metering component in ethanol by ball milling ₂ CO ₃ Al ₂ O ₃ Ge ₂ O ₃ With H ₄ H ₂ PO ₄ . The mixture was dried, ground to a powder, and then calcined at 750 ° C for 1 hour. The synthesized powder was reground to produce an abrasive powder. The ground powder was melted at 1300 ° C for 2 hours. The melt is quenched by casting onto an electric reel to form a glass sheet. The glass sheet was annealed at 500 ° C for 1 hour and then cooled to room temperature at a rate of 1 ° C/min to produce Li. ⁺ Conductive LAGP. LAGP glass is crushed, ground, and mixed with 5% by weight of gold redox active additive gold, and then ball milled in ethanol; ground powder and 5% by weight of polyvinyl butyral binder and 1% by weight The dibutyl phthalate plasticizer is mixed in ethanol to form a slurry which is cast to form a belt. The cast strip system was burned at 850 degrees Celsius for 4 hours to form a redox additive complex.
Example LG2: Li ⁺ Conductive LAGP-SnO ₂ Redox additive composite electrolyte
Also use the above procedure for instance LG1, except for SnO ₂ Replace Au.
Mixed battery-capacitor with redox active additive composite electrolyte:
In another embodiment, a hybrid battery capacitor, such as a Li-plug-in battery-capacitor, using a redox active additive composite electrolyte membrane is disclosed. A hybrid battery capacitor using a film containing a redox active additive composite electrolyte (for example, any one or more of a redox active additive composite polymer electrolyte and a redox active additive glass ceramic electrolyte) can be used in a short period of time It is charged, discharged in a short period of time, and can exhibit better energy storage and power density than conventional supercapacitors or batteries.
A hybrid battery capacitor using a film containing a redox active additive composite electrolyte exhibits a very fast initial discharge rate characteristic of the capacitor followed by a relatively slow discharge rate of the battery. The voltage output of the hybrid battery capacitor device using the redox active additive composite electrolyte varies from about 1 V to about 7 V, preferably from about 1 V to about 5.5 V.
The hybrid battery-capacitor shown in Figures 1A and 1B comprises a continuous anode, a multi-section cathode, and an intermediate redox active additive composite electrolyte. The electrolyte contacts both the anode and the multi-section cathode. The anode contains a source of lithium ions and is a reversible redox reaction. The multi-section cathode (as shown in Figure 1B) comprises cathode segments (A) and (B). The cathode section (A) of the battery contacts a first portion of the composite redox active additive composite electrolyte such that the battery-capacitor system can be discharged in the form of battery characteristics. The cathode section (B) of the capacitor contacts a second portion such that the battery capacitor discharges in the form of a capacitor characteristic. The cathode segments (A) and (B) are in continuous contact or have a spacing of between 0 mm (i.e., continuous) to several millimeters between materials. The cathode section (A) is preferably LiCoO ₃ And the cathode section (B) is preferably carbon.
The electrolyte used in the redox active additive composite electrolyte includes, but is not limited to, a glass ceramic electrolyte, a polymer electrolyte, and a mixture thereof. The glass ceramic electrolyte used includes, but is not limited to, Li ₂ S-Li ₂ P, LAGP and mixtures thereof. The polymer electrolytes used include, but are not limited to, PVDF, PEO, and mixtures thereof. When a glass ceramic electrolyte is used, the redox active additive is generally present in the glass ceramic electrolyte (based on the weight of the glass ceramic electrolyte) in an amount of from about 0.1% by weight to about 40% by weight. When a polymer electrolyte is used, the redox active additive is generally present in the polymer electrolyte (based on the weight of the polymer electrolyte) in an amount of from about 0.1% by weight to about 30% by weight.
A hybrid battery-capacitor having a redox active additive composite electrolyte is further illustrated by the following non-limiting examples:
Example HB1: with Li ⁺ -PVDF-Li _x CoO ₂ With MoO _3-x Hybrid battery-capacitor of redox active additive composite electrolyte membrane
Example P7 (Li ⁺ -PVDF-Li _x CoO ₂ ) with P8 (Li ⁺ -PVDF- MoO _3-x The 150 micron thick composite electrolyte isolating film is aligned with a lithium intercalated carbon anode electrode. Mixed cell-capacitor capacitor section of activated carbon paste and hybrid battery-capacitor battery section LiFePO ₄ The paste system is screen printed to form a multi-segment cathode pattern on a current collector foil. The screen printed foil is combined with a film to form a hybrid battery-capacitor.
Multi-section cathode:
Materials for battery cathode sections (A) that can be used for multi-section cathodes include, but are not limited to, LiCoO ₃ LiVO _x (where 0<x<3), Li ₂ Ti ₄ O ₁₂ (ie "LiTiO"), LiFePO ₄ And mixtures thereof. The materials in the cathode section (B) of the capacitor that can be used for the multi-section cathode include, but are not limited to, carbon, metals (e.g., antimony, iron, nickel), alloys thereof, intermetallics thereof, and mixtures thereof. The cathode section (B) of the capacitor has a reinforced surface area to increase the electrical double layer capacitance value.
As shown in Fig. 1A, the battery cathode section (A) of the multi-section cathode AB is used as a battery cathode. The cathode section (A) of the multi-section cathode AB contains LiVO, LiCoO ₂ LiMn ₂ O ₃ And mixtures thereof. In Fig. 1A, the capacitor section (B) of the multi-section cathode A- is made of, for example, carbon, carbon nanotubes, a barrier metal foil (e.g., tantalum), a barrier metal (e.g., iron, iron-chromium-nickel, tantalum). , tungsten, and mixtures thereof).
Multi-section cathodes using redox active composite electrolytes are further illustrated by the following non-limiting examples.
Example MSC1: Cast Battery Cathode - LiMn ₂ O ₄ With capacitor cathode - AC
Mixing molar ratio 1:4 in a ball mill in ethanol ₂ O ₃ With MnO ₂ Before the drive. The mixture was dried, ground to a powder, and then calcined at 650 ° C for 8 hours. The synthesized powder is then ground again. LiMn can be obtained by heat treatment in air at 750 ° C for 20 hours. ₂ O ₄ Spinel structure. LiMn ₂ O ₄ An activated carbon (AC) paste containing 10% by weight of a Teflon binder was cast on a current collector of a copper foil by screen printing to form a multi-section cathode electrode. The multi-section cathode electrode sheet was dried in a vacuum at 120 ° C for 48 hours to serve as a cathode electrode in a hybrid battery-capacitor.
Example MSC2:
The procedure described above with respect to example MSC1 was also used, except that the copper foil was replaced with aluminum.
Hybrid battery - capacitor electrode configuration:
2 to 10 illustrate an electrode configuration for illustrative purposes only and not limitation, which is used in a hybrid battery-capacitor using a redox active additive composite electrolyte. Figure 11 illustrates a multilayer configuration of a hybrid battery-capacitor.
A hybrid battery-capacitor system using a redox active additive composite electrolyte can be produced by coating a continuous side of a first side of a redox active additive composite polymer electrolyte membrane. The battery section cathode and cathode section anodes are coated to opposite sides of the film.
The redox active additive composite polymer suitable for use in a hybrid battery-capacitor is processed into a film by casting a redox active additive composite polymer electrolyte into one or more ribbons. The tape system can be formed into a tape stack structure that is then heat treated to produce a film. Alternatively, a single strip can be heat treated to produce a film. When a plurality of tape bodies are used in a stacked structure, the same or different polymer electrolytes are used for the tape system used in the stacked structure.
The first side of the film is coated with an anode material. Anode material coatings are formed by a variety of conventional methods, such as chemical vapor deposition, sputtering, silk screen printing, and combinations thereof. A first portion of the opposite side of the film is coated with the battery cathode material and another portion of the opposite side of the film is coated with the capacitor cathode material. Cathode material coatings are formed by a variety of conventional methods, such as chemical vapor deposition, sputtering, silk screen printing, and combinations thereof.
A proton supercapacitor using a thin film formed by a redox active additive composite polymer electrolyte:
In another aspect, a proton supercapacitor using a redox active additive complex polyelectrolyte, an anode, and a cathode is disclosed. These proton supercapacitors achieve improved energy storage compared to proton supercapacitors that do not use redox active additive complex polyelectrolytes.
The polymer electrolyte which can be used in the redox active additive composite polymer electrolyte includes, but is not limited to, Nafion, polyvinyl alcohol, polybenzimidazole, polyacetic acid, and mixtures thereof. The redox active additive for use in the redox active additive composite polymer electrolyte may include, but is not limited to, MnO _2-x (where 0<x<0.2), RuO _2-x (where 0 < x < 0.2), double layer hydroxide (DLH), such as cobalt hydroxide, nickel aluminum hydroxide, cobalt aluminum hydroxide, cobalt chromium hydroxide, nickel chromium hydroxide, and mixtures thereof. The redox active additive used can have various forms such as filaments, tubes, spheres, flakes, and mixtures thereof. The redox active additive can also be incorporated and deposited into the mesh holes that are embedded and surrounded by the electrolyte. The redox active additive may be used in the redox active additive composite polyelectrolyte in an amount of from about 0.01% by weight to about 50% by weight based on the weight of the polyelectrolyte.
A proton supercapacitor of a film formed using a redox active additive composite polyelectrolyte can be prepared according to the procedure disclosed in U.S. Patent No. 5,136,474, the entire disclosure of which is incorporated herein by reference. A proton supercapacitor using a thin film formed by a redox active additive composite polymer electrolyte is further described with reference to the following non-limiting procedures:
Procedure A: A symmetric electrochemical capacitor using activated carbon (about 100 microns thick) as the positive and negative electrodes is sandwiched together using a polymer composite film having a thickness of from about 20 microns to about 50 microns. The polymer film can be oxidized by proton conductive polymers such as, but not limited to, Nafion, sulfonated polydiether ketone, polyvinyl alcohol hydrated gel, polymethyl methacrylate methyl ester, and combinations thereof. Reducing an active filler (eg, one or more metal oxides having from about 1% to about 50% by weight manganese dioxide, molybdenum oxide, iron oxide; one or more metal double layer hydroxides, such as hydroxide a mixture of cobalt, cobalt aluminum hydroxide, nickel aluminum hydroxide or a mixture thereof; and one or more conductive polymers such as, but not limited to, a mixture of polyaniline, polypyrrole, and PEDOT thereof, for casting form. Typically, a slurry of about 85% by weight of activated carbon, about 10% by weight of tetrachloroethylene (Teflon) and about 5% by weight of acetylene black is mixed together using tetrahydrofuran as a solvent. The resulting mixture was applied to a thin carbon paper, dried and used as an electrode. Next, 5 g of polyvinyl alcohol was dissolved in about 20 ml of water to form a solution, and about 5% by weight of polyaniline (based on the weight of polyvinyl alcohol) was added to the solution. Then, about 2% by weight of glutaraldehyde (crosslinking agent) was added to the solution (based on the weight of the polyvinyl alcohol). The resulting solution ribbon is cast to a thickness of from about 20 microns to about 40 microns to form a film. The cast-formed film was dried and immersed overnight in about 1 M sulfuric acid to form a soaked composite film. Symmetrical capacitors (for example, in 2032 stainless steel coin cells or tetrachloroethylene Swagelok cells) can be made by laminating carbon electrodes with a soaked composite film.
Procedure B: an asymmetric electrochemical aqueous capacitor using activated carbon as a negative electrode and any one or more of manganese dioxide, nickel hydroxide or lead dioxide as a positive electrode, and a proton conductive polymer (for example, any one or more Nafion, sulfonated polydiether ketone, polyvinyl alcohol hydrated gum, polymethyl methacrylate methyl ester) together with any one or more redox active fillers (eg, metal oxides having about 1% by weight to About 50% by weight of any one or more of manganese dioxide, molybdenum oxide, iron oxide; or any one or more of double layer hydroxides, such as cobalt hydroxide, cobalt aluminum hydroxide, nickel aluminum hydroxide; The polymer composite film made of any one or more of conductive polymers such as, but not limited to, polyaniline, polypyrrole or PEDOT) is laminated.
Typically, about 85% by weight of activated carbon, about 10% by weight of tetrachloroethylene (Teflon) and about 5% by weight of acetylene black are mixed together using tetrahydrofuran (THF) as a solvent. The resulting mixture was applied to a thin carbon paper, dried, and used as a negative electrode. Similarly, a slurry containing about 70% by weight of manganese dioxide, about 20% by weight of acetylene black, and about 10% by weight of tetrachloroethylene (Teflon) was dissolved in tetrahydrofuran and applied to carbon paper. The dried paper was used as a positive electrode. The weight ratio of the positive electrode to the negative electrode can be changed from about 1:1 to about 3:1, respectively. Next, 5 grams of polybenzimidazole was dissolved in dimethylformamide overnight under reflux to form a solution, and about 5% by weight of cobalt hydroxide (based on the weight of polybenzimidazole) It is added to the solution to form a polymer solution. The polymer solution is cast into a film to form a film of from about 20 microns to about 50 microns thick. The cast formed film was dried and immersed overnight in about 4 M potassium hydroxide to form a soaked composite film. An asymmetric capacitor in a 2032 stainless steel coin cell or a tetrachloroethylene Swagelok battery can be obtained by laminating a positive electrode and a negative electrode with a soaked composite film.
Lithium ion capacitor with redox active additive composite electrolyte:
In another aspect, a lithium ion capacitor using a redox active additive composite electrolyte is disclosed. These capacitors achieve a significant increase in output voltage and capacitance. A lithium ion capacitor using a redox active additive composite electrolyte may use a cathode containing activated carbon, and an anode including lithium metal, lithium fossil mill, lithium titanate, ruthenium, gold, tin, and a mixture thereof.
The polyelectrolytes useful in the redox active additive composite electrolyte used in lithium ion capacitors include, but are not limited to, PVDF, HFP, PEO, mixtures thereof, and copolymers thereof. The redox active additive for use in the redox active additive composite electrolyte can include, but is not limited to, molybdenum trioxide, tin oxide, zinc oxide, and mixtures thereof. The amount of the redox active additive in the redox active additive complex polyelectrolyte is usually from about 0.05% by weight to about 50% by weight based on the weight of the polyelectrolyte. A lithium ion capacitor having a redox active additive composite electrolyte can be prepared in accordance with the procedures disclosed in U.S. Patent No. 7,00, 947, 778 and U.S. Patent No. 7,817, 403, the entire disclosure of which is incorporated herein by reference.
Fig. 12 shows the charging performance of a lithium ion capacitor using lithium metal as an anode, carbon as a cathode, and a PVDF polyelectrolyte containing various manganese dioxide, molybdenum trioxide and antimony as redox active additives. Manganese dioxide has an oxidation-reduction potential of 3 volts and is present in the PVDF polymer in an amount of 5% by weight (based on the weight of the PVDF polymer); molybdenum trioxide has an oxidation-reduction potential of 2 volts, and is 5 The amount by weight % (based on the weight of the PVDF polymer); and the ruthenium has an oxidation-reduction potential of 0.1 volt and is present in the PVDF polymer in an amount of 5% by weight based on the weight of the PVDF polymer in. The anode, cathode, and redox active additive polyelectrolyte were packaged in a glove box environment and assembled into coin cells. The charging performance of the battery was measured by a fixed current charging/discharging method using a standard potentiometer from Gamry.
A lithium ion capacitor using activated carbon as a positive electrode and any one or more of lithium, lithium titanate, lithium-doped stone mill, and lithium-doped ruthenium as a negative electrode is further described below. The electrode and the polymer colloid (for example, any one or more of polyvinylidene chloride, polyvinylidene chloride-co-hexafluoropropylene, polymethyl methacrylate, and polyacrylonitrile) together with about 5 weights A polymer composite film of from % to about 20% by weight of a redox filler (for example, any one or more of molybdenum oxide, tin oxide, vanadium oxide, and manganese dioxide) is laminated. For example, an activated carbon electrode is prepared by kneading a mixture of 85% by weight of activated carbon, 10% by weight of tetrachloroethylene (Teflon), and 5% by weight of acetylene black. The mixture was rolled up on an aluminum foil to be used as a positive electrode (thickness: 100 μm). A small amount of lithium was pressed on a 25 μm thick copper foil to be used as a negative electrode. Next, 5 g of PVDF-HFP was dissolved in 20 ml of DMF and stirred overnight to form a polymer solution. 5 wt% of molybdenum trioxide (based on the weight of PVDF-HFP) was added to the polymer solution, and ultrasonic vibration was performed. The resulting solution was cast to form a film, and dried for 4 hours, and then reversed with a large amount of ethanol. The cast film was then peeled off and dried under vacuum. The treated film will then be in 1 M LiPF ₆ Soak for 2 days in /EC/DMC to form a soaked film. A lithium ion capacitor is assembled by sandwiching the positive and negative electrodes together with the soaked film. The performance of the capacitor is illustrated in Figures 23-25. Figure 23 compares a fixed current discharge curve for a capacitor fabricated using a film treated with a molybdenum oxide redox active additive electrolyte compared to a film not treated with a redox active electrolyte. The capacitance shown in Figure 23 is increased by a factor of three under a similar discharge rate. Figure 24 shows the cycle stability of the capacitor, and Figure 25 shows the charge-discharge curve of the capacitor. The capacitor shows a capacitance of 250 Faradays/gram at the beginning and then a brief burst of high current cycling. Thereafter, when the capacitor was re-measured at a current of 100 mA/g, the capacitance was only slightly reduced.
Non-planar lithium ion hybrid composite film:
In another example, a non-planar lithium ion hybrid composite film using a redox active additive composite electrolyte is disclosed. The non-planar lithium ion hybrid composite film includes, but is not limited to, a cylindrical lithium ion mixed composite film as shown in FIG.
Figure 13 shows a cylindrical lithium ion hybrid composite film using an internal cathode, an external anode, and an intermediate redox active additive composite electrolyte. The electrolyte used in the redox active composite electrolyte may include, but is not limited to, ferric oxide and SiO _x (where 0.1<x<1.0). The redox active additive for use in the redox active composite electrolyte may include, but is not limited to, molybdenum trioxide. The amount of the redox additive in the electrolyte is usually from about 0.01% by weight to about 50% by weight based on the weight of the electrolyte. Non-planar lithium ion hybrid composite films can be made according to the procedures disclosed in U.S. Patent No. 6,426,863, the entire disclosure of which is incorporated herein by reference.
A film that polymerizes a composite electrolyte using a redox active additive can be used in many applications such as, but not limited to, supercapacitors, ultra high capacitors, primary batteries, secondary batteries, fuel cells, ion barrier films, gas barrier films, chemistry Sensor and desalting membrane. The polyelectrolyte used in the redox active additive composite electrolyte (note that the filler may be homogeneously or heterogeneously dispersed) includes, but is not limited to, polymers such as PVDF, PEO, and mixtures thereof, and compatible with electrolysis Salts and solvents are used together.
The redox active additive useful in the electrolyte (e.g., polyelectrolyte) can include, but is not limited to, manganese dioxide, iron oxide, nickel oxide, ruthenium, tin dioxide, molybdenum trioxide, gold, platinum, and mixtures thereof. The redox active additive may be present in the electrolyte in an amount sufficient to cause enhanced ionic conductivity, as well as a modified space charge distribution, one or more electrolytes, and an electrode. In general, the redox active additive may be present in the electrolyte in an amount of from about 0.01% by weight to about 99.9% by weight (based on the weight of the electrolyte), preferably from about 0.1% by weight to about 50% by weight, more preferably about 1% From % by weight to about 15% by weight. The redox active additive can be surrounded by the electrolyte and isolated from the cathode and anode. The size of the redox active additive can vary from about 0.1 nm to about 1 mm and can have a wide variety of configurations, such as dodecahedrons, cubes, irregular polyhedrons, sheets, rods, filaments. , cylindrical and their mixture.
The redox active additive may be randomly distributed in the electrolyte as a single type of form, may have a mixed form and a random distribution, may be mixed with the mixed form and coated on the surface of another active phase (eg, molybdenum trioxide) On the platinum). The redox active additive can also be aligned in parallel or perpendicular to the electrode passing through the electrolyte, which can be supported by an electric field and/or a magnetic field (depending on the electrical properties of the redox fill content). The redox active additive may also be continuously laminated with the electrode. When the redox active additive is in the form of a rod having a length of from about 1 nm to about 10 microns or in the form of a diameter of from about 0.1 nm to about 1 micron, the rod typically has a porosity of from about 0% to about 90%. Sex. When the redox active additive is in the form of a sheet, the sheet may have a width of from about 1 nanometer to about 100 microns and a thickness of from about 1 nanometer to about 1 micrometer, and from 0% to about 90% of the porous. Sex.
Production of a film comprising a redox active additive composite electrolyte:
The redox active additive composite electrolyte (for example, a redox active additive polyelectrolyte) can be formed on the belt by a method such as casting molding and extrusion. The tape body typically has a thickness of from about 0.1 microns to about 1000 microns, preferably from about 10 microns to about 400 microns.
The film comprising the redox active additive composite electrolyte can form a film by stacking a layer of a redox active additive composite electrolyte ribbon and compressing the stack. As an illustration, a redox-active iron oxide particle having a diameter of 1 nm was mixed with a ferrite rod having a diameter of 10 nm and a length of 1.0 μm to form a mixture. The mixture is then mixed with a PVDF polyelectrolyte to form a mixture. The mixture can be cast and formed, for example, by strip casting or extrusion to form a film. Casting can be carried out under strong magnetic fields, strong electric fields, or a combination thereof. When an electric field is used, the strength of the electric field is sufficient for the redox additive to be aligned with the direction in which the electric field is applied. Any one or more of an alternating current and a direct current electric field having a field strength of from about 0.1 volts/cm to about 10 volts/cm can be applied. When a magnetic field is applied to the redox additive (for example, those with magnetic anisotropy, such as ferric oxide, nickel oxide, and mixtures thereof), the field strength is sufficient to allow the redox additive to adjust with the direction of the applied magnetic field. quasi. Generally, the magnetic field that can be used has a strength of about 1000 Gauss or more.
The redox additives may be randomly distributed within the band, may have a spatially varying amount within the band, or may be present in a variety of sizes and shapes (as shown in Figures 15-21). For example, the ribbon used in the film comprising the redox additive can be placed parallel or perpendicular to the electrode (e.g., anode or cathode), and the redox additive can be distributed semi-continuously or discontinuously to the ribbon. Furthermore, the embedded regions of the redox additive can be placed parallel or perpendicular to the cathode or anode. In other aspects, such as shown in Figure 14, an unfilled air space may be present between the film and the electrode.
The tape bodies used in the specific embodiments shown in, for example, Figs. 15 to 21 may be laminated into a film to pass the ion conductive property through one or more layers of the film. The film may have a thickness of from about 0.01 microns to about 1 micron, preferably from about 0.1 microns to about 400 microns, and most preferably from about 1 micron to about 200 microns. The electrodes can be printed on the film by a number of methods such as, but not limited to, screen printing.
Solid oxide fuel cell using a redox active additive composite electrolyte:
In another embodiment, the invention is directed to a solid oxide fuel cell (SOFC) using a redox active additive composite electrolyte membrane. Compared with a solid oxide fuel cell using a conventional electrolyte, a solid oxide fuel cell using a redox active additive composite ceramic electrolyte film can have higher efficiency, increased ion current, long-term stability, and greater fuel elasticity. , lower divergence, shorter start-up time, improved ion diffusion kinetic energy, lower operating temperature, and improved dependence. A solid oxide fuel cell using a redox active additive composite electrolyte membrane can be operated at a lower temperature.
The electrolyte used in the redox active additive composite electrolyte film may include, but is not limited to, a ceramic electrolyte, a polyelectrolyte, and a combination thereof. Ceramic electrolytes that can be used include, but are not limited to, Y ₂ O ₃ -ZrO ₂ , Sc ₂ O ₃ -ZrO ₂ Bi ₂ V _1-x Me _x O _5.5-x/2 (where 0.05 < x < 0.3, Me is copper, titanium, zirconium, nickel, aluminum, cobalt, manganese, cerium, zinc, magnesium, and mixtures thereof). Polyelectrolytes that can be used include, but are not limited to, Nafion and mixtures thereof.
The redox active additive that can be used in the redox active additive composite electrolyte (for example, in a ceramic electrolyte) includes, but is not limited to, MnO _2-x (where 0<x<0.2), PbO, NiO _1-y (where 0<y<0.1), CuO, V ₂ O _5-z (where 0 < z < 0.5) and mixtures thereof. The amount of the redox active additive in the ceramic electrolyte is usually about 25% by weight based on the weight of the ceramic electrolyte. When the SOFC is a proton-based SOFC, the ceramic electrolyte may be a perovskite, such as BaCeO. ₃ , Y ₂ O ₃ Doped BaZrO ₃ And mixtures thereof. When ceramic electrolyte Y ₂ O ₃ Doped BaZrO ₃ Redox active additives that can be used with ceramic electrolytes include, but are not limited to, nickel, platinum, MnO _2-x (where 0<x<0.2), RuO _2-z (where 0 < z < 0.2), a double layer hydroxide (for example, cobalt hydroxide, nickel aluminum hydroxide, cobalt aluminum hydroxide, cobalt chromium hydroxide, nickel chromium hydroxide or a mixture thereof).
A solid oxide fuel cell that can use a redox active composite electrolyte is further illustrated by the following non-limiting examples:
Example FC1: 100 g of yttria-stabilized zirconia and 5 g of manganese monoxide were mixed by ball milling in ethanol. The mixture was dried, crushed to a powder, and formed into a ceramic disc by hydraulic compaction. The disc was rapidly burned in an oven at 1,700 ° C for 20 minutes under reduced pressure. After the platinum electrode was applied to either side by burning the air-dried platinum ink for 1500 degrees Celsius for 15 minutes, the sintered ceramic sheet was polished to be used as an electrode in a solid oxide fuel cell.
Redox Active Additive Composite Polymer Electrolyte Thin Film Fuel Cell (PEMFC):
In another embodiment, a polymer electrolyte membrane fuel cell (PEMFC) using a redox active additive complex polyelectrolyte is disclosed. The redox active additive composite polyelectrolyte used in PEFMC allows the fuel cell to operate at about 220 degrees Celsius or higher to achieve improved efficiency, improved energy density, improved current, improved cooling ease, and reduced Sensitivity to carbon monoxide poisoning of platinum catalysts. The polymer electrolyte of the redox active composite polymer electrolyte which can be used in the film of PEFMC includes, but is not limited to, Nafion. The redox active additive that can be used in the redox active additive complex polyelectrolyte includes, but is not limited to, MnO _2-x (where 0<x<0.2) and RuO _2-x (where 0 < x < 0.2) and mixtures thereof. The redox active additive may be present in the composite electrolyte in an amount of from about 0.1% by weight to about 20% by weight based on the weight of the polyelectrolyte.
Ceramic gas barrier film using a redox active additive composite electrolyte:
A film using a redox active additive composite ceramic electrolyte, such as for fluid isolation (e.g., gas barrier), is disclosed in another embodiment. These films can be used at temperatures up to about 1200 degrees Celsius and at temperature gradients up to about 700 degrees Celsius. Operation at these temperatures and gradients increases oxygen permeation (relative to gas barrier films that do not use redox active additive composite electrolytes).
The ceramic electrolyte which can be used in the redox active additive composite ceramic gas barrier film includes but is not limited to Y ₂ O ₃ -ZrO ₂ , Sc ₂ O ₃ -ZrO ₂ (La _1-x Ca _x ) _y FeO _3-δ (where 0 < δ < 0.3, 0.5 < x < 1.0, and 1.0 < y < 1.1) and mixtures thereof. The redox active additive that can be used in the ceramic electrolyte includes, but is not limited to, nickel, CeO _2-x (where 0<x<0.2), MnO _2-y (where 0 < y < 0.2) and mixtures thereof. The redox additive may be present in the ceramic electrolyte in an amount of from about 0.1% by weight to about 50% by weight based on the weight of the ceramic electrolyte. The redox active additive morphology can vary widely. The size of the redox active additive can also vary from about 1 nanometer to 1.0 micron. The redox active additive may be randomly distributed within the ceramic electrolyte or have a graded distribution.
The ceramic gas barrier film using the redox active ceramic electrolyte can be formed by a multilayer laminated board obtained by, for example, a belt casting and extrusion method. The electrodes can be bonded to the ceramic film by co-combustion or post-combustion of the electrode material on a ceramic film, as shown in US 20070237710 (the entire teachings of which are incorporated herein by reference).
A hydrogen barrier film using a redox active additive to polymerize a proton conductive electrolyte:
In another embodiment, a hydrogen barrier film using a redox active additive substance-conductive composite electrolyte is disclosed. These hydrogen barrier films can be used to isolate hydrogen from the mixed gas at temperatures ranging from about 20 degrees Celsius to about 200 degrees Celsius.
The polymeric proton conductive electrolyte that can be used with the redox active additive complexed polyelectrolyte includes, but is not limited to, Nafion, sulfonated polybenzimidazole, sulfonated polydiether ketone, polyimide, polyphosphazene, and Its composition. Sulfonated polybenzimidazoles which may be used include, but are not limited to, poly(2,5-benzimidazole), phosphoric acid doped poly(2,2'-(1,3-phenylene)-5,5 '-Bibenzimidazole) and a copolymer of PBI with a sulfonated polyfluorene, a sulfonated polydiether ketone, a pyridine-based PBI, and mixtures thereof; the polyimine that can be used includes, but is not limited to, 3'-bis(sulfophenoxy)benzidine, 2,2'-bis(sulfophenoxy)benzidine, 3,3'-bis(sulfopropoxy)benzidine, 2,2'-bis ( Sulfopropoxy)benzidine and mixtures thereof; polyphosphazenes which may be used include, but are not limited to, imidazolyl, ethylamino, ethylalanine, benzylalanine, ethylglycine, and mixtures thereof .
The redox active additive which can be used in the redox active additive composite polymeric proton conductive electrolyte includes, but is not limited to, cerium oxide, manganese oxide, and mixtures thereof. The redox active additive may be included in the polymeric proton conducting electrolyte sufficient to increase the amount of ion transport of protons through the membrane. Typically, the redox active additive is present in the polymeric proton conducting electrolyte in an amount of from about 5% by weight to about 10% by weight, based on the weight of the polymer.
A hydrogen barrier film using a redox active additive composite polymerized proton conductive electrolyte can be prepared by forming a mixture of one or more polymeric proton conductive electrolytes and one or more redox active additives to form a mixture. The mixture can then be cast into a film according to the procedure of U.S. Patent No. 4,664,761, the entire disclosure of which is incorporated herein by reference.
Electrode double layer capacitor (EDLC) electrode for desalination and purification of water:
In another embodiment, an electric double layer capacitor electrode utilizing a redox active additive composite electrolyte (eg, a redox active additive complex polyelectrolyte) can be used to desalinate water flowing through the electrode. In this aspect, water flows through a charged porous electric double layer capacitor rod electrode comprising a redox active additive composite electrolyte. The charged rod moves ions (such as hydrogen ions, sodium ions, calcium ions, potassium ions) in the water to a relatively charged EDLC rod electrode, wherein the ions can be adsorbed on the rod electrode. Voltage can be applied to the rod by various known means, such as solar cells, thermoelectric generators, and combinations thereof. The EDLC rod electrode can be regenerated by turning off the applied voltage so that the adsorbed ions can be released. The release of adsorbed ions can be controlled to enable current generation, such as discharge of a capacitor or battery.
The polymer electrolyte that can be used in the redox active composite polyelectrolyte in the rod can include, but is not limited to, Nafion, polybenzimidazole, polyetheretherketone, and combinations thereof. Redox active additives that may be used include, but are not limited to, molybdenum trioxide. The redox active additive may be present in the polyelectrolyte in an amount of from about 0.1% by weight to about 30% by weight based on the weight of the polyelectrolyte. For the sake of explanation, PVDF (molecular weight = 5.73 × 10) ⁵ And PMMA (molecular weight = 1.04 × 10) ⁵ Mixing to provide a mixture of 25% by weight copolymer mixture and 75% by weight cyclobutanide to form a polymer solution. The mixture was heated to 180 degrees Celsius for 3 hours under nitrogen. Then, 10% by weight of a stacked double layer hydroxide (LDH) powder (e.g., cobalt-aluminum, nickel-aluminum, manganese-aluminum, zinc-aluminum, based on the weight of the mixture) is added to the mixture. The LDH powder is prepared by coprecipitating a mixture of individual nitrate solutions in sodium hydroxide solution (using sodium carbonate as a stabilizer). The precipitate thus prepared was refluxed at 60 ° C for 18 hours, and then washed and dried. The LDH powder was added to the polymer suspension and mixed for about 2 hours. Next, the polymer suspension is rapidly quenched, cracked, chopped and ground at a liquid nitrogen temperature to grind the polymer into a powder. The polymer powder is compressed into a crystal stone composite sheet at from about 10,000 to about 50,000 pounds per square inch, at about 180 degrees Celsius. These composite sheets were quenched in ice and then exposed to deionized water to extract the cyclopentane. After this, the composite sheet was vacuum dried at 50 degrees Celsius for 24 hours.
Potential type chemical sensor:
In another aspect, a redox active additive composite electrolyte (eg, a redox active additive composite glass electrolyte, a redox active additive composite ceramic electrolyte, and mixtures thereof) can be used in a potential type chemical sensor, such as oxygen sensing. And pH sensor. Potentiometric chemical sensors using any one or more redox active additive glass composite electrolytes and redox active additive ceramic composite electrolytes can be used to detect trace gases (eg, nitrogen dioxide, oxygen, nitrogen in carbon monoxide, The ability to improve sulfur dioxide and its mixtures). These sensors can show improved sensitivity to proton concentration and can increase the voltage potential at a given proton concentration (as compared to a silver wire reference electrode).
The glass electrolyte that can be used in the redox active additive composite glass electrolyte potential type chemical sensor includes, but is not limited to, glass, such as a sulfur-based compound glass, a lithium-doped borosilicate glass, and mixtures thereof.
The sulfur-based compound glass that can be used includes, but is not limited to, manganese-doped As ₂ S ₃ Ge ₂₈ Sb ₁₂ Se ₆₀ And mixtures thereof. Lithium-doped borosilicate glasses that can be used include, but are not limited to, lithium-doped borosilicate glass.
When the potential type chemical sensor is a pH sensor, the ceramic electrolyte used in the redox active additive composite electrolyte may be included but not limited to Y ₂ O ₃ Doped ZrO ₂ . When the potential type chemical sensor is an oxygen sensor, the ceramic electrolyte used in the redox active additive composite electrolyte may be included but not limited to Y ₂ O ₃ Doped ZrO ₂ , bismuth copper vanadium oxide and mixtures thereof.
The redox active additive for use in any one or more redox active additive composite ceramic electrolytes and redox active additive glass electrolytes may include, but is not limited to, MoO ₃ FeO _x (where 0<x<1.5), MnO _y (where 0<y<1), NiO _z (where 0<z<1.5), CuO _x (where 0<x<1.5), TiO _y (where 0<y<2), FeO, Si, Pb, Ni, (La,Sr)(Mn,Co)O ₃ And mixtures thereof.
The redox active additive may be present in any one or more of the glass electrolyte and ceramic electrolyte in an amount sufficient to cause a potential enhancement. Typically, these amounts are from about 1% to about 30% by weight, based on the weight of the electrolyte.
Electrofilm extraction film:
In another embodiment, the redox active additive composite polymer electrolyte can be used as a thin film in an electrical thin film extraction of an ionic species by applying an electric field as electroplating-dialysis and electroplating-electrodialysis. The thin film system using the redox active additive composite polymer electrolyte can be used for water desalination, wastewater treatment to recover electroplating bath such as gold, platinum, silver, copper, palladium, zinc, tin, lead, nickel, cadmium and mixtures thereof. Equal heavy metals, wet metallurgy, paper and photography. Other applications include deacidification of proteins, amino acids, sugars, etc. in the food and pharmaceutical industries, removal of peptides, and removal of toxic/harmful drugs from water.
The polymer electrolyte used in the redox active additive composite electrolyte used in the film for electric film extraction contains polyvinyl alcohol, polyacrylic acid, polybenzimidazole, polydiether ketone, and a mixture thereof.
The active additive used in the redox active additive composite electrolyte used in the film for electric thin film extraction includes, but is not limited to, manganese dioxide, double layer hydroxide ("LDH", such as cobalt hydrate, nickel aluminum hydrate , cobalt nickel hydrate, cobalt chromium hydrate, nickel chromium hydrate), lead dioxide, and mixtures thereof. The amount of the redox active additive used in the redox active additive composite electrolyte such as the redox active additive composite polymer electrolyte in the film for electric thin film extraction is sufficient to produce a higher separation rate. In general, the redox active additive is present from about 0.1% to about 25% by weight, based on the weight of the polymer electrolyte.
The electro-film-extracted film is made by the following procedure shown in U.S. Patent No. 4,226,688, the disclosure of which is incorporated herein in its entirety by reference. Electrofilm-extracted films are further illustrated by the following non-limiting examples:
Example EM1: A 25% by weight scientific polymer product, PMMA (Mw = 93300, Mn = 46,400), and 75% by weight of tert-butanol (reagent grade JT Baker Chemical Co.) were mixed to form a solution. In this solution, a WO which has been ball milled to have an average particle diameter of 1 μm is added. _3-d Powder (5% by weight) was annealed at 750 ° C for 3 hours in a forming gas (hydrogen 5%, nitrogen 95%). The polymer solution and suspension were continuously stirred for 120 minutes at 55 degrees Celsius to maximize mixing of the filler particles. Thereafter, the mixture was quenched to room temperature in 1 minute by cooling water, and cast on a glass plate to form a film. The mixture was then placed in a desiccator and a rotary vacuum pump was used to remove the solvent. Next, the vacuum was replaced with argon and steamed again for 5 hours for 5 hours to have a redox inclusion WO. _3-d The microporous PMMA film is formed.
Electrochromic device using a redox active additive polymer electrolyte composite electrolyte:
In another embodiment, an electrochromic device comprising an anode, a cathode, and a redox active additive polymer electrolyte composite electrolyte is disclosed. The electrochromic device comprises an electrochemical unit that can change color during the redox reaction occurring at the electrodes of the unit. Electrochromic behavior such as color change is due to anode material (eg WO ₃ ) caused by a change in the oxidation state.
An electrochromic device using a redox active additive polymer electrolyte uses a cathode made of a conductive material such as polyaniline, cerium oxide, vanadium oxide, and a mixture thereof. The polymer electrolyte used includes, but is not limited to, a gel electrolyte (eg, a gel mixture (eg, PVDF-HFP/LiClO) ₄ /EC/DMC) and its combinations. The redox active additive that can be used in the redox active additive composite polymer electrolyte includes, but is not limited to, MoO ₃ V ₂ O ₅ And mixtures thereof. The amount of redox active additive is between about 1% and about 5% by weight based on the weight of the polymer electrolyte. However, when using such as PEO-H ₃ PO ₄ In the case of the gel electrolyte, the amount of the redox active additive in the gel electrolyte is between about 0.1% by weight and about 10% by weight based on the weight of the gel electrolyte. An electrochromic device utilizing a redox active additive composite polymer electrolyte exhibits improved electrochromic opacity (for example, in an electrochromic device in a color translucent state (usually blue) with a transparent Occurs when the state changes.) The electrochromic device using the redox active additive polymer electrolyte composite electrolyte can be manufactured by the method disclosed in, for example, U.S. Patent Nos. 5,099,356 and 4,773,741, the disclosure of which is incorporated herein by reference. Into this article.
An energy storage device using a redox active additive composite electrolyte film or a thick film:
The energy storage device using the thin film formed by the redox active additive composite electrolyte exhibits a shorter inter-electrode ion transport diffusion length, which can lower the neutral time constant of the device and increase the power density. The film formed from the redox active additive composite electrolyte can be used to reduce the size of a miniaturized energy storage device in a surface-mounted energy storage element. These miniaturized devices include sub-micron thick layers and provide energy storage points on multiple boards in an electrical system and eliminate the need to use a central, single energy source. These miniaturized devices provide backup power when the primary power source fails.
The film layer using the redox active additive composite electrolyte is prepared by a gas gel deposition method and by a sol-gel deposition method, preferably by a gas gel deposition method. The thickness of the film layer is between about 100 nanometers and about 300 microns. The gas gel deposition method and the sol-gel deposition method can be used to form a film layer combination in which the film layer is formed of a redox active additive composite electrolyte. An energy storage device using a redox active additive composite electrolyte film or thick film is further illustrated by the following non-limiting examples:
Example CF1:
A lithium aluminum bismuth phosphate (LAGP) composite system and a thin film of a redox active phase having a thickness of from about 10 nm to about 1 micron are co-deposited using radio frequency sputtering/DC sputtering techniques. The LAGP glass material is cast into a 2 inch diameter die to form a transparent glass sheet which is annealed at about 850 degrees Celsius for about 2 hours to 4 hours to form a suitable sputtering. Target. Gold as a redox active phase, and at about 10 ^-6 The torch is co-sputtered with LAGP in an argon atmosphere under vacuum. The deposition rate of each component is controlled to obtain a volume ratio of 95/5 to produce a film which is annealed between 300 degrees Celsius and 600 degrees Celsius for about 30 minutes to about 4 hours to form a composite electrolyte membrane layer. .
A gas-gel deposited ion-conducting composite thin/thick film electrolyte composite containing redox active inclusions:
Films having a thickness of from about 100 nm to about 10 microns, and generally thick films having a thickness of from about 1 micron to about 300 microns, can be obtained from a wide variety of redox active additives by gas gel deposition. A composite ionic conductive electrolyte is formed. The ionic conductive electrolyte used includes, but is not limited to, a sodium ion conductive electrolyte, a lithium ion conductive electrolyte, and a mixture thereof. When a lithium ion conductive electrolyte is used, a lithium ion conductive electrolyte (eg, LLT electrolyte, LAGP glass electrolyte, glass electrolyte of LiS-chalcogenide, and mixtures thereof) is mixed with one or more redox active additives, and by gas A lithium conductive electrolyte membrane layer having a thickness of from about 1 micrometer to about 300 micrometers is formed by a gel deposition method.
Lithium ion conductive electrolytes and redox active additives (such as, but not limited to, MoO) ₃ Particles) are used together for use in a gas gel deposition process. The relative amounts of the lithium conductive electrolyte and the redox active additive can vary widely to provide a redox active additive composite electrolyte composition suitable for gas gel deposition of a film layer (e.g., a film and a thick film).
By way of non-limiting example, from about 1% to about 99% by weight of LLT powder (eg, 95% by weight of LLT) and from about 1% to about 99% by weight of MoO ₃ (for example, 5% by weight of MoO ₃ The mixture of powders is ball milled to form a blend having an average particle size of from about 100 nanometers to about 10 microns. LLT and MoO ₃ The powders were each lyophilized. The ball milling is carried out under drying or in the presence of a liquid such as ethanol or propan-2-ol. The milled blend is combined with a fluid (eg water) for use in MoO ₃ Redox active additive LLT composite electrolyte film and MoO ₃ The redox active additive LLT composite electrolyte thick film in the gas gel deposition.
The gas gel deposition process can be used to deposit a thin film or thick film on a substrate material such as germanium wafer, stainless steel or other oxide. The substrate is previously coated with an electrode material. The electrode material is varied depending on the type of structure to be formed. When a supercapacitor structure is to be formed, suitable electrode materials include, but are not limited to, Pt, Au, Ni, Ta, W, Al, Fe, high surface area carbon (e.g., carbon nanotubes), and mixtures thereof. When a cell structure is to be formed, the electrode material comprises a redox active species, such as a lithium intercalation material such as, but not limited to, Si, LTO, LiCoO, LiMnO, and mixtures thereof. The composition of the anode electrode and the cathode electrode is matched to a battery structure type device.
The composite electrode is formed by simultaneous gas-gel deposition of two powders (by a double deposition stream of premixed powder or by a single deposition stream). The composite will comprise an ionic conductive species and a lithium barrier material that will produce a high surface area electrode material. The thin film coated substrate (both in electrode form and non-electrode form) is annealed under a wide range of temperatures and in a variety of environments at a pressure range to enhance the crystallinity of the film and to enhance the interface of the film to the substrate. Bonding. Annealing can be carried out under a variety of temperature, pressure, time and environmental conditions to minimize diffusion of the film to the substrate. When a LTO electrolyte film is composited on a redox active additive (for example, MoO on one of substrates such as stainless steel) ₃ The active additive LTO composite electrolyte film is annealed in an atmosphere of about 0.01 to about 16 psig at about 0.01 to about 16 psig for about 5 hours at about 300 degrees Celsius to about 600 degrees Celsius. It takes about 10 hours.
An electrochemical energy storage device (such as a battery or supercapacitor) can use a lithium metal-deposited anode (e.g., by evaporation) to provide a reversible source of lithium. The lithium metal electrode is protected by a protective coating of an epoxy resin or polymer such as polypropylene or Teflon to protect the lithium from oxidation. The electrical contacts to the lithium electrodes are provided via a contact metal, such as silver, aluminum, alloys thereof, and mixtures thereof. The contact metal is applied to the electrode prior to application of the protective coating. A gas-gel deposited ion-conducting composite thin/thick film electrolyte composite having redox active inclusions is further illustrated by the following non-limiting examples.
Example AF1:
Thick films having a thickness of from about 100 nm to about 10 microns are made by a gas gel deposition process. A fine powder of lithium aluminum strontium phosphate and tin oxide (about 100 nm to about 900 nm) is deposited on a platinum or carbon substrate by gas gel deposition to produce a film layer. The film is post-annealed from about 500 degrees Celsius to about 800 degrees Celsius for 30 minutes to about 2 hours to form an electrolyte.
Sol-gel deposited composite lithium conductive film electrolyte:
A MoO can be produced using a sol-gel program ₃ The redox active additive LLT composite electrolyte. By using sol-gel, nano-sized MoO can be dispersed in LHT precursor solution dissolved in 2-methoxyethanol, such as lithium ethoxide, titanium isopropoxide, and bismuth isopropoxide. ₃ The particles (having a size ranging from about 10 nm to about 500 nm) are used to form the sol.
Use deionized water (DI H ₂ O) The metered lithium ethoxide, titanium isopropoxide, bismuth isopropoxide and 2-methoxyethanol are partially hydrolyzed to form a precursor solution. Adding MoO in a ratio of 5 wt% to 50 wt% (relative to the amount of LLT) in the precursor solution ₃ The particles are added and stirred vigorously to make MoO ₃ Particles are dispersed to produce a MoO ₃ Active Additive LLT Electrolyte Composite Precursor Solution. The composite precursor solution is used to prepare a sol-gel film by a method such as drop coating or spin coating on a suitable substrate (for example, a substrate coated with platinum). Whether using a drop coating method or a spin coating method, the deposited first layer is pyrolyzed at 400 degrees Celsius (for example, in a rapid thermal annealing furnace). Next, on the pyrolyzed layer, the other layers are deposited and pyrolyzed to establish a desired film thickness. After reaching the desired film thickness, the film was heat treated in an oxidizing atmosphere for about 6 hours at about 700 degrees Celsius.
Sputtered redox active additive composite electrolyte film:
The redox active additive composite electrolyte film can also be prepared by sputtering, in which two or more sputtering targets are used. A first sputter target is an ionic conductive electrolyte such as, but not limited to, LLT. Another sputtering target is a redox active additive material such as, but not limited to, LiCoO ₂ .
The sputter deposition of the thin film and the thick film is performed by alternately sputtering the target to produce a chemically heterogeneous film of one of the redox active additive composite electrolytes. Typical film thicknesses range from 10 nanometers to 2 microns. The sputtering temperature is sufficient to mitigate significant internal diffusion. The sputtering temperature used was varied from about 100 degrees Celsius to about 800 degrees Celsius. When the sputtering of the redox active additive is performed, the sputtering period of the redox active additive may be pulsed. This can result in a diversity of chemical distributions from separate island to continuous layers.
The thin film of the redox active additive composite electrolyte can also be prepared by sputtering a single composite target to produce a homogeneous film, wherein the single composite target comprises a conductive glass ceramic electrolyte (such as but not limited to LAGP). With a redox active additive (such as, but not limited to, gold). When LAGP is used, the gold system can act as a redox active additive, for example, the amount of gold is about 5% by weight (based on the weight of the LAGP). The deposited film is annealed at a suitable temperature to precipitate a redox active additive in the electrolyte, whereby the redox active additive acts as a redox active site. When gold is used with LAGP, the annealing is carried out at about 800 degrees Celsius to precipitate gold in the LAGP glass-ceramic substrate to allow gold to act as a redox active center.

A, B. . . Cathode section

MnO ₂ . . . manganese dioxide

MnO ₃ . . . Manganese trioxide

1A and 1B are respectively a top view and a side view of a hybrid battery capacitor having a multi-section cathode.
Figures 2 through 10 illustrate electrode configurations that can be used in hybrid battery capacitors.
Figure 11 depicts a multilayer configuration for a hybrid battery capacitor.
Figure 12 illustrates the charging performance of a lithium ion capacitor.
Figure 13 depicts a cylindrical lithium ion hybrid composite film.
Figure 14 depicts a device for the presence of an unfilled air space between the membrane and the electrode.
Figures 15 to 21 respectively show the bands of redox active additives having different morphologies in the film.
Figure 22 depicts a lithium-air battery using a ceramic film.
Figure 23 depicts the effect of a redox active electrolyte on the constant current discharge of a capacitor.
Figure 24 depicts the effect of redox active electrolyte on cycle stability.
Figure 25 depicts the effect of redox active electrolyte on charge-discharge behavior.

A, B. . . Cathode section

Claims (26)

An ion conductive redox active additive composite electrolyte comprising an ion conductive component and a redox active additive, wherein the ion conductive component is selected from the group consisting of an ion conductive polymer, an ion conductive glass-ceramic, and an ion A group of conductive ceramics and mixtures thereof. A capacitor comprising an anode, a cathode and an ion conductive redox active additive composite electrolyte, the ion conductive redox active additive composite electrolyte comprising an ion conductive polymer and a redox active additive, The ion conductive component is selected from the group consisting of an ion conductive polymer, an ion conductive glass-ceramic, an ion conductive ceramic, and a mixture thereof. A galvanic cell comprising an anode, a cathode and an ion conductive redox active additive composite electrolyte, the ion conductive redox active additive composite electrolyte comprising an ion conductive component and a redox active additive, The ion conductive component is selected from the group consisting of an ion conductive polymer, an ion conductive glass-ceramic, an ion conductive ceramic, and a mixture thereof. A secondary battery comprising an anode, a cathode and an ion conductive redox active additive composite electrolyte, the ion conductive redox active additive composite electrolyte comprising an ion conductive polymer and a redox active addition And the ion conductive component is selected from the group consisting of an ion conductive polymer, an ion conductive glass-ceramic, an ion conductive ceramic, and a mixture thereof. The electrolyte according to claim 1, wherein the ion conductive polymer is selected from the group consisting of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polyvinylidene fluoride-tetrafluoroethylene, and polyethylene terephthalate. A polymer of the group consisting of difluoroethylene-chlorotrifluoroethylene, polyvinylidene fluoride-trifluoroethylene, and mixtures thereof. The electrolyte according to claim 1, wherein the ion conductive polymer is selected from the group consisting of a silver ion (Ag ⁺ ) conductive polymer, a hydrogen ion (H ⁺ ) conductive polymer, and a hydroxide ion (OH ^- a conductive film, a lithium ion (Li ⁺ ) conductive polymer, a magnesium ion (Mg ⁺ ) conductive polymer, a sodium ion (Na ⁺ ) conductive polymer, an oxygen ion (O ^- ) conductive polymer, and A group of mixtures. The electrolyte of claim 5, wherein the redox active additive is selected from the group consisting of redox active oxides, redox active metals, and mixtures thereof. The electrolyte of claim 5, wherein the polymer is a lithium ion (Li ⁺ ) polymer, and the redox active additive is selected from the group consisting of molybdenum trioxide (MoO ₃ ), tin oxide (SnO ₂ ) , tungsten oxide (WO ₃ ), lead monoxide (PbO), zinc oxide (ZnO), iron oxide (Fe ₂ O ₃ ), chromium oxide (Cr ₂ O ₃ ), vanadium pentoxide (V ₂ O ₅ ), A group consisting of manganese dioxide (MnO ₂ ), lithium titanium oxide (LiTiO ₃ ), and mixtures thereof. An ion-conductive redox active oxide composite electrolyte comprising a lithium ion (Li ⁺ ) conductive polyvinylidene fluoride-hexafluoropropylene polymer and a mixture of molybdenum trioxide, tin oxide, platinum (Pt) and mixtures thereof One of the constituent redox active additives is selected from the group consisting of. A battery unit comprising an ion conductive polymer redox active oxide composite electrolyte comprising lithium ion (Li ⁺ ) conductive polyvinylidene fluoride-hexafluoride One of a redox active additive selected from the group consisting of molybdenum trioxide, tin oxide, platinum (Pt), and mixtures thereof, a activated carbon cathode, a lithium metal anode, and a carbon paper current collection Device. An ion conductive glass-ceramic redox additive composite electrolyte comprising an ion conductive glass-ceramic and a redox additive, wherein the ion conductive glass-ceramic is selected from the group consisting of a sulfur-based compound glass-ceramic, fluoride A group consisting of glass-ceramic, oxide glass-ceramic, phosphate glass-ceramic, sulfide glass-ceramic, and mixtures thereof. The electrolyte according to claim 11, wherein the redox active additive is selected from the group consisting of a redox active metal, a redox active oxide, a redox active nitrogen oxide, and a mixture thereof. The electrolyte according to claim 11, wherein the redox active additive is selected from the group consisting of gold, platinum, palladium, tin, aluminum, iron, bismuth, copper-tin alloy, copper-bismuth alloy, bismuth, and alloy thereof. A redox active metal of the group consisting of a mixture thereof. The electrolyte according to claim 11, wherein the redox active additive is selected from the group consisting of cerium oxide, cerium oxide, cerium oxide, boron oxide, calcium oxide, chromium oxide, cobalt oxide, copper oxide, cerium oxide, and oxidation. Indium, iron oxide, lead oxide, lithium cobalt oxide, lithium oxide, lithium titanate, lithium iron phosphorus oxide, iron phosphorus oxide, phosphorus oxide, lithium vanadium oxide, manganese oxide, molybdenum oxide, cerium oxide, oxidation A redox active oxide of the group consisting of silver, tin oxide, titanium oxide, tungsten oxide, vanadium oxide, zinc oxide, and mixtures thereof. The electrolyte of claim 11, wherein the redox active additive is a redox active nitrogen oxide. An electrochemical capacitor comprising an anode, a cathode, and an electrolyte as described in claim 1. A solid state battery comprising a composite ion conductive polymer-redox active additive electrolyte body, a cathode layer, an anode layer, a first collector electrode and a second collector electrode, the cathode layer being bonded to the a surface of the electrolyte body comprising an electrode active material and the composite electrolyte, the anode layer being bonded to a surface of the composite electrolyte and comprising an electrode active material and the composite electrolyte, the first collector electrode being electrically connected to the A cathode layer, the second collector electrode being electrically connected to the anode layer. A fuel cell comprising an anode, a cathode, an ion conductive composite electrolyte and a fluid oxidant, the ion conductive composite electrolyte comprising an ion conductive polymer having a redox in the ion conductive polymer Active additive. A fuel cell comprising an anode, a cathode, and an ion conductive composite electrolyte, the ion conductive composite electrolyte comprising an ion conductive ceramic and having a redox active additive. A film suitable for use in a hybrid capacitor or battery, wherein the film comprises an anode, a cathode, and a redox active additive composite electrolyte, wherein the film comprises a separation region as a battery or a capacitor. A lithium-air battery comprising a lithium anode, an air cathode, and a redox active additive composite electrolyte, wherein the composite electrolyte comprises an ion conductive glass ceramic and a redox active additive. A magnesium-air battery comprising a magnesium anode, an air cathode, and an ion conductive redox active additive composite electrolyte. A film suitable for electro-optical film extraction of ionic substances, comprising an ion-conductive redox active additive composite electrolyte, wherein the composite electrolyte comprises an ion conductive polymer and a redox active additive. A potential type chemical sensor, wherein the improvement comprises a film comprising an ion conductive redox active additive composite electrolyte, wherein the composite electrolyte comprises an ion conductive component and a redox active additive, wherein the ion The conductive component is selected from the group consisting of ion conductive glass ceramics, ion conductive ceramics, ion conductive polymers, and mixtures thereof. An electrochromic display film comprising an anode, a cathode and an ion conductive redox active additive composite electrolyte, wherein the ion conductive redox active additive composite electrolyte comprises an ion conductive component polymer and an oxidation The active additive is reduced, wherein the ion conductive component is selected from the group consisting of an ion conductive polymer, an ion conductive glass ceramic, and a mixture thereof. A water desalination film comprising an ion conductive redox active additive composite electrolyte, wherein the composite electrolyte comprises an ion conductive polymer and a redox active additive.